Perovskite Solar Cells

C H A P T E R
9
Perovskite solar cells
Amol Nande1, Swati Raut2, S.J. Dhoble2
1
Guru Nanak College of Science, Ballarpur, Maharashtra, India; 2Department of Physics, RTM
Nagpur University, Nagpur, Maharashtra, India
9.1 Introduction
In the 19th and 20th centuries, the human race increased fossil fuel energy consumption to
satisfy its demand for electrical energy. Unfortunately, fossil fuels are limited but global de-
mand for energy for day-to-day use continues to grow. Moreover, carbon emissions have also
grown on average by 2% [1]. Furthermore, fossil fuels have many disadvantages regarding
extraction, transportation, and consumption. There are high risks involved in the transporta-
tion and accidental spills of fossil fuels, which can cause very serious problems. Therefore hu-
mankind has to find alternative sources of easily available and clean energy. The available
options for clean and safe energy are solar energy, wind energy, biomass, and geothermal
energy. Of these energy sources, solar energy is easily available and can be directly converted
to electrical energy [2].
Solar energy offers an easy solution to produce electricity in a clean and safe way. The ma-
terials or devices that convert solar energy to electrical energy are termed photovoltaic or so-
lar cells. Daryl Chapin, Gerald Pearson, and Calvin Fuller from Bell's Laboratory invented a
silicon-based solar cell that ultimately revolutionized the photovoltaics industry [3,4]. Due to
advancements in fundamental physics and device fabrication along with silicon wafer-based
solar technology, other thin film technologies such as GaAs, Cu(In,Ga)Se2, CdS, CuZnSnSe2,
CdTe, organic molecule and polymer solar cells, quantum dot solids, dye-sensitized solar
cells, and perovskite solar cells (PVSCs) have been established and researchers are intensively
investigating materials and systems for efficient solar cells [5e8]. The major photovoltaics in-
dustries still dominate silicon photovoltaics, but it has high manufacturing and installation
costs [9e11], although it is expected that the cost of silicon photovoltaics will decrease. But
for now, PVSCs are a potentially proven candidate for photovoltaic technology. The materials
used are cheap and easily processable organiceinorganic hybrid perovskite semiconductors
used as absorber materials [11e14]. This is the third generation of solar cells and the first
work on this subject was published in 2009 by Kojima et al. [15]. Researchers have seen var-
iations in power conversion efficiencies from 3.78% to 28% and they are expecting to see
Energy Materials
https://doi.org/10.1016/B978-0-12-823710-6.00002-9 249 Copyright © 2021 Elsevier Ltd. All rights reserved.
250 9. Perovskite solar cells
further improvements in efficiencies in the coming years [13,16,17]. This chapter discusses the
photovoltaic and solar cell properties of perovskite materials. First, the chapter explains
perovskite materials, where we focus on their common structure and the literature devoted
to inorganic and organic perovskite materials. This will lead to synthesis techniques, espe-
cially for perovskite solar cells, which consist of topics such as device anatomy, requirements
of each layer, working principles, and characterization techniques. Later, the chapter dis-
cusses the fabrication approach and device evaluation of PVSCs. The chapter concludes
with key challenges and the future outlook of PVSCs.
9.2 Perovskite materials
Perovskite was first used for calcium titanium oxide (CaTO3) and is named after Lev Per-
ovski. Later, perovskite was used to explain any material having the same structure as
CaTO3. To express perovskite material, the more generalized formula ABX3 is deployed,
where A (such as metal ions and organic cations) and B (such as metal ions) are cations
and X (such as oxides and halides) is the anion. Also, their valences are in a ratio of 1:2:1
with a cubic structure of conventional perovskite. Cations A are larger than cations B, as
shown in Fig. 9.1 [18]. The figure shows that perovskite materials have a cubic crystal struc-
ture where the smallest cation B is surrounded by an octahedral anion. Twelvefold octahedral
coordination with 12 X anion neighbors is covered by cation A. It is well known that when
discussing the stability of perovskite structures, including oxidesand
pffiffiffi halides,Goldschmidt's
tolerance factor is widely accepted. This is given as t ¼ ðrA þrX Þ 2ðrB þrX Þ , where, rA, rB,
FIGURE 9.1 Ideal perovskite crystal structure in which B cations are linked at the corners of an octahedron to
form a cubic lattice [18]. Used with permission granted from Copyright © 2001, American Chemical Society.
II. Photovoltaic materials and devices

9.2 Perovskite materials 251
and rX are the ionic radii of A, B, and X, respectively, and for all perovskite structures t values
should be in the range of 0.75e1 so as to maintain stability [18,19]. However, for a few ma-
terials, the t range is not the ideal condition for the formation of perovskite structures,
because for some materials even if t is in the most favorable range, no stable perovskite struc-
ture is formed [19,20]. A detailed study of the stability of perovskite materials is discussed by
Li and coworkers [19,20]. According to their work, the modified range of t values is
0.813e1.107, excluding CsBeF3. Further formation on perovskite crystal structures in AXe
BX2 complex halide systems the tolerance factor is not the necessary factor (as for solar cells
application perovskite materials with halides as anions are more useful [7,12,21]). The octa-
hedral factordif anion X and cation B form a sixfold coordination octahedral structure,
then the ratios of rB/rX are in the range of 0.377 and 0.895 for perovskite halides (except
for TlMnI3 and CsBeI3) [19,22]. Therefore tolerance and octahedral factors are used to span
the two-dimensional structure and are considered as the criteria of formability of halide
perovskite materials. These two factors can be summarized in a two-dimensional plot, which
is an effective model to predict perovskite materials, as shown in Fig. 9.2. From the figure it is
clear that the materials with perovskite structure are in the rectangular dotted box repre-
sented by open circles, which obeys both conditions (a list of the compounds is present in
the cited article) [19].
The ability of perovskite materials to create cation- and anion-deficient structures makes
them special and these materials show extraordinary physical properties such as magnetic,
electrical, superconducting, optical, ferroelectric, photovoltaic, and photocatalytic properties
FIGURE 9.2 Tolerance versus octahedral map for perovskite compounds [19]. Used with permission of the Inter-
national Union of Crystallography.

[11,12,18]. Perovskite materials have either oxygen anions (oxides) or halogens. Perovskite
materials with halides are of great interest due to their exceptional optoelectronic properties.
Therefore it is observed that the materials have halides (Cl, Br, I, and F) at the X position in
ABX3 and their optoelectronic properties make them better candidates for solar cell applica-
tion compared to oxides. Also, the published work shows that highly efficient perovskite ma-
terials for solar cells contain lead (Pb) or tin (Sn) at position B. These compounds have low
bandgaps that enhance photon absorption in visible and near-infrared regions. One can
tune the perovskite bandgap by varying the composition of perovskite elements. Also, by
changing any elements in the ABX3 perovskite stoichiometry, the bandgap can be tuned
throughout the visible spectrum. The energy bandgap depends on the size of cation A,
and it is observed that by increasing the size of A, the bandgap size decreases and vice versa
[23e25]. Also, one can tune the bandgap by keeping the same composition of materials and
by changing the quantum confinement in perovskite nanoparticles. There are organometallic
perovskite materials for which the experimental bandgap value of ~1.6 eV is an ideal
bandgap value for single junction solar cells.
Another interesting parameter used for photovoltaics is absorption coefficient, which de-
termines the intensity of light as it passes through a given material. It is observed that perov-
skite materials, especially organometallic perovskite materials, have higher absorption
coefficient compared to other photovoltaic materials [26e28]. Along with absorbance coeffi-
cient, carrier diffusion length also plays an important role in the performance of the solar cell
device; the higher the carrier diffusion length, the better the performance of the device. Liter-
ature dictates that perovskite materials exhibit longer carrier diffusion lengths compared to
traditional semiconductors or solar materials; for example, the single crystal of MAPbI3
showed ~175 mm [29]. Thus this large diffusion length allows a planar heterojunction with
a selective charge interface for perovskite materials. This gives perovskite materials both p-
type and n-type interfaces, which form p-i-n or n-i-p structures. The performance of these
structures is similar to mesoporous structures. Thus perovskite materials are both excellent
light absorbers and electron and hole transporters, which make them outstanding candidates
for solar cells.
9.3 Synthesis techniques
The structure and morphology of perovskite materials or layers play a vital role in their
inherent properties and hence their solar cell performance. The homogeneity and uniformity
of the photovoltaic grains are also responsible for the performance of solar cells. The crystal-
line nature, grain size, and quality of perovskite thin film depend highly on depositing
parameter and substrate. Here, we explain the most commonly used techniques to deposit
dense and uniform perovskite layers. The perovskite absorber can be deposited by
solution-based methods (such as dip coating, spin coating, inkjet printing, doctor blading,
etc.), vapor-based methods (such as thermal evaporation, chemical vapor deposition, sputter-
ing, pulsed laser deposition, sequential evaporation, etc.), and hybrid vaporesolution-based
deposition methods. Some of these are described next.

