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Review

pubs.acs.org/CR

Laser Synthesis and Processing of Colloids: Fundamentals and


Applications
Dongshi Zhang, Bilal Gökce, and Stephan Barcikowski*
Technical Chemistry I and Center for Nanointegration Duisburg-Essen (CENIDE), University of Duisburg-Essen,
Universitaetsstrasse 7, 45141 Essen, Germany

ABSTRACT: Driven by functionality and purity demand for applications of inorganic


nanoparticle colloids in optics, biology, and energy, their surface chemistry has become a
topic of intensive research interest. Consequently, ligand-free colloids are ideal reference
materials for evaluating the effects of surface adsorbates from the initial state for
application-oriented nanointegration purposes. After two decades of development, laser
synthesis and processing of colloids (LSPC) has emerged as a convenient and scalable
technique for the synthesis of ligand-free nanomaterials in sealed environments. In
addition to the high-purity surface of LSPC-generated nanoparticles, other strengths of
LSPC include its high throughput, convenience for preparing alloys or series of doped
nanomaterials, and its continuous operation mode, suitable for downstream processing. Unscreened surface charge of LSPC-
synthesized colloids is the key to achieving colloidal stability and high affinity to biomolecules as well as support materials,
thereby enabling the fabrication of bioconjugates and heterogeneous catalysts. Accurate size control of LSPC-synthesized
materials ranging from quantum dots to submicrometer spheres and recent upscaling advancement toward the multiple-gram
scale are helpful for extending the applicability of LSPC-synthesized nanomaterials to various fields. By discussing key reports on
both the fundamentals and the applications related to laser ablation, fragmentation, and melting in liquids, this Article presents a
timely and critical review of this emerging topic.

CONTENTS 5.3.2. Solid Additives 4036


5.3.3. Concentration 4036
1. Introduction 3991 5.3.4. Layer Thickness 4038
1.1. Overview 3991 5.3.5. Flow 4039
1.2. Status of Specific LSPC Fields 3992 5.3.6. Viscosity, Temperature, Pressure, and
1.3. Scope of the Current Review 3993 Supercritical Fluids 4040
2. Principal Laser Synthesis Methods 3994 5.4. Laser Parameters 4042
2.1. Laser Ablation in Liquids (LAL) 3994 5.4.1. Pulse Duration 4042
2.1.1. Plasma and Bubble Dynamics 3995 5.4.2. Laser Wavelength 4045
2.1.2. Nanoparticle Formation 3999 5.4.3. Laser Fluence and Focusing 4047
2.1.3. Reactive Laser Ablation in Liquids (RLAL) 4000 5.4.4. Spatial Laser Pulse Delivery 4048
2.2. Laser Fragmentation in Liquids (LFL) 4002 5.4.5. Repetition Rate 4050
2.3. Laser Melting in Liquids (LML) 4007 6. Applications 4051
3. Size Control 4010 6.1. Magnetism 4051
3.1. Laser Modulation 4012 6.2. Optics 4053
3.2. In Situ Size Control by Surface Chemistry 4013 6.2.1. Semiconductor Optics 4053
4. Upscaling 4016 6.2.2. Carbon Dots 4055
4.1. Laser Parameters for LAL Upscaling 4017 6.2.3. Doping, Upconversion 4055
4.2. Material Geometry for LAL Upscaling 4019 6.2.4. Optical Limiters 4056
4.3. Liquid Properties and Process Parameters for 6.3. Plasmonics 4056
LAL, LFL, and LML Upscaling 4021 6.4. Biology 4058
5. Material, Process, Liquid, and Laser Parameters 4023 6.4.1. Toxicity 4058
5.1. Material Properties 4023 6.4.2. Bioconjugates 4058
5.1.1. Composition 4023 6.4.3. Antibacterial and Ion Release 4060
5.1.2. Shape 4026 6.4.4. Micronization and Solubilization of
5.2. Process Parameters 4027 Drugs 4061
5.2.1. Processing Time 4027 6.4.5. In Vitro Application 4061
5.2.2. Downstream Processing 4029
5.3. Liquid Properties 4031
5.3.1. Composition 4031 Received: July 19, 2016
Published: February 13, 2017

© 2017 American Chemical Society 3990 DOI: 10.1021/acs.chemrev.6b00468


Chem. Rev. 2017, 117, 3990−4103
Chemical Reviews Review

6.4.6. In Vivo Application 4063 This increased attention is highlighted by the growth of
6.5. Analytical Chemistry (SERS, SEIRA, and LDI- citations in the past decade obtained by searching the ISI Web of
MS) 4064 Science with the keywords “laser” and “nanoparticle” (Figure
6.6. Catalysis and Energy 4065 1a). The underlying reason for this rapid advancement is the
6.6.1. Reference Materials, Model Reactions 4066 steadily increasing output power of pulsed laser systems,
6.6.2. Supported Catalysts 4067 enabling an increased yield of NMs through laser synthesis
6.6.3. Water Oxidation (Splitting) 4068 (Figure 1b) and significantly reducing the investment cost per
6.6.4. Photocatalyst 4068 laser power (Figure 3b). As compared to laser ablation synthesis
6.6.5. Hydrogen Fuel Cell 4068 in air, which may endanger researchers’ health by causing
6.6.6. Biofuel Cell and Glucose Oxidation 4068 workplace contamination with aerosols,13 a liquid is a relatively
6.6.7. Solar Cell 4069 safe medium for laser synthesis and processing (Figure 1c) and
6.6.8. Friction Reduction 4070 has the advantage of confining the resulting NMs. In contrast to
6.7. Environmental Protection 4070 pulsed laser deposition,14−16 in which thin films or nanostruc-
7. Summary of Advantageous Properties Correlated tures are formed in place and immobilized on a substrate via
to Application Prospects 4072 vacuum techniques, liquid processing facilitates the transfer of
8. Outlook and Challenge 4075 NMs to different substrates and requires simple processing
Author Information 4075 apparatus (often just a solid plate and a vial of water). The laser
Corresponding Author 4075 synthesis and processing of colloids (LSPC, Figure 2a) can be
ORCID 4075 classified into three methodologies: laser ablation in liquids
Notes 4076 (LAL), laser fragmentation in liquids (LFL), and laser melting in
Biographies 4076 liquids (LML). Overall, the field is interdisciplinary, involving
Acknowledgments 4076 chemistry, physics, and related subdisciplines (Figure 1d). Since
References 4076 the pioneering reports of Patil et al.17 on LAL and of Fojtik and
Henglein on the laser synthesis of colloids,18,19 LAL has been
demonstrated to be a scalable20−22 and versatile method for NP
synthesis. The derivative LSPC techniques of LML and LFL
1. INTRODUCTION allow precise size control of the synthesized colloidal NMs over a
wide range from several micrometers23 to ∼1 nm,24 where gold
1.1. Overview particles have been studied most intensively because of their
The past decade has witnessed the fast expansion of nano- tunability from 400 to 4 nm11 or even smaller, approaching gold
technology and nanoscience and their extensive application in atom cluster sizes.25
almost every field related to industry.1−4 Associated therewith, Today, the chemical industry emphasizes the development of
the urgent global demand for diverse nanomaterials (NMs) has sustainable production processes,26 and thus sustainable NM
stimulated rapid advances in the development of both chemical synthesis is highly desirable. In this regard, it is worth mentioning
and physical nanoparticle (NP) synthesis techniques. Conven- that this technique conforms to the 12 principles of “green
tional chemical synthesis methods as a means to synthesize chemistry”27,28 and benefits from the elimination of the particle
inorganic NP colloids are based on a precursor reaction or ligand surface-blocking effect of chemical ligands or the residues of
exchange and are negatively affected by the inevitable reducing agents. Because no molecular precursors are required
contamination of the nanoproduct solution, resulting in for laser-based synthesis, the energy demand and reagent costs
aggregation,5,6 background noise in analytical chemistry,7 are lower. Target raw materials (e.g., powder, bulk, wire, and
toxicity,8 and catalyst deactivation.9 Thus, in biomedical or particle-containing solutions) for LSPC-based NP production
catalysis applications, the chemical synthesis of stable and “pure” are often 5−10 times less expensive than commonly used metal
NP dispersions always requires extra purification procedures to salts or metal−organic precursor compounds.29 A simple
eliminate excess of surfactants and residual reactants before being economic consideration of cumulative synthesis costs of laser
processed toward functional NMs. Given that particles coated by ablation synthesis as compared to wet chemical synthesis is
different ligands may have different biomedical performances,10 shown in Figure 3a. Because of the high cost of laser systems, the
“naked” NPs are favored to be used to unveil the ligands’ effect by investment costs for LAL are typically higher than for chemical
comparative studies.11,12 To improve the NPs’ purity and to reduction, where the centrifuge required for nanoparticle
develop functional particles starting from scratch, increasing purification is the most expensive investment. However, in
attention has been devoted to exploiting novel techniques to majority, the running costs consist of material and labor costs. As
fabricate purely electrostatically stabilized NPs. Moreover, labor costs are identical for both techniques if permanent
current research and industry efforts require scalable and assistance is assumed, the difference in material costs is the
reproducible NMs. driving factor and leads to the different slopes of the lines in
To celebrate the entry into the “photon century”, the United Figure 3a. Typically 1 g of a gold foil costs approximately 100
Nations dedicated the year 2015 as the year of light. Industry Euro, while 1 g of the precursor gold(III) chloride costs almost
workers and researchers have been urged to advance initiatives twice as much. Accordingly, there should be a break-even point,
exploring the nearly limitless future applications of light. after which LAL is more cost-efficient than chemical reduction.
Nanotechnology, in turn, is one of the most vibrant areas of This in turn leads to the conclusion that higher productivities
research and economy in the 21st century. The integration of (section 4) are necessary to catch up with wet chemical synthesis
nanotechnology with “light” has created a new active field, economically. The main cost advantage of LAL is derived from
termed “laser synthesis of colloids”, which has attracted lower educt (bulk vs chemical precursor) costs. Of course, there
increasing attention worldwide because of its extensive are more dimensional effects involved in a proper comparison,
applicability in energy science, catalysis, optics, and biomedicine. such as concentration and batch size effects, as shown in a recent
3991 DOI: 10.1021/acs.chemrev.6b00468
Chem. Rev. 2017, 117, 3990−4103
Chemical Reviews Review

Figure 1. Prospects of laser-based colloid synthesis. (a) Citations per year in the past decade determined by a ISI Web of Science search using the
keywords “laser” and “nanoparticle”. (b) The development of the available average power of pulsed laser systems over time. Solid lines are fits to the data
points to guide the eye. (c) Schematic illustration of laser synthesis of colloids based on the two key enabling technologies: photonics and
nanotechnology. (d) Overview of the subdisciplines of chemistry and connected disciplines involved in laser synthesis research.

study by Jendrzej et al.30 Therefore, in the long run, despite the continents, including Particular GmbH in Germany and in-
initial capital investment required to obtain the laser system, the house spin-offs at IMRA in the USA and Hamamatsu
mass-specific production costs of the synthesized NMs will be Nanotechnology in Japan. As compared to chemically synthesized
lower than those of the chemical reduction method if the NPs, the advantages of laser-generated NPs include higher
cumulative NP productivity reaches the break-even point in grafting density, higher conjugation efficiency, higher electro-
Figure 3a. To this end, laser investment costs at a given laser affinity toward charged biomolecules, and (heterogeneous)
power or throughput will continue to decrease as laser systems catalyst functionality (Figure 2b).
become more powerful (Figure 1b) and the price-to-laser power 1.2. Status of Specific LSPC Fields
ratio decreases (Figure 3b). Additionally, the 100% yield relative
to the solid educt mass and no waste of reagents may save costs Since the first report of LAL, many articles have been published
for waste treatment and disposal as compared to chemical on this topic. In addition to five themed journal issues that
synthesis methods and represent environmental benefits intrinsic addressed specific aspects of both laser-based NP formation
to LSPC. For research purposes, milligram-scale NPs are often mechanisms and NP applications,29,74−77 several groups have
required for characterization of solid-state materials. For published reviews of specific LSPC fields. For example, Yang et
industrial applications, colloids are becoming relevant at the al. reviewed LAL-induced functional nanostructures with
multiple-gram-scale, which recently became accessible by metastable phases and novel shapes,78 and this group was the
LSPC.22,31 Because the processing parameters (e.g., bulk target, first to review79 and publish a book80 on novel LAL-produced
solvent and solutes, and system temperature and pressure) and nanocrystals and their corresponding formation mechanisms.
laser parameters (e.g., wavelength, pulse duration, pulse energy, Zeng et al.,81 Amendola and Meneghetti,28,32 Yan and Chrisey,82
repetition rate, and number of laser pulses) can be flexibly as well as Besner and Meunier83,84 contributed comprehensive
adjusted, a library of NMs covering nearly the entire periodic insights on mechanistic scenarios involving LAL. LFL was first
table can be produced.32 In addition to the crystalline spheres demonstrated by Kamat85 and significantly advanced by the
that are usually generated, soluble, reactive, or supersaturated groups of Hashimoto86−88 and Meunier.89,90 Koshizaki et al.
seed concentrations during LSPC may lead to the formation of described the principles underlying the influence of laser
nonspherical NMs through ripening, and the resulting parameters on the size of LML-synthesized NMs.91 Tsuji et al.
morphologies include fractal,33−35 hexagonal,36 flower-like,37,38 briefly introduced the impact of polyvinylpyrrolidone (PVP) on
football-like,23 fullerene-like,39 leaf-like,40 nanocube,41−45 nano- LAL-obtained NPs and described how these NPs were altered by
wire,46−49 nanospindle,50,51 nanoribbon,52 hollow,53−60 core− laser postirradiation.92 Sasaki et al. summarized the preparation
shell,61−65 necklace,66 nanotruffle,67 nanosheet,68−70 tubular,71 of metal oxide-based NMs using nanosecond (ns) pulsed LAL.93
and nanodisk.72 These features of LSPC have recently stimulated Majima and co-workers reviewed photoinduced synthetic
product commercialization by start-ups on at least three strategies to obtain metal NPs under different conditions.94
3992 DOI: 10.1021/acs.chemrev.6b00468
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Chemical Reviews Review

Figure 2. (a) Classification scheme of LSPC according to the typical sequence of increased laser fluence (LML, LFL, and LAL). (b) (left) Ligand- or
reactant-coated NP with different molecules representative of wet-chemical NP synthesis. (right) Laser-synthesized ligand-free NP and the multiple
advantages they provide.

Figure 3. Key scaling figures for LAL. (a) Absolute costs as a function of cumulative NP mass yield for the discontinuous synthesis of 1 g of colloidal gold
by pulsed laser ablation in water and chemical reduction (the Turkevich method) (sum of 3-mg batches). (b) Relative price (=laser price/laser power) of
capital investment per laser power (ns and ps pulsed lasers). Reprinted with permission from ref 73. Copyright 2014 Aachener Kolloquium für
Lasertechnik.

Tveryanovich et al. summarized multiple factors that could LSPC methodology for the laser synthesis of colloids32,82,95 and
influence the properties of nanodispersed materials and thin do not address all three (LAL, LFL, LML) methodologies.
films prepared by LAL and laser ablation in air.95 In addition, 1.3. Scope of the Current Review
design approaches for experimental liquid flow configurations96
and their use in synthesizing complex composite/compound This Review covers all three LSPC methodologies (LAL/LFL/
NPs,97,98 approaches to manipulate the size of noble metal LML) to provide insight regarding their similarities and
NPs,28 origin of carbon allotropes fabricated by LSPC,99 differences. For example, LAL is often accompanied by
techniques for femtosecond (fs) laser ablation synthesis of unintended LFL. If a high liquid layer is used for LAL, the
colloids,100 and the types of fabricated NMs101 have also been fluence gradient as indicated in Figure 2a will lead to LFL or LML
specifically reviewed. Liz-Marzán and co-workers recently along the beam path. This Review is intended to describe the
reviewed the reshaping and assembly of gold NPs using pulsed following: the chemical reactions between laser-excited solids
lasers.102 Barcikowski et al. briefly introduced the current trends and the liquids confining their energy dissipation during
and some emergent topics in this field29,75,103 and the use of size- synthesis, how to tailor the chemical and physical properties of
controlled metallic/alloy NPs made by LSPC as ligand-free colloids by adjusting various parameters, and how to apply these
reference materials for nanotoxicological assays.11 Zhang et al. colloids in a variety of fields (see Figure 4, in which the orange
described the approaches for rapid prototyping of NP−polymer sections indicate topics highlighted in this Review). Some aspects
composites.104,105 Following a different approach, Gökce and co- of LSPC are intentionally described from different perspectives
workers published a handbook describing the practical aspects of (e.g., laser parameters for size control or upscaling) to emphasize
LSPC to facilitate the entry of new researchers into this field.106 the coupling of various parameters within the laser−liquid−
The applications of LSPC-generated NMs in optics, biology, and target system.
catalysis have been shortly reviewed in brief sections.81,100,107 In the following, we first introduce the three main laser
Ma’s group recently reviewed the use of LSPC-synthesized metal synthesis methods (LAL, LFL, and LML) with a focus on NM
nanoparticles for catalytic applications,108 and Stratakis et al. formation mechanisms and the dynamic processes involved.
briefly reviewed laser-generated NP-based photovoltaics.109 Subsequent sections illustrate the strategies and difficulties in size
Although Rao et al. summarized the applications of LAL- control and the NM productivity of LSPC. We then review the
synthesized NPs in nonlinear optics, SERS, and antibacterial influential factors of targets, processing, liquid, and laser
activities in detail,110 yet most of the literature they cited are parameters, which are crucial factors in controlling the physical
based on their works using ultrafast LAL, not representative for and chemical properties of the synthesized NMs. In this section,
all laser systems. Additionally, most reviews focus on only one we also present a panorama of the integration abilities of LSPC
3993 DOI: 10.1021/acs.chemrev.6b00468
Chem. Rev. 2017, 117, 3990−4103
Chemical Reviews Review

the material/liquid. If Au0 is ablated in water, a chemical reaction


takes places, and a minor fraction of Au+ surface atoms is
obtained (Table 4). However, the reactive nature is not
dominant. An example of RLAL is the reaction that takes place
when Ti0 is ablated in water, and the dominant synthesis
products are Ti3+ and Ti4+ oxides.111 In this section, the three
main laser synthesis and processing methods (LAL, LFL, and
LML) are introduced, and some typical examples and a
corresponding discussion of the chemical reactions involved
are provided.
2.1. Laser Ablation in Liquids (LAL)
Material ablation by lasers is one of the predominant processes in
laser machining and is well-known for cutting, drilling, and
microstructuring under atmospheric conditions with the surface
Figure 4. Table of contents of this Review, which contains five sections
of an ablated workpiece being the object of interest.112 Micro-
addressing fundamentals and synthesis determinants and a sixth section
describing seven emerging fields in which LSPC has applications, and nanomanufacturing using ultrafast lasers is a versatile route
including magnetism, optics, plasmonics, biology, analytical chemistry, for advanced materials processing and constitutes the basis of an
catalysis and energy, and environmental protection. emerging international field.113−115 The use of liquid environ-
ments has also been a focus of laser machining with regard to
with other techniques and external stimulus resources to develop controlling the surface quality116 and ablation efficiency.117−119
new classes of NMs. In the Applications, the existing applications Immersing a workpiece into a liquid or employing a liquid film
of LSPC-generated NMs (including magnetism (section 6.1), has many advantages, such as lowering the heat load on the
optics (section 6.2), plasmonics (section 6.3), biology (section workpiece, producing debris-free treated surfaces,116 confining
6.4), analytical chemistry (section 6.5), catalysis and energy the vapor and plasma, and increasing the shock pressure on the
(section 6.6), and environmental protection (section 6.7)) are surface.120,121 As a result, LAL has long been used in laser
thoroughly discussed to provide a more comprehensive view of cleaning117 and laser shock peening.122 In contrast to laser
the field, as shown in Figure 4. In the final sections, we briefly machining (in which the target surface is the main product),
summarize the unique advantages of LSPC and its applicable when LAL is used to synthesize colloids, the ablated materials
fields, followed by statements on the challenges and prospects of dispersed into the liquid become the product, as shown in Figure
LSPC. 6. Generally, a fraction of the ablated material is inevitably

2. PRINCIPAL LASER SYNTHESIS METHODS


LSPC can be classified methodologically between nanotechnol-
ogy and laser application in liquids, and it can be subdivided into
laser ablation (synthesis) in liquid (solution) (LAL/LASIS) and
laser processing of colloids (LPC) methods (Figure 5). LASIS/

Figure 6. Scheme of LAL. A laser beam interacts with a target material,


leading to the formation of a plasma (not shown) and a cavitation bubble
(shown here at its initial size) in which the ablated matter condenses.
After the cavitation bubble collapses, NPs are dispersed into the liquid.
Figure 5. Classification of LSPC methods.
chemically oxidized or reduced at the surface of the NPs during
LAL (see section 5), for example, the oxidized noble metal NP
LAL includes pulsed LAL (PLAL) and continuous-wave LAL surface123 or NPs reduced by oxygen vacancies.124 These defects
(CLAL). LPC can, in turn, be categorized into LFL and LML. A in the synthesized colloids are essential to provide surface charge
clear classification of the individual experiments and simulations and thus electrostatic stabilization. Volume or surface defects are
reported in the literature is expected to help the community also often beneficial for potential applications, such as optics
understand the important methodological features. Of course, (section 6.2) or catalysis and energy (section 6.6). However, the
there are some emerging topics, such as reactive laser ablation or major mass fractions of the colloids are often preserved with the
fragmentation or melting in liquid (RLAL/RLFL/RLML), in same chemical composition as the bulk targets, including
which both the solid and the liquid dominantly react after alloys,125,126 binary,127 and even ternary materials.128 Therefore,
excitation by a laser beam. The reactive nature of the process LAL is universally considered to be a physiochemical combined
depends on the intention of the experiment and the reactivity of top-down (macroscopic solid targets) and bottom-up (initially
3994 DOI: 10.1021/acs.chemrev.6b00468
Chem. Rev. 2017, 117, 3990−4103
Chemical Reviews Review

Figure 7. Plasma and bubble dynamics: (a) The main stages occurring during the relaxation of the laser−target-liquid system for each laser pulse.
Reprinted with permission from ref 143. Copyright 2014 Royal Society of Chemistry. (b−m) Cavitation bubble phenomenon during LAL: images and
two-dimensional (2D) sketches of the temporal evolution of a cavitation bubble for single-pulse irradiation. Times in % of lifetime (definition: initial
laser−solid interaction until second bubble collapses) are approximates rather than precise values and depend on the solid, the liquid, and the laser
parameters. Shadowgraph images: (c) Reprinted with permission from ref 144. Copyright 2008 Elsevier. (e) Reprinted with permission from ref 145.
Copyright 2015 Elsevier. (l) Reprinted with permission from ref 146. Copyright 2010 International Union of Pure and Applied Chemistry.

formed plasma, atoms, and clusters) method with initial When a laser pulse with an intensity >109 W/cm2 interacts
processes governed by laser plasma and cavitation physics.129,130 with a target immersed in a liquid (Figure 7b), a plasma is
Typical laser beam parameter requirements for LAL are generated on the target surface (Figure 7c). This plasma is
wavelengths from ultraviolet131 (UV) (if the liquid allows UV composed of highly ionized or atomic species with an initial
transmission) and visible132 (vis) to near-infrared133 (NIR, density of about 1020 cm−3 (depending on the laser pulse energy)
where most liquids are transparent), a typical laser fluence of originating from the target material,147 and thus its emission can
approximately 0.1−100 J/cm2, and pulse durations from fs134 to be spectroscopically probed.148,149 Note that plasma emission
picosecond135 (ps), nanosecond (ns),136 microsecond137 (μs), spectroscopy is sensible only to emitting species, which are not
and millisecond138 (ms) regimes, extending to continuous-wave necessarily the majority of species in the ablation plume. For
(CW) lasers.139−142 Note that CLAL is currently limited to example, it has been reported for laser ablation in air that emitted
second-scale processing times because of target-heating-induced species consist of both atomic and ionic species, and their ratio
liquid boiling. Pulsed lasers are typically used for LAL, and their depends on plasma temperature.150 In addition, overlapping of
detailed effects are discussed in section 5.4. In the following, we some peaks in the spectra may also take place.151 Therefore,
first introduce the plasma and cavitation bubble dynamics to extracting quantitative information about the kinetics of chemical
analyze their roles in particle formation and discuss which reactions in plasma is complex, and may not represent the whole
parameters can influence their properties, thus providing an mass emitted during LAL. Also, ballistic emission has been
overview to interpret the complex physicochemical processes reported in the literature on ablation of liquid at the liquid/air
occurring during LAL. We then address where NPs form during boundary directly ejecting species out of the bubble’s phase
LAL and why the size distribution is seldom monodisperse in the boundary.152 The duration of the plasma is generally in the range
absence of additional measures. In the last subsection, possible of tens of ns153 to a few μs143 for each laser pulse and depends on
chemical reactions linked to LAL (RLAL) are summarized to the surrounding environment (e.g., liquid composition) and laser
present options for synthesizing different classes of NMs, parameters as demonstrated by the Park group (e.g., intensity or
including novel materials that are difficult to obtain using pulse trains).153 Amans and co-workers reported that the
conventional chemical methods. electron density decays from 1018−1019 cm−3 at 200 ns by 1
2.1.1. Plasma and Bubble Dynamics. Distinctive events order of magnitude after 800 ns, and an exponential fit of the
related to the plasma and cavitation bubble that occur during electron density decay can be extrapolated to a value of 1014 cm−3
LAL are summarized in Figure 7. These events can be classified after 2 μs.143 Time-resolved imaging of the plasma revealed that
into three stages: the plasma phase, the gas phase (or cavitation increasing the laser energy from 50 to 150 mJ increases the
bubble phase), and a phase in which particles are dispersed and plasma lifetime from 80 to 420 ns (Figure 8a) during LAL of a
interact (or react) with liquid molecules after bubble collapse silver target in water.153 The addition of an electrolyte (e.g.,
(Figure 7a).143 NaCl) further extends the plasma lifetime (Figure 8a) because of
3995 DOI: 10.1021/acs.chemrev.6b00468
Chem. Rev. 2017, 117, 3990−4103
Chemical Reviews Review

The plasma’s temperature and pressure can be as high as


thousands of kelvins (Figure 9e) and hundreds of pascals.129
During plasma decay, the energy is transferred to the liquid,
producing a layer of vapor with roughly the same volume as the
plasma (Figure 7d). Approximately 1 μs after the first material
expansion-related shockwave, a second shockwave parallel to the
target is observed (Figure 7e). This shockwave usually
propagates at a speed of approximately 1500 m/s in water145
and 1200 m/s in acetone157 and undergoes anisotropic
expansion along the directions parallel and perpendicular to
the target surface.158 Thus, at least two different physicomechan-
ical processes contribute to the initial process. Tanabe et al.
identified the second parallel wave as a sound wave generated
during the shockwave reflection.145 They based their conclusion
on the fact that a sound wave undergoing a roundtrip in the target
would produce planar soundwaves (Figure 7e). Nguyen et al.
studied the influence of the shockwaves on the target by
photoelastic imaging techniques and found that the number of
photoelastic fringes depends on the pulse energy and the laser-
induced shockwave.159 Tamura et al. investigated the relation-
ship between the evolution of the plasma and the formation of a
cavitation bubble and found that the plasma and bubble coexist in
Figure 8. Early phase of LAL. (a) Time-resolved images of a plasma the early stage (already during the ns pulse), as shown in Figure
plume induced by the laser ablation of a silver target in deionized water 8b,c.130 The reason why both the bubble and the plasma exhibit
at energies of 50, 100, and 150 mJ/pulse and in NaCl solution at an asymmetric cloud-like shapes is not fully understood yet because
energy of 100 mJ/pulse. Adapted with permission from ref 153. the cavitation bubble forms a sharp quasi-hemispherical
Copyright 2015 American Institute of Physics. (b) Plasma emission
boundary in the liquid μs later. However, this result indicates
image and (c) shadowgraph image of LAL of a Cu target in water with a
30 ns pulse. In the initial state of bubble expansion (about 25 ns after that the ablated species (ions, atoms, and atom clusters) may
laser pulse, 5 ns ICCD gating), an asymmetric and cloud-shaped interact with the surrounding liquid and undergo early chemical
cavitation bubble is evident. Reprinted with permission from ref 130. reactions inside the cavitation bubble. During this period, fast
Copyright 2015 The American Institute of Physics. (d) Schematic plasma quenching occurs, and the vapor layer grows into a
showing the phases involved in the initial stages of the cavitation bubble: cavitation bubble whose initial size is similar to that of the laser
A phase of liquid matter containing atom clusters, primary and focus (Figure 7c−e). This initial state is schematically shown in
secondary particles, and a (supercritical) vapor phase in which chemical Figure 8d. Most probably, the supercritical vapor phase is the
reactions occur. location where reported chemical reactions such as galvanic
replacement,160 water splitting,161,162 or oxidation143,155 occur.
enhanced Bremsstrahlung emission from the electrolytes and the The vapor encloses a region that initially includes liquid matter. It
abundant Ag+, H3O+, and OH− ions and electrons generated is assumed that in this region solid crystallization occurs leading
during LAL.153 De Giacomo et al. extended the plasma lifetime to atom clusters163,164 as well as primary particles,165 but also
using double-pulse LAL (DP-LAL; Figure 9a).149 Because of the droplets163 are formed here that lead to secondary particles.165
effective recombination of ions with electrons and Bremsstrah- Soon after, the cavitation bubble then undergoes a periodic
lung emission, plasma decay is often accompanied by continuum evolution of further expansion and shrinkage until its collapse
emission (gray dots in Figure 9b),154 which should be (Figure 7f−m), after which it rebounds once or more (at least the
differentiated from the signal of LAL-generated species for first collapse generates another hemispherical shockwave).
plasma analysis, for example, C2 species154 during LAL of Depending on the various influential factors, which will be
graphite in water (▲ in Figure 9b) or Al and AlO species during described in section 5, different phenomena may arise during this
LAL of a Al2O3 target in water (Figure 9c).143 Consequently, to process. Tsuji et al. observed a shockwave accompanied by an
calculate the species’ density, the continuum background must be ejection of light-scattering objects along the laser incident axis at
removed. On the basis of the AlO rovibronic emission between approximate 1% of the lifetime.166 A similar observation with
the B2∑+ and X2∑+ states in the range of 448−528 nm and the more distinct particle ejection was reported by Sasaki at
AlI 2P0−2S doublet emission at 394/396 nm in the plasma approximately 10% of the lifetime.146 However, through
spectra (Figure 9c), Lam et al. successfully observed the comparison with single pulse LAL, Tanabe et al. recently
alteration of the density ratio between the Al atoms and AlO concluded that these “jets” only occur when the liquid medium
molecules over time (Figure 9d)155 and used it to analyze the includes NPs before the pulse arrives or when multiple pulses are
kinetics of the chemical reactions inside the cavitation bubble used, which is consistent with the “jet” being aligned with the
leading to the formation of Al2O3.143 Sakka et al. observed that laser beam’s incident axis.145 Thus, these jets could be caused by
atoms disappear on a time scale of 1−10 μs, indicating that the either spallation167,168 or the microbubbles formed during LFL
chemical reactions may last for several μs.156 Note that this time (or shockwave propagation heating) of the NPs generated by the
range of chemical reactions is far shorter than the lifetime of the previous ablative pulse.145 After the cavitation bubble reaches its
cavitation bubble. These plasma spectroscopy results are valuable maximum height at approximately 20% of its lifetime and
for determining where and when the chemical reaction of the proceeds through a quasi-hemispherical stationary phase (Figure
ablated matter with the liquid constituents occurs, and thereby 7g), it begins to shrink. The shrinking first bubble is almost
predicting the possible products of LAL. perfectly hemispherical (Figure 7h), whereas the second
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Figure 9. Plasma decay and reaction: (a) Temporal evolution of the ionization degree (ionic density/(ionic density + atomic density)) of single-pulse
(SP) and double-pulse (DP) laser-induced plasmas of a Ti target under water. Reprinted with permission from ref 149. Copyright 2011 American
Chemical Society. (b) Continuum emission (gray ■) and C2 molecular emission superimposed upon the underlying continuum emission (▲).
Reprinted with permission from ref 154. Copyright 2009 Elsevier. (c) Spectra of molecular AlO and Al emissions from LAL-generated plasma and (d)
their density ratio over time. Adapted with permission from ref 143. Copyright 2014 Royal Society of Chemistry. Reprinted with permission from ref
155. Copyright 2015 American Chemical Society. (e) Temporal evolution of plasma continuum intensities and plasma temperatures as determined by a
Planck-like distribution during the ablation of Ti and Cu bulk targets immersed in water. Reprinted with permission from ref 129. Copyright 2015
Elsevier.

Figure 10. (a) Temporal evolution of the cavitation bubble radius after the initial pulse ablation at pulse energies of 100 mJ (□) and 50 mJ (△).
Reprinted with permission from ref 145. Copyright 2015 Elsevier. (b) Maximum cavitation bubble height as a function of laser fluence. Reprinted with
permission from ref 169. Copyright 2015 Royal Society of Chemistry. (c,d) Simulation of the temperature (c) and pressure (d) of the gas vapor inside
the cavitation bubble as a function of time at four different liquid pressures (P = 1, 4, 20, and 146 atm). Reprinted with permission from ref 149.
Copyright 2011 American Chemical Society.

(rebound) bubble is neither hemispherical nor symmetric shrinking of the first bubble is reported,169 with inward jet, and
throughout its evolution (Figure 7i,j). Sometimes asymmetric this effect could be linked to the wetting angle of the initial
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Figure 11. Interior of the LAL-induced cavitation bubble. Height and mass scans of the cavitation bubble at maximum expansion. (a) SAXS
measurement configuration, (b) sketch of the relevant species in a laser-induced cavitation bubble during its largest extension, and (c) experimental
results of primary particles and secondary particles (larger spheres or agglomerates) at different heights. Dashed lines indicate the relative bubble
thickness. Reprinted with permission from ref 183. Copyright 2012 American Institute of Physics. (d) Diameters of primary and secondary particles
found inside laser-induced cavitation bubbles at different times and bubble heights. Second dashed red line marks collapse, and the horizontal bar at
approximately the first dashed line marks the detector gating time. Reprinted with permission from ref 186. Copyright 2013 Royal Society of Chemistry.
(e) X-ray radiography density mapping of the first, second, and third bubbles, confirming the inhomogeneous internal density distribution in the second
and third bubbles. Adapted with permission from ref 165. Copyright 2015 Nature Publishing Group. The experiments mentioned above were performed
by ns lasers (6 ns183,186 and 10 ns165) with pulse energies in the range of 10−20 mJ.

bubble,165 indicating that shrinking symmetry may depend on and for fast freezing of metastable phase NMs (e.g., hexagonal
target wettability and temperature. The dynamics during the final close-packed Ni,172 AuFe,173,174 AgFe67 solid solutions), which
collapse is shown in Figure 7j,k. Shockwaves precede each are difficult to obtain by conventional chemical methods.
sufficiently intense collapse (Figure 7k). The subsequent However, this is only one-half of the picture. In contrast,
“collapse” and “rebound” of the bubble are often asymmetric, abundant reports on low-temperature phases derived from LAL
exhibiting irregular shapes and, sometimes, division into have also been reported, for example, cubic boron nitride,175
“daughter bubbles”, as shown in Figure 7l,m. Some authors TiO2 with rutile and anatase phases,111,158,176 and Al2O3 with α-
have observed stable spherical bubbles (Figure 7l) that remain and γ-phases.177,178 De Giacomo developed a model to simulate
attached to the target surface at the end of the bubble lifetime;146 the pressure and the temperature inside the cavitation bubbles as
however, in many cases the cavitation bubble vanishes a function of time, based on two assumptions: (1) that the mass
completely (Figure 7m). The lifetime of the first cavitation and momentum conservation equations are valid in the liquid
bubble depends on the laser fluence,145 as shown in Figure 10a. phase and (2) that the vapor pressure inside the bubble is
Because the ablated mass scales linearly with the laser fluence,22 balanced by the pressure on the bubble wall facing the
one would expect it to be proportional to the heat available to liquid.149,179 These results indicate that only the initial (tens or
vaporize a certain volume of the liquid. Accordingly, the bubble hundreds of ns129,143,180) and collapse moments are “hot”
volume387 scales with fluence (Figure 10b),169 and at the same (>1000 K) as extracted from calculations that are based on the
laser fluence, the bubble volume may increase with the liquid’s Rayleigh Plesset model.181 However, please note this model does
compressibility134 and decrease with the liquid’s density.144 Note not account for the compressibility of the liquid and fails to
that bubble sizes are not always on the millimeter (mm) scale;387 describe the bubble dynamics after the collapse of the first bubble
indeed, bubbles generated by ps lasers (with typically lower pulse as suggested by recent reports of Sasaki182 and Plech.183 On the
energies) are at least 1 order of magnitude smaller than those basis of studies of laser-induced spherical bubbles in liquid,184 the
induced by high pulse energy ns lasers.22,31,170 Gilmore model185 might be better suited to describe the
LAL is often described as a “high temperature and high cavitation bubble dynamics occurring during LAL. In contrast,
pressure” process. This terminology is closely related to the during bubble expansion and compression, the temperature
initial plasma state rather than the cavitation bubble, although the inside the cavitation bubble is only hundreds of kelvins (Figure
NPs are located inside the “cold” cavitation bubble vapor most of 10c).149 Recently, these simulation results were experimentally
the time. The initial high pressure, high temperature, and high verified.129 Regarding the bubble pressure, similar to the
density of the plasma and its fast cooling period provide a temperature evolution, high pressures inside the bubble are
favorable thermodynamic environment for the formation of reached only initially. After several μs have passed, the pressure
some NMs in high-temperature environments (e.g., MoC171) decreases to nearly that of the external liquid (Figure 10d).149
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Figure 12. (a) Bimodal size distribution of gold NPs prepared by fs laser ablation. Reprinted with permission from ref 191. Copyright 2005 Springer. (b)
Different fluence thresholds using a laser beam with a Gaussian profile, including the ablation threshold, annealing threshold, and modification
threshold. Reprinted with permission from ref 192. Copyright 2002 Springer. (c) Crater generated by fs laser ablation of silicon in ethanol with a
Gaussian beam profile and (d) deduced ablated mass as a function of the laser fluence with a Gaussian profile. Adapted with permission from ref 193.
Copyright 2010 Elsevier.

Therefore, the internal environment of the bubble is relatively ≥40 to >60 nm after the first bubble collapse (Figure 11d). The
cold rather than hot, and the terminology of “high pressure and findings to date indicate that the excited species from the ablated
high temperature” is only applicable to the initial plasma and final substrate are in direct contact with the liquid vapor, which may
collapse phases. From a quantitative perspective, this potentially trigger chemical reactions, and that NPs are already confined
misleading simplified terminology should not be used to describe inside the cavitation bubble. However, most spectroscopic
particle formation because the temperature and pressure oscillate studies on LAL bubble dynamics only address the first bubble,
over several orders of magnitude in the gas phase. Therefore, and thus at least two additional bubble effects must be
accurate in situ detection techniques and thermodynamically investigated. The plasma-heated supercritical water phase and
theoretical modeling163 are essential to gain insight into the the cold bubble vapor may provide a perfect environment for NP
formation of molecular inorganic intermediates and the crystal crystallization; however, the temperature and pressure peak
phase transformation of NPs over time. during bubble collapse creates conditions that may reset the NP
2.1.2. Nanoparticle Formation. Understanding where, structure and composition that have formed before the bubble
when, and how NPs form and grow is of great importance to collapse. Moreover, bubble collapse itself may mechanically
control at least the size of the LAL-synthesized particles. Zhigilei ablate materials with a mechanism completely different from that
et al. theoretically demonstrated that the condensation of clusters of laser ablation.188,189 Also, cavitation collapse may generate an
from the material vapor might be the main particle formation additional plasma from the liquid or solid.190 Thus, although
mechanism (assuming the absence of chemical reactions to significant progress has been made in probing the interior of the
simplify molecular dynamics (MD) simulation) (Figure first bubble, a missing link related to the structure and
13b,c).163 Using small-angle X-ray scattering (SAXS), Plech composition of the NPs found outside the bubble in the free
and co-workers revealed the dispersion of nanoscale particles liquid remains. X-ray videography of the first and second
inside the cavitation bubble, as shown in Figure 11a−d.165,183,186 cavitation bubble rebound (second and third bubbles, Figure
The primary (<10 nm) particles exhibit a smooth concentration 11e) has been performed to provide part of this missing
profile vertically from the target surface toward the top of the information.165 In contrast to the homogeneity of the X-ray
cavitation bubble, and their mass abundance varies according to transmission image of the first bubble, the second bubble exhibits
the bubble’s shape, indicating that no steep particle density an interestingly bright (less dense) hemisphere center.
gradient exists once the bubble reaches its maximum height. Furthermore, the third bubble has an inhomogeneous discrete
Some of these primary particles are detected (at a signal intensity density distribution. The discovery of mass emission occurring
slightly above the noise level) in the close vicinity of the during the third bubble phase also hints at the complexity of the
cavitation bubble (Figure 11a,b), as was also reported by Soliman LAL-induced cavitation and NP release process.
et al.,187 who observed the plasma and bubble dynamics using The formation of primary and secondary NPs (a bimodal size
laser-light scattering and shadowgraph imaging. However, it distribution, which is often found after performing LAL11) is not
cannot be excluded that these “escaped” particles are artifacts fully understood. A typical bimodal size distribution of gold NPs
caused by the integration of multiple bubble events because obtained by fs LAL in water is shown in Figure 12a.191 The
bubble-to-bubble height variation is known to occur. Also, authors attributed this phenomenon to multiple factors,
ballistic emission152 at the initial LAL phase could be the origin of including target thermal heating by the plasma and bubble-
these particles at the bubble’s expansion front. Larger secondary induced mechanical erosion.191,194 Nichols et al. reported that
particles (>40 nm spheres or agglomerates) are dominant in the thermal vaporization and explosive boiling mechanisms are
center and upper parts of the cavitation bubble, and there is no responsible for the bimodal size distribution of Pt NPs obtained
indication that they penetrate into the liquid before the bubble by ns LAL.195 In addition to pulse duration-related mechanisms,
collapses (Figure 11b−d). The (mass-weighted) diameter of the the formation of this pronounced bimodal distribution could be
large particle fraction significantly and transiently increases from associated with the beam intensity distribution on the target
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Figure 13. Simulated LAL phase diagrams: (a) Time-space phase diagram for fs ablation of gold in water with local intensity of I0 = 5 × 1013 W cm−2.
Reprinted with permission from ref 168. Copyright 2013 Royal Society of Chemistry. (b) Atomistic MD simulated contour plots of the initial spatial and
temporal evolution of the lattice temperature in the direction away from the laser (40 fs, effective fluence of 40 mJ/cm2) ablated 20 nm Ag film substrate
in water. (c) The enlarged view of the atomic structure of two crystalline nanoparticles located in the upper part of the mixing region. (b,c) Reprinted
with permission from ref 163. Copyright 2016 Elsevier. (d) Size histogram showing the predicted number frequency of particles obtained by LAL at an
effective laser fluence of 70 mJ/cm2 1, 2, 3 ns after the laser pulse. Adapted with permission from ref 163. Copyright 2016 Elsevier.

surface (Figure 12b, which describes the transmission beam) in finite element (cavitation) simulation of LAL at time scales from
terms of three different excitation regimes and three correspond- several ns to hundreds of μs. Unfortunately, the optimal settings
ing thresholds.192 The highest fluence regime in the center spot is for gaining fundamental information are opposite to those
defined as the ablation area, the lower-fluence regime ring optimized for high yield, in which high-repetition rate lasers are
corresponds to the approximate annealing area, and the often applied with temporal pulse delays shorter than the
outermost area is termed the modification area. Although these cavitation bubble lifetime, causing an interaction between the
definitions were deduced from fs laser ablation of silicon in air, pulses and the bubble and colloidal particles, shielding the
they also apply to LAL,22,193 as shown in Figure 12c. Accordingly, incoming beam.
the ablated morphology can be classified into two or three 2.1.3. Reactive Laser Ablation in Liquids (RLAL). Lam et
regions of different ablated mass density (Figure 12d), which al. demonstrated that ablated species react with (dissolved
may influence the nucleation and growth of the NPs and result in molecular or water-bound) oxygen delivered by the liquid on the
the formation of differently sized NPs. Povarnitsyn et al. time scale of plasma cooling.155 Because of the conditions that
simulated the ablation process and predicted that smaller arise during plasma generation and decay, photoionization of the
particles form in the liquid−gas region (l+g zone, Figure 13a target materials and photothermal decomposition of the solvent
[orange]), that the larger NPs originate in the molten layer (l occur simultaneously, creating an excited environment for
zone, Figure 13a [yellow]), and that both regions depend on the reactions to form carbides,198 oxides,199 nitrides,200 sulfides,43
laser fluence.168 Recently, Zhigilei and co-workers theoretically dopants,111,201 or defects202 within the particles. These material−
predicted that during LAL the liquid will be transformed into a liquid reactions are sometimes accompanied by a reaction
supercritical state, and that therefore an expanding low-density between the species ablated from a multielement target, for
metal−water mixing region will form (Figure 13b).163 Materials example, the formation of MoO3, MoO3−x, and MoS2 NPs by
in different regions are “incubators” for particle formation at LAL of a MoS2 target in water.203 Because of the high density of
different sizes. The authors predict that in this initial phase of atoms and ions during the initial phase of LAL, a series of
LAL < 3 ns a trimodal size distribution (Figure 13c) consisting of reactions may take place within a short time scale, including the
atom clusters (1−2 nm), nanoparticles (some nm) and large possibility of an in situ catalytic reaction. For example, da Cunha
droplets (tens of nm) exists.163 Interstingly, the prediction of et al. found that the Pb atoms or ions generated during LAL of a
atom clusters agrees well with the experimental findings of Pb target in alcohols may act as catalysts to decompose alcohol
Jendrzej et al.164 into CO2 and H2O, which then react with the synthesized PbO
Although transforming a Gaussian beam profile into a top- particles to form hydrocerussite (Pb3(CO3)2(OH)2).36 Addi-
hat196 or Bessel beam197 profile can vary the size distribution, tional attention should be directed toward photochemical
monomodal colloidal particles remain difficult to obtain reactions occurring directly in the liquid (e.g., FeOCl nanosheets
practically by varying the laser parameters during LAL. Note formed during LAL in FeCl3 aqueous solutions), in which the Au
that the optical components (axicons) that create Bessel beams NPs generated from the target ablation contribute to the physical
distribute the laser pulse energy in a larger trapezoidal column adsorption on the FeOCl nanosheets, as demonstrated by the
along the beam path, making it difficult to attribute the laser Cai group.68
intensity distribution effects exclusively to LAL. Additionally, The chemical reaction rate and the phase of the nanoproducts
larger volumes of the colloid are excited at higher fluences, are correlated with the ratio of the active species and their
resulting in LFL of NPs synthesized by previous pulses. Thus, collision rate. Therefore, because of plasma quenching, reaction
studying single pulses could facilitate a better understanding of products (e.g., SiC) and the relevant elemental species (e.g., Si)
the influence of the lateral intensity distribution on the particle may nucleate and grow into particles, as verified by high-
size. resolution transmission electron microscopy.204 Moreover, the
Further understanding of the fundamentals of LAL could be temperature/pressure differences in different local regions may
achieved by decreasing the gating times of spectroscopic or X-ray trigger several reactions, thereby leading to the formation of
imaging techniques, performing single pulse experiments to mixed-phase NPs. Supersaturated concentrations of different-
probe the NP size, and conducting cavitation shadowgraphy and phase nuclei may allow collision and growth into a mixed-phase
molecular dynamics (MD) (particle nucleation and reaction) or particle (e.g., anatase and rutile TiO2)205 or a polycrystalline
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Figure 14. (a) Schematic diagram showing the formation of PtCo NPs via LAL of Co in aqueous K2PtCl4 solution and galvanic replacement reaction
(GRR)-LAL based on the GRR between Co and PtCl42− ions and (b) the Pt atomic ratio (%) distribution across the line scan of a PtCo alloy NP; TEM
and the electron energy loss spectroscopy (EELS) mapping images are shown in the inset. Adapted with permission from ref 160. Copyright 2016
Elsevier. (c) Layered seed growth of AgGe microspheres during continuous LAL of Ag-doped Ge wafers in water. Adapted with permission from ref 23.
Copyright 2015 Nature Publishing Group. (d) Effect of thin film layer sequence during LAL of bilayers on the FeAu NP alloy composition. A topmost
layer of Fe leads to Fe-rich AuFe alloy NPs (upper row), while an Au topmost layer leads to low-Fe AuFe alloy NPs (lower row). The topmost layer can
be considered as a “sacrificial” layer that protects the underlying material from interaction with oxidizing species in the vapor phase. Adapted with
permission from ref 208. Copyright 2016 Elsevier.

