Bulletin of the Chemical Society of Japan, 2024, 97, uoad025

https://doi.org/10.1093/bulcsj/uoad025
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Materials chemistry for metal halide perovskite
photovoltaics
Tomoya Nakamura1, Yoshio Kondo2, Noboru Ohashi1, Chihiro Sakamoto1, Akio Hasegawa1,
Shuaifeng Hu1, Minh Anh Truong1, Richard Murdey1, Yoshihiko Kanemitsu1, Atsushi Wakamiya1,*
1
Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan
2
Life Science, Global Business Creation, Corporate NV Creation, NGK Insulators, Ltd., 2-56 Suda-cho, Mizuho, Nagoya 467-8530, Japan
*Corresponding author: Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011. Email: wakamiya@scl.kyoto-u.ac.jp

Atsushi Wakamiya
Atsushi Wakamiya received his Ph.D. degree from Kyoto University in 2003. He began his academic career
at Nagoya University as an assistant professor in 2003. In 2010, he moved to Kyoto University as an asso­
ciate professor and was promoted to full professor in 2018. He has received several awards: The Chemical
Society of Japan Award for Creative Work (2020), Commendation for Science and Technology by MEXT
Japan: Award for Science and Technology Research Category (2022), etc. He is a project leader of the Green
Innovation Program (NEDO) and JST-Mirai Program. He is a co-founder and a director (as Chief Scientific
Officer, CSO) of “EneCoat Technologies, Co. Ltd.”, a startup company for perovskite solar modules. His
research interests include physical organic chemistry, elemental chemistry, and materials chemistry.

Abstract
Metal halide perovskite semiconductors are excellent materials for next-generation solar cells. As a result of research and development all over
the world, the photoelectric conversion efficiency for single-cell devices has rapidly improved to over 26% (as of July 2023), while the record
efficiency for silicon-on-perovskite tandem devices currently stands at 33.7% (reported in May 2023). Materials chemistry has made many
important contributions toward these remarkable results. In this account, we will introduce our achievements in these areas of material
chemistry research for improving the performance of perovskite photovoltaics, including the development of high-purity precursor materials,
and precursor inks tailored for large-area printed perovskite films. Studies of the nucleation and crystallization process, including simulations,
have led to the reliable fabrication of high-quality perovskite films. Diverse new charge collection materials, as well as compounds to
effectively modify perovskite surfaces, have improved solar cell performance.
Keywords: numerical simulation, organic semiconductors, perovskite solar cells, printable materials, surface passivation.

Graphical Abstract
Solution-based Film Fabrication for Perovskite PVs
Coating & Drying Dense & Flat
Perovskite Thin Film

In this account, we introduce the following topics in perovskite photovoltaics

research, focusing on materials chemistry: (1) the development of high-purity
precursor materials, and precursor inks; (2) studies and simulations of the
nucleation and crystallization process for reliable fabrication of high-quality
perovskite films; (3) an overview of new charge collection materials, as well
as compounds to effectively passivate the perovskite surfaces.

[Received on 30 October 2023; revised on 23 November 2023; accepted on 23 November 2023; corrected and typeset on 7 March 2024]
© The Author(s) 2024. Published by Oxford University Press on behalf of the Chemical Society of Japan. All rights reserved. For permissions, please e-mail:
journals.permissions@oup.com
2 Bulletin of the Chemical Society of Japan, 2024, Vol. 97, No. 3

1. Introduction
Metal halide perovskites are ionic crystalline materials with a
general formula of ABX3.1–5 Sometimes called “organic-
inorganic hybrid perovskites”, the A-site monovalent cation