9.3 Synthesis techniques 253
9.3.1 Solution-based methods

From earlier published works, it is observed that one-step spin coating was used to deposit
perovskite thin films on mesoporous substrate using a blended precursor solution of AX and
BX2. However, spin coating is a slow process and hence it is difficult to deposit a uniform
layer of perovskite materials [30,31]. Due to the slow process, the nucleation rate automati-
cally decreases, which often causes pinhole structures in film or uneven films [32,33]. Slow
nucleation in the simple spin-coating technique or nucleation and growth of perovskite films
can be induced by adding antisolvents such as toluene or chlorobenzene during spinning of
the precursor solution. Therefore this technique is called the antisolvent dripping method
[34]. It is observed that due to fast nucleation, more uniform films are produced, which in-
creases the power conversion efficiency (PCE) values of PVSCs [35,36].
The nucleation and growth of perovskite thin films also increases when hot precursor so-
lution is deposited on the hot substrate. This method is termed the hot casting method [37].
Perovskite thin films with larger grain size can be produced using the hot casting method.
This suggests that a bigger grain size would have fewer bulk defects, which improve the
charge carrier mobility and PCE value of PVSCs [37]. This is one of the important and
most used methods because it provides control over two-dimensional crystallographic orien-
tation, which facilitates efficient charge transport and good stability against light sources [38].
Furthermore, it is possible to deposit two- and three-dimensional hybrid structures using this
method, which opens a new scope for the PVSC field. This provides high and efficient charge
transport, and hence PCE value and stability rise [39,40].
Another approach to deposit the perovskite layer is the sequential two-step deposition
method. In PVSCs, two-step deposition follows spin coating of AX and BX2 followed by ther-
mal annealing to form a uniform layer by the interfusion of perovskite grains [37,41]. In this
method, perovskite morphology can be controlled by precursor materials, spin-coating
parameter, and annealing conditions. This process also provides better PCE values than sim-
ple spin-coating methods [42].
9.3.2 Vacuum-based deposition

In the solution processing method, it is virtually impossible to obtain completely homoge-
neous, dense, and compact thin film. This difficulty can be overcome by depositing perovskite
film using vacuum-based methods. This process also forms a dense and uniform thin film over
a large area. It also provides control over substrate temperature, thickness of films, and de-
posits even on rough surfaces. This kind of method is necessary to develop large-scale PVSCs
with high PCE values [43]. In this method, AX and BX2 are coevaporated to a synthesized
pure ABX3 thin layer [44]. Coevaporation can be achieved by the thermal evaporation method
or pulse laser method. In all deposition methods, the perovskite-deposited layer would be uni-
form, free from solution contamination, and independent of smoothness of substrates.
9.3.3 Hybrid solution and vapor method

In this method, BX2 is deposited on the electrode or substrate via sputtering or thermal
evaporation. Later, a solution of AX is added by spin coating to form the perovskite layer

[45]. This method is used to deposit perovskite thin film over a large surface. In this process,
one could replace the spin-coating step with the inkjet printing technique or the dip-coating
technique. This method allows comparatively fast formation of perovskite even at room tem-
perature, and controls deposition rate and substrate temperature to deposit BX2. By varying
these two conditions, the formation of size, shape, and arrangement of grains can be
controlled. This will provide a controlled porous nanostructured BX2 thin film, which defines
the formation and structure of the perovskite layer when AX is deposited onto it.
9.4 Perovskite solar cell

As discussed in earlier sections, there are many alternatives to traditional silicon-based so-
lar cells but the materials should match power conversion efficiency, long-term stability, and
cost effectiveness. PVSCs are promising materials for photovoltaic cells due to their PCE and
low costs [16,21,46]. Due to their crystal structure, availability of cations and anions, high
absorbance coefficient, large diffusion length, and bandgap comparable to visible and
near-infrared photon region, these materials show significant optical properties, which are
used in diode, superconductor, and transistor technologies [47e51].
As discussed earlier, CH3NH3PbBr3 (MAPb) cells reported 2.2% efficiency and a sudden
rise in efficiency was observed when bromine was replaced by iodine [15]. Afterward,
iodine-based perovskite was used as a sensitizer in photoelectrochemical cells and an
observed PCE value of ~3.8% was documented for this kind of system. However, when a
hole transporting layer was used in the device, the PCE suddenly increased to ~9.7% [31].
Later, when the evolution of PVSCs started, researchers began modifying PVSCs to increase
the efficiency and stability of the devices by modifying perovskite composition. The literature
depicts various previous compositions of photovoltaic cells, which contained perovskite ma-
terials; a summary of selected perovskite materials used from 2018 with their device PCE
values and hole transport layers is provided in Table 9.1.
9.4.1 Inorganic perovskite

Due to the poor thermal instability of organic cations, inorganic materials for PVSCs have
been studied intensively due to their visible light absorbance with bandgap and thermal sta-
bility [69]. Inorganic materials like cesium lead halides, mixed cesium lead halide, cesium tin
halide, cesium germanium halide, cesium tinegermanium halide, and silverebismuth halide
have also been studied for PVSCs. Inorganic perovskite materials such as CsPbI3-based solar
cells demonstrated a PCE value of ~17% and stability up to 500 h [70,71]. Mixed cesium lead
halide perovskite, e.g., CsPbI3exBrx solar cells, has better thermal stability and bandgap. For
example, CsPbI3exBrx perovskite carries thermal stability from CsPbBr3 and bandgap from
CsPbI3. Mixed halide perovskite inorganic materials when used as a gradient annealing
method in combination with the antisolvent method formed large grains and hence produced
high-quality film. This material had an efficiency of ~16% and better stability [72,73] than
earlier types.
Due to the poisonous nature of Pb, researchers began working on lead-free inorganic
perovskite materials. Tin (Sn) or germanium (Ge) were used in place of Pb and iodine and

9.4 Perovskite solar cell 255
TABLE 9.1 A summary of perovskite materials used since 2018 along with their efficiency and hole trans-
port materials used for the device.
Efficiency
Perovskite Hole transport material (%) References
CsPbI3 quantum dots Spiro-MeOTAD 70 [52]

CsPbI3xBrx Metal oxide Above 7 [21]
CsPbI2þxBr1ex 14.45 [53]
(FA0.79MA0.16Cs0.05)0.97Pb(I0.84Br0.16)2.97 LiTFSI 22.70 [54]
FAPbI3 Spiro-MeOTAD 20.64 [55]

Cesiumeformamidiniumemethylammonium triple cation Spiro-MeOTAD 20.80 [46]
PVSCs [(FAPbI3)1x(MAPbBr3)x]
Formamidiniumelead triiodide perovskite films Spiro-MeOTAD 20.64 [55]

