Scalable Deposition Methods For Large-Area Production Ofperovskite Thin Films

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REVIEW
Scalable Deposition Methods for Large-Area Production of

Perovskite Thin Films
Richard Swartwout, Maximilian T. Hoerantner* , and Vladimir Bulovic
performances, as well as most other demonstra-

The recent steady improvements in the performance of the nascent hybrid tions of perovskite PV advancements, have been
perovskite photovoltaic (PV) devices have led to power conversion tested on small device areas below 1 cm2,
efficiencies that rival the best-performing established PV technologies. necessitating that the next big step into the
direction of market introduction has to be the
However, to scale these laboratory demonstrations to PV module-scale
development of perovskite PV structures over a
production will require development of scalable deposition methods for large area, comparable to today’s commercially
perovskite thin films. Every record result for perovskite PVs so far was available solar cells and modules.
achieved via spin coating, a technique that is popular in research laboratories Metal organic perovskite thin films have tra-
for thin-film coating over relatively small device areas, but not considered to ditionally been fabricated through solution-pro-
cessed spin coating. While this technique
be a method that could be used to scale up the manufacturing of perovskite
allows for fast iteration, optimization, and
PVs. Significantly larger thin-film areas are needed for future commercial PV research development, the process is inherently
products. Hence, some researchers have focused their efforts on perovskite non-uniform over large areas (more than
deposition techniques that can be considered as scalable for mass production 1 cm2) and therefore not a scalable method for
and have achieved notable results even on large areas. Here, we present an making solar cells. Note that we define a scal-
overview of the solution-based and vapor-based deposition processes; we able deposition process as one that can lead to
commercially viable manufacturing of a prod-
explain their influence on the molecular crystal growth behavior of
uct. Consequently, the main requirement for a
perovskite thin films and discuss the morphology as well as other material scalable production method is low cost, which
quality characteristics. By presenting a comprehensive comparison of the is comprised of capital expenditure (CAPEX) for
deposition techniques and the corresponding performance parameters for the required equipment and operational expen-
different device sizes, we intent to guide the growing research community diture (OPEX) including the energy usage,
involved material costs, quality control, and the
through the methods that might enable mass production of perovskite solar
cost of post-treating of production waste and
products. toxic side products. High throughput, high
yield, and reproducibility, as well as good mate-
rial utilization, significantly benefit low manufacturing cost. We note
1. Introduction that the cost of the currently used starting perovskite materials is negli-
gibly low due to their abundance.[3,4] Hence, the costs of perovskite PV
The urgent need for technologies leading to even more affordable manufacturing will be dominated by the CAPEX, which will be less
renewable energy sources has motivated the drive to commercialize costly per produced module with faster throughput.
photovoltaics based on inexpensive and abundant metal organic hybrid There are, however, unanswered questions that may disrupt this
perovskites. Thin films of this material have proven to be easy to pro- viewpoint. It is currently unknown what level of encapsulation is
cess into solar photovoltaic (PV) devices, some of which have power required for the long-term stable operation of these devices and there-
conversion efficiencies that now exceed g = 24%[1] and others that fore how much encapsulation costs will contribute to the final module
have stable operation over thousands of hours.[2] These record price. Furthermore, the lead content of current high-performing per-
ovskite compositions may require recycling schemes to reduce heavy
R. Swartwout, Dr. Maximilian T. Hoerantner, Dr. V. Bulovic metal pollution, which also has the potential to negatively affect final
Department of Electrical Engineering and Computer Science, Massachusetts module prices. Therefore, more work is required on achieving long
Institute of Technology, 77 Massachusetts Avenue , Cambridge MA 02139, operational lifetimes without expensive encapsulation as well as
USA
E-mail: maxhoer@mit.edu addressing the use of heavy metals.
Richard Swartwout and Maximilian T. Hoerantner contributed equally to In this review, we distinguish between solution-based and vapor-
the work. based processing techniques, which have both been used to deposit the
[Correction added on 22 August 2019, after first online publication: this perovskite active layer for PVs. Solution-based deposition processes have
article has been revised for style and clarity.]
been demonstrated in several film coating industries to allow for roll-
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/eem2.12043.
to-roll deposition speeds of hundreds of meters per minute.[5,6] Note
that the stringent requirements of solution quality control and solvent
DOI: 10.1002/eem2.12043 treatment, as well a likely reduction in the yield with high throughput,
Energy Environ. Mater. 2019, 2, 119–145 119 © 2019 Zhengzhou University

25750356, 2019, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/eem2.12043 by Library Dep. Of Science & Technology, Wiley Online Library on [27/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
can all counterbalance the benefits of the fast deposition speeds. Addi-
tionally, handling of toxic solvents can add substantial operational cost Richard Swartwout is a fourth
to the production process despite being difficult to quantify. Con- year PhD student in Electrical
versely, vapor-based deposition techniques are generally associated with Engineering and Computer Sci-
higher CAPEX and slower throughput, which leads to higher overall ence in the group of Professor
manufacturing costs. Significant advantages of vapor-based deposition Vladimir Bulovic at MIT. Previ-
include the possibility of high process control that leads to high preci- ously, he received his B.S. in
sion and uniformity needed in thin-film fabrication as well as not hav- Materials Engineering from
ing to recycle and treat solvents or ensure the often expensive quality Rensselaer Polytechnic Institute
control for ink formulations. The resulting high reproducibility and in 2015 and his M.S. in Electri-
high yield can lower the OPEX for quality control. Unfortunately, it is cal Engineering in 2018 from
currently not common practice to report about the device quality yields MIT. He is a previous MIT Tata
that result from laboratory performed deposition methods, which Center for Design and
would allow proper evaluation for production. It is known that the lab- Entrepreneurship Fellow and is currently associated with the
oratory-to-laboratory reproducibility is poor even among small-scale MIT GridEdge Program. His current work focuses on large
devices. It is unclear whether these deviances result from environmental area manufacturing techniques and solution chemistry for
or other factors. Logically, the environmental parameters may be easier perovskite solar cells.
controlled in a vacuum environment. Indeed, the current PV industry
relies heavily on vacuum deposition techniques, as coatings for silicon Maximilian T. Hoerantner is
solar cells such as amorphous silicon for heterojunction devices or anti- currently acting as the Vice
reflective coatings are typically deposited via chemical vapor deposition President of Engineering at the
(CVD) processes. Thin-film solar cells, such as copper indium gallium start-up company Swift Solar
selenide (CIGS), are mainly manufactured through thermal co-evapora- Inc., which aims to produce
tion, and CdTe solar panels are produced by a high-throughput vapor ultralight, efficient perovskite
transport deposition (VTD) process.[6–8] The organic light emitting photovoltaics. Previously he
diode (OLED) applications that have recently successfully entered the was a post-doctoral associate
consumer electronic market are also commonly produced by vapor in the Organic and Nanostruc-
deposition. tured Electronics research
Here, we present a summary of scalable thin-film deposition meth- group of Professor Vladimir
ods for the light-absorbing layer, as needed for PVs, which have been Bulovic at Massachusetts Insti-
demonstrated in the perovskite research field. We intend to inform the tute of Technology. There he focused on high-throughput
reader about the background of the methods that have been explored, manufacturing processes for perovskite solar cells through the
the underlying physical and chemical mechanisms, the effect the depo- MIT-TATA GridEdge Solar program. He holds a BS and MS in
sition technique has on the perovskite film quality, and the resulting Mechanical Engineering from ETH Zurich and a PhD in Con-
device performance. Finally, we make a comparison of the analyzed densed Matter Physics from the University of Oxford, where
techniques and the future directions needed to scale the perovskite he conducted his research on novel device architectures for
absorber layer deposition to large areas. perovskite solar cells under the supervision of Henry Snaith.
For his PhD he received a EPSRC DART fellowship as well as
an industrially funded studentship by Oxford Photovoltaics
2. Solution Processing Ltd. The projects he worked on have been published in high
impact journals, received scientific awards and produced com-
Solution processing is a physical (in the case of nanoparticle or material mercially viable patents.
dispersions) or a chemical process (in the case of perovskites) in which
a solution is utilized as a carrier for a given material. A solution in this
case is a solvent, often a liquid or a mixture of liquids that is capable of Hybrid perovskite inks are generally composed of polar aprotic coor-
dissolving solutes. Solutes can be molecular or polymer organics, ionic dinating solvents with a mixture of inorganic salts and organic salts.
components, nanoparticles, or a combination of all three. Solution pro- Table 1 summarizes the most commonly used solvents, additives, and
cessing techniques for deposition of thin films all rely on the creation anti-solvents used in perovskite research. Table 2 summarizes the
of a wet liquid film by some mechanical means. This wet film then health and safety and regulated and recommended industrial limits of
dries, usually at standard pressure and low temperatures (<120°C) to these same chemicals. The majority of thin-film research and material
create a solid film of the desired material and thickness. Dry or semi- chemistry studies utilize either dimethylformamide (DMF), dimethyl
dry films can then be thermally annealed or cured at higher tempera- sulfoxide (DMSO), or a mixture of the two solvents in the preparation
tures in ovens to remove residual solvent, recrystallize, or remove film of perovskite inks, usually at concentrations of 0.5–2 M. Perovskite inks
strain after deposition. A combination of environmental conditions, are commonly prepared using metal halide and organic halide precur-
solution chemistry, rheology, and drying microfluidics processes there- sors. Solubility of these components varies, with organic halides being
fore can all influence final material-phase quality and morphology. more soluble and simpler to dissolve, while metal halides can be more
Almost all high-efficiency reports for perovskite solar cells utilize solu- challenging. Solubility of the metal components seems to be driven by
tion processing techniques to deposit perovskite absorber layers, as well halide–metal complexation and solvent–metal coordination. Landford
as other layers in the solar cell. et al.[9] studied the effects of lead iodide solubility in the presence of

additional iodine anion and found that solubility increased due to the Vladimir Bulovic is a Professor
formation of lead–iodine complexes. This effect is widely seen by many of Electrical Engineering at the
researchers in the preparation of perovskite inks as dissolving organic Massachusetts Institute of
halides into the DMF-based inks before lead halides often decreases sol- Technology, holding the Fari-
vation time. In addition, Moore et al.[10] and Hamill et al.[11] found that borz Maseeh Chair in Emerging
the lead center and solvent complexation to the lead center are impor- Technology. He directs the
tant for proper phase formation and thin-film crystallization. Interest- Organic and Nanostructured
ingly, Hamill proposed that the Gutmann donor number, a Electronics Laboratory, co-leads
measurement of organic solvent–metal complexation and Lewis basic- the MIT-Eni Solar Frontiers
ity, was an important factor in crystallization kinetics and material for- Center, leads the Tata Grid-
mation. DMF and DMSO based perovskite inks are self-consistent with Edge program, and is the
Gutmann’s theory of inorganic dissolution[12]; where a coordinating Founding Director of MIT.nano.
solvent induces a polarization. This polarization then induces dissolu- He is an author of over 250 research articles (cited over
tion and therefore increases solubility. A simple schematic of the mech- 40,000 times) and an inventor of over 100 U.S. patents in
anism can be seen in Figure 1. areas of light emitting diodes, lasers, photovoltaics, photode-
An important consideration in Gutmann’s theory is that the coordi- tectors, chemical sensors, programmable memories, and
nating mechanism and the dissolution mechanism do not necessarily micro-electro machines, majority of which have been licensed
be driven by the same component; therefore, both coordinating sol- and utilized by both start-up and multinational companies.
vents and halide–metal complexes may both be important for thin film The three start-up companies Bulovic co-founded jointly
growth and crystallization. Moore et al.[10], Yan et al.[19], and later employ over 450 people, and include Ubiquitous Energy, Inc.,
extended by Hu et al.[20] and McMeekin et al.[21] showed that lead Kateeva, Inc., and QD Vision, Inc. (acquired in 2016). Bulovic
polyhalide and lead salt colloidal particles played a role in crystallization was the first Associate Dean for Innovation of the MIT School
growth and morphology for both simple methylammonium lead triio- of Engineering and the Inaugural co-Director of MIT’s Innova-
dide as well as mixed-cation varieties in DMF and DMSO systems. tion Initiative, which he co-led from 2013 to 2018. For his
McMeekin extended this further and showed that acid additives were passion for teaching Bulovic has been recognized with the
shown to help break these colloids and create a controllable nucleation MacVicar Fellowship, MIT’s highest teaching honor. He com-
and crystallization, thereby also improving morphology, mobility, and pleted his Electrical Engineering B.S.E. and Ph.D. degrees at
efficiency when structured in a device. Noel et al.[22] as well as Dou Princeton University.
et al.[23] then showed that because DMF is known to hydrolyze to for-
mic acid over time, there can be shift in solution properties and final
Table 1. Properties of solvents and additives common in perovskite ink preparation.
Solvent Type Molecular weight Dielectric Boiling point Donor number dD dP dH

