Chemistry of Inorganic Materials 1 (2023) 100026

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Chemistry of Inorganic Materials

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

Hole and electron transport materials: A review on recent progress in

organic charge transport materials for efficient, stable, and scalable
perovskite solar cells
B. Gopal Krishna a, *, Dhriti Sundar Ghosh b, Sanjay Tiwari a
a
Photonics Research Laboratory, School of Studies in Electronics & Photonics Pt. Ravishankar Shukla University, Raipur, India
b
Department of Physics Indian Institute of Technology, Dharwad, India

A R T I C L E I N F O A B S T R A C T

Keywords: Charge transporting materials are essential for fabricating stable and efficient perovskite solar cells. The high-
Organic hole transport material temperature processing, surface defects, and low mobility are common issues in inorganic charge transport ma-
Dopant-free terials which can hinder the fabrication of low-cost, efficient, and stable perovskite solar cells. Dopants increase
Organic electron transport material
the processing cost of the hole transport materials. Surface defects are observed in the high-temperature processed
Perovskite solar cell
Efficiency
inorganic electron transport materials. There is a need to develop organic compounds for charge transportation in
Stability perovskite solar cells. Herein, the advancements in the organic materials for charge transport in the perovskite
solar cells are reviewed. The low-cost processing, better solubility, efficient charge mobility, tunable molecular
orbitals, and better stability of organic compounds are some properties for their utilization as charge transport
materials in perovskite solar cells. Organic small molecules, polymers, and phthalocyanine compounds can be
utilized as dopant-free hole transport materials. Fullerene and non-fullerene derivatives like C60, C70, azaacenes,
indacenodithiophene, polymers, and rylene diimides are promising electron transport materials. The function-
ality, engineering, charge transport properties, and device characteristics of different organic materials are dis-
cussed. The review will offer a forecast for improving device stability and efficiency in terms of architecture,
engineering, and materials to realize the commercialization of perovskite solar cells soon.

1. Introduction mostly been attributed to the exceptional light absorption capabilities of

The research community has shown significant interest in perovskite
solar cells (PSCs) due to their exceptional optoelectronic characteristics,
including a long diffusion length, adjustable energy band gap, high light
absorption coefficient, and superior carrier mobility [1,2]. The archi-
tectural configuration of a photovoltaic cell based on perovskite is either
of the n-i-p type or the p-i-n type, wherein a layer of perovskite material is
positioned between an electron transport material (ETM) and a hole
transport material (HTM). The perovskite material functions as a layer
that absorbs light, resulting in the generation of charge carriers through
the process of photogeneration. The charge carriers created by light are
collected and delivered to their corresponding electrodes by the use of
electron and hole transport layers [3]. In recent years, there has been
notable progress in the effectiveness of PSCs due to advancements in the
perovskite material itself, as well as the electron transport layer (ETL)
and hole transport layer (HTL) components. These advancements have
perovskite, as well as the ability to effectively extract and transport
charges inside the device by ETL and HTL. Perovskite solar cells have
demonstrated a remarkable power conversion efficiency (PCE) above 25
%. Fig. 1 depicts the device featuring n-i-p and p-i-n type perovskite solar
cells.
In the context of architecture, the symbols ‘i', ‘n', and ‘p' are used to
denote negative-intrinsic-positive characteristics in n-i-p type architec-
ture, while they represent positive-intrinsic-negative characteristics in p-
i-n type architecture. In recent years, notable progress has been made in
enhancing the characteristics of the constituent materials of the PSC,
including improved light absorption capabilities, efficient charge carrier
extraction, and reduced recombination losses [4–8]. The ETM and HTM
are crucial components in improving the PCE of PSCs. Hence, it is
imperative to consider the design and development of charge transport
materials incorporated inside the PSC structure. Fig. 2 illustrates the
energy level diagram of the n-i-p type design. The occurrence of direct

* Corresponding author.
E-mail address: krishna_burra85@yahoo.com (B.G. Krishna).

https://doi.org/10.1016/j.cinorg.2023.100026
Received 20 July 2023; Received in revised form 26 October 2023; Accepted 7 November 2023
Available online 13 November 2023
2949-7469/© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
B.G. Krishna et al.
Fig. 1. Shows (a) p-i-n type and (b) n-i-p type perovskite solar cells.
Fig. 2. Shows the energy level diagram of n-i-p type device configuration.
contact between the perovskite layer and electrodes in PSCs has been
observed resulting in the recombination of photogenerated charge car-
riers, hence contributing to diminished device performance. Conse-
quently, the perovskite layer is positioned between the ETL and HTL in
order to enhance the process of charge separation prior to recombination.
The deposition process in n-i-p type architecture involves initially
applying a transparent ETL atop the transparent conducting oxide (TCO).
This is followed by the deposition of a perovskite layer and an HTL. In
this architectural design, the incident light rays will penetrate the ETL
and then the rays will be absorbed by the perovskite layer. In the initial
stage (step 1), the perovskite layer will produce electrons and holes
subsequent to the absorption of light with suitable energy. In step 2, the
ETL and HTL are responsible for extracting the electrons and holes,
respectively, from the perovskite layer. During the third step, the
extracted electrons and holes are transported to their corresponding
electrodes. The energy level of the conduction band minima (CBM) in the
ETM should be situated at a lower position compared to that of the
perovskite layer. It is imperative that the energy levels of the HTM and
perovskite layers exhibit a high degree of alignment.
In the context of PSCs, a hole transport material is employed to
facilitate the extraction and transportation of photogenerated holes to-
wards the electrode, namely the cathode. The appropriate alignment of
energy levels between the light-absorbing layer and the HTMs is a crucial
factor to consider when selecting HTMs for use in PSCs. This alignment is
important in order to facilitate efficient hole extraction and effective
electron blocking within the PSCs. Additional factors for consideration
include increased mobility, favorable solubility properties, cost-effective
production methods, and stability under ambient conditions. The choice
2
Chemistry of Inorganic Materials 1 (2023) 100026
of HTMs is contingent upon the design of the device. In the context of n-i-
p type device design, it is imperative for the HTM to have a high degree of
hydrophobicity. This characteristic is crucial as the HTM is applied onto
the perovskite layer during the manufacturing process, serving the pur-
pose of safeguarding the perovskite material against moisture infiltra-
tion. In the context of p-i-n type device design, it is necessary to utilize a
hydrophobic HTM with minimum hydrophobicity. This is crucial in order
to mitigate potential issues related to wetting and crystallization. The
inherent hydrophobic nature of the material restricts its solubility in
solvents like DMF and DMSO, hence preventing the removal of the HTM
during the deposition process of the perovskite layer. During the pro-
duction process of p-i-n type PSCs, it is advisable to opt for a wide band
gap HTM due to its ability to prevent the absorption of visible light.
Spiro-OMeTAD is commonly employed as an HTM in the production
of high-performance perovskite solar cells. Nevertheless, the hole
mobility of Spiro-OMeTAD exhibits a significantly low value without
dopants. Spiro-OMeTAD is subjected to doping with several materials,
including Li-TFSI, FK209, and t-BP, in order to enhance its hole mobility
to a significant extent. The fundamental p-doping technology is estab-
lished upon the charge transfer interaction between the HTM and the
dopant. The utilization of a p-type dopant in the Spiro-OMeTAD material
facilitates the efficient extraction of electrons from its highest occupied
molecular orbital. This process effectively enhances the material's hole
density and conductivity. The effectiveness of the p-type dopant in this
regard can be attributed to its strong electron affinity [9–14]. Never-
theless, the use of dopants such as Li-TFSI, FK209, and t-BP in the hole
transport material can expedite the deterioration of the perovskite ma-
terial. The t-BP dopant has the ability to degrade both the perovskite and
HTM layers of the PSCs due to its rapid evaporation and exceptionally
low boiling point [15–18].
The perovskite layer may also experience degradation during the
doping method due to the post-oxidation process of spiro-OMeTAD
[19–21]. The lack of covalent bonding between the dopant and the
HTM raises significant concerns regarding the long-term stability of the
doped HTMs [22–24]. Hence, the utilization of Spiro-OMeTAD as an
HTM in PSCs is expected to result in elevated manufacturing expenses
and pose challenges to widespread industrial-scale production and
commercial viability. Dopants, such as ionic liquids, acids according to
Brønsted/Lewis, salts based on metals, salts containing oxidized radical
cations, and derivatives of tetracyanoquinodimethane (TCNQ), have the
potential to enhance Spiro-OMeTAD-based device performance and
enable cost-effective processing. The Spiro-OMeTAD compound will
undergo doping using the aforementioned dopants in order to enhance its
hole mobility while maintaining a relatively low processing cost.
Nevertheless, it is worth noting that the dopants typically exhibit hy-
drophilic characteristics, which have the potential to expedite the
degrading mechanism of the perovskite material [25]. The deterioration
of the perovskite material within the solar device may lead to instability
B.G. Krishna et al.
in the device. Hence, there is a strong imperative to conceive and
fabricate HTMs that are devoid of dopants, possess high efficacy, exhibit
long-term stability, and are economically viable, in order to facilitate the
widespread use of PSCs in commercial applications [26].
Electron transport materials are employed in PSCs to facilitate the
extraction and transportation of photogenerated electrons. It is impera-
tive for the ETM to exhibit appropriate energy level alignment with the
perovskite layer, while also possessing characteristics such as low-cost
manufacturing, enhanced stability, and efficient electron transportation
qualities [27,28]. The three most often utilized ETMs in n-i-p device
designs are titanium dioxide (TiO2), zinc oxide (ZnO), and tin dioxide
(SnO2). The perovskite solar cell, which utilizes TiO2 as ETM, demon-
strates a notable enhancement in electron mobility through the process of
sintering TiO2 at elevated temperatures. The utilization of
high-temperature sintering techniques for TiO2 can contribute to the
enhancement of device performance. Nevertheless, the economic feasi-
bility of large-scale industrial manufacturing and commercialization of
TiO2-based PSCs is impeded by the significant processing expenses
associated with high-temperature sintering. Extensive research has been
conducted on organic ETMs as potential substitutes for their inorganic
counterparts, primarily owing to their advantageous characteristics such
as low-temperature solution-processability. Hence, the utilization of
organic HTMs and ETMs in perovskite solar cells presents a notable
benefit, as it enables the facile fabrication of PSCs due to the ability of
organic charge transporting layers to be deposited at low temperatures.
Fullerenes and non-fullerenes materials, including C60, C70, PCBM,
NDIs, PDIs, and naphthalene diimide derivatives, have been identified as
potential candidates for electron transport materials in PSCs [29]. PCBM
is commonly regarded as the most prevalent ETM. The ability to adjust
the lowest unoccupied molecular orbital (LUMO) energy level of
fullerene ETMs is restricted, hence limiting the spectrum of possible
material combinations for perovskite/ETL interfaces during fabrication.
The range of potential ETL combinations involving perovskite and
fullerene materials is limited because of the conduction band variations
observed in perovskite solar cells. These variations span from
3.36 eV
(methylammonium tin chloride, abbreviated as MASnCl3) to
4.74 eV
(formamidinium lead iodide, abbreviated as FAPbI3). The change of the
conduction band noted above can be attributed to the presence of Sn and
Pb atoms in the halide perovskite materials. The restricted modulation of
the LUMO energy level in fullerene ETMs can be attributed to the rela-
tively feeble bonding between the fullerene cage and its substituents. The
manufacture of efficient, stable, and large-scale PSCs for commerciali-
zation can be hindered by the expensive processing and limited stability
of fullerene due to its weak intermolecular interactions [29–39]. Perov-
skite and organic solar cells incorporating non-fullerene ETMs exhibit
superior device features when compared to other types of solar cells. This
can be attributed to their desirable characteristics, including excellent
thermal and chemical stability, as well as the ability to tune the energy
levels of their LUMOs [40–42]. Azaacenes, indacenodithiophene, n-type
conjugated polymers, and rylene diimides are examples of non-fullerene
ETMs that exhibit superior electrical, optical, and morphological char-
acteristics in comparison to other materials. The features of non-fullerene
ETMs are influenced by both substituents and molecular configuration
design approaches [43].
This article provides a comprehensive summary of the progress made
in the development of organic compounds that facilitate the flow of holes
and electrons in perovskite solar cells. The efficiency of the PSCs in
collecting holes and electrons from the perovskite material is signifi-
cantly dependent on the characteristics of the hole and electron-
transporting components employed in its structural design. The deteri-
oration of the material is caused by the presence of hygroscopic dopants
within the HTMs. In order to optimize device performance to its highest
extent, it is imperative to utilize dopant-free organic small molecules,
polymers, and phthalocyanine hole-transporting materials that are effi-
cient, reliable, and cost-effective. This article systematically summarizes
the progress made in the development of organic dopant-free HTMs for
3
Chemistry of Inorganic Materials 1 (2023) 100026
perovskite solar cells, with the aim of providing a view for their future
development. In order to enhance electron injection and transportation
within the device, it is imperative to focus on the morphology and
microstructure of the materials employed for electron transportation.
This necessitates the development of an advanced composite structure
and pore-filling mechanism. The characteristics of open-circuit voltage
and fill factor of the perovskite solar cell are influenced by the micro-
structure and morphology of ETMs. Through the advancement of charge-
transporting layers, there exists the potential to explore organic ETMs
and augment the operational capabilities of the device. The compre-
hensive discussion focuses on both fullerene and non-fullerene organic
ETMs in order to enhance charge injection, collection, separation, and
transportation. This article will provide a prognostication on the
enhancement of device stability and efficiency in relation to architecture,
engineering, and materials, with the ultimate objective of expediting the
commercialization of perovskite solar cells in the near future.
2. Dopant-free organic hole transport materials
The important characteristics for utilizing hole transport material in
various device designs with enhanced performance include characteris-
tics such as hole mobility, stability, and bandgap. The aforementioned
properties can be adjusted by the manipulation of molecules. Fig. 3 il-
lustrates several essential characteristics required for the development of
an optimal hole transport material, which plays a crucial role in the
fabrication of highly efficient perovskite solar cells.
HTMs encompass a diverse range of substances, such as polymers,
small molecules, and compounds featuring phthalocyanine constituents.
Dopants have the potential to boost the conductivity of the HTM. The
thickness of the HTM is subject to variation based on the specific archi-
tecture of the device. The usual thickness of HTM is typically larger than
50 nm for conventional architectures and less than 20 nm for inverted
architecture [44–46]. Hence, the utilization of p-i-n architecture with
reduced hole mobility may be considered as viable alternative in com-
parison to the n-i-p architecture. Procedures such as donor-acceptor
(D-A) alternation, incorporation of counter ions, and expansion of
π-conjugation are employed in the development of the molecular struc-
ture of HTMs with the aim of improving hole mobility. The utilization of
these chemical structures may facilitate the development of HTMs that
are free from dopants. The perovskite solar cells based on HTMs without
dopants demonstrated a PCE that is either comparable to or higher than
the PCE of PSCs that utilized doped spiro-OMeTAD and PTAA as HTMs
[47,48]. The enhancement of stability and efficiency in perovskite solar
Fig. 3. Shows the properties for engineering the ideal hole transport materials
for perovskite solar cells.
B.G. Krishna et al.
cells can be achieved through the incorporation of passivating groups
into organic HTMs, as illustrated in Fig. 4. This approach involves the
defect passivation of perovskite films. The incorporated passivating
groups into organic HTMs can act as dopant-free materials. The incor-
poration of Lewis base, halogen atom, and zwitterion group into the
organic HTM matrix can be employed as a means of defect passivation in
the perovskite layer within solar cells. Hence, the atomic or molecular
entities, such as Lewis bases, halogen atoms, or zwitterion groups, have
the capability to function as surface passivators in perovskite solar cells
or as dopant-free HTMs [49]. In Fig. 4, Aþ is a monovalent organic or
inorganic large cation such as CH3 NH þ þ
3 or Cs , B
2þ
is a divalent cation
such as Pb or Sn , and X is a halide anion such as I
or Cl
.
2þ 2þ
2.1. Small molecules
The optimization of device performance relies heavily on the energy
band alignment at the interfaces between the perovskite layer and the
HTM as well as the ETM. Hole transport materials possess the ability to
effectively extract and facilitate the transit of photogenerated holes
originating from the perovskite layer, concurrently impeding the move-
ment of electrons. In order to ensure effective charge transport, it is
necessary for the energy levels of the highest occupied molecular orbital
(HOMO) and LUMO in the charge transport layers to be appropriately
aligned with the valence band maxima (VBM) and CBM of the perovskite
light absorption layer. It is imperative for the LUMO of the ETM to
possess a lower energy level than the CBM of the perovskite layer. In
order to enhance charge carrier transit at the interface between the
perovskite and the HTM, it is necessary for the HOMO of the HTM to
possess a slightly higher energy level than the VBM of the perovskite.
This energy level offset facilitates the effective blocking of electrons and
promotes improved charge carrier transport. Additionally, it is advan-
tageous for the perovskite to have a high energy level for its LUMO to
further enhance this charge transport mechanism. PSCs can benefit from
Fig. 4. Shows the introduction of passivating groups into organic HTM structure for defect passivation of perovskite films in solar cells. The incorporated passivating
groups into organic HTMs can also act as dopant-free materials.
4
Chemistry of Inorganic Materials 1 (2023) 100026
the utilization of HTMs possessing high hole mobility, since they have the
potential to significantly improve hole transport within the system. The
hydrophobic nature of the hole transport material confers several bene-
fits, including the prevention of water penetration and the enhancement
of device performance for perovskite material [50–53].
Liu et al. presented findings on a highly effective tetrathiafulvalene
derivative (TTF-1) HTM that was free of dopants. This HTM incorporated
four long alkyl chains, resulting in improved solubility, carrier mobility,
and greater energy level alignment with the CH3NH3PbI3 perovskite
material. The hole conductivity of TTF derivatives was enhanced due to
the presence of intrinsic π-π stacking and strong SS interactions (S ¼
sulfur) between nearby conjugated units. The device based on TTF-1
demonstrated a PCE of 11.03 %. The unsealed TTF-1-based PSCs
exhibited remarkable stability when exposed to ambient conditions with
a relative humidity of 40 % [52].
The synthesis of HTM1, a dopant-free hole-transporting material, was
described by Franckevi
cius et al. The synthesis involved the utilization of
a spiro-cyclopenta [2,1-b:3,4-b']dithiophene (spiro-CPDT) derivative as
the core unit and triarylamine as the terminal unit. The Spiro-CPDT
compound was chemically linked with p-methoxy-substituted triphe-
nylamine moieties. The compound HTM1 was successfully synthesized
through the application of the Pd-catalyzed Suzuki cross-coupling
method. This synthesis involved the interaction between a tetrabromo-
derivative and a boronic ester of methoxy-substituted triphenylamine.
The solar cell based on HTM1, CH3NH3PbI3, demonstrated a PCE of 13.2
%, whereas the spiro-MeOTAD-based device achieved a PCE of 6.98 %.
Fig. 5 displays the J-V characteristics, IPCE spectra, and SEM micro-
graphs of the manufactured device incorporating HTM1 without and
spiro-MeOTAD with additives and dopant. The J-V characteristics of the
PSC based on HTM1 were better without additives as compared to spiro-
MeOTAD with additives and dopant because the HTM1-based device
experienced a light-soaking phenomenon (Fig. 5(a)). There was a strong
correlation between the JSC values derived from the J-V measurements
and the integrated current densities estimated from the IPCE spectra
B.G. Krishna et al.
Fig. 5. (a) J-V characteristics, and (b) IPCE spectra of the fabricated device containing HTM1 without and spiro-MeOTAD with additives and dopant. (c) SEM
micrograph of the fabricated device [54].
(Fig. 5(b)). Fig. 5 (c) displays scanning electron microscopy (SEM) im-
ages of the perovskite solar cell, indicating the presence of an overlayer
resulting from the infiltration of the perovskite layer into the mesoporous
titanium dioxide (mp-TiO2). To address the issue of residual pores in the
mp-TiO2/perovskite layer, a thick HTM capping was deposited to plug
these pores. The gold electrode was ultimately fabricated using the
thermal evaporation technique [54].
The synthesis of two novel dopant-free HTMs, X61 and X62, was re-
ported by Wang et al. These HTMs were synthesized using the spiro
[fluorine9,90 -xanthene] (SFX) backbone as the core unit. The SFX unit
comprised a tetrahedral sp3-hybridized carbon atom positioned between
two orthogonal π systems, resulting in a three-dimensional structural
framework that had the potential to improve the transit of charge carriers
and minimize recombination and electrical coupling inside the HTM. The
enhanced alignment of energy levels between the molecules and the
perovskite material resulted in an improvement in the performance of the
device. The devices based on X61 and X62 exhibited a retention rate of
49 % and 80 % respectively, in terms of their initial PCE, when subjected
to ambient environments at a relative humidity of 50 % for a duration of
10 days. The primary factor contributing to the improved efficiency of
hole transport and greater performance of the X62 HTM was the presence
of a larger conjugated system and structural extension, which facilitated
tight π
π stacking [55].
The doping procedure commonly employed in organic HTMs involves
chemical oxidation, charge transfer, and redox reactions. The imple-
mentation of doping techniques has the potential to enhance the con-
ductivity of spiro-OMeTAD. The triarylamine present at the highest
degree of purity in spiro-OMeTAD is protonated by the protic ionic liquid
(PIL). The TFSI anions form a surrounding environment around the
radical cation due to the release of hydrogen gas resulting from the in-
jection of electrons from the pristine spiro-OMeTAD molecule. The en-
ergy level of the singly occupied molecular orbital (SOMO) of the radical
cation is slightly lower in comparison to the HOMO of the pristine ma-
terial. Charge hopping is facilitated by the thermodynamic driving force
between the pure material and the radical cation. The observed phe-
nomenon of hole removal from the perovskite absorbing layer exhibits a
consistent pattern across the HTM. The heating technique in the Li-TFSI/
FK209 doping approach is conducted in an oxygen-free environment and
5
Chemistry of Inorganic Materials 1 (2023) 100026
serves to initiate the redox reaction with the PIL. To boost the hole
mobility and conductivity of the HTMs, one possible approach is to in-
crease the concentration of cations. The intrinsic mobility of dopant-free
HTMs can be improved by incorporating counter ions into the HTM
molecules [13,56].
Zhang et al. successfully synthesized a novel class of ionic organic
molecules, namely dopant-free X41 and X44 HTM. For the formation of
X41, the tail end of the alkyl chains of AS37 were modified by connecting
tertiary amine groups. The synthesized X41 compound was then
employed in the synthesis of the X44 molecule. The X41 molecule un-
derwent modifications by introducing quaternary ammonium groups,
which were connected with accompanying counter ions TFSI
, resulting
in the formation of the X44 molecule. The device based on X44 HTM
demonstrated a PCE of 16.2 %, whereas the devices based on AS37 and
X41 molecules achieved PCEs of 7.8 % and less than 0.1 %, respectively
[57]. The chemical structures of different organic small molecule HTMs
without dopants for photovoltaic applications are shown in Fig. 6.
The creation and development of HTMs that do not require dopants,
can be achieved through the use of A-D-A type conjugated molecules.
Cheng et al. successfully synthesized a conjugated molecule, namely M7-
TFSI, which followed an A-D-A structure. This molecule was utilized as
the HTM, with a core unit consisting of 2-ethylhexyloxy substituted BDT.
The TFSI
anion, which served as a non-coordinating ion, was introduced
into M7-TFSI in order to enhance its mobility. The device based on M7-
TFSI demonstrated a PCE of 17.7 % and maintained 64 % of its original
PCE when exposed to ambient conditions at a temperature of 25  C and
relative humidity (RH) of 30 %. The increased hydrophobicity of M7-
TFSI resulted in improved device performance and stability [58].
Figs. 7 and 8 illustrate the photovoltaic properties associated with the
molecular structure of the HTM. In Fig. 7, the photovoltaic parameters of
the solar cell based on the A-D-A type conjugated molecule type HTMs
were excellent because of the enhanced hole mobility, charge transfer
rate, and hole extraction efficiency of these HTMs.
Dopant-free HTMs can be engineered to possess adjustable energy
levels through the incorporation of alternating donor (D) and acceptor
(A) units. This is due to the significant impact of D-A units on the HOMO
and LUMO levels of the HTMs. The inherent characteristics of the D-A
molecular backbone, such as its efficient intramolecular charge transfer
B.G. Krishna et al. Chemistry of Inorganic Materials 1 (2023) 100026