CH3NH3PbI3 films m-PEDOT:PSS/spiro- 15.57/ [56e58]
MeOTAD 22.70
(PEA)2(MA)ne1PbnI3nþ1 m-PEDOT:PSS 11.01 [59]
Cs2AgBiBr6 film Poly(3-hexylthiophene-2,5- 1.44 [17]
diyl) (P3HT)
CH3NH3PbI3 layer sandwich by carbon Spiro e MeOTAD, PTTA, 17 [60]
P3HT
FA0.75MA0.25Sn1exGexI3 PEDOT:PSS 20 [61]
CsxFA1xPbI3 Spiro-MeOTAD 14.16 [62]
HTABx(FAPbI3)0.95(MAPbBr3)0.05 Poly(3-hexylthiophene) 22.70 [63]
MAPbI3/MAPbIxBr3x perovskite stacking structure Carbon-based solar cells 16.2 [64]
CsPbI2Br films Carbon-based solar cells 10.95 [65]
FA0.85MA0.15PbI3 Tris(pentafluorophenyl) 21.6 [66]

boron
CsPbBr3 No 9.92 [67]
[CH(NH2)2]0.9Cs0.1PbI3 Spiro-MeOTAD 20.60 [68]
Abbreviations: CsPbI3, Cesium lead iodide; Spiro-OmeTAD, 2,20 ,7,70 -Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9 0 -spirobifluorene;
Spiro-MeOTAD, 2,20 ,7,70 -Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9 0 -spirobifluorene; PEDOT:PSS, poly(3,4-ethyl-
enedioxythiophene) polystyrene sulfonate; P3HT, Poly(3-hexylthiophene-2,5-diyl); PTTA, purified terephthalic acid.
bromine were used as a halide in the perovskite combination. Sn and Ge have good optoelec-
tronic properties similar to Pb. However, the perovskite structure of these used materials is
less stable and hence efficiency is less as compared to previously studied perovskite
materials. Further studies are required to understand the optical and electrical properties
of Sn or Ge used for perovskite materials [73e76]. A mixture of Sn and Ge is used instead
of monometallic counterparts due to its stable narrow bandgap absorbers [77]. Instead of

two-dimensional structures, three-dimensional structures (like Cs2TiI6, Rb2TiI6, In2TiI6,

AgBi2I7, etc.) are efficient candidate PVSCs because of their higher electronic dimensionality
and promising light absorbency.
Thus all inorganic perovskites are stable under ambient conditions and they do not un-
dergo chemical degradation like organic perovskites. The efficiency of inorganic perovskites
has reached 17% in recent years.
9.4.2 Organometal perovskite

Miyasaka and coworkers reported and provided new directions for solar cells [15]. They
reported MAPbI3 and MAPbBr3 perovskite as sensitizers in dye-sensitized solar cells with
electrolyte solution. This kind of structure is termed organometal perovskite. The efficiency
of the first PVSCs was 3.81%. PVSC materials are easy to prepare and deposit but there
was a problem with their stability. This was resolved when the hole transport layer changed
to spiro-MeOTAD.
Later experiments started to increase the efficiency and stability of PVSCs. Therefore apart
from changing other layers’ components, researchers also started experimenting with compo-
nents of MAPbI3. In other cations, including ethylammonium (EA) and formamidinium (FA),
the radius of the cation rMA < rFA < rEA was investigated for a replacement for methylammo-
nium (MA). Replacing MA with a larger cation disorders the three-dimensional arrangement
resulting in a two-dimensional orthorhombic crystalline morphology with larger bandgap
[78]. It was observed that when MA (2.17 Å) was replaced with FA (2.53 Å), it modified
the bandgap of the perovskite. FAPbI3 has a small bandgap compared to MAPbI3; therefore
the absorption wavelength increases [79]. Replacing MA with FA increases the tolerance fac-
tor and hence enhances thermal stability.
Mixed A cation perovskites like MAFA1exPbI3, by changing the composition proportion of
MA to FA, eventually attain an efficiency of 14.9% [80]. Mixed cation perovskites like
FA0.85Cs0.15PbI3 PVSCs showed better performance and stability against FAPbI3 [81].
Three-dimensional perovskites like (PEA)2(MA)2Pb3I10 improved stability [82]. Other exper-
iments changed the B cation from Pb to Sn or Ge in MAPbI3 perovskite. It is observed that by
changing the cation to Sn, the bandgap reduced to 1.17 eV [83]. Later, changing the halide
from iodine to another halide or mixed halide again affected the bandgap of the perovskite
and hence increased the absorption wavelength of the perovskite layer [84]. Theoretical cal-
culations showed that lead-free organometallic perovskites (like MASnI3, MASrI3, MABiSI2,
MABi0.5Tl0.5I3, and MACaI3) are prominent candidates for PVSCs [85].
The commonly studied perovskite materials for photovoltaic applications are MAPbI3,
MAPbI3exClx, MAPbBr3, MAPbI3e3xBr3x, MASnI3, HC(NH2)2PbI3, etc. Although the effi-
ciency of organometallic PVSCs is matched with traditional solar cells, degradation of organic
molecules affects their stability. Ambient conditions like temperature, humidity, and oxygen
affect the degradation of organic molecules. The efficiency and stability of perovskite mate-
rials also depend on hole transport and electron transport materials. Details of these two
layers are discussed further in this chapter.

9.5 Fabrication approach and device anatomy 257
9.5 Fabrication approach and device anatomy

A PVSC device schematic is shown in Fig. 9.3, where the front contact or electrode on the trans-
parent glass substrate is deposited. An electron transport material layer is deposited on top of the
front contact to increase the mobility or transport of the photogenerated electrons in the perov-
skite material layer, which is directly deposited on the electron transport material layer. Mobility
of the photogenerated holes is controlled by a hole transport material layer, which is deposited
onto the perovskite material layer; finally a back electrode is deposited onto the hole transport
layer.
There are several methods and approaches for synthesizing PVSCs, of which three ap-
proaches are well known: (1) mesoporous approach, (2) planer n-i-p approach, and (3) planer
p-i-n approach.
9.5.1 Mesoporous perovskite solar cells

Dye-sensitized solar cells are generally prepared using mesoporous perovskite solar cells.
As discussed earlier and shown in Fig. 9.4A, a transparent electron transport layer like TiO2
or ZnO of 50e70 nm thickness and a mesoporous layer like Al2O3 of 150e200 nm thickness
are deposited on the transparent glass substrate. When the perovskite material layer is depos-
ited onto the mesoporous layer, the perovskite fills the mesopores. A spiro-MeOTAD layer is
deposited on top of the perovskite layer, which acts like a hole transport layer. Finally, a
metal electrode like gold, silver, or aluminum is deposited, which also acts like an opaque
layer of the device [86].
It is observed that the mesoporous layer has significant impact on the performance of the
solar cell device. This forms a matrix of perovskite materials, which enhances the generation
of more electron and hole pairs. Furthermore, the comparatively higher thickness of the
perovskite layer also allows light to absorb more effectively [87,88]. The mesopores do not
form a uniform perovskite layer and hence do not control the growth of perovskite grains.
This leads to the formation of highly disordered phases [89]. These disordered phases limit
the open-circuit voltages and short-circuit density of the devices. The literature shows that
by decreasing the thickness of the mesoporous layer, the crystallinity of the perovskite mate-
rials and hence the performance of the devices are increased [90,91]. The study also shows
FIGURE 9.3 Simple representation of a perovskite solar cell device.

FIGURE 9.4 (A) Schematic for a mesoporous perovskite solar cell (PVSC) indicating different layers of the device.
(B) Schematic for the n-i-p approach to the synthesis of the PVSC indicating different layers. (C) Schematic for the p-i-n
approach to the synthesis of the PVSC indicating different layers.
that if the thickness of nanoporous materials is increased up to certain values (~300 nm), the
number of pores filled with perovskite materials will also increase, which causes an increase
in pore-filling fraction. Therefore an increase in charge carriers is observed and hence the
transportation of charge carriers increases. This leads to increases in efficiencies at the elec-
tron transport layer interface and hence there is a rise in the PCE of PVSC devices [32,92].
The highest PCE recorded for MA chloride PVSCs, which are prepared using the mesoporous
approach, is 24.02% [93].
9.5.2 N-i-p structure approach

It is observed that for PVSCs, without separating the interface between electron transport
layer and perovskite material layer, the perovskite is capable of efficient ambipolar charge
transport [90,91]. Therefore PVSCs do not need mesoscopic configuration and hence we
can discard the mesoporous layers. This will significantly reduce the size of the device,
and also the high sintering step to deposit the mesoporous layer is no longer required. If
the same device arrangement is maintained as explained in the last section by excluding
the mesoporous layer, an n-i-p structure is formed.
In this approach, a transparent substrate like glass or indium tin oxide (ITO) is coated with
a transparent electrode and later an electron transport layer (ionic dopant layer) is deposited
on top of it, as shown in Fig. 9.4B. A perovskite layer is deposited on the electron transport
layer and this follows the deposition of the hole transport layer. Finally, a metal electrode is
deposited. In this approach, the PCE value can be tuned by changing the composition of the
perovskite layer and the interface between the perovskite layer and the holeeelectron trans-
port layer [94]. This is the most efficient approach to construct PVSC devices in which the
hole transport layer with ionic dopants is deposited on top of the perovskite materials, which
acts like a window layer. These hole transport layers have parasite absorption and they accel-
erate the degradation of PVSCs due to mobile ionic dopants [95].
9.5.3 Planar p-i-n approach

In this approach, the hole transport layer is deposited before the perovskite layer opposite
the n-i-p structure, as shown in Fig. 9.4C. Therefore it is also called an inverted architecture.