[g/mol] constant [°C] [kcal/mol] [MPa1/2] [MPa1/2] [MPa1/2]
Dimethylformamide (DMF) Solvent 73[13] 36.1[13] 153[13] 26.6[12] 17.4[14] 16.7[14] 11.3[14]
[13] [13] [13] [12] [14] [14]
Dimethyl sulfoxide (DMSO) Solvent 78 45 189 29.8 18.4 16.4 10.2[14]
[13] [13] [13] [12] [14] [14]
N-Methyl-2-pyrrolidinone Solvent 99 32.2 202 27.3 18 12.3 7.2[14]
(NMP)
Gamma-butyrolactone (GBL) Solvent 86[15] 39.0[15] 204[15] 18[11] 19[14] 16.6[14] 7.4[14]
Ethyl acetate (EA) Solvent 88[13] 6.7[13] 77.1[13] 17.1[12] 15.8[14] 5.3[14] 7.2[14]
[15] [16] [15] [11] [14] [14]
Propylene carbonate (PC) Solvent 102 66.6 242 15.1 20 18 4.1[14]
[13] [13] [13] [12] [14] [14]
Dimethylacetamide (DMAC) Solvent 87 37.8 165 27.8 16.8 11.5 10.2[14]
Acetonitrile (ACN) Solvent 41[13] 37.5[13] 82[13] 14.1[12] 15.3[14] 18[14] 6.1[14]
†a
Methylamine (MA) Solvent/ 31.1 [15]
16.7 [15]
6.32 [15] a
29 – – –
additive
N,N0 -Dimethylpropyleneurea Additive 128[17] 36.12[17] 246[17] 33[18] – – –
(DMPU)
Pyridine (PY) Additive 79.1[13] 12.3[13] 115[13] 33.1[12] 19[14] 8.8[14] 5.9[14]
[15] [15] [15] [12] [14] [14]
Water (H2O) Additive 18 79.7 100 18 15.5 16 42.3[14]
Chlorobenzene (CB) Anti-solvent 113[13] 5.62[13] 131[13] 3.3[18] 19[14] 4.3[14] 2[14]
[13] [13] [13] [18] [14] [14]
Toluene Anti-solvent 92 2.4 110.6 0.1 18 1.4 2[14]
[15] [15] [15] [18] [14] [14]
Anisole Anti-solvent 108 4.30 155 9 17.8 4.1 6.7[14]
a
Methylamine is estimated from similar single amine compounds, as no experimental data could not be found.

Table 2. Health and safety parameters for perovskite solvents. Aggregated from OSHA, NIOSH, ACGIH, NIL, and NOAA databases.
Solvent Type Odor threshold LD50-oral LC50-air OSHA-PEL NIOSH-REL ACGIH TLV NIOSH-IDLH LEL Industrial
[ppm] [mg/kg] [ppm] [ppm] [ppm] [ppm] [ppm] [%] compatibility
Dimethylformamide Solvent 0.47–100 1100–6200 3092 10 10 5 500 2.2 No
(DMF)
Dimethyl sulfoxide Solvent N/A 14 500 – – – – – 2.6 Yes
(DMSO)a
N-Methyl-2-pyrrolidinone Solvent 4–10 3914 – 1 (Cal) – – – – Yes
(NMP)
Gamma-butyrolactone Solvent – 19 000 – – – – – 1.4 Yes
(GBL)b
Ethyl acetate (EA) Solvent 6.4–50 1600–16 000 12 000– 400 400 400 2000 2 Yes
16 000
Propylene carbonate (PC) Solvent – – – – – – – 4.7 Yes
Dimethylacetamide Solvent 21–47 4800 2475 10 10 10 300 1.8 No
(DMAC)
Acetonitrile (ACN) Solvent 40–1161 170–520 7551 40 20 20 500 3.0 No
b
Methylamine (MA) Solvent/ 0.0009–4.68 100–200 448 10 10 5 100 4.9 No
additive
N,N0 - Additive – 1300 – – – – – – Unknown
Dimethylpropyleneurea
(DMPU)
Pyridine (PY) Additive 0.021 1000 9000 5 5 1 1000 1.8 Unknown
Water (H2O) Additive – – – – – – – – Yes
Chlorobenzene (CB) Anti- 0.2–62 2250 8000 75 – 10 1000 1.3 No
solvent
Toluene Anti- 8 1150–7500 400 200 100 20 500 1.1 Yes
solvent
Anisole Anti- – 3700 – – – – – – Yes
solvent
a
DMSO is nontoxic but can increase transport of toxics through skin.
b
Methylamine and GBL are List 1 precursors in the United States.
Figure 1. Gutmann theory of donor solvation of inorganic salts in organic solvents, a higher number of donors would push the reaction forward and create
full ionization.
films over time due to changes in colloid formation. There may also be complexes to create a perovskite ink as well, but combined the ink with
dimethylamine contamination due to this degradation as well. a novel deposition process. Recently, Kerner et al.[27,28] provided addi-
Noel also showed in two other works[24,25] that precursor dissolu- tional insight on Pb–alkylamide complex formation using primary ami-
tion is possible in low boiling point polar aprotic solvents so long as a nes and its role in solubility as well as perovskite degradation.
nucleophilic agent is added into solution in small amounts. For both Other fast crystallization techniques include a variety of quenching
studies, Noel used acetonitrile as the base solvent due to its high polar- methods from air to solvent to vacuum.[29–31] The most popular is the
ity and methylamine, due to its highly basic nature (DN = 29). Methy- anti-solvent quenching method first demonstrated by Xiao et al.[29]
lamine is ideal, as it is a molecular component in traditional precursor which is used for the majority of mixed-cation perovskite formulations.
solutions, thereby prevents trap state formation, and is known to leave The technique introduces an anti-solvent onto a perovskite wet film
the crystal upon thermal annealing if in excess. For both studies, Noel during processing, thereby destroying solvent–solute complexes, reduc-
showed that nucleation and crystallization of thin films processed from ing overall perovskite solubility, and inducing crystallization. Other
these inks were quite fast but retained good morphology and high per- quenching methods rely on similar techniques, where air or hot air
formance. A similar study by Chen et al.[26] used methylamine quenching relies on convention forces to quickly pull coordinating

solvent from the film and begin crystallization. Vacuum quenching
relies on changes in pressure to remove coordinating solvent and initi-
ate crystallization.
Since many polar aprotic solvents are hazardous to human health,
there have been a few studies on safe solvent mixtures, mostly using
the Hansen model of solubility to predict solvent combinations.[32,33]
The Hansen model is traditionally known for being a good predictor of
solvent systems for organic compounds in organic solvents.[14,34,35]
These reports use GBL, ethanol, and acetic acid (which can react to
form ethyl acetate), propanol and acetic acid (which can react to propyl
acetate), and triethylene phosphate and PEG (polyethylene glycol). As
these solvents are all aprotic and polar, or weakly protic and polar, the
reports do not conflict with previous examples that study solvent–solute
interactions and metal polyhalide complexes. Therefore, both the Gut-
mann and Hansen models both may be useful for explaining both the
organic and inorganic solubility properties of perovskite precursor solu-
tions. However, there is more work to be done on understanding all
chemical interactions between all components of the perovskite inks
and the solvents, especially as the number of components increase over
time. We also note that most small-molecule amines are toxic to human
health, as well as lead and therefore a perovskite ink retains toxicity
concerns even if the purified solvents are safe. Figure 2. Descriptive illustration of the ultrasonic spray coating process.
Lastly, all solvent studies neglect government-regulated permissible
exposure limits (PEL); recommended exposure limits (REL), and other ink systems, it can likely be concluded that most ink systems can be
industrially limiting factors (immediate danger to life and health optimized to yield high-efficiency devices.
[IDLH], lower explosion limit [LEL]) in their selection and use of vari-
ous solvents. Therefore, these solvent systems may be safe but not
industrially relevant or scalable due to other factors. These limits aggre- 3. Spray Coating
gated from the United States Occupational Safety and Health Adminis-
tration (OSHA), National Institute for Occupational Safety and Health Spray coating is a process by which a subjected fluid is mechanically
(NIOSH), and Association Advancing Occupational and Environmental driven to exhibit capillary waves.[40] If these waves are of high enough
Health (ACGIH) are in Table 2. amplitude, the fluid is ejected from the fluid surface, creating atomized
Although it is possible to deposit perovskites from a single ink sys- droplets. Droplets of fluid can then fall naturally by gravity to a surface
tem, sequential or multi-step deposition processes are also feasible. The or be directed by a carrier gas in any direction. The high mass of the
general technique is to deposit each material component separately and droplets relative to the carrier gas allows momentum to cause the dro-
then thermally anneal the film, inter-diffusing all the components and plets to impact a surface while the carrier gas flows around. This pro-
forming a homogeneous crystalline perovskite phase. Metal halides tend cess then allows for fluid transfer and the generation of a thin film of
to be deposited from complexing solvents such as DMF and/or DMSO. liquid.[5,40]
The organic halides tend to be deposited from alcohols such as iso- Of all scalable techniques, spray coating is the most diverse.
propyl alcohol (IPA) and ethanol (EtOH). This has been shown to be Atomization can be generated from a variety of ways: with high-flow
effective for not only simple MAPI films, but also multi-cation and mul- gas, with ultrasonic stimulation, and with cavitation of the ink itself. All
ti-halide compositions as well as good film morphology with which of these different methods have their own purposes at scale. Spray sys-
high efficiencies have been achieved.[36–38] Kinetics seems to be differ- tems that use a high-flow feed gas, generally flowing over a liquid
ent, and nucleation has been attributed to the formation of crystalline feeding needle, are generally found in industrial paint equipment and
PbI2 followed by structural re-organization and crystalline ripening, all paint airbrushes. Liquid pressure fed cavitation style airbrushes can be
in the solid state.[39] found in water cooling fixtures, engines, painting equipment, and
Since all of these studies are self-consistent, it is important to aerosol cans, and before aluminized mirrors became popular, these style
remember that solvent–solute interactions as well as metal polyhalide heads were used to deposit precursor solution for silvering glass for
complexes play an important role in nucleation, crystal growth, and mirrors. Ultrasonic spray coaters are the newest technology to be devel-
final morphology as well as final material properties. It is therefore oped,[41,42] claiming more uniform droplet size, better airflow, and
important to consider the chemistry of a perovskite ink just as much as spray cone control. They have become the status quo for liquid thin-
the method by which it is deposited in order to obtain high-quality film coating technology for a variety of applications. As the majority of
films and devices. That being said no study compares different solvent spray coating work utilizes ultrasonic atomization, a pictorial descrip-
carriers side by side with a single deposition method and instead opti- tion of the ultrasonic spray coating process can be seen in Figure 2.
mizes a single ink system with a single method. Therefore, it is difficult Perovskite films deposited from spray coating currently encompass
to judge robustness of various ink systems or the robustness of the two techniques of deposition: They are either single-step or two-step.
deposition method. However, with the diversity and tunability most of Single-step films are deposited from solutions comprised of aprotic sol-
deposition methods and parameters along with the diversity of solvent vents such as DMF and GBL.[43–51] Two-step methods involve metal

