Journal of Colloid and Interface Science 488 (2017) 373–389

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Journal of Colloid and Interface Science

journal homepage: www.elsevier.com/locate/jcis

Feature Article

Organic and perovskite solar cells: Working principles, materials

and interfaces
Nevena Marinova a, Silvia Valero a, Juan Luis Delgado a,b,⇑
a
POLYMAT, University of the Basque Country UPV/EHU, Avenida de Tolosa 72 & Faculty of Chemistry, P. Manuel Lardizabal 3, Donostia – San Sebastián, Spain
b
Ikerbasque, Basque Foundation for Science, 48011 Bilbao, Spain

g r a p h i c a l a b s t r a c t

a r t i c l e i n f o a b s t r a c t

Article history: In the last decades organic solar cells (OSCs) have been considered as a promising photovoltaic technol-
Received 29 July 2016 ogy with the potential to provide reasonable power conversion efficiencies combined with low cost and
Revised 4 November 2016 easy processability. Unexpectedly, Perovskite Solar Cells (PSCs) have experienced unprecedented rise in
Accepted 7 November 2016
Power Conversion Efficiency (PCE) thus emerging as a highly efficient photovoltaic technology. OSCs and
Available online 11 November 2016
PSCs are two different kind of devices with distinct charge generation mechanism, which however share
Dedicated to Prof. J.-F. Nierengarten on the some similarities in the materials processing, thus standard strategies developed for OSCs are currently
occasion of his 50th birthday. being employed in PSCs. In this article, we recapitulate the main processes in these two types of photo-
voltaic technologies with an emphasis on interfacial processes and interfacial modification, spotlighting
Keywords: the materials and newest approaches in the interfacial engineering. We discuss on the relevance of well-
Photovoltaics known materials coming from the OSCs field, which are now being tested in the PSCs field, while main-
Interfaces taining a focus on the importance of the material design for highly efficient, stable and accessible solar
Perovskite-based solar cells cells.
Organic solar cells
Ó 2016 Elsevier Inc. All rights reserved.

⇑ Corresponding author at: Ikerbasque, Basque Foundation for Science, 48011 Bilbao, Spain, POLYMAT, University of the Basque Country UPV/EHU, Avenida de Tolosa 72 &
Faculty of Chemistry, P. Manuel Lardizabal 3, Donostia – San Sebastián, Spain.
E-mail address: juanluis.delgado@polymat.eu (J.L. Delgado).

http://dx.doi.org/10.1016/j.jcis.2016.11.021
0021-9797/Ó 2016 Elsevier Inc. All rights reserved.
374 N. Marinova et al. / Journal of Colloid and Interface Science 488 (2017) 373–389

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 374
2. Charge generation in OSCs and PSCs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 374
2.1. Light absorption and generation of free carriers in OSCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 374
2.2. Light absorption and generation of free carriers in PSCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
3. The role of morphology and interfaces in OSCs and PSCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379
3.1. The morphology of the BHJ in OSCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379
3.2. Interfaces and interlayers in OSCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
3.2.1. n-type materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
3.2.2. p-type materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
3.3. VOC and recombination in OSCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
3.4. Crystallinity of the perovskite layer in PSC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382
3.5. Interfacial processes, hysteresis, energetic barriers and interlayers in PSCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
3.6. VOC and recombination in PSCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385
3.7. Interfacial degradation in PSCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385
4. Conclusion and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 386
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 386
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 386

1. Introduction type and n-type material blend, serves as light harvester and at
the same time ensures charge separation.
The field of OSCs represents a promising class of new photo- To convert efficiently sunlight into electricity, a photovoltaic
voltaic technology, which has the potential to provide good PCE device needs to harvest a significant fraction from the solar radia-
employing cheap, easily tunable polymeric or small molecule tion spectra. The absorption efficiency depends on the absorption
organic materials. Furthermore, these materials are compatible coefficient (a) of the absorbing material as well as the reflectance
with industrial processes, which implies possible low cost upscal- of the absorbing surface, since reflected photons are lost. Generally,
ing. The progress in this field, has shed light on the operation prin- organic materials are characterized by high absorption coefficient
ciples of OSCs and allowed optimization of the materials and thus providing efficient light harvesting at a specific wavelength
devices. The interfacial engineering has been recognized as funda- with relatively thin layer (100–200 nm) [7]. However, organic
mental approach for maximizing the PCE [1–6]. The interfacial lay- molecules usually have narrow absorption spectra, with small cov-
ers in OSCs have multiple function including adjusting the ering in the near infrared region (Fig. 1). Therefore, tuning of the
energetic barrier at the metal/semiconductor interface, provide band gap and broadening of the absorption by appropriate molec-
selectivity of the contacts, prevent chemical or photophysical reac- ular design is often required.
tion between the active layer and the electrode and behave as an In OSCs the light is absorbed by an active layer formed by an
optical spacer for maximizing photocurrent. electron donor (organic p-type material) blended with an electron
PSCs are a younger class of photovoltaic devices, which have acceptor (organic n-type material). One approach for shifting the
experienced an unprecedented rise in PCE and have emerged as a absorption of the donor to lower energies is to employ materials
highly efficient photovoltaic technology. In PSCs, the outstanding with high degree of delocalization due to large p-conjugated sys-
efficiency has been achieved mainly by optimization of the individ- tem. Low band gap polymers and dyes are the most frequently
ual layers employed in the device, and currently the interfacial pro- employed donor materials while fullerene derivatives, perylenedi-
cesses and their impact on device operation and stability are imide or other n-type material serve as an electron acceptor [12].
subject of investigation. Both OSCs and PSCs, have the advantage
to be processed by a great versatility of methodologies, including
solution or vacuum processing techniques. Besides, both types of
devices are built in similar architectures and there is a growing
trend materials from OSCs to be used in PSCs.
In a photovoltaic device, the conversion starts with light
induced charge generation, followed by transport of the generated
charges and collection of the charges by the electrodes [7,8]. OSCs
and PSCs differ in the mechanism of charge generation due to the
significantly different nature of the active layer materials, namely
organic semiconductors and hybrid organic-inorganic perovskite.
In this article, we summarize the main operation principles of OSCs
and PSCs, the materials, and discuss the interfacial processes and
interfacial engineering in both types of devices with regard to effi-
ciency optimization and proper long-term device operation.