9.6 Requirement of each layer 259
In this case, a p-type conducting layer (such as the conducting polymer poly(3,4-
ethylenedioxythiophene) polystyrene sulfonate [PEDOT:PSS]) is deposited on the transparent
electrode (which is deposited on the transparent glass or ITO substrate). The peroxide layer is
deposited atop the hole transport layer and on top of the perovskite layer, and the electron
transport layer is deposited. Finally, the metal or opaque electrode is deposited on it. Recent
work has shown that p-type semiconductors like PEDOT:PSS, poly(triaryl amine) (PTAA),
NiO, Cu2O, CuSCN, etc. are used as hole transfer materials to construct PVSCs with the p-
i-n approach. The planar p-i-n approach is effective at harnessing high-energy photons and
is compatible with an ionic dopant-free transport layer [96e99].
The p-i-n approach (inverted planar structure) is considered the best choice for the fabri-
cation of perovskite:silicon tandems [100]. However, the inverted approach of PVSCs with an
inorganic hole transport layer affects the PCE of the devices. The architecture decreases the
PCE value for the inorganic hole transport layer; the highest certified value for the p-i-n
approach with an inorganic hole transport layer is 19.2%, which is very small compared to
the n-i-p approach [101]. Also, the stability of these kinds of cells is less than 20 h [102]. There-
fore the efficiency of this approach is increased using organometallic perovskite as an organic
hole transport layer [103]. As far as we know, a methylamineedimethylamine lead iodate
(MA1exDMAxPbI0) perovskite structure used to form a p-i-n structure for PVSCs showed
the highest PCE of 21.60% [100].
9.6 Requirement of each layer
The working PVSCs is explained as e when photons are incident on substrate it passes
from the transparent electrode to absorbing layer like perovskite layer. Incident photons
are absorbed by the absorbing layer; excitons are generated and propagate to the perovskitee
electron transport layer interface. At the interface, excitons are separated into electrons and
holes. The electrons are collected by the electronehole layer and holes are collected by
hole transport layers. The PCE of PVSCs depends on transparency of the electrode or photo-
anode, mobility, and collection of photogenerated charges. Also, a metal electrode in the
topmost layer in PVSCs, which is directly in contact with the environment, affects the stability
of devices. Therefore it is necessary to understand the requirements and properties of each
layer.
9.6.1 Photoanode and electron transport layer

As shown in Figs. 9.3 and 9.4, the transparent anode layer is deposited on the ITO or glass
transparent substrate. The electron transport layer is deposited on top of the anode layer;
sometimes the electron transport layer acts like a transparent anode in PVSC devices. It plays
an important role in the efficient working of PVSCs, as it provides sufficient charge collection
and formic ohmic contact with the electrode.
The main function of the electron layer in PVSCs is to extract electrons from the absorbing
layer, transport them to the cathode, and minimize recombination of holeseelectrons
[104,105]. This can be done by selecting electron transport materials that can reduce the

potential barrier (between electron transport layer and perovskite layer) for electrons and
block the holes [105,106]. The common electron transport materials are TiO2, SnO2, ZnO,
fullerene butyric acid methyl ester (PCBM), tin-doped zinc oxide, SrTiO3, B2S3, BaSnO3,
and IndeneeC60 bisadduct as well as doped metal oxides [107e110]. The basic requirements
to qualify for the layer are high electron mobility, easy dissolution in organic solvent, inability
to absorb ultraviolet light, and good air stability. Also, there must be good alignment be-
tween the perovskite layer and the electron transport layer [111].
The electron transport layer can be deposited using atomic layer deposition, electrochem-
ical deposition, the solution-processed method, the hydrothermal method, radiofrequency
sputtering, and electrodeposition [112e115]. These methods, like atomic layer depositions,
facilitate large surface deposition of the electron transport layer; the large surface area of
the electron transport layer (ZnO, TiO2, and SnO2) allows better contact with the perovskite
layer. Better contact provides efficient extraction of electrons and hence increases the PCE
value of PVSCs. To increase the extraction ability and improve electron-transporting proper-
ties, metal oxide electrodes are doped with n-type impurity [115]. Because of their high elec-
tron mobility, transparency to ultraviolet-visible light, and high electron affinity, carbon
materials like fullerene and its derivatives are used as electron transport layers [116,117].
It is observed that this layer directly affects the stability and performance of the PVSC de-
vice. For better performance, the layer should be resistant to air and humidity, transparent to
ultraviolet-visible light, and have high ability to extract electrons from the perovskite layer,
high electron mobility, high tolerance to holes to avoid recombination of electronehole pairs,
and zero degradation over time. It can be concluded that the electron transport layer should
have negligible degradation because degradation in the layer causes a decrease in carrier
collection and damages ohmic contact with the electrode. Therefore efficiency of PVSCs
decreases.
9.6.2 Absorption layer

In PVSCs, perovskite materials are used as an absorption layer. When energy photons are
closer to their bandgap, the photons are absorbed by the perovskite layer. The electrons jump
from the valence band to the conduction band; hence, electronephoton pairs are generated
[87,118]. The efficiency of PVSCs depends on several factors, such as migration of electrons
toward the electron transport layer and holes toward the hole transport layer. It also depends
on structure, the components of perovskite materials, and stability of the layer. Structures and
their stabilities are well explained in Section 2.
The stability of perovskite directly affects the PCE values of the device. Long-term stability
of the perovskite layer depends on ambient conditions like temperature or thermal, moisture,
and structural stability. Perovskite materials like MAPbI3 are hygroscopic in nature and
create a degradation process in which the methylamine group is lost and PbI2 is formed
[47,119]. This happens due to high polarity of a water molecule and it attributes to structural
ability. Research work showed that mesostructured materials like TiO2 help to stabilize
ambient conditions [88]. Apart from humidity, temperature also plays a vital role in layer sta-
bility, as the perovskite materials’ phase changes from tetragonal to cubic at 54e56 C [120]. A
study showed that for efficient solar cells, PVSCs must be stable up to 85 C, but perovskite

9.6 Requirement of each layer 261
materials decompose to PbI2 when they are heated at 85 C in a nitrogen environment [121].
Therefore for efficient performance of PVSCs, the absorbance layer should be tolerant to the
moisture and temperature of the environment.
9.6.3 Hole transport layer

