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Growth Mechanism of Thermally Evaporated γ-CsPbI3 Film

Chong Dong, Dayu Liu, Liang Wang, Kanghua Li, Xuke Yang, Zhe Li, Haisheng Song,
Ling Xu, Chao Chen,* and Jiang Tang*

photovoltaics is the core technology to

Cesium lead triiodide (CsPbI3) inorganic perovskite possesses excellent
thermal stability and matched bandgap for silicon-based tandem photo-
voltaics. The solution method with high-temperature annealing process
for CsPbI3 film preparation creates challenges to scalable application and
conformal growth on the textured silicon. Although additives can decrease
the annealing temperature, it will introduce undesired organic components
and increase material cost. Thermal co-evaporation for CsPbI3 has intrinsic
advantages to overcome these issues, but the vague growth mechanism
impedes the photovoltaic device development. In this study, γ-CsPbI3 films
are directly obtained through co-evaporation at 50 °C without any additives or
high-temperature post-annealing. Focusing on the molecular thermodynamic
calculations, it is proposed that the unique kinetic energy of evaporated
molecules and the in-situ substrate thermal energy synergistically provide the
energy prerequisite for γ-CsPbI3 formation. Furthermore, the γ phase stabiliza-
tion is clarified by the crystal grain size effect with regard to the Gibbs free
energy difference between the γ and δ phases, which is adjusted through
substrate temperature and evaporation rate. The obtained p-i-n device real-
izes an efficiency of 12.75%, which is the highest value for the thermally
evaporated γ-CsPbI3 photovoltaics at low temperature without additives. This
study deepens the understanding of thermal evaporation process, benefiting
to high-performance CsPbI3-textured silicon tandem photovoltaics.
1. Introduction
Photovoltaic industry has got a huge investment due to the
global environmental crisis. As the current mainstream of the
industry, silicon-based solar cell has realized a laboratory effi-
ciency of 26.7%, approaching the upper limit of 29.4%.[1] Tandem
C. Dong, D. Liu, L. Wang, K. Li, X. Yang, H. Song, L. Xu, C. Chen, J. Tang
Wuhan National Laboratory for Optoelectronics and School of Optical
and Electronic Information
Huazhong University of Science and Technology
Wuhan, Hubei 430074, China
E-mail: cchen@mail.hust.edu.cn; jtang@mail.hust.edu.cn
H. Song, C. Chen, J. Tang
Optics Valley Laboratory
Hubei 430074, China
Z. Li
School of Engineering and Materials Science
Queen Mary University of London
London E1 4NS, UK
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.202214414.
DOI: 10.1002/adfm.202214414
break the single-junction efficiency limit.
For two-terminal silicon-based tandem
solar cells, the most matched bandgap of
top cell is 1.60–1.75  eV, which enables a
high theoretical limit efficiency of 44%.[2]
Halide perovskite materials are promising
selections for the top cell of silicon-based
tandem photovoltaics because of their tun-
able bandgap and compatible low-temper-
ature deposition. Because the excellent
photoelectric properties of these materials,
the single-junction perovskite solar cell has
realized an impressive efficiency of 25.7%
in the past decade.[3] For the wide-bandgap
perovskite (Eg = 1.7 eV) solar cells, an effi-
ciency exceeding 20% has been attained.[4]
Further combining with monocrystalline
silicon solar cells, a preeminent efficiency
of 32.5% has been achieved for two-ter-
minal perovskite-silicon tandem devices.[3]
However, the complex compositions of
the widely-used organic-inorganic hybrid
perovskite material (at least five ele-
ments) give rise to the phase separation
and instability at operating conditions,
which creates great obstacles to the pro-
spective large-scale commercialization.[5,6]
Although incorporating at least 10  mol.% MA+ and up to
5 mol.% inorganic cations in FA+-based perovskite allow a stable
formulation and photovoltaic device under a temperature lower
than 100 °C, the higher-temperature stability cannot be guar-
