Review of Two-Step Method For Lead Halide Perovskite Solar Cells

REVIEW
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Review of Two-Step Method for Lead Halide Perovskite

Solar Cells
Yipeng Han, Haibing Xie, Eng Liang Lim, and Dongqin Bi*
(MAI) is deposited atop the carrier trans-

The quality of the perovskite film is crucial to the technological breakthrough of porting layer, followed by heat treatment
perovskite solar cells (PSCs). The two-step method can facilitate the formation of to improve the crystal quality of the film.
a perovskite film with high quality and reproducibility. Many milestones have Even though this method is simple to oper-
ate, surface coverage and uniformity of the
been made in the development of hybrid lead halide PSCs by using the two-step
resultant film arouse concern due to the
method, which has a significant impact on their practical application. Herein, the uncontrollable film crystallization rate.[10,23]
reaction mechanism of the two-step method including two-step immersion The two-step method was first proposed
method and two-step spin coating method is summarized. The strategies such as by Mitzi et al.[24] The PbI2 film was
component engineering, solvent engineering, and additive engineering of the immersed in the MAI, and the crystalliza-
tion process could be finished upon the
two-step method in preparing high-quality films are introduced systematically
interaction between the organic component
and in detail. In addition, current issues of the two-step method and its appli- and the inorganic component. The two-step
cations in lead-free PSCs, all-inorganic PSCs, large areas, and tandems are method has the advantages of easy fabrica-
introduced and some suggestions are put forward for future research. tion and good repeatability. The develop-
ment of the two-step method is shown in
Figure 1. In 2013, Grätzel et al.[25,26] first
applied the two-step method in PSCs,
1. Introduction achieving a PCE of 15%. To understand the mechanism of the
two-step method, Park et al.[27] developed two-step spin coating
In recent years, hybrid lead perovskite solar cells (PSCs) have method, and revealed the influence of the concentration of the
attracted great attention because of their high absorption coeffi- organic component, reaching a PCE of 17%. In addition, the ratio
cient, long carrier diffusion length, and adjustable bandgap.[1–7] of cations in the organic components has also been shown to have
The structural formula of perovskite material is ABX3, in which an important influence on the crystal structure of the perov-
A represents organic and/or inorganic cation, i.e., methylammo- skite.[28] In order to reduce hysteresis, You et al.[29] achieved a
nium (CH3NH3þ or MAþ), formamidinium (NH(CH3)2þ or PCE of 19.9% by utilizing SnO2 as the electron transport layer
FAþ), or cesium (Csþ); B is divalent metal cations such as lead (ETL), which enhanced the electron extraction ability and made
or tin; X is halide anion including chlorine, bromine, or iodine. it possible for the preparation of large-scale devices. With the
In just a few years, the power conversion efficiency (PCE) of rapid development of PSCs, more delicate work is needed to fur-
PSCs has increased from 3.8%[5] to over 25%,[8] making them ther improve the performance of the device. Huang et al.[30] and
currently one of the most promising thin-film solar cells.[9–11] Sang et al.[31] used a surface passivation strategy and a bulk defect
It is well known that the PCE of PSCs is highly dependent on passivation strategy to improve the PCE of the devices up to 21.0%
the quality of perovskite film.[12–16] Till now, various methods, and 22.3%, respectively. Through surface passivation, You
such as the one-step method,[17,18] two-step method,[19,20] and et al.[20] achieved a certified PCE of 23.3%, attributed to the largely
vapor-solution assistant method,[21,22] have been developed to improved open-circuit voltage (VOC) of the device. Zhou et al.[8]
obtain high-quality perovskite films with good optoelectronic prop- obtained a PCE of over 25% at low temperature inside aerospace
erties. For the one-step solution deposition method, an equimolar simulation warehouse through self-elimination of intrinsic
solution of lead (II) iodide (PbI2) and methylammonium iodide defects strategy, which was the highest efficiency achieved by
the two-step method up to now at low temperature. Besides,
two-step method has also been applied in perovskite photodetec-
Y. Han, H. Xie, E. L. Lim, D. Bi tors.[32,33] These indicate that two-step method has great potential
State Key Laboratory of Optoelectronic Materials and Technology
Guangdong Provincial Key Laboratory of Low Carbon Chemistry and
in the preparation of efficient and stable PSCs and other photo-
Process Energy Conservation electric devices. The schematic diagrams of the one-step and
School of Materials Science and Engineering two-step methods are shown in Figure 2.
Sun Yat-sen University In this review, we focus on the research progress of two-step
Guangzhou 510275, P. R. China deposition techniques in PSCs. Herein, we introduce the engi-
E-mail: bidongqin@mail.sysu.edu.cn
neering and mechanism of two-step deposition method, followed
The ORCID identification number(s) for the author(s) of this article by discussion of component, solvent, and additive engineering.
can be found under https://doi.org/10.1002/solr.202101007. We conclude with the challenges and outlooks upon the future of
DOI: 10.1002/solr.202101007 the two-step method application in PSCs.
Sol. RRL 2022, 6, 2101007 2101007 (1 of 22) © 2022 Wiley-VCH GmbH

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Figure 1. Development map of two-step method for hybrid lead halide PSCs.
Figure 2. Schematic illustration of perovskite film prepared by one-step method, two-step immersion method, and two-step spin coating method.
2. Method and Reaction Principle morphology of the PbI2 film, concentration of the MAI solution,
and the immersion time have a great influence on the morphol-
2.1. Immersion Method ogy of the resultant perovskite film.[36–39] Zhu et al.[40] found that
the method can also be used to prepare planar perovskite films.
In 2013, for the first time, Grätzel et al. treated inorganic and The PbI2 film spontaneously transformed to mesoporous struc-
organic components separately, in which MAI was deposited ture, which was observed by angle-dependent grazing incidence
on mesoporous PbI2, and the crystallization of perovskite was X-ray scattering (GISAXS), and the quality of MAPbI3 film could
completed through full contact of PbI2 with organic solution. be effectively manipulated by precise controlling of the PbI2 film
They obtained shiny film with good surface morphology and morphology. Wei et al.[41] revealed the relationship between the
achieved a PSC with a PCE of 15%.[26] In the same year, Kelly structure of the perovskite film and the immersion time in the
et al.[34] used ZnO as the ETL based on the same deposition second step. Through an interfacial reaction, PbI2 film reacted
method to prepare the perovskite layer and achieved a PCE of with the MAI solution and formed MAPbI3 crystals, followed
15.7%. On the basis of the two-step method, Yang et al.[35] used by the dissolution–recrystallization process. With the extension
all inorganic NiO and ZnO transport layers to improve the sta- of the immersion time, defects gradually formed on the film sur-
bility of PSCs. After 60 days of storage at room temperature, 90% face, followed by the dissolution and shedding of perovskite
of the initial efficiency can still be maintained. crystals.
In the immersion method, perovskite forms through the reac- There are two mechanisms for the conversion of PbI2 to perov-
tion between solid PbI2 film and MAI solution. Thus, skite crystals: one is a solid–liquid interface conversion reaction,

