Adv. Manuf.

(2017) 5:105–119
DOI 10.1007/s40436-017-0172-y

State-of-the-art developments in metal and carbon-based

semiconducting nanomaterials: applications and functions
in spintronics, nanophotonics, and nanomagnetics
Sergio Manzetti1,2 • Francesco Enrichi3,4,5,6

Received: 10 August 2016 / Accepted: 10 April 2017 / Published online: 14 June 2017
Ó Shanghai University and Springer-Verlag Berlin Heidelberg 2017

Abstract Nanomaterials composed of metals and metal
alloys are the most valuable components in emerging
micro- and nano-electronic devices and innovations to date.
The composition of these nanomaterials, their quantum
chemical and physical properties, and their production
methods are in critical need of summarization, so that a
complete state of the art of the present and future of nan-
otechnologies can be presented. In this review, we report
on the most recent activities and results in the fields of
spintronics, nanophotonics, and nanomagnetics, with par-
ticular emphasis on metallic nanoparticles in alloys and
pure metals, as well as in organic combinations and in
relation to carbon-based nanostructures. This review shows
that the combinatory synthesis of alloys with rare metals,
such as scandium, yttrium, and rare earths imparts valuable
qualities to high-magnetic-field compounds, and provides
unique properties with emphasis on nanoelectronic and
computational components. In this review, we also shed
light on the methods of synthesis and the background of
spintronic, nanomagnetic, and nanophotonic materials,
with applications in optics, diagnostics, nanoelectronics,
and computational nanotechnology. The review is impor-
tant for the industrial development of novel materials, and
for summarizing both fabrication and manufacturing
methods, as well as principles and functions of metallic
nanoparticles.
Keywords Metal  Alloy  Nanoparticle  Spintronics 
Nanophotonics  Nanomagnetics  Method  Synthesis

1 Introduction

Applications of metal and semiconductor nanomaterials

& Sergio Manzetti represent one of the most intriguing areas in nanotechnol-
sergio.manzetti@fjordforsk.no ogy for the development of future technologies for energy
1
harvesting, green and renewable energy, portable micro-
Fjordforsk A/S, NanoFactory, Midtun, 6894 Vangsnes,
Norway
electronic devices, advanced electronics, and beyond-state-
2
of-the-art computational units and devices [1–5]. Metal and
Computational Biology and Bioinformatics, Uppsala
University, 751 24 Uppsala, Sweden
semiconductor nanomaterials are associated with three
3
disciplinary areas, namely spintronics, nanophotonics, and
Historical Museum of Physics and Research and Study
Center Enrico Fermi, 00184 Rome, Italy
nanomagnetics [6–14], which have derived a series of
4
applications for nanomaterials in recent years [11, 15–17].
Division of Materials Science, Department of Engineering
Sciences and Mathematics, Luleå University of Technology,
Many of these technologies and their inherent methods of
971 87 Luleå, Sweden manufacturing are dependent on the electronic properties
5 of metal alloys and scarce transition metals, including rare-
Department of Molecular and Nanosystems Sciences,
University of Ca ‘Foscari Venice, 30172 Mestre, Venetia, earth metals. These properties are critical for beyond-state-
Italy of-the-art engineering and are outlined in theoretical and
6
Institute of Photonics and Nanotechnologies, CSMFO Lab. & practical engineering for development of advanced
FBK-CMM, IFN-CNR, 38123 Povo, Trento, Italy materials.