Fig. 6. Depicts the chemical structures of organic small molecules for their utilization as HTMs in perovskite solar cells.

Fig. 7. (a), (b), (c) are J–V characteristics, and (d) is IPCE spectra of perovskite solar cells re-containing different HTMs such as M6, M7-Br, and M7-TFSI, (e) His-
togram for power conversion efficiency of M7-TFSI based PSC, (f) steady-state photocurrent-density and power conversion efficiency at the maximum power
point [58].

6
B.G. Krishna et al.
Fig. 8. Structures of hole transport material M6, M7-Br, and M7-TFSI [58].
and significant dipole moment, are expected to contribute to the
advancement of more effective HTMs. These characteristics are antici-
pated to enhance charge extraction by facilitating a self-doping mecha-
nism. The molecular derivatives, namely malononitrile, ethylrhodanine,
and benzothiadiazole (BT), serve as fundamental components in the
creation of donor-acceptor (D-A) compounds in which the acceptor unit
encompasses BDT, phenoxazine (POZ), and dithienosilole (DTS) as donor
units [59–63]. Liu et al. successfully synthesized a D-A conjugated
DOR3T-TBDT molecule, which was utilized as an HTM. The resulting
device, using this HTM, demonstrated a PCE of 14.9 %, surpassing the
PCE of 14 % observed in the device utilizing a doped
spiro-OMeTAD-based HTM [64].
The intramolecular dipole-dipole interaction can be augmented by
the utilization of the donor-acceptor (D-A) alternating approach. Xu et al.
successfully synthesized a new donor-acceptor-donor hole transport
material (referred to as YN2) with triphenylamine as the donor core and
either benzothiadiazole or thienopyrazine as the acceptor core. The de-
vice based on YN2 demonstrated a PCE of 19.27 %. After a duration of
1000 h, it was observed that the YN2-based device, which had not been
sealed, maintained 91.3 % of its original PCE while subjected to dark
conditions at a temperature of 25  C and a humidity level ranging from
7
Chemistry of Inorganic Materials 1 (2023) 100026
40 % to 45 % [65].
The utilization of the D-D0 molecular configuration, characterized by
the presence of two electron donor units, holds promise for the devel-
opment of enhanced dopant-free HTMs. This molecular architecture
demonstrates notable attributes such as efficient charge transport capa-
bilities and favorable molecular packing, rendering it a viable candidate
for HTM applications. The synthesis of ST1 HTM was described by Zhao
et al. by the one-step Heck reaction technique, utilizing precursors tris(4-
bromophenyl)amine and N,N-dibutylaminostyrene. The perovskite solar
cell based on ST1 demonstrated a PCE of 15.4 %, whereas the PCE of the
p-doped Spiro-OMeTAD was found to be 16.3 % under irradiation of 100
mW cm
2 (AM 1.5G) [66].
Chen et al. successfully synthesized two D-π-D compounds, namely
BDT-PTZ and BDT-POZ, which consisted of a π-conjugated linker. The
presence of bromohexyl groups in the HTMs led to the formation of
structured assemblies due to the dipole-dipole interaction. Additionally,
these groups acted as Lewis bases by coordinating with Pb2þ ions,
thereby passivating the perovskite material. The device that was artifi-
cially created, consisting of BDT-PTZ and BDT-POZ, demonstrated PCEs
of 18.26 % and 19.16 % respectively [67]. Fig. 9 displays the molecular
structures of HTMs and the current-voltage (J-V) curves of the PSCs. The
B.G. Krishna et al.
Fig. 9. Molecular structures of HTMs (a) BDT-PTZ and (b) BDT-POZ. (c) J–V curves of the fabricated device [67].
BDT-POZ-based device comparatively showed better photovoltaic char-
acteristics because of the superior hole transport and extraction as
compared to the BDT-PTZ counterpart (Fig. 9 (c)).
2.2. Polymers
Polymers are viable choices for the development of dopant-free
HTMs. The mechanisms facilitating the transfer of charge in polymers
encompass intramolecular charge transfer and intermolecular charge
hopping. The exceptional hole mobility exhibited by polymeric HTMs
enables their utilization as dopant-free substances. There are two distinct
categories of polymer HTMs, namely homopolymers and copolymers.
Polymeric HTMs are associated with certain limitations, such as chal-
lenges in their purification process and the potential for change in mo-
lecular weight from one manufacturing batch to another. Poly (3-
hexylthiophene) (P3HT) is a hole transport material that exhibits
exceptional hole mobility and possesses optoelectronic features that are
well-suited for many applications. P3HT exhibits some limitations, such
as the presence of non-radiative recombination loss at the interface be-
tween the perovskite and P3HT layers, elevated electronic coupling, and
insufficient physical contact [68].
Xu et al. conducted a study in which they described the production of
a newly developed non-conjugated polymer, PVCz-OMeDAD, which was
utilized as an HTM. This polymer exhibited a flexible non-conjugated
polyvinyl backbone, resulting in improved solubility and film-forming
properties. The enhanced hole mobility exhibited by PVCz-OMeDAD
could be attributed to the intermolecular stacking interaction facili-
tated by the methoxydiphenylamine-substituted carbazole side groups.
The PVCz-OMeDAD-based perovskite solar cell demonstrated a PCE of
16.09 % [69].
The production of a polymeric hole-transporting material (HTM-P1)
was described by Wu et al. They incorporated a methoxytriphenylamine-
conjugated-thiophene moiety onto a polystyrene side chain. The dynamic
interaction of moieties within the side chain of the HTM-P1 resulted in an
enhancement of its hole mobility. The photovoltaic device based on
HTM-P1 had a PCE of 16.8 % [70].
Wu et al. conducted a study in which they investigated the synthesis
of carbazole-based P2 HTMs that were covalently linked to a polystyrene
polymer chain. The HTM P2 molecules with substituents at the 3,6-loca-
tions were synthesized by modifying the positions of the triphenylamine
groups on the carbazole moieties. This modification resulted in improved
photophysical properties, electrochemical properties, and charge mo-
bilities. The PCE of the P2-based device was reported to be 18.45 % [71].
8
Chemistry of Inorganic Materials 1 (2023) 100026
Zhang et al. conducted a study on a polymeric HTM referred to as DTB
(3%DEG). The researchers aimed to modify the polarity of the DTB
polymer through side-chain engineering, specifically by including
diethylene glycol (DEG) groups to replace a portion of the alkyl groups in
the side chains. The introduction of diethylene glycol (DEG) into the DTB
polymer resulted in the decrease of π–π stacking interactions and the
strengthening of lamellar packing. The device based on DTB (3%DEG)
demonstrated a PCE of 20.19 % [72]. The chemical structures of different
organic small molecules and polymers for their utilization as HTMs
without dopants in the PSCs are shown in Fig. 10.
Cai et al. conducted a study in which they described the synthesis of
donor-acceptor copolymers based on carbazole and benzothiadiazole
(BT). These copolymers were designed to serve as HTMs and featured
alkoxy side chains of varying lengths that were grafted onto the BT unit.
The perovskite film exhibited a reduction in trap density due to the
introduction of methoxy side chains on the thiophene units of the BT
unit, which resulted in a passivation impact on the perovskite film.
Passivation was observed to effectively mitigate the recombination
occurring at the interface between the perovskite layer and HTM. The
aforementioned characteristics of the PCDTBT1 based device was the
reason for demonstrating excellent photovoltaic values with a PCE of
19.1 % as compared to other polymers-based devices (Fig. 11). Fig. 11
presents the J-V curves, EQE spectra, power conversion efficiency, and
steady-state power output at the maximum power point of the manu-
factured PSCs using various HTMs [73].
Liao et al. successfully fabricated a π-conjugated in-chain donor-
acceptor (D-A) copolymer molecule, designated as pBBTa-BDT2, which
served as an HTM. This copolymer was synthesized using 4,8-dithien-2-
yl-benzo [1,2-d; 4,5-d0 ]bistriazole-alt-benzo [1,2-b:4,5-b0 ]dithiophene as
the main building block. The pBBTa-BDT2 polymer demonstrated pro-
nounced interchain interactions and significant quinoidal π-character.
The PSC demonstrated a PCE of 14.5 % [74].
The synthesis of a polymeric HTM known as RCP was reported by Kim
et al. This HTM was developed using benzo [1,2-b:4,5-b']dithiophene
(BDT) and 2,1,3-benzothiadiazole (BT) as the building blocks. The RCP-
based PSC demonstrated a PCE of 16.5 % [75].
Lee et al. conducted the synthesis of a polymeric HTM known as
alkoxy-PTEG. This material was developed using benzo [1,2-b:4,5-b0 ]
dithiophene (BDT) and tetraethylene glycol (TEG)-substituted 2,1,3-ben-
zothiadiazole (BT) as the building blocks. The presence of TEG and
alkoxy side groups in alkoxy-PTEG resulted in a notable influence on
solvent interactions, solubility, and polymer aggregation, leading to a
strong correlation among these factors. The PCE of the photovoltaic cell
B.G. Krishna et al. Chemistry of Inorganic Materials 1 (2023) 100026

Fig. 10. Shows the chemical structures of dopant-free small molecules and polymers.

Fig. 11. (a) J-V curves, (b) steady-state power output at the maximum power point, (c) EQE spectra, and (d) histograms of PCE of the fabricated PSCs containing
PCDTBT, PCDTBT1, and PCDTBT8 HTMs [73].

was approximately 21 % [76].
The two most commonly utilized hole transport materials in p-i-n type
perovskite solar cells are PTAA and PEDOT:PSS. The aforementioned
HTMs are plagued by issues like instability, hygroscopicity, and high
cost.
Zheng et al. incorporated surface-anchored alkylamine ligands (AAL)
into the perovskite precursor solution in order to enhance the charac-
teristics of the perovskite material. The enhancement in device perfor-
mance, resulting in a PCE of 23 %, could be attributed to the alterations
in perovskite parameters, including defect density, grain development,
mobility, recombination, and diffusion length [77].
The synthesis of PFDT2F–COOH was carried out by Wan et al. by
utilizing a mixture of 9,9-alkyl carboxylatedfluorene and 3,3‘-difluoro-
2,2‘-bithiophene units. The utilization of synthesized HTM in the PSC
resulted in enhanced charge transportation characteristics, leading to a
notable increase in the PCE of 21.68 % [78]. This improvement could be
attributed to a decrease in charge carrier recombination.

9
B.G. Krishna et al.
2.3. Organometallic compounds with phthalocyanine derivatives
Hybrid organic-inorganic molecules, known as organometallic com-
pounds, are synthesized by incorporating divalent metal cations such as
Cu2þ, Ni2þ, Co2þ, and Zn2þ into phthalocyanine or porphyrin cores, thus
serving as HTMs. Organometallic compounds have notable thermal and
photochemical stability. The optoelectronic properties of these HTMs can
be tuned by modifying the substituents at their peripheral, non-
peripheral, and metal central positions. The inherent mobility of organ-
ometallic HTMs is notably high, and this characteristic is attained
without the requirement of dopants. Organometallic HTMs including
phthalocyanine or porphyrin cores exhibit pronounced light absorption
properties. However, these chemicals responsible for facilitating hole
transport exhibit suboptimal characteristics when employed in inverted
perovskite photovoltaic devices.
Ke et al. conducted a study in which they investigated the use of
copper phthalocyanine (CuPc) as an HTM in fully vacuum-processed
PSCs. The small-molecule organic CuPc HTM exhibited several notable
characteristics, including enhanced stability, increased hole mobility,
and cost-effectiveness. The copper phthalocyanine (CuPc)-based PSC
demonstrated a PCE of 15.42 %, while the spiro-OMeTAD-based PSC
achieved a PCE of 14.3 % [79].
The synthesis of CuPc-TIPS was conducted by Jiang et al. by intro-
ducing triisopropylsilylethynyl (TIPS) substituents at the outside edge of
the Pc ring of CuPc. The CuPc-TIPS material exhibited enhanced solu-
bility and hydrophobicity compared to the CuPc material. The copper
phthalocyanine (CuPc)-tetrakis (isopropylsiloxy) silicon (TIPS) based
PSC demonstrated a PCE of 14.0 % when subjected to 100 mW cm
2
illumination with the AM 1.5G solar spectrum [80].
The synthesis of CuPc-OBu was achieved by Jiang et al. through the
modification of the non-peripheral substituents in the Pc rings. The CuPc-
Fig. 12. Shows the structures of polymers and organometallic compounds with phthalocyanine derivatives.
10
Chemistry of Inorganic Materials 1 (2023) 100026
OBu compound consisted of both butyl and butoxy groups, which were
incorporated to enhance the hole transportation capabilities. The device
that contained CuPc-OBu demonstrated PCEs of 14.3 % and 17.6 %
respectively [81].
Liu et al. successfully synthesized a derivative of copper phthalocy-
anine (CuPC) known as CuPrPc, which exhibited notable characteristics
such as high hole mobility and hydrophobicity. CuPrPc possessed
exceptional characteristics that resulted in the formation of a face-on
molecular orientation of the HTL on the perovskite material. This mo-
lecular arrangement contributed for enhanced device performance, as
evidenced by a PCE of 17.8 %. The unsealed device had a PCE retention
rate of 94 % after being subjected to 800 h of exposure at a relative
humidity of 75 % [82].
The synthesis of methoxytriphenylamine-substituted copper phtha-
locyanine (OMe-TPA-CuPc) was described by Feng et al. The synthesized
material exhibited enhanced π–π interactions when the Pc cores were
arranged in parallel orientations inside bulk aggregates. The organic
metal-free tetraphenylamine copper phthalocyanine-based PSC demon-
strated a PCE of 19.67 % [83].
The synthesis of a solution-processable nickel phthalocyanine com-
pound (NiPc-(OBu)8), was reported by Cheng et al. This compound was
subsequently employed in a PSC, resulting in an achieved PCE of 9.7 %.
The PCE of the undoped nickel phthalocyanine (NiPc-(OBu)8) device was
enhanced by using a vanadium pentoxide (V2O5) buffer layer, resulting in
a PCE of 18.3 % [84]. The chemical structures of polymers and organo-
metallic compounds with phthalocyanine derivatives for the utilization
as HTMs in perovskite solar cells are shown in Fig. 12.
The derivatives of porphyrins demonstrate significant light absorp-
tion capabilities and possess good charge transport properties, making
them promising candidates for the development of HTMs. Chen et al.
conducted a study on a porphyrin molecule, ZnP, which was replaced
B.G. Krishna et al.
with a meso-arylamine group. The researchers found that the incorpo-
ration of a methoxy-substituted triphenylamine group into the molecule
resulted in improved solubility. This enhancement could be attributed to
the bulky and twisted structure of the methoxy-substituted triphenyl-
amine group. The PSC including zinc phthalocyanine (ZnP) demon-
strated a PCE of 17.78 % [85].
The synthesis of 2,9,16-triphenoxy-23-nitrophthalocyaninatozinc
(ZnPcNO2-OPh) was reported by Guo et al. This compound exhibited
improved solubility, optical absorbance, and conductivity. The improved
molecular packing and prolonged π-π interaction resulted in an
enhancement in the properties of the synthesized HTMs. The incorpo-
ration of flexible phenoxy groups has been found to significantly enhance
the characteristics of the HTM. The observed changes in the holes could
be attributed to the existence of the D-π-A configuration found in met-
allophthalocyanines, which consisted of three phenoxy and nitro groups.
The zinc phthalocyanine nitrooxyphenyl-based PSC demonstrated a PCE
of 14.35 % [86]. The J-V and IPCE curves of the fabricated PSCs with
various HTMs are depicted in Fig. 13 (a, b, c, and d). Fig. 13 (e) illustrates
the process of synthesizing asymmetric 2,9,16-triphenoxy-23-nitrometal-
lophthalocyanines. The excellent photovoltaic characteristics of the solar
cell based on metallophthalocyanines HTMs were caused because the
metallophthalocyanines exhibited fewer surface traps, higher hole
extraction efficiency, and higher charge carrier mobility.
Cao et al. conducted a study in which they investigated a combination
of Co(II) and Co(III)-based porphyrin compounds as an HTM. The TiO2/
perovskite interface was subjected to modification through the incor-
poration of sinapoylmalate (SM). The photovoltaic device, which utilized
undoped Co(II)/Co(III) porphyrins, demonstrated a PCE of 20.47 % [87].
Tables 1 and 2 present a comprehensive overview of the photovoltaic
characteristics exhibited by perovskite solar cells that have been pro-
duced using several types of hole transport materials and the chemical
formula of different organic molecules for their utilization as HTMs
respectively.
3. Electron transport materials
Titanium dioxide (TiO2), zinc oxide (ZnO), tin dioxide (SnO2), silicon
dioxide (SiO2), and zirconium dioxide (ZrO2) are frequently employed as
ETMs in the context of extracting and facilitating the transfer of photo-
generated electrons from the perovskite layer to the respective electrode.
Fig. 13. J–V curves for fabricated PSCs containing (a) ZnPcNO2-OPh (b) CuPcNO2-OPh (c) Spiro-OMeTAD under AM 1.5G illuminations in ambient atmosphere, (d)
IPCE curves of different HTM based PSCs, and (e). Synthesis of asymmetric 2,9,16-triphenoxy-23-nitrometallophthalocyanines [86].
11
Chemistry of Inorganic Materials 1 (2023) 100026
Yella et al. described a chemical bath deposition method employed to
synthesize nanocrystalline titanium dioxide onto fluorine-doped tin
oxide (FTO) substrates. The successive deposition approach was
employed to deposit the perovskite onto the nanocrystalline TiO2 layer.
The control over the size and aggregation of nanocrystalline TiO2 parti-
cles was achieved by manipulating the concentration of TiCl4 during the
hydrolysis process. The role played by particle size was crucial in eluci-
dating the electrical properties of the junction established by the TiO2-
perovskite layer. The nanocrystalline interface between TiO2 and the
perovskite layer showed better efficiency in the extraction of photo-
generated electrons. The solar cells based on TiO2 demonstrated a PCE of
13.7 % [88].
Some drawbacks in the fabrication of low-cost TiO2-based PSCs arise
from the features of TiO2, including its high annealing temperature, poor
charge carrier mobility, and the presence of relatively dense trap states.
The limited stability of ZrO2 material in typical environmental circum-
stances is a challenge for its application as an electron transport layer in
PSCs. The hygroscopicity of SnO2 is comparatively lower when compared
to TiO2 and ZrO2. Nevertheless, photovoltaic cells (PSCs) based on SnO2
demonstrate a rather low PCE. Consequently, metal oxide ETMs have
stability and performance concerns. Organic electron transport materials
have gained significant popularity in the field of perovskite solar cells
due to their exceptional electron transport characteristics. Fig. 14 illus-
trates the characteristics pertaining to the development of electron
transport materials with superior quality for the purpose of enhancing
the efficiency of solar cells in the field of engineering.
4. Organic electron transport materials
Organic semiconductors have the potential to function as ETMs in
perovskite solar cells, thereby replacing metal oxide counterparts.
Organic semiconductors, including PCBM, PEHT, and PEHT: PCBM, are
utilized as ETMs in p-i-n type perovskite solar cells with excellent effi-
ciency. The utilization of organic or polymer semiconductors in
conjunction with a metal oxide scaffold or electron blocking layer (EBL)
has been found to boost the performance of perovskite solar cells. The
energy level of the LUMO in different organic materials is comparatively
lower than that of the perovskite layer. Fig. 15 displays many electron
transport materials, both fullerene and non-fullerene, that are utilized in
perovskite solar cells.
B.G. Krishna et al. Chemistry of Inorganic Materials 1 (2023) 100026