and the other is a dissolution–recrystallization growth mecha-

nism (Figure 3). In low concentration of MAI solution, the PbI2 ðsÞ þ 2I ðsolÞ ! PbI4 2 ðsolÞ (3)
solid–liquid interface contact reaction is dominant. During
immersion progress, MAI molecules diffuse into the layered The above is the dissolution process. When the concentration
structure of PbI2 and react with PbI2 molecules at the interface of PbI42 reaches supersaturation, the lead iodine complex reacts
directly, and transformed to MAPbI3 crystals. The solid–liquid with the organic cation CH3NH3þ to form MAPbI3 crystals
interface conversion mechanism and the dissolution– through a slow crystallization process. The reaction equation
recrystallization growth mechanism play a competing role in is as Equation (4)
the growth of perovskite crystals, and this depends on the reac-
tion kinetics of the concentration of iodide ions in the solu- PbI4 2 ðsolÞ þ CH3 NH3 þ ðsolÞ ! CH3 NH3 PbI3 ðsÞ þ I ðsolÞ
tion.[38] At low concentration, the conversion equation for the (4)
reaction as shown in Equation (1)
PbI2 ðsÞ þ CH3 NH3 þ ðsolÞ þ I ðsolÞ ! CH3 NH3 PbI3 ðsÞ (1)
2.2. Spin Coating Method
In the initial stage of the reaction, conversion reactions con-
tinue to occur at the PbI2 interface, forming perovskite crystals. The two-step immersion method is a typical solid–liquid hetero-
As the reaction progresses, the perovskite crystals crystallized at geneous reaction, among which the solid PbI2 and the MAI solu-
the interface will prevent the further diffusion of organic cations tion react through the interface contact directly.[43] Huang
from reacting with PbI2. As a result, the conversion reaction is et al.[44] developed a new two-step spin coating process, of which
inhibited. PbI2 and MAI were dissolved in N,N-dimethylformamide (DMF)
At high MAI solution concentration (≥10 mg mL1), crystal- and isopropanol (IPA) solutions, respectively. After the PbI2 solu-
line perovskite film will rapidly form on the surface of PbI2, tion was spin-coated and heated on the substrate, the MAI solu-
and the diffusion of organic cation is largely prevented, which tion was directly coated on the PbI2 film. Due to the low solubility
hinders the formation of perovskite crystals.[38] Yang et al.[42] of PbI2 in IPA, spin-coated PbI2 will not be washed away by the
found that at high MAI concentration component, PbI2 tends IPA solution. A dense perovskite film formed through the inter-
to react with organic components to form lead iodine complex nal diffusion of PbI2 and MAI during the spin coating process.
PbI42. When the concentration of organic components is fur- Due to the simple operation, this method opens a new window
ther increased (≥20 mg mL1), the concentration of iodide ions for the two-step method. You et al.[40] used this method to achieve
increases and facilitates the formation of lead iodine complex a PCE of 21.6% through precisely adjusting the rotation speed of
PbI42. Excess iodide ions in the solution promote the dissolu- the organic component solution. Zhao et al.[45] explored the pas-
tion of the previously crystallized MAPI3 and unconverted PbI2 sivation effect of residual PbI2 through speed adjustment. Yan
until the concentration of the local lead iodine complex in the et al.[46] skipped the PbI2 sintering step and directly spin-coated
solution reaches the chemical equilibrium. The reaction progress the organic component solution on the wet PbI2 film, obtaining a
is as Equation (2) and (3) PCE of 21.2%. Shi et al.[47] systematically studied the one-step
method and the two-step method in MAPbI3-based PSCs and
CH3 NH3 PbI3 ðsÞ þ I ðsolÞ ! CH3 NH3 þ ðsolÞ þ PbI4 2 ðsolÞ found that the two-step method has better reproducibility and
(2) PCE than the one-step method. These results show that the
Figure 3. Schematic illustration of two-step immersion reaction mechanism. The interface reaction mechanism at lower MAI concentration and
the dissolution–recrystallization growth mechanism at higher MAI concentration. Conversion through interfacial reaction is faster than dissolution–
recrystallization growth reaction rate. Reproduced with permission.[38] Copyright 2015, American Chemical Society.

two-step spin coating method is effective in preparing efficient and found laterally confined crystal growth at the beginning of
PSCs. crystallization. In the MAI solution, the growth rate of the
In the two-step spin coating method, the inorganic component MAI crystal nucleus has little correlation with the MAI concen-
is usually spin-coated before the organic component, but it is not tration. Panzer et al.[50] observed that the growth rate of the crys-
limited to this. Hussain et al.[48] developed a new three-step spin tal nucleus was 11 nm s1 in a 40 mg mL1 MAI solution. Cho
coating method, in which the spin coating sequence was MAI et al.[51] used a low-concentration MAI solution of 4–8 mg mL1,
layer–PbI2 layer–MAI layer. Results showed that the surface traps and observed that the growth rate of crystal nuclei was
and grain boundaries of the perovskite film were reduced due to 10–20 nm s1, which indicated that the growth rate of perovskite
the passivation of MAI. Matsuda et al.[49] combined the one-step crystals in the solution had little dependence on the solution
method and the two-step spin coating method, using organic concentration. Park et al.[52] proposed a new theoretical
component solutions (FABr, FAI, MACl, FACl in IPA) to treat calculation method, using Gibbs free energy thermodynamic
excess PbI2, and the devices reached a fill factor (FF) of analysis to explain the growth of MAPbI3 crystals, and found that
83.4%, with a PCE of 21.3%. the grain size of MAPbI3 crystals depends largely on the reaction
To understand the reaction mechanism of the two-step spin temperature. Therefore, the photovoltaic performance of the
coating method (Figure 4a), Panzer et al.[50] used in situ optical device changes with temperature.
spectroscopy to monitor the MAPbI3 crystallization process The concentration of MAI solution is caused by solvent evap-
(Figure 4b,c). Through analyzing the absorption spectrum and oration. Specifically, when the PbI2 is covered with a perovskite
photoluminescence (PL) spectrum, different steps in the film for- crystal layer, a dense layer will be formed on the top, which can
mation process were identified. The analysis found that the for- prevent the further diffusion of MAI solution due to the higher
mation of the perovskite film could be divided into five density of PbI2.[38,53] Therefore, the formation of MAPbI3 crystals
consecutive progresses: 1) the formation of the perovskite cap- is suppressed. Because of the suppression of solution penetra-
ping layer; 2) the change of MAI solution concentration caused tion and the volatility of the IPA solution, the volume of the
by solvent evaporation; 3) the initial dissolution of the capping MAI solution exposed to air decreases and the concentration
perovskite; 4) rapid dissolution–recrystallization process; and continues to increase.
5) the complete conversion of PbI2 to perovskite crystal. The concentration of the MAI leads to a high concentration
The formation of the perovskite capping layer takes place in of I solution, which will produce a similar dissolution–
the second step of spin coating, that is, MAPbI3 crystals com- recrystallization phenomenon as in the two-step immersion
posed of small grains form on the surface of the PbI2 immedi- method.[54] The reaction process can be explained by the follow-
ately after the MAI organic component solution is deposited on ing chemical reaction
the PbI2 inorganic component. Cho et al.[51] revealed that as the
concentration of the MAI solution was increased, the perovskite CH3 NH3 PbI3 ðsÞ þ I ðsolÞ ↔ CH3 NH3 þ ðsolÞ þ PbI4 2 ðsolÞ
coating time decreased accordingly, and the size of the grains (5)
gradually decreased. Schlipf et al.[36] prepared a MAPbI3xClx
perovskite film using a mixed MAI:MACl solution and observed From Equation (5), we can see that volatilization of the MAI
it with grazing-incidence small-angle X-ray scattering (GISAXS), solution can increase the I concentration. Thus, the chemical
Figure 4. Schematic illustration of the reaction mechanism of the two-step spin coating method. a) Different stages of the perovskite film formation
process after the organic component is dropped. b) Perovskite film thickness as a function of spin coating time. c) Schematic diagram of MAPbI3 film
preparation and in situ optical property measurement of the perovskite film. Reproduced with permission.[50] Copyright 2019, Wiley-VCH.