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106
2 General theoretical foundations for advanced
metallonanomaterials: classification and physics
Advanced technologies that devise transition metals and
high-electronic-energy elements often depend on the
spintronic properties of metallonanomaterials. Spintronic
devices depend on quantum effects such as spin hall effects
[18–21] and quantum hall effects (QHEs) [22], which
respectively give the possibility of tuning the spin of
electrons [21] in a metallic/semiconductor material, and
localizing free electrons in a defined two-dimensional (2D)
space in a metallic or semiconductor lattice or quantum
fluid [22, 23]. The implications of spintronics in
nanometals and semiconductor nanomaterials yield pri-
mary applications of the materials in computational pro-
cessing units, such as RAM and memory units [24–26], and
form a basis for future quantum computing units. Fur-
thermore, advanced metal nanomaterials, semiconductor
and carbon-based nanomaterials, including their fabrication
in combination with dichalogenides [17, 27, 28], attribute
charge-transfer and magneto-transport effects [29] for
field-effect transistors in radiofrequency (RF) devices
[29, 30], and allow for ultra-sensitive functioning of
miniature-sized components for frequency detection [10].
Metal and semiconductor-based nanomaterials are
additionally critical components in the fields of nanopho-
tonics, because of their plasmonic properties and size-de-
pendent optical properties at the nanoscale, with
quantistically tunable properties, such as in quantum dots,
quantum wires, and plasmonic nano-antennas
[6, 12, 13, 31–33]. A crucial application of nanophotonics
using metal nanomaterials is in optically active devices and
optoelectric systems, from which new and more efficient
solar cell technologies can be developed [34–36], such as
in units composed of combinations of metal nanomaterials
and silicon materials [37–41], where the nanophotonic and
plasmonic properties [42] are the source for energy har-
vesting functionalities [43, 44].
Nanophotonic applications also include metal-based
nanomaterials applied in photon-scanning tunneling
microscopy [45–48], where a nano-probe maps the light
field above a sample material in order to detect the light
signal emitted in the allowed quantum region, as well as
the evanescent light occurring in forbidden regions [33].
Metal-based nanomaterials are furthermore critical in
nanophotonics for the development and fabrication of
nanomaterials via nanoscaling, a process where nanopho-
tonic signals are applicable for canvassing nanomaterials at
an ultra-accurate spatial confinement [33].
Metal and semiconductor-based nanomaterials are
finally also critical for the novel field of nanomagnetics
[49], which applies metal nanomaterials and alloys to
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S. Manzetti, F. Enrichi
manufacture nanomagnets and molecular magnets [50–53].
The fabrication of nanomagnets derives from its own
branch, where metal alloys with magnetic properties are
engineered and structured through the use of emerging
techniques of nanofabrication [54, 55], with applications in
biomedical diagnostics [56], as well as manufacturing
microtransistors and memory devices [57]. Nanomagnetics
relates also to the synthesis of molecular magnets, with
applications in quantum computing, where molecular
magnets switch spin-identity at a given site during excita-
tion reactions by photonic absorption [53, 58]. Nanomag-
netics also involves the synthesis of carbon-based
molecular nanowires [52, 59] and is particularly relevant to
thin films and alloys with microstructural strength com-
bined with tensile flexibility and high magnetic momen-
tum, which play a pivotal role for high-precision
manufacturing of components for research equipment and
sensors for the medical field, based on rare-earth metals
and rare transition metals [60–62].
Each of the three described areas in this section and their
inherent routes of engineering, where synthesis and appli-
cation of metal and semiconductor-based nanomaterials is
the main focus, are hereby reviewed with the respective
types of metal-based nanomaterials, alloys, and
organometallic materials. Every section for spintronics,
nanophotonics, and nanomagnetics contains a state-of-the-
art review of respective materials.
3 Spintronics in metal and semiconductor-based
nanoparticles
The term ‘‘spintronics’’ attributes to the ability to modulate
the spin of electrons in the electron gas in metals and
alloys, organometallic compounds, and in semiconductor
materials [28, 63, 64]. Transition metals are widespread in
spintronic applications because their high-energy valence
electrons [65] and spin-state multiplicity allow for spin-
torque effects for magnetic and electric field tuning, which
are critical for next-stage nanomaterials and nanoarchi-
tectures [66–68]. In combination with organic atoms, such
as carbon, spin-tuning and spin-state splitting have been
achieved for spintronic organometallic materials. Examples
include valleytronic metallorganic compounds, where
electrons of the same spin occupy an area in the electron
gas, and the electrons of the opposite spin polarize in a
separated (often opposite) density volume of the surface of
the nanomaterials [69–72]. The term ‘‘valleytronics’’, rep-
resenting a critical part of spintronic theory, is the foun-
dation for isolating pseudospins (total spins of an electron
layer or an electron valley) in two or several ways, coupled
with the azimuthal momentum of the electrons or directed
State-of-the-art developments in metal and carbon-based semiconducting nanomaterials...
in the opposite direction of the azimuthal momentum of the
electrons (see Fig. 1).
Valleytronics allows for ‘‘localized magnetism’’ in the
nanostructures, a property that was first observed in the 2D
electron gas of a silicon inversion layer by Ohkawa and
Uemura [73–75]. From this stage, the first approximations,
both theoretical and experimental [28, 76–79], were
derived to prepare information storage by attributing the
sign of the electron spin in a specific polyatomic ‘‘valley’’
of the material, being a conductor or semiconductor. Val-
leytronics has also been applied in non-metallic materials,
such as graphene [29, 64, 80, 81], and has particular
advantages in tuning the low-energy dynamics of electrons
within an extra wide gap of the semiconducting or con-
ductive material [77, 78], which has direct implications for
emerging technologies such as femtosecond electron
diffraction and imaging [82, 83] and for medical applica-
tions such as cancer treatment [84].
The metallic nanomaterials devised in spintronics have
unique properties that make them ideal for spintronics.
These properties are the abundance of their occupied and
non-occupied d-electron orbitals (see Fig. 2) [85–88],
which differ from p-electrons in organic compounds in that
they have a higher variation of the magnetic quantum
number, resulting in more manifolds than other lower-en-
ergy electrons (see Fig. 3) [89, 90].
Fig. 1 Pseudospin and momentum in two valleys across a nuclear
barrier (transparent rectangle) (The momentum of the electron and the
spin is constructively coupled in the case of co-linear arrows, and
coupled destructively in case of opposite-oriented arrows. The results
net effect is a pseudospin (A) of multiple electrons on one side of a
group of nuclei, and a different pseudospin in (B) forming a magnetic
momentum. The illustration is analogous to a graphene sheet’s
valleytronic properties, where groups of spins (pseudospins) occur on
one facet of the graphene sheet, and the pseudospin of opposite sign
occurs on the opposite facet of the graphene sheet [17])
107
This offers a higher number of combinations for spin-
orbit coupling between the electron momentum and the
spin state, making transition metals indispensable in spin-
tronic applications; these also form hybridization gaps
within their electronic manifolds [87]. Interestingly, some
of the most recent studies of spintronics and valleytronics
report on breaking the electron-hole symmetry of the
electron gas, resulting in a strong magnetic exchange field
located in a narrow space in the nanomaterial lattice [77].
New studies also report the application of QHE in silicene
and germanium alloys, in the form of the charge-quantum
hall effects and spin-QHEs [91–94], which illustrate further
how spintronics and its theoretical origin yield a series of
nanoelectronic and microelectronic qualities derived by
tuning and subdividing the spin-identity populations of
electrons in a material, yielding critical advances for
information storage and processing basis units (quantum
computing and quantum-dot based communications)
[17, 95, 96], memory resistors and radio-frequency devices
[97, 98], magnetochaloric and inverse magnetochaloric
effects [99–101], and other materials for nanooscillation
and nanodynamics applications [102–104].
4 Nanophotonics in metal and semiconductor
nanoparticles
Metal and semiconductor nanoparticles and nanostructures
have exceptional effects when interacting with light and
have shown promising applications in recent years. The
collective plasmonic oscillations of the electrons in a metal
structure, the bandgap, and the position of the energy levels
in semiconductors and their size-dependent properties at
the nanoscale determine their optical properties and can be
used for photon management and manipulation, becoming
the fundamental building blocks of the field known as
nanophotonics.
The use of metal nanoparticles and their plasmonic
properties are dated: the first example of their engineering
application is the 4th century Roman glass cage, the
Lycurgus Cup, now at the British Museum, which contains
gold and silver nanoparticles in colloidal form which give
it peculiar optical properties [105]. Similarly, other
examples like the shining brilliant reflections of luster
pottery and the colors of ancient cathedral windows contain
silver, gold and copper nanoclusters. Since then, much
progress has been made in the field, both in theoretical and
experimental aspects, and many new applications of plas-
monic nanoparticles have been developed, spreading from
health monitoring and treatment [106, 107] to energy
conversion enhancement in solar cells [39, 40].
Concerning biomedical research, plasmonic nanopar-
ticles can be used as highly efficient contrast agents for
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108
Fig. 2 Manifolds of the electrons in the electron gas of a niobium cluster a the r-type bonding orbitals between two niobium atoms in a tetramer
cluster, b the p-type bonding orbitals between the same niobium pair c the r-type anti-bonding orbital d the p-type anti-bonding orbitals
(calculated with the Amsterdam Density Functional package [88])
Fig. 3 Magnetic quantum number and its relationship with the
angular momentum (Each of the shown values of ml originates from
the solutions to the Schrödinger equation [89, 90] for the electron, and
displays the spatial orientations that an electron’s angular momentum
(l) is allowed to occupy. The occupied quantum numbers ml yield the
total angular momentum in the z-dimension, Jz)
123
S. Manzetti, F. Enrichi
optical imaging because their light-scattering cross sec-
tions greatly exceed the absorption cross section of
standard fluorescent dyes [108]. Moreover, the local
enhanced electromagnetic field that is generated by
plasmonic nanoparticles can excite the vibrational modes
of molecules attached or close to their surface, yielding a
characteristic response that can be easily recognized. For
examples, Sanders et al. [109] demonstrated the effi-
ciency of a gold nano-disc array capable of label-free,
sensitive detection of a cancer protein biomarker, free
prostate-specific antigen (f-PSA). Silver nanoparticles
have been used well by Xu et al. [110] for label-free
detection of typical biological proteins: lysozyme, avidin,
bovine serum albumin, cytochrome c, and hemoglobin.
The silver nanoparticles provide a significant enhance-
ment to boost the Raman signal of proteins, which can be
easily detected thanks to surface-enhanced Raman scat-
tering (SERS).
The use of plasmonic nanoparticles as therapeutic
actuators has also been a field of intense investigation in
recent years. Nanoparticles indeed exhibit passive accu-
mulation at tumor sites through a process known as
enhanced permeability and retention (EPR) [111]. This
facilitates their potential application in cancer treatment by
photothermal therapy (PTT) [112] and light-controlled
drug release [113].
State-of-the-art developments in metal and carbon-based semiconducting nanomaterials...
In the field of energy harvesting, plasmonic nanoparti-
cles can increase solar cell efficiency by at least two dif-
ferent physical principles. Firstly, light can be scattered and
trapped into the semiconductor active region of the device
by multiple and high-angle scattering, increasing the
effective optical path length in the cell. Moreover, a strong
localization and enhancement of the near-field intensity in
the proximity of the particles can be used as an optical
concentrator, increasing the number of electron-hole pairs
generated in the semiconductor. A significant amount of
numerical simulation papers have been published, consid-
ering different nanoparticle materials (Au, Ag, Al), such as
that of Catchpole and Polman [114] who investigated the
best design for increasing the efficiency of solar cells by
depositing metal nano-objects. In particular, they tested
different shapes, such as spherical, cylindrical, or hemi-
spherical particles, obtaining a maximum 28-fold increase
in efficiency at 800 nm wavelength for 100-nm-diameter
Ag hemispheres against Ag full spheres, which showed
only a 9-fold increase. The choice of Au nanostructures
instead of Ag resulted in a reduction in performance.
An important problem in using metal nanoparticles is
the related absorption losses. Indeed, Lim et al. [115]
reported that when using 100-nm-diameter Au nanoparti-
cles, the enhancement of the efficiency had a dip in the
400–600 nm spectral regions and a peak near 700 nm.
Alternative low-cost metals such as Al were recently
investigated by Zhang et al. [116]. They showed that a
regular array of 100-nm-diameter Al nanoparticles with a
150 nm period resulted in an increase of the cell absorption
up to 40%. It is worth observing that all the described
studies deal with numerical simulations. Experimental tests
were reported by Zhang et al. [116], who demonstrated a
significant photocurrent enhancement at specific wave-
lengths (16-fold at 1 050 nm) and an overall 30% effi-
ciency increase for the cell by using Ag nano-islands (large
120–350 nm) obtained by depositing a thin Ag coating by
thermal evaporation and annealing at 200 °C in nitrogen.
Concerning semiconductor materials, Martin-Rodriguez
et al. [117] have recently synthesized quantum dots com-
posed of cadmium and selenium doped with ytterbium
ions, which induce photo-functionalization of the CdSe
lattice by electronic interaction with the rare-earth metal f-
electrons, forming luminescent quantum dots. A similar
approach for functionalizing nanocrystals for photonic
purposes was published in Ref. [118], which attributed
luminescence to ZnS nanocrystals by post-synthetically
adding europium and terbium ions to Ln(NO3)3xH2O salt
solutions of ZnS and CdS nanoparticles. The quantum yield
of the particles was registered for various formulae of the
salt solutions of the ZnS nanoparticles. Quantum yield
defines the number of times a specific radiation-induced
event occurs per photon absorbed by the system, thus
109
increasing with higher luminescent properties of the
materials. The Zn(Tb)S/Tb solutions displayed the highest
quantum yield of value of 2.5 ± 0.3, a feature that is
attributed to the energy transfer resulting from the multi-
coordinating ability of the rare earth Tb3? of zinc and
sulfur atoms. In both CdSe and CdS/ZnS nanoclusters, the
rare earths localize first on the surface and then take place
internally in the nanocrystals, forming the energy trans-
ferring network with the other elements [117, 118]. This
coordination is visible in the excitonic emission spectra,
which show that Yb3? reduces CdSe excitonic emission,
yielding an upper limit of energy transfer probability of
about 80% from the nanocrystal to the rare earth [117].
5 Nanomagnetics: functional metal
and semiconductor nanoparticles
The aforementioned particles, particularly for the spin-
tronics section, are also relevant to the field of nanomag-
netics as components for computing and logic [10] and
nanomagnetics for biotechnology [119]. Nanomagnetics is
defined by the manufacturing of nanoparticles with
exceptional magnetic properties, often defined by advanced
spin-state orders of the metal and alloys. Such spin-state
properties can be achieved by considering ferrofluids as a
starting point. Ferrofluids are organic polymers mixed with
ferromagnetic nanoparticles from Fe2?, Fe3?, Mn2?, or
other transition metals precipitated with oxides [120].
Hematite-based (Fe2O3) nanomagnetic polymers have been
synthesized by polymerizing N-isopropylacrylamide
(NIPAM) as the main monomer, with methylene-bis-
acrylamide as the cross-linker and potassium persulfate as
the initiator of the chain reaction [120]. Particles generated
by this method remained discrete with a mean diameter of
12 nm, and magnetic measurements revealed that the par-
ticles showed superparamagnetic properties only with a
decrease of magnetism after binding with the polymer
because of the increase in surface spin disorientation. This
feature is of particular interest because it indicates that the
nanomagnetic materials of Fe2O3 yield a sharing of elec-
trons with the polymeric framework of organic molecules,
providing the ability to delocalize the magnetic momentum
from the ferrous molecules to their surroundings. Poly-
merization was carried out for 6 h, where mercaptoethanol
was used as the chain transfer reagent. The mercapto group
donates a sulfur atom which forms a covalent bond to the
Fe2O3 units, yielding coated nanoparticles with polymeric
chains [120].
A similar approach was used by Shamin et al. [121] in a
second study, where nanoparticles were prepared in the
same approach as mentioned previously and used for
attaching and adsorbing lysozyme. This approach of
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110 S. Manzetti, F. Enrichi