Table 1
Photovoltaic parameters of the perovskite solar cells with different types of HTMs.
Dopant-free hole Device Structure HOMO/LUMO Hole Mobility Open-circuit Short- circuit PCE(%) Ref.
transport material (eV) cm2V
1s
1 voltage Voc (V) current
Jsc (mA/
cm
2)

TTF-1 FTO/c- TiO2/mp- TiO2/perovskite/TTF-1/Ag ~-5.0/-1.98 0.1 0.86 19.9 11.03 52

HTM1 FTO/c- TiO2/mp- TiO2/perovskite/perovskite
5.0/-2.57 6.0  10
6 0.97 19.3 13.2 54
overlayer/HTM1/Au
X61 FTO/c-TiO2/mp-TiO2/Mixed-perovskite/X61/Au
5.11/
2.09 3.91  10
5 0.97 17.2 8.00 % 55
X62 FTO/c-TiO2/mp-TiO2/Mixed-perovskite/X62/Au
5.14/
2.22 7.95  10
5 1.01 21.9 15.9 55
X41 FTO/TiO2/perovskite/X44/Au
5.06/-2.12 – 1.08 21.04 16.2 57
M7-TFSI FTO/TiO2/perovskite/M7-TFSI/Au
5.28 eV/ 3.24  10
4 1.09 22.81 17.7 58

3.58 eV
DOR3T-TBDT ITO/TiO2/CH3NH3PbI3-XClX/DOR3T-TBDT/MoO3/
5.5 eV/
3.3 0.26 0.97 20.7 14.9 64
Ag
YN2 FTO/TiO2/perovskite/YN2/Au
5.40/-3.57 9.65  10
4 1.11 22.87 19.27 65
ST1 FTO/TiO2/perovskite/ST1/Au 5.24/-2.63 4.57  10
4 1.059 21.07 15.4 66
BDT-POZ ITO/BDT-POZ/CH3NH3PbI3/C60/BCP/Ag
5.35/-2.78 2.1  10
4 1.04 22.56 19.16 67
PVCz-OMeDAD FTO/bl-TiO2/mp-TiO2/FA0.85MA0.15Pb(I0⋅85Br0.15)3/
5.24/
2.49 3.44  10
4 1.08 21.96 16.09 69
PVCz-OMeDAD/Au
HTM-P1 FTO/c-TiO2/m-TiO2/
5.18/-2.35 1.6  10
4 1.07 24.3 16.8 70
Cs0.05FA0.81MA0.14PbI2⋅55Br0.45/HTL/Au
P2 ITO/SnO2/perovskite/P2/Au
5.21/
2.02 1.32  10
4 1.13 22.34 18.45 71
DTB (3%DEG) FTO/c-TiO2/m-TiO2/
4.97/– 2.83 3.22  10
4 1.106 25.22 20.19 72
Cs0.05FA0.81MA0.14PbI2⋅55Br0.45/DTB (3%DEG)/Au
PCDTBT1 ITO/PEDOT:PSS/Perovskite/undoped PCDTBT1/ – – 1.1 22.2 19.1 73
MoO3/Au
pBBTa-BDT2 FTO/TiO2/perovskite/pBBTa-BDT2/Au
5.21/-3.84 1.2  10
3 0.95 20.3 14.5 74
RCP FTO/SnO2/CH3NH3PbI3/RCP/Au
5.41/–3.77 3.09  10
4 1.08 21.9 16.5 75
alkoxy-PTEG FTO/ETL/perovskite/alkoxy-PTEG/Au
5.31/- 3.56 4.06  10
4 1.14 23.2 21 76
CuPc FTO/C60/Perovskite/CuPc/Au
5.20/- 10–2 1.04 18.91 15.42 79
CuPc-TIPS FTO/c- TiO2/mp- TiO2/perovskite/CuPc-TIPS/
5.42/
3.69 – 1.01 21.4 14.0 80
carbon
CuPc-OBu FTO/c-TiO2/mp-TiO2/perovskite/CuPc-OBu/Au
5.11/-3.44 4.30  10
4 1.06 22.80 17.6 81
OMe-TPA-CuPc FTO/SnO2/Cs0.05 (MA0.13FA0.87)0.95 Pb(I0⋅87Br0.13)3/
5.14/
3.63 6.39  10
3 1.09 23.41 19.67 82
OMe-TPA-CuPc/Au
NiPc-(OBu)8 FTO/c-TiO2/mp-TiO2/Perovskite/NiPc-(OBu)8/Au
5.06/-3.61 1.90  10
4 0.895 18.50 9.7 84
ZnP FTO/c- TiO2/mp- TiO2/Perovskite/ZnP/Au
5.29/-3.35 3.06  10
4 1.099 21.75 17.78 85
ZnPcNO2-OPh FTO/TiO2/Perovskite/ZnPcNO2-OPh/Au
5.13/-3.09 2.80  10
5 1.07 20.83 14.35 86

perovskite films of superior quality under normal atmospheric conditions

Table 2
at room temperature. The resulting PCE was measured to be 16.31 %
Chemical formula of the organic hole transport materials.
[90].
Hole transport Formula Ref. Malinkiewicz et al. successfully fabricated perovskite solar cells
material
through the utilization of organic charge-transporting layers, specifically
TTF-1 tetrathiafulvalene derivative 52 PEDOT: PSS and PCBM. The electron-blocking layer employed in this
HTM1 2,2'-6,6'-Tetrabromo-4,4'-spirocyclopenta [2,1-b:3,4-b'] 54
study was PolyTPD. The efficacy of hole- and electron-blocking layers
dithiophene (
X61 N2',N2',N7',N7'-tetrakis (4-methoxyphenyl)spiro [dibenzo 55 resulted in the observation of low recombination and efficient charge
[c,h] xanthene-7,9'-fluorene]-2',7'-diamine transfer. Exciton separation was observed at the interface between the
X62 N2',N2',N5,N5,N7',N7',N9,N9-octakis (4-methoxyphenyl) 55 perovskite/PCBM and perovskite/polyTPD materials. The PSC demon-
spiro [dibenzo [c,h]xanthene-7,9'-fluorene]-2',5,7',9- strated a PCE of 12.04 % [91].
tetraamine
The efficiency of perovskite solar cells fabricated on both rigid and
ST1 4-(4-(bis(4-(4-(dibutylamino)styryl)phenyl)-amino) 66
styryl)-N,N-dibutylaniline flexible substrates was compared by You et al. The solar cell design
PCDTBT1 poly [9-(heptadecan-9-yl)-9H-carbazole-2,7-diyl-alt-(5,6- 73 incorporated PEDOT:PSS as the HTL and PCBM as the ETL. The PSCs that
bis(methyloxy)-4,7-di(thiophen-2-yl) benzo [c] [1,2,5] utilized both rigid and flexible substrates demonstrated PCEs of 11.5 %
thiadiazole-5,5-diyl]
and 9.2 % respectively [92]. Fig. 16 displays the J-V curves and EQE
pBBTa-BDT 4,8-dithien-2-yl-benzo [1,2-d;4,5-d0 ]bistriazole-alt-benzo 74
[1,2-b:4,5- b0 ]dithiophenes
spectra of the manufactured perovskite solar cells. The photovoltaic pa-
OMe-TPA-CuPc methoxytriphenylamine-substituted copper 83 rameters of the perovskite solar cells having rigid glass/ITO substrate
phthalocyanine were excellent because the fabricated device showed characteristics such
as long carrier lifetime, and enhanced charge transport properties with
good morphology (Fig. 16(a–b). The fabricated device having PET/ITO
The utilization of BCP as a hole-blocking layer in the PSCs was re-
substrate exhibited a loss in PCE because the JSC and FF were reduced
ported by Wang et al. The utilization of PCBM and C60 materials
(Fig. 16 d). The reduction in the Jsc and FF was caused because of the
demonstrated efficacy in mitigating trap density and minimizing dark
higher series resistance in the flexible devices.
current leakage. The photovoltaic (PV) device demonstrated a PCE of
The utilization of ETL as a scaffold material exhibits a positive in-
9.22 % [89].
fluence on the crystallization process of the perovskite layer, resulting in
Chiang et al. conducted the fabrication of perovskite solar cells
the formation of a perovskite film characterized by excellent quality and
through the utilization of PEDOT: PSS as a hole-transport layer and
the absence of pin-holes, together with the presence of big grains. The
PC71BM as an acceptor layer. The photovoltaic (PV) device was fabri-
presence of a nucleation site on the substrate plays a crucial role in
cated using the two-step spin-coating deposition technique to achieve
facilitating the appropriate crystallization and nucleation processes of

12
B.G. Krishna et al. Chemistry of Inorganic Materials 1 (2023) 100026

Fig. 14. Shows the properties of engineering high-quality electron transport materials for perovskite solar cells.

Fig. 15. Shows the use of fullerene and non-fullerene materials as ETLs in perovskite solar cells.

perovskite materials. Hence, it is imperative to form a perovskite coating 4.1. Fullerene

on the electron transport layer that exhibits uniformity, extensive surface
coverage, and compactness in order to mitigate the occurrence of current
leakage.
Ke et al. employed a fabrication technique for perovskite solar cells
that did not include the use of an electron transport material. Instead,
they deposited the perovskite layer over FTO substrates that had been
treated with ultraviolet-ozone. A planar solar cell, produced using solu-
tion processing techniques, was successfully developed with the objec-
tive of achieving a PCE of 14 % [93]. Several fullerene and non-fullerene
compounds are outlined below as electron transport materials for the
advancement of efficient and stable perovskite solar cells.
Fullerenes, including C60, C70, and PCBM, are widely utilized as ETMs
in p-i-n perovskite solar cells. PCBM demonstrates remarkable electron-
accepting properties as a Lewis acid, hence possessing the ability to
effectively passivate the perovskite material. This is mostly attributed to
PCBM's capacity to form stable complexes with under-coordinated ha-
lides. The PCE of the p-i-n device using PCBM as the ETM experienced a
significant enhancement, rising from 3.9 % to 20.9 %, as a result of
employing improved processing techniques [94,95]. The
halide-noncovalent interaction seen in PCBM-based PSCs has the po-
tential to impede the migration of halide ions originating from the