(a) (b) (c)
(a) (b)
(d) (e) (f)
(c) (d)
(a) (b) (c)
(e) (f)
Figure 3. Morphology of spray-coated perovskite films as reported from different sources: (top left) ultrasonic spray coated[43]; (right) ultrasonic spray
coated[44]; (bottom left) is airbrush coated.[47]
salts deposited by either spray coating or spin coating in an aprotic sol- polyhalide complexes, or that solution optimization and temperature
vent. Organic salts are then deposited by spray coating or dipping in an control for a given method is critical for good morphology. Morphol-
alcohol solution, usually with isopropyl alcohol (IPA) as the sol- ogy differences across reports can be seen in Figure 3. A comparison of
vent.[52–57] all identified reports is summarized in Table 3.
Results differ depending on the method of perovskite deposition. Two-step methods encompass more perovskite chemistries, from
For single-step deposition, reported compositions encompass methy- simple methylammonium lead iodide to mixed cation to mixed halide
lammonium lead iodide and iodide–chloride varieties.[43–51] Solvents varieties.[52–57] Morphology seems similar to spin-coated two-step
are exclusively DMF, DMF, and DMSO or DMF and GBL with some approaches[36] and has high efficiencies with a maximum reported effi-
reports also using processing additives such as HI.[46] Maximum ciency of g = 16.2%.[58] Maximum device area reported is 1.1 cm2
reported PV efficiency for perovskite films made via this technique is with g = 13%.[56] However, it should be noted that not all reports use
g = 18% PCE for small-area samples, with g = 15.5% for the maxi- spray coating for each step, and some reports spin-coat lead iodide first
mum reported device area of 40 cm2.[47] In general, the deposited per- before spray depositing organic halides.[53,55,58] Such processing route
ovskite film morphology seems to be poor across all single-step reports, is inherently non-scalable, despite using a spray coating technique.
with crystallization being non-uniform, mostly dendritic, or without Other scalable two-step perovskite deposition methods are summa-
full coverage of the underlying transport layer. This results in PV cell rized in Table 3. Figure 4 (top left) shows the morphology of spray-
performance with lower open-circuit voltages (VOC), lower short-cir- coated PbI2 with dipped MAI, a process that could be translated to R2R
cuit currents (ISC), and lower fill factors (FF) than their spin-coated systems. Figure 4 (bottom left) shows morphology of a both PbI2 and
counterparts, potentially stemming from low shunt resistances. Surface MAI spray coated. Figure 4 (right) shows the morphology of spin-
morphology of these films can be seen in Figure 3 (top left)[43] and coated CsI and PbI2 with spray-coated FAI. Since morphology and per-
(right).[44] Both reports are single cation (methylammonium only) formance is similar across all reports, translation to new techniques and
mix halide perovskites spray coated onto heated substrates. Interest- chemistries seems promising.
ingly, the report that holds the highest efficiency and device area record
did not use an ultrasonic spray coater and shows good morphology.
Morphology is shown in Figure 3 (bottom).[47] Perovskite formulation 4. Inkjet Printing
was a single cation mixed halide, and spray coating was done on a
heated substrate. This may indicate that ultrasonic atomization is play- Inkjet printing is a technique where a microfluidic cavity is subject to a
ing a role in nucleation, potentially affecting the formation of the metal pressure change, thereby causing solution to “jet” out of a microfluidic

Table 3. Comparison on published spray-coating results.
Perovskite deposition type Steps Structure Area (cm2) g Ref.

[43]
Ultrasonic spray coating 1 ITO/TiO2/MAPbI3/Spiro/Au 0.065 11.0%*
[44]
Ultrasonic spray coating 1 ITO/PEDOT:PSS/MAPbI3/PCBM/CA/Al 0.025 11.1%
[45]
Ultrasonic spray coating 1 ITO/TiO2/MAPbI3/Spiro/Au 0.13–3.8 13.7%*
[52]
Vibration-assisted sequential spray coating 2 FTO/PEDOT:PSS/MAPbI3-Cl/PCBM/Al 0.3 5.08%
[46]
Ultrasonic spray coating 1 FTO/TiO2/MAPbI3/Spiro/Au 0.04–1.5 8.6%
Spin-coated PbI2–spray-coated MAI 2 FTO/PEDOT:PSS/MAPbI-Br/PCBM/BCP/Al 0.08 13.35% [53]
[47]
Airbrush spray-coated 1 FTO/TiO2/MAPbI-Cl/PTAA/Au 0.096–40 18.3%
Vacuum-deposited PbI2–Spray-coated MAI 1 ITO/PEDOT:PSS/MAPbI3/PCBM/Al 0.06 7.77% [59]
[48]
Ultrasonic spray coating 1 ITO/PEDOT:PSS/MAPbI3/PCBM/Ag 0.04 11.6%*
[49]
Airbrush spray coated 1 FTO/TiO2/MAPbI3/Spiro/Au 0.0671 13.53%
[50]
Ultrasonic spray coating 1 ITO/PEDOT:PSS/MAPbI3/PCBM/LiF/Al 0.025 12.80%
[51]
Airbrush spray coated 1 FTO/TiO2/MAPbI3/Spiro/Au 0.04 6.93%
[54]
Airbrush spray coated 2 FTO/TiO2/CsPbIBr2/Spiro 0.159 6.30%
Spin-coated PbI2–Airbrush spray-coated MAI 2 FTO/TiO2/MAPbI3/Spiro/Au 0.15 15.1%* [58]
[55]
Spin-coated PbI2 and CsI–Airbrush spray-coated FAI 2 FTO/TiO2/FACsPbI3/Spiro/Au 0.15 14.8%*
Ultrasonic spray-coated PbI2–dipped MAI 2 FTO/TiO2/MAPbI3/Spiro/Au 1 13.0% [56]
[57]
Ultrasonic sequential spray-coated 2 FTO/TiO2/MAPbI3/Spiro/Au 0.1–1 15.4*%
Samples with * are stabilized power conversion efficiency. All others are maximum.
nozzle. This pressure change can be caused by a variety of methods that the two steps in the two-step process were processed differently,
including thermal sources and structural sources acting on the with lead iodide being processed by inkjet printing and methylammo-
microfluidic nozzle. For inkjet printing of the perovskite films, the nium iodide introduced into the film through annealing with a dry
majority of inkjet-printed demonstrations utilize piezoelectric MEMs powder.[65] The as-annealed films were then washed and post-an-
print heads which provide controllable microfluidic jetting through a nealed, possibly to remove excess MAI. This technique may not be
silicon-etched nozzle. To improve reliability and speed of printing, such transferrable to other cation systems due to higher thermal stability of
inkjet printers utilize multiple jetting nozzles in a single moving print these systems. There is a report of an inkjet-printed triple-cation solu-
head to form planar thin films of controlled thickness. Furthermore, the tion with a single-step ink deposition and postvacuum annealing to
inkjet printing process enables for direct patterning of the printed lay- remove solvent and to drive the perovskite crystal nucleation and
ers, obviating the need for laser scribing of photoactive films, as would growth.[61] This report may also not be scalable due to the need for fast
be needed in a PV module fabrication and result in high material uti- atmospheric pressure changes, something that would be challenging to
lization. A pictorial description of the coating process can be seen in implement in a full roll-to-roll manufacturing setup. Therefore, a high
Figure 5. efficiency and stable perovskite PVs deposited using the inkjet printing
The reported results of inkjet printing (Table 4) are similar to method with either single-step or two-step deposition remains to be
spray-coating techniques. This may be due to similar mechanisms and seen. The commercial feasibility of perovskite inkjet printing is cur-
geometry of thin-film formation. In general, single-step deposition has rently being proven by Saule Technologies, one of the industrial entities
poor morphology, potentially due to the overlap of droplets which can that are trying to enter the market.[66]
change nucleation and chemical concentration or be due to dissolving
and recrystallizing films.[60–63] Similar to spray coating, two-step inkjet
processes exhibit better morphology, with more uniform and larger 5. Slot-Die Coating
grains.[64,65] A comparison of film morphology can be seen in Figure
6. The first report of inkjet printing by Li et al.[60] seen in Figure 6 Slot-die coating is a process in which ink is metered through a
(left) has similar morphology to early spray coating reports for MAPI; microfluidic metal die. In general, the die is machined or structured to
rough and dominated by drop drying. Recent reports, shown in Fig- have a thin channel to spread an ink over a moving surface (the
ure 6 (top right), shows a two-step method with good morphology, “web”).[5] A pictorial description of the process can be seen in Figure
and Figure 6 (bottom right) shows a single-step deposition. Both meth- 7. The surface is usually a plastic, flexible substrate, and the head is usu-
ods, both for MAPI, show similar morphology and resulting PV device ally positioned horizontally on a roller to negate the effects of gravity
efficiencies. These studies show that with proper control of the solvent, on the fluid in the head as well as to better control the wet film forma-
processing parameters, and post-annealing treatments, max efficiency tion in high-speed coating applications (Figure 7, right). In sheet-to-
for both methods is similar, with the max PCE of single-step deposition sheet systems, or desktop proofing systems, the head is commonly
being g = 17.04%[63] and the max efficiency for two-step being positioned vertically over a glass substrate or flattened surface (Figure 7,
g = 18.64%[65] on small-area devices. It should be noted, however, left). In both orientations, wet film formation is due entirely to the

(a) (b) (c)
(a) (e)
(d) (e) (f)

(b) (f)
(c) (g)
(a) (b) (c)
(d) (h)
(d) (e) (f)
Figure 4. Morphology of as reported two-step perovskite film deposition using spray coating: (top left) spray-coated PbI2 with dipped MAI[56]; (bottom left)
two-step spray-coated[57]; (right) spin-coated PbI2 + CsI with spray-coated FAI.[55]
chemistries due to the possibility of a fully enclosed environment until

deposition. In this way, composition changes due to solvent evapora-
tion loss can be mitigated.
Presently, there are very few reports of using slot-die coating as a
perovskite deposition technique. This may be due to the prevalence of
slot-die coating use in non-academic (and proprietary) PV development
partnerships, such as Soliance[68] and NREL.[69] The published reports
describe the sequential two-step slot-die[70–72] and single-step slot-die-
coated perovskite layers[71,73–79] and fully slot-die-coated heterostruc-
tures.[74] Morphology of perovskite films deposited by a two-step slot-
die process appears to be similar to the spin-coated films, as seen in
Figure 8 (left), thereby showing that both methods yield similar
Figure 5. Descriptive illustration of the inkjet printing process. results. Morphology and performance for single-step systems varies
between reports; however, both air and vacuum quenching[73,76–78]
are promising and with the deposited films having good morphology
geometry, web speeds, and fluid feeding rate. Coating properties when deposited from DMF-based systems. This departure from spin-
depend on the wet film thickness, chemistry, and stable microfluidic coating methods may be due to the higher wet film thicknesses at the
boundary conditions affected by the geometry.[67] Slot-die coating has start of the slot-die-coating process, therefore requiring lower concen-
traditionally been a popular process in the organic PV community and trations of solutes in the ink for similar thicknesses. Film morphology
in general is a popular process for non-viscous and low boiling point from a study that used an air quenching technique can be seen in

Table 4. Comparison of published inkjet printing results.

