Current Progress of Efficient Active Layers For Organic, Chalcogenide and Perovskite-Based Solar Cells A Perspective

energies
Review
Current Progress of Efficient Active Layers for Organic,
Chalcogenide and Perovskite-Based Solar Cells: A Perspective
Francisca Werlinger 1,2 , Camilo Segura 1 , Javier Martínez 1 , Igor Osorio-Roman 1 , Danilo Jara 3 ,
Seog Joon Yoon 4 and Andrés Fabián Gualdrón-Reyes 1, *
1 Facultad de Ciencias, Instituto de Ciencias Químicas, Isla Teja, Universidad Austral de Chile,
Valdivia 5090000, Chile; [email protected] (F.W.); [email protected] (C.S.);
[email protected] (J.M.); [email protected] (I.O.-R.)
2 Facultad de Ciencias Químicas y Farmacéuticas, Departamento de Química Orgánica y Fisicoquímica,
Universidad de Chile, Santiago 8380492, Chile
3 Facultad de Ingenieria y Ciencias, Universidad Adolfo Ibáñez, Av. Padre Hurtado 750,
Viña del Mar 2580335, Chile; [email protected]
4 Department of Chemistry, College of Natural Science, Yeungnam University,
Gyeongsan 38541, Republic of Korea; [email protected]
* Correspondence: [email protected]
Abstract: Photovoltaics has become one of the emerging alternatives to progressively supply/replace
conventional energy sources, considering the potential exploitation of solar energy. Depending on the
nature of the light harvester to influence on its light-absorption capability and the facility to produce
electricity, different generations of solar devices have been fabricated. Early studies of organic
molecules (dye sensitizers) with good absorption coefficients, going through metal chalcogenides
and, lastly, the timely emergence of halide perovskites, have promoted the development of novel and
low-cost solar cells with promising photoconversion efficiency (PCE), close to the well-established
Si-based devices. However, main drawbacks such as the degradation/photocorrosion of the active
layer, the existence of intrinsic defect sites, and the inherent toxicity of the material due to the presence
Citation: Werlinger, F.; Segura, C.; of some harmful elements have blocked the future commercialization of the above kind of solar cells.
Martínez, J.; Osorio-Roman, I.; Jara, In this review, we highlight the current progress in achieving efficient photomaterials for organic,
D.; Yoon, S.J.; Gualdrón-Reyes, A.F. chalcogenides and halide perovskites-based solar cells with the purpose of achieving high PCE values,
Current Progress of Efficient Active some of which are breakthroughs in this research topic, and the diverse approaches used to extend
Layers for Organic, Chalcogenide
the stability of the active layer and improve the performance of the solar devices.
and Perovskite-Based Solar Cells: A
Perspective. Energies 2023, 16, 5868.
Keywords: light harvesting; organic molecules; metal chalcogenides; metal halide perovskites;
https://doi.org/10.3390/
active layer
en16165868
Academic Editor: Adalgisa

Sinicropi
Received: 27 June 2023

1. Introduction
Revised: 25 July 2023 Photovoltaics (PVs) is one of the most important topics in the development of promi-
Accepted: 4 August 2023 nent strategies for finding sustainable energies, with sunlight being an unlimited energy
Published: 8 August 2023 source [1]. This factor has been pivotal considering that both the high energy demand
around the world and the subsequent replacement of traditional energy sources such as
fossil fuels, coke, and natural gas, among others, have been promoted to mitigate the
growing environmental contamination and global warming [2,3]. To guarantee a max-
Copyright: © 2023 by the authors.
imum capability of light absorption, the main component of solar devices is based on
Licensee MDPI, Basel, Switzerland.
semiconductor materials, which collect the sunlight to produce free electrons (sunlight-to-
This article is an open access article
current transformation), which are transported through the fabricated cell [4,5]. In order
distributed under the terms and
to optimize the absorption of sunlight, various light trapping techniques, including tex-
conditions of the Creative Commons
turing [6], anti-reflective coatings [7,8] and plasmonic effects [9], can be employed. These
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
methodologies are implemented to enhance the capture of light within the active layer
4.0/).
of a solar cell. Furthermore, it is relevant to mention that to certify the performance of
Energies 2023, 16, 5868. https://doi.org/10.3390/en16165868 https://www.mdpi.com/journal/energies

Energies 2023, 16, 5868 2 of 35
the fabricated devices, some operational parameters are established, such as the simu-
lated sunlight intensity, which should contain the AM 1.5 G filter, and the direction of
the voltage scanning (forward/reverse) during the photovoltaic measurements. For this
contribution, we show the maximum photoconversion efficiency developed by the different
solar cells, independent of the direction of voltage scanning, considering that the reported
performance is established for optimized devices (ideally similar efficiency in forward and
reverse measurements).
For decades, silicon (Si)-based solar cells have dominated the photovoltaics market
because these devices can reach photoconversion efficiencies (PCEs) of more than 20%,
the photomaterial is non-toxic, providing good photoconductivity properties, resistance
to corrosion, and high light intensities and temperatures [4,5,10]. However, even though
Si-based solar cells can be obtained by using different Si active layers (monocrystalline,
polycrystalline, nanostructured and amorphous Si films), the material preparation and
processing are high energy demanding processes to melt the Si source, which increases the
fabrication cost for Si-based solar cells [11]. Hence, the final costs of the device production
and installation increases, which is a huge challenge in solar technologies. With the purpose
of offering a step forward in the fabrication of lower-cost solar cells with promising PCE,
another kind of semiconductor has been introduced, as in the case of II-VI type CdTe
thin films [12,13]. This type of chalcogenide can be directly deposited as a polycrystalline
film through low-cost techniques including close vapor transport [14], laser ablation [15],
sputtering [16] and electrodeposition [17]. CdTe thin films have also been prepared by
using chalcogenide nanoparticles dispersed in organic or aqueous solutions and deposited
by dip-coating/spin-coating techniques, followed by an annealing process [18–20].
On the other hand, CdTe shows an optimal band gap ~1.42 eV (indicating a suit-
able light harvesting feature in a wide range of the UV-vis-NIR spectrum), direct band
transitions, and a high absorption coefficient ~104 cm–1 [21]. This feature is adequate for
absorbing ~90% of incident illumination for 1 µm thickness CdTe film. Additionally, this
chalcogenide can be produced with n- or p-type semiconductivity, making it ideal for
establishing heterojunctions for carrier transfer. Nevertheless, some disadvantages, such
as a high resistance to carrier transport and fast surface recombination, hinder electron
mobility through the solar devices, decreasing their operational performance [22]. In this
way, reasonable approaches such as the preparation of chalcogenide-based heterostructures,
for instance, CdS/CdTe ones, are known to enhance carrier injection and transfer into the
solar cell, which increases the net PCE [23,24]. Unfortunately, the recent PCE is far from the
established record of solid-state solar cells, some of them based on tandem perovskite-Si
devices (whose main properties are highlighted below), and it is deductible that a wide
understanding of the required components of the solar cells and the quality of the active
layer should be pivotal in order to increase the PV efficiency.
The first step to maximizing the sunlight harvesting in low-cost PV devices was
introduced by Grätzel in 1991 [25], to fabricate dye-sensitized solar cells (DSSCs) by using
natural/synthetic organic materials. These molecules favored carrier generation and
transport, obtaining an initial PCE of 10%. As shown in Figure 1 [26], DSSCs are based on
the deposition of ruthenium (II) polypyridyl complex monolayers on TiO2 films acting as
working electrodes (photoanodes). Meanwhile, platinum-transparent glass is used as a
counter electrode (also called a cathode), being coupled with the active layer to achieve the
expected device. The operational performance of the DSSCs to produce electricity depends
on the efficiency of exciton formation. In this scenario, the photogenerated electrons coming
from the highest occupied molecular orbital (HOMO) of the organic complex (hereafter
named sensitizer) are accumulated in the lowest unoccupied molecular orbital (LUMO),
and then transferred to the conduction band (CB) of the TiO2 layer. Then, these carriers
are transported to the external circuit of the PV cell to reach the cathode, generating
photocurrent. The electron depletion in the HOMO of the dye is filled by electrons from the
electrolyte, which is composed of a redox system based on the I− /I3 − pair. Lastly, iodide is
regenerated by reducing the triiodide species through electrons collected by the cathode,
Energies 2023, 16, x FOR PEER REVIEW 3 of 37
Energies 2023, 16, 5868 3 of 35

from the electrolyte, which is composed of a redox system based on the I−/I3− pair. Lastly,
iodide is regenerated by reducing the triiodide species through electrons collected by the
cathode, closing the circuit where the current is produced. This contribution opened the
closing
door the organic
to new circuit where the current
photomaterials is produced.
based This contribution
on dyes, polymers, and smallopened the door
molecules withto
new organic photomaterials based on dyes, polymers, and small molecules with suitable
suitable electronic properties, giving the possibility to fabricate organic solar cells [27–29].
electronicthe
Although properties,
selectivegiving the(electron
contacts possibility to fabricate
and organic solar
hole transporter cells
layers, ETL[27–29]. Although
and HTL, re-
the selective contacts (electron and hole transporter layers, ETL and HTL,
spectively) impact carrier generation and transport into the PV device, organic moleculesrespectively)
impactlimited
exhibit carrierlight
generation andintransport
harvesting into the
a wide range PV device,
of the organic molecules
energy spectrum exhibit
and restrained
limited light harvesting in a wide range of the energy spectrum and restrained
exciton diffusion [30]. These features favor a decrease in carrier density to be transported exciton
diffusion
into [30].
the solar These
cells, features their
hampering favoroperational
a decrease in carrier density to be transported into the
performance.
solar cells, hampering their operational performance.
Figure
Figure1.1.Schematic illustration
Schematic illustrationofof
a atypical
typicaldye–sensitized
dye–sensitizedsolar cell.
solar cell.The
Thedevice
devicedescribes carrier
describes carrier
transport from the dye (after carrier excitation from the ground state, S o/S+ to the excited state, S*)
o +
transport from the dye (after carrier excitation from the ground state, S /S to the excited state, S*)
to the semiconductor. Redox electrolyte renews the carriers to the sensitizer for carrying out the
to the semiconductor. Redox electrolyte renews the carriers to the sensitizer for carrying out the
photovoltaic process. Reproduced with permission [26]. Copyright 2014. Elsevier.
photovoltaic process. Reproduced with permission [26]. Copyright 2014. Elsevier.
Attending
Attending totothetheabove
above device
device configuration
configuration from
from the DSSCs,
the DSSCs, organic
organic molecules
molecules have
have
been replaced by inorganic hybrid sensitizers, as in the case of Cd-free
been replaced by inorganic hybrid sensitizers, as in the case of Cd-free chalcogenides chalcogenides (in
form of quantum
(in form dots, QDs);
of quantum see Figure
dots, QDs); 2a [31–34]
see Figure and then
2a [31–34] andhalide perovskite
then halide (HPs) type
perovskite (HPs)
active
type active layers (in the form of bulk); see Figure 2b [35,36], with fascinatingsuch
layers (in the form of bulk); see Figure 2b [35,36], with fascinating features as
features
high absorption coefficient, long carrier diffusion length, and modulable
such as high absorption coefficient, long carrier diffusion length, and modulable optical optical proper-
ties depending
properties on the photomaterial
depending size and
on the photomaterial composition.
size and composition.These These
advantages allowallow
advantages for
the extension of the the light harvesting even to the IR range of the energy
for the extension of the the light harvesting even to the IR range of the energy spectrum, spectrum, im-
proving
improvingthe capability
the capability of the sensitizer
of the to generate
sensitizer to generate thethe
photocarriers
photocarriers required
required to to
favor
favor aa
high
highPCEPCE[37].
[37].InInthis
thiscontext,
context, thetheband
bandgapgapandandrelative
relativeband
bandpositions
positions ofofthe
theQDsQDsand and
bulk
bulkperovskites
perovskitescan canbebemodified
modifiedtotomatch
matchthe theETLETLand andHTLHTLand andthereby
therebyfacilitate
facilitatethe the
carrier injection to the selective contacts to generate the expected photoresponse
carrier injection to the selective contacts to generate the expected photoresponse [38,39]. [38,39].
Chalcogenide
Chalcogenide QDsQDs havehavereached
reacheda maximum
a maximum PCEPCE of 14.4% [40], while
of 14.4% HP bulk
[40], while HPfilmsbulkhave
films
achieved PCE close
have achieved PCEtoclose26% to [41,42], overpassing
26% [41,42], the actual
overpassing the performance
actual performanceof the Si- andSi-
of the
CdTe-based
and CdTe-basedtechnologies. Interestingly,
technologies. most of
Interestingly, the abovementioned
most of the abovementioned features of bothof
features kind
both
ofkind
activeof layers
activeare alsoare
layers useful
also for another
useful kind of kind
for another research application,
of research such as such
application, the fabri-
as the
cation of photodetectors
fabrication of photodetectorswith high
withresponsivity and specific
high responsivity detectivity
and specific [43–51].
detectivity [43–51].
The combination of HPs-based solar cells (PSCs) and Si-solar devices has promoted the
development of tandem solar cells, with PCE values of 33.2% [52]. The transparency and
thickness control of the active layers and the band gap tuning have been considered to be
promising devices for future commercialization. Despite the light-to-current transformation
being eventually improved in current prototypes of solar cells, the use of inorganic materials
is found to be restrained due to their ionic nature, which produces photocorrosion in
chalcogenides [53] and the formation of non-photoactive crystalline phases in HPs, as in
the case of iodide-HPs.
Energies2023,
Energies 2023,16,
16,5868
x FOR PEER REVIEW 44 of
of 35
37
Figure2.2.(a)
Figure (a)Schematic
Schematicrepresentation
representationofof
thethe working
working principle
principle of aofquantum
a quantum dot-sensitized
dot-sensitized solarsolar
cell
cell (QDSSC). A, B and C describe the possible ways of carrier transport: A–QDs-semiconductor, B–
(QDSSC). A, B and C describe the possible ways of carrier transport: A—QDs-semiconductor, B—
redox electrolyte–QDs, C–counter electrode to redox electrolyte. Yellow arrows indicate the possible
redox electrolyte—QDs, C—counter electrode to redox electrolyte. Yellow arrows indicate the possible
carrier recombination pathways in each component of the QDSSC; reproduced with permission [34].
carrier recombination
Copyright pathways
2018. American in each
Chemical component
Society. of the QDSSC;
(b) Schematic reproduced with
of a conventional permission
architecture of a [34].
per-
Copyright 2018.
ovskite solar cell American
(PSC) and Chemical Society. (b)
the corresponding Schematic
relative energyofpositions
a conventional architectureofofthe
of the components a
perovskite solar
solar device; cell (PSC) with
reproduced and the corresponding
permission relative energy
[36]. Copyright positions
2019. John Wileyof&the components
Sons, Inc. of the
solar device; reproduced with permission [36]. Copyright 2019. John Wiley & Sons, Inc.
The combination of HPs-based solar cells (PSCs) and Si-solar devices has promoted
As shown above,
the development reportssolar
of tandem have cells,
widely discussed
with the fundamentals
PCE values of 33.2% [52].ofThethe transparency
photovoltaic
effect in solar cells, which have been adopted to describe the way that
and thickness control of the active layers and the band gap tuning have been considered the active layers,
or
to be promising devices for future commercialization. Despite the light-to-currentphoto-
sensitizers, capture the sunlight to produce electricity through the formation of trans-
carriers,
formation which
beingare separatedimproved
eventually and transported through
in current the devices.
prototypes of solar This factthe
cells, has ledofsome
use inor-
researchers
ganic materialsto believe
is foundthat
tothe emergencedue
be restrained of the following
to their generation
ionic nature, whichof solar
producescells photo-
offers
more advantages
corrosion than the previous
in chalcogenides [53] and one, but it has of
the formation not been deeply explained
non-photoactive crystalline from the
phases
point of view
in HPs, as in of
theindividual components how the fabrication of innovative solar devices can
case of iodide-HPs.
be more efficient and exhibit enhanced long-term stability. More specifically, few reports
As shown above, reports have widely discussed the fundamentals of the photovoltaic
have consolidated the advantages/disadvantages of using different types of materials as
effect in solar cells, which have been adopted to describe the way that the active layers, or
active layers, where the photovoltaic effect starts, and some explanation about how the
sensitizers, capture the sunlight to produce electricity through the formation of photocar-
integration of these sensitizers into a coupled solar system can magnify the net performance
riers, which are separated and transported through the devices. This fact has led some
of a solar cell to be competitive with the actual commercialized Si-based ones has not been
researchers to believe that the emergence of the following generation of solar cells offers
widely highlighted.
more advantages than the previous one, but it has not been deeply explained from the
Overall, in this review, we highlight the current progress in the preparation of novel
point of view of individual components how the fabrication of innovative solar devices
active layer materials to fabricate more efficient organic, chalcogenide, and perovskite solar
can be more efficient and exhibit enhanced long-term stability. More specifically, few re-
cells, obtaining valuable information about their operational stability, and including the
ports have consolidated the advantages/disadvantages of using different types of materi-
use of less toxic species to produce more profitable solar technologies in the near future.
als as active layers, where the photovoltaic effect starts, and some explanation about how
Unlike actual reports where a general description of the characteristics of each component
the integration
of the solar deviceof these sensitizerstransporting
(electron/hole into a coupled andsolar system
active canismagnify
layers) provided, thewenetmainly
perfor-
mance of a solar cell to be competitive with the actual commercialized
focused on the light absorption and carrier separation/transport capabilities of suitable Si-based ones has
not been widely highlighted.
active layers to fabricate efficient solar cells from diverse device generations. Some critical
Overall, in such
disadvantages, this review,
as bandwe highlightmismatch,
structure the current lowprogress in thecoefficient,
absorption preparationpresence
of novel
active layer materials to fabricate more efficient organic, chalcogenide,
of defect sites for carrier recombination, and degradation of the photoactive crystalline and perovskite so-
lar cells, obtaining valuable information about their operational stability,
phase, are mentioned throughout the manuscript. Nevertheless, some benefits, such as a and including
the use band
tunable of lessgap
toxic species toon
depending produce moreofprofitable
the nature solar technologies
the photomaterial in the near
and a versatile fu-
surface
ture. Unlike actual reports where a general description of the characteristics
chemistry, are analyzed to understand the actual challenges of using several types of active of each com-
ponentoffering
layers, of the solar device (electron/hole
the opportunity to establishtransporting
an adequateand oneactive layers)
for future is provided, we
commercialization
mainly focused
purposes. on the light
In this context, absorption
a perspective and carrierand
on prominent separation/transport
suitable photomaterials capabilities of
acting as
suitable active layers to fabricate efficient
active layers in solar devices is also addressed. solar cells from diverse device generations.
Some critical disadvantages, such as band structure mismatch, low absorption coefficient,
Energies 2023, 16, 5868 5 of 35
The review is divided into three main topics: organic solar cells, chalcogenide solar
cells, and halide perovskite-based solar cells, and the application of novel photomaterials
as active layers in solar devices is thoroughly addressed. This order of showing the main
features of each active layer was chosen, considering the level of actual interest in the
development of this type of photomaterial. Although the current interest in some of them
has decreased, we consider these materials have opened the door to understanding the
photovoltaic process in a solar cell configuration and what the most relevant properties of
the material itself are to make it suitable for photovoltaics.
2. Progress in the Development of Active Layers for Efficient PV Devices

2.1. Organic Solar Cells
Organic solar cells (OSCs) have recently attracted attention worldwide since they are
one of the most promising energy sources due to their distinctive advantages, such as
light-weight mechanical flexibility, being colorful, translucent, nontoxic and being solution-
processable for huge area fabrication [54–58]. Over the last three decades, the area of OSCs
has made impressive progress in efficiency, which probably makes them a competitive
alternative to inorganic solar cells in the near future. In this review, we are going to classify
OSCs into three different groups based on their structure: binary, ternary, or tandem OSCs
and dye-sensitized solar cells (DSCs).
2.1.1. Binary, Ternary, and Tandem Organic Solar Cells

The first manufacture of organic photovoltaic solar cells was based on single organic
films inserted between two metal electrodes of different work functions [59,60]. Initially,
organic materials with p- and n-type conductivities are deposited on a transparent electrode,
and then the metal electrode is placed over them. The operation of OSCs consists of the
fact that sunlight is absorbed by organic layers, and produced excitons are dissociated to
electrons and holes at the interface amongst p- and n-type organic layers. Finally, holes and
electrons are diffused at the electrodes, generating electricity [59–61]. The PCEs reported
by these devices were really poor (around 0.01%), although they reached a significant 0.7%
with the incorporation of merocyanine dyes [62,63]. The next evolution in this area was
performed by introducing the heterojunction concept, in which two organic films with
special electron- or hole-transporting properties were sandwiched between the electrodes.
Tang and coworkers [64] manufactured the first organic photovoltaic device based on planar
heterojunction (PHJ) of two organic materials (phthalocyanine and perylene derivatives),
one carrier donor, and one carrier acceptor, which were used to distribute the excitons.
These organic layers were sandwiched between a transparent conducting oxide and a
semitransparent metal electrode, affording effective charge extraction. Although there were
very few donor/acceptor interfaces, this device was quite limited. This solar cell afforded
around 1% of PEC, which was the best result obtained for almost 10 years.
On the other hand, the development of conjugated polymers grew enormously in the
early 1990s, although their incorporation as single-layer devices was not initially successful
since the values of PCEs obtained by this type of material were less than 0.1% [65,66]. Nev-
ertheless, the discovery of photoinduced electronic transference between optically excited
conjugated polymers and the fullerene molecule (C60 ) [67,68], along with the elevated
photoconductivities shown by the addition of C60 to the conjugated polymers [69], allowed
the fabrication of devices based on polymer-fullerene bilayer heterojunction [70,71] or bulk
heterojunction (BHJ) [72–74]. This advance significantly increased the values of PCEs of the
corresponding devices for almost two decades (Table 1) [75–82]. The photoinduced electron
mobility favorably happens in the polymer-fullerene system when the electron in the ex-
cited state of the polymer is transferred to the fullerene, which is quite more electronegative
since the electron is injected from a p-type hole belonging to the conducting polymer,
donor (D), to the n-type electron from the conducting C60 molecule, acceptor (A) [83]. This
occurs because fullerene derivatives present a fully conjugated structure, which gives
them powerful electron-accepting and isotropic electron-transport abilities and favors
Energies 2023, 16, 5868 6 of 35
electron delocalization at the D:A interfaces [84,85]. Some time ago, it was believed that
fullerene materials such as PC61 BM ([6,6]-phenyl-C61 -butyric acid methyl ester) [86], F1
([6,6]-phenyl-C61 -propionic acid methyl ester) [87], and F [88] (Figure 3) were a basic com-
ponent for efficient operation of OSCs. However, this scenario has recently changed with
the appearance of non-fullerene acceptors (NFA) such as ITIC (3,9-bis(2-methylene-(3-(1,1-
dicyanomethylene)-indanone)-5,5,11,11-tetrakis(4-hexylphenyl)-ditheno [2,3-d:20 ,30 -d0 ]-s-
indaceno [1,2-b:5,6-b0 ]-dithiophene) [89], ITIC-Th1 (3,9-bis(2-methylene-(5&6-fluoro-(3-(1,1-
dicyanomethylene)-indanone)-5,5,11,11-tetrakis(4-hexylthienyl)-dithieno [2,3-d:20 ,30 -d0 ]-
s-indaceno [1,2-b:5,6-b0 ]-dithiophene) [90], FOIC [91], and Y6 ((2,20-((2Z,20Z)-((12,13-bis(2-
ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo [3,4-e]thieno [2,”300 :40 ,50]thieno
[20,30:4,5]pyrolo [3,2-g]thieno [20,30:4,5]thieno [3,2-b]indole-2,10-diyl)bis(methanylylidene))
bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile)) [92] (Figure 3),
which have increased notably the values of PCEs obtained [84,93]. The performance of
the NFA-based OSCs is closely related to the morphology of the functional layers and the
material processing, although in some cases the change in the stratification of the donor
and acceptor in the BHJ [94–96] and the chemical stability at the BHJ/contact interfaces [97]
have also played a decisive role in increasing the PCE values in these devices. The fast
development of OSCs based on NFA has caused these devices have crossed the PCE barrier
of 19% over the last years; see Table 1 [98–105]. Nevertheless, the broad range of donor
molecules previously used for fullerene OSCs provided a splendid library for direct use
in NFA OSCs. From the device perspective, excitons in NFA OSCs can be effectively
separated by negligible driving energies, which contributes to increasing their PCEs. Conse-
quently, this type of devices regularly shows elevated photocurrent and low voltage losses
simultaneously; nonetheless, fullerene-based OSCs present problems under low driving
energies frequently [99].
The PCE is calculated in OSCs by multiplying the values of open-circuit voltage (Voc ),
short-circuit current density (Jsc ), and a fill factor (FF). The value of Voc essentially depends
on the level of the donor’s HOMO and acceptor’s LUMO; the Jsc value is correlated to the
absorption and surface of the active layer; and the value of FF is related to the charge carrier
mobility. Table 1 includes the highest PCE values recently reported for binary OSCs [106].
Table 1. Photovoltaic performances of the recently reported binary OSCs.
Binary OSCs Jsc (mA/cm2 ) Voc (V) FF PCE (%) Stability Ref.
PF2:PC71 BM 15.00 0.75 0.744 8.40 72% of initial performance, 3.33 h, air [75]
DCPY2 22.24 0.90 0.650 13.02 90% of initial performance, 700 h, 85 ◦ C, air [77]
PM6:L8-BO 26.68 0.88 0.805 19.02 70% of initial performance, 130 h, air [107]
BTI-2T-CNA:IDIC 12.90 0.89 0.581 6.70 - [108]
BTP-eC9:BTP-ICBCF3 27.40 0.85 0.778 18.20 - [109]
PBDB-TF:HF-PCIC 17.24 0.89 0.710 10.90 90% of initial performance, 700 h, 130 ◦ C, air [110]
BTP-O-S 24.40 0.90 0.782 17.10 - [111]
PM6:BTP-eC9 27.88 0.86 0.804 19.31 70% of initial performance, 1000 h, air [98]
D18:L8-BO 26.70 0.89 0.800 19.00 74% of initial performance, 200 h, 80 ◦ C, air [101]
PEDOT:PSS 25.70 0.87 0.791 18.03 88% of initial performance, 1200 h, air [113]
In general, the working mechanism in bulky heterojunction OSC devices occurs as