NP.206 However, the mechanisms by which nuclei evolve into the alloying degree could be controlled by finely adjusting the pH
particles and different structures remain under debate for LAL- value (for CoOx etching) and Pt2+ concentration. In detail, the
synthesized NMs. Thanh et al. summarized five principal chemical reduction of the dissolved noble metal cations is
nucleation−growth mechanisms that can lead to chemical hypothesized to happen at the bubble’s “boundary phase”
colloid formation,207 including the LaMer mechanism, Ostwald (Figure 14a). Note that this boundary most likely is not the outer
ripening and digestive ripening, the Finke−Watzky two-step phase boundary of the bubble during its expanded volume phase
mechanism, coalescence and orientated attachment, and intra- (Figure 11, Figure 7g), but rather in the (supercritical) vapor
particle growth. In the case of LAL, the concentration of local phase and mixing region during the initial phase of LAL (Figure
nuclei can be kept supersaturated by continuously adding 8d). This mixing region, atomistically simulated on the ns time
materials through repetitive “seed and feed” emission, which may scale in Figure 13b, is in contact with an underneath layer of
lead to prolonged particle coalescence and ripening (Figure liquid metal droplets. Amendola et al. compared LAL of a thin
14c).23 film bilayer with different sequences (Au on Fe vs Fe on Au)
The solvent decomposition fraction remains difficult to coated on glass (Figure 14d).208 Interestingly, this allowed the
quantify, and precisely predicting and controlling the reaction formation of AuFe alloy NPs with larger Fe content when using
during LAL is challenging. To estimate the main educt ratio in the Fe/Au/glass instead of the Au/Fe/glass targets. They
the gas phase (during cavitation), the density of the ablated hypothesized that the upper layer acts as a “sacrificial” layer that
matter (7 × 1015 ± (5 × 1015) atoms per pulse) relative to the reacts with the liquid molecules, protecting the underlying
liquid molecule abundance ((1−1.5) × 1017) may be helpful.209
material from interaction with reactive oxygen species in the
This ratio indicates that the gas-phase reaction is unlikely to be
vapor phase. Hence, RLAL may also be used to produce a variety
limited by the liquid molecules’ kinetic availability and that
of core−shell NMs by adding specific ions to the solutions to
species dissolved in the liquid may contribute to the final NP
initialize galvanic reactions during LAL. Further examples
composition, even at low (e.g., micromolar) concentrations.
Increasing attention has been focused on the addition of ions or include the generation of metal/oxide (e.g., TiO2@Ag by LAL
surfactants to the liquid to let them react with the excited species of a Ti target in AgNO3 solution) nanocomposites212 and
from the ablated target in the bubble’s gas phase or adsorb onto semiconductor (e.g., Si@metal (e.g., Au, Ag, Au−Ag, Pd, and
the particle surface to induce anisotropic growth. For example, Pt)) core−shell structures by LAL of a silicon target in different
CdS can be obtained by reactive LAL of a sulfur target in a CdCl2 salt solutions.213,214 Another finding is the formation of football-
solution because of the reaction of Cd2+ from CdCl2 salt and S2− like AgGe microparticles as large as 7 μm following layered seed
from the ablated target.210 A further example was reported by growth triggered by a rapid GRR between Ge atoms/clusters and
Thareja et al., who demonstrated that (CH3COCH2)− ions Ag+ ions during laser ablation of silver-coated germanium targets
generated through LAL-induced acetone decomposition could (Figure 14c).23 LAL is a continuous process that allows the GRR
bind to zinc-coordinated sites to prevent the dehydration of zinc to proceed so that the AgGe spheres can grow into microscale
hydroxides from evolving into ZnO NPs during Zn-LAL.211 The rather than stay on the nanoscale.23 As suggested by these
GRR-LAL is an emerging route for novel NM synthesis. For experimental examples, RLAL offers the advantage of manipulat-
instance, Hu et al. successfully synthesized PtCo nanoalloys by ing the NP composition using reactive targets, solvents, or
LAL of a cobalt target in aqueous K2PtCl4 salt solution (Figure additives. The drawback of RLAL is that it is associated with
14a) and found that the alloy consisted of an outer shell that was complex chemical processes because, as is well-known in
more enriched in Pt than the inner core (Figure 14b), which is photochemistry, ions can be reduced directly by laser
highly relevant for catalytic application.160 They discovered that irradiation,215 resulting in parallel reactions (target ablation,
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plasma−solvent reaction, solvent decomposition, and ion redox outside of the focal volume are melted instead of fragmented.219
reaction) that are challenging to control. Thus, LML side products are frequently found in the processed
Overall, in most cases, the chemical composition or surface samples obtained via LFL with short focal distances and must be
chemistry of LAL-synthesized NPs is not completely identical to removed by postprocessing treatment. These side products can
that of the raw material because of the possible reaction between be avoided by either minimizing the liquid layer limiting the
the ablated materials and the liquid during LAL. Because the beam path to the focal Rayleigh length (e.g., using a liquid jet
compositions of the material and liquid determine the chemical setup)218 or by applying high-pulse energy lasers that do not
reactions, the influence of each requires thorough investigation; require focusing (but may be limited by a low repetition rate, and
the results to date for the material and liquid are summarized in thus lead to lower yield). Size selectivity can be achieved by LFL
sections 5.1 and 5.3, respectively. However, note that it still lacks because the energy absorption cross-section of the product is
strong evidence indicating where and when the reactions occur. often smaller than that of the particulate educt.220 However,
The literature suggests that reactions may occur during each continuous educt−product mixing is inherent to the LFL
phase of LAL: plasma cooling209 or bubble expansion151 or after method, and therefore physisorption of the product on the
bubble collapse.160 Because the ablated matter is confined in the educt may lower the efficiency and reproducibility. Typical laser
bubble,183,186 after the bubble collapse, the dispersed NPs may requirements for LFL are wavelengths from the UV to NIR
adsorb liquid molecules and undergo liquid-phase reactions. In regime, pulse durations from the fs to the ns regime, and laser
contrast, inside the bubble, plasma physics and gas-phase fluences above the material-dependent threshold, for example,
chemistry will dominate NP crystallization and composition, >1−100 mJ/cm2.221,222 Because the extinction of the laser
and thus agents designed for RLAL may be useful if they are wavelength strongly depends on the NP material (particularly for
effective in both the gas and the liquid phases. Here, LSPC often plasmonic particles in the VIS range), either selective LFL is
involves liquid-phase reagents, but concepts applied in the caused or broadband extinction may even allow the simultaneous
mature field of chemical gas-phase synthesis216,217 could support LFL of NP mixtures. Thus, as an alternative, a white light filament
further developments in RLAL. (supercontinuum) can also be used to fragment dispersed
2.2. Laser Fragmentation in Liquids (LFL) particles efficiently, and this process can be initiated by high-
Laser fragmentation of microparticle powder suspensions or NP energy pulses in the fs regime.223,224 As mentioned previously,
colloids is induced by the NPs’ absorption of laser energy (Figure the laser intensity must remain below the optical breakdown
15). To initiate LFL in a liquid, commercial solid-state lasers are threshold,225 and consequently the window of laser parameters
that can fragment plasmonic particles in a fs supercontinuum is
narrow, as reported by the Meunier group.226,227
On the basis of theoretical calculations and experimental
confirmation, the mechanisms of photothermal evaporation and
Coulomb explosion are believed to be responsible for the size
reduction during LFL,96 as illustrated in Figure 16. However, the
the heat transfer from a NP to a liquid causes the liquid to reach
its spinodal temperature (which is much higher than its boiling
point), and this in turn leads to the formation of a nanobubble
around the particle (Figure 16a).229 Hence, it cannot be excluded
that photothermal vaporization already starts during conditions
expected to purely form nanobubbles (which are thermal
isolators). Accordingly, Figure 16a does not show any temporal
evolution during LFL but is rather meant to show the factors
(pulse energy, pulse duration, and initial particle properties) that
influence the dominant mechanism.
The photothermal vaporization LFL mechanism was
proposed in 1999 by Koda and co-workers, who investigated
the size reduction of Au NPs by ns laser irradiation.230 Size
Figure 15. Scheme of LFL. An initially micrometer- or nanometer-sized reduction through surface evaporation is thought to initiate when
(not necessarily spherical) particle suspension or colloid is fragmented the particle temperature exceeds the boiling point of the bulk
by a laser beam into smaller NPs. material. The degree of size reduction depends on the laser
fluence, irradiation period, and number of pulses. Generally, the
often combined with focusing optics to generate a laser focal spot higher is the laser fluence and the longer is the irradiation period,
with a diameter of several tens to hundreds of micrometers, the smaller the particles will be.231 Amendola et al. observed that
similar to that of LAL, in which a deviation of the focus position increasing the ns-pulsed laser fluence from 88 to 442 mJ cm−2
leads to a pronounced change in the laser fluence. Thus, the decreased the average diameter of Au NP products from 24 to 4.6
efficiency of LFL is quite sensitive to focus shift.218 In general, nm via LFL.232 Lower laser energy (relative to the boiling
LFL efficiency (mass-specific downsizing throughput) strongly temperature of the solid in water) has also been reported to
increases with the laser fluence,218 and the maximum efficiency enable size reduction when the formation of a vapor layer of
lies just below the optical breakdown of the liquid. Therefore, material that is approximately the educt particle size after laser
strong focusing is required unless high-pulse energy lasers are irradiation is considered.233 Subsequent cooling of these
available. However, high-numerical aperture lenses cause not vaporized atoms leads to their condensation into significantly
only higher fluence but also higher fluence gradients within the smaller particles. Through computational simulations using the
irradiated volume. Because of the fluence gradient along the two-temperature model coupled to a surface evaporation
beam path volume in the liquid, NPs in this volume and areas mechanism, Hashimoto and co-workers clearly demonstrated
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Figure 16. Schematic illustration of the size-reduction and fragmentation mechanisms of plasmonic NPs in a colloidal solution. (a) Nanobubble
formation, photothermal evaporation, Coulomb explosion. (b) Bathtub profile of the fluence threshold for bubble formation as a function of NP
diameter and LFL pulse duration. Adapted with permission from ref 220. Copyright 2015 American Chemical Society. (c) Beam attenuation along the
optical path in the solution as a function of the distance from the target for laser energies of 5, 10, 15, and 20 mJ/pulse. The irradiated volume as a
function of the distance from the target is shown by the dashed line. Reprinted with permission from ref 228. Copyright 2016 Institute of Physics.

the viability of NP size reduction below the material boiling increasing temperature within the duration of the excitation
temperature.234 Heat transfer from a NP colloid to a liquid causes pulse.234 This dependence is crucial, because the refractive index
the liquid to reach its spinodal temperature and bubble formation of the medium also changes dramatically with the temperature
around the particle,229 which provides an incubation atmosphere (fluence) as was shown by Werner and Hashimoto.86 This means
in which the emitted fragments can coagulate and coalescence that the refractive index of the NP cannot be assumed as a
into small particles. As a result, NP evaporation may occur at constant but is subject to dynamic changes during the time lapse
ambient pressure. Recently, Hashimoto reported that the Au NP of excitation. Further, the heat transfer to the liquid is often not
surface evaporation threshold is close to the bubble formation accurately considered.86 These important refinements have to be
threshold, suggesting that bubble nucleation will not inhibit NP considered when energy balancing during LFL is performed.
evaporation, but instead actually facilitate it.235 Consequently, a A fundamental understanding of these laser-induced nano-
polydisperse colloid containing a significant fraction of smaller bubbles is all the more imporant because nanobubble creation is
NPs is often observed during incomplete LFL. It should be noted an emerging field with numerous applications, for example,
that bubble generation depends on both the pulse duration and photoacoustic imaging and cancer therapy or drug delivery via
the laser fluence but is minimally influenced by the laser the optoporation of living cells by transient pore generation upon
wavelength (UV or green for LFL of AuNPs).220 Metwally et al. the laser excitation of gold NPs seeded on the cell
calculated that the fluence threshold is significantly higher for ns membrane.229,236−238
lasers than for fs lasers with respect to Au NPs, especially when The second mechanism for LFL is the Coulomb explosion
the particle size is below 50 nm (Figure 16b).220 Thus, ultrashort model (Figure 16a), which states that electrons are ejected from
pulses offer a clear advantage in LFL, particularly when pulse the solid educt (photochemical bleaching) to generate ionized
durations are shorter than the electron−phonon coupling time of NPs that are immediately fragmented because of internal charge
the NP material (typically a few ps). However, please note that in repulsion. According to the liquid-drop model for Coulomb
this calculation the transient temperature effect is neglected even explosion,239 a multiply charged particle becomes unstable when
though the absorption cross section (which is antiproportional to the disruptive Coulombic force exceeds the attractive cohesive
the fluence threshold for nanobubble formation) decreases with force. The criterion for the Coulomb explosion is expressed by
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Figure 17. (a−d) TEM images and corresponding size distributions of 60 nm Au NPs before (a,c) and after 60 min (b,d) of laser irradiation at 1 kHz and
an excitation wavelength of 400 nm. Reprinted with permission from ref 86. Copyright 2006 American Chemical Society. (e) Decay of the extinction at
700 nm after 355 nm laser irradiation under nearly identical conditions and different SDS concentrations: 2 × 10−2 M (●), 6 × 10−3 M (○), and 2 × 10−3
M (▼). Reprinted with permission from ref 243. Copyright 2006 American Chemical Society. (f) Mean NP size after laser fragmentation as a function of
the initial concentration of Si microcolloids. Reprinted with permission from ref 244. Copyright 2013 Royal Society of Chemistry.

the “fissility”, which is defined as X ≡ EC/2ES, where EC is the proposed that the absorption of pulsed laser beams by
Coulombic energy and ES is the surface energy, and is given for microparticles causes the particles to burst from inside because
metals by X = (q2/n)/(16πr3wsσ/e2) with the charge state q, the of pressure and temperature gradients and that this process is
number of particle atoms n, the Wigner−Seitz radius rws, the influenced by the pulse duration (Figure 18).245 Recently, on the
surface tension σ (both rws and σ are temperature-dependent
quantities), and the elementary charge e.240 For gold nano-
particles, the fissility parameter is given by X = 0.9 q2/n.241
Nanoparticles dissociate into smaller entities when X ≥ 1
(Rayleigh limit). For 0.3 < X < 1, both evaporation and Coulomb
explosion competitively occur, and for X < 0.3 only evaporation
takes place.242 Coulomb explosion becomes relevant at high laser
intensities and short wavelengths as was shown for LFL of Au
NPs by Hartland et al.85 By monitoring the transient bleaching
and the increase of maximum absorbance as a function of laser
intensity, the authors showed that the photoejection of electrons
may turn into a multiphotonic process and that the charge state
has a nonlinear dependence on the excitation laser intensity.85
Similarly, Mafuné’s group observed gradual “bleaching” Figure 18. Simulation of LFL. Snapshots from MD simulations of laser
absorption signals (Figure 17e) during ns laser irradiation of irradiation of individual particles (∼100 nm) versus deposited laser
Au NPs using ns transient absorption spectroscopy243 and found energy. The results obtained at 500 ps after the end of the laser pulses are
that this phenomenon is related to the solvated electrons.241 By shown for pulse durations of 15 and 300 ps. Adapted with permission
analyzing the correlation of the size-reduction extent with the from ref 245. Copyright 1998 Elsevier.
charge state after laser irradiation at different SDS concen-
trations243 and different laser wavelengths (e.g., 355 and 532 basis of the two-temperature model, Delfour and Itina
nm),241 they concluded that Coulomb explosion is responsible demonstrated the applicability of Coulomb explosion to fs
for the size reduction of the highly charged NPs. Because laser LFL and theoretically confirmed that high laser fluence is
photothermal evaporation may also occur in the case of ns laser required to trigger Coulomb explosion; otherwise, only NP
irradiation, competition between Coulomb explosion and reshaping occurs.246 Similarly, Fahdiran et al. reported
photothermal evaporation together with the threshold depend- energization-dependent fragmentation in terms of Eo/Ecoh,
ence on the ratio of the Coulomb energy to the surface energy of where Eo is the energy input per atom in the irradiated spheres,
the particle were assumed.243 and Ecoh is the cohesive energy.247 In the case of low energization
Further insight on how Coulomb explosion occurs was (Eo/Ecoh = 0.63), abundant voids appear inside the sphere and
provided by theoretical simulations. For example, Zhigilei et al. lead to splitting of the spheres, whereas for high energization
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Figure 19. Temporal LFL cascade of events: (a) Schematic of the Coulomb explosion mechanism of fs laser-induced fragmentation. Reprinted with
permission from ref 86. Copyright 2011 American Chemical Society. (b) Routes to final LFL products: concentration-driven coalescence [Reprinted
with permission from ref 248. Copyright 2014 American Chemical Society], aggregation [Reprinted with permission from ref 249. Copyright 2015
Royal Society of Chemistry], and dispersion or adsorbate stabilization [left, Reprinted with permission from ref 250. Copyright 2013 Nature Publishing
Group; right, Reprinted with permission from ref 251. Copyright 2002 American Chemical Society].

Figure 20. Simulated ablation and bisection mechanisms for LFL. (a) Calculated nanoparticle diameter distribution functions at laser intensities of 4/3
× 107 W cm−2, 2 × 107 W cm−2, 8/3 × 107 W cm−2, 10/3 × 107 W cm−2, and 11/3 × 107 W cm−2. Reprinted with permission from ref 252. Copyright
2013 Institute of Physics. (b) Calculated weight distribution functions of Al particle sizes at different moments of time. Reprinted with permission from
ref 253. Copyright 2014 Elsevier.

(Eo/Ecoh = 1.86), sphere fragmentation occurs uniformly without ps, because of the thermionic electron emission and subsequent
void formation.247 hot electron relaxation, the lattice temperature of the plasmonic
Numerical insights were recently provided by Delfour and NPs initially increases to 700 K, causing Au NP reshaping below
Itina regarding how the size of Au NPs determines the the melting point. After the liquid NP charge exceeds the
occurrence probability of either Coulomb explosion or photo- Rayleigh instability threshold, Coulomb explosion occurs, and
thermal evaporation.246 Coulomb explosion tends to occur when the NPs split into many nanodroplets that eventually separate (or
Au NPs are below a well-defined size R* (R* = 30 nm for a 400 reaggregate). The entire process lasts ∼100 ps and is dependent
nm, 150 fs laser), whereas photothermal evaporation takes place on the employed materials and the laser fluence.
when the particles are larger.246 Hashimoto’s group verified Two novel mechanisms have recently been proposed by
thermionic emission during fs LFL of gold NPs based on in situ Shafeev and cowokers,252,253 deducing from the numerical
extinction spectroscopy and transient absorption spectroscopy solution of the kinetic equation for distribution function, which is
and obtained very small particles with diameters of 3.5 nm in accordance with the particle size evolution recorded by
(Figure 17a−d).86 On the basis of their experimental data, they analytical disc centrifugation (ADC) analysis during experi-
constructed a Coulomb explosion model and estimated the time ments. The first one is the detachment of smaller fragments from
scale for each process, as shown in Figure 19a.86 At times of 3−10 a molten nanoparticle (Figure 20a), similar to the scenario of
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ablation of the particles upon laser irradiation.252 The other is changing the particulate educt particle size.258 These defect sites
bisection of larger particles (Figure 20b) induced by the weaken the material’s cohesion, possibly enhancing the
oscillation of nanodroplets with a frequency of ∼ σ /ρr 3 fragmentation efficiency. Lau et al. compared fragmentation
with ultrasonication and found that LFL (at 5−70 kJ/g) leads to
(where σ is surface tension, r is particle radius, and ρ is particle
a decrease of the hydrodynamic diameter, while it was not
mass density). Here, the radii of the particles will follow the possible to reduce the size by ultrasonication (up to 20 000 kJ/
sequence of r → 2−1/3r → 2−1/3r.253 These two mechanisms have g).218
been validated experimentally by laser irradiation of Au NPs and Although the LFL process mainly comprises physical effects, it
Al powders, respectively.252,253 is sometimes accompanied by chemical reduction,259 chemical
The size of the LFL-generated products depends on the laser oxidation,25,260 or phase transformation.231 Singh et al. reported
parameters and the solid educt properties.221 For high pulse that LFL of nickel powders (1−5 μm) in an oxidizing
energies and ultrashort pulse durations, the resulting laser environment (e.g., water) led to the formation of spherical and
intensities may induce self-focusing (sensitized by the presence spiral-like Ni@NiO core−shell structures.261 Kawasaki indicated
of NPs223), optical breakdown, and liquid vaporization effects, that reductive LFL of CuO in acetone generated elemental Cu
which influence the overall laser energy input to the dispersed NPs or Cu@Cu2O NPs and that this process depended on the
particles. Such nonlinear optical effects reduce the energy solvent (e.g., acetone and diethyl ketone) because of the different
absorbed by particles in the laser beam path, even if the pulse high-temperature cooling periods.260 They also presented the
energy emitted from the laser source is increased. These effects reductive LFL of Ag2O micropowders into AgNPs (10−20 nm in
must be considered when working close to the relevant fluence diameter).262 In a follow-up study in which the solid educt’s
and intensity thresholds. Tuning the wavelength to the materials’ chemistry was systematically varied, Schaumberg et al.
surface plasmon resonance (SPR) band or the semiconductors’ demonstrated that LFL of Cu3N powders in ethyl acetate led
interband absorption has successfully been employed.21,254,255 to the formation of elemental Cu NPs.248,259 Interestingly, under
Intartaglia et al. demonstrated that LFL of Si particles was much nearly identical LFL conditions (except for the educt particle
more pronounced for 355 nm ps laser pulses than for those at size), fragmentation of the CuI microparticles altered neither the
1064 nm because the absorbance at the former wavelength was oxidation state of Cu nor the composition, thereby yielding CuI
higher, and, as a result, the size of silicon NPs was dramatically NPs.259
reduced to 3 nm.21 Surface chemistry also usually changes during LFL. For
Interestingly, Kabashin and co-workers reported that the size partially oxidized silicon particles, Švrček et al. depicted three
of the crystalline product Si NPs could be controlled by changing alteration stages affecting Si NP surface chemistry during LFL,
the initial educt concentration (Figure 17f).244 This finding including Si−dimer cleavage and OH/OH− condensation with
suggests a coalescence-based formation mechanism during LFL, H atoms, by analyzing photoluminescence (PL) and fourier
emphasizing the importance of the particulate educt concen- transform infrared spectroscopy (FTIR) transmission spectra.263
tration. LFL may create a liquid that is supersaturated with NP Through these stages, oxidation occurs increasingly close to the
fragments in which the collision frequency of the fragments is Si core, resulting in strained bonds and defects on the surface that
significantly increased, allowing them to coalesce into larger can provide nonradiative paths to exciton recombination.
particles248 or aggregate into long chains249,253 (Figure 19b). Nakamura et al. recently found that LFL of porous Si powders
Thus, the final size distribution of the colloid reflects the in organic solvents (1-octene) generates organic molecule-
equilibrium between fragmentation by laser pulses and NP passivated Si NPs with improved PL quantum efficiencies (20−
growth via coalescence or aggregation. If a minimal size is 23%) relative to the educt (1−3%).264 Thus, the particles are also
desired, the educt particle concentration must not exceed the involved in chemical reactions during LFL, similar to LAL, which
critical local concentration that favors the coalescence or alters the particle composition and surface chemistry and
aggregation of fragmented seeds with neighboring fragments. expands LFL toward RLFL.
To inhibit coalescence and aggregation, either dilution or The creation of oxygen vacancies during LFL can be regarded
capping agents are good options for LFL to obtain well- as a partial chemical reduction process. These defects can be
dispersed, small NPs (Figure 19b).250,251 Very often, small introduced into the nanoproducts during LFL of semiconductor
monodisperse NPs are found in the supernatant after LFL, not materials, as elucidated by Cai and co-workers265 and Lau et al.218
representing a high mass fraction. In contrast, higher for ZnO. Introducing abundant topological defects and vacancies
concentrations promote higher throughput (see section 4). into the synthesized semiconductor NPs during LFL enhances
Furthermore, higher seed concentrations favor the chemistry of the charge transport in bulk heterojunctions. Also, LFL of
seed-growth and ripening, resulting in high variation and large electrochemically etched Si nanocrystals in water can transform
particles composed of ultrasmall building blocks. Accordingly, NP surface wettability from hydrophobic to hydrophilic,263
NPs generated by LFL are spherical, unless dissolution, allowing the easy functionalization of the NPs with water-soluble
subsequent chemical reactions (e.g., resulting from surface polymers to enhance the external quantum efficiency. However,
adsorbates), or external fields cause morphological or geo- defects may be disadvantageous for certain applications in optics,
metrical changes256,257 during the ripening of the supersaturated such as lighting (electroluminescence) or phosphors. During the
colloids. For microparticle or submicroparticle educt, the fragmentation of K2SiF6:Mn4+ phosphor particles, the PL
irradiated material is often not entirely vaporized, and, as a quantum efficiency decreased, and the authors attributed this
result, the size of the solid educt gradually decreases in a linear phenomenon to the increased nonradiative recombination
fashion, depending on the educt mass-specific laser energy input channels resulting from the formation of defects.266 Decreasing
(kJ/g).218 One method to increase the LFL efficiency of the NP size of noble metals during LFL requires the delivery of
microscale educt was described by Wagener et al., who combined surface charge to achieve NP repulsion and colloidal stability and
LFL with mechanical pretreatment of microparticles in a stirred- therefore benefits from the presence of an oxidative additive.267
media mill to introduce defect sites in the educt particles without Surface defects on noble metal NPs after LFL increase the surface
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charge density.268 Thus, LFL of noble metal NPs can be regarded applications), and semiconductors (longer electron−phonon
as oxidative LFL.25 Overall, LFL may lead to oxidation (e.g., Au coupling times), is anticipated.
→ Au(+)25), partial reduction (e.g., CuO → Cu with traces of 2.3. Laser Melting in Liquids (LML)
oxides depending on the solvent248) and full reduction (Ag2O → Mild isochoric photothermal NP processing by pulsed lasers in
Ag262), or the preservation of educt stoichiometry (e.g., CuI259). liquids was reported more than two decades ago269,270 and has
Although systematic research on the determinants of redox-LFL recently been advanced for the synthesis of submicron spheres
remains challenging, the predictive factors of dominant pathways (SMSs) by LML (Figure 21). Synthesizing SMSs by LML is
during RLFL include the redox potential of the liquid25 and the
educt composition248,259 but not yet the laser parameters.
However, the latter are important for LFL efficiency (see section
5.1.1). The downsizing of colloids to particle sizes ≪20 nm
clearly benefits from ultrashort pulse durations as these require
far lower threshold fluences. Additionally, the required ultra-
short-pulsed fluence values are nearly independent of the
particulate educt size when it is less than 100 nm. In contrast,
the bathtub threshold fluence profile220 (Figure 16b) for ns
pulses could allow the selective fragmentation of NPs with sizes
in the intermediate range (approximately 50 nm) because 20−60
nm AuNPs have lower fluence thresholds for bubble formation.
However, laser attenuation in liquid must also be considered.
Attenuation can reach up to 50% after 300 s of laser
processing,228 which means that the volume that is irradiated
creates mild (low fluence) LML conditions (Figure 16c) and may
explain why a 20−60 nm NP mode byproduct is often detected, Figure 21. Scheme of LML. Initially nanometer-sized (not necessarily
particularly at high liquid levels (high irradiated volume). Hence, spherical) primary particles are aggregated/agglomerated, and the
a thin liquid layer is required to achieve LFL without LML. Note secondary particles are melted by a laser beam into submicrometer
that the model presented in Figure 16c is only qualitatively (not particles that typically exhibit increased sizes as compared to the educt
quantitatively) reliable because heat transfer to the liquid and primary NPs. Note that irregularly shaped particles can also be
isochorically reshaped through this method.
bubble formation are not considered.
Overall, large (≫100 nm) educt particles or dielectric
materials (i.e., semiconductors and ceramics) can be fragmented remarkable because the transformation process does not require
effectively by both ns and ultrashort (ps/fs) lasers, particularly any chemical reagents or surfactants in the process chain271,272
when using high pulse energies (at intensities below the colloid’s and because it is a comparably simple method to increase the
optical breakdown) and repetition rates adjusted to the colloid particle size in a controlled, product-selective manner.
mass concentration (see section 4). Ionic crystal powders Koshizaki’s group performed pioneering work in this field and
expanded the applicability of LML toward metals,272−274
(ceramics, phosphors, and semiconductors) are available in
semiconductors,275,276 oxides,277,278 and carbides.279,280 In
larger sizes and are more brittle than the well-studied metal
general, LML can be divided into two classes: (1) fusion-LML,
colloids. Laser excitation of dispersions of such educt materials
which increases the size of a particle crystal (Figure 22a−g), and
could contribute to elucidating the full suite of LFL mechanisms.
(2) reshaping-LML, which is an isochoric process (Figure 22k−
Nakamura et al. hypothesized two different fragmentation
n). A representative example of fusion-LML is the trans-
mechanisms during LFL of 100 μm phosphor powder that formation of raw CuO NPs into single-crystalline SMSs in
contributed to bimodal (2 μm and 100 nm) product formation acetone,272 as shown in Figure 22a−h. The raw materials with a
via shockwave/thermal stress and heating−evaporation, respec- primary size of 34 nm (Figure 22c) are transformed into SMSs
tively.266 Lau et al. analyzed the decreasing hydrodynamic with an average diameter of 300 nm (Figure 22d), as confirmed
diameter of ps-LFL-processed, submicrometer ZnO educt by scanning electron microscopy (SEM) (Figure 22b) and TEM
particles fragmented from ∼450 to ∼180 nm with crystal (Figure 22f). The selected-area electron diffraction (SAED)
diameters from 250 to 100 nm218 and hypothesized that LFL pattern indicates that these SMSs are crystalline (Figure 22h).
could be regarded as a comminution process with the Note that SAED tells that crystalline domains are present in the
nonspherical particle product originating from educt disaggre- SMS, but cannot exclude the coexistence of amorphous domains,
gation, breaking sintering bonds by LFL. Although a small as deduced from LSPC-synthesized magnetite281 or AuFe
fraction of spherical 60 nm particle products was observed, the alloys.282 More importantly, increasing the laser fluence tunes
attrition mechanism dominated the mass yield.218 Interestingly, the SMS size from 260 to 370 nm, demonstrating the possibility
under the same conditions, during LFL of boron carbide, the of SMS size control. Note that the SMSs are not always single
evaporation/ablation pathway dominates because the microsized crystalline but are sometimes a mixture of single-crystal and
solid educt is mostly converted into spherical NPs with diameters polycrystalline spheres, as revealed by electron back-scattering
of ∼100 nm.218 Similarly, Schaumberg et al. found that the diffraction (EBSD) analysis.283 Inspired by their work, Okamoto
dominant LFL mechanism of micropowder dispersions changes et al. extended the application of LML to transform anisotropic
from photomechanical (CuI educt) to ablation/evaporation materials (e.g., CeO2) into single-crystalline SMSs with high
(CuO, Cu3N educt).248,259 sphericity.284 Rehbock et al. demonstrated surface roughness
Given that most theoretical work and fundamental experi- alteration of Au SMSs dependent on the laser fluence and the
ments have focused on Au NPs, extending the derived model to particle size distribution using salinity-adjusted aggregation
other materials, especially Pt, Pd (relevant for catalysis where the yield of particles with wrinkled surface increased
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Figure 22. Fusion and reshaping LML. (a−h) FESEM image, particle size distribution histogram (number frequency), TEM image, and SAED pattern
of raw CuO NPs and submicrometer spheres obtained by pulsed laser irradiation of CuO NPs in acetone (355 nm, 66 mJ pulse−1 cm−2, 30 min).
Adapted with permission from ref 272. Copyright 2010 Wiley-VCH. (i,j) Fusion LML of NPs into nanowires. Reprinted with permission from ref 49.
Copyright 2003 American Chemical Society. (k,l, and m,n) TEM images of gold nanooctahedra [Reprinted with permission from ref 285. Copyright
2015 Nature Publishing Group] and nanorods [Reprinted with permission from ref 286. Copyright 2000 American Chemical Society] before reshaping
LML and the obtained Au NPs.

Figure 23. Fundamentals and variants of pulsed LML: (a) fusion-LML and (b) isochoric LML. Adapted with permission from ref 295. Copyright 2013
Japan Laser Processing Society. (c) Schematic illustration of the ns laser-irradiation-induced shape transformation of octahedral Au NPs in water.
Adapted with permission from ref 285. Copyright 2015 Nature Publishing Group. (d) Schematic illustration of the evolution from Au NPs adsorbed on
ZnO (supported particles) via an intermediate state consisting of size-increased Au NPs on reshaped ZnO to the embedment of Au NPs into the
spherical crystalline ZnO matrix (product). Adapted with permission from ref 267. Copyright 2015 Royal Society of Chemistry.

with laser fluence and monomodality of the educt particles.271 assembly resulting from variation of the colloidal electrostatic
This phenomenon was hypothesized to be based on a balance and attractive dipolar interactions.249
disaggregation−melting−deposition mechanism.271 Subse- Using LML for isochoric reshaping can transform not only
quently, Lau et al. advanced the LML ability to invert supported gold nanooctahedra285 (Figure 22k,l) but also nanorods269,286
particles (Au on ZnO) into SMSs resulting in Au NPs embedded (Figure 22m,n) and partially nanospheres. This isochoric LML
inside of ZnO SMSs.267 Clearly, simple LML not only allows size educt−product relationship can be described as a nanoscale-
control of the synthesized SMSs but also enables the adjustment equivalent chemical isomer in which the solid educt and product
of their surface roughness and composition; thus, many other have identical volumes. Link et al. reported that the LML-
types of SMSs will likely be reported in the near future. induced rod-to-sphere shape transformation is initiated by defect
LML can also be used to fuse nanorods287,288 or NPs289,290 (twin and stacking) generation and proceeds through surface
(Figure 22i,j) into wires or nanochains with higher aspect diffusion and crystal growth.293
ratios.102 This phenomenon is also observed after long-term Typical laser requirements for LML are wavelengths from
LAL, in which postirradiation leads to anisotropic coalescence of UV267 to NIR,273 a “mild” fluence regime of approximately 10−
the gold particles.291 Serkov et al. proposed that the ionization of 350 mJ/cm2,271,294,295 and pulse durations in the order of ns.275
Au NPs by either thermionic emission of electrons or two- Because the primary aim is mild selective absorption and laser
photon absorption of laser radiation would lead to the formation heating of the dispersed particles, UV lasers providing interband
of highly charged particles that attract neutral particles to form absorption and longer pulse durations (ns regime) are often
multipole structures, which eventually evolve into the nanowires advantageous. At a relatively low laser pulse fluence of ≤150 mJ/
after further laser irradiation.292 Poletti et al. also observed the cm2, the laser melting of agglomerated NPs causes the merging of
fusion-LML behavior of gold NPs forming nanocorals and agglomerates into SMSs.295 Because this low fluence is required,
attributed the formation of this structure to the particles’ laser beam focusing is unnecessary, minimizing the problems of
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Figure 24. (a) Au SMS formation via growth processes during LML in citrate and NaCl solutions with a citrate induction period. Reprinted with
permission from ref 274. Copyright 2015 Elsevier. (b) Influence of fluence on the SMS particle size: calculated phase diagrams for silver NPs during 532
nm LML. J1, the start of melting; J2, melting complete; J3, the start of evaporation. Reprinted with permission from ref 91. Copyright 2015 Wiley-VCH.

LFL associated with fluence deviation. If the laser fluence must be essential induction period during LML with no occurrence of
increased at a constant pulse energy, using a parallel unfocused agglomeration or fusion of the educt particles and only the
beam with a smaller radius is a good method and can be easily removal of stabilizers (Figure 24a).274 They compared electro-
managed with a lens system. However, even in this case, a fluence static (chloride anions) and electrosteric (citrate) stabilizers and
gradient will arise because of the absorption and scattering of the found that a holding period was required to remove the citrate
beam as it penetrates the liquid; thus, thinner liquid layers (see stabilizers during the initial stage of LML. Subsequently, the size
section 5.3.4) are advantageous for fluence gradient minimiza- of the SMSs suddenly increased; in contrast, in sodium chloride
tion, which is important for selective LML in which the product’s solution, because no induction period was required, the SMS size
size is strongly influenced by the applied fluence. increased gradually.274
Aggregated or agglomerated NPs are currently the most The Meunier group irradiated gold NPs in methanol with 532
common dispersed particle educts used to produce SMSs via nm ns pulses of up to 20 mJ/pulse with a beam diameter of 8
LML, which involves fusion (volume increase) and subsequent mm.219 Despite the increasing bimodality of the resulting
isochoric reshaping of the educt. Wang et al. hypothesized two particles (successful LML), they emphasized that Ostwald
LML mechanisms for the shape transformation into SMSs ripening can be excluded as a reason for the changes in particle
(Figure 23a,b).296 Dispersed, less-aggregated educt particles diameter. At higher laser powers, the growth rate decreased,
undergo conversion to final SMSs via three primary LML- which cannot be explained by the redeposition of dissolved
induced steps: sphere formation in a low laser fluence irradiation species on the surfaces of larger particles. In this case, increasing
volume, fusion of the (reshaped) primary particles, and, finally, the NP temperature would lead to a faster exchange of atoms
SMS formation at higher LML fluence (Figure 23a). In and, therefore, more rapid growth of the large particles. Their
comparison, hydrodynamically larger educt aggregates follow “diffusion coalescence” model explains the slow increase of the
the second mechanism and directly undergo fusion and isochoric solvent temperature caused by the NPs, which in turn slowly
reshaping into final SMS morphologies (Figure 23b). In both increases the NP collisions. During reshaping by LML (Figure
routes, incomplete fusion of the particles leads to the generation 23c),285 the energy could be much lower than that required for
of anisotropic particles, which are an intermediate state of the the sequential melting of agglomerates into spheres. For instance,
SMSs. Similar intermediates have been observed for dimers of Inasawa et al. calculated that a surface temperature ∼110 K lower
LML-molten particles.285 Detailed material characterization of than the melting point of Au (i.e., 1337 K) was sufficient to
the intermediates of LML in a liquid jet passage reactor has transform ellipsoidal Au NPs into spheres using a heat balance
revealed that AuNP fusion by LML may also occur on the surface and surface melting model.297
of the support particles (ZnO crystals), which then undergo The pulse energy fraction absorbed by a single NP is related to
isochoric structural inversion to become ZnO SMSs with interior its absorption cross-section. To determine the laser fluence that
AuNPs (Figure 23d).267 Thus, fusion-LML and isochoric LML facilitates particle melting, Wang et al. estimated the absorption
may be material selective. cross sections of particles of different dimensions using the Mie
To this end, defined educt particle agglomeration in LML has theory and calculated the energy absorbed by a particle irradiated
been achieved by the following strategies: stabilizer removal273 or by a single laser pulse.91,277 As expected, the results indicated that
salt destabilization.271 Thus, the key to achieving controlled smaller particles require higher energy because of their low
fusion-LML is controlling the source particle’s agglomeration optical cross sections and higher specific surface areas (Figure
state, which is, in most cases, represented by the hydrodynamic 24b).91 Shim et al. demonstrated that larger particles require
diameter difference relative to the primary particle size. This more energy to melt or evaporate because of their larger heat
agglomeration brings nearby educt particles together, which is capacity.298 However, for the example of gold NPs in water,
essential for aggregation, fusion, and volume increase. The Baffou et al. reported that the temperature increase was
isochoric reshaping step is less critical because it is driven by maximized when the particle size was 40 nm and was damped
surface energy. In general, colloidal agglomerates are metastable because of inefficient absorption by larger NPs, whereas for
and difficult to synthesize without steric stabilizers. In water, smaller NPs, the temperature increase was restricted by their
electrostatic destabilization and aggregation may be readily faster heat release.299 For agglomerated NPs, in the ns pulse
triggered by charge screening (salinity and pH), thermophoresis regime, Feldmann’s group demonstrated a further increase of the
(heat), or surfactant removal. Recently, Tsuji et al. observed an local heating effect.300 Agglomerated gold NPs were shown to
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Figure 25. Size range of the NMs accessible by LSPC and methodologies for obtaining monomodal and monodisperse NPs through LAL via in situ size
control. (a) Size ranges accessible via LSPC shown by representative images (from left to right): 1 nm to 10 μm (LAL): carbon dots (C-dots) [Adapted
with permission from ref 24. Copyright 2015 Wiley-VCH], Au NPs [Adapted with permission from ref 313. Copyright 2010 American Chemical
Society], Si@Au core−shell submicrospheres [Adapted with permission from ref 213. Copyright 2015 American Chemical Society], and AgGe
microspheres [Adapted with permission from ref 23. Copyright 2015 Nature Publishing Group]; 1 nm to 10 μm (LFL) PbS quantum dots (QDs)
[Adapted with permission from ref 250. Copyright 2013 Nature Publishing Group], Cd NPs [Adapted with permission from ref 311. Copyright 2015
Wiley-VCH], Al NPs [Adapted with permission from ref 253. Copyright 2014 Elsevier], and K2SiF6:Mn4+ phosphor particles [Adapted with permission
from ref 266. Copyright 2014 Elsevier]; 10 nm to 10 μm (LML): Au NPs [Adapted with permission from ref 285. Copyright 2015 Nature Publishing
Group], ZnO SMSs [Adapted with permission from ref 296. Copyright 2014 American Chemical Society], and ZnO microspheres [Adapted with
permission from ref 284. Copyright 2014 Nature Publishing Group]. (b−e) Monodisperse Cd colloids after LFL of the LAL-synthesized Cd NPs (LAL
+LFL). Adapted with permission from ref 311. Copyright 2015 Wiley-VCH. (f) Polydispersity control during LAL synthesis of Y2O3. Reprinted with
permission from ref 306. Copyright 2011 American Chemical Society.

accumulate heat between the individual NPs, which created a yielding up to 40% elemental Cu particles.272 This example
“nanostove” in the agglomerate center. When a NP absorbs strongly indicates that RLML is possible, thereby extending the
enough laser energy to enable local heating of the particle surface applications of LML from simple SMS fabrication and NP
beyond the melting temperature, particles in close contact merge shaping toward the chemical conversion of solids. Moreover,
to reduce their surface energy, thus leading to the formation of reactions with the liquid during LML have been reported. For
larger particles with improved SMS properties (size homogeneity example, Nakamura et al. used dissolved salts (ferric301 and
and stability) and even initiating particle alloying. For example, ferrous302 ions) as laser sensitizers for the liquid and were able to
Hodak et al. provided evidence for laser-induced interparticle embed magnetite into calcium phosphate SMSs. Kawasoe et al.
diffusion in AuAg core−shell NPs.270 Large particles have been reported that during LML of TiN colloidal NPs in water, both
reported to take up small particles during LML,277 and as this TiN SMSs and some byproducts (e.g., TiO2 and TiOxNy) were
process continues, smaller particles are steadily consumed, produced because of reactions between oxygen species and the
resulting in larger SMSs. Consequently, the hydrodynamic TiN compound and decomposed Ti species.294 Therefore,
diameter of the educt agglomerates can be far smaller than that of chemical reactions may be triggered to accompany LML.
the SMS product, indicating that LML of SMSs is a multipulse Although reactive LSPC has been primarily investigated via
process (and that LML itself triggers aggregation). This process LFL and LAL, it also occurs during comparable “mild” LML.
is also quite robust, leading to comparable SMS diameters for More research is needed to understand how chemical conversion
educt colloids with different hydrodynamic particle size can be controlled independently from the product’s particle size.
distributions. Generally, increasing the laser fluence leads to a
gradual increase in the particle size.91 For instance, the average
3. SIZE CONTROL
diameter of CuO SMSs increased from 260 to 370 nm when the
laser fluence was increased from 50 to 200 mJ/cm2.272 Notably, Although significant advancements in size control during LSPC
further increasing the laser fluence resulted in a dramatic have been achieved for metal NPs in recent years,11 especially
decrease of the particle diameters to below 10 nm because the with LFL and LML, monomodal and monodisperse colloids are
LFL fluence threshold was exceeded. challenging to produce by LAL without compromising colloidal
Similar to LFL, the size and the chemical composition of LML- purity. Even LAL at very low fluence (resulting in low
generated SMSs depend on the laser fluence. X-ray diffraction throughput) produces a secondary size mode of particles,194 as
(XRD) measurements revealed that the LML process was is clearly evident in the volume-weighted particle diameter
accompanied by the chemical reduction of CuO and Cu2O, histograms.11 The origin of this second size mode remains under
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Figure 26. Statistics of LAL, LFL, and LML product particle diameters reported in the literature on the basis of 150 articles cited in this Review.