Hole transport layers mainly work as blockade layers for electrons between perovskite and
transporting holes, and protect the perovskite layer and electrode with reduced carrier
recombination to boost efficiency of PVSCs [106,122].
Initially, the redox couple iodineetriiodine in an organic liquid electrolyte can be found in
PVSCs, but the redox couple is highly corrosive, volatile, and photoreactive. These properties
decrease the stability and performance of the device [15,123]. A lot of research is happening to
find appropriate materials for the hole transport layer. The hole transport layer affects the
PCE values of the device. Solid-state organics and p-type conducting materials or polymers
are used as hole transport layers to improve PCE values of the devices [13,19,52,55]. Spiro-
MeOTED and PCBM/piezoforce microscopy are other strong candidates for the hole trans-
port layer as the efficiency values are high for these materials. However, the market price
of these materials is quite high, so PVSCs synthesized using these materials are also high.
Inorganic materials or composites like CuI or C are hole conductors and replace hole-
conducting layers.
Initially in PVSCs, organic electrolyte containing lithium halide and a similar halogen
formed the hole-transporting medium [15]. It is observed that this solution base can be
replaced by spiro-MeOTAD as a solid-state hole transport material [30]. It is also observed
that the PCE value increases to 9.70% as well as the stability of the device [15]. At this point,
PVSCs started following standard solar cell structures (as shown in Figs. 9.3 and 9.4). After-
ward, researchers started performing experiments by changing hole transport materials, the
composition of perovskite, and electron transport layer to increase the efficiency and stability
of PVSCs. Other materials for the hole transport layer are PEDOT:PSS, MoO3, PTAA,
CuGaO2, CuSCN, and NiOx [26,33,57,122]. Metal oxides are considered to be better than
organic layers due to their nontoxicity and ambient condition stability [57,124]. Cheap poly-
mers like PEDOT:PSS with high conductivity are used as replacements for regular hole trans-
port material. These materials have good processability, high thermal stability, good
mechanical flexibility, sufficient optical transparency, and proper energy levels. Polymer
hole transport layers also make flexible PVSCs in inverted devices [125,126].
The hole transport layer affects the stability and efficiency of PVSCs. It is necessary to have
a highly transparent layer so that it does not affect the perovskite layer and allows the trans-
portation of holes. It should also stop electronehole recombination and protect the perovskite
layer from external factors. A high-performance hole transport layer is necessary to increase
the performance and stability of PVSC devices.
9.6.4 Metal electrode

Metal electrodes directly affect the stability and operation of PVSCs; the electrode is the
uppermost layer and is closer to the environment [106,127]. Initially, the electrode perovskite

absorber layer was deposited in the PVSC device; therefore the electrode could protect or
decrease the transfer of moisture from air to the perovskite layer. Metals, like silver,
aluminum, and gold, are the most commonly used electrodes in PVSCs. Metal electrodes
have stability issues as well as affect the PCE values. Silver and aluminum electrodes undergo
corrosion from ion migration from perovskite layers. These generated ions from metal halides
have stability issues with perovskite cells [128e130].
Other elements like chromium and carbon are used for metal electrodes. A chromium elec-
trode has been used in MAPbBr3 PVSC devices. According to studies [131,132], chromium
increases the interfacial resistance and reduces the amount of interfacial recombination.
Sometimes a chromium layer is deposited between the metal electrode and perovskite layer,
which prevents diffusion of the metal electrode into the perovskite layer, and leads to stable
PCE. As the layer is chemically inert toward iodine, it does react with PVSCs [133,134]. Re-
searchers have also started working on hole transport layer-free PVSC devices by using car-
bon electrodes [60,65]. A thick carbon electrode protects the perovskite layer from humidity
and increases the stability of the device. PVSCs with porous carbon back electrodes usually
exhibit exceptional long-term stability under light and ambient conditions [135].
Thus to fabricate stable PVSCs, diffusion barrier layers should be inserted to separate the
metal electrodes and perovskite layer. Although electrodes do not directly affect the efficiency
of PCE values of PVSCs, they affect their stability.
9.7 Working mechanism of PVSCs or device operation
In PVSCs, the perovskite layer acts as an absorber layer, which absorbs light and gives rise
to free electrons and holes. These photogenerated free charge carriers diffuse and drift under
the influence of an electric field. The holes move toward the hole transport layer while elec-
trons move toward the electron transport layer. The efficiency of extraction depends on the
transporting ability of holes and electrons toward their respective layers. When holes and
electrons are collected by respective electrodes, the electrons dissipate energy and produce
power before returning to the device at the opposite electrode and recombine with the
hole. If electrons are not extracted by the electron transport layer from the perovskite layer,
then it will eventually recombine with the hole. This is nothing but radiative transition, which
emits a photon of energy equal to the bandgap of the perovskite material.
Fig. 9.5 depicts the general working principle of PVSC devices. When light falls on PVSCs,
perovskite acts as an absorber layer and absorbs light leading to the creation of free carriers
(electronseholes). Charge separation occurs through the injection of photogenerated elec-
trons like TiO2 into the electron transport layer, e.g., spiro-MeOTAD. When a large number
of photons are incident on PVSCs, a number of electrons are generated in the perovskite
absorber. Therefore electrons are captured by the electron transport layer from which elec-
trons move externally to the metal electrodes. However, photogenerated holes are extracted
from the perovskite layer and these electrons flow to the metal electrode (such as gold, silver,
or aluminum). The holeeelectron recombines externally to produce electrical potential due to
the absorption of light [25,28]. At zero cell voltage, the cell current reaches its maximum
limiting value and is called a short-circuit current. This depends on the production of charge

9.8 Characterization technique 263
FIGURE 9.5 Schematic diagram showing the working principle of perovskite solar cells.
carrier in the perovskite layers and the extraction of charge carriers by the respective charge
carrier layers. This directly affects the efficiency and stability of PVSCs. Thus it is concluded
that the device configuration of PVSCs is a perovskite layer sandwiched between the electron
and hole blocking layer. This configuration leads to stable and efficient photovoltaic devices.
9.8 Characterization technique
This section deals with specific characterizations and supporting examples from the liter-
ature used for PVSC devices. Also, a brief introduction to general characterization is dis-
cussed, which is used to analyze PVSC devices; detailed information on these general
devices is provided in Chapter 3.
9.8.1 Specific characterization

9.8.1.1 Current densityevoltage characteristics
This is the most important characterization of solar cells as it estimates solar cell efficiency.
Therefore this technique is discussed in detail. In this measurement, PVSC electrodes are con-
nected, a certain bias voltage ramp is applied, and simultaneously the current produced is
measured. The measurements are taken in both dark and light conditions. In the dark, PVSCs
behave like a p-n junction diode with the characteristic that in reverse bias no current should
pass through it, while in forward bias a huge current (and sharp increase after the breakdown
region) is observed. In the presence of light, the diode shows similar behavior to the normal
diode after breakdown voltage, but before the finite negative current, reverse bias is observed
before the breakdown region. This produces power in solar cells when JeV measurements are
performed in the presence of light.
From these measurements, important parameters like short-circuit current, open-circuit
voltage, and maximum power are estimated. Short-circuit density is the current density pro-
duced by the cell at 0 V and it is the maximum current produced by the illuminating solar

cell. Open-circuit current density is the voltage at which no net current flows through the de-
vice and it depends on the bandgap of the absorber, in this case the bandgap of the perovskite
layer. The power of the solar cell is estimated by combining applied voltage and current pro-
duced in the PVSCs. Maximum power of the devices is the product of the current maximum
power point and voltage maximum power point. One can also estimate the fill factor of the
solar cells; it is the ratio of maximum power of the devices to the product of short-circuit cur-
rent density and open-circuit voltage.
The JeV characteristics of PVSC change with the illumination time of solar cells. The per-
formance generally increases with the increase in illumination time as there is an increase in
fill factor and open-circuit voltage. This effect is termed the light-soaking effect. This effect is
due to the presence of mobile ions (ABþ and Ie) inside the perovskite layer [136,137]. When
the JeV scan is performed from negative to positive voltage and vice versa, PVSCs show a
difference in response time. This phenomenon is termed hysteresis [65,92]. Apart from
scan speed, temperature, and prescanning conditions, hysteresis depends on the movement
of ions in the perovskite layer and the PVSC architecture [92,138e140]. If hysteresis is only
because of movement of ions in the perovskite layer, then hysteresis can be tuned by chang-
ing either the electronehole transport layer or the device architecture [136,141,142].
The inherent hysteresis and soaking effect change the JeV characteristics and therefore
change the PCE values of PVSCs. Therefore it is obviously an essential tool for PVSCs [142].
9.8.2 Time-resolved photoluminescence