devising Fe2O3 particles as carriers of layers of sorptive

organic compounds introduces a novel approach for fab-
rication of biotechnology-oriented applications, such as
ELISA, protein separation, and other methods for
biotechnology. Horng et al. [122] also devised a similar
rationale, in order to perform immunoassays with nano-
magnetic Fe2O3 particles, coated with a biotin probe,
synthesized also through a co-precipitation process to
probe the bio-target (avidin). The published method
showed that the same particles used by Shamin et al. [121]
could be synthesized in hydrodynamic diameter from
30 nm to 90 nm. Parekh and Upadhyay [123] reported
magnetic Mn0.5Zn0.5Fe2O4 nanoparticles with dimension of
0.82 nm. The Mn-Zn coated ferrite nanoparticles were
synthesized using a thermal deposition technique with
acetic acid solutions of the metals, in combination with 1,2-
hexadecanediol, oleic acid, oleyamine, and dioctyl ether.
The nanoparticles show zero remanence and coercivity at Fig. 4 Ni0.35Zn0.65Fe2O4 nanoparticles generated by mill pulveriza-
room temperature, whereas at 5 K coercivity was regis- tion method (Image reproduced with permissions from Chakraverty
tered to 1:934  104 A/m. The nanoparticles are super- et al. [126] CopyrightÓ 2006 American Institute of Physics)
paramagnetic above 100 K and experience finite magnetic
coercivity below the freezing temperature. Interestingly, temperatures of different-sized particles [126]. From this
this combination of Mn, Zn, and Fe in nanoparticles point, a sudden increase in the externally applied magnetic
exhibits a non-saturizing behavior at 5 K, which suggests a field can also be stored in the system as long as the field is
core structure in the magnetic system, where the core is not too high [126]. The results from this study show that a
ordered in terms of spin populations, and the surface results nanomagnetic particle system can be used to encode a
in disordered spins due to the high surface energy. This sudden increase or decrease in magnetic field while the
registered pattern of spin-population forms the basis for a system is being cooled, forming a logical switch for
possible quantum-tunneling effect in the Mn-Zn ferrite information processing. This can in turn be decoded by
nanoparticles, which has also been reported for a frozen measuring the magnetic response curve generated during
fluid for Mn-Zn [124]. The tunneling effect in magnetic heating [126].
nanoparticles can be explained by geometrical phase
effects [125] and indicates the formation of an energy
cavity in the tunneling path of the magnetic energy 6 Nanomaterial engineering methods
potential of the lattice. This provides an effect that can be
measured in a qualitative analysis of the energy structure of Many different approaches have been followed and
the dominant tunneling paths in the phase space [125]. developed in recent years for the controlled synthesis and
The coordination of magnetic nanoparticles and engineering of metal/semiconductor nanoparticles. In
arrangement to one another is also an interesting aspect of general these can be divided into chemical and/or physical
nanomagnetics, and can be used for memory-processing methods and combinations of the two methods.
functions in computational units. Chakraverty et al. [126]
prepared nanoparticles of Ni0.35Zn0.65Fe2O4 by mechanical 6.1 Chemical methods
alloying processes utilizing Fritsch Planetary Mono Mill
Pulverisette 6, giving a mean particle diameter of 27 nm, Engineering nanoparticles for special applications as
with sizes up to 100 nm (see Fig. 4). According to the described above requires tuning the nanoparticles’ dimen-
rationale of the study, the use of the dispersion pattern of sions and shapes, because both the chemical reactivity and
the particles forms the foundation for devising these par- the physical properties of the nanoparticles are directly
ticles in memory processing units. The polydispersity of related to the lattice symmetries, geometries, and
the particle volumes leads to a wide distribution of nanoparticle shapes and forms [127–130]. The processes
blocking temperatures, where the memory effects are a for engineering nanoparticles comprise several methods,
consequence of the polydispersed state of the system at a where thermal methods by microwave heating are con-
given temperature, which lies between the blocking ventional [131, 132]. Microwave heating has been used to