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can be either a monovalent metal (Cs+, Rb+) or a small organic
ammonium ion such as methylammonium (MA+ = CH3NH+3)
or formamidinium [FA+ = CH(NH2)+2]. The B-site divalent
metal cation is typically lead (Pb2+) or tin (Sn2+), while halides
I–, Br–, or Cl– occupy the X-site (Fig. 1a). A prototypical mater­
ial is methylammonium lead iodide, MAPbI3, which has been
researched mainly as a conductor6–9 or luminescent mater­
ial.10,11 Metal halide perovskites were first successfully used
as the light-absorbing layer in dye-sensitized solar cells
(DSSC)12,13 by Miyasaka et al. in 2009, with a resulting power
conversion efficiency (PCE) of 3.8% (Fig. 1b).14 Following this
encouraging result, the groups of Nam-Gyu Park in Korea15
and Henry Snaith in the United Kingdom16 independently
developed solid-state solar cells by removing the liquid
electrolyte and coating the perovskite layer directly with
2,2’,7,7’-tetrakis(N, N-di-p-methoxyphenylamino)-9,9’-
spirobifluorene (Spiro-OMeTAD). The PCE of these early
perovskite solar cells exceeded 10%, sparking an intense
research drive to further increase cell performance. Based on
compositional engineering,17 the development of so-called
“triple cation” perovskites, in combination with many other
advances, brought the efficiency to above 20% by 2016.18
The highest reported PCE currently exceeds 26% in 2023.19
In addition, “lead-free” tin-based perovskite solar cells,20,21 Fig. 1. Basics of perovskite solar cells. a) Structure of ABX3-type
which overcome the toxicity issue of lead, have also seen sig­ perovskite semiconductor, b) chart of power conversion efficiency (PCE),
nificant recent progress.22–24 and c) device structures of perovskite solar cells. The data in panel b) was
The structure of typical perovskite solar cells is illustrated in taken from the Best Research Cell Efficiencies Chart.19
Fig. 1c. The perovskite layer, which is responsible for both the
absorption of light and the generation of electron-hole pairs, is
2. Results and discussion
sandwiched between charge collection layers. A significant
feature of perovskite films is their fabrication via crystalliza­ 2.1 Development of high-purity precursor
tion directly from precursor materials, either through materials
solution-based wet deposition14–16,25 or vacuum-based dry During the initial phase of perovskite solar cell research, re­
processing.26,27 For wet processing, thin perovskite layers searchers around the world experienced poor reproducibility
suitable for solar cell devices are readily fabricated using com­ in their results. Even when the solar cell devices were fabri­
mon thin film deposition methods like spin-coating, blade- cated following the exact methods described in the literature,
coating, etc., though scaling these processes to large areas only some groups could successfully reproduce photovoltaic
has proved challenging.28 For dry processing, thermal evapor­ conversion efficiencies over 10%, while others found their de­
ation allows for the conformal deposit of thin films on rough vices were limited to efficiencies of a few percent, or produced
substrates such as textured silicon. However, it is difficult to negligible power output. The fabrication of high-quality per­
control the evaporation ratios of the precursor materials or ovskite semiconductor thin films is the key to realizing high-
introduce passivation compounds necessary for high-quality efficiency solar cells. We, therefore, started by thoroughly
films. Intriguingly, the relatively low processing temperatures, purifying the various starting materials used to fabricate per­
typically bellow 150°C for both methods, permit the fabrica­ ovskite thin films, including dehydrating and degassing the
tion of perovskite solar cells on plastic film substrates for light­ solvents. During this initial investigation, the one material
weight and flexible devices.29–31 that we never questioned was the perovskite precursor lead
In this account, we present our investigations in this field iodide (PbI2). This was because we were using the PbI2 with
from the standpoint of materials chemistry in solution-based a purity as high as 99.999% (trace metal basis), the highest
perovskite film fabrication. First, we introduce the importance purity commercially available. We noticed, however, that
of material purity in the reproducible fabrication of high- this PbI2 was only partially dissolved by dehydrated polar sol­
quality perovskite film. Second, we present the unique proper­ vents such as dimethylformamide (DMF; Fig. 2a). Filtering
ties of perovskites and review the methods for fabricating this suspension and using the filtrate to fabricate the solar cells
perovskite films. The mechanism responsible for the forma­ resulted in poor performance with a PCE of around 5%
tion of crystallites during film deposition is revealed with the (Fig. 2b). When the amount of water in the PbI2 used was
aid of numerical simulations. Finally, we elaborate on the de­ measured, we found, to our surprise, that it contained as
velopment of charge-collecting materials and the surface much as 2,000 ppm of water. Since inorganic materials are
modification of perovskite films. generally sintered at high temperatures, their purities are
Nakamura et al. 3