Figure 27. Size control of gold NPs by four different methods: (I) LML, (II) delayed conjugation, (III) size quenching by salts during LAL, and (IV)
LFL. Reprinted with permission from ref 11. Copyright 2014 Beilstein-Institut. Delayed conjugation is a method to downstream-conjugate NPs shortly
after the NP formation.

debate, and reported methods capable of achieving monodisper- reported for LAL are unclear. Regarding the primary particle
sity often require particle growth quenching by surface diameter, precise size control in the range of 1−20 nm (Figure
adsorbates or conventional downstream processing, such as 26) has been realized by LAL with the assistance of surfactant
centrifugation.303,304 Moreover, no theoretical model has yet termination,305 complexing (Figure 25f),306 polymer capsu-
been constructed to correlate the material and liquid properties lation,307 bioconjugation,308 organic molecule polarity con-
with the primary particle diameter resulting from LAL. Despite trol,219 support loading,309 and salt quenching.310 As a
the current inability to quantitatively predict the NP size solely downsizing method, LFL naturally covers the size range of
on the basis of the physicochemical properties of the solid and available educt particles, reducing their sizes down to between
liquid, multiple pathways can be effectively used to tailor the size ∼2 nm (educt: 20 nm)25 and 2 μm (educt: 110 μm),266
and narrow the size distribution of laser-synthesized NMs depending on the evaporation/attrition mechanism (Figure
(Figures 25−30). This section first provides an overview of the 25a). As compared to LAL, LFL exhibits better size control in the
size ranges accessible by LSPC, and then size control strategies range of 1−20 nm, especially for 1−5 nm (Figure 26). One
are explained in detail based on laser processing with liquid particular feature of LFL is its compatibility with LAL, which
(surface chemistry) parameters. In general, among the three enables the transformation of LAL-synthesized NPs with a
LSPC methods, the primary NP diameters fabricated by LAL to polydisperse distribution (Figure 25c) into highly monodisperse
date cover a broad size range from ∼1 nm24 to 10 μm23 (Figure NPs (Figure 25d,e).311 Furthermore, LML allows the generation
25a). However, on the basis of the experimental design, the of SMSs with typical diameters of 100−1000 nm (Figure
extents to which LFL (size decrease) and supersaturation-driven 26)272,294,312 or even up to several micrometers.284 LML can also
ripening (size increase) contribute to the particle diameters be used to fuse NPs into nanowires/nanorods291 and reshape
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Figure 28. LAL: (a) Average size of Pd NPs fabricated at different LAL wavelengths (355, 532, and 1064 nm) and fluence values (9, 13, and 20 J/cm2).
Adapted with permission from ref 314. Copyright 2014 Elsevier. (b) Mean size of the Au NP two modes as a function of laser fluence using an fs laser.
Reprinted with permission from ref 194. Copyright 2003 American Institute of Physics. LFL: (c) Correlation between the average radius of Au NPs and
fluence during ns LFL in H2O. Reprinted with permission from ref 232. Copyright 2007 Royal Society of Chemistry. (d) Mean size of Au NPs after fs
LFL as a function of input laser energy. Adapted with permission from ref 315. Copyright 2015 Institute of Physics. LML: (e) Laser fluence-dependent
size changes of CuO NPs obtained via pulsed laser irradiation (532 nm). Adapted with permission from ref 272. Copyright 2010 Wiley-VCH. (f) Laser
fluence dependence of the mean size and yield of B4C particles prepared by laser irradiation for 300 min in ethyl acetate. Reprinted with permission from
ref 279. Copyright 2010 Springer.

nanorods269,286 or octahedral particles285 into spherical NPs with results in smaller particles.322 These contradictory findings
sizes in the range of 10−100 nm. originate from the fact that it is difficult to exclude in situ LFL of
Overall, LSPC is an emerging technique with the capability for the NPs resulting from the energy absorption by NPs during
wide-range size manipulation from several micrometers down to long-term LAL.21 Also, the pulse-number-induced incubation
1 nm. In particular, Au NPs with diameters from 400 to 2 nm can and screening effects323 and the possible modulation of the laser
be obtained (Figure 27).11,25 Realizing size control in LSPC is fluence by the focus position324 may also affect the size
often achieved by modulating the laser or processing parameters fluctuation under different conditions; consequently, clearly
and the liquid medium, as explained below. identifying the impact of laser fluence on NP size control during
3.1. Laser Modulation LAL remains difficult. Elucidating the influence of laser fluence
on LAL requires excluding LFL effects; thus, SP-LAL fluence
Most laser systems have multiple tunable laser parameters (e.g.,
studies are needed. As compared to LAL, the laser fluence-
laser fluence, pulse duration, repetition rate, and laser wave-
dependent size control is relatively straightforward for LPC. Two
length). However, one parameter often affects the others. For
instance, increasing the repetition rate always leads to higher LFL laser fluence thresholds exist for NP size tuning. When the energy
effects, whereas decreasing the laser wavelength often decreases is well above the fragmentation threshold, the particles evaporate
the laser pulse energy and leads to sharper focusing and stronger or explode, producing smaller particles and dramatically reducing
LFL (absorbance of colloids at wavelength of λ). In the case of the NP size; in contrast, when the laser energy is above the
LAL, high-energy laser pulses have often been reported to favor melting energy threshold but below the fragmentation threshold,
the formation of larger NPs,84,316 at least in terms of the diameter LML occurs, and the NP size increases. This trend has been
of the modes in the number-weighted size histogram (Figure thoroughly confirmed by ns lasers, in which the heating−melting
28a,b).194,314 This may be attributable to the enhanced mechanism is responsible for the size variation.325 Clear fluence
aggregation and coalescence of the particles resulting from dependence is also observed in LML, in which the SMSs increase
explosive boiling and higher NP yield.317 Reduced laser energy in size as the laser fluence increases279 (Figure 28f). In contrary,
has been reported to decrease both the size and the size the NP size decreases as the laser fluence increases232 via LFL
distribution of LAL-synthesized particles, as observed independ- until a certain size limit (Figure 28c). However, the laser fluence
ent of the laser pulse duration (e.g., fs,84,318 ns,306 and CW140) must be constrained to the LFL window; otherwise, secondary
and for various materials (e.g., Si,318 C,319 Au,194 and Ag305). nucleation of the fragmented NPs into larger ones may occur at
Although low pulse energy may reduce the size of NPs, it leads to high fluence (Figure 28d).315 At a certain point, however,
a drawback of lower productivity.320 In contrast, the opposite fragmentation of the melted particles occurs (Figure 28e).272
effect has been reported as well, where increasing the laser pulse The ripening and growth of LFL-synthesized NPs may also be
fluence narrows the size distribution of the generated NPs321 and triggered by the aging of supersaturated naked atom clusters.164
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Note that this ripening (LFL of noble metals in water) is parameters, the existence of mutual cross-effects between these
generally more rapid than TEM sampling and can extend over parameters makes it difficult to develop a general concept.
multiple days, severely compromising the colloidal stability.164 Indeed, it is straightforward to narrow the size distribution and
This finding implies that rechecking the NP size (or carefully minimize particle diameter sufficiently to avoid NP excitation
setting the sampling interval following LFL) is indispensable with LFL, resulting in monodisperse colloids. However,
after LFL, particularly during the early storage of the colloid. stabilizer-free colloids undergo ripening and may be super-
Hamad et al. reported that increasing the laser pulse duration saturated with atom clusters,164 and thus should be immediately
resulted in smaller LAL-synthesized Ag, Au, and TiO2 NPs in postprocessed into their final matrix or supports to stabilize their
deionized water.326 Notably, not only the average (number- size. In contrast, intermediate sizes are much more difficult to
weighted) particle diameter but also the fraction of large particles synthesize by LFL, in which educt−product mixtures often
(>40 nm) and polydispersity significantly decreased with exhibit a bimodal size distribution, requiring one to perform
increasing pulse duration for the investigated fs, ps, and ns further fractionation, for example, by centrifugation. As a general
laser systems. Unfortunately, the laser wavelength, fluence, and rule, IR ns lasers have been shown to be beneficial for producing
repetition rate also differed in those experiments (fs, 800 nm, 28 monomodal products via LAL and LML, whereas ultrashort (and
J/cm2, 1 kHz; ps, 1064 nm, 0.4 J/cm2, 200 kHz; and ns, 532 nm, shorter wavelength) pulses are beneficial for LFL. During LAL,
12 J/cm2, 30 kHz); thus, drawing robust conclusions is difficult. lower fluences seem to favor smaller sizes, but higher fluences
As for the fs lasers, thermal-free ablation and plasma-induced may benefit from combined LAL−LFL (in particular at lower
heating/ablation of a target dominate at lower and higher wavelength), narrowing size distribution. Further investigation is
fluences (i.e., so-called soft and hard ablation), respectively.194 recommended to elucidate the impact of each parameter on NP
Tsuji et al. defined two types of laser pulse absorption by nucleation and growth while keeping all other parameters
particles:327 “inter-pulse” absorption of the following pulses’ constant.
energy by colloidal particles generated by the former pulses and 3.2. In Situ Size Control by Surface Chemistry
“intra-pulse” absorption of a later part of a pulse. As a result, intra-
pulse absorption is negligible for fs lasers but should be In addition to laser parameters, surface chemistry can effectively
considered for ns-LFL. For ps pulse durations, the LFL threshold be used to control the size of synthesized NPs during both LPC
depends on the electron−phonon coupling time (τep) of the and LAL. Surfactants, electrolytes, polymers, biomolecules,
NPs.220 If the ps pulse duration exceeds τep, heat delivery from organic solvents, and support materials have been applied to
the electrons to lattice occurs during the laser pulse. In contrast, if tune the NP size (Figure 29), and their effects are straightforward
it is shorter than τep, the heat delivery is negligible during the to control in LAL experiments. Sometimes, this basic concept
excitation. Therefore, the energy increase is negligible in the also works for LFL and LML. Because LAL often suffers from a
particle lattice in the case of fs pulse irradiation328 because the wider size distribution and bimodality, most efforts relating to
photon−phonon relaxation occurs in the dark; this circumstance LSPC in situ quenching research have focused on LAL. The
does not occur when ns lasers are used because photons general principle of in situ NP surface deactivation by
continuously irradiate the particle during photon−phonon physisorption or chemisorption is the same for all cases of
relaxation (providing inefficiently larger energy flux duration inorganic NP seeds, which are released into the liquid during
than minimally required for LFL). Therefore, the intra-pulse LSPC (Figure 30).
effect is negligible for ps and fs laser fragmentation, making fs- First, the growth termination of embryonic particles by
LFL more efficient than ns-LFL for the size reduction of Au surfactant molecules in increasing concentrations generally shifts
NPs.329 Also, the second-harmonic generation during nonlinear the NP size toward smaller values.336,337 This phenomenon has
fs laser ablation can shift the initial laser wavelength close to the been widely investigated using CTAB338 and SDS305,336,337
SPR band of plasmonic NPs, providing the possibility of inducing (Figure 29a,b). The surface coverage increases with the SDS
resonant NP fragmentation.330 Note that LFL efficiency does not concentration, and a double layer coating forms on the surface,
always correlate with the quality of the resulting NPs’ size thus increasing the yield of small NPs.339 However, the surfactant
distribution. However, because the LFL fluence threshold (Fth) concentration should not be too low or too high.339 Initially,
drastically increases for small particles if ns pulses are applied increasing the SDS concentration screens the repulsive electro-
(whereas Fth is less size dependent for ultrashort pulses),220 static force between the NPs because of the cumulative coating in
much higher pulse energies must be applied to minimize the NP which the amphiphilic surfactant points its hydrophobic tail
diameter with ns lasers. Overall, ultrashort-pulsed LFL is less outward at submonolayer and monolayer concentrations.339 At
sensitive to particulate educt diameter variation, rendering fs and higher concentrations, a double layer forms, and the hydro-
ps LFL robust. phobic, charged surface groups contribute to electrosteric
In addition to the laser fluence and pulse duration, another stabilization. Finally, when the surfactant concentration exceeds
important laser parameter is the laser wavelength. Under the the level of double layer formation, unbound free ligands
same pulse duration, the use of shorter-wavelength (e.g., 532 and contribute to the solvent’s bulk salinity and screen the
355 nm) lasers favors the generation of smaller NPs326,331 electrostatic charge repulsion of the electrosterically stabilized
because of self-absorption-induced fragmentation332 or laser AuNPs−SDS− conjugate. Mafuné et al. convincingly demon-
wavelength located around the NP extinction maximum, which strated that steric contributions are beneficial for stabilization by
has been verified for many materials, such as Au,333,334 Pd,314 comparing surfactants with different carbon chain lengths and
ZnO,321 and Ag NPs.327,335 This behavior implies that showed that n ≥ 12 (CnH2n+1SO4Na) resulted in superior particle
postirradiation using the second or third harmonic wavelength stabilization.339 Note that in this LAL study, as in a series of
is often much more effective for LFL-induced size reduction than studies by Mafuné’s group in that decade, the long focal length
using the fundamental wavelength. Taking together all of the (∼250 mm) and large beam diameter (1−3 mm) may have
effects of laser parameters on NP size control, it can be concluded caused progressive LFL in the 10-mL metal NP sample,
that, although one laser system offers multiple size-affecting particularly with the second harmonic wavelength. Conse-
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Figure 29. In situ size control during LAL and LFL by surfactants, solvents, biomolecules, and anions. (a) Surfactant effects during LAL: average radius
of the NPs (●) and average dispersion of the radius distribution (○) as a function of the SDS concentration. Reprinted with permission from ref 305.
Copyright 2000 American Chemical Society. (b) Surfactant effects during LFL: size-quenching effect depending on SDS surfactant concentration. Note
that the critical micelle concentration (CMC) is 0.008 M. Reprinted with permission from ref 243. Copyright 2006 American Chemical Society. (c)
Solvent effects on LAL/LFL: average Co NP diameter as a function of solvent polarity with ablation for 4 min (◇) and 60 min (○). Reprinted with
permission from ref 219. Copyright 2012 American Chemical Society. (d) Solvent chemistry during LAL: size-quenching effect of acetone via its enolate
tautomer on LAL-synthesized Au NPs. Reprinted with permission from ref 334. Copyright 2012 Springer. (e) Biomolecule chemisorption during LAL:
size distribution determined for AuNP-oligonucleotide bioconjugates as compared to unconjugated gold NPs and a TEM micrograph of the
monodisperse bioconjugates. Reprinted with permission from ref 308. Copyright 2009 WILEY-VCH. (f) Charge delivery by anions during LAL: Au NP
diameters resulting from size quenching with sodium phosphate buffer (NaPP) of different ionic strengths observed by SEM and ADC. Reprinted with
permission from ref 310. Copyright 2013 Royal Society of Chemistry.

quently, their follow-up studies addressed surfactant effects PVP to water slightly quenched the (number-weighted) particle
during LFL, demonstrating the importance of reaching the size but did not narrow the size distribution.144 Although
surfactant’s CMC (Figure 29b).243,336 One general drawback of encapsulated NPs are small, and the colloid is typically very
using surfactants is the risk of pyrolysis during high-fluence LAL, stable, their hydrodynamic diameters are enlarged (and their zeta
which may contaminate NP purity, as shown by infrared (IR) potential, which is indicative of the particle mobility, is screened)
spectroscopy.169 Even in LML with comparably low fluence, the by the polymer capsule.307 In addition to chemical polymers,
ionic surfactant citrate decomposes.273 interest in studying the size-quenching effect of biopolymers,
In contrast to electrostatic or electrosteric stabilization, which such as albumin,310,344,346 starch,347,348 gelatin,349,350 and
is sensitive to stability screening by salting-out effects (including chitosan,351−353 is increasing because of their excellent
overdoses of the ionic surfactant itself during LAL339), the steric biocompatibility and biodegradability. The dispersions and
stabilization of particles with biomacromolecules or polymers is sizes of AgNPs and AuNPs prepared by laser ablation in such
even compatible at physiological salinity35,310 or in nonpolar biopolymer-containing solutions have been found to be narrower
solvents.307 By physisorbing onto the synthesized NP surfaces and smaller than those prepared in neat water.349,350 These
through van der Waals interactions, polymers can easily exert results constitute the basis for the single-step synthesis of NP−
size-quenching effects. Additionally, functionalized polymer end- biopolymer composites. However, because of the high molecular
groups, especially thioether and thiols, allow chemisorption on weight of these polymers, high volume fractions of additives are
growing particles.227,340−342 Singh and Soni demonstrated that required for LSPC size quenching.
poly(vinylpyrrolidone) [PVP] (keto) and poly(vinyl alcohol) Organic solvents play different roles in size quenching and
(PVA) (alcohol) were much more efficient at aborting NP particle stabilization because (i) organic solvents may shift bonds
growth during laser synthesis and producing smaller NPs than or decompose under laser irradiation, and the newly formed
polyethylene glycol (PEG) (ether).343 When conjugated with molecules may quench the NPs growth354 or react with the
mPEG-SH, LAL-generated gold colloids could be frozen and ablated matter;355 (ii) the solvent molecules bear functional
thawed several times, and even freeze-dried (complete water groups with high surface affinity, such as thiols, ketones (e.g.,
removal) and redispersed without impairing colloidal quality or acetone260,334 and cyclopentanone356), or esters (e.g., ethyl
stability.344 Tsuji et al. investigated the effect of PVP on LSPC in acetate248); and (iii) the polarity of the solvent contributes to
detail,144,345 as summarized in their review.92 In their studies on colloid stabilization. First, solvent decomposition may be
Ag NP synthesis, PVP was more efficient for LFL than LAL, and regarded as pyrolysis,198 and only a few reports are available on
laser-fragmented particles underwent shape conversion and the compositional change of the liquid.357 One example is
crystallization in PVP but not in PVA.345 During LAL, adding chloroform, which can induce reactions during LAL of copper,
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resulting in Cu2OCl2 NPs with diameters as small as 3.7 nm.358 strength from 1 to 50 millimolar (mM) was found to reduce the
The volatile byproducts and the reactions of the solvent with AuNP size from ∼20 to ∼6 nm (Figure 29f).310 Although
NPs359 will be discussed in section 5. Second, ketones as a electrolytes can quench the size of synthesized NPs and sharpen
functional group and LAL-induced enolates have been related to their size distribution, the production of large metallic NPs
the size-quenching and stabilization effects of acetone (Figure cannot be totally inhibited, as observed by Marzun et al. in the
29d).334 Third, regarding the effect of the liquid’s polarity on NP LAL of palladium targets in phosphate buffer, carbonate buffer,
size, opposing trends have been reported. Studying free ripening and sodium hydroxide.135 It is important to note that electrolytes
kinetics after short (5 min) LAL revealed that less-polar liquids with different affinities toward the synthesized NP surface and
resulted in larger NPs (with smaller particles forming in water ions are present and may strongly affect NP stability.365−367
and acetone as compared to those forming in ethanol and ethyl Investigating the anion-specific size-quenching and colloid
acetate).360 In contrast, a long LAL irradiation period (60 min), stabilization effects during LAL of gold revealed a clear
during which LFL side effects are known to play a dominant role, correlation between the anion polarizability and hydration
yielded smaller particles in nonpolar solvents (hexane and diethyl number with its effectivity (stabilization per anion dose), and
ether) and larger NPs in 2-propanol and methanol, as confirmed the strength of this correlation could be ranked as follows: SO42−
using solvent mixtures (Figure 29c).219 Thus, liquid polarity ≈ F− < Cl− ≈ NO3− < I− ≈ SCN− ≈ Br−. Clearly, chaotropic
effect may vary as the irradiation time increases and leads to NP anions most effectively deliver charge to the noble metal NP
heating. Indeed, Meunier’s group reported that kinetic energy surface.268 Hence, not only the size is quenched effectively, but
allows NPs to overcome repulsion more easily in polar solvents also colloidal stability increased during LAL in μM, chaotropic
during growth.219 Fundamentally, one would expect that salt solution. Quantitatively comparing the colloid charge effects
relatively more polar solvents (higher relative permittivity) with X-ray photoelectron spectroscopy (XPS) data revealed that
would better stabilize charged NPs because the Debye length particle stabilization and size quenching were dominated by
(which reflects the electrostatic stabilization) is proportional to anion adsorption rather than surface oxidation.268 The surface
the solvent’s dielectric constant. Thus, water should be superior charge density-driven growth-quenching mechanism was verified
to, for example, methanol or hexane. Most studies on size control by identifying the linear correlation of the anion concentration
have utilized metal NPs; however, the surface adsorbates used for with the surface area of the NPs fabricated using LAL in μM
noble metal NPs usually differ from those used for the growth saline water.310 The constant of proportionality (1.5−1.9
quenching of oxides. Naturally, optimal surface adsorbates for nanomolar of anion per cm2 NP surface) enables adjusting the
noble metal NPs are soft Lewis bases (thiols, polarizable charges, total NP surface in a colloid. The absolute NP surface in a given
chaotropic anions), whereas oxides require hard Lewis bases or volume is a useful parameter in ex situ conjugation studies to
complexing agents. Carboxylic acids are a class of organic adjust the intended final molecule grafting density independent
molecules that enable size control through different modes of of the NP size; indeed, this value can be easily set on the basis of
coordinating their carboxylate groups to LAL-generated oxide the anion concentration if the LAL ablation rate is known.
NPs. Amans et al. demonstrated that the polyether chain of 2-[2- Another elegant strategy for NP size manipulation using
(2-methoxyethoxy) ethoxy]acetic acid (MEEAA) stabilized inorganic additives is to directly load the charged NPs onto
Y2O3 NPs in aqueous media, whereas the complexing group oppositely charged supports (e.g., silica, titania, or ceria), thereby
limited the NP size and drastically narrowed the size distribution controlling the size and fabricating supported particles in one
by bidentate binding to the oxide NP surface (Figure 25f).306 step with high potential for catalysis applications. Hashimoto et
Size tailoring of LAL-synthesized NPs is also achievable by in al. synthesized Au NP-loaded zeolite crystals by ns LAL of Au
situ bioconjugation, such as by thiolated oligonucleotides flakes in a gel containing zeolite L crystals and successfully
dissolved in water (Figure 29e).308 Petersen et al. found that visualized the embedded Au NPs with dark field microscopy
there is a critical concentration of biomolecules to achieve because of their strong light-scattering effect.254 Mafuné reported
maximal growth quenching.308 Lower concentrations led to NP that the presence of silica during LAL of a Ni plate immediately
aggregation because of partial coverage, whereas higher caused size quenching of Ni NPs and resulted in the anchoring of
concentrations produced no further change in the size 1−3 nm Ni NPs on silica supports, whereas the absence of silica
distribution because the NP surface was completely covered by caused aggregation of Ni NPs into 5−30 nm particles that
molecules. This concept of in situ bioconjugation can be used to precipitated after a few hours.368 Similar to the surfactant- or
achieve monomodal NPs with both narrow size distributions and anion-based growth quenching mechanism, the surface footprint
the grafting of biologically functional groups in one step, as of the quenching agent that must be applied to the surface of the
validated for a set of biomolecules, including nucleic acids,308 laser-synthesized NPs is the most important parameter. Because
aptamers,361 antibodies,362 and peptides.363 However, in all of these supports’ volumes are larger as compared to those of the
the in situ size-quenching methods summarized above, the alternative quenching agents, the concentration of quenched
addition of molecules and their possible degradation (even if NPs is limited by the maximum mass of supports that can be
their byproducts are often volatile or biocompatible and despite dispersed in the liquid without attenuating the laser beam, and
the fact that they are employed to a lesser extent than in chemical thus transparent support materials are desirable. Note that the
synthesis) cannot be totally avoided. support concentration should be optimized to maximize the
Salt quenching is convenient for ligand-free size manipulation collision rate between the support and the synthesized NPs. Too
and has been widely implemented.135,268,310 The first study on in many supports may result in the low loading mass of NPs,
situ size quenching was reported by Procházka et al., who showed whereas too few supports may not quench the NP growth
that the presence of chloride anions enabled size reduction of efficiently. Santagata et al. confined Ag NPs in nanoporous silica
LAL-generated Ag NPs.364 In general, salts with higher ionic by laser ablation of a silver target in an aqueous suspension of
strengths produce smaller NPs at micromolar (μM) concen- ordered mesoporous SBA-15 and MCM-41 silica.64,309 The
trations.268 For example, the quenching effects of NaCl, NaBr, choice of the mesoporous silica material significantly affected the
and NaPP have been investigated, and increasing the ionic Ag NP size distribution. The size of the Ag/SiO2 composites
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Figure 30. Size-quenching agent types and related effects during LSPC. In general, agents can be classified as organic molecules (solvents, ligands,
surfactants, and polymers) and inorganic anions or supporting particles. The growth-quenching effects are essentially the same during LAL and LFL and
are driven by purely electrostatic (anions), electrosteric (surfactants, biomolecules), or steric (polymer, supports) mechanisms, kinetically blocking and
thermodynamically deactivating the NP surface against coalescence and aggregation.

synthesized in SBA-15 was smaller (15.4 ± 5.7 nm) than that of precisely,310 as will be reviewed in section 5.3.5. Because the
those obtained in MCM-41 (22.6 ± 2.6 nm) and pure Ag NPs whole set of size-quenching methods works quite well during
(21 ± 1.3 nm) generated in water.64 Kim and co-workers LSPC, particularly for metal NPs, the effective agents may be
synthesized Pd/CeO2 nanocomposites by inhibiting Pd NP selected primarily on the basis of the intended application of the
growth in CeO2 colloids and found that the growth of Pd NPs NPs, for example, biomolecules for cellular uptake studies,
terminated at 5−20 nm.369 anions, which provide bare surfaces, for analytical chemistry
Figure 30 summarizes the agent types (organic and inorganic) studies, or support particles for heterogeneous catalysis
for in situ size quenching during LSPC. Organic agents with applications (see section 6.6).
different molecular weights provide many options for size control
and include organic molecules, surfactants, biomolecules, and 4. UPSCALING
polymers, which act via physisorption- and chemisorption-based As a promising cross-disciplinary research field that integrates
mechanisms and result in electrosteric and steric stabilization. chemistry, physics, and engineering, the upscaling of NP
Inorganic agents offer two methods for size control: salt synthesis via LSPC to multigram per hour22 is essential for
quenching and support loading, which are achieved by adjusting preseries testing and many applications. Quantitatively, the
the surface charge density and steric adsorption, respectively. multiple-gram range is important for two reasons. First, preseries
Because size-quenching effects address the NP surface, the testing requires large amounts of material with minimal batch-to-
surface adsorbate amount must be adjusted so that the total NP batch variation. Examples include biomedical applications, in
surface area is proportional to its mass at a given intended size. which the in vitro testing of NP−polymer composites often
Note that one of the major problems in surface-quenching requires more than 1000 samples371,372 for statistical reasons,
approaches during LSPC in batch processing is that the NP with the overall weight of the composite quickly reaching the kg
concentration changes with time. Thus, excess adsorbates are scale. Additionally, in systematic catalysis research, 100-g
required at the beginning to reach the optimal grafting density samples of heterogeneous catalyst powders may be required,
(critical quenching concentration) at the end of the synthesis. If for example, during fuel cell function preseries testing. For the
the emission of nanoparticles during LAL or LFL is considered as bioactivation of 1 kg of polymer with laser-generated metal
a point source emission (as ablation/cavitation space is negligible NPs,373 loading of 0.5−2 wt % is often required, and for oxidative
as compared to ablation chamber dimension), one can assume on gold catalysis, several wt % of NPs on supports is required.374 In
the basis of volumetric considerations that the local concen- turn, approximately 1−20 g of NPs enables nanointegration on
tration gradients from this point source scale with the cube of the the kg scale for functionalized materials testing. This regime of
distance z.370 As a result, the ligand-to-NPs surface ratios upscaling would allow the LSPC community to test whether the
required experimentally that lead to effective size quenching are claimed advantages of LSPC-specific synthesis reported since
higher than those expected on the basis of monolayer more than a decade ago are truly applicable at all and at a relevant
calculations, particularly for high-molecular weight (i.e., small scale. Second, on the basis of simple economic considerations,
diffusion coefficient) surface adsorbates. Liquid flow techniques LAL is expected to cross the break-even point in terms of wet
may help to minimize these problems, allowing the amount of chemical synthesis once it reaches a certain scale (Figure 3a). To
adsorbate employed for size control to be adjusted more increase the throughput, many researchers have investigated
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Figure 31. NP productivity (ablation rate) as a function of laser and beam guidance parameters. (a) Laser fluence: Silicon ablation efficiency of ps LAL in
water and the result of a logarithmic fit of the ablation efficiency model. Reprinted with permission from ref 21. Copyright 2014 Optical Society of
America. (b) Fluence limit: Trends of ablation yield per surface unit irradiated, estimated by analyzing the Pd colloid absorption spectra, as a function of
laser fluence. Reprinted with permission from ref 382. Copyright 2010 American Chemical Society. (c) Scan speed: Gravimetric Al2O3 ablation-rate
productivity as a function of lateral interpulse distance using a laser pulse energy of 4.6 mJ with a 4-kHz repetition rate and a 4 mm liquid layer. Inset
figures are schemes of the processes that occur during LAL, demonstrating the impact of the cavitation bubble and preheated zone on the subsequent
laser pulse. Reprinted with permission from ref 20. Copyright 2010 American Chemical Society. (d) Repetition rate: Zn ablation per pulse in
tetrahydrofuran (THF) with 125-μJ ps pulses as the repetition rate varies at lateral interpulse distances of 175 μm (○) and 125 μm (●), and NP
productivity (mg h−1) at interpulse distances of 175 μm (△) and 125 μm (▲). Below 5 kHz, the ablation per pulse is constant (regime A), and,
consequently, the productivity is linearly correlated with the repetition rate. At higher repetition rates (>5 kHz), the ablation per pulse decays
monoexponentially (regime B), and the productivity gradually plateaus. Reprinted with permission from ref 381. Copyright 2010 American Chemical
Society. (e) Focusing: NP productivity depending on the focal plane position. The thickness of the water layer above the target was 6 mm. Reprinted
with permission from ref 380. Copyright 2013 Springer (f) Pulse duration: Intensity of the absorption spectra of colloidal gold as a function of pulse
duration for a pulse energy of 5 mJ. Reprinted with permission from ref 386. Copyright 2012 Institute of Physics.

methods of increasing the yield, whereas other researchers have of this assumption, they predicted that the maximum yield per
explored accurate particle-yield monitoring techniques (e.g., second is equal to η × Pavg, where Pavg = E0 × RR is the average
pulsed photoacoustics)375 to augment conventional methods, laser power, and RR is the repetition rate. They concluded that
including comparing UV−vis colloidal absorption intensity,376 the maximal ablation productivity could be as high as ∼6 g/h for a
weighing the target before and after LSPC (gravimetrical typical ps laser system with Pavg = 100 W (e.g., E0 = 1 mJ and RR =
measurement),320 and using volumetric measurements. After a 100 kHz) and a wavelength of 1064 nm. Note that the
decade of such investigations, substantial progress has been experimental throughput the authors achieved was only 0.4 mg/
made, enabling us to envisage the great potential of this h21 because of the low laser power used, and therefore this model
technique for pilot-scale colloid production. In the following
relies on extrapolation over 4 orders of magnitude. The
sections, key factors for increasing NP throughput are
productivity reaches saturation in this model (Figure 31a), as
summarized.
observed experimentally,381 because many other factors are
4.1. Laser Parameters for LAL Upscaling involved in LAL, such as water breakdown,382 the hydrolysis/
Among all of the available laser parameters, laser fluence might be decomposition of liquid molecules,383 cavitation bubble
the most important factor for high LAL throughput (defined as shielding,20 the screening effect of colloids,323 and the material-
ablated NP mass per time),20,84 irrespective of the pulse duration dependent ablation threshold and limited optical penetration
(ns,20 ps,21 fs,377 and CW laser378). In 2008, Abdolvand et al. depth.384 These factors should be considered during the
used a high-power (250 W) CW fiber laser to ablate titanium in extension and experimental validation of the LAL productivity
liquids and achieved a removal rate of ∼0.4 mg in 1 s.378 model described above. There is no LAL productivity model
However, because of the heat accumulation resulting from the until now that takes parameters of the liquid into account, such as
use of CW lasers, the liquid medium boils readily, and the
specific heat, permittivity, or compressibility. Thus, systematic
throughput is severely diminished thereafter. Therefore, pulsed
studies and the development of an advanced “LAL law” are
laser systems prevail for upscaling purposes. For many materials
(e.g., silicon,320 alumina,178,379 and gold380), the laser fluence required. Note that for the highest NP productivity, a fluence just
dominates NP throughput. Recently, Intartaglia et al. developed below the water breakdown threshold (not the highest fluence) is
a model to predict the productivity based on ablation and in situ optimal (Figure 31b).382 Similarly, during high-power ultrashort-
photofragmentation of Si NPs (Figure 31a).21 They assumed pulse laser machining in air, the laser fluence corresponding to
that the ablation efficiency was proportional to the laser energy the highest ablation efficiency was calculated to be the product of
and, thus, that the maximum ablation efficiency (Ma) was the ablation threshold fluence and e2 (where e is the Euler
dependent on the fluence without energy loss during constant).385 This productivity-predicting ablation law was
propagation (E0) and the ablation efficiency (η). On the basis recently confirmed for high-power LAL.22
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Figure 32. Cavitation bubbles in batch chamber induced at different pulse numbers: (a) irradiation geometry, (b) at the first pulse (fresh water), (c) at
the 100th pulse, and (d) at the 3000th pulse. The ablated material was Zn, the pulse energy was 100 mJ at 1064 nm with a duration of 10 ns, and the spot
size was 0.65 mm. Adapted with permission from ref 388. Copyright 2016 Angel Conference.

The average laser power is correlated with the number of repetition rate regime, is desired. The repetition rate limit is
pulses, and each pulse will generate a cavitation bubble during normally determined by the time scale of the cavitation bubbles;
LAL that may laterally and temporally shield the subsequent however, temporal effects are limited by other transient
pulse.381 Therefore, optimizing the scanning speed and phenomena, such as material accumulation or beam attenuation
repetition rate to reduce the bubble-shielding effect should be by sticky bubbles. Generally, successive laser pulses hit the target
considered when evaluating the ablation efficiency.323,381 In with a pulse interval that is controlled by the repetition rate.
2010, Sajti et al. achieved the gram-scale LAL by temporally and Recently, Momeni et al. reported that double-pulse ablation
spatially bypassing the previously formed cavitation bubbles to enabled a higher material removal rate than single-pulse ablation
minimize the shielding effect.20 Through adjusting the interpulse when the interpulse delay time was less than the pulse duration.
distance by changing scanning speed at an optimal repetition rate In this case, the second laser pulse exhibited a higher coupling
of 4 kHz with a thin liquid layer, a maximum corundum ablation efficiency with the melted target induced by the former pulse.389
rate of 1.3 g/h was extrapolated on the basis of 5−30 min of De Giacomo’s group also demonstrated enhanced LAL
processing time, as shown in Figure 31c.20 It should be noted that productivity and argued that the interpulse delay should
uncertainty exists in this experiment: NP production was not approximate the time period required for the first pulse-induced
confirmed by colloid analysis but rather by the ablated target bubble to expand maximally; in other cases (early bubble
mass. Ceramics made of pressed powders can release expansion and after bubble collapse), the second laser pulses only
mechanically ablated microparticles, thereby contributing to fragmented the ejected particles along their pathway.390 These
the target mass difference but not to the NP yield.818 When a investigations provide useful insights and may support future
laser scanner is set to a constant speed, and the repetition rate is systematic studies on the repetitive application of so-called pulse
varied, the productivity typically follows the curve shown in trains or bursts, which have been shown to be advantageous in
Figure 31d, limiting the applicability of high repetition rates for laser machining and structuring.391 By using MHz pulse bursts,
high-pulse energy LAL; that is, a linear increase is observed until Kerse et al. recently showed that it is possible to ablate a target
the temporal bubble-shielding effect arises.381 The lifetime of the material in air before the residual heat deposited by previous
cavitation bubble correlated with the ablated mass is proportional pulses diffuses away from the processing region leading to a huge
to the laser fluence387 (intensity) and the pulse energy increase in efficiency for the removal process.392
(duration), as discussed in section 2.1.1. A shorter bubble The available maximal pulse energy above the Kerr intensity
lifetime may increase the applicable repetition rate limit and lead threshold that leads to unintended excitation of the liquid is
to a higher ablation efficiency per pulse. However, in commercial normally higher for longer wavelengths than for shorter
laser systems operated at maximal (fixed) laser power, the pulse wavelengths in the same laser system. Additionally, more LAL
energy is inversely proportional to the repetition rate, which power is available for longer wavelengths, and thus a higher NP
leads to the assumption that an optimal valley may exist at a low productivity is often achieved using larger wavelengths. For
pulse energy (less ablation per pulse with lower bubble shielding) example, the maximal ablation rate at λ = 1030 nm is nearly twice
and high repetition rate or at a high pulse energy and moderate that using the second harmonic at 515 nm because of the higher
repetition rate. Finding this optimal value theoretically is not laser fluence (0.35 J/cm2) at λ = 1030 nm as compared to that at
straightforward because the bubble diameter scales nonlinearly λ = 515 nm (0.22 J/cm2) because frequency conversion
with the pulse energy, whereas the (unshielded) ablation rate decreases the pulse energy.393
scales linearly with Ep (F); the shielding effect is also not linear At different pulse durations, different degrees of self-focusing
because of the complex interactions between the existing bubble (see section 5.4) increase the complexity of evaluating LAL
and the incoming laser pulse. Thus, systematic experimental productivity. Self-focusing is a nonlinear optical phenomenon
studies on LAL with a process duration of ≥1 h are necessary,22 that tends to narrow the beam diameter as the laser pulse moves
and the relevant NP concentration must also be determined. through the aqueous medium, causing the beam to focus in front
Regarding the latter, Ito et al. have reported that the bubble size of the geometric focal plane; as a result, the target position must
and lifetime decrease sharply after several pulses (Figure 32) be moved slightly toward the lens. Menén dez-Manjón
attributed to beam attenuation by the produced colloid.388 theoretically simulated the laser beam caustic at different pulse
Shadowgraphy experiments are often used to measure bubble durations and concluded that ns laser beams are minimally
lifetime and size at negligible NP concentrations, and thus are affected by nonlinear propagation but are refracted by the liquid,
less relevant for determining the productivity-related (multiple leading to a focus position below the original one (and requiring
pulse) bubble shielding effects. Thus, correlating the cavitation a longer target−lens distance as compared to the geometrical
dynamics with productivity-relevant NP concentrations in focus in air); in contrast, ultrashort pulsed laser beams, especially
liquids at higher repetition rates, especially in the threshold fs lasers, are strongly influenced by self-focusing (see section
4018 DOI: 10.1021/acs.chemrev.6b00468
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Figure 33. Realization of g/h-scale NP productivity. (a) Experimental configuration for MHz LAL using a high-power, high-repetition rate ps laser at a
scan speed of 500 m/s. (b) NP productivity for different materials at 1 h experiments, each. Reprinted with permission from ref 22. Copyright 2016
Optical Society of America.

5.4).394 Bärsch et al. experimentally demonstrated the self- 4.2. Material Geometry for LAL Upscaling
focusing phenomenon of ps lasers.395 They found that the In addition to the laser parameters, upscaling LAL throughput by
ablation rates were different at different positions along the material-based methods has also been discussed in the literature.
focusing beam, and the beam radius changed by only 2%, causing Generally, 3D bulk targets with thicknesses of several millimeters
NP productivity to decrease by 90%.395 Maciulevičius et al. are adopted rather than 2D thin films, which suffer from rapid
reported that the maximal Au NP productivity of ns LAL in water consumption and difficulties in material feed during LAL.
was obtained with a focus 1 mm above the geometrical focus in Interestingly, a quasi one-dimensional (1D), continuously fed
air (Figure 31e).380 This finding suggests that self-focusing may wire target has been shown to be a good substitute for bulk
also occur in ns lasers because of the higher power (5 W) used in targets to enhance productivity, despite its more complex
these experiments, which exceeds the critical power threshold experimental setup (Figure 34a).396 The maximal ablation
(3.1 W for 1064 nm lasers, as calculated using Pcr = 3.77λ2/ efficiency of 1D wire ablation was far higher than that of the
8πn0n2, where n0 is the refraction index of the medium and n2 is bulk material (Figure 34b).396 By comparing the difference in
the coefficient of the nonlinear Kerr index)223 at which the self- cavitation bubble dynamics between wire ablation and bulk
focusing phenomenon is triggered in water. As a compromise ablation, De Giacomo et al. concluded that the unique cavitation
between high intensity (peak power) and moderate nonlinear
liquid side effects, ps lasers are desirable for the industrial-scale
LAL synthesis of NPs. This was demonstrated by van’t Zand et al.
in terms of the ablation efficiency of LAL of Zn in THF357 and
Riabinina et al. according to the maximum ablation rate of LAL of
Au in aqueous sodium citrate solution.386 At 40−150 fs, the LAL
efficiency was constant, but it steeply increased by a factor of 100
(maximum) at 2 ps; simultaneously, the photoionization of the
liquid (at a pulse energy of 5 mJ) decreased (Figure 31f). For
even longer pulses (2−200 ps), the laser energy was absorbed by
the expanding plasma in front of the target.386
In summary, ps lasers are the most efficient lasers for
synthesizing NPs via LAL, but these lasers often have limited
pulse energies; consequently, increasing the laser power requires
a high pulse repetition. In turn, the high repetition rate implies
higher shielding effects, whereas higher pulse energies lead to the
excitation of the liquid. Thus, unless the cavitation bubble is
spatially bypassed, ns lasers at moderate repetition rates
constitute an uncomplicated and affordable substitute. Recent
studies by Gökce and co-workers successfully demonstrated g/h-
scale NP productivities for many materials (maximum >4 g/h for
Pt NPs, Figure 33b) by spatially bypassing the cavitation bubbles Figure 34. (a) Schematic diagram of the experimental configuration for
(Figure 33a) using a high scanning speed of 500 m/s and a laser wire ablation. Reprinted with permission from ref 268. Copyright 2014
with a repetition rate of 10 MHz, a laser power of 500 W, and a American Chemical Society. (b) Ablation efficiency of silver targets at
1.5 J cm−2 as a function of wire diameter. The efficiency value for a bulk
pulse duration of 3 ps.22,31 These are the first studies to report target is also reported for comparison. Reprinted with permission from
that when the cavitation bubble is completely spatially bypassed, ref 396. Copyright 2013 Royal Society of Chemistry. (c,d) Time-
LAL converges to laser machining in air in terms of its scaling resolved shadowgraph (top) and laser-scattering images (bottom) of
factors (ablation law). Thus, pilot-scale productivities are well laser-induced bubbles on a Cu wire target and a Ti bulk target in water.
within the range of the current LAL method. Adapted with permission from ref 129. Copyright 2015 Elsevier.

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Table 1. Comparison of Absolute and Power-Specific NP Productivities of Bulk Target Ablation Reported in the Literature
process
target duration quantification (extrapolated) laser power-specific
material laser system liquid chamber geometry [min] method productivity (mg/h) productivity (mg/hW) ref
Au 1064 nm, 5 kHz, 32 water static 1D 15 extrapolation 550 16.9 398,399
W, 10 ns
Ag 1064 nm, 100 Hz, 25 water flow 1D not specified extrapolation 317 12.7 396
W, 10 ns
Pt 1030 nm, 10 MHz, water flow 3D 60 l h experiment 4050 8.1 22,31
500 W, 3 ps
Au 1030 nm, 10 MHz, water flow 3D 60 l h experiment 3970 7.9 22,31
500 W, 3 ps
Ag 1064 nm, 5 kHz, 32 water static 1D 15 extrapolation 220 6.8 398
W, 10 ns
Ni 1064 nm, 5 kHz, 32 water static 1D 15 extrapolation 215 6.6 398
W, 10 ns
Ag 1064 nm, 50 kHz, 5.5 water flow 3D 0.5 extrapolation 31 5.6 400
W, 10 ps
Cu 1064 nm, 5 kHz, 32 water static 1D 15 extrapolation 175 5.4 398
W, 10 ns
Ag 1030 nm, 10 MHz, water flow 3D 60 l h experiment 1900 3.8 22,31
500 W, 3 ps
Al 1030 nm, 10 MHz, water flow 3D 60 l h experiment 1500 3.0 22,31
500 W, 3 ps
Cu 1030 nm, 10 MHz, water flow 3D 60 l h experiment 1400 2.8 22,31
500 W, 3 ps
Ti 1030 nm, 10 MHz, water flow 3D 60 l h experiment 800 1.6 22,31
500 W, 3 ps
Ag 1030 nm, 200 kHz, acetone static 3D 0.5 extrapolation 300 6.0 395
50 W, 10 ps
Ag 800 nm, l kHz, 0.4 W, water static 3D not specified extrapolation 0.1 0.3 377
120 fs

Figure 35. Effects of liquid flow and height on productivity. (a−c) Ablated line geometries on bulk silver samples produced by ps laser pulses (5.5 W, 50
kHz, 20 repetitions per line) in stationary (a and b) and flowing liquids (c). In all cases, the liquid vessel was moved linearly relative to the laser beam at a
constant speed of 0.5 mm/s. Reprinted with permission from ref 400. Copyright 2007 American Institute of Physics. (d) Local NP concentration
gradients during batch processing and flowing liquid LAL. Adapted with permission from ref 310. Copyright 2013 Royal Society of Chemistry. (e) Laser
ablation rate of Si depending on water layer thickness at a laser fluence of 3.1 J/cm2. Reprinted with permission from ref 403. Copyright 2001 American
Institute of Physics. (f) Au NP productivity in water as a function of the liquid flow velocity using a focused laser pulse energy of 100 μJ. Reprinted with
permission from ref 402. Copyright 2010 Springer.

bubble dynamic behaviors were responsible for the NP and then collapses back toward the target (Figure 34d).129 When
productivity increase for wire-LAL.397 First, the bubble grows the wire diameter is too large, the bubble dynamics are similar to
spherically during the initial bubble stages in wire-LAL, then those of bulk target LAL, and thus there are no differences in the
encompasses the wire, and is finally expelled from the wire, productivity. Integrating this experimental design with high-
thereby releasing ablated matter into the liquid (Figure 34c). In repetition rate laser pulses deserves further investigation because
contrast, during bulk ablation, the bubble grows hemispherically the first bubble trajectory and the cloud of daughter bubbles
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emerging after the first bubble collapse are directed toward the steadily increased by a factor of 7 as the liquid flow rate was
incoming beam, thereby shielding subsequent pulses. In general, increased to 450 mL/min (Figure 35f).402
LAL of a wire offers two essential advantages over 3D and 2D Note that the laser beam absorbance of the NPs can be
target geometries, which are independent of productivity but calculated from their extinction coefficient; for example, using a
highly relevant for continuous production. First, achieving a 10 mm cuvette, Au NPs (7 nm) at a concentration of 100 mg/L
continuous feed rate of cubic centimeters per hour (g/h) using a would attenuate approximately 0.01%, 0.16%, and 0.13% of the
2D target is difficult, and 3D target replacement interrupts the intensity of 1064 nm, 532 nm, and 355 nm beams, respectively.
process and disturbs the steady state of the drained colloid Additionally, intensifying the irradiation provokes bubble
concentration. Second, colloidal application often requires a formation adjacent to the NPs beyond the threshold fluence (1
certain concentration or total NP mass, which can be directly mJ/cm2 for 200 fs and 10 mJ/cm2 for 1 ns), which is below
controlled by simply setting the length of the wire fed into the typical LAL fluence values,220 additionally attenuating the beam
ablation chamber. While the NP concentration can be monitored by bubble scattering before it reaches the target. Hence, the
for 2D targets as well (e.g., gravimetrically or spectroscopically), liquid thickness must be considered because the laser power is
the control is not as convenient as for a wire. Table 1 summarizes increasingly attenuated as the liquid thickness82 (UV lasers) and
the NP laser power-specific productivity for different geometrical NP concentration increase.376 The optimal water thickness to
targets. As can be seen, experimental ablation setup using 1D achieve the maximum NP productivity is in the range of 1−5 mm,
wires allows continuous output with laser power-specific depending on the ablation efficiency or pulse energy. The lower
productivities comparable to those studies using 3D targets. limit is set by the onset of bubbles breaking through the liquid
However, only a few metals can be wired, but almost all materials and splashing; additionally, optical windows (used in closed
can be obtained in 2D films and 3D bulk targets. On the one chambers) require a minimum distance from the target surface to
avoid damage. For higher-energy pulsed ns lasers, this minimum
hand, substitution of 2D films or 3D bulk targets takes a few
safe distance is approximately 4−6 mm. An optimal thickness of
minutes, whereas wire ablation does not require process
1−1.5 mm was reported by Jiang et al. during the laser ablation of
interruption for target feeding. On the other hand, beam
a Ge target with a Nd:yttrium aluminum garnet (YAG) laser
focusing on a microscale wire is difficult and requires time-
(wavelength of 532 nm, pulse width of 10 ns)376 and Zhu et al. via
consuming adjustment at start. After elucidating the productivity the laser ablation of silicon wafers using a KrF excimer laser
and processing strategy effects with target geometries confined (wavelength of 248 nm, pulse width of 30 ns).403 Similar results
from 3D to 1D, the scale-up effects on 0D targets (particles) will have been reported by other researchers. For example, Sajti et al.
be investigated in section 5.1. Because NP productivity is related noted that the minimum liquid layer required for stable ns laser
to the liquid as well, LSPC scaling figures will be addressed in the (4 kHz, 18.5 W) processing of corundum was 2.5 mm, which
following section. resulted in a NP productivity that was 350% of that obtained at a
4.3. Liquid Properties and Process Parameters for LAL, LFL, higher liquid thickness (8 mm).20 The reason that the ablation
and LML Upscaling productivity changes as the liquid thickness varies will be further
Liquid handling is crucial during NP production because of its discussed in section 5.3.4.
impact on the local concentration of the colloid and the Size-quenching additives also affect NP productivity. Dis-
cavitation bubble size and mobility. In a stationary liquid (Figure solved micromolar salts and organic solutions should positively
35a,b), bubbles adhering to a hydrophobic metal surface will affect NP throughput because the laser light-scattering intensity
decreases with the sixth power of the particle diameter.404 As size
scatter and shield the laser, reducing the incident energy on the
quenching measures also contribute to colloidal stability
target and, therefore, decreasing the ablation rate.400 Further-
reducing the abundance of aggregates, size-quenching additives
more, it will cause the beam path to deviate, making the ablation
increase the productivity by reducing both types of scatterers,
process uncontrollable and irreproducible. In comparison,
large spheres, and secondary aggregates of primary particles.
transporting the bubbles from the pathway of the laser beam
However, the degradation of additives (e.g., molecular
and draining the newly generated NPs over time via flowing adsorbents) can contaminate the colloids.405 Moreover, bulky
liquid310 (Figure 35d) could significantly reduce both the bubble additives may also alter the liquid viscosity, which affects not only
and the NP shielding effects and ensure a uniformly successive the bubble dynamics but also the NP throughput. For example,
ablation pattern (Figure 35c).400 In addition, liquid-flow LSPC an increase of approximately 50% of LAL productivity in aqueous
would establish steady-state synthesis conditions with regard to solution was obtained by adjusting the PVP additive concen-
NP concentration. In batch processes, strong spatial and tration and was maintained even when it exceeded the threshold
temporal concentration gradients arise, but these gradients can concentration at which no further size-quenching effect was
be minimized by liquid flow (Figure 35d),310 which is beneficial observed.144 The temporal cavitation bubble size and lifetime
for steady-state particle formation kinetics. Hence, flowing liquid measured by shadowgraphy were significantly shorter when
also ensures a constant molar ratio of the size-quenching agent adding PVP. These differences were attributed to the tighter
relative to the NP surface. A 20% increase in LAL productivity plasma confinement in PVP solution induced by its higher liquid
has been obtained using flowing liquid with the flow rate of 190 density and viscosity, which supports the secondary ablation
mL/min.379 A further support is provided by Resano-Garcia et effect by plasma confinement (and verified by higher acoustic
al., who reported that the width of the laser-cut kerf signal).166 Moreover, the liquid viscosity also influences the NP
(proportional to productivity) obtained in the stationary liquid stability against aggregation and can be used to improve the
was nonrepeatable and approximately 30−35% narrower than ablation rate. Wagener et al. reported that 0.3 wt % thermoplastic
that achieved in flowing liquid.401 In contrast to a conventional polyurethane (TPU) is optimal for the fabrication of well-
liquid flow apparatus, here, the liquid flow was achieved by dispersed Ag NPs; below this loading, no stabilization of NPs was
rotating the target. The productivity of fs-LAL-synthesized Au observed, whereas above it, the highly viscous liquid reduced the
NPs strongly benefits from liquid flow: the NP productivity NP production rate.307
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Figure 36. (a) Depiction of a passage reactor design with a free liquid jet and magnification of the laser irradiation area with the parameters required for
process characterization. (b) Laser fragmentation efficiency plotted versus laser fluence. (c) Particle size according to laser fragmentation of ZnO in
flowing liquid with a controlled energy dose. Reprinted with permission from ref 218. Copyright 2015 Elsevier. (d) Relative jet illumination plotted
versus the fluence for different laser energies in a geometry with a water jet diameter of 1.3 mm, a raw laser beam diameter of 3.5 mm, a focal length of 100
mm, a pulse length of 10 ps, a wavelength of 532 nm, a repetition rate of 100 kHz, and a particle mass concentration of 0.1 wt %. Reprinted with
permission from ref 406. Copyright 2016 Springer.