reaction equilibrium is shifted to the right and the surface- (MET). After spin coating PbI2, the film was immediately
covered perovskite layer reacts can react with I to form lead immersed in IPA solution to form a loose porous film, and then
iodine complex ions PbI42. Because PbI42 can dissolve the IPA-treated PbI2 film was soaked in MAI solution to complete
MAPbI3 capping layer, the MAI solution on the top permeates the crystallization of perovskite. In the second step, Meng
downward to react with underneath PbI2 layer to form et al.[62] developed a multiple spin coating strategy that MAI/
MAPbI3 crystals.[38,50] In this process, the dissolution of the cover FAI was dropped on the PbI2 film and dried during each coating
layer generally occurs at the grain boundaries and smaller cycle. By optimizing the number of cycles, they achieved a PCE of
grains.[41] There is no material loss during the entire dissolution more than 20%. In addition, the multiple spin coatings
process. Obviously, the newly formed perovskite crystals do not of organic components have also been used to prepare low-
occupy the vacancies of the newly dissolved perovskite crystals, temperature solution-processed perovskite films. Song et al.[63]
which increases the size of existing grains, very similar to the used this technique to deposit FA0.9MA0.1I solution on PbI2 films
Ostwald ripening process. and the result showed that the grain boundary was reduced in the
Due to the further volatilization of the solvent and the disso- case of low-temperature sintering without the assistance of mois-
lution process, the dissolution–recrystallization process pro- ture. Moreover, multiple dipping methods have also been devel-
ceeded to the left side of the equation, and the MAPbI3 oped. In the two-step immersion method, Nateghi et al.[64]
crystal was formed. The Gibbs free energy decreased, and the immersed the inorganic film in organic solution, and after sin-
reaction continued to move to the left until all PbI2 in the bottom tering, the immersing step was repeated to reduce the PbI2 resi-
layer is completely converted into perovskite crystals. In the end, due and the carrier recombination.
all the inorganic and organic components are transformed into The solution-processed spin coating method has made many
MAPbI3 crystals. achievements in the preparation of high-quality perovskite film,
but it is limited to small-scale area device. To accelerate the prog-
ress of commercialization of PSCs, methods to prepare large-
2.3. Evaporation Method
area perovskite films are highly demanded. Another problem
needs to be solved urgently is the precise control of the film com-
Compared with the solution method, the perovskite film pre-
position. The gas-phase assisted solution method has outstand-
pared by the evaporation method is more uniform and denser,[55]
ing performance in the preparation and precise composition
which is conducive to the preparation of large-area perovskite
control of large-area devices.[65] Yim et al.[66] used MAPbCl3
films. The evaporation method can be divided into coevaporation
vapor to treat PbI2 films for controlling the stoichiometric ratio
method and sequential evaporation method. In the sequential
of film elements. A similar method has also been adopted by
evaporation method, different components are successively evap-
Mohammadi et al.[67] on the PbCl2–PbI2 mixed lead inorganic
orated onto the substrate to form perovskite films. This method
film. Chaudhary et al.[68] found that the use of organic vapor
can be used to prepare multication perovskite thin films.[56] For
to treat PbI2 films increased the reaction area of the conversion
the first time, Lin et al.[57] used the sequential evaporation
and improved the film quality. Besides the vapor-solution
method to prepare perovskite films. PbCl2 was first deposited
method, the blade-solution method is also suitable for large-area
on the substrate, MAI vapor reacted with PbCl2 to form perov-
components. Carlo et al.[69] found that appropriate amount of
skite in situ, and a large-area uniform crystal structure film was
MAI inorganic components can promote PbI2 filling of the stent
obtained.
in blade coating process. Shin et al.[70] proposed surface energy of
Sublimation in vapor processes requires precise control due to
the blade is an important parameter of the blade coating process,
the different vapor pressures of organic and inorganic compo-
which helps for a deep understanding of the mechanism.
nents. To address this problem, Jeangros et al.[58] developed a
In the two-step spin coating method, the spin coating of the
new chamber that physically separates the evaporation of organic
organic component may be on a stationary or a rotating PbI2 film.
materials. Recently, Bolink et al.[59] integrated solution evapora-
Li et al.[71] proposed the method of dynamic dropping for the first
tion into the solution process. On the PbI2 substrate prepared by
time in which, after the spin coating of the PbI2 film, the MAI
evaporation, the solution was spin-coated with organic compo-
solution was spin-coated on the rotating PbI2 film. Compared
nents. By introducing diffusive ions such as Br, I, etc. into
with the traditional two-step method, perovskite film was more
the organic component solution, the transformation of PbI2 layer
uniform and denser, which greatly reduced the degree of carrier
into perovskite layer was greatly promoted. The perovskite films
recombination, achieving a PCE of 20.1% with good reproduc-
prepared by sequential evaporation method can still be postpro-
ibility. Ho-Baillie et al.[72] studied the effects of the dynamic
cessed. Xu et al.[60] formed a 2D–3D structure on the perovskite
and static drop in the two-step method. The authors found that
surface, which enhanced the stability of the device, and the unen-
during the first step of rotation, the organic component was
capsulated device maintained 81% PCE after 30 days under 55% directly dropped, thereby effectively forming the mesophase,
relative humidity (RH). which promoted stronger precursor intercalation and avoided
excessively fast reactions of organic and inorganic components.
2.4. Other Methods Lee et al.[73] studied the effect and influence of two-step dynamic
spin coating in the FAI-MAI mixed system. The precursor solu-
Other methods have also been developed based on the two-step tion with different spin coating times was continuously dropped
spin coating and immersion method. Seo et al.[61] developed a on the predeposited PbI2 layer. Through the exchange reaction
new two-step method, namely, mediator extraction treatment between cations, a pinhole-free and high-quality perovskite film

was obtained. Compared with the traditional static spin coating CH3NH3PbI3x(SCN)x perovskite thin film was successfully pre-
method, the film prepared by the dynamic spin coating method pared through a two-step solution spin coating method, and the
showed better morphology and larger grain size with less resid- incorporation of thiocyanate ions in the crystal lattice signifi-
ual of PbI2. cantly improved the humidity stability of the perovskite film.
In the two-step spin coating method, FAI, as an organic com- Bouazizi et al.[84] used a two-step immersion method to prepare
ponent, forms the perovskite film. Besides, it can be spin-coated the MAPbBr3 perovskite film by dipping the PbBr2 film in the
directly on the perovskite film for defect passivation. Zhang MABr solution.
et al.[74] prepared the FAPbI3 perovskite thin film by a two-step A mixture of PbI2 and other ingredients could also be applied.
spin coating method. In addition, a series of FAI solutions were Nechache et al.[86] used a mixture of PbI2 and Pb(SCN)2 as lead
dropped on the perovskite film as posttreatment to passivate the sources. The stability of SCN-doped perovskite films in air was
grain boundary defects. Here, the FAI solution underwent two significantly improved due to the strong ionic interaction
spin coatings, the one for organic components to form perovskite between SCN and Pb atoms and the hydrogen bonding between
crystals and the other for passivation of defects on the perovskite SCN and organic components, and the PCE only declined by
surface. The experimental results showed that the efficiency of 12% when stored in a humid environment after 480 h. Cheng
the FAI-treated device has increased from 16.5% to 19.3%, et al.[87] introduced a certain amount of CsBr into the inorganic
and the stability of the device was also improved. component and prepared the CsxFA1xPbBrxI3x thin film by a
The environmental condition during the preparation process two-step immersion method. Studies have shown that the pres-
is vital to the perovskite film, and studies have shown that the ence of Csþ and Br could effectively prevent the phase transfor-
PSCs prepared in the ambient air showed a higher Voc.[75] mation of FAPbI3 perovskite from α phase to δ phase, and the
Proper exposure to ambient air results in a water-assisted crys- device maintained 87% initial PCE placed after 120 days under
tallization, which enhanced stability of the device.[76] Powalla RH. Hao et al.[88] proposed a mixed film of MA1yFAyPbI3xClx
et al.[77] compared the inert and humid environments (45% by using a mixed lead source of PbI2 and PbCl2.
RH) of preparing perovskite by using two step methods. In both Studies have shown that partly substitution of small radius cat-
environments, the devices with additive showed enhanced per- ions, such as Csþ, with organic cations could improve device per-
formance. While in the ambient air, the experimental group formance.[89–92] Sargent et al.[93] developed a new method of
demonstrated a higher Voc at optimized concentration of the introducing Cs into the perovskite lattice, which was different
additive, which may be due to the additional interaction between from the direct addition of Cs element in the inorganic compo-
the environment, solvents, and additives. Tsang et al.[78] system- nent. The perovskite precursors containing different mass frac-
atically studied the effect of moisture on the crystallization pro- tions of Cs were added to the inorganic components, and the
cess of the perovskite film. With the assistance of moisture and perovskite “seeds” serve as the source of Cs (Figure 5a), which
toluene, PbI2 formed a scaffolded porous structure and promoted played a role in promoting crystallization during the formation of
perovskite crystallization. Annealed in a humid environment, the the perovskite crystals (Figure 5b–d). By adjusting the Cs content,
grain size of the perovskite was enlarged as moisture partially the perovskite grains became larger, the film quality was substan-
dissolves the perovskite precursor, which enhanced the photovol- tially improved, and the PCE reached 21.5%. Yang et al.[94] stud-
taic performance of the device. ied the role of Cs ions in the two-step method by adding a certain
amount of CsI to the inorganic component. The results showed
that the introduction of Cs ions helped to form high-quality
3. Component Engineering perovskite films with higher crystallinity and fewer film defects
3.1. Inorganic Components (Figure 5e). In addition, the bandgap of perovskite became wider
and open-circuit voltage of the device was improved, leading to a
The commonly used inorganic component in the two-step maximum PCE of 20.5%. To reduce the difference between solar
method is PbI2 precursor. Due to flexible operation of the cell efficiency and operational stability, Meng et al.[95] found that
two-step method, other types of inorganic components such the introduction of Cs element could inhibit the crystallization of
as PbS,[79] PbO,[80] Pb(SCN)2,[81,82] PbAc2,[83] PbBr2,[84,85] and PbI2 and nonphotoactive perovskite phase and the device PCE
other mixed lead sources[86] have also be adopted. Lu et al.[79] pre- has reached 20.3% based on Cs0.1(MA0.4FA0.6)0.9PbI3 film
pared PbS thin films by chemical bath deposition(CBD), and sub- (Figure 5f–g). Song et al.[96] demonstrated that the introduction
sequently formed MAPbI3 thin film by vapor deposition. The of Cs enhanced the thermal stability of the device, attributed to
results showed that the PbS thin films prepared by the CBD the suppression of defect formation in Cs-treated perovskite
method had a dense structure, uniform coverage, and the defects films.
were reduced compared with the PbI2 thin film prepared by the Due to the poor diffusion rate of the organic salt in the second
coating method. Song et al.[80] prepared PbO thin film on the ETL step, it is difficult to convert the dense PbI2 precursor film to
using the electrochemical deposition method, and thickness and perovskite during the deposition process.[7,97] The residual
quality of the thin film could be optimized by controlling the PbI2 not only affected the reproducibility of device fabrication,
deposition time, deposition potential, and other deposition but also affected the stability of the perovskite film. To overcome
parameters. After that, the PbO film was reacted with MAI by the problem, Wong et al.[83] proposed PbAc2 and MAI as perov-
spin coating to form MAPbI3. By using pseudohalide group skite precursor. Due to volatile of Ac, it led to fully conversion of
SCN¬, whose ionic radius was very close to I, Yan et al.[81] PbI2 to perovskite by forming nanoholes on the surface of the
adopted Pb(SCN)2 as the inorganic component. A PbI2 film during the sintering process.