123
State-of-the-art developments in metal and carbon-based semiconducting nanomaterials...
prepare metal nanoparticles very rapidly to produce metal
nanopowders, and has been a central part of microwave-
assisted chemistry [133]. The approach of using micro-
waves takes advantage of the formation of electric fields
and charges in the phase where nanoparticles are formed,
which are nano-confined regions where temperatures as
high as 10 000 °C and pressures up to 1 GPa are generated
[133]. The metal nanoparticles are formed using reactions
with reductive organic compounds, often applied as polyols
[133–135]. Polyols have a low viscosity, which contributes
to the reaction environment by forming a gel-like medium
that forms localized spots where chemical reactions and
nanoparticle formation take place [133]. Microwave-as-
sisted reactions have a higher kinetic rate of reaction than
non-microwave methods, and contribute to the synthetic
process by forming more novel phases [136] than chemical
reactions, which makes microwave methods a critical
component for synthesizing dispersions and powders of
even and uneven shapes [133, 137]. During this synthesis
processes, the metal nanoparticles are formed by catalytic
reduction of their metalhydroxide form M(OH)x, which
accepts electrons from the polyol liquid [133]. This gen-
erates an oxidized form of the polyol that remains in liquid
solution, where platinum nanoparticles deposit into parti-
cles of 5–25 nm diameter within 10–15 min [133, 137].
The approach is applied to various transition metals with
the potential of modifying the shape and dimensions by
modulating the pH value of the metal hydroxide solutions
[133].
Other chemical methods for nanofabrication include
electrochemical reduction of ionic liquids. Ionic liquids are
based on metal ions in ionic state with an organic com-
pound of opposite charge. Ionic liquids are highly appli-
cable as reagents for nanomaterial engineering and have
been used to prepare cadmium nanoparticles [138] and
gold nanoparticles from the imidazolium cation [139], and
to provide for accuracy in shaping and controlling the size
of metal nanoparticles [140]. Using this method, applying
polymers in the solution assists furthermore in shaping and
altering the properties of the formed nanoparticles, which
can also lead to generation of other shapes and sizes [141].
Electrochemical synthesis has also been combined with
multi-walled carbon nanotubes (MWCNTs) as support
material to further alter the properties of the nanoparticles,
as performed by Guo and Li [142] in the synthesis of
palladium nanoparticles. The surfaces of MWCNTs have
super-aromatic properties [143], which have a particular
ability to trap positively charged ions, particularly metal
ions, given the partial negative charge that emerges across
the center of the aromatic ring of the hexagonal moieties of
MWCNTs [144]. Electrochemical methods of synthesis
provide the smallest nanoparticle diameters, among all
chemical methods, and can achieve particles as small as
111
2–7 nm in diameter [145]. The disadvantage of electro-
chemical synthesis of nanoparticles is the reduced level of
particle growth speed, because electric charges and cur-
rents can be challenging to tune for intensity, towards
specific ionic concentrations, sample volumes, and other
components in the chemical reaction. However, the inclu-
sion of scaffolds and support materials can increase the
accuracy and reproducibility of nanoparticle synthesis
when using electrochemical impulses, where for instance
encapsulation in single-walled nanotubes [52] can be par-
ticularly efficient for synthesizing nanoparticles with uni-
form dimensions.
Functionalization of nanoparticles is an additional
chemical process that enhances the electronic qualities of
the nanomaterial, required for spintronic applications or
other avenues; it has also been applied to provide ferro-
magnetic properties in diamagnetic materials after combi-
nation of ZnO nanorods with Al2O3 shells [146]. The
ferromagnetic effect results at the interface between the
two materials, after annealing the ZnO/Al2O3 core-shell
nanowires and activating the formation of the ZnAl2O4
phase. The magnetic functionality of the nanoparticles was
found to be stable up to 750 K [146]. The study showed
that fully diamagnetic materials (ZnO and Al2O3) could
impart intriguing ferromagnetic properties in combination,
which otherwise would be more challenging to achieve per
se. Another group recently achieved ferroelectric and
magnetocapacitive properties in scandium-doped BiFeO3
nanocubes [147], where scandium increased significantly
the electric polarization in the nanoparticles, attributing
magnetoelectric effects to the nanocubes. This effect
results from the ten unoccupied d-orbitals of the scandium
ion (Sc3?) (see previous section on d-orbitals), which can
take part in forming a new electronic framework in the
Fig. 5 Magnetoelectric BiFe0.95Sc0.05O3 nanoparticles imaged by
Dutta et al. [147] (Image reproduced with permissions from Dutta
et al. [147] CopyrightÓ 2013 American Chemical Society)
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112
nanocubes. This functionalization approach contributes in
establishing a new magnetoelectric coupling in the nano-
cubes where the magnetic moment is primarily given by
the Fe2?/Fe3? ions in the BiFeO3 nanostructures (see
Fig. 5) [147]. Interestingly, the re-coordination of the
nanocubes after Sc-doping induced changes in the struc-
tural geometry, which shows that the Sc ions compete with
the existing frameworks between Fe3?/Fe2? and the bis-
muth and oxygen ions, forming potentially a completely
new lattice unit and thus altering the physical qualities of
the material. Such events at the nanoscale during func-
tionalization have been reported previously [148, 149].
One of these studies [148] showed that the rare earth ele-
ment lanthanum in the lanthanide form altered the ground
structure, size, and shape of alkaline-earth fluoride
nanocrystals, which resulted in a tuning approach of the
emission spectra and paramagnetism of the given
nanocrystals. A similar mechanism was reported for ZnO
nanocrystals after doping with Mg2? ions [148], with the
induction of new shapes and geometries from tetrapods of
ZnO. This approach was also used to tune the optoelec-
tronic properties of ZnO, thus yielding new functionalities
at various dopant concentrations [146]. Nanoparticles can
also be synthesized with accurate and uniform dimensions
by using metal-organic frameworks (MOFs) [150], where
the metal nanoparticles are embedded in the carbon matrix
by the controlled thermolysis of the MOF. Nanoparticles
synthesized by this method include CuO, Co3O4, ZnO,
MgO, CdO, and CdS [150]. In this context, a study pub-
lished by Pal et al. [151] shows that simple thermolysis of
MOFs in inert (N2) and partial oxygen (air) environments
leads to the formation of single phase crystalline metal and
metal oxide nanoparticles, which are passivated in the
carbon matrix. The approach of in situ synthesis of Cu and
Co nanoparticles [150], embedded in a porous carbon
matrix, uses [Cu2(hfbba)2(3-mepy)2](DMF)2(3-mepy)
(F-MOF-4) and [Co2(hfbba)2(3-mepy)2](DMF)3 (Co-HFM
OF-D), which are synthesized according to the reported
synthesis protocol [152], where the synthesized blue-col-
ored crystals of F-MOF-4 are placed on a silica substrate
and heated in a tube furnace to 900 °C under N2 atmo-
sphere, with a heating rate of 10 °C/min to thermolyze the
organic species to yield pure Cu/Co nanoparticles. The
material is cooled to room temperature and analyzed for
purity. The catalytic carbonization process is another
method of nanoparticle production of most recent origin
[153], which uses a water-soluble sodium chloride (NaCl)
solution as a supporting material, and encapsulates cobalt
nanoparticles in carbon cages with a productivity of about
100%. This method allows for production of smaller
quantities than other methods, such as the arc-discharge
method; however its products can be fully separated from
the supporting materials by a simple washing process and
123
S. Manzetti, F. Enrichi
the method itself requires less energy. The method of
catalytic carbonization also allows for tuning the mor-
phologies of the products, by altering the salts used in the
supporting material. For instance, when NaCl, NaF, and
Al2O3 were used as supporting materials [153], the mor-
phologies of the carbon products changed from carbon-
encapsulated magnetic nanoparticles (CEMNs) to an
intermediate state (quasi-nanocages) between CEMNs and
carbon nanotubes (CNTs), and further to CNTs, respec-
tively. The catalytic carbonization method allows for a
more predictable morphology-tuning of embedded metal
nanoparticles, compared to other methods such as tem-
perature annealing, because the ionic compounds used at
specific concentrations yield a better predictability of the
resulting charge-to-charge steering of the forming
nanoparticles.
6.2 Physical methods
Nanoparticle synthesis by physical methods is mainly
based on thermal impulse generation as in electro-explo-
sion, plasma formation by superconducting magnets, laser
ablation, and plasma-vaporization (see Fig. 6) [154–164].
The first of these methods, electro-explosion, devises a
metallic wire as a source for nanoparticle generation, and
applies a high-voltage impulse on the wire in elec-
troshocks, which form nanoparticles rapidly as volatile
nanopowders [158, 161, 165]. The laser-ablation method
(see Fig. 7) is a frequently applied alternative to the above-
mentioned method and offers higher precision, and can be
used for gram-quantity synthesis of metallic or ceramic
nanoparticles [166, 167]. A laser pulse at femtosecond and
millisecond intervals is directed on the bulk metal material,
and often offers particle production without generating
excessively high temperatures. Production rates of nano-
materials are 100–300 lg/s with the results of 1 000–
1 500 mg/h of nanoparticles [168]. Recent advances in
laser ablation include modifications of the pulse intensity,
pulse overlap [169], and pulse frequency amplification.
Additionally, the water layer used to cool the material
during metal ablation plays a critical role for the produc-
tivity of nanoparticles, and is inversely proportional to the
amount of nanoparticles generated [167]. The scan speed of
the laser pulse is also a critical property for nanoparticle
yield during the ablation process. For instance, with a
100 mm/s laser pulse movement across the metal surface,
the nanoparticle productivity is increased by 300% over
smaller laser scan speeds, which increases linearly in the
range of 50–500 mm/s in scan speed [167]. The laser pulse
repetition furthermore affects the yield of nanoparticles
constructively by low repetition frequencies (4–6 kHz)
[167]; in other words, the frequency of the laser pulse is
directly related to particle yield.
State-of-the-art developments in metal and carbon-based semiconducting nanomaterials... 113

Fig. 6 Nanoparticle formation steps by thermal methods a metal nanoparticle synthesis from ionic state, b synthesis of nanoparticles from bulk
material by laser ablation [154–157], c electro-explosion synthesis by high-voltage impulse [161–163], d plasma vaporization synthesis of
nanoparticles [161–163], e periodical synthesis of nanoparticles by forming plasma by supermagnets [164]

Plasma vaporization is a conventionally applied method

Fig. 7 A graphical illustration of the laser-ablation method (the
source moving at a constant speed, v, emitting a laser-pulse to the
surface of the bulk material. This generates water-dispersed nanopar-
ticles of tunable diameter, which are collected from the water sample)
for nanoparticle production. Plasma vaporization, initially
introduced in 1999 by Bica [162], melts steel or a metal
alloy for subsequent sputtering through an argon plasma
jet. The first tests gave the production of iron-pentacar-
bonyl, Fe(Co)5 in plasma, with mean particle diameters of
12.2 nm. Smaller diameters down to 6 nm were obtained
by thermal decomposition of Fe 2-etilhexamaleath, which
gave amorphous and crystalline graphite particles with
applicability for conductive magnetic liquids. Furthermore,
the plasma vaporization in either argon plasma or in helium
plasma yields nanoparticles of a-Fe and Fe3O4 with
diameters in the range of 3–90 nm. In recent years, plasma
vaporization has been widely used in nanomaterial engi-
neering, and has been combined with encapsulation in
carbon cage structures [170]. Plasma vaporization is par-
ticularly suitable for production of carbon-coated
nanoparticles; however, other techniques are equally
compatible, such as arc discharge [171], RF plasma torch
[172, 173], combustion [174], magnetron and ion beam co-
sputtering [175], and high-temperature annealing [176].
The RF plasma torch method is of particular interest,
because it deposits thin films with exact chemical compo-
sitions on a substrate, of quite considerable molecular

