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The impact of moisture on the stability and

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degradation of perovskites in solar cells

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Cite this: Mater. Adv., 2024,

5, 2200
Bhushan P. Kore, Mahboubeh Jamshidi and James M. Gardner *

Efficiency and stability are the two most important factors in commercially scalable solar cells. In spite
the high-power conversion efficiencies (PCE), the commercialization of perovskite solar cells (PSC) has
been limited due to their low stability under ambient conditions. Environmental factors like moisture,
heat, and light can all adversely affect PSC performance and limit device lifetime. In this review, we refer
to the literature addressing the moisture induced stability issue of perovskite based solar cells. We
present an overview on the moisture stability of the perovskite solar cells and clarify the effect of
moisture on different layers in perovskite solar cells and the corresponding degradation process. Then
we extend the discussion highlighting the strategies to prevent the moisture induced degradation in
hybrid perovskite solar cells. The methods include composition engineering (cation and halide
Received 10th October 2023, engineering) and interfacial layer engineering/surface passivation. We further summarize the utilization
Accepted 12th January 2024 of doping techniques and use of organic/Inorganic passivators. We address methods of producing
DOI: 10.1039/d3ma00828b moisture stable 2D perovskites and admixtures of 2D and 3D perovskites. Lastly, the review highlights
research directions focused on improving perovskite stability without compromising power conversion
[Link]/materials-advances efficiency.

1. Introduction improvements have been made and these effects have been
largely suppressed.9–14
According to international standards, commercially available From commercialization point of view, external encapsula-
solar cells for outdoor use should have a lifespan of 25 years tion technique can be a straightforward process to prevent the
and should survive temperature fluctuations from 40 1C to infiltration of moisture and oxygen,15,16 but two factors have
85 1C.1 While there are challenges that need to be addressed, impeded the progress toward enhancing the efficiency and
there are number of reasons to think that organic inorganic stability of PSCs. Firstly, the presence of interfacial and bulk
metal halide perovskite solar cell (PSC) panels can exceed vacancy defects creates a primary pathway for the diffusion or
present international standards. The organic inorganic metal migration of halide ions, consequently leading to the degrada-
halide perovskite materials with ABX3 formula (where A- tion of devices due to light exposure. Secondly, the surplus PbI2
CH3NH3+, NH2CHNH2+, Cs+; B–Pb2+, Sn2+; and X–Cl, Br, I) within perovskite absorbers undergoes decomposition when
will be referred to solely as perovskites unless otherwise stated. subjected to light, resulting in compromised illumination
Perovskites readily react with water/moisture, that causes stability. Additionally, it is important to building shields within
degradation into their precursor materials or formation of the PSCs to boost their own internal resistance to water and
hydrated phases and results in lower power output and short oxygen.17,18
circuit in the solar cells.2–4 Perovskites are susceptible to If we look at the PV triangle (efficiency, cost, stability)
chemical decomposition from moisture due to the presence requirements for commercialization, then it is only long-term
of hygroscopic ammonium and Pb(II) salts. Moisture instability stability that remains a challenge for perovskite photovoltaic
is a persistent concern for perovskite solar cells and compre- (PV) technology. The ionic crystal structure, and weakly bonded
hensive strategies are required to overcome this problem.4–8 organic cations make perovskite vulnerable to moisture, heat,
While impressive progress has been made on increasing PSC and oxygen. In this review, we summarize the stabilization
efficiency, stability under ambient conditions remains a strategies against moisture for PSCs and highlighted the chal-
major concern. Thermal degradation, and ion migration lenges/outlook for the future research. Our perspective in
are also challenges to perovskite stability; however, significant writing this review is to give readers an overview of major
advances in PSCs, which either resulted in significant improve-
Department of Chemistry, Division of Applied Physical Chemistry, KTH Royal ment in the solar cell stability or shows promise for commer-
Institute of Technology, SE-100 44 Stockholm, Sweden. E-mail: jgardner@[Link] cializing this technology.

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2. Device architecture of hybrid layer, whereas in p–i–n structure the perovskite layer is depos-
perovskite device ited onto transparent electrodes covered with HTM such
as poly(3,4-ethylene dioxythiophene):polystyrene sulfonic acid
PSCs emerged from dye sensitized solar cells (DSSC) when the (PEDOT:PSS). Both mesoporous and planer structures are
light absorbing dye was replaced with perovskite nanocrystals known to deliver high efficiency and stable solar cells, however,
material by Kojima and co-workers.19 The rapid reaction of the comparison of stability of two different structures is still
perovskite with the liquid electrolyte promoted its replacement under debate7,20 though there are several reports published
with the solid-state hole conducting material (Spiro-OMeTAD). in literature claiming the advantage of one structure over
This advancement created a tremendous interest in the photo- other.21,22
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voltaic community and drew the attention of experts from

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various other scientific communities. 2.1. Mesoporous structure

Inspired by CIGS and CdTe architectures, monolithic A certified 16.2% efficiency was achieved by depositing MAPbI3
devices were developed in which the light absorbing perovskite perovskite film on TiO2 mesoporous layer using the ‘antisolvent’
material was sandwiched between electron transporting mate- method.23 Later this has become one of the most preferred
rial (ETM) and hole transporting material (HTM), as shown methods of perovskite deposition. Furthermore, efficiencies
in Fig. 1(a)–(c). Mesoscopic and planar are the two basic more than 20% were achieved by incorporating multiple
structures that are used in the fabrication of PSCs. The meso- (organic/inorganic) cations into the perovskite like Cs/FA/
scopic structure has n–i–p configuration with compact ETM/ MA.24–26 The substitution of multiple cations was found to help
mesoscopic ETM/perovskite/HTM/electrode stacking, as in stabilizing the perovskite structure. The inclusion of meso-
shown in Fig. 1a. The planar configuration is further divided porous scaffold in the PSCs greatly facilitates the charge collec-
into two categories n–i–p planar and p–i–n planar, as shown tion particularly in perovskite absorbers where light absorption
in Fig. 1b and c. Usually in n–i–p structure, the perovskite length is longer than the carrier diffusion length. As an example,
material is deposited onto transparent substrates covered tin halide perovskites with mesoscopic scaffolds show external
with compact TiO2 and then mesoporous TiO2 scaffold quantum efficiency (EQE) of B80% whereas in planer structure

Fig. 1 Device structures of (a) n–i–p mesoscopic, (b) n–i–p planar, and (c) p–i–n planar PSCs. If the incident light goes through ETM then it is known as n–i–p
(regular) structure and if the light goes through the HTM then it is known as p–i–n (inverted) structure. (d) shows the structure of MAPI3 in its cubic phase, (e) shows
the structure of the monohydrate phase, CH3NH3PbI3H2O, and (f) displays the structure of the dihydrate, (CH3NH3)4PbI62H2O. The position of the hydrogens on
the (CH3NH3)+ ions and the water is not assigned in panels (d) and (f) Reprinted with permission from ref. 2. Copyright 2015 American Chemical Society.