[60]
Inkjet printing 1 FTO/TiO2/MAPbI3/Spiro/Au 0.04 12.3%
Inkjet-printed PbI2–powder-reacted MAI 2 FTO/TiO2/MAPbI3/Spiro/Au 0.04–2 18.3%* [65]
[61]
Inkjet printing 1 FTO/TiO2/CsFAMAPbIBr/Spiro/Au 0.09 12.9%*
[62]
Inkjet printing 1 FTO/TiO2/MAPbI3/Spiro/Au 0.09 11.3%
[63]
Inkjet printing 1 FTO/TiO2/MAPbI3/Spiro/Au 0.04–2 16.6%*
Spin-coated PbI2–Inkjet-printed MAI/FAI 2 ITO/PEDOT:PSS/MAFAPbI3/PCBM/Ca/Al N/R 11.10% [64]
(a) (b) (c)
(A) (B)
(d) (e) (f)
(C) (D)
(a) (b) (c)
(E) (F)
(d) (e) (f)
Figure 6. Comparison of inkjet-printed morphology: (left) single-step MAPbI3[60]; (right top) two-step MAPbI3 where PbI3 is inkjet printed from DMF and
MAI is reacted with the film in solid state[65]; (right bottom) Triple-cation single-step printed perovskite with vacuum annealing.[61]
Figure 8 (top right).[77] A non-quenched sample can be seen in Fig- morphologies for the slot-die coated perovskite films can be seen in
ure 8 (bottom right).[79] Differences in morphology may be due to the Figure 8, with the comparison of reported devices listed in Table 5.
acetate method of film preparation being present in Figure 8 (bottom
right)[79] which has been demonstrated in the past to have better mor-
phology; however, the quenching method cannot be ruled out. There 6. Blade Coating
are currently no multi-cation reports using slot-die coating, and there-
fore, all reports use traditional methylammonium and multi-halide for- Blade coating (also known as “doctor-blading” and “knife-over-edge
mulations. Current efficiency maximum is g = 16.80% for a standard coating”) is a technique where a blade is moved across a surface, or
n-i-p structure on a small area, published by the Soliance consor- vice versa in the case of roll-to-roll coating.[5] The blade then spreads a
tium,[79] with related news reports indicating that the consortium has pre-dispensed ink and forms it into a liquid thin film. This film then
achieved even higher performance efficiencies.[68] Common dries creating a solid thin film. Of all the single directional coating

Figure 7. Descriptive illustration of the blade coating process: (left) sheet to sheet; (right) roll to roll.
(a) (b)
(a) (b) (c) (d)
(c) (d)
(a) (b)
(e) (f)
Figure 8. Left: Comparison of one-step and two-step deposition on slot-die coating and spin coating.[71] Right top: one-step air quenched slot-die showing
dendritic growth.[77] Right bottom: comparison of one-step slot-die and spin coating, with homogeneous growth.[79]
methods, blade coating is the lowest cost for small-scale systems and unlike the other methods discussed, blade coating in its simplest form
generally the most adjustable. Blades can come in all different shapes; does not have a fully enclosed ink reservoir, and therefore, ink chem-
they can be held above the surface or pressed into it, and they can be istry may change over time. A pictorial description of the process can
tilted with respect to the surface. When the blade is held above a sur- be seen in Figure 9.
face, usually with less viscous inks, deposition is similar to slot-die coat- Blade coating has been extensively explored as a single-step deposi-
ing where wet film thickness is defined by geometry. When held tion technique for perovskite films[84–105] and is currently the only scal-
against the surface (at least before coating), hydrodynamic and able solution technique to produce perovskite PVs with
mechanical forces determine the wet film thickness. In this way, blade g = 20%.[103,104] Blade-coated perovskite films are typically polycrys-
coating can create very thin films. talline, homogeneous, and pinhole free and show long-lived photolu-
Blade coating can be as simple as drawing a standard razor blade minescence. Such results are achieved through control of the nucleation
across a surface in the presence of an ink droplet, suggesting a cost-ef- temperature, crystallization temperature, and solution chemistries to
fective deposition that is tunable to a specific application. However, a improve grain growth.[85,90,91,93,101] Figure 10 shows the examples of
significant variability in the coating quality might also be observed as, blade-coated films from the published reports: Top left shows the

Table 5. Comparison of published slot-die results.

[70]
Sequential slot-die 2 ITO/ZnO/MaPbI3/P3HT/Ag 0.1 11.96%
[73]
Slot-die 1 FTO/TiO2/MaPbI-Cl/Spiro 0.0625 8.1%*
[74]
4-layer Slot-die 1 FTO/TiO2/MaPbI3/Spiro/Au 0.09 7.01%*
[71]
Slot-die and screen printing 1&2 ITO/PEDOT:PSS/MaPbI-Cl/PCBM/ZnO/Ag 0.2 7.9%
ITO/ZnO/PCBM/MaPbI-Cl/P3HT/PEDOT:PSS/Ag 4.6%
[75]
Slot-die 1 ITO/PEDOT:PSS/MaPbI-Cl/PCBM/Ag 0.12 2.9%
[76]
Slot-die with vacuum quench 1 FTO/ZnO/MaPbI3/Carbon 1–17.6 15.1%
[77]
Slot-die with air quench 1 ITO/ZnO/MaPbI3/Bifluo/MoO3/Ag 0.0672 12.73%
[78]
Slot-die with air quench 1 ITO/PEDOT:PSS/MaPbI-Cl/C60/PCBM/BCP/Ag 0.01–10 13.30%
[79]
Slot-die 1 ITO/TiO2/MaPbI-Cl/Spiro/Au 0.09–168 14.1%*
[72]
Slot-die and dipping 2 ITO/ZnO/MaPbI3/Bifluo/Ag 0.1 14.75%
[80]
Slot-die 1 ITO/SnO2/MaPbI-Cl/Spori/Au 0.06 15.2%*
[81]
Slot-die 2 ITO/ZnO/MAPbI3/P3HT/Au 1 3.6%
[82]
Slot-die 2 ITO/PEDOT:PSS/MAPbI3/PCBM/BCP/Ag 0.15 9.38%
[83]
Slot-die 1 ITO/SnO2/CsFAPbIBr/Spiro/Au 0.04 13.9%*
the coating direction.[87,96] Therefore, it is

possible to use blade coating not only for ink
deposition and polycrystalline growth, but
also for crystallization orientation and direc-
tional control.[96] It has also been shown that
a similar technique can be used to select for
and fabricate single-crystal films by forcing
the grain boundary phase front to be close to
the blade. Therefore, it may be possible for
blade coating to generate single-crystalline
solution-processed structures.[106] This sin-
gle-crystal film can be seen in Figure 11.
Lastly, blade coating is the only known
method that has reports with both major
types of perovskite ink formulations: high
Figure 9. Descriptive illustration of the slot-die coating process. (Left) sheet to sheet. (Right) roll to roll. boiling point traditional (using DMF,
DMSO)[103] and low boiling point Pb–alky-
lamide systems (using Acetonitrile and
morphology of blade-coated perovskites using a lead acetate route with MA).[107] Both systems have been optimized
[91]
controlled nucleation and growth temperatures ; top right shows and yield high-efficiency devices.
morphology changes through solution doping of MACl, used to blade
coat large grains[85]; and bottom shows growth differences at different
thicknesses using MACl as a growth modifier.[92] All of these reports 7. Vapor Deposition Techniques
show dense compact films with high efficiency but use either control
the mechanics of deposition or the chemistry of the solution. These The alternative to solution-based coating methods for perovskite films
reports indicate that blade coating may be the most tolerant deposition is the deposition through the vapor phase of the precursor materials,
method discussed. Overall, blade-coated perovskite ink solutions are often operated at pressures well below the atmosphere. Typical tech-
diverse, with solvent mixtures and processing additives being common, niques that fall under this category and which are commonly used for
as for example for the perovskite PVs with the highest reported stabi- large-scale manufacturing are physical vapor deposition (PVD), sputter
lized power conversion efficiency of g = 19%.[85,92] A comparison of coating, chemical vapor deposition (CVD), and atomic layer deposition
all recent reports is presented in Table 6. (ALD). Many vapor-based deposition processes require high vacuum
In addition, many groups have noticed that under the right condi- conditions for faster sublimation or to increase the mean free path of
tions, blade coating can result in crystallization growth fronts parallel to evaporated materials.

(a) (b) (a) (b)
(c) (d) (c) (d)
(a) (b) (c)
(d) (e) (f) (g)
(h) (i) (j) (k)
Figure 10. (Top left) Surface morphology of blade-coated lead acetate-based inks.[91] (Top right) Blade-coated triple-cation, double-halide films with MACl as
a grain growth modifier.[85] (Bottom) Crystallization and uniformity of blade-coated perovskite films at different thicknesses using MACl as a crystallization
growth modifier.[92]
Understanding and controlling the nucleation and growth mecha- pressure and substrate temperature as well as substrate material surface
nisms of perovskite films in vapor deposition techniques is equally as properties and morphology. The typical growth mode for perovskite
important as for solution-based processing. The crystal growth process films from the vapor phase is the Volmer–Weber growth in which small
is driven by the processing parameters such as the deposition chamber molecular clusters are directly nucleated on the substrate surface. This is

Table 6. Comparison of published blade coating results.