2. Charge generation in OSCs and PSCs

2.1. Light absorption and generation of free carriers in OSCs
A typical OSC comprises an active layer, charge transporting
layers and electrodes. The active layer, which is composed of p-
Fig. 1. Absorption coefficient (a) versus wavelength of thin films of P3HT, PC61BM,
PC71BM, Zn-phthalocyanine and perovskite CH3NH3PbI3 plotted together with the
AM 1.5G solar spectrum [9]. The data for of P3HT, PC61BM, PC71BM and Zn-
phthalocyanine are taken from Ref. [10], in the case of CH3NH3PbI3 data is obtained
from Ref. [11].
 N. Marinova et al. / Journal of Colloid and Interface Science 488 (2017) 373–389
Fig. 2. Band diagram and main processes in OSCs: 1 Absorption of photon followed
by exciton formation; 2 Exciton diffusion; 3 Charge separation; 4 Charge extraction.
When a molecule absorbs light an electron is excited from the
highest occupied molecular orbital (HOMO) to the lowest unoccu-
pied molecular orbital (LUMO, Fig. 2). This process resembles the
promotion of electron from the valence band to the conduction
band in inorganic semiconductors. However, in organic materials
instead of free carriers a tightly bound electron-hole pair, namely
exciton is formed. The exciton has a relatively large binding energy
(0.3–1 eV) [13]. To produce photocurrent, the exciton needs to
overcome the binding energy and dissociate into free charges elec-
trons and holes. In OSCs the exciton dissociation takes place at the
junction where p-type and n-type semiconductors are in contact
forming a D/A interface [8,14]. Thus, any exciton created in the
Fig. 3. Examples of donor and acceptor materials for OSCs.
375
material has to migrate towards the D/A interface. The exciton
migration is a diffusive process from regions with high to regions
with low exciton concentration [15]. The efficiency of exciton dif-
fusion depends on the exciton diffusion length LD, described by Eq.
(1) and the thickness of the film [7]. Typically, the exciton diffusion
length in organic semiconductor is in the range of 1–10 nm, which
serious limits the absorbing layer thickness. For thicker layers,
excitons generated at a distance from the D/A interface larger than
LD, will decay to ground state before dissociating, thus decreasing
the efficient conversion of sunlight into electricity.
LD ¼ ðDsÞ2
1
ð1Þ
D – Diffusion coefficient
s – Exciton lifetime
Once the exciton reaches the D/A interface it should undergo
dissociation into free charges. The concept of a two component
D/A active layer in a OSC which facilities the exciton dissociation
was introduced by Tang in 1986 [16]. Tang’s planar heterojunction
(PHJ) device employed thermally evaporated layers of copper-
phthalocyanine (1, Fig. 3) as electron donor and perylene tetracar-
boxylic derivative (PDI, 7) as electron acceptor to afford a PCE of
1%. The importance of this work consists in the demonstration that
efficient exciton dissociation takes place at the interface of two
materials with different electron affinities and ionization poten-
tials. The first step of the dissociation is electron transfer from
the exciton to the LUMO of the acceptor resulting in D+/A at the
interface, namely charge transfer state (CT). The driving force for
this event, is provided by the offset of the LUMOD-LUMOA as shown
in Fig. 3. In the CT state the electron and the hole are located at
neighboring molecules at the D/A interface and are kept close by
376 N. Marinova et al. / Journal of Colloid and Interface Science 488 (2017) 373–389
coulombic attraction [8]. If the distance between the electron and
hole becomes greater than the Coulomb capture radius, complete
charge separation takes place and the CT state could become
charge separated state (CS) in which free charges, electrons and
holes are generated.
The PHJ device is limited by the exciton diffusion length since
only excitons generated near the D/A interface live long enough
to dissociate at this interface. To address this major shortcoming,
Bulk Heterojunction (BHJ) active layer structure was proposed
[17–19]. In a BHJ device the active layer is a D-A blend formed
by co-deposition of the two materials. The blended active layer
provides a large increase in the interfacial area compared to the
PHJ and relatively short distance from any point in the active layer
to a charge-separation interface. The proposal of the BHJ concept, is
considered as a major breakthrough in the development of these
devices, as the most efficient devices have fabricated following this
concept [20].
The first BHJ cell was reported in 1995 when a blend of two
different semiconductors was used as active layer. The device
comprised the polymer MEH-PPV as an electron donor and a
[60]fullerene derivative, namely [6,6]-phenyl-C61-butyric acid
methyl ester known as PC61BM (5) as electron acceptor, sand-
wiched between two electrodes. The authors found that a blend
of donor with acceptor materials results in an improvement of
the carrier collection efficiency due to the large increase in
the interfacial area and from the relatively short distance from
any point in the polymer to a charge-separation interface [19].
The utilization of poly (3-hexylthiophene) as electron donor
polymer (P3HT, 2) allowed an outstanding increase of PCE
(4.5–5%) and this material is one of the most widely used poly-
mers in OSCs. P3HT shows suitable optical and electrical prop-
erties and good thermal and chemical stability. These excellent
characteristics together with its high processability and scalabil-
ity make it a potential candidate for the mass-fabrication of
OSCs [12,21–24].
Fig. 4. Push-pull chromophores based on the 10-(1,3-dithiol-2-ylidene)anthracene core and their absorption spectra 8 (red), 9 (blue), and 10 (green) recorded in
dichloromethane at room temperature.
In recent years, conjugated polymers with narrow band-gap
and deep-lying HOMO level have been developed as donor materi-
als for OSCs. Among these low bandgap polymers PTB derivatives
are often the materials of choice [25]. This family of molecules con-
sist of two basic fused-ring co-monomers namely benzodithio-
phene and thieno[3,4-b]thiophene. Among them PTB7 (3) stands
out as the most widely used material for solar cell studies [26–
28]. In order to improve the co-planarity of the main chain and
to extend the absorption band towards longer wavelength a new
PTB material, namely PTB7-Th (4) has been recently proposed. In
this polymer 2-ethylhexyl-thienyl group is incorporated in the
benzodithiophene core, which gave rise to a 25 nm red shift of
the absorption spectrum [29]. Using this innovative polymer and
PC71BM as acceptor, a PCE of 11.3% in tandem architecture was
achieved [30].
In spite of these remarkable results, conjugated polymers dis-
play also some drawbacks related to the reproducibility of their
synthesis, purification, and hence electronic properties [31]. In
contrast to polymers, small molecule semiconductors have well
defined molecular structure and weight, and exhibit lower charge
motilities compared to their polymeric counterparts. The energet-
ics of small molecule absorbers can be finely tuned through the
appropriate employment of organic synthesis.
An example of small molecule donor, widely used in OSCs are
the- phthalocyanine complexes. Phthalocyanines (1) are relatively
planar molecules, which chelate a single metal or metalloid ion
within their internal cavity. They were used as p-type materials
in OSCs due to their absorption in the low-energy region, high
molar absorptivity, and good thermal stability [32–34].
In this regard, organic chromophores such as push-pull systems,
displaying suitable absorption properties, are promising materials
to obtain highly efficient OSCs. Recently, we have synthesized
novel push-pull chromophores, based on the 10-(1,3-dithiol-2-yli
dene)-anthracene core absorbing in a broad region of the visible
spectrum (Fig. 4). The new dyes bear 10-(1,3-dithiol-2-ylidene)
 N. Marinova et al. / Journal of Colloid and Interface Science 488 (2017) 373–389
anthracene group as electron donor unit, a conjugated p-bridge,
3,4-ethylenedioxythiophene, as well as two kinds of electron
accepting units, an ester group for (8), a dicyanovinylene group
for (9) and (10). A decrease of the optical band gap is observed,
when the push-pull effect in the compounds is reinforced due to
the efficient electronic communication between the donor and
acceptor moieties, giving rise to very intense charge-transfer bands
[35–37]. This example demonstrates the importance of appropriate
molecular design to increase the light-harvesting properties of the
materials.
The most commonly employed materials as electron acceptor in
OSCs are based on fullerenes due to their high electron mobility,
high electron affinity and ability to transport charges. Usually the
donor material, polymeric or small molecule, is blended with [60]-
fullerene or [70]fullerene derivatives such as PC61BM (5), to form
the BHJ active layer. The main disadvantages of the pristine fullere-
nes are that they lack absorption in the visible region therefore
limiting the PCE, and their low solubility in organic solvents, which
reduces their possibilities to be deposited through spin coating.
Thus, they require synthetic modifications to improve their solubil-
ity in organic solvents. When replacing the [60]fullerene acceptor
with [70]fullerene derivative PC71BM, the photogeneration current
is increased due to improved absorption of light in the visible
region [38,39].
An efficient way for improving the absorption properties of the
fullerene acceptor is to connect two fullerene units in heterodimer,
which increases the absorption coefficient compared to PC61BM
[40–42]. In our recent work, we have shown that bridging C60
and C70 units in a heterodimer (11, Fig. 5) via covalent linking pro-
vides electron coupling of the two fragments. Furthermore, the
electronic properties of the fullerene acceptors can be tuned by
proper adjustment of bridge structures between fullerene cages
or introduction of multiple bridges to fix the desired conformation
which in turn have an impact on the charge carrier generation effi-
ciency in organic solar cells [43,44].
To avoid the issues related to the fullerene acceptors in OSCs a
significant amount of research effort is focused on the develop-
ment of non-fullerene acceptors with enhanced absorption and
solubility. PDI derivatives offer a potential replacement of fullere-
nes in BHJ organic photovoltaic and, as mentioned, they were used
as n-material in the first reported PHJ. Currently, a promising trend
is the developing of bulky or twisted PDI structures with decreased
aggregation, thereby suppressing the formation of too large
domains and undesired excimers, which serve as charge traps
[45]. Nuckolls and coworkers have reported two helical molecules
constructed by fusing either three or four PDI units together with a
two-carbon bridge. These molecules show strong light absorption
and lack aggregation because of their nonplanar molecular struc-
Fig. 5. Novel acceptors for OSCs.
377
tures due to the steric congestion in the cove areas defined by
the junction point between the PDIs. The advantages of these
molecules over [60]fullerene and its derivatives are the signifi-
cantly higher optical absorption cross-section in the visible part
of the solar spectrum and easily tunable bandgap. The helical elec-
tron acceptor (12), depicted in Fig. 5, can thus complement low-
bandgap electron donors for an efficient harvesting of solar radia-
tion in a broad wavelength region and contribute to the photocur-
rent generation. The authors showed that these novel materials
allowed the fabrication of OSCs with PCE of 8.3% which is compa-
rable with the PCE of fullerene containing devices [46].
2.2. Light absorption and generation of free carriers in PSCs
Contrary to that observed for OSCs, the absorption of photons in
perovskite materials within PSCs does not lead to the formation of
a large lifetime exciton. The most widely used material for active
layer in PSC is the methylammonium lead iodide perovskite,
(MAPbI3), which is placed between electron transporting layer
(ETL), usually mesoporous, but also planar TiO2, and hole trans-
porting layer (HTL, Fig. 6). In the standard device configuration,
the front transparent electrode is FTO-coated glass and the back
electrode is thermally evaporated gold layer (Fig. 14).
A schematic illustration of the crystal structure of organic-
inorganic perovskite is shown in Fig. 7. The general formula for
hybrid perovskites is ABX3, where A is methyl ammonium or other
monovalent cation, B is Pb (II) or Sn (II), and X is Cl, Br, or I.
The MAPbI3 absorber has a direct bandgap of approximately
1.55 eV, corresponding to an absorption onset of about 800 nm
Fig. 6. Band diagram and main processes and PSC: 1 Absorption of photon and free
charges generation; 2 Charge transport; 3 Charge extraction.
378 N. Marinova et al. / Journal of Colloid and Interface Science 488 (2017) 373–389