13
B.G. Krishna et al.
Fig. 16. (a, d) J-V curve of the fabricated perovskite solar cells on rigid and flexible substrates under 1000 Wm-2 (b) EQE spectra of the fabricated perovskite solar cell
on rigid glass/ITO substrate. (c) Photo image of flexible PET/ITO-based perovskite solar cells [92].
perovskite layer. Such interactions will lead to an increase in electron
transit within the ETMs [96]. The hysteresis phenomena, particularly the
influence of scan direction and scan rate on the performance character-
istics of PSCs, have been proposed as a challenge in the advancement of
these photovoltaic devices for commercial purposes. Hysteresis is subject
to various influencing factors, including ion migration, the ferroelectric
property of the perovskite layer, and the presence of charge traps
generated internally and externally on the outermost surface of the
perovskite layer [97].
Shao et al. observed the phenomenon of photocurrent hysteresis in
PSCs, which could be attributed to the elevated charge trapping density
on the perovskite's surface and grain boundaries. The incorporation of a
PCBM/C60 double fullerene layer onto the perovskite surface resulted in
a reduction in trap density and an increase in photocurrent. This
enhancement could be attributed to the passivation of charge traps and
the elimination of photocurrent hysteresis. The PCE of the polymer solar
cell utilizing PCBM/C60 as the active layer was significantly improved
from 7.3 % to 14.9 %. This improvement was attributed to the enhanced
short-circuit current and fill factor resulting from the proper thermal
annealing process used for the PCBM layer [98].
Chiang et al. conducted a study in which they fabricated inverted
PSCs based on a bulk heterojunction (BHJ) structure utilizing a two-step
spin-coating method. In their research, they used hybrid films of PbI2 and
PCBM as ETL. The solar cells exhibited a notable level of performance,
with a PCE of 16.0 % and a fill factor of 82 %. The achievement of
exceptional device performance was accomplished through the regula-
tion of the PCBM concentration in the PbI2 precursor solution and the
introduction of an additional layer of PCBM onto the BHJ perovskite-0.1
wt% PCBM film. The enhanced performance of the device, characterized
by the absence of photocurrent hysteresis, could be attributed to the
properties of the BHJ perovskite-PCBM layer, including its high con-
ductivity, long charge diffusion length, and improved balance in electron
and hole mobility [99].
Dai et al. conducted the fabrication of p-i-n planar heterojunction
PSCs through the use of a straightforward and cost-effective solution
processing method. They incorporated a blend of unmodified fullerenes
14
Chemistry of Inorganic Materials 1 (2023) 100026
(C60 and C70) as the ETL. The device based on a 1:1 ratio of C60:C70
demonstrated a PCE of 14.04 %, whereas the device based on PC61BM
achieved a slightly lower PCE of 13.74 %. The improvement in the PCE
can be attributed to the superior morphology of the C60:C70 mixture,
which exhibited a more compact film [100].
4.1.1. Doped fullerene derivatives
The application of fullerene materials in PSCs presents several chal-
lenges, including expensive production methods, fixed boundary orbital
position, and insufficient control over morphology [38,101–103]. The
incorporation of dopants and the implementation of an interfacial layer
between the ETL and the cathode have been identified as potential
strategies to address the aforementioned challenges. The process of
n-doping in organic semiconductors involves the introduction of n-type
materials into fullerenes, resulting in the generation of free electrons.
Dopants have the potential to enhance the electrical conductivity, elec-
tron mobility, and stabilization properties of fullerene materials, such as
PCBM [104].
Li et al. demonstrated the enhanced shelf life and thermal stability of
conductive fulleropyrrolidinium iodide (FPI) and FPI-PC61BM blended
films when subjected to an inert atmosphere. The conductivity of the FPI-
PC61BM blended film, as stated, was found to be 3.2 S/m, which
exhibited a greater level of conductivity compared to the FPI film, which
had a conductivity of 2.0 S/m. The enhanced conductivity seen in the
doped-fullerene films could be attributed to the electron transfer process
from iodine to the core of the fullerene. The observed results were highly
atypical, as it is uncommon for n-doped systems to exhibit this reaction
under ambient conditions at room temperature and room light. Hence,
the technique employed for the n-doping of organic semiconductors had
high efficiency in the realm of organic electronics, particularly in the
production of perovskite solar cells [105].
Yan et al. conducted a study on the production of solar cells utilizing
fullerene surfactants, namely FPPI, Bis-FPPI, Bis-FIMG, and Bis-FITG. The
presence of the quaternary ammonium halide moiety inside the molec-
ular structure of these fullerenes facilitated the movement of electrons
from the Lewis basic halides present in the structure to the adjacent
B.G. Krishna et al.
π-acidic fullerene. This electron transfer process was facilitated by the
anion-induced n-doping effect. The performance of the device could be
enhanced by the qualities exhibited by these fullerenes, including suit-
able conductivities, adjustable work function, and compatibility with
orthogonal solution processes. The device utilizing Bis-FIMG demon-
strated a PCE of 19.01 % [106]. Fig. 17 displays the device structure, J-V
characteristics, and EQE spectra of perovskite solar cells. The photovol-
taic characteristics of the fullerene ETM-based PSCs were enhanced
because the charge extraction of the fullerene ETMs was improved.
Li et al. successfully fabricated graphdiyne films on a copper substrate
with a substantial surface area of 3.61 cm2. This was achieved through
the implementation of a cross-coupling reaction utilizing hex-
aethynylbenzene. A novel device was developed utilizing graphdiyne
layers for the purpose of detecting electrical qualities. The measured
conductivity of 2.516  10
4 S m
1 suggested that the device exhibited
semiconductor characteristics. The semiconductor property of graph-
diyne sheets was found to be a highly promising material for photovoltaic
applications, exhibiting similarities to both silicon and graphene [107].
Hence, it possesses the potential to be utilized as ETM.
4.1.2. Modified fullerene composites
The introduction of an n-type dipolar interfacial layer between the
ETL and the electrode has the potential to enhance charge transport. The
presence of an interfacial layer results in a reduction of the work function
Fig. 17. Depicts the architecture of (a) conventional and inverted perovskite solar cells with different solar parameters. (c) and (e) shows the (c) J-V curves and (e)
EQE spectra of the inverted perovskite solar cells with ZnO and Bis-FPPI: PFN-Br as ETMs. (d) and (f) shows the (c) J-V curves and (e) EQE spectra of the conventional
perovskite solar cells with Bis-FIMG, Bis-FITG, and PFN-Br as ETMs [106].
15
Chemistry of Inorganic Materials 1 (2023) 100026
of the metal electrode, hence enhancing the charge transport character-
istics within the device.
Azimi et al. successfully developed perovskite solar cells by inte-
grating a dipolar interface layer known as DMAPA-C60. This incorpora-
tion resulted in a notable enhancement in the PCE, with a recorded value
of 13.4 %. In comparison, solar cells without the interface layer had a
lower PCE of 9.1 %. The enhancement in the operational efficiency of the
PSC was noted as a result of reducing the work function of the electrode
by the appropriate alignment of energy levels at the interface between
the perovskite and PCBM, achieved by introducing the interface layer
[108].
Xie et al. conducted a study in which they investigated the imple-
mentation of an interface layer composed of PCBDAN between the ETL
and the electrode. The researchers successfully manufactured efficient
and stable PSCs under ambient circumstances. The device based on
PCBDAN demonstrated a PCE of 17.2 % and maintained 90 % of its
original PCE when exposed to a humidity level of 45 % for a duration of
20 days. Efficient electron transportation by implementing an interface
layer resulted in a reduction of the interfacial barrier. The interface layer
served the purpose of safeguarding various components of the device
against ambient moisture and improving overall stability [109].
Zhu et al. conducted a study in which they synthesized a cathode
interlayer for PSCs by combining F–C60 with perfluoroalkyl side-chain
and bis-C60 surfactant. The device that was fabricated and incorporated
B.G. Krishna et al.
an interlayer demonstrated a PCE of 15.5 %. Furthermore, it maintained
80 % of its original PCE when exposed to ambient conditions with a
relative humidity of 20 % for a duration of 14 days. The introduction of a
cathode interlayer resulted in an enhancement of charge transportation
and a decrease in recombination [110].
4.1.3. Modified fullerene derivatives
The limited solubility of PCBM in aromatic solvents at ambient con-
ditions can impede the achievement of the appropriate thickness in
photovoltaic systems. The solubility of the fullerene derivative can be
enhanced through modification.
Escrig et al. employed fullerene derivatives, namely PCBM, PCBH,
PCBB, IPB, and IPH, as the layer responsible for electron transport and
hole blocking in PSCs. The methyl-PCBM-based PSC exhibited improved
layer morphology, resulting in higher performance of the device. The
devices based on IPB and IPH showed enhancements in current density,
open-circuit voltage, and PCE due to a decrease in non-radiative decay
[111]. Hence, it can be inferred that the careful choice of the appropriate
fullerene derivative holds significance in augmenting the photovoltaic
response.
Sieval et al. conducted the fabrication of polymer: fullerene BHJ de-
vices, which consisted of rr-P3HT as the polymer component and several
fullerene derivatives including [60]PCBM [60],IPE [60],IPB, or [60]IPH.
The utilization of synthesized C60-fullerene derivatives facilitated the
enhancement of interactions between rr-P3HT and the fullerene de-
rivatives through deliberate modification of the ester group's size. The
devices based on the polymer: fullerene attained an average PCE of 4.8
%, whereas the PCE for the PCBM-based device was 4.3 % under illu-
minating conditions at AM 1.5G [112].
Ela et al. conducted a synthesis of BAFB and then employed it as an
ETL in perovskite photovoltaic cells. The perovskite heterojunction
photovoltaic cells based on BAFB demonstrated a PCE of 9.63 %, whereas
the PCE of the PCBM-based equivalents was 10.27 %. The defects in the
perovskite layer were passivated by the BAFB in order to improve the
photovoltaic performance [113]. Hence, the synthesized material can be
employed for the advancement of efficient PSCs due to the comparable
efficiencies seen in both BAFB and PCBM-based devices.
Xing et al. successfully synthesized fullerene derivatives, namely C60-
DPM-OE, C60-(DPM-OE)2, C70-DPM-OE, and C70-(DPM-OE)2. These
Fig. 18. Shows the chemical structures of the fullerene and non-fullerene molecules.
16
Chemistry of Inorganic Materials 1 (2023) 100026
derivatives were formed through the combination of diphenylmethano-
fullerene (DPM) phenyl groups with oligoether (OE) chains. Subse-
quently, these derivatives were employed as ETLs in planar
heterojunction (PHJ) perovskite solar cells. The devices using C60/C70-
DPM-OE demonstrated a PCE of 16 %. The PCE of devices based on
synthesized fullerene derivatives was found to be 23 % better than that of
devices based on PC71BM counterparts. This improvement could be
attributed to two factors: a decrease in the work function of the metal
cathode and the passivation of trapping states in the perovskite layer
facilitated by the electron-rich oligoethylene (OE) chains of the C60/C70-
DPM-OE compound. At the interfaces, the diversity in the organic elec-
tronic (OE) chains had the potential to adjust the characteristics of the
material, including energy levels, carrier mobility, and surface energy
[114].
Stranks et al. provided a theoretical framework in their study that
intended to elucidate the dynamic interactions among free charges, ex-
citons, and electronic sub gap states in metal-halide perovskite materials.
It was predicted that there was an influence of electronic traps on the
evolution of photoexcited species at low excitation fluences. At high
excitation fluences, the dominant mechanism governing the evolution of
photoexcited species was shown to be radiative bimolecular recombi-
nation occurring in filled electronic traps. The findings suggested that
achieving high values of photoluminescence quantum efficiency (PLQE)
was possible by either filling or removing the traps at low excitation
fluences. The experimental results indicated that the PLQE might be
enhanced to reach 100 % when low temperatures and high fluences were
applied [115]. Hence, this theoretical study has the potential to
contribute to the development of a material that may effectively improve
the performance of optoelectronic devices. The chemical structures of
different fullerene and non-fullerene molecules for their utilization as
ETMs in PSCs are shown in Fig. 18.
4.2. Non-fullerene
4.2.1. Rylene diimide small molecules
The rylene molecule contains two diimide groups in its terminal lo-
cations. The rylene diimide, characterized by its conjugated planar
structure, has notable chemical and thermal stabilities, while also of-
fering the advantage of being easily processed at a cheap cost. Rylene
B.G. Krishna et al.
diimides possess an additional attribute that facilitates their modifica-
tion, namely the presence of several functionalized reaction sites. The
PDIs and NDIs refer to a class of n-type rylene diimides that possess
adjustable optoelectronic properties [42,116].
4.2.1.1. Perylene diimides. Perylene diimides (PDIs) are a class of non-
fullerene ETMs that possess notable characteristics, including facile
modification using straightforward processing techniques, shallow en-
ergy levels, and exceptional stability. Nevertheless, the PCE of PDI-based
perovskite solar cells remains lower in comparison to their counterparts
that utilize PCBM. The pronounced π-π stacking interactions exhibited by
PDI derivatives result in substantial aggregation, hence exerting a
notable influence on the film shape and charge transport properties.
Consequently, the introduction of functional groups or the strategic
design of certain geometries for PDI derivatives can disrupt the inherent
planarity of PDIs. The variability in the planarity of the PDI planarization
technique will contribute to the improvement of its passivation charac-
teristics and the adjustment of energy levels. The substitution of halogens
in the PDIs leads to variations in intermolecular forces, as it affects both
the molecular organization and solubility. The shape and charge mobility
of PDI films that have been replaced with halogens exhibit variability
[117–121].
Wu et al. conducted the synthesis of mono-halogenated perylene
diimides, specifically H-PDI, F-PDI, and Br-PDI materials. These materials
were subsequently employed as ETLs in the context of PSCs. The device
utilizing Br-PDI with ZnO nanoparticles as the cathode buffer layer
demonstrated a PCE of 10.5 %, whilst the PCE for the PC61BM/ZnO-
based device was 11.1 %. Devices utilizing F-PDI and H-PDI as ETLs
exhibited inferior photovoltaic (PV) response in comparison to devices
employing Br-PDI as an ETL. The PCE of devices based on F-PDI and H-
PDI, without the inclusion of ZnO nanoparticles as a cathode buffer layer,
was found to be 0 % and 7.78 % respectively. The lower device perfor-
mance could be attributed to the low solubility of F-PDI, resulting in poor