[84]
Blading 1 ITO/PEDOT:PSS/MAPI/PCBM/Bis-C60/Al 0.1 10.44%
[85]
Blading 1 ITO/PTAA/CsFAMAPbIBr/C60/BCP/Cu N/R 19.30%*
[86]
Blading 1 ITO/PEDOT:PSS/MAPI-Cl/PCBM/Bis-C60/Ag 0.0314 12.21%
[87]
Blading 1 ITO/PTAA/MAPbI3/C60/BCP/Al N/R 12.20%
[88]
Blading 1 ITO/PEDOT:PSS/MAPbI3/C60/BCP/Al N/R 15.10%
[89]
Blading 1 FTO/TiO2/MAPI/Spiro/Au 0.1 13.30%
[90]
Blading 1 FTO/TiO2/MAPI/Spiro/Au 0.09 17.53%
[91]
Blading 1 ITO/PEDOT:PSS/MAPbI3/C60/BCP/Al 0.1 16.40%
[92]
Blading 1 FTO/TiO2/MAPI-Cl/Spiro/Au 0.12 19.05%*
[93]
Blading 1 TiO2/MAPbI3/Spiro/Au 0.09 18.74%
[94]
Blading 1 ITO/TiO2/MAPbI-Cl/Spiro/Au 4 10.10%
[95]
Blading 1 ITO/PTAA/FAMAPbI/PCBM/C60/BCP/Cu N/R 18.00%*
[96]
Blading 1 ITO/PTAA/MAPbI3/C60/BCP/Al 0.08 19.00%*
[108]
Blading PbI2, dipping MAI 2 TiO2/MAPbI3/Spiro/Au/Pt N/R 11.90%
[97]
Blading 1 ITO/PEDOT:PSS/MAPbCl3/C60/BCP/Al 1 7.32%
[98]
Brushing 1 ITO/PEDOT:PSS/MAPbI3/PCBM/Li/Ag 0.0464 7.75%
[99]
Bar coating 1 ITO/PEDOT:PSS/MAPbI3/PCBM/Ag 0.021 13.03%*
[100]
Blading 1 ITO/M-PEDOT:PSS/MAPbI-Cl/PCBM/Ca/Al 0.035 10.15%*
[101]
Blading 1 ITO/PEDOT:PSS/MAPbI3/PCBM/Ag 0.09 11.29%
[102]
Blading 1 FTO/TiO2/FAMAPbIBr/PTAA/Ag 0.1 19.8%*
[103]
Blading 1 ITO/PTAA/MAPbI3/C60/BCP/Cu 0.075 20.3%
[104]
Blading 1 ITOMAPbI3:F4TCNQ/C60/BCP/Cu 0.08 20.2%*
[105]
Blading 1 FTO/TiO2/MAPbI3/Spiro/Au 0.11 17.5%
[109]
Blading 1 FTO/TiO2/MAPI/Spiro/Au 0.11–1.53 16.1%
(a) (b)
(c) (d)
Figure 11. Single-crystal perovskite thin films produced by a modified blade-coating technique.[106]

due to deposited molecules being stronger bound to each other than to source evaporation can lead to efficient planar heterojunction per-
the substrate. These then coalesce to form continuous films. By chang- ovskite solar cells with g = 15.4% over a small area and, at that
ing processing parameters, one can induce the Stranski–Krastanov time, unmatched thickness uniformity (shown in cross-sectional
growth mode,[110] which first forms continuous films that later form SEM of Figure 12c). It was an immensely important result, since it
into 3D islands. The specific dynamics depend heavily on the process meant that there would definitely be a feasible route to produce
employed to grow the perovskite thin films, as not all reported tech- perovskite-based photovoltaics on commercial scale as this had been
niques are solely utilizing vapor deposition but are often a combination proven by the CIGS and OLED industry. Despite the relatively small
of solution processing of the metal halide base layer and a subsequent number of research groups focusing on VTE, the improvements
deposition of the organic halide to then form the desired perovskite film that followed led to PVs with g = 20%, almost matching the best
with varying conditions. These so-called two-step methods require the results from spin-coated devices.[114,115] Bolink and co-workers
adjustment of processing parameters to alter the morphology of the base made early progress in scaling the size of the VTE-deposited PVs
layer and improve inter-diffusion, in contrast to the one-step co-evapo- by demonstrating the entirely vacuum-processed devices with
ration process, which requires precise control of the deposition rates to g = 12% over a small area and g = 8.27% for 1 cm2 device
improve the stoichiometry needed for good crystal growth. The most active area.[116] They also demonstrated the substrate independence
critical material parameter for vapor deposition processes is the tempera- of this method by making the first evaporated flexible perovskite
ture-dependent vapor pressure, which can be expressed with the solar cell with g = 7% over a small area.[117]
enthalpy of sublimation ΔHsub, assuming that the sublimation behavior Due to the precise control of film thickness and the uniform, smooth
follows the Clausius–Clapeyron relationship. These parameters were morphology, as well as the compatibility with other vapor-deposited
determined for the relevant lead halides via Knudsen effusion measure- materials, co-evaporation was used as the processing technique for
ments[111] and for methylammonium iodide (MAI) as well as methy- many optical and interface material comparison studies that require
lammonium chloride (MACl) via thermogravimetric analysis.[112] high reproducibility.[118–121] The use of solely organic materials as
charge transport layers[122] and purely inorganic hole transport materi-
als[123] has shown that with the right optimization of thicknesses and
7.1. Vacuum Thermal Evaporation (VTE) alignment of energy bands, perovskite PVs could reach above g = 10%
on a larger area of 1 cm2.
Vacuum thermal evaporation (VTE) refers to sublimating materials by Arguably, the biggest challenge lies in controlling the evaporation
heating them under high vacuum conditions (pressures < =106 Pa) rate of MAI because of its high vapor pressure. To counteract this prob-
and letting the resulting vapor condense onto a cooler substrate. The lem, Ono et al.[124] evaporated MAI from a separate Knudsen cell and
mean free path of the evaporated particles is elongated under high vac- PbCl2 from a large crucible. The well-controlled stoichiometry leads to
uum conditions, and the sublimated particles ballistically move away high current densities and small area g = 9.9% despite the thin absor-
from the heated source within a deposition cone to reach the substrate (il- ber films of only 135 nm thickness. In a similar report,[110] the metal
lustrated in Figure 12a). The longer the path length between the evapora- halide evaporation crucible was shielded away to prevent uncontrolled
tion source and the substrate, the more uniform the deposition becomes. heating of the MAI source, which yielded smoother films. Teuscher
This comes with the trade-off: There is reduced material yield from para- et al.[125] used in situ mass spectroscopy and studied the changing mor-
sitic condensation on the vacuum chamber walls. Large-scale manufactur- phology and device performance, which was optimized to g = 12%
ing processes make use of linear deposition sources with a substrate that on a small area. The in-depth studies of the, at the time, heavily debated
is moving orthogonally through the elongated evaporation cone. role of chlorine were also carried out through evaporation experiments,
Many materials can be thermally evaporated, ranging from organics to and while Gao et al.[126] reported that the PbCl2 first converts into PbI2
metals, typically limited only by the molecule size or the required subli- upon MAI exposure, Ng et al.[127] measured a high chloride content in
mation temperature. Usually, there is no need for post-annealing, which the resulting perovskite films.
makes VTE a low-temperature process that can be used for coating of flexi- One of the advantages of the vapor-deposited MAPI films is the lack
ble plastic substrates with typical glass transition temperatures well below of need for the annealing step in order to form a high-quality crys-
200°C. The evaporation rate is dependent on the source temperature and talline material.[128] The annealing step can limit the throughput of a
the pressure inside the deposition system and is limited by the thermal PV production line. SEM images of the VTE-deposited perovskite film
decomposition temperature of the source materials. The deposited film surface (Figure 12d) show that the perovskite crystallite grain size
thickness can be monitored via quartz crystal microbalance (QCM), which appears significantly smaller than previous solution-based reports,
needs to be positioned within the deposition cone and calibrated to reflect which also leads to smoother films. Interestingly, the performance of
the correct growth rate of the films at the substrate position. these devices does not seem to suffer significantly compared to solu-
Perovskites have been evaporated in three different ways: co-evapo- tion-coated films with much larger grain size despite numerous discus-
ration of the different material components, sequentially evaporating sions in the literature that larger grains should lead to less
the materials from single sources, and flash evaporation of a perovskite recombination losses.[129,130] Patel et al.[131] demonstrated that for dif-
bulk material. ferent interface layers, evaporated perovskite films will grow as either
amorphous or crystalline, affecting the current–voltage hysteresis of
completed PV devices.
7.2. Co-evaporation Momblona et al.[132] reported on all evaporated perovskite PVs with
g = 20% for a small active area. Surprisingly, the charge transport does
The first report about the successful vapor deposition of high-qual- not seem to suffer from the small grain size of these well-performing
ity methylammonium lead iodide (MAPI) perovskite films was pre- VTE-deposited perovskite films (depicted in the cross-sectional SEM
sented in mid-2013 by Liu et al.[113] They demonstrated that dual- image in Figure 12e) despite the fact that the charge carriers have to

(a) (b)
(c)
(d) (e)
(f) (g)
Figure 12. a) Illustration of a vacuum thermal evaporation process. b) Photograph of large-area vapor-deposited FAPI film.[139] c) Cross-sectional SEM image
of highly thickness uniform vapor-deposited MAPI film within solar cell device.[113] d) Top-view SEM image of co-evaporated MAPI film.[128] e) Cross-
sectional SEM image of vapor-deposited MAPI film showing small grain size and horizontal grain boundaries.[132] f) Comparison of J-V characteristics of fully
evaporated n-i-p and p-i-n devices [132]. g) Maximum power point tracked power output over time of wide-bandgap evaporated perovskite solar cell under
continuous illumination.[143]
cross-multiple grain boundaries when traveling in the vertical direction. perovskite tandem configuration in which the narrowband bottom
By inverting the device structure with the exact same organic charge absorber Cs0.15FA0.85Pb(I0.3Br0.7)3 fabricated via spin coating. Despite
transport layer materials from n-i-p to p-i-n, the authors were able to the fact that this bandgap combination is not ideally matched for opti-
analyze the individual charge carrier extraction of holes and electrons. mal performance,[133] a small-area device with g = 18.1% was
The result was a slightly better performing structure in which the light demonstrated.[134] Recently, the optimization of the electron transport-
passes the n-type charge extraction layer first, as can be seen in Fig- ing layer interface allowed for a co-evaporated MAPI device with an
ure 12f. The same device stack was also used as the top cell for an all- outstanding g = 20.8% for a small-area device.[135]