Fig. 8. IPCE spectra of MAIPbI3, FPbI3, and mixed cation perovskite devices
Fig. 7. Perovskite structure where A stands for monovalent cation, B Pb(II) or Sn (II) (reprinted from Ref. [53] with permission from Wiley-VCH).
cation, and is Cl, Br, or I.

performance devices. The efficient generation of free electrons

and large absorption coefficient in the visible range (105 cm1,
and holes in one step is one of the main advantages of PSCs since
Fig. 1) thus guaranteeing efficient light-harvesting by creating a
in excitonic solar cells significant losses in energy occur through
high density of photoexcited charges with small thickness of per-
exciton migration and exciton dissociation [61,62].
ovskite layer [47,48]. The valence and the conduction band of the
In PSCs charge separation can occur either by injection of photo
MAPbI3 are formed exclusively from Pb and I orbitals. The methy-
generated electrons into ETL or injection of holes in HTL. Further-
lammonium cation does not participate electronically in the band
more, free electrons created near the perovskite/HTL interface have
structure, but governs the formation of the 3D perovskite crystal
to diffuse through the entire width of the absorber layer before
and therefore influence the optical properties of the material.
being extracted at the ETL/perovskite interface, with increased
The optical properties of the perovskite harvesting materials,
chances of recombination. Similar considerations apply to the
may be finely tuned, by varying either the monovalent cation or
holes near the ETL/perovskite interface. Recent reports demon-
the halogen component. The MAPbBr3 has a larger bandgap of
strated that both events electron injection and hole injection in
around. 2.3 eV with a higher voltage potential suggesting that it
the respective transporting layers occur in similar timescale [63].
is suitable for tandem solar cell applications [49,50]. Interestingly,
Moreover, a large photoinduced dielectric constant was reported
the mixed CH3NH3PbI3xBrx perovskite which contains 0.2 parts
for MAPbI3xClx, which removes Coulomb attraction between car-
bromide, shows better stability, compared to the pure iodide mate-
riers and facilitates ambipolar transport by effective charge screen-
rial, while keeping the high photovoltaic efficiency [50]. The sug-
ing [64].
gested stabilization mechanism is related to the fact that MAPbI3
Edri and co-workers studied the mechanism of charge separa-
exists in tetragonal phase at room temperature in contrast to
tion applying direct measurement of electron beam-induced cur-
MAPbBr3, which crystallizes in the more stable cubic form [51].
rent profiles of cross-sections of PSCs. These experiments allowed
Substitution of I with smaller Br leads to the reduction of the lat-
the authors to determine where the current is generated as well
tice constant and a transition to the more stable cubic phase.
as its efficiency degree. The experiments revealed that the current
The formamidinium lead iodide (FAPbI3) show a narrower band
increases in regions close to the ETL/perovskite and perovskite/HTL
gap of 1.48 eV thus allowing theoretical larger currents to be
interfaces, which indicates efficient electron and hole extraction
obtained when employed as absorber, but this material shows
near these interfaces respectively, with electron extraction effi-
lower stability compared to MAPbI3 [52].
ciency somewhat higher than that of holes [59]. Thus MAPbI3 pro-
Pellet et al. demonstrated that mixed composition of MAPbI3
vides ambipolar transport and shows both electron diffusion
and FAPbI3 show enhanced light harvesting, improving therefore
length and hole diffusion length exceeding 1 lm [63,65]. There-
the Incident Photon to Current Efficiency (IPCE) of a photovoltaic
fore, the perovskite material permits effective charge separation
device. PSCs with the composition MA0.6FA0.4PbI3 exhibited supe-
and collection even without ETL or HTL [66–69]. Nevertheless,
rior PV performance compared to that of the single-cation ana-
selective contacts are important prerequisite for stable, highly effi-
logues, owing to a greater harvesting and collection of red
cient devices with reduced recombination [70].
photons, which results in higher short circuit photocurrents with-
Relevant parameters, including bandgap, exciton binding
out sacrificing photovoltage (Fig. 8) [53]. Similar bandgap tuning
energy, electron mobility and hole mobility of the active materials
was shown also for mixed halide mixed cation perovskite with
employed in OSCs and PSCs are summarized in Table 1. In order to
the formula FAPbIyBr3y [52]. This approach allowed the fabrica-
tion of devices with PCE of 20.8% and currently the mixed cation
mixed halide perovskite is the state-of-the-art material for highly Table 1
efficient PSCs [54,55]. The concept of mixed cation perovskite Relevant parameters of the active layer materials for OSCs and PSCs.
was further extended and inorganic Cs+ and Rb+ were employed Parameter OSCs PSCs
in PSCs to achieve 21.6% PCE, which is the highest published effi- P3HT/PC61BM MAPbI3
ciency up to date [56,57]. Bandgap 1.8 eVa 1.55 eVd
Numerous studies reported a small exciton binding energy for Exciton binding energy 0.3–0.5 eVb <0.05 eVe
perovskite absorber in the range of a few milli-electronvolts, which Electron mobility 2  103 cm2 V1 s1c 2–10 cm2 V1 s1f
indicates that practically the photon absorption leads to free- Hole mobility 104 cm2 V1 s1c 5–12 cm2 V1 s1f