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configuration this ratio is quite low.27,28 Thus, the advantage of crystallization of perovskite layer, it further helps in improving
mesoscopic configuration is that it greatly facilitates the collec- the thin film quality and grain growth/size distribution,2,39–43
tion of charge carriers and enhance the performance of PSCs.29 on the other hand excess amount of water damages the crystal
structure of the perovskite and disintegrate into the starting
2.2. Planar structure compounds and hydrated phases.
The planar n–i–p architecture of PSC came into existence when Mainly the water molecule interacts with the perovskite by
the mesoporous layer was completely removed from the solar the hydrogen bond between the organic cation and inorganic
cell configuration.30 The inverted p–i–n planar structured solar units and then forming new bonds with perovskite giving rise
cells initially exhibited lower PCE values of 1.6% which was to hydrated phases.3,44 For example by reacting with H2O, solid
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further improved by Snaith et al., to 9.8% with the help of MAPbI3 will first decompose through hydrolysis reaction into
Open Access Article. Published on 12 February 2024. Downloaded on 11/20/2024 [Link] AM.

mixed halide composition of perovskite and replacing the HTL CH3NH3I solution (aq.) and solid (s) PbI2. Furthermore, in the
by PC61BM.31 Solar cell efficiencies exceeding 15% were next step MAI (aq.) gets decompose into volatile compounds
reported by Tong et al., using NiO nanocrystals as HTL and like CH3NH2 (aq.) and HI (aq.). Thus, in the presence of
PCBM/BCP as ETL.32 The PCE over 20% was achieved by Yang moisture there is high probability that MAI, PbI2, CH3NH2
et al., in 2018.33 They proposed Cs doped FAPbI3 perovskite and HI will coexist within the thin film. Furthermore, the
with EDTA complex tin oxide (SnO2) as ETM and Spiro- presence of crystalline defects in perovskite act as a channel
OMeTAD as HTM to achieve high performance solar cells. for infiltration of water molecules this enables more severe
The PSCs attained record PCE of 21.6% and the unsealed accelerated degradation by breaking the interactions of alkyla-
devices show drop of only 8% PCE when exposed to ambient mine cations with other ions.6
condition for 2880 h. A similar explanation has been proposed by Walsh et al., by
considering a simple acid base reaction.3 According to their
study, in case of water exposure, the H2O molecules can interact
3. Effect of moisture on different with MAPbI3 and can take away one proton from the organic
layers in perovskite solar cells cation (ammonium) this will form an intermediate phase/
3.1. Effect of moisture on light absorbing perovskite material compound [(CH3NH3+)n1(CH3NH2)nPbI3][H3O]. The formed
intermediate then subsequently decompose into the volatile
Among the various hybrid perovskite materials, MAPbI3 CH3NH2, HI and solid PbI2.3,45
(CH3NH3PbI3) has been most thoroughly studied and exten- The hydrated structure of perovskite can be fully reverted
sively used in the solar cells as a light absorbing material owing back to the perovskite phase (without H2O) by keeping the
to its appropriate band gap for solar cell material and ideal hydrated perovskite sample in a dry air for 48 h, as shown in
optical and electrical properties. However, it has been now well Fig. 1d–f.2 The incorporation of H2O molecule significantly
established that MAPbI3 undergoes degradation when exposed deforms the crystal structure by separating the [PbI6]4 octahe-
to moisture or water. The perovskite MAPbI3 visibly degrades: dra, as shown in Fig. 1e and f. This makes the perovskite
its black color fades and transforms into the yellow PbI2 and structure transform from a 3D network of [PbI6]4 octahedra to
gases CH3NH2 and HI as given in eqn (1).2,34–36 The impact of a 1D and 0D chain of octahedra for monohydrated and dehy-
water on the perovskite layer can be understood through the drated phase, respectively.6,46
following reactions. The moisture induced degradation of perovskite can be
CH3NH3PbI3 (s) 2 PbI2 (s) + CH3NH3I (aq.) 2 PbI2 (s) further accelerated by UV light and O2.34,47,48 The degradation
of perovskite under moisture along with UV light and oxygen
+ CH3NH2 (aq.) + HI (aq.) (1)
can be expressed as follows,
Moreover, when CH3NH3PbI3 is exposed to moisture this can
CH3NH3PbI3 H2O 2 CH3NH3I (aq.) + PbI2 (s) (5)
led to formation of hydrated phases.

4CH3NH3PbI3 + 4H2O 2 4[CH3NH3PbI3H2O] CH3NH3I (aq.) 2 CH3NH2 (aq.) + HI (aq.) (6)

2 (CH3NH3)4PbI62H2O + 3PbI2 + 2H2O (2)
4HI (aq.) + O2 2 2I2 (s) + 2H2O (7)
(CH3NH3)4PbI62H2O 2 4 CH3NH3I + PbI2 + 2H2O
(3) 2HI (aq.) hv 2 H2(g) + I2 (s) (8)

CH3NH3I 2 CH3NH2 + HI (4) Eqn (7) and (8) demonstrate how perovskite degradation is
accelerated due to the presence of oxygen and light when
The perovskites are soluble in polar solvents, like water, thus exposed to moisture. Presence of oxygen leads to the oxidation
when the perovskites come in contact with water/moisture they of HI resulting in formation of I2 vapor and water whereas UV
rapidly degrade.37 The hydrogen bond between organic and light decomposes HI with H2 gas and I2 vapor as biproducts.
inorganic units defines the structural stability of perovskite and With the help of Fourier transform infrared spectroscopy
it is strongly affected by the moisture.38 However, an appro- measurements Peng et al., showed that the activation
priate percentage of moisture is known to be favorable for the energy for the degradation of MAPbI3 under N2 atmosphere is

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120 KJ mol1 whereas the presence of oxygen and heat reduces moreover the poor morphology of the PCBM creates passage
the activation energy of degradation to nearly half (50 KJ mol1).47 for the water permeation.6
It is noteworthy to mention that oxygen gas and water vapor
can influence the energetics for degradation by significantly
changing the energy levels in organometal halide perovskite
4. Strategies to enhance perovskite
films, such as CH3NH3PbI3 and CH3NH3PbI3xCl shown by solar cells’ stability against moisture
J. Yang et al.49 Exposure to oxygen gas causes a surface dipole-
In this section we will discuss the different strategies to
induced shift in perovskite films, leading to an upward shift in
enhance the overall stability of the perovskite materials.
the vacuum level (work function increase). This shift saturates
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due to the surface dipole effect. The valence band remains