anteed and the light-induced phase separation still exists.[7] An
effective strategy for the problem is to substitute organic cations
(e.g., MA+ and FA+) by inorganic ions (e.g., Cs+ and Rb+) and to
avoid mixed-halogen (e.g., I− and Br−) usage. Thus, cesium lead
halide perovskites (CsPbX3, XCl, Br, and I) have attracted wide
interest in photovoltaic field. Among them, CsPbI3 is a good
choice in silicon-based tandem solar cells owing to its suitable
bandgap (1.68–1.73 eV), as well as the enhanced inherent chem-
ical and thermal stability compared to the organic-inorganic
hybrid perovskite materials.[8,9] As shown in Figure 1, there are
four structural phases for CsPbI3 named α, β, γ, and δ. The first
three belong to the perovskite black phases, whose structures
are cubic, tetragonal, and orthogonal, respectively, and the last
one is the non-perovskite yellow phase. Because of the low Gold-
schmidt tolerance factor, the structural symmetry of CsPbI3 is
attenuated with the decreased temperature, causing the cushy
transfer from the black to the yellow phase upon exposure under
ambient conditions.[10,11] Therefore, it is significant to obtain the
stable black phase of CsPbI3 at room temperature.

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Figure 1.  Four phases of CsPbI3 and their transformation condition.
A lot of researches have given some feasible ways such as
decreasing crystal size, additive incorporation, and strain engi-
neering.[12–18] For example, DMAI or HI is often introduced to
decrease the formation energy of CsPbI3, thereby reducing the
annealing temperature for preparing β-CsPbI3 or γ-CsPbI3 film
(Figure 1). If there are no additives, the black phase is normally
stabilized through rapidly cooling the high-temperature-stable
α-CsPbI3, during which the residual lattice stress can assist the
stabilization of γ-CsPbI3 (Figure  1). At present, the solution-
processing CsPbI3 solar cells demonstrated a rapid develop-
ment with the highest efficiency of 21.14%.[19] Notably, the open-
circuit voltage can reach 1.33  V, indicating the great potential
of CsPbI3.[20] For high-performance silicon-perovskite tandem
solar cells, it is necessary for the perovskite layer to persist the
textured surfaces of the silicon layer for the sake of the better
light absorption and charge carrier collection.[21–24] It is also of
great industrial value to cut down the polishing input.[21] How-
ever, it is difficult for the solution method to conformably grow
CsPbI3 film on the textured silicon.
Thermal evaporation has the inherent advantage to achieve
the conformal perovskite growth including sequential vacuum
deposition and co-evaporation.[21,25,26] Moreover, this method
eschews the participation of toxic organic solvents and is com-
patible with the present product line of organic light-emitting
diodes. Yonezawa et al. successively deposited CsI and PbI2 to
fabricate the CsPbI3 solar cell with an efficiency of 5.71%.[27]
The sequence and the frequency of the layer-by-layer deposi-
tion can be adjusted for easier reaction and higher reproduc-
ibility.[28,29] Compared with sequential deposition, co-evapo-
rating PbI2 and CsI with a high-temperature (≈350 °C) post-
annealing process presents more complete reaction and better
crystallization quality, but high-temperature tolerance of sub-
strate and transport layer is required.[30] In addition, the extra
high-temperature post-annealing process has the potential risk
to degrade the performance of silicon bottom cells and also
complexes the tandem manufacturing process. Becket et  al.
used high throughput experimentation to obtain stable ther-
mally evaporated γ-CsPbI3 under a substrate temperature of
50 °C, and indicated the Schottky defect pairs contributing to
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the γ phase stabilization.[31] In contrast to the well-understood
solution method, the deposition process of CsPbI3 film and the
mechanism of phase stability is unclear, impeding the develop-
ment of thermally evaporated CsPbI3 solar cells.