follows: (a) photons are absorbed and excitons are generated; (b) excitons are diffused to
D/A interfaces; (c) excitons are dissociated in holes and electrons at D/A interfaces, which
are transported to the electrodes; see Figure 4 [114,115]. The BHJ system was first introduced
by combining two polymers with acceptor and donor properties in solution [116], which
solved the problems shown by PHJ systems. One of the best OSCs reported to date is
based on this type of structure due to its numerous advantages, such as semi-transparency,
light weight, and high mechanical flexibility [117–120]. However, BHJ structure has some
drawbacks, such as their morphology; it is difficult to control them since an inadequate
morphology could promote a fast charge recombination, affecting electron diffusion at the
interface between donor and acceptor moieties, which also influences the recombination
Energies 2023, 16, 5868 7 of 35
between holes and electrons [120]. These disadvantages could influence the industrial
development of OSCs based on BHJ because controlling the nanostructure of the donor and
acceptor is a complicated task. Accordingly, the performance of OSCs has been significantly
improved by efforts to design new donor and acceptor materials.
rgies 2023, 16, x FOR PEER REVIEW 8 of 37
In general, the working mechanism in bulky heterojunction OSC devices occurs as

follows: (a) photons are absorbed and excitons are generated; (b) excitons are diffused to
D/A interfaces; (c) excitons are dissociated in holes and electrons at D/A interfaces, which
are transported to the electrodes; see Figure 4 [114,115]. The BHJ system was first intro-
duced by combining two polymers with acceptor and donor properties in solution [116],
which solved the problems shown by PHJ systems. One of the best OSCs reported to date
is based on this type of structure due to its numerous advantages, such as semi-transpar-
ency, light weight, and high mechanical flexibility [117–120]. However, BHJ structure has
some drawbacks, such as their morphology; it is difficult to control them since an inade-
quate morphology could promote a fast charge recombination, affecting electron diffusion
at the interface between donor and acceptor moieties, which also influences the recombi-
nation between holes and electrons [120]. These disadvantages could influence the indus-
trial development of OSCs based on BHJ because controlling the nanostructure of the do-
Figure 3. Chemical structure of fullerene derivatives such as PC61BM [86], F1 [87], and F [88] and
nor and acceptor
Figure is
3. aChemical
complicated task.
structure ofAccordingly, the performance
fullerene derivatives such as PC61of BM OSCs has[87],
[86], F1 beenand F [88] and
NFA derivatives such as ITIC [89], ITIC-Th1 [90], FOIC [91], and Y6 [92] employed in OSCs.
significantlyNFA
improved by efforts
derivatives such asto design
ITIC new donor
[89], ITIC-Th1 [90],and
FOICacceptor
[91], andmaterials.
Y6 [92] employed in OSCs.
The PCE is calculated in OSCs by multiplying the values of open-circuit voltage (Voc),
short-circuit current density (Jsc), and a fill factor (FF). The value of Voc essentially depends
on the level of the donor’s HOMO and acceptor’s LUMO; the Jsc value is correlated to the
absorption and surface of the active layer; and the value of FF is related to the charge
carrier mobility. Table 1 includes the highest PCE values recently reported for binary OSCs
[106].
Table 1. Photovoltaic performances of the recently reported binary OSCs.
Binary OSCs Jsc (mA/cm2) Voc (V) FF PCE (%) Stability Ref.
PF2:PC71BM 15.00 0.75 0.744 8.40 72% of initial performance, 3.33 h, air [75]
DCPY2 22.24 0.90 0.650 13.02 90% of initial performance, 700 h, 85 °C, air [77]
BTI-2T-CNA:IDIC 12.90 0.89 0.581 6.70 - [108]
BTP-eC9:BTP-ICBCF3 27.40 0.85 0.778 18.20 - [109]
PBDB-TF:HF-PCIC 17.24 0.89 0.710 10.90 90% of initial performance, 700 h, 130 °C, air [110]
BTP-O-S 24.40 0.90 0.782 17.10 - [111]
PM6:L8-BO Figure 4. (a) Steps 25.81 involved 0.90 0.801
in energy production18.69upon86% of initial performance,
illumination 500 h, air [112]
Figure 4. (a) Steps involved in energy production upon (From exciton
illumination generation
(From excitonuntil
generation until
PM6:BTP-eC9 charge carrier27.88 collection). 0.86
(b) Band0.804
diagram 19.31
of the 70% of initial generation
photocurrent performance,mechanism
1000 h, air in a BHJ [98]
charge carrier collection). (b) Band diagram of the photocurrent generation mechanism in a BHJ solar
D18:L8-BO 26.70
solar cell. Reproduced with0.89 0.800 [115]. 19.00
permission Copyright 74% of initial
2018. performance, 200 h, 80 °C, air
Elsevier. [101]
PEDOT:PSS cell.
25.70Reproduced0.87 with0.791
permission [115]. Copyright
18.03 88% of initial2018. Elsevier. 1200 h, air
performance, [113]
The main limitation of OSCs is that organic materials show an absorption width of
only about 0.5 eV, so the binary single-junction can only take advantage of a small part of
the solar radiation, hindering the improvement in device efficiency [84,121]. For these rea-
sons, the introduction of a ternary blend based on a dye, nanoparticle, polymer, or small
molecule into the device could solve the aforementioned problems [100], and ternary
Energies 2023, 16, 5868 8 of 35
The main limitation of OSCs is that organic materials show an absorption width of
only about 0.5 eV, so the binary single-junction can only take advantage of a small part
of the solar radiation, hindering the improvement in device efficiency [84,121]. For these
reasons, the introduction of a ternary blend based on a dye, nanoparticle, polymer, or small
molecule into the device could solve the aforementioned problems [100], and ternary OSCs
have recently focused the attention of the scientific community because these devices could
Energies 2023, 16, x FOR PEER REVIEW
afford great PCE values (Table 2). Basically, ternary OSCs are formed by three units, 9 two
of 37
acceptor moieties, and one donor (or two donor moieties and one acceptor) (Figure 5) [122].
Figure5.5. Schematic,
Figure Schematic, working
working principles
principles in
internary
ternaryOSCs.
OSCs. (a)
(a) Mechanism
Mechanism of ofcharge
chargetransportation
transportation
(additional donor functions for charge transport). (b) Mechanism of energy transfer
(additional donor functions for charge transport). (b) Mechanism of energy transfer (from (from photo-
photo-
excited sensitizer to host donor). (c) The parallel like mechanism (formation of independent hole
excited sensitizer to host donor). (c) The parallel like mechanism (formation of independent hole
transport network from the additional donor). (d) The alloy model (coupling of new charge-transfer
transport network from the additional donor). (d) The alloy model (coupling of new charge-transfer
state by host donor). The arrows show the proposed path for charge carrier and charge transporta-
state
tion.by host donor).
Reproduced Thepermission
with arrows show the Copyright
[122]. proposed path forJohn
2018. charge carrier
Wiley andand charge
Sons, Inc. transportation.
Reproduced with permission [122]. Copyright 2018. John Wiley and Sons, Inc.
Firstly, the third component has been used as a sensitizer, assisting in extending the
Firstly, the third component has been used as a sensitizer, assisting in extending the
maximum absorption of the acceptor and the donor based on the 1-(3-methoxycarbonyl)
maximum absorption of the acceptor and the donor based on the 1-(3-methoxycarbonyl)
propyl-1-phenyl [6,6] methano-fullerene (PCBM) matrix. In addition, considering the first
propyl-1-phenyl [6,6] methano-fullerene (PCBM) matrix. In addition, considering the first
reports about ternary OSCs, scientists have employed a huge variety of organic entities as
reports about ternary OSCs, scientists have employed a huge variety of organic entities
third components, which act as an efficient charge transport pathway, boosting charge
as third components, which act as an efficient charge transport pathway, boosting charge
transport and exciton dissociation for OSC devices [100]. These ternary devices, which are
transport and exciton dissociation for OSC devices [100]. These ternary devices, which are
mainly based on polymer/small molecule/PCBM, polymer/PCBM/non-fullerene, and pol-
mainly based on polymer/small molecule/PCBM, polymer/PCBM/non-fullerene, and
ymer/ICBA/PCBM (ICBA, indene-C60 bis-adduct), reported PCE values above 10% (Figure
polymer/ICBA/PCBM (ICBA, indene-C60 bis-adduct), reported PCE values above 10%
6) [123–125]. Ternary OSCs can be classified in four categories according to their function:
(Figure 6) [123–125]. Ternary OSCs can be classified in four categories according to their
charge transfer,
function: charge energy
transfer,transfer, parallel like,
energy transfer, andlike,
parallel alloyand
models. It is important
alloy models. to mention
It is important to
that the most efficient ternary OSCs operate under an alloy-like model since
mention that the most efficient ternary OSCs operate under an alloy-like model since the gradual
the
changeschanges
gradual in Voc depend
in V on the third
depend element.
on the third element.
oc
Table 2. Photovoltaic performances of the recently reported ternary OSCs.
Ternary OSCs Jsc (mA/cm2) Voc (V) FF (%) PCE (%) Stability Ref.
TO:PEDOT:PSS (S11) 17.62 0.95 0.701 11.78 70% of initial performance, 1008 h, 85 °C, air [126]
PM6:PY-V-γ:PFBO-C12 25.80 0.91 0.770 18.00 80% of initial performance 1000 h, air [127]
PEDOT:PSS:LiF 25.60 0.86 0.742 16.70 55% of initial performance, 360 h, air [128]
PM6:Y6:7.5%FPDI-2PDI 27.47 0.85 0.772 18.00 55% of initial performance, 30 h, air [129]
PM6:M-Cl:O-Cl 27.40 0.87 0.762 18.10 - [130]
D18:Y6:SN-O 26.80 0.88 0.781 18.30 - [131]
PBQx-TF:eC9-2Cl:F-BTA3 26.70 0.88 0.809 19.00 - [105]
PBDB-T-2F:Y6:SF(BR)4 29.31 0.89 0.800 20.87 - [132]
PBQx-TCl:PBDB-TF:eC9-2Cl 27.15 0.89 0.811 19.51 - [133]
Energies 2023, 16, 5868 9 of 35
Table 2. Photovoltaic performances of the recently reported ternary OSCs.
Ternary OSCs Jsc (mA/cm2 ) Voc (V) FF (%) PCE (%) Stability Ref.
TO:PEDOT:PSS (S11) 17.62 0.95 0.701 11.78 70% of initial performance, 1008 h, 85 ◦ C, air [126]
PM6:PY-V-γ:PFBO-C12 25.80 0.91 0.770 18.00 80% of initial performance 1000 h, air [127]
PEDOT:PSS:LiF 25.60 0.86 0.742 16.70 55% of initial performance, 360 h, air [128]
PM6:Y6:7.5%FPDI-2PDI 27.47 0.85 0.772 18.00 55% of initial performance, 30 h, air [129]
PM6:M-Cl:O-Cl 27.40 0.87 0.762 18.10 - [130]
D18:Y6:SN-O 26.80 0.88 0.781 18.30 - [131]
PBQx-TF:eC9-2Cl:F-BTA3 26.70 0.88 0.809 19.00 - [105]
PBDB-T-2F:Y6:SF(BR)4 29.31 0.89 0.800 20.87 - [132]
PBQx-TCl:PBDB-TF:eC9-
27.15 0.89 0.811 19.51 - [133]
2Cl
Since single organic materials have the ability to absorb at different wavelength regions
between the blue and the infrared regions, “tandem” architectures have been designed
to accomplish higher performances in OSCs with better use of near-infrared (NIR) solar
energy [134]. Tandem OSCs are formed by two sub-cells, a front and back sides, both made
of organic materials. For certain types of OSCs with a specific bandgap and absorption
region, the balance between the loss of photon energy by thermalization and spectrum
unitization is limited [135]. However, in tandem OSCs, the absorption spectrum can be
extended by using a wide bandgap sub-cell to employ high-energy photons and another
narrow bandgap sub-cell for employing low energy photons [136]. In this context, the Voc
value presented by tandem OSCs is normally higher than that of binary or ternary OSCs
because it is the sum of those of the two sub-cells, whereas the Jsc value usually derives
from the sub-cell with relatively lower Jsc ; hence, the PCE in tandem OSCs depends directly
to the balance between Voc and Jsc for each sub-cell, which is decisive for the high efficiency
of the device [134,137]. At the current stage, the PCE values of tandem OSCs are very
similar to those presented by binary or ternary OSCs, as seen in Table 3. The main difficulty
for the development of tandem OSCs is related to their design since the current of each
sub-cell has to be matched, so the total current of the device is limited by the lowest current
generating sub-cell [85]. Another limitation of this device is related to the low efficiency
presented by organic materials for narrow band gap sub-cells, which would allow the use
of the NIR region of the solar spectrum.
Table 3. Photovoltaic performances of the recently reported tandem OSCs.
Tandem OSCs (Front/Back Cell) Jsc (mA/cm2 ) Voc (V) FF PCE (%) Stability Ref.
PTB7-Th:BTPV-4F/PTB7-Th:BTPV-
14.50 1.65 0.690 16.40 - [120]
4F:PC71 BM
PBDT [2F]T:PC71 BM/PCE10:PC61 BM 7.10 1.61 0.705 8.30 - [138]
PBDB-T:F-M/PTB7-Th:O6T-
14.35 1.64 0.737 17.36 96% of initial performance, 3984 h, air [139]
4F:PC71 BM
PM7:TfIF-4Cl/PTB7-
14.59 1.64 0.780 18.71 95% of initial performance 500 h, air [140]
Th:COi8DFIC:PC71BM
PM6:GS-ISO/PM6:BTP-eC9 13.14 2.01 0.768 20.27 87% of initial performance, 450 h, air [141]
2.1.2. Dye-Sensitized Solar Cells

Conceptually similar to the BHJ, there is another broad research field based on
DSSCs. The early development of these devices was performed by the Grätzel research
group [25,142–144]. As discussed previously, DSSCs have greatly focused the attention
of the scientific community over the last few years due to their promising performance
and low fabrication cost [145,146]. It is important to highlight that water-based electrolytes
DSSCs are being developed owing to their interesting advantages such as reduced volatility,
non-flammability, and environmental compatibility, affording a PCE value over 7% [147].
Additionally, DSSCs are able to be produced on a large scale and present a commercial
application for self-powering systems and portable electronics [148,149]. On the other hand,
Energies 2023, 16, 5868 10 of 35
specifically DSSCs prepared with copper-complex-based redox mediator have shown great
progress in obtaining PCE values close to 13%, since their Voc can achieve values over
1.0 V [148,149], lower compared to the values observed by high performance tandem OSCs;
see Table 3. However, these devices exhibit low Jsc values, considerably reducing their
PCE performance. Probably, the principal disadvantage of DSSCs compared with other
OSCs is related to the relatively low PCE values reported for these devices; it is difficult to
find DSSCs with PCE values over 14%. On the contrary, the most important advantage of
DSSCs is their ability to exhibit outstanding stability, maintaining high percentages of their
initial PCE after long periods of time.
2.1.3. Comparison of J–V Curves and Normalized PCE vs. Time for Different Types of
Organic Solar Cells
Binary, ternary, and tandem OSCs or DSSCs are devices with different characteristics
that are determined by their values of Voc , fill factor (FF) and Jsc . These variables are
defined by the current density and voltage (J–V curves) properties of the solar cells [99].
These parameters are closely related to the photoactive materials (acceptor and donor
materials). Thus, the number of free carriers collected at the electrodes at zero applied
potential (Voc = 0) is what determines the value of Jsc . The energy difference amongst the
HOMO and LUMO orbitals of the acceptor and donor materials influences the highest
voltage that a solar cell could extract for an external circuit, ascribed to the value of Voc . For
example, in PM1:BTP-eC9 systems, device efficiency improved from 17.86% to 19.10% with
TCB processing. It is important to comment that the TCB-ISM device exhibits the highest
PCE value (19.31%) reported to date for a binary OSCs; see Figure 6a [98]. Additionally,
the ternary blend PBQx-TCl:PBDB-TF:eC9-2Cl displays a maximum PCE of 19.51%, a Voc
of 0.886 V, a Jsc of 27.15 mA cm−2 , and an FF of 81.14%; see Figure 6b [133]. The tandem
OSC based on ICLs of e-TiOx/PEDOT:PSS system achieved a Voc value over 2.0 V, which is
considerably higher than the values of Voc showed by binary or ternary OSCs, affording
a PCE value of 20.27%; see Figure 6c [141]. It is important to highlight that DSSCs with
ZS4 performed a Jsc of 16.3 mA cm−2 , as well as a great Voc value of 1.05 V, accomplishing
an impressive PCE of 13.2% under AM1.5G sunlight. This efficiency is the highest one
reported for copper-electrolyte-based DSSCs with a single sensitizer; see Figure 6d [145].
Having discussed the typical performance of the binary, ternary, tandem OSCs and
DSSCs, it is pivotal to focus on studying their stability over time. To address this point, we
highlight the stability presented by some of the previously mentioned devices; see Figure 7.
The operational stability of binary PM6:BTP-eC9-based OSCs showed a stronger initial
decay in PCE, dropping a 17% efficiency during the first 75 h when DIO (1,8-diiodooctane)
was used as an additive, while the efficiency of the TCB (1,3,5-trichlorobenzene) treated
device only decreased by 7% at the same time. After 1000-h simulated 1-sun illumination
stress test at maximum power point (MPP), the TCB-treated device maintained a 78% of
initial efficiency; see Figure 7a [98]. The ternary PBDB-TF/HC-PCIC/PC71 BM experienced
an intense drop in efficiency (15%) after only 1 h. However, its efficiency remained constant
during the following 10 h; see Figure 7b [110]. Tandem cells dropped sharply in the first 10 h
and became stable within 456 h under continuous 1 sun illumination; see Figure 7c [141].
Finally, DSSC fabricated with ZS4 exhibited excellent stability, keeping 95% of their initial
PCE under continuous light soaking at 45 ◦ C for 1000 h; see Figure 7d [145]. In general,
binary and ternary OSCs reported high PCE values (~20%); however, most of these devices
are not very stable over time since their efficiency decreases significantly after a few hours.
In contrast, although the PCE values shown by DSCs are moderate (~14%) compared to
binary or ternary OSCs, the most important benefit of these types of devices is possibly
their capability to display outstanding stability, maintaining elevated percentages of their
initial PCE after long periods of time.
19.51%, a Voc of 0.886 V, a Jsc of 27.15 mA cm−2, and an FF of 81.14%; see Figure 6b [133].
The tandem OSC based on ICLs of e-TiOx/PEDOT:PSS system achieved a Voc value over
2.0 V, which is considerably higher than the values of Voc showed by binary or ternary
OSCs, affording a PCE value of 20.27%; see Figure 6c [141]. It is important to highlight
that DSSCs with ZS4 performed a Jsc of 16.3 mA cm−2, as well as a great Voc value of 1.05
Energies 2023, 16, 5868 V, accomplishing an impressive PCE of 13.2% under AM1.5G sunlight. This efficiency is 11 of 35
the highest one reported for copper-electrolyte-based DSSCs with a single sensitizer; see
Figure 6d [145].
illumination stress test at maximum power point (MPP), the TCB-treated device main-
tained a 78% of initial efficiency; see Figure 7a [98]. The ternary PBDB-TF/HC-
PCIC/PC71BM experienced an intense drop in efficiency (15%) after only 1 h. However, its
Figure 6.6. (a)(a)
J–VJ–V
curves for thefor
curves DIO theprocessed
DIO and TCB processed
processed and OSCs based on PM6:BTP-eC9.
Figure
efficiency remained
Reproduced under the constant
terms of the during
CC-BY the following
license 10 h;
[98]. Copyright seeTCB
Figure
2023.
processed
7bAuthors.
The
OSCs based
[110]. Tandem
Published cells
by
on PM6:BTP-eC9.
Reproduced
droppedNature.
Springer under
sharply (b)in
J–V the
the terms
first
curves 10the
of hof
andthe
OPV CC-BY
became
cells license
stable
based within
on the [98].
456Copyright 2023. The1 sun
h under continuous
PBQx-TCl:eC9-2Cl, PBDB-TF:eC9-2Cl,Authors. Published by
illumination;
Springer
and see Figure
Nature. (b) J–V
PBQx-TCl:PBDB-TF:eC9-2Cl 7c curves
[141]. Finally, DSSC cells
of thesystems.
(0.5:0.5:1.2) OPV fabricated
basedwith
Reproduced on
with ZS4
the exhibited excellent
PBQx-TCl:eC9-2Cl,
permission [133]. Copy- PBDB-TF:eC9-2Cl,
stability,
right 2023.keeping
John Wiley95% andof Sons.
their (c)
initial
ThePCE underof
J–V curves continuous
tandem OSCs light soaking
based at 45
on ICLs of°C for 1000
e-TiOx/PE-
and PBQx-TCl:PBDB-TF:eC9-2Cl2 (0.5:0.5:1.2) systems. Reproduced with permission [133]. Copyright
DOT:PSS under 7d
h; see Figure AM[145].
1.5G, In mW/cm .binary
100general, Reproduced with permission
and ternary [141]. Copyright
OSCs reported high PCE2021. Else-
values
2023.
vier
(~20%); John
Inc. (d) Wiley
J–V
however, curvesand
most Sons.
of of
thethese
DSCs(c) TheZS4
with
devices J–V curves
and
are notZS5very ofstable
tandem
measured OSCs
under
over based
AM1.5G
time since onefficiency
ICLs Re-
illumination.
their of e-TiOx/PEDOT:PSS
produced
under AMwith permission
1.5G, 100 after [145].
mW/cm 2
Copyright 2023. John Wiley and Sons.
decreases significantly a few .hours.
Reproduced
In contrast, with permission
although the PCE[141].
valuesCopyright
shown by 2021. Elsevier Inc.
DSCs
(d) J–V are moderate
curves (~14%)
of the DSCs compared
with ZS4 to binary
and ZS5 or ternary
measured OSCs,under
the most important
AM1.5G ben-
illumination. Reproduced
Having
efit of discussed
these types the typical
of devices performance
is possibly of the binary,
their capability ternary,
to display tandem OSCs
outstanding and
stability,
with
DSSCs, permission
it is pivotal [145].
to focusCopyright
on 2023.
studying John
their Wileyover
stability andtime.
Sons.To address this point,
maintaining elevated percentages of their initial PCE after long periods of time.
we highlight the stability presented by some of the previously mentioned devices; see
Figure 7. The operational stability of binary PM6:BTP-eC9-based OSCs showed a stronger
initial decay in PCE, dropping a 17% efficiency during the first 75 h when DIO (1,8-diio-
dooctane) was used as an additive, while the efficiency of the TCB (1,3,5-trichlorobenzene)
treated device only decreased by 7% at the same time. After 1000-h simulated 1-sun
Figure 7. (a) Light stability tests for PM6:BTP-eC9-based OSCs with different treatments, all OSCs
Figure 7. (a) Light stability tests for PM6:BTP-eC9-based OSCs with different treatments, all OSCs
were encapsulated and stored under continuous illumination equivalent to 1 sun in air. Reproduced
were
under encapsulated and stored
the terms of the CC-BY licenseunder continuous
[98]. Copyright illumination
2023. The equivalent
Authors. Springer Nature. to(b)1PCEs
sun in air. Reproduced
for the the
under devices based
terms of on
thePBDB-TF:HC-PCIC, PBDB-TF:HC-PCIC:PC
CC-BY license [98]. Copyright 2023. 71BM, and PBDB-TF:PC71BM
The Authors. Springer Nature. (b) PCEs
(CN) blended films after thermal treatment at 130 °C for various times. Reproduced with permission
for the
[110]. devices© based
Copyright on PBDB-TF:HC-PCIC,
2018. American PBDB-TF:HC-PCIC:PC
Chemical Society. (c) The BM,
cell degradation diagram of71the and PBDB-TF:PC71 BM
tandem
(CN) blended
cells with variousfilms after thermal
ICLs. Reproduced with treatment at 130
permission [141]. ◦ C for2021.
Copyright various times.
Elsevier. Reproduced with permis-
(d) Evolution
of PCE of DSCs based on dye ZS4 measured under standard AM1.5G sunlight during continuous
sion [110]. Copyright © 2018. American Chemical Society. (c) The cell degradation diagram of
light soaking at 45 °C for 1000 h. Reproduced with permission [145]. Copyright 2023. John Wiley
the
and tandem
Sons. cells with various ICLs. Reproduced with permission [141]. Copyright 2021. Elsevier.
(d) Evolution of PCE of DSCs based on dye ZS4 measured under standard AM1.5G sunlight during
2.2. Chalcogenide Solar Cells
continuous light soaking at 45 ◦ C for 1000 h. Reproduced with permission [145]. Copyright 2023.
Chalcogenide solar cells are a class of thin-film solar cells that utilize semiconductor
John Wiley and Sons.
materials from the chalcogenide group (e.g., sulfur, selenium, tellurium) to absorb the so-
lar radiation, produce photocarriers, and thereby generate electricity. These solar cells
have the advantage of being cost-effective, with good conversion efficiencies. They typi-
cally consist of a substrate, transparent conductive oxide layer, p-type and n-type chalco-
genide layers, and an intrinsic layer. Here, we will explain some characteristics of binary,
ternary, and quaternary chalcogenides usually employed for the fabrication of solar de-
vices.
Energies 2023, 16, 5868 12 of 35
2.2. Chalcogenide Solar Cells