Figure 5. a) Schematic illustration of preparing perovskite film by seed engineering. b) The steady-state power output of the control device (w/o Cs) and perovskite
seeding growth (PSG) devices (with Cs). c) Histogram of PCE for control and PSG devices. d) J–V curves of the best-performing control and PSG devices.
Reproduced with permission.[93] Copyright 2018, Springer Nature. e) Time-resolved PL spectra of FA/MA and FA/MA/Cs films, respectively. Reproduced with
permission.[94] Copyright 2018, Wiley-VCH. f ) UVvis absorption spectra of the precursor films without and with 10% CsI for different storage time in air. g) FTIR
spectra of the PbI2 DMSO precursor films without and with 30% CsI. Reproduced with permission.[95] Copyright 2018, American Chemical Society.
3.2. Organic Components Meanwhile, studies have shown that chlorine could increase
carrier diffusion distance of the free carriers and improved the
MAI is the commonly used organic component precursor in the device performance.[100–102] In the two-step method, Huang's
two-step deposition method to derive MAPbI3 thin film. With the group[103] introduced Cl element into the perovskite lattice by
continuous development of PSCs, the composition of the organic mixed MAI/MACl solution and they found that Cl element could
component becomes more and more flexible. The Grätzel's alter crystallization kinetics of the perovskite crystals. As the
team[98] was the first to develop a mixed organic component solu- grain size became larger, the recombination lifetime of carrier
tion that dissolved MAI and FAI in IPA at a certain stoichiomet- charges was extended, and PCE of the best device has reached
ric ratio. Although the light absorption range of FAPbI3 18.9%. In addition to the positive effect of Cl element, Br element
perovskite was wider, the photoelectric conversion efficiency has also been reported to improve device performance.[85] Yang
was reduced due to the ease of formation of the yellow δ phase et al.[104] prepared a series of MAPbBrxI3x devices by immersing
at room temperature. By replacing FAþ with a small amount of PbI2 film in a certain stoichiometric organic solution, and the
MAþ, the device performance was improved compared to that of effect of Br element content was systematically studied. The
single cation, which could be attributed to MAþ ions broadened results showed that ion migration was suppressed, and the hys-
light absorption of the perovskite film and stabilized the crystal teresis was mitigated with the increasing amount of Br element.
structure. The Seok team[99] developed a new intramolecular
exchange reaction technique. By preparing the PbI2 (DMSO) 4. Solvent Engineering
complex, FAI and DMSO completed the intramolecular
exchange to form a highly crystalline FAPbI3 thin film and In the two-step method, crystallized PbI2 with different sizes
achieved PCE over 20%. could suppress the fully conversion of PbI2 to perovskite. This

phenomenon is due to the weak coordination between PbI2 mol- (NMP) complexes.[107] By adding a specific proportion of NMP
ecule and DMF molecule in the inorganic component and fast solvent to the DMF solution, the intramolecular exchange of
crystallization rate of PbI2.[105] For the first time, Han the formed complex with the FAI-based molecule could form
et al.[106] proposed DMSO as the solvent for the inorganic com- a high-quality perovskite film. Besides, the NMP was also used
ponent in the two-step method due to that DMSO is a strong in organic solvents IPA.[108]
coordination solvent (Figure 6a,b) and has a strong binding effect The quality of the perovskite film is not only related to the
with PbI2 molecules. It was found that the force between the lead degree of reaction conversion but also to the reaction conversion
and DMSO molecules could inhibit the excessively rapid crystal- rate. In order to solve the excessive reaction between organic and
lization of PbI2 and promoted the reaction between the organic inorganic components, Seok et al.[99] used the hydrothermal
and inorganic components. In addition to DMSO, N-pyrrolidone method to prepare PbI2/DMSO complex by a mixed DMF and
(NMP) could also be embedded in layered PbI2 to form PbI2 DMSO solvents. In the subsequent conversion of organic
Figure 6. Solvent engineering in the two-step process. a) Schematic illustration of using strong coordination solvent DMSO to inhibit PbI2 crystallization.
b) J–V curve of the best performing cells prepared by DMSO-based PbI2 films. Reproduced with permission.[106] Copyright 2014, Royal Society of
Chemistry. c) Histogram of solar cell efficiencies for FAPbI3-based cells fabricated by intramolecular exchange process and conventional process.
d) Schematic illustration of the intramolecular exchange process. Reproduced with permission.[99] Copyright 2015, American Association for the
Advancement of Science. e) Schematic illustration of DMF solution assisting MAI organic components to form perovskite and. f ) J–V curves of nanowire
perovskite and original perovskite. g) Energy level of materials used in PSC fabrication. Reproduced with permission.[113] Copyright 2018, Elsevier Ltd.