123
114 S. Manzetti, F. Enrichi

weight (Co50Pt15C35), with a grain size ranging from 5 nm

to 15 nm [175]. The role of the carbon cages in the syn-
thesis by the RF plasma torch process has induced partic-
ularly interesting chemical and physical conditions, which
lead to a hexagonal close-packed phase separated by gra-
phite-like carbon boundaries. The role of carbon in the
synthesis process is highly valuable, and can affect both the
symmetry and chemical formula of the produced films.
Other studies, which have mapped the formation of crystals
in carbon cages, have shown that carbon cages affect the
morphology of the packing [177]. Indeed, the method of
devising carbon cages in the RF plasma synthesis process
has given a higher coercivity of the synthesized film by
9:55  105 A/m, compared to the regular case of cobalt-
carbon. Figure 6 illustrates further the amplitude of the Fig. 8 Biosynthesized gold nanoparticles (Gold nanoparticles syn-
physical methods. thesized in the algae Prasiola crispa chloroauric acid by Sharma et al.
[182]. Reproduced with permissions. Ó 2013 Elsevier B. V. All rights
reserved)
6.3 Biological methods
Algae have also been used successfully to synthesize
gold nanoparticles [182], via the reduction of an aqueous
Plants can also be suitable reactors to synthesize
chloroauric acid solution with dried biomass of a fresh-
nanoparticles, as recent studies have shown [178]. Algae,
water epilithic green alga, Prasiola crispa. The particles
fungi, plants, bacteria, yeast, and actinomycetes are
formed were of face-centered cubic structure of gold with
organisms that can be used to synthesize nanoparticles in
an average crystallite diameter of 9.8 nm and smallest
reactors. The mode of synthesis follows the reduction of
diameter of 5 nm (see Fig. 8). However, more diverse
ions to solid nanometals, by the activity of metallo-en-
methods have been used in producing gold nanoparticles
zymes, which are regularly used for detoxification and
recently [183], where the flower Lantana camara (L.
transformation purposes of toxic metal ions. Gold
camara) was used as a vehicle for nanoparticle formation.
nanoparticles in the range of 20–40 nm have been syn-
The shape and size of gold nanoparticles were successfully
thesized using sterilized geranium leaves (P. graveolens),
controlled by introducing small amounts of L. camara
after exposure to chloroaurate ions [179]. The time for
flower extract to an ionic solution of gold, where spherical
reduction was registered to 60 min, where nanoparticles of
nanoparticles of average size (10.6 ± 2.9) nm were pro-
decahedral and icosahedral shapes were synthesized.
duced. Paul et al. [184] used leaf extracts of Pogestemon
Similar rates were found for palladium nanoparticles,
benghalensis to produce gold nanoparticles in a similar
produced to 55–80 nm in diameter [180]. Cinnamomum
fashion as the studies mentioned previously. The
camphora (C. camphora) leaves have also been used to
nanoparticles had a mean crystalline size of 13 nm, and the
synthesize nanoparticles of silver with the additional use of
nanoparticles arranged predominantly in spherical and tri-
reducing agents. The produced silver nanoparticles ranged
angular shapes with sizes from 10 nm to 50 nm. Catalytic
from 5 nm to 40 nm [181]. The method of production by
activity was registered for these particles, as it was for the
Huang et al. [181] was described as follows: silver nitrate
same particles produced in L. camara. In general, the
(AgNO3) was mixed with an extract of sun-dried C. cam-
amount of nanoparticles and their purity are lower by
phora leaf, with 50 mL of deionized water, which were
biological methods compared to chemical and physical
vigorously shaken. The mixtures in the flasks were then
methods. The biological methods can be optimized by
centrifuged and precipitates removed. The procedure then
blending chemical reactions with the biological compo-
followed an experimental setup designed to carry out
nents, because the majority of the biological approaches
continuous-flow biosynthesis of silver nanoparticles, where
are reduction reactions with biological components such as
two helical tubular microreactors were employed in the
enzymes or other types of cell components.
setup. Combined with another tubular microreactor, the
In conclusion, the future of nanoparticle production can
mixture, the resulting lixivium and aqueous AgNO3 were
be centered particularly on physical methods, where the
continuously fed into the reactors by a peristaltic pump,
production rates are higher and defined by more approa-
resulting in a silver hydrosol effluent containing silver
ches that are predictable. However, the costs and energy
nanoparticles.