Chalcogenide solar cells are a class of thin-film solar cells that utilize semiconductor
materials from the chalcogenide group (e.g., sulfur, selenium, tellurium) to absorb the solar
radiation, produce photocarriers, and thereby generate electricity. These solar cells have
the advantage of being cost-effective, with good conversion efficiencies. They typically
consist of a substrate, transparent conductive oxide layer, p-type and n-type chalcogenide
layers, and an intrinsic layer. Here, we will explain some characteristics of binary, ternary,
and quaternary chalcogenides usually employed for the fabrication of solar devices.
2.2.1. Binary, Ternary, and Quaternary Chalcogenides

Binary chalcogenide solar cells use semiconductor materials composed of two ele-
ments, one from the chalcogenide group, such as sulfur (S), selenium (Se), or tellurium (Te)
and a metal. These materials are abundant and relatively low-cost, making them attractive
for solar cell applications. The structure of binary chalcogenide solar cells typically consists
of a substrate, a transparent conductive oxide layer (TCO), a p-type chalcogenide layer,
an intrinsic layer, and an n-type chalcogenide layer. The TCO layer allows light to pass
through while providing electrical conductivity. The p-type and n-type chalcogenide layers
help in creating an electric field and facilitating the movement of charge carriers. When
sunlight is absorbed by the chalcogenide layers, electron-hole pairs are created, which are
then collected to generate an electric current [150]. Among the main types of binary solar
cells are as follows:
Cadmium Telluride (CdTe)

A thin-film of CdTe semiconductor absorbs radiation in the visible part of the spectrum,
creating electron-hole pairs. The generated electrons and holes are separated at the junction,
resulting in a flow of electric current [150]. One of the examples of efficient CdTe solar
devices has been described by Rashid and coworkers [151] where a silicon carbide (3C–SiC)-
based buffer layer was introduced into the preparation of CdTe films and subsequently
device fabrication. By improving the crystallinity of the active layer and providing an
adequate heterojunction of the chalcogenide and the 3C-SiC, a PCE value up to 17.29%;
see Figure 8a. Clearly, diverse device optimizations have been incorporated during the
fabrication of CdTe solar cells, allowing PCE values up to 23% [106]. Among its advantages
are cost-effectiveness due to abundant and low-cost materials and compatibility with
large-scale manufacturing. However, its main problem is the use of toxic materials [152].
To improve the stability of these devices and avoid the possible lixiviation of Cd, the
incorporation of small amounts of cupper during chalcogenide etching process (chemical
etch), can be carried out [153]. In this context, optimized CdTe solar devices can preserve
80% of initial performance for close to 1200 h in air; see Figure 8b.
Cadmium Selenide (CdSe)

These thin-film solar cells operate in the same way as CdTe ones, changing the layer
that absorbs the sun’s photons for one of CdSe [154].
Lead Sulfide (PbS)

These solar cells are known for their ability to efficiently absorb infrared light. PbS
solar cells can be fabricated using low-cost solution-based processes [155]. They have
shown promise for applications in low-light conditions. For PbS solar cells, PCEs have
reached values up to 13.8% [156].
Meanwhile, ternary and quaternary chalcogenides solar cells are a type of thin-film
solar cells that are composed of three or four different elements from groups 11–16 of the
periodic table, typically including a combination of metal, chalcogen, and sometimes halide
elements [157]. These materials have unique electronic properties, such as their tunable
bandgap and high absorption coefficient, that make them promising candidates for use in
Energies 2023, 16, 5868 13 of 35
solar cells. Some of the principal ternary and quaternary chalcogenides used in solar cell
applications are as follows:
Copper-Indium-Gallium Selenide (CIGS)

The CIGS solar cell structure consists of several layers, including a back contact, a
p-type CIGS absorber layer, an n-type buffer layer, and a transparent front contact [158].
CIGS solar cells have advantages including high efficiency, low temperature coefficient,
and the ability to be manufactured using a variety of techniques [158]. The high efficiency
of CIGS solar cells is due to the material’s ability to absorb a large fraction of the solar
spectrum, including both visible and infrared light [159,160]. Additionally, CIGS solar
spectrum,
cells have aincluding both visible
low temperature and infrared
coefficient light [159,160].
[161], meaning Additionally,
their efficiency CIGS
is less solar
sensitive
cells have a low temperature coefficient [161], meaning their efficiency
to changes in temperature compared to other types of solar cells [162]. CIGS solar cells is less sensitive to
changes in temperature compared to other types of solar cells [162].
have achieved record PCE of up to 23.35% [163]. The main drawbacks that CIGS cells CIGS solar cells have
achieved
have record
are the usePCE of up
of toxic to 23.35%
materials [163].
and the The
highmain drawbacksthat
temperatures thatare
CIGS
neededcells for
have are
their
the use of toxic materials and the high temperatures that are needed
manufacture [164]. On the other hand, by taking advantage of the band gap modulation, for their manufacture
[164]. can
CIGS On the other
reach hand,
PCEs by taking
higher advantage
than 21.8% [165],ofwhich
the band gap modulation,
becomes useful for CIGS can reach
the fabrication
PCEs higher than 21.8% [165], which becomes useful for the fabrication
of tandem devices; see Figure 8c. Some optimized devices for this type of active of tandem devices;
layer
can keep ~88% of initial efficiency in harsh conditions of H2 O/O2 for close to 350 h initial
see Figure 8c. Some optimized devices for this type of active layer can keep ~88% of [166];
efficiency
see Figure in8d.harsh conditions of H2O/O2 for close to 350 h [166]; see Figure 8d.
Figure
Figure 8. 8. Operational
Operational performance
performance and and stability
stability of
of some
some chalcogenide
chalcogenide solar
solar cells.
cells. (a)
(a) J–V
J-V curve
curve of
of
CdTe
CdTe solar
solar cell.
cell. Reproduced
Reproduced with permission
permission [151] Copyright
Copyright 2022,
2022, Elsevier.
Elsevier. (b) Stability
Stability of of CdTe
CdTe
solar cell
solar cell in
in function
function of etching cycles. Reproduced with permission [153]. Copyright 2017. Elsevier. Elsevier.
(c) J-V curve of CIGS solar cell in function of modulated band gap. Reproduced with
(c) J–V curve of CIGS solar cell in function of modulated band gap. Reproduced with permission [165] permission
[165] Copyright
Copyright 2020. 2020. Elsevier.
Elsevier. (d) Stability
(d) Stability of CIGS
of CIGS solar solar cells under
cells under short-circuit
short-circuit condition
condition (SCC)(SCC)
and
and open-circuit condition (OCC). Reproduced with permission [166]. Copyright
open-circuit condition (OCC). Reproduced with permission [166]. Copyright 2015. Elsevier. 2015. Elsevier.
Copper-Zinc-TinSulfide
Copper-Zinc-Tin Sulfide(CZTS)
(CZTS)
CZTS has
CZTS has aa similar
similar structure
structure to
to CIGS
CIGS and
and offers
offers the
the advantage
advantage of
of using
using abundant
abundant andand
non-toxic elements [167]. The CZTS solar cell structure typically consists of
non-toxic elements [167]. The CZTS solar cell structure typically consists of a molybdenuma molyb-
denum
back back contact,
contact, a CZTS aabsorber
CZTS absorber
layer, alayer,
buffera layer,
bufferand
layer, and a transparent
a transparent conductive
conductive oxide
oxide front contact [168]. CZTS solar cells have lower PCE than CIGS solar cells,
front contact [168]. CZTS solar cells have lower PCE than CIGS solar cells, reaching valuesreaching
values
of up toof11.0%
up to[169].
11.0% [169].
Copper-Zinc-Tin Selenide (CZTSe)

CZTSe solar cells operate in a similar manner to other thin-film solar cells. They con-
sist of a substrate, a back contact, a CZTSe absorber layer, a buffer layer, and a transparent
Energies 2023, 16, 5868 14 of 35
Copper-Zinc-Tin Selenide (CZTSe)

CZTSe solar cells operate in a similar manner to other thin-film solar cells. They consist
of a substrate, a back contact, a CZTSe absorber layer, a buffer layer, and a transparent
conductive oxide front contact [168]. CZTSe solar cells are like copper indium gallium
selenide (CIGS) solar cells in terms of their crystal structure, which is a kesterite struc-
ture [170]. CZTSe has a higher bandgap than CIGS, which means that it can absorb a larger
portion of the solar spectrum and potentially achieve higher efficiencies. CZTSe also has
the advantage of being composed of earth-abundant and non-toxic materials. CZTSe solar
cells face several challenges, such as low open-circuit voltage and fill factor due to the
presence of defects and recombination centers in the absorber layer [171]. PCE currently
reached values ~12.5% [172].
Cadmium-Free Copper Zinc Tin Sulfide (CZTSSe)

In cadmium-free CZTS solar cells, alternative cadmium sulfide. This allows for the
elimination of toxic cadmium, resulting in a more environmentally friendly and sustain-
able solar cell technology [173]. CZTSSe solar cells have achieved PCE values of up to
12.6% [174].
Due to the fact that most of the fabricated chalcogenide devices do not report stability
measurements, Table 4 shows a summary of the conversion efficiencies of the main solar
cells of this generation and their corresponding parameters.
Table 4. Photovoltaic parameters of main chalcogenide-based solar cells.
JSC VOC
Active Layer FF PCE Ref.
(mA/cm2 ) (V)
CdTe 26.30 0.81 0.808 17.3 [151]
CdTe 30.25 0.87 0.794 21.0 [175]
CdTe 31.69 0.88 0.785 22.1 [106]
CIGS 39.80 0.72 0.765 21.8 [165]
CIGS 39.68 0.73 0.804 23.4 [163]
CIGS 39.33 0.73 0.805 23.3 [176]
CZTS 21.77 0.71 0.826 10.0 [177]
CZTS 21.74 0.73 0.693 11.0 [169]
CZTSe 38.30 0.46 0.663 11.8 [178]
CZTSe 37.40 0.49 0.682 12.5 [172]
CZTSSe 35.60 0.51 0.697 12.6 [174]
CZTSSe 35.20 0.51 0.698 12.6 [179]
2.2.2. Chalcogenide Tandem Solar Cells

Chalcogenide tandem solar cells have emerged as a promising candidate for achieving
high-efficiency photovoltaic devices. In this type of solar cells, two or more different
chalcogenide-based semiconductors with diverse bandgaps are assembled to absorb a
broader range of the solar spectrum; see Figure 9a [180]. The upper cell absorbs the higher-
energy photons, while the lower cell absorbs the lower-energy photons that pass through
the upper cell [181]. This allows for a more efficient utilization of the solar spectrum and can
lead to a higher overall efficiency. Chalcogenide-based materials, such as copper indium
gallium selenide (CIGS), cadmium telluride (CdTe) [182], lead sulfide (PbS) [183,184]
and earth-alternative materials such as kesterite-based chalcogenides [185,186] have been
extensively studied for use in tandem solar cells. CIGS is particularly attractive due to its
high absorption coefficient and tunable bandgap, making it suitable for use in both the top
and bottom cells of the tandem device. Besides, CIGS tandem solar cells have high carrier
mobility, scalability, potential for low-cost, and compatibility with alternative materials.
In recent years, perovskite-chalcogenide tandem solar cells have gained significant
attention due to their high-power conversion efficiencies and potential for low-cost, scalable
production [187–190]. Perovskites are inorganic materials that have unique optical proper-
ties. For more details, see Section 2.3. This kind of tandem solar cell typically combines a
Energies 2023, 16, 5868 15 of 35
perovskite material and other material as a different perovskite, CIGS and CdTe [191,192].
The perovskite material is used to absorb high-energy photons, while the other materials
are used to absorb low-energy photons. High-energy photons absorbed by the perovskite
generate electron-hole pairs. The electrons and holes then move to the interface between
the perovskite and other material layers, where they are separated by a built-in electric field.
The electrons flow through the bottom layer, while the holes flow through the perovskite
layer, generating a photocurrent. The two currents are then combined at the electrode, pro-
ducing a higher overall current than a single junction solar cell. These kinds of cells have a
maximum efficiency of around 31% [106]. For instance, Al-Ashouri and workers [193] have
fabricated a monolithic CIGSe/perovskite tandem solar cells, introducing the concept of
self-assembled monolayers to choose suitable hole selective contacts and favor an efficient
carrier separation/transport. For the optimized device, a maximum PCE of 23.26% was
reached (Figure 9b) keeping the 97% of initial performance after 2400 h under operation;
see Figure 9c. Table 5 shows different examples of tandem chalcogenide solar cell, their
efficiencies, and parameters such as VOC , JSC , and FF.
Table 5. Photovoltaic parameters of main chalcogenide tandem solar cells.
JSC VOC
Active Layer FF PCE Stability Ref.
(mA/cm2 ) (V)
kinds of cells have a maximum efficiency of around 31% [106]. For instance, Al-Ashouri
Perovskite/CIGS 19.2 1.68 0.719 23.3
Perovskite/CIGS and
19.24 workers
1.77 [193] have fabricated
0.729 24.2 a 97% of initial performance, 2400 h, air
-monolithic CIGSe/perovskite tandem solar cells,
[193]
[194] in-
DSSC/CIGS troducing1.17
14.6 the concept
0.77 of self-assembled
13.0 monolayers
67% of to choose
initial performance, 12 h suitable hole selective con-
[180]
Perovskite/PbS - - - 20.3 90% of initial performance, 12.5 h, without encapsulation [195]
Perovskite/Perovskite tacts and2.01
16.0 favor an0.800
efficient carrier
25.6 separation/transport.
88% of initial performance, For
500 h,the
air optimized device, a[196] max-
CuInSe2 /Perovskite 12.9
imum PCE 1.34of 23.26%
0.635 was reached
11.0 ~70% of9b)
(Figure initial performance,
keeping the2400
97% h, in
ofainitial
desiccator
performance[197]
after
Perovskite/PbS 16.67 1.79 0.783 23.4 - [198]
GaInP/AlGaAs/CIGS 2400 h under
11.72 2.95 operation;
0.818 see 29.1
Figure 9c.
90%Table 5 performance,
of initial shows different examples
after 50 cycles of tandem[199]
of operation chal-
GaAs0.75 P0.25 /Si 20.47 1.91 0.798 31.3 - [200]
cogenide solar cell, their efficiencies, and parameters such as VOC, JSC, and FF.
9. (a) Representation
Figure 9. Representation of
of aa tandem
tandem solar
solar cell
cellbased
basedon
onaaDSSC/CIGS
DSSC/CIGS assembly.
assembly. Reproduced
Reproduced
under the terms of the CC-BY license [180]. Copyright 2015. The authors. Springer
under the terms of the CC-BY license [180]. Copyright 2015. The authors. Springer Nature. (b)Nature. (b) J–V
J-V
curve and (c) stability measurements of a tandem perovskite-CIGS solar cell. Reproduced
curve and (c) stability measurements of a tandem perovskite-CIGS solar cell. Reproduced under the under the
terms of the CC-BY license [193]. Copyright 2019, The authors, Royal Society of Chemistry.
terms of the CC-BY license [193]. Copyright 2019, The authors, Royal Society of Chemistry.
Table 5. Photovoltaic parameters of main chalcogenide tandem solar cells.

2.2.3. New Chalcogenide Materials
JSC VOC materials such as MgSnN (MTN) and ZnSnN (ZTN) are being investigated
II-IV-N
Active layer 2 FF PCE 2 Stability
2 Ref.
(mA/cm 2)
for their(V)
potential as absorber layers in solar cells [201,202]. Both materials are nitrides that
Perovskite/CIGS 19.2belong to1.68 0.719 crystal
the wurtzite 23.3structure
97% of initial
and are performance,
composed 2400 h, air
of earth-abundant elements[193]
[203].
Perovskite/CIGS 19.24 1.77 0.729 24.2 -
MTN and ZTN have bandgap energies in the visible range, making them well-suited [194]
for
DSSC/CIGS 14.6 1.17 0.77 13.0 67% of initial performance, 12 h [180]
solar absorption [203]. They also have high carrier mobility, which is important for efficient
Perovskite/PbS - - - 20.3 90% of initial performance, 12.5 h, without encapsulation [195]
charge transport in solar cells [203]. However, there are still challenges to the manufacture
Perovskite/Perovskite 16.0 2.01 0.800 25.6 88% of initial performance, 500 h, air [196]
of these materials. For instance, to create high-quality thin films of MTN and ZTN high-
CuInSe2/Perovskite 12.9 1.34 0.635 11.0 ~70% of initial performance, 2400 h, in a desiccator [197]
temperature growth techniques such as molecular beam epitaxy or metalorganic chemical
Perovskite/PbS 16.67 1.79 0.783 23.4 - [198]
vapor deposition are used, which can be expensive and difficult to scale up for large-scale
GaInP/AlGaAs/CIGS 11.72 2.95 0.818 29.1 90% of initial performance, after 50 cycles of operation [199]
production. Moreover, the properties of the films can be sensitive to the growth conditions,
GaAs0.75P0.25/Si 20.47 1.91 0.798 31.3 - [200]
2.2.3. New Chalcogenide Materials

II-IV-N2 materials such as MgSnN2 (MTN) and ZnSnN2 (ZTN) are being investigated
for their potential as absorber layers in solar cells [201,202]. Both materials are nitrides that
Energies 2023, 16, 5868 16 of 35
leading to variations in their electronic and optical properties. Another challenge is the
development of suitable heterojunctions and contacts for efficient charge collection in solar
cells based on MTN and ZTN. Several studies have explored the use of different materials,
such as graphene or molybdenum disulfide, as contacts for MTN and ZTN solar cells, but
further research is needed to optimize their performance. Efficiencies of ZTN solar cells
reach 1.5% [204], which is still low compared to conventional solar cells.
Antimony chalcogenides (Sb2 X3 , where X is a chalcogen element such as sulfur, se-
lenium, or tellurium) have recently gained attention as potential materials for solar cell
applications due to their advantageous optoelectronic properties such as high absorption
coefficients and suitable bandgap energies for solar energy conversion [205]. One advantage
of using antimony chalcogenides is that they are relatively abundant and less toxic com-
pared to other chalcogenide materials such as cadmium telluride (CdTe) [206]. Additionally,
antimony chalcogenides have shown promising photovoltaic efficiencies, with reported val-
ues ranging from 2% to 10.7% for various device structures [207,208]. However, challenges
remain for antimony chalcogenide-based solar cells, including issues related to material
stability and durability. For example, Sb2 Se3 is prone to degradation when exposed to mois-
ture and air, which can limit its practical application. Furthermore, antimony chalcogenides
have relatively low carrier mobilities, which can affect device performance [209,210].
2.3. Halide Perovskite Based Solar Cells