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4.1. Composition engineering

unchanged, resulting in an increase in ionization potential (IP)
that corresponds to the work function increase. Additionally, Though hybrid perovskite materials have shown great potential
oxygen exposure triggers a minor conversion from CH3NH3PbI3 as a light absorbing layer their stability remains an important
to PbI2 within the films. Water vapor has distinct effects on concern before the industry. Since the fabrication of the first
perovskite films as compared to oxygen gas. Specifically, expo- PSC, there have been significant improvements in the stability
sure to water vapor leads to a downward shift in the vacuum of the light absorbing perovskite through multiple cation
level (resulting in a decrease of the work function), while substitution, mixed halide substitution, and doping of inor-
simultaneously causing an increase in the binding energy of ganic/organic cations has been observed. The partial or com-
the valence band in relation to the Fermi level. This combined plete substitution of cations/halides significantly improves the
effect ensures that the ionization potential (IP) of the perovskite stability of the perovskite layer and boosts the efficiency of the
films remains unaltered. PSCs. Composition tuning of perovskite alters the lattice para-
meters and bonding environment, which helps in retaining the
perovskite structure and improves their moisture stability.56
3.2. Effect of moisture on other layers 4.1.1. Cation engineering. The general formula of 3D per-
Not only perovskite but the presence of moisture can also degrade ovskites is ABX3, where A is a monovalent cation (MA+, FA+,
the HTMs which also leads to further drop in the solar Cs+), B is a divalent metal cation (Pb2+, Cd2+, Sn2+, Mn2+) and X
cell performance. The 2,2 0 ,7,70 -tetrakis(N,N-di-p-methoxyphenyl- is a halide anion (Cl, Br, I). The organic cation A in the
amine)-9,9 0 -spirobifluorene (Spiro-OMeTAD) is the most com- hybrid perovskite (ABX3) is a key part of the composition as it
monly used HTM in the regular n–i–p structured PSCs. The pure can determine both the crystal structure and its stability.
form of Spiro-OMeTAD shows poor electrical properties owing to Furthermore, the size of the A site cation decides the structure
its incompletely conjugated structure and intermolecular and stability of the perovskite phase.56–58 There is small varia-
spacing.50 In order to improve the electrical properties of Spiro- tion in the size of the A cation that can be substituted into the
OMeTAD it is doped with mild oxidants and salts such as lithium- structure without destroying the perovskite structure.56,57 The
bis-(trifluoromethane)sulfonimide (Li-TFSI).51 Spiro-OMeTAD concept of Goldschmidt tolerance factor (t) is used to describe
doped with Li-TFSI shows improved hole mobility and conductivity. the structural stability of the perovskite. It is defined as,57,59
However, Li-TFSI is hygroscopic in nature which induces moisture pffiffiffi
t ¼ ðrA þ rX Þ= 2ðrB þ rX Þ (9)
and degrades the device/HTM.52,53 Furthermore, the presence of Li+
ions in Li-TFSI initiates Li+ migration into the perovskite and ETM. where, rA is the radius of A cation, rB is the radius of the B
This acts as a channel for the moisture penetration and accelerates cation, rX is the radius of the X anion.
the degradation of HTM and perovskite layer leading to the drop in For obtaining the perovskite structure the value of ‘t’ should
the device performance.6 It is therefore equally important to select a be between 0.8 and 1, if this value is lower than 0.8 and greater
moisture resistive HTM, which can not only act as an efficient HTM than 1 then the formation of non-perovskite structure can be
but also help in encapsulating perovskite and further improving expected.60 There are very few organic/inorganic cations avail-
the stability of the PSC devices. able for the substitution at A site. In most of the solar cell MA
Compared to HTM the ETM are less susceptible towards cation-based perovskite were explored but due to the lower
moisture. The most commonly used ETM in regular n–i–p stability of MAPbI3 under moist conditions people started
structure TiO2 is hydrophilic in nature whereas [6,6]-phenyl exploring partial substitution of other perovskites such as
C61 butyric acid methyl ester (PCBM) used in inverted PSCs can FAPbI3 and CsPbI3. The FAPbI3 and CsPbI3 perovskites are
absorb moisture.54 In regular structure of PSCs, mesoporous not stable in the cubic a-phase and relax to the orthorhombic
TiO2 layer adsorb atmospheric water that is later retained in the phase at room temperature. A site cation substitution with
final device structure. In inverted structure PSCs, most com- other cations such as FA+, Cs+, Rb+, and K+ led to enhancement
monly PCBM is used which has higher water contact angle in the device performance and stability. The A site cation
compared to TiO2 but still undergoes water induced degrada- engineering also helps in tuning the band gap or absorption
tion. Though PCBM helps in reducing the trap states it cannot edge. Number of studies on A site cation engineering have been
efficiently passivate the undercoordinated Pb2+ ion defects.55 reported in the literature for enhancing the moisture stability of
This causes degradation of PSC like in the case of TiO2, the PSCs.56,58,61

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In 2022, F. Cao et al. investigated the degradation mecha- investigations reported in literature where several combina-
nism of FA-based perovskites and proposed the existence of tions of possible cations such as MA+/FA+, CS+/MA+, Cs+/FA+,
FABr–H2O.62 They implemented an approach where MABr Cs+/FA+/MA+ are explored.26,59,64,66–68 Based on the first princi-
powder was introduced into a PbI2 precursor solution, creating ple calculations, Zhu et al., reported that alloying of FAPbI3 and
a seed solution through a two-step preparation method. This CsPbI3 can effectively tune the tolerance factor and enhance the
technique was employed to boost the efficiency and durability stability of photoactive FA1xCsxPbI3 a phase.59 Further, they
of FA-based perovskite solar cells (PSCs). As a result, the experimentally confirmed that alloyed FA0.85Cs0.15PbI3 demon-
degradation rate of the resulting perovskite film exhibited a strate improved stability under high humidity environments, in
notable reduction when subjected to high humidity, in com- contrast to FAPbI3 which degrades to d phase under humid
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parison to films prepared using a two-step method without the conditions. Due to the structural stabilization the alloyed
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application of a seed solution. The resulting device demon- FA0.85Cs0.15PbI3 solar cells showed improved performance and
strated an impressive power conversion efficiency of 23.22%, better device stability in comparison with FAPbI3 perovskite. These
and even after being exposed to air for 900 hours, the efficiency results confirmed that Cs alloying at A site could significantly
of this device remained unchanged. improve the stability of perovskite under humid conditions.
The improved photovoltaic properties of the mixed cation Despite efforts to exclude all moisture from the triple cation
MAxFA1xPbI3 perovskite have attracted many researchers into perovskite solar cells, a minimal quantity of moisture within
the fundamental investigation and further development of the perovskite films was found to enhance the growth of triple
mixed cation PSCs and large number of studies on A-site cation cation perovskite (Cs0.05FA0.85MA0.15Pb(I0.85Br0.15)3) crystals
engineering have been carried out to improve the moisture and amplify the difference in potential energy between indivi-
stability of the perovskites.26,63–66 There are various systematic dual crystals and their grain boundaries (Fig. 2a). This, in turn,

Fig. 2 (a) Water molecules in contact with (Cs0.05 FA0.85MA0.15Pb(I0.85Br0.15)3) perovskite crystal grain boundaries form a hydrated phase; PVSK in the
figure. Continuous heating during the annealing process returns partially hydrated phases to the original perovskite phase, while a portion of the samples
underwent degradation to form CsI, CH3NH2, HC(QNH)NH2, HI, PbI2, PbBr2, and H2O. Increasing the humidity levels to 50% accelerated degradation,
resulting in the formation of large quantities of CH3NH2, HC(QNH)NH2, and PbI2. Reproduced from ref. 69 with permission from John Wiley and Sons,
copyright 2022. (b) Schematic crystal structure and JV plots of FAPbI3 before and after TMS+ incorporation. Reproduced from ref. 73 with permission
from Elsevier, copyright 2022.