thin film quality and inferior electron mobility and conductivity for H-
PDI. The thin film characteristics and electron transfer exhibited by Br-
PDI were superior to those of F-PDI and H-PDI. Consequently, Br-PDI
demonstrated a comparatively enhanced performance as an ETL [121].
Fig. 19. (a) Shows XRD peaks for the TiO2/perovskite film and TCI-PDI/perovskite film; (b), (c), and (d) show J-V curves, PCE of 20 devices, and EQE spectra of the
perovskite solar cell based on TiO2 and TCl-PDI respectively [123].
17
Chemistry of Inorganic Materials 1 (2023) 100026
Wen et al. employed density functional theory and Marcus electron
transfer theory to make predictions regarding the charge transport be-
haviors of perylene diimides with various substituents, namely X-PDI
(where X represents H, F, Cl, or Br). According to theoretical calculations,
it had been projected that the Cl-PDI molecule exhibited superior hy-
drophobicity, stability, and solubility in comparison to other X-PDI
molecules. The electron mobility values for both Cl-PDI and Br-PDI were
found to be identical. The researchers reached the conclusion that both
Cl-PDI and Br-PDI exhibited promising potential as ETMs for the pro-
duction of inverted PSCs with enhanced efficiency and stability [122].
Zou et al. employed the utilization of (TCl-PDI) as an electron trans-
port material in the fabrication process of planar perovskite solar cells.
The device based on TCI-PDI demonstrated a PCE of 14.73 %, which was
higher than the c-TiO2-based device with a PCE of 12.78 %. This
improvement in performance could be attributed to a reduction in non-
radiative recombination, achieved through enhanced energy level
alignment at the TCl-PDI/perovskite interface [123]. Fig. 19 displays the
morphology of thin films, J-V characteristics, PCE, and external quantum
efficiency (EQE) of the perovskite solar cells. Fig. 19 (a) confirmed the
formation of a highly crystalline black phase perovskite film on the
TCl-PDI layer as compared to perovskite film on the TiO2 layer. The
photovoltaic characteristics of the device based on the TCl-PDI layer were
comparatively better because of the reduced non-radiative recombina-
tion and efficient charge transfer (Fig. 19(b–d)).
The pronounced π-π stacking interactions among PDI molecules result
in reduced solubility in solvents, leading to the manifestation of unfa-
vorable film morphology [123]. The utilization of the steric-hindrance
effect is a viable approach to mitigate the formation of PDI aggregates
and enhance the overall film morphology. The utilization of twisted
dimer designs or three-dimensional PDI structures has been shown to
offer enhanced ETLs in terms of density and uniformity. This improve-
ment in ETL characteristics can be attributed to the reduction in the
direct interaction between the perovskite layer and the cathode, leading
to enhanced charge transport capabilities [124].
Karuppuswamy et al. employed the monomer and twisted dimer
forms of BPTI in the fabrication of inverted planar heterojunction PSCs.
The devices that incorporated a double t-BPTI layer and a single BPTI
B.G. Krishna et al.
layer demonstrated average PCEs of 10.73 % and 8.92 % respectively.
The devices based on BPTI had a higher PCE compared to their PC61BM
counterparts (15.08 % PCE). This improvement could be attributed to the
reduction in the hysteresis effect achieved through the utilization of BPTI
[124].
The dimeric PDI derivative Bis-PDI-TEG was employed by Ye et al. in
the fabrication of planar inverted PSCs. The Bis-PDI-TEG compound
possessed energy levels that could be effectively matched and exhibited
excellent charge transport characteristics. These properties contributed
to the reduction of the hysteresis effect in the PSC and assisted in
achieving higher power conversion efficiency. The charge transport
property and shape of Bis-PDI-TEG were affected by the presence of ad-
ditives, namely 1,8-diiodooctane, 1-chloronaphthalene, 1-phenylnaph-
thalene, and 1-methylnaphthalene. The device utilizing Bis-PDI-TEG
with the inclusion of 1-Methylnaphthalene as an additive demonstrated a
PCE of 14.96 %, surpassing the performance of other additives. A
reduction in the aggregation of Bis-PDI-T-EG was observed, contributing
to the formation of a uniform and dense film of the PDI layer. Hence, the
present study successfully mitigated the issues of current leakage and
recombination in the manufactured PSCs [125].
The enhancement of charge transport characteristics in graphene-like
planar molecule configurations can be achieved by expanding the con-
jugate plane of dimer or multimer nanoribbons. This expansion process
leads to an increase in the extent of π-extension within the material
[126].
Castro et al. successfully synthesized two types of graphene nano-
ribbons, namely hPDI2-Pyr-hPDI2 and hPDI3-Pyr-hPDI3. These nano-
ribbons exhibited remarkable characteristics, including strong light
absorption, improved energy level alignment with perovskite, and high
electron mobility. The aforementioned characteristics facilitated the
achievement of PCEs of 15.6 % and 16.5 % for PSCs based on hPDI2-Pyr-
hPDI2 and hPDI3-Pyr-hPDI3, respectively [126].
Yang et al. employed the utilization of an n-type π-conjugated helical
perylene diimide (PDI2) interfacial layer in the fabrication of n-i-p type
PSCs. This approach was found to exhibit low reliance on the thickness of
the interlayer. The electron conductivity at the interface was enhanced
by the incorporation of a conjugated π-π extension of PDI2. The passiv-
ation of surface imperfections in perovskite was facilitated by the crea-
tion of bonds between carbonyl groups located at the margins of PDI2 and
non-coordinated Pb2þ ions. Consequently, the device equipped with PDI2
demonstrated a notable enhancement in PCE of 19.84 % as a result of
Fig. 20. Shows the chemical structures of PDIs.
18
Chemistry of Inorganic Materials 1 (2023) 100026
mitigating hysteresis and light-soaking instability [127].
The ladder-conjugated perylene diimide dimer incorporating an
indacenodithiophene unit (IDTT2FPDI) was synthesized by Wang et al.
The synthesized material possessed several fused thiophene rings that
contributed to the formation of a broad ladder-conjugated framework.
This structural feature enabled the material to demonstrate several
desirable features, including appropriate energy level alignment with
perovskite, high electron mobility, and exceptional hydrophobicity. The
device demonstrated a higher PCE of 19.4 % in comparison to the PCBM
equivalent, which had a PCE of 17.2 %. The enhancement in device
stability was observed due to the increased hydrophobicity of the
IDTT2FPDI layer [128]. The chemical structures of the different PDIs for
their utilization as ETMs in PSCs are shown in Fig. 20.
The utilization of amino and sulfur-modified PDIs as an interfacial
layer in PSCs served as an ETM to enhance energy level alignment and
decrease the work function of metallic electrodes. This was attributed to
the presence of lone pair electrons in the modified PDIs, which enhanced
electron transportation in the ETM and mitigated defects in the perov-
skite layer [43].
Miao et al. employed the solvent 2,2,2-Trifluoroethanol to build a
film of PDIN (perylene diimides derivative) on the surface of the
perovskite layer. Subsequently, they proceeded to fabricate p-i-n type
PSCs. The utilization of the solvent effectively mitigated the issue of
erosion caused by traditional alcohol solvents. The device based on PDIN
demonstrated a PCE of 15.28 % due to the quenching of photo-
luminescence in the perovskite layer by the PDIN layer, which effectively
facilitated the extraction of electrons from the perovskite material [129].
Li et al. successfully synthesized a sulfur-annulated fused-2PDI-2S
compound and employed it as an acceptor material in organic solar cells.
This approach resulted in a PCE of 6.9 %. The results of this study
demonstrated the efficiency of the twisted core design in inhibiting the
formation of extensive ordered domains, hence impeding charge gener-
ation in planar PDI non-fullerene acceptors. The electron affinities of
these materials might vary due to differences in the quantity of sulfur
atoms bonded to the PDI units [130]. In order to enhance our compre-
hension of the mechanisms underlying charge transfer between donors
and acceptors in bulk heterojunctions (BHJs) and its potential for
improving PCE, it is advisable to employ non-fullerene acceptors that
possess adjustable energy levels.
4.2.1.2. Naphthalene diimides (NDIs). Naphthalene diimides (NDIs) are
B.G. Krishna et al.
analogs of perylene diimides whereby the perylene core is substituted
with a naphthalene core. The photoelectric properties of NDIs exhibit a
high degree of similarity to those of PDIs. NDIs are seen as more
appropriate as ETMs in n-i-p type devices due to their greater optical
band gap compared to PDIs. The enhancement of several characteristics
of NDIs, including stability, solubility, and charge transport, can be
achieved by implementing modifications to the π-π packing of NDIs using
cost-effective processing techniques. In a similar manner, the intermo-
lecular interaction within mono-NDIs can be modified through the
introduction of N- or side-substituents. The process of passivating defects
in NDIs can be achieved by the concurrent introduction of heteroatoms,
such as oxygen (O), sulfur (S), and nitrogen (N) atoms [131,132]. In
order to enhance the solubility over time, alkyl chains that are
N-substituted are included. Nevertheless, the substitution of alkyl groups
in perovskite solar cells will result in a deterioration in their long-term
stability. This is due to the fact that the high conformational freedom
and flexibility of the alkyl groups may lead to different mesophase
transitions and have an impact on the overall stability of the cells [63].
The introduction of N-substituted aromatic groups in NDIs has been
found to enhance long-term temporal stability and reduce the solubility
in organic solvents. Hence, the selection of appropriate nitrogen atom
substitutions in NDIs is of utmost importance [133,134].
The design technique proposed by Jung et al. to use the homochiral
asymmetric-shaped groups for the preparation of NDI-PhE. The authors
demonstrated that this approach resulted in a high solubility of NDI-PhE
in various organic solvents. The enhanced characteristics of the synthe-
sized material, including its solubility, film formation, and charge
transport capabilities, enabled the constructed device to achieve a
maximum PCE of 20.5 %. In comparison, the PCE of the PCBM equiva-
lents was 20.2 % [135].
Jung et al. conducted the design and synthesis of chiral stereoisomers
of NDI derivatives, incorporating two chiral substituents. The N-sub-
stituents exhibited chirality and were composed of both homo- and
hetero-chiral side groups, with RR and RS configurations, respectively.
The unsealed PSCs based on NDI-ID (RR) and NDI-ID (RS) demonstrated
a PCE of 18.2 % and 16.2 % respectively, in contrast to the PCBM
counterparts which attained a PCE of 11.8 % at a temperature of 100  C
for a duration of 1000 h in an air environment [136].
Nakamura et al. employed a vacuum deposition technique to deposit
NDI-H onto the perovskite layer in order to construct PSCs. The resulting
PSCs demonstrated a PCE of 10.7 %. This notable performance could be
attributed to the anisotropic charge-carrier transport properties exhibited
by the NDI-H film, which displayed enhanced mobility in the direction
perpendicular to the film plane. The perovskite was subjected to thermal
conversion, resulting in the deposition of NDI-H. The built device uti-
lizing this deposited NDI-H demonstrated a PCE of 4.8 % [137].
By introducing side substitution to the NDI core, desirable charac-
teristics of NDIs such as the formation of smooth films, uniform
morphology, decreased aggregation, and enhanced electron mobility can
be attained. Thiophene-containing side substituents have the capability
to be incorporated into the NDI core, so altering its molecular stack and
facilitating the passivation of defects in the perovskite material
[138–140].
Shaikh et al. successfully synthesized dithiafulvenyl-NDI derivatives,
namely DS1 and DS2. These compounds were subsequently integrated
into PSCs, resulting in PCEs of 9.6 % and 11.4 % for DS1 and DS2,
respectively. The presence of two dithiol units and sulfur atoms at the
NDI core resulted in a decrease in the band gap and facilitated the
passivation of the perovskite layer. The improved performance of the
DS2-based device could be attributed to the higher concentration of
sulfur atoms in DS2, which led to enhanced passivation of the perovskite
layer [138].
Shaikh et al. conducted the synthesis of two NDI derivatives, namely
NDI-BTH1 and NDI-BTH2. The derivatives NDI-BTH1 and NDI-BTH2
demonstrated properties of n-type semi-conductivity and ambipolarity.
The photovoltaic cells based on NDI-BTH1 and NDI-BTH2 had a
19
Chemistry of Inorganic Materials 1 (2023) 100026
maximum PCE of 13.7 % and 15.4 % respectively. The device based on
NDI-BTH2 exhibited superior performance as a result of reduced charge
recombination, which was achieved by increasing the forward biassing
values and enhancing charge transit efficiency [139].
Liu et al. developed a series of side chains for NDI derivatives,
including NDIF1, NDIF2, and DNDIF3, with the objective of controlling
molecular interactions and achieving varying levels of aggregation. The
molecular accumulation and surface properties of electron transport
layers could be influenced by the design of NDI derivatives including
chains of varying lengths. The perovskite solar cells utilizing NDIF1,
NDIF2, and DNDIF3 achieved PCEs of 15.6 %, 11.1 %, and 11.7 %
respectively, in contrast to the 15 % PCE for the PCBM counterparts.
Enhanced photocurrent performance can be achieved by promoting
appropriate aggregation and molecular interaction, resulting in the for-
mation of a more uniform and thicker ETL surface. The strong molecular
interactions had the potential to enhance the formation of uniform and
dense ETLs and impeded the thermal diffusion of the cathode metal,
hence leading to improved performance of perovskite solar cells [140].
Just like in the case of PDIs, the aggregation resulting from planar
aromatic rings in NDIs will adversely impact the solution's processability
and the quality of the resulting film. In addition to N- and side-
substituents, the utilization of twisted NDI dimers is a viable and un-
complicated approach to address this matter [141,142]. Furthermore,
the utilization of sulfur and nitrogen atoms for the purpose of passivating
lead atoms within the perovskite layer can also be employed. The spatial
arrangement of NDI dimers undergoes deformation, resulting in
enhanced isotropic charge transfer and reduced molecular aggregation,
facilitating the production of a uniform and smooth ETL.
Ge et al. successfully synthesized two core-expanded NDI derivatives,
namely NDI3HU-DTYM2 and (DTYM-NDI-DTYA)2. These derivatives
exhibited coplanar and twisted molecular backbones, and demonstrated
promising characteristics including isotropic charge transport, enhanced
electron mobility, appropriate energy level alignment, and favorable film
formation on perovskite layers. The devices based on NDI3HU-DTYM2
and (DTYM-NDI-DTYA)2 demonstrated favorable PCEs of 8.7 % and
12.9 % respectively, as compared to PCBM counterparts which reached a
PCE of 14 % [141]. Hence, it can be inferred that NDI derivatives with
enlarged cores and twisted molecular backbones possess favorable
characteristics as ETMs in the production of highly efficient
solution-processed PSCs. The chemical structures of different fullerene,
NDIs, and azaacenes molecules for their utilization as ETMs in PSCs are
shown in Fig. 21.
Said et al. conducted a synthesis of NDI derivatives, namely PDPT and