2.3.1. Pb-Based Perovskites Active Layers
Since Miyasaka and coworkers integrated HPs as promising light harvesters to provide
a step forward in a new generation of solar cells in 2009 [211], these materials have been
consolidated as the most prominent semiconductors for photovoltaics. Typically, HPs
show a 3D structure based on ABX3 formula (A = Cs+ , cesium; MA+ , methylammonium;
FA+ , formamidinium; B = Pb2+ , Sn2+ ; X = Cl− , Br− , I− , or combinations), where the
composition and particle size engineering can promote the preparation of HPs with diverse
photophysical, chemical, and electronic properties [212–214]. Due to the fact that a solar
device should collect as much incident illumination as possible in a broad range of the
energy spectrum to reach an efficient light-to-current transformation, low-band gap HPs
are ideal for this process. Therefore, HPs with high iodide content are in the focus of many
research groups, obtaining different strategies to reach a suitable active layer, compatible
and stable with the selective contacts of the solar cell, to facilitate the carrier mobility
through the device [215,216]. Although an acceleration in the number of publications
have been reported to show current alternatives to prepare adequate HPs active layers
(open the door to an extensive number of reviews), here, we will highlight some of these
contributions where the modification of the perovskite layer has been vital to increasing
the performance of the solar devices.
Similar to the generations of solar devices shown above, PSCs are composed by
an electron transporter layer (ETL) and hole transporter layer (HTL), which favor the
carrier transport through the device [217]. Moreover, a transparent conducting glass as
fluorine-doped tin oxide (FTO) is used to promote the carrier mobility and allow the direct
illumination of the active layer, while on top of the PSC architecture, metals such as silver
or gold are deposited [218]. As we previously mentioned, iodide HPs are the most relevant
photomaterials to achieve a high photoconversion efficiency (PCE) in PSCs, especially
perovskites based on FAPbI3 . This material presents a band gap around 1.4 eV, indicating a
broad absorption capability of solar energy in the UV-vis-NIR spectrum [219–221]. This
band gap value also corresponds to a theoretical PCE ~32.3%, near to the Shockley–Queisser
limit of efficiency [222]. Unfortunately, this feature is achieved for the photoactive phase
of the FAPbI3 , denominated as black α-phase, which is stable at high temperatures, but is
eventually transformed into the yellow δ-phase at room conditions; see Figure 10a [223]. To
suppress the fast α-to-δ phase conversion into this kind of perovskite, Meng and cowork-
ers [224] have prepared bulk films based on FA0.94 MA0.06 Pb(I0.94 ,Br0.06 )3 , which have been
coupled with carbon electrodes on top, in a n-i-p device configuration, to accelerate the
Energies 2023, 16, 5868 17 of 35
carrier separation and transport into the fabricated solar cell. Here, bromide anions were
incorporated into the perovskite to provide better stability to the material since iodide
species are more labile, being rapidly diffused from the perovskite lattice to create struc-
tural defects. However, the presence of Br also offers the enlargement of the band gap,
hampering the sunlight absorption capability of the perovskite. In this context, a high FA
content ~94% was introduced into the material, to guarantee a narrow band gap. Attending
to the final device, the PCE was estimated to be 20.04% at 1 sun illumination. At this point,
the 94% of the initial performance of the solar cell was maintained for 1000 h.
On the other hand, Kim and coworkers [225] have deeply investigated the impact of the
addition of MACl as an additive for the stabilization of FAPbI3 to obtain highly-performance
solar cells. Here, they demonstrated that the α-to-δ phase transition is promoted by the
weak interaction between FA+ cations and the iodide species from the [PbI6 ]4− octahedra
building blocks, which is one of the key factors to trigger the octahedra tilting [226–228].
Thus, the presence of Cl provides a better p orbital localization from I, improving the
FA-I interactions beyond compensating halide vacancies into the perovskite structure.
Then, MA+ cations also facilitate the perovskite stabilization, causing a contraction of
the cubo-octahedra sites in the material. MA+ shows a higher dipolar moment than that
of FA cations (~10 times), strengthening the volume shrinkage, making closer a direct
interaction between FA and I. Therefore, authors have estimated a PCE ~24% (under 1 sun)
in the devices containing the mixed cation FA/MA-perovskites, keeping 90% of their initial
performance after 1200 h of operation. In this context, it is well known that the lattice
distortion of the perovskites negatively impacts the net performance of the PSCs, favoring
the emergence of non-radiative recombination traps, hindering the carrier transport into
the fabricated device [227,229]. Thus, it is suitable to decrease the level of local strain into
the perovskite structure to increase the PCE and thereby, extend the device stability. In
these studies, Seok and coworkers [230] have proposed the combination of A-site cations to
replace some FA+ species from the FAPbI3 and delay the phase conversion of its photoactive
black α-phase. Here, a dual substitution of FA+ by larger methylenediammonium (MDA2+ )
and small Cs+ cation in a same molar ratio (0.03 mol fraction) relaxes the lattice strain
into the perovskite (denominated as (FAPbI3 )1−x (MC)x ) also contributing to suppress the
carrier traps and improving the radiative recombination pathway in the photomaterial.
At this point, a maximum PCE ~25.2% was achieved in fabricated PSCs under 1 sun
illumination; see Figure 10b, keeping 80% of their initial efficiency for 1300 h, at 85 ◦ C;
see Figure 10c. In addition, Seok’s research group have introduced some alkylammonium
chlorides (RACl) as the case of propylammonium and butylammonium chloride to improve
the crystallinity and compensate for structural defects contained into the FAPbI3 based
HPs [42]. Here, a maximum PCE of 26.08%, retaining over 88% of the initial efficiency for
600 h under operation.
To date, the octahedral tilting is induced by the loss of halide species such as iodide
anions during the perovskite film preparation [223,231,232], generating a high density of
halide vacancies (thereby, high density of carrier traps is produced), leading to the degra-
dation of the photophysical and electronic features of the material. More specifically, the
I− anions released from the perovskite structure are easily oxidized to obtain I0 , which is
the main species to trigger chemical chain reactions and accelerate the quenching of the
intrinsic properties of the active layer [232]. For this purpose, different organic agents have
been introduced to avoid the formation of halide vacancies and strengthen the Pb-I bonds
in the octahedra building blocks, as in the case of caffeine [233], theobromine [234], alky-
lammonium halides [234], phosphonopropionic acid [235] and some amino-based organic
ligands [236]. Although some of these organic agents show a high binding capability to
the [PbI6 ]4− octahedra units, avoiding the halide deficiency, they also exhibit fast decom-
position under heating or can acts as barrier layers (due to their long carbon chains). This
fact hinders the carrier extraction from the perovskite, hampering the net performance of
the solar device. Therefore, with the purpose of reducing the iodide migration and thereby
inhibit the formation of halide defect sites in the perovskite layer, Zhao and coworkers [237]
Energies 2023, 16, 5868 18 of 35
have added 3-amidinopyridine (3AP) during the material preparation, inducing the coordi-
nation between amidino moieties and the Pb-I frameworks. In this scenario, a maximum
PCE of 25.3% was obtained in optimized PSCs under 1 sun irradiation, preserving ~92% of
the initial efficiency for 5000 h in ambient air.
Other alternatives to stabilize the perovskite active layer have been focused on the
direct incorporation of large alkylammonium species to react with the 3D HPs to form
multidimensional 2D/3D systems with longer durability [236,238,239]. Considering that
big cations do not match with the Goldschmidt tolerance factor, breaking the 3D prefer-
ential crystalline structure of the perovskite, the [PbX6 ]4− octahedra in form of stacking
layers are separated by these of organic agents [240,241]; see Figure 10d. The 2D per-
ovskites are environmentally stable and promote Vander Waals interactions with the
Pb-X frameworks. However, these materials exhibit a large band gap and poor car-
rier transport capability, decreasing the PCE in modified PSCs. In this way, it is fa-
vorable the mixture of 2D/3D systems to facilitate the separation/mobility of electrons
through the device. Grancini and coworkers [242] have proposed the incorporation of
2-thiophenemethylammonium halides, 2-TMAX (X = Cl, Br and I) during the preparation
of triple-cation [(FAPbI3 )0.87 (MAPbBr3 )0.13 ]0.92 (CsPbI3 )0.08 perovskite, where the thiophene
organic species react with the photomaterial to create the 2D layer. By adding 2-TMABr
and 2-TMAI agents, a suitable band structure (valence band shift) in between the 2D-3D
perovskites is mediated, favoring the hole extraction into the heterojunction, contrary to
2-TMACl, where the carrier diffusion was hampered. Accordingly, PSCs with a maximum
PCE of 20.8% (under 1 sun) were fabricated, keeping 74% of their initial performance for
1000 h of operation without any encapsulation. Another example is mentioned by Zhou
and coworkers [241], where the 2-thiophenemethylammonium (ThMA) spacer was also
added during the preparation of FA/MA based 3D perovskite. Here perovskite crystals
were orientally grown, inducing the passivation of a high density of carrier traps to avoid
the non-radiative recombination losses. Here, devices provided high PCE up to 21.5%; see
Figure 10e, preserving 99% of its initial performance after 1680 h ambient air; see Figure 10f.
Then, a mixture of organic spacers such as iso-butylammonium iodide (i-BAI) and
FA-iodide (FAI) reported by Cho and coworkers [243] suppressed the interfacial carrier
traps and thereby reduced the interfacial energy barrier to avoid carrier diffusion. A PCE
as high as 21.7% was obtained for the optimized solar device, keeping 87% of the original
efficiency after 912 h with a relative humidity of 75%.
To maximize the absorption ability and electronic features of the bulk HPs, these mate-
rials have also been integrated with other types of solar devices such as Si, copper indium
gallium selenide, different PSCs, DSSCs and QDs-based solar cells to fabricate tandem de-
vices, as shown above [192]. Some works have reached near to 30%, as the case of the contri-
bution reported by Albrecht and coworkers [244], where a monolithic perovskite tandem so-
lar cell (PTSC) was fabricated. Here, a wide-band gap Cs0.05 (FA0.77 MA0.23 )0.95 Pb(I0.77 Br0.23 )3
bulk film was integrated with a Si-based solar device, also incorporating diverse hole trans-
porter layers such as C60 , 2PACz and Me-4PACz, to accelerate the carrier extraction. A
maximum of PCE ~29% was achieved for the optimized PTSC, retaining the 95% of the
initial performance after 300 h under operation. Interestingly, De wolf and coworkers [245]
have incorporated MgF2 as an interlayer between the perovskite based on triple cation
Cs0.05 FA0.8 MA0.15 Pb(I0.755 Br0.255 )3 and C60 to improve the electron extraction (better ad-
justment of the relative energy positions in the perovskite) and separate the C60 from the
active layer surface to restrain the non-radiative recombination dynamics. Accordingly, a
stabilized PCE of 29.3% was achieved, where the optimized PTSC device retained ~95% of
its initial performance after 1000 h of operation, even carrying out damp-heat testing at
85 ◦ C with 85% relative humidity. Recently, this research group provided a new record of
the PCE ~33.2% using a similar perovskite layer on top of the cell, while a textured Si solar
device is in the bottom of the configuration.
20.8% (under 1 sun) were fabricated, keeping 74% of their initial performance for 1000 h
of operation without any encapsulation. Another example is mentioned by Zhou and
coworkers [241], where the 2-thiophenemethylammonium (ThMA) spacer was also added
during the preparation of FA/MA based 3D perovskite. Here perovskite crystals were ori-
entally grown, inducing the passivation of a high density of carrier traps to avoid the non-
Energies 2023, 16, 5868 19 of 35
radiative recombination losses. Here, devices provided high PCE up to 21.5%; see Figure
10e, preserving 99% of its initial performance after 1680 h ambient air; see Figure 10f.
Figure10.10.(a)
(a)Typical
Typicalphase
phase transformation
transformation of the
of the FAPbIFAPbI 3 crystalline structure. The δ–to–α phase
Figure 3 crystalline structure. The δ–to–α phase tran-
transition is promoted at high temperature. Reproduced with permission [223]. Copyright 2020.
sition is promoted at high temperature. Reproduced with permission [223]. Copyright 2020. American
American Chemical Society. (b) Performance and (c) long-term stability measurements of the
Chemical Society. (b) Performance and (c) long-term stability measurements of the (FAPbI3 )1−x (MC)x
(FAPbI3)1−x(MC)x (x = 0.03 mol%) and control–based PSCs (uncapsulated devices). Reproduced with
(x = 0.03 mol%)
permission and
[230]. control–based
Copyright PSCs (uncapsulated
2020. Science devices). of
AAAS. (d) Schematic Reproduced
the proposedwith permission
2D/3D FA/MA[230].
per-
Copyright 2020. Science AAAS. (d) Schematic of the proposed 2D/3D FA/MA
ovskite film where ThMA spacer is incorporated between the [PbI6] octahedra layers,4− perovskite film where
which is
ThMA spacer istoincorporated between − octahedra layers, which is perpendicular to
the [PbI6 ]4and
perpendicular the substrate. (e) Performance (f) stability test of the control and 2D/3D
FA/MA–based
the PSC.
substrate. (e) Reproduced
Performance with
and (f) permission
stability test[241].
of theCopyright
control and2019. John Wiley
2D/3D & Sons, Inc.
FA/MA–based PSC.
Reproduced with permission [241]. Copyright 2019. John Wiley & Sons, Inc.
Even though the surface passivation with interesting alkylammonium ligands and
the incorporation of 2D/3D heterostructures enhance the operational performance of the
solar devices, it is reasonable that some differences in the PCE values are obtained. So,
the highest PCE value is reached by filling/replacing structural defects in the active layer,
improving its optical and electronic properties, suppressing carrier traps, and facilitating
carrier transport. Although 2D/3D assembly can also achieve defect passivation in the
perovskite, the appearance of a heterostructure can promote the emergence of interfacial
energy levels where the carriers can be trapped, hampering the development of a higher
device efficiency.
2.3.2. Partially Pb-Substituted/Pb-Free Perovskite Active Layers

As we have highlighted above, a series of approaches are prominent to reach long-
term stability and suitable electronic properties in perovskites to favor carrier separa-
tion/extraction and mobility through the fabricated device. However, it is also known that
one of the main drawbacks of the PSCs is the inherent toxicity of Pb, which hampers the
future commercialization of this technology [246,247]. Therefore, the fact of substituting
Pb partially or completely with less toxic metals, preserve/increase the final properties
of the active layer, and thereby, reaching high performance in the solar device, is still a
huge challenge. One of the most attractive metals to replace Pb is Sn, which also generate
[SnX6 ]4− octahedra units to generate multidimensional HPs structures as the case of Pb
and provide HPs lower band gap than that of Pb-analogous [248]. Nevertheless, Sn-HPs
exhibit a poor stability consequence of the fast Sn2+ -to-Sn4+ oxidation under ambient con-
ditions, degrading the net efficiency in solar devices [249,250]. Hence, we will focus on the
FASnI3 HPs), is suppressed. This fact makes that the recombination lifetime is longer th
that of the absence of the organic molecules, associated with the reduction of high dens
of trap states. In context, a high PCE of 17.51% was reached (Figure 11a), keeping 90%
Energies 2023, 16, 5868
the initial performance after 1200 h into a glove box (Figure 11b), and 70% of initial e
20 of 35
ciency close to 400 h under ambient air; see Figure 11c.
Then, Xu and coworkers [253] employed the surface passivation concept to prolo
the stability
fabrication ofofthePSCsFAbased
0.7MA on Pb
0.3a 0.7Sn0.3of
mixture I3 Sn/Pb-
HPs and remove
or Sn-HPs structural
introducing noveldefects from
strategies to the ma
avoid Sn oxidation in the active layer and thereby increase
rial using guanidinium bromide (GABr). Considering that GA cations provide m the performance + of Sn-PSCs.
Firstly, for Sn/Pb-HPs
charge density than FA+ andsystems, Wang and coworkers [251] have studied the addi-
MA+ cations, this could be one of the main explanations
tion of antioxidants such as tea polyphenol (TP) during the preparation of optimized
restrain
CsPbthe fast Sn -to-Sn transformation. In addition, iodide vacancies are formed
2+ 4+
0.5 Sn0.5 I2 Br bulk film to avoid the rapid Sn oxidation. Through the coordination bonds
the depletion
between high of Lewis
Sn2+, creating
acidity Sn high content
sites and of halidegroups,
hydroxybenzene vacancies the Sninto the
4+ /Sn perovskite.
2+ ratio into Th
Br domains
− the HP was fill/replace
decreased from these empty
68.1% states
to 5.85%, to enhance
deducing that TP the
is afinal
goodproperties
reducing agent.of theIn prepar
addition, this antioxidant mediated an improved HP crystallization,
active layer. The optimized device has reached a maximum PCE of 20.63% without a making that at 0.5 wt%
TP, a homogeneous film with a low content of pinholes is obtained. Therefore, low density
encapsulation; see Figure 11d, conserving over 85% of the original efficiency after 100
of grain boundaries appears to hinder the carrier extraction. A maximum PCE of 8.1%
under ambient
was reached underair; see Figure
1 sun 11e, and
illumination, 80% of95%
retaining theoforiginal
original efficiency
performanceafter after 24 h ofh operat
~1440
at 80into
°C;asee Figure
N2 -filled glove11f.box.
Lastly, HuangGuo
Meanwhile, andandcoworkers
coworkers [252][245]havehave useddemonstrated
the mixture that
of 2D/3D HPs in order to prepare suitable heterostructures
addition of an alkylammonium pseudo-halide additive based on octylammonium for PSCs. Here, authors have tet
introduced bulky alkylammonium based on 2-(4-fluorophenyl)ethylammonium iodide
fluoroborate (OA BF4 ) for the preparation of MA-free Sn/Pb HPs. While OA cations c
+ − +
(FPEAI) during the preparation of (MAPbI3 )0.75 (FASnI3 )0.25 films. In presence of the organic
fill some A-site
cation, highlycations
orientedinto the are
crystals HPs, BF4−and
grown, species
phasecompensate the iodide
segregation occurring as thevacancies
result gen
ated ofbythe
theSnSn oxidation,
oxidation also two
(emerging reducing the likelihood
distinguished signals from of MAPbI
emerging3 andinterstitial
FASnI3 HPs),iodide a
is suppressed. This fact makes that the recombination
iodine. The suppression of defect density, main factor to promote carrier lifetime is longer than thattrapping,
of the fac
tates the fabrication of PSCs with PCE up to 23.7% (a record for Sn/Pb-PSCs),trap
absence of the organic molecules, associated with the reduction of high density of keeping o
states. In context, a high PCE of 17.51% was reached (Figure 11a), keeping 90% of the initial
88% performance
of the initial performance after 1000 h of continuous operation at 50 °C in air a
after 1200 h into a glove box (Figure 11b), and 70% of initial efficiency close to
tracking
400 hthe
underdevice
ambient under MPP.
air; see Figure 11c.
Figure 11. (a) Photovoltaic performance of the optimized (MAPbI3 )0.75 (FASnI3 )0.25 PSC in presence
and absence of 3.75 wt% FPEAI. Stability measurements for the Sn/Pb-based PSCs with and without
the FPEAI additive under (b) N2 atmosphere and (c) in ambient air. Inset of Figure 4a shows the
randomly oriented 3D HP structure, which is vertically aligned in presence of the FPEAI organic agent.
Reproduced with permission [252]. Copyright 2020. American Chemical Society. (d) Performance,
(e) environmental and (f) thermal stability measurements of the 2D/3D FA0.7 MA0.3 Pb0.7 Sn0.3 I3 -based
PSCs in presence and absence of 12% wt GABr. Reproduced with permission [253]. Copyright 2020.
John Wiley & Sons, Inc.
Energies 2023, 16, 5868 21 of 35
Then, Xu and coworkers [253] employed the surface passivation concept to prolong the
stability of the FA0.7 MA0.3 Pb0.7 Sn0.3 I3 HPs and remove structural defects from the material
using guanidinium bromide (GABr). Considering that GA+ cations provide more charge
density than FA+ and MA+ cations, this could be one of the main explanations to restrain the
fast Sn2+ -to-Sn4+ transformation. In addition, iodide vacancies are formed by the depletion
of Sn2+ , creating high content of halide vacancies into the perovskite. Thus, Br− domains
fill/replace these empty states to enhance the final properties of the prepared active layer.
The optimized device has reached a maximum PCE of 20.63% without any encapsulation;
see Figure 11d, conserving over 85% of the original efficiency after 1000 h under ambient
air; see Figure 11e, and 80% of the original efficiency after 24 h of operation at 80 ◦ C; see
Figure 11f. Lastly, Huang and coworkers [245] have demonstrated that the addition of
an alkylammonium pseudo-halide additive based on octylammonium tetrafluoroborate
(OA+ BF4 − ) for the preparation of MA-free Sn/Pb HPs. While OA+ cations can fill some
A-site cations into the HPs, BF4 − species compensate the iodide vacancies generated by
the Sn oxidation, also reducing the likelihood of emerging interstitial iodide and iodine.
The suppression of defect density, main factor to promote carrier trapping, facilitates the
fabrication of PSCs with PCE up to 23.7% (a record for Sn/Pb-PSCs), keeping over 88% of
the initial performance after 1000 h of continuous operation at 50 ◦ C in air and tracking the
device under MPP.
For the case of the stabilization of Sn-based PSCs, some examples can be addressed.
Mora-Seró and coworkers [254] have made use of the chemical engineering strategy, where
Dipropylammonium iodide (DipI) and sodium borohydride (NaBH4 ) (known as a good
reducing agent) have been added to the preparation of FASnI3 films and prevent the Sn
oxidation. While DipI can block the loss of iodine in form of I2 , NaBH4 reduce the released I2
to produce iodide into the HPs, avoiding the halide migration. Therefore, the Sn2+ /Sn4+ and
I− /I2 ratios are increased, inhibiting the formation of interstitial iodine/iodide vacancies,
which are the main energy states where the hole/electrons can be trapped. In this alternative
for stabilizing Sn, optimized devices boost a high PCE of 10.61%; see Figure 12a, providing
up to 96% of the initial performance after 1300 h of continuous operation at MPP in N2
condition; see Figure 12b,c. Another approach to stabilizing the black phase of the FASnI3 ,
Mi and coworkers [255] have introduced trimethylthiourea (3T) during the spin-coating
process for HPs preparation. The presence of this bifunctional ligand induces coordination
bonds with Sn2+ cations through the formation of Sn-S species. Simultaneously, N-H moiety
from the organic agent produces hydrogen bond iodide species from the octahedra building
blocks to avoid their diffusion out from the HPs lattice. Due to these effects, the carrier
recombination is prolonged in comparison to the pristine HPs, hindering the emergence
of carrier traps. In this context, PSCs were able to develop a maximum PCE up to 14%,
maintaining 100% of the original efficiency for more than 700 h, under N2 atmosphere.
On the other hand, He and coworkers [256] have included 4-fluoro-phenethylammonium
bromide (FPEABr) into the precursor solution to prepare 2D/3D Sn-HPs with low density
of structural defects. FPEA cations are incorporated into the perovskite surface, while
F- and Br-anions fill/replace halide vacancies. In terms of the device architecture, the
2D Sn-perovskite acts as an interface layer between the active layer and PEDOT:PSS hole
transporter layer, restraining the iodide migration into the device. In presence of 10 wt%
FPEABr, encapsulated 2D/3D PSCs generate a PCE up to 14.81%; see Figure 12d, exhibiting
over 80% initial performance after 432 h under operation at room temperature (Figure 12e),
and 60% of initial efficiency after 1 h at 80 ◦ C (Figure 12f), both kinds of tests under
ambient air.
Energies 2023, 16,
Energies 2023, 16, 5868
x FOR PEER REVIEW 22 of
23 of 35
37
Figure 12.
Figure 12. (a) Photovoltaic
Photovoltaic performance
performanceof ofthe
theFASnI
FASnI3-3-based
basedPSCs
PSCsin inpresence
presenceofofDipI/NaBH
DipI/NaBH44. Inset
of Figure 5a exhibits the architecture of the optimized device. Stability measurements
of Figure 5a exhibits the architecture of the optimized device. Stability measurements of of the
the FASnI
FASnI3
3
devices in presence and absence of the additives (b) under N 2 atmosphere and (c) at MPP under
devices in presence and absence of the additives (b) under N2 atmosphere and (c) at MPP under inert
inert conditions. Reproduced with permission [254]. Copyright 2022. Elsevier. (d) Photovoltaic per-
conditions. Reproduced with permission [254]. Copyright 2022. Elsevier. (d) Photovoltaic perfor-
formance of the FASnI3 PSCs by varying the amount (wt%) of FPEABr to prepare the 2D/3D struc-
mance of the FASnI3 PSCs by varying the amount (wt%) of FPEABr to prepare the 2D/3D structure.
ture. Stability measurements of the FASnI3 and 2D/3D perovskite-based PSCs (e) at room tempera-
Stability
ture and measurements
(f) at 80 °C, bothof the
set FASnI 3 and 2D/3Dunder
of measurements perovskite-based
ambient air. PSCs (e) at room
Reproduced withtemperature
permission
and ◦
[256].(f)Copyright
at 80 C, both
2021.set of Wiley
John measurements
& Sons, Inc.under ambient air. Reproduced with permission [256].
Copyright 2021. John Wiley & Sons, Inc.
Table 6. Summary of photovoltaic parameters of the optimized devices based on Pb-, Sn/Pb-, Sn-
Tablefilms.
perovskite 6 shows the comparison in photovoltaic performances of the above perovskite-
based solar devices, providing main parameters, such as Jsc , Voc , and FF, to estimate the
corresponding PCE. Pb-Based Perovskite
It is evident thatFilms
PSCs fabricated with Pb-based HP films are more
Active Layer stable and still offer
Jsc (mAcm −2) Voc (V)
a high performance, FFmainly
PCEassociated
(%) Stability oxidation condition
to hampered Ref.
of Pb itself. However, 94% of initial performance, 1000
FA0.94MA0.06Pb(I0.94,Br0.06)3 23.60 even 1.11
though 0.765
the net efficiency
20.04 offered by Sn/Pb- or Sn-PSCs are
[224]
lower compared to their Pb-analogous, diverse alternatives h, air are presented to improve their
long-stability in room 90%Sn of oxidation),
initial performance,
which 1200
FAPbI3–40 wt% MACl 25.92 conditions
1.13 (inhibiting
0.820 the fast
24.02 is pivotal
[225]to
h, air
finding the suitable conditions to increase the PCE in future Pb-free PSC technologies.
80% of initial performance, 1300
(FAPbI3)1−x(MC)x, x = 0.03 mol% 26.23 1.17 0.822 25.20 [230]
h, 85 °C, air
Table 6. Summary of photovoltaic parameters of the optimized devices based on Pb-, Sn/Pb-,
88% of initial performance, 600
FAPbI3–10 mol% RACl Sn-perovskite films.25.69 1.18 0.862 26.08 [42]
h, air
Pb-Based Perovskite Films 92% of initial efficiency, 5000 h,
FAPbI3–4 mol% 3AP 26.04 1.18 0.822 25.30 [237]
Jsc
air
Active Layer Voc (V) FF PCE (%)74% of initial Stability Ref.
2-TMABr–modified (mAcm−2 ) efficiency, 1000 h,
23.20 1.15 0.780 20.80 [242]
(FAPbI3)0.87(MAPbBr3)0.13]0.92(CsPbI3)0.08 air 94% of initial performance,
FA0.94 MA0.06 Pb(I0.94 ,Br0.06 )3 23.60 1.11 0.765 20.04 [224]
99% of 1000itsh, initial
air performance,
ThMA–modified 2D/3D FA/MA perovskite 22.88 1.16 0.810 21.49 [241]
1680 h, air
90% of initial performance,
FAPbI3 –40 wt% MACl 25.92 1.13 0.820 24.02 [225]
i-BAI/FAI–modified 87% of 1200theh, air
original efficiency,
~23 ~1.18 ~0.825 21.70 [243]
(FAPbI3)0.85(MAPbBr3)0.15 912 h,80%
air of initial performance,
(FAPbI3 )1−x (MC)x , x = 0.03 mol% 26.23 1.17 0.822 25.20 [230]
95% of 1300 85 ◦ C, air
theh, initial performance,
Cs0.05(FA0.77MA0.23)0.95Pb(I0.77Br0.23)3/Si PTSC 19.26 1.90 0.795 29.05 [244]
300 h,88%
air of initial performance,
FAPbI3 –10 mol% RACl 25.69 1.18 0.862 26.08 [42]
MgFx–modified 95% of 600the
h, air
initial performance,
20.58 1.92 0.807 29.30 [245]
Cs0.05FA0.8MA0.15Pb(I0.755Br0.255)3 1000 h, 85 °C, air
Partially Pb-Substituted/Pb-Free Perovskite Films
Perovskite Layer Jsc (mAcm−2) Voc (V) FF PCE (%) Stability Ref.
Energies 2023, 16, 5868 23 of 35
Table 6. Cont.
Pb-Based Perovskite Films