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aids the movement and capture of charge carriers across these their pioneering work Seok et al., reported the mix halide
boundaries.69,70 composition perovskite by mixing fraction of Br in place of
Apart from small cation doping in perovskite there are also I in the MAPb(I1xBrx)3, x = 0, 0.06, 0.20, and 0.29 perovskite
reports of substituting organic cations at A site present. PEA (Fig. 3a and b).74 The PSCs were kept under controlled humid
was reported to partially substitute the FAPbI3 using phenyl- environment to check for their stability. They found that cells
ethylammonium iodide (PEAI) to form FAxPEA1–xPbI3. The fabricated with mixed halide compositions were more stable
substitution of PEA alleviates both the phase stability and with better performance compared to pure MAPbI3 based cells.
moisture degradation of FAPbI3 as well as the performance of The bromide substitution in place of larger size Iodide shrinks
the PSCs.61 A similar study of substitution of acetamidinium at the perovskite structure resulting in a more stable cubic per-
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MA+ sites led to improved perovskite crystal structure and ovskite structure. Further the lattice shrinkage improves the
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significant enhancement in the stability of the PSCs.71 Seok strength of the organic cation-lead halide bond, which prevents
et al., stabilized the a-FAPbI3 phase by doping methylenediam- the permeability of moisture in the lattice (Fig. 3c).75 Since
monium dichloride (MDACl2) into perovskite. This doping then, in most of the high performing optimized PSCs, the
facilitates the stable PCE of 23.7% after 600 hours of operation. mixed halide composition of I and Br is used with lower
Moreover, the unencapsulated devices show high thermal percentage of Br concentration.1,68,76–85
stability and retained more than 90% efficiency under contin- An early breakthrough work by Snaith et al., suggested that
uous annealing at 150 1C in air for 20 hours.72 In 2022, the stability of MAPbI3xClx was remarkably enhanced com-
S. Sandhu et al. introduced trimethylsulfonium (TMS+), as a pared with MAPbI3, when both processed under ambient
moisture-stable and aprotic organosulfonium cation to form a conditions.30 Similarly, other studies have found that the
mixed-cation (TMS)x(FA)1xPbI3 perovskite with enhanced iodide-chloride mixed-halide perovskite CH3NH3PbI3xClx per-
moisture stability with PCE of 17.69% (Fig. 2b).73 formed well when the cells were fabricated under ambient
4.1.2. Mixed halide engineering. Like A site cation mixing, conditions.30,76,86 The small amount of chloride substitution
the mixed halide substitution approach has also shown pro- leads to a smoother and more crystalline surface morphology of
mising results in stabilizing the perovskite materials under the thin films.87,88 Grätzel et al., reported the introduction of
ambient conditions. Mixing of different halide anions also help small amount of methylammonium chloride (MACl) to the
in oxidation suppression and improved oxygen stability. In perovskite precursor solution facilitate improved photovoltaic

Fig. 3 (a) Crystal structures and energy levels of MAPbI3 and MAPbBr3, and CBM and VBM of MAPbI3, MAPbBr3, and TiO2 are represented in eV. (b) Power
conversion efficiency variation of the heterojunction solar cells based on MAPb(I1–xBrx)3 (x = 0, 0.06, 0.20, 0.29) with time stored in air at room
temperature without encapsulation. Reprinted with permission from ref. 74. Copyright 2013 American Chemical Society. (c) Replacing the methylam-
monium cation with alternative protonated cations allows an increase in the stability of the perovskite by forming strong hydrogen bonds with the halide
anions. Reproduced from ref. 75 with permission from John Wiley and Sons, copyright 2016.

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performance, suppresses the formation of bulk and surface

defects with high quality and larger grain size perovskite thin
films.87 In a similar study Kim et al., demonstrated addition of
MACl into the FAPbI3 perovskite induces an intermediate to the
pure FAPbI3 a-phase without annealing with increased gain size
and phase crystallinity.88 A successful use of blade coating
technique was reported by Zhu et al., for realization of high
efficiency large area PSCs having comparable efficiencies with
small area solar cells fabricated through spin coating
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technique.89 They used excess MACl to achieve a highly crystal-

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line film with a very wide thermal processing window and Fig. 4 Schematic illustration of two neighboring grain structures (in
achieved a similar perovskite morphology and device efficiency which the methyl ammonium groups are shown as one sphere for clarity)
and the PbI64 octahedra (shown in red) are crosslinked by butylpho-
for both spin coated and blade coated devices. sphonic acid 4-ammonium chloride (4-ABPACl) hydrogen-bonding inter-
Partial substitution of acetate ions (OAc, CH3COO) in actions (OH  I and N–H  I) of the iodide from the iodoplumbate
place of I ions also significantly enhance the device efficiency complex with the phosphonic acid (–PO(OH)2) and the ammonium
and stability. The introduction of saturated Pb(OAc)2 solution (–NH3+) end groups of the 4-ABPACl species. Reproduced from ref. 94
with permission from Springer Nature, copyright 2015.
on the top of the MAPbI3 perovskite precursor restructures the
lattice to form MAPbI3x(OAc)x resulting in perovskite film with
high crystallinity, large grain size and uniform film morphol-
ogy. Moreover, the OAc ions enable bond with uncoordinated 4.3. Doping
Pb2+ resulting in reduction of uncoordinated Pb2+, leading to Prolonging the stability of the light absorbing perovskite
stable perovskite film.90 In another study Pan et al., substituted material is the highest priority for achieving the high stability
super halide BH4 to simultaneously immobilize methylammo- and high efficiency solar cells devices. As discussed in the above
nium and substitute iodide vacancy based on the dihydrogen sections, the effect of mixing of multiple cations and anions is
bonding interactions for achieving high-performance PSCs. The encouraging and promising. In addition to this method,
incorporation of BH4 anion inhibits the decomposition of dopant engineering in perovskites has proven to further stabi-
CH3NH3+ cation by forming CH3NH3PbI3x(BH4)x perovskite.91 lize the perovskite and ultimately enhance their performance in
devices.
4.2. Interfacial layer engineering/surface passivation Grätzel’s group in 2015 used a one step solution processing
Most of the PSC devices are fabricated with sandwich like strategy using phosphonic ammonium additives that result in
structure, where light absorbing perovskite layer is sandwiched efficient PSCs with enhanced moisture stability.94 They used
between ETM and HTM. To effectively transport and extract butylphosphonic acid 4-ammonium chloride ((4-AB2PACl)) as
the photogenerated charge carriers in the device, the band additive into the perovskite precursor solution and achieved
alignment of the interfaces must be optimized in order to a uniform perovskite surface. As illustrated in Fig. 4a, the
reduce the potential barrier and charge trapping. In general, additives act as a cross linker between neighboring grains in
the performance of a PSC relies on efficient charge transporta- the perovskite film through hydrogen bonding of PO(OH)2 and
tion, charge extraction, and lastly collection of charge carriers. NH3+ terminal groups. The PSCs show an increase in photo-
The processing of hybrid perovskites via low temperature voltaic performance from 8.8% to 16.7% and robust air stability
solution methods and use of near ambient temperatures over 1000 h after the addition of (4-ABPACl). Use of a self
induces the formation of polycrystalline films with vacancies healing polymer scaffold architecture has been demonstrated
at the interfaces and this significantly impacts the PSC by Zhao et al., to prevent the moisture induced degradation of
performance.92 Based on the defect formation energy, the perovskite.95 The use of polyethylene glycol (PEG) helps in
defects are categorised as shallow and deep trap defects. achieving uniform perovskite film, humidity resistance and
Vacancies are known to be shallow defect whereas interstitials self healing perovskite crystals. Though they found that light
and uncoordinated ions as deep trap defects, which act as a has a strong destructive influence on the stability of PSC, due to
charge trapping/recombination center enabling the loss of the the light accelerated decomposition of perovskite with the aid
photogenerated charges. of hydrolysis by water molecules under illumination. Moreover,
Grain boundaries, interfaces, crystallographic defect, and in moisture stability tests the devices retain PCE for up to 300 h
surface imperfections within traditional polycrystalline perovs- under highly humid environment (RH 70%). Air stable and
kites can function as reactive entry points for moisture and efficient PSCs have been reported by Bi et al., by adding
oxygen into the cell. Single crystal perovskites have lower aliphatic fluorinated amphiphilic additive, 1,1,1-trifluoro ethyl
densities of defects and grain boundaries that act as suscep- ammonium iodide (FEAI), to the perovskite precursor
tible areas for deterioration. Further, single-crystalline perovs- solution.96 The FEAI treated PSCs imparts greater moisture
kites have a reduced trap density, extended charge carrier tolerance when compared to pristine devices after 4 months
diffusion lengths, longer carrier lifetimes, and improved carrier under ambient conditions. Most importantly, the moisture
mobility.93 tolerance is enhanced without formation of 2D perovskite due