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Fig. 3. Structure of perovskite solar cells. a) Cross-sectional
Fig. 2. High-purity precursor materials. a) The appearance of the DMF scanning-electron microscope (SEM) image and the working mechanism
solution of unpurified (left) and purified (right) PbI2 and b) current–voltage of perovskite solar cells. b) Schematic illustrations showing the
(J–V ) characteristics of the solar cells prepared using each starting importance of perovskite layer uniformity.
material. c) Crystal structures of solvent-coordinated complexes of tin
halides: SnI2(dmf), SnBr2(dmf), and SnCl2(dmf). Data in panels b) and c) found that the photoluminescence intensity increases in pro­
were taken from refs 32 and 33, respectively.
portion to the square of the excitation light intensity in
MAPbI3.35 This suggested that ABX3-type perovskite semicon­
usually defined based on residual metal standards without the ductors emit light through two-body recombination from the
consideration of water content. We therefore purified PbI2 by excited state. This was the first experimental demonstration
sublimation under reduced pressure to remove water. The that ABX3-type perovskite semiconductors generate free car­
purified PbI2 (water content <100 ppm) was found to dissolve riers (holes and electrons) upon light absorption,35–39 rather
well in the dehydrated DMF, and the solar cell devices using than excitons like organic materials. Note that in wide
this material showed PCEs exceeding 13% and improved re­ band-gap perovskite, photoluminescence in MAPbCl3 is
producibility (Fig. 2b).32 This material has been commercial­ caused by exciton recombination.40 We also investigated the
ized by a Japanese material manufacturer (Tokyo Chemical dynamic photophysical properties of perovskite single crystals
Industry Co., Ltd., TCI), and is widely used as a standard ma­ with a multi-photon absorption technique and time-resolved
terial in the field of perovskite solar cells. PL spectroscopy. The PL peak under one-photon excitation
Similarly, we worked on the purification of tin halide shows a red shift with elapsing time, while two-photon PL is
(SnX2). Divalent tin is readily oxidized, and the contamination time-independent and appears at lower energy levels. The low-
of tetravalent species deteriorates the perovskite semiconduct­ energy two-photon PL can be attributed to emissions from the
or characteristics. We found that commercially available SnI2 localized states. These results revealed that high-quality per­
(a red solid), with a purity of 99.9% (trace metal basis), ovskite semiconductor crystals exhibit a “photon recycling
contained as much as 10 wt% of SnI4. Purified SnI2 can be phenomenon”, in which light is repeatedly emitted and ab­
obtained by sublimation and/or recrystallized from a coordin­ sorbed, reflecting the high stability of the photo-excited state.41
ating solvent to obtain highly purified materials as colorless It is also known that perovskite semiconductors are ambipolar
crystals such as SnI2(dmf) (Fig. 2c).33 This complex turns red­ semiconductors with relatively high mobility (diffusion length)
dish brown on oxidation, providing a convenient indication of for both holes and electrons.52 Owing to these unique photo­
the purity of the SnI2. physical properties of perovskite semiconductors, efficient so­
lar cells can be realized with a simple structure consisting of a
perovskite layer sandwiched by p-type and n-type semicon­
2.2 Properties of metal halide perovskite ductor layers (Fig. 3a). The photon-to-electricity conversion
Why are ABX3-type perovskite semiconductors excellent ma­ mechanism53–63 of perovskite solar cells can be simply under­
terials for power generation in solar cells? We have revealed stood as follows: Free carriers (holes and electrons) with suffi­
the unique photophysical properties of these perovskite semi­ ciently long diffusion lengths are generated in the perovskite
conductors using advanced spectroscopy.34–51 The perovskite layer upon light absorption, which can be selectively extracted
materials are direct bandgap-type semiconductors, and the sta­ by the semiconductor layer to each electrode to generate elec­
ble excited states make them highly emissive.34 Because of the tricity (Fig. 3a).
high absorption coefficients of perovskite semiconductors,
even thin films with a thickness of about 400 to 800 nm can suf­
ficiently absorb sunlight in the covered wavelength. We inves­ 2.3 Perovskite film fabrication
tigated the correlation between the intensity of irradiated light To improve the performance of solar cells, it was first neces­
(excitation light) and photoluminescence (PL) properties and sary to develop appropriate process techniques to reliably
4 Bulletin of the Chemical Society of Japan, 2024, Vol. 97, No. 3