Jsc
Active Layer Voc (V) FF PCE (%) Stability Ref.
(mAcm−2 )
92% of initial efficiency,
FAPbI3 –4 mol% 3AP 26.04 1.18 0.822 25.30 [237]
5000 h, air
2-TMABr–modified 74% of initial efficiency,
23.20 1.15 0.780 20.80 [242]
(FAPbI3 )0.87 (MAPbBr3 )0.13 ]0.92 (CsPbI3 )0.08 1000 h, air
ThMA–modified 2D/3D FA/MA 99% of its initial
22.88 1.16 0.810 21.49 [241]
perovskite performance, 1680 h, air
i-BAI/FAI–modified 87% of the original
~23 ~1.18 ~0.825 21.70 [243]
(FAPbI3 )0.85 (MAPbBr3 )0.15 efficiency, 912 h, air
Cs0.05 (FA0.77 MA0.23 )0.95 Pb(I0.77 Br0.23 )3 /Si 95% of the initial
19.26 1.90 0.795 29.05 [244]
PTSC performance, 300 h, air
95% of the initial
MgFx–modified
20.58 1.92 0.807 29.30 performance, 1000 h, [245]
Cs0.05 FA0.8 MA0.15 Pb(I0.755 Br0.255 )3
85 ◦ C, air
Partially Pb-Substituted/Pb-Free Perovskite Films
Jsc
Perovskite Layer Voc (V) FF PCE (%) Stability Ref.
(mAcm−2 )
95% of original performance,
TP–modified CsPb0.5 Sn0.5 I2 Br 20.10 0.62 0.650 8.10 [251]
~1440 h, N2 –atmosphere
90% of the initial
performance, 1200 h
(MAPbI3 )0.75 (FASnI3 )0.25 –3.75 wt% FPEAI 28.42 0.79 0.780 17.51 N2 –atmosphere, [252]
70% of initial efficiency,
400 h, air.
85% of original efficiency,
1000 h, air
FA0.7 MA0.3 Pb0.7 Sn0.3 I3 –12 wt% GABr 26.61 1.02 0.760 20.63 [253]
24 h, 80 ◦ C, air
1000 h, continuous
OABF4 –modified Cs0.2 FA0.8 Pb0.5 Sn0.5 I3 33.80 0.88 0.800 23.70 [245]
operation at 50 ◦ C, air,
tracking under MPP
1300 h, continuous
DipI/NaBH4 –modified FASnI3 22.13 0.65 0.731 10.61 [254]
operation at MPP,
N2 -atmosphere
3T–modified FASnI3 20.50 0.91 0.757 14.06 [255]
>700 h, N2 –atmosphere
432 h, continuous operation,
FPEABr–modified 2D/3D FASnI3
24.91 0.84 0.708 14.81 air [256]
(10 mol%)
60% of initial efficiency, 1 h
at 80 ◦ C, air
After describing the main characteristics of each kind of active layer used to fabricate
the corresponding solar devices, some advantages and disadvantages of the related systems
can be compared. Even aromatic moieties can promote carrier mobility in the organic
sensitizers; carrier extraction is facilitated by the preparation of bulk heterojunctions, where
an organic carrier acceptor and donor are assembled. Nevertheless, the formation of these
heterostructures produce inhomogeneous morphology of the active layer, being of the
critical reasons to favor the carrier recombination and the decrease in the PCE of the OSCs.
In this line, chalcogenides were then integrated for the fabrication of more innovative
solar devices, where the carrier injection depends on the relative energy positions of these
kind of sensitizers, which can be modulated through material composition or particle size.
Unfortunately, chalcogenides are prone to photocorrosion, damaging their optical and
Energies 2023, 16, 5868 24 of 35
electronic properties. Under this view, it seems that halide perovskites are the unique and
most prominent option to be incorporated as active layer for solar cells, taking into account
their high absorption coefficient, better electronic properties and versatile surface chemistry.
However, some reports and review articles disagree with the former qualification, attending
to the fact that the ionic structure of perovskites is highly labile, generating high density of
defect sides, which decreases the stability of the photomaterial. Therefore, one interesting
question emerges at this point: what is the suitable active layer to produce a solar device
with high light-harvesting capability, efficient PCE with long-term stability? According to
the results exposed through the different operational parameters of each generation of solar
cells (Tables 1–6), the tandem systems are the most promising devices to have an important
impact in photovoltaics, covering the absorption of the light in a broad range of the energy
spectrum (UV-vis-NIR) by integrating wide- and narrow-band gap active layers (from
diverse generation of solar cells), improving carrier generation/separation and diffusion.
At this scenario, these types of devices offer one step forward the commercialization of
solar technologies and are competitive against the well-established Si-based solar cells.
3. Concluding Remarks
This review shows the different generations of solar cells, considering the most im-
portant advances in the preparation of efficient active layers (organic, chalcogenide and
halide perovskites) with improved capability to harvest most of the solar energy spectrum
and promote the photocarrier transport into the solar device. As highlighted first, dye
sensitizers were the first low-cost active layers to be incorporated with the purpose of
replacing conventional and expensive silicon-based solar cells, taking advantage of their
good absorption coefficient and facile carrier extraction. However, most of the organic
materials show optical properties at specific wavelengths, hindering the photocarriers
generation and lowering the PCE values. Therefore, organic molecules or species based
on phthalocyanine and perylene derivatives have gained growing interest and are being
integrated into novel OSCs. This fact provides the opportunity to achieve a better light
harvesting performance and increase the density of carriers flowing into the device. Then,
highly conductive materials such as fullerenes, and the concept of “bulk heterojunction”
have been taken advantage to enhance the electron diffusion into the solar cell component
interfaces, facilitating the photocarrier separation. Unfortunately, the inhomogeneity in
the morphology of the organic active layers and their relatively fast deterioration make the
density of carrier traps increase, hindering the electrons reach the external circuit of the
solar cell. Here, the best OSCs can achieve PCE of more than 20% recently, but low stability
in the range of hours can be achieved.
To overcome the above issues, chalcogenide-based solar cells have emerged to expand
the light absorption capability of the active layer in a broad range of the energy spectrum
(with a higher absorption coefficient than organic sensitizers), also considering the multiple
pathways to prepare suitable films for efficient device prototypes. In this way, by attending
to the chemical composition of the metal chalcogenides such as CdTe, PbS or some of
them with metal combinations to obtain CZTSe/CZTSSe derivatives, light harvesting in
the IR range is unlocked to provide more photocarriers, and thereby, more photocurrent
is developed. Moreover, p-type and n-type chalcogenides can be assembled to offer an
adequate band structure with electron and hole transporting layers, promoting effective
carrier injection and mobility through the solar cells. Accordingly, PCE values close to
25% can be reached, also enhancing the stability of the device for long time of operation,
even under harsh conditions such as H2 O, O2 , and high temperatures. Nevertheless, some
disadvantages, such as high resistance for carrier mobility, the appearance of high density
of energy traps favoring the surface recombination, and the use of toxic elements such
as Cd, S, Te among others, decrease the possibility of using chalcogenides for further
improvements in device performance.
Attending to the latter, HPs active layers have emerged as the most prominent semi-
conductors, gaining attention in photovoltaics due to their exponential enhancement in
Energies 2023, 16, 5868 25 of 35
light-to-electricity transformation capability is some couple of years. Because of their

versatile surface chemistry and variable composition, intrinsic properties of perovskites
such as band gap can be easily modifiable, in order to improve the material stability with-
out modifying their photoactivity. In this context, diverse strategies to delay the α-to-δ
phase transformation in iodide-HPs have been applied in order to decrease the density of
structural defects (main reason to promote the octahedra titling and thereby favoring the
phase transition), preserve the optical performance and restrain the carrier recombination
dynamics. Mainly, bulky organic cations are introduced to prepare 2D/3D perovskite
systems, where a suitable heterojunction is established to facilitate the carrier extraction.
In addition, the introduction of alkylammonium halides is pivotal to suppress halide defi-
ciency (carrier traps), contributing to the carrier diffusion to the external circuit of the cell,
increasing the net efficiency of the solar cell. Therefore, PCE values higher than 25% have
been reached, with long-term stability for hours in air ambient, being competitive with
recent Si-based devices. However, like chalcogenides, inherent toxicity of HPs is found due
to the presence of Pb, one of the main explanations to hinder their future commercialization.
Therefore, partially Pb-substituted/Pb-free HPs have been prepared replacing Pb instead of
Sn, including promising additives to prevent the progressive oxidation of the metal. Even
the net performance of Sn-based HPs layers is not so high compared to their Pb-analogous,
long-term stability under ambient air has been analyzed, being the first step to find the
device parameters with the purpose to increase the operational efficiency. Attending to the
fact that innovative strategies are being studied to produce a more stable photomaterial
with good optical performance and stability, the use HPs have reached an exponential
interest during recent years, establishing them as the most prominent active layers to
fabricate solar cells. Unlike organic sensitizers and metal chalcogenides, the facile control
of the surface chemistry of HPs, mainly surface passivation, make them versatile materials
with improved intrinsic properties, even to be applied in other interesting research topics
such as optoelectronics, solar-driven chemical reactions and so on.
From the perspective of developing solar devices with maximum photovoltaic perfor-
mance, the combination of different generations of solar cells to fabricate tandem devices
will be the most rentable/profitable option to maximize sunlight absorption, carrier photo-
generation, and transport, due to the use of wide-band gap and narrow-band gap active
layers, increasing the density of electrons to flow through the cell. At this point, match-
ing the relative energy positions of the components into the device provides the suitable
pathway for the carrier injection and mobility, avoiding the carrier trapping. On the other
hand, the partial or total replacement of toxic metals, such as Cd of Pb from chalcogenides
and perovskites, respectively, are recently one of the top research challenges to provide
a step forward to future commercialization and being competitive with Si-solar cells. In
this way, some ultrathin or flexible perovskite devices could be competitive with the recent
state-of-the art. Without a doubt, more prominent works will be focused on this topic,
preserving of increasing the optical performance, operational efficiency, and stability of
innovative devices. This contribution gives an insight about the different active layers
useful to continue future studies in photovoltaics and fabricate more efficient, less toxic,
and stable devices with promising potential to compensate for energy consumption in the
coming years.
Author Contributions: Conceptualization, writing—original draft preparation, writing—review and

editing, F.W., C.S., J.M., I.O.-R., S.J.Y., D.J. and A.F.G.-R. Supervision, A.F.G.-R., F.W. and C.S. have
equally contributed on this work. All authors have read and agreed to the published version of
the manuscript.
Funding: F.W. is grateful for the FONDECYT Postdoctorado fellowship 3220023. C.S. is grateful for
the FONDECYT de Postdoctorado fellowship 3220178. J.M. thanks to the FONDECYT Iniciación fel-
lowship 11230124 and Innova ConCiencia Consorcio Sur-Subantártico Ci2030 20CEIN2-142146. I.O.R
acknowledges to international collaboration project Innoving2030 16ENI2-66903. D.H.J. would like to
thank Fondecyt de Iniciación 11200280. S.J.Y. for this work was supported by the National Research
Foundation of Korea (NRF) grant funded by the Korea government (MSIT) and 2022R1C1C1011860.
Energies 2023, 16, 5868 26 of 35
Data Availability Statement: Not applicable.