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to the presence of CF3-terminal group on the surface of the 3D passivation of perovskite surface the use of organic salts make
perovskite which prevents the direct chemical reaction between the surface of the perovskite more hydrophobic and prevents
MAPbI3 and water molecules. In another study, Priya et al., the intrusion of water molecules into the perovskite layer.
proposed a formation of highly stable MAPbI3 perovskite In most of the studies, ammonium halide salts have been
through a ‘‘green’’ self assembly.97 In this study poly(methyl explored for passivating the perovskite film. Zhu et al., used two
methacrylate) (PMMA) was added to the 2D layered MAPbI3 different passivators phenylethylammonium iodide (PEAI) and
perovskite intermediates. This gives rise to 3D perovskite with 4-tert-butyl-benzylammonium iodide (tBBAI) in PSCs and com-
grain boundaries covered with PMMA which effectively blocks pared the passivation effects.112 They observed that the surface
the moisture from intrusion, of boundary coated perovskites treatment with tBBAI significantly accelerates the charge extrac-
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through the self-assembly process. The PMMA treated PSCs tion from perovskite to HTM and suppresses the non-radiative
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exhibit no degradation under high humid conditions (70% RH) carrier recombination. The PSCs retain over 95% of their initial
for over a month and excellent device performance. PCE (23.5%) after 500 h of continuous operation at maximum
Recently, Bakr et al., reported a methodology to reduce the power point (MPP) and over 90% of their initial PCE (23.5%)
efficiency gap between inverted PSCs and regular PSC by using after 55 days of storage under ambient conditions with RH 50–
a trace amount of surface anchoring alkylammonium ligands 70%. Yang et al., demonstrated the constructive molecular
(AAL) with varying length as grain and interface modifiers/ configurations for surface defect passivation of PSC.113 The
passivators.82 The addition of long chain AAL to the precursor chemical environment of a functional group was systematically
solution supresses non-radiative recombination, trap-state for- studied with theophylline, caffeine and theobromine treatment,
mation, and improves the optoelectronic properties of the through hydrogen bond formation (between N–H and I) assisted
perovskite. The devices with AAL showed PCE of 22.3% and CQO binding with anti-site Pb defects. Notably, the theophylline
improved operational stability of over 1000 h at maximum treated PSCs maintained 95% of their original PCE value when
power point (MPP) without any loss of efficiency under N2 stored under ambient conditions (with RH 20–30%) for 60 days.
atmosphere. Unfortunately, the study does not report the Yang et al., successfully fabricated stable PSCs using moisture
moisture stability of the devices. Ding et al., adopted a cost tolerant molecules on the surface of the perovskite. They used
effective and widely available water soluble additive polyvinyl some hydrophobic tertiary and quaternary alkyl ammonium
alcohol (PVA) to improve the quality of the perovskite film and cations on the perovskite surface by facile surface functionaliza-
enhance the moisture stability of PSCs without compromising tion technique. They demonstrated that these molecules can
the efficiency.98 The incorporation of PVA have been found to protect the perovskite film under high relative humidity (90 
enhance the efficiency by nearly 12% compared to those with- 5%) for about a month.114 Furthermore, Guo et al.,115 reported
out additives. Moreover, the devices with PVA additive show that the use of Cs oleate in the interface between perovskite and
retention of more than 90% efficiency even after 30 days of HTM has the similar effect.
storage under high humidity environments (around 90% RH). The use of polymer as an insulating tunnelling layer in PSCs
Moreover, some other additives such as alkylamines,82 1,3,7- was proposed by Wang et al.116 They used cross linked fluoro-
trimethylxanthine (caffeine)99 2-aminoterephthalic acid,100 silane polymer as the tunnelling layer between perovskite and
thioctic acid,101 have also been used and successfully imple- ETL, this layer can significantly improves the device perfor-
mented in developing highly efficient and stable PSCs. Overall, mance by suppressing the carrier recombination at cathode
the use of additives suppresses the non-radiative losses, and prevents the penetration of water or moisture into the
decreases the trap density, permits self healing of the perovs- perovskite film. Niu et al., demonstrated the use of ultrathin
kite, and stabilizes the surface of the perovskite film by Al2O3 layer on the top of the perovskite to fabricate moisture
terminating the grain boundaries with moisture resistant stable PSCs.34 Later a similar strategy with ALD deposited
groups. There are several fullerene derivatives and organic/ ultrathin Al2O3 layer on top of perovskite and on top of HTL
polymer materials such as phenyl-C61-butyric acid methyl ester was investigated to prolong the lifetime of the PSCs.117 In both
(PCBM),102–105 a fullerene derivative (a-bis-PCBM),54 cross- these studies efficiencies were retained after several days of
linkable [6,6]-phenyl-C61-butyric styryl dendron ester storage in air. Poly(3-hexylthiophene) (P3HT) is an organic,
(PCBSD),106 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodi- polymer with p-type conductivity. P3HT is thermally stable
methane (F4TCNQ),107,108 graphitic carbon nitride (g-C3N4),109 and hydrophobic. When applied in PSC, P3HT modifies the
have been explored and found to reduce the ion migration, interface between the perovskite and electrode, which boosts
excellent photo and thermal stability, improved solar cell moisture stability and device efficiency.118–122
performance, growth of perovskite crystallite size, enhanced In 2022, T. H. Han et al. synthesized polyurea (PU) with
charge transfer efficiency, and most importantly enhanced polydimethylsiloxane (PDMS) elastomer blocks and and poly-
moisture resistance by hindering moisture from infiltrating urea with diisocyanate linkages and introduced the molecules
the perovskite layer.95–97 into the perovskite precursor.123 The inclusion of the polymers
in the perovskite solar cells regulated crystal growth, mitigated
4.4. Organic passivator/inorganic passivators defect formation, safeguarded against moisture, increased
The organic cations or organic salts have been widely explored structural integrity, and demonstrated a power conversion
for passivating the perovskite surface.110,111 Along with efficiency of 23.25%. This is attributed to the robust covalent