carrier generation, unlike OSCs [58–60]. This non-excitonic nature The data displayed in Table 1 can be found in: a [71], b [72], c [73], d [48], e [74], f
of the charge generation is crucial for the development of high- [75].
 N. Marinova et al. / Journal of Colloid and Interface Science 488 (2017) 373–389
present a representative comparison between OSCs and PSCs, we
have chosen the most commonly used materials in each field. Thus,
for OSCs we have chosen the P3HT/PC61BM blend, while MAPbI3
has been elected for PSCs. It is important to underline here, that
values for both OSCs and PSCs vary in the literature depending
on material composition, layer morphology, thickness, film crys-
tallinity and processing conditions.
3. The role of morphology and interfaces in OSCs and PSCs
3.1. The morphology of the BHJ in OSCs
In order to ensure efficient light harvesting and charge genera-
tion in OSCs, the thickness of the active layer should be in the range
of 50–100 nm but this thickness exceeds the exciton diffusion
length. Furthermore, for efficient exciton dissociation an energetic
offset is required which implies a two component active layer.
Importantly, the interface where the dissociation takes place
should be large enough in order to provide efficient dissociation
of the greatest possible number of excitons. Additionally, the
domains of donors and acceptors should be around 10–15 nm, to
ensure that the exciton reaches the interface. Consequently, in
order to realize efficient photoconversion, the active layer architec-
ture must strike a balance between the relatively long optical
absorption length (La  50 nm) and the length scale for exciton dif-
fusion (LD  10 nm) [76].
Thus the above mentioned, planar PHJ device was limited by the
exciton diffusion length, and only excitons generated near the D/A
interface could dissociate at this interface. Consequently, excitons
created far from the D-A junction recombine before diffusing to
the heterojunction. The BHJ solar cells contains an active layer,
consisting of a nanoscale blend of donor and acceptor organic
material, providing large interfacial area and overcoming the exci-
ton diffusion limitation of the PHJ architecture. The large interfa-
cial area in BHJ (Fig. 9) facilitates the charge separation even for
active layers significantly thicker than the exciton diffusion length.
A critical parameter for the PCE of BHJ devices is the morphology of
the interface.
The control over morphology and the domain size of the D/A
interface is a challenging task as it is difficult to theoretically pre-
dict the properties and consequences over charge transport on a
Fig. 9. Schematics of D/A interfacial morphology in OSCs, A planar, B bulk heterojunction.
379
given D/A interface. Usually different processing conditions and
post-treatment are employed to improve charge separation. Some
of the approaches employed for morphology control are varying
the solvent [77] (different polarity, boiling point, etc.) or the use
of mixed solvents systems [78] use of additives [79], post-
deposition solvent annealing [80], etc. Moreover, the morphology
of the interface depends on the properties of the material and
the intermolecular interaction. Unfavorable morphological struc-
tures such as islands and bottlenecks could lead to charge trapping
and limit charge extraction and transport [81].
The morphology and crystallinity of D/A interface influences the
charge recombination and also the charge separation [82]. In our
recent work, we have reported that interface morphology could
influence the recombination mechanism in the device as well
[83–87]. The geminate recombination, which is characteristic for
OSCs, takes place at the D/A interface in the CT state and occurs
when electron and hole which originate from the same photon
recombine before being separated. Commonly, in order to avoid
geminate recombination and improve CT large LUMOD-LUMOA off-
set are employed. Thus, when replacing the standard PC61BM with
pyrazoline fullerene derivatives in blend film, much finer
nanomorphology is obtained and smaller domain sizes are
observed. This inhibits the exciton dissociation since charges
remain physically captured by the small domains. This in turns
leads to an enhanced geminate recombination prevailing over the
bimolecular recombination. Accordingly, the generated photocur-
rent in devices employing these fullerene derivatives is lower,
compared to the standard PC61BM containing devices. Conse-
quently, the charge generation is seriously hampered, and proper
morphology design is required to inhibit the geminate recombina-
tion in OSCs.
The BHJ devices reported in the literature have been prepared
either in standard (regular) or inverted architecture, shown in
Fig. 10. In both types the BHJ donor-acceptor layer is placed
between a transparent front electrode and a reflective back elec-
trode. In order to achieve good performances, however, it is
mandatory that a BHJ device comprises both an HTL and an ETL
for selective charge extraction, which are often referred as interlay-
ers [88,89]. These layers should be transparent and are preferred to
grow amorphous in order to form a smooth layer [10]. The inter-
layers have several functions and are discussed in Section 3.2.
380 N. Marinova et al. / Journal of Colloid and Interface Science 488 (2017) 373–389

Fig. 10. Regular (left), inverted (middle) and tandem architecture (right) of OSCs.