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Fig. 5. Fabrication of MAPbI3 film by wide-process window using 1.40 M
Fig. 4. The pictures of films during spin-coating of precursor solution: MAPbI3·DMF in DMSO solution. Adapted with permission from ref 67.
a) PbI2 + MAI, 1.55 M in DMF, b) PbI2 + MAI, 1.55 M in DMF/DMSO Copyright 2018 Wiley-VCH.
(3:1), and c) MAPbI3·DMF 1.40 M in DMSO. Adapted with permission
from ref 67. Copyright 2018 Wiley-VCH.
forming on the substrate. In the case of the perovskite compo­
nent of MAPbI3, for example, colorless and transparent needle-
fabricate dense, flat, and high-quality perovskite thin films. As like intermediate microcrystals such as MA2Pb3I8·2DMSO
described above, perovskite solar cells are composed of a (DMSO: dimethyl sulfoxide) and MA2Pb3I8·2DMF were
stacked structure of multiple layers. If the perovskite layers formed when DMSO and DMF were used as solvents, respect­
are rough, the upper charge collection layer cannot fully cover ively.66 During the subsequent heating process up to 100°C, the
the perovskite layer, resulting in the recombination of the gen­ intermediate microcrystals further react with the remaining
erated free carriers and thereby the decrease of the photoelec­ MAI while releasing the solvent to form a thin film of
tric conversion efficiency (Fig. 3b). Perovskite semiconductors MAPbI3. The precise control of these deposition processes real­
are essentially cubic crystals, however, making it difficult to ized the fabrication of dense and flat perovskite thin films, lead­
form a dense and flat thin film. In addition, unlike paints ing to the photoelectric conversion efficiency exceeding 20%.66
and inks made of organic materials, perovskite semiconduc­ The optimum time for dripping the antisolvent depends on the
tors only transform into the characteristic black semiconduct­ drying rate of the liquid film. The optimized time using DMF/
or in the solid state. The precursor solution itself is yellow. The DMSO mixed solvent for MAPbI3 film in our laboratory was
constituent ions of these precursors assemble into a black col­ 8 s after starting spin-coating. The process window, the period
or perovskite structure as the solvents are released during the of time allowed for antisolvent dripping in this case, can be wid­
drying and heating process. Precise control of this coating pro­ ened by the choice of the solvent and precursor materials used,
cess from the viewpoint of “chemical equilibrium” and “crys­ which is important to realize the fabrication of large area
tal growth” is crucial to reducing defect structures and modules.67
fabricating high-quality semiconductor thin films. This is As a key precursor material for MAPbI3 film fabrication
where the knowledge of organic chemistry and complex chem­ with a wider process window, we obtained MAPbI3·DMF
istry can make significant contributions. crystals by the slow diffusion of CH2Cl2 onto DMF solution.67
Various materials and additives have been developed to fa­ Single crystal X-ray structural analysis confirmed that a DMF
cilitate film fabrication and improve film quality. Various coat­ molecule is intercalated between a [Pb2I6]2– layer and MA cat­
ing and drying methods have also been developed, in which the ions (MAPbI3) in a ratio of 1:1. We found that MAPbI3·DMF
organic solvent was carefully selected in the points of solubility, crystals dissolve more readily and show higher solubility (satu­
coordinating properties, boiling point, volatility, etc. These ad­ rated concentration: 2.0 M at room temperature) in DMSO
vances enabled us to fabricate high-quality perovskite semicon­ compared to the mixture of PbI2 + MAI (1.2 M), while no dif­
ductor thin films with better reproducibility, greatly increasing ference was observed in DMF (2.2 M). Taking advantage of
the performance of solar cells. One representative example is high solubility in DMSO of high purity MAPbI3·DMF crys­
the antisolvent treatment, in which a nonpolar solvent (poor tals, we could expand the process window.
solvent) is dripped during coating.64,65 This involves dripping As mentioned above, the optimal antisolvent dripping time
a low-soluble nonpolar antisolvent such as toluene onto the li­ is restricted by the drying speed of the precursor solution.
quid film just before the perovskite precursor solution is com­ While both DMSO (189˚C) and DMF (153˚C) are the solvents
pletely dried. This process can be understood as a rapid with high boiling points, DMF has a higher vapor pressure at
reprecipitation of microcrystals leading to many crystal nuclei room temperature (360 Pa) than DMSO (56 Pa) and thus dries
Nakamura et al. 5

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Fig. 7. Background for crystal nuclei formation simulation. a) Diagram of
classical nucleation theory and b) solubility curves of MAPbI3 in various
solvent systems (experimental data indicated by symbols, curves show
the theoretical fit).

