Cite this article Energy Related Materials Keywords: optical properties/solar cells/

Lin L and Ravindra NM (2020) Research Article thin films

CIGS and perovskite solar cells – an overview. Paper 2000124
Emerging Materials Research 9(3): 812–824, Received 14/05/2020; Accepted 22/07/2020
https://doi.org/10.1680/jemmr.20.00124 Published online 11/08/2020

ICE Publishing: All rights reserved

Emerging Materials Research

CIGS and perovskite solar cells – an overview

Leqi Lin MSc
Research Assistant, Department of Civil and Environmental Engineering,
New Jersey Institute of Technology, Newark, NJ, USA (Orcid:0000-0002-
8944-2483)
Nuggehalli M. Ravindra PhD
Professor, Interdisciplinary Program in Materials Science & Engineering,
New Jersey Institute of Technology, Newark, NJ, USA (Orcid:0000-0003-
0610-3310) (corresponding author: n.m.ravindra@njit.edu;
nmravindra@gmail.com)

Thin-film solar cells based on copper indium gallium selenide (CIGS) and perovskites continue to enhance their
market share as promising energy conversion devices for indoor and outdoor applications. CIGS has been known for
its high absorption coefficient, tunable bandgap and flexibility. Nevertheless, the use of toxic, regulated elements
(cadmium) and reliance on rare elements create a huge barrier in the efforts to enhance the commercial market of
CIGS. Perovskite solar cells have attracted increasing scientific and technological interest because of their high
efficiency. This is due to their ability to fulfil the multiple roles of light-absorption, charge separation and transport
of holes and electrons in materials. Furthermore, they contain low amounts of rare earth materials. However, this
technology is still limited by the stability, scale-up and composition of materials. CIGS–perovskite tandem solar
cells continue to demonstrate very high efficiencies over 24%. In this study, an overview of the recent developments
in material specifications, deposition techniques and device architecture of CIGS and perovskite solar cells is
presented.

Notation b constant characteristic of the material

C constant characterising the combined doping and h power conversion efficiency
material parameters of solar cells
Dn diffusion coefficient of minority carriers in the n region 1. Introduction
Dp diffusion coefficient of minority carriers in the p region Thin-film solar cells continue to enhance their role as a high-
E photon energy efficiency, reliable and cost-effective alternative to conventional
Eg(T ) energy bandgap of the semiconductor at temperature T monocrystalline silicon solar cells. Several solar cell technologies
En irradiation under nominal conditions including wafer-based, organic and thin films have been studied
h Planck’s constant in the literature, and crystalline silicon has remained the most
Jo reverse saturation current density successful solar cell material candidate from laboratory scale to
Jph photogenerated current density the commercial sector and makes up ~90% of the global
Jsc short-circuit current density photovoltaic (PV) market.1 Since the first report of copper indium
k Boltzmann constant gallium selenide (CIGS) solar cells by Devaney and Mickelsen in
Ln diffusion length of minority carriers in the n region 1987,2 the technology has grown over the years. As an emerging
Lp diffusion length of minority carriers in the p region mature material, CIGS is in high demand because of its better
me effective mass of electrons energy conversion efficiency (associated with its high absorption
mh effective mass of holes coefficient, tunable bandgap and flexibility3,4) than that of its
NA number of net acceptor impurities per unit volume crystalline counterparts as well as of amorphous silicon.
Nc effective density of states in the conduction band Normally, the structure of CIGS solar cell consists of a soda-lime
ND number of net donor impurities per unit volume glass (SLG) substrate and molybdenum (Mo) back contact at the
ni intrinsic carrier density bottom, CIGS as the interlayer, zinc oxide (ZnO)/aluminium (Al):
Nv effective density of states in the valence band zinc oxide at the top and n-type cadmium sulfide (CdS) as the
Pin intensity of incident radiation window layer, and it is usually fabricated through the co-
Pmax maximum power output at maximum power point evaporation and precursor reaction processes (Figure 1).
q electric charge Although, in general, the market share of thin-film solar cells is
Rs series resistance decreasing (4.5%, 2017), CIGS represents more than 40% of the
Rsh shunt resistance total thin-film market.5 Furthermore, thin-film solar cells have
T temperature in Kelvin significant potential and critical advantage in sunbelt countries
v speed of light in a medium with better temperature coefficients and ideal power conversion
Voc open-circuit voltage efficiencies (PCEs) in adverse environments over crystalline
Vocn open-circuit voltage under nominal conditions silicon solar cells.6
Vth Vth = (kT/q)
X concentration of sunlight Perovskite solar cells (PSCs) have also attracted significant
a constant characteristic of the material scientific and technological interest in recent years because of

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 Emerging Materials Research CIGS and perovskite solar cells – an
Volume 9 Issue 3 overview
Lin and Ravindra

of the comparison of solar cell efficiency h against energy gap Eg

Au CH3NH3 for various semiconductors in the temperature range of
273–673 K, by Wysocki and Rappaport,25 was reported 60 years
Spiro-OMeTAD
Pb
TCO-ZnO:Al Perovskite
Compact TiO2 I, CI, Br