When light is incident on the perovskite layer, an incident photon is absorbed by the layer.
Thus electrons jump from the valence band to the conduction band and electronehole pairs
are generated in it. The bandgap of perovskite materials is in the visible near-infrared region.
Therefore these materials absorb incident photons and generate electron photon pairs, which
combine either by radiative or nonradiative transition with liberation of energy in the form of
photons. This gives rise to the photoluminescence effect in perovskite materials [143e145]. It
is seen that the efficiency of PVSCs depends on the combination of photogenerated holes and
electrons produced in perovskite layers [11,28]. Thus it is useful to study radiative and non-
radiative transitions in the perovskite method from which the recombination time can be
estimated.
Time-resolved spectroscopy characterizes the dynamics of radiative and nonradiative tran-
sition in both organic and inorganic materials. With this method, the intensity of lumines-
cence material depends on the energy of incident photons. Therefore it is necessary to
adjust the laser so that it can emit one photon at a time or per pulse. During this measure-
ment, when a pulse leaves the laser, time measurements are simultaneously started by the
instrument. The emitted photon excites the studied sample as soon as photons are detected
by the detector. The procedure starts with the measurement of time-resolved decays at a fixed
number of wavelengths across the emission spectrum, which is discovered from photolumi-
nescence measurements. The intensity decays once the sample is excited by the source and is
quicker at shorter wavelengths due to spectral relaxation but slower at longer wavelengths
[146]. This technique is useful to study the recombination and injection dynamics of solar cells
using time-resolved photoluminescence and photocurrent measurements [147]. This

9.8 Characterization technique 265
technique is also used for investigating the carrier recombination process, electrical perfor-
mance, and intrinsic physical processes in solar cell devices [148e151].
9.8.3 General characterization

This section deals with general characterizations required to analyze devices. Structural,
surface, and optical characterization like absorption and photoluminescence spectroscopy
are discussed here.
9.8.3.1 X-ray diffraction spectrometer

This is a well-known technique for discovering the crystal structure of the deposited ma-
terial. The X-rays are diffracted in a specific direction by crystal atoms. By measuring dif-
fracted rays and angles, one can decide the crystal structure of given materials. Along with
three-dimensional crystal structures, lattice parameters, chemical bonds, and disorders can
be estimated. The principle of the X-ray diffraction (XRD) spectrometer is Bragg's law,
2d sin q ¼ nl, where d is the interplanar distance, q is the angle of diffraction, n is the order
of diffraction, and l is the wavelength of the X-ray. One can estimate the crystal structure and
orientation of the examined sample. One more measurement that can be carried out using
XRD is low-angle XRD or X-ray reflectivity. This measurement is recorded between angles
of 0 and 5 degrees, which allow us to estimate the thickness of each layer along with rough-
ness of the interface.
9.8.3.2 Scanning electron microscopy

Scanning electron microscopy (SEM) is an important technique used to study the surface
morphology of thin films and devices. It is even possible to estimate grain size using SEM.
However, the top view only provides surface morphology of the top layer, as shown in
Fig. 9.6A. It is possible to study surface morphology even up to 10 nm. The literature dictates
FIGURE 9.6 (A) An illustration of surface morphology using scanning electron microscopy for perovskite solar
cell (PVSC) devices. (B) Illustration of cross-sectional analysis of a PVSC device. ITO, Indium tin oxide; PCBM, butyric
acid methyl ester; RGO, reduced graphine oxide. Copied with permission. Copyright © 2014 Elsevier.

that in the interface between layers, the crystallinity of absorbing layers and uniformity of
layers directly affect the stability and performance of PVSC devices [3,6,21,55,92].
It is important to study the interface between the layers as well as to discover the unifor-
mity and exact thickness of each layer in the devices. The interface between layers and an es-
timate of the exact thickness of each layer cross-sectionally can be studied using cross-section
SEM images [152,153]. Fig. 9.6B shows the cross-section of a PVSC device. This confirms the
fabrication quality of the device and the uniformity and thickness of each layer [153].
9.8.3.3 Transmission electron microscopy

It is well known that the PCE values of PVSCs are dependent on the grain size of the
perovskite layer. To provide the exact grain size of perovskite materials, transmission elec-
tron microscopy (TEM) is the best technique to study and discover the crystal structure of
particular grains. By this method, the nature and functionality of PVSCs can be studied
[154e156].
Fig. 9.7A shows a TEM image of a PVSC device used for studying particle size analysis. By
studying their electron diffraction patterns, one can study the transformation occurring in
nanocrystals or perovskite induced by an electron beam at low temperature [157]. Using
TEM, one can image and study the domain patterns of perovskite nanocrystals [156,158].
Orientation and disorientation of adjacent grains are characterized and studied using TEM
[156,159]. PVSC thickness of each layer, grain boundaries, orientation, and interface between
each layer are studied and imaged (as shown in Fig. 9.7B) using this instrument.
9.8.3.4 Atomic force microscopy measurement

For very high-resolution surface analysis, atomic force microscopy (AFM) is used; this is a
very sophisticated instrument with very high resolving power up to the order of a nano-
meter. Information is collected using an extremely small piezoelectric mechanical probe
with precise movement on electronic command. AFM consists of a cantilever with a sharp
tip at its end, which is used to scan the sample surface. The cantilever is made of silicon or
silicon nitride and the tip has a curvature scaled in nanometers. The working principle is
FIGURE 9.7 Standard examples showing particle size analysis and cross-sectional morphology using trans-
mission electron microscopy [156]. ITO, Indium tin oxide.

9.9 Device evaluation 267
to obtain images according to Hooke's law, which acts between the force exerted by the tip on
the surface of the sample and the deflection produced in the cantilever. Using this instrument,
one can estimate thickness, morphology, and roughness of the film.
Fig. 9.8A and E depicts illustrations for typical examples of AFM images of perovskite ma-
terials. In AFM, one can also scan electric potential variation using conducting cantilevers.
One can map IeV characteristics with imaging using conducting AFM studies. Studies
show that conductivity is high at gain boundaries; an example is shown in Fig. 9.8A and
E, where the boundaries shown in greenish color represent conducting areas. Moreover,
Fig. 9.8A shows the overlapping of grains, which causes hysteresis in IeV characteristics
(Fig. 9.8BeD), but Fig. 9.8E shows that higher conductivity near the boundaries provides
continuous pathways for free electrons (for details of IeV characteristics studies refer to
the cited paper) [160]. This clearly suggests that AFM is an efficient tool to study grain bound-
aries, size of grains, and mapping of IeV characteristics studies.
FIGURE 9.8 Contact mode atomic force microscopy study of the hysteresis of ion relationships for control films
(AeD) and hybrid films (EeH) with IeV characteristics [160]. Copyright © 2015, Springer Nature.
9.9 Device evaluation

PVSCs strongly depend on the composition of perovskite, hole transport materials, electron
transport materials, and their interfaces. The evaluation of PVSC devices depends on the
roughness of the interface, the cost of the devices, PCE values, and stability. When PVSCs
were introduced to the world they were highly unstable and PCE values were very low. How-
ever, progress in PVSCs happened when the electrolyte-based hole transport layer was
replaced by spiro-MeOTAD, a solid-state material. This increased the stability as well as