The composition of the perovskite film is normally defined

by the composition ratio of A site (Cs+, MA+, and FA+) and
X site (I– and Br–) ions in the precursor solution. Based on
this composition engineering strategy, mixed-ion perovskite
films, such as Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3,18
were found, which exceeded the film quality of pure compo­
nent films such as MAPbI3 or FAPbI3. Since then, solar cells
using these ion-mixed Pb-based perovskite semiconductors
Fig. 6. Fabrication of high-quality Sn perovskite films. a) SEM images have become mainstream, and many groups have achieved
showing the effect of HAT and SVA methods. b) Schematic illustration of power conversion efficiencies exceeding 20%.68,69
the Sn(IV)-scavenging treatment using dihydropyrazine derivatives. On the other hand, the deposition of Sn-based perovskite thin
Panel a) was adapted with permission from ref 67. Copyright 2018
Wiley-VCH. Panel b) was adapted from ref 71. Copyright 2020 the films was found to be more difficult than their lead counterparts.
authors, licensed under the Creative Commons Attribution 4.0 This is likely because the Sn perovskites are more reluctant to
International License. form crystal nuclei than the Pb-based material, while the subse­
quent crystal growth is faster. Our idea was to use chlorobenzene
preheated to 65°C as an antisolvent [hot antisolvent treatment
more quickly. Figure 4 shows the pictures of the film surface (HAT) method], which promotes the formation of crystal nuclei
during spin-coating of precursor solution (PbI2 + MAI, and gives a uniform thin film with a high surface coverage and no
1.55 M) in DMF, DMF/DMSO (3:1), and MAPbI3·DMF pinholes (Fig. 6a).70 Crystallinity can be improved by controlling
(1.40 M) in DMSO, respectively. While the film formed by the vapor of the solvent by covering the substrate with a petri dish
spin-coating of DMF-only solution gives opaque film soon during the annealing process [solvent vapor annealing (SVA)
after 5 s—thus providing no operational window for antisol­ method].70 By combining these techniques, it became possible
vent dripping—that of DMF/DMSO (3:1) solution maintains to fabricate Sn-based perovskite solar cells with relatively good
transparent film until 20 s, which leads to the optimal dripping reproducibility.
time of 8 s. The film formed from a DMSO-only solution of The power conversion efficiency of Sn-based perovskite so­
MAPbI3·DMF remains transparent until ca. 60 s owing to lar cells was limited to around 7% to 8%, however. We as­
the longer drying time of DMSO, suggesting the possibility sumed that the semiconductor characteristics of the Sn
of more relaxed timing of the antisolvent dripping step. perovskites were degraded by Sn(IV) impurities still remaining
Indeed, this characteristic allows us to fabricate good quality in the perovskite film. We therefore developed a Sn(IV) scaven­
MAPbI3 film with a wide process window: the timing of anti­ ging method, in which a strong reducing agent, a dihydropyr­
solvent dripping can be more flexibly adjusted without affect­ azine derivative, is added to the precursor solution just before
ing the film morphology and the device performance. For coating to remove the Sn(IV) impurities (Fig. 6b).71 Sn per­
example, as shown in Fig. 5a, low-speed spin programs (0 to ovskite semiconductor thin films could be fabricated as free
1,000 rpm) up to 70 s long could be inserted before the final of Sn(IV) species for the first time, which was confirmed by
5,000 rpm step, and antisolvent dripping could be performed X-ray photoelectron spectroscopy (XPS) measurements. The
at any point over a 13 s interval (at 82 to 95 s) with little solar cell devices using this method showed PCE exceeding
change in film morphology and device performance. SEM im­ 11%. At present, the PCE of lead-free perovskite solar cells
ages confirm the formation of dense and flat perovskite layers is still less than 15%, which we expect to be improved by
in each case (Fig. 5b). Taking advantage of this method, a the development of charge-collecting materials and passiv­
5×5 cm2 size eight-cell perovskite module could be fabricated ation materials as will be discussed later.24,72–79
with PCE of >15%.67
In addition to the development of fabrication methods, flat
and dense perovskite films can also be facilitated via compos­ 2.4 Numerical simulation on crystal nuclei
ition engineering.17,18 A wide variety of ions can be substi­ formation
tuted into ABX3-type perovskites as long as the size It was revealed that the efficient formation of crystal nuclei is
constraints for forming the perovskite structure are satisfied. the key for obtaining dense and flat perovskite films which are
6 Bulletin of the Chemical Society of Japan, 2024, Vol. 97, No. 3

R(t′ ) = 1–exp(–t′ /τ)