ZnO n-doped FTO CH3CH3PbI2-x-y,BrxCly

CdS n-doped OCH3 OCH3
N N
CIGS p-doped H3CO OCH3
H3CO OCH3
N N
Mo
Glass OCH3 OCH3 spiro-OMeTAD
(a) (b)
Figure 1. The fundamental structure of (a) CIGS and (b) PSC with
its detailed chemical structure (reproduced with permission from
Suzuki et al.)19
their high efficiency due to their ability to fulfil the multiple roles
of light-absorption, charge separation and transport of holes and
electrons in materials7 and due to their low amounts of earth-
abundant materials. As high-potential candidates of choice, PSC
materials are commercially available, and thousands of research
projects are in progress, resulting in a large number of related
publications. PSCs, based on either mesoscopic or planar and
normal (n-i-p) or inverted (p-i-n) structure architectures, are
typically described by the formula ABX3, where X is an anion
and A and B are cations (A being larger than B).8
Organic–inorganic halide PSCs have been demonstrated to be
efficient light absorbers with low excitation recombination rate,
high carrier mobility and high PCE, which can exceed 20%.9–12
This impressive improvement in PCE is still obstructed by
performance losses, stability and degradation under standard test
conditions (STCs), which are 25°C, 1000 W·m−2 and AM
1.5 G.13–15 The temperature-activated formation and migration of
ionic defects within the organic-inorganic ABX3 perovskite lattice
remain potential sources of instability for perovskite PVs.16–18
ago (Figure 2). It is interesting and relevant to note that while
there have been significant improvements in solar cell materials
and device technology, not much has changed in relation to the
absolute solar cell efficiencies as a function of temperature.
The PV effect is the process of direct conversion from light to
electricity in a solar cell system. The PV effect was first
discovered in 1839 by the French physicist Edmond Becquerel
while investigating the electronic behaviour of metal electrodes in
electrolytes. The process includes the generation of charge carriers
from the absorption of photons in the materials that form a
junction, the separation of the photogenerated charge carriers in
the junction and the collection of the photogenerated charge
carriers at the terminals of the junction.26 In general, in real-time
utility and applications in the field, solar cells/solar cell panels
operate at a lower or higher temperature than in the laboratory
under STC and predominantly under varying light intensities;
therefore, it is necessary to realise the relationship between solar
cell parameters and temperature. The performance of solar cells is
determined by the key PV parameters, for example, short-circuit
current density (Jsc), open-circuit voltage (Voc), fill factor (FF) and
PCE. These parameters are temperature dependent and hence
affect the performance of solar cells.20,25,27–30 Voc decreases
32
CdTe
GaAs AlSb CASE I
InP Y (70% GaAs N = 1017/cm2
28 30% GaP)
Si Z (50% GaAs –
50% GaP)
24
CdS

In this review, these and similar issues will be discussed, 20 Ge

providing the newcomers to the field not only with a summary of T = 273ºK
what has been achieved so far but also with practical details they
η: %

16 298ºK
need to pay attention to in developing and characterising high-
performance devices. Moreover, the influence of alkali elements 373ºK
423ºK
such as potassium (K) and sodium (Na) on CIGS substrates will 12 473ºK
be discussed in detail. The series resistance (Rs) and shunt 523ºK
573ºK
resistance (Rsh) relation with the efficiency and stability will be
8 673ºK
discussed under varying light intensities for the PSCs.

2. Solar cell fundamentals 4

The fundamental equations governing the performance of solar
cells have been described in a large number of studies in the
0
literature.20–24 However, for the benefit of a complete study, some 0.2 0.6 1.0 1.4 1.8 2.2 2.6 3.0
Eg: eV
of these solar cell parameters and their temperature dependence
have been reviewed here. In a previous study, Singh and
Figure 2. Efficiency against Eg for various semiconductors in the
Ravindra20 investigated the temperature dependence of silicon,
temperature range of 273–673 K (reproduced with permission
germanium, gallium arsenide, indium phosphide, cadmium from Wysocki and Rappaport)25
telluride and cadmium sulfide solar cells. The first detailed study

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 Emerging Materials Research CIGS and perovskite solar cells – an
Volume 9 Issue 3 overview
Lin and Ravindra

with increasing temperature, whereas Jsc increases slightly with !

increasing temperature.20,25,27–30 Both FF and PCE decrease with Dn Dp
Jo ¼ q þ n2
increasing temperature, and efficiency degradation is mainly due 5. Ln NA Lp ND i
to the decrease in Voc.20,25,27–30 The variation of Rs and Rsh with
temperature slightly affects the efficiency,20,25,27–30 while with
increasing temperature, Jo increases exponentially and Voc where ni is the intrinsic carrier density, NA and ND are the
decreases rapidly. Therefore, Jo is a critical PV parameter in densities of acceptor and donor atoms and Dn and Dp are
determining the PCE of solar cells. diffusion constants of minority carriers in p and n regions,
respectively. As seen from Equation 5, Jo is strongly determined
The temperature dependence of the bandgap (Eg) of by the proportionality to ~ni2, and ni can be represented as in
semiconductors is described by the well-known Varshni relation31 Equation 6.
in Equation 1.


Eg
aT 2 n2i ¼ Nc Nv exp −
Eg ðT Þ ¼ Eg ð0Þ − kT
ðT þ b Þ


1. 2pkT 3 3=2 3=2 Eg
¼4 m e m h exp −
6. h2 kT
where Eg(T ) is the bandgap of the semiconductor at temperature
T, Eg (0) is its value at 0 K and a and ß are constants that are where Nc and Nv are the effective density of states in the
characteristic of the material. conduction and valence bands and me and mh are the effective
mass of electrons and holes, respectively. By combining
As shown in Equation 2, Jsc depends on the solar spectral Equations 5 and 6, the expression for Jo can be written in terms of
irradiance; the value of Jsc may be limited by reflection losses temperature and bandgap energy33 as in Equation 7.
(series and shunt resistance), shadowing losses (front metal
coverage) and recombination losses.20

Eg
Jo ¼ C  T exp − 3
7. kT

E
∞
dNph
Jsc ¼ q dðhvÞ
dhv FF is defined as the ratio of the maximum power output (Pmax) at
2. hv¼Eg
the maximum power point (MPP) to the product of Voc and Jsc
and can be expressed as in Equation 8.

Voc is the maximum voltage of a solar cell; by setting J = 0, the

expression for Voc is given by Equation 3. The temperature Pmax
FF ¼
dependence of Voc can be further obtained from Equation 3 as 8. Voc Jsc
shown in Equation 4.

 The efficiency of a solar cell is the ratio of the power output

kT Jsc (corresponding to the MPP) to the power input and is represented
Voc ¼ ln þ1
3. q Jo as in Equation 9.

Voc Jsc FF
where (kT/q) is the thermal voltage and Jo is the reverse saturation PCE ¼
9. Pin
current density; it is a measure of the leakage (or recombination)
of minority carriers across the solar cell in reverse bias.
where Pin is the intensity of the incident radiation. At each

 temperature, corresponding to the calculated Voc, Jsc and FF, PCE is
dVoc Voc 1 dJsc 1 dJo
¼ þ Vth ln − calculated using Equation 9. Under the influence of solar
4. dT T Jsc dT Jo dT
concentrators, the open-circuit voltage V0 oc in a solar cell is given by


where Vth = (kT/q). 0 nkT X Isc nkT
Voc ¼ ln ¼ Voc þ ln X
10. q Io q
For a solar cell, Jo has been modelled32 as in Equation 5.

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 Emerging Materials Research CIGS and perovskite solar cells – an
Volume 9 Issue 3 overview
Lin and Ravindra

where X is the concentration of sunlight.34 The open-circuit
voltage, under illumination, can be described by the equation


nkT E
Voc ≈ Vocn þ ln
11. q En
where Vocn and En are the open-circuit voltage and the irradiation
under nominal conditions, respectively.35
3. Overview of CIGS solar cells
3.1 Processing of CIGS solar cells
CIGS can be fabricated by the co-evaporation process and by
depositing a precursor film followed by high-temperature
annealing. Recent progress in the development of diverse kinds of
structures and materials of CIGS are summarised in Table 1. In
1987, Devaney and Mickelsen2 created the first thin-film CIGS
solar cell with 10% PCE using the vacuum deposition method for
the preparation of each layer in quaternary-based CIGS/cadmium
zinc sulfide (CdZnS) solar cell. In 1993, Chen et al.36 reported a
13.7% PCE with the quaternary CIGS layer as the p-type absorber
and cadmium zinc sulfide mixed alloys as the n-type layer. This
improvement was due to the improved CIGS grain structure
resulting from over 500°C of the substrate processing temperature.
In 1996, in collaboration with the National Renewable Energy
Laboratory (NREL), Deb1 reported a 17.7% PCE by using a
CIGS alloy film solar cell. The CIGS was synthesised by
converting a copper-rich CIGS precursor to a high-quality PV
material by exposing it to indium, gallium and selenium at 550°C,
which was completed by chemical bath deposition (CBD) with
intrinsic zinc oxide layer on top of cadmium sulfide, aluminium-
doped zinc oxide as the front contact, nickel–aluminium grid
contacts and a 100 nm magnesium fluoride (MgF2) as the
antireflection coating. This was considered to be a remarkable
achievement at that time when compared with the most efficient
and practical polycrystalline solar cells. In 2006, Wang et al.37
investigated the impact of rapid thermal annealing (RTA), with
fast ramp rate, on CIGS films under peak annealing temperatures
(100, 200, 300 and 350°C) and holding times (30, 60 and 120 s).
An optimal annealing temperature of around 200°C RTA
treatments and less than 1 min holding time in inert gas ambient
has been reported to significantly improve the performance of
large-area CIGS solar cells. In 2008, Repins et al.38 reported a
19.9% efficiency for CIGS solar cells that was achieved due to a
clear improvement in FF value (81.2%); this was higher than
previous records at NREL. According to the J–V data analysis,
the improved FF was due to decreased recombination from
lowering the bandgap; this was achieved by a three-stage
deposition process. In 2011, Jehl et al.39 investigated the influence
of reducing the thickness of the CIGS absorber layer by hydrogen
bromide/dibromine etching from the standard thickness of 2.5 µm
to 500 nm without altering the material quality. The impact of
etching on the solar cell parameters shows PCE greater than 10%
even for thickness down to 500 nm; this enhancement in PCE is
caused by the smoothening of the surface during etching. In 2016,
Garris et al.40 reported 16.4% PCE with a hybrid cadmium
sulfide/Zn(O,S) buffer layer for CIGS to meet the standard of
hazardous cadmium for those products imported into or
manufactured within the European Union (EU). This is an
example of a beforehand investment in manufacturing for those
who consider the potential enforcement of the Restriction of
Hazardous Substance Directive (RoHS) on PV worldwide. In
2019, Ulicna et al.41 presented a hydrazine-free solution-
processed molybdenum–nitrogen back contact barrier layer with

Table 1. Summary of recent progress in the development of diverse structures of CIGS solar cells
Reference Voc: mV Jsc: mA·cm−2 FF: % Temperature: °C PCE: % Structure
19872 – – – – 10 CIGS/CdZnS
200637 652 34.85 68.40 STC 15.55 Annealing temperature at 200°C
200838 690 35.50 81.20 STC 19.90 Three-stage deposition with reduced recombination without
cadmium
200943 540 30.00 58.00 STC 7.50 12 nm sodium fluoride precursors modified layer CIGS
201058,59 740 35.40 77.50 STC 20.30 High-efficiency small area
201139 680 20.00 74.00 STC 10.30 500 nm absorber layer thickness after etching with hydrogen
bromide/dibromine
201445 746 36.60 79.30 STC 21.70 Alkali post-deposition treatment
201640 666 32.90 74.80 STC 16.40 CdS/Zn(O,S) hybrid buffer layer with annealing
201640 585 32.10 65.00 STC 12.20 CdS/Zn(O,S) hybrid buffer layer without annealing
201648 452 37.70 70.00 STC 11.90 NaF/CIGS/Mo/SiO2/glass
201749 610 32.68 73.00 STC 14.40 Thermally decomposed zinc sulfide nanoparticles layer
201862 617 36.30 76.30 STC 17.10 Three-stage co-evaporation process
201950 649 35.40 72.80 STC 16.70 CIGS film grown at 440°C with anti-reflection layer (magnesium
fluoride)
201941 622 28.67 67.53 STC 12.05 Molybdenum–nitrogen back contact deposition with amine-thiol
solvent solution process
202051 697 35.90 74.80 STC 18.70 Mo/KF-NaF PI/Mo/CIGS/CdS/i-ZnO/ITO/(Ni)Al/MgF2
202051 640 36.10 67.80 STC 16.20 Mo/KF-doped PI/Mo/CIGS/CdS/i-ZnO/ITO/(Ni)Al/MgF2

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Lin and Ravindra

12.05% PCE, which is a scalable deposition technique without the
need for an inert atmosphere of a glovebox. This process reduced
the thickness of the molybdenum diselenide interface layer
formation and prevented any delamination after longer
selenisation times, which further improved the FF of the device.
3.2 Importance of flexible substrate material
Flexible substrates are more advantageous than conventional SLG
substrates for various applications. SLG is well known for its
low-cost materials that can tolerate high temperatures during the
fabrication process. Polyimide (PI) foils can only tolerate a
maximum process temperature below 500°C, which is a barrier
for CIGS under a high-temperature processing condition.42
However, due to the significant progress in recent years, flexible
PI has become the state-of-the-art option as a substrate than its
glass counterpart. Currently, most of the high-efficiency CIGS
solar cells on flexible substrates are made by the incorporation of
alkali elements such as sodium and potassium. Besides SLG, PI
substrates are preferable due to nonmetallic impurities.
In 2009, Caballero et al.43 reported 10% PCE with a sodium
fluoride (NaF) layer grown on molybdenum-coated PI foil using a
three-stage co-evaporation process. Figures 3(a) and 3(b) show
the performance of solar cell parameters when incorporated with
different sodium fluoride layer thicknesses (0, 4, 8 and 16 nm) in
CIGS solar cells. The results show that Voc and FF increase and
Jsc decreases with increasing sodium content in the absorber;
moreover, the lower Jsc prevents an increase in the PCE of the
solar cell. The FF is calculated by Pmax, Voc and Jsc as shown in
Equation 8. Voc is limited by the Eg of a material, which implies
that the upper limit of Voc will not exceed its Eg. Lower Eg yields
higher Jsc due to the larger fraction of the absorption spectrum
range. Lower Eg leads to a decrease in the Voc. Once the value of
Jsc is not sufficient enough to compensate for the decrease in Voc,
it further decreases the FF. Further, the FF decreases as Voc
decreases for a lower Eg. It can also be ascribed to a high
recombination probability in the cell. Thus, the relationship
between FF and Eg of a semiconductor material is complex.
Figure 3(c) shows that lower capacitance values are observed with
lower sodium content in the temperature range of 70 to 300 K.
Moreover, the capacitance for the lower temperature range
decreases when the available thermal energy increases. In 2013,
Chen et al.44 reported their studies of low-temperature (<300°C)
femtosecond pulsed laser deposition (fs-PLD) growth of sodium

80 21
64
540
18
60 56
Jsc: mA/cm2

480 15
48
Voc: mV

η: %
FF: %

40 12
40
420
9
32
360 20
24 6

0 4 8 12 16 0 4 8 12 16
Sodium flouride: nm Sodium flouride: nm
(a) (b)
9 10 kHz
0 nm NaF
8 2.30 × 10−3
4 nm NaF
2.25
7
C: F

2.20 8 nm NaF
Capacitance, C: F

2.15
6 2.10
16 nm NaF
80 100 120 140
5 T: K

2 × 10−9
100 150 200 250 300
Temperature, T: K
(c)

Figure 3. (a) Voc and Jsc, (b) FF and h and (c) the capacitance spectra as a function of temperature with different sodium fluoride layer
thicknesses. In (a) and (b), identical symbols indicate identical absorber growth processes, in which samples with different sodium fluoride
precursor thicknesses were processed simultaneously (reproduced with permission from Caballero et al.)43

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 Emerging Materials Research CIGS and perovskite solar cells – an
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Lin and Ravindra

1.2 1.40

1.1 1.35

SLG: 1.18 eV 1.30

1.0
1.25
0.9 1.20
Voc: V

Eg
1.20
0.8 SLG
1.15 1.15 1.13 wo PDT
0.7 wo PDT: 1.02 eV Na PDT
1.10 1.12
Na®K PDT
Na PDT: 1.07 eV
0.6 1.05
Na®K PDT: 1.11 eV
0.5 1.00
0 50 100 150 200 250 300 0 0.5 1.0 1.5 2.0 2.5 3.0
Temperature: K Thickness: µm
(a) (b)

Figure 4. (a) Voc–temperature plots of solar cells with different compositions under illumination. (b) Bandgap profile of each cell
determined using the obtained gallium/gallium + indium compositional ratios (reproduced with permission from Kim et al.)51

fluoride-doped CIGS, which has better conductivity than undoped 24

CIGS with 78 mA·cm−2Jsc at 0.8 V applied voltage. In 2014, Sample 1
23 (Mo/CIGS/CdS/i-ZnO/ZnO:B)
Jackson et al.45 reported an improvement of 21.7% PCE from the
optimisation of the alkali post-deposition treatment (PDT) of 22
CIGS solar cells. In recent years, the utility of potassium, sodium 21
and other alkali elements (cesium and rubidium) has become
20
more essential for CIGS solar cells to improve the performance
PCE: %

beyond 20%.46,47 In 2016, He et al.48 used PDT involving the 19

thermal annealing process for the growth of sodium fluoride on 18
CIGS with a maximum 11.9% PCE. Sodium incorporation
17
passivates the trap states and increases the Voc and PCE of solar
cells. In 2017, Liao et al.49 reported 14.4% PCE by utilising an 16
improved method of thermally decomposing zinc sulfide 15 Sample 2
nanoparticle layer, which exhibited a 32% improvement in PCE (Mo/CIGS/CdS/ZnO/Ni/Al)
14
of conventional CBD buffer layer process for CIGS solar cells. In
2019, Kim et al.50 investigated a simple fabrication route to 260 280 300 320 340 360
utilise PI substrate and obtained 16.7% PCE by adjusting the Temperature: K
microstructure and intergrain properties of the absorber films by
controlling the process temperature during a three-stage co- Figure 5. Temperature dependence of the PCE of two different
CIGS solar cells
evaporation. PI has a high glass transition temperature (>350°C)
and a high decomposition temperature (>500°C). CIGS absorbers
deposited on PI films can maintain excellent flexibility and low
impurity concentration. In 2020, Kim et al.51 proposed CIGS Simulation – 1 Dimension (SCAPS-1D) for a 1D solar cell device.
incorporation with both sodium and potassium on PI substrates SCAPS-1D is based on the continuity of holes and electrons and
using low-temperature in situ PDT without affecting the growth the resolution of the Poisson’s equation. It is used to describe the
and microstructural properties of CIGS films. Figure 4 shows a transport phenomena in a semiconductor device. The simulation is
comparison between SLG (conventional CIGS film on SLG), performed by considering the variation of Eg (1–1.7 eV) with
without PDT (CIGS film on PI without alkaline doped), sodium temperature and thickness (100 to 3000 nm) for the CIGS absorber;
PDT (CIGS film on PI with sodium fluoride PDT doped) and the parameters of other layers (e.g. n-zinc oxide, i-zinc oxide and n-
sodium–potassium PDT (CIGS film on PI with sodium fluoride cadmium sulfide) are fixed.52,53 Results of sample 2 in Figure 5 are
followed by potassium fluoride (KF) PDT doped). obtained from a physics-based model of an I–V characteristic on a
certified solar cell module simulated from the solar cell equations as
In Figure 5, a case study of the comparison of PCE of two CIGS a function of temperature. As can be seen in the figure, in general,
solar cells is presented. Results of sample 1 in Figure 5 are acquired the PCE of CIGS solar cells decreases with an increase in
from a numerical simulation by using Solar Cell Capacitance temperature. This is consistent with the general behaviour of

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 Emerging Materials Research CIGS and perovskite solar cells – an
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Lin and Ravindra

74 cost, high-yield and high-efficiency solar cell production. In

24 2014, Solibro Hi-Tech GmbH55,56 (Bitterfeld-Wolfen, Germany)
PCE
FF reported studies on a CIGS module with 14.4% PCE; with
21 72 increased CIGS deposition rate, the module exhibited 1.39 A for
Isc and 91.8 V for Voc. MiaSolé FLEX SERIES-02 N (Santa
18 Clara, CA, USA) CIGS module57 reported 14.4–17.0% PCE at

FF: %
PCE: %

15
12
9
1.0 1.2 1.4 1.6
Eg: eV
Figure 6. Variation of PCE and FF with Eg of CIGS solar cells
decreasing efficiency with increasing temperature for solar cells. In
Figure 6, the variation of PCE and FF with the energy gap of CIGS
solar cells is presented. These results are acquired from the
numerical simulation as in Figure 5 for sample 1. As can be seen in
the figure, PCE increases with the energy gap and reaches a
maximum of ~22% at 1.7 eV. The FF reaches a maximum of ~0.73
at ~1.38 eV and subsequently decreases. The data in Figures 5 and
6 are based on studies in the literature.52,53
3.3 Commercial status of CIGS solar cells
CIGS has been commercially available for the past decade.
Although laboratory-scale devices have already exceeded 20%
PCE, commercial CIGS modules typically have PCE in the range
of 12–18%.54 In solar cell manufacturing, the primary mission
of manufacturers and researchers worldwide is to focus on low-
70
STC. In 2010, in Germany, The Center for Solar Energy and
Hydrogen Research (ZSW)58,59 reported 20.3% PCE with a cell
thickness of 4 µm including metal contacts. In 2015, Japanese
68
Solar Frontier60 reported 22.3% PCE that was achieved by
improvement in the CIS absorber layer and junction formation
66 process. In 2020, scientists from Kaunas University of
Technology,61 in cooperation with Helmholtz Zentrum Berlin
1.8 (HZB), produced 23.26% PCE with a self-assembled intermediate
layer of organic materials (2PACz and MeO-2PACz). This new
technology has recently been acquired by an unnamed Japanese
company and will be commercially available soon.61
Conventionally, glass substrates have provided a more mature
production process; however, more companies are focusing on
flexible CIGS solar cells.
4. Overview of PSCs
4.1 Structures and fabrication methods
Halide PSCs are usually fabricated using methylammonium lead
halide (CH3NH3PbX3 (MAPbI3), where X = chlorine (Cl),
bromine (Br) and/or iodine (I)) semiconductor, which is
sandwiched between an electron transport material (ETM) – that
is, an n-type material – and a hole transport material (HTM) – that
is, a p-type material.63 Recent progress in the development of
diverse types of structures and fabrication methods of PSCs is
summarised in Table 2. In 2013, Seok et al.64 reported 12.3%
PCE by using the mixed-halide CH3NH3PbI3−xBrx (10–15%
bromine). A low bromine content (<10%) yielded better initial

Table 2. Recent progress in the development of diverse types of structures of PSCs

Reference Voc: V Jsc: mA·cm−2 FF: % Temperature: °C PCE: % Structure
64
2013 0.91 19.30 70.00 STC 12.30 FTO/TiO2/CH3NH3PbI3−xBrx (10–15% Br)/PTAA/Au
201465 0.84 18.30 50.00 STC 7.50 FTO/TiO2/FAPbI3/P3HT
201972 1.05 19.60 72.00 45 15.10 FTO/TiO2/b-CsPbI3/spiro-OMeTAD/Ag
201972 1.11 19.60 82.00 45 18.40 FTO/CHI-TiO2/CHI-CsPbI3/spiro-OMeTAD/Ag
201973 1.30 15.30 82.00 STC 16.20 ITO/SnO2/PN4N/CsPbI2Br/PDCBT/MoO3/Ag
201971 1.16 22.60 80.00 65 21.10 ITO-glass/PTAA/lead-sulfate treated-CsFAMA/C60/BCE/Cu
202074 1.10 23.13 75.28 STC 19.17 Cu/Ti/MAPbI3 + CQDs/PTAA/ITO/glass
201880 1.06 22.50 76.00 STC 18.00 FTO/SnO2/PCBM/(FAPbI3)0.85(MAPbI3)0.15/BTF4/MoO3/Au
201981 0.99 19.50 77.00 STC 14.90 Glass/FTO/TiO2/(FAPbI3)0.85(MAPbI3)0.15 + meso-TiO2/FH-0 HTM/Au
201981 1.07 22.10 78.00 STC 18.40 Glass/ITO/TiO2/MAPbI3+meso-TiO2/FH-3 HTM/Au
201981 1.09 23.10 78.00 STC 19.60 Glass/ITO/TiO2/MAPbI3+meso-TiO2/spiro-OMeTAD/Au
201982 0.93 16.40 56.00 STC 8.28 ITO/SnO2/CH3NH3PbI3−xClx/BTA2/Au
201982 0.91 20.70 64.00 STC 13.20 ITO/ SnO2/CH3NH3PbI3−xClx/DT2/Au
201684 1.07 20.60 75.00 STC 16.50 Glass/ITO/Low temperature derived NiOx nanoparticles
201668 1.07 22.60 81.00 STC 19.50 ITO/PTAA/MAPbI3/Doped C60-SAM/TCO
201685 0.99 19.51 67.00 STC 12.90 PET/ITO/N-PDI/MAPbI3−xClx/spiro-OMeTAD/Au
201685 1.08 21.80 75.00 STC 17.70 Glass/FTO/N-PDI/MAPbI3−xClx/spiro-OMeTAD/Au
201786 1.08 23.00 77.00 STC 19.10 Glass/ITO/IDIC/MAPbI3−xClx/spiro-OMeTAD/Au
201786 1.05 22.20 74.00 STC 17.40 Glass/ITO/TiO2/MAPbI3−xClx/spiro-OMeTAD/Au

818
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 Emerging Materials Research
Volume 9 Issue 3
efficiency due to the lower bandgap; however, higher bromine
contents (>20%) provided better stability under high humidity
with a poly-triarylamine HTM. In 2014, Pang et al.65 first
reported a nearly cubic NH2CH=NH2PbI3 (formamidinium lead
triiodide (FAPbI3)) perovskite, with poly(3-hexylthiophene)
(P3HT) as the HTM for the fabrication of a mesoscopic solar cell
with 7.5% PCE. Formamidinium lead triiodide has a bandgap of
1.43 eV, and its corresponding absorption edge reaches 870 nm,
showing better performance than methylammonium lead triiodide
(820 nm) as a light harvester.66 Conventional lead halide PSCs
have reached a high PCE of 24.2%; however, the stability with a
long running time under STC limits the development.67,68
Besides, they suffer from instability under stimuli of heat, oxygen,
moisture, light irradiation and electric field69,70 due to the weak
secondary bonding protection between passivation molecules and
the perovskite material surfaces. In 2019, Yang et al.71 reported
their studies on a protection layer to reduce the defect density by
capping water-insoluble lead(II) oxysalt for PSCs. These PSCs
maintained 96.8% of their initial efficiency after operation at MPP
under AM 1.5 G irradiation for 1200 h at 65°C. This step prevents
the degradation of PSCs by chemically passivating the defects on
the surface of perovskites with this water-insoluble lead(II)
oxysalt. Finally, a 19.16% PCE was achieved under the
experimental conditions as described above. Besides this water-
insoluble lead(II) capping technology, there are several alternative
ways for protecting the perovskite surface/interface in order to
achieve better stability in PSCs. In 2019, Wang et al.72 reported a
crack-filling interface engineering method with choline iodine
(CHI), which provides a better matching between b-CsPbI3
perovskite and the titanium dioxide (TiO2) layer. This method
demonstrated the ability of purely inorganic PSCs with the
protected interface, choline iodine (CHI), to mitigate surface
defect sites and improve the energy level in the perovskite/HTM
interface. These CHI-perovskite materials also exhibited high
thermal stability without phase change after annealing at
temperatures around 110°C. Finally, an 18.4% PCE was
accomplished for thermodynamically stabilised PSCs, under 45 ±
5°C ambient condition. In order to develop high photostability
against phase separation for long-term operation of inorganic
PSCs, Tian et al.73, in 2019, developed a synergic interface
design with 16.2% PCE by applying an amino-functionalised
polymer (PN4N) as cathode interlayer and poly[2,2‴0 -bis[[(2-
butyloctyl)oxy]carbonyl][2,20 :50 ,2″:5″,2‴-quaterthiophene]-5.5‴-diyl]
(PDCBT) as dopant-free anode interlayer. This device exhibited a
less than 10% drop in PCE after 400 h of continuous run under 1
sun equivalent illumination. In 2020, Wen et al.74 first proposed
carbon quantum dots (CQDs) as an additive in methylammonium
lead triiodide for reducing the defects that are caused by grain
migration. PSCs achieved 19.17% PCE with 0.04 mg·ml−1
concentration of CQDs additive and at the same time improved the
stability. In 2020, the most recent report from the Helmholtz
Association of German Research Centres shows 29.15% PCE for
the perovskite silicon tandem solar cell.75 This type of PSC
provides a new electrode contact layer with an improvement of the
perovskite compound, which is more stable when illuminated in a
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CIGS and perovskite solar cells – an
overview
Lin and Ravindra
tandem solar cell. Initial experiments have already shown these new
PSCs to be suitable for large surface areas with the help of vacuum
deposition processes.
4.2 Hole transport materials
In order to improve the efficiency of PSCs, different HTMs have
been tested with several types of alternative materials. HTMs play a
key role in the process of extraction, collection and transport of
photogenerated holes; they are responsible for the PV performance
and stability of PSCs.76–79 Although Spiro-OMeTAD (2,20 ,7,70 -
tetrakis-(N,N-di-4-methoxyphenylamino)-9,90 -spirobifluorene) is the
most widely used organic HTM, the verbosely and costly synthetic
process hinders the possibility of its commercialisation.63 Thus, it is
necessary to develop new HTMs as potentially commercial
candidates for PSCs. In 2018, Sun et al.80 reported new fluoranthene-
based dopant-free HTMs (dopant-free BTF4) with an impressive
18.03% PCE. In comparison with conventional Sprio-OmeTAD, this
novel dopant-free BTF4 has better PCE and enhanced stability. In
2019, Chen et al.81 developed two potential alternatives (taking the
prototypical spiro-bifluorene core in spiro-OMeTAD as a reference),
non-spiro (FH-0) and mono-fluorene(FH-3), as the cores to link two
methoxyl-triphenylamine terminals. The performance of these two
FH-0- and FH-3-based PSCs are assessed under STC with 14.9%
and 18.3% PCE separately. FH-3, especially, displays a moderate
energy level, good thermal stability, proper structure packing trends
and comparable efficiency with the spiro-OMeTAD type under STC,
which makes it a promising HTM material for future development.
Besides new HTM materials, the interest in dopant-free HTMs is
continuing for several reasons, notably that dopants are
environmentally unfriendly and can easily deteriorate the stability of
the entire device.80,82,83 In 2019, Ye et al.82 investigated the effect on
PV performance with four novel benzotriazole-based donor-acceptor-
donor (D-A-D) type HTMs BTA1-2 and DT1-2 in PSCs (Figure 7).
The dopant-free HTMs DT1-2 with dithienopyrrolobenzotriazole
(DTBT) core exhibits better PV performance than BTA1-2 HTMs,
which have achieved 13.22% PCE. These four novel HTM materials
also show better stability than conventional spiro-OMeTAD.82
4.3 Electron transport materials
In the inverted n-i-p-type PSCs, inorganic metal oxides such as
titanium dioxide and tin (IV) oxide (SnO2) are often used as ETMs,
while organic materials such as C60 and phenyl-C61-butyric acid
methyl ester (PCBM) are often used as ETMs. In order to
overcome some drawbacks of fullerenes such as limited energy
level variation, thermal instability and poor flexibility, non-fullerene
organic semiconductors were incorporated into PSCs. The
non-fullerene material ETMs can be categorised into electron-
transporting materials, fused-ring electron acceptors, interface-
modifying materials, additive materials and light-harvesting
materials in accordance with their functions. In 2016, Yin et al.84
employed a low-temperature solution-derived NiOx nanoparticle
film as the hole contact by depositing it on indium tin oxide (ITO)-
coated glass substrate and obtained 16.47% PCE. The NiOx
nanoparticle hole contact layer can be fabricated at a low
temperature of 130°C without post-treatments, which is more
819
 Emerging Materials Research CIGS and perovskite solar cells – an
Volume 9 Issue 3 overview
Lin and Ravindra

25

Au 80 nm

Current density: mA cm–2

20
HTM 80 nm

Perovskite 400 nm 15
SnO2 50 nm
ITO 10
BTA1
BTA2
1 µm 5 DT1
DT2
Spiro-OMeTAD
0
(a) 0 0.2 0.4 0.6 0.8 1.0
Voltage: V
100 (b)
25

80
Current density: mA cm–2

20

60 15
PCE: %

40 BTA1 10
BTA2 BTA1
BTA2
DT1
20 DT1
DT2 5 DT2
Spiro-OMeTAD Spiro-OMeTAD
0 0
400 500 600 700 800 0 0.2 0.4 0.6 0.8 1.0 1.2
Wavelength: nm Voltage: V
(c) (d)

Figure 7. (a) PSCs cross-sectional SEM image of the DT2-based device. (b) J–V curves based on the HTMs BTA1-2, DT1-2 and spiro
OMeTAD without dopants. (c) PCE performance based on the HTMs BTA1-2, DT1-2 and spiro-OMeTAD without dopants. (d) J–V curves
of PSCs based on the HTMs BTA1-2, DT1-2 and spiro-OMeTAD with dopants (reproduced with permission from Ye et al.)82

suitable for flexible PSC systems. In 2016, Bai et al.68 reported
19.5% PCE of a water-resistant cross-linkable silane-functionalised
fullerene ETM with improved moisture stability of p-i-n planar
PSCs. In 2016, Zhang et al.85 reported a PCE of 17.66% by
utilising n-type organic semiconductor, perylenediimide derivatives
(PDIs) as the ETMs within n-i-p structure PSCs. The PDIs are low
lowest unoccupied molecular orbital (LUMO) energy level
molecules due to the electron affinity of their imide parts. Due to
small-molecule PDIs, they are easier to functionalise and can be
easily purified than polymeric molecules. In 2017, Zhang et al.86
reported 19.1% PCE using low-temperature processing of fused-
ring electron acceptors (Freas) based on indacenodithiophene
(IDIC) as new promising non-fullerene ETMs. IDIC ETMs
facilitate efficient electron extraction and transportation due to their
high mobility and suitable energy levels within perovskites in
comparison with the conventional titanium dioxide-based n-i-p
PSCs.
resistance (Rsh) are being neglected with size below 1 mm2. This
generates problems during scale-up. The variation in PCE for
different structures of PSCs can be partially explained by the
change in Rs and Rsh. Especially in the mesoporous structure
PSCs, the PCE is critically limited by several types of resistive
losses such as the leakage current, the trapping of charge carriers
at the titanium dioxide/perovskite interfaces and charge carrier
recombination,87,88 which are dominated by both Rs and Rsh.89,90
The reduction in Rs and Rsh can improve the stability and
efficiency even under low light intensity; therefore, the influence
of interfacial engineering on Rs and Rsh is highly desirable for the
optimisation of PSCs. Under ideal one-sun illumination condition,
the typical behaviour of J–V characteristics can be described
using the Shockley equation, as in Equations 12 and 13.91

 
qðV − J Rs Þ V − J Rs
Jsc ¼ Jph − Jo exp −1 −
12. nkT Rsh

4.4 Resistance and shunt resistance dependence

PSC technology is currently limited by the scale-up and stability.
 ( !)
nkT Jph V
Although there have been a large number of studies on small- Voc ¼ ln 1 − oc
sized PSCs with higher PCE under light intensity in the literature, 13. q Jo Jph Rsh
it has been reported that the series resistance (Rs) and shunt

820
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 Emerging Materials Research
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m-TiO2 (a = 0.94)
c-TiO2 (a = 0.93)
c-/mTiO2 (a = 0.98)
2c-/mTiO2 (a = 0.91)
JSC: mA cm–2
3c-/mTiO2 (a = 0.91)
10
10 20 40 60 80 100
Light intensity: mW cm–2
(a)
Figure 8. Light intensity-dependent (a) Jsc and (b) Voc of PSCs. Dotted lines in (a) show the fits according to the power law96 and in
(b) shows the fits according to the equation Voc = b (kbT/q) (reproduced with permission from Singh et al.)93
where Jph is the photocurrent density, Jo is the reverse saturation
current density, Rs and Rsh represent the series and shunt resistance,
respectively, and k is the Boltzmann’s constant (1.38 × 10−23 JK−1).
In 2017, Liao et al.92 analysed the performance of PSCs
(ITO/TiO2/CH3NH3PbI3−xClx/Spiro-OMeTAD/Au), their resistance
dependence, carrier recombination in double heterojunctions,
methylammonium indium (m1, MAI) and methylammonium
chloride (m2, MACl). By varying the ratio of chlorine and iodine
ions, the authors found out that the performance of PSC has
apparent improvement with decreasing m (diode ideal factor). In
2019, Singh et al.93 studied the effect of Rs and Rsh on compact
titanium dioxide (c-TiO2), mesoporous titanium dioxide (m-TiO2),
c-/m-TiO2, 2c-/m-TiO2 and 3c-/m-TiO2 (single, double and triple
layers of c-titanium dioxide film followed by m-titanium dioxide
film) layer thickness (Figure 8). The extent of trap-assisted
recombination loss can be determined by extracting b values (the
thermal carrier ejection rate coefficient).94 The smaller b value of
the c-/m-TiO2 suggests decreasing trap-assisted recombination
losses in comparison with m-TiO2, in which the reduction in b
value has been described as the reason for having a smaller
hysteresis and better performance of PSC. In 2019, Baig et al.95
reported the Rs-dependent performance of a 9-mm2 PSC as a
function of varying light intensity. The Voc can be observed to have
a maximum value between 1 and 2 Suns, and it further stabilises
when reaching a maximum value of 1.18 V at 10.8 Suns. The FF
decreases from 0–10.8 Suns due to the increased current being
drawn from the PSC along with the internal Rs of the module. This
also reduces the PCE and the Pmax that could be extracted from the
solar cell device.
5. Conclusions
CIGS solar cells and PSC technology continue to grow at a rapid
pace. Their contribution to thin-film PVs is increasing and can be a
potential complementary technology to silicon solar cells in the
next decade. In recent years, scientists have attained a 23.26% PCE
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CIGS and perovskite solar cells – an
overview
Lin and Ravindra
1.4
m-TiO2 (b = 1.51)
c-TiO2 (b = 1.11)
c-/mTiO2 (b = 1.12)
1.2
2c-/mTiO2 (b = 1.68)
3c-/mTiO2 (b = 1.74)
Voc: V
1.0
0.8
0.6
10 20 40 60 80 100
Light intensity: mW cm–2
(b)
in the self-assembled intermediate layer of organic materials
(2PACz and MeO-2PACz) CIGS solar cell and a 29.15% PCE with
perovskite/silicon tandem solar cells in cooperation with HZB
team. In addition to power conversion applications, thin-film solar
cells have enhanced applications in numerous areas such as
supercapacitors, flexible optoelectronics, rechargeable batteries and
other hybrid systems that are coupled with PV cells. In CIGS, the
usage of toxic, regulated elements (cadmium) and reliance on rare
elements constrain the market share in its commercialisation. High-
temperature processing of CIGS is one of the issues that could be
solved by the three-stage deposition followed by potassium
fluoride and sodium fluoride PDT on PI substrate. The performance
losses, stability and degradation under standard test conditions in
PSCs are the main problems for their commercial availability. The
characterisation techniques for the PV parameters as a function of
temperature, processing, thermal treatment and material properties
are therefore necessary to be developed and realised
comprehensively. Understanding and quantifying the physical
mechanisms as a function of characterisation techniques are
prerequisites for further progress in the research of stable and high-
PCE commercial CIGS solar cells and PSCs. This review considers
recent reports and progress relating to various semiconductors,
HTMs, ETMs, substrate materials and solar cell performance under
various temperature and light intensity conditions. PCE inhibited
by multiple loss mechanisms has been briefly discussed. For future
development, novel materials that are environmentally friendly
with high stability in space and near-space applications may
provide motivation for further development. Costs, reliability,
stability and efficiency of installed solar cell panels will continue to
be the prime drivers of the technology. Characteristics such as light
weight, flexibility and radiation hardness will be the additional
incentives for new and existing applications.
Acknowledgments
The authors contributed equally to this work.
821
 Emerging Materials Research
Volume 9 Issue 3
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