Although substantial research efforts have been directed after a defined number of passages together with the laser pulse
toward the ablation rate of LAL, investigations of LML and LFL energy enables the key parameters of LFL scaling, particularly the
productivity are still rare. One reason is that quantifying LPC cumulative PPP and the energy-specific mass throughput
productivity requires quantitative fractionation of the educt and converted to particles, to be characterized (Figure 36c).218
product, which are both in the colloidal state. Also, the partial This upscaling parameter allows the LFL productivity to be
irradiation of the liquid volume and the beam propagation extrapolated to higher laser powers (at fixed fluence). The crucial
through both the educt and the product makes defining factors to increase LFL productivity are the particle mass
normative parameters difficult. As will be demonstrated in the concentration and liquid flow speed (or educt mass flow) with
discussion of liquid flow in section 5.3.5, in general, two different respect to the laser fluence and repetition rate; the limiting factor
experimental configurations, a vessel (cuvette) and a flow is the optical breakdown of the liquid. A typical plot illustrating
arrangement (e.g., a free liquid jet), are used for both LFL and the fragmentation efficiency for this geometry is shown in Figure
LML. The laser processing of particles in a vessel265 is a less- 36b. After passing the fragmentation threshold, the LFL
controlled process than that in a liquid jet218,253 because the efficiency increases linearly until the laser fluence is close to
geometry of a vessel does not allow full illumination of the the optical breakdown point, at which the LFL efficiency starts to
particles inside. Thus, the educt particles are not uniformly decrease. Figure 36d shows the calculation of the relative jet
affected by the laser pulses, and the irradiation time must be illumination as a function of the applied laser fluence at different
prolonged (with exponentially decreasing efficiency) to increase pulse energies. This calculation is based on a liquid jet diameter
the chance of processing all of the particles. For LFL, strong of 1.3 mm, a laser pulse duration of 10 ps, a wavelength of 532
focusing conditions are generally beneficial because productivity nm, and a repetition rate of 100 kHz. A “relative jet illumination”
scales with fluence. However, in the case of a thicker liquid layer, of 1 is defined as the case in which every passing particle is
the deviation of laser fluence within the irradiated volume is large. illuminated by the laser beam; thus, for upscaling purposes, this
Relative to the vessel geometry, a free liquid jet with a passage value should be as close to 1 as possible. Clearly, to achieve a
reactor, as shown in Figure 36a, appears to be a good alternative higher fragmentation efficiency and a higher throughput, either
for LFL and LML productivity studies because it facilitates a the illuminated volume at constant fluence or the laser fluence at
relatively controlled illumination process of the particle constant jet illumination (ideally 1) should be increased. In both
stream.218 Because the educt mass and particle number cases, higher laser power is needed. For the example given in
concentration are fixed at the beginning of the process during Figure 36d, 100% educt LFL illumination is achieved at a power
sample preparation, controlling the laser repetition rate allows of 75−150 W. Specifically, 100% illumination efficiency during
the precise tuning of the number of nominal pulses per particle LFL of 0.1 wt % ZnO (430 nm in diameter) in water enables a
(PPP). Comparing the particulate educt and product properties productivity of 1.8 g/h with a size reduction (Δd) of 50 nm and a
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bandgap variation (ΔE) of 0.2 eV.218,406 As compared to LFL, 5. MATERIAL, PROCESS, LIQUID, AND LASER
low levels of fluence deviation during LML will not strongly affect PARAMETERS
NP productivity because an unfocused laser beam is used.279 The The decisive factors shown in Figure 37 impose synergistic
LFL and LML productivity parameters can be summarized as effects during LSPC: material properties, liquid parameters, laser
follows. Liquid flow should be used and the LFL fluence should
be as high as possible but below the optical breakdown point of
the working liquid to avoid significantly decreasing the LFL
efficiency and productivity. Compared to LFL, LML is a more
straightforward process, but its product size is sensitive to fluence
deviation.91 Thus, both LFL and LML benefit from a short beam
path and full illumination of the liquid volume. Fundamental
research indicates that single pulses may be sufficient for LFL.
However, multiple pulses are often required (LFL of larger NPs
at lower laser energy and, in most cases, LML). Thus, demand
exists for the experimental quantification of the “minimal
required PPP” values for well-defined nanoproducts achieved
by LFL or LML processing. Identifying key parameters for
obtaining minimal PPP would enable one to determine the
Figure 37. Influencing factors responsible for determining the purity,
optimal educt concentration that allows 100% educt-to-product productivity, shape, size, charge, crystal phase, stability, and dispersion of
conversion, thereby avoiding educt−product mixing down- NMs synthesized by LSPC.
stream.
For LML-synthesized SMSs, the productivity is already parameters, and process adjustment, with each determinant
moderate, with values such as 100 mg/h of CuO,272 but further including several branching factors.
systematic investigations are required for upscaling. Because 5.1. Material Properties
SMS productivity depends on the material’s laser absorbance,407
5.1.1. Composition. Precisely determining the time scales
studying the relationship between the material absorbance and for NP nucleation and their chemical reactions on the atomic/
the SMS productivity is necessary. The absorption efficiency cluster scale, including the rough time frame32 based on
(Qabs) is correlated with the material’s refractive index and spectroscopic studies147,180,187 and simulations,163,410,411 is an
extinction coefficient and the laser wavelength;91 thus, these are ongoing task in LSPC. Additionally, the extent to which NP
the governing parameters determining LML productivity. formation is kinetically or thermodynamically controlled remains
Generally, UV lasers (e.g., λ = 355 nm) and VIS lasers (e.g., λ unclear. In this regard, LAL of a target containing two or three
= 532 nm) enable higher absorption efficiency than IR lasers miscible elements to produce bimetallic or trimetallic alloyed
(e.g., λ = 1064 nm).91 Pulse duration is another critical factor for NPs could contribute to our understanding of the formation
LML productivity. For SMS formation, the laser fluence mechanism, particularly the interplay between the target
threshold increases with the pulse duration.408 Indeed, the composition and NP stoichiometry. To date, a large variety of
productivity achieved using longer pulse durations is inefficient alloys have become available for processing by LSPC, including
as compared to that at shorter ns-scale pulse durations (e.g., 50 ns AuAg,125 AgCu,412 PtAu,413,414 PtPb,415 and FeMn.416 The
appealing features of these alloys include stoichiometric
vs 7 ns), because heat tends to dissipate from the SMSs to the
compositions nearly identical to those of the target125,417 and
surrounding liquid within several tens of ns.409 high composition uniformity within the synthesized alloy
Overall, LSPC-upscaling comprises a systematic optimization NPs.108,125,412,413 However, because of the possible oxidization
process that involves every aspect of the laser−liquid−target and leaching of alloy atoms, in some instances, nonstoichiometric
system. At the lab scale, noncost-effective measures to increase alloying and segregation occur.356,418 The probability of
productivity include using a 3−6 mm liquid layer (for LAL) and stoichiometric alloying depends on the materials’ resistance to
flowing liquid (for LAL, LFL, and LML). For LFL and LML, a oxidization and, specifically, on the redox potentials of the
simple funnel or, even better, a Marriott flask with a 1 mm ablated elements. No deviation has been observed for noble
capillary outlet irradiated by the perpendicular laser beam works metals that have no miscibility gap and produce perfectly
well. monophasic crystals (e.g., AgAu125), as confirmed by UV−vis
With advances in laser technology, increasing power will spectroscopy (Figure 38a) and TEM-energy-dispersive X-ray
become more accessible for all laser systems, especially pulsed spectroscopy (EDX) line scans (Figure 38b,c). The SPR peak
laser systems (Figures 1 and 3). Consequently, even higher NP position of colloidal AgAu alloy NPs linearly increases with the
productivities are anticipated in the future. The successful gold molar fraction (GMF); however, at a given molar ratio, it
also depends on the synthesis method used to generate the NPs.
decoupling of the cavitation processes has already enabled a NP
Unlike alloy NPs derived from LAL, red-shifts of the SPR peak
productivity of 4 g/h for high-power, high-repetition rate LAL,22
occur in alloy NPs synthesized by chemical and biological
demonstrating that the liquid medium is not a barrier blocking methods (Figure 38d).125 These differences are attributed to the
LSPC from utilization in series production with industrial-scale presence of ligands during chemical and biological syntheses,
productivity. Furthermore, new possibilities, such as beam and which increase the refractive index in the nanovicinity of the
pulse shaping with spatial light modulators or multibeam particle surface and cause a bathochromic shift of the SPR peak
processing by diffractive optical elements, also offer straightfor- maximum.419−421 Thus, laser-generated plasmonic AgAu alloy
ward strategies to increase the productivity of LSPC further. NPs have the lowest SPR peak wavelengths. In addition to these
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Figure 38. LSPC synthesis of alloy and doped NPs. (a−c) Comparison of UV−vis spectra of Ag−Au colloids and the elemental distribution (TEM-EDX
line scans) and composition of single Ag−Au NPs generated during LAL of bulk AgAu alloys with a GMF of 0.4. (d) Comparison of plasmon wavelength
of laser-generated NPs with chemically and biologically synthesized AgAu NPs. Reprinted with permission from ref 125. Copyright 2014 Royal Society
of Chemistry. (e) PL properties of Cu-doped ZnO NPs for different Cu concentrations (inset). Adapted with permission from ref 428. Copyright 2011
Elsevier.

Figure 39. AgCu alloy NP phase structure after LAL synthesis. (a−d) TEM images showing the phase segregation dependence on the Cu mole fraction
for 20 nm. (e,f) Calculated free energy of the biphase (twin) and core−shell structures. (g) Calculated composition and size effects on the phase
boundary surface energy. Reprinted with permission from ref 412. Copyright 2014 American Chemical Society.

bathochromic effects, the generation of monophasic AgAu NPs However, large deviations occur when alloying elemental Fe or
by chemical precursor reduction synthesis is challenging because Cu with Pt,126 Ag,412 or Au.174 To increase the stoichiometric
of the inherent differences between the reduction potentials of alloying of non-noble elements, corrosive liquids or liquid
Ag and Au precursors.422 The coreduction of Ag and Au molecules that decompose in the laser plasma into reactive
precursors leads to the formation of NPs with a gradient in which oxygen species, especially water, are unfavorable, and organic
the more noble metal (Au) is reduced first and is thus more solvents are preferable,356,418,429 unless galvanic replacement via
abundant in the core of the resulting NP.423 Overall, LAL not RLAL is intended,160,430 as we will discuss in the “liquids” section
only allows the synthesis of colloids of plasmonic AgAu alloys (section 5.3.1). When designing materials for laser alloying, the
without any initial ligand-attributed SPR shift, facilitating the interface energies (at the intraparticle phase boundaries) and
relative volume fractions should be considered because these
precise observation of the effects on the refractive index in the
parameters determine whether the synthesized NMs will exhibit
particle’s vicinity, but also provides access to a monophasic
a two-phase microstructure or a core−shell structure.412
intraparticle structure inaccessible by aqueous chemical reduc- Recently, Malviya and Chattopadhyay synthesized AgCu alloy
tion methods without time-consuming tempering steps, which NPs by LAL of the bulk alloy in an aqueous medium.412 They
could be used to obtain ideal alloy model materials for catalysis reported a Cu concentration-dependent morphological tran-
and biomedicine.11,346,413,424 Beyond using a binary material sition within the NPs, from a defined two-phase intraparticle
target for alloy NP synthesis by LAL, laser reirradiation of mixed structure to a structure with random segregation, and, finally, a
LAL-synthesized elemental colloids (e.g., Au and Ag NPs425 or core−shell structure at a high molar fraction of Cu (Figure 39a−
Au and Ni NPs426) and successive LAL of two elemental (e.g., Ag d). Their formation mechanism hypothesis was rationalized
and Au) targets427 are two additional routes to synthesize alloy through the thermodynamic modeling of the free energy of phase
NPs. mixing and the wettability of the alloying phases. The surface
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energy as a function of both size and composition is shown in enhanced by increasing the laser fluence.272 Attention should be
Figure 39g. At a given particle size, the surface energy increases as paid to the LFL yield and product composition difference
the Cu composition in the alloyed particles increases (Figure originating from the source materials’ ablation threshold. By
39g). Additionally, the free energy increases as the particle size investigating the formation of Cu colloids by LFL of CuO, Cu3N,
decreases (Figure 39e,f), and thus smaller or Cu-rich particles Cu(N3 ) 2, Cu 2C 2, and CuI powders in organic liquids,
tend to form core−shell structures (minimizing their Gibb’s Schaumberg et al. determined that LFL of suspensions is an
energy) rather than asymmetric segregation phases. Overall, this educt powder composition-dependent process.259,449 The LFL
study indicates that the final phase structure of NP synthesized by efficiency of copper nitride (29.7 μg/J) is several times higher
LAL is determined by equilibrium solid-state thermodynamics. It than that of copper oxide (2.5 μg/J) (Figure 40) under the same
seems that, although the net composition of a particle is set in a
fast nucleation process, its final alloy phase structure builds up on
a far longer time scale.418
In addition to metal alloys, the laser synthesis of doped NMs
with variable dopant concentrations has also been investigated.
LAL of a solid Zn/Cu composite caused the corresponding PL
properties of the synthesized colloid to depend on the Cu
concentration in the ablated target (Figure 38e).428 Ledoux et al.
confirmed the feasibility of preserving the phase (with some
lattice disorders) and stoichiometry of the targets by trans-
forming them into Y2O3:Eu3+, Lu2O2S:Eu3+, Gd2SiO5:Ce3+,
Lu3TaO7:Gd3+, and Tb3+ NPs with sizes as low as 5−10 nm using
LAL.431 Other doped NMs have also been successfully Figure 40. Yields of copper NPs after 1200 laser pulses with different
produced,432−434 and researchers’ interest in doped NMs with LFL precursors. Reprinted with permission from ref 248. Copyright
upconversion properties is rapidly increasing.435−438 Overall, 2014 American Chemical Society.
obtaining doped ternary or multinary oxides by LAL of doped
solids is straightforward, and the colloids often exhibit related
dopant functionalities (section 6.2.3). However, more studies LFL conditions (532 nm, 45 mJ/pulse, 6 ns, 1200 laser pulses)
that focus on the selectivity of the synthesis related to a defined because of the lower ablation threshold of copper nitride as
crystal phase, amorphous byproducts, or lattice defects are compared to that of copper oxide.248 Interestingly, LFL of CuO
required. Oxygen vacancies and interstitial cations can be and Cu3N and Cu(N3)2 follows a reductive mechanism, whereas
regarded as dopants also (i.e., defect dopants) and have relevance that of CuI and Cu2C2 follows a fragmentation mechanism
in (e.g., titania-based) photocatalysis.439 Depending on the without the formation of elemental Cu NPs.
target, LSPC reduces or oxidizes the solid during its conversion In addition to investigations into the chemical composition of
into a colloid. For example, LFL of rutile TiO2 resulted in synthesized NMs, intensive effort has been focused on the
anatase, brookite, and amorphous species with Ti3+ defects synthesis of high-pressure crystal-phase NMs. For instance, after
identified in the TiOx colloids.111 LAL of elemental Ti resulted in performing LFL in water, monoclinic H-type Nb2O5 powders
particle oxidation and the formation of TiO and Ti2O3 in were transformed into either orthorhombic T- or pseudohex-
addition to TiO2 with a significantly reduced bandgap.440 Such agonal TT-type materials, with the amorphous phase acting as a
LAL-synthesized defect-rich TiOx crystals show the room- precursor for the high-pressure phases.450 Irradiating rutile-type
temperature ferromagnetism of TiO2 NPs.441 Although precise SnO2 powders led to the formation of a high-pressure-stabilized
adjustment of the oxidation degree during LAL remains difficult, α-PbO2-type structure.451 Other high-pressure-phase NMs that
the oxygen affinities of many metallic materials (e.g., Cu, Zn, and have been successfully developed by LSPC include doped γ- and
Sn) provide opportunities to conveniently obtain (sub)oxides θ-Al2O3 nanocrystals,201 defective calcite II and hydrates,452
(e.g., CuOx,442,443 ZnOx,444,445 and SnOx446,447) by LAL of pure wurtzite-type (W)-ZnO and ε-Zn(OH)2 composite nano-
metal targets in oxygen-containing solutions. Furthermore, LAL condensates,453 baddeleyite-type TiO2,454 and the high-pressure
of a bulk target consisting of binary elements (e.g., Ag/Ti) with phase of tetragonal Ge.455 The creation of high-pressure phase
different resistances against oxidation may allow the direct, one- NMs has been hypothesized to result from the fast cooling of the
step synthesis of doped oxides (e.g., Ag−TiO2448). plasma plume, which causes densification during nucleation.456
When ablating oxidation-sensitive metal targets in water, Similarly, defects and surface adsorbates resulting from solvent
synthesized NMs with mixed chemical compositions are often molecules may also stabilize the high-pressure crystal phases of
obtained, as shown for Ti-LAL.440 Lam et al. started with AlxOy as the NPs, making it difficult to attribute the obtained crystal phase
a simulation prototype and found that the stoichiometry of Al2O3 to the initial “high-pressure and high-temperature” character-
formation is coupled to the temperature in the early phase of istics of LSPC alone. Low-pressure phases, such as Al2O3457 and
LAL.155 High temperatures in the first submicrosecond time ZrO2,458 have also been reported to be produced by LAL.
period determine the oxidation rates of Al3+ to Al2O or AlO NPs, However, because the thermodynamically stable crystal phase at
and later during cooling, based on the molecular simulations of a given composition also depends on the particle size,
the nucleation phase, Al2O3 is formed.143 This result indicates the differentiating the determining parameters would require a
occurrence of chemical reactions at the ns time scale, during thorough analysis, that is, size-dependent crystal structure
which ablated species react with the liquid in the vapor phase in histograms. Both oxides and carbon can undergo a phase
the early phase of cavitation. In contrast to oxidative LAL, transformation into allotropes, with the carbon sp2 to sp3 bond,
reductive laser ablation and excitation has also been observed graphite to diamond, transformation being the most intensively
during LAL,449 LFL,260 and LML272 of CuO, producing either studied.459−463 Substantial effort has been devoted to the
Cu or Cu2O NPs. During LML, the reduction ratio can be synthesis of diamond. For example, Qiu and his co-workers
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Figure 41. (a) Advantages (green) and drawbacks (red) of using 0D/1D/2D/3D materials for LFL and LAL. (b) Au NP mass in dependence of film
thickness (red dots) and theoretical yield (black line). (c) Size distribution obtained from LAL of 1 mm (black), 226 nm (red), 154 nm (green), and 50
nm (blue) films (as shown on the right). Inset shows NP size in dependence of the target film thickness. Reprinted with permission from ref 484.
Copyright 2016 American Chemical Society.

synthesized diamond QDs with tunable particle size and see section 6.4.4) is used to improve water solubility and
adjustable PL properties.461 As for the diamond formation bioavailability.480,481 Thus, in contrast to inorganic or carbon
mechanism, Tian et al. theoretically analyzed the growth targets, in which phase changes and the introduction of defects
dynamics of nanodiamonds during LAL and reported that the are often envisaged, LFL of organic crystals aims to preserve the
radius and density of the plasma plume determined the cooling NM composition, which is often difficult to achieve quantita-
velocity, which in turn influenced the nanodiamond size.464 Yang tively.
et al. used time-averaged optical emission spectroscopy to Overall, LSPC enables the synthesis of a wide variety of NMs,
evaluate the plume produced by 532 nm laser ablation of graphite including alloys, doped NMs, and crystalline NPs. Therefore, the
in water and concluded that atomic H is necessary for diamond design of the target composition is important for controlling the
growth,465 which may explain why most diamonds have been composition of the synthesized NMs. If the synthesis of an alloy
synthesized in H-containing solutions (e.g., water,460 acetone,461 or doped NPs is intended, consolidated powder targets are a
and ethanol461). However, negative control experiments would good option. Thereby mixing the LAL target on the microscale
be required to validate this formation model. More recently, Xiao presents an elegant approach to result in atomically “mixed”
et al. discovered a reversible phase transformation between alloys on the nanoscale. It is possible to synthesize solid-solution
nanodiamond and carbon onion via an intermediary bucky AuPt and AuAg NPs via this method, as demonstrated by Guay,
diamond phase462 and a phase transformation from nano- who mixed Au and Pt as well as Au and Mn powders,413,482 and
diamond to n-diamond via an intermediate carbon onion466 by Neumeister et al.,125 who mixed Au and Ag, as well as Marzun et
laser irradiation. Although much of this work on nanodiamond al., who mixed Ni with Mo.483 The synthesis of a doped NP oxide
synthesis was focused on hypothetical formation mechanisms by mixing a powder of the host oxide with a powder of the dopant
and the laser irradiation synthesis of carbon allotropes, could represent a flexible and rapid method of tuning the doping
nanodiamonds are often extracted in the supernatant after laser level of the NPs, similar to the metal alloy series.
synthesis, and their yields relative to the total ablated mass are 5.1.2. Shape. If the characteristic target length or diameter
seldom reported. In this regard, the formation of sp bonds during (optical cross-section) is smaller than the beam diameter (typical
LAL of carbon, resulting in polyynes467 and multiwall graphene for LFL), it can be regarded as quasi-0D matter that is excited in
species,468 has also been reported by Compagnini and co- the liquid, whereas micrometer-thick wires are considered 1D
workers. Thus, more research is required to assess the yields and targets. According to a recent work, ablation dynamics for LAL of
formation mechanisms of different carbon species during LSPC. a bulk Au target changes if the target thickness is lower than tens
Organic particles with defined molecular structures, such as of micrometers (Figure 41b,c).484 Hence, we consider targets
quinacridone,469,470 vanadyl phthalocyanine,471,472 paclitaxel,473 <10 μm as 2D films and targets >10 μm as 3D. Of course,
buckminsterfullerene (C60),474,475 3,4,9,10-perylenetetracarbox- intermediate geometries exist, such as large micropowders, which
ylic dianhydride,476 melamincyanurate,477 dendronized peryle- often exhibit characteristics of both LFL and LAL. Also, free-
nediimide,478 and melamine cyanurate,479 have also been standing 2D film ablation will have similarities to 1D wires, which
produced by laser treatment. Here, LFL of semipolar or poorly display an elastic effect during ablation.398 The target geometries
water-soluble educt particles (e.g., aiming at drug micronization, can be extensively varied during LSPC to achieve different goals.
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For example, 0D powders,260,469,485 NPs,486 and nano- of solid into colloid (Figure 41). In the ideal case, the wire is
flakes487,488 are processed by LFL during investigations of the completely ablated after one run of laser ablation; in that case, we
interaction mechanisms between materials and liquid mole- have 100% conversion because nothing is left; even if there is
cules248 or for size reduction489,490 and phase transforma- debris (redeposits) it will be ablated by subsequent pulses. Yet
tion111,491 or by LML for SMS synthesis.273 Both chemically imprecise focus adjustment or immoderate wire feed may cause
cosynthesized NPs492,493 and almost all LAL-synthesized NPs494 wire splitting off, reducing the effective conversion rate. Another
are appropriate LFL particulate educts. Also, both the physical disadvantage is evident in ref 183 where a hundreds of μm thick
state and the size of the educt powders affect the LFL yield. When gold belt was continuously fed like a tape recorder. This
adopting microparticles for fragmentation, a simple mechanical configuration led to a limited target consumption because a belt
pretreatment (e.g., wet-grinding) enhances both the laser with certain residual thickness is required for automated feeding.
fragmentation efficiency and the NP productivity.258 The laser Previously, only a few researchers have used 1D material to
processing of powders at the millimeter scale enables the synthesize NMs by LAL, and considerable work is still necessary
generation of nonspherical submicron particles with sharp to uncover the potential advantages and to understand the effects
edges.495 Consequently, the LFL efficiency is insufficient to of the wire’s physical and mechanical properties on the ablation
completely fragment large educt powder, leading to the following process. Recent findings further show that the polydispersity of
drawback: the difficulty in separating the transient mixtures NPs obtained from LAL of 1D wires decreases for thinner wires if
consisting of the educt and products.218 Downsizing from the ablation is performed without cavitation intereference (i.e.,
micropowders to NPs can cause a band-edge shift of materials low repetition rates).484
(e.g., CoO), enabling the activation of water-splitting capacity 3D bulk targets,186 foils,171 and 2D films484,499 are the most
under VIS light irradiation, which cannot be achieved with frequently used targets for LAL because they are immobilized by
micropowders.485 When the educt is on the nanoscale (or at least their mass density, thereby avoiding the creation of an educt−
smaller than the excitation beam diameter and well dispersed in product mixture; however, continuous NP output is limited
the liquid to minimize light scattering), they undergo the because target replacement is required. When flowing liquid is
transformation to the tens-of-nanometers scale much more employed or the targets are insufficiently heavy to stabilize
readily and may even reach sizes of a few nanometers.25 NP themselves in the liquid, anchoring bulk targets with clamps or
suspensions in the agglomeration state are employed in LML to using special customized chambers is necessary to ensure the
obtain SMSs.279 Particular attention has been paid to preparing stability of laser ablation process. As compared to those of 1D
alloys by the supercontinuum irradiation of 0D material wires and 0D suspensions, the features of 3D bulk targets are
mixtures.226 LSPC can be used to fuse two miscible NP elements compatible with using a galvanometric scanner for high-scanning
(e.g., Ag and Au) into a single nanosphere. By mixing different speed beam guidance (even up to the m/s range) during LAL;500
ratios of LAL-generated AgNPs and AuNPs, alloyed NPs with in contrast, 1D wires are affected by the delivery speed of the
different Ag:Au ratios can be prepared.496 After alloying, the wire, and 0D suspensions suffer from precise excitation of the
surface of the LSPC-synthesized NPs can be further passivated educt without product reirradiation during laser synthesis in a
with hydrophobic molecules to improve the NP stability by batch chamber. The 3D target surface may also be porous, such
irradiating the NPs in a liquid mixture of oleic acid and as porous silicon in liquid.501,502 Moreover, the micro-
oleylamine with sonication.497 For submicrometer-sized prod- structures503 and nanostructures504 generated from previous
ucts, LML also enables the alloying of immiscible metals into new laser scanning will cause fluctuations in the energy absorption by
metastable Au1−xNix nanoalloys.498 Agglomeration of the NPs the substrate surface.505 The particles that deposit on the target
facilitates energy transfer from Au NPs to NiO NPs to surface may also act as absorption centers, changing the effective
decompose NiO NPs into Ni and enable subsequent fusion laser fluence on the underlying substrate surface and affecting
with Au NPs when the temperature during laser irradiation is LAL process stability. Therefore, it is possible that subsequent
above their melting points.498 Therefore, alloying different laser ablation will generate different NPs from these modified
colloids using LML may pave a new pathway for the preparation areas. Determining how the ablated target surface geometry
of various metastable alloys using both miscible and immiscible influences the formation of NPs requires further investigation.
materials. The main disadvantage of using 0D targets is the
5.2. Process Parameters
requirement for postfractionating (section 5.2.2, downstream
processing) of the educt and product mixture (Figure 41a). 5.2.1. Processing Time. The processing time affects the
As illustrated in the upscaling section (section 4), because of processes and products of LAL, LFL, and LML differently.
the unique bubble dynamics during LAL of a wire-shaped During LAL, increasing the processing time leads to a higher
target,397 1D materials exhibit a higher ablation efficiency than concentration of NMs (Figure 42c),393,506,507 as characterized by
bulk targets.396 However, the enhancement ratio depends to productivity studies with the aid of UV−vis absorbance
some extent on the thickness of the wires, with the optimum spectroscopy.376,393 However, the concentration of the LAL-
diameter being approximately 500 μm. Indeed, when the wire is synthesized NMs should not be too high. Otherwise, they will
too thin, the absolute removal mass is limited, whereas for very gradually aggregate over time and attenuate the beam. The effect
thick wires (quasi-2D), the cavitation bubble does not propagate of minute amounts of NPs in the liquid, for example, volume
into the liquid while releasing the matter trapped inside. The fraction as low as 0.5 × 10−6, will alter the optical properties of
latter case is similar to the laser ablation of a bulk target, in which the colloid, as shown by Karimzadeh and Mansour,508 who
the bubble collapses toward the 2D target.397 Moreover, because reported that the absorbance increased proportionally to the Ag
the bubble propagation can be varied by using 1D wires rather NP concentration and that the thermal nonlinear refractive index
than a bulk target, bypassing the cavitation bubble by adjusting (−0.1 × 10−8 cm2/W) of the same colloid also changed.
the repetition rates should be reevaluated.396 Using an In general, moderate particle concentrations (well below 1 g/
automated target feed allows full continuous operation, and L) are preferred if no stabilizers are used. Subjected to the light
this 1D target omits any waste, yielding highest conversion rates absorption and scattering by the synthesized NMs over time, the
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Figure 42. Effect of processing time on morphology and productivity in LAL, size change in LFL, and morphology evolution in LML. (a,b) TEM images
of C3N4 nanostructures synthesized at a laser fluence of 75 mJ/pulse after 3-h and 5-h ablation. Reprinted with permission from ref 200. Copyright 2006
American Chemical Society. (c) Effect of wavelength and material on NP productivity; cumulative ablated mass as a function of the ps LAL processing
time of silver. Reprinted with permission from ref 393. Copyright 2011 Springer. (d) Evolution of the mean diameter of PbS QDs with the laser
fragmentation duration; the inset shows the evolution of the size dispersions of QDs with the ablation duration. Reprinted with permission from ref 250.
Copyright 2013 Nature Publishing Group. (e) Evolution of the average size of ZnO QDs with increasing irradiation time during LFL. Reprinted with
permission from ref 265. Copyright 2011 American Chemical Society. (f−h) SEM images of products obtained by LML of Ag NPs with irradiation times
of (f) 0 min, (g) 30 min, and (h) 60 min (355 nm, third harmonic, in acetone, 0.5 mg mL−1, 30 mJ per pulse per cm2). Reprinted with permission from ref
515. Copyright 2013 Royal Society of Chemistry.

ablation efficiency generally decreases as the ablation time Recently, the successive laser ablation of two materials was
increases,61,375,506 resulting in the fragmentation of existing suggested to have the potential to enrich nanoproduct diversity
particles305 and decreased particle size.393 This saturation and because of extreme sensitivity to the ablation period. Singh and
shielding phenomenon has prompted investigations into using Soni found that increasing the irradiation period of Ag and Al
flowing liquid to drain the NPs from the incident beam path, NPs in water caused the particles first to evolve into a network-
which will be discussed in section 5.3.5. Note that longer ablation type structure, then into core−shell structures, and finally into
times may also increase the liquid temperature until saturation at rattle-type Ag@Al2O3 because of the Kirkendall effect.511
a value dependent on the laser fluence.134 Additionally, even Varying the ablation period of gold or zinc targets in LAL-
ultrashort pulses deliver residual heat to the target, which synthesized Ag colloids allowed the modulation of the Au or
accumulates during the processing time,509 and the surface may ZnO shell thickness of the resultant Ag@Au512,513 and Ag@
transfer this heat to the liquid. Continuous heating will ZnO514 core−shell structures, respectively. Nevertheless, most
compromise the colloidal stability according to the Stokes− studies on the processing time during LAL either focus on the
Einstein equation (stronger diffusion causes particle aggrega- concentration or supersaturation effects in batch reactors or
tion). Increased fluence and colloid concentration during a 1-h trigger LFL processes that are naturally more pronounced at
laser ablation of Pd in 2-propanol caused photofragmentation elevated concentrations. Although it may be convenient to have
and an increased ratio of Pd(0) to Pd(II), as measured by XPS of multiple effects triggered in one step and one batch,
the resulting colloids.510 In contrast, when the concentration was reproducibility may be an issue if the LAL processing time is
kept constant during the 1-h ablation in a flowing liquid system, mechanistically coupled with concentration-dependent LFL.
the composition and the oxidation state of the synthesized NPs The processing time interval is a key factor governing LFL
did not change, as shown by the Gökce group for the ablation of efficiency258 and has been extensively studied in terms of its
Pt and Ni in water by collecting the XRD and XPS spectra of the correlation with particle size variation253,516 and corresponding
products over a 1-h period.31 Furthermore, dispersed particles (Au, Ag) SPR position shift107,487 or colloid color change.516
were shown to evolve into different 3D structures under Yang et al. quantitatively investigated the effect of laser
continued laser processing.38,200 After ∼30 min of laser ablation, fragmentation duration on the evolution of the average size of
C3N4 particles were found to exhibit leaf-like features (Figure PbS QDs.250 Raw PbS nanocrystals with sizes of tens of
42a), and they transformed into nanorods after 5 h of ablation nanometers were converted to fairly small PbS QDs (3.5 ± 0.3
(Figure 42b),200 possibly triggered by concentration effects. nm) after approximately 20 min (Figure 42d). Moreover, the
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Table 2. Downstream Techniques Combined with LSPC To Produce Novel Functional Materials for Various Applications
technique effect material potential applications ref
aging phase change, defect control Ge submicrospheres/leaf-like WO3/tree- catalysis, PL, water 40,521,522
like Zn/ZnO nanostructures cleaning
annealing defect control GaAs crystals PL 520
centrifugation size classification Si, Ag, AuNPs PL, plasmon resonance 304,526
membrane filtration ligand removal/size classification bioconjugated Au NPs biomedicine 528
crystal inclusion host−guest composite production Au NP-doped zeolite L crystals catalysis 254
drop casting film deposition Co3O4-highly ordered pyrolytic graphite electrocatalysis 536
(HOPG) electrode
EPD film deposition Cu(In,Ga)Se2 (CIGS) thin film/Au film/ solar cells, sensing, 263,303,529,530,532−535,563
Si-TiO2 heterojunction/Pt electrodes photovoltaics, medical
implants
ex situ conjugation conjugation Au−ssO, immunoglobulin conjugates cellular uptake, 558,559,564
reproduction biology
mixing at right pH supported particles Pt, Au, Ag... on TiO2, BaSO4, graphene catalysis 135,565,566
hydrothermal solidification, doped-hematite Ag−TiO2; Zn2SnO4, ZnSnO3; (Ge, Si, photocatalysis, 544,545,551,553
nanocrystal synthesis Mn, Sn, Ti)-doped α-Fe2O3 photoelectrochemistry
polymerization powder coating Au-prepolymer blend UVE3003/P3307 optical filters 567
polymerization and 3D parts of polymer composites TPU-barium sulfate/Ag medical devices (e.g., 372
3D prototyping catheters)
polymerization and LAL-NP grafting into electrospun ZnO NP-polycaprolactone biocompatibility 357
electrospinning macroscopic polymer fiber pads nanocomposites
selective etching core−shell transformation into hollow ZnO shell PL, photocatalysis 568
hollow NPs
spin coating film deposition InN film solar cells 537
sol−gel NP−polymer composites Au NPs into a DETA cross-linked thermosets 543
encapsulation GPTMS:TMOS matrix
solvent drying dilm patterning; NP decoration on Tb3+-Cu-PVA film; ZnO/fabric conductive films, 538,539,569
fabric, NP strand formation composite, FeNi-PMMA film antibacterial products
solvent drying and increased photosensitivity 3D polymer structures doped with Au biomedicine 570
3D laser NPs
lithography
ultrasonic waves size reduction/redispersion silicon nanocrystals PL 527

polydispersity of the QDs decreased from 16.0% to 8.6% after have no effect on the products, as demonstrated by Sun and
prolonged irradiation (inset of Figure 42d). In addition to Tsuji.359
semiconductor NPs, the applicability of size and dispersity When using LML, the irradiation time is often used to control
control to LFL-synthesized noncoinage-metal NPs was also the size,279 chemical composition301 and morphology of the SMS
recently demonstrated by changing the irradiation period.311 products. Because the educt is aggregated (e.g., Ag, as shown in
Because the selenium NP size is associated with the band gap Figure 42f), time is needed to melt the particles and form
energy,231 LFL irradiation time can alter the optical properties of homogeneous SMSs (Figure 42g,h).515 Adjusting the irradiation
the synthesized NPs. Additionally, the sizes of organic drug time also helps to clarify the temporal formation dynamics of
particles monotonically decrease with increasing irradiation SMSs in different solutions.273,274 SMSs were shown to begin to
time.517 However, growth and ripening stages may occur after form in NaCl solution immediately after laser irradiation and
certain fragmentation periods (Figure 42e), leading to size subsequently grew slowly with irradiation time. In contrast, in
increase of the products.265 This behavior can be ascribed to the citrate solution, SMS growth was first inhibited (defined as the
nucleation and growth of fragmented species and the subsequent induction period) and then increased rapidly because of citrate
Ostwald ripening of small nanocrystals into large ones.164 By decomposition during the initial phase of laser irradiation.274
Clarifying the SMS formation mechanism in different ligand
recording their extinction spectra over time, Jendrzej et al.
solutions is beneficial to control the LML process and ensure the
confirmed that the growth of LFL-synthesized Pt atom clusters/
desired characteristics. Furthermore, if the educt added as
NPs follows two kinetic models: a rapid barrierless model for the dissolved light absorbers is sensitive to laser irradiation, the
early stage (<1 day) and a combination of coalescence and reaction could be switched on and off by the irradiation time to
Lifshitz−Slyozov−Wagner (LSW) kinetics for ripening during form novel SMSs, such as calcium iron phosphate spheres
the prolonged period of slower growth.164 Similarly, Mafuné originating from CaP LML with ferric ions (as sensitizers) under
reported the gradual growth of LFL-synthesized gold clusters via laser irradiation.301 Thus, it can be concluded that the processing
NP attachment and mutual aggregation using optical absorption time primarily influences the NP concentration productivity in
spectroscopy.251 Notably, the coalescence effect may be batch LAL and the NP size in LFL and LML and that it
applicable not only between the seeds but also between the sometimes imposes additional effects on NP assembly and
fragmented educt particles.451 This possibility offers an chemical reactions with the particulate educt, which often reach
opportunity to induce the assembly of the NPs into 3D either the steady state or the supersaturation-coalescence after
entities.256,516 Because the educt is not supplemented during tens of minutes (at typical milliliter batch sizes and moderate
LFL, once all of the educt has undergone size reduction, the laser power).
conversion efficiency will eventually reach saturation at a certain 5.2.2. Downstream Processing. Currently, downstream
irradiation time, and further extending the irradiation period will colloid processing methods are routinely applied to the products
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of LSPC. This downstream processing mainly aims to improve technique for generating films,536 but it is limited by nonuniform
the quality (i.e., to narrow the size dispersion or remove excess surface roughness and imprecise process control. Spin coating is
ligands) or to integrate the product into/onto a host structure an alternative used to produce laser-synthesized indium nitride
(i.e., in NP polymer composites or an heterogeneous catalyst films for solar cell applications.537 To prepare NP−polymer
support). Laser irradiation is often used for post treatment; composite films, solvent drying after LAL is a widely used
however, other methods have also been reported in the literature. technique538 in which a magnetic field can be introduced to align
As a result of the broad or bimodal size distributions of the NPs magnetic NPs into nanochains;539 the conductivity provided by
produced by LAL without size quenching, their post-treatment is these chains can be used to create transparent conductive
necessary in some cases to obtain colloids with the desired size coatings.540 Taking advantage of the purity of NPs obtained from
range. Post laser irradiation has been shown to be a highly LAL, the magnetic field can also be used to assemble electrodes
efficient method to decrease or increase the particle size by for oxygen evolution reactions541 or substrates with plasmonic
fragmentation311,518 or melting,232 respectively. Similarly, the arrays for SERS analysis.542 The sol−gel approach is a
postirradiation of LAL-synthesized NPs with added reactive salts downstream method for producing solid NP−polymer compo-
also enables morphology and composition changes; one example sites of LSPC-synthesized NPs incorporated in epoxy amine
is the irradiation of AgNPs in iodides and chlorides.519 In resins.543 Additionally, hydrothermal treatment is particularly
addition, the postirradiation of mixed LAL-produced particles interesting regarding the creation of various defect-mediated
(such as Au, Ag, and Co) allows the preparation of alloys (e.g., noble-metal/semiconductor Schottky junction, oxide, stannate,
AuAg255) and heterostructured NPs (e.g., AuCo89) with both and titanate photocatalysts.544−547 Because hydrothermal treat-
magnetic and plasmonic resonance properties. In addition to ment triggers electron release from TiOx NPs (x = 1.4) and
laser-based post-treatment, Table 2 summarizes alternative post- reduces Ag+ ions to Ag NPs to form Ag/TiO2 heterogeneous
treatment techniques that have been combined with LSPC to catalysts,544 many other LSPC-synthesized, incompletely oxi-
increase the quality of the colloid or to develop functional dized (with oxygen vacancies) semiconductor NPs (e.g.,
materials for various applications. The latter downstream ZnO2,199 SnOx,548 InOx,549 and TiOx550) can be used as
processing techniques used to integrate desired functions into photocatalyst adsorbents to reduce additive ions and form
macroscopic products are termed “nanointegration” techni- core−shell photocatalysts. Moreover, these LSPC-synthesized
ques.74 Post annealing of laser-synthesized NPs allows phase suboxides often contain hydroxyl groups, such as MOx(OH)y
transformations (e.g., the combination of Cu and Cu2O into (e.g., M: Ge, Si, Mn, Sn, and Ti).551 The hydrothermal treatment
CuO NPs)442 and altering of the defect density of semiconductor of these colloids with FeCl3 solutions at various temperatures and
NPs to tailor their optical properties.520 However, the simplest durations allows the MOx(OH)y-like clusters to react with the H+
post-treatment is aging. Colloid aging can prompt LAL-produced ions to generate stable ionic Mn+, which can affect the growth of
ligand-free NPs to self-assemble into diverse morphologies, such α-Fe2O3 nuclei and form doped α-Fe2O3 structures with different
as submicrosphere,521 microtube,71 spindle-like,51 and tree-like morphologies (Figure 43) that have photoelectrochemical
structures.522 Additionally, it is often adopted to alter the PL applications.551−554
properties of semiconductor NPs, such as Si523 and ZnO.51 Electrospinning is a versatile approach for processing polymers
Crystallization inclusion allows the encapsulation of LAL- into continuous fibers with diameters ranging from several
induced NPs that are larger than the pore openings to produce micrometers to nanometers;357 this method can extend LAL−
host−guest composites (e.g., gold NP-doped zeolite L polymer composites’ macroscopic applications to various fields,
crystals254). Selective etching and galvanic replacement con- including catalysis, filtering, tissue engineering, and wound
stitute a downstream method that has been reported to generate healing.555 Injection molding and extrusion enable the 3D
hollow structures524 and nanocages525 with interesting PL and
photocatalytic properties, respectively. Physical methods, such as
centrifugation526 and membrane/paper filtering,304,527 are good
choices to sort LSPC-synthesized NPs into different size
distributions without changing their composition.528 Electro-
phoretic deposition (EPD) takes advantage of the highly charged
surface of LAL-synthesized NPs303,529,530 and their well-behaved
mobility. In particular, the ligand-free nature of LAL-synthesized
NPs makes them superior to chemically synthesized ligand-
coated NPs for EPD coating because they do not cause the side
effects (e.g., drag force or deposition barriers) imposed by
ligands.303 Thus, EPD and LAL are natural partners for NP
deposition303,529,531 and may even have in vivo applications.532
Indeed, EPD is not only suitable for constructing films530 but is
also capable of depositing NPs from LAL onto nanoarrays.533
The film configuration can be easily adjusted by the electric field
strength,529 colloidal size,534 morphology,535 and charge.417 The
advantages of films prepared by the EPD technique will be
discussed in detail later with regard to specific applications, such
as biomedical implants, solar cells, sensors, and photovoltaics. Figure 43. Schematic of the doping process and the resulting doped-
Downstream fabrication of heterogeneous catalysts also benefits hematite nanocrystals synthesized by the hydrothermal post treatment
from the ligand-free NP surface, and is driven by electrostatic of LAL-generated MOx(OH)y-like clusters with FeCl3 solution.
(and van der Waals) forces to create supported particles simply Reprinted with permission from ref 551. Copyright 2012 American
by mixing at the right pH value.135 Drop casting is another Chemical Society.

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Table 3. Matrix of Liquids and NMs Synthesized by LSPC

prototyping of artificial medical and clinical devices, such as solvents, and polymer solution) are typically used to fabricate
catheters, using LAL-induced inorganic/polymer composites.372 NMs, including elemental, alloy, doped oxide, carbide, sulfide,
The process chain includes particle generation in monomers, and hydroxide materials, as summarized in Table 3. In Table 3,
subsequent polymerization, and final melt processing.556 A the nonspherical morphologies of LSPC-synthesized NMs are
recent review summarizes the nanointegration strategies of laser- also listed to illustrate the possibility of changing the particle
generated NPs into polymers.105 The ultrasonic bath post shape by varying the liquid composition. Oils,571−574 ionic
treatment of LAL-produced Si NPs can reduce their (hydro- liquids,24,310,367,575 liquid nitrogen,576−578 supercritical liquids
dynamic) size over time,527 and performing this treatment in HF (SCLs),579−582 and superfluids583−587 are attracting increasing
can help remove oxygen from the synthesized particles.136 As attention because of their properties, which differ from those of
expected, ultrasonication is also effective at redispersing the five more commonly used liquids. Mass transport in a liquid is
precipitated laser-generated NPs in solution.557 For biological a function of pressure and temperature, and this relationship is
applications,363,558−560 ex situ and in situ bioconjugation complex in SCLs and superfluids. Therefore, this topic will be
methods allow the efficient functionalization of laser-produced specifically addressed in section 5.3.6. Note that during LAL and
charged particles with proteins, DNA, and functional LFL, even normal liquids can be considered an SCL as well,
ligands.232,308,561 Ex situ conjugation is much more effective in
particularly in the initial bubble state and the bubble collapse
preserving the molecular function as compared to in situ
state; thus, understanding SCL−LAL is highly important for
conjugation because LFL-triggered degradation does not occur
understanding fundamental LAL mechanisms.66
during the conjugation period.363,562 Additionally, the ex situ
downstream processing method has been reported for LAL to Distilled or deionized water is the most frequently employed
produce similar biological targeting properties as compared to liquid medium for synthesizing NMs via LAL. Generally, during
the in situ bioconjugation method.558 laser ablation, the dissolved oxygen or an oxidizing species from
the plasma-induced decomposition of water will react with the
5.3. Liquid Properties matter from the target during laser ablation, leading to the
5.3.1. Composition. Among the liquid compositions, five generation of diverse oxides (e.g., Ag2O,657 ZnO,658,659 TiO2,33
types of liquids (water, saline solution, surfactants, organic Al 2 O 3 , 6 6 0 MgO, 6 0 0 MnO, 6 4 9 Mn 2 O 3 , 4 1 6 γ-MnO 2 , 4 1 6
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Mn3O4,416,661 Co3O4,662 and Cu4O3443) and hydroxides (e.g., NPs into Al@Al2O3 core−shell NPs.343 Moreover, the NPs in
Mg(OH)2600,663). In this process, the redox potentials play a neat/distilled water may also grow into larger NPs after LAL607
dominant role in determining the degree of oxidation of the LAL- or LFL164 (Figure 44b,c) or aggregate670 or precipitate over
generated products. For the ablation in water, XPS and surfactant time.671 Such ripening effects could be inhibited by using a
titration results have shown that the Au, Pt, Pd, and Ni surfaces polymer-containing solution to rapidly encapsulate and sterically
are oxidized by 3.3−12%, 20−73%, 71%, and 100%, stabilize the NPs and form oxide-free metallic Ag and Cu NPs.672
respectively.31,123,135,268,566,664,665 The laser parameters of these Although water has the drawbacks that it will contribute to NP
experiments are shown in Table 4. oxidization if decomposed by the plasma and supports the
complexing/dissolution of cations, nonoxidized NPs can be
Table 4. Oxidation Measured by XPS or Surfactant Titration successfully synthesized,39 as shown in Table 3. Additionally,
of Different NPs Obtained by LAL in Pure Water water is extensively used for LPC of oxides, 450,451,673
carbonate,452 graphene,674 and AuNPs273,315 and postirradiation
oxidation
material (%) laser parameters method ref of the LAL-synthesized products107 for size reduction. Moreover,
Au 3.3−6.6 5 ns, 1064 nm, 80 mJ/pulse, surfactant 664
small bubbles originating from the photodissociation and
10 Hz titration evaporation of water during laser ablation are assumed to
Au 5±3 8 ns, 1064 nm, 45 mJ/pulse, XPS 268 facilitate the formation of hollow NPs with larger surface areas.639
100 Hz Additionally, ice deserves more attention because it yields more
Au 12 120 fs, 800 nm, 1 mJ/pulse, XPS 123 TiO2 and Ag−TiO2 NPs than does room-temperature water.675
1 kHz
Hydrogen peroxide has a higher oxidative potential than water
Pt 20 40 ns, 1064 nm, 6.4 mJ/ XPS 566
pulse, 5 kHz and enhances the oxidative LFL of Au NPs down to 2 nm.25
Pt 30 3 ps, 1030 nm, 500 W, XPS 31 During LAL of a Cu plate, Gondal et al. found that the addition of
10 MHz hydrogen peroxide to deionized water could transform the
Pt 42−73 355 nm, 1−110 J/cm2 XPS 665 phases from Cu/Cu2O to Cu/CuO.676 However, Scaramuzza et
Pd 71 9.8 ps, 1064 nm, 126 μJ, XPS 135 al. showed that the use of H2O2 in ethanol allowed the formation
100 kHz
of alloy NPs with lower oxidation than using H2O.174 Therefore,
Ni 100 3 ps, 1030 nm, 500 W, XPS 31
10 MHz the role of H2O2 during LAL should be further elucidated under
different conditions. Additionally, the addition of H2O2 during
Additionally, the surface adsorbates on the LAL-generated LAL of Zn has been reported to yield ZnO2 NPs.199 Adding an
particles (e.g., Au,666 Ag,667 and Pt668), such as (deprotonated) oxidative reagent (H2O2) to water during LAL synthesis of
hydroxy groups,123 lead to highly charged surfaces that Eu3+:Y2O3 NPs also improves PL emissions.677
contribute to the electrostatic stabilization of the synthesized The interactions of colloidal NPs with local ions play critical
NPs. The AuNPs synthesized by laser ablation in deionized roles in determining colloidal stability and the charges of LAL-
water, for example, contain Au+ and Au3+.123 Analyzing the synthesized NPs because the nanoenvironment salinity and pH
concentration of the anionic surface adsorbates on the particle differ from those of the bulk liquid, as mentioned in the review by
surface suggested that approximately 3.3−6.6% of the surface Pfeiffer et al.367 LAL-synthesized Au NPs, for example, are
gold atoms are oxidized.664 negatively charged because of their partial oxidization and
Although scientific evidence indicates that oxidation occurs hydroxyl anion adsorption in water,123 leading to an intrinsic
during the early phase of cavitation,143 it is highly possible that buffer capacity at the NP surface.367 Dissolved anions affect
the thermodynamically driven oxidation of NPs is prolonged in LSPC in two opposing manners. The electrolyte concentration
the liquid, at least for oxidation-sensitive elements.657,669 causes the well-known screening of the NP surface charges that
Accordingly, aging the LAL-synthesized AlOx NPs in water compromises colloidal stability in water of LAL-produced ligand-
could also lead to gradual oxidization of the NPs and a shift of the free NPs. Surprisingly, low electrolyte concentration significantly
corresponding SPR band on the time scale of hours,337,343 as improves the stability of pure metal colloids by increasing their
shown in Figure 44a. The SPR band of Al NPs at 225 nm shifts to surface charge density via anion-specific adsorption on the
264 nm as the aging time increases because of the evolution of Al surface of the noble metal particles.268 Micromolar chaotropic

Figure 44. Ripening effects in water: (a) Temporal evolution of the absorption spectra of aluminum NPs in water at a low fluence of 2 J/cm2. Reprinted
with permission from ref 343. Copyright 2014 Springer. (b) Size increase after four months of AgNPs prepared by LAL in water. Adapted with
permission from ref 607. Copyright 2012 Springer. (c) Normalized extinction increase caused by atom cluster coalescence and ripening of a laser-
fragmented Pt colloid as a function of the time elapsed after the termination of laser irradiation as measured by optical absorption spectroscopy.
Reprinted with permission from ref 164. Copyright 2016 Elsevier.

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Figure 45. Stabilization and size quenching by charge delivery during LAL. Correlation between the slope of the primary particle index (equal to the
stabilizing effect per amount of ion) in the low-ionic strength Hückel regime driven by increasing the anion hydration (a) and anion polarizability (b)
during the synthesis of ligand-free gold NPs. (c) Hofmeister sequence of the anion effects that stabilize ligand-free NPs, with kosmotropes on the left and
chaotropes on the right. The anions are drawn to their approximate relative scale. (d,e) XPS spectrum of LAL-generated Au NPs in NaCl and NaI. (f)
Portion of oxidized Au surface atoms after synthesis in the presence of deionized water, NaF, NaCl, NaBr, and NaI (100 μM). Adapted with permission
from ref 268. Copyright 2014 American Chemical Society.