where t′ is the time after antisolvent dripping and τ is the func­

tion of the antisolvent temperature.83

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We started by examining the solubility of perovskite precursor
at various temperatures. The solubility of MAPbI3 at 25°C, 50°C,
75°C, and 100°C was experimentally found to be 1.73 M,
2.10 M, 2.34 M, and 2.65 M, respectively, showing increased
solubility at high temperatures (Supplementary Table S1,
Fig. 7b). The solubility of MAPbI3 in DMSO shows a similar
trend with the solubility of 1.29 M, 1.90 M, 2.34 M, and
2.65 M at 25°C, 50°C, 75°C, and 100°C, respectively. To evalu­
ate the decrease in solubility induced by the antisolvent, the solu­
bility in a mixed solvent of DMSO and toluene at the volume ratio
of 1:2 and 1:5 was also measured (Supplementary Table S2). The
solubility at 50°C, for example, decreases from 1.90 M in DMSO
to 0.30 M in DMSO/toluene (1:2) and 0.025 M in DMSO/tolu­
ene (1:5). These solubility data were fitted with logistic curves
(Fig. 7b), which are used for the following calculations.
Using the obtained solubility curves, the effect of the antisol­
vent dripping during the spin-coating process can be dis­
cussed. The spin-coating process is schematically illustrated
in Fig. 8a, while the change in the simulated degree of super­
saturation (S) is plotted in Fig. 8b.
From the precursor solution (state A), the solvent volatilizes
as the substrate spins to form a supersaturated solution (state
B). When it reaches a critical concentration, crystal nuclei start
to form (state C). Here, the degree of supersaturation is only
moderate (Fig. 8b, green line), resulting in the formation of
a small number of crystal nuclei (Fig. 8a, left). When the anti­
solvent such as toluene is dripped at t = 3 s, the rapid mixing of
solvents increases the degree of supersaturation (Fig. 8b, red
line, state C’). An instant increase in the degree of supersatur­
ation (>2.0) immediately forms numerous crystal nuclei
(Fig. 8a, right). The maximum nucleation rate can be realized
if the antisolvent is dripped at the instant where the degree of
Fig. 8. The effect of antisolvent dripping on nucleation rates. supersaturation is the highest, i.e. the solution is sufficiently
a) Schematic illustration of the spin-coating process, b) plots of the solution concentrated but crystal nuclei have not yet formed.
concentration change, and c) simulation results of the nucleation rate. Figure 8c shows the simulation results comparing the condi­
tions with (t = 3 s) and without antisolvent dripping. After
suitable for efficient solar cells. To get insight into the film fab­ spinning the precursor solution of MAPbI3 in DMF for ca.
rication technique described above, numerical simulations on 3.3 s, nucleation starts with the maximum nucleation rate of
the crystal nuclei formation were conducted based on the clas­ 0.06 × 1021 m−2s−1 (Fig. 8c, green line). If the toluene antisol­
sical nucleation theory (Fig. 7a).80–82 The details are shown in vent is dripped onto the supersaturated solution at t = 3 s, it
the online supplementary material. When the initial solution leads to the rapid formation of crystal nuclei with the max­
(state A) is concentrated over its saturation concentration imum rate of 1.8 × 1021 m−2s−1 (Fig. 8c, red line). The effect
(CS), a supersaturated solution is formed (state B). of antisolvent dripping could be rationally explained by our
Crystallization starts when it reaches the critical concentration numerical simulation.
(C*min) for nuclei formation (state C). In the classical nucle­ We have reported that the use of less volatile DMSO instead
ation theory, the nucleation rate J can be expressed as follows: of DMF can widen the process window of perovskite film fab­
􏼠 􏼡 rication.67 The toluene antisolvent needs to be dripped at the
−16πγ3 υ2 exact time for DMF-based solutions, while for DMSO-based
J = Aexp solutions, the window for antisolvent dripping is wider, over
3k3B T 3 (ln S)2
10 s (Fig. 9a). Here, the difference in the process window is an­
where A is the frequency factor, γ is the surface energy, υ is the alyzed by the simulation. Figure 9b shows the change in the nu­
molecular volume, kB is the Boltzmann constant, T is the solu­ cleation rate when the toluene antisolvent was dripped at
tion temperature, and S is the degree of supersaturation. The different times after the spin speed reached 5,000 rpm
nucleation rate is strongly dependent on the degree of super­ (t = 0 s). In the case of DMF solution, dripping toluene at
saturation (S), defined as the ratio of the solution concentra­ t = 3 s, where the degree of supersaturation reaches its max­
tion and the solubility (S = C/CS); the higher the degree of imum, gives the highest nucleation rate of 1.8 × 1021 m−2 s−1
supersaturation, the larger the number of nuclei. For the simu­ (Fig. 9b, top). If the antisolvent addition is made 1 or 2 s later,
lation of antisolvent dripping, the mixing rate of the main however, the nucleation rate significantly decreases to
solvent and the antisolvent was expressed as 0.73 × 1021 m−2 s−1 and 0.32 × 1021 m−2 s−1, respectively.
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Fig. 10. Analysis of the HAT tin perovskite film formation method.
a) Calculated nucleation rate when 25°C or 65°C chlorobenzene is
dripped at t = 15 s and b) schematic illustration of the crystal nuclei
formation process.