123
State-of-the-art developments in metal and carbon-based semiconducting nanomaterials...
requirements for physical methods can be a deficiency of
this type of nanoparticle production, and require method
optimization by developing better magnetic and high-en-
ergy alloys to exert rapid and more energy- and cost-effi-
cient paths of nanoparticle production. Chemical and
biological methods are equally important, particularly the
former. However, the generation of large quantities with a
high degree of uniformity can be a challenge, particularly
with the latter method.
7 Conclusions
We have here surveyed the literature on spintronics,
nanophotonics, and nanomagnetics, and derived a com-
prehensive study on the recent and emerging avenues of
development in these fields of applied nanosciences. Our
study shows that the most valuable materials are still alloys
of transition metals and oxides. However, carbon nano-
materials can form the basis for future emerging magnetic
and spintronic materials once large-scale methods of pro-
duction arise with the development of nanotechnologies for
electronic, diagnostic, and computational applications. It is
a noteworthy approach to study the effects that occur
between materials in either nanoparticle form, crystals,
dots, or nanowires, particularly after post-synthetical
modification [118], encapsulation of metals in nanotubes
[52, 59], and most importantly in the interface between
metal oxides, rare earth oxides, and transition metals,
because it is here that the true potential of nanomaterials
emerges. Interface properties, re-coordination of elements
in nanocrystals, and growth of functional materials can
give valuable future approaches for engineering functional
nanomaterials based on ubiquitous and rather common
substrates, because the ferromagnetic and magnetic prop-
erties are critical for applications in spintronics, nanopho-
tonics, and nanomagnetics.
Funding information This publication is part of the project number
264086, ‘‘Nanoactivities’’, funded by the Norwegian Research
Council, SkatteFUNN scheme.
References
1. Trauzettel B, Bulaev DV, Loss D et al (2007) Spin qubits in
graphene quantum dots. Nat Phys 3:192–196
2. Zhu S, Zhang J, Qiao C et al (2011) Strongly green-photolu-
minescent graphene quantum dots for bioimaging applications.
Chem Commun 47:6858–6860
3. Pradhan A, Holloway T, Mundle R et al (2012) Energy har-
vesting in semiconductor-insulator-semiconductor junctions
through excitation of surface plasmon polaritons. Appl Phys Lett
100:061127
115
4. Park K, Lee M, Liu Y et al (2012) Flexible nanocomposite
generator made of BaTiO3 nanoparticles and graphitic carbons.
Adv Mater 24:2999–3004
5. Gittins DI, Bethell D, Schiffrin DJ et al (2000) A nanometre-
scale electronic switch consisting of a metal cluster and redox-
addressable groups. Nature 408:67–69
6. Huang Y, Duan X, Lieber CM (2005) Nanowires for integrated
multicolor nanophotonics. Small 1:142–147
7. Brongersma ML, Kik PG (2007) Surface plasmon nanophoton-
ics. Springer, Netherlands
8. Wolf SA, Lu J, Stan MR et al (2010) The promise of nano-
magnetics and spintronics for future logic and universal mem-
ory. Proc IEEE 98:2155–2168
9. Awschalom DD, Flatté ME (2007) Challenges for semicon-
ductor spintronics. Nat Phys 3:153–159
10. Wolf S, Awschalom D, Buhrman R et al (2001) Spintronics: a
spin-based electronics vision for the future. Science
294:1488–1495
11. Mourachkine A, Yazyev O, Ducati C et al (2008) Template
nanowires for spintronics applications: nanomagnet microwave
resonators functioning in zero applied magnetic field. Nano Lett
8:3683–3687
12. Ohtsu M, Kobayashi K, Kawazoe T et al (2002) Nanophotonics:
design, fabrication, and operation of nanometric devices using
optical near fields. IEEE J Sel Top Quantum Electron 8:839–862
13. Qian F, Li Y, Gradecak S et al (2004) Gallium nitride-based
nanowire radial heterostructures for nanophotonics. Nano Lett
4(10):1975–1979
14. Žutić I, Fabian J, Sarma SD (2004) Spintronics: fundamentals
and applications. Rev Mod Phys 76:323
15. Ling X, Zhou X, Shu W et al (2013) Realization of tunable
photonic spin hall effect by tailoring the Pancharatnam-Berry
phase. Sci Rep 5:5557
16. Thibeault SA, Kang JH, Sauti G et al (2015) Nanomaterials for
radiation shielding. MRS Bull 40:836–841
17. Xu X, Yao W, Xiao D et al (2014) Spin and pseudospins in
layered transition metal dichalcogenides. Nat Phys 10:343–350
18. McAlister S (1978) The hall effect in spin glasses. J Appl Phys
49:1616–1621
19. Senthil T, Marston J, Fisher MP (1999) Spin quantum hall effect
in unconventional superconductors. Phys Rev B
60(6):4245–4254
20. Hirsch JE (1999) Spin hall effect. Phys Rev Lett
83(9):1834–1837
21. Dyakonov M, Perel V (1971) Possibility of orienting electron
spins with current. Sov J Exp Theor Phys Lett 13:467–469
22. Girvin SM (1999) The quantum hall effect: novel excitations
and broken symmetries. In: Comtet A, Jolicoeur T, Ouvry S et al
(eds) Topological aspects of low dimensional systems. Springer,
Berlin, pp 53–175
23. Laughlin RB (1983) Anomalous quantum hall effect: an
incompressible quantum fluid with fractionally charged excita-
tions. Phys Rev Lett 50:1395–1398
24. Burr GW, Kurdi BN, Scott JC et al (2008) Overview of candi-
date device technologies for storage-class memory. IBM J Res
Dev 52:449–464
25. Wang KL, Alzate JG, Amiri PK (2013) Low-power non-volatile
spintronic memory: STT-RAM and beyond. J Phys Appl Phys
46(7):074003
26. Wang X, Keshtbod P, Wang Z et al (2015) Spin-orbitronics
memory device with matching and self-reference functionality.
IEEE Trans Magn 51:1–4
27. Jiang Z, Zhang Y, Tan YW et al (2007) Quantum hall effect in
graphene. Solid State Commun 143(1–2):14–19
123
116
28. Zibouche N, Philipsen P, Kuc A et al (2014) Transition-metal
dichalcogenide bilayers: switching materials for spintronic and
valleytronic applications. Phys Rev B 90:125440
29. Chua C, Connolly M, Lartsev A et al (2014) Quantum hall effect
and quantum point contact in bilayer-patched epitaxial gra-
phene. Nano Lett 14:3369–3373
30. Klitzing KV (1995) Physics and application of the quantum hall
effect. Phys B Condens Matter 204(1–4):111–116
31. Kirchain R, Kimerling L (2007) A roadmap for nanophotonics.
Nat Photonics 1:303–305
32. Cortes C, Newman W, Molesky S et al (2012) Quantum
nanophotonics using hyperbolic metamaterials. J Opt
14(6):063001
33. Shen Y, Friend CS, Jiang Y et al (2000) Nanophotonics: inter-
actions, materials, and applications. J Phys Chem B
104:7577–7587
34. Callahan DM, Munday JN, Atwater HA (2012) Solar cell light
trapping beyond the ray optic limit. Nano Lett 12:214–218
35. Yu Z, Raman A, Fan S (2010) Fundamental limit of nanopho-
tonic light trapping in solar cells. Proc Natl Acad Sci
107:17491–17496
36. Mokkapati S, Catchpole K (2012) Nanophotonic light trapping
in solar cells. J Appl Phys 112:101101
37. Teperik TV, De Abajo FG, Borisov A et al (2008) Omnidirec-
tional absorption in nanostructured metal surfaces. Nat Pho-
tonics 2:299–301
38. Podolskiy VA, Sarychev AK, Shalaev VM (2002) Plasmon
modes in metal nanowires and left-handed materials. J Nonlin-
ear Opt Phys Mater 11:65–74
39. Polman A (2008) Plasmonics applied. Science 322:868–869
40. Atwater HA, Polman A (2010) Plasmonics for improved pho-
tovoltaic devices. Nat Mater 9:205–213
41. Green MA, Pillai S (2012) Harnessing plasmonics for solar
cells. Nat Photonics 6:130–132
42. Delacour C, Blaize S, Grosse P et al (2010) Efficient directional
coupling between silicon and copper plasmonic nanoslot
waveguides: toward metal-oxide-silicon nanophotonics. Nano
Lett 10:2922–2926
43. Tsakalakos L, Balch J, Fronheiser J et al (2007) Silicon nano-
wire solar cells. Appl Phys Lett 91:233117
44. Kim HS, Lee CR, Im JH et al (2012) Lead iodide perovskite
sensitized all-solid-state submicron thin film mesoscopic solar
cell with efficiency exceeding 9%. Sci Rep 2(8):591
45. Ferrell T, Sharp S, Warmack R (1992) Progress in photon
scanning tunneling microscopy (PSTM). Ultramicroscopy
42:408–415
46. Paesler M, Moyer P, Jahncke C et al (1990) Analytical photon
scanning tunneling microscopy. Phys Rev B 42:6750
47. Bourillot E, Fornel FD, Goudonnet JP et al (1995) Imaging of test
quartz gratings with a photon scanning tunneling microscope:
experiment and theory. J Opt Soc Am A 12(8):1749–1764
48. Carminati R, Greffet JJ (1995) Two-dimensional numerical
simulation of the photon scanning tunneling microscope. Con-
cept of transfer function. Opt Commun 116:316–321
49. Skomski R (2003) Nanomagnetics. J Phys Condens Matter
15:R841
50. Saywell A, Magnano G, Satterley CJ et al (2010) Self-assembled
aggregates formed by single-molecule magnets on a gold sur-
face. Nat Commun 1:75
51. del Carmen Giménez-López M, Moro F, La Torre A et al (2011)
Encapsulation of single-molecule magnets in carbon nanotubes.
Nat Commun 2:407
52. Manzetti S (2013) Molecular and crystal assembly inside the
carbon nanotube: encapsulation and manufacturing approaches.
Adv Manuf 1(3):198–210
123
S. Manzetti, F. Enrichi
53. Leuenberger MN, Loss D (2001) Quantum computing in
molecular magnets. Nature 410:789–793
54. Haynes CL, Van Duyne RP (2001) Nanosphere lithography: a
versatile nanofabrication tool for studies of size-dependent
nanoparticle optics. J Phys Chem B 105:5599–5611
55. Rokhvarger AE, Chigirinsky LA (2004) Design and nanofabri-
cation of superconductor ceramic strands and customized leads.
Int J Appl Ceram Technol 1:129–139
56. Krishnan KM (2010) Biomedical nanomagnetics: a spin through
possibilities in imaging, diagnostics, and therapy. IEEE Trans
Magn 46:2523–2558