Acknowledgments: A.F.G.-R. acknowledges to Universidad Austral de Chile for the financial support.
Conflicts of Interest: The authors declare no conflict of interest.
References
1. Fthenakis, V.M. End-of-Life Management and Recycling of PV Modules. Energy Policy 2000, 28, 1051–1058. [CrossRef]
2. Carneiro, A.L.; Martins, A.A.; Duarte, V.C.M.; Mata, T.M.; Andrade, L. Energy Consumption and Carbon Footprint of Perovskite
Solar Cells. Energy Rep. 2022, 8, 475–481. [CrossRef]
3. Dissanayake, P.D.; Yeom, K.M.; Sarkar, B.; Alessi, D.S.; Hou, D.; Rinklebe, J.; Noh, J.H.; Ok, Y.S. Environmental Impact of Metal
Halide Perovskite Solar Cells and Potential Mitigation Strategies: A Critical Review. Environ. Res. 2023, 219, 115066. [CrossRef]
[PubMed]
4. Mathan Kumar, P.; Das, A.; Seban, L.; Nair, R.G. Fabrication and Life Time of Perovskite Solar Cells. In Perovskite Photovoltaics
Basic to Advanced Concepts and Implementation; Academic Press: Cambridge, MA, USA, 2018; pp. 231–287. [CrossRef]
5. Sundaram, S.; Benson, D.; Mallick, T.K. Overview of the PV Industry and Different Technologies. Sol. Photovolt. Technol. Prod.
2016, 7–22. [CrossRef]
6. Campbell, P.; Green, M.A. High Performance Light Trapping Textures for Monocrystalline Silicon Solar Cells. Sol. Energy Mater.
Sol. Cells 2001, 65, 369–375. [CrossRef]
7. Khezami, L.; Al Megbel, A.O.; Jemai, A.B.; Ben Rabha, M. Theoretical and Experimental Analysis on Effect of Porous Silicon
Surface Treatment in Multicrystalline Silicon Solar Cells. Appl. Surf. Sci. 2015, 353, 106–111. [CrossRef]
8. Karyaoui, M.; Bardaoui, A.; Ben Rabha, M.; Harmand, J.C.; Amlouk, M. Effect of Rapid Oxidation on Optical and Electrical
Properties of Silicon Nanowires Obtained by Chemical Etching. EPJ Appl. Phys. 2012, 58, 20103. [CrossRef]
9. Tan, H.; Santbergen, R.; Smets, A.H.M.; Zeman, M. Plasmonic Light Trapping in Thin-Film Silicon Solar Cells with Improved
Self-Assembled Silver Nanoparticles. Nano Lett. 2012, 12, 4070–4076. [CrossRef]
10. Wang, Z.; He, J.; Wang, W.; Lin, H.; Xu, Z.; Liu, Q.; Peng, S.; Hou, J.; He, D.; Gao, P. Twenty Percent Efficiency Crystalline Silicon
Solar Cells with Solution-Processed Electron-Selective Contacts. ACS Appl. Energy Mater. 2021, 4, 3644–3650. [CrossRef]
11. Barkhouse, D.A.R.; Gunawan, O.; Gokmen, T.; Todorov, T.K.; Mitzi, D.B. Yield Predictions for Photovoltaic Power Plants:Empirical
Validation,Recent Advances and Remaining Uncertainties. Prog. Photovolt. Res. Appl. 2015, 20, 6–11. [CrossRef]
12. Chavan, K.T.; Chandra, S.; Kshirsagar, A. Half-Metallicity in Smallest Cage-like Cluster of CdTe with Doping of Transition Metal
Atoms. Mater. Today Commun. 2022, 30, 103104. [CrossRef]
13. Chu, T.L.; Chu, S.S. Thin Film II–VI Photovoltaics. Solid. State. Electron. 1995, 38, 533–549. [CrossRef]
14. Kumarasinghe, P.K.K.; Dissanayake, A.; Pemasiri, B.M.K.; Dassanayake, B.S. Thermally Evaporated CdTe Thin Films for Solar
Cell Applications: Optimization of Physical Properties. Mater. Res. Bull. 2017, 96, 188–195. [CrossRef]
15. Rivera, L.P.; García, E.; Cardona, D.; Pérez-Centeno, A.; Camps, E.; Santana-Aranda, M.A.; Gómez-Rosas, G.; de Moure-Flores, F.;
Chávez-Chávez, A.; Quiñones-Galván, J.G. CdTe:Sn Thin Films Deposited by the Simultaneous Laser Ablation of CdTe and Sn
Targets. Mater. Res. Express 2020, 7, 015905. [CrossRef]
16. Camacho-Espinosa, E.; López-Sánchez, A.; Rimmaudo, I.; Mis-Fernández, R.; Peña, J.L. All-Sputtered CdTe Solar Cell Activated
with a Novel Method. Sol. Energy 2019, 193, 31–36. [CrossRef]
17. Ling, J.; Zhang, X.; Mao, T.; Li, L.; Wang, S.; Cao, M.; Zhang, J.; Shi, H.; Huang, J.; Shen, Y.; et al. Electrodeposition of CdTe Thin
Films for Solar Energy Water Splitting. Materials 2020, 13, 1536. [CrossRef]
18. Vaishanav, S.K.; Korram, J.; Pradhan, P.; Chandraker, K.; Nagwanshi, R.; Ghosh, K.K.; Satnami, M.L. Green Luminescent CdTe
Quantum Dot Based Fluorescence Nano-Sensor for Sensitive Detection of Arsenic (III). J. Fluoresc. 2017, 27, 781–789. [CrossRef]
[PubMed]
19. Kini, S.; Kulkarni, S.D.; Ganiga, V.; Nagarakshit, T.K.; Chidangil, S. Dual Functionalized, Stable and Water Dispersible CdTe
Quantum Dots: Facile, One-Pot Aqueous Synthesis, Optical Tuning and Energy Transfer Applications. Mater. Res. Bull. 2019, 110,
57–66. [CrossRef]
20. Duan, J.; Song, L.; Zhan, J. One-Pot Synthesis of Highly Luminescent CdTe Quantum Dots by Microwave Irradiation Reduction
and Their Hg2+ -Sensitive Properties. Nano Res. 2009, 2, 61–68. [CrossRef]
21. Rangel-Cárdenas, J.; Sobral, H. Optical Absorption Enhancement in CdTe Thin Films by Microstructuration of the Silicon
Substrate. Materials 2017, 10, 607. [CrossRef]
22. Kavanagh, S.R.; Walsh, A.; Scanlon, D.O. Rapid Recombination by Cadmium Vacancies in CdTe. ACS Energy Lett. 2021, 6,
1392–1398. [CrossRef]
23. Mendoza-Pérez, R.; Aguilar-Hernández, J.; Sastre-Hernández, J.; Ximello-Quiebras, N.; Contreras-Puente, G.; Santana-Rodríguez,
G.; Vigil-Galán, O.; Moreno-García, E.; Morales-Acevedo, A. Photoluminescence Characteristics of CdS Layers Deposited in a
Chemical Bath and Their Correlation to CdS/CdTe Solar Cell Performance. Sol. Energy 2006, 80, 682–686. [CrossRef]
24. Morales-Acevedo, A. Thin Film CdS/CdTe Solar Cells: Research Perspectives. Sol. Energy 2006, 80, 675–681. [CrossRef]
25. O’Regan, B.; Grätzel, M. A Low-Cost, High-Efficiency Solar Cell Based on Dye-Sensitized Colloidal TiO2 Films. Nature 1991, 353,
737–740. [CrossRef]
Energies 2023, 16, 5868 27 of 35
26. Parisi, M.L.; Maranghi, S.; Basosi, R. The Evolution of the Dye Sensitized Solar Cells from Grätzel Prototype to Up-Scaled Solar
Applications: A Life Cycle Assessment Approach. Renew. Sustain. Energy Rev. 2014, 39, 124–138. [CrossRef]
27. Azaid, A.; Raftani, M.; Alaqarbeh, M.; Kacimi, R.; Abram, T.; Khaddam, Y.; Nebbach, D.; Sbai, A.; Lakhlifi, T.; Bouachrine, M.
New Organic Dye-Sensitized Solar Cells Based on the D-A-π-A Structure for Efficient DSSCs: DFT/TD-DFT Investigations. RSC
Adv. 2022, 12, 30626–30638. [CrossRef] [PubMed]
28. Lee, C.P.; Li, C.T.; Ho, K.C. Use of Organic Materials in Dye-Sensitized Solar Cells. Mater. Today 2017, 20, 267–283. [CrossRef]
29. Kwaku Asiam, F.; Mahbubur Rahman, M.; Kumar Kaliamurthy, A.; Muthu, S.; Yadagiri, B.; Cheol Kang, H.; Chen, C.; Yoo,
K.; Lee, J.-J. Role of Pi-Electron Density at the Interface of Small Molecule-Sensitized Solar Cells. J. Phys. Chem. C 2023, 127,
3928–3939. [CrossRef]
30. Soonmin, H.; Hardani; Nandi, P.; Mwankemwa, B.S.; Malevu, T.D.; Malik, M.I. Overview on Different Types of Solar Cells: An
Update. Appl. Sci. 2023, 13, 2051. [CrossRef]
31. Crisp, R.W.; Kirkwood, N.; Grimaldi, G.; Kinge, S.; Siebbeles, L.D.A.; Houtepen, A.J. Highly Photoconductive InP Quantum Dots
Films and Solar Cells. ACS Appl. Energy Mater. 2018, 1, 6569–6576. [CrossRef]
32. Wu, J.; Li, M.-H.; Jiang, Y.; Xu, Q.; Xian, L.; Guo, H.; Wan, J.; Wen, R.; Fang, Y.; Xie, D.; et al. Carrier Management via Integrating
InP Quantum Dots into Electron Transport Layer for Efficient Perovskite Solar Cells. ACS Nano 2022, 16, 15063–15071. [CrossRef]
33. Pidluzhna, A.; Stakhira, P.; Baryshnikov, G.; Zavaraki, A.J.; Ågren, H. InP/ZnS Quantum Dots Synthesis and Photovoltaic
Application. Appl. Nanosci. 2022, 13, 4969–4975. [CrossRef]
34. Halder, G.; Ghosh, D.; Ali, M.Y.; Sahasrabudhe, A.; Bhattacharyya, S. Interface Engineering in Quantum-Dot-Sensitized Solar
Cells. Langmuir 2018, 34, 10197–10216. [CrossRef]
35. Young Kim, J.; Lee, J.-W.; Suk Jung, H.; Shin, H.; Park, N.-G. High-Efficiency Perovskite Solar Cells. Chem. Rev. 2020, 120,
7867–7918. [CrossRef]
36. Mehrabian, M.; Dalir, S.; Mahmoudi, G.; Miroslaw, B.; Babashkina, M.G.; Dektereva, A.V.; Safin, D.A. A Highly Stable All-
Inorganic CsPbBr3 Perovskite Solar Cell. Eur. J. Inorg. Chem. 2019, 2019, 3699–3703. [CrossRef]
37. Valluvar Oli, A.; Li, Z.; Chen, Y.; Ivaturi, A. Near-Ultraviolet Indoor Black Light-Harvesting Perovskite Solar Cells. ACS Appl.
Energy Mater. 2022, 5, 14669–14679. [CrossRef]
38. Al-Ahmed, A.; Afzaal, M.; Mahar, N.; Khan, F.; Pandey, S.; Zahir, M.H.; Al-Suliman, F.A. The Synergy of Lead Chalcogenide
Nanocrystals in Polymeric Bulk Heterojunction Solar Cells. ACS Omega 2022, 7, 45981–45990. [CrossRef]
39. Tao, S.; Schmidt, I.; Brocks, G.; Jiang, J.; Tranca, I.; Meerholz, K.; Olthof, S. Absolute Energy Level Positions in Tin- and Lead-Based
Halide Perovskites. Nat. Commun. 2019, 10, 2560. [CrossRef] [PubMed]
40. Song, H.; Lin, Y.; Zhou, M.; Rao, H.; Pan, Z.; Zhong, X. Zn-Cu-In-S-Se Quinary “Green” Alloyed Quantum-Dot-Sensitized Solar
Cells with a Certified Efficiency of 14.4%. Angew. Chemie-Int. Ed. 2021, 60, 6137–6144. [CrossRef]
41. Min, H.; Lee, D.Y.; Kim, J.; Kim, G.; Lee, K.S.; Kim, J.; Paik, M.J.; Kim, Y.K.; Kim, K.S.; Kim, M.G.; et al. Perovskite Solar Cells with
Atomically Coherent Interlayers on SnO2 Electrodes. Nature 2021, 598, 444–450. [CrossRef]
42. Park, J.; Kim, J.; Yun, H.-S.; Paik, M.J.; Noh, E.; Mun, H.J.; Kim, M.G.; Shin, T.J.; Seok, S. Il Controlled Growth of Perovskite Layers
with Volatile Alkylammonium Chlorides. Nature 2023, 616, 724–730. [CrossRef]
43. Sulaman, M.; Yang, S.; Imran, A.; Zhang, Z.; Bukhtiar, A.; Ge, Z.; Song, Y.; Sun, F.; Jiang, Y.; Tang, L.; et al. Two Bulk-
Heterojunctions Made of Blended Hybrid Nanocomposites for High-Performance Broadband, Self-Driven Photodetectors. ACS
Appl. Mater. Interfaces 2023, 15, 25671–25683. [CrossRef]
44. Sulaman, M.; Yang, S.; Song, Y.; Bukhtiar, A.; Hu, J.; Zhang, Z.; Jiang, Y.; Cui, Y.; Tang, L.; Zou, B. Hybrid Nanocomposites
of All-Inorganic Halide Perovskites with Polymers for High-Performance Field-Effect-Transistor-Based Photodetectors: An
Experimental and Simulation Study. Adv. Mater. Interfaces 2022, 9, 2200017. [CrossRef]
45. Sulaman, M.; Yang, S.Y.; Zhang, Z.H.; Imran, A.; Bukhtiar, A.; Ge, Z.H.; Tang, Y.; Jiang, Y.R.; Tang, L.B.; Zou, B.S. Lead-Free
Tin-Based Perovskites Nanocrystals for High-Performance Self-Driven Bulk-Heterojunction Photodetectors. Mater. Today Phys.
2022, 27, 100829. [CrossRef]
46. Sulaman, M.; Yang, S.; Bukhtiar, A.; Tang, P.; Zhang, Z.; Song, Y.; Imran, A.; Jiang, Y.; Cui, Y.; Tang, L.; et al. Hybrid Bulk-
Heterojunction of Colloidal Quantum Dots and Mixed-Halide Perovskite Nanocrystals for High-Performance Self-Powered
Broadband Photodetectors. Adv. Funct. Mater. 2022, 32, 2201527. [CrossRef]
47. Dastgeer, G.; Khan, M.F.; Nazir, G.; Afzal, A.M.; Aftab, S.; Naqvi, B.A.; Cha, J.; Min, K.A.; Jamil, Y.; Jung, J.; et al. Temperature-
Dependent and Gate-Tunable Rectification in a Black Phosphorus/WS2 van Der Waals Heterojunction Diode. ACS Appl. Mater.
Interfaces 2018, 10, 13150–13157. [CrossRef]
48. Perveen, A.; Hussain, S.; Xu, Y.; Raza, A.; Saeed, F.; Din, N.; Subramanian, A.; Khan, Q.; Lei, W. Solution Processed and Highly
Efficient UV-Photodetector Based on CsPbBr3 Perovskite-Polymer Composite Film. J. Photochem. Photobiol. A Chem. 2022,
426, 113764. [CrossRef]
49. Sulaman, M.; Sulaman, M.; Song, Y.; Yang, S.; Yang, S.; Saleem, M.I.; Li, M.; Perumal Veeramalai, C.; Zhi, R.; Jiang, Y.; et al.
Interlayer of PMMA Doped with Au Nanoparticles for High-Performance Tandem Photodetectors: A Solution to Suppress Dark
Current and Maintain High Photocurrent. ACS Appl. Mater. Interfaces 2020, 12, 26153–26160. [CrossRef]
50. Saleem, M.I.; Yang, S.; Zhi, R.; Sulaman, M.; Chandrasekar, P.V.; Jiang, Y.; Tang, Y.; Batool, A.; Zou, B. Surface Engineering of
All-Inorganic Perovskite Quantum Dots with Quasi Core–Shell Technique for High-Performance Photodetectors. Adv. Mater.
Interfaces 2020, 7, 2000360. [CrossRef]
Energies 2023, 16, 5868 28 of 35
51. Saleem, M.I.; Sulaman, M.; Batool, A.; Bukhtiar, A.; Khalid, S. Suppression of Mid-Gap Trap State in CsPbBr3 Nanocrystals with
Br-Passivation for Self-Powered Photodetector. Energy Technol. 2023, 11, 2300013. [CrossRef]
52. Pv-Magazine KAUST Claims 33.2% Efficiency for Perovskite/Silicon Tandem Solar Cell. Available online: https://www.pv-
magazine.com/2023/04/13/kaust-claims-33-2-efficiency-for-perovskite-silicon-tandem-solar-cell/ (accessed on 15 June 2023).
53. Lee, W.; Son, H.J.; Lee, D.K.; Kim, B.; Kim, H.; Kim, K.; Ko, M.J. Suppression of Photocorrosion in CdS/CdSe Quantum
Dot-Sensitized Solar Cells: Formation of a Thin Polymer Layer on the Photoelectrode Surface. Synth. Met. 2013, 165, 60–63.
[CrossRef]
54. Zhan, L.; Yin, S.; Li, Y.; Li, S.; Chen, T.; Sun, R.; Min, J.; Zhou, G.; Zhu, H.; Chen, Y.; et al. Multiphase Morphology with Enhanced
Carrier Lifetime via Quaternary Strategy Enables High-Efficiency, Thick-Film, and Large-Area Organic Photovoltaics. Adv. Mater.
2022, 34, 2206269. [CrossRef]
55. Zheng, X.; Zuo, L.; Zhao, F.; Li, Y.; Chen, T.; Shan, S.; Yan, K.; Pan, Y.; Xu, B.; Li, C.-Z.; et al. High-Efficiency ITO-Free Organic
Photovoltaics with Superior Flexibility and Upscalability. Adv. Mater. 2022, 34, 2200044. [CrossRef]
56. Zuo, L.; Jo, S.B.; Li, Y.; Meng, Y.; Stoddard, R.J.; Liu, Y.; Lin, F.; Shi, X.; Liu, F.; Hillhouse, H.W. Dilution Effect for Highly Efficient
Multiple-Component Organic Solar Cells. Nat. Nanotechnol. 2022, 17, 53–60. [CrossRef]
57. Kim, T.; Kim, J.-H.; Kang, T.E.; Lee, C.; Kang, H.; Shin, M.; Wang, C.; Ma, B.; Jeong, U.; Kim, T.-S.; et al. Flexible, Highly Efficient
All-Polymer Solar Cells. Nat. Commun. 2015, 6, 8547. [CrossRef]
58. Inganäs, O. Organic Photovoltaics over Three Decades. Adv. Mater. 2018, 30, 1800388. [CrossRef]
59. Wöhrle, D.; Meissner, D. Organic Solar Cells. Adv. Mater. 1991, 3, 129–138. [CrossRef]
60. Chamberlain, G.A. Organic Solar Cells: A Review. Sol. Cells 1983, 8, 47–83. [CrossRef]
61. Yeh, N.; Yeh, P. Organic Solar Cells: Their Developments and Potentials. Renew. Sustain. Energy Rev. 2013, 21, 421–431. [CrossRef]
62. Morel, D.L.; Ghosh, A.K.; Feng, T.; Stogryn, E.L.; Purwin, P.E.; Shaw, R.F.; Fishman, A.C. High-efficiency Organic Solar Cells.
Appl. Phys. Lett. 1978, 32, 495–497. [CrossRef]
63. Ghosh, A.K.; Feng, T. Merocyanine Organic Solar Cells. J. Appl. Phys. 1978, 49, 5982–5989. [CrossRef]
64. Tang, C.W. Two-layer Organic Photovoltaic Cell. Appl. Phys. Lett. 1986, 48, 183–185. [CrossRef]
65. Antoniadis, H.; Hsieh, B.R.; Abkowitz, M.A.; Jenekhe, S.A.; Stolka, M. Photovoltaic and Photoconductive Properties of Alu-
minum/Poly (p-Phenylene Vinylene) Interfaces. Synth. Met. 1994, 62, 265–271. [CrossRef]
66. Marks, R.N.; Halls, J.J.M.; Bradley, D.D.C.; Friend, R.H.; Holmes, A.B. The Photovoltaic Response in Poly (p-Phenylene Vinylene)
Thin-Film Devices. J. Phys. Condens. Matter 1994, 6, 1379. [CrossRef]
67. Smilowitz, L.; Sariciftci, N.S.; Wu, R.; Gettinger, C.; Heeger, A.J.; Wudl, F. Photoexcitation Spectroscopy of Conducting-PolymerC60
Composites: Photoinduced Electron Transfer. Phys. Rev. B 1993, 47, 13835–13842. [CrossRef]
68. Sariciftci, N.S.; Smilowitz, L.; Heeger, A.J.; Wudl, F. Photoinduced Electron Transfer from a Conducting Polymer to Buckminster-
fullerene. Science 1992, 258, 1474–1476. [CrossRef]
69. Morita, S.; Kiyomatsu, S.; Yin, X.H.; Zakhidov, A.A.; Noguchi, T.; Ohnishi, T.; Yoshino, K. Doping Effect of Buckminsterfullerene
in Poly (2,5-dialkoxy-p-phenylene Vinylene). J. Appl. Phys. 1993, 74, 2860–2865. [CrossRef]
70. Roman, L.S.; Mammo, W.; Pettersson, L.A.A.; Andersson, M.R.; Inganäs, O. High Quantum Efficiency Polythiophene. Adv. Mater.
1998, 10, 774–777. [CrossRef]
71. Halls, J.J.M.; Pichler, K.; Friend, R.H.; Moratti, S.C.; Holmes, A.B. Exciton Diffusion and Dissociation in a Poly (P-
phenylenevinylene)/C60 Heterojunction Photovoltaic Cell. Appl. Phys. Lett. 1996, 68, 3120–3122. [CrossRef]
72. Yang, C.Y.; Heeger, A.J. Morphology of Composites of Semiconducting Polymers Mixed with C60 . Synth. Met. 1996, 83, 85–88.
[CrossRef]
73. Yu, G.; Gao, J.; Hummelen, J.C.; Wudl, F.; Heeger, A.J. Polymer Photovoltaic Cells: Enhanced Efficiencies via a Network of
Internal Donor-Acceptor Heterojunctions. Science 1995, 270, 1789–1791. [CrossRef]
74. Gnida, P.; Amin, M.F.; Pajak, A.K.; Jarzabek, B. Polymers in High-Efficiency Solar Cells: The Latest Reports. Polymers 2022,
14, 1946. [CrossRef]
75. Labiod, A.; Ibraikulov, O.A.; Dabos-Seignon, S.; Ferry, S.; Heinrich, B.; Méry, S.; Fall, S.; Tchognia Nkuissi, H.J.; Heiser, T.;
Cabanetos, C.; et al. Photo-Degradation in Bulk Heterojunction Organic Solar Cells Using a Fullerene or a Non-Fullerene
Derivative Electron Acceptor. Org. Electron. 2022, 107, 106549. [CrossRef]
76. Kaim, A.; Piotrowski, P.; Zar˛ebska, K.; Bogdanowicz, K.A.; Przybył, W.; Kwak, A.; Skompska, M.; Gnida, P.; Schab-Balcerzak, E.;
Iwan, A. Thermal Imaging and Deep Optical and Electrochemical Study of C70 Fullerene Derivatives with Thiophene, Pyrrolidine
or Indene Moieties along with Electropolymerization with Thiophene Substituted Imine: Blends with P3HT and PTB7. Electrochim.
Acta 2022, 426, 140741. [CrossRef]
77. Liang, S.; Xiao, C.; Xie, C.; Liu, B.; Fang, H.; Li, W. 13% Single-Component Organic Solar Cells Based on Double-Cable Conjugated
Polymers with Pendent Y-Series Acceptors. Adv. Mater. 2023, 35, e2300629. [CrossRef]
78. Shaheen, S.E.; Brabec, C.J.; Sariciftci, N.S.; Padinger, F.; Fromherz, T.; Hummelen, J.C. 2.5% Efficient Organic Plastic Solar Cells.
Appl. Phys. Lett. 2001, 78, 841–843. [CrossRef]
79. Levitsky, A.; Schneider, S.A.; Rabkin, E.; Toney, M.F.; Frey, G.L. Bridging the Thermodynamics and Kinetics of Temperature-
Induced Morphology Evolution in Polymer/Fullerene Organic Solar Cell Bulk Heterojunction. Mater. Horizons 2021, 8, 1272–1285.
[CrossRef]
Energies 2023, 16, 5868 29 of 35
80. Sprau, C.; Kattenbusch, J.; Li, Y.; Müller, E.; Gerthsen, D.; Berger, R.; Michels, J.J.; Colsmann, A. Revisiting Solvent Additives for
the Fabrication of Polymer:Fullerene Solar Cells: Exploring a Series of Benzaldehydes. Sol. RRL 2021, 5, 2100238. [CrossRef]
81. Grodniski, D.C.; Benatto, L.; Gonçalves, J.P.; de Oliveira, C.C.; Pacheco, K.R.M.; Adad, L.B.; Coturi, V.M.; Roman, L.S.; Koehler,
M. High Photothermal Conversion Efficiency for Semiconducting Polymer/Fullerene Nanoparticles and Its Correlation with
Photoluminescence Quenching. RSC Chem. Biol. 2022, 4, 486–503. [CrossRef]
82. Li, S.; Hamada, F.; Nishikubo, R.; Saeki, A. Quantifying the Optimal Thickness in Polymer:Fullerene Solar Cells from the Analysis
of Charge Transport Dynamics and Photoabsorption. Sustain. Energy Fuels 2022, 6, 756–765. [CrossRef]
83. Hoppe, H.; Sariciftci, N.S. Organic Solar Cells: An Overview. J. Mater. Res. 2004, 19, 1924–1945. [CrossRef]
84. Hou, J.; Inganäs, O.; Friend, R.H.; Gao, F. Organic Solar Cells Based on Non-Fullerene Acceptors. Nat. Mater. 2018, 17, 119–128.
[CrossRef] [PubMed]
85. Kietzke, T. Recent Advances in Organic Solar Cells. Adv. Optoelectron. 2007, 2007, 40285. [CrossRef]
86. Kim, H.U.; Kim, J.-H.; Kang, H.; Grimsdale, A.C.; Kim, B.J.; Yoon, S.C.; Hwang, D.-H. Naphthalene-, Anthracene-, and Pyrene-
Substituted Fullerene Derivatives as Electron Acceptors in Polymer-Based Solar Cells. ACS Appl. Mater. Interfaces 2014, 6,
20776–20785. [CrossRef] [PubMed]
87. Zhao, G.; He, Y.; Xu, Z.; Hou, J.; Zhang, M.; Min, J.; Chen, H.-Y.; Ye, M.; Hong, Z.; Yang, Y.; et al. Effect of Carbon Chain Length in
the Substituent of PCBM-like Molecules on Their Photovoltaic Properties. Adv. Funct. Mater. 2010, 20, 1480–1487. [CrossRef]
88. Mikroyannidis, J.A.; Kabanakis, A.N.; Sharma, S.S.; Sharma, G.D. A Simple and Effective Modification of PCBM for Use as an
Electron Acceptor in Efficient Bulk Heterojunction Solar Cells. Adv. Funct. Mater. 2011, 21, 746–755. [CrossRef]
89. Xu, X.; Yu, T.; Bi, Z.; Ma, W.; Li, Y.; Peng, Q. Realizing Over 13% Efficiency in Green-Solvent-Processed Nonfullerene Organic
Solar Cells Enabled by 1,3,4-Thiadiazole-Based Wide-Bandgap Copolymers. Adv. Mater. 2018, 30, 1703973. [CrossRef]
90. Lin, Y.; Zhao, F.; He, Q.; Huo, L.; Wu, Y.; Parker, T.C.; Ma, W.; Sun, Y.; Wang, C.; Zhu, D.; et al. High-Performance Electron
Acceptor with Thienyl Side Chains for Organic Photovoltaics. J. Am. Chem. Soc. 2016, 138, 4955–4961. [CrossRef]
91. Li, T.; Dai, S.; Ke, Z.; Yang, L.; Wang, J.; Yan, C.; Ma, W.; Zhan, X. Fused Tris (Thienothiophene)-Based Electron Acceptor with
Strong Near-Infrared Absorption for High-Performance As-Cast Solar Cells. Adv. Mater. 2018, 30, 1705969. [CrossRef]
92. Liu, Q.; Jiang, Y.; Jin, K.; Qin, J.; Xu, J.; Li, W.; Xiong, J.; Liu, J.; Xiao, Z.; Sun, K.; et al. 18% Efficiency Organic Solar Cells. Sci. Bull.
2020, 65, 272–275. [CrossRef]
93. Zhang, S.; Ye, L.; Hou, J. Breaking the 10% Efficiency Barrier in Organic Photovoltaics: Morphology and Device Optimization of
Well-Known PBDTTT Polymers. Adv. Energy Mater. 2016, 6, 1502529. [CrossRef]
94. Fu, Y.; Lee, T.H.; Chin, Y.-C.; Pacalaj, R.A.; Labanti, C.; Park, S.Y.; Dong, Y.; Cho, H.W.; Kim, J.Y.; Minami, D.; et al. Molecular
Orientation-Dependent Energetic Shifts in Solution-Processed Non-Fullerene Acceptors and Their Impact on Organic Photovoltaic
Performance. Nat. Commun. 2023, 14, 1870. [CrossRef]
95. Wang, Y.; Lee, J.; Hou, X.; Labanti, C.; Yan, J.; Mazzolini, E.; Parhar, A.; Nelson, J.; Kim, J.-S.; Li, Z. Recent Progress and Challenges
toward Highly Stable Nonfullerene Acceptor-Based Organic Solar Cells. Adv. Energy Mater. 2021, 11, 2003002. [CrossRef]
96. Lan, W.; Gu, J.; Wu, S.; Peng, Y.; Zhao, M.; Liao, Y.; Xu, T.; Wei, B.; Ding, L.; Zhu, F. Toward Improved Stability of Nonfullerene
Organic Solar Cells: Impact of Interlayer and Built-in Potential. EcoMat 2021, 3, e12134. [CrossRef]
97. Wang, X.; Zhao, C.X.; Xu, G.; Chen, Z.K.; Zhu, F. Degradation Mechanisms in Organic Solar Cells: Localized Moisture Encroach-
ment and Cathode Reaction. Sol. Energy Mater. Sol. Cells 2012, 104, 1–6. [CrossRef]
98. Fu, J.; Fong, P.W.K.; Liu, H.; Huang, C.-S.; Lu, X.; Lu, S.; Abdelsamie, M.; Kodalle, T.; Sutter-Fella, C.M.; Yang, Y.; et al. 19.31%
Binary Organic Solar Cell and Low Non-Radiative Recombination Enabled by Non-Monotonic Intermediate State Transition. Nat.
Commun. 2023, 14, 1760. [CrossRef]
99. Tarique, W.B.; Uddin, A. A Review of Progress and Challenges in the Research Developments on Organic Solar Cells. Mater. Sci.
Semicond. Process. 2023, 163, 107541. [CrossRef]
100. Adnan, M.; Irshad, Z.; Hussain, R.; Lee, W.; Kim, M.; Lim, J. Efficient Ternary Active Layer Materials for Organic Photovoltaics.
Sol. Energy 2023, 257, 324–343. [CrossRef]
101. Li, D.; Deng, N.; Fu, Y.; Guo, C.; Zhou, B.; Wang, L.; Zhou, J.; Liu, D.; Li, W.; Wang, K.; et al. Fibrillization of Non-Fullerene
Acceptors Enables 19% Efficiency Pseudo-Bulk Heterojunction Organic Solar Cells. Adv. Mater. 2023, 35, 2208211. [CrossRef]
102. Zhang, Y.; Lang, Y.; Li, G. Recent Advances of Non-Fullerene Organic Solar Cells: From Materials and Morphology to Devices
and Applications. EcoMat 2023, 5, e12281. [CrossRef]
103. Gu, X.; Lai, X.; Zhang, Y.; Wang, T.; Tan, W.L.; McNeill, C.R.; Liu, Q.; Sonar, P.; He, F.; Li, W.; et al. Organic Solar Cell With
Efficiency Over 20% and VOC Exceeding 2.1 V Enabled by Tandem with All-Inorganic Perovskite and Thermal Annealing-Free
Process. Adv. Sci. 2022, 9, e2200445. [CrossRef] [PubMed]
104. Zhu, L.; Zhang, M.; Xu, J.; Li, C.; Yan, J.; Zhou, G.; Zhong, W.; Hao, T.; Song, J.; Xue, X.; et al. Single-Junction Organic Solar Cells
with over 19% Efficiency Enabled by a Refined Double-Fibril Network Morphology. Nat. Mater. 2022, 21, 656–663. [CrossRef]
105. Cui, Y.; Xu, Y.; Yao, H.; Bi, P.; Hong, L.; Zhang, J.; Zu, Y.; Zhang, T.; Qin, J.; Ren, J.; et al. Single-Junction Organic Photovoltaic Cell
with 19% Efficiency. Adv. Mater. 2021, 33, 2102420. [CrossRef]
106. Green, M.A.; Dunlop, E.D.; Siefer, G.; Yoshita, M.; Kopidakis, N.; Bothe, K.; Hao, X. Solar Cell Efficiency Tables (Version 61). Prog.
Photovolt. Res. Appl. 2023, 31, 3–16. [CrossRef]
107. Ding, G.; Chen, T.; Wang, M.; Xia, X.; He, C.; Zheng, X.; Li, Y.; Zhou, D.; Lu, X.; Zuo, L.; et al. Solid Additive-Assisted
Layer-by-Layer Processing for 19% Efficiency Binary Organic Solar Cells. Nano-Micro Lett. 2023, 15, 92. [CrossRef]
Energies 2023, 16, 5868 30 of 35
108. Balakirev, D.O.; Mannanov, A.L.; Emelianov, N.A.; Sukhorukova, P.K.; Kalinichenko, A.K.; Troshin, P.A.; Paraschuk, D.Y.;
Ponomarenko, S.A.; Luponosov, Y.N. Star-Shaped Benzotriindole-Based Donor Compounds for All–Small–Molecule Non-
Fullerene Organic Solar Cells. Dye. Pigment. 2023, 216, 111343. [CrossRef]
109. Shi, Y.; Zhu, L.; Yan, Y.; Xie, M.; Liang, G.; Qiao, J.; Zhang, J.; Hao, X.; Lu, K.; Wei, Z. Small Energetic Disorder Enables Ultralow
Energy Losses in Non-Fullerene Organic Solar Cells. Adv. Energy Mater. 2023, 13, 2300458. [CrossRef]
110. Zhan, L.; Li, S.; Zhang, S.; Chen, X.; Lau, T.-K.; Lu, X.; Shi, M.; Li, C.-Z.; Chen, H. Enhanced Charge Transfer between Fullerene and
Non-Fullerene Acceptors Enables Highly Efficient Ternary Organic Solar Cells. ACS Appl. Mater. Interfaces 2018, 10, 42444–42452.
[CrossRef]
111. Hai, J.; Song, Y.; Li, L.; Liu, X.; Shi, X.; Huang, Z.; Qian, G.; Lu, Z.; Yu, J.; Hu, H.; et al. High-Efficiency Organic Solar Cells Enabled
by Chalcogen Containing Branched Chain Engineering: Balancing Short-Circuit Current and Open-Circuit Voltage, Enhancing
Fill Factor. Adv. Funct. Mater. 2023, 33, 2213429. [CrossRef]
112. Xu, X.; Jing, W.; Meng, H.; Guo, Y.; Yu, L.; Li, R.; Peng, Q. Sequential Deposition of Multicomponent Bulk Heterojunctions
Increases Efficiency of Organic Solar Cells. Adv. Mater. 2023, 35, e2208997. [CrossRef]
113. Zhang, G.; Chen, Q.; Zhang, Z.; Fang, J.; Zhao, C.; Wei, Y.; Li, W. Co-La-Based Hole-Transporting Layers for Binary Organic Solar
Cells with 18.82% Efficiency. Angew. Chemie-Int. Ed. 2023, 62, e202216304. [CrossRef]
114. Cheng, P.; Li, G.; Zhan, X.; Yang, Y. Next-Generation Organic Photovoltaics Based on Non-Fullerene Acceptors. Nat. Photonics
2018, 12, 131–142. [CrossRef]
115. Rafique, S.; Abdullah, S.M.; Sulaiman, K.; Iwamoto, M. Fundamentals of Bulk Heterojunction Organic Solar Cells: An Overview
of Stability/Degradation Issues and Strategies for Improvement. Renew. Sustain. Energy Rev. 2018, 84, 43–53. [CrossRef]
116. Halls, J.J.M.; Walsh, C.A.; Greenham, N.C.; Marseglia, E.A.; Friend, R.H.; Moratti, S.C.; Holmes, A.B. Efficient Photodiodes from
Interpenetrating Polymer Networks. Nature 1995, 376, 498–500. [CrossRef]
117. He, C.; Bi, Z.; Chen, Z.; Guo, J.; Xia, X.; Lu, X.; Min, J.; Zhu, H.; Ma, W.; Zuo, L.; et al. Compromising Charge Generation
and Recombination with Asymmetric Molecule for High-Performance Binary Organic Photovoltaics with over 18% Certified
Efficiency. Adv. Funct. Mater. 2022, 32, 2112511. [CrossRef]
118. Yao, J.; Ding, S.; Zhang, R.; Bai, Y.; Zhou, Q.; Meng, L.; Solano, E.; Steele, J.A.; Roeffaers, M.B.J.; Gao, F.; et al. Fluorinated
Perylene-Diimides: Cathode Interlayers Facilitating Carrier Collection for High-Performance Organic Solar Cells. Adv. Mater.
2022, 34, 2203690. [CrossRef]
119. Heeger, A.J. 25th Anniversary Article: Bulk Heterojunction Solar Cells: Understanding the Mechanism of Operation. Adv. Mater.
2014, 26, 10–28. [CrossRef]
120. Wang, Z.; Gao, K.; Kan, Y.; Zhang, M.; Qiu, C.; Zhu, L.; Zhao, Z.; Peng, X.; Feng, W.; Qian, Z.; et al. The Coupling and Competition
of Crystallization and Phase Separation, Correlating Thermodynamics and Kinetics in OPV Morphology and Performances. Nat.
Commun. 2021, 12, 332. [CrossRef]
121. Dey, S. Recent Progress in Molecular Design of Fused Ring Electron Acceptors for Organic Solar Cells. Small 2019, 15, 1900134.
[CrossRef]
122. Fu, H.; Wang, Z.; Sun, Y. Advances in Non-Fullerene Acceptor Based Ternary Organic Solar Cells. Sol. RRL 2018, 2, 1700158.
[CrossRef]
123. Zhang, J.; Zhang, Y.; Fang, J.; Lu, K.; Wang, Z.; Ma, W.; Wei, Z. Conjugated Polymer–Small Molecule Alloy Leads to High Efficient
Ternary Organic Solar Cells. J. Am. Chem. Soc. 2015, 137, 8176–8183. [CrossRef]
124. Cheng, P.; Li, Y.; Zhan, X. Efficient Ternary Blend Polymer Solar Cells with Indene-C60 Bisadduct as an Electron-Cascade Acceptor.
Energy Environ. Sci. 2014, 7, 2005–2011. [CrossRef]
125. Lu, L.; Chen, W.; Xu, T.; Yu, L. High-Performance Ternary Blend Polymer Solar Cells Involving both Energy Transfer and Hole
Relay Processes. Nat. Commun. 2015, 6, 7327. [CrossRef] [PubMed]
126. Liu, B.; Sun, H.; Lee, J.-W.; Jiang, Z.; Qiao, J.; Wang, J.; Yang, J.; Feng, K.; Liao, Q.; An, M.; et al. Efficient and Stable Organic Solar
Cells Enabled by Multicomponent Photoactive Layer Based on One-Pot Polymerization. Nat. Commun. 2023, 14, 967. [CrossRef]
127. Yu, H.; Wang, Y.; Zou, X.; Yin, J.; Shi, X.; Li, Y.; Zhao, H.; Wang, L.; Ng, H.M.; Zou, B.; et al. Improved Photovoltaic Performance
and Robustness of All-Polymer Solar Cells Enabled by a Polyfullerene Guest Acceptor. Nat. Commun. 2023, 14, 2323. [CrossRef]
[PubMed]
128. Liu, Z.; Wang, L.; Zhao, H.; Chen, P.; Xie, X. High-Performance Inverted Ternary Organic Solar Cells Using Solution-Processed
Tin Oxide as the Electron Transport Layer. Org. Electron. 2023, 120, 106828. [CrossRef]
129. Liu, M.; Ge, X.; Jiang, X.; Chen, D.; Guo, F.; Gao, S.; Peng, Q.; Zhao, L.; Zhang, Y. 18% Efficiency of Ternary Organic Solar Cells
Enabled by Integrating a Fused Perylene Diimide Guest Acceptor. Nano Energy 2023, 112, 108501. [CrossRef]
130. Lv, J.; Yang, Q.; Deng, W.; Chen, H.; Kumar, M.; Zhao, F.; Lu, S.; Hu, H.; Kan, Z. Isomeric Acceptors Incorporation Enables 18.1%
Efficiency Ternary Organic Solar Cells with Reduced Trap-Assisted Charge Recombination. Chem. Eng. J. 2023, 465, 142822.