When more emphasis was put onto intrinsic stability and bandgap of continuous operation, the power output appeared to increase instead
tunability for tandem applications, the field turned to mixed perovskite of an expected decline (shown in Figure 12e).
compositions that included more cations and anions into the crystal lat-
tice.[136] Such compositional mixing is challenging due to the complex
stoichiometry control of the evaporated materials. Ma et al.[137] demon- 7.3. Sequential Evaporation
strated the dual-source evaporation of CsI and PbBr2 to form a thermally
stable film of the all-inorganic wide-bandgap perovskite CsPbIBr2. The sequential evaporation process consists of the independent vapor
Devices made with this technique showed g = 4.7%. Entirely vacuum- deposition of multiple film layers on top of each other and a subse-
deposited devices were later optimized with the same absorber material quent conversion of the materials through diffusion and recrystalliza-
to g = 11.8% for a small-area device.[138] Phase-stable FAPI perovskite tion. This allows for the optimization individual layers, and the
films can be thermally evaporated by replacing MAI with formami- stoichiometry control is approached differently. Typically, the metal
dinium iodide (FAI).[139] As shown in Figure 12b, large areas can be halide layer is deposited first and then converted by the organic halides.
coated uniformly and small-area device efficiencies of g = 14.2% were The first sequential deposition demonstration of MAPI perovskite
achieved with this narrower bandgap absorber. Longo et al.[140] were films by Hu et al.[144] came almost a year after the first co-evaporation
able to introduce a third vapor source with PbBr2 and achieved a wide- results and showed a significantly lower small-scale PCE of g = 5.4%
bandgap material combination of MAPb(Br0.2I0.8)3 with Eg = 1.72 eV for a device without hole-transporting layer. However, a subsequent
leading to small-area efficient devices with g = 15.9%. By adding a report by Chen et al.[145] demonstrated that this technique can also
fourth evaporation source and co-depositing controlled combinations of lead to well-performing perovskite solar cells of g = 15.4% for small-
MAI, CsBr, FAI, and PbI2, the stable high-performance material combi- area devices when optimized. They first evaporated a layer of PbCl2
nations Cs0.5FA0.5Pb(I0.83Br0.17)3 and Cs0.5FA0.4MA0.1Pb(I0.83Br0.17)3 then converted to MAPI via evaporation of MAI while heating the sub-
from solution-based results[141,142] could be reproduced.[143] The stabi- strate. Patel et al.[146] rigorously studied the nascent intermixed phase
lized small-area efficiency reached g = 16%, and the bandgap can be of MAI and PbI2 before a crystalline MAPI phase is formed. They
varied precisely. These devices show remarkable stability, as after 120 h found that the perovskite transformation is supported by exposure to
moist air to facilitate the MAI ion mobility
needed to form a complete crystal.
(a) (d)
In order to overcome the inter-diffusion
and conversion inefficiencies, alternating
sequential vapor deposition was pre-
sented[147,148] in which thin layers of the
materials are sequentially evaporated and this
cycle is repeated multiple times until the film
has reached the desired thickness. This
approach leads to suppressed crystal defects
and well-performing devices with g = 16%
for small-area devices and g = 13.8% PCE for
(b) (e) 1 cm2 devices, as well as a long storage stabil-
ity. However, this technique might prove dif-
ficult for commercial scaling as the
throughput and/or material utilization might
be slowed down by the alternating evapora-
tion. The highest efficiency for a sequentially
evaporated perovskite solar cell of g = 17.6%
was achieved for small-area devices by opti-
mizing the pressures of the system during the
evaporation steps, which also had a significant
(c) (f) effect on the morphology, as can be seen in
the SEM images of Figure 13.[149] A compar-
ison of all identified thermal evaporation
reports is summarized in Table 7.
7.4. Flash Evaporation and Close Space

Sublimation (CSS)
Typically, the individual precursor com-

pounds of perovskite materials are evapo-
Figure 13. Morphology analysis through top view (left column) and cross-sectional (right column) SEM rated separately as their sublimation and
imaging of sequentially evaporated MAPI films with MAI deposition pressures of 105 Torr, a, d), 104 decomposition temperatures differ substan-
Torr, b, e), and 103 Torr, c, f).[149] tially. A technique called flash evaporation

circumvents this challenge by heating up the final material alloy with a this technique show a PCE of g = 12.2% on small device areas. The
very high heat flux, which results in simultaneous evaporation of all of thickness of the resulting film is solely controlled by the thickness of
the perovskite components and the subsequent condensation of the the bulk precursor film. Xu et al.[152] followed this work and developed
materials on the substrate to form a thin film (illustrated in Figure an approach to increase the grain size with a flash evaporation process
14a). Longo et al.[151] demonstrated that flash evaporation can be by varying the pressure and the precursor composition ratios. The
applied in the deposition of perovskite materials. They used a 1.2-mm- resulting morphology change can be seen in Figure 14b. The most sali-
thick layer of MAPI, prepared by meniscus coating which is subse- ent aspect of flash evaporation is the high deposition speed that this
quently placed on a large tungsten sheet and later heated rapidly under process offers (the authors describe instantaneous deposition upon
high vacuum conditions (0.1 mbar) to instantaneously evaporate and heating), which makes it particularly attractive for large-scale manufac-
then deposit as thin-film onto a substrate. Solar cell devices made with turing of perovskite PVs.
Table 7. Comparison of published evaporation results.

[113]
Co-evaporation 1 FTO/TiO2/CH3NH3PbI3xClx/spiro/Ag 0.076 15.4%
[116]
Co-evaporation 1 ITO/PEDOT:PSS/polyTPD/MAPI/PCBM/Au 0.98 8.27%
0.09 12.04%
[117]
Co-evaporation 1 PET/AZO/Ag/AZO/PEDOT:PSS/polyTPD/MAPI/PCBM/Au 0.12 7.0%
[123]
Co-evaporation 1 FTO/NiO/MAPIxClx/PCBM/Ag 0.07 7.26%
[122]
Co-evaporation 1 ITO/PEDOT:PSS/polyTPD/MAPI/PCBM/3TPYMB/Au 0.065 14.8%
0.95 10.9%
[119]
Co-evaporation 1 ITO/F6-TCNNQ/spiro-MeO-TPD/MAPIxClx/C60/Ag 0.064 10.9%
[118]
Co-evaporation 1 ITO/PEDOT:PSS/polyTPD/MAPI/PCBM/Au 0.06 12.7%
[124]
Co-evaporation 1 FTO/c.l.-TiO2/MAPIxClx/spiro/Ag 0.05 9.9%
[120]
Co-evaporation 1 ITO/PEDOT:PSS/PCDTBT/MAPI/PC60BM/LiF/Ag 0.2 16.5%
[127]
Co-evaporation 1 ITO/CH3NH3PbI3xClx/C60/Bphen/Al 0.1 6.1%
[121]
Co-evaporation 1 ITO/MoO3/NPB/MAPI/C60/BCP/A 0.04 13.7%
[126]
Co-evaporation 1 FTO/PEDOT:PSS/CH3NH3PbI3xClx/PCBM/Ag 0.12 10.5%
[110]
Co-evaporation 1 FTO/TiO2/MAPI/spiro/Au 0.05 11.5%
[125]
Co-evaporation 1 FTO/c.l.-TiO2/MAPI/spiro/Au 0.16 12.0%
[128]
Co-evaporation 1 FTO/C60/MAPI/spiro/Au 0.08 14.6%*
[137]
Co-evaporation 1 FTO/c-TiO2/CsPbIBr2/Au 0.159 4.7%
[132]
Co-evaporation 1 ITO/C60:PhIm/C60/MAPI/TaTm/TaTm:F6-TCNNQ/Ag 0.1 19.7%*
0.85 15.0%*
[134]
Co-evaporation 1 ITO/TiO2/IPH/CsFAPbIBr/TaTm/TaTm:F6-TCNNQ/C60:PhIm/C60/MAPI/TaTm/TaTm:F6-TCNNQ/Au 0.06 18.1%*
[131]
Co-evaporation 1 FTO/c-TiO2/PCBM/MAPI/Spiro/Ag 0.0919 15.0%*
[138]
Co-evaporation 1 ITO/Ca/C60/CsPbIBr2/TAPC:MoO3/MoO3/Ag 0.051 11.8%*
[139]
Co-evaporation 1 FTO/C60/FAPI/Spiro/Ag 0.0919 14.2%*
[140]
Co-evaporation 1 ITO/C60:PhIm/C60/MAPIBr/TaTm/TaTm:F6-TCNNQ/Au 0.06 15.7%*
[143]
Co-evaporation 1 ITO/C60:PhIm/C60/CsFAMAPIBr/TaTm/TaTm:F6-TCNNQ/Au 0.06 16.0%*
[135]
Co-evaporation 1 ITO/TiO2/C60/MAPI/TaTm/TaTm:F6-TCNNQ 0.06 20.8%*
[150]
Co-evaporation 1 FTO/c-TiO2/CsPbBr3/Spiro/Au 0.09 6.95%
1 5.37%
[144]
Sequential evaporation 2 ITO/MAPI/C60/Ag 0.09 5.4%
[145]
Sequential evaporation 2 ITO/PEDOT:PSS/CH3NH3PbI3xClx/C60/Bphen/Ca/Ag 0.05 15.4%
[147]
Sequential evaporation 14 FTO/TiO2/MAPI/spiro/MoO3/Al 0.09 12.5%
[148]
Sequential evaporation 4 FTO/c.l.-TiO2/CH3NH3PbI3xClx/spiro/Au 0.07 16.03%
1 13.84%
[149]
Sequential evaporation 2 ITO/Ca/C60/MAPI/TAPC/TAPC:MoO3/MoO3/Ag 0.1 17.5%*
Samples with * are stabilized power conversion efficiency. All others are the maximum measurements.

(a) (b) (a) (b) (c)
(d) (e) (f)
(c) (d)
Figure 14. a) Illustration of flash evaporation process. b) SEM images of morphology changes from flash evaporation with different processing
parameters.[152] c) Illustration of close space sublimation process. d) Photograph of perovskite film deposited via close space sublimation.[153]
Table 8. Comparison of published close space sublimation and flash evaporation results.

[153]
Close space sublimation 2 FTO/c-TiO2/mp-TiO2/MAPI/Spiro/Ag 0.1 16.2%
[154]
Close space sublimation 2 FTO/PEDOT:PSS/MAPI/PCBM/Al 0.04 16.2%
0.25 12.9%
1.00 10.8%
[155]
Flash evaporation 1 ITO/PEDOT:PSS/MAPI/PCBM/Ag 0.09 10.9%
[151]
Flash evaporation 2 ITO/PEDOT:PSS/MAPI/polyTPD/PCBM/Ba/Ag 0.09 12.2%
[152]
Flash evaporation 1 FTO/PCBM/MAPI/spiro-OMeTAD/Au 0.09 10.01%
Pulsed laser flash evaporation 1 FTO/NiOx/MAPI/C60/BC/Ag N/A N/A [156]
Another processing technique which is named close space sublima- demonstrated by Liang et al.[38] and has later been utilized by Burschka
tion (CSS) involves the sublimation of material over a large area and et al.[36] to work well for MAPI perovskite-based solar cells. Later Chen
positioning the substrate very close to the deposition source to facilitate et al.[157] replaced the MAI conversion step that had been carried out in
a uniform deposition process (illustrated in Figure 14c). This method solution before by exposing the PbI2 film to MAI in the vapor phase (il-
allowed Li et al.[153] to convert previously spin-coated PbI2 films with lustrated in Figure 15a). Due to the high vapor pressure of MAI, a
MAI at a very fast rate (depending on pressure) to MAPI perovskite heated and covered petri dish was sufficient to achieve the conversion
films and produce devices with PCE of g = 16.2% for small area and in a contained environment and solar cells with g = 12% for small-
g = 13.8% for 1 cm2 devices. Figure 14d shows that deposition uni- area devices were shown. This vapor-assisted solution process (VASP)
formity over a 3 cm 9 3 cm area can be achieved with this technique. led to an understanding that the formation of hybrid perovskite thin
A comparison of all identified flash evaporation and CSS reports is sum- films allows for much flexibility. The layers can be individually depos-
marized in Table 8. ited either via solution or vapor and then converted similarly via solu-
tion or vapor exposure. Others followed the same technique to refine
the crystal growth and morphology to improve the defects and inter-
8. Vapor-assisted Solution Process and Ion faces (shown in Figure 15b,c)[158] for devices with small-area PCE of
Exchange g = 10.5% or to form higher bandgap MAPbBr perovskites[159] with
small-area PCE of g = 8.7%. Similarly, Liu et al.[160] used a petri dish
It was discovered early that sequential conversion of a metal halide film to employ a typical VASP method for which they spread the MAI pow-
can lead to high-quality micro-crystalline perovskite films upon expo- der around the substrate and compare the morphology for planar and
sure to an organic halide component. This has been originally mesoscopic electron extraction layers and their hysteretic device