Figure 46. (a) Normalized Pt LIII edge XANES spectra of ligand-free Pt NPs in H2O, sodium phosphate buffer, sodium citrate, and a Pt reference foil.
Inset: EXAFS Fourier transform magnitudes. (b) Schematic of LAL-generated ligand-free Pt particles increased surface charge density by ex situ addition
of ions/ligands and preserved properties of naked particles after particle adsorption on TiO2 supports. Reprinted with permission from ref 566.
Copyright 2016 American Chemical Society.

anions (e.g., SCN−, Br−, and I−) tend to significantly stabilize Au significant size quenching310,365 (section 3) or change the NP
NPs, whereas kosmotropic anions (e.g., F− and SO42−) tend to surface charge and its composition. The adsorption of anions on
destabilize the colloids, and some other species (e.g., NO3− and the NP surface may lead to a negative shift in their redox
Cl−) produce an intermediate effect (Figure 45a−c).268 Using potential. For example, when the AgNP surface is covered by
the simplest approach, the surface charges of LAL-synthesized halides, the reduction of cytochrome c can be initiated when the
NPs can be increased if the pH is far from the isoelectric point of potential reaches a certain value.679 Anion or ligand adsorption
the NPs, for example, for ZnO NPs678 and Au NPs.123 can also cause an increase in the surface charge density. Fisher et
XPS spectra also revealed that by varying the electrolytes, one al. demonstrated a way to watch surface atoms and their direct
could control the degree of surface oxidization of LAL- interaction with adsorbates by X-ray absorption near-edge
synthesized Au NPs. Indeed, 7% and 4% of Au surface atoms structure (XANES) on naked Pt nanoparticles in water.566 The
have been shown to undergo oxidation into Au1+ species and increasing order of zeta potential of Pt NPs in different liquid
Au3+ in NaBr and NaCl (Figure 45d), respectively, whereas 4% media is in accordance with the white-line intensity order (Figure
and 2% of Au surface atoms become oxidized into Au1+ and Au3+ 46a) in the normalized XANES spectra of Pt NPs: Pt in citrate <
species in pure water and NaF (Figure 45e), respectively.268 Pt in phosphate < Pt in H2O. Because the Pt LIII edge white line is
Therefore, the extent of surface oxidization of LAL-synthesized associated with the Pt atom oxidation state and EXAFS indicates
Au NPs in NaI and NaBr (11%, Figure 45f) is nearly twice as high an increase of Pt−O bond numbers, it can be concluded that
as those generated in H2O, NaF, and NaCl (5−7%). In addition dissolved ions added ex situ interact electrostatically with the
to the effect on NP stability, different electrolytes may also cause Stern plane, thus directly influencing the particle’s Pt−OH
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Figure 47. Effect of the liquid on the crystal structure obtained via LAL and LFL. (a) AuFe alloy laser ablation in water yields iron oxide shells, whereas
acetone leads to unoxidized iron−gold core−shell particles. Adapted with permission from ref 418. Copyright 2016 Nature Publishing Group. (b)
Solvent-influenced crystal structure of Ni NPs by post LFL treatment, with elemental fcc Ni synthesized in hexane and hcp in acetonitrile. Reprinted
with permission from ref 172. Copyright 2014 American Chemical Society. (c) CuO or Cu3N LFL creates nonoxidized Cu NPs in an organic liquid and
oxidized NPs in water, whereas LFL of CuI yields CuI NPs, regardless of the liquid. Middle: Reprinted with permission from ref 248. Copyright 2014
American Chemical Society. Left and right: Adapted with permission from ref 259. Copyright 2015 Royal Society of Chemistry.

bonds. Note that the surface properties of LAL-synthesized formation of hollow Al@Al2O3 core−shell particles due to
adsorbate-free Pt NPs could be well preserved (Figure 46b) after hydrogen dissolution in molten Al and release after the Al
deposition of LAL-synthesized metallic NPs on supports yielding solidification and crystallization was facilitated.57 Further,
supported particles (Pt−TiO2).566 Therefore, they are good precisely controlled experiments are required to identify the
candidates as heterogeneous catalyst model materials to identify origin of oxidation species and determine from which substance
the effects of adsorbates on catalytic performance. (dissolved gases, such as O2 and CO2, or water) and where/when
Galvanic replacement based on the difference in reduction oxidation occurs (inside/outside the cavitation/plasma).
potentials between two metals can be achieved by simply adding Usually, solutions containing surfactants are used as protective
suitable electrolytes during or after laser ablation.680−683 Hu et al. agents to inhibit NP growth and stabilize NPs sterically or
showed that laser ablation of Co targets in K2PtCl4-containing electrosterically.338 Surfactants with different sizes and carbon
solutions resulted in the formation of PtCo alloys160 and PtCo/ chains usually exhibit different performances in controlling the
CoOx nanocomposites430 due to the occurrence of galvanic stability and size of synthesized products.686 Surfactants with
replacement reactions. longer hydrocarbon chains stabilize the NPs more efficiently,
Gas dissolved in the liquid medium for laser treatment may whereas those with shorter chains result in larger NPs.686
affect multiple properties of the synthesized particles. For However, surfactants not only contribute to colloid stabilization
example, the continuous injection of oxygen in the vicinity of a but may also guide crystal growth and particle ripening. Some
laser ablated plasma plume decreased the NP size and surfactants, such as SDS627,687 and CTAB,51 may affect particle
distribution and the ZnO/Zn(OH)2 ratio and increased the coalescence and ripening, allowing nanoring,688 ellipsoidal,625 or
crystallinity.684 Degassing water with nitrogen results in the layered127,629 growth to enrich the morphologies of laser-
formation of a metastable β-Co(OH)2 intermediate, whereas synthesized NPs. In addition to stability improvement and size
oxygen-containing water creates CoO intermediates; in both control, surfactants can also increase LAL productivity by
cases, Co3O4 NPs were finally produced.317 However, even after decreasing particle shielding.689
complete oxygen removal by nitrogen, Ti ablation in water gave Figure 47a shows different NP crystal structures obtained by
rise to TiOx NPs,685 possibly because of the consumption of the LAL of a FeAu alloy target in an organic liquid and water. As seen,
residual oxygen in water or the decomposition of water laser ablation in an organic solvent (acetone or methyl
molecules into reactive oxygen species. Molecular hydrogen methacrylate) yields crystalline Fe-core Au-shell particles, unlike
formation has been evidenced during laser excitation of aqueous water, in which the iron is oxidized at the shell, even though
media, where collected gas bubbles were analyzed by gas acetone’s oxygen solubility is even higher than that of water
chromatography.161,162 This indicates laser-induced water (Figure 47a).418 Laser fragmentation is also sensitive to liquid
splitting. Barmina et al. demonstrated that the laser irradiation properties, yielding face-centered cubic (fcc) Ni in hexane and
of colloids could produce abundant H2 in ethanol and water, hexagonal close-packed (hcp) Ni in acetonitrile (Figure 47b);
indicating the occurrence of water splitting during LAL and this difference was attributed to the different specific heats of the
LFL.161 Upon further reaction to yield γ-Al2O3 in water, excess respective liquids.172 LFL of CuO and Cu3N but not CuI is
O2 did not affect the ratio of Al2O3/Al, whereas H2 bubbling into sensitive to changes in the solvent, with only organic solvents
the liquid did.177 Similarly, in ethanol saturated with H2, also the yielding elemental Cu NPs from CuO or Cu3N, whereas CuI
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microparticle LFL yields CuI NPs independent of the liquid and that the subsequent LFL product crystal phase is controlled
(Figure 47c).248,259 by the liquid, with elemental fcc Ni NPs derived from LFL in
Organic solvents have been widely investigated for LSPC, methanol or hexane and elemental hcp Ni NPs by LFL synthesis
especially for LAL, and include methanol,172 ethanol,690 in acetonitrile (Figure 47b).172 The authors reported that the
isopropanol,607,691 acetonitrile,692 dichloroethane,693 toluene,694 specific heat of the organic liquids influenced the NP’s crystal
and ethylene glycol.355 The higher dipole moment of organic phase because acetonitrile, which has the largest bubble volume
molecules (e.g., acetone > ethanol) has been reported to result in during expansion, quenched the metastable hcp Ni NP crystal
higher ablation efficiency and smaller particles.506,607 This effect structure.172 Thus, according to their findings, the crystal phase
was attributed to the increased electrostatic interactions resulting of fabricated NPs is associated with the specific heat of the
from the higher molecular dipolar moment of the solvent organic solvents used for LFL. Yet it is unknown if the particle
molecules, which generates a stronger electric double layer in the size is affected during plasma cooling. In a recent study on LAL,
NP surface and enhances the repulsive force between NPs.695 Zhigilei et al. reported that solidification and crystallization of the
The Meunier group observed the opposite trend for LAL- and smaller NP fraction (atom clusters) theoretically are finished
LFL-synthesized Co and Au NPs, with higher solvent polarity within less than some nanoseconds,163 indicating that earlier or
resulting in a weaker quenching effect; they concluded that more effective plasma cooling could also affect particle
kinetic energy allows NPs to overcome repulsion more easily in solidification dynamics during LAL. Yet similar MD studies on
polar solvents during NP growth.219 These reports suggest that LFL have not been done yet.
solvent polarity indeed influences the particle size, but this effect Polymer molecules are efficient steric capping agents used to
requires more accurate experiments to exclude other factors encapsulate inorganic NPs during or after laser ablation to form
involved during particle formation, such as solvent’s specific heat, NP−polymer core−shell composites.104 Because the shell is
solvent reactivity, and viscosity, which affect particle ripening and identical to the matrix and because no dispersants are needed,
the particle collision rate, and to differentiate the effects on LAL particle−polymer coupling can be directly achieved. Given that
and LFL. In addition to the size distribution, alcohols with no matrix binders are needed between polymers (e.g., poly-
different chain lengths may influence the stability of the particles (methyl methacrylate) [PMMA],589 polydimethylsiloxane
under air-/Ar-/N2-saturated atmospheres.488 Short chain lengths [PDMS],709 PVP,206,429 polyethylenimine [PEI],710 polyamido-
(e.g., methanol and ethanol) result in unstable particles, whereas amine [PAMAM],595 poly(N-isopropylacrylamide) [PNI-
alcohols with chain lengths from C-3 to C-5 give rise to stable, PAM],227 poly(9-vinylcarbazole) [PVK],711 PVA,712 polystyrene
smaller particles as compared to those produced in alcohols with [PS], 713 and poly(2-(diethylamino)ethyl methacrylate)
chain lengths exceeding C-5.488 Longer hydrocarbon chains (n- [PDEAEMA]714) and inorganic NPs (e.g., metals, alloys, and
decane > n-pentane) in alkanes lead to a lower thermalization semiconductors), in principle, unlimited types of polymer
speed during LAL, and thus enable the assembly of Au particles composites are obtainable.104 In addition, various biopolymers,
with higher aspect ratios.696 In addition to the chain length, the such as starch,348,715 gelatin,349 and chitosan,351,715 or the
functional groups of the solvent govern size quenching and biomacromolecule bovine serum albumin (BSA)716,717 are
stabilization. The adsorption of organic molecules via the increasingly interesting for use as biocompatible stabilizers to
carbonyl groups on LAL-synthesized NPs could improve the realize size-controlled and well-dispersed NPs, endowing NPs
NP dispersion.260 Furthermore, enolate or alcoholate groups with much better stability than water.718 Investigating the effect
could form upon the laser irradiation of acetone or ethanol, and, of the polymer structure on the synthesized products has
as a result, adsorption onto the gold NPs could endow them with attracted increasing attention in recent years. For example, Singh
long-term stability.334 However, it should be noted that LAL and Soni demonstrated that the end-group hydrophobicity of
sometimes triggers solvent pyrolysis357 or organic molecule polymers played a critical role in quenching the particle size and
decomposition,697,698 thereby raising the risk of organic increasing the stability against oxidation of Al NPs,343 thus
contamination. The amounts of this byproduct are expected to shedding light on the strength of polymer adsorption required to
be proportional to the (initially hot) NP surface area, and the achieve steric stabilization. In that work, PVA and PVP were
resulting carbonaceous shell may also contribute to the found to be superior to PEG and SDS in minimizing both particle
protection of the inorganic core, as shown by Amendola et al. size and oxidation. Thus, another advantage of dissolving
for LAL of Fe in toluene.198 Note that the reaction between the polymers in the liquid medium during LSPC is that they inhibit
target materials and the solvent (reactive LSPC) may lead to the oxidization and may help to produce oxide-free particles.672
generation of novel carbides, oxides, and doped NMs, such as Barry et al. demonstrated that chitosan stabilizes negatively
metastable phase Cr3C2−x;699 carbon shells and fullerene-like charged AuNPs, preventing aggregation and precipitation not
carbon spheres;700 (LiNbO3, Au, or Si)@C,697 (TaC, NbC, HfC, only during ns laser ablation but also after 24 months of aging.353
or MoC)@C,701 Pd@C,702 Ag@C,703 HfC,704 W2C@C core− The Meunier group reported that irradiating Au nanosized seeds
shell NPs,62 and SiC nanorings;705 onion-like carbon-encapsu- (<10 nm) with a fs laser-induced white-light supercontinuum
lated cobalt carbide (Co3C) core/shell NPs;383 Si−H-doped allowed precise size control from 3 to 80 nm that was
graphene-based lamellae;609 and C−H-doped anatase nano- proportional to the dextran concentration.227 Schwenke et al.
condensates.610 In addition, bonding of the dissociative by- compared the stability of gold particles produced by laser
products to the surface of LAL-produced NPs706 may also occur, ablation in MMA with and without dissolved PMMA and found
which is beneficial for PL emission enhancement707 or excitation that the steric stabilization was sufficiently strong only when the
wavelength-dependent multicolor emission of carbon-protected mixed solution of PMMA−MMA, not the pure monomer MMA,
NPs.697 Reaction of liquid silica precursors and metal atoms was used.589 These findings indicate that, although no specific
during RLAL enables the formation of metal@silica core−shell matrix binders are required for polymer composites, the
particles.708 By comparing the phases of the nanostructures synthesized products must be sterically stabilized before they
obtained after primary LAL and secondary LFL, Jung and Choi can be used in practical applications. LAL-synthesized TiO2 NPs
discovered that Ni/NiO phase mixtures were generated by LAL could act as photoinitiators for the polymerization of the
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monomer shell (ε-caprolactam),719 and monomers can be ripening/growth of some particles into large particles (up to 100
grafted and polymerized on ZnO NP during LAL of Zn,720 nm), resulting in nonhomogeneous particle size. When
thus opening a novel pathway for straightforward nanocomposite mesoporous silica materials are used as adsorbents, LAL-
production in aqueous monomer solutions. The applications of generated particles may block some pores of the silica materials,
LSPC-synthesized polymer-capped NP composites have been slightly decreasing the specific surface area and total pore volume
systematically reviewed recently.105 as compared to those of the bare silica materials.309 One possible
Some efforts have focused on synthesizing NPs by LAL using advantage of in situ LAL-synthesized supported composites (e.g.,
vegetable oils, such as walnut oil,574 coconut oil,571 or castor Ag−SiO2) is that their metallic adsorbates (e.g., Ag) are smaller
oil.572 Lubricant oils are also attractive as the LAL liquid medium and more uniform than those obtained via hydrothermal
because the synthesized particles in the oil medium can be synthesis.309 Note that the risk of support damage should be
directly used for tribological tests.573 Attempts have also been considered. Seyedeh Zahra et al. showed that longer ablation of a
made to synthesize nitrides in liquid N2, for example, TiN Pd target in the suspension of multiwalled carbon nanotubes
particles.577 The oxygen-free environment of liquid N2 is (MWCNT) would induce damage to MWCNT supports,
beneficial for obtaining pure Si particles with negligible resulting in reduced hydrogen storage capacity when using
oxidation.577 Interestingly, this technique has been extended to these Pd/MWCNTs as catalysts.405 Sai Siddhardha et al.
graphene via the exfoliation LAL of graphite in liquid N2,576,578 in reported that LAL of a gold target in a functionalized layered
which liquid nitrogen penetrates into the interlayer spacing of hydrogen exfoliated graphene (f-HEG) suspension led to the
graphite and subsequent gasification upon laser heating causes simultaneous deoxygenation of f-HEG and loading of AuNPs to
the dissociation of graphene layers.578 form laser-converted, graphene-supported gold NPs.722 Partial
5.3.2. Solid Additives. Solid additives in liquid media during structure destruction of the MCM-41 silica suspension has also
LAL allow size quenching (see section 3) of NPs and one-step in been reported by Szegedi et al.309
situ synthesis of hybrid (adsorbate−absorbent) composites. For Driven by the extensive applications of graphene and graphene
instance, LAL of metals in a dispersion of silica spheres directly oxide (GO), increasing attention has recently been focused on in
produces supported particles (e.g., Cu/SiO2 and Al/SiO2, Au/ situ LAL synthesis of layered supported composites. Ye et al.
SiO2, Sn/SiO2, and Ag/SiO2). This process has been reported to demonstrated that an oxidation−reduction reaction may occur
be driven by the adhesion energy values of the respective material between GO and LAL-synthesized suboxide (e.g., SnOx) colloids
pairing and not by the additive size (Figure 48d,e).721 that are rich in electrons, surface hydroxyls, and defects.723 LAL
of Mg in aqueous GO produces LAL-generated positive
Mg(OH)2 nanosheets and negative GO sheets that form porous
Mg(OH)2/GO nanosheet composites, which exhibit high
adsorption efficiency toward water pollutants, such as methylene
blue (MB) and heavy metal ions.663 During LML, codispersing
carbon black has been employed by the Koshizaki group as a laser
incoupling sensitizer that enables fabrication of ZrO2 SMSs.724
Guo et al. reported the possibility of using solid metallic
particles (e.g., Au NPs) as the adsorbates for in situ conjugation
with LAL-generated oxides to form hybrid composites (Figure
49e), such as Au−CoFe2O4 (Figure 49a−d) and Au−SrTiO3.725
The Bayberry tannin-stabilized size-tunable Au particles behave
as heterogeneous nucleation sites for the LAL-generated oxides
to form heterodimer hybrids with well-defined structures and
compositions.
Particles generated by LSPC, and especially LAL (elemental,
Figure 48. Solid SiO2 spheres serve as adsorbates for LAL-generated alloy, and oxide particles), are also good candidates for the
NPs in hybrid composites: (a) Au−SiO2 and (b−f) Cu−SiO2 particles synthesis of hybrid composites. This method is termed two-step
by LAL at different pulse energies (100 or 200 mJ), ablation periods (10, or consecutive LAL (laser ablation of another material inside the
20, or 30 min), and different sizes of SiO2 (100 or 1000 nm). Adapted former LAL-synthesized colloidal solution) and has enabled the
with permission from ref 721. Copyright 2013 Institute of Physics. fabrication of doped/core−shell nanocomposites (e.g., Pt−
TiO2,726 Ag−TiO2,675 Au−Si,727 Ag@ZnO,514 Al2O3@Ag,728
Nonuniform Ag or Au spherical islands (Figure 48a) and Al2O3@AgAu,728 and Ag@Au512). These two-step LAL-
irregular Sn and Al islands cover the SiO2 core, whereas uniform, generated composites can be further used as colloidal additives
smaller Cu particles (Figure 48b) cover the SiO2 core and form for the in situ conjugation synthesis of trimetallic composites by a
uniform shells after 30 min of LAL at a pulse energy of 100 mJ third LAL step. Subsequent laser irradiation can transform these
(Figure 48b).721 The pulse energy and ablation time, which affect trimetallic composites into multishell structures, such as Al@
the particle size and concentration, also affect the particle Al2O3@Ag@Au and Al@Al2O3@AuAg.729 Hence, adding solids
uniformity on the SiO2 adsorbents (Figure 48b,c and e,f).721 In in situ to LAL or LFL may be a convenient step to create
general, longer ablation or irradiation periods during LAL or LFL supported particles, in particular if size quenching of the NPs is
result in higher colloid concentrations. Consequently, the intended, and modification of the dispersed solid by the laser is
collision rate between adsorbents and their adsorbates is intended as well (or at least does not have to be totally avoided).
increased, leading to more particle loadings on the adsorbents. Alternatively, solid supports may also be added downstream
When the ablation period is too long, for example, 1 h, the (section 5.2.2), not being excited by the laser.
particles (e.g., Pd NPs) may exceed the maximal “occupancy” 5.3.3. Concentration. The concentration of the solvate
capacity of the absorbents (e.g., CeO2).369 This will cause the affects LSPC sterically (macromolecules), electrosterically
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trations will result in more stable colloidal solutions and smaller


particle sizes,594 as discussed in section 3.2. For example, as the
concentration of aqueous cyclodextrins is increased, the size of
the LAL-synthesized AuNPs can decrease to 2−2.4 nm (number-
weighted) and exhibit a size width of less than 1−1.5 nm.731,732
To obtain larger NPs with LML, a higher concentration of
polymer is unfavorable, as demonstrated by increasing the
dextran concentration from 0.01 to 1 g/L to decrease the size of
Au NPs (from 80 to 3 nm) via fs laser irradiation (Figure 50a).227
In general, an optimal concentration threshold exists at which
both stabilization and particle dispersion are achieved.308,336,618
However, more is not always better. First, at a certain threshold
ligand concentration, the minimal size is achieved, and further
increasing the concentration only decreases the conjugation
efficiency without affecting the NP size.733 Furthermore, in the
case of copper and silver NPs obtained by laser ablation in TPU
polymer-containing THF solution, the optimal concentration is
approximately 0.3 wt % TPU; above this value, the particle
dispersion does not improve further, but the production rate of
the NPs decreases.307 By comparing the emergence of AuIII or
Au0 on the AuNP surface at different CTA+ concentrations, Fong
Figure 49. In situ conjugation with solid additives: (a−d) Au−CoFe2O4 et al. concluded that only when the surfactant CTAB fraction
heterodimer hybrid composites with solid Au NP additives and LAL-
generated CoFe2O4 NPs as adsorbates. (e) Schematic diagram showing
approximates the aqueous CMC (0.94 mM) the colloid
the one-step in situ particle-conjugation process. Scale bars represent 5.0 stabilized.734 Because this threshold depends on the final
nm. Adapted with permission from ref 725. Copyright 2013 Wiley. concentration of NPs, such values are reported as the grafting
density of ligands per NP surface area (pmol/cm2) to facilitate
comparison.308 Interestingly, at lower CTAB concentrations (in
(surfactants), and electrostatically (pH, anions), influencing anion solutions and pure water), no trace of oxidized Au could be
colloidal stability, surface charge density, and reaction or observed by XPS.734 This finding is contradictory to the report of
oxidation of the ablated matter. The adsorption of anions310 or Merk et al., who found 5% oxidized surface atoms in Au NPs
molecular ligands, such as surfactants,305 biomolecules,730 and laser-synthesized in water values as high as 11% in halide anion
polymers,104 will not only prevent particle growth but also inhibit solutions.268 Also, Mafune et al., who did work at CMC of CTA+
their aggregation. Solutions containing higher ligand concen- as well, found signs of oxidation by XPS and calculated the

Figure 50. Solvate concentration effect: (a) Size variation of gold NPs as a function of the dextran-to-gold molar ratio after white-light fs laser irradiation
determined from TEM micrographs. Adapted with permission from ref 227. Copyright 2009 American Chemical Society. (b) ζ-potentials of LAL-
synthesized gold NPs in aqueous SDS (○) and CTAB (●) with different concentrations. Adapted with permission from ref 664. Copyright 2009
American Chemical Society. (c−e) Influence of surfactant concentration on ZnO formation. (c) Illustration of the formation process of ZnO/Zn
composite NPs with increasing SDS concentration. (d) Fourier transform IR spectra of NPs fabricated at different SDS concentrations. (e) XRD
patterns of the products prepared in pure water and surfactant solutions with different SDS concentrations: 0.0001, 0.001, 0.01, 0.05, and 0.1 M (from
bottom to top). Adapted with permission from ref 597. Copyright 2005 American Chemical Society.

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surface oxidation by the particle’s charge.664 Note that the laser


parameters, liquid flow, and target geometry of both studies were
different, indicating that controlling surface charge of laser-
synthesized Au NPs is based on more than just the adsorbate
concentration. The matching between the ligand charge and the
NP charge is another important factor that influences the stability
and size of the synthesized NPs, especially for RLAL.447 Taking
the ablation of a tin metal plate, for example, the neutral solution
becomes acidic (pH = 4.5−5.3) after laser ablation, which may
result in a positive zeta potential of the synthesized semi-
conductor NPs (e.g., SnO2).735 In this case, the negatively
charged C12H25SO4− (SD−) ions preferably attach to the particle
surface by electrostatic forces and thereby stabilize the NPs.
When the SDS concentration is above its CMC (8.6 mM), the
LAL-produced NMs are well-dispersed with a very narrow size
distribution; however, when its concentration is below the CMC,
small particles coagulate and form large particles.447 In LAL
synthesis of Au NPs, because their surfaces are negatively
charged in neutral water, the addition of anionic (e.g., SDS) and
cationic surfactants will result in different effects on the surface
charge of Au NPs. Muto et al. demonstrated that increasing the
CTAB concentration gradually increases Au NP surface charge
because of the adsorption of CTA+ ions, rendering the Au NP
surface positively charged, whereas those synthesized in SDS
remained negatively charged (Figure 50b).664 In addition to
stability control, increasing the anion concentration increases the
number density of the nascent charge state of Au NPs by a factor
of 10−710 at the CMC, which positively affects the Coulomb
explosion-driven ns LFL of gold NPs.243
Competition between surface oxidization and capping
protection occurs during LAL of Zn in SDS solution,597 as
shown in Figure 50c−e. Laser ablation in water gives rise to the
formation of ZnO and less Zn; however, the ablation products
transform as the SDS concentration changes. When the SDS is
below its CMC, only wurtzite ZnO NPs are formed. As the SDS
concentration increases, Zn crystals reappear and spread, and the
ZnO peaks decrease. When the SDS concentration reaches 0.1
M, the ZnO crystal completely evolves into Zn(OH)2, which
coexists with abundant Zn crystals, as evidenced by the FTIR and
XRD spectra shown in Figure 50d,e. The schematic of the UV ns
laser ablation products of Zn at different SDS concentrations597
is presented in Figure 50c. Similarly, Liu et al. synthesized various
core−shell structures by mediating the copper oxidization in
SDS-containing solutions, which affected the position and
intensity of the copper localized surface plasmon resonance
Figure 51. Effect of the liquid thickness on LAL productivity and NP
(LSPR) peaks.337 Note that Zn(OH)2 may also generate layered size. (a) Liquid splashing and fume emission from the liquid when the
structures in the presence of different concentrations of SDS liquid thickness is too thin (regions A). (b) Optimal liquid level for
(wavelength: 1064 nm).629 Jung et al. reported the production of maximized LAL and minimized volume (V) of LFL (regions B). (c)
NaOH-concentration-dependent Cu-based nanoproducts (Cu, Beam attenuation when using a high liquid thickness, resulting in lower
Cu2O, and CuO) with Cu and Cu2O formation occurring at productivity but intensified LFL and producing smaller NPs (regions
lower pH values and increased oxidation to Cu2O and CuO C). (d) Al2O3 NP production in distilled water conducted under various
observed at higher NaOH concentrations or pH values,736 as water heights. A laser pulse energy of 3.8 mJ at a 5-kHz repetition rate
expected on the basis of the Nernst equation. and 120 mm/s scan speed were employed. Adapted with permission
5.3.4. Layer Thickness. Controlling the liquid layer height from ref 20. Copyright 2010 American Chemical Society. (e) Ge NP
mean diameter versus water layer thickness at a pulse energy of 60 mJ/
above the target is crucial for maximizing the yield of LAL-
pulse. Adapted with permission from ref 376. Copyright 2011 Springer.
generated NPs,20,178,376 and the layer thickness can be optimized (f) Dependence of the sound amplitude (proportional to productivity)
to achieve maximum productivity (Figure 51d; see also section on the liquid layer thickness during excimer LAL of Si. Adapted with
4.3). The liquid always attenuates the laser intensity, particularly permission from ref 403. Copyright 2001 American Institute of Physics.
if the light is absorbed or scattered by dispersed NPs and bubbles,
both of which reduce the energy absorbed by the target substrate.
When the liquid layer thickness is too thin, the plasma cannot be to splashing and the emission of fumes or mist into the workplace
fully confined by the liquid,403 and, as a result, the plasma or (Figure 51a). Yet the liquid layer does not only affect the
cavitation bubble breaks through the liquid−air interface, leading productivity. A thick liquid layer during LAL will increase the
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Figure 52. Liquid handling configuration for LAL and LFL. Laser ablation in (a) batch processing, (b) semibatch processing, and (c) flow chamber
configurations and the corresponding NP concentrations as a function of time (t) and liquid depth (z). (d) Configuration of laser fragmentation and
melting in flow jet and the corresponding NP concentrations as a function of time and liquid flow axis. (e) Laser fragmentation in batch processing. (f)
Example experimental schemes. From left to right: Reprinted with permission from ref 739. Copyright 2015 American Chemical Society. Reprinted with
permission from ref 740. Copyright 2015 Royal Society of Chemistry. Reprinted with permission from ref 363. Copyright 2014 American Chemical
Society. Adapted with permission from ref 310. Copyright 2013 Royal Society of Chemistry. Adapted with permission from ref 1027. Copyright 2017
Nature Publishing Group.

portion of LFL effects that occurs within the excitation volume Figure 51f shows that the ablation rate correlates with the sound
fraction above the target (V in Figure 51b,c). Thus, increasing the amplitude. A specific sound frequency (10 kHz) far higher than
liquid thickness may indirectly decrease the particle diameter and the repetition rate of the laser (not specified in ref 403, although
size distribution.178,737 Accordingly, interpretations of the effects it is noted that the laser LPX 100 has a maximum frequency of
of the liquid level reported in the literature should consider this 100 Hz) was found to be optimal for correlation of LAL
effect, particularly for high-repetition rate or ultrashort-pulsed productivity of Si at 248 nm, 30 ns, and 31 J/cm2.403
lasers (which are efficient for LFL). Another side effect is 5.3.5. Flow. Liquid batch and liquid flow processing are two
triggered if the vessel diameter is constant, which causes the different strategies used for LSPC, especially LAL and LFL, and
liquid volume to increase with the liquid height: For example, less have several fundamental differences regarding process control,
concentrated seeds ripen into smaller germanium particles.376 yield, and byproducts.106 In batch LAL (Figure 52a), the incident
Thus, an increased liquid level may lead to opposing effects on light is scattered by both the bubbles rising upward and those
the particle size, depending on the sensitivity to the LFL (e.g., Au, adhering to the surface.400 This effect can be minimized in batch
Ag) and supersaturation ripening (e.g., Ge) conditions (Figure reactors using horizontal LAL (e.g., cuvette LAL with the target
51e). Overall, liquid layer minimization is a simple, cost-effective on the side). However, in any batch case, the newly formed NPs
method to increase the NP yield.106 Upper and lower limits of the will accumulate in the liquid and consume some of the laser
optimal liquid thickness for ablation productivity exist. Generally, energy arriving at the target surface, leading to NP saturation and
a minimal layer is required to avoid instability from the cavitation decreased productivity.401 Additionally, the colloidal concen-
splashing of ablated matter through the liquid−air boundary, and tration c changes temporally and spatially according to the trends
lower pulse energies cause smaller cavitation bubbles, allowing (∼t1/A, A ≥ 1; ∼1/z3, t is the ablation/processing time, A is a
the use of even thinner liquid. If LFL parallel to LAL is desired (at constant, z is the distance away from the laser ablation spot)
the expense of productivity) to minimize particle size, a high marked in Figure 52a−c. In batch processing, the ablation
liquid level may be a simple method. In this case, reproducibility reproducibility is weak because both the effective fluence and the
will be an issue because this method is not stable, and decoupling ablation rate change with time. Therefore, NP and bubble
LAL by second-step LFL may be an alternative providing better removal by liquid draining are essential for controlling LSPC.
control. Adjusting the optimal liquid layer thickness for high Resano-Garcia et al. reported that the yield of LAL-synthesized
ablation rates can be facilitated using an external microphone. AgNPs in stirred liquid was approximately 30% higher than that
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Figure 53. Impact of liquid flow on the NP size distribution, NP productivity, and biomolecule degradation. (a,b) Size distribution of Ag NPs obtained
by LAL in flowing and stationary liquid, respectively, and the corresponding TEM images of the NP morphologies. Reprinted with permission from ref
401. Copyright 2015 American Institute of Physics. (c) Relationship of the volumetric flow rate with the productivity and outflow concentration of Cu-
LAL at 500 W, 10.1 MHz, 3 ps, and a scanning speed of 484 m s−1. Reprinted with permission from ref 31. Copyright 2016 Institute of Physics. (d)
Biomolecule degradation during fs LAL of Au in aqueous oligonucleotide solution as a function of the liquid flow rate with increasing laser pulse
energies. Reprinted with permission from ref 402. Copyright 2010 Springer.

in unstirred liquid, that the ablation reproducibility was also pumped liquid may induce fluctuations of the liquid surface
significantly improved (over four repeated experiments), and during LAL, which may refract or reflect the laser light in
that the NP size distribution was narrower (Figure 53a,b).401 different directions and change the beam profile. Thus, liquid
Similar findings were reported by researchers using a semibatch flow chambers should include an entrance window for the laser
apparatus equipped with a magnetic stirrer380,738 (Figure 52b) beam on top of the liquid or comprise a vertical chamber when a
and single-pass flowing liquid experimental configurations310 horizontal beam is used. The same is true for LFL or LML, in
(Figure 52c). The removal of NPs by flowing liquid is effective which the cuvette or vial arrangement usually suffers from mixing
and inhibits bubble settlement in the vicinity of the ablation of the particulate educt with the product (Figure 52e). Liquid
grooves,400 thereby improving the ablation reproducibility and flow diminishes these side effects, particularly if the whole flow
dramatically increasing the NP productivity (by 380% for ns LAL channel diameter is irradiated (Figure 52d). In fully irradiated
of alumina and 700% for fs LAL of gold) relative to the stationary flowing liquid channels, unirradiated solid educt is avoidable, and
liquid by adjusting the flow rate.20,402 Note that the NP the transmitted laser energy may be measured to determine the
productivity increases linearly with the flow rate at the expense of energy-specific process efficiency parameters. These parameters
the outflow concentration (Figure 53c), as was recently help to provide energy-specific mechanistic insights and to
demonstrated by Streubel et al. using a single-pass flow identify the scale-up parameters for LFL218 and LML (see
configuration.31 Additionally, the degradation of biomolecules section 4.3).267 Because of the constant downstream conditions,
during LAL of gold NP in an oligonucleotide solution was flowing liquid may also allow well-controlled ripening,
significantly reduced when the liquid was drained from the conjugation, and size quenching, and thus the characterization
processing zone, thus minimizing the unintended post irradiation of LFL and LML intermediates.218,267 In general, the batch
of the Au NP bioconjugates (Figure 53d).402 In a semibatch processing of both LFL and LAL causes nonstationary laser
chamber (Figure 52b), because the colloids remain within the excitation conditions, which may compromise the quality of the
constant volume even though they are locally dispersed just after colloid. Semibatch processing (and stirring) may help to avoid
their formation, the NP concentration will gradually increase, particle sintering (by fluence fluctuation), as shown for LAL of
and the colloid shield effect will be further enhanced, diminishing Ag in water.401 Overall, flowing liquid is superior to stationary
the laser efficiency. That is, semibatch or stirred processing liquid for laser-based colloid generation96 for three reasons: (i)
constitutes a compromise that exhibits temporal changes in the stationary synthesis conditions without particle melting or
NP concentration, bubble removal, and a technically simple fragmentation occurring in the beam path, (ii) bubble removal,
colloid concentration method. When flowing liquid is used, and (iii) stationary conditions of continuously drained colloidal
because the inflow is fresh, colloid saturation will not occur, and particles for downstream processing. These factors perfectly
the NP concentration will remain constant at all times (t) and all match with the continuous particle emission source character of
positions z (stationary fluid condition), as shown in Figure 52c. LSPC, which would improve both the processing reproducibility
However, the concentration may be lower, and either a high- and the yield for all LSPC methods.
power laser or subsequent evaporation of the colloidal solution is 5.3.6. Viscosity, Temperature, Pressure, and Super-
required to increase the outflow concentration. Note that the critical Fluids. The liquid viscosity determines the solvent mass
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Figure 54. Influence of the liquid viscosity on the particle morphology and cavitation bubbles: (a) Au NP chain aspect ratio and position of the high-
wavelength plasmon peak as a function of the hydrocarbon chain length (liquid viscosity) during LAL. Reprinted with permission from ref 696.
Copyright 2003 American Institute of Physics. (b,c) TEM images of gold and platinum nanowires deposited on a carbon-coated copper grid after
superfluid LAL. (d) Schematic of nanowire formation mechanism from the quantized vortices during ablation in superfluid helium. Reprinted with
permission from ref 585. Copyright 2014 American Chemical Society. (e) Inner bubble and outer, partly transparent shell acquired during LAL CO2
near the critical point (T = 302.0 K, P = 7.30 MPa). Adapted with permission from ref 748. Copyright 2013 American Institute of Physics. (f,g) Particle
populations generated during LAL in supercritical CHF3 with (f) dominant morphologies at reduced densities of 0.8 and (g) 0.2. Reprinted with
permission from ref 34. Copyright 2012 American Chemical Society.

flow, the diffusion constant of the particle nuclei, and their Compagnini et al. described the relationship between the
collision rate to form larger particles and aggregates. According hydrocarbon chain of alkanes and the asymmetry of plasmonic
to the LSW theory,741 the final particle size is related to the aggregates after LAL of Au696 and observed that the aspect ratio
viscosity through the reaction constant k = CT/η for diffusion- increased from 4 to 6.5 (extracted from the longitudinal plasmon
limited reactions: R3 = R03 + CTt/η, where T is the liquid band) as the hydrocarbons became lighter (C10 to C5). They
temperature, η is the liquid viscosity, C is a constant, t is the hypothesized that either higher thermalization (at lower liquid
growth time, and R0 is the initial radius. Thus, theoretically, a mass) or lower viscosity favors NP chain formation (Figure
liquid with a high viscosity should generate smaller particles 54a).696 Indeed, the viscosity changes by a factor of 4 from
during LSPC or reduce the particles’ aggregation. LSW theory pentane to decane. Notably, increasing the liquid viscosity may
was applied to the ripening (growth and aggregation) kinetics of decrease the ablation productivity by reducing the solution
Cu, Ag, and Au NPs fabricated by fs LAL and revealed two-step transport, thus hampering the removal of scattering bubbles or
diffusion-controlled ripening in ethanol (1.04 mPa s) and ethyl particles.720 The liquid viscosity is known to decrease as the
acetate (0.43 mPa s).360 For gold and silver, both kinetic steps temperature increases. Therefore, increasing the temperature
were quicker in the less viscous liquid, whereas the opposite was may increase the hydrodynamic diameter of LAL−AuNPs by
observed for copper.360 During LFL of Pt and Au in water, the raising the collision probability of the particles.134 Similarly,
initial LSW kinetics were also observed, followed by Ostwald increasing the liquid temperature to 70 °C promotes the
ripening, and the kinetics were accelerated by increasing the formation of Au NPs and Ag NP nanochains and nanonet-
temperature, which decreased the viscosity and increased the works.742 For ZnO in water, dissolution effects may trigger
diffusion constant.164 Several reports have addressed the crystalline growth as the liquid temperature is increased. For
influence of viscosity on LAL. For example, the Ag NPs instance, ZnO particles grow into columnar structures743 or
generated in propanol (1.94 mPa s) are smaller than those nanoflakes744 when the water temperature is above 60 °C.
obtained in H2O (0.89 mPa s).607 Liquid viscosity also affects To date, motivated by “nonviscosity” and unusual mass
cavitation bubble dynamics, and the Chrisey group attributed the transport properties, LAL has been conducted in various
formation of larger hollow spheres in ethanol−water mixtures superfluids, including trifluoromethane,34 helium,583,585,587
than in water to the generation of larger cavitation bubbles with xenon,745 and carbon dioxide,66,581,746 and some unique features
longer lifetimes and less damped bubble oscillation. 55 of using superfluids as LAL liquid media have been identified.
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Time-resolved shadowgraphy revealed that superfluid helium fluid density and temperature. Gold nanonecklaces and large
could give rise to different cavitation and cooling processes that nanospheres are produced at lower and higher densities of
include two separate phase transitions (gas to normal liquid and supercritical CO2, respectively.66 Moreover, LAL in supercritical
normal liquid to superfluid) because of the high thermal CO2 triggers the formation of sp3-hybridized materials because of
conductivity of superfluids and their photoinduced break- the selective dissociation of C−H bonds, such as diamantane and
down.584 Approximately 20% of the laser pulse energy could higher-order diamondoids (M > 12).581 For pressurized LFL, the
be directly delivered to the superfluid, thereby leading to the size reduction ability is very different between atmospheric and
formation of a large cavitation bubble of up to several millimeters high pressures.87 At ambient pressure with a spinodal temper-
in diameter depending on the laser pulse energy.584 Quasi-1D ature of ∼573 K, explosive evaporation will create a layer of
quantized vortices (Figure 54d) produced during LAL in superheated water in the vicinity of Au NPs.87 Subsequent
superfluid He dominate particle growth, resulting in thin and bubble formation reduces the stability of fragments and causes
long nanowires with regular internal structures585 (Figure 54b,c). them to aggregate because of insulated heat transfer (Figure
These synthesized nanostructures, which exhibited improved 55a,b). In contrast, at high pressures (e.g., p > 22 MPa), the
conductivity, were determined to be suitable for use as
superconducting materials583 because an electrical interconnec-
tion exists between the nanowires in the webs,585 and they exhibit
good stability at room temperature.586 In liquid He, Bulena et al.
recently concluded that most of the ejected nanometer- and
micrometer-sized metal particles originate directly from the
primary ablation event (and not the collapse) because the
typically observed tightly focused cavity collapse events are
absent in superfluid helium.747 LAL in He can help one to study
the mechanism of the primary ablation process and the
noncollapse ejection of nanoparticles into the liquid. Remark-
ably, Saitow et al. reported that two particle populations are
formed during LAL in supercritical CO2 and CHF3.34,66 They
discovered that the larger population, which has an average
diameter of 400 nm (Figure 54g), is dominant at high pressures
(stabilizing large Au droplets because of the higher liquid
density) and acts as a precursor for the nanonetworks (20 nm
primary particles assembled into micrometer-long networks)
(Figure 54f). This fragmentation of the large fraction was found
to be governed by the permittivity of the supercritical fluid rather
than by its thermal properties, as found by comparing nonpolar
CO2 and bipolar CHF3.34
Varying the laser ablation/irradiation process induced by Figure 55. Effect of the liquid pressure on LFL: (a) Schematic
external pressure is a novel area in which interesting mechanistic illustration of ns laser-induced size reduction of Au NPs in water at
insights are emerging. Interestingly, together with temperature atmospheric pressure and above the critical pressure of 22.1 MPa and
modulation, the ambient environment can be tailored con- (b,c) the resultant AuNP morphology. Reprinted with permission from
ref 87. Copyright 2012 American Chemical Society.
tinuously from gas-like to liquid-like by varying the ambient
pressure, with the gas−liquid critical point acting as the
supercritical fluid threshold.749 The maximum volume of a formation of a SCL layer around the gold particles allows precise
cavitation bubble produced during laser ablation can be fitted control of particle evaporation. However, a higher laser fluence is
with the empirical formula Vmax ∝ Pext−1, where Pext is the applied necessary at higher ambient pressures to achieve the same LFL
pressure;182 thus, the dynamics of cavitation bubbles respond efficiency as at lower pressures.88 At the expense of slightly lower
strongly to external pressure. For example, increasing the liquid efficiency, using higher pressures provides a good opportunity to
pressure from atmospheric pressure to 3 MPa dramatically precisely control the particle size (Figure 55) and elucidate the
shortens the cavitation bubble lifetime from 185 to ∼11 μs.182 LFL mechanisms.87
Additionally, near the critical point of liquid CO2 (T = 302 K, P = Overall, the SCL state plays an important role during LAL and
7.30 MPa), cavitation bubbles are capped by partially transparent LFL, not only during ablation in SCL medium, but also an SCL-
shells via solvent gasification748 (Figure 54e), and the bubble size layer is created in the vicinity of the ablation and fragmentation
is maximized at the pressure (8.8 MPa) associated with the space in normal liquid, anyway.
maximal density fluctuation.750 Furthermore, high pressures (up 5.4. Laser Parameters
to the supercritical state) also facilitate controlling the atomic 5.4.1. Pulse Duration. The pulse duration, which is also
emission density and the degree of hydrolysis.579 Moreover, known as the pulse width, determines both the degree of self-
because both the bubble lifetime and size and the physical focusing during laser propagation in liquid394 (Figure 56a) and
properties of the environment can be varied by changing the the efficiency of LAL, LFL, and LML.269,286,357,400 Ns lasers do
pressure, the cooling rate of the NPs and their coalescence rate not suffer from severe self-focusing when typical LSPC
can also be altered, directly affecting the particle size, phase, and parameters are employed, and the laser focus is always located
assembly, as revealed by time-resolved spectroscopy.751 For at longer focal distance than in air because of liquid refraction
example, silicon clusters with different electronic structures749 (Figure 56b).394 In contrast, ultrafast (ps and fs) lasers are
and various near-UV, violet, blue, green, and red PL emissions752 subject to a stronger self-focusing effect (Figure 56c), and, as a
have been selectively generated by changing the supercritical result, the focus position is elevated above the ns-LAL focus
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Figure 56. Self-focusing and refraction at different pulse durations. (a) Nonlinear effects: Calculated caustic of a laser beam with different pulse durations
focused in water. (b) Linear effects: Variation of the focus position caused by ns laser beam refraction in a liquid. (c) Sketch of the focal displacement
caused by the combined refraction and self-focusing effect during LAL. Reprinted with permission from ref 394. Copyright 2011 American Chemical
Society. Adapted with permission from ref 395. Copyright 2009 Institute of Physics.

Figure 57. Effect of the pulse duration on the ablation threshold, ablation mechanism, NP productivity, and photoionization. (a) Threshold laser fluence
for the ablation of gold targets versus the laser pulse duration. Reprinted with permission from ref 762. Copyright 2002 American Institute of Physics.
(b) Thermodynamic trajectories under fs (dashed-dotted line), ps (dotted line), and ns (thick solid line) laser irradiation. Thin solid line, binodal;
dashed line, spinodal; cross, critical point. L, liquid; G, gas. Reprinted with permission from ref 759. Copyright 2003 American Physical Society. (c)
Intensity of the absorption spectra (productivity) of colloidal gold as a function of the pulse energy for pulse durations of 1 ps and 150 fs. Reprinted with
permission from ref 386. Copyright 2012 Institute of Physics.

point, especially for fs lasers.395 Hammer et al. demonstrated that they are used, thermal effects or a solid−vapor transition may
the energy threshold of laser-induced breakdown in water for ns occur depending on the pulse duration. The threshold is closely
lasers is higher (∼10−4 J for 5 ns) than that of ultrashort lasers related to the electron−phonon relaxation time, which is particle-
(∼10−6 J for 3 ps to 300 fs),753 whereas Ganeev et al. reported size dependent and is typically on the order of several ps (e.g., Au,
that slow thermal-induced self-defocusing processes occur as well 3−4 ps;755 Cu, 1−4 ps;756 Si, 0.35 ps;757 ZnO, 0.5 ps,758 with
when the pulse duration is on the ns scale.754 Both studies values depending on experimental setup and mathematical
indicated that different energy attenuation mechanisms arise for function). Lorazo et al. identified the thermodynamic pathways
different pulse durations during LAL. of the ablated material for short and ultrashort pulsed laser
The effects of the pulse duration are dependent on the electron ablation using a combined MD and Monte Carlo approach
cooling time (electron−phonon coupling constant) of the (Figure 57b).759 The same trend was also reported by Lewis and
material. For fs lasers, the pulse duration is shorter than the Perez using an MD model.760,761 According to their simulations,
electron cooling time; thus, the electron−lattice (phonon) fs laser ablation induces isochoric heating followed by fluence-
coupling is negligible, and the ablation process can be considered dependent mechanisms, including spallation, phase explosion,
as a solid−vapor transition.328 Fs laser−matter interactions are fragmentation, and vaporization plasma ablation.100 Extending
common when the intensity exceeds 1013 W/cm2, at which point the pulse duration to the ns regime leads to a situation in which
any dielectric can be fully ionized in the interaction zone. the materials are heated along the solid−vapor and liquid−vapor
Kabashin and Meunier experimentally confirmed that the coexistence lines (binodal).
thermal-free mechanism dominates the fs laser ablation of gold The pulse duration also affects the ablation thresholds of
in water, leading to the formation of small (3−10 nm) gold metallic and dielectric materials. Preuss et al. demonstrated a 2
colloids at low fluence.194 However, when the laser fluence is orders of magnitude reduction of the ablation threshold for
high (e.g., F > 400 J/cm2), plasma-induced heating and ablation nickel films by decreasing the pulse duration from 14 ns to 0.5
are triggered and result in a bimodal particle size distribution. ps.763 Link et al. discovered that the threshold for the complete
The ablation process associated with ns pulses is believed to be a melting of gold nanorods into nanodots for 100 fs pulses was 100
thermal ablation process involving laser heating and laser times lower than that for 7 ns laser pulses.286 Gamaly et al.
melting. Ps lasers lie between fs lasers and ns lasers, and when calculated ablation thresholds and ablation rates for metals and
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Figure 58. Effect of the pulse duration on LPC-induced cavitation bubbles. (a,b) Schematic comparison of thermo-mediated and plasma-mediated
nanocavitation mechanisms. Adapted with permission from ref 765. Copyright 2014 American Chemical Society. (c) Simulated temporal evolution of
electron temperature Te (dashed red curve), lattice temperature TL (solid black curve), and maximum water temperature Tm at the NP−water interface
(dashed−dotted blue curve) for a 55 nm-diameter gold sphere absorbing a 150 fs laser pulse (full-width at half-maximum [fwhm] of the Gaussian time
profile) at 400 nm and a laser fluence of 10 mJ cm−2 (Pmax = 6.3 × 1010 W cm−2). Horizontal lines represent the temperatures corresponding to Tce,
electron temperature; Tbp, boiling point of bulk gold (∼3100 K); Tmp, melting point of bulk gold (1336 K); Tcp, critical point of water (647 K); and Tcav,
cavitation threshold (573 K). Adapted with permission from ref 221. Copyright 2012 Elsevier.