PMDPT, which exhibited notable characteristics including suitable en-
ergy alignment with perovskite materials and a high degree of electron
mobility. The reduction in carrier recombination within the device could
be attributed to the inherent features of the synthesized material. The
perovskite solar cell based on PMDPT and PDPT demonstrated PCEs of
9.2 % and 7.6 %, respectively [142].
4.2.2. Azaacenes
Azaacene derivatives have demonstrated remarkable charge trans-
port characteristics and have found utility in various optoelectronic ap-
plications, including field-effect transistors (FETs) and solar cells [143].
The electron-deficient character of pyrazine on azaacene contributes to
its effective n-type electron transport. The use of azaacenes derivatives in
PSCs is hindered by their limited solution processability and substantially
elevated LUMO energy levels. The aforementioned difficulties can be
effectively addressed with the incorporation of sulfur-substituents into
azaacenes derivatives.
Gu et al. successfully synthesized a derivative of azaacene, known as
QCAPZ, and included this material in an inverted perovskite solar cell.
The utilization of QCAPZ resulted in the achievement of a PCE of 10.26 %
[144]. Gu et al. employed an n-type sulfur-containing azaacene deriva-
tive, TDTP, in inverted planar PSCs. The device that was with incorpo-
rated TDTP, demonstrated a PCE of 18.2 %, whereas the PCE of the
B.G. Krishna et al.
Fig. 21. Shows the chemical structures of fullerene, NDIs, and azaacenes molecules.
device based on PCBM was 17 % [145]. The enhanced performance seen
in this study could be attributed to a more robust interaction between the
TDTP and perovskite surfaces. The chemical structures of the different
NDI and azaacene molecules for their utilization as ETMs in PSCs are
shown in Fig. 22.
4.2.3. Indacenodithiophene (IDT)
Zhan et al. introduced and effectively employed IDT derivatives
(IDTs) as organic acceptor materials in organic solar cells (OSCs) [146].
The enhanced charge transport, improved solubility, and
electron-deficient characteristics of IDTs could be attributed to their
electron-donating fused ring core, the presence of side chains, and
electron-withdrawing end groups. The optical and electrical character-
istics of IDTs can be adjusted by including fluorine atoms or methyl
groups into their terminal groups. The hydrophobicity of IDTs is influ-
enced by the insertion of halogen atoms [147–150].
Liu et al. effectively synthesized aromatic ladder-type semiconductors
using small molecules similar to ITIC (IT-4X). These synthesized mate-
rials were then employed in solar cell applications. The IT-4X compounds
were synthesized through the process of substituting fluorine (F),
hydrogen (H), or methyl (Me) groups, resulting in the formation of IT-4F,
Fig. 22. Shows the chemical structures of NDI and azaacene molecules.
20
Chemistry of Inorganic Materials 1 (2023) 100026
IT-4H, and IT-4M derivatives with adjusted energy levels. The presence
of fluorine atoms in IT-4F resulted in a decrease in the energy level of the
LUMO compared to IT-4H. Conversely, the introduction of a methyl
group in IT-4M led to an elevation in the LUMO energy level. The
perovskite solar cells based on IT-4M, IT-4F, and IT-4H demonstrated
PCEs and open-circuit voltages (VOC) of 17.65 % and 1.083 V, 15.94 %
and 1.037 V, and 17.04 % and 1.072 V, respectively. The internal po-
tential of perovskite solar cells was affected by the LUMO of the IT-4X
material, resulting in variations in both Voc and PCEs. These differ-
ences were entirely caused by the distinct LUMOs shown by the IT-4X
molecules. Furthermore, it was worth noting that the PSCs incorpo-
rating IT-4X ETLs exhibited improved long-term stability compared to
the reference devices in ambient circumstances, owing to their enhanced
hydrophobic characteristics [149].
Fan et al. incorporated indacenodithieno [3,2-b]thiophene (IT-like)
non-fullerene acceptors into inverted planar heterojunction PSCs. The
ITIC, ITIC-Th, and ITM-based perovskite solar cells demonstrated an
average PCE of 13.73 %, 13.09 %, and 12.50 % respectively. These values
were found to be equivalent to the PCE of 12.07 % observed for the
PCBM-based device, as illustrated in Fig. 23. The better photovoltaic
characteristics of devices based on IT-like non-fullerene acceptors could
B.G. Krishna et al.
Fig. 23. (a)–(d) shows the J-V curves of the ITIC, ITIC-Th, IT-M, and PCBM-based perovskite solar cells [150].
be attributed to several factors. Primarily, the non-fullerene acceptors
demonstrated enhanced charge transportation capabilities, allowing for
efficient movement of charges within the device. Additionally, these
acceptors exhibited lower recombination losses, minimizing the loss of
charges and maximizing the overall efficiency of the device. The aberrant
hysteresis effect was mitigated and the PCE was enhanced by the char-
acteristics exhibited by non-fullerene acceptors [150].
Wu et al. employed multifused rigid ladder-type backbone ITCPTC-
based n-type small molecules as components in PSCs. The compounds
ITCPTC-Th and ITCPTC-Se were synthesized by introducing n-hexylth-
ienyl and n-hexylselenophenyl as substituents to the ITCPTC molecule.
These compounds exhibited remarkable characteristics in terms of film
shape, electron mobility, and electron transport. The device based on
ITCPTC-Th and ITCPTC-Se demonstrated PCEs of 17.11 % and 16.12 %
respectively, surpassing the PCE of 15.97 % achieved by PCBM coun-
terparts. This improvement in performance could be attributed to the
unique features of the synthesized material [151]. The chemical struc-
tures of NDI and IDT molecules for their utilization as ETMs in PSCs are
shown in Fig. 24.
The enhancement of electron mobility, light absorption, and film
Fig. 24. Shows the chemical structures of NDI and IDT molecules.
21
Chemistry of Inorganic Materials 1 (2023) 100026
morphology can be achieved through the strategic manipulation of
asymmetric molecules and the modification of conjugation length in
fused rings during the design and development process. Enhancing the
film morphology can be achieved through the synthesis of asymmetric
molecules, as this will introduce a distinct change in the material's mo-
lecular dipole moment [152].
Wu et al. successfully synthesized an A-D-A configuration type IDT
derivative known as ITCP-M. This derivative exhibited notable charac-
teristics including exceptional electron transport capabilities and effi-
cient light absorption features. The device based on ITCP-M
demonstrated a PCE of 19.15 %, whereas the PCE of its PC61BM coun-
terpart was 16.57 % [152].
Jiang et al. made alterations to the surface of anatase TiO2 film
through the utilization of small-molecule ITIC in order to mitigate trap
density. The device utilizing ITIC-modified TiO2 demonstrated a PCE of
20.08 %, while the device without this modification produced a PCE of
17.12 %. The enhanced operational efficiency of the device could be
attributed to the measures taken by the ITIC, which involved optimizing
the band alignment of the device and passivating defects on the surface of
TiO2 through the development of a smooth coating. The utilization of the
B.G. Krishna et al.
thin ITIC layer has been found to promote the development of high-
quality and uniform perovskite films characterized by bigger grain
sizes and improved surface coverage. This observation suggested that the
incorporation of TiO2, known for its high mobility, in conjunction with
ITIC, which possessed a low trap density, effectively enhanced the per-
formance of the device [153].
Noh et al. applied a coating of ITIC onto SnO2 in order to enhance the
electron transport characteristics of the ETL. The device utilizing the
ITIC-SnO2 double ETL exhibited a PCE of 14.30 %, surpassing the PCE of
8.01 % observed in the device based solely on SnO2. The efficiency and
stability of devices were enhanced by implementing the ITIC-SnO2
double ETL at the interfaces of perovskite. This resulted in an increase in
efficiency of over 16 % for a duration of 200 h [154].
4.2.4. Polymers
The presence of a dipole layer at the interface between the ETL and
the perovskite material has the potential to mitigate charge recombina-
tion. The influence of oriented permanent dipoles at the interface be-
tween mp-TiO2 and perovskite was analyzed by Roiati et al. The presence
of directed dipoles at the interface and local interactions facilitated the
organized growth of the material within the pores, leading to an
improvement in the charge transport characteristics within the perov-
skite layer. The utilization of electron and photoinduced absorption
analysis techniques allowed for the determination that the Stark signal
observed in the experiment was a result of the combined influence of
non-oriented permanent dipoles and anticipated bulk polarization ef-
fects. The induction of a dipole moment between the ETL and perovskite
layer has been observed to be possible by the implementation of a thin
polymer layer [155].
Mahmood et al. employed a deposition technique to fabricate poly-
ethyleneimine (PEI)-capped zinc oxide (ZnO) nanorods on an indium tin
oxide (ITO) substrate. The objective was to generate a surface dipole
moment while ensuring minimal interference with carrier extraction
processes. The work function was decreased by the interfacial dipole
layer of PEI. The decrease in work function could be ascribed to the
diminished electrostatic potential observed at the surface of N:ZnO,
which could be related to the presence of a surface dipole. The formation
of the surface dipole was facilitated by the establishment of an ionic
double layer at the interface of the ZnO and PEI surface [156].
Zhou et al. applied a layer of polyethyleneimine ethoxylated (PEIE)
over the indium tin oxide (ITO) substrate in order to decrease its work
function from 4.6 eV to 4.0 eV. The ITO/PEIE interface played a crucial
role in enhancing the electron transport efficiency between the electron
transport material and ITO layers, resulting in the attainment of PCE of
15 % for the manufactured device. The dipole layer effectively facilitated
the separation of electrons from the perovskite layer. Hence, the per-
formance of the device was influenced by the polymer-induced dipole
effect [157].
The morphological stability and film-forming capabilities exhibited
by polymers can be effectively utilized in the synthesis of high-quality
ETMs or acceptors for perovskite solar cells [158,159]. The utilization
of NDI and PDI polymers, along with polyfluorene derivatives, has been
observed as a viable option for implementing ETMs in perovskite solar
cells. The utilization of NDI polymers as ETMs can be advantageous due
to their notable attributes, including robust electron mobility, elevated
stability, capacity for chemical structure modification, and improved
solution processability. The modification of NDI-based polymer ETMs
has predominantly involved the utilization of thiophene or fluorene
units. The electron mobility can be enhanced by optimizing the order and
conjugation of NDI polymers through the incorporation of copolymerized
units. Thiophene and fluorene were recognized as electron-donating
moieties [160]. Consequently, modifying their quantities or intro-
ducing substituents onto these moieties are effective strategies for con-
trolling the energy levels of NDI-based polymers.
Shao et al. successfully synthesized three distinct polymers, namely
P(NDI2OD-T2), P(NDI2DT-T2), and P(NDI2OD-TET), which belonged to
22
Chemistry of Inorganic Materials 1 (2023) 100026
the n-type naphthalene diimide-bithiophene family. These polymers
were subsequently incorporated into PSCs. The devices based on
P(NDI2OD-T2), P(NDI2DT-T2), and P(NDI2OD-TET) demonstrated PCEs
of 10.82 %, 10.83 %, and 0.18 %, respectively, in contrast to a negligible
PCE in the absence of an electron extraction layer. The introduction of an
electron extraction layer effectively mitigated the recombination mech-
anism in the PSCs. This was primarily attributed to the significant role
played by the bulk electron mobility of the electron extraction layer in
facilitating charge collection, rather than relying solely on the energy
difference between the LUMO of the perovskite and the electron
extraction layer [161]. Fig. 25 presents the device structure, J-V prop-
erties, and EQE spectra of the perovskite solar cells. The photovoltaic
characteristics of the fabricated devices were enhanced because of the
improved charge collection.
Yan et al. conducted the synthesis of naphthalene-diimide polymers,
specifically NDI-Se, NDI-BiSe, and NDI-TriSe, and subsequently
employed them as ETLs in perovskite solar cells. The observed polymers
demonstrated enhanced thermal stability, a significant level of crystal-
linity, and an energy level that is suitably compatible with perovskite
materials. The device structure, which incorporated NDI-Se, NDI-BiSe,
and NDI-TriSe as ETLs, demonstrated PCEs of 9.51 %, 7.66 %, and 14.0
%, respectively. The PCE of NDI-TriSe was found to be similar to that of a
C60/BCP-based device, which exhibited a PCE of 14.6 % [162]. The
copolymerized units of PDI polymers can be modified to their tune en-
ergy levels and electron mobility. Nitrogen and sulfur can be added to the
copolymerization units of PDI polymers for passivating the defects of the
perovskite layer.
Meng incorporated an interlayer consisting of an amino-
functionalized perylene diimide polymer, denoted as PPDIN6, within
planar p-i-n type PSCs. The purpose of including this interlayer was to
mitigate trap density and recombination phenomena occurring at the
interface between the PCBM and Ag layers. The device exhibited a PCE of
20.43 % due to enhancements in its electron transport characteristics.
The device lacking the presence of PPDIN6 had a PCE of 17.38 % [163].
Wan et al. synthesized an n-type conjugated polymer PFPDI,
comprising pendant polar phosphite ester groups and perylene diimide.
The self-assembled and nanostructured PFPDI on the perovskite layer
improved the light absorption to achieve a PCE of 15.01 % for the
fabricated device as compared to 15.34 % for PCBM counterparts [164].
Hu et al. employed the cross-linkable conjugated polymer PFN-OX as
the n-type interface layer in planar heterojunction PSCs. The electron-
selective layers of the device, which utilized a PFN-OX:ZnO hybrid
composite, resulted in a PCE of 16 %. This high efficiency could be
attributed to the effective extraction of electrons and the prevention of
hole-blocking [165].
Chen et al. conducted the synthesis of two distinct n-type polymers,
namely PBTI and PDTzTI. These polymers were developed using
bithiophene imide and thienylthiazole imide as the respective building
blocks. The device based on PBTI and PDTzTI demonstrated PCEs of
10.60 % and 20.86 % respectively, in comparison to a PCE of 19.87 % for
the device based on PCBM. The significance of the energy level alignment
at the perovskite/ETL interface was identified in relation to efficiency.
The suboptimal performance observed in PBTI-based solar cells was
attributed to the presence of a significant barrier impeding electron
extraction and transportation. In contrast, the utilization of PDTzTI
demonstrated enhanced performance in terms of both efficiency and
stability as compared to PCBM. The augmentation of the photovoltaic
(PV) response in PDTzTI could be attributed to several factors, namely,
improved morphology, interface trap passivation, and enhanced hydro-
phobicity [166]. The chemical structures of NDI polymers for their uti-
lization as ETMs in PSCs are shown in Fig. 26.
4.2.5. Phthalocyanines
Phthalocyanine (Pc) has exhibited exceptional characteristics,
including enhanced stability and light absorption, which make them
highly suitable for implementation as ETMs in perovskite solar cells.
B.G. Krishna et al. Chemistry of Inorganic Materials 1 (2023) 100026