components, the FAI solution was spin-coated on the PbI2/ commercialization process. Among them, additive engineering
DMSO composite film. As the FAI molecule and the PbI2 mole- is considered to be an effective method to improve the perfor-
cule were covalently bonded, the PbI2 molecule and the DMSO mance of devices and various types of additives have been
passed through van der Waals force, which was weaker applied.[18,118–125] In the one-step method, organic and inorganic
than covalent bonds, so FAI combines with PbI2 through the salts are mixed together, so the main location of the additive is
intermolecular exchange, thereby slowing down the reaction the perovskite precursor solution. In the two-step method,
(Figure 6c,d). The FAPbI3 film prepared by this method has organic and inorganic salts are dissolved in different solutions,
perovskite grains with (111) preferential crystal orientation so the location of additives is more flexible, and different solution
and a flat surface without residual PbI2, and the corresponding can be chosen according to the solubility. Some typical additive
device achieved a PCE of more than 20%. strategies in the two-step method are summarized in Table 1.
In addition to using a single solvent to dissolve PbI2, the use of
DMF and DMSO mixed solvents can also improve film quality.
5.1. Additives in Inorganic Components
Yan et al.[46] prepared a series of inorganic components by con-
trolling the amount of DMSO added in the DMF solution and
The perovskite light-absorbing layer prepared by the solution
explored the effect of the residual amount of DMSO on the film.
method may have considerable defects, which not only become
By systematically studying the volume ratio of DMSO to DMF in
the center of carrier recombination, leading to a decrease in
the cosolvent, the importance of the residual DMSO solvent in
device efficiency but also easily cause device degradation, reduc-
the wet PbI2 layer was confirmed. In addition to being an additive
ing the stability the devices.[126–132] Zhou et al.[19] introduced
for inorganic components, DMSO could also act in organic com-
inorganic Eu3þ–Eu2þ ion pair in PbI2 solution. The results
ponents. He et al.[109] systematically studied the role of the
showed that the Pb0 and I0 defects in the perovskite were passiv-
DMSO in the IPA solution. By adjusting the DMSO content
ated during the redox process of europium (Figure 7a,b). The
in the second step solution, a series of compositions of
Eu3þ–Eu2þ redox ion pair will not be consumed during the
FA0.85MA0.15Pb(Br0.07I0. 93)3 were prepared, and the study found
cycling due to the nonvolatility of the europium element and
that DMSO affects the crystallinity, grain size, and residual
the appropriate redox potential. The PCE of the device reached
amount of PbI2 of the perovskite film.
21.5%, and the stability was greatly improved. Especially, 92%
The use of solvents affects not only the quality of the perov-
initial PCE could be maintained after 1500 h under one sun illu-
skite film, but also the morphology and structure of the perov-
mination. Zhan et al.[133] used [(CH3)3NCH2I]I (TMIMI) to pre-
skite.[110–112] Cho et al.[113] found that during the preparation
pare a 1D/3D hybrid perovskite film that showed excellent
of perovskite by the two-step spin coating method, it is helpful
ferroelectric properties. It was worth noting that the polarization
to grow perovskite nanowire by spin coating solutions containing
different MAI concentrations on the dried lead iodide film of 1D/3D hybrid ferroelectric solar cells could increase the aver-
(Figure 6e–g). The shape and size of the nanowire perovskite age VOC from 1.13 to 1.16 V, and the average PCE from 20.7%
could be adjusted by changing the concentration of DMF in to 21.5%.
the MAI solution. The PCE of the device based on nanowire Anionic additives are also used in the two-step process. Zhou
perovskite has reached 18.7%. et al.[126] added NaF to lead iodide solution (Figure 7c–e). Results
Yang et al.[114] used cyclohexane as a solvent and added it to showed that NaF was mainly distributed on the surface of perov-
organic components. The introduction of nonpolar cyclohexane skite crystals. F atoms formed ionic bonds and hydrogen bonds
reduced the polarity of the solution and adjusted the exchange rate with Pb atoms and organic cations, respectively, which not only
of DMF and MABr in the second step of the reaction. A uniform suppressed the formation of defects but also prevented the dif-
thin film with a preferred crystal orientation of (001) direction was fusion of ions, which lead to a champion PCE of 21.3%.
obtained. What is more, the light absorption capacity was Recently, it was reported that the introduction of ammonium
enhanced and the defect states of the film were reduced. Park chloride induced the formation of intermediate phases
et al.[115] used ethanol instead of IPA to dissolve MAI and found of x[NH4þ]·[PbI2Clx]x and HPbI3xClx (Figure 7f ), which
that the ethanol solution was more conducive to the diffusion could effectively promote perovskite crystallization, improved
between PbCl2 and MAI. Therefore, the crystallinity of the surface morphology, and increased the coverage uniformity.[134]
perovskite film was improved and a PCE of 11.2% was obtained Wang et al.[135] reported the defect passivation by Ni2þ in the
with good stability in a humid environment. Qiang et al.[116] used two-step method. By adding NiCl2 to the inorganic PbI2 solution,
n-butanol as the second-step organic solvent additive and found a loose and porous iodide was formed due to the different solu-
that n-butanol increased the grain size of the perovskite and bility of NiCl2 and PbI2 after the first step of the spin coating.
achieved higher visible light absorption and carrier lifetime. This was conducive to the diffusion of MAI in the second step
Zhu et al.[117] used a mixed solvent of cyclohexane and IPA, which reaction, resulting in perovskite crystals with large grain size. At
shortened the Ostwald ripening process through a two-step soak- the same time, Ni2þ could coordinate with halide anions to pas-
ing method and promoted the conversion of PbI2 to MAPbI3. sivate PbI3 translocation defects, thereby inhibiting the forma-
tion of Pb0 defects. Nd3þ element has also been reported in
defect passivation. Gong et al.[136] added a certain amount of
5. Additive Engineering Nd3þ in the PbI2 precursor solution. Compared with undoped
device, neodymium-doped ones obtained better film quality
Although the PCE of PSCs has exceeded 25%, research is still and lower density of trap states. In addition, the charge carrier
needed to further improve the performance and accelerate the lifetime was significantly extended, achieving a PCE of 21.2%.

Table 1. Summary of some additive strategies in the two-step process.
Additive Structure/formula Location Perovskite Component Functional groups Champion efficiency [%] References
Eu2O3 Eu2O3 Inorganic component MAPbI3 Eu –Eu
3þ 2þ
21.5 [19]
NdCl3 NdCl3 Inorganic component MAPbI3 Nd3þ 21.2 [135]
NiCl2 NiCl2 Inorganic component MAPbI3 Ni2þ 20.6 [136]

NaF NaF Inorganic component (Cs0.05FA0.54MA0.41)Pb(I0.98Br0.02)3 F 21.5 [126]
NH4Cl NH4Cl Inorganic component Cs0.05FA0.54MA0.41Pb(I0.98Br0.02)3 NH4þ Cl 22.1 [134]
DBEA Inorganic component MAPbI3 –OH, alkyl chain 11.5 [139]
GITC Inorganic component MAPbI3 SCN 16.9 [138]
TBP Inorganic component MAPbI3 N donor 16.2 [37]
TMA Inorganic component MAPbI3 –OH, benzene ring 17.2 [147]
PEAI Organic component MAPbI3 PEAþ 17.7 [148]
DTA Organic component MAPbI3xClx –COOH 21.5 [149]
TBP Same as above Organic component MAPbI3 N donor 14.6 [150]

TACl Organic component MAPbI3 TAþ, Cl 20.9 [152]
PVP Organic component MAPbI3 N donor 19.1 [153]
DI monomer Organic component FA1xMAxPbI3 C¼O 23.0 [154]
Table 1. Continued.
Additive Structure/formula Location Perovskite Component Functional groups Champion efficiency [%] References
ML Organic component FA0.82MA0.13Cs0.05PbI2.87Br0.13 –SH 21.4 [155]
CDQ C Organic component MAPbI3 CDQ 19.2 [156]