n-type90–92 semiconductors) is also crucial to efficiently ex­

tract each free carrier generated in the perovskite layer to
each electrode. In solar cells with an n-i-p structure, in which
an electron collection layer (e.g. TiO2 or SnO2), a perovskite
layer, and a hole collection layer are stacked from the substrate
side, a p-type organic semiconductor containing a triaryl­
amine skeleton such as Spiro-OMeTAD is used as a hole col­
lection layer. We have developed a series of p-type
Fig. 9. Analysis of the comparison of a process window for antisolvent semiconductor materials using azulene core structure and
treatment on DMF and DMSO-based precursor solutions. a) Spin coating
program for Pb perovskite film fabrication and b) calculated nucleation introducing quasi-planar skeletons in which triarylamine is
rate when toluene is dripped at different times. partially tethered with oxygen atoms (Fig. 11a).93–95 By com­
paring the electronic structures of these molecules with the re­
This is because the crystallization already starts before drip­ sultant solar cell properties, we were able to clarify the
ping the antisolvent due to the high volatility of DMF, making molecular design guidelines required for hole collection mate­
the antisolvent treatment less effective. In contrast, for the rials (Fig. 11b).94 It was revealed that to selectively and effi­
DMSO solution with lower volatility, the supersaturated con­ ciently extract holes and to block electrons from the
dition is much more stable. As a result, dripping the antisolvent perovskite layer, the highest occupied molecular orbital
at the time between t = 3 and 11 s gives the nucleation rate of (HOMO) level of the p-type semiconductor needs to be at least
more than ca. 1 × 1021 m−2 s−1 (Fig. 9b, bottom). A higher tol­ 0.1 eV shallower than the valence band (VB) of the perovskite,
erance for the antisolvent dripping time in DMSO than in DMF and the lowest unoccupied molecular orbital (LUMO) level at
is supported by the results of our numerical simulation. least 0.25 eV shallower than the conductive band (CB) level
Finally, we discuss the effect of the HAT method for fabri­ (Fig. 11b). Similarly, for the electron collection materials, their
cating a uniform Sn perovskite thin film with a high surface LUMO and HOMO levels should generally be at least 0.1 eV
coverage. The solubility curves of a representative Sn perovsk­ and 0.25 eV deeper than the CB and VB levels, respectively.94
ite, FASnI3, were measured analogous to Pb perovskite In addition to the molecular design of charge-collecting mate­
(Supplementary Table S3). rials, the effects of energy alignment and interfacial recombin­
The temperature of the antisolvent is expected to affect the ation are discussed in terms of quasi-Fermi level splitting
mixing rate of solvents on the film (online supplementary (QFLS) in the perovskite layer.96,97
material, equations 6 and 7). Based on this difference, we si­ Based on this molecular design guideline, various
mulated the rates of crystal nuclei formation of FASnI3 with p-type98,99 and n-type semiconductors100 have been devel­
chlorobenzene antisolvent at 25°C and 65°C. The maximum oped for hole and electron collection materials, respectively.
nucleation rate was calculated to be 0.20 × 1021 m−2 s−1 and Most of them are used as bulk layers with thicknesses ranging
0.84 × 1021 m−2 s−1 for 25°C and 65°C antisolvent treatment from several tens of nanometers to several hundreds of nano­
at t = 15 s, respectively (Fig. 10a). The higher nucleation rate meters. These materials are usually used with additives (dop­
(larger number density of crystal nuclei) for 65°C antisolvent ing materials) such as lithium bis(trifluoromethanesulfonyl)
dripping can be explained by the faster mixing with DMSO so­ imide (LiTFSI) for p-type semiconductors because of the inher­
lution, leading to the rapid decrease of solubility and signifi­ ent low conductivity of organic semiconductors. It has also be­
cant increase of the degrees of supersaturation (Fig. 10b). come clear, however, that the ions of the additives greatly
Our numerical simulation could successfully reproduce the ex­ reduce the durability of the solar cell device.101 Considering
perimental observations and is a powerful tool for a deeper the working mechanism of solar cells, the role of the charge
understanding of the crystallization mechanisms. collection layer is to selectively extract each charge from the
ambipolar perovskite layer to the electrode. In this sense, using
thick films is not always necessary. Carbazole derivatives with
2.5 Charge collecting materials alkyl phosphonic acid anchoring groups that adsorb on trans­
For further performance enhancement of the solar cells, the parent conductive substrates such as ITO or FTO have recent­
development of charge collection materials (p-type84–89 and ly been reported to function as hole collection materials as a
8 Bulletin of the Chemical Society of Japan, 2024, Vol. 97, No. 3

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Fig. 12. Interface passivation materials. a) Top and bottom interface
modification with EDA2+ and GlyH+ and b) improved carrier collection by
surface dipole formation. Taken from ref 108 with modification.