Fig. 25. Shows (a) and (b) the device architecture of the hybrid perovskite solar cells and energy levels diagram. (c) and (d) shows J-V curves and EQE of the hybrid
perovskite solar cells with different n-type polymers as electron extraction layers [161].

Fig. 26. Shows the chemical structures of the NDI polymers.

Pindolia et al. conducted a comprehensive analysis of the characteristics
of copper phthalocyanine (CuPc) and halogen-substituted copper
phthalocyanine (X16CuPc; X ¼ F, Cl, Br, I) using density functional
theory (DFT) calculations. Their findings led them to propose that
F16CuPc and CuPc exhibited potential as ETM and HTM, respectively, in
methylammonium lead iodide (MAPbI3)-based PSCs. The charge trans-
port materials provided protection to the perovskite layer from the
deleterious effects of dampness. The designed device had a theoretical
PCE of 22.30 % [167].
Raissi et al. successfully synthesized copper phthalocyanine TS-CuPc
and employed it as an electron-collecting material in bulk heterojunction
(BHJ) devices. The device based on TS-CuPc demonstrated a PCE of 3.6
%, while the reference device exhibited a PCE of 3.4 %. The reduction of
mismatch energy between ITO and TS-CuPc resulted in an enhancement
in device performance, attributed to the favorable conductivity proper-
ties of TS-CuPc [168]. Beaumont et al. successfully synthesized
Cl–Cl6BsubPc as an electron acceptor for use in organic solar cells. This
novel compound led to enhancements in both the open-circuit voltage
and stability of the solar cells [169].
Morse et al. demonstrated the utilization of pentafluoro phenoxy
boron subphthalocyanine (F5BsubPc) within a planar heterojunction
organic photovoltaic cell. The F5BsubPc had the potential to serve as
either an HTL or an ETL. The devices with unoptimized device archi-
tectures ITO/MoO3/F5BsubPc/C60/BCP/Al and ITO/MoO3/ClBsubPc/
F5BsubPc/BCP/Al exhibited open-circuit voltages and PCEs above 1 V
and 1.49 %, respectively. In each configuration of the device, a notable
contribution to the photocurrent was observed at energies below the
minimum energy excitonic state. Charge transfer complexes with an
energy measurement of 1.7 eV were detected at the interface between
F5BsubPc/C60 and Cl-BsubPc/F5BsubPc [170]. The potential of
F5BsubPc to exhibit significant promise has been observed in many de-
signs of organic electronic devices.