Indium tin oxide (ITO) is the most common material employed
as transparent electrode due to its high conductivity and high
transmittance in the visible region. In the regular BHJ architecture
the high work function ITO serves as a hole collecting electrode
(anode). The back electrode, where electrons are collected, is usu-
ally made of low work function materials as Al and Ag [90]. In the
inverted BHJ cell electrons are collected at the transparent ITO
electrode and holes at the back electrode.
In both types of architectures, light enters the device trough the
transparent electrode and passes through the active layer where it
is absorbed. In the ideal case the transmitted light is reflected by
the non-transparent back electrode and provides a double light
pass through the active layer and enhanced absorption [91].
An efficient way to improve the light harvesting and conse-
quently the PCE of OSCs is the implementation of the tandem
architecture. Tandem devices contain multiple active layers with
complementary absorption thus forming multiple D/A interfaces
(multiple junctions). Typically, for a double-junction cell, such a
tandem structure consists of a front cell with a large-band gap
active layer, an interconnecting layer, and a rear cell with a low-
band gap active layer. The front cell absorbs the higher energy pho-
ton, and transmits the lower energy photons, which are in turn
absorbed by the rare cell. The interconnect layer which separates
the two active layers allows holes from one sublayer to recombine
with the electrons from the other [92]. Following this concept, a
tandem OSC with PCE of 10.6% was described. The device contains
two polymer based active layers with complementary absorption
which contribute to VOC of 1.53 V [93]. In a similar way a triple
junction device, which comprises three distinct active layers with
complementary absorption spectra up to 960 nm allowed record
efficiency of 11.83% [94].
improving contacts and for ensuring selective charge transport.
For a p-type contact the valence band of the interfacial material
needs to match the HOMOD while for n-type material the electron
transfer from the LUMOA to the conduction band of the interfacial
semiconductor should be energetically favorable (Fig. 11). A wide
band gap of the interface material ensures selective charge trans-
port of only one type of carriers while blocking the other and trans-
parency to the visible region [4].
3.2.1. n-type materials
For n-type transport layer inorganic oxides such as TiOx [3] and
ZnO [95] enhance the electron extraction when employed as inter-
facial layers. TiOx can act as an optical spacer as well and enhance
the absorption of the BHJ layer. However, since the efficiency of the
optical spacer depend on refractive indices and thicknesses of all
the layers as well as on multiple reflection processes within the
solar stack, it is difficult to accurately predict the impact of the
optical spacer on the device efficiency [96].
Another compounds which find application as n-type transport-
ing materials in OSCs are salts such as LiF, Cs2CO3 [97] as well as
some organic compounds as bathophenantroline and bathocu-
proine [98].
The development of fullerene derivatives with improved solu-
bility for electron transporting interlayers has also attracted wide
attention. due to similar energy levels and structures as PCBMs
(Fig. 12) [1]. PEG modified [60]fullerene (13) derivative with

3.2. Interfaces and interlayers in OSCs

In OSCs, the formation of non-ohmic contact impedes the

charge collection efficiency of the electrodes and decrease the pho-
tovoltaic performance [1]. To prevent the formation of a barrier at
the metal/semiconductor interface, additional buffer layers
between the semiconductor and the metal are needed [89]. These
layers are selected accordingly to provide suitable energetic align-
ment and facilitate charge extraction. Furthermore, they influence
the built-in field in the device, morphology of the interfaces, pro-
tect the photoactive material from reaction with the metal elec-
trode as well as function as buffer layers for preventing the
diffusion of the metal electrode material into the organic material.
Similarly, inorganic and organic semiconductors are employed for Fig. 11. Band diagram of a OSC employing interlayers.
 N. Marinova et al. / Journal of Colloid and Interface Science 488 (2017) 373–389
Fig. 12. Fullerene derivatives employed as interlayers in OSCs.
Fig. 13. Organic p-type materials for OSCs.
improved solubility was employed as an interlayer in OSCs for
three donor:acceptor systems, namely P3HT:PCBM, PBDTTT-C:
PC70BM and PBDTTT-C-T:PC70BM, resulting in PCE of 3.84%,
6.22%, and 7.45%, respectively. The efficiency is slightly higher than
the corresponding devices with Ca interlayer [99]. Similarly, two
alcohol-soluble PCBM derivatives (14) and (15) were synthesized
for their application of cathode buffer layer in OSCs. The polar side
chain with the amine end group allowed the formation of dipole
interfacial layer between the active layer and Al electrode when
these materials were used as the cathode buffer layer in OSCs. In
comparison with the traditional low work function active metal
Ca cathode, both (14) and (15) cathode buffer layers demonstrated
identical or slightly improved photovoltaic performance in OSCs.
The results indicate that (14) and (15) can be used as the cathode
buffer layer instead of the unstable Ca cathode, so that the device
stability can be improved significantly [100].
Conjugated polyelectrolytes comprising p-conjugated back-
bones with ionic functional groups, such as quaternized amino
group, have been developed as interlayer materials, able to reduce
the electron-injection barrier between the metal cathode and the
active layer in OSC. The work-function tunability results from the
formation of an aligned interfacial dipole assembly at the metal/
organic semiconductor interface, which modifies the energy-level
alignment and improves charge injection [101–103].
A series of water/alcohol soluble zwitterionic polyelectrolytes
comprising sulfobetaine side chains groups were synthesized and
employed as interfacial layers in OSCs with the structure ITO/
PEDOT:PSS/PTB7:PC71BM/interlayer/Al. It was found that the inter-
face modification can boost the photovoltaic performances of the
devices and PCE of 8.74% was achieved when employing the novel
polyelectrolytes with a control device showing a PCE of 5.03%. The
zwitterionic polyelectrolytes have the advantages over the tradi-
tional polyelectrolytes of excellent alcohol solubility and mobile-
ion-free nature which are desirable for fabricating efficient and
stable organic optoelectronic devices by an orthogonal solution
processing method [104].
3.2.2. p-type materials
The most commonly used p-type interfacial layer is PEDOT [p
oly(3,4-ethylenedioxythiophene)] usually doped with poly(styrene
381
sulfonate) (PSS). PEDOT:PSS (Figs. 13 and 16) can be processed
from water solution and it is transparent in the visible range.
PEDOT:PSS is used to modify the anode work function and
improves the selectivity and the quality of the contacts
[105,106]. The main disadvantage of this material when employed
in regular architecture is its intrinsic acidity resulting in corrosion
of the ITO electrode [107]. In the case of the inverted OSCs this
problem is avoided, since ITO serves as electron collecting elec-
trode and it is covered with n-type material.
An effective way to overcome the low conductivity of the
organic materials is the use of dopants [108]. Doped wide-gap
transport layer based on small molecule triarylamine derivative
MeO-TPD (17) was employed in OSC using Zn-Phthalocyanine/[6
0]fullerene as active layer [109]. The device was constructed in
the MIP-type (metal-intrinsic-p-doped) structure. The effective
doping of the MeO-TPD increases its conductivity to 1  105 S/
cm at doping concentration of 4 mol%, which results in improve-
ment in the fill factor of the device due to decreased series
resistance.
Inorganic oxides such as NiO, V2O5 and MoO3 have been
employed as hole-extracting layers in regular and inverted OSCs
[110–112]. The devices showed increased fill factor and decreased
series resistance for very thin interlayers, which make this inor-
ganic oxides promising candidates for replacing PEDOT:PSS.
The modification of the electrode work function can be achieved
by surface treatment with chemicals, which can form a dipole
layer. Thus acidic treatment of the ITO leads to protonation of
the electrode surface and interfacial dipole formed with the anions,
pointing away from the electrode, which increase the work func-
tion of the later. Basic treatment creates dipole which points
towards the electrode and the work function is reduced [4,113].
3.3. VOC and recombination in OSCs
The open circuit voltage (VOC) in OSCs is related to the difference
between the HOMO of the donor and the LUMO of the acceptor.
More specifically, it is determined by the difference between the
quasi-Fermi levels of holes and electrons under illumination pro-
vided that barrierless contacts to the electrodes are formed
(Fig. 2) [1,2,114]. Furthermore, the open circuit voltage is limited
382 N. Marinova et al. / Journal of Colloid and Interface Science 488 (2017) 373–389