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Fig. 5 (a) Schematic illustration of hybrid cross-linked network and its energy-dissipation and self-recovery mechanism. Reproduced from ref. 123 with
permission from John Wiley and Sons, copyright 2022. (b) Schematic design of a MOF/perovskite hybrid layer to facilitate charge transfer and increase
moisture stability in a PSC. Reprinted with permission from ref. 124. Copyright 2022 American Chemical Society.

interaction between the polymer and the perovskite material. perovskite structure. As a result of incorporating DN-DP, the
Significantly, the incorporation of polymers led to a substantial open-circuit voltage (Voc) of the resulting perovskite solar cell
enhancement in the mechanical durability of PSCs through (PSC) is enhanced from 1.107 V (in the control device) to
thermal-induced healing effect. The inclusion of the PDMS 1.153 V, leading to a notable increase in power conversion
blocks resulted in an elastic response to mechanical stress, efficiency (PCE) to 24.02% (Fig. 6). Furthermore, owing to the
coupled with the hydrophobic encapsulation of the MHP thin moisture resistance conferred by the hydrophobic nonyl group,
film. Furthermore, interchain hydrogen bonding helped dis- the PCE maintains 90.4% of its initial performance after
sipate strain energy when stretching the MHP thin film. Sub- enduring 1000 hours of storage in ambient conditions.
sequently, the reconfiguration of the hydrogen bonding
network following mechanical damage contributed to the 4.5. 3D-2D perovskites
development of the self-repairing feature (Fig. 5a). The devices Over the past few years, tremendous efforts have been made to
without encapsulation remained stable for over 1000 hours. improve the photovoltaic performance of perovskite solar cells
An organic/inorganic hybrid approach was introduced by by passivating the interfaces and minimizing the surface trap
J. Lee et al., wherein a perovskite-MOF hybrid was synthesized.124 defects by means of a long chain organic cation coating or 2D
The MOF was a hygroscopic copper(II) benzene-1,3,5-tricarboxylate perovskite coating on the top of the light absorbing perovskite
metalorganic framework (Cu-BTC MOFs) that bound up moist- layer.84,94,112,114,127–136 The enhanced stability of devices
ure instead of the perovskite, which lead to larger perovskite against moisture in 2D layered perovskites is attributed to the
crystal grains. Additionally, the MOF facilitated charge transfer presence of a large organic cation, rendering the 2D perovskite
when exposed to light by transferring photoexcited electrons from hydrophobic.137,138 Additionally, the stacking of organic–inor-
the perovskite to TiO2 (Fig. 5b). ganic layers creates a natural quantum well structure, where
Recently, J. Sun et al. fabricated PSCs with 4,4 0 -dinonyl-2,2 0 - inorganic layers act as potential wells and organic layers serve
dipyridine (DN-DP) instead of hygroscopic DMSO.125 DN-DP as potential barriers.139,140 This quantum well structure allows
exhibits a stronger ability to coordinate with Pb2+ ions com- for easy tuning of dielectric and excitonic properties by adjust-
pared to the SQO group present in DMSO. This heightened ing halide anions and varying the thickness of the inorganic
coordination effect is essential for eliminating adducts derived layer.141,142 Coating 2D layer on the top of 3D perovskite is one
from DMSO and minimizing the formation of empty spaces. of the most commonly used approach these days for preventing
Through the electron-donating characteristics of pyridine, the the 3D perovskite from the moisture.143 There are several 2D
presence of DN-DP within the perovskite film can effectively perovskite materials have been explored using this approach
address defects and fine-tune the energy level alignment of the and significant improvement in the device stability was

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Fig. 6 The influence of DN-DP on the formation of the perovskite film. First, DN-DP exchange with DMSO to forms a new adduct of DN-DP–PbI2
following the extension of the PbI2 lattice. Then FA ions were inserted into the layered PbI2 and exchanged with DN-DP.126 The coordination between
DN-DP and PbI2 can retard the fast reaction between organic ammonium halides and PbI2, thus slowing down the crystallization rate and ensuring large
grain growth. DN-DP reduces the residual DMSO in perovskite film, optimizes the contact of the buried interface, passivates the defects and changes the
energy level, and finally improves the performance of the device. Reproduced from ref. 125 with permission from Elsevier, copyright 2023.

achieved but very few of them showed higher photovoltaic films to obtain stable and efficient PSCs. The BEAI2 reacts with
efficiencies.130,144,145 PbI2 from 3D perovskite at 110 1C to form 2D BEAPbI4 per-
Wang et al., demonstrated the introduction of n- ovskite on the surface of the 3D perovskite. The PSCs kept at
butylammonium (BA, C4H9NH3) cations in the mixed cation 55% RH show drop of only 13% of its initial PCE when
mixed halide 3D perovskite to realize efficient and ambient air monitored for 1000 h.
stable solar cells (Fig. 7a).143 The incorporation of BA into the In 2022, Y. Ge et al. developed an internal encapsulation
system led to formation of thin films with increased crystal- strategy involving the incorporation of NbCl5 at the concealed
linity and preferentially oriented growth of grains and 2D-3D junction between the perovskite layers.147 Simultaneously, a
perovskite heterostructure with 3D and 2D perovskite domains layer of BABr was applied atop the perovskite through spin
and 2D perovskite platelets interspersed between 3D perovskite coating. The NbCl5 treatment leads to a notable decrease in
grains. The PSCs with optimal amount of BA exhibit average oxygen vacancies within the SnO2 layer. This, in turn, yields a
efficiency of 17.5% with 1.61 eV band gap perovskite. The PSCs more uniform and well-crystallized perovskite layer, along with
with BA cations sustain more than 80% of their efficiency after a diminished presence of PbI2 on the surface of the perovskite.
1000 h in air. In a similar study, Chen et al.,146 proposed the Following the deposition of BABr onto the perovskite layer, the
reaction of 1,4-butanediamine iodide (BEAI2) vapor with 3D formation of 2D perovskites occurs (Fig. 7b). This process
perovskite facilitate crystallization of large grain perovskite effectively addresses defects on the surface, leading to their

Fig. 7 (a) Schematic illustration of the proposed self-assembled 2D-3D perovskite film structure. Reproduced from ref. 143 with permission from
Springer nature, copyright 2017. (b) Schematic illustration of channels for iodide ion diffusion provided by the vacancy defects inside the device and the
effect of the internal encapsulation. Reproduced from ref. 147 with permission from John Wiley and Sons, copyright 2022.