Figure 59. Comparison of fs lasers and ns lasers for biomedical applications. (a) Maximum temperature increase of (*, Te) electrons, (●, Tl) lattice, and
(■, Tm) water at the Au/water interface for different fluence levels. (b) Maximum temperature increases on the surface of Au nanoshells in water as a
function of the fluence of a 5 ns laser pulse at 800 nm. Adapted with permission from ref 770. Copyright 2015 Elsevier. (c,d) Particle size distributions of
laser-fragmented naproxen obtained by fs and ns laser irradiation. Adapted with permission from ref 480. Copyright 2014 Springer.

dielectrics that agreed with the experimental results,762 as shown 3 λn


Fthm ≡ (εb + εesc) e
in Figure 57a. Clearly, the laser ablation fluence thresholds of the 8 2π (1)
target for ps and fs lasers are similar and are well below the value
for ns laser ablation. Additionally, the ablation threshold 3 ln
Fthd = (εb + Ji ) s e
increases as the pulse duration increases from the ps toward ns 4 A (2)
domains, with the tipping point at ∼100 ps. Thus, a ps pulse
(κt p)1/2 εbna
duration may be a good compromise between high ablation Fth ≈
efficiency and moderate system investment costs. The ablation A (3)
thresholds of metal and dielectric materials for ultrashort laser where Ji is the ionization potential, εe is the electron kinetic
pulses are calculated according to eqs 1 and 2, and the ablation energy, εesc is the work function, tp is the pulse duration, ne is the
threshold for long pulses is described by eq 3 number density of free electrons, na is the number density of
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atoms in the target, ls is the skin-depth, and A is the absorption optoporation (section 6.4.5). In addition, fs lasers are more
coefficient. A low ablation threshold and a higher laser fluence efficient than ns lasers for pharmaceutical applications in the
substantially increase (3 orders of magnitude larger762) the context of drug micronization (Figure 59c,d),480 and thus the fs
ablation efficiency of fs laser ablation relative to that of ns laser laser excitation of NPs is a viable tool for biomedical applications.
ablation.357 The quantitative pulse duration effect in the ablation Despite being physically less efficient, ns lasers for optoporation
efficiency observed experimentally is lower in liquid than in air can be very compact (e.g., microchip lasers) and can be easily
but still pronounced.386,400 Riabinina et al. reported that LAL integrated into live-cell imaging instruments.772
productivity using a 1 ps laser is 20−30 times higher than that Microsecond pulsed lasers have much longer lattice heating
obtained with a 150 fs laser (Figure 57c), as indicated by the times than short (ns) or ultrashort (ps and fs) pulsed lasers and
absorption intensity of the colloid.386 By investigating the NP have been less extensively studied in the context of LSPC.
concentration (deduced from the absorption intensity) with Examples include fcc silicon crystals137 and nanodiamonds.773
pulse durations from 40 fs to 200 ps, they also found that a pulse CW laser-induced NP fabrication140 is a separate branch of the
duration of 2 ps is optimal for maximizing the Au NP LSPC tree relative to pulsed lasers because it occurs via a purely
productivity; below this pulse duration, photoionization photothermal process.774 The CW laser excitation of particles
attenuates the beam at 5 mJ (Figure 31f). Saraeva et al. observed reveals how particle surfaces evaporate,139,775 and varying the
a minimum Au NP productivity at approximately the same pulse exposure time and laser intensity may help elucidate the
duration value,764 which coincides with the electron−phonon nanoscale cooling effects of substrates and the surrounding
coupling time of Au. However, they used a 500-kHz laser system media for a single gold NP.776 Figure 60a,b shows that the
causing LFL of the LAL-generated particles.764 These two temperature distribution of Au NPs strongly depends on the
opposite pulse-duration dependencies indicate that high LFL difference in the thermal conductivity between the substrate and
efficiency decreases LAL efficiency at high repetition rates. the liquid medium.776 The rate at which the temperature
Because of the higher ablation efficiency of fs lasers as increases in a Au particle on a glass substrate (Figure 60a) in
compared to ps and ns lasers, the efficiency of fs LSPC has also water at a defined laser power is substantially higher than that of a
attracted substantial attention and was reviewed by Tan et al. in Au particle on a sapphire substrate (Figure 60b) in water for
2013.100 Recently, Meunier and co-workers reported that irradiation with ∼30 K·μm2/mW, respectively (Figure 60c), and
plasma-mediated nanobubbles (Figure 58b) could be generated ∼6 K·μm2/ mW (Figure 60d). When the laser intensity is above
from plasmonic Au NPs using a fs laser with a considerable the evaporation temperature of gold, the particle will undergo
discrepancy between the ps−ns laser thermo-mediated nano- explosive splitting and generate many small hot droplets that
bubbles (Figure 58a).765,766 The dimensions of the plasma- immediately solidify. Higher CW laser intensities and longer
mediated nanobubbles depend on the pulse polarization, and exposures lead to stronger particle evaporation and the
linear polarized pulses caused larger bubbles than circular ones. generation of abundant smaller particles.139
Hashimoto et al. theoretically demonstrated the electron The LAL processing time using a CW laser is limited by liquid
relaxation dynamics of a Au NP as a function of time after 150 boiling because of the heat transfer from the target to the
fs laser pulse irradiation using the two-temperature model and liquid.777 However, CW lasers are less costly than pulsed lasers
concluded that photothermal bubble formation occurs over with the same output power and may be competitive for future
several tens to several hundreds of ps upon laser excitation and is NP production if the problem of liquid heating during CW LAL
associated with heat dissipation from the phonon of the Au NPs can be solved.
to the liquid medium (Figure 58c).221 Note that bubble In laser precision manufacturing, ultrashort pulses are often
formation will shield the pulse energy, leading to reduced laser the first choice, although applications are sometimes limited by
transmittance; this phenomenon is termed optical limiting (see the higher laser system price as compared to ns lasers. However,
section 6.2.4).603,767 A laser fluence of 10 J/cm2 was found to high-power ps and fs lasers are currently available (see section 4
induce the optical limiting effect for a 3 ns laser at wavelengths of on upscaling), and the costs of some ps lasers are already similar
532 and 1064 nm during the laser irradiation of LAL-generated to those of high-quality ns lasers. Thus, in the future, the laser
Au, Ag, and AuAg NPs.768 Also, optical limiting in laser- pulse duration may be primarily determined by the application.
generated colloids was observed for laser fluences <1 J/cm2 with Because a liquid is present during LSPC, linear (refraction and
ns-lasers769 as well as ps-lasers.692 Please note that laser fluence absorbance) and nonlinear (self-focusing and multiphoton
and pulse duration are the relevant laser parameters for nonlinear absorption) effects must be considered. Minimizing the laser
optical effects. Moreover, the optical limiting effect is also interaction with the liquid and dispersed NPs during LAL would
concentration dependent: Higher particle concentrations lead to require longer pulse durations with intensities below the Kerr
greater energy attenuation.640 This is an important issue that limit of the colloid. On the other hand, because ns laser ablation
must be considered when upscaling NP productivity (see section may cause heat accumulation at the target and heat transfer to the
4) because less laser energy is available for LAL. Consequently, liquid, gradually generating destabilized colloids, ps pulses may
draining the colloids away from the laser beam pathway is a good be a good compromise. Very short pulse durations excite the
strategy, as discussed in section 5.3.5. liquid before reaching the target, which is often unintended
By comparing the rate of the maximum temperature increase during LAL but desirable for LFL. In the context of fs-LAL, liquid
in hollow Au shells, Meunier’s group reported that fs laser excitation may be minimized by adjusting the liquid level height
irradiance is much more efficient (113 K cm2/mJ, Figure 59a) (section 5.3.4) to increase the target ablation efficiency of
than irradiance from a CW laser (32.5 K cm2/mJ) or a ns laser ultrashort pulses.
(3.4 K cm2/mJ, Figure 59b).770 This finding indicates that the 5.4.2. Laser Wavelength. The laser wavelength (λ) of
fluence required for a plasmonic NP to reach a certain incident beams has multiple effects on LSPC. Because the
temperature is substantially lower for fs pulses than for ns or ablation threshold is proportional to the laser wavelength for
CW laser irradiation. This result is valuable for biomedical metals,762 longer wavelength lasers typically have higher ablation
applications,771 such as photothermal cancer therapy and cell thresholds. Additionally, the laser wavelength determines the
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skin depth (penetration depth) and, consequently, the ablation


depth. As quantified by the skin depth δ = (2/μσω)1/2, where μ is
the target permittivity, σ is the target conductivity, and ω is the
electromagnetic field angular frequency, the penetration depth of
a 532 nm pulsed laser in the target is less than that of a 1064 nm
pulsed laser, which indicates that the ablated mass per pulse may
increase with the laser wavelength (if reflectivity is the same at
both wavelengths). However, LAL results frequently deviate
from the expectations derived from fundamental laser ablation
physics. Tsuji et al. reported that the ablation efficiency at higher
wavelengths was higher for silver NPs for 12 mJ/pulse and an
ablation time of 30 min (Figure 61b).335 This finding is further
supported by the work of Patra et al., who performed LAL of
NiTi in water778 (Figure 61a). A better understanding of the
wavelength dependence of the LAL efficiency can be achieved by
examining the NP size distributions obtained at different
wavelengths. Generally, NPs synthesized by LAL at higher
wavelengths are larger than those obtained using lower
wavelengths; examples include Pd NPs (Figure 28a),314 Cu
NPs,327 Ag NPs,779 and Au NPs.334 However, this size reduction
is most likely caused by LFL, is inevitable in LAL batch processes,
and is usually amplified by shorter wavelengths. This behavior
can be attributed to the higher absorbance of the colloids at lower
wavelengths, in which the energy is consumed by the
fragmentation of the already formed particles, reducing the
energy available for the ablation process. Note that the
absorption of different wavelengths by NP may cause crystal
phase differences in the synthesized NPs (e.g., N4Ti3 and Ni3Ti at
355 nm; Ni3Ti and NiTi at 532 nm; NiTi at 1064 nm achieved at
40 J/cm2).778 Matsutani et al. demonstrated a wavelength
dependence of polyyne synthesis via LAL of graphite pellets in n-
hexane: The highest mass was achieved at 1064 nm, whereas at
355 nm, a lower productivity was observed because of the
Figure 60. CW laser heating of NPs. (a,b) Computationally determined increasing decomposition rates of C20H2 and C22H2, resulting
2D temperature distributions of a laser-irradiated Au NP (100 nm in from their absorption of ∼355 nm laser light.780
diameter) on glass and sapphire in water. (c,d) Temperature of the Au The role of the laser wavelength also varies with the pulse
NP as a function of the laser intensity for water/glass and water/ duration. For ultrashort pulses, multiphoton absorption may be
sapphire substrates. Reprinted with permission from ref 776. Copyright the predominant ablation mechanism. The laser pulse-induced
2013 American Chemical Society. (e) A series of SEM images of single electron density n0 depends on the photon energy E and the
Au NPs supported on a glass substrate after irradiation in water for number of photons (N).781 Shorter wavelength laser pulses with
various durations (125 μs, 10 ms, and 5 s) using a CW laser at various higher photon energies (the photon energies at 532 and 1064 nm
laser peak-power densities (10, 20, 30, and 40 mW μm−2). Scale bars:
are 6.4 and 3.2 eV, respectively) are more likely to trigger
100 nm. Reprinted with permission from ref 139. Copyright 2014 Royal
Society of Chemistry. multiphotonionization. Using PAMAM as a stabilizer for gold
NPs, Giusti et al. conducted multiphoton 532 nm ps-LFL and

Figure 61. Effect of the laser wavelength. (a) Variation in the synthesized NiTi NP mass as a function of the laser pulse fluence at different wavelengths.
Reprinted with permission from ref 778. Copyright 2016 Elsevier. (b) SEM images and extracted size distributions of Ag NPs synthesized by LAL at
1064, 532, and 355 nm. Reprinted with permission from ref 335. Copyright 2002 Elsevier.

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characterized the resulting UV−vis spectra. No multiphoton reverse configuration, Cu@Cu2O, arose because of the oxidation
fragmentation was assumed at 1064 nm.132 Intuitively, LPC in of the formed Cu NPs. They also reported that the shell thickness
the UV−vis range is more efficient than that in the IR range of the core−shell Ag@Ag2O NPs was inversely proportional to
because of the higher excitation at the interband or the plasmon the fluence,63 which is very different from the typically formed
resonance of the NPs.782,783 In summary, decreasing the laser Zn@ZnO core−shell NPs, in which the shell thickness increases
wavelength results in higher photon energies and, thus, a higher as the laser fluence increases (Figure 63a−d).786,787 As
probability for multiphotoionization and more efficient mentioned above, LAL and LFL cross-effects are inherent in
excitation, which may be useful for LFL. During LAL, decreasing such studies. One important issue is the laser fluence threshold,
the wavelength leads to smaller particle sizes because of which corresponds to the liquid’s optical breakdown. Above this
simultaneous LFL. However, in both cases, the laser power value, the abundance of reactive oxygen species is dramatically
decreases with the wavelength, which in turn decreases the increased, increasing the oxidization of Al NPs in water during
productivity of the process. As a result, in LAL, the fundamental LAL.788 Water breakdown allows the ratio of ZnO to ZnOOH
wavelength, which is normally between 800 and 1064 nm, is products to be tuned626 and, potentially, the PL properties of
typically used to achieve maximum productivity, whereas for LFL ZnO NPs to be tailored from violet to green emission.789
and LML, the wavelength with the maximum excitation When the focus is below, just on, or above the target, both the
efficiency for the educt NPs (e.g., UV for semiconductors, 532 laser fluence arriving at the target394,790 and the ionization degree
nm for gold, UV−vis for Pt) is preferred. of the surrounding liquid medium and the strength of the shock
5.4.3. Laser Fluence and Focusing. Laser fluence and laser waves vary,791 creating an opportunity to change the particle
output power are the two most important factors for increasing morphology, phase, and size.792,793 However, the detailed
fabrication throughput. As described in section 4, which mechanism is not yet understood. For example, the tightly
addresses upscaling, the laser fluence is a crucial laser parameter focused condition favors the formation of rutile TiO2794 and
that determines the LAL efficiency, regardless of the pulse CuO,795 whereas defocusing leads to the formation of smaller
duration. Above the ablation threshold, increasing the laser anatase TiO2794 and CuO2,795 attributed by the authors to
fluence gradually increases the LAL productivity until limitations, insufficient oxidation and the rapid cessation of particle growth.
such as the optical breakdown point, are reached.21,379 As For the LPC processes, laser fluence is a critical factor to tune
discussed in section 2.1, NP productivity is governed by the the size and composition efficiently. Figure 63e−h shows the
cavitation bubble. In general, the cavitation bubble lifetime morphologies of indium tin oxide (ITO) particles before and
increases with the laser fluence, and as a result, when the pulse after laser fragmentation at different fluence levels and the
interval (determined by the repetition rate of pulsed lasers) is corresponding variation of absorption coefficient α of the ITO
faster than the bubbles’ lifetimes, the bubbles substantially shield NPs.673 A vague halo was observed by the Koshizaki group for
and reflect the incoming pulse, reducing the ablation rate. To the irradiated NPs above 20 mJ/pulse (Figure 63g). At 150 mJ/
maximize NP productivity, the cavitation bubble induced by the pulse, small (3.0 nm) ITO particles were obtained (Figure 63h),
former pulse must be temporally (by using a moderate repetition and higher laser fluence levels effectively increased the optical
rate) or spatially (by increasing the scan speed) bypassed. When band gap for ITO NPs (Figure 63e).673 As compared to LFL, the
the cavitation bubble is completely bypassed, the laser ablation low laser fluence used for LML results in the photothermal
law established for laser machining in air784 can be used to reshaping285 and photomelting of raw materials, producing
describe LAL as well,22 and the maximal ablation rate perfectly spheres with smooth surfaces.515 The laser fluence is a key factor
coincides with e2·ϕth (Figure 62), with e being the Euler constant for controlling the SMS size via LML: Higher laser fluences lead
and ϕth the threshold fluence.22 to the formation of larger SMSs,272,279 as illustrated in Figure
28e,f. Note that for either fusion or reshaping LML, the laser
fluence should be precisely controlled between the melting and
evaporation thresholds;796 otherwise, if the laser fluence is too
high, the size of the synthesized NPs will be dramatically reduced
by LFL,272 possibly resulting in a bimodal distribution (e.g., 70
and 500 nm TiO2 SMSs obtained at 225 mJ cm−2 pulse−1).797
The phase transformation (e.g., CuO → Cu2O/Cu) during
reductive LML also depends on the laser fluence,59 as shown in
Figure 63i. A similar trend was observed during LML of FeOx, in
which FeOx was first reduced into FeO and finally into Fe SMSs
Figure 62. Specific ablation rate of a copper target as a function of the via gas phase (vapor)-mediated reactions in the bubbles.409
laser fluence at 1.2, 2.7, and 10.1 MHz. Adapted with permission from ref Rehbock et al. reported that laser fluence could significantly affect
22. Copyright 2016 Optical Society of America. the surface texture, with the resulting ligand-free Au SMSs
exhibiting wrinkled surfaces: Higher fluence values result in
rougher SMSs,271 as shown in Figure 63j−l. In addition to the
Also, extensive research efforts are currently underway to study smoothening of faceted gold NPs,285 laser melting also enables
the laser-energy-dependent modulations of morphologies and the transformation of gold nanorods into banana-shaped NPs as
NP phases. Scaffardi and co-workers found that an energy a function of the laser fluence and irradiation time.798 Relatively
threshold existed that determined the types of core−shell NPs by high laser fluence (3.6 mJ cm−2) leads to the breaking of single
fs laser ablation of a copper target.785 They showed that beyond nanorods and their subsequent reshaping into banana-shaped
this threshold value, the Cu2O@Cu core−shell configuration NPs because of surface defects, whereas no banana-shaped NPs
dominates because of the initial complete oxidization of CuNPs were obtained using a moderate laser fluence (1.4 mJ cm−2). In
and subsequent surface reduction of Cu2O to Cu at high summary, higher laser fluence values result in higher NP
temperatures (over 500 °C), whereas, below this value, the productivity for LAL and larger SMS by LML; however, high
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Figure 63. Effect of the laser fluence or pulse energy on the NP morphology during LAL, LFL, and LML. (a) Shell thickness of ZnO NPs versus the
applied laser power and (b−d) HRTEM images of NPs obtained at different LAL energies: 70, 50, and 35 mJ/pulse. Reprinted with permission from ref
787. Copyright 2007 American Chemical Society. (e) Variation of the square of the absorption coefficient α2 of indium tin oxide (ITO) colloids with
different photon energies obtained at different LFL fluence values. (f−h) TEM images of raw ITO NPs and the LFL-synthesized ITO NPs at 20 and 150
mJ/pulse, respectively. Reprinted with permission from ref 673. Copyright 2006 American Chemical Society. (i) Laser fluence-dependent phase changes
of CuO during LML. Reprinted with permission from ref 272. Copyright 2010 Wiley-VCH. (j−l) SEM images of ligand-free Au-SMSs with smooth and
rough surface textures acquired at LML fluence values of 40, 60, and 80 mJ cm−2, respectively. Adapted with permission from ref 271. Copyright 2014
Chemical Society of Japan.

Figure 64. Effects of the beam angle and profile. (a−c) Schematic diagram depicting the effects of solution pH and target inclination. Adapted with
permission from ref 457. Copyright 2013 Elsevier. (d) Average size of Ag NPs prepared by laser ablation at different angles. Adapted with permission
from ref 799. Copyright 2014 Elsevier. (e,f) Geometry of a focused Gaussian pulse using a conical lens (axicon) and formation of a Bessel beam pattern
and UV−vis absorption spectra of Ag colloids prepared in water at different laser energies. Reprinted with permission from ref 197. Copyright 2015
Institute of Physics.

fluences may trigger LFL, and elevated oxidation effects of water operators. When the laser beam is vertical relative to the target
breakdown or byproducts from the decomposition of non- surface, the energy of the second pulse may be consumed by
aqueous liquid molecules may cause contamination. bubbles rising vertically or the previously formed particles or
5.4.4. Spatial Laser Pulse Delivery. In addition to aggregates along the propagation pathway of the first pulse,
modulating the laser parameters before preparing NMs, the resulting in the fragmentation of the irradiated particles and the
experimental configuration, pulse profile, scanning methods, and reduction of the pulse energy incident on the target surface.457
beam delivery must also be considered. Most experimental This phenomenon is especially apparent when the pH is in the
configurations for LSPC involve a laser transmitting vertically range of pHPZC ± 2 (Figure 64a), where pHPZC is the pH value of
down to the horizontally configured targets because of the zero charge at which condition particles become easier to
simplicity of using open vessels and the high beam safety for the agglomerate, as determined by Al-Mamun et al. by LAL of a
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Figure 65. Effect of orthogonal DP-LAL. (a,b) TEM images of Au NPs ablated in distilled water containing 1 wt % starch by single-beam LAL and
orthogonal DP-LAL, respectively. Adapted with permission from ref 715. Copyright 2014 Annex Publishers. Effect of collinear DP-LAL. (c) Absorbance
(I) of AgNPs in water, silver mass concentration (II), Ag ablated mass per laser shot (III), and molar concentration of NPs (IV) of solution ns obtained
by SP-LAL and DP-LAL as a function of the interpulse delay. (d) Number size distributions obtained by dynamic light scattering (DLS) experiments for
AgNP solutions obtained by SP-LAL and DP-LAL at two representative interpulse delays. Adapted with permission from ref 390. Copyright 2013 Royal
Society of Chemistry.

corundum target with a ns laser in water.457 To reduce the of a precipitated powder target from the bottom of a piriform
shielding effect of the agglomerated particles, the pH value can be flask may be a good strategy.801
adjusted to enhance the surface charge of the particles (Figure Gaussian pulses focused by a convex lens constitute the most
64b). However, in this case, although the particles are highly frequently used laser beam configuration. A Gaussian distribu-
disperse, some particles will still exist along the beam path. To tion has its highest energy in the center beam axis, and, outward,
further reduce the laser shielding effect, inclined irradiation can the energy gradually decreases, which may trigger energy-
be used to enable the second pulse to bypass the particles dependent laser ablation in the local area. A preliminary study
synthesized by the first pulse (Figure 64c).457 Similarly, Krishna investigated nondiffracting Bessel beams (Figure 64e), which
Podagatlapalli et al. also reported that changing the incident exhibit nearly constant intensity profiles and constant fluence
beam angle toward the target alters the particle size, yield, SPR along their propagation in the focal volume because of axicon
position, and SERS response, with the smallest Ag particles focusing.197 Podagatlapalli et al. used a repetition rate of 1 kHz
produced at an angle of 30° (Figure 64d).799 Tilting the angle can and assumed that the Bessel beam may have affected LFL and
also be realized by inclining the target. Moreover, varying the LAL, as deduced from the absorption spectra of Ag NPs obtained
incident angle was also shown to cause broadening of the laser at different pulse energies (Figure 64f).197 This work may trigger
spot from a circular to oval shape, thereby reducing its fluence further studies in which the beam profile is varied. Under Bessel
decreasing the NP size and its standard deviation.457 This beam exposure, the formation process and dynamics of the
phenomenon was shown for alumina NPs, and the smallest value cavitation bubble should also change and need further
was achieved at an incident angle of 30°. Al-Mamun et al. also investigation. One clear advantage of using a Bessel beam over
conducted a control experiment with reduced fluence at a fixed Gaussian focusing during LAL is that the exact positioning of the
angle of the incident laser, which resulted in the opposite effect target at a defined distance from the geometrical focal plane (with
(larger NPs).457 Laser sources generally emit their beams a small depth of focus, the so-called Rayleigh length) is no longer
horizontally, and arranging the target plane vertically will allow necessary because the depth of constant fluence is significantly
bubbles rising from the target surface to naturally move away increased. Because fluence gradients also define the postirradia-
from the beam path (instead of toward it, as occurs when the laser tion conditions, axicon focusing may be an option for future LFL
is focused from above) by the buoyant force, thereby maximizing studies.
the ablation productivity by minimizing bubble scattering (see Double-pulse (DP)-LAL is a LAL technique in which two
section 4, Upscaling). This can be easily realized in cuvettes800 or consecutive pulses are delivered in either an orthogonal or a
flow chambers.363 To augment the NP yield by LFL, irradiation collinear configuration.149,179,802,803 In orthogonal DP-LAL, two
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Figure 66. (a,b) Mean Ag-NP size and zeta potential as functions of the repetition rate during 532 nm LAL (60 mJ/pulse; 10 ns) in an aqueous starch
solution (1 wt %) or distilled water. Adapted with permission from ref 806. Copyright 2013 Dovepress. (c) The productivity of copper-PLAL as a
function of laser fluence for repetition rates of 1.2, 2.7, and 10.1 MHz. The circle indicates the threshold fluences. Adapted with permission from ref 31.
Copyright 2016 Institute of Physics.

laser beams are intercrossed above the target surface at an angle 66b. This finding highlights the possibility of controlling the
of 90°; one beam is used to ablate the target, and the other beam stability by adjusting the repetition rate; however, further study is
is used to irradiate the plasma plume or bubble after an required to explain this phenomenon fully. Increasing the
appropriate delay.804 The size distributions of gold particles repetition rate also increases the Ag NP size in both cases (Figure
synthesized by DP-LAL in chitosan and starch are narrower 66a), in accordance with the trend observed by Darroudi et al.
(Figure 65a,b) than those of particles prepared by single-beam regarding the Ag NP size synthesized by ns LAL of silver in
ablation because the second beam induces the fragmentation.715 gelatin sol because of the initiation of laser melting at high
Collinear DP-LAL allows the second pulse to affect the repetition.349 In contrast, increasing the repetition rate may
oscillation of the cavitation bubble induced by the former laser reduce the Au NP size during fs LAL because of the decreased
pulse during its ∼200-μs lifetime without changing the repetition pulse energy.807 Zamiri et al. also observed increased NP
rate during laser ablation; it also permits one beam to interfere productivity as the repetition rate was increased from 10 to 40
with the previous pulse’s bubble at a defined interpulse delay to Hz806 because the interpulse interval (25−100 ms) was sufficient
increase LAL productivity (Figure 65c). These effects alter the to bypass the cavitation bubble, which had a lifetime <1 ms.183,209
NP size and productivity as compared to those of normal, For higher repetition rates, more sophisticated laser scanners are
successive pulse-generated NPs (Figure 65d).390 This method required. Physically, the incident beam is shielded by the
may also affect the composition of the NPs, as is standard for Si cavitation bubble, and bubble-rebounding oscillation,504 the
colloids synthesized by DP-LAL with an interpulse delay time of ejection of daughter bubbles, and the presence of ablated matter
∼5 ns.802 The PL emission intensity of the DP-LAL-synthesized in the path of the subsequent incident pulse limit the maximum
Si NPs is much greater (approximately 5−10-fold) in the 550− effective repetition rate. A certain temporal repetition delay is
700 nm region than Si-nc NPs obtained by SP ablation, possibly required to allow the transmission of a subsequent pulse to the
because of the different types of Si−OH surface terminations that
target without excessive intensity attenuation. Consequently, an
protect the nanocrystal core upon inward oxidation.802
optimal repetition rate is expected to exist for each intensity−
Multiple/double-line laser ablation, which draws periodic lines
liquid−material system. Note that if the second pulse arrives
with a given pitch on a target surface, facilitates decreasing the
during the cavitation caused by the first pulse, ablation shielding
ablation threshold relative to single line ablation because of the
inhomogeneity of the tips and microprotrusions formed on the occurs, shortening the lifetime of the second bubble because a
target surface.692 Consequently, the NP productivity is increased, lower pulse energy results in a decreased cavitation bubble
and their nonlinear performance and SERS intensity are size.397 This repetition rate-induced bubble fluctuation will
enhanced.692 Regardless of the type of line scan strategy continue until it reaches the steady state after several pulses.
employed, the machining speed that determines the “pulse When the repetition rate is ≤1 kHz, NP productivity increases as
overlap” is another factor affecting LAL.379,805 the repetition rate increases, even at high pulse energies (see
5.4.5. Repetition Rate. The repetition rate, which is defined section 4.1).
as the number of output pulses per second, exerts both technical If repetition rates in the (tens of) kHz or even in the MHz
and physical-chemical effects on the LSPC process. From a regime are desired, the pulse energy must be decreased to reduce
technical viewpoint, laser investment scales with power. the size and lifetime of the cavitation bubble or the relative
Additionally, at a given power, decreasing the repetition rate movement speed between the beam and the target must be
increases the pulse energy, yielding a higher ablation rate per substantially increased (see section 4).22 In the MHz range, heat
pulse (and larger cavitation bubbles) because of the higher laser accumulation (incubation) reduces the threshold fluence392 and
fluence. The effect of the repetition rate can only be precisely increases the NP ablation rate (Figure 66c).31 In summary, the
determined at a fixed pulse energy. For example, Zamiri et al. repetition rate is an important factor, and its order of magnitude
investigated the influence of the repetition rate on the NP is often set by the selection of the laser type or model. For a given
throughput, size, and surface charge during LAL of Ag in water pulse energy (and material/liquid), an optimal repetition rate
with starch at repetition rates of 10−40 Hz with a pulse energy of that maximizes material ablation should exist, and increasing the
60 mJ (Figure 66a,b).806 They found that an optimal repetition repetition rate beyond this value will primarily contribute to
rate exists in terms of the liquid-dependent NP stability, as colloid excitation or beam−cavitation interactions if a fast laser
revealed by the zeta potential measurements shown in Figure scanner is not used.
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6. APPLICATIONS shell or with defects, which are all properties highly relevant for
As shown in the previous sections, LSPC has recently become a applications in optics (section 6.2). Among the most utilized
mature method for the scalable and continuous synthesis of properties of laser-generated nanoparticles is their high-purity
various size-controlled nanomaterials. Accordingly, the next surface, which leads to their use as toxicity reference materials, a
natural step for LSPC-generated nanoparticles is their utilization featureless spectral background, higher catalytic activity, and
in real-world applications (Figure 67). In addition to their ability greater adsorption efficiency, and can thus be exploited for
applications in biology (section 6.4), analytical chemistry
(section 6.5), catalysis and energy (section 6.6), and environ-
mental protection (section 6.7). Herein, we summarize selected
applications in the seven aforementioned fields in which the
advantages of using LSPC nanoparticles are evident.
6.1. Magnetism
Magnetic nanoparticles (MNPs) have attracted widespread
interest over the past decades, in particular because of their
promising applications in biology and biomedicine.808 Because of
the high flexibility in combination of material and liquid, the
number of LSPC-synthesized MNPs has been rapidly increasing,
and a large variety of MNPs have been synthesized, including
Figure 67. Word cloud showing applications of LSPC-NP reported in elemental NPs (e.g., Co,809 and Ni628), oxide MNPs (e.g.,
the literature. The larger is the size of a word, the greater is the number of Mn3O4,810,811 FeOx,198,541,620,812−817 NiO,41 Y3Fe5O12,818
mentions in the literature. Zn1−xMnxO,128 and TiFeOx653), carbide MNPs (e.g., Fe3C819
and Co3C820), and alloy MNPs (e.g., AuCo,821 AuFe,173,418,822
to match the performance of conventionally synthesized colloids AuNi,426 FeNi,539 NiCo,809 and NiMnIn823), as shown in Table
for their intended applications, LSPC-generated NP dispersions 5. LSPC is especially strong in producing alloy MNPs as well as
can also exploit the unique properties that result from their oxide and carbide MNPs through RLAL in combination with
formation process. “Convenience” is an advantage of both the hydrolysis or decomposition of liquid (e.g., water,824 organic
synthesis process and the synthesized particles. First, using LSPC solvents,198 etc.). Accordingly, adjusting the liquid composition
is convenient because of its simple and scalable experimental enables one to obtain different kinds of MNPs (Table 5) easily.
setup, which consists of a laser source, a liquid-containing vessel, For example, the Fe2O3 and Fe3O4 mixture,815 the Fe3O4 and
and a target. Second, LSPC is a convenient method for Fe3C mixture,819 and the Fe@FeOx core−shell particles198 are
synthesizing nanoparticles that are difficult to synthesize using synthesized by RLAL of a Fe target in water, ethanol, and
conventional methods, such as alloy nanoparticles that can be tetrahydrofuran (THF), respectively. The crystal phase and
used in magnetism- (section 6.1) and plasmonic-related particle interface of the synthesized MNPs are crucial to
applications (section 6.3). Additionally, laser-generated NPs obtaining high magnetism as shown by Zhang et al., who
are intrinsically charged and can also be generated with a carbon reported that Fe@Au core−shell NPs have a mass magnetization

Table 5. MNPs Prepared by LSPC

target liquid method products


Au and Co−oxide NPs ethanol LML AuxCoy821
AuxFey bulk alloy targets ethanol, acetone LAL Fe11Au89,173,822 Fe@Au418
Co targets water, ethanol, acetone LAL Co,809 CoO,824,836 Co3C820
combined Gd−Si targets ethanol LAL Gd5Si4839
Fe targets ethanol, water, THF, acetonitrile LAL Fe3O4, Fe3C;819 Fe2O3;812 Fe3O4;814 FeOx (Fe3O4, Fe2O3, FeO, Fe);815
(AN), DMF, DMSO, toluene, Fe3C, Fe3O4, γ-Fe2O3, Fe@ Fe3O4;198,837α-Fe2O3, γ-Fe2O3;817 Fe3C;833
ethanol FeO, Fe3O4813
Fe50Mn50 bulk alloy targets ethanol LAL Fe-rich FeMn@FeMn2O4416
Fe52Ni48 and Sm2Co17 targets cyclopentanone, acetone LAL FexNiy356,539
Gd targets water, DEG LAL Gd2O3826,828,838
Gd2O3 targets Gd2O3 and water LAL Gd2O3@SiO2;840,841Gd2O3:Tm3+, Gd2O3:Tb3+, and Gd2O3:Eu3+829
(Tm2O3, Tb2O3, and Eu2O3)
powders
Mg, Zn, and Ti targets ethanol, water, mercaptoethanol LAL TiO2 and ZnO;441 MgO, Zn@ZnO, and ZnS43
Mn targets water/water−ethanol mixtures LAL Mn3O4;416,810,811 Mn2O3 and Ramsdellite γ-MnO2416
Nd2Fe14B powders cyclohexane LFL Nd2Fe14B800
Ni powder/suspended Ni water/ethanol/liquid CO2 LFL/LML/LAL Ni,628 Ni@NiO,261 NiO41,61
particles/Ni targets
NiAl2O4 powders water LFL NiAl2+xO4, Ni:γ-Al2O3, Al:NiO, and β-Ni(OH)2202
Ni50Co50 targets ethylene glycol LAL NixCoy809
Ni50.3Mn33.7In16.0 alloy targets water LAL Ni−Mn−In823
titanium and iron rods water LAL TiFeOx653
Zn1−xMnxO (x = 0.05−0.1) water LAL ZnMnO128
targets

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Figure 68. LSPC-synthesized MNPs for MRI-related and multimodal applications. (a) Illustration of high longitudinal relaxivity (r1) of ultrasmall
Gd2O3 nanoparticles (hydration number of two for each Gd3+ on the surface of Gd2O3) as compared to Gd-DTPA (hydration number of one for Gd3+).
Reprinted with permission from ref 826. Copyright 2013 American Institute of Physics. (b) MRI-CT-SERS performances using LSPC-synthesized
Au89Fe11 NPs. Adapted with permission from ref 822. Copyright 2014 Wiley-VCH. (c−f) In vivo MR images of an NPC CNE-2 xenografted tumor after
intravenous administration of the Gd2O3:Eu3+ NPs (Gd3+, 15 μmol kg−1) at 0, 10, 35, and 70 min, respectively. (g) Dynamic enhancement curve of
xenografted tumor. Reprinted with permission from ref 648. Copyright 2014 American Chemical Society. (h) Bimodal (CT, MRI) contrast agents made
by Mn2+-chelate adsorbing AuNPs. Reprinted with permission from ref 831. Copyright 2016 Royal Society of Chemistry.

Figure 69. Magnetic chains and strands obtained by LAL in the presence of magnetic field (in situ) or magnetic field applied during solvent drying post
LAL (ex situ). (a) SEM image of Fe3C magnetic chains obtained by LAL in the presence of magnetic field and (b,c) their magnetic properties. Adapted
with permission from ref 833. Copyright 2013 Nature Publishing Group. (d) Light microscopy image and TEM image of FeNi-nanowires and
nanostrands obtained by solvent evaporation of the polymer-containing colloidal solution and (e) the length and aspect ratio of FeNi-strands at different
NPs concentrations as well as (f) the anisotropic magnetic properties of the nanostrands. Adapted with permission from ref 539. Copyright 2015 Royal
Society of Chemistry.

per Fe content of 210 emu/g, which is ∼96% of the Fe bulk value Because of the absence of a shielding effect induced by ligands,
(218 emu/g) due to the highly crystalline Fe core.825 more coordination sites are available from LAL-generated Gd2O3
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Figure 70. ZnO defects with blue, violet, and green emission. (a) Temperature-dependent PL spectra of LAL-synthesized Zn/ZnO core/shell NPs from
8 to 300 K at 380 nm excitation. Reprinted with permission from ref 787. Copyright 2007 American Chemical Society. (b,c) TEM images of LAL-
synthesized core−shell Zn@ZnO NP and the disordered ZnO shell. Reprinted with permission from ref 444. Copyright 2010 Wiley-VCH. (d)
Evolution of relative intensity of different PL bands as function of irradiation time of LFL. Reprinted with permission from ref 265. Copyright 2011
American Chemical Society. (e) Direct bandgap energies for the cerium oxide nanoparticles as a function of laser irradiation time of LFL. Reprinted with
permission from ref 870. Copyright 2014 Elsevier.

NPs for water ligation (Figure 68a), making them better data storage and spintronic device sensing.832 To this end, LSPC
candidates as positive contrast agents for magnetic resonance provides two convenient ways to align 1D magnetic chains by
imaging (MRI) application826 than chemically synthesized LAL in the presence of magnetic field833 or by magnetic-field-
commercial clinical MRI contrast agents (e.g., Gd-DTPA, assisted solvent drying.539 With the help of a magnetic field,
where DTPA is diethylenetriaminepentaacetic acid) with only various magnetic (e.g., Fe3C,833 FeNi,834 and CoxO820) particles
one coordination site. As a result, the longitudinal relaxivity value have been assembled into 1D microfibers or strands (Figure
(r1) value of 4.4 nm LAL-synthesized diethylene glycol (DEG)- 69a,b).833 Such microfibers consisting of submicron iron carbide
coated Gd2O3 NPs (10.12 s−1 mM−1)826 is 2.5 times higher than spheres are ferromagnetic with a saturation magnetization up to
that of the 4.6 nm chemical-synthesized counterparts (4.4 s−1 261 and 295 emu/g at 300 and 5 K (Figure 69b,c),833 much
mM−1).827 Because no acute toxicity is observed after the in vivo better than 212 emu/g for bulk iron. As compared to the MNPs
test,828 LSPC-synthesized Gd2O3 NPs are good candidates as T1- in situ alignment route, post LAL synthesis solvent drying in the
weighted MRI contrast agents. Doping the LAL-generated presence of magnetic field allows well-controlled alignment of
Gd2O3 NPs with Tm3+, Tb3+, and Eu3+ will further enhance the magnetic alloy NPs into magnetic strands.356 Using this method,
MRI performance (r1 = 34.26 s−1 mM−1) and also allows Gökce and co-workers successfully embedded LAL-synthesized
fluorescence imaging,829 together with the in vivo MRI ability FeNi nanostrands (Figure 69d) in a PMMA film with anisotropic
(Figure 68c−g) of tumor tissues,648 indicating their suitability as magnetism (Figure 69f).539 FeNi strands as long as 600 μm are
multimodal imaging agents for cancer therapies. Hence, dopants achievable (Figure 69e), which is much longer than the longest
are easily introduced into MNPs by LAL, which endow aligned (15 μm) iron oxide NP chains reported so far.835 The
luminescence to MNPs. Alternatively, attempts have been aspect ratio can reach up to 160 by adjusting the NPs
devoted to developing magneto-plasmonic multimodal imaging concentration (Figure 69e) with transparency being kept in the
agents using alloy MNPs via LSPC, such as Au89Fe11 NPs for range of 75−97%. Such long-strand transparent polymer
SERS-MRI-CT (computed X-ray tomography) multiplexing822 composites could be good candidates for transparent conductive
(Figure 68b) or elemental iron NPs protected against oxidation window coatings540 or Faraday isolators. The combination of
by the crystalline gold shell,418 difficult to achieve by chemical ferromagnetism with an optical function is easily achieved by
synthesis. In addition, due to the surface charge of the LAL- LAL either by cation doping for semiconductor optics (section
synthesized MNPs, dual functional NP (superparamagnetic and 6.2) or by alloying with plasmonic elements for magneto-
plasmonic applications (section 6.3).
SERS properties) aggregation by simply mixing oppositely
charged LAL-generated (positive) FeOx MNPs with (negative) 6.2. Optics
AuNPs is possible for imaging-assisted cell sorting.830 In similar, 6.2.1. Semiconductor Optics. PL is the optical emission
high affinity of LAL-made AuNPs to Mn2+ chelates allowed the induced by photon excitation of a material and is mainly used for
Guay group to fabricate bimodal CT/MRI contrast agents, which biomedical imaging,842 solid-state lighting,843 and as indicators of
were assessed in vivo in chicken embryo (Figure 68h).831 photocatalysts’ performance.844 As compared to metal NPs
LSPC-synthesized MNPs can be further assembled into 1D whose PL properties often originate from surface coating845 or
chains, wires, or strands because 1D magnetic chains have gained quantum-confined atom clusters with bleached plasmonic state
increasing attention for many applications such as high-density (e.g., Au25,595), PL emission of NPs made by LSPC is widely
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Figure 71. (a,b) HRTEM image of Co3C@C NPs with different sizes and their proposed formation mechanism. (c,d) Magnetic and wavelength-
dependent PL properties of Co3C@C NPs. Reprinted with permission from ref 383. Copyright 2013 Elsevier. (e,f) The typical TEM image, HRTEM
image, size distribution and PL properties of C-dots synthesized by LAL of bagasse in ethanol. Reprinted with permission from ref 603. Copyright 2014
Elsevier.

investigated using different kinds of semiconductor nanomateri- ZnO NPs formation. As shown in Figure 70c, besides the
als. Because of simplicity and flexibility, LSPC has been utilized ultrafine crystalline ZnO in the shell structure, disordered areas
to synthesize a large variety of luminescent NMs, including are also observed, which have been assigned to the interstitial
elemental semiconductor NPs (e.g., Si,133,204,846−852 Ge,604,605 zinc defects in ZnO shells.444 The interstitial zinc defect
Se,231 etc.), oxides (e.g., ZnO,124 In:ZnO,673 SnO2,446 TiO2,853 concentration can be modulated by varying the laser power,
etc.), II−VI semiconductors (e.g., ZnSe,854 CdS,855 CdSe,856 which in turn offers a chance to tailor the violet emission intensity
PbS,250 etc.), III−V semiconductors (e.g., InN,537 GaN,857 because of the electronic transition from interstitial zinc defects
GaAs,855 etc.), and IV−IV semiconductors (e.g., SiC,858 SiSn,643 to the valence band by altering the excitation energy.444,786 A
etc.). By changing the influential process parameters, rich PL decreased green emission intensity due to the passivation by the
emission properties can be obtained for specific semiconductor anionic oxygen of the amphoteric surfactant LDA molecules
NPs, such as ZnO NPs with emission in UV, violet, blue, and might be a hint that green emission from ZnO NPs comes from
green spectral regions,444,597,859 and silicon NPs with emission in the oxygen vacancy sites.124 Similarly, LDA has been reported to
blue,860,861 violet-blue,501 blue-green,862,863 blue-green-yel- stabilize (passivate) defects in ITO during LFL.673 High pressure
low,864 near-ultraviolet-violet-blue-green-red PL emissions,752 allows faster quenching of ZnO NPs and leads to the formation
and white-light-emitting properties.582 LSPC, in particular its of more oxygen-related surface defects with enhanced green
methodological branches of LAL, LFL, and their combination, emission,871 while thermal treatment of ZnO NPs enables one to
paves a way to realize micronization/nanonization of phos- reduce the concentration of oxygen defects resulting in the
phors266,434 and to produce ultrasmall dots (e.g., Si,865 Bi,866 quenching of green emission.872 PL emission evolution from
Se,231 ZnO,265 PbS,250 graphene,867 carbon,868 diamond461), blue to green and final to ultraviolet during LFL of ZnO hollow
enabling them to become QDs to switch on the excitation nanospheres by a ns laser has been reported, which is
wavelength dependent PL emissions. The hybrid inorganic/ accompanied by quenching and diffusion of zinc interstitial
organic light-emitting diode (LED) made of LAL-synthesized Si defects or oxygen vacancy defects and the formation of crystalline
QDs has shown unparalleled performance with current (280 ZnO QDs (Figure 70d).265 Stepwise LFL can offer precise
mA/cm) and optical power densities (700 nW/cm2),865 about control of the bandgap energy of semiconductor NPs, as also
280 and 350 times those of such devices reported previously.869 shown by Takeda and Mafuné for cerium oxide870 (Figure 70e)
LSPC-synthesized NPs are featured by their ligand-free and Lau et al. for zinc oxide.218 Note that LFL for bandgap
surfaces, which is helpful to identify the origin for specific engineering even works at laser wavelengths higher than the
luminescent emission and understand the defect chemistry particulate educt’s main interband excitation wavelength,218
involved in the particle formation during the LSPC process, as indicating that the laser couples into the educt particles at initial
shown for TiOx.111 Through analysis of the temperature- defect levels.
stimulated red−blue shift of the emission band (Figure 70a), Although these works demonstrate that different kinds of
Zeng et al. proposed that the interstitial zinc defect centers are defects (e.g., oxygen and interstitial defects) can be created
the origin of the blue emission of LAL-synthesized Zn@ZnO during LAL, and that LFL allows bandgap control, it is still
NPs.444,787 These interstitial zinc defects are “frozen” in the ZnO unclear how to control the ratio of different defect types
lattice of the nanoshell (Figure 70b) during the core−shell Zn@ (vacancies vs interstitials, volume vs surface) precisely.
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Figure 72. Confocal microscope images of macrophage cell incubated with Gd2O3:Tm3+, Gd2O3:Tb3+, and Gd2O3:Eu3+ nanoparticles, respectively. (a,
d, and g) Bright-field images. (b, e, and h) Fluorescence images under 405 nm wavelength excitation. (c, f, and i) Merged images. Adapted with
permission from ref 829. Copyright 2014 Royal Society of Chemistry. (j,k) Optical image and fluorescence microscope images of cancer cells with LAL-
synthesized Y2O3:Er,Yb NPs. Adapted with permission from ref 436. Copyright 2015 Elsevier.

6.2.2. Carbon Dots. If adopting organic solvents as RLAL 6.2.3. Doping, Upconversion. Applications in optics are
medium, carbon delivered by the solvents’ decomposition may addressed by deliberately introducing doping agents (e.g.,
provide the luminescent properties for the formed inorganic transition metal or lanthanides) during LAL, for example, by
(e.g., LiNbO3, Au, and Si)−NP@C core−shell composites,697 using a doped target. Doping (e.g., Eu3+) introduction via LAL
similar to the PL property of pure C-dots (Figure 71e,f).603 can not only render PL properties to intrinsically non-
These composites are of great interest to generate multifunc- luminenscent biodegradable materials (e.g., hydroxyapatite
tional NMs by integrating a functional core NP with the outer (Ca10(PO4) 6(OH)2 NPs),877 but also leads to superior
luminescent carbon shell, such as the Co3C@C composites with bioimaging performance (e.g., blue, green, and red) of cells
both PL and magnetic properties (Figure 71c,d).383 The carbon (Figure 72a−i) by varying the dopants (e.g., Tm3+, Tb3+, and
shell could be as thick as 10 nm with 28 carbon layers on the Eu3+) of magnetic Gd2O3 colloids.829 When it comes to intrinsic
Co3C core (Figure 71a,b), and it seems that larger particles carry luminescent particles, doping introduction often changes or
thicker carbon shell. Because PL properties of LSPC-synthesized paves a new radiative transition path between valence band and
core−shell (inorganic@carbon) composites depend on carbon conduction band and results in an emission color change (e.g.,
shells, a better understanding of the PL mechanism for carbon blue emission and yellow emission of LAL-synthesized undoped
NPs is necessary. To this end, Nguyen et al. studied the carrier and Mn-doped ZnS NPs,647 respectively) or color multiplexing
(e.g., simultaneous blue/green emission of Cu-doped ZnS
dynamics of C-dots by analyzing their time-resolved PL spectra
QDs,646 and green/red emission of Eu3+ doped ZnO NPs432).
at different detection wavelengths and proposed two pathways of
If the acceptor level is close to the valence band, significant PL
electron−hole radiative recombination.868 One is the carrier
emission enhancement is obtained with only a little shift of the
relaxation from carbogenic core onto the surface states with a
PL peak;428 otherwise an apparent doping concentration-
slow decay (>14 ns) occurring at short-wavelength emissions, dependent PL shift is observed (e.g., Mg doped ZnO NPS).433
and the other is the direct radiative recombination of carriers Other than bioimaging, another significant application for LSPC-
between the surface states with a fast decay (∼1.3 ns) taking synthesized doped NPs is solid-state lighting. For example, Ce3+-
place at long-wavelength emissions.868 Systematic material doped yttrium aluminum garnet (Y 3 Al 5 O 1 2 :Ce or
variation by LSPC could provide valuable insights to YAG:Ce)619,878 and YVO4:Eu3+ nanophosphors879 are excellent
comprehend the underlying mechanism of excitation-dependent yellow and red emitters for lighting applications. Coated on
PL properties with respect to both C-dots and inorganic@carbon commercial overhead transparency films, LSPC-synthesized
core−shell composites. Note that LSPC of carbon NPs may yield YAG:Ce nanophosphors show better transmittance (90% vs
not only sp2 C-dots, but also sp3 nanodiamond462,745,773,873 or sp 82%) than commercial YAG:Ce phosphors and limited back-
polyynes874,875 under often very similar LSPC conditions. The scattering effect (44%).880 Water-insoluble long-afterglow NPs
educt for carbon NP synthesis may either be a target,876 a (e.g., Sr2MgSi2O7:Eu2+,Dy3+) synthesized by LAL are another
powder,24 or even a carbon-rich liquid.700 Carbon NP synthesis is interesting group of luminescent nanophosphors for lighting
a complex topic, and often an educt−product mixture is devices because they allow prolonged emission after switching off
obtained, demanding studies that address the selectivity of C- the excitation light.881,882 Among all of the doped luminescent
dot or nanodiamond synthesis and the colloid’s PL origin. particles, upconverting NPs with anti-Stokes upconversion
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(high-energy photons generation via low-energy photons’ C6H6,606 etc.). When OL NPs are synthesized by LSPC in
absorption) luminescent emission are particularly attractive for polymer-containing solutions, the encapsulated NPs have a high
bioimaging, volumetric displays, and photonics applications.883 stability589 and are suitable for solid optical limiters components
Direct synthesis of Y2O3:Er,Yb upconverting NPs884 by LAL and after postprocessing solidification. Flexible control of the OL
their dispersibility control885 by silane coupling and PEG performance with respect to specific OL material (e.g., C-dots)
conjugation have been presented by the Wada group. The has been proven for both fs laser603 and ns laser.893 Although
LAL-prepared Y2O3:Er,Yb NPs maintain high crystallinity of the empirical conclusions are difficult to draw from these LAL-
target437 and have upconversion optical properties comparable synthesized OL materials because of the difference in materials
to those synthesized by the sol−gel method.437 The red emission and performance setups used in LAL literature so far, the
from LAL-synthesized (Y2O3:Er,Yb) upconversion NPs upon references mentioned above clearly show that LAL is a facile
NIR light irradiation can be used to excite the photosensitizer method to create diverse OL nanomaterials.
(chlorin e6) to generate reactive oxygen species, which might be 6.3. Plasmonics
used to treat lung cancer cells by photodynamic therapy (Figure
72j,k).436 Embedding upconverting nanoparticle in a optically Because of the wide array of applications such as optical tweezers
relevant polymer presents a further promising route for to hold and manipulate individual metallic NPs for force
applications in optics as recently demonstrated for Y2O3:Er,Yb measurement as well as photonic force microscopy, optical
NPs in polycarbonate by the Gökce group.886 particle trapping has been the subject of considerable interests.894
6.2.4. Optical Limiters. With increasing use of powerful Despite limited reports covering this emerging area on the basis
lasers, optical limiters (OL) that allow a decreased light of LSPC, the already published results have proven the viability
transmittance upon higher laser fluence irradiation603 (Figure of using LSPC-synthesized NPs for optical trapping applications.
73a) become more important for the protection of human eyes For example, Messina et al. successfully optically trapped LAL-
synthesized Au nanoaggregates with sizes ranging from 20 to 750
nm (Figure 74b−e).895 As compared to an individual gold
sphere, the Au-aggregates’ trapping efficiency is 50 times higher
due to their strong field-enhancement. If assembled by Raman
reporter molecules, these optically trapped metal aggregates
allow the generation of “hot spots” for SERS detection (Figure
74a,f).896 This work suggests that simultaneous trapping and
exciting “hot spot” regions of LSPC-synthesized nanoaggregates
show the possibility to allow for surface-enhanced Raman
tweezing using a single laser source. Similarly, Krawinkel et al.
Figure 73. Optical limiters: (a,b) Optical limiting effects of laser-
showed the advantage of aggregated small AuNPs (over large Au
generated C-dots under different fluences. Adapted with permission spheres) by proving their intracellular photodispersibility during
from ref 603. Copyright 2014 Elsevier. optoporation-triggered molecule delivery.897
Taking advantage of the plasmonic properties of metal NPs,
SERS has become a versatile analytical tool. LSPC-synthesized
and sensitive optical devices.887 The optical limiting threshold NPs with high “purity” are clearly favorable for SERS, which in
(OLT) of optical limiters is normally defined as the incident combination with the strength of LSPC to synthesize elemental
fluence where the transmittance equals to 50% of normalized NPs (e.g., Au,898 Ag,899 Cu,900 etc.), alloys, and composites (e.g.,
linear transmittance (Figure 73b),603 serving as the criteria to AuFe,822,901 Ag@Pd,681 Cu@Ag,902 Ag-GO,903 etc.) have
evaluate the performance of optical limiters. A large variety of already expanded their applications to many fields, such as
optical limiting (OL) nanomaterials have been produced by LAL selective localization of ovalbumin in ancient painting904 and
by changing the material compositions (e.g., nanoparticle− quantitative assays,898,905 identification of highly energetic
polymer composite,589 Al,606 AgAu alloy,768 ZnO,888 C,467,889,890 material (e.g., 2,4,6-trinitoluene (TNT)),899 multimodal MRI-
etc.) and liquid (e.g., DMSO,891 ethylene glycol (EG),892 CT-SERS imaging,822 recording catalytic reaction,681 or to

Figure 74. (a) Simplified sketch of the Raman tweezing. (b,c) Images of optically trapped gold nanoaggregates and the same free aggregate when the
trapping laser is switched off. (d,e) A large (about 2 μm) aggregate rotation while optically trapped. The light-driven rotation is induced by the
geometrical anisotropy (“windmill effect”). (f) SERS spectrum on a trapped aggregate. The asterisks highlight the enhanced pyridine vibrational peaks,
while the BSA Raman modes are indicated in blue. Reprinted with permission from refs 895 (a,f) and 896 (b−e). Copyright 2011 American Chemical
Society.