FAAc Organic component (FA,MA,Cs)Pb(I, Br)3 FAþ, Ac 21.0 [158]
BABr Organic component (FA,MA)Pb(I, Br)3 BAþ 23.2 [133]
MTP Organic component MAPbI3 Thiophene 21.5 [205]
KCl KþCl Electron transport layer (FAPbI3)0.95(MAPbBr3)0.05 Kþ, Cl 22.2 [159]
Besides metal cations, some simple cationic additives such as 5.2. Additives in Organic Components
NH4þ[137] were also used in the inorganic component solution.
Some small organic molecules can be used as additives in lead Alex et al.[148] used phenethylamine iodide (PEAI) to form a
iodide inorganic solutions. Li et al.[138] added a small amount of quasi-3D structure. The quasi-3D structure improved the phase
guanidine isothiocyanate (GITC) additive in PbI2 precursor to stability of the perovskite lattice. Besides, the iodinated phenethyl
improve perovskite film quality. More importantly, GITC group was introduced into the inorganic component as a hydro-
additives significantly improved the thermal stability of the phobic group. Through both theoretical and experimental
perovskite film. Choy et al.[37] added a small molecule additive research, it was found that the large radius of cationic PEAþ
4-tert-butylpyridine (TBP) to inorganic PbI2 solutions. mainly concentrated on the surface and grain boundaries of
Assembled porous lead iodide film was formed because TBP the perovskite film, and the formation of quasi-3D existence
has nitrogen donor ligands, which could coordinate with lead improved humidity stability of the device. Meanwhile, PEAI
iodide molecules (Figure 8a,b). On one hand, this was beneficial was also used for interface passivation. You et al.[20] adopted
for the transformation of perovskite and suppression of the PbI2 PAEI as surface passivation layer, effectively reducing surface
residues. On the other hand, a denser and more uniform high- defect states and increasing the open-circuit voltage to 1.18 V,
quality perovskite film was obtained at higher MAI concentra- and certified PCE of 23.3% was obtained. Li et al.[149] applied
tion. Recently, dibutylethanolamine[139] was used as a multifunc- small molecule named 2,5-di(thiophen-2-yl)terephthalic acid
tional morphology control additive (Figure 8c) to deposit a high- (DTA) with dicarboxyl and thienyl structure (Figure 9a) as addi-
quality uniform film with a particle size of 5 μm (Figure 8d). tive in organic components. Theoretical calculations and experi-
The high boiling point of this additive slowed down the crystalli- mental studies showed that the carboxyl group of the DTA
zation process and increased the crystal size to micrometer molecule had the highest distribution of electron clouds and
range. formed coordination with uncoordinated Pb2þ cations, which
The use of acidic additive improves the quality of the perov- was beneficial to reduce trap defects in the perovskite active layer
skite film and the performance of the device. Studies showed that (Figure 9b,c). In addition, tetra-tert-butylpyridine (TBP) was also
acidic additives affected distribution of the perovskite micelles in used as an additive. Due to strong polarity of N atoms and the
precursor solution, improved the solubility of the salt, and thus interaction between TBP and Pb atoms, the quality of the perov-
improved the crystal structure and morphology of the perovskite skite film and the grain size were improved.[150] Li et al.[151]
film.[140–146] Zhu et al.[147] added trimesic acid to inorganic PbI2 employed n-butylammonium bromide (BABr) as a template
solution. The use of additives improved morphology of the film, for the directional growth of perovskite crystals. The introduction
which was crucial for photoelectric performance of the device. of the large organic cation BABr facilitated formation of the inter-
More importantly, the thermal stability of the device was greatly mediate phase, improved crystallinity of the film, and reduced
improved due to the rigidity of benzene in small molecules and crystal defects. The resultant device could maintain 95% of
π–π bond effect. the initial PCE after ambient storage for 2600 h.
Figure 7. Additives in inorganic components. a) Schematic illustration of periodic passivation of Pb0 and I0 defects by Eu2þ–Eu3þ ion pairs. b) The J–V
curve, stable output, and parameters of 0.15% Eu3þ-incorporated champion devices. Reproduced with permission.[19] Copyright 2019, The Authors, some
rights reserved; exclusive licensee American Association for the Advancement of Science. c) A cross-sectional scanning electron microscope image of NaF
doped and undoped perovskite films. d) Schematic illustration of the strongest hydrogen bonds and ionic bonds formed by F atoms with hydrogen and
lead atoms, respectively. e) Stability performance of PSCs under humid air conditions. Reproduced with permission.[126] Copyright 2019, Springer Nature.
f ) Illustration of the formation process of the NH4Cl-based perovskite films. Reproduced with permission.[134] Copyright 2021, Wiley-VCH.
Ionic liquid is widely used as an additive in PSCs. Wang can also enhance the performance of the device through poly-
et al.[152] added ionic liquid additive of trimethylammonium chlo- merization. The Yang group[154] added dimethyl itaconic acid
ride (TACl) in MAI solution to alter the crystallization process of monomer as additive in PbI2 solution. During the sintering pro-
the perovskite. With the help of quaternary ammonium salt cess, the monomers polymerized and formed macromolecules at
groups and Cl, the defect in the crystal was passivated, thereby the grain boundaries (Figure 9g,h). After the perovskite film was
improving diffusion distance of the free carriers (Figure 9d–f ). formed, polymer anchored at the grain boundaries could effec-
Apart from small molecules, polymers can also be used as tively passivate uncoordinated Pb atoms, thereby reducing the
additives. Yang et al.[153] used polymer poly(4-vinylpyridine) density of defect states and the highest PCE of 23% was achieved.
(PVP) as additive in organic component. Through the diffusion Meanwhile, multicoordinated molecules have been proved to be
into mesoporous PbI2, polymers with different functional groups an effective additive to passivate Pb defects. Qi et al.[155] intro-
were successfully introduced into the perovskite structure. The duced a molecule with multiple ligands named pentaerythritol
PCE of the polymer-treated device reached 20.18%, and the tetrayl (3-mercaptopropionic acid) to modify the surface of the
VOC reached 1.16 V. In addition, the stability of the polymer- perovskite. In addition to passivating the uncoordinated Pb on
treated device was also improved, with 85% of the initial PCE the surface, the intermediate disulfide compound produced by
maintaining after 90 days of storage. Small monomer molecules the reaction with O2 could oxidize Pb0 defects to Pb2þ. As a
Figure 8. PbI2 and perovskite film formed by a) traditional PbI2 and b) porous PbI2 formed by self-assembly method. Reproduced with permission.[37]
Copyright 2015, Wiley-VCH. c) Mechanism of dibutylethanolamine intercalation and defect passivation of perovskite surface. d) Morphology of perovskite
film based on dibutylethanolamine additive and I–V curve of corresponding device. Reproduced with permission.[139] Copyright 2021, American Chemical
Society.
result, the PCE of the PSCs was significantly improved from 6. Outlook and Challenges
19.0% to 21.4%. Nanomaterials have also been attempted.
Shao et al.[156] used carbon quantum dots (CQDs) as additives 6.1. Application of Two-Step Method in Lead-Free Perovskite
in MAI solutions to passivate trap states and improved morphol-
ogy of the MAPbI3 film. Based on this strategy, the PCE of the PSCs have attracted much attention due to their low exciton bind-
device was improved from 16.2% to 19.2%. ing energy[160] and high efficiency.[18] In order to achieve better
Alkalinity is an important parameter that can greatly affect the performance, the development of multijunction PSCs devices
crystallization kinetics and photoelectric properties of perovskite becomes more and more popular, which has promoted the
films.[157] Zhou et al.[158] selected a series of additives with dif- research of narrow bandgap PSCs. In recent years, the research
ferent alkalinity and used them to explore the influence on thin of Sn/Pb mixed perovskite becomes a hot spot due to its less toxic
film and photovoltaic performance. Studies have found that in composition and narrower bandgap,[161,162] which has excellent
alkaline environments, I2 defects were passivated by its own dis- optical and electrical properties compared to germanium-,
proportionation reaction. As a result, a certified PCE of 20.9% bismuth-, and tellurium-based perovskites.[163–166] However,
was achieved. due to the competition reaction between PbI2 and SnI2, it is dif-
Additives used in the perovskite layer can also be applied to ficult to prepare high-quality perovskite thin film.[167] Besides,
carrier transport layers. Tan et al.[159] used KCl in the ETL. Sn2þ is easily oxidized into Sn4þ in air causing severe carrier
The results showed that the presence of KCl improved the layer recombination in devices.[168,169] Compared to one-step method,
contact between ETL and the perovskite layer, thus inhibiting the two-step method has the advantages of high repeatability and
nonradiative recombination in the perovskite film. high film quality, which may have a bright prospect in the
Figure 9. Additives in organic components. a) Chemical structure of 2,5-di(thiophen-2-yl)terephthalic acid (DTA). b) Histogram of PCE distribution with/
without DTA addictive. c) Electrostatic potential distribution of DTA. Reproduced with permission.[149] Copyright 2019, Royal Society of Chemistry.
d) Device architecture. e) J–V curves of the devices without and with optimized addition of TACl additive and f ) steady-state power output at the maximum
power point. Reproduced with permission.[152] Copyright 2018, Wiley-VCH. g) Fourier infrared spectroscopy (FTIR) of dimethyl itaconate (DI) monomer
and DI-PbI2 intermolecular exchange between perovskite films. h) Digital photograph of the pure DI monomers before and after the polymerization
process. Reproduced with permission.[154] Copyright 2020, Wiley-VCH.
preparation of Sn/Pb hybrid PSCs.[170] Yu et al.[171] prepared Sn/ DMSO-assisted thermal sintering, a dense and uniform
Pb based PSCs using a two-step spin coating method for the perovskite film was prepared, and the efficiency of the device
first time with a structure of ITO/PEDOT:PSS/CH3NH3Sn1x was enhanced. In addition to the two-step spin coating method,
PbxI3(x ¼ 0.1 and 0.25)/PC61BM/C60/BCP/Au. The inorganic the two-step vapor method was also applied to Sn/Pb mixed
component is a mixture of PbI2 and SnI2 in a specific ratio, perovskite. Jiang et al.[172] proposed a cation displacement reac-
and the organic component was an IPA solution of MAI. By tion method and prepared a dense and uniform MASnI3 film.
The N2H5SnI3 film was prepared by the solution spin coating advantages in tin-based perovskites. Yan et al.[175] developed a
method, and after that cation conversion was completed under two-step interlayer diffusion growth process in FA-based Sn/
CH3NH2 vapor to form MASnI3 film. Pb perovskites with both high PCE and stability. This strategy
Similar to the two-step method for preparing lead-based PSCs, enabled the PCE of narrow-bandgap devices to reach 20.4%.
techniques such as solvent engineering and additive engineering Other narrow bandgap PSCs can also be prepared by the
are conducive to improving the quality of thin films and device's two-step method. Due to the excellent air stability and low toxic-
performance. DMSO was used to assist the crystallization pro- ity, Bi-based perovskite PSCs are proved to be one of the best
cess of thin films.[173] Mai et al. inserted DMSO into the alternatives for lead-based perovskite with promising potential.
PbI2/SnI2 lattice by introducing a certain proportion of DMSO The two-step preparation of Bi-based perovskites can be achieved
solvent into the inorganic component solution, which helped by partially or completely replacing PbI2 with BiI3. Mobin
to form PbI2/(SnI2)·(DMSO)x intermediate compound and ulti- et al.[176] reported for the first time the use of a two-step spin
mately a good film morphology (Figure 10a–c). Chen et al.[170] coating method to prepare (CH3NH3)3Bi2I9 perovskite films.
used bifunctional additive MASCN to improve the Sn/Pb binary Studies showed that Bi-based devices exhibited excellent humid-
perovskite film prepared by the two-step spin coating method. In ity stability and could be stored at 40–50% RH for 60 days. The
the mixed inorganic solution of PbI2–SnI2, different molar frac- two-step immersion method has also been reported to prepare
tions of MASCN were added. On the one hand, SCN sup- Bi-based perovskite,[177] which has good stability in air. Mobin
pressed the rapid crystallization of the film through the et al.[178] used less toxic Sb instead of lead as an inorganic com-
coordination with metal iodide and improved the film morphol- ponent. MASbI3 perovskite light-absorbing layer film was
ogy and density (Figure 10d,e). On the other hand, MASCN acted formed by using a two-step spin coating method with the