Fig. 14. Regular PSC with mesoporous TiO2 scaffold (left), planar (middle) and inverted (right) architecture in PSCs.

Fig. 15. SEM images of the perovskite surface demonstrating the variation of the grain size, prepared by stoichiometric precursor solution, with 10% PbI2 excess and 20%
excess. (reprinted from Ref. [130] with permission from The Royal Society of Chemistry).

Fig. 16. Normal (A) and inverted (B) J-V hysteresis in PSCs – discrepancy between the J-V curve when scanned from positive to negative voltage (black) and from negative to
positive (red) which hampers proper device characterization and efficiency estimation.

by the recombination rate in the device. Unlike geminate recombi-
nation losses which can be completely overcome, all OSCs are sub-
ject to non-geminate recombination [82]. The bimolecular
recombination depends on the charge mobility, faster the charges
move, faster they find each other and recombine resulting higher
recombination rate [115]. Trap-assisted recombination is a two-
step process in which first an energetic trap state, created by imper-
fections of the material, captures a free charge carrier which then
recombines with another mobile carrier with opposite charge [116].
Another type of recombination in OSCs is the surface recombi-
nation at the contacts. Surface recombination occurs when a
minority carrier diffuses towards the electrode and recombines
rapidly there, with a carrier with opposite sign. To decrease the
surface recombination in an OSC and improve the charge collection
efficiency, selective contacts are used. Selectivity to only one car-
rier type is achieved by employing interfacial layers with suitable
energy levels as described in the previous section [89,117].
3.4. Crystallinity of the perovskite layer in PSC
Initially, the perovskite absorber was employed as a sensitizer
of mesoporous TiO2 in liquid dye sensitized solar cell [118]. The
device showed PCE of 3.8% but was unstable due to rapid degrada-
tion of the MAPbI3 under the corrosive effect of the liquid
electrolyte. The first solid state perovskite solar cell, which
employs solid organic semiconductor as HTL showed improved
stability and better performance of 10.9% [119]. This type of device
architecture, often referred as regular, up to now remains the most
widely employed PSC.
The ambipolar transport in the perovskite absorber allowed the
development of planar heterojunction PSCs, which resembles the
PHJ in OSCs. Furthermore, OSCs and PSCs share similarities in the
way that the materials can be processed i.e. from solution or by
evaporation techniques, thus promoting standard stacks architec-
tures and materials used in OSCs to be employed in PSCs [120–
122]. Therefore, a PSC employing organic electron transfer layer
was constructed in inverted architecture in analogy with fre-
quently used layout for OSCs, as demonstrated by Malinkiewicz
et al. [123]. In the proposed structure perovskite layer of
300 nm, formed by evaporation technique, is sandwiched
between two spin-coated 10 nm thick organic charge transport
layer. The ETL material of choice is PC61BM (5) and the efficiency
recorded was above 12%. Similarly, Sun et al. reported all-
solution PSCs with inverted architecture processed at low temper-
ature (<150 °C). The device has the configuration ITO/PEDOT:PSS/
MAPbI3/PC61BM/Al and the efficiency obtained was 7.4% [11]. All
components except the electrodes were deposited by solution spin
coating.
 N. Marinova et al. / Journal of Colloid and Interface Science 488 (2017) 373–389
Crystallization of the perovskite, including grain size and mor-
phology, determines the device performance of PSCs. To control
the crystal growth and provide smooth perovskite surface different
approaches were developed such as the solvent engineering, sol-
vent annealing, and microwave annealing [124–127]. Im and
coworkers demonstrated that the size of the perovskite capping
layer cuboids in PSCs fabricated by two step procedure, can be con-
trolled by the concentration of the methylammonium iodide (MAI)
solution. High MAI concentration (0.063 M) leads to smaller crys-
tals, reduced charge extraction at the grain boundaries and lower
photocurrent and VOC are obtained. On the other hand, bigger crys-
tals formed by employing relatively low MAI concentration
(0.038 M) provide better light harvesting due to increased scatter-
ing. Finally, the efficiency of the devices peaks at concentration of
0.05 M with cuboid size of about 200 nm allowed efficiency of 17%
[128].
Currently the most widely employed method for the fabrication
of high efficient PSCs is the anti-solvent approach in which a sec-
ondary solvent (anti-solvent) is added to the perovskite solution.
In the so-called ‘‘anti-solvent” the perovskite is insoluble, thus
causing supersaturation and inducing rapid crystallization
[124,129].
Gratia et al. showed that when using non-stoichiometric pre-
cursor solution, with PbI2 in excess, the unreacted PbI2 improves
the crystallinity of the perovskite (Fig. 15) film and the electron
transfer to the TiO2 layer, both leading to improved performances
even for a molar excess of 20% [130].
3.5. Interfacial processes, hysteresis, energetic barriers and interlayers
in PSCs
Interfacial processes have a strong influence on the photovoltaic
performance and stability in PSCs. However, in PSCs these pro-
cesses are not yet fully understood. Thus in PSCs the high perfor-
mance results mainly from the targeted optimization of the
isolated layer such as optimization of the absorber thickness, mor-
phology and crystallinity or use of highly doped HTL with
improved conductivity [131]. Nevertheless, interface studies have
been reported and interfacial engineering approaches have been
proposed for device improvement.
An important feature of the PSCs which cannot be ignored when
discussing efficiency is the hysteresis in the J-V curve. The standard
method for measuring the PCE of a solar cell consists in recording a
current–voltage curve, while sweeping the voltage under simu-
lated solar illumination and specified ambient conditions. For per-
ovskite solar cells, however, the real, i.e. steady-state, J-V curve
strongly depends on the voltage sweep rate, the operational point
before the scan and the scanning direction (backward - from open
circuit to short circuit or the opposite way, denoted as forward).
This phenomenon results in J-V hysteresis, as shown in Fig. 16,
and imposes a drawback on the accurate determination of PSCs
efficiencies [132,133]. Several possible origins of hysteresis have
been discussed in the literature, such as the existence of surface
traps in perovskite material and field modulated trapping and
detrapping process, ferroelectric effect, or ionic movement under
applied bias [132,134–136].
Tress et al. demonstrated that in PSCs electronic processes at
the ls scale generate the photocurrent, whereas additional slow
process defines the surrounding conditions. During a voltage
sweep at moderate speed, this slow process takes place, continu-
ously changing the conditions and affecting the charge collection
efficiency. The slow process has been identified as ionic movement
resulting in ions accumulating at electrodes which screens the
electric field in the perovskite film when the device is kept at
low voltages. The ionic charge accumulation at low bias is rational-
ized by the presence of a built-in electric potential driving negative
383
ionic charge toward the FTO and/or positive charge toward the Au
electrode [132].
Recently, the same group reported the inverted hysteresis for
mixed cation mixed halide PSCs which, contrary to the common
hysteresis, manifests itself in a decreased fill factor for backward
scan. For this type of devices electrons on the mixed perovskite
face an extraction barrier at the TiO2. The study shows that in
the case of extraction barriers, ionic movement and the pilling-
up of ions at the contacts can be beneficial, because it introduces
dipole layers which enhance the electric field close to the contacts.
The latter results in an enhanced fill factor for a forward scan in
case of extraction barriers.
Thus the phenomenon of hysteresis is a result from a complex
interplay between charge transport in the perovskite layer, charge
extraction at the contacts, and a slow process that changes the
electric field in the perovskite and at interfaces to the electrodes.
Whether and in which way the hysteresis becomes apparent is
related to the relevance of the electric field on charge collection
[137].
Depending on the architecture of the device, different interfaces
are formed and consequently different trends in the solar cells
have been observed. For instance, the planar TiO2 based devices
show much more pronounced hysteresis than the mesoporous
ones, which indicates that the perovskite/ETL interface is crucial
for the device operation [138–140]. Currently the role of the meso-
porous TiO2 surface is not completely clear, but it has been demon-
strated that devices which comprise such a mesoporous TiO2
scaffold perform better than the planar devices based on compact
TiO2 [141]. Correa and coworkers showed that in planar devices at
the TiO2/perovskite interface, a charge extraction barrier is formed,
therefore limiting the device efficiency and give rise to large hys-
teresis. Replacing TiO2 with SnO2 switches on the charge extraction
at the Perovskite/ETL interface, increases efficiency and decreases
hysteresis [142].
It has been suggested that the instability of perovskite under UV
light is possibly due trap states in TiO2. In TiO2 surface adsorbed
oxygen is desorbed upon UV irradiation, thereby exposing the deep
electronic trap sites to which it was adsorbed. These trap sites then
function as a rapid recombination pathway for photogenerated
electrons, resulting in a dramatic drop in charge collection effi-
ciency [143]. Furthermore, the electron transfer at the per-
ovskite/TiO2 heterojunction in planar PSCs is very slow due to
band misalignment and require further interfacial adjustment
[142,144]. For overcoming this issue Snaith and co-workers
demonstrated that by interfacial modification of the TiO2 surface
with organic electron accepting fullerene self-assembled mono-
layer (C60-SAM, Fig. 17), the charge extraction at the TiO2/per-
ovskite is switched on, resulting in largely improved photovoltaic
performance and decrease in hysteresis behavior [144]. Moreover,
by entirely removing the standard TiO2 blocking layer and replac-
ing it by n-type organic selective contact based of a solution-
processed [60]fullerene (18), improved electron extraction from
the photoexcited perovskite to the C60, as compared to the com-
monly employed TiO2 compact layer, was achieved. Besides, the
devices display negligible hysteresis and improved stability
[145]. Further studies confirm that fullerene derivative layer at
the perovskite/ETM interface reduces the hysteresis thanks to trap
states passivation [138,146]. Similarly, surface passivation with
PC61BM decrease the trap density at the perovskite surface by
two orders of magnitude and the hysteresis is reduced [147].
Water soluble derivative [60]fullerenol (20) was shown to facili-
tate the charge transport from perovskite to TiO2 and decrease
the interfacial resistance [148].
Very recently we have demonstrated that PSCs which comprise
[70]fullerene (19) as ETM can be fabricated by solution process. In
this report we have introduced the ‘‘Fullerene Saturation
384 N. Marinova et al. / Journal of Colloid and Interface Science 488 (2017) 373–389