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Figure 75. Plasmonics induced photothermal effect and magneto-amplified SERS signal. (a) Raman spectra of an MG/Fe−Ag NPs dispersion and (b)
photothermal heating before (magnetic field H off, black line) and after (H > 0, blue line) magnetic focusing. MG is a cationic molecule which can
interact with negatively charged NPs. Reprinted with permission from ref 67. Copyright 2015 Springer. (c,d) Thermal imaging of an Au NP aqueous
solution in a quartz cuvette irradiated with a CW-laser from the visible to NIR region. Thermal imaging of polymer−AuNP nanocomposites before (left)
and after (right) 785 nm laser irradiation. Adapted with permission from ref 249. Copyright 2015 Royal Society of Chemistry.

Figure 76. NP cytotoxicity: (a) Oocyte maturation (embryo development) exposed to different LAL-synthesized NPs showing how alloying may render
Ag NPs safe. Reprinted with permission from ref 424. Copyright 2014 Royal Society of Chemistry. TEM micrographs of spermatozoa after coincubation
with (b) ligand-free NPs and (c) ligand-covered NPs, (d) sperm motility, and (e) embryo development with ligand-free AuNP (violet bars) and
oligonucleotide-conjugated AuNP (blue bars). Adapted with permission from ref 915. Copyright 2014 Informa UK Ltd.

understand the protein−particle interactions902 and to detect photothermal heating (Figure 75b).67 Note that the thermal
trace amounts of organic pollutants.903 It is found that the SERS heating effect of LSPC-synthesized NPs is dependent on the
performance can be further enhanced with magnetic focusing
surrounding medium. Embedment of plasmonic Au NPs in
using LSPC-synthesized magneto-plasmonic alloy AgFe NPs
(Figure 75a).67 Similarly, magnetophoretic amplification of polymers (PVA, PS, PMMA) enables one to achieve higher
plasmonic properties of AgFe NPs can further enhance temperature increments upon laser irradiation than directly using
4057 DOI: 10.1021/acs.chemrev.6b00468
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colloidal plasmonic NPs (Figure 75c,d) due to a lesser heat processes often result in particle aggregation914 and are time-
dissipation rate.249 consuming.
For a multimodal application, LAL-generated (negatively Rath and co-workers found that LAL-synthesized Ag NP
charged) plasmonic (e.g., Au) NPs can also be mixed with coincubation in BSA-containing media has no adverse effect on
(positively charged) magnetic NPs to assemble aggregates with sperm cell motility, sperm cell membrane integrity, and sperm
both superparamagnetic and SERS properties for imaging- cell morphology, but shows strong toxicity toward oocyte
assisted cell sorting830 or can be melted into a semiconductor maturation rates (Figure 76a) and causes a slight decrease of
(e.g., ZnO) SMSs to tune the material’s bandgap.267 Lysyakova et blastocyst development rates.346,424 Therefore, mammalian
al. designed and successfully synthesized a type of novel embryo development is vulnerable to Ag NP but not to Au NP
plasmonic conjugate with a light-controlled plasmonic response exposure.346,424 Hence, one possible solution to reduce
by neutralizing or overcompensating the AuNP surface charge detrimental reprotoxicic effects is to alloy Ag NPs with Au,
with an azobenzene-modified cationic surfactant.906 Note that creating AuAg NPs whose toxicity is negligible as compared to
achieving positive charge always requires crossing the point of pure Ag NPs when the silver molar fraction is 50% or less.346,424
zero charge through an intermediate state because the original The reduction of silver-related cytotoxic effect using AgAu
charge of naked NP is negative in the case of noble metals.363 nanoalloys is also accompanied by a decreased antibacterial
There are several clear advantages of LSPC-synthesized activity (see section 6.4.3).716 For fundamental toxicity studies,
plasmonic NPs. First, if a particle surface is covered by ligands, in particular, those addressing mechanisms of nanobioresponse,
the refractive index of the particle surface increases and will cause LAL provides ideal reference materials.11,12 First, NP alloy series
a bathochromic shift of the SPR peak,421 hence LSPC- and mixtures are easily synthesized, unraveling stoichiometrically
synthesized alloy NPs typically have lower SPR wavelengths disproportional effects.11,424,716 Second, ligand effects can clearly
than those of chemically and biologically synthesized NP be distinguished from effects of the inorganic core (Figure 76b−
counterparts (Figure 38d).125 Second, given that the SPR d),11,915−917 contributing to mechanistic understanding and
providing testing material closer to realistic exposure scenarios.
wavelength can be linearly tuned simply by adjusting the molar
For example, using sperm cells as a very sensitive toxicity model,
ratio of two materials in the alloy LAL-target and thereby the
unable to undergo NP uptake, it has been shown that only ligand-
alloy NPs,125 it is expected that alloy NPs allow broadband
free NPs compromise their biofunctionality, whereas sterically
optical control (e.g., OL) of the plasmonics-related behaviors.
(BSA or oligonucleotide) stabilized NPs did not compro-
For example, Dengler et al. showed that the OL properties of Ag mise.346,915 Mimicking unintended exposure like implant debris
or Au NPs could be tuned by alloying them.768 Moreover, requires a synthesis method that delivers ligand-free colloids,
Dallaire et al. demonstrated a higher stability of LSPC- ideally represented by LSPC. These mechanistic insights could
synthesized alloy AgAu NPs over both LSPC-synthesized and serve to render NPs safer (nanosafety-by-design), for example,
chemically synthesized elemental Au NPs after oligonucleotide alloying Ag NPs popular for high plasmonic activity (e.g., in
hybridization, making them promising for nucleic acid SERS) with gold, creating less toxic AgAu NPs made by LAL.346
sensing.907 Hence, LAL has manifested its strength to Mechanistic studies on toxicological effects caused by NP’s ion
“conveniently” fabricate binary and ternary alloys. It can be release greatly benefit from the availability of ligand-free
concluded that LAL is particularly advantageous for producing reference materials. Mimicking ion release from Nitinol (widely
plasmonically or catalytically active alloy NPs that are still a used for stent application) for implant debris toxicity studies
challenge to synthesize by conventional methods. Today, showed that the ligands cysteine (an amino acid present in serum
advanced LSPC gives access to a defined alloy NP crystal proteins) and citrate significantly affected the Ni ion release from
structure and allows the high-throughput synthesis of molar Ni and NiTi alloy nanoparticles. Interestingly, although cysteine
fraction series of nanoalloys. enhanced more Ni ion release from Ni, NiFe and NiTi alloy NPs
6.4. Biology than citrate did, the metabolic activity of endothelial and smooth
muscle cells in cysteine solution is almost the same as in citrate
6.4.1. Toxicity. Biological applications of laser-generated solution which is attributed to the cysteine’s ability to complex
colloidal NMs and NPs are often motivated by their purity or heavy metal ions.918
facile nanointegration capability. Purity is of particular 6.4.2. Bioconjugates. Noble metal NPs with a low degree of
importance for fundamental studies of the nanobioresponse,346 surface oxidation (Table 4) present hydrophobic adsorbent
in particular mimicking unintended exposure to engineered NPs. surfaces with soft Lewis acid character, prone to facile
It is known that stabilizers such as citrate,908 which is generally conjugation with soft Lewis base functional groups. Hence,
believed to be biocompatible as well as cytotoxic CTAB,909 laser ablation of a noble metal in a liquid medium containing
interfere with toxicological assays.910 Uboldi et al. have shown biomolecules allows one-step in situ conjugation of any
that initial citrate surface coverage after chemical reduction biomolecule bearing an electron-donating function (e.g.,
synthesis of NPs negatively affected cell viability and significantly thiols/cysteine, disulfides) with the synthesized NPs without
reduced cell proliferation. In their study, they further showed that any limitation in the biomolecule type.361,558,730,919 Until now, a
the biocompatibility could be partly improved by citrate large variety of bioconjugates have been synthesized by in situ
removal.8 Accordingly, a ligand-covered surface makes the LAL, including nucleic acids (e.g., oligonucleotides308,561,919),
evaluation of the NP toxicity very complicated. With ligands aptamers,361 proteins (e.g., immunoglobulin E,558 Staphylococcus
on the surface, even those kind of ligands (like citrate) that are aureus protein,848 S-ovalbumin730), biopolymers (e.g., chito-
not toxic at equivalent bulk solution concentration, it is san351,352,715,920), and peptides (e.g., penetratin,733 nuclear
impossible to distinguish between “real” nanotox effects and localization sequence-NLS,363,917 sweet arrow peptide-SAP303).
cross-effects caused by the nanoparticle’s surface adsorbates.12 The conjugation process is very rapid; for example, synthesizing
Surface ligands can be removed by centrifugation911 or 20 μg of prostate cancer targeting aptamer oligonucleotide-
diafiltration912 or tangential-flow filtration.913 However, these functionalized gold NPs only takes less than 1 min at optimal
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Figure 77. High grafting densities: (a) Regimes of AuNP surface coverages obtained by in situ and ex situ conjugation during laser ablation as compared
to literature values. Reprinted with permission from ref 561. Copyright 2009 American Chemical Society. (b) Biomolecule grafting density of laser-
generated Au NPs as compared to chemically prepared Au NPs. Reprinted with permission from ref 923. Copyright 2013 AT-Fachverlag.

Figure 78. In situ and ex situ conjugation effect: (a,b) Size quenching effect of Si NPs during in situ conjugation with SSO-biomolecules. Reprinted with
permission from ref 847. Copyright 2012 Royal Society of Chemistry. (b) Cell imaging using in situ LAL-synthesized Staphylococcus aureus protein A-
conjugated Si nanoparticles. Adapted with permission from ref 848. Copyright 2013 Institute of Physics. Ex situ conjugation effect: (c) Scheme of ex situ
conjugation and (d) colloidal stability of laser-generated and chemically prepared gold nanoparticles during surface modification with thiolated PEG.
Reprinted with permission from ref 341. Copyright 2011 American Chemical Society.

laser and process parameters, sufficient to validate selectivity of balancing the charges of the net-negative noble metal NP and the
prostate cancer tissue targeting.361 Despite some reports net-negative (e.g., oligonucleotides) or net-positive (e.g., cationic
showing the degradation of biomolecules during LAL402 or peptides) ligands is the key to controlling ligand grafting density
LFL,921 in most cases, no significant degradation of the and colloidal stability after LAL.344,363 As LAL delivers naked
molecules is observed during in situ bioconjugation at an NPs and bioconjugation starts from scratch, the effective ligand
optimized condition,308,730 which is promising for their further dose is exactly known during ex situ conjugation, without any
functionality in biological applications. Degradation can be trade-off for kinetic or thermodynamic barriers that typically have
minimized by liquid flow during LAL402 or tuning the pH during to be overcome after chemical citrate-based synthesis based on
LFL.921 In general, conjugation efficiency is molecule-depend- ligand exchange. In detail, the uniqueness of having ligand-free
ent. Because of the coiling effect of the flexible strand of spacer- Au NP or Pt NP building blocks allows one to freely “titrate”
prolonged single-stranded oligonucleotides (ssO) on the particle different types of biomolecules sequentially on the NP surface.344
surface that increases deflection angle of oligonucleotides and In situ conjugation will yield dense monolayers, whereas ex situ
due to the repulsion force induced by the highly negative charged conjugation allows, for example, one to add a submonolayer dose
ligand’s phosphate backbone, the number of biomolecules of biomolecule A and subsequently saturate the surface (by the
attached to the NPs is significantly reduced for longer nucleotide way improving colloidal stability) with biomolecule B. Hence,
sequences.559 In both in situ and ex situ conjugation protocols, these naked building blocks give convenient access to bivalent
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and even charge-twisted conjugates,363,917 that is, a net-negative ciency308,561,919 and biological functionality558 yielded by both
NP bioconjugate having negatively and positively charged methods are similar for monovalent (single biomolecule type)
ligands. Net negative NPs have improved biocompatibility,922 nanoparticle bioconjugates.
whereas the cationic submonolayer nanoenvironment may 6.4.3. Antibacterial and Ion Release. The development of
trigger cellular uptake.917 In terms of the higher conjugation novel antibacterial agents, especially in the form of nanomateri-
efficiency toward DNA (>90%), in situ conjugation of NPs als, is of great importance for biomedical applications because
during laser-ablation is quite advantageous as it leads to far higher microorganisms gradually become resistant toward traditional
surface coverages than conjugation of chemically synthesized antibiotics or disinfecting agents. Because of the absence of
NPs (Figure 77).561,923 Note that grafting density (surface ligands, LAL-synthesized NPs are better candidates in
coverage) has been reported to be proportional to biofunction- comparison to wet-chemical synthesized NMs, enabling to
ality. For Au−oligonucleotide conjugates, this effect has been clarify the effect of surface ligands on the resultant antibacterial
known for more than a decade and is based on cooperative performance.916 Many kinds of antibacterial nanomaterials have
binding theory.924,925 The phenomenon of binding avidity is been produced by LSPC, including Ag NPs,931−934 Cu NPs,935
generally believed to be a universal concept, which is also TiO2,439 and Ag−TiO2,448 as shown in Table 6. It can be seen
transferable to folate loaded dendrimers, where multivalency that the most frequently studied NPs are based on Ag. It is
could increase binding constants up to 170 000-fold.926 Recent confirmed that Ag+ ions released from the Ag NPs contribute to
studies seem to indicate that a precise control of ligand coverage the antibacterial effect rather than the Ag NPs themselves.936 As
is a vital prerequisite to harvest the benefits of avidity.915,927 expected, the antibacterial efficacy of Ag NPs is Ag-concentration
However, it should also be noted that the highest surface dependent with higher concentration leading to enhanced
coverage is not necessarily the condition with the highest avidity antibacterial performance.675 Yet at the same time, increasing
as ligands at too close proximity may also hinder efficient the concentration of Ag NPs from 5 to 70 μg mL−1 gradually
binding. On the basis of these findings, it can be assumed that causes toxicity, reducing the viability of the human tissue cells
systematically altering the surface coverage of biomolecules on gingival fibroblasts as well.937 Hence, often the intended
nanoparticles, easily adjustable if the particles are naked, could be antibacterial effect is accompanied by the unintended toxicity.
a key factor in achieving optimal biofunctionality. Similarly, it has The applicable therapeutic window may be quite narrow and
been shown that bare planar gold surfaces adsorb 2 times more depends on ligand effects. Accordingly, LAL-synthesized ligand-
protein ligands than a citrate-covered gold surface.928 Fur- free Ag NPs are helpful to identify how the presence of a ligand or
thermore, in situ conjugation is a simple one-step approach with protein influences the antibacterial activity. Interestingly, silver
size quenching involved simultaneously, both for Au308 and for ion release and antibacterial effect of LAL-synthesized Ag NPs
Si.847,848 For instance, Intartaglia et al. showed that the average can be slightly enhanced by white light illumination (1.8 mW/
size of silicon NPs synthesized by in situ bioconjugation with cm2).933 The groups of Bubb and Klein could clearly attribute
oligonucleotides is 5 nm (Figure 78a), whereas that synthesized this effect to enhanced ion release, rather than creation of reactive
without conjugation is 60 nm.847 Bagga et al. reported that in situ oxygen species and evidenced by TEM that mild irradiation of
conjugation decreases the size of LAL-synthesized Si NPs from the colloid causes narrowed and smaller Ag NP size.933 The
15 nm (in water) to 8 nm.848 The conjugated Si NPs had PL authors concluded a new clinical pathway for treatment of open
property and could be used for cell imaging (Figure 78b).848 Ex wounds where the antimicrobial agent may be stimulated locally
situ conjugation requires anion-based size quenching310 and/or by white LED illumination.933 Moreover, LAL-generated AgNPs
centrifugation before conjugation (for monodisperse NPs). A have shown potent antibacterial activity against Gram-positive
direct comparison showed that both methods yield similar results bacteria (e.g., B. subtilis, S. typhi, S. typhimurium, and S. aureus)
regarding grafting density of biomolecules and biomolecular and Gram-negative (e.g., K. pneumonia, P. aeruginosa, and E. coli)
functionality test with cytokine production.558 Advantages of ex human enteropathogenic bacterial strains.932 Interestingly,
situ conjugation include precise control of biomolecule number addition of the steric stabilizer BSA to the ligand-free LAL-
per NP starting from zero (e.g., 0−350 ligands per particle363), synthesized Ag NPs significantly reduced effectiveness (anti-
NP dispersity control by a combination of different biomolecule bacterial effect against bacteria and toxicity against fibroblasts) of
types,929 and molecule combinations on NP surfaces (Figure Ag NPs, diminishing the therapeutic window.937 On account of
78c),341 yielding bivalent bioconjugates (such as cationic peptide the antibacterial property, LAL-generated AgNPs are discussed
plus oligonucleotide).562 The ability to create such bivalent as candidates to be embedded in a biopolymer (e.g., Agar) for
bioconjugates is the key to transfect biological cells that do not food packaging to suppress foodborne pathogenic bacteria.938
undergo endocytosis, such as sperm cells.930 Besides this Also, Klein et al. found Gram-positive bacteria to be more
advantage of LSPC-synthesized NP, the higher stability of resistant against Ag NPs attributable to their thicker
LSPC-synthesized NPs after PEGylation than chemically peptidoglycan cell wall as compared to Gram-negative strains.933
synthesized analogous NPs (Figure 78d) is another property Embedding Ag NP in a thermoplastic polymer (e.g., TPU) via
allowing steady application of the PEG-conjugates in the LAL in THF solution of TPU and subsequent part fabrication by
biomedical field (as PEG is known to cause “stealth particles” polymer injection molding and extrusion allows the development
invisible to the immune system).341 In ex situ conjugation, the of antibacterial medical devices (e.g., catheter) for series testing
unique LSPC-property of “building a NP from scratch” is toward clinical application.372
utilized. Alloying 30% of Au to Ag disproportionally reduced the
Simply speaking, in situ bioconjugation is often more adverse effects to both fibroblasts and bacteria, with the
convenient and yields size-quenching in parallel, whereas ex antibacterial effect reduced by 80%.716 Note that this mechanism
situ bioconjugation provides more precise control over can only be observed clearly for ligand-free NPs, because
biomolecule grafting density and charge manipulation but addition of citrate diminishes this disproportional effect, making
requires prior size control preferably in the absence of ligands LSPC powerful for mechanistic studies on antibacterial effects of
by salinity quenching or LFL. The conjugation effi- NPs.716 To reduce the cytotoxic effect but simultaneously
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preserve moderate antibacterial effect of Ag NPs, embedment of

935

937

932

716

933

934

939
371

448

439
ref
Ag NPs inside polymer to form nanoparticle−polymer
composites is a feasible approach; for example, TPU capping

higher antimicrobial activity of Ag NPs synthesized in chloride as compared to those synthesized in


a reduced fraction of silver in AgAu nanoalloys disproportionally decreased the antibacterial effect;
minimum inhibitory concentration (MIC) values (2−6 μg/mL) for both Gram-positive and Gram-

improved antibacterial efficacy by mixing Ag−TPU and Mg−TPU composites due to improved Ag
an increased antibacterial activity with ligand-free as compared to BSA addition in AgNP-embedded

85% antibacterial efficiency at concentration of 100 μg/mL after 60′ exposure by UV irradiation,
makes Ag NPs become less cytotoxic toward cells but still toxic to
some bacteria strains.371 Mixing Ag NPs and Mg NPs into a
a cell load equal to 6.0 Log CFU/mL lower than that measured in control polymeric matrix

irradiation of AgNPs stimulates an increase (31 ± 8.5%) of silver ion release and enhances

Ag−TiO2 NPs have better antibacterial effect than laser-generated TiO2 nanoparticles and
BSA maintains antibacterial activity, whereas sodium citrate reduces antibacterial effects
polymer matrix even enhances the antibacterial effect against S.
aureus due to the improved Ag+ release from the sacrificial
volumetric effect of Mg, whereas mixing Ag NPs with either Zn
or Cu NPs leads to a diminished antibacterial effect.371 As
suggested by the authors, alloying Ag NPs with other functional
metals or mixing Ag NPs with other metal NPs in a polymer

>95% antibacterial efficiency against 105 CFU/mL of bacteria in 3 h


matrix may pave a way to find a compromise between cytotoxic
and antibacterial effects.
negative bacteria; more sensitive to Gram-negative bacteria

6.4.4. Micronization and Solubilization of Drugs.

much better than 75% commercial TiO2 nanoparticles


Micro-/nanonization of insoluble drugs (e.g., megestrol acetate,
key aspects

fenofibrate, and naproxen, etc.) by LFL to improve drug


solubility for intravenous administration is a developing subject
of great significance for preclinical drug evaluation.480,517,940,941
Figure 79a shows that LFL of the model drug megestrol acetate
leads to a size reduction from >3 μm to <300 nm.940 As
water attributed to surface charge

chemically synthesized Ag NPs

compared to ns LFL, fs LFL displays a better performance for


drug size reduction, even comparable with media milling.940
solid agar hydrogel matrix

Impurity analysis by chromatography revealed that the


antibacterial efficacy
(7.4 Log CFU/mL)

degradation of beclomethasone dipropionate (BDP, a steroid


medication used for asthma, dermatitis, and psoriasis treatment)
is almost negligible (0.8 ± 0.1%) after 30 min of fs LFL at low
ion release

laser power.481 Increasing laser power will increase the micro-/


nanonization efficiency but cause an increase in drug
degradation. Hence, as expected, there is a compromise between
the LFL efficiency and the drug degradation, but even the
maximal (2%) degradation caused by varying BDP concentration
is still limited and in the same order of milling-caused
degradation.481 Although there is a minimal degradation
B. subtilis, S. aureus, E. coli, E. aerogenes, K.
pneumonia, P. aeruginosa, S. typhi, and S.
S. salivarius, S. aureus, E. coli, P. aeruginosa

(primarily oxidative in nature940) during the LFL process, in


a mix of P. fluorescens and P. putida

vitro dissolution rate (Figure 79b) and in vivo bioavailability


bacterial Strain

(Figure 79c) of LFL-synthesized nanosuspensions show


performances similar to those achieved by media milling
technique.940 These features together with the improved drug
permeability517 (Figure 79d) demonstrate that LFL is a good
E. coli and B. subtilis

approach in replacing media milling for size reduction of


typhimurium

S. epidermidis

microcrystalline pharmaceutical powders. As compared to media


milling, which is subjected to contamination by abrasion of the
S. aureus

E. coli

E. coli

E. coli

E. coli

grinding media and in need of a large amount of the solid educt,


Table 6. Antibacterial Activity of LSPC-Synthesized NPs

the products are cleaner, and the educt amount for LFL is far
smaller in the preclinical phase of drug discovery.480
stabilized Ag NPs, AgAu

after without irradiation


9−27 nm, polycrystalline
10−60 nm with peak at

2−222 nm with peak at


19 and 25 nm with and

6.4.5. In Vitro Application. Nanoparticle aided diagnosis


particle properties
36 ± 9 nm, 20−41%

and therapy aiming at nanomedicine is a rapidly developing field.


100−200 nm, cubic
surface oxidation

BSA- and citrate-

Recently, many studies have been devoted to using LSPC-


1 wt % Ag+Mg
0.9−2.2 nm

synthesized NPs for this purpose; examples include immuno-


34 ± 1 nm
21 nm

31 nm

chromatographic assay labeling by depositing Au NPs on


alloys

membranes,942,943 selective detection of L-cysteine based on


absorption spectrum triggered by the interaction between Bi
colloids and amino acids,944 nonenzymatic glucose detection
LAL of Ti/Ag in water
containing solutions

LAL in NaCl solution


LAL in PVP or SDS-

LAL in TPU−THF

using SnO2 assembled electrode,723 and photothermal therapy


LAL in citrate and

LAL in water and


BSA solutions
synthesis
LAL in acetone

by irradiating Au NPs.249 This diversity of applications indicates


LAL in water

LAL in water

LAL in water

that LSPC is a convenient method providing biofunctional NPs


chloride

solution

for various in vitro biomedical studies.


Because the ligand-free feature allows NP functionalization
starting from scratch, functional molecules can be easily grafted
with LSPC-synthesized NPs to assemble “biofunctional”
Mg)−TPU
(Ag, Cu, Zn,

Ag−TiO2
Ag, AuAg
NPs

materials. For example, Salmaso and co-workers successfully


grafted LAL-synthesized Au with thermosensitive copolymers
AgCl

TiO2
Cu

Ag

Ag

Ag

Ag

poly(N-isopropylacrylamide-co-acrylamide) (pNIPam-co-Am)
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Figure 79. Drug micronization by LFL. (a) Size analysis of untreated, ns laser and fs laser micro-/nanonization of megestrol acetate (MA). (b,c)
Dissolution and in vivo blood plasma concentration of untreated MA powder (□), media milled MA (×), and fs laser (250 mW, 30 min, 2 mL)
fragmented MA (○), respectively. (d) Permeability of irradiated and nonirradiated clobetasone butyrate suspensions across Caro-2 cell monolayers.
Reprinted with permission from ref 940. Copyright 2011 Elsevier. Reprinted with permission from ref 517. Copyright 2014 Elsevier.

Figure 80. Thermoresponsive nanoparticle−polymer composites starting from LAL-synthesized Au NPs (a), and temperature controlled
biorecognition (b and c). (d,e) Confocal microscopy examination of KB cells treated with AuNPs functionalized with folic acid/pNIPAM-co-Am.
Reprinted with permission from ref 945. Copyright 2011 Royal Society of Chemistry.

to realize triggered cell binding and internalization (Figure binding and particle uptake by cells is observed (Figure 80b,e);
80a).945,946 When the temperature of the particle surface is below whereas above LCST, the ligands stick out sterically and show
the lower critical solution temperature (LCST), the targeting affinity to the cell-surface receptors, allowing surface binding and
ligands are shielded by polymers, in which case no surface cell uptake (Figure 80c,d).945,946 As was demonstrated in section
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6.1, MNPs are extensively used in biomedical applications, partly


because of their response to a magnetic field enabling “action at a
distance” (e.g., cell targeting) or “remote control” (e.g., cell
sorting) once they are taken up by cells. To this end, Amendola et
al. investigated the magnetic labeling and manipulation of
macrophage cells using LAL-synthesized FeOx NPs.815 Flow
cytometry showed that 95% of the macrophages could be
effectively sorted by an NdFeB magnet after only 10 min of
exposure. The cell sorting efficiency was also maintained even
when the FeOx NPs are combined with LAL-synthesized Au NPs
to AuFeOx aggregates for rendering magneto-plasmonic SERS
function. Multimodal use of LSPC synthesized MNPs for in vitro
tests can be further enriched, for example, photoluminescent
bioimaging by cation doping, which has been reported by the Li Figure 81. Cell perforation and laser transfection. (a) Schematic
and Chen groups.648,829 Ligand-free Au and Pt particles also illustration showing uptake and laser-based release of molecules using ex
allow biomedical researchers to increase the binding affinity of situ LAL-synthesized cell-penetrating peptides (CPP)-AuNPs into cells
relevant for human mammalian adenoma. (b,c) Visualization of calcein
Aβ-specific small molecules to inhibit Aβ peptide aggregation
uptake and release before and after laser irradiation. Adapted with
into fibrils in vitro,344 relevant for Alzheimer disease. Binding permission from ref 897. Copyright 2016 BioMed Central.
affinities of AuNP-immobilized D3 (Aβ-specific D3 dodecapep-
tide) can be enhanced by a factor up to 7 as compared to the free
ligands. Surprisingly, cellular excretion of neurotoxic small Aβ Some attempts have been made to use LSPC-synthesized NPs
oligomers while using AuNP-immobilized D3 conjugates is as (e.g., silica,949 TiO2,950 etc.) as “nanofertilizer” to increase the
low as ∼20%, much better than pure particles (51%) and pure germination percentage and enhance the seed growth, but up to
ligands (40−85%).344 Hence, effective ligand conjugation to the now it is still difficult to make any conclusion whether LSPC-
NP surface amplified the ligand’s application potential. Overall, synthesized NPs are advantageous over chemical-synthesized
D3-conjugated nanoparticles convert Aβ into nonamyloido- NPs for this type of bioapplication because of the limited number
genic, amorphous, nontoxic aggregates. This finding may of studies.
stimulate further comparative studies on bioresponse of ligands 6.4.6. In Vivo Application. Successful in vivo tests pave the
and their biofunctional particle conjugates, based on ligand-free way for nanoparticles toward clinical use. Increasing studies are
building blocks. now directed toward using LSPC-synthesized NPs for in vivo
To overcome the lack of cell adhesion property of alginate, applications. For instance, Baati et al. systematically investigated
Blaeser et al. deliberately introduced metal (Au or Fe) the biodistribution, biodegradability, and toxicity of LAL-
nanoparticles in alginate by laser ablation in alginate solution.947 synthesized Si/SiOx NPs.951 Their results showed that these
In vitro tests showed that endothelial cells seeded on iron-loaded particles were biocompatible and biodegradable with negligible
gels have the highest viability in comparison to the alginate toxicity or biopersistence. The small LSPC-synthesized Si/SiOx
NPs were completely cleared within 1 week,951 while in
control and gold-loaded alginates. This is attributed to the release
comparison, electrochemically synthesized Si/SiOx NPs took
of Fe ions over a prolonged period, which improves the
longer (4 weeks) for clearance,952 maybe due to their larger size.
adsorption of cell adhesion proteins, relevant for extrusion-based
These findings have aroused increasing interest to apply laser-
biofabrication.947
generated Si NPs for drug delivery and cancer theranostics.
With molecular medicine delivery in mind, Krawinkel et al.
Tamarov et al. applied both LAL-synthesized and chemically
reported the photodispersion effect of cell-internalized (cell- synthesized Si NPs as sensitizers to inhibit Lewis lung carcinoma
penetrating peptides-conjugated) NP agglomerates by ns laser development.953 Figure 82a shows the mechanism that the
irradiation (Figure 81a) for intracellular release of molecules authors proposed for radio frequency (RF) radiation-induced
carried by the agglomerates (Figure 81b,c).897 Key innovation of hyperthermia using RF-absorbing Si NP-based sensitizers: First,
using aggregates of primary small particles over the widely used Si NPs will be accumulated in the tumor cells and then heated by
large spheres, nanoshells, or nanorods is that NPs with primary RF radiation to increase local temperature leading to selective
diameters of ≤5 nm are considered to be biodegradable (not death of cancer cells without negative effects toward healthy
biopersistent).897 At the same time, the aggregates benefit from tissues (Figure 82b,c). Figure 82d supports the finding that LAL-
plasmon coupling increasing their photosensitivity. Also, LAL synthesized Si NPs perform superior to chemically synthesized
creates negatively charged bare Au NPs, which can be precisely porous silicon (PSi) NPs against cancer growth, which can be
aggregated by oppositely charged, cationic peptides crossing the attributed to a better in vivo delivery and uptake of LAL-
isoelectric point during conjugation and stabilized against further synthesized Si NPs as well as their ideal spherical shape, smaller
aggregation by BSA.897 mean size, and low size-dispersion.
In a different study on molecule delivery (plasmids), Durán As introduced in section 6.1, LSPC-synthesized AuFe alloy
showed that LAL-synthesized ligand-free AuNPs were superior particles are promising candidates for bimodal SERS-MRI-CT
to chemically synthesized Au NPs for nanoparticle-mediated imaging; hence their in vivo biocompatibility becomes important
transfection in terms of higher transfection efficiency and lower for their practical applications in clinical trials. Figure 83 shows
cytotoxicity,930 indicating that LSPC-synthesized NPs are good the in vivo biodistribution in different organs of a syngeneic
candidates for in vitro transfection assays.948 Another advantage mouse deduced from MR images at 4.7 T within 24 h. It is clearly
of LSPC is its convenience for micronization or nanominzation seen that liver and tumor display different extents of NPs
of drugs (section 6.4.4), which will lead to the improved drug accumulation at different times. Figure 83a shows a ∼10%
bioavailability in vivo and dissolution in vitro.940 decrease of the T2 signal in the tumor and an increase of the T2
4063 DOI: 10.1021/acs.chemrev.6b00468
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Figure 82. In vivo radio frequency (RF) radiation-induced hyperthermia using chemically synthesized and LAL-synthesized Si NPs as sensitizers. (a)
Schematic representation of the treatment procedure. Parts (b) and (c) are histology images of a tumor area 1 h and 3 days after the PSi NP injection and
RF-based treatment using PSi NPs as nanosensitizers, respectively. (d) Inhibition of the tumor growth under different conditions. Reprinted with
permission from ref 953. Copyright 2014 Nature Publishing Group.

signal in the liver, meaning an increase in NPs accumulation in 6.5. Analytical Chemistry (SERS, SEIRA, and LDI-MS)
the tumor and a decrease of NPs accumulation in the liver. Laser spectroscopy using the surface plasmon resonance of
Selective accumulation in tumor and their retention effect render metallic nanostructures has given rise to a highly sensitive and
AuFe agents interesting for tumor detection and treatment. Yet label-free spectroscopic analysis technique: SERS,954 which
from the Raman spectra (Figure 83b) and the images of the allows single molecule detection by measuring the enhanced
pellets from organ lysates (Figure 83c), AuFe agents also Raman signal from the molecules adhering to the metallic NP
accumulated in liver, spleen, and kidneys with only lungs and surfaces for biomedical applications955 as well as quantification of
blood free from nanoparticle accumulation. NP accumulation in SERS active NP uptake by specific cells (see also section 6.1 and
organs is a common drawback while using insoluble or larger NPs section 6.3 for magneto-plasmonic SERS).898 Increasing efforts
as contrast agents for bioimaging in vivo, pointing at further are currently underway to prepare various SERS agents by LSPC
research needed addressing the long-term biocompatibility of the driven by the cleaner spectral background of the Raman spectra
biopersistent (bioaccumulated) NP fraction. in comparison with chemically synthesized counterparts. This
In a work on NPs immobilized on implant surfaces, Angelov et phenomenon was first reported by Neddersen et al. in 1993
al. revealed that LSPC-synthesized NPs increased the (shortly after Fojtik and Henglein18 discovered laser synthesis of
impedance/stability of neural electrodes in vivo, which are NPs) who showed that LAL-synthesized Ag, Au, Pt, Pd, and Cu
good candidates for neuroprosthetic devices for recording colloids had SERS activity comparable to or superior than
neuronal activity and neural stimulation.532 This can be chemically prepared colloids,956 which was later supported by the
attributed to the tight bonding of ligand-free Pt NP to Pt studies of Kneipp et al.957 and Intartaglia et al., who used LAL-
electrode surface after EPD and controlled electrophoresis synthesized AuNPs (Figure 84a).783 In comparison to the
during EPD. The latter feature originates from the ligand-free featureless Raman background signal of LAL-synthesized NPs,
NPs, which have reduced drag force and barrierless deposition chemically synthesized NPs have an apparent fluorescence
during EPD, allowing linear control of deposition rate.303 background and a feature peak band from 2800 to 3100 cm−1 due
Through evaluating the gliosis and the number of neurons at the to the C−Hx stretching vibrational band of the contaminants
electrode tip implanted in rat brains, no adverse effect was (Figure 84a).783 The featureless Raman background using LSPC-
observed toward the neuronal cells,532 which indicates safe use synthesized NPs is assigned to the ligand-free surface, unlike
and biocompatibility for practical biomedical treatment. Most chemically synthesized NPs with stabilizing ligands on their
importantly, long-term in vivo impedance of the neural electrode surfaces, which show a significant background noise and might
was stabilized,532 making neural stimulation more energy- hinder precise molecule labeling. Moreover, the reproducibility
efficient and motivating further research on these LSPC-NP of surface-enhanced resonance Raman scattering (SERRS)
modified implants for treatment of Parkinson’s disease. spectral monitoring of the kinetics of a free base porphyrin
4064 DOI: 10.1021/acs.chemrev.6b00468
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Another type of widely used analytical methods is LDI-MS,


which is a technique useful for detecting various analytes.
Recently, a comparative study of the LDI-MS performance of
LAL-produced AuNPs and chemically synthesized citrate-
AuNPs revealed that laser-generated ligand-free AuNPs are
better candidates for LDI-MS7 (Figure 84b,c) because of their
remarkably cleaner background (Figure 84c) and almost no
spectrum disturbance in the whole mass range during detection
of different molecular structures (e.g., arginine, fructose, atrazine,
and anthracene). The stabilizers’ presence on citrate-AuNPs
causes a strong background spectrum of the LDI-MS spectra
even after dialysis (Figure 84d),7 whereas only a small amount of
analyte-sodium adducts on LAL-synthesized AuNPs lead to an
almost negligible background peak in the LDI-MS spectra
(Figure 84e).
Hence, in studies on laser-generated nanoparticles as a matrix
for matrix-assisted laser desorption/ionization mass spectrosco-
py (MALDI-MS), the low detection limit for low molecular
weight analytes resulting from the ligand-free matrix7,960 and the
good reproducibility resulting from electrophoretically deposited
Figure 83. In vivo biodistribution of AuFe alloy NPs multimodal nanoparticles for surface-assisted laser desorption/ionization
contrast agents (MCAs). (a) Plot of in vivo relaxation time in liver (■) mass spectrometry (SALDI-MS) using laser ablation in liquids961
and tumor (red ●), rationed to the value before injection of the CAs
(T2/T2(0)), versus time after injection. The plot shows that MCAs in the
were highlighted. Accordingly, the ligand-free feature of LAL-
liver decrease and accumulate in the tumor over a time scale of several synthesized NPs has clearly proven to be beneficial for areas of
hours, as sketched in the left side of the figure. (b) Plot of Raman analytical chemistry such as SERS in the visible and infrared
intensity at 1505 cm−1 in different organ lysates, showing preferential regions as well as LDI-MS.
accumulation in liver, spleen, kidneys, and tumor, while negligible 6.6. Catalysis and Energy
accumulation was found in lungs and blood. (c) Image of pellets
obtained from organ lysates, derived from MCAs treated or mocktreated Catalysts are the most important building blocks of devices for
mice sacrificed 24 h after the injection. Dark-brown staining depends on chemical energy storage and conversion. Nowadays, the most
the loading of MCAs. Reprinted with permission from ref 822. commonly used nanoscale catalysts are often synthesized by
Copyright 2014 Wiley-VCH. chemical bottom-up methods such as impregnation or salt
reduction,962 where indispensably ligands or reactants are
metalation is low for chemically prepared Ag colloids but high for needed to aid the synthesis or stabilize the colloids. After the
LAL-synthesized colloids.364 Thus, this analytical test proves the colloid synthesis, catalysts’ postcleaning procedures like
advantages of the LAL-generated colloids over the chemically calcination,963 centrifugation,964 or ozonolysis965 are necessary,
prepared ones for SERS and SERRS analysis. LSPC-synthesized which may cause particle growth and/or agglomeration, leading
NPs have also been applied for surface-enhanced infrared to the loss of catalytic activity.966 Although facile cleaning of
absorption spectroscopy (SEIRAS),958 which is a complemen- chemically prepared Au−TiO2 catalysts by reflux significantly
tary technique of SERS for biochemical applications due to its increases its performance, only 20% of residuals are removed by
ability to probe almost all bands of the adsorbed species, this method.9 In comparison, LSPC is an efficient technique,
resistance to fluorescence interference, high sensitivity, and good which allows one-step synthesis of the nanoparticle catalysts
enhancement factor (10−100× enhancement of vibrational without any requirement of ligands or postsynthesis cleaning.967
bands).959 Given that very promising pioneering works have Today, relevance of LSPC has been shown for hydroxides,601
covered SERS and SEIRAS, further investigations are expected in semiconductors,439,968 as well as noble metals967,969 and
the future. alloys.970 Easy LSPC synthesis of metal and alloy nano-

Figure 84. Featureless background of LSPC-synthesized NPs in analytical chemistry because of the absence of ligands on the surface. Raman spectra (a)
using picosecond laser ablated Au NPs (psLA-NPs, ligand-free surface) and chemically synthesized NPs (chem-NPs, citrate-capped surface). Adapted
with permission from ref 783. Copyright 2013 Royal Society of Chemistry. LDI-MS spectra (b,c) using citrate-AuNPs (green) and bare LAL-AuNPs
(red) and (d,e) schematics of surface chemistry. Adapted with permission from ref 7. Copyright 2013 American Chemical Society.

4065 DOI: 10.1021/acs.chemrev.6b00468


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Figure 85. Reference material for catalytic reaction modeling: (a) Schematic of modeling by Langmuir−Hinshelwood kinetics of reduction of 4-
nitrophenol (Nip) to 4-aminophenol (Amp) using (b) LAL-generated ligand-free Au NPs (Adapted with permission from ref 969. Copyright 2015
Springer) as compared to (c) chemically generated Au NPs. Reprinted with permission from ref 980. Copyright 2014 Springer. Process stability: (d)
SPR shift after reaction as compared to initial SPR position before reaction, and (e) catalytic activity comparison between LAL-AuNPs/TiO2 and
commercial AUROlite catalyst AuTiO2. Reprinted with permission from ref 967. Copyright 2015 Elsevier.

catalysts108 (e.g., AuPt,970 PtCo160,430), a good size control of features of LSCP-synthesized NPs for energy applications are
both LSPC-synthesized (section 3) and chemically synthesized clarified.
NPs (e.g., size reduction of encapsulated Ag NPs of Ag@ 6.6.1. Reference Materials, Model Reactions. The most
SiO2493) by LFL, as well as “smart” catalysts assembly/ valuable feature of LSPC-synthesized NPs for catalysis
construction (CO2-switchable poly(N,N-diethylaminoethylme- application is their ligand-free, naked surface where ligands
thacrylate) (PDEAEMA)−AuNPs,714 AuNP decorated NaY- cannot block the catalytic activity like at chemical-synthesized
F4:Yb3+,Er3+,Tm3+-core@porous-TiO2-shell microspheres971) catalysts, which indicates that LSPC-synthesized NPs are
starting from LAL-synthesized ligand-free NPs facilitate excellent catalytic reference materials for kinetic modeling of
optimization of the catalytic performance. For example, the various catalytic reactions. For example, LSPC-synthesized Au
highest reported performance has been achieved for LSPC- NPs have been successfully used as reference materials for
synthesized heterogeneous catalysts, such as LAL-AuNP/CeO2- mechanistic studies of the reduction of 4-nitrophenol (Nip) by
NT catalysts972 for 4-nitrophenol reduction with 1.40 × 10−2 s−1 sodium borohydride using Langmuir−Hinshelwood kinetics
(Figure 85a).969 As shown in Figure 85b, the experimental data
(μmol Au)−1, LAL-Co3O4 NPs536 for water oxidation with a high
fit well with the kinetic scheme based on the reduction
mass activity of 1.02 × 108 mA cm−2 g−1 and a high turnover
mechanism of metallic NPs on the direct route; even after 70%
frequency of 0.21 mol O2 (mol Cosurface)−1 s−1, and Pt/rGO
Nip conversion, the experimental data still fit,969 much better
catalysts973 for methanol oxidation with 333.3 mA mg−1. than mere fitting by the chemically synthesized reference
The purpose of synthesizing catalysts by LSPC and evaluating material (Figure 85c).980 Heterogeneous Au/TiO2 catalysts
their performance is to utilize them for catalysis-based energy consisting of such ligand-free Au NPs have higher “process
devices, such as water oxidation/splitting for fuel cells,974 glucose stability” (durability) than commercial AUROlite Au/TiO2
oxidation for biofuel cells, etc. In light of decreasing energy catalysts due to less NP aggregation and/or particle growth
consumption, LSPC has addressed many routes to save energy after reaction with less SPR shift (Figure 85d).967 At elevated
by friction reduction573,975−977 or develop sustainable energy temperature, the activity of laser-generated Au/TiO2 is 1.5 times
(e.g., solar cells,263,978 supercapacitor,601 Li-battery979) . In this higher than that of AUROlite catalysts even though their size (7.8
section, we first demonstrate the advantage of using LSPC- nm) is much larger than 3.0 nm of AUROlite catalysts (Figure
synthesized NPs as reference materials for model reactions and 85e).967 These works indicate that LAL-synthesized ligand-free
for creating supported catalysts and photocatalysts. Subse- NPs are durable good reference materials for evaluating the
quently, taking solar cells and fuel cells as typical examples, the ligand’s effects during various reactions. Because productivity of
advantages of high purity (ligand-free) and surface charge such reference materials (e.g., Au,374,972 etc.) generated by LSPC
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Figure 86. Higher adsorption efficiency and turnover rates using LSPC-synthesized NPs due to the ligand-free surface. (a) Adsorption efficiency (of
metal NP on catalyst support) as a function of citrate ligand concentration on LAL-synthesized metal NPs. Adapted with permission from ref 984.
Copyright 2012 American Chemical Society. Reduced incubation time and higher activity due to surface charge: (b) “Free” AuNPs remaining in the
solution as a function of incubation time for LAL-AuNPs and Chem-AuNPs after the addition of CeO2 NT supports, respectively. Catalytic activity: C/
C0 and −ln(C/C0) as a function of reaction time for the reduction of 4-nitrophenol using (c) LAL-AuNPs/CeO2-NTs and (d) Chem-AuNPs/CeO2-
NTs. (e) Superior performance of LAL-synthesized Au/CeO2 during heterogeneous CO oxidation reaction. Adapted with permission from ref 972.
Copyright 2013 Elsevier.

has reached a high throughput (4 g/h),22,31 expansion of LSPC- LAL-AuNPs/CeO2-NTs are much more active than the Chem-
NPs as reference materials for catalysis can be anticipated. AuNPs/CeO2-NTs for the reduction of 4-nitrophenol into 4-
Moreover, for screening purposes of catalysts of different aminophenol (Figure 86b). The reaction almost ends within
composition such as alloys or mixed metal oxides, LSPC is 1200 s for LAL-AuNPs/CeO2-NTs with a reaction rate constant
probably the only method to achieve a high throughput of (kapp) of 1.40 × 10−2 s−1 m−2 (Figure 86c), while in their
different catalyst materials in a limited amount of time such as chemically derived analogue (Chem-AuNPs/CeO2-NTs), the
shown for a NiFe layered double hydroxide (LDH)981,982 series rate constant kapp = 2.25 × 10−3 s−1 m−2 (Figure 86d) is 1 order of
testing for water oxidation and PtAu alloy series for electro- magnitude lower, and after 1500 s only a yield of 0.5 is
chemical reactions.413,414,983 reached.972 The same catalyst was tested in heterogeneous CO
6.6.2. Supported Catalysts. The synthesis of heteroge- oxidation, yielding high conversion rates at lower temperature for
neous catalysts is a widely adopted strategy, often aiming at the laser-generated catalyst (Figure 86e). Other evidence to
defined metal−support interactions (MSI), in which case the support the amenities of LSPC-synthesized NPs over chemically
adsorption efficiency of adsorbates on adsorbents should be as synthesized counterparts was shown by Li et al., who reported
high as possible because it determines the active site quantity that LAL-Au NPs/BiFeO3 nanowires are ∼30% more active than
available for the reaction. Because of the absence of shielding and the chemically synthesized Au NPs, evaluated by the water
pH effect by ligands, LSPC-synthesized colloidal NPs are more oxidation (water splitting) reaction.374 Furthermore, although
prone to reach the dispersed adsorbent surface efficiently. the ligands on the NP surface are deleterious to the catalytic
Wagener et al. showed that adsorption efficiency of LAL- performance in many cases, recent reports showed that some
synthesized Ag NPs on BaSO4 microparticles is 20 times higher agents (e.g., organic ligands, polymers) provide metal−organic
in the ligand-free state than those covered by citrate-stabilizers interfaces that can significantly enhance strong metal−support
(Figure 86a).984 Those NPs with less than 50% ligand coverage interactions (SMSI).985 From this perspective, the ligand-free
show an adsorption efficiency of almost 100%, providing properties of LSPC-synthesized metallic NPs allow the surface
unparalleled high noble metal adsorption yield. Transferability and interface control from scratch for SMSI useful for catalytic
has also been proven for metal (Ag, Au, Pt) adsorption onto and electrocatalytic applications.
various supports (BaSO4, TiO2, CaCO3).984 Hence, the The Liang group reported three routes to synthesize
cumulative material yield of precious metal in the process supported catalysts using LAL-produced active nonstoichiomet-
chain from precursor over the colloid to the catalyst is almost ric MOx oxides (e.g., SnOx, TiOx, MnOx, etc.). One is to utilize
100%,135 presenting an economic (and ecologic) advantage. MOx oxides (e.g., SnOx) as a sacrificial template to reduce metal
Additionally, the intrinsic surface charge of LAL-synthesized NPs ions (e.g., [PtCl6]2−) in the support (e.g., GO) suspension
(e.g., Au) is also beneficial to increase the adsorption efficiency solution.973 Other routes include the development of metal−
and reduce the induction period in combination with oppositely oxide (e.g., Ag−TiO2544) and M-doped (M: Ge, Sn, Mn, etc.)
charged supports (e.g., CeO2-NTs) (Figure 86b).972 Because of hematite (α-Fe2O3) nanostructures551,554 by hydrothermal
the high adsorption efficiency (∼100%) and ligand-free surfaces, treatment of MOx colloids and metal ions (e.g., AgNO3 and
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Figure 87. Biofuel cells based on a catalytic reaction of glucose oxidation using LAL-synthesized Au NPs. (a) Schematic presentation of a hybrid biofuel
cell for implantable biodevices. (b) Voltammograms of CTAB-Au NPs (red), Citr-Au NPs (blue), and LAL-Au NPs (black) electrodes in 0.1 mol L−1
NaOH recorded at 20 mV s−1 and 25 °C in the presence of 10 mmol L−1 glucose. Adapted with permission from ref 998. Copyright 2015 American
Chemical Society.