as a strong ligand to coordinate with Sn2þ to avoid direct contact inorganic component of SbI3. The lead-free PSC showed a good
of Sn2þ with amine and oxygen, which inhibited the oxidation of performance with a VOC of 740 mV. These results show that the
Sn2þ and improved the stability of the solution. Similarly, Jen use of a two-step method for preparing narrow-bandgap
et al.[161] selected an additional Lewis base trimethylamine. perovskites, especially Sn/Pb mixed perovskites, has a good
Due to the formation of intermediate phases, the use of additives maneuverability and a bright future.
promoted the exchange rate of FAþ and formed a dense perov-
skite film. Diau et al.[174] compared the difference between the 6.2. Application of Two-Step Method in All-Inorganic Perovskite
one-step method and the two-step method in the preparation
of FASnI3 film and found that the two-step method was easier For organic–inorganic hybrid PSCs, the organic components are
to obtain a uniform and stable perovskite film, which has easily volatilized and decomposed under illumination and
Figure 10. Application of solvent engineering and additive engineering in the preparation of Sn/Pb mixed perovskite film by two-step method.
a) Preparation of perovskite film using DMSO as inorganic component solvent. Reproduced with permission.[173] Copyright 2016, Springer Nature.
b) Device architecture of Sn/Pb binary PSCs. c) J–V curves of the device with MASCN. d,e) SEM top view of PbI2/SnI2 film with and without
MASCN at a molar ratio of 0.25 relative to metal iodide. Reproduced with permission.[170] Copyright 2018, Wiley-VCH.
heating conditions, which restricts the commercial application of an airbrush gun. Le et al.[185] compared the application of one-
PSCs. To obtain higher device stability, the formation of step spraying method and two-step spraying method on
CsPbX(I, Br, Cl) all-inorganic perovskites by replacing organic MAPbI3 perovskite film and found that the two-step spraying
cations with inorganic Csþ has become an effective strategy. method obtained larger grain size and negligible pinholes,
Like the two-step method for preparing organic–inorganic hybrid and the PCE reached 9.6% based on 40 cm2 area. Qi et al.[186]
perovskite films, the two-step method for preparing all-inorganic reported a technique of combining ultrasonic spray coating
perovskite films includes spin coating a PbX2 layer and deposit- and chemical vapor deposition (CVD). The DMF and DMSO
ing a CsX layer (spin coating or immersion). During the anneal- mixed solution of PbI2 was first deposited by ultrasonic spraying,
ing process, CsX reacts with PbX2 to form the perovskite crystal. and then the organic components were deposited by CVD equip-
This method is widely used to prepare CsPbBr3 and CsPbIBr2 ment. Based on the FAPb(I0.85Br0.15)3 perovskite film, a PCE of
thin films. Two-step method in preparing all-inorganic perov- 14.7% for a 12 cm2 device was obtained. And the preparation pro-
skite films reduces the difficulty of the process and can obtain cess avoids waste of lead, which was more environmentally
more uniform thin films with good repeatability. friendly. Kim et al.[187] investigated the application of a two-step
Qi et al.[179] used a two-step immersion method to vacuum method, where the PbO precursor was first sputtered
prepare a series of Mn-doped all-inorganic perovskite onto the substrate, then MAI was deposited by CVD, and finally
films CsPb1xMnxI1þ2xBr22x to compensate for the issue of a uniform perovskite film was formed on a 100 cm2 textured sil-
CsPbIBr2 in the bandgap. The doping of manganese was icon substrate. Recently, Rousset et al.[188] reported a two-step
achieved by adding MnI2 to the PbI2 solution. It was found that blade coating method to prepare mixed cation perovskite thin
the bandgap of the perovskite gradually decreased with increas- films, in which PbI2 and CsI were first deposited, and finally
ing Mn2þ, which reduced the energy loss during hole transfer. In mixed cations were deposited on top. By carefully adjusting
addition, a suitable amount of manganese doping improved crys- the composition and deposition parameters of the ink, a
tallinity and surface morphology of the films. Fabrication of all- 5 10 cm2 perovskite film was obtained. Hung et al.[189]
inorganic perovskite films usually requires higher sintering tem- promoted the transformation of black perovskite (FAPbI3)1x
peratures, resulting in high fabrication costs. Yan et al.[180] (MAPbBr3)x by a modified two-step blade coating method
reported a pyridine vapor-assisted preparation of CsPbBr3 thin using a continuous porous structure. The PCE of the 5 5
films, and the spin-coated PbBr2 thin films were annealed under and 10 10 cm2 module was 16.5% and 13.3%, respectively.
pyridine atmosphere. The annealing temperature of the perov-
skite was reduced to 160 C, and the mechanism was that pyri-
6.4. Application of Two-Step Method in Tandem Solar Cell
dine reacted with lead bromide to form an intermediate phase,
resulting in a lower activation energy of CsPbBr3 during thermal
Tandem solar cells have received intensive attention because of
annealing. Qu et al.[181] prepared CsPbI2Br perovskite films by a
the potential to overcome the Shockley–Queisser limit for single-
two-step spin coating method along with methylamine acetate
junction cells. PSCs are suitable top solar cells for silicon-based
(MAAc) as an additive. By introducing MAAc in the CsX precur-
tandem solar cells due to their high efficiency, low fabrication
sor, the PbX2 in the films could be completely converted into
cost, and adjustable bandgap. The two-step method of preparing
δ-CsPbI2Br phase.
perovskite films generates interesting results to tandems.
To address the incomplete conversion caused by insufficient
Tiwari et al.[190] reported a hybrid thermal evaporation, spin
component diffusion in the two-step spin coating method, Wang
coating technique to fabricate perovskite layers for tandem cells,
et al.[182] developed a multistep deposition strategy by introduc-
allowing the introduction of PCBM layers in regular devices.
ing different antisolvents on the first deposited PbI2 films to
Based on this strategy,[191] they developed a translucent planar
form porous PbI2(DMSO) thin films. Subsequently, the CsBr
perovskite structure with a Voc of 1.116 V. PbI2 was deposited
solution was spin-coated on the loose film, which effectively pro-
onto the substrate by thermal evaporation, and the organic com-
moted the close contact of the reactants and the complete anneal-
ponents were subsequently spin-coated on the PbI2 film. In this
ing reaction. The similar isopropanol-assisted strategy[183] has
way, the growth of a high-quality absorber layer was promoted,
also been used in CsPbBr3 films by two-step spin coating to
resulting in high device performance without hysteresis. Ballif
improve the crystallinity of perovskite thin films.
et al.[192] coevaporated PbI2 and PbBr2, and then mixed organic
component was spin-coated by a dynamic dripping technique. A
6.3. Application of Two-Step Method in Large-Area PSC conformal perovskite absorbing layer was formed at the bottom
of the silicon heterojunction bottom cells. The PCE of the tan-
The one-step method has poor repeatability and fast crystalliza- dem cell was certified to 25.2%, without any modification to
tion, while the two-step method with higher repeatability and the textured c-Si bottom cell. The same technique could also
film quality, which is more suitable for large-scale modules be used in CsFA-based perovskite thin films.[193] By adjusting
toward commercial applications. Some two-step methods are the parameters in the preparation process, the optical bandgap
widely used, such as the two-step spray coating method, the could be changed from 1.5 to 1.8 eV.
two-step blade coating method, and the two-step vacuum In addition, the two-step solution spin coating method has also
method. been used in tandem devices. Zhou et al.[194] reported a
Chu et al.[184] combined spin coating and spray coating for the technique for fabricating perovskite tandem cells by a low-
first time. PbI2 (in DMSO solution) solution was first spin-coated temperature solution method. The perovskite layer was fabri-
on the substrate, and then MAI (in IPA solution) was sprayed by cated by a typical two-step spin coating method. Through precise
Figure 11. Issues and methods of two step method for PSCs. Reproduced with permission.[204] Copyright 2017, American Chemical Society.
control of the components, the PCE of the tandem device reached makes it difficult to accurately control the chemical composition
22% and the Voc reached 1.42 V. Furthermore, the introduced Cs of the film.[198] In order to solve this problem, the mechanism of
could effectively promote the crystal growth and reduced the den- the two-step reaction, such as how the molecules are exchanged,
sity of defect states. Using a similar approach, Janssen et al.[195] the factors that affect the film formation, and the impact on the
fabricated high-quality narrow-bandgap perovskite films with performance of the device, needs to be further studied, which
different bandgaps, with minor adjustments to the fabrication may require more complicated characterization methods.[199,200]
process. By combining these perovskite subcells, the PCE of Another typical problem in the two-step method is incomplete
all-perovskite triple-junction solar cells reached 16.8%, with conversion. As the inorganic components are deposited on the
low potential energy. This method was also applicable to substrate, it is inevitable to form crystals, which may hinder
narrow-bandgap Sn/Pb hybrid perovskite tandem cells.[196] the subsequent molecular exchange with organic cations, result-
ing in incomplete reaction conversion. To resolve the problem,
6.5. Challenges and Solutions many methods and strategies have been developed, such as the
use of solvents with different polarities,[106] changing the crystal-
Although the two-step method for preparing PSCs shows good lization process of perovskite,[99,201] and forming loose and
morphology and repeatability, some existing problems still need porous PbI2 structures,[135] which have been already discussed
to be addressed to further improve performance of the device above. Facing the challenge of large area and stability, many
(Figure 11). other methods, such as the two-step blade coating method[119,202]
In the traditional one-step preparation of the perovskite film, and the two-step vapor method,[60,203] have been derived.
organic and inorganic components are dissolved in the same sol-
vent (usually a mixed solution of DMF and DMSO) according to a
certain stoichiometric ratio, and then spin-coated on the sub- 7. Conclusion
strate by a single deposition. Therefore, the chemical composi-
tion of the film can be easily controlled precisely.[197] However, in In conclusion, we have systematically reviewed the two-step
the two-step method, the formation of the perovskite film method, including the two-step immersion method and the
depends on the molecular exchange, while the organic compo- two-step spin coating method, which has the advantages of high
nent in the second-step reaction is usually excessive, which repeatability and high film quality. In terms of reaction
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Yipeng Han is currently a master student under the supervision of Prof. Dongqin Bi at the School of
Materials Science and Engineering of Sun Yat-sen University. He received his bachelor's degree from the
College of Materials Science and Engineering at Huaqiao University (HQU) in 2019. His research
interests include high-performance and stable perovskite solar cells.
Haibing Xie worked as an associate researcher under the supervision of Prof. Dongqin Bi at the School
of Material Science and Engineering of Sun Yat-sen University in 2021. He received his master's degree
from the University of Science and Technology of China (USTC) and Ph.D. degree from the University of
Barcelona and Catalonia Institute for Energy Research (IREC). His current interests include understanding
the mechanism of defects in the efficiency and stability of perovskite solar cells, and exploring emerging
optoelectronic materials for photovoltaic and luminescence applications.
Eng Liang Lim worked as a postdoctoral researcher under the supervision of Prof. Dongqin Bi at the
School of Material Science and Engineering of Sun Yat-sen University from 2020 to 2021. He received
his Ph.D. degree in physics from the National University of Malaysia in 2015. In 2015–2018, he joined
the School of Applied Physics at National University of Malaysia as a postdoctoral researcher. His
current research interest includes working on the development of highly efficient and stable perovskite
solar cells.
Dongqin Bi worked as a professor at the School of Material Science and Engineering of Sun Yat-sen
University after she finished her postdoctoral research in École Polytechnique Fédérale de Lausanne
(EPFL). Her current research is developing highly efficient and stable perovskite solar cells,
understanding the mechanism of defects in the efficiency and stability of perovskite solar cells, and
exploring emerging optoelectronic materials for photovoltaic and luminescence applications.