operation behavior. Fakharuddin et al.[161] showed that placing the There are various ways that were reported to induce the ion
MAI powder around previously PbI2-coated substrates and facilitating exchange. The first demonstrations were carried out with a stream of
the vapor conversion process by a custom vacuum lid that seals off with formamidine gas to convert MAPI films to FAPI films (as illustrated in
the hotplate, large-area mini-modules could be achieved with a PCE of Figure 15g), and this process is reversible in the opposite direction
g = 8.1% over 8.8 cm2 illuminated area. Photographs of the films with exposure to methylamine gas.[163] Solar cell devices made with
before and after the conversion process are shown in Figure 15e,f. Li this cation exchange technique yielded g = 18.1% PCE on a device
et al.[162] managed to fabricate a perovskite with a lower-dimensional small area. The change of the bandgap through the cation exchange is
crystal structure by doping the PbI2 base layer with phenyl ethyl-am- visualized in the absorbable spectra of the films before and after the
monium iodide and then vapor convert the film with MAI, which lead process in Figure 15h,i. Other routes that focused on the exchange of
to a notable small-area record PCE of g = 19.1% due to an impressive cations were carried out by dipping the perovskite films into IPA solu-
fill factor above 0.8. tions with dissolved FAI or MAI and leave them for controlled periods
Remarkably, an additional conversion process has been demon- of time until the right ratio of FA to MA is reached.[164] g = 12.5%
strated that allows to exchange the cations and/or anions in the PCE was achieved on small areas with films of FAMAPI resulting from
perovskite crystal after the crystal has already been formed. This is this technique. Similarly, B-site cations could be exchanged by immer-
particularly interesting in fabrication of mixed compound per- sion of complete perovskite films into trioctylphosphine solutions of
ovskites which, apart from a tunable bandgap, have recently led to PbI2 or SnI2.[165] The FASnI2 films show pure crystal phases but devices
the highest performing PV devices and show the longest stability were not demonstrated.
upon thermal exposure and illumination. As such compounds have Not only cations but also the anions I, Br, and Cl were
proven to be challenging to make through vapor processing, prob- shown to be exchangeable by a closed space vapor transport
ably due to the lack of precise control of stoichiometry, this route of MAI and MABr with various exposure intensities.[166]
could represent a viable technique to produce high-quality material Small-scale devices with g = 14% PCE were the result of this
films in a scalable way. conversion, which allowed for equal or even better
Figure 15. a) Illustration of individual steps of vapor-assisted solution process. AFM images analyzing morphology of x b) and y c).[158] Photographs of mini-
module size PbI2 film e) and MAPI film after MAI vapor exposure f).[161] Illustration and chemical reaction g) and absorbable spectra with magnification h,i)
of MA to FA cation exchange for MAPI to FAPI film conversion.[163] J-V characteristics of MAPBr j)- and MAPI k)-based devices made via direct deposition
or via exchange reaction.[166]

performance than with directly deposited films, as shown in shown in Figure 16b,c) of the perovskite film than does converting a
Figure 15j,k. In the report by Zhou et al.,[167] ammonia lead mesoporous PbI2 film.
iodide was used as a base compound, which was subse- We note that many VASP experiments were carried out in a tube fur-
quently converted into FAPI by immersion into formamidine nace to maintain controllable conditions such as pressure and tempera-
acetate. The film with stable crystal phase yielded small-area ture, but the tube furnaces were not used for carrier gas flow
device PCE of g = 12.4%. A comparison of all identified experiments. Reports of devices that were fabricated by utilizing this
VASP and ion exchange reports is summarized in Table 9. technique approached PCEs of g = 12.2% for a small device area.[177]
Others used the tube furnace to create a humidity-controlled atmo-
sphere to carry out the vapor conversion processes and report devices
9. Chemical Vapor Deposition Processes with PCE of g = 12.7% for a small device area.[178] Liu et al.[179]
refrained from the use of a carrier gas but included NH4Cl for the crys-
Chemical vapor deposition typically defines a process that involves the tal growth assistance that chlorine addition can provide. Peng et al.[180]
initiation of chemical reactions through defined pressure, temperature, demonstrated that the MAPI conversion carried out in a tube furnace
or plasma conditions as well as the presence of specific chemicals that with very precise temperature control can lead to enhanced stability that
support the reaction. Often, these chemicals are directed to the substrate retained above 80% of the original PCE after 30 days of storage in a
by an inert transport gas. Tubular flow reactors allow for simple and glovebox. They propose that a slower controlled reaction rate can lead
customizable experimental setups to carry out the desired reactions. to a denser crystal structure which in turn leads to better long-term
Such reactors are usually composed of a long quartz tube surrounded by stability.
a heated furnace that often allow for multiple controlled temperature Leyden et al.[181] followed with the first tube furnace conversion of
zones (see illustration in Figure 16a). The tube commonly contains a PbI2 with chemical vapor transport of FAI to form a stable gamma-phase
transport gas inlet on one side and a vacuum pump outlet on the other FAPI film, and they demonstrated g = 14.2% PCE for a small device
end. area and approximately half the performance, g = 7.7%, on a 1 cm2
In 2014, Leyden et al.[175] demonstrated that simple sequential per- device. The deposition was later refined and scaled up to coat substrates
ovskite conversions of PbCl2 with MAI can be successfully performed with up to 12 cm2 in area (see photographs in Figure 16d,e) with
in such a tube furnace. They fabricated perovskite solar cells that yielded impressive PCE of g = 9%.[182] They compared the large-scale coating
g = 10.8% PCE on a small device area. Li et al.[176] followed with a of MAPI as well, which performed worse on the large area, with
similar technique at low pressure of 0.3 Torr that showed a remarkable g = 5.8% on 15.4 cm2. This decline supposedly stems from larger ion
small-area PCE of g = 16.8%. They discovered that, similar to sequen- migration effects that are due to more severe light soaking on large
tial thermal evaporation, the morphology of the PbI2 base film has a areas. The FAPI device was continuously kept at the maximum power
significant impact on the conversion to perovskite. They demonstrated point and did not show any decline after 3h of operation under illumi-
that more compact PbI2 films lead to smaller grain sizes (SEM images nation.
Table 9. Comparison of published vapor-assisted solution processing and ion exchange method results.

[160]
Vapor-assisted solution processing 2 FTO/c-TiO2/mp-TiO2/MAPI/Spiro/Ag 0.071 10.2%
[157]
Vapor-assisted solution processing 2 FTO/c-TiO2/MAPI/Spiro/Au 0.12 12.1%
[168]
Vapor-assisted solution processing 2 FTO/c.l.-TiO2/MAPI/P3HT/Au 0.104 13.7%
[158]
Vapor-assisted solution processing 2 FTO/c-TiO2/mp-TiO2/MAPI/Au 0.08 10.5%*
[159]
Vapor-assisted solution processing 2 FTO/c-TiO2/mp-TiO2/MAPBr/Spiro/Au 0.1 8.7%
[161]
Vapor-assisted solution processing 2 FTO/TiO2 nanorods/MAPI/Spiro/Au 8.8 8.1%
[169]
Vapor-assisted solution processing 3 FTO/TiO2/CsMAPI/Spiro/Au 0.1 14.1%
[170]
Vapor-assisted solution processing 3 FTO/c-TiO2/C60/MAPI/Spiro/Au 0.09 18.2%*
[171]
Vapor-assisted solution processing 2 FTO/c-TiO2/C60-MAPI/Spiro/Au 0.09 18.3%
[172]
Vapor-assisted solution processing 2 ITO/PEDOT/MAPI/C60/Ag 0.05 13.1%
[173]
Vapor-assisted solution processing 2 FTO/c-TiO2/MAPI/Spiro/Au 0.09 11.5%
[162]
Vapor-assisted solution processing 2 FTO/c-TiO2/mp-TiO2/MAPI/Spiro/Ag 0.2 19.1%
[164]
Ion exchange 2 FTO/c-TiO2/FAMAPI/Spiro/Au 0.0919 12.5%
[166]
Close space sublimation, ion exchange 3 FTO/c-TiO2/mp-TiO2/MAPI/Spiro/Ag 0.1 14.0%
[167]
CVD, ion exchange 2 FTO/c-TiO2/mp-TiO2/FAPI/Spiro/Ag 0.09 12.4%*
[163]
Ion exchange 3 FTO/c-TiO2/mp-TiO2/FAPI/Spiro/Ag 0.12 17.4%*
[174]
Ion exchange 2 FTO/c-TiO2/FAMAPI/Spiro/Ag 0.1 16.2%*

(a)
(b) (c)
(d) (e)
(f) (g)
Figure 16. a) Illustration of transport gas-assisted vapor deposition process in tube furnace. Top-view SEM images showing morphology of MAPI films made
by MAI vapor conversion of continuous PbI2 films b) and on mesoporous PbI2 films c).[176]. Photographs of large-area mini-modules of MAPI d) and FAPI e)
films made via CVD.[182] f) PCE dependence on active device area fabricated via hybrid CVD method and via anti-solvent spin coating. g) I-V characteristic of
modules made via hybrid CVD method with increasing number of interconnected cells g).[189]
Tavakoli et al.[183] were the first, and for a long time, the only team to et al.[184] The best outcome of the study was a g = 12.3% PCE
show that a PbI2 and MAI co-deposition can be achieved in a single tube small-scale MAPI device which showed no decline of performance
furnace by placing the material sources into different temperature even after 100 days of storage in humid air and 40% relative
regimes and transporting the vaporized material through the tube to co- humidity. Another report demonstrated the tuning of grain size,
deposit on the substrate located in the cooler area. A small-scale PCE of achieved by initially converting a PbI2 film with MACl to MAPI-Cl
g = 11.1% has been achieved with this technique. To this date, only one seed crystals and then subsequently exposing it to a vapor stream
other report has shown the deposition of PbI2 in a tube furnace.[183] of MAI.[185] As larger grain sizes tend to lead better performance,
Experiments with different metal halide base layers of PbI2, PCE of g = 13.8% for a small device area could be reached with
PbBr2, and SnI2 to then convert with MAI were reported by Wang enhanced photocurrent and open-circuit voltage.