57. Welser J, Wolf SA, Avouris P et al (2011) Applications:
nanoelectronics and nanomagnetics. In: Nanotechnol. Res. Dir.
Soc. Needs 2020. Springer, Berlin, pp 375–415
58. Bogani L, Wernsdorfer W (2008) Molecular spintronics using
single-molecule magnets. Nat Mater 7:179–186
59. Manzetti S, Lu T (2013) Alternant conjugated oligomers with
tunable and narrow HOMO-LUMO gaps as sustainable nano-
wires. RSC Adv 3:25881–25890
60. Li C, Lin J (2010) Rare earth fluoride nano-/microcrystals:
synthesis, surface modification and application. J Mater Chem
20:6831–6847
61. Vetrone F, Naccache R, Zamarron A et al (2010) Temperature
sensing using fluorescent nanothermometers. ACS Nano
4:3254–3258
62. Bünzli JCG, Comby S, Chauvin AS et al (2007) New opportu-
nities for lanthanide luminescence. J Rare Earths 25:257–274
63. Bloss W, Sham L, Vinter V (1979) Interaction-induced transi-
tion at low densities in silicon inversion layer. Phys Rev Lett
43:1529
64. Cserti J, Dávid G (2006) Unified description of Zitterbewegung
for spintronic, graphene, and superconducting systems. Phys
Rev B 74:172305
65. Manzetti S, Patek M (2016) The accurate wavefunction of the
active space of the rhenium dimer resolved using the ab initio
Brueckner coupled-cluster method. Struct Chem
27(4):1071–1080
66. Tulapurkar A, Suzuki Y, Fukushima A et al (2005) Spin-torque
diode effect in magnetic tunnel junctions. Nature 438:339–342
67. Ohno H (2010) A window on the future of spintronics. Nat
Mater 9:952–954
68. Locatelli N, Cros V, Grollier J (2014) Spin-torque building
blocks. Nat Mater 13:11–20
69. Mai C, Barrette A, Yu Y et al (2013) Many-body effects in
valleytronics: direct measurement of valley lifetimes in single-
layer MoS2. Nano Lett 14:202–206
70. Zeng M, Feng Y, Liang G (2011) Graphene-based spin
caloritronics. Nano Lett 11:1369–1373
71. Myoung N, Seo K, Lee SJ et al (2013) Large current modulation
and spin-dependent tunneling of vertical graphene/MoS2
heterostructures. ACS Nano 7:7021–7027
72. Cheng Y, Zhu Z, Tahir M et al (2013) Spin-orbit-induced spin
splittings in polar transition metal dichalcogenide monolayers.
EPL Europhys Lett 102:57001
73. Ohkawa FJ, Uemura Y (1977) Theory of valley splitting in an
N-channel (100) inversion layer of Si I: formulation by extended
zone effective mass theory. J Phys Soc Jpn 43:907–916
74. Ohkawa FJ, Uemura Y (1977) Theory of valley splitting in an
N-channel (100) inversion layer of Si II: electric break through.
J Phys Soc Jpn 43:917–924
75. Ohkawa FJ, Uemura Y (1977) Theory of valley splitting in an
N-channel (100) inversion layer of Si III: enhancement of
splittings by many-body effects. J Phys Soc Jpn 43:925–932
76. Behnia K (2012) Condensed-matter physics: polarized light
boosts valleytronics. Nat Nanotechnol 7:488–489
State-of-the-art developments in metal and carbon-based semiconducting nanomaterials...
77. Ezawa M (2013) Spin valleytronics in silicene: quantum spin
hall-quantum anomalous hall insulators and single-valley
semimetals. Phys Rev B 87:155415
78. Ezawa M (2014) Valleytronics on the surface of a topological
crystalline insulator: elliptic dichroism and valley-selective
optical pumping. Phys Rev B 89:195413
79. Nebel CE (2013) Valleytronics: electrons dance in diamond. Nat
Mater 12:690–691
80. Maassen J, Ji W, Guo H (2010) Graphene spintronics: the role of
ferromagnetic electrodes. Nano Lett 11:151–155
81. Novoselov K, Blake P, Katsnelson M (2001) Graphene: elec-
tronic properties. Encycl Mater Sci Technol 244:1–6
82. Pronschinske A, Pedevilla P, Murphy CJ et al (2015)
Enhancement of low-energy electron emission in 2D radioactive
films. Nat Mater 14:904–907
83. Sundaram SK, Mazur E (2002) Inducing and probing non-
thermal transitions in semiconductors using femtosecond laser
pulses. Nat Mater 1:217–224
84. Sanche L (2015) Cancer treatment: low-energy electron therapy.
Nat Mater 14:861–863
85. Mattheiss LF (1973) Energy bands for 2H–Nb Se2 and 2H–Mo
S2. Phys Rev Lett 30:784–787
86. Mattheiss LF (1966) Band structure and Fermi surface for rhe-
nium. Phys Rev 151:450–464
87. Mattheiss LF (1973) Band structures of transition-metal-
dichalcogenide layer compounds. Phys Rev B 8:3719–3740
88. Te Velde G, Bickelhaupt FM, Baerends EJ et al (2001) Chem-
istry with ADF. J Comput Chem 22:931–967
89. Schrödinger E (1926) An undulatory theory of the mechanics of
atoms and molecules. Phys Rev 28:1049–1070
90. Schrödinger E (1940) A method of determining quantum-me-
chanical eigenvalues and eigenfunctions. Proceedings of the
Royal Irish Academy, pp 9–16
91. Tahir M, Schwingenschlögl U (2013) Valley polarized quantum
hall effect and topological insulator phase transitions in silicene.
Sci Rep 3:1075
92. Kaloni TP, Singh N, Schwingenschlögl U (2014) Prediction of a
quantum anomalous hall state in Co-decorated silicene. Phys
Rev B 89(3):208–220
93. Liu CC, Feng W, Yao Y (2011) Quantum spin hall effect in
silicene and two-dimensional germanium. Phys Rev Lett
107(7):2989–2996
94. Zhang XL, Liu LF, Liu WM (2013) Quantum anomalous hall
effect and tunable topological states in 3D transition metals
doped silicene. Sci Rep 3:2908
95. Wu G, Lue NY, Chang L (2011) Graphene quantum dots for
valley-based quantum computing: a feasibility study. Phys Rev
B 84:195463
96. Lee MK, Lue NY, Wen CK et al (2012) Valley-based field-
effect transistors in graphene. Phys Rev B 86:165411
97. Macià F, Kent AD, Hoppensteadt FC (2011) Spin-wave inter-
ference patterns created by spin-torque nano-oscillators for
memory and computation. Nanotechnology 22:95301
98. Wang X, Chen Y, Xi H et al (2009) Spintronic memristor
through spin-torque-induced magnetization motion. IEEE
Electron Device Lett 30:294–297
99. Kainuma R, Imano Y, Ito W et al (2006) Magnetic-field-induced
shape recovery by reverse phase transformation. Nature 439:957–960
100. Mañosa L, González-Alonso D, Planes A et al (2010) Giant
solid-state barocaloric effect in the Ni-Mn-In magnetic shape-
memory alloy. Nat Mater 9:478–481
101. Krenke T, Duman E, Acet M et al (2005) Inverse magne-
tocaloric effect in ferromagnetic Ni-Mn-Sn alloys. Nat Mater
4:450–454
117
102. Khalsa G, Stiles MD, Grollier J (2015) Critical current and
linewidth reduction in spin-torque nano-oscillators by delayed
self-injection. Appl Phys Lett 106:242402
103. Locatelli N, Mizrahi A, Accioly A et al (2014) Noise-enhanced
synchronization of stochastic magnetic oscillators. Phys Rev
Appl 2:034009
104. Keatley P, Gangmei P, Dvornik M et al (2013) Isolating the
dynamic dipolar interaction between a pair of nanoscale ferro-
magnetic disks. Phys Rev Lett 110:187202
105. Barber D, Freestone I (1990) An investigation of the origin of
the colour of the Lycurgus cup by analytical transmission
electron microscopy. Archaeometry 32:33–45
106. Webb JA, Bardhan R (2014) Emerging advances in nanomedi-
cine with engineered gold nanostructures. Nanoscale
6:2502–2530
107. Anker JN, Hall WP, Lyandres O et al (2008) Biosensing with
plasmonic nanosensors. Nat Mater 7:442–453
108. Hellebust A, Richards-Kortum R (2012) Advances in molecular
imaging: targeted optical contrast agents for cancer diagnostics.
Nanomed 7:429–445
109. Sanders M, Lin Y, Wei J et al (2014) An enhanced LSPR fiber-
optic nanoprobe for ultrasensitive detection of protein
biomarkers. Biosens Bioelectron 61:95–101
110. Xu LJ, Zong C, Zheng XS et al (2014) Label-free detection of
native proteins by surface-enhanced Raman spectroscopy using
iodide-modified nanoparticles. Anal Chem 86:2238–2245
111. Yu MK, Park J, Jon S (2012) Targeting strategies for multi-
functional nanoparticles in cancer imaging and therapy. Thera-
nostics 2:3
112. Huang X, El-Sayed MA (2011) Plasmonic photo-thermal ther-
apy (PPTT). Alex J Med 47:1–9
113. Carregal-Romero S, Ochs M, Rivera-Gil P et al (2012) NIR-
light triggered delivery of macromolecules into the cytosol.
J Controll Release 159:120–127
114. Catchpole KR, Polman A (2008) Design principles for particle
plasmon enhanced solar cells. Appl Phys Lett 93:191113
115. Lim S, Mar W, Matheu P et al (2007) Photocurrent spectroscopy
of optical absorption enhancement in silicon photodiodes via
scattering from surface plasmon polaritons in gold nanoparti-
cles. J Appl Phys 101:104309
116. Zhang D, Yang X, Hong X et al (2015) Aluminum nanoparticles
enhanced light absorption in silicon solar cell by surface plas-
mon resonance. Opt Quantum Electron 47:1421–1427
117. Martı́n-Rodrı́guez R, Geitenbeek R, Meijerink A (2013) Incor-
poration and luminescence of Yb3? in CdSe nanocrystals. J Am
Chem Soc 135:13668–13671
118. Mukherjee P, Sloan RF, Shade CM et al (2013) A postsynthetic
modification of II–VI semiconductor nanoparticles to create
Tb3? and Eu3? luminophores. J Phys Chem C 117:14451–14460
119. Chen CJ, Haik Y, Chatterjee J (2004) Nanomagnetics in
biotechnology. In: Proceedings of the international workshop on
materials analysis and processing in magnetic fields, Tallahas-
see, Florida, 17–19 March 2004
120. Shamim N, Hong L, Hidajat K et al (2007) Thermosensitive
polymer (N-isopropylacrylamide) coated nanomagnetic parti-
cles: preparation and characterization. Colloids Surf B Bioint-
erfaces 55:51–58
121. Shamim N, Liang H, Hidajat K et al (2008) Adsorption, des-
orption, and conformational changes of lysozyme from ther-
mosensitive nanomagnetic particles. J Colloid Interface Sci
320:15–21
122. Horng HE, Yang SY, Huang Y et al (2005) Nanomagnetic
particles for SQUID-based magnetically labeled immunoassay.
IEEE Trans Appl Supercond 15:668–671
123
118
123. Parekh K, Upadhyay R (2010) Static and dynamic magnetic
properties of monodispersed Mn0.5Zn0.5Fe2O4 nanomagnetic