In this work, γ-CsPbI3 film was directly obtained through low-
temperature co-evaporation without any additives or post-treat-
ments. To elucidate the formation mechanism of the γ phase,
thermodynamic calculation of the formation energy origin con-
sisting of the average kinetic energies of the thermally evapo-
rated high-speed substances and the substrate thermal energy
was conducted. Comparing these energy components with the
reaction potential barrier, the formation of γ-CsPbI3 at ≈50 °C
is proposed to originate from the synergy of the two parts of
energy rather than the normally-believed pure thermal energy
in the solution method. Also, we prove that it is easy for the
γ phase to be δ phase during co-evaporation under exothermic
energy during the γ-CsPbI3 formation reaction and the constant
substrate heating, the sum of which is higher than the γ-δ phase
transition potential barrier. Moreover, the γ-CsPbI3 stabiliza-
tion is further attributed to the size effect, which changes the
Gibbs free energies of the two phases and thereby makes the
γ-CsPbI3 be more thermodynamically stable. Guided by the size
effect, the grain size of the γ-CsPbI3 film was adjusted at dif-
ferent substrate temperatures and evaporation rates. Finally, the
optimized inverted γ-CsPbI3 photovoltaic device demonstrated a
champion efficiency of 12.75%, which is the highest efficiency
for low-temperature CsPbI3 solar cells without any additives.
The thorough comprehension about thermally evaporated
γ-CsPbI3 is worthwhile for the growth kinetics understanding in
other vapor deposition systems, and it also advances the fabrica-
tion of perovskite-textured silicon photovoltaics.
2. Results and Discussion
2.1. γ-CsPbI3 Film Fabrication Through Co-Evaporation
As shown in Figure  2a, CsI and PbI2 were co-evaporated to
prepare CsPbI3 films participating with a substrate tempera-
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Figure 2.  a) Schematic illustration of the thermal co-evaporation process for CsPbI3 film preparation. b) XRD pattern and c) PL spectrum of the as-
obtained thermally evaporated CsPbI3 film.
ture of 50 °C. The color of the evaporated film is black (the
insert of Figure  2b), suggesting the direct formation of black-
phase CsPbI3 without high-temperature post-annealing pro-
cess. According to the X-ray diffraction (XRD) measurement,
the phase-type of the as-obtained CsPbI3 film is assigned to
γ-CsPbI3 (Figure  2b). Also, the photoluminescence (PL) spec-
trum of the thermally evaporated γ-CsPbI3 film displays a peak
at 703 nm (Figure 2c). Therefore, it is reliable that γ-CsPbI3 film
is directly obtained through the low-temperature co-evaporation
process. In the sense that γ-CsPbI3 is not the thermodynami-
cally stable phase at room temperature, it is difficult to directly
acquire γ-CsPbI3 film without the quasi-quenching processes
(a common approach for solution-processed black-phase
CsPbI3). According to the practical experience of solution
methods, the low-temperature (<  100 °C) process can only
form the yellow δ-CsPbI3 (Figure  S1a and Note  S1, Sup-
porting Information). An effective way to obtain γ-CsPbI3 film
from precursor solutions is post-annealing above 300  °C and
then rapidly cooling, which can stabilize the γ phase with the
residual stress during the α-γ phase transition (Figure  S1b,
Supporting Information). Hence, it is significant to reveal the
growth kinetics of the thermally evaporated γ-CsPbI3 film.
2.2. Formation Mechanism of Thermally Evaporated
γ-CsPbI3 Film
For solution method, the thermodynamically stable δ-CsPbI3
film is formed first during the solvent evaporation process.