Review of Two-Step Method For Lead Halide Perovskite Solar Cells

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Review of Two-Step Method For Lead Halide Perovskite Solar Cells

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Review of Two-Step Method for Lead Halide Perovskite

(MAI) is deposited atop the carrier trans-

Sol. RRL 2022, 6, 2101007 2101007 (1 of 22) © 2022 Wiley-VCH GmbH

Sol. RRL 2022, 6, 2101007 2101007 (2 of 22) © 2022 Wiley-VCH GmbH

and the other is a dissolution–recrystallization growth mecha-

Sol. RRL 2022, 6, 2101007 2101007 (3 of 22) © 2022 Wiley-VCH GmbH

Sol. RRL 2022, 6, 2101007 2101007 (4 of 22) © 2022 Wiley-VCH GmbH

Sol. RRL 2022, 6, 2101007 2101007 (5 of 22) © 2022 Wiley-VCH GmbH

Sol. RRL 2022, 6, 2101007 2101007 (6 of 22) © 2022 Wiley-VCH GmbH

Sol. RRL 2022, 6, 2101007 2101007 (7 of 22) © 2022 Wiley-VCH GmbH

Sol. RRL 2022, 6, 2101007 2101007 (8 of 22) © 2022 Wiley-VCH GmbH

Sol. RRL 2022, 6, 2101007 2101007 (9 of 22) © 2022 Wiley-VCH GmbH

Table 1. Summary of some additive strategies in the two-step process.

GITC Inorganic component MAPbI3 SCN 16.9 [138]

TBP Inorganic component MAPbI3 N donor 16.2 [37]

TMA Inorganic component MAPbI3 –OH, benzene ring 17.2 [147]

PEAI Organic component MAPbI3 PEAþ 17.7 [148]

DTA Organic component MAPbI3xClx –COOH 21.5 [149]

TBP Same as above Organic component MAPbI3 N donor 14.6 [150]

PVP Organic component MAPbI3 N donor 19.1 [153]

DI monomer Organic component FA1xMAxPbI3 C¼O 23.0 [154]

ML Organic component FA0.82MA0.13Cs0.05PbI2.87Br0.13 –SH 21.4 [155]

CDQ C Organic component MAPbI3 CDQ 19.2 [156]

BABr Organic component (FA,MA)Pb(I, Br)3 BAþ 23.2 [133]

MTP Organic component MAPbI3 Thiophene 21.5 [205]

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