PCE values of PVSCs [15,30,31]. Instead of using a single halide in perovskite materials, a
mixed halide CH3NH3PbI3exClx composition was used. It was observed that PCE values
and stability increased [31,161]. Furthermore, modification of the nanoporous layer, which
replaced conducting material (TiO2) with nonconducting material (Al2O3), improved the
open-circuit voltage of PVSCs, which increased the PCE to 10.90% [161]. Later, it was shown
that the performance of PVSC devices increased for CH3NH3PbI3exBrx mixed halide perov-
skites. The result was that efficiency increased for lower concentrations of Br, and for higher
concentrations perovskite films provided better stability against humidity [162]. Subsequently,
researchers tried to change deposition methods: instead of single-step deposition they used
two-step deposition for perovskite films, which improved their morphology [163]. The effi-
ciency of PVSCs further increased when solvent deposition was replaced by thermal evapora-
tion and CH3NH3PbI3exClx mixed perovskite. The observed efficiency for this was 15.40%
[164]. Further increase in efficiency of PVSC devices was reported for poly(triarylamine) as
a hole transport material and CH3NH3PbI3exBrx mixed halide perovskites [25,163]. There fol-
lowed a further modification in deposition technique, and cations of larger radii were used,
which had a symmetrical cubic phase and increased the t factor. This modification improved
the devices. Researchers also tried different proportions of inorganic cations and halide anions
in mixed perovskite, which allowed their properties to be tuned [66,165,166].
Around 2014, experiments began with electron transport layers. The reported electron
transport material was TiO2, which was replaced by fluorine-doped TiO2 and a TiO2 combi-
nation. Later, this combination was replaced by ITO as transparent material combined with a
thin layer of zinc oxide [115]. Other metal oxides (like ZrO2, NiO2, SiO2, and SnO2) and nano-
core shell nanoparticles (such as Al2O3/ZnO, TiO2/MgO, and WO3/TiO2) were used as elec-
tron transport material and for charge retardation or to avoid recombination of
photogenerated holes and electrons, which enhanced PCE values [127,167e169]. As dis-
cussed in an earlier chapter, materials with a lower highest occupied molecular orbital
band but a higher lowest unoccupied molecular orbital band than the active perovskite layer
can be used as electron extraction or electron transport layer [170]. Researchers also tried to
make metal oxide-free PVSC devices. Organic materials like P3HT, PCBM composites to
achieve better efficiency in p-i-n architecture of the PVSCs device [127,171e173]. It is
observed that when organic material was used as an electron transport layer and a perovskite
layer was deposited onto it, perovskite materials crystallized well to form compact, uniform,
smooth, and pinhole-free film [174]. So, an organic electron transport layer provides flexible
PVSC devices and uniform perovskite films, and increases stability and PCE values of PVSC
devices. The flexible PVSC device even fabricates under ambient air and humidity providing
a PCE value of ~21% and a high open-circuit voltage of 1.15 V [46].
In 2006, dye-sensitized solar cells based on an organicemetal hybrid semiconductor within
a nanoporous TiO2 layer achieved a PCE of 2.2% [25]. Miyasaka suggested the use of
organicemetal perovskite (CH3NH3PbI3) for solar cells [15]. As discussed earlier in this chap-
ter, the crystal structure of perovskite is defined as ABX3; Miyasaka’s group chose A to be the
organic molecule, B as Pbemetal, and X as Brehalide. The observed efficiency value was
~3.8% as shown in Fig. 9.9. In the last decade, researchers have extensively worked on
PVSC; the progress in PCE values is shown in Fig. 9.9, which was plotted by taking values
from published research papers and published solar efficiency tables every year. So far, the
maximum recordable power efficiency achieved for PVSCs is 25.2% [175]. The overall perfor-
mance of PVSCs is shown in Fig. 9.9. It is clear that perovskites are the fastest developing

9.9 Device evaluation 269
FIGURE 9.9 Year versus power conversion efficiency for perovskite solar cells. PCE, Power conversion efficiency.
Data taken from research papers and from a solar efficiency table published every year.
solar cell technology. However, more work has to be performed to increase their stability and
bring them to the commercial world.
The PCE values of PVSCs depend on many parameters: quality of perovskite film, electron
transport layer, hole transport layer, metal electrode, and interface between layers. A high-
quality polycrystalline perovskite layer and continuous defect-free junctions with electron
transport layer and hole transport layer are essential to obtain stable and high-
performance solar cells [176]. It is obvious that uniform grains with a minimal area of grain
boundaries provide faster transportation of charge carriers which increases the performance
of PVSCs [177]. The uniform grains can be achieved by using double cation perovskites like
formamidinium/MA, which provide better thermal stability but have high hysteresis in JeV
characterizations. Table 9.2 summarizes notable PVSC devices with their PCE values, cutoff
voltage, and current density.
It is also observed that although perovskite materials have excellent defect-tolerant proper-
ties, the ionic migration in perovskite makes their characterization more difficult. Ionic migra-
tion in perovskite layers also affects the interface between perovskite and the charge transport
layers [176]. This is also one of the reasons for the presence of hysteresis in JeV characteristics.
Later, studies showed that hysteresis decreases if lithium, potassium, or sodium and their bis(-
trifluoromethane) sulfonimide salt are doped to the TiO2 electron transport layer in triple
cation perovskite solar cells; also, PCE values increased [188,189]. Surface analysis showed
that sulfur chemically bridges TiO2 and perovskite at their interface by forming TieSePb
bonding, thereby forming a structural continuity. This decreases grain boundary effects;
hence, the hysteresis effect decreases and the PCE value increases to 21.10% in this case
[190]. Another factor to improve PVSCs is the presence of hysteresis in JeV characteristics.
Based on the discussions, it can be concluded that for superior performance and better sta-
bility of PVSCs (1) high optical absorption coefficient of perovskite thin film, (2) long carrier
diffusion length and suppressed recombination, (3) defect tolerance, and (4) well-balanced
charge transfer are needed.

TABLE 9.2 Notable perovskite solar cell devices with power conversion efficiency, cutoff voltages, and
short-current density.
Power
consumption JSC
Fabricated devices efficiency (%) VOC (V) (mA/cm2) References
FTO/bl-TiO2/mp-TiO2/MAPb(I1xBrx)3/Au 12.3 0.87e1.13 5e18 [162]

Glass/FTO/TiO2/TiO2/CH3NH3PbI3/HTM/Au 13 0.992 17.1 [163]
FTO-glass/bl-TiO2/mp-TiO2/FAPbI3/PTAA/Au 20.1 1.06 24.7 [178]
FTO/d-TiO2/mp-TiO2/NBH/P3HT/Au 22.70 1.152 24.97 [63]
ITO/SnO2/FAPbI3/spiro-MeOTAD/Au 21.06 1.06 22.70 [179]
Perovskite/HIT tandem cell 23.58 1.6506 18.093 [180]
FTO/c-TiO2/mesoTiO2/MAPbI3exBrx/spiro-MeOTAD/Ag 13.56 0.97 22.05 [181]

ITO/PEDOT:PSS/MAPbI3/PC61BM/Al 14.6 1.01 21.0 [182]
FTO/c-TiO2/meso-TiO2/MAPbI3/spiro-MeOTAD/Au 4.69 0.86 11.11 [183]
ITO/PEDOT:PSS/MAPbI3exClx/PC61BM/Ag 10.83 0.899 17.10 [184]
Glass/BieTiO2/MpeTiO2 þ SnO2/ 21.6 1.18 [185]
(FAPbI3)0.875(MAPbBr3)0.125(CsPbI3)0.1/spiro-MeOTAD/Au
FTO/compact-TiO2(c-TiO2)/mesoporous TiO2 (mp-TiO2)/ 22 1.19 23.2 [186]
Cs0.05FA0.80MA0.15Pb(I0.85Br0.15)3/spiro-MeOTAD/Au
FTO/SnO2/CsPbBr3/carbon 10.71 1.588 7.64 [187]
CH3NH3PbBr3/TiO2 and CH3NH3PbBr3/TiO2 3.13/3.81 0.96/0.61 5.57/11.0 [15]
Abbreviations: CsPbI3, Cesium lead iodide; Spiro-OmeTAD, 2,20 ,7,70 -Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9 0 -spirobifluorene;
Spiro-MeOTAD, 2,20 ,7,70 -Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,90 -spirobifluorene; PEDOT:PSS, poly(3,4-ethyl-
enedioxythiophene) polystyrene sulfonate; P3HT, Poly(3-hexylthiophene-2,5-diyl); PTTA, purified terephthalic acid; Peht, Phospha-
tidylethanol; FTO, Fluorine doped tin oxide; ITO, Indium tin oxide; Perovskite/HIT tandem cell, Perovskite/ Heterojunction
amorphous/Crystalline Silicon tandem cell.
9.10 Key challenges
Solar cells are considered to be the best alternative for fossil fuels and other energy sources.
However, traditional solar cells have good PCE but installation and production charges are
quite high. So, PVSCs are ideal alternatives. Although PVSCs are certified with high PCEs
such as 25.20%, they still face problems such as toxicity, long-term stability, and cost effec-
tiveness. As highly efficient PVSCs mostly contain Pb atoms, which are toxic and can cause
serious problems like cancer and mental retardation, it has been a big challenge to make Pb-
free PVSCs with high PCE values and better stability. At the same time, devices should have
long-term stability in terms of temperature and efficiency because Si cell stability is more than
20 years. Moreover, perovskite absorbers and charge transporting layers are sensitive to
moisture and temperature, which may affect the long-term stability of PVSCs. Furthermore,
for commercialization, these solar cells should be cost effective for everyone.