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Fig. 8 Schematics of the device incorporating polycrystalline 3D perovskite film with 2D perovskite at grain boundaries and band structure of each layer
in device. Reproduced from ref. 131 with permission from Springer nature, copyright 2018.

passivation, and additionally results in a further reduction of printable PSCs with 11.2% efficiency without any drop in the
PbI2 content. A PCE of 24.01% and an excellent stability of 88% performance for 410 000 h.
remaining PCE after 1000 h were achieved. In one of our recent studies, we demonstrated the use of
Formation of phase pure a-FAPbI3 was observed by Lee et al. long chain alkylammonium chain cation based 2D perovskite
after incorporation of small percentage of PEA2PbI4 2D perovs- (C14H29NH3)2PbI4, (C16H33NH3)2PbI4, and (C18H37NH3)2PbI4 to
kite to 3D perovskite precursor solution.131 The formation of 2D prevent the moisture induced degradation of 3D perovskite.127
perovskite at the grain boundaries of FAPbI3 helps in preventing The 2D perovskites were selected based on previous literature
the moisture induced degradation of 3D perovskite and also indicating that as a powders these perovskites were stable in
helps in reducing ion migration, as illustrated in Fig. 8. The water.150 We observed that 2D perovskite coating not only
nonpolar aromatic rings and longer alkyl chains of the 2D encapsulate the 3D perovskite but also suppress PbI2 impurity
perovskite protects the grain boundaries of 3D perovskite and and aids improvement in the Voc by passivating the surface trap
significantly enhanced the moisture stability of the film. They states. The 2D perovskite incorporated PSCs achieved B17%
achieved certified PCE close to 20% in 2D perovskite incorpo- efficiency, which is slightly lower than its 3D counterpart
rated devices and these devices show less than 20% drop in the (18.19%). In stability test the 2D incorporated PSCs retained
PCE when kept at 40 1C and 50% RH for about 400 h under 1 sun about 80% of their PCE after more than 200 days of storage
illumination. During this time 3D only, devices decreased more under ambient conditions with RH 25–80%, within this period
than 60% in the PCE values under similar circumstances. 3D only devices show more than 60% loss in PCE (Fig. 9a). More
In a similar study, stabilization of all inorganic a-CsPbI3 importantly when the 3D@2D film was dipped in water it
phase has been achieved, by adding small amount of EDAPbI4 remains unaffected at least for few minutes before the degrada-
perovskite.148 The efficiency of the devices drops from 13% to tion started indicating 2D perovskite strongly prevent the pene-
10% within a month while retaining the a-CsPbI3 phase, when tration of water molecules into the 3D perovskite, see Fig. 9b.
stored in a dry box (in dark) without any encapsulation. Bismuth based 2D perovskites like MA3Bi2I9 have also been
In situ incorporation of an ultrathin (5-AVA)2PbI4 (5-AVA = 5 explored in PSCs owing to their strong moisture stability. Hu
ammoniumvaleric acid) 2D perovskite passivation layer at the et al., demonstrated the coating of vertically aligned MA3Bi2I9
interface between the perovskite and hole transporting layer platelets on the top of MAPbI3 grains, exhibits excellent photo-
(CuSCN) is demonstrated.149 This passivation layer improves electric properties and robust tolerance against moisture and
both moisture stability and photostability of the PSC. The oxygen.145 They achieved PCE of 18.97% with significantly
unencapsulated devices retain 98% of initial PCE after 60 days reduced hysteresis and remarkably enhanced air stability. There
of storage in dark with relatively low humidity of 10%. A PSC are several other studies, which successfully demonstrate the use
device stable for 1-year was achieved by Grancini et al., by of 2D perovskites for encapsulating 3D perovskites and achieved
engineering an ultra-stable 2D/3D (HOOC(CH2)4NH3)2PbI4/ improved stability and photovoltaic performance.45,128,149,151,152
MAPbI3 perovskite interface.130 The 2D/3D multidimensional By adjusting the dimensional components of room
interface yields B15% PCE in standard mesoporous solar cell temperature-formed two-dimensional perovskite layers using
structure. They also demonstrated fabrication of large area fully oleylammonium iodide molecules, R. Azmi et al., created PSCs

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Fig. 9 (a) Variation in PCE of nonencapsulated 3D-only PSCs and (C14H29NH3)2PbI4 (C14), (C16H33NH3)2PbI4 (C16), and (C18H37NH3)2PbI4 (C18)
perovskite-coated PSCs kept under ambient atmosphere (RH 25–80%, 10–25 1C, in the dark). (b) After 3 minutes of direct immersion in water, the
purely 3D perovskite has reacted with water to form PbI2 (left film) while same 3D perovskite coated with (C18H37NH3)2PbI4 perovskite (right film) is
unaffected. Reproduced from ref. 127 with permission from Springer nature, copyright 2021.

that are resistant to damp heat.153 These layers serve to passivate can retain over 90% of their efficiency upon storage for over
the perovskite surface at the electron-selective contact. As a 1000 h under high humidity conditions (RH 85%).
result, the inverted PSCs achieved an impressive 24.3% power Recently Ren et al., demonstrated use of bulky alkylammo-
conversion efficiency (PCE). Even under rigorous damp-heat nium MTEA cations in 2D perovskite framework.159 The
testing for over 1000 hours, these cells maintained over 95% of (MTEA)2(MA)4Pb5I16 2D perovskite based solar cell devices were
their initial efficiency. This accomplishment fulfills a crucial fabricated and the photovoltaic parameters were compared
industrial stability benchmark for photovoltaic modules. with that of (BA)2(MA)4Pb5I16. The MTEA cation based 2D PSCs
show better photovoltaic properties than the BA based 2D
4.6. 2D perovskite only perovskites, with highest PCE of 18.06% for MTEA based PSCs
Lower dimensional materials, especially 2D perovskite materi- and 15.94% for BA based PSCs. Furthermore, in stability tests
als, are found to be the most suitable materials for passivating MTEA-based PSCs retain more than 85% of initial PCE after
the interface between HTM and perovskite. Both 2D perovskite continuous power output at MPP for 1000 h and better moist-
and organic cations offer excellent surface passivation, suppres- ure tolerance of up to 1512 h (under 70% RH) for (MTEA)2-
sion of defects, and improved grain size and film quality, while (MA)4Pb5I16 thin films.
making the surface of perovskite films more hydrophobic and
thus delivering moisture stable devices. Researchers took moti- 4.7. Charge-transporting materials
vation from the above findings and started exploring 2D only As discussed above, the performance of the PSCs is not solely
PSCs.154–156 hampered due to the degradation of perovskites but also the
The early pioneering work on 2D perovskite based solar cells degradation of charge-transporting layers is responsible for
delivered an efficiency of up to 4.73% but with greater moisture decreasing PSC performance. While this is beyond the scope
resistance compared to 3D perovskite based PSCs.157 Later, after of this review, we summarize and cite some of the important
significant investigations higher efficiencies up to B13% have reports on them. As an example, a solution processed strategy
been achieved by fabricating near single crystal quality thin films to stabilize the interface between perovskites and graphene
out of layered 2D Ruddlesden–Popper (RP) perovskites.158 Even oxide charge-transporting heterostructures was proposed by
higher certified PCE (17.8%) have recently been reported in bulky Wang et al.160 Strong bonding between Pb-rich perovskite and
2-(methylthio)ethylamine hydrochloride (MTEACl) based 2D RP graphene oxide (GO) favors the formation of stable heterostruc-
PSCs.159 Apart from the improved moisture stability 2D perovskite tures based on ionic Pb–Cl and Pb–O bonds. As a demonstration
capping layers offer reduced ion migration and ion accumulation of the stabilized structure, the PCSs with perovskite/Cl–GO
resulting in reduced hysteresis and increased Voc compared to 3D heterostructures retained 490% of their initial efficiency after
only PSCs.58,149 Tsai et al., reported (BA)2(MA)2Pb3I10 (n = 3) and 1000 h of continuous light soaking at 60 1C. The use of hydro-
(BA)2(MA)3Pb4I13 (n = 4) 2D perovskites, which were derived from phobic HTM or carbon-based electrodes help in improving the
the parent 3D perovskite (MAPbI3) using a hot casting device longevity; however, these materials have suppressed the
technique.158 In stability tests, for over 2250 h under constant efficiency of the PSCs.161–164 Following the initial exploration of
illumination and relative humidity of 65%, the encapsulated PSC carbon based perovskite solar cells introduced by Chang et al. in
devices showed negligible degradation compared to 3D PSCs that 2016,165 a range of strategies has been suggested to enhance
lost 90% in PCE. In another study Ma et al., reported excellent device performance and reaching to 15.35% PCE.166 These
moisture and thermal stability in propane 1,3 diammonium strategies encompass optimizing fabrication techniques, engi-
(PDA) cation based 2D perovskite.129 PDA based 2D perovskites neering solvents, adjusting compositions, refining interfaces,