glycinium (GlyH+) were used as modification materials for

these exposed and buried interfaces, respectively.109 EDA2+
and GlyH+ were designed so that the methylammonium group
enters the A site on the surface of the perovskite layer, while
the remaining methylammonium and carboxyl groups could
form positive and negative dipoles from the surface to the elec­
Fig. 11. Charge collection materials. a) The chemical structure of tron and hole charge collection layers, respectively. This sur­
azulene-based p-type material, b) desired electronic structures for charge face dipole modification strategy was expected to enable
collection materials, and c) molecular design of tripodal hole collecting efficient extraction of each charge carrier with minimal volt­
monolayer material, PATAT. Data in panel b) was taken from ref 94. Panel
age loss (Fig. 12b).109 Modification of the top surface of the
c) was taken from ref 105 with modification.
perovskite layer can be achieved by depositing a passivation
material under conditions with minimum damage to the per­
monolayer.102 The monolayer material is also useful for tan­ ovskite film. On the other hand, modifications to the bottom
dem103 solar cells because it does not require any additives, of the perovskite layer are generally more difficult.
and has high durability and high transparency104 We have re­ Fortunately, when 2 mol% HCl salt of glycine was added to
cently developed a new monolayer hole collection material, the precursor solution of Sn–Pb perovskite semiconductors,
PATAT, with three alkyl phosphate groups introduced into GlyH+ was found to mainly present at the bottom of the per­
the triazatruxene backbone (Fig. 11c).105 By introducing mul­ ovskite films, which was confirmed by time-of-flight second­
tiple anchoring groups, we envisioned that the π-conjugated ary ion mass spectrometry (ToF-SIMS) measurements. The
skeleton would be oriented in a face-on manner concerning method was found to be highly generalizable to Sn–Pb per­
the transparent conductive substrate, increasing the overlap ovskite semiconductor films, regardless of the surface material
of orbitals at the interface of the perovskite layer compared of the substrate used. Dynamic light scattering (DLS) and
to that of the conventional monopod-type carbazole deriva­ NMR spectroscopy measurements confirm the formation of
tives. It was found that holes could be extracted more efficient­ Sn–Pb perovskite colloidal particles in the precursor solution
ly by using the multipodal molecules, resulting in an improved with oriented GlyH+ cations bound to the surface. It’s possible
photoelectric conversion efficiency of 23.0% with excellent that during film formation these colloidal particles segregate
durability.105 We expect that the research on monolayer out as sediment on the substrate, leading to the observed accu­
charge collection materials considering the adsorption mode mulation of GlyH+ at the buried interface. The solar cell devi­
and molecular orientation on the substrate will become ces fabricated using mixed Sn–Pb perovskite with these
more active in the future. interface modifications showed an open circuit voltage of up
to 0.91 V. The voltage loss from the band gap (1.25 eV) was
as small as 0.34 V, close to the theoretical limit. A PCE of
2.6 Interface modification materials 23.6% was obtained, which is the world’s highest value for
Interface modification is also important for efficient charge Sn-containing perovskites.109
collection.106,107 Because ABX3-type perovskite semiconduc­ As an interfacial passivation material on the electron collec­
tors have A and X sites on their surfaces, various organic cat­ tion layer side, EDA2+ was found to be also effective in im­
ions such as alkylammonium and organic anions can be used proving the open-circuit voltage in p-i-n solar cells with Pb-
as surface modification materials. The passivation of the inter­ and neat Sn-based perovskite semiconductors, demonstrating
face with these organic compounds can also improve durabil­ the universality of this dipole strategy.110,111 Furthermore, di­
ity by suppressing ion migration in the solar cell devices. We amines/diammonium used as interface modifiers are not lim­
have developed interface passivation materials for mixed Sn– ited to EDA/EDA2+. A synergistic surface modification
Pb perovskite semiconductor films with a narrow band gap method combining piperidinium salt with a carboxylic acid
of 1.24 eV (absorption onset at 1000 nm).108–111 In mixed functionalized fullerenes has been developed, in which the pas­
Sn–Pb perovskite solar cells with a p-i-n structure, electrons sivation mechanism was revealed in detail.112 Thanks to these
are extracted from the top (exposed) interface of the perovsk­ robust and simple surface modification strategies being ex­
ite layer whereas holes are extracted from the bottom (buried) plored, mixed Sn–Pb perovskite solar cells with superior per­
interface (Fig. 12a). Ethylenediammonium (EDA2+) and formance can be reproducibly fabricated. We expect that
Nakamura et al. 9

interface modification technologies, especially from a materi­ for the Integrated Research Consortium on Chemical
als chemistry perspective, will be extensively studied, which Sciences, Grant-in-Aid for Research Activity Start-up
will aid the community to fabricate perovskite photovoltaics (20K22531), Grant-in-Aid for Early-Career Scientists
with substantially improved efficiency and stability. (21K14694, 22K14744), Grant-in-Aid for Scientific

Downloaded from https://academic.oup.com/bcsj/article/97/3/uoad025/7512679 by Chittagong University of Engineering & Technology (CUET) user on 12 October 2024
Research (C) (19K05666), and Grant-in-Aid for Scientific
3. Conclusion Research (A) (21H04699). T. N. acknowledges research
grants from the Tokyo Ohka Foundation for the Promotion
This account summarizes our recent successes in improving of Science and Technology, the Sumitomo Foundation, the
the performance of perovskite photovoltaics from the view­ Mazda Foundation, and the Kyoto Technoscience
point of materials chemistry. The following topics were dis­ Center. M. A. T. gratefully acknowledges a research grant
cussed; purification technologies of starting materials, film from the Iwatani Naoji Foundation. S. H. thanks JSPS for a
deposition methods to produce high-quality perovskite thin Research Fellowship for Young Scientists (21J14762), and
films, organic semiconductor materials that efficiently extract the China Scholarship Council (CSC). A. H. thanks JST for
charges from perovskite layers, and passivation technologies the establishment of university fellowships towards the cre­
for perovskite interfaces. In solar cells using ABX3-type per­ ation of science technology innovation, Grant Number
ovskite semiconductors as photoelectric conversion materials, JPMJFS2123.
organic cations, and anions can be used as the A and X site
components. In these “organic-inorganic composite materi­ Conflict of interest statement. A. W. is a co-founder and CSO
als”, the development of new materials from the viewpoint of EneCoat Technologies, Co., Ltd.
of organic chemistry as well as inorganic and complex chem­
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