Then the phase transition from δ to α-CsPbI3 is motivated
by the thermal energy from the high-temperature annealing
process (>  300 °C). For the vacuum thermal evaporation, the
raw materials are heated to the specific temperatures, so that
they are pyrolyzed into vapor states. These high-speed gaseous
substances transport and aggregate on the substrate to form
perovskite film. (Figure  3a) Although the synthesis of CsPbI3
from CsI and PbI2 is exothermic, the premise for the reaction
germination is that the energy of the initial state is sufficient
to surmount the reaction potential barrier (ΔE1 or ∆E 1′ ) of the
intermediate state, which sets the criterion to judge whether
the formation reaction will happen (Figure  3b). The energy
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supply for the black γ-CsPbI3 formation can come from two
aspects, including the substrate thermal energy and the kinetic
energy of the evaporated particles (Figure  3a). Next, the two
energy compositions will be quantificationally calculated to
evaluate their impact on the formation of the thermally evapo-
rated γ-CsPbI3 film.
The in-situ substrate heating can constantly provide thermal
energy (ET), but it needs to be evaluated whether the energy is
enough to impel the γ-CsPbI3 formation reaction. In our experi-
ments, the substrate temperature was maintained at 50 °C cor-
responding to the ET of 0.028 eV per atom. It has been reported
that higher substrate temperature will cause in situ CsPbI3
phase transition or even decomposition.[32] The process is shown
in Figure  S4 (Supporting Information). To conduct the evalua-
tion, it is essential to eliminate the effect of the kinetic energy of
the evaporated particles. We thus carried out a reaction between
CsI and PbI2 powders under different temperatures to make a
simple analogy for the virtual static reaction process during the
thermal evaporation (Note S2, Supporting Information). Notably,
the powders were ground fine enough to resemble the actual sit-
uation (Figure S2a,b, Supporting Information). It is apparent in
Figure S2c (Supporting Information) that the color of the mixed
powder does not change until the temperature reaches 80 °C,
which indicates that only substrate thermal energy cannot satisfy
the formation energy requirement of γ-CsPbI3. Thus, apart from
the substrate heating, the kinetic energy from the high-speed
evaporated materials should be considered to play an important
part in the γ-CsPbI3 formation process.
Before calculating the kinetic energy, the evaporated prod-
ucts of the two evaporation material sources (CsI and PbI2
powders) should be confirmed. The mass spectrometry was
widely employed to analyze the vapor products.[33,34] As shown
in Figure S3a (Supporting Information), the positively charged
spectrum for PbI2 detected under 350 °C exhibits four intense
peaks corresponding to I+, Pb+, PbI+, and PbI2+, respectively,
which implies that the evaporation temperature of PbI2 powder
is lower than its melting point (402 °C). As for CsI, the evapo-
rated substances with positive charge are Cs+ and (CsI)Cs+
clusters (Figure  S3b, Supporting Information). Additionally,
it has been reported that the negative ion clusters are (CsI)nI−
where n is non-negative integer.[35]
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Figure 3.  a) Schematic illustration of molecule deposition process from the hot crucible to the continuous CsPbI3 film and correlated energies
(Ek: average kinetic energy from the high-speed evaporated materials, ET: in situ substrate thermal energy, ΔH: exothermic energy from the CsPbI3
formation reaction) during the process. b) Two paths (purple line: α phase is first formed and then transfer to be γ phase, blue line: direct formation
of γ phase) to obtain γ-CsPbI3 and the energy variation during every path. c) Phase transition process γ-CsPbI3 to δ-CsPbI3 induced by ET and ΔH.

During thermal evaporation process, the evaporated sub- Moreover, considering the ballistic transport of the evaporated
stances of PbI2 and CsI undergo an approximate random substances, the kinetic energy will not lose from the crucible to
thermal motion without collision process under the high the substrate due to extra collisions. Therefore, the initial kinetic
vacuum degree (≈10−4  Pa) due to the long mean free path energy obtained from the hot crucible is equal to the kinetic
(Note  S3, Supporting Information). Thus, the evaporated sub- energy that reaches the substrate. The average evaporation rates
stances can be regarded as ideal gases. On basis of this assump- of CsI and PbI2 are 0.95 and 0.75  Å  s−1, corresponding to 460
tion, the average kinetic energy (Ek) of the evaporated particles and 330 °C, respectively