[CrossRef]
131. Xu, R.; Jiang, Y.; Liu, F.; Su, W.; Liu, W.; Xu, S.; Fan, H.; Jiang, C.; Zong, Q.; Zhang, W.; et al. Efficient Ternary Organic Solar Cells
Enabled by Asymmetric Nonfullerene Electron Acceptor with Suppressed Nonradiative Recombination. Chem. Eng. J. 2023,
464, 142507. [CrossRef]
132. Ram, K.S.; Singh, J. Over 20% Efficient and Stable Non-Fullerene-Based Ternary Bulk-Heterojunction Organic Solar Cell with
WS2 Hole-Transport Layer and Graded Refractive Index Antireflection Coating. Adv. Theory Simul. 2020, 3, 2000047. [CrossRef]
Energies 2023, 16, 5868 31 of 35
133. Bi, P.; Wang, J.; Cui, Y.; Zhang, J.; Zhang, T.; Chen, Z.; Qiao, J.; Dai, J.; Zhang, S.; Hao, X. Enhancing Photon Utilization Efficiency
for High-Performance Organic Photovoltaic Cells via Regulating Phase-Transition Kinetics. Adv. Mater. 2023, 35, e2210865.
[CrossRef]
134. Jia, Z.; Qin, S.; Meng, L.; Ma, Q.; Angunawela, I.; Zhang, J.; Li, X.; He, Y.; Lai, W.; Li, N.; et al. High Performance Tandem Organic
Solar Cells via a Strongly Infrared-Absorbing Narrow Bandgap Acceptor. Nat. Commun. 2021, 12, 178. [CrossRef] [PubMed]
135. Lu, S.; Ouyang, D.; Choy, W.C.H. Recent Progress of Interconnecting Layer for Tandem Organic Solar Cells. Sci. China Chem. 2017,
60, 460–471. [CrossRef]
136. Guo, B.; Li, W.; Luo, G.; Guo, X.; Yao, H.; Zhang, M.; Hou, J.; Li, Y.; Wong, W.-Y. Exceeding 14% Efficiency for Solution-Processed
Tandem Organic Solar Cells Combining Fullerene-and Nonfullerene-Based Subcells with Complementary Absorption. ACS
Energy Lett. 2018, 3, 2566–2572. [CrossRef]
137. Li, Y.; Huang, W.; Zhao, D.; Wang, L.; Jiao, Z.; Huang, Q.; Wang, P.; Sun, M.; Yuan, G. Recent Progress in Organic Solar Cells: A
Review on Materials from Acceptor to Donor. Molecules 2022, 27, 1800. [CrossRef] [PubMed]
138. Almuqoddas, E.; Neophytou, M.; Widianto, E.; Nursam, N.M.; Shobih; Pranoto, L.M.; Firdaus, Y. Semi-Transparent Fullerene-
Based Tandem Solar Cells with Excellent Light Utilization Efficiency Enabled by Careful Selection of Sub-Cells. Org. Electron.
2022, 109, 106633. [CrossRef]
139. Meng, L.; Zhang, Y.; Wan, X.; Li, C.; Zhang, X.; Wang, Y.; Ke, X.; Xiao, Z.; Ding, L.; Xia, R.; et al. Organic and Solution-Processed
Tandem Solar Cells with 17.3% Efficiency. Science 2018, 361, 1094–1098. [CrossRef]
140. Liu, G.; Xia, R.; Huang, Q.; Zhang, K.; Hu, Z.; Jia, T.; Liu, X.; Yip, H.-L.; Huang, F. Tandem Organic Solar Cells with 18.7%
Efficiency Enabled by Suppressing the Charge Recombination in Front Sub-Cell. Adv. Funct. Mater. 2021, 31, 2103283. [CrossRef]
141. Zheng, Z.; Wang, J.; Bi, P.; Ren, J.; Wang, Y.; Yang, Y.; Liu, X.; Zhang, S.; Hou, J. Tandem Organic Solar Cell with 20.2% Efficiency.
Joule 2022, 6, 171–184. [CrossRef]
142. Grätzel, M. Photoelectrochemical Cells. Nature 2001, 414, 338–344. [CrossRef]
143. Kalyanasundaram, K.; Grätzel, M. Applications of Functionalized Transition Metal Complexes in Photonic and Optoelectronic
Devices. Coord. Chem. Rev. 1998, 177, 347–414. [CrossRef]
144. Grätzel, M. Dye-Sensitized Solar Cells. J. Photochem. Photobiol. C Photochem. Rev. 2003, 4, 145–153. [CrossRef]
145. Grobelny, A.; Shen, Z.; Eickemeyer, F.T.; Antariksa, N.F.; Zapotoczny, S.; Zakeeruddin, S.M.; Grätzel, M. A Molecularly Tailored
Photosensitizer with an Efficiency of 13.2% for Dye-Sensitized Solar Cells. Adv. Mater. 2023, 35, 2207785. [CrossRef] [PubMed]
146. Ren, Y.; Cao, Y.; Zhang, D.; Zakeeruddin, S.M.; Hagfeldt, A.; Wang, P.; Grätzel, M. A Blue Photosensitizer Realizing Efficient and
Stable Green Solar Cells via Color Tuning by the Electrolyte. Adv. Mater. 2020, 32, 2000193. [CrossRef]
147. Dou, J.; Chen, Q. MOFs in Emerging Solar Cells. Chin. J. Chem. 2023, 41, 695–709. [CrossRef]
148. Bandara, T.M.W.J.; Hansadi, J.M.C.; Bella, F. A Review of Textile Dye-Sensitized Solar Cells for Wearable Electronics. Ionics 2022,
28, 2563–2583. [CrossRef]
149. Devadiga, D.; Selvakumar, M.; Shetty, P.; Santosh, M.S. The Integration of Flexible Dye-Sensitized Solar Cells and Storage Devices
towards Wearable Self-Charging Power Systems: A Review. Renew. Sustain. Energy Rev. 2022, 159, 112252. [CrossRef]
150. Barbato, M.; Artegiani, E.; Bertoncello, M.; Meneghini, M.; Ortolani, L.; Zanoni, E.; Meneghesso, G. CdTe Solar Cells: Technology,
Operation and Reliability. J. Phys. D Appl. Phys. 2021, 54, 333002. [CrossRef]
151. Sameera, J.N.; Islam, M.A.; Islam, S.; Hossain, T.; Sobayel, M.K.; Akhtaruzzaman, M.; Amin, N.; Rashid, M.J. Cubic Silicon Carbide
(3C–SiC) as a Buffer Layer for High Efficiency and Highly Stable CdTe Solar Cell. Opt. Mater. 2022, 123, 111911. [CrossRef]
152. Buitrago, E.; Novello, A.M.; Meyer, T. Third-Generation Solar Cells: Toxicity and Risk of Exposure. Helv. Chim. Acta 2020,
103, e2000074. [CrossRef]
153. Rimmaudo, I.; Salavei, A.; Artegiani, E.; Menossi, D.; Giarola, M.; Mariotto, G.; Gasparotto, A.; Romeo, A. Improved Stability of
CdTe Solar Cells by Absorber Surface Etching. Sol. Energy Mater. Sol. Cells 2017, 162, 127–133. [CrossRef]
154. Zhang, H.; Cheng, K.; Hou, Y.M.; Fang, Z.; Pan, Z.X.; Wu, W.J.; Hua, J.L.; Zhong, X.H. Efficient CdSe Quantum Dot-Sensitized
Solar Cells Prepared by a Postsynthesis Assembly Approach. Chem. Commun. 2012, 48, 11235–11237. [CrossRef] [PubMed]
155. Zheng, S.; Chen, J.; Johansson, E.M.J.; Zhang, X. PbS Colloidal Quantum Dot Inks for Infrared Solar Cells. iScience 2020, 23, 101753.
[CrossRef]
156. Sun, B.; Johnston, A.; Xu, C.; Wei, M.; Huang, Z.; Jiang, Z.; Zhou, H.; Gao, Y.; Dong, Y.; Ouellette, O.; et al. Monolayer Perovskite
Bridges Enable Strong Quantum Dot Coupling for Efficient Solar Cells. Joule 2020, 4, 1542–1556. [CrossRef]
157. Aldakov, D.; Lefrançois, A.; Reiss, P. Ternary and Quaternary Metal Chalcogenide Nanocrystals: Synthesis, Properties and
Applications. J. Mater. Chem.C 2013, 1, 3756–3776. [CrossRef]
158. Ramanujam, J.; Singh, U.P. Copper Indium Gallium Selenide Based Solar Cells—A Review. Energy Environ. Sci. 2017, 10,
1306–1319. [CrossRef]
159. Belghachi, A.; Limam, N. Effect of the Absorber Layer Band-Gap on CIGS Solar Cell. Chin. J. Phys. 2017, 55, 1127–1134. [CrossRef]
160. Bouich, A.; Ullah, S.; Ullah, H.; Mari, B.; Hartiti, B.; Ebn Touhami, M.; Santos, D.M.F. Deposit on Different Back Contacts: To
High-Quality CuInGaS2 Thin Films for Photovoltaic Application. J. Mater. Sci. Mater. Electron. 2019, 30, 20832–20839. [CrossRef]
161. Stuckelberger, M.E.; Nietzold, T.; West, B.M.; Farshchi, R.; Poplavskyy, D.; Bailey, J.; Lai, B.; Maser, J.M.; Bertoni, M.I. How Does
CIGS Performance Depend on Temperature at the Microscale? IEEE J. Photovoltaics 2018, 8, 278–287. [CrossRef]
162. Vaillon, R.; Parola, S.; Lamnatou, C.; Chemisana, D. Solar Cells Operating under Thermal Stress. Cell Reports Phys. Sci. 2020,
1, 100267. [CrossRef]
Energies 2023, 16, 5868 32 of 35
163. Nakamura, M.; Yamaguchi, K.; Kimoto, Y.; Yasaki, Y.; Kato, T.; Sugimoto, H. Cd-Free Cu(In,Ga)(Se,S)2 Thin-Film Solar Cell with
Record Efficiency of 23.35%. IEEE J. Photovoltaics 2019, 9, 1863–1867. [CrossRef]
164. Kwak, J.I.; Nam, S.H.; Kim, L.; An, Y.J. Potential Environmental Risk of Solar Cells: Current Knowledge and Future Challenges.
J. Hazard. Mater. 2020, 392, 122297. [CrossRef]
165. Nakamura, M.; Tada, K.; Kinoshita, T.; Bessho, T.; Nishiyama, C.; Takenaka, I.; Kimoto, Y.; Higashino, Y.; Sugimoto, H.; Segawa,
H. Perovskite/CIGS Spectral Splitting Double Junction Solar Cell with 28% Power Conversion Efficiency. iScience 2020, 23, 101817.
[CrossRef] [PubMed]
166. Theelen, M.; Foster, C.; Steijvers, H.; Barreau, N.; Vroon, Z.; Zeman, M. The Impact of Atmospheric Species on the Degradation of
CIGS Solar Cells. Sol. Energy Mater. Sol. Cells 2015, 141, 49–56. [CrossRef]
167. Ito, K. (Ed.) Copper Zinc Tin Sulfide-Based Thin Film Solar Cells, 1st ed.; John Wiley and Sons Ltd.: Hoboken, NJ, USA, 2015;
ISBN 9781118437872.
168. Sravani, L.; Routray, S.; Pradhan, K.P.; Piedrahita, M.C. Kesterite Thin-Film Solar Cell: Role of Grain Boundaries and Defects in
Copper–Zinc–Tin–Sulfide and Copper–Zinc–Tin–Selenide. Phys. Status Solidi Appl. Mater. Sci. 2021, 218, 2100039. [CrossRef]
169. Sun, K.; Yan, C.; Liu, F.; Huang, J.; Zhou, F.; Stride, J.A.; Green, M.; Hao, X. Over 9% Efficient Kesterite Cu2 ZnSnS4 Solar Cell
Fabricated by Using Zn1−x Cdx S Buffer Layer. Adv. Energy Mater. 2016, 6, 4–9. [CrossRef]
170. Pal, K.; Singh, P.; Bhaduri, A.; Thapa, K.B. Current Challenges and Future Prospects for a Highly Efficient (>20%) Kesterite CZTS
Solar Cell: A Review. Sol. Energy Mater. Sol. Cells 2019, 196, 138–156. [CrossRef]
171. Wei, Y.; Zhuang, D.; Zhao, M.; Gong, Q.; Sun, R.; Ren, G.; Wu, Y.; Zhang, L.; Lyu, X.; Peng, X.; et al. An Investigation on the
Relationship between Open Circuit Voltage and Grain Size for CZTSSe Thin Film Solar Cells Fabricated by Selenization of
Sputtered Precursors. J. Alloys Compd. 2019, 773, 689–697. [CrossRef]
172. Li, J.; Huang, Y.; Huang, J.; Liang, G.; Zhang, Y.; Rey, G.; Guo, F.; Su, Z.; Zhu, H.; Cai, L.; et al. Defect Control for 12.5% Efficiency
Cu2ZnSnSe4 Kesterite Thin-Film Solar Cells by Engineering of Local Chemical Environment. Adv. Mater. 2020, 32, e2005268.
[CrossRef] [PubMed]
173. Dwivedi, S.K.; Tripathi, S.K.; Tiwari, D.C.; Chauhan, A.S.; Dwivedi, P.K.; Eswara Prasad, N. Low Cost Copper Zinc Tin Sulphide
(CZTS) Solar Cells Fabricated by Sulphurizing Sol-Gel Deposited Precursor Using 1,2-Ethanedithiol (EDT). Sol. Energy 2021, 224,
174. Liu, Y.; Hu, C.; Qi, Y.; Zhou, W.; Kou, D.; Zhou, Z.; Han, L.; Meng, Y.; Yuan, S.; Wu, S. Li/Ag Co-Doping Synergistically Boosts the
Efficiency of Kesterite Solar Cells Through Effective SnZn Defect Passivation. Adv. Mater. Interfaces 2022, 9, 2201677. [CrossRef]
175. Romeo, A.; Artegiani, E. CdTe-Based Thin Film Solar Cells: Past, Present and Future. Energies 2021, 14, 1684. [CrossRef]
176. Ward, J.S.; Ramanathan, K.; Hasoon, F.S.; Coutts, T.J.; Keane, J.; Contreras, M.A.; Moriarty, T.; Noufi, R. A 21·5% Efficient
Cu(In,Ga)Se2 Thin-Film Concentrator Solar Cell. Prog. Photovolt. Res. Appl. 2002, 10, 41–46. [CrossRef]
177. Yan, C.; Huang, J.; Sun, K.; Johnston, S.; Zhang, Y.; Sun, H.; Pu, A.; He, M.; Liu, F.; Eder, K.; et al. Cu2 ZnSnS4 Solar Cells with over
10% Power Conversion Efficiency Enabled by Heterojunction Heat Treatment. Nat. Energy 2018, 3, 764–772. [CrossRef]
178. Giraldo, S.; Saucedo, E.; Neuschitzer, M.; Oliva, F.; Placidi, M.; Alcobé, X.; Izquierdo-Roca, V.; Kim, S.; Tampo, H.; Shibata, H.; et al.
How Small Amounts of Ge Modify the Formation Pathways and Crystallization of Kesterites. Energy Environ. Sci. 2018, 11,
179. Wang, W.; Winkler, M.T.; Gunawan, O.; Gokmen, T.; Todorov, T.K.; Zhu, Y.; Mitzi, D.B. Device Characteristics of CZTSSe Thin-Film
Solar Cells with 12.6% Efficiency. Adv. Energy Mater. 2014, 4, 1301465. [CrossRef]
180. Moon, S.H.; Park, S.J.; Kim, S.H.; Lee, M.W.; Han, J.; Kim, J.Y.; Kim, H.; Hwang, Y.J.; Lee, D.K.; Min, B.K. Monolithic DSSC/CIGS
Tandem Solar Cell Fabricated by a Solution Process. Sci. Rep. 2015, 5, srep08970. [CrossRef]
181. Hadipour, A.; de Boer, B.; Blom, P.W.M. Device Operation of Organic Tandem Solar Cells. Org. Electron. 2008, 9, 617–624.
[CrossRef]
182. Enam, F.M.T.; Rahman, K.S.; Kamaruzzaman, M.I.; Sobayel, K.; Chelvanathan, P.; Bais, B.; Akhtaruzzaman, M.; Alamoud, A.R.M.;
Amin, N. Design Prospects of Cadmium Telluride/Silicon (CdTe/Si) Tandem Solar Cells from Numerical Simulation. Optik 2017,
139, 397–406. [CrossRef]
183. Hosokawa, H.; Tamaki, R.; Sawada, T.; Okonogi, A.; Sato, H.; Ogomi, Y.; Hayase, S.; Okada, Y.; Yano, T. Solution-Processed
Intermediate-Band Solar Cells with Lead Sulfide Quantum Dots and Lead Halide Perovskites. Nat. Commun. 2019, 10, 4–6.
[CrossRef]
184. Andruszkiewicz, A.; Zhang, X.; Johansson, M.B.; Yuan, L.; Johansson, E.M.J. Perovskite and Quantum Dot Tandem Solar Cells
with Interlayer Modification for Improved Optical Semitransparency and Stability. Nanoscale 2021, 13, 6234–6240. [CrossRef]
185. Todorov, T.; Gershon, T.; Gunawan, O.; Sturdevant, C.; Guha, S. Perovskite-Kesterite Monolithic Tandem Solar Cells with High
Open-Circuit Voltage. Appl. Phys. Lett. 2014, 105, 173902. [CrossRef]
186. Saha, U.; Alam, M.K. Proposition and Computational Analysis of a Kesterite/Kesterite Tandem Solar Cell with Enhanced
Efficiency. RSC Adv. 2017, 7, 4806–4814. [CrossRef]
187. Song, Z.; Chen, C.; Li, C.; Awni, R.A.; Zhao, D.; Yan, Y. Wide-Bandgap, Low-Bandgap, and Tandem Perovskite Solar Cells.
Semicond. Sci. Technol. 2019, 34, 093001. [CrossRef]
188. Gu, S.; Lin, R.; Han, Q.; Gao, Y.; Tan, H.; Zhu, J. Tin and Mixed Lead–Tin Halide Perovskite Solar Cells: Progress and Their
Application in Tandem Solar Cells. Adv. Mater. 2020, 32, e1907392. [CrossRef] [PubMed]
Energies 2023, 16, 5868 33 of 35
189. Wang, R.; Huang, T.; Xue, J.; Tong, J.; Zhu, K.; Yang, Y. Prospects for Metal Halide Perovskite-Based Tandem Solar Cells. Nat.
Photonics 2021, 15, 411–425. [CrossRef]
190. Fang, Z.; Zeng, Q.; Zuo, C.; Zhang, L.; Xiao, H.; Cheng, M.; Hao, F.; Bao, Q.; Zhang, L.; Yuan, Y.; et al. Perovskite-Based Tandem
Solar Cells. Sci. Bull. 2021, 66, 621–636. [CrossRef]
191. Shen, H.; Duong, T.; Peng, J.; Jacobs, D.; Wu, N.; Gong, J.; Wu, Y.; Karuturi, S.K.; Fu, X.; Weber, K.; et al. Mechanically-Stacked
Perovskite/CIGS Tandem Solar Cells with Efficiency of 23.9% and Reduced Oxygen Sensitivity. Energy Environ. Sci. 2018, 11,
192. Li, H.; Zhang, W. Perovskite Tandem Solar Cells: From Fundamentals to Commercial Deployment. Chem. Rev. 2020, 120,
9835–9950. [CrossRef] [PubMed]
193. Al-Ashouri, A.; Magomedov, A.; Roß, M.; Jošt, M.; Talaikis, M.; Chistiakova, G.; Bertram, T.; Márquez, J.A.; Köhnen, E.;
Kasparavičius, E.; et al. Conformal Monolayer Contacts with Lossless Interfaces for Perovskite Single Junction and Monolithic
Tandem Solar Cells. Energy Environ. Sci. 2019, 12, 3356–3369. [CrossRef]
194. Jošt, M.; Köhnen, E.; Al-Ashouri, A.; Bertram, T.; Tomšič, Š.; Magomedov, A.; Kasparavicius, E.; Kodalle, T.; Lipovšek, B.; Getautis,
V.; et al. Perovskite/CIGS Tandem Solar Cells: From Certified 24.2% toward 30% and Beyond. ACS Energy Lett. 2022, 7, 1298–1307.
[CrossRef]
195. Manekkathodi, A.; Chen, B.; Kim, J.; Baek, S.W.; Scheffel, B.; Hou, Y.; Ouellette, O.; Saidaminov, M.I.; Voznyy, O.;
Madhavan, V.E.; et al. Solution-Processed Perovskite-Colloidal Quantum Dot Tandem Solar Cells for Photon Collection
beyond 1000 Nm. J. Mater. Chem. A 2019, 7, 26020–26028. [CrossRef]
196. Xiao, K.; Lin, R.; Han, Q.; Hou, Y.; Qin, Z.; Nguyen, H.T.; Wen, J.; Wei, M.; Yeddu, V.; Saidaminov, M.I.; et al. All-Perovskite
Tandem Solar Cells with 24.2% Certified Efficiency and Area over 1 cm2 Using Surface-Anchoring Zwitterionic Antioxidant. Nat.
Energy 2020, 5, 870–880. [CrossRef]
197. Jang, Y.H.; Lee, J.M.; Seo, J.W.; Kim, I.; Lee, D.K. Monolithic Tandem Solar Cells Comprising Electrodeposited CuInSe2 and
Perovskite Solar Cells with a Nanoparticulate ZnO Buffer Layer. J. Mater. Chem. A 2017, 5, 19439–19446. [CrossRef]
198. Madan, J.; Singh, K.; Pandey, R. Comprehensive Device Simulation of 23.36% Efficient Two-Terminal Perovskite-PbS CQD
Tandem Solar Cell for Low-Cost Applications. Sci. Rep. 2021, 11, 19829. [CrossRef] [PubMed]
199. Makita, K.; Kamikawa, Y.; Mizuno, H.; Oshima, R.; Shoji, Y.; Ishizuka, S.; Müller, R.; Beutel, P.; Lackner, D.; Benick, J.; et al.
III-V//Cux In1−y Gay Se2 Multijunction Solar Cells with 27.2% Efficiency Fabricated Using Modified Smart Stack Technology with
Pd Nanoparticle Array and Adhesive Material. Prog. Photovolt. Res. Appl. 2021, 29, 887–898. [CrossRef]
200. Grassman, T.J.; Chmielewski, D.J.; Carnevale, S.D.; Carlin, J.A.; Ringel, S.A. GaAs0.75 P0.25 /Si Dual-Junction Solar Cells Grown by
MBE and MOCVD. IEEE J. Photovolt. 2016, 6, 326–331. [CrossRef]
201. Greenaway, A.L.; Loutris, A.L.; Heinselman, K.N.; Melamed, C.L.; Schnepf, R.R.; Tellekamp, M.B.; Woods-Robinson, R.;
Sherbondy, R.; Bardgett, D.; Bauers, S.; et al. Combinatorial Synthesis of Magnesium Tin Nitride Semiconductors. J. Am. Chem.
Soc. 2020, 142, 8421–8430. [CrossRef] [PubMed]
202. Sun, W.; Bartel, C.J.; Arca, E.; Bauers, S.R.; Matthews, B.; Orvañanos, B.; Chen, B.R.; Toney, M.F.; Schelhas, L.T.; Tumas, W.; et al. A
Map of the Inorganic Ternary Metal Nitrides. Nat. Mater. 2019, 18, 732–739. [CrossRef] [PubMed]
203. Choi, J.W.; Shin, B.; Gorai, P.; Hoye, R.L.Z.; Palgrave, R. Emerging Earth-Abundant Solar Absorbers. ACS Energy Lett. 2022, 7,
1553–1557. [CrossRef]
204. Javaid, K.; Wu, W.; Wang, J.; Fang, J.; Zhang, H.; Gao, J.; Zhuge, F.; Liang, L.; Cao, H. Band Offset Engineering in ZnSnN2 -Based
Heterojunction for Low-Cost Solar Cells. ACS Photonics 2018, 5, 2094–2099. [CrossRef]
205. Lei, H.; Chen, J.; Tan, Z.; Fang, G. Review of Recent Progress in Antimony Chalcogenide-Based Solar Cells: Materials and Devices.
Sol. RRL 2019, 3, 1900026. [CrossRef]
206. Akshay, V.V.; Benny, S.; Bhat, S.V. Solution-Processed Antimony Chalcogenides Based Thin Film Solar Cells: A Brief Overview of
Recent Developments. Sol. Energy 2022, 241, 728–737. [CrossRef]
207. Ríos-Ramirez, B.; Nair, P.K. On the Stability of Operation of Antimony Sulfide Selenide Thin Film Solar Cells under Solar
Radiation. Phys. Status Solidi Appl. Mater. Sci. 2018, 215, 1800479. [CrossRef]
208. Zakutayev, A.; Major, J.D.; Hao, X.; Walsh, A.; Tang, J.; Todorov, T.K.; Wong, L.H.; Saucedo, E. Emerging Inorganic Solar Cell
Efficiency Tables (Version 2). J. Phys. Energy 2021, 3, 032003. [CrossRef]
209. Chen, C.; Tang, J. Open-Circuit Voltage Loss of Antimony Chalcogenide Solar Cells: Status, Origin, and Possible Solutions. ACS
Energy Lett. 2020, 5, 2294–2304. [CrossRef]
210. Dong, J.; Liu, Y.; Wang, Z.; Zhang, Y. Boosting VOC of Antimony Chalcogenide Solar Cells: A Review on Interfaces and Defects.
Nano Sel. 2021, 2, 1818–1848. [CrossRef]
211. Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic
Cells. J. Am. Chem. Soc. 2009, 131, 6050–6051. [CrossRef]
212. Tien, C.H.; Lai, H.Y.; Chen, L.C. Methylammonium Halide Salt Interfacial Modification of Perovskite Quantum Dots/Triple-Cation
Perovskites Enable Efficient Solar Cells. Sci. Rep. 2023, 13, 5387. [CrossRef]
213. Dey, A.; Ye, J.; De, A.; Debroye, E.; Ha, S.K.; Bladt, E.; Kshirsagar, A.S.; Wang, Z.; Yin, J.; Wang, Y.; et al. State of the Art and
Prospects for Halide Perovskite Nanocrystals. ACS Nano 2021, 15, 10775–10981. [CrossRef]
214. Feng, B.; Duan, J.; Tao, L.; Zhang, J.; Wang, H. Enhanced Performance in Perovskite Solar Cells via Bromide Ion Substitution and
Ethanol Treatment. Appl. Surf. Sci. 2018, 430, 603–612. [CrossRef]
Energies 2023, 16, 5868 34 of 35
215. Niu, T.; Lu, J.; Tang, M.-C.; Barrit, D.; Smilgies, D.-M.; Yang, Z.; Li, J.; Fan, Y.; Luo, T.; McCulloch, I.; et al. High Performance
Ambient-Air-Stable FAPbI3 Perovskite Solar Cells with Molecule-Passivated Ruddlesden–Popper/3D Heterostructured Film.
Energy Environ. Sci. 2018, 11, 3358–3366. [CrossRef]
216. Jeong, J.; Kim, M.; Seo, J.; Lu, H.; Ahlawat, P.; Mishra, A.; Yang, Y.; Hope, M.A.; Eickemeyer, F.T.; Kim, M.; et al. Pseudo-Halide
Anion Engineering for α-FAPbI3 Perovskite Solar Cells. Nature 2021, 592, 381–385. [CrossRef]
217. Hossain, M.K.; Toki, G.F.I.; Kuddus, A.; Rubel, M.H.K.; Hossain, M.M.; Bencherif, H.; Rahman, M.F.; Islam, M.R.; Mushtaq, M. An
Extensive Study on Multiple ETL and HTL Layers to Design and Simulation of High-Performance Lead-Free CsSnCl3 -Based
Perovskite Solar Cells. Sci. Rep. 2023, 13, 2521. [CrossRef]
218. Juarez-Perez, E.J.; Wuβler, M.; Fabregat-Santiago, F.; Lakus-Wollny, K.; Mankel, E.; Mayer, T.; Jaegermann, W.; Mora-Sero, I. Role
of the Selective Contacts in the Performance of Lead Halide Perovskite Solar Cells. J. Phys. Chem. Lett. 2014, 5, 680–685. [CrossRef]
219. Li, F.; Zhou, S.; Yuan, J.; Qin, C.; Yang, Y.; Shi, J.; Ling, X.; Li, Y.; Ma, W. Perovskite Quantum Dot Solar Cells with 15.6% Efficiency
and Improved Stability Enabled by an α-CsPbI3 /FAPbI3 Bilayer Structure. ACS Energy Lett. 2019, 4, 2571–2578. [CrossRef]
220. Yao, D.; Zhang, C.; Pham, N.D.; Zhang, Y.; Tiong, V.T.; Du, A.; Shen, Q.; Wilson, G.J.; Wang, H. Hindered Formation of
Photoinactive δ-FAPbI3 Phase and Hysteresis-Free Mixed-Cation Planar Heterojunction Perovskite Solar Cells with Enhanced
Efficiency via Potassium Incorporation. J. Phys. Chem. Lett. 2018, 9, 2113–2120. [CrossRef] [PubMed]
221. Xue, J.; Lee, J.-W.; Dai, Z.; Wang, R.; Nuryyeva, S.; Liao, M.E.; Chang, S.-Y.; Meng, L.; Meng, D.; Sun, P.; et al. Surface Ligand
Management for Stable FAPbI3 Perovskite Quantum Dot Solar Cells. Joule 2018, 2, 1866–1878. [CrossRef]
222. Sha, W.E.I.; Ren, X.; Chen, L.; Choy, W.C.H. The Efficiency Limit of CH3 NH3 PbI3 Perovskite Solar Cells. Appl. Phys. Lett. 2015,
106, 221104. [CrossRef]
223. Masi, S.; Gualdrón-Reyes, A.F.; Mora-Seró, I. Stabilization of Black Perovskite Phase in FAPbI3 and CsPbI3 . ACS Energy Lett. 2020,
5, 1974–1985. [CrossRef]
224. Zhang, H.; Li, Y.; Tan, S.; Chen, Z.; Song, K.; Huang, S.; Shi, J.; Luo, Y.; Li, D.; Meng, Q. High-Efficiency (>20%) Planar Carbon-
Based Perovskite Solar Cells through Device Configuration Engineering. J. Colloid Interface Sci. 2022, 608, 3151–3158. [CrossRef]
[PubMed]
225. Kim, M.; Kim, G.H.; Lee, T.K.; Choi, I.W.; Choi, H.W.; Jo, Y.; Yoon, Y.J.; Kim, J.W.; Lee, J.; Huh, D.; et al. Methylammonium
Chloride Induces Intermediate Phase Stabilization for Efficient Perovskite Solar Cells. Joule 2019, 3, 2179–2192. [CrossRef]
226. Yin, J.; Xu, Z.; Hu, Q.; Teobaldi, G.; Liu, L.-M.; Prezhdo, O.V. Tuning Octahedral Tilting by Doping to Prevent Detrimental Phase
Transition and Extend Carrier Lifetime in Organometallic Perovskites. J. Am. Chem. Soc. 2023, 145, 5393–5399. [CrossRef]
227. Wang, A.; Wang, J.; Niu, X.; Zuo, C.; Hao, F.; Ding, L. Inhibiting Octahedral Tilting for Stable CsPbI2 Br Solar Cells. InfoMat 2022,
4, 2–9. [CrossRef]
228. Menahem, M.; Dai, Z.; Aharon, S.; Sharma, R.; Asher, M.; Diskin-Posner, Y.; Korobko, R.; Rappe, A.M.; Yaffe, O. Strongly
Anharmonic Octahedral Tilting in Two-Dimensional Hybrid Halide Perovskites. ACS Nano 2021, 15, 10153–10162. [CrossRef]
229. Lee, J.-H.; Bristowe, N.C.; Ho Lee, J.; Lee, S.-H.; Bristowe, P.D.; Cheetham, A.K.; Myung Jang, H. Resolving the Physical Origin of
Octahedral Tilting in Halide Perovskites. Chem. Mater. 2016, 28, 4259–4266. [CrossRef]
230. Kim, G.; Min, H.; Lee, K.S.; Lee, D.Y.; Yoon, S.M.; Seok, S.I. Impact of Strain Relaxation on Performance of A-Formamidinium
Lead Iodide Perovskite Solar Cells. Science 2020, 370, 108–112. [CrossRef]
231. Zhao, Q.; Hazarika, A.; Schelhas, L.T.; Liu, J.; Gaulding, E.A.; Li, G.; Zhang, M.; Toney, M.F.; Sercel, P.C.; Luther, J.M. Size-
Dependent Lattice Structure and Confinement Properties in CsPbI3 Perovskite Nanocrystals: Negative Surface Energy for
Stabilization. ACS Energy Lett. 2019, 5, 238–247. [CrossRef]
232. Doherty, T.A.S.; Nagane, S.; Kubicki, D.J.; Jung, Y.K.; Johnstone, D.N.; Iqbal, A.N.; Guo, D.; Frohna, K.; Danaie, M.; Tennyson,
E.M.; et al. Stabilized Tilted-Octahedra Halide Perovskites Inhibit Local Formation of Performance-Limiting Phases. Science 2021,
374, 1598–1605. [CrossRef] [PubMed]
233. Wang, R.; Xue, J.; Meng, L.; Lee, J.W.; Zhao, Z.; Sun, P.; Cai, L.; Huang, T.; Wang, Z.; Wang, Z.K.; et al. Caffeine Improves the
Performance and Thermal Stability of Perovskite Solar Cells. Joule 2019, 3, 1464–1477. [CrossRef]
234. Wang, R.; Xue, J.; Wang, K.L.; Wang, Z.K.; Luo, Y.; Fenning, D.; Xu, G.; Nuryyeva, S.; Huang, T.; Zhao, Y.; et al. Constructive
Molecular Configurations for Surface-Defect Passivation of Perovskite Photovoltaics. Science 2019, 366, 1509–1513. [CrossRef]
[PubMed]
235. Xie, H.; Wang, Z.; Chen, Z.; Pereyra, C.; Pols, M.; Gałkowski, K.; Anaya, M.; Fu, S.; Jia, X.; Tang, P.; et al. Decoupling the Effects
of Defects on Efficiency and Stability through Phosphonates in Stable Halide Perovskite Solar Cells. Joule 2021, 5, 1246–1266.
[CrossRef]
236. Feng, W.; Tan, Y.; Yang, M.; Jiang, Y.; Lei, B.X.; Wang, L.; Wu, W.Q. Small Amines Bring Big Benefits to Perovskite-Based Solar
Cells and Light-Emitting Diodes. Chem 2022, 8, 351–383. [CrossRef]
237. Yang, T.; Gao, L.; Lu, J.; Ma, C.; Du, Y.; Wang, P.; Ding, Z.; Wang, S.; Xu, P.; Liu, D.; et al. One-Stone-for-Two-Birds Strategy to
Attain beyond 25% Perovskite Solar Cells. Nat. Commun. 2023, 14, 839. [CrossRef]
238. Li, G.; Song, J.; Wu, J.; Song, Z.; Wang, X.; Sun, W.; Fan, L.; Lin, J.; Huang, M.; Lan, Z.; et al. Efficient and STable 2D@3D/2D
Perovskite Solar Cells Based on Dual Optimization of Grain Boundary and Interface. ACS Energy Lett. 2021, 6, 3614–3623.
[CrossRef]
Energies 2023, 16, 5868 35 of 35
239. Campos, T.; Dally, P.; Gbegnon, S.; Blaizot, A.; Trippé-Allard, G.; Provost, M.; Bouttemy, M.; Duchatelet, A.; Garrot, D.;
Rousset, J.; et al. Unraveling the Formation Mechanism of the 2D/3D Perovskite Heterostructure for Perovskite Solar Cells Using
Multi-Method Characterization. J. Phys. Chem. C 2022, 126, 13527–13538. [CrossRef]
240. Weidman, M.C.; Seitz, M.; Stranks, S.D.; Tisdale, W.A. Highly Tunable Colloidal Perovskite Nanoplatelets through Variable
Cation, Metal, and Halide Composition. ACS Nano 2016, 10, 7830–7839. [CrossRef]
241. Zhou, T.; Lai, H.; Liu, T.; Lu, D.; Wan, X.; Zhang, X.; Liu, Y.; Chen, Y. Highly Efficient and Stable Solar Cells Based on Crystalline
Oriented 2D/3D Hybrid Perovskite. Adv. Mater. 2019, 31, e1901242. [CrossRef] [PubMed]
242. Sutanto, A.A.; Caprioglio, P.; Drigo, N.; Hofstetter, Y.J.; Garcia-Benito, I.; Queloz, V.I.E.; Neher, D.; Nazeeruddin, M.K.; Stolterfoht,
M.; Vaynzof, Y.; et al. 2D/3D Perovskite Engineering Eliminates Interfacial Recombination Losses in Hybrid Perovskite Solar
Cells. Chem 2021, 7, 1903–1916. [CrossRef]
243. Cho, Y.; Soufiani, A.M.; Yun, J.S.; Kim, J.; Lee, D.S.; Seidel, J.; Deng, X.; Green, M.A.; Huang, S.; Ho-Baillie, A.W.Y. Mixed 3D–2D
Passivation Treatment for Mixed-Cation Lead Mixed-Halide Perovskite Solar Cells for Higher Efficiency and Better Stability. Adv.
Energy Mater. 2018, 8, 1703392. [CrossRef]
244. Al-Ashouri, A.; Köhnen, E.; Li, B.; Magomedov, A.; Hempel, H.; Caprioglio, P.; Márquez, J.A.; Vilches, A.B.M.; Kasparavicius, E.;
Smith, J.A.; et al. Monolithic Perovskite/Silicon Tandem Solar Cell with >29% Efficiency by Enhanced Hole Extraction. Science
2020, 370, 1300–1309. [CrossRef] [PubMed]
245. Wang, J.; Uddin, M.A.; Chen, B.; Ying, X.; Ni, Z.; Zhou, Y.; Li, M.; Wang, M.; Yu, Z.; Huang, J. Enhancing Photostability of Sn-Pb
Perovskite Solar Cells by an Alkylammonium Pseudo-Halogen Additive. Adv. Energy Mater. 2023, 13, 2204115. [CrossRef]
246. Ren, M.; Qian, X.; Chen, Y.; Wang, T.; Zhao, Y. Potential Lead Toxicity and Leakage Issues on Lead Halide Perovskite Photovoltaics.
J. Hazard. Mater. 2022, 426, 127848. [CrossRef]
247. Torrence, C.E.; Libby, C.S.; Nie, W.; Stein, J.S. Environmental and Health Risks of Perovskite Solar Modules: Case for Better Test
Standards and Risk Mitigation Solutions. iScience 2023, 26, 105807. [CrossRef] [PubMed]
248. Aftab, A.; Ahmad, M.I. A Review of Stability and Progress in Tin Halide Perovskite Solar Cell. Sol. Energy 2021, 216, 26–47.
[CrossRef]
249. Mahmoudi, T.; Rho, W.Y.; Kohan, M.; Im, Y.H.; Mathur, S.; Hahn, Y.B. Suppression of Sn2+ /Sn4+ Oxidation in Tin-Based Perovskite
Solar Cells with Graphene-Tin Quantum Dots Composites in Active Layer. Nano Energy 2021, 90, 106495. [CrossRef]
250. Chen, Z.; Liu, M.; Li, Z.; Shi, T.; Yang, Y.; Yip, H.L.; Cao, Y. Stable Sn/Pb-Based Perovskite Solar Cells with a Coherent 2D/3D
Interface. iScience 2018, 9, 337–346. [CrossRef]
251. Ban, H.; Sun, Q.; Zhang, T.; Li, H.; Shen, Y.; Wang, M. Stabilization of Inorganic CsPb0.5 Sn0.5 I2 Br Perovskite Compounds by
Antioxidant Tea Polyphenol. Sol. RRL 2020, 4, 1900457. [CrossRef]
252. Li, C.; Pan, Y.; Hu, J.; Qiu, S.; Zhang, C.; Yang, Y.; Chen, S.; Liu, X.; Brabec, C.J.; Khaja Nazeeruddin, M.; et al. Vertically Aligned
2D/3D Pb–Sn Perovskites with Enhanced Charge Extraction and Suppressed Phase Segregation for Efficient Printable Solar Cells.
ACS Energy Lett. 2020, 5, 1386–1395. [CrossRef]
253. Zhou, X.; Zhang, L.; Wang, X.; Liu, C.; Chen, S.; Zhang, M.; Li, X.; Yi, W.; Xu, B. Highly Efficient and Stable GABr-Modified
Ideal-Bandgap (1.35 EV) Sn/Pb Perovskite Solar Cells Achieve 20.63% Efficiency with a Record Small Voc Deficit of 0.33 V. Adv.
Mater. 2020, 32, e1908107. [CrossRef]
254. Sanchez-Diaz, J.; Sánchez, R.S.; Masi, S.; Kreĉmarová, M.; Alvarez, A.O.; Barea, E.M.; Rodriguez-Romero, J.; Chirvony, V.S.;
Sánchez-Royo, J.F.; Martinez-Pastor, J.P.; et al. Tin Perovskite Solar Cells with >1300 h of Operational Stability in N2 through a
Synergistic Chemical Engineering Approach. Joule 2022, 6, 861–883. [CrossRef] [PubMed]
255. Zhu, Z.; Jiang, X.; Yu, D.; Yu, N.; Ning, Z.; Mi, Q. Smooth and Compact FASnI3 Films for Lead-Free Perovskite Solar Cells with
over 14% Efficiency. ACS Energy Lett. 2022, 7, 2079–2083. [CrossRef]
256. Yu, B.B.; Chen, Z.; Zhu, Y.; Wang, Y.; Han, B.; Chen, G.; Zhang, X.; Du, Z.; He, Z. Heterogeneous 2D/3D Tin-Halides Perovskite
Solar Cells with Certified Conversion Efficiency Breaking 14%. Adv. Mater. 2021, 33, e2102055. [CrossRef] [PubMed]
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual
author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to
people or property resulting from any ideas, methods, instructions or products referred to in the content.