9.11 Future outlook 271
It is also difficult to deposit high-quality perovskite films on planar surfaces with mini-
mum hysteresis in voltageecurrent measurements, and they also have high photovoltaic per-
formance. Also, in PVSCs, metal back contacts are used, which are not transparent to visible
and near-infrared light. In stacking or tandem applications, the metal contacts must be
replaced by highly transparent and conductive contacts through which low-energy photons
must pass to perovskite cells. In addition to these, it is observed that in PVSCs, light incident
on the cell thorough the substrate. Therefore, glass substrate is used. However, the observed
efficiency of the device is increased when light photons directly fall on PVSCs. Therefore it is
necessary to consider the appropriate choice of substrate, which does not sacrifice the effi-
ciency of the device.
Thus there are many challenges but ample scope for research work to improve PVSCs by
increasing their stability up to 25 years. This can be achieved by appropriate choice of sub-
strate and the use of visible near-infrared transparent electrodes, which will allow low-
energy photons to the cell. Also, it is important to find a replacement for Pb to reduce toxicity
of the solar cell.
The main challenges to develop a process to fabricate PVSCs with high efficiency and
negligible hysteresis and improve ultraviolet to near-infrared transparent devices. The de-
vices should have long-term operational stability under ambient temperature, at least up
to ~100 C. The extraction efficiency of charge carrier layers needs to increase but there will
be a minimum recombination of photogenerated holeseelectrons. Fabrication and material
costs should be reduced considerably, thereby reducing the cost of the solar cells.
9.11 Future outlook

Over the last decade, the development of PVSCs has provided huge scope and another
promising candidate in the field of photovoltaics. Perovskite materials exhibit impressive
performance in solar cells due to their tunable bandgap, which converts a significant
portion of the solar cell into photocurrent. They also possess large charge-carrier mobilities,
which make them capable of effectively transporting the resultant photocurrent to charge a
selective layer of electrodes. By comparing these properties with other existing photovoltaic
materials makes them a better option for solar cell devices. In spite of all these benefits, all
highly efficient PVSCs are Pb-based hybrid perovskites. So, researchers are now working on
lead-free and organic-free PVSCs. However, uniform and defect-free films similar to Pb pe-
rovskites are still a challenge. This seems to be the first step toward PVSC improvement in
the near future. Another challenge is to establish methods to create a voidless high-quality
interface at the junction between perovskite and charge-carrier transport layers. Interface
improvement methods have been developed for Pb-based PVSCs but Pb-free PVSCs have
to be developed.
Apart from these, PVSCs are easy to fabricate and optimize, and even mass production is
possible. Also, they provide high efficiency and thermal stability. However, the practical
durability of devices in operation is widely affected by photoinduced degradation, humidity,
and oxygen penetration in materials. To compete with traditional solar cells, PVSCs should

be durable at least for 20 years. However, these perovskites are a better option for relatively
short-life applications, e.g., in the car and electronic industries. For these applications, the re-
quirements are low cost of modules, Pb-free PVSCs, light weight, and stability up to 10 years.
Also, to replace traditional solar cells, PVSCs should be Pb free (to avoid pollution), highly
efficient, thermally stable, and have long-term stability. These can be achieved by modifying
perovskite films so that absorption increases, the quality of the carrier transporting layer is
maintained to increase the extraction of charge carriers and avoid degradation of the perov-
skite layer, and the quality of electrodes is preserved so that external recombination can easily
happen and be protected from the ambient environment.
9.12 Conclusion
It is interesting to note that perovskite materials were invented over a century ago. These
materials and their thin films have witnessed technological applications in the fields of tran-
sistors, light-emitting diodes, spintronics, and superconductivity. Due to their outstanding
optical properties and absorbance in the visible near-infrared region, it has been noticed
that they could be used in solar cell devices. This possibility is enhanced due to high effi-
ciency, low-cost starting materials and an easy fabrication approach. Both inorganic and
organometallic perovskites have proved their acceptance as absorbance layers in solar cells
and could replace traditional solar cell materials [14,127].
The wide range bandgap and high absorption coefficient of perovskite materials makes
them an ideal absorber material for solar cells. Also, the literature shows that perovskites
have high carrier mobilities and long carrier lifetime resulting in long carrier diffusion length.
High diffusion length decreases the possibility of recombination of photogenerated carriers.
These devices can be synthesized effectively by two approaches: n-i-p and p-i-n junction
structures. Another approach (which is not discussed here) is the perovskite tandem
approach, which is proven to have good efficiency and stability. However, some important
issues like hysteresis in JeV characteristics, long-term stability, and toxicity need to be
addressed.
These PVSCs are easy to fabricate and have strong solar absorption and low nonradiative
recombination rate and efficiency, making them a replacement for traditional solar cells.
PVSCs also have high carrier mobility to increase the overall PCE values. However, better
performing PVSCs contain Pb, which is highly toxic. Hence, this raises the toxicity issue dur-
ing the fabrication, development, and disposal of devices. Also, most of the PVSCs undergo
degradation when they are exposed to moisture. Although the efficiency of organometallic
PVSCs is good, the materials are highly unstable in humid environments. It is possible to
replace organometallic perovskites with inorganic perovskites. Still, a lot of research is
required to obtain commercial PVSC devices. However, it is still considered a better candi-
date for traditional solar cells than other semiconductor solar cells.
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Perovskite Solar Cells

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Perovskite Solar Cells

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C H A P T E R

9.2 Perovskite materials

II. Photovoltaic materials and devices

II. Photovoltaic materials and devices

9.3 Synthesis techniques

II. Photovoltaic materials and devices

9.3.1 Solution-based methods

9.3.2 Vacuum-based deposition

9.3.3 Hybrid solution and vapor method

II. Photovoltaic materials and devices

9.4 Perovskite solar cell

9.4.1 Inorganic perovskite

II. Photovoltaic materials and devices

CsPbI3 quantum dots Spiro-MeOTAD 70 [52]

FAPbI3 Spiro-MeOTAD 20.64 [55]

Formamidiniumelead triiodide perovskite ﬁlms Spiro-MeOTAD 20.64 [55]

FA0.85MA0.15PbI3 Tris(pentaﬂuorophenyl) 21.6 [66]

[CH(NH2)2]0.9Cs0.1PbI3 Spiro-MeOTAD 20.60 [68]

II. Photovoltaic materials and devices

two-dimensional structures, three-dimensional structures (like Cs2TiI6, Rb2TiI6, In2TiI6,

9.4.2 Organometal perovskite

II. Photovoltaic materials and devices

9.5 Fabrication approach and device anatomy

9.5.1 Mesoporous perovskite solar cells

FIGURE 9.3 Simple representation of a perovskite solar cell device.

II. Photovoltaic materials and devices

9.5.2 N-i-p structure approach

9.5.3 Planar p-i-n approach

II. Photovoltaic materials and devices

9.6 Requirement of each layer

9.6.1 Photoanode and electron transport layer

II. Photovoltaic materials and devices

9.6.2 Absorption layer

II. Photovoltaic materials and devices

9.6.3 Hole transport layer

9.6.4 Metal electrode

II. Photovoltaic materials and devices

9.7 Working mechanism of PVSCs or device operation

II. Photovoltaic materials and devices

9.8 Characterization technique

9.8.1 Speciﬁc characterization

II. Photovoltaic materials and devices

9.8.2 Time-resolved photoluminescence

II. Photovoltaic materials and devices

9.8.3 General characterization

9.8.3.1 X-ray diffraction spectrometer

9.8.3.2 Scanning electron microscopy

II. Photovoltaic materials and devices

9.8.3.3 Transmission electron microscopy

9.8.3.4 Atomic force microscopy measurement

II. Photovoltaic materials and devices

9.9 Device evaluation

II. Photovoltaic materials and devices

II. Photovoltaic materials and devices

II. Photovoltaic materials and devices

FTO/bl-TiO2/mp-TiO2/MAPb(I1xBrx)3/Au 12.3 0.87e1.13 5e18 [162]

FTO/c-TiO2/mesoTiO2/MAPbI3exBrx/spiro-MeOTAD/Ag 13.56 0.97 22.05 [181]

9.10 Key challenges

II. Photovoltaic materials and devices

9.11 Future outlook

II. Photovoltaic materials and devices

II. Photovoltaic materials and devices

II. Photovoltaic materials and devices