particles. J Appl Phys 107:053907
124. Taketomi S (1998) Spin-glass-like complex susceptibility of
frozen magnetic fluids. Phys Rev E 57:3073
125. Yoo SK, Lee SY (2000) Geometrical phase effects in biaxial
nanomagnetic particles. Phys Rev B 62:5713–5718
126. Chakraverty S, Ghosh B, Kumar S et al (2006) Magnetic coding
in systems of nanomagnetic particles. Appl Phys Lett 88:042501
127. Miller J, Kropf A, Zha Y et al (2006) The effect of gold particle
size on Au-Au bond length and reactivity toward oxygen in
supported catalysts. J Catal 240:222–234
128. Carlson C, Hussain SM, Schrand AM et al (2008) Unique cel-
lular interaction of silver nanoparticles: size-dependent genera-
tion of reactive oxygen species. J Phys Chem B
112:13608–13619
129. El-Sayed MA (2001) Some interesting properties of metals
confined in time and nanometer space of different shapes. Acc
Chem Res 34:257–264
130. Nikoobakht B, El-Sayed MA (2003) Preparation and growth
mechanism of gold nanorods (NRs) using seed-mediated growth
method. Chem Mater 15:1957–1962
131. Sreeprasad T, Nguyen P, Kim N et al (2013) Controlled, defect-
guided, metal-nanoparticle incorporation onto MoS2 via chem-
ical and microwave routes: electrical, thermal, and structural
properties. Nano Lett 13:4434–4441
132. Gawande MB, Shelke SN, Zboril R et al (2014) Microwave-
assisted chemistry: synthetic applications for rapid assembly of
nanomaterials and organics. Acc Chem Res 47:1338–1348
133. Komarneni S, Li D, Newalkar B et al (2002) Microwave-polyol
process for Pt and Ag nanoparticles. Langmuir 18:5959–5962
134. Zhao Y, Zhu J, Hong J et al (2004) Microwave-induced
polyol-process synthesis of copper and copper oxide
nanocrystals with controllable morphology. Eur J Inorg Chem
2004:4072–4080
135. Cheng W, Cheng HW (2009) Synthesis and characterization of
cobalt nano-particles through microwave polyol process. AIChE
J 55:1383–1389
136. Komarneni S, Roy R, Li Q (1992) Microwave-hydrothermal
synthesis of ceramic powders. Mater Res Bull 27:1393–1405
137. Gao F, Lu Q, Komarneni S (2005) Interface reaction for the self-
assembly of silver nanocrystals under microwave-assisted
solvothermal conditions. Chem Mater 17:856–860
138. Manzetti S (2017) NANOGEL: Synthesis of cadmium
nanoparticles from a carefully selected ionic liquid of Cd2? and
benzoic acid. www.fjordforsk.no/nanogel.php
139. Itoh H, Naka K, Chujo Y (2004) Synthesis of gold nanoparticles
modified with ionic liquid based on the imidazolium cation.
J Am Chem Soc 126:3026–3027
140. Grzelczak M, Pérez-Juste J, Mulvaney P et al (2008) Shape
control in gold nanoparticle synthesis. Chem Soc Rev
37:1783–1791
141. Yin B, Ma H, Wang S et al (2003) Electrochemical synthesis of
silver nanoparticles under protection of poly (N-vinylpyrroli-
done). J Phys Chem B 107:8898–8904
142. Guo D, Li H (2004) Electrochemical synthesis of Pd nanopar-
ticles on functional MWNT surfaces. Electrochem Commun
6:999–1003
143. Manzetti S, Andersen O, Garcia C et al (2016) Molecular sim-
ulation of carbon nanotubes as sorptive materials: sorption
effects towards retene, perylene and cholesterol to 100 degrees
Celsius and above. Mol Simul 14:1–10
144. Manzetti S (2012) Chemical and electronic properties of poly-
cyclic aromatic hydrocarbons: a review. Handb Polycycl Aro-
mat Hydrocarb Chem Occur Health Issues 309–330
123
S. Manzetti, F. Enrichi
145. Rodriguez-Sanchez L, Blanco M, Lopez-Quintela M (2000)
Electrochemical synthesis of silver nanoparticles. J Phys Chem
B 104:9683–9688
146. Xing G, Wang D, Cheng CJ et al (2013) Emergent ferromag-
netism in ZnO/Al2O3 core-shell nanowires: towards oxide
spinterfaces. Appl Phys Lett 103:022402
147. Dutta DP, Mandal BP, Naik R et al (2013) Magnetic, ferro-
electric, and magnetocapacitive properties of sonochemically
synthesized Sc-doped BiFeO3 nanoparticles. J Phys Chem C
117:2382–2389
148. Ghosh S, Yang R, Kaumeyer M et al (2014) Fabrication of
electrically conductive metal patterns at the surface of polymer
films by microplasma-based direct writing. ACS Appl Mater
Interfaces 6:3099–3104
149. Chen D, Yu Y, Huang F et al (2010) Modifying the size and
shape of monodisperse bifunctional alkaline-earth fluoride
nanocrystals through lanthanide doping. J Am Chem Soc
132:9976–9978
150. Yang Y, Jin Y, He H et al (2010) Dopant-induced shape evo-
lution of colloidal nanocrystals: the case of zinc oxide. J Am
Chem Soc 132:13381–13394
151. Pal S, Bhunia A, Jana PP et al (2015) Microporous La–metal–
organic framework (MOF) with large surface area. Chem Eur J
21:2789–2792
152. Dey R, Bhattacharya B, Pachfule P et al (2014) Flexible
dicarboxylate based pillar-layer metal organic frameworks:
differences in structure and porosity by tuning the pyridyl based
N, N0 linkers. Cryst Eng Commun 16:2305–2316
153. Liu BH, Ding J, Zhong Z et al (2002) Large-scale preparation of
carbon-encapsulated cobalt nanoparticles by the catalytic
method. Chem Phys Lett 358:96–102
154. Lowndes DH, Rouleau CM, Thundat T et al (1998) Silicon and
zinc telluride nanoparticles synthesized by pulsed laser ablation:
size distributions and nanoscale structure. Appl Surf Sci
127:355–361
155. Mafuné F, Kohno J, Takeda Y et al (2000) Formation and size
control of silver nanoparticles by laser ablation in aqueous
solution. J Phys Chem B 104:9111–9117
156. Mafuné F, Kohno J, Takeda Y et al (2000) Structure and sta-
bility of silver nanoparticles in aqueous solution produced by
laser ablation. J Phys Chem B 104:8333–8337
157. Becker MF, Brock JR, Cai H et al (1998) Nanoparticles gen-
erated by laser ablation. Conf Lasers Electro-Opt 10(5):151–152
158. Sen P, Ghosh J, Abdullah A et al (2003) Preparation of Cu, Ag,
Fe and Al nanoparticles by the exploding wire technique.
J Chem Sci 115:499–508
159. Andrievski R (2003) Modern nanoparticle research in Russia.
J Nanoparticle Res 5:415–418
160. Goswami N, Sen P (2004) Water-induced stabilization of ZnS
nanoparticles. Solid State Commun 132:791–794
161. Phillips J, Perry WL, Kroenke WJ (2004) Method for producing
metallic nanoparticles. U.S. Patent No. 6,689,192, 10 February
2004
162. Bica I (1999) Nanoparticle production by plasma. Mater Sci Eng
B 68:5–9
163. Swihart MT (2003) Vapor-phase synthesis of nanoparticles.
Curr Opin Colloid Interface Sci 8:127–133
164. Kaneko T, Hatakeyama R, Takahashi S (2013) Plasma process
on ionic liquid substrate for morphology controlled nanoparti-
cles. INTECH Open Access Publisher. Chapter 24
165. Graneau P (1983) First indication of Ampere tension in solid
electric conductors. Phys Lett A 97:253–255
166. Amendola V, Meneghetti M (2009) Laser ablation synthesis in
solution and size manipulation of noble metal nanoparticles.
Phys Chem Chem Phys 11:3805–3821
State-of-the-art developments in metal and carbon-based semiconducting nanomaterials...
167. Sajti CL, Sattari R, Chichkov BN et al (2010) Gram scale
synthesis of pure ceramic nanoparticles by laser ablation in
liquid. J Phys Chem C 114:2421–2427
168. Abdolvand A, Khan SZ, Yuan Y et al (2008) Generation of
titanium-oxide nanoparticles in liquid using a high-power, high-
brightness continuous-wave fiber laser. Appl Phys A
91:365–368
169. Wang X, Shephard JD, Dear FC et al (2008) Optimized
nanosecond pulsed laser micromachining of Y-TZP ceramics.
J Am Ceram Soc 91:391–397
170. Borysiuk J, Grabias A, Szczytko J et al (2008) Structure and
magnetic properties of carbon encapsulated Fe nanoparticles
obtained by arc plasma and combustion synthesis. Carbon
46:1693–1701
171. Scott JHJ, Majetich SA (1995) Morphology, structure, and
growth of nanoparticles produced in a carbon arc. Phys Rev B
52:12564–12571
172. Delaunay JJ, Hayashi T, Tomita M et al (1997) CoPt-C
nanogranular magnetic thin films. Appl Phys Lett 71:3427–3429
173. Li T, Yan H, Wang H et al (2005) CoPt/C nanogranular mag-
netic thin film. Int J Mod Phys B 19:2261–2271
174. Lu Y, Zhu Z, Liu Z (2005) Carbon-encapsulated Fe nanoparti-
cles from detonation-induced pyrolysis of ferrocene. Carbon
43:369–374
175. Hayashi T, Hirono S, Tomita M et al (1997) Magnetic thin films
of cobalt nanocrystals encapsulated in graphite-like carbon.
Cambridge University Press, Cambridge, p 33
176. Harris P, Tsang S (1998) A simple technique for the synthesis of
filled carbon nanoparticles. Chem Phys Lett 293:53–58
119
177. Britz DA, Khlobystov AN (2006) Noncovalent interactions of
molecules with single walled carbon nanotubes. Chem Soc Rev
35:637–659
178. Iravani S (2011) Green synthesis of metal nanoparticles using
plants. Green Chem 13:2638–2650
179. Shankar SS, Ahmad A, Pasricha R et al (2003) Bioreduction of
chloroaurate ions by geranium leaves and its endophytic fungus
yields gold nanoparticles of different shapes. J Mater Chem
13:1822–1826
180. Yang X, Li Q, Wang H et al (2010) Green synthesis of palla-
dium nanoparticles using broth of Cinnamomum camphora leaf.
J Nanoparticle Res 12:1589–1598
181. Huang J, Lin L, Li Q et al (2008) Continuous-flow biosynthesis
of silver nanoparticles by lixivium of sundried Cinnamomum
camphora leaf in tubular microreactors. Ind Eng Chem Res
47:6081–6090
182. Sharma B, Purkayastha DD, Hazra S et al (2014) Biosynthesis of
gold nanoparticles using a freshwater green alga, Prasiola
crispa. Mater Lett 116:94–97
183. Kumar B, Smita K, Cumbal L (2016) Biofabrication of nanogold
from the flower extracts of Lantana camara. IET
Nanobiotechnol 10:154–157
184. Paul B, Bhuyan B, Purkayastha DD et al (2015) Green synthesis
of gold nanoparticles using Pogestemon benghalensis (B) O.
Ktz. leaf extract and studies of their photocatalytic activity in
degradation of methylene blue. Mater Lett 148:37–40
123