Fig. 17. Schematic representation of a PSC structure which employs fullerene based SAMs for TiO2 surface modification. Reprinted from Ref. [144].

Approach”, a simple solution processing protocol which allows the
fabrication of [70]fullerene based devices with efficiency similar to
the devices fabricated with [60]fullerene or TiO2 as ETM. The dam-
ages by dissolution of the [70]fullerene film during the perovskite
deposition, are avoided through the saturation of the perovskite
processing solution with [70]fullerene. Additionally, this fullerene
saturation strategy has been proven to significantly improve the
performance of the perovskite film, resulting in an enhancement
of the PCE of solar cells based on different ETLs (i.e. [60]fullerene,
[70]fullerene, and TiO2). This universal-like solution processing
protocol paves the way towards wide opportunities for further
development of PSCs based on fullerene derivatives [149,150].
A functionalized fullerene derivative (21) was synthesized and
employed for ETL interface engineering on low temperature-
processed TiO2 in the planar PSCs. The molecule is a PC61BM
derivative and was especially designed to circumvent the limita-
tions of the most commonly employed fullerenes and PCBMs.
These limitations are the hydrophobicity, which hampers the wet-
tability and the uniform coverage of the fullerene modified TiO2
surface and dissolution of the layer during the multistep spin coat-
ing solution deposition. Compound (21) contains C60 as the main
building block for ensuring the desired electrical properties, while
dioctyloxy chains and cyano-groups aim to minimize the solubility
in polar solvent such as DMF, while keeping the solubility in non-
polar chlorobenzene. By suitable molecular design the authors
accurately address processing compatibility, interface recombina-
tion loss, work function tuning of electrodes, hysteresis and inter-
face induced degradation, allowing the preparation of devices with
PCE around 16% [151].
Novel benzoic acid fullerene bis adducts (22) have been
recently employed in heterojunction PSCs. The introduction of
these fullerene derivatives as ETM in inverted PSCs allowed similar
PCE to that reported for PC61BM containing devices to be obtained
[152].
As expected, evolving from the OSCs, fullerene and its deriva-
tives are the most widely used n-type materials for ETMs in
inverted PSCs. C60 (18) and derivatives with different energy level
and electron mobility, such as PC61BM (5), ICBA (6) and PC71BM are
ideal candidates for efficient electron extraction materials because
of their low temperature fabrication, suitable energy level align-
ment, and good electron mobility [153–155]. Recently, Wu and
co-workers have developed an inverted MAPbBr3 cell using ICBA

Fig. 18. Fullerene derivatives, employed in PSCs.