Current Progress of Efficient Active Layers For Organic, Chalcogenide and Perovskite-Based Solar Cells A Perspective

Uploaded by

Copyright:

Available Formats

Current Progress of Efficient Active Layers For Organic, Chalcogenide and Perovskite-Based Solar Cells A Perspective

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Current Progress of Efficient Active Layers For Organic, Chalcogenide and Perovskite-Based Solar Cells A Perspective

Uploaded by

Copyright:

Available Formats

energies

Academic Editor: Adalgisa

Received: 27 June 2023

Energies 2023, 16, 5868. https://doi.org/10.3390/en16165868 https://www.mdpi.com/journal/energies

Energies 2023, 16, 5868 3 of 35

2. Progress in the Development of Active Layers for Efficient PV Devices

2.1.1. Binary, Ternary, and Tandem Organic Solar Cells

Table 1. Photovoltaic performances of the recently reported binary OSCs.

In general, the working mechanism in bulky heterojunction OSC devices occurs as

rgies 2023, 16, x FOR PEER REVIEW 8 of 37

In general, the working mechanism in bulky heterojunction OSC devices occurs as

Table 1. Photovoltaic performances of the recently reported binary OSCs.

Table 2. Photovoltaic performances of the recently reported ternary OSCs.

Table 2. Photovoltaic performances of the recently reported ternary OSCs.

Table 3. Photovoltaic performances of the recently reported tandem OSCs.

2.1.2. Dye-Sensitized Solar Cells

Energies 2023, 16, x FOR PEER REVIEW 12 of 37

2.2. Chalcogenide Solar Cells

2.2.1. Binary, Ternary, and Quaternary Chalcogenides

Cadmium Telluride (CdTe)

Cadmium Selenide (CdSe)

Lead Sulfide (PbS)

Copper-Indium-Gallium Selenide (CIGS)

Copper-Zinc-Tin Selenide (CZTSe)

Copper-Zinc-Tin Selenide (CZTSe)

Cadmium-Free Copper Zinc Tin Sulfide (CZTSSe)

Table 4. Photovoltaic parameters of main chalcogenide-based solar cells.

2.2.2. Chalcogenide Tandem Solar Cells

Table 5. Photovoltaic parameters of main chalcogenide tandem solar cells.

2.2.3. New Chalcogenide Materials

2.3. Halide Perovskite Based Solar Cells

2.3.2. Partially Pb-Substituted/Pb-Free Perovskite Active Layers

Pb-Based Perovskite Films

light-to-electricity transformation capability is some couple of years. Because of their

Author Contributions: Conceptualization, writing—original draft preparation, writing—review and

Data Availability Statement: Not applicable.

You might also like