FeCl3) mixtures, respectively. Hence, LSPC-synthesized oxygen- presence of rich defects of the LSCP-synthesized oxides, some of
defect-rich nonstoichiometry MOx oxides are good reducing them have already been proven to be superior to TiO2 (P25) for
agents and sacrificial reagents to elegantly synthesize oxide or photodegradation of methyl orange, which is considered to be
metal supported catalysts via RLAL or RLFL. the best commercial photocatalyst.993
6.6.3. Water Oxidation (Splitting). Water oxidation 6.6.5. Hydrogen Fuel Cell. Hydrogen is considered as a very
(2H2O → O2 + 4H+ + 4e−) catalysts, generally characterized promising next-generation fuel (energy carrier) that could
by oxygen evolution reaction (OER) or oxygen reduction replace fossil fuels because of its high energy density (142 MJ
reactions (ORR), are widely studied materials.974 This trend is kg−1) and abundance (e.g., water, organic solutions, biomass).
driven by the fact that water oxidation is the first step of water Many researchers have shown the feasibility to generate
splitting (2H2O + hν → 2H2 + O2) for sustainable energy hydrogen through water splitting (section 6.6.3) and hydro-
resources and requires robust catalysts to extract 4H+/4e− from carbon oxidization (methanol,994 ethanol,995 and formic acid983)
two water molecules and to form an oxygen−oxygen bond.974 via LSPC-generated reduced TiO2/GO,996 Au/MwCNTs,995
Recently, Müller and co-workers have shown the potential to Au/graphene,994 CoO,485 and PtAu983 nanoalloys as well as the
produce the most active electrocatalysts for water oxidation via hydrogen storage by Mg@PMMA composites.588 In the
LAL. 536,982 For instance, Ti 4+ and La 3+ ion doped literature, one apparent advantage of using LSPC-synthesized
[Ni1−xFex(OH)2](NO3)y(OH)x−y·nH2O yielded a very low NPs as compared to chemical-synthesized catalysts is the
overpotential (260 mV at 10 mA cm−2).982 Their work bandgap decrease of the photocatalysts caused by non-
demonstrated the possibility to systematically screen mixed- stoichiometry oxides (e.g., TiO2−x996) and electronic recon-
metal catalysts’ composition series using aqueous solutions with struction (e.g., α-Ag2WO4997), which can significantly increase
metal ions (e.g., Ti4+ and La3+) during RLAL.981 Mukherjee and the visible light absorption485 and result in the enhancement of
co-workers further confirmed superior ORR/OER activities of
photocatalytic performance.
RLAL-synthesized PtCo nanoalloys and PtCo/CoOx nano-
6.6.6. Biofuel Cell and Glucose Oxidation. Biofuel cells
composites.160,430 The mass-specific activities of LAL-synthe-
are a kind of power suppliers that are different from hydrogen
sized PtCo NPs with a Co molar ratio of 22.1% are approximately
fuel cells in two aspects. First, the chemical energy is obtained
2.7 and 5.5 times higher than commercial Pt/C catalysts toward
from abundant biomass (typically glucose or other sugars), which
water oxidation, respectively.160 PtCo/CoOx composites at the
optimal mixture (33.3 M%, 62.3 wt %) allowed a combined makes them available to supply power for implanted biosensors
overpotential of 756 mV vs RHE (reversible hydrogen electrode) or pacemakers (Figure 87a).998 Second, biofuel cells can be used
toward water oxidation in alkaline media taking into account at ambient temperatures. Enzymes serve as biocatalysts for
both ORR and OER activities, which is the highest value reported glucose oxidation, but considering their vulnerability to the
so far using carbon black as supporting material.430 In a different formed hydrogen peroxide, there is a demand for developing
study, Liao et al. achieved the highest (∼5%) solar-to-hydrogen selective electrocatalysts for glucose. Hebié et al. recently showed
efficiency of water splitting under visible-light irradiation taking the promising prospect of electrodes containing LAL-generated
advantage of LFL-CoO NPs.485 Au NPs for biofuel cell applications.998 They compared the
6.6.4. Photocatalyst. Because of the ability to mineralize glucose oxidation performances of LAL-synthesized Au NPs,
various organic pollutants, such as dyes, herbicides, pesticides, CTAB-, and citrate-capped Au NPs and showed that the current
aromatics, etc., and photocatalytic reduction of heavy metal ions densities (at 0.4 V) obtained from LAL-generated Au NPs are ∼5
(e.g., Cr(VI)),986,987 photocatalysts have occupied an important times higher than those from ligand-coated Au NPs, and the ratio
position in the field of pollutant removal.988 Although the stays almost constant for the successive oxidation of lactone
investigation of LAL-synthesized NMs as photocatalysts just (Figure 87b), as indicated by the second peak in the range of
started several years ago,989 applying LSPC-synthesized NPs as 1.15−1.3 V. The mass activity of LAL-generated Au NPs was 65
photocatalysts for pollutant removal has advanced rapidly, as A g−1 (6 mA cm−2), that is, much more active and more efficient
indicated by the synthesis of TiO2,176,968 α-Bi2O3,612 TaxO@ than chemically synthesized Au NPs for glucose oxidation, which
Ta2O5,615 TiO2−Ti5O9,990 Pt−TiO2,726 ZnO/TiO2,991 ZnS/ was ascribed to the high “purity” of LAL-generated NPs, thus
Zn,986 MWCNT/ZnO,992 Sn6O4(OH)4,993 etc. Because of the demonstrating the great promise of LAL-synthesized Au NPs to
large surface-to-volume ratio of LFL-synthesized NPs and the be applied for biofuel cells.998
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Figure 88. Effect of NP surface chemistry on bulk-heterojunction (BHJ) solar cells performance. (a) Schematic representation of the BHJ organic
photovoltaic (OPV) cell architecture with an active layer embedded with either LAL-synthesized ligand-free bare or chemically synthesized TOAB-
terminated or P3HT-terminated Au NPs, (b) I−V characteristics of reference and BHJ solar cells of the configuration ITO/PEDOT:PSS/
P3HT:PCBM/Al incorporating different types of Au NPs into the active layer, and (c) the incident photon-to-current conversion efficiency (IPCE)
curves of reference and OPV devices incorporating different types of Au NPs into the P3HT:PCBM. Adapted with permission from ref 999. Copyright
2015 American Chemical Society.

6.6.7. Solar Cell. Conventional chemically synthesized NPs (Figure 88a), including LAL-synthesized Au NPs, TOAB-
are always covered by insulating ligands, which inevitably exert terminated Au NPs, and P3HT-terminated Au NPs.999 A
barriers for electron transfer and arouse a side effect for tailoring 20.3% increase in the power conversion efficiencies (PCE) is
the band gap of semiconductor NPs. In the preparation of solar observed for LAL-generated bare Au NPs (Figure 88b), much
cells, expensive equipment such as chemical vapor deposition better than TOAB-terminated Au NPs, which is even inferior to
(CVD) is often employed for material deposition. Ligand-free the reference device. The same trend is also achieved regarding
NPs and cheaper film deposition devices are desirable for a cost- the enhancement of the incident photon-to-current conversion
saving preparation of solar cells with high efficiency.109 efficiency (IPCE) (Figure 88c). As compared to P3HT-
Addressing these problems by LAL-synthesized semiconductor terminated Au NPs, better performance for IPCE enhancement
NPs are of great appeal because of their ligand-free and highly is displayed by LAL-generated bare Au NPs. Through analysis of
charged surface. For example, Guo and Liu have fabricated the active layer structures by atomic force microscopy (AFM)
Cu(In,Ga)Se2 (CIGS) solar cells on Mo sheet substrates by and time-resolved PL spectroscopy, the authors concluded that
combining LAL and EPD (a method for film deposition based on only when the plasmonic NPs are in direct contact with the active
electrokinetic mobility of the charged colloids under an external layer polymer donor can the solar cells’ performance be
electric field) techniques,530 which eliminates the risk of film enhanced, while for an extra ligand that does not consist of the
contamination by impurities (e.g., adhesives or binders). The
same materials the active layer will deteriorate the active layer
energy conversion efficiency was already quite well 7.37%, but
morphology and result in exciton quenching, which is
further studies are required to elevate the efficiency above 10%,
unfavorable for BHJ solar cells.999 Besides plasmon-enhanced
which is needed for practical solar cell applications.
Bulk-heterojunction (BHJ) solar cells are another potential absorption effects, embedment of LSPC-synthesized Al, Ag, and
low-cost, lightweight photovoltaic technology because of their Au NPs in the photoactive layer can also enhance the structural
hybrid polymer blends’ layout (polymer/nanocrystal serves as stability of the active blend to decrease the device degradation
donor/acceptor for hole/electron transport)1000 and the simple rate upon long-period illumination due to NP-mediated
manufacturing process by roll-to-roll coating or printing. To mitigation of the photo-oxidation effect.1002−1004 Analogously,
address the conflict between efficient light absorption, which is the PCE and the stability of ITO/GO/AuNPs/P3HT:PCBM/Al
higher in thicker devices, and efficient photogenerated carrier organic photovoltaic devices are both improved by anchoring
collection, which is higher in thinner devices, plasmonic metal LSCP-synthesized Au NPs between the interface of the active
NPs are designed to be embedded inside BHJ solar cells to trap layer (P3HT:PCBM) and the hole transport layer (GO).1005
incident light and increase the optical absorption.1001 Hence, These works clearly demonstrate the positive effect of ligand-free
evaluation of the embedded plasmonic NPs is important for the plasmonic NPs on the performance of BHJ solar cells. Hence, the
performance of BHJ solar cells. Kymakis et al. compared the application of LSPC-synthesized NPs as plasmonic additives to
effect of three types of Au NPs with different surface chemistry optimize organic solar cells in various configurations (e.g., active
on the performance of poly(3-hexylthiophene-2,5-diyl): phenyl- layer, hole transport layer, and between their interfaces) may
C61-butyric acid methyl ester (P3HT:PCBM) BHJ solar cells become fertile.109,1006
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Figure 89. Heavy metal, food pollutant, and hazardous gas detection using LSPC-synthesized NPs assembled electrodes. Heavy metal detection: (a)
TEM images of LAL-synthesized Au NPs. (b) Differential pulse anodic stripping voltammetry (DPASV) response of the AuNPs/GC electrode for the
simultaneous detection of Cd2+, Pb2+, Cu2+, and Hg2+ over a concentration range of 0−1.4 μM for each metal ion. Reprinted with permission from ref
563. Copyright 2013 American Chemical Society. Food pollutant detection: (c) TEM image of LAL-synthesized Ni NPs. (d) Electrochemical response
studies of BSA/a-AfB1/DMSO/RnNi-film/ITO bioelectrode with respect to AfB1 toxin concentration (5−100 ng dL−1). Reprinted with permission
from ref 1009. Copyright 2012 American Institute of Physics. Hazardous gas detection: (e) TEM image of LAL-synthesized mesocrystal CuO NPs (M−
CuO) and (f) real-time gas-sensing response of mesocrystalline (M−) (black), singlecrystalline (S−) (red), and polycrystalline (P−) (blue) CuO NPs
toward ethanol at concentrations of 12.5−200 ppm. Reprinted with permission from ref 1010. Copyright 2016 Royal Society of Chemistry.

Quantum dot-sensitized solar cells (QDSSC) are thin film for the rubbing surface, thus reducing the friction under
devices benefiting from the efficient charge transfer of photo- tribologic pressure strength over time. Because ZnO has a
generated carriers and diffusion of redox couples in the small hardness of 4.5 on the Mohs scale, the LML-synthesized
electrolyte. Many LSPC-synthesized semiconductor QDs (e.g., ZnO SMSs may not be resistant to friction over time. Harder
ZnSe and CdS,613 CdTe,1007 and CdSe1008) and TiO2 SMSs278 materials (e.g., Al2O3) may show increased antiwear proper-
are promising for use as either film building blocks or absorbers ties,977 enabling them to be used for long-lasting frictional
for QDSSC application, respectively. Until now, due to limited applications.
investigations, whether they perform better in comparison with 6.7. Environmental Protection
chemically synthesized counterparts still needs to be explored.
Industrial wastewater discharge, motor vehicle exhaust, and
6.6.8. Friction Reduction. The addition of nanomaterial
extensive use of pesticides and chemical fertilizer in agriculture
additives in lubricating oil/grease to reduce friction, improve
have produced many kinds of pollutants, including heavy metals,
antiwear ability, or retard the thermo-oxidation of lubricating oil/
poisonous gases, and biopersistent molecules. Portable mini-
grease may become increasingly attractive for industry, mainly aturized electrochemical detectors are strongly desirable for
motivated by energy saving and lowering the maintenance cost. pollutant detection.
The potential of LSPC-synthesized NMs for this applications lies Driven by increased electron transfer rate from pure NP
in two aspects. One is directly producing lubricant nanofluids by surfaces and large surface areas from ultrasmall dimensions,
LAL in lubricating oil/grease, and the other is the suitability of LSPC-synthesized NMs have been widely employed for trace
LML-synthesized SMSs for rolling friction reduction. Flores- detection of poisonous substances, such as heavy metal ions, food
Castañeda et al. recently showed the feasibility to achieve or water pollutants (e.g., xanthine,1011 pathogen,1012 phenyl
lubricating oil with bismuth NPs as the additives by direct LAL of hydrazine1013), as well as flammable and explosive gases (e.g.,
a bismuth metal target in both heavy and light viscous mineral CO, ethanol, HCl, H2).53,68,1014−1017 Note that selectivity is very
base oils (BS6500 and BS900).573 The concentration and the size important for pollutant detection, for example, during HCl gas
of bismuth NPs could be tuned by adjusting the processing sensing using LAL-synthesized FeOCl nanosheets.68 In the
parameters, which in turn affect the friction performance of the following, one representative detector is introduced to show the
synthesized bismuth NP-containing lubricant fluids.573 Cao et al. potential of LSPC-synthesized NPs for various detection
tested the performance of LML-generated ZnO/TiO2/CuO/ applications, covering heavy metal ion detection, biotoxin
Fe3O4 SMSs as lubricant oil additives.975,976 When such SMSs are detection (immunosensing), and selective sensing of volatile
introduced into the lubricating oil, the friction coefficient could compounds. Xu et al. assembled LAL-synthesized spherical Au
be dramatically reduced dependent on the concentration of the crystalline grains with a size of 5 and 35 nm (Figure 89a) into a
SMSs. Such LML-generated SMSs are thought to act as spacers sensitive electrochemical detector for heavy metal ions via
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Figure 90. Pollutant adsorption (a) Comparison of the equilibrium isotherms between the experimental and theoretical data of amorphous LFL-
synthesized NiO nanostructures. (b) The effect of initial pH on MB adsorption using NiO nanostructures. Adapted with permission from ref 1018.
Copyright 2015 Nature Publishing Group.

Figure 91. Advantages of the LSPC process and synthesized materials.

EPD.563 This sensor can simultaneously detect four heavy metals surface area) originating from the quasi-monocrystal lattice,
(Cd, Pb, Cu, and Hg) through four peak currents (Figure 89b) higher density of oxygen vacancies, and branched structures of
with potentials of −0.78, −0.56, 0.00, and 0.25 V corresponding the M−CuO assembled spindles. Therefore, similar to the
to the oxidation potentials of Cd(0), Pb(0), Cu(0), and Hg(0), catalysis applications (section 6.6), the ligand-free surfaces
respectively.563 Besides the most frequently investigated Au NPs feature of LSPC-synthesized NPs is very appealing for designing
for colorimetric assays, other kinds of nanomaterials are also and constructing electrocatalyst-based detectors.
good candidates as electrochemical catalysts for detection Because of the high toxicity, once the pollutants enter the food
applications. For example, Kalita et al. developed an chain or are directly exposed to living beings, they may cause fatal
immunosensor for aflatoxin (AfB1) detection with a broad diseases. Many approaches have been proposed for pollutant
detection range (5−100 ng/dL), high sensitivity (0.59 μA/(ng/ removal and were generally classified into physical and chemical
dL)), and low detection limit (32.7 ng/dL) using LAL-generated methods. Physical adsorption is a widely adopted physical
ring-like nickel NPs (Ni ≈ 10−20 nm, Figure 89c) as a good method, not only effective for heavy metals but also for dyes and
conductor for electrons to be transferred to the electrode via preservatives. Recently, LFL-synthesized NiO NPs have shown
Ni2+/Ni3+ redox couple (Figure 89d).1009 This detector has been their promise as adsorbents for pollutant removal in light of the
claimed to be fine for AfB1 toxin detection in grains, nuts, rice, highest adsorption capacity (beyond 104 mg/g) toward MB dyes
and oil seeds to prevent the carcinogenic, mutagenic, teratogenic, reported so far (Figure 90a).1018 Many factors lead to this
and hepatotoxic effects in the case of an overdose. Furthermore, substantial adsorption capacity as compared to the starting NiO
Li et al. recently reported an ethanol detector using LAL- NPs with only ∼255 mg/g. The first reason is related to the high
synthesized self-assembled CuO (M−-CuO) interconnected surface area of synthesized amorphous NPs, which is about 10−
spindles (Figure 89e), which showed the highest sensitivity from 30 times larger than the raw materials. Second, a strong reaction
12.5 to 200 ppm (Figure 89f), fastest response, and the best between the dye and OH radicals on the NiO NP surface
selectivity ever reported (as claimed by the authors).1010 The provides more adsorption sites for MB’s adsorption. Third, the
superior performance as compared to chemically synthesized formed positively charged center M(Fe, Co, and Ni) (OH+) at
single/poly(S−/P−) crystalline CuO structures is ascribed to the pH = 6.5 enables surface bonding toward the negatively charged
unique properties (e.g., lower initial resistance in air/higher functional groups of dye (−SO3−), allowing further adsorption
working resistance in ethanol, active sites, and larger specific (Figure 90b). All of these features can be easily achieved by LFL
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Table 7. Advantages of LSPC-Generated NPs and Corresponding Exemplary Applications


advantage of employed
LSPC product technique model substance or reaction potential applications
convenience PtAu LAL formic acid electro-oxidation catalysis983
Fe@Au LAL PMMA substrates transparent and electrical conducting
coatings418,540
AuFe LAL mouse mammary tumor cells multimodal imaging (SERS-MRI-
CT)822
AuAg LAL nonlinear scattering and nonlinear optical limiting768
absorption
mixed metal (NiFe) hydroxides RLAL water oxidation catalysis981,982
doped semiconductor NPs (e.g., Cu- RLAL Cu doping-induced band-edge emission photoluminescence428
doped ZnO)
ternary oxide (e.g., NiCo2O4) RLAL Co2O4 + OH− + H2O ↔ NiOOH + pseudocapacitors1020
+hydrothermal 2CoOOH + e−
high purity Gd2O3 RLAL nasopharyngeal carcinoma xenografted MRI828
tumor
AuAg, Au LAL cresyl violet and Rd6G SERS783
Au LAL arginine, fructose, atrazine, anthracene, LDI-MS7
and paclitaxel
Au LAL reduction of 4-nitrophenol catalysis969
Au/TiO2 LAL+adsorption ethanol oxidation stable catalytic process967
Au LAL glucose oxidation biofuel cell998
Au, Pt LAL neurotoxic fibril inhibition biomedicine344
Au LAL germ cell function and embryo toxicity mechanism346
development
Au LAL plasmid DNA transfection930,1021
Au LAL P3HT:PCBM BHJ system solar cell999
start from scratch Au LAL PEGylated Au biomedicine341
Au LAL pNIPAm-co-Am coated AuNPs cell-specific internalization945,946
Au LAL CO2-switchable Au-PDEAEMA catalysis714
composite
Pt LAL EXAFS, supported particles catalysis566
AgGe RLAL 4Ag+ + Ge → 4Ag + Ge4+ photoelectronics23
supersaturation Au nanocorals LFL human fibroblasts and tumor cell lines photothermia249
CuO spindles RLAL ethanol gas gas detection1010
charged surface Mn3O4 RLAL pentachlorophenol pollution remediation810
Au/CeO2 LAL+adsorption nitrophenol reduction Co oxidation catalysis972
Pt LAL+EPD neural implant Parkinson’s disease device (in vivo)532
defect ZnO LAL interstitial-zinc-related defect photoluminescence218,444
introduction TiO2 RLAL Escherichia coli and methylene-blue dye photocatalysis439
Ag/TiO2 RLAL Ag/TiO2 pentachlorophenol (PCP) photocatalysis544
+hydrothermal degradation
M-doped α-Fe2O3 (M: Ge, Mn, Si, Sn, RLAL reversible hydrogen electrode (RHE) catalysis552,554
Ti, etc.) +hydrothermal
Pt/rGO RLAL methanol oxidation electrochemical catalysis973
+hydrothermal
α-Ag2WO4 RLEL MO degradation and H2 evolution photocatalysis997
TiO2−x/GO mixed RLEL water splitting photocatalysis996
carbonization Pd@C RLAL nitrobenzene reduction catalysis702
Co3O@C RLAL magnetic and C-shell photoluminescence multiplexing383
size control ZnO, TiO2, CuO SMSs LML rolling friction friction reduction296,975
Si QDs LAL photoluminescence LED869
PtCo LAL oxygen reduction of HClO4 electrolyte electrocatalysts160

in water where water breakdown is thought to provide the OH Therefore, in light of the capacities of LFL-size control and
radicals for surface functionalization,263 and the educt particles LSPC-surface chemistry, many other effective adsorbents’
are transferred into an ultrasmall size that provides a high surface fabrications may be anticipated for adsorption and removal of
area for pollutant adsorption. Meanwhile, surface charge is an dyes as model pollutants from two routes of LFL and LAL.
intrinsic property of LFL-synthesized nanoproducts. Another
often investigated series of adsorbents for pollutant removal are 7. SUMMARY OF ADVANTAGEOUS PROPERTIES
mesoporous nanomaterials, which can also be obtained by LSPC. CORRELATED TO APPLICATION PROSPECTS
For example, Wang et al. synthesized layered mesoporous
Mg(OH)2/GO composites by RLAL of a Mg target in GO As demonstrated by the studies discussed in section 6, LSPC has
solution, which were shown to efficiently adsorb both dye model proven to be a synthesis method that provides nanoparticles with
contaminants (MB) and heavy metal ions (Zn2+ and Pb2+).663 numerous advantages. Figure 91 and Table 7 summarize these
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advantageous properties that can be related to both LSPC itself their chemically synthesized counterparts.374,972 Elimination of
as well as the resulting nanomaterials. the ligand effect also makes LSPC-synthesized “naked” nano-
LSPC offers a continuous, steady-state process, where seeds catalysts unparalleled reference materials for modeling chemical
can be continuously supplied for downstream unit operations reactions with perfect fits to theory969 and results in significantly
(e.g., ex situ conjugation or catalyst adsorption onto supports) to greater process stability (durability) during alcohol oxidation in
allow for direct integration of the synthesized NPs into stable heterogeneous catalysis at elevated temperatures than the
hybrids that are easy to handle and store. The use of state-of-the- chemically prepared “gold standard” reference catalysts.967 For
art laser systems with MHz repetition rates and subkilowatt laser the purpose of constructing stable supported heterogeneous
powers has demonstrated that NP productivities greater than 4 catalysts using LSPC-synthesized NPs as adsorbates, greater
g/h are possible,22,31 and that the productivity is linearly scalable adsorption efficiency984 and net charge transfer to the supports
and goes along with the advances made in laser system during the adsorption process135,565 are beneficial. From
technology. From the perspective of occupational safety, LSPC ecological and economic perspectives, LSPC synthesis of
is a safe technique that can prevent health hazards caused by NPs’ heterogeneous catalysts produces a cumulative yield of nearly
inhalation because it is operated in a sealed environment (the 100% of the noble metal throughout the entire process
liquid). Having a sealed vessel that can be sterilized along with chain.135,967 Additionally, because of their ligand-free nature,
the target and liquid provides advantages for sterile synthesis LSPC-synthesized colloidal NPs can contribute to our under-
conditions, for example, for the synthesis of immunogold. These standing of the principles of barrier-less charge-transfer-to-
process-related advantages are all clearly important properties for solvent (CTTS), allowing particles to chemisorb to the naked
any method intended to be used at an industrial scale. NP surface directly.164
A very attractive feature of LSPC for use at laboratory or pilot Because no ligands or surfactants are present to interfere with,
scales is that it provides a quick and convenient platform for the LSPC-synthesized ligand-free NPs offer a complete noise-free
rapid prototyping of various NMs at room temperature and spectral/imaging background for analytical chemistry methods
under ambient conditions in a short period (from several (section 6.5), such as LDI-MS7 and SERS.783 Regarding SERS
seconds361 to 1 h22,31). Simple replacement of the solid target or applications, ligand-free particles are also helpful for adsorbing
the liquid enables the high throughput synthesis of systematic analyte molecules to achieve highly active SERS detection with
colloid variations (e.g., bioconjugates), which is particularly very good stability and reproducibility.535 The absence of ligands’
attractive for biological tests where normally only milligrams of blocking effect on MNPs is also advantageous for enhancing the
NPs are needed. Consequently, the easy operation and quick longitudinal relaxation rate in T1-weighted MRI applications
synthesis of LSPC make it highly accessible to researchers from a because of the shortened distance between ions of MNPs and
wide range of fields. water protons828 and because of the increased number of
Another important convenience provided by LSPC is the easy coordination sites for water hydration.811,826 For biomedical
synthesis of nanoalloy series by simply ablating an alloy125,174 applications, the absence of ligands is also uniquely advantageous
(e.g., AuAg, AuFe) or irradiating a mixed colloids (e.g., Ag and for distinguishing the toxicity of NP surface ligands from NP-
Au).593,1019 Because alloy targets may not be available in various related toxicity in vivo and in vitro.346,917 In this way, unintended
mole fractions, a very convenient approach is LAL of a powder nanoparticle exposure scenarios may be mimicked more
mixture, consolidated by pressing. Here, LAL converts a realistically, as for example implant abrasion will not involve
“micromixture” into atomically mixed (solid−solution) any stabilizing ligand but biofluid’s protein corona, only. Hence,
NPs,125,413,483 which are much more convenient than complex the nanotoxicities of ligand-coated and ligand-free NPs may be
chemical alloy-NP synthesis methods, in particular for alloy compared on the basis of LSPC-synthesized reference materials.
series with tunable composition. LSPC-synthesized alloy NPs Thereby, these materials essentially contribute to the rational
have been successfully used for multimodal imaging822 (section design of NP toxicology assays as reviewed recently.12 Note that
6.1, magnetism), optical limiting,768 magneto-amplified SERS ligand-coated nanoparticles are not inferior per se in comparison
detection67 (section 6.3, plasmonics), toxicity reduction11,346,424 with LSPC ligand-free nanoparticles for biomedical applications
(section 6.4, biology), and catalysis413,970,983 (section 6.6, because ligands have the double function of increasing NPs
catalysis and energy). LSPC also allows for facile and stability in vivo (for instance, stealth effect provided by polymers
unparalleled synthesis of mixed metal (e.g., Ni−Fe) catalyst affecting protein corona10 and capping the surface of toxic metals
series for high throughput screening and the systematic variation containing NPs to reduce the leakage of toxic ions).918 That is,
of molar ratios981,982 as well as metal cation doped luminescent ligand-free particles are good candidates as naked building blocks
NPs with tunable dopant concentrations.428 Selectively mixing where functional ligand carriers can be precisely set and
two series of RLAL-synthesized oxide/hydroxide colloids and combined. For example, Streich et al. successfully used LAL-
subsequent hydrothermal treatment offers a convenient synthesized gold and platinum nanoparticles to increase the
approach for the production of ternary oxide nanocrystals for binding affinity of Aβ-specific small molecules to inhibit
optoelectronic and electrochemical applications, such as Alzheimer Aβ peptide aggregation into fibrils in vitro.344
Zn2 GeO4 , NiCo 2O4, Zn 2SnO 4, ZnFe2O 4, ZnMnO3, and Increasing efforts have been devoted to embedding plasmonic
Fe2GeO4.1020 Therefore, LSPC has emerged as a NM synthesis NPs in bulk-heterojunction solar cells to promote photo-
technique with greater convenience than other synthesis conversion,1022 for which LAL-synthesized pure NPs are
methods and unparalleled flexibility. preferable because of the exciton quenching effect induced by
The extreme purity achieved by the ligand-free synthesis ligands.999 To develop precise nanostructured coatings via NP-
process is probably the most unique feature of LSPC-synthesized EPD, two clear advantages result from ligand-free, charged NPs.
NPs. In the absence of the hindering effect of ligands or First, no barrier build-up is observed during deposition. Second,
surfactants, more active sites of the LSPC-synthesized catalysts fully linear electrophoretic mobility is a property of LSPC-
are available to be exposed to the reactants; as a result, LSPC- synthesized ligand-free NPs, which allows for the precise scaling
synthesized catalysts display better catalytic performance than of the deposited NP mass with EPD time.303 Because no steep
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phase boundary originating from direct hard binding of the for recording neuronal activity in vivo with an improved long-
ligand-free NPs to the EPD-produced implant surface was term stability.532 Additionally, the surface charge of LSPC-
observed via cross-sectional analysis,1023 EPD coating of ligand- synthesized NPs is beneficial for in situ308,717,730 and ex situ558
free NPs is preferable to conventional “coating” methods that conjugation with proteins, DNA, or other biomolecules for
often require postannealing or ligand removal steps. As for medical and clinical applications.
plasmonic-related applications, without a bathochromic shift of The introduction of high defect densities is normally
the SPR peak maximum as a result of ligand-induced refractive conducted by LAL of ignoble metals in water (section
index variation, LSPC-synthesized plasmonic NPs have lower 5.3.1).440 These defects either facilitate PL emission of the
SPR wavelengths as compared to their chemically or biologically host nanoparticles444 or delay the electron−hole recombination
synthesized counterparts,125 making them favorable for the and result in enhanced photocatalytic performance.439 Because
design of optical applications. Hence, pure colloids not only charge transport is proportional to the defect quantity, small
provide application-oriented advantages but also bring the semiconductor particles with many defects will increase the
studied NP properties closer to textbook-like fundamental charge transport and have been reported to enhance photovoltaic
behaviors such as exhibiting ideal Stokes’ hard spheres (as an performance.1024 Sacrificial substoichiometric defect-rich oxides
assumption for calculating charge-mobility relations) or ideal (e.g., TiOx, x < 2) derived from RLAL can reduce metal ions (e.g.,
plasmonic particles (for experimental evaluation of the plasmon Ag+) during hydrothermal treatment, which enables the direct
ruler equation or the Mie−Gans fit). synthesis of conjugated photocatalysts for pollutant degrada-
Defined surface functionalization starting from scratch is an tion.544
advantage rendered from the ligand-free surface of the LSPC- Carbonization is another attractive characteristic of LSPC-
synthesized NMs. Different types of molecules can be precisely synthesized NMs. The carbon shell capsule is produced in
grafted onto the naked surfaces of LSPC-synthesized NMs to organic solvents (e.g., acetone,383 acetonitrile,702 etc.) where the
develop “smart” nanomaterials for catalytic and biological carbon of the organic molecules serves as the resources during
applications, such as CO2-switchable PDEAEMA-Au NPs714 RLAL or RLFL. The carbon shell is particularly appealing for
and thermosensitive pNIPAm-co-Am functionalized Au catalytic applications because it may increase the adsorption rate
NPs.945,946 Additionally, multiple types of molecules (e.g., PEG of the reagent and the electron concentration due to efficient
with different functional groups341 or biofunctional biomolecules interfacial electron transfer from the carbon shell to the
with twisted charges363,917) are available to be functionalized in a palladium core, while also acting as a barrier to prevent the
sequence of specific ligand-free NPs, which enables them to be aggregation of catalysts during reactions.702 Additionally, a
selectively used in surface-chemistry sensitive bioenvironments. carbon shell can impart carbon-triggered PL properties to the
A high local supersaturation concentration increases the synthesized NMs.383
collision rate between the atoms or the clusters (i.e., the seeds) As discussed in section 3, LSPC provides access to a wide
and results in particle attachment and asymmetrical growth into range of sizes from 1 nm to 10 μm. With respect to LAL, multiple
high aspect ratio structures after LAL1010 or after laser irradiation choices are selectable to realize in situ size quenching during NP
(LPC);200,249 the resulting structures are suitable for use in gas formation. For example, using micromolar saline solution310 to
detection1010 (section 6.7) and biotherapy249 (section 6.3). inhibit NP growth enables the generation of monodisperse noble
Surface charge is an additional useful feature provided by LAL metal NPs. The use of solid additives725,903 or biomolecules11,848
and results in electrostatic stability of the synthesized NPs. enables direct fabrication of supported particles or bioconjugates
Surface charge is also the reason why some LAL-synthesized NP for catalytic, environmental, and biological applications,
colloids are stable when highly pure (at moderate concen- respectively, thus providing an opportunity to realize NP size
trations), without the need for surfactants. Surface charge is control and function introduction in a single step. Although LAL
beneficial for many applications. First, it facilitates the NPs to sometimes produces bimodal size distributions with large
physically attract and adsorb the oppositely charged contami- particles, LFL of these LAL-synthesized NPs can not only
nants for pollution protection.1018 Surface charge can also reduce the particle size substantially but also improve the NP
substantially enhance the adsorption efficiency984 of LSPC- monodispersity,25,90,1025 resulting in NPs with a coefficient of
synthesized NPs on adsorbents via a purely electrostatically variation less than 10% under optimized conditions.250 In
driven adsorption process. This simple process is realized by addition to the post-treatment of LAL-synthesized NPs, LFL also
colloid mixing and is unparalleled for the direct assembly of allows for fragmentation of micropowders or particles, extending
highly active supported heterogeneous catalysts without the the size control ability of LSPC to additional classes of materials,
calcination process often required for chemically synthesized thus facilitating their applications in various fields, including
NPs.972 Additionally, catalyst loading can be set independent of catalysis,493 LED,865 organic/inorganic hybrid solar cells,674 and
particle diameter, unlike conventional wet-impregnation-derived pollutant removal.1018 For specific materials, LFL enables the
NPs whose loading capacity is correlated with particle size. This generation of atom clusters with size less than 2 nm in size, which
independence is valuable for fundamental studies on catalysis not only help to clarify the particle nucleation mechanism164 but
where the effect of loading must be distinguished from size also enable anisotropic growth of plasmonic structures for
effects. Moreover, the electrokinetic mobility of charged NPs photothermal applications.249 LML is a unique method to
under an external electric field allows them to be directly produce crystalline SMS particles294,296 that have also the
assembled into thin films or electrodes through EPD (without potential for friction reduction application because of the size-
the need for any surface functionalization or modification for dependent friction mechanism of additives.975
charge manipulation) for electrochemical detection,563 solar In summary, as compared to chemical-synthesis methods,
cell,530 and biomedical applications.532 In particular, the LSPC is appealing for two reasons. First, a scalable, continuous,
electrode impedance of neural implant electrodes has been and convenient process is performed in a sealed environment,
demonstrated to be lower after 3 weeks operating in vivo, created which enables high throughput of a large variety of NPs in a
by EPD of LAL-synthesized Pt NPs, making the electrodes useful steady state with high occupational safety. Second, the
4074 DOI: 10.1021/acs.chemrev.6b00468
Chem. Rev. 2017, 117, 3990−4103
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advantages of laser-generated nanomaterials, which include high the mechanism of both LAL and LFL could be supported by well-
purity, “starting from scratch”, defect introduction, carbon- defined single-pulse experiments. Another goal of the
ization, and size control, may not only help to clarify the fundamental research involved in LSPC is to accurately
fundamentals in nanoscience, but also facilitate the surface manipulate the NPs surface chemistry, size, and crystal phase
chemistry control/functionalization of LSPC-synthesized col- of NPs with the aid of external stimuli or by adjusting target
loids. properties (e.g., geometry208) or the local liquid environment
(e.g., bilayer liquids,1026 liquid mixtures,55,416 or reactive
8. OUTLOOK AND CHALLENGE liquids445). Currently, LAL often leads to the formation of
As laser technology and nanotechnology have become vital parts phase mixtures with yet-unknown determinants (laser, liquid)
of our daily lives, laser synthesis and processing of colloids has governing the crystal phase. Because of the possible chemical
become an advanced discipline for addressing real-world reactions (RLEL) originating from the laser-stimulated active
problems. Only a few years ago, LSPC was described as a very species of materials and liquids, both the NP composition and the
promising synthesis method with unique properties, but lacked size quenching effect of NPs should be understood from the
size control and high productivity. After recent advances in this perspective of chemical reactions within LSPC time scales.
field, these shortcomings have been remedied, resulting in the Additionally, most research groups primarily study LSPC-
capability to synthesize monodisperse nanomaterials ranging synthesized colloids. Only a few correlate their findings to the
from 1 nm to 10 μm with monodisperse size distributions at the structured surface or grooves after ablation,116,400,401 where new
lower end (<10 nm) being accessible. However, despite the information can be obtained to better understand the properties
successful synthesis of an enormous number of functional of the synthesized NPs and to better understand the laser−
nanoparticles, many challenges remain to be solved. First, their liquid−target system and its productivity/reproducibility char-
limited productivity is a technologically challenging problem in acteristics. The long-term prosperity of the LSPC technique
many laser synthesis laboratories that limits the implementation depends on a clearer understanding of the aforementioned
of LSPC in real-world applications. Sometimes even character- aspects, particularly in a wider field than the most-studied
ization methods such as XRD, thermogravimetric, or catalytic platinum-group-element colloids. Recently, facilitated by ad-
tests always require multiple milligrams of NPs; thus, statistical vances in LFL, ligand-free monodisperse noble metal NP colloids
experiments may require subgram scale nanoparticle amounts. have become accessible.164 Their size “cartography” is well-
However, in light of increasingly available laser power and established approximately as 1 nm to 10 μm (Figure 26);
cavitation bubble-bypassing optimized processing parameters, however, the size map still contains some nearly blank ranges.
LAL productivity is anticipated to be substantially improved in Medium-sized monodisperse NPs (which are relevant for many
the near future. Recently, gram scale productivities of LSPC- applications) such as 50 nm Au NPs are still difficult to obtain.
generated NPs have been reported,22,31 demonstrating com- Driven by their wide plasmonic-related applications, size control
petitiveness with other colloidal synthesis methods. Given that of metal NPs has reached an advanced stage; by comparison,
∼1 wt % of NP is utilized in applications such as catalysis or studies on oxides are still limited and therefore require further
bioactive NP−polymer composites, a multiple-gram production investigation. In the case of LML, the synthesized SMSs are often
scale of NPs would result in kilogram-scale production of polydisperse (sometimes approaching monodispersity) and
catalysts or NP−polymer composites.886 To achieve high yields, educt size-dependent,1027 which raises the question of how to
NP reproducibility and steady-state processing setups are precisely narrow the size distribution of SMSs. Solutions to this
important. Here, the laser scanning strategies and fluid dynamics problem require extensive studies on beam attenuation, beam
within the processing chamber are critical. LAL in batch shaping, and particle educt aggregation/dispersion control.
chambers is not ideal because bubbles sticking to the ablated The high purity of LSPC-synthesized NPs is well acknowl-
targets will substantially shield the laser energy and reduce the edged to be their main advantage over chemically synthesized
reproducibility of the ablation. In advanced experimental setups, ligand-covered NPs. However, although LSPC-synthesized
semibatch chambers are employed, but they are still subject to particles are referred to as ligand/surfactant-free, they are not
NP reirradiation and serious NP shielding. For steady-state NP totally naked and still have their own surface chemistry; that is,
production, flow chambers that allow the continuous drainage of some of the NP surface atoms are oxidized or complexed.
NPs are needed, as described in a recent handbook dealing with Therefore, differentiation of the surface chemistry for multiple
practical aspects of LSPC.106 applications (e.g., catalyst, energy conversion and storage,
Another challenge is the precise clarification of the LAL and analytical chemistry, and biology) should be performed in the
LFL mechanisms, both experimentally and theoretically future (e.g., using in situ EXAFS566,831) to realize performance-
regarding not only the laser interaction with the substrate but oriented colloidal synthesis and processing.
also the mechanistic process of the ablated materials during LAL Although many other challenges remain and new questions
bubble dynamics. Substantial theoretical links between the early will arise during the fast-paced accumulation of knowledge in this
NP generation phase (<100 ns) and the subsequent phase in the field, the progress made since the development of LSPC only a
cavitation bubble (∼μs) are still missing. A better understanding generation of scientists ago is encouraging for the following
of LAL dynamics is required to predict the oxidation or advances yet to come.
carbonization ratio of the products and is also beneficial for
elucidating the NPs’ nucleation, growth, and termination. A AUTHOR INFORMATION
deeper understanding of the LFL mechanism is also required. Corresponding Author
LPC-induced bubble formation around Au NPs is beginning to *E-mail: stephan.barcikowski@uni-due.de.
be understood; however, knowledge transfer to other materials
ORCID
and the extension of the laser-induced bubble model to a
comprehensive model of NP fragmentation require further work Bilal Gökce: 0000-0001-6368-9659
by theoreticians and experimentalists. Conceivably, insights into Stephan Barcikowski: 0000-0002-9739-7272
4075 DOI: 10.1021/acs.chemrev.6b00468
Chem. Rev. 2017, 117, 3990−4103
Chemical Reviews Review

Notes (6) Ojea-Jiménez, I.; Puntes, V. Instability of Cationic Gold


Nanoparticle Bioconjugates: The Role of Citrate Ions. J. Am. Chem.
The authors declare the following competing financial Soc. 2009, 131, 13320−13327.
interest(s): SB is co-founder of Particular GmbH, providing (7) Amendola, V.; Litti, L.; Meneghetti, M. LDI-MS Assisted by
NPs made by laser synthesis. The authors DZ and BG declare no Chemical-Free Gold Nanoparticles: Enhanced Sensitivity and Reduced
competing financial interest. Background in the Low-Mass Region. Anal. Chem. 2013, 85, 11747−
11754.
Biographies (8) Uboldi, C.; Bonacchi, D.; Lorenzi, G.; Hermanns, M. I.; Pohl, C.;
Baldi, G.; Unger, R. E.; Kirkpatrick, C. J. Gold Nanoparticles Induce
Dr. Dongshi Zhang obtained his doctor degree in Electronic Science and
Cytotoxicity in the Alveolar Type-II Cell Lines A549 and NCIH441.
Technology from Xi’an Jiaotong Univesity (China) in 2014 and soon Part. Fibre Toxicol. 2009, 6, 18.
after joined the Barcikowski group at University of Duisburg-Essen (9) Lopez-Sanchez, J. A.; Dimitratos, N.; Hammond, C.; Brett, G. L.;
(Germany) as a postdoc researcher in technical chemistry. His research Kesavan, L.; White, S.; Miedziak, P.; Tiruvalam, R.; Jenkins, R. L.;
interests include laser ablation, laser microfabrication, and laser cutting Carley, A. F. Facile Removal of Stabilizer-Ligands from Supported Gold
as well as their combination with surface chemistry for wettability Nanoparticles. Nat. Chem. 2011, 3, 551−556.
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Landfester, K.; Mailänder, V.; Wurm, F. R. Protein Adsorption is
Dr. Bilal Gökce studied physics and received his “Diplom” degree from Required for Stealth Effect of Poly(ethylene glycol)- and Poly-
RWTH Aachen University in 2008. From 2007 to 2009, he worked on (phosphoester)-Coated Nanocarriers. Nat. Nanotechnol. 2016, 11,
laser material processing of metals at Fraunhofer Institute for Laser 372−377.
Technology. During his Ph.D. studies at North Carolina State University (11) Rehbock, C.; Jakobi, J.; Gamrad, L.; van der Meer, S.; Tiedemann,
from 2009 to 2012, he studied fundamental phenomena in condensed D.; Taylor, U.; Kues, W.; Rath, D.; Barcikowski, S. Current State of Laser
matter through ultrafast laser spectroscopy. Afterward, he worked as a Synthesis of Metal and Alloy Nanoparticles as Ligand-Free Reference
researcher on laser applications for semiconductors at the company T- Materials for Nano-Toxicological Assays. Beilstein J. Nanotechnol. 2014,
5, 1523−1541.
Systems International. In 2014 he joined the Faculty of Chemistry at
(12) Taylor, U.; Rehbock, C.; Streich, C.; Rath, D.; Barcikowski, S.
University of Duisburg-Essen as a “Habilitand” to establish his own Rational Design of Gold Nanoparticle Toxicology Assays: a Question of
group, which focuses on functionalization of laser-generated nano- Exposure Scenario, Dose and Experimental Setup. Nanomedicine 2014,
particles and polymer−nanoparticle composites, strategies and 9, 1971−1989.
applications for high-power ultrafast lasers, and laser materials (13) Barcikowski, S.; Walter, J.; Hahn, A.; Koch, J.; Haloui, H.;
processing. Herrmann, T.; Gatti, A. Picosecond and Femtosecond Laser Machining
May Cause Health Risks Related to Nanoparticle Emission. J. Laser
Prof. Dr. Stephan Barcikowski studied chemistry in Braunschweig and
Micro/Nanoeng. 2009, 4, 159−164.
Hannover, and obtained his Ph.D. in Mechanical Engineering (14) Schneider, C. W.; Lippert, T. Laser Ablation and Thin Film
(Materials). At the Laser Zentrum Hannover e.V., Barcikowski built Deposition. In Laser Processing of Materials: Fundamentals, Applications
up the Nanomaterials group, and later led the institute’s Materials and Developments; Schaaf, P., Ed.; Springer Berlin Heidelberg: Berlin,
Processing Department. In 2010, he cofounded the company Particular Heidelberg, 2010; pp 89−112.
GmbH and the biannual international conference “ANGEL” on LSPC. (15) Ashfold, M. N. R.; Claeyssens, F.; Fuge, G. M.; Henley, S. J. Pulsed
Since 2011, he chairs the Institute of Technical Chemistry I at the Laser Ablation and Deposition of Thin Films. Chem. Soc. Rev. 2004, 33,
University of Duisburg-Essen and founded the scientific video channel 23−31.
(16) Chrisey, D. B.; Piqué, A.; McGill, R. A.; Horwitz, J. S.; Ringeisen,
“nanofunction”. He has been scientific director of the Center for
B. R.; Bubb, D. M.; Wu, P. K. Laser Deposition of Polymer and
Nanointegration Duisburg-Essen (CENIDE) since 2015. Biomaterial Films. Chem. Rev. 2003, 103, 553−576.
(17) Patil, P. P.; Phase, D. M.; Kulkarni, S. A.; Ghaisas, S. V.; Kulkarni,
ACKNOWLEDGMENTS S. K.; Kanetkar, S. M.; Ogale, S. B.; Bhide, V. G. Pulsed-Laser−Induced
Reactive Quenching at Liquid-Solid interface: Aqueous oxidation of
We dedicate this Review to the discoverers of laser synthesis of Iron. Phys. Rev. Lett. 1987, 58, 238.
NPs in liquids, Arnim Henglein (2012) and Anton Fojtik. (18) Fojtik, A.; Henglein, A. Laser Ablation of Films and Suspended
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