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optimizing charge transport layers, and more.167–171 Carbon- engineering, and using moisture resistant 2D perovskite/
based electrodes were developed to address the challenges organic cations. However, modification of perovskites using
associated with metal electrodes in perovskite solar cells—such the strategies above complicates the understanding of degrada-
as high-temperature and low pressure deposition conditions, tion and charge transport processes and there is an urgent need
sensitivity to humidity, limited scalability, and cost concerns. to obtain a simple and sustainable solution to overcome these
Carbon materials offer numerous advantages over metal electro- complications. To achieve stable working PSC the HTM, ETM,
des, including a reduced environmental impact, compatibility and electrodes need further stabilization. This opens a wide
with flexible materials, hydrophobicity, high surface area, and scope for exploration of dopant-free HTM and inorganic HTM
porosity. Utilizing carbon as both the HTM and the top electrode to increase device stability.
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can safeguard the device from moisture, leading to the develop- The PSC lifetime is limited by two major factors, the first is
Open Access Article. Published on 12 February 2024. Downloaded on 11/20/2024 [Link] AM.

ment of an air-stable solar cell even in the absence of intrinsic instability of the halide perovskite absorber and
encapsulation.172–174 To resolve the stability issue in carbon- second is poor resistance to environmental factors such as heat
based electrode, the inorganic HTMs such as NiO,175–179 and moisture. An in-depth knowledge of intrinsic and extrinsic
Al2O3,180 CuSCN,181–185 and Cu2O186 have been investigated. degradation mechanism in materials and devices is prerequi-
Apart from HTM, the interface contact between the electron site to achieve stable and robust solar cell devices. The moisture
transport layer (ETL) specifically TiO2, SnO2, and ZnO-based induced degradation of MAPbI3 is very well understood, but in
ETLs and perovskite affects the stability of PSCs.187–189 As an most of the high performing PSCs mixed cation (Cs/MA/FA) and
example, the impact of UV-induced O2 desorption in TiO2 mixed anion (I/Br) composition of perovskites are used and
accelerates PSC degradation. Q. Ye et al.190 investigated moisture induced degradation of mixed cation-mixed halide
NaTaO3, a perovskite oxide, as a novel ETL for PSCs. It effec- perovskites is not investigated in detail and therefore, it is
tively shields against UV damage, suppresses perovskite layer equally important to understand the moisture induced degra-
degradation, and enhances overall PSC stability. PSCs incor- dation of these high performing perovskites.
porating NaTaO3 demonstrated a power conversion efficiency The lifetime of PSCs has been significantly prolonged from
(PCE) of 21.07%, maintaining over 80% of the initial PCE after few hours to ten thousand of hours by employing interface
240 minutes of UV irradiation in air. In contrast, the reference engineering and mixed cation–anion substitution but still the
device, with a PCE of 20.16%, retained only approximately 53% stability is far away from commercialization requirements.
of its initial PCE under the same testing conditions. In 2023, Furthermore, the future work should be focused on prolonging
J. Liu et al.191 presented SnO2 ETL embedded with carbon the stability of PSC up to 5 to 10 years or even longer. The
quantum dots (CQDs). The power conversion efficiency (PCE) inclusion of 2D perovskite in PSCs along with 3D perovskite has
saw a substantial increase from 21.62% to 24.05%, attributed to provided promising results with significantly enhanced stabi-
improved charge extraction. Notably, perovskite solar cells with lity under humid conditions and at elevated temperatures.
the CQD-SnO2 ETL retained over 84% of their initial PCE after However, the stability tracking over several months is lacking
1000 hours of continuous irradiation under 1-sun illumination, in the literature, which hinders the actual use of 2D perovskite
effectively suppressing perovskite degradation from the bottom as long term encapsulation. Moreover, the crystallization
contact. Moreover, utilizing a TiO2/SnO2 double ETL192 and mechanism of perovskite after molecular passivation/2D per-
surface modification of ZnO by anchoring fullerene material,193 ovskite have not been fully understood.
and interlayer modifiers between oxide ETLs and perovskite External encapsulation techniques can be straightforward
can improve stability in PSCs.194 processes to prevent the infiltration of moisture and oxygen;
however, internal encapsulation is still needed. In this regard It
is important to select a moisture resistive HTM, or organic/
5. Conclusion and outlook inorganic compounds as passivators in perovskite layers. Moreover, we
anticipate that the combination of 3D/2D heterostructure and appro-
The hybrid perovskites have evolved as low cost, solution priate internal encapsulation techniques can proficiently alleviate
processable material for third generation solar cells owing to perovskite instability in the presence of humidity. Appropriate encap-
their large absorption coefficient, high charge carrier mobility, sulation strategies need to be developed in order to achieve high
longer diffusion lengths and high-power conversion efficiency. performance and stable PSC within a universally acceptable strategy.
The fabrication of PSCs through facile and cost-effective screen
printing, spin coating, and roll-to-roll printing methods makes
these materials an easy technology for commercialization. Conflicts of interest
However, the instability of the perovskite material under ambi-
There are no conflicts to declare.
ent conditions presently limits the prospects for commerciali-
zation of this technology.
In this review, we discussed the major advancements to Acknowledgements
improve the stability of the perovskites under ambient air
through, mixed cation-mixed anion substitution, doping of The authors gratefully acknowledge the support from the
organic/inorganic materials into perovskite, interface Swedish government through the research initiative ‘‘STandUP

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