 N. Marinova et al. / Journal of Colloid and Interface Science 488 (2017) 373–389 385

Fig. 19. Fluorescence image before (A) and after treatment with pyridine showing activation of the perovskite film (B). Reprinted from Ref. [162] with permission from AAAS.

(6) as an electron acceptor to obtain a remarkably high VOC of 1.61 photogenerated holes in this region of the absorber, which enhance
V and PCE of 7.5%. The reported VOC is the highest value among all the electroluminescence quantum yield and the VOC. Furthermore,
reported perovskite solar cells [156]. Fig. 18 shows examples of PbI2 crystallites, which are present within the mesoporous TiO2
fullerene derivatives which have already been employed in PSCs. layer, favor the growth of bigger perovskite crystallites, which
Other inorganic based NiOx, MoOx and VOx interlayers were exhibit a reduced area of grain boundaries and, therefore, fewer
employed in inverted type perovskite solar cells to modify the defects [54].
work function of the ITO electrode, leading to improved VOC
[157]. Additionally, the modification of the electrode with a solu-
3.7. Interfacial degradation in PSCs
tion processed interfacial layer of ethoxylated polyethyleneimine
was recently employed, allowing the reduction of the Schottky bar-
Apart from the electronic process at the interfaces, the degrada-
rier formed at the interface of TiO2 and the transparent conductive
tion processes which take place at the interfaces should also be
electrode ITO [158].
considered as device limiting factor [163].
The most commonly employed HTM in PSCs, namely Spiro-
3.6. VOC and recombination in PSCs
MeOTAD (Fig. 20), in its pristine form do not provide the necessar-
ily conductivity for proper device operation. For ensuring sufficient
Since the perovskite solar cell is a nanoscale device the thick-
conductivity partial oxidation of Spiro-MeOTAD to Spiro MeOTAD+
ness and morphology of each layer strongly affects the photo-
is required. This is achieved either by use of oxidizing dopants or
voltaic parameters including recombination and VOC. Tress et al.
when devices are stored or operating in the presence of oxygen.
reported that thickness of the HTL layer can play an important role
Another additive, namely LiTFSI, is found to have a critical role
in the device performance. Sufficiently thicker HTL ensures full
on the doping efficiency because it stabilizes the oxidized form
coverage of the rough perovskite surface thus increasing the charge
of Spiro MeOTAD+, which governs the conductivity of the HTM
carrier collection efficiency and reducing the rate of non-radiative
layer [164,165].
recombination. Moreover, the evaporated Au electrode on top of
A recent report shows that an irreversible chemical reaction
the smooth thick HTL layer serves as a reflecting mirror which pro-
between spiro-MeOTAD+ and migrating I takes place at the Spir-
vides a second light pass through the absorber and enhances the
oMeOTAD/perovskite interface, which progressively reduces the
light harvesting efficiency [159].
HTM conductivity and deteriorates the solar cell performance
Analyses of the electroluminescence efficiency and the diode
[166]. This important finding raises the question whether the com-
ideality factor in several studies show that the dominant recombi-
monly employed highly doped HTM composition could really pro-
nation mechanism in PSCs is the non-radiative trap-assisted
vide the required long term stability of PSCs.
recombination [54,159,160]. The limit for VOC of PSCs in case of
A possible solution to this issue, is the introduction of interfacial
solely radiative recombination is determined to 1.32–1.34 V
layers of montmorillonite to avoid contact between HTM and per-
[161]. Non-radiative losses at VOC decrease further his value to
ovskite and to prevent the corrosion of the perovskite by the polar
around 1.1 V for state-of the-art devices and even below if contacts
are not selective. Investigation on the photoluminescence of per-
ovskite films show that intensity and lifetimes vary between differ-
ent grains in the same film and that at the grain boundaries faster
non-radiative decay is observed (Fig. 19). The authors demonstrate
that pyridine vapor exposure can brighten dark domains indicating
passivation of grain boundaries, thus remediating non-radiative
defects in the perovskite film. Reducing the non-radiative recombi-
nation by minimizing defects in the perovskite material and opti-
mizing the interface at the contacts will lead to higher VOC
approaching the theoretical limits for open-circuit voltage and effi-
ciency [162].
Furthermore, the approach of non-stoichiometric PbI2-enriched
perovskite precursor allowed the fabrication of devices with VOC of
1.18 V and high electroluminescence yield. It was found that the
role of excess PbI2 is to reduce recombination close to the per-
ovskite/TiO2 interface. Thus, PbI2 crystallites, which are located
within the mesoporous TiO2 scaffold, prevent recombination of Fig. 20. Molecular structure of Spiro-MeOTAD.
386 N. Marinova et al. / Journal of Colloid and Interface Science 488 (2017) 373–389
solvent and active additive in the HTM, which enhances the stabil-
ity of the devices [167].
Domanski et al. showed that elevated temperature (>70 °C)
causes irreversible changes in an operating PSCs employing a
spiro-MeOTAD and an Au or Ag back contact, since considerable
amounts of the Au from the electrode diffuse across the HTM into
the perovskite layer. The diffused Au cause irreversible loss of VOC,
FF, and JSC in the aged devices. Insertion of a thin Cr interlayer
between the HTM and Au alleviates the problem of severe device
degradation at elevated temperatures. Therefore, it is important
to investigate other interlayer materials that can hinder this phe-
nomenon [168].
4. Conclusion and outlook
In this article, we have summarized the operation principles,
materials employed, the basics of the interfacial engineering and
the latest advances and trends in the field of OSCs and PSCs.
Undoubtedly, the interfacial modification has promoted the
improvement of OSCs and has allowed a remarkable enhancement
of the PCE. In contrast, the interfacial processes in PSCs are not fully
understood nowadays, and only a few examples of interlayers and
interfacial modification for device improvement are known. This is
mainly due to the fact that optimized active layers in PSCs allow
very high efficiencies to be achieved in record short time. In PSCs,
further research is needed on the limiting interfacial processes as
well as on the development of new materials. Thus, major draw-
backs in these devices, such as hysteresis and stability under oper-
ation conditions, can be overcome in the near future. All the
aforementioned issues will be critical for the sustainability and
future commercialization of PSCs as source of affordable renewable
energy.
Acknowledgements
This work was supported by Basque Government, MINECO
(Ministerio de Economía y Competitividad, Spain) and Gipuzkoa
Council under projects PC2015-1-03 (16-79), CTQ2015-70921-P
and MSFP (Macromolecules for Single Fission Photovoltaics). J.L.
D. acknowledges Ikerbasque, the Basque Foundation for Science,
for an ‘‘Ikerbasque Research Fellow” contract, Polymat Foundation,
MINECO of Spain for IEDI-2015-00666 grant and Iberdrola Founda-
tion for financial support. S.V. and N.M. acknowledge Polymat
Foundation for a PhD and a Postdoctoral research position,
respectively.
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