In a report by Shen et al.[186], they attempted to increase the Table 10. Comparison of published inkjet printing results.
deposition area and presented a module with 8.4 cm2 area and
g = 6.2% by low-pressure chemical vapor converted MAPI. A Perovskite Steps Structure Area g Ref.
deposition type (cm2)
small-area PCE of g = 15.4% was achieved with this process that
[175]
involved the spreading of MAI powder around the PbI2 covered CVD 2 FTO/c.l.-TiO2/ 0.085 10.8%
substrates and using a high vacuum during the deposition. The CH3NH3PbI3xClx/spiro/Au
highest performing tube furnace coated results were reported to be CVD 2 FTO/c.l.-TiO2/CH3NH3PbI3/ 0.12 12.7% [178]
achieved by using hot air as the transport gas for MAI to convert spiro/Ag
heated PbI2-coated substrates.[187] With this technique, g = 18.9% CVD 2 FTO/c-TiO2/MAPI/Spiro/Au 0.062 16.8% [176]
PCE could be shown on small area of 0.11 cm2. The stabilized CVD 2 FTO/c.l.-TiO2/CH3NH3PbI3/ 0.12 12.2% [177]
maximum power point with g = 17.8% was kept over 60 min, spiro/Ag or Au
which proves good short-term stability. [180]
CVD 2 FTO/c-TiO2/mp-TiO2/MAPI/ 0.09 14.7%
Since most of the chemical vapor deposition results for perovskites
Spiro/Au
represent two-step processes, the thickness of the PbI2 base layer [181]
CVD 2 FTO/c.l.-TiO2/HC 0.17 14.2%
plays an important role for the MAI diffusion and crystal growth
(NH2)2PbI3xClx/spiro/Au
conversion and therefore the final thickness of the resulting per- 1 7.7%
ovskite layer. Wei et al.[188] found that the best devices required a CVD 1 FTO/c-TiO2/MAPI/Spiro/Au N/A 11.1% [183]
final MAPI thickness of roughly 300 nm to achieve g = 15.5% for CVD 2 FTO/c-TiO2/MAPI/Spiro/Ag 0.12 12.3% [184]
small device areas. Jiang et al.[189] demonstrated large, 12 cm2 area [185]
CVD 3 FTO/c-TiO2/MAPI/Spiro/Ag 0.12 13.76%
films of CsFAPbI3, produced with a technique that combined the
[153]
tube furnace conversion to FAPI by the typical pre-coated PbI2 and CVD 2 FTO/c-TiO2/mp-TiO2/MAPI/ 1 13.8%
subsequent FAI vapor conversion with an additional cation exchange Spiro/Ag
[186]
in cesium acetate solution. This led to high-performance devices CVD 2 FTO/c-TiO2/MAPI/Spiro/Au 0.24 13.99%
with g = 14.6% PCE, which operated significantly better than solu- *
tion-deposited control devices. The active area-dependent PCE decline 8.4 6.22%
is shown in Figure 16f. Smaller 0.1 cm2 devices had slightly higher CVD 2 FTO/c-TiO2/MAPI/Spiro/Ag 0.12 13.3%* [179]
fill factors (see plotted IV curves in Figure 16g) and showed [187]
CVD 2 FTO/c-TiO2/mp-TiO2/MAPI/ 0.11 17.8%*
g = 16.6% PCE. The fill factor decrease with increased active area is
Spiro/Au
a common problem that has most likely to do with increased series [182]
CVD 2 FTO/c-TiO2/MAPI/Spiro/Au 0.09 15.6%*
resistance from higher currents and longer distances that the charges
need to travel through the transparent conductors. Such PCEs, the 15.4 5.8%*
uniform deposition onto large area, and the possibility to grow films FTO/c-TiO2/FAPI/Spiro/Au 2 10.4%*
with more complex perovskite compositions are motivating enough 12 9%*
to deem this technique as a commercially feasible technique. A com- [189]
CVD 3 FTO/c-TiO2/CsFAPbI3/Spiro/ 12 14.6%*
parison of all identified chemical vapor deposition reports is summa-
Au
rized in Table 10. 0.1 16.6%*
[188]
CVD 2 FTO/c-TiO2/MAPI/Spiro/Au 0.09 15.5%
[190]
CVD 2 FTO/c-TiO2/MAPI/SWCNT/ 0.25 7.9%
10. Conclusion and Outlook Spiro/Au
[188]
CVD 2 FTO/c-TiO2/MAPI/Spiro/Au 0.09 15.5%
In the past few years, the perovskite solar cell field has seen a substan- [191]
CVD 2 FTO/c-TiO2/CsFAPbIBr/Spiro/ 0.09 18.2%
tial effort toward adopting processing techniques that are able to scale
Ag
perovskite thin-film deposition to large areas, paying attention to
improving the morphology of deposited perovskite films to exclude
Samples with * are stabilized power conversion efficiency. All others are a maximum
pinholes, which is easily investigated by SEM imaging, and also testing measurement.
the compositional variations via XRD analysis. Furthermore, the spec-
troscopic assessment via time-resolved photoluminescence studies or
transient absorption can help with investigation[192] but ultimately the publications developing the evaporation (VTE) technique were initially
fabrication of a full device and testing its resulting performance is a focus of a lot of publications, the interest in this technique has since
mandatory for scale-up research.[193] In addition, a focus on the inter- declined. A similar trend is true for spray coating and blade coating,
actions between deposition technique and resultant film properties which have all had more publication reports from 2015 to mid-2017,
would give insight into how these materials will behave in a real than in the past year. In the meanwhile, inkjet printing and slot-die
industrial setting. Lastly, incorporating fully scalable processing and fast coating have picked up attraction and might see more records very
processing such as photonic flash annealing[194] and near-IR[195] soon. It is very clearly visible that recently we have seen an increase in
annealing is a must in order to reduce manufacturing time and cost of publications about scalable deposition techniques, with the second half
these materials. of 2018 showing almost twice as many reports than any other semi-an-
Since the achieved record efficiencies are often a result of improved nual period from before. It is a good indicator that the perovskite
learning, we plotted the number of publications over time for the vari- research community is focusing on the challenges that are crucial for
ous deposition methods in Figure 17a. We notice that while the market entry of large-area perovskite PVs.

Figure 17. a) Counted published results of different scalable deposition techniques in half-year periods since 2013. Reported PCE on aperture area below b)
and above c) 1 cm2 of devices fabricated with different scalable perovskite deposition techniques plotted over time. d) Reported total power output of
devices made with different scalable perovskite deposition methods plotted over time.
The results appear to be constantly improving by understanding and To account for the very large-area devices that have been demon-
controlling the processing parameters influencing large-scale unifor- strated, we plotted the total power output of the published results by
mity, surface morphology, and the material quality that lead to higher multiplying the PCE with the aperture area and the corresponding irra-
performances and longer stability. To visualize this trend, we plotted diation power over that area in Figure 17d. We notice that the by far
the PCE progression over time for the different scalable deposition tech- largest devices with reasonable efficiencies have been demonstrated
niques on reported aperture sizes below and above 1 cm2 in Fig- with slot-die coating, making it a promising technique for commercial
ure 17b,c, respectively. From these plots, we can hardly conclude that applications in the near future. The next four techniques for fabrication
there are processing methods that seem to have a clearly faster progres- of devices that showed the most power output are blade coating, spray
sion than the other methods. The overall slopes of performance evolu- coating, chemical vapor deposition, and inkjet printing, which has only
tion are similar but when comparing Figure 17b,c, we notice that only lately seen a lot more effort.
few technologies have been used to demonstrate large-area solar cells. The perovskite solar cell field has seen an unmatched rise in
There were significantly more small-area device efficiencies reported the performance improvements, primarily demonstrated through
than on large areas, even though the processing methods would allow the spin-coating process, but also recently matched in the demon-
for large perovskite film deposition. Specifically, for thermal evapora- strations of perovskite PVs fabricated through a set of scalable
tion it is surprising that there have not been more attempts to show deposition techniques. These scalable fabrication methods will be
large-area devices. This might be due to the fact that for a long time, the key to enabling the eventual commercialization of perovskite
the perovskite field simply did not focus on the production of large-area solar cells.
devices. Another reason could be that the other layers in the devices
might have not been deposited with scalable techniques, or due to the
complexity that is involved with larger device fabrication, especially Acknowledgements
when interconnection of several cells to a module is required. High ser- This research was funded by the MIT-Tata GridEdge Solar research program. R. S.
ies resistance is typically a resulting effect that influences the device effi- and M. T. Hoerantner contributed equally to the work.
ciency substantially.

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Scalable Deposition Methods For Large-Area Production Ofperovskite Thin Films

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Scalable Deposition Methods For Large-Area Production Ofperovskite Thin Films

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25750356, 2019, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/eem2.12043 by Library Dep. Of Science & Technology, Wiley Online Library on [27/01/2023].

Scalable Deposition Methods for Large-Area Production of

performances, as well as most other demonstra-

Energy Environ. Mater. 2019, 2, 119–145 119 © 2019 Zhengzhou University

Energy Environ. Mater. 2019, 2, 119–145 120 © 2019 Zhengzhou University

Table 1. Properties of solvents and additives common in perovskite ink preparation.

Solvent Type Molecular weight Dielectric Boiling point Donor number dD dP dH

Energy Environ. Mater. 2019, 2, 119–145 121 © 2019 Zhengzhou University

Energy Environ. Mater. 2019, 2, 119–145 122 © 2019 Zhengzhou University

Energy Environ. Mater. 2019, 2, 119–145 123 © 2019 Zhengzhou University

(d) (e) (f)

(a) (b) (c)

Energy Environ. Mater. 2019, 2, 119–145 124 © 2019 Zhengzhou University

Perovskite deposition type Steps Structure Area (cm2) g Ref.

Energy Environ. Mater. 2019, 2, 119–145 125 © 2019 Zhengzhou University

(d) (e) (f)

(d) (e) (f)

chemistries due to the possibility of a fully enclosed environment until

Energy Environ. Mater. 2019, 2, 119–145 126 © 2019 Zhengzhou University

Perovskite deposition type Steps Structure Area (cm2) g Ref.

(a) (b) (c)

(d) (e) (f)

(a) (b) (c)

(d) (e) (f)

Energy Environ. Mater. 2019, 2, 119–145 127 © 2019 Zhengzhou University

Energy Environ. Mater. 2019, 2, 119–145 128 © 2019 Zhengzhou University

Perovskite deposition type Steps Structure Area (cm2) g Ref.

the coating direction.[87,96] Therefore, it is

Energy Environ. Mater. 2019, 2, 119–145 129 © 2019 Zhengzhou University

(c) (d) (c) (d)

(a) (b) (c)

(d) (e) (f) (g)

(h) (i) (j) (k)

Energy Environ. Mater. 2019, 2, 119–145 130 © 2019 Zhengzhou University

Perovskite deposition type Steps Structure Area (cm2) g Ref.

Energy Environ. Mater. 2019, 2, 119–145 131 © 2019 Zhengzhou University

Energy Environ. Mater. 2019, 2, 119–145 132 © 2019 Zhengzhou University

Energy Environ. Mater. 2019, 2, 119–145 133 © 2019 Zhengzhou University

7.4. Flash Evaporation and Close Space

Typically, the individual precursor com-

Energy Environ. Mater. 2019, 2, 119–145 134 © 2019 Zhengzhou University

Table 7. Comparison of published evaporation results.

Perovskite deposition type Steps Structure Area (cm2) g Ref.

Energy Environ. Mater. 2019, 2, 119–145 135 © 2019 Zhengzhou University

(d) (e) (f)

Perovskite deposition type Steps Structure Area (cm2) g Ref.

Energy Environ. Mater. 2019, 2, 119–145 136 © 2019 Zhengzhou University

Energy Environ. Mater. 2019, 2, 119–145 137 © 2019 Zhengzhou University

Perovskite deposition type Steps Structure Area (cm2) g Ref.

Energy Environ. Mater. 2019, 2, 119–145 138 © 2019 Zhengzhou University

Energy Environ. Mater. 2019, 2, 119–145 139 © 2019 Zhengzhou University

Energy Environ. Mater. 2019, 2, 119–145 140 © 2019 Zhengzhou University

Energy Environ. Mater. 2019, 2, 119–145 141 © 2019 Zhengzhou University

Energy Environ. Mater. 2019, 2, 119–145 142 © 2019 Zhengzhou University

Energy Environ. Mater. 2019, 2, 119–145 143 © 2019 Zhengzhou University

Energy Environ. Mater. 2019, 2, 119–145 144 © 2019 Zhengzhou University

Energy Environ. Mater. 2019, 2, 119–145 145 © 2019 Zhengzhou University

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