23
B.G. Krishna et al.
Dang et al. conducted a synthesis of phenoxylated derivatives, namely
PhO-ClnBsubNc and F5-ClnBsubNc, with the intention of employing
them as electron acceptors in PHJ OPV devices. The devices based on
PhO-ClnBsubNc and F5-ClnBsubNc had PCEs of 0.70 % and 0.38 %
respectively [171]. The chemical structures of phthalocyanines are
shown in Fig. 27.
Tables 3 and 4 present a comprehensive overview of the photovoltaic
characteristics of perovskite solar cells that have been produced using
various types of electron transport materials and chemical formula of
different organic molecules for their utilization as ETMs respectively.
5. Critical issues
5.1. Hole transport material
The issue of deterioration in liquid electrolyte-based PSCs is
addressed through the integration of spiro-OMeTAD as the HTM within
the device. Nevertheless, the spiro-OMeTAD exhibits limited hole
mobility, inadequate conductivity, and a tendency for thin-film self-ag-
gregation. Hence, it is imperative to develop innovative hole transport
materials devoid of dopants in order to enhance the efficiency of PSCs.
5.1.1. Dopant
Dopants, such as Li-TFSI and FK209, are employed to enhance the
mobility characteristics of spiro-OMeTAD. Nevertheless, the incorpora-
tion of dopants in the HTMs is expected to result in an elevation of the
overall processing expenses. Dopant-free organic HTMs exhibiting
enhanced hole mobilities have the potential to serve as substitutes for
spiro-OMeTAD in PSCs. There are several strategies that can be employed
to enhance the hole mobility of organic HTMs, including the utilization of
donor and acceptor moieties, modifying the packing of molecules,
boosting conjugation, and enhancing planarity.
5.1.2. Efficiency
The hole transport material serves the purpose of gathering the
photogenerated holes originating from the perovskite material and sub-
sequently facilitating their transmission to the appropriate electrode.
Ensuring the appropriate alignment of energy levels between HTM and
Fig. 27. Shows the chemical structures of phthalocyanines.
24
Chemistry of Inorganic Materials 1 (2023) 100026
perovskite is crucial in order to optimize the open-circuit voltage and
minimize energy losses. The desirable characteristics of organic HTMs,
including complete surface covering, absence of pinholes, and a smooth
surface, hold significant importance due to their ability to prevent direct
contact between the perovskite and electrode, hence minimizing series
resistance. The passivation characteristic of HTMs has been shown to
effectively reduce charge recombination [153,154]. Dopant-free organic
HTMs possessing the aforementioned characteristics have the potential
to enhance the efficiency of PSCs.
5.1.3. Stability
The rapid degradation of PSCs can be attributed to the hygroscopic
properties exhibited by HTMs when they are doped with volatile sub-
stances. The design of dopant-free organic HTMs should incorporate
measures to mitigate the harmful effects of moisture, oxygen, light, and
temperature. The organic HTMs should possess the capability to enhance
the stability of perovskite solar cells by meeting the requirements out-
lined by the International Electrotechnical Commission (IEC) and the
International Summit on Organic and Hybrid PV Stability (ISOS) pro-
tocols [172,173].
5.1.4. Cost
The consideration of processing costs associated with organic HTMs
holds significant importance in the context of the commercialization of
PSCs. Organic HTMs exhibit cost-effectiveness due to their utilization in
conjunction with easy production processes. Dopant-free HTMs in
perovskite solar cells can consist of organic small molecules, polymers,
and organometallic compounds. The characteristics of organic HTMs,
such as shape, solubility, mobility, and energy levels, can be modified by
several methods. These methods include the introduction of donor or
acceptor molecules, manipulation of molecular packing, augmentation of
conjugation, and improvement of planarity.
5.1.4.1. Electron transport materials. Electron transport materials play a
crucial role in enhancing the efficiency of electron collecting in PSCs.
Electron transport materials play a crucial role in enabling the thermo-
dynamically efficient operation of photogenerated carrier populations.
Additionally, ETMs contribute to achieving high open-circuit voltage,
B.G. Krishna et al. Chemistry of Inorganic Materials 1 (2023) 100026

Table 3 Table 4
Photovoltaic parameters of the perovskite solar cells with different types of Chemical formula of the organic electron transport materials.
ETMs. Electron transport Formula Ref.
Electron Device Structure Open- Short- PCE(%) Ref. material
Transport circuit circuit
FPPI Fullropyrrolidine pyridinium iodide 106
Material voltage current
Bis- FPPI Bis fullropyrrolidine pyridinium iodide 106
Voc (V) Jsc
Bis-FIMG bisfulleropyrrolidinium tris(methoxyethoxy)phenyl 106
(mA/
iodide
cm
2)
(Bis-FITG) bisfulleropyrrolidinium tris(methoxtriglycol)phenyl 106
PCBM/C60/ ITO/PEDOT: PSS/ 0.89 14.5 9.22 89 iodide
BCP perovskite/PCBM/ PCBDAN [6,6]-phenyl-C61-butyric acid 2-((2-(dimethylamino) 109
C60/BCP/Al ethyl) (methyl)amino) ethyl ester
PC71BM ITO/PEDOT: PSS/ 1.05 19.98 16.31 90 BAFB Benzoic acid fullerene bis adducts 113
perovskite/PC71BM/ t-BPTI twisted benzo [ghi]perylenetriimide dimer 124
Ca/Al NDI-PhE N,N'-Bis((R)-1-phenylethyl)naphthalene-1,4,5,8- 135
PCBM ITO/PEDOT:PSS/ 1.05 16.12 12.04 91 tetracarboxylic diimide
polyTPD/ DS1 4-(5-((4,5-bis(octylthio)-1,3-dithiol-2-ylidene)methyl) 138
CH3NH3PbI3/PCBM/ thiophen2-yl)-2,7-dioctylbenzo [lmn] [3,8]phen
Au anthroline-1,3,6,8(2H,7H)- tetraone
PCBM substrate/ 0.86 16.5 9.2 92 DS2 4,9-bis(5-((4,5-bis(octylthio)-1,3-dithiol-2- ylidene) 138
PEDOT:PSS/ methyl)thiophen-2-yl)-2,7-dioctylbenzo [lmn] [3,8]
CH3NH3PbI3_xClx/ phena nthroline-1,3,6,8(2H,7H)-tetraone
PCBM/Al PDPT (4,4'-(piperazine-1,4-diyl)bis (2,7-dioctylbenzo [lmn]- 142
without ETM Au/hole-transporting 1.06 19.76 14.0 93 [3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone)
material/ QCAPZ 1,4,9,16- tetrakis ((triisopropylsilyl)ethynyl) 144
CH3NH3PbI3-xClx/ quinoxalino [2000 ,3000 :400 ,5’’]cyclopenta [100 ,200 ,3’’:50 ,6’]
substrate acenaphtho [10 ,2’:5,6]pyrazino [2,3-b]phenazine
Mixture of FTO/PEDOT: PSS/ 0.946 21.01 14.04 100 TDTP 10,14-bis(5-(2-ethylhexyl)thiophen-2-yl)-dipyrido 145
pristine CH3NH3PbI3/ [3,2-a:20 ,30 -c] [1,2,5]thiadiazolo [3,4-i]phenazine
fullerenes fullerenes/Ag ITIC (3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)- 149
(C60 and indanone))
C70)
5,5,11,11-tetrakis (4-hexylphenyl)-dithieno [2,3-
PCBM/Bis- ITO/NiOx/MAPbI3/ 1.08 22.92 19.01 106 d:20 ,30 -d’]-s-ind aceno [1,2-b:5,6-b’]-dithiophene))
FIMG PCBM/Bis-FIMG/Ag ITCPTC (3,9-bis(2- methylene-(3-(1,1-dicyanomethylene)- 151
TCl-PDI ITO/TCl-PDI/ 1.07 17.86 14.73 123 cyclopentane-1,3-dione-[c]-thiophen))-5,5,11,11-
perovskite/P3HT/ tetrakis (4-hexylphenyl)-dithieno [2,3-d:20 ,30 -d']-s-
MoO3/Ag indaceno [1,2-b:5,6-b']dithiophene)
t-BPTI glass/ITO/ 0.96 19.74 10.73 124 (P(NDI2OD-T2)) poly{[N, N0 -bis(2-octyldodecyl)-naphthalene-1, 4, 5, 8 161
PEDOT:PSS/ bis(dicarboximide)-2, 6-diyl]-alt-5, 50 -(2, 20 -
perovskite/ETL/C60 bithiophene)}
BPTI glass/ITO/ 0.87 16.87 8.92 124 (P(NDI2DT-T2)) poly{[N, N0 -bis(2-dodecyltetradecyl)-naphthalene-1, 4, 161
PEDOT:PSS/ 5, 8-bis(dicarboximide)-2, 6-diyl]-alt-5, 50 -(2, 20 -
perovskite/ETL/C60 bithiophene)}
IDTT2FPDI ITO/PTAA-F4-TCNQ/ 23.9 1.10 19.4 128 (P(NDI2OD-TET)) poly{[N, N0 -bis(2-octyldodecyl)-1, 4, 5, 8-naphthale- 161
PMMA/MAPbI3/ nedicarboximide-2, 6-diyl]-alt-5, 5-diyl 2-diyl 2-
IDTT2FPDI/PCBM/ ethanediyl)bithiophene]}
Bphen/Al PBTI poly (2,20 -bithiophene-3,30 -dicarboxyimide) 166
2PDI-2S ITO/ZnO/PTB7- 0.863 12.9 6.9 130 PDTzTI 2,20 -bithiazolothienyl-4,40 ,10,100 -tetracarboxydiimide 166
Th:2PDI-2S/MoO3/
Ag
NDI-TriSe ITO/NiOx/ 0.92 20.2 12.4 162 provided evidence that the integration of mesoscale control and doping
MAPbCl0.2I2.8/NDI- exhibits a synergistic effect, leading to advantageous outcomes for PSCs.
TriSe/Ag
The expansion of the conductive band's edge is a consequence of doping,
PPDIN6 FTO/NiO/ 1.08 22.68 20.43 163
CH3NH3PbI3/PCBM/ wherein the reduction of charge recombination in inorganic ETMs oc-
PPDIN6/Ag curs. Two limitations of the doping method include extended annealing
PFPDI ITO/P3CT/ 0.963 23.43 15.01 164 durations required for activation and challenges in achieving precise film
perovskite/PFPDI/Ag thickness for specific materials. Hence, it is crucial to fabricate organic
TS-CuPc ITO/TS-CuPc/P3HT: 0.51 12.35 3.6 168
PCBM/MoO3/Ag
ETMs that possess exceptional photoelectric characteristics, such as
PhO- ITO/PEDOT:PSS/ 1.013 2.07 0.70 170 elevated electron mobility, a broad energy band gap, and a suitable band
ClnBsubNc P3HT/ClnBsubNc/ arrangement.
BCP/Ag
F5- ITO/PEDOT:PSS/ 0.853 1.23 0.38 170
5.1.6. Efficiency
ClnBsubNc P3HT/ClnBsubNc/
BCP/Ag The incorporation of electron transport materials plays a pivotal role
in enhancing the overall efficiency and performance of perovskite solar
cells. An example of a scenario where a perovskite film is deposited onto
high fill factor, enhanced charge transfer efficiency, and increased light the scaffold ETM can lead to a significant increase in internal quantum
absorption efficiency. The following section will discuss the challenges efficiency. This configuration will facilitate optimal efficiency enhance-
associated with electron transport materials. ment of the external quantum efficiency through the enhancement of
charge separation and transport between the perovskite material and the
5.1.5. Dopants ETM. In order to address the limitations of current materials, it is crucial
The optical and electrical properties of ETMs can be enhanced by to develop ETMs that possess sufficient energy levels and stability.
manipulating their composition and structure through the process of
doping. The introduction of dopants into specific materials has the po-
tential to modify their Fermi energy. Moreover, previous studies have

25
B.G. Krishna et al.
5.1.7. Stability
In order to improve the performance and stability of devices, a range
of deposition methods are employed to integrate organic or inorganic
components as ETLs in perovskite solar cells. Perovskite solar cells
exhibit instability as a result of the deterioration occurring at the inter-
face between the perovskite layer and the ETM. The resolution of this
matter can be achieved through the use of organic substances as electron
transport materials. Enhancing the intrinsic chemical stability of these
materials can potentially lead to the production of stable PSCs. There is a
need to search for novel ETMs that exhibit enhanced chemical stability
and greater selectivity in electron collection.
5.1.8. Cost
PCBM has been found to enhance the selectivity of electron collecting
in perovskite solar cells. However, the cost associated with the produc-
tion of this material is substantial. Consequently, the task of identifying
suitable ETMs with low processing costs and efficient charge collection is
a challenging endeavor. The deposition of ETLs through the sintering
technique may lead to increased manufacturing costs due to its signifi-
cant energy consumption. In order to produce a cost-effective PV device,
it is imperative to advance the development of low-temperature pro-
cessed ETMs. In order to minimize production expenses, it is necessary to
employ ETM synthesis procedures and engage in property optimization
[173].
6. Conclusion
Perovskite solar cells exhibit considerable potential as a photovoltaic
technology, offering enhanced device performance, straightforward
fabrication methods, and cost-effectiveness relative to alternative solar
cell technologies. The effectiveness of PSCs is contingent upon various
factors, including the utilization of appropriate production techniques,
the design of the device architecture, and the optimal integration of
perovskite materials, ETMs, HTMs, and electrodes. Enhanced outdoor
device performance and stability are imperative prerequisites for the
successful commercialization of perovskite solar cells. The utilization of
organic compounds as charge transport materials in PSCs offers several
advantages, including cost-effective fabrication processes and improved
device performance. Dopant-free HTMs have the potential to address the
challenges associated with the deterioration of perovskite solar cells
caused by the presence of hygroscopic dopants. Organic small molecules,
polymers, and organometallic compounds have been found to be viable
HTMs in the fabrication of PSCs, exhibiting improved efficiency and
stability compared to other materials. Molecular engineering has the
potential to enhance the hole mobilities of organic HTMs. There exists a
necessity to nurture inventive methodologies for the synthesis of dopant-
free HTMs, hence facilitating the advancement of an optimal hole
extraction substance for PSCs. Both fullerene and non-fullerene ETMs
have exhibited various desirable qualities, including enhanced passiv-
ation properties, high electron mobilities, appropriate energy level
alignment, and improved stability. The presence of conjugate effect and
steric hindrance in ETMs serves to inhibit self-aggregation and facilitate
the creation of defect-free electron transport layers that exhibit improved
electron mobility. The utilization of organic materials in engineering
applications might facilitate the achievement of optimal charge transfer,
hence enabling the attainment of photovoltaic parameters that approach
their theoretical limits. There exists a necessity to advance cost-effective
processing methodologies in order to facilitate the creation of stable
organic materials that exhibit enhanced charge transport capabilities.
This work aims to present a comprehensive analysis of organic charge
transport materials that exhibit exceptional functionality and stability,
while also being compatible with cost-effective processing methods. The
findings of this study are expected to contribute to the development of
commercially viable perovskite solar cells in the near future.
26
Chemistry of Inorganic Materials 1 (2023) 100026
CRediT authorship contribution statement
B. Gopal Krishna: Conceptualization, Investigation, Data curation,
Formal analysis, Writing – original draft. Dhriti Sundar Ghosh: Formal
analysis, Data curation, Writing – review & editing. Sanjay Tiwari: Su-
pervision, Formal analysis, Writing – original draft, Writing – review &
editing, Visualization.
Funding
This research did not receive any specific grant from funding agencies
in the public, commercial, or not-for-profit sectors.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
Authors acknowledge the support of staff of SoS in Electronics and
Photonics, Pt. Ravishankar Shukla University, Raipur for their support,
valuable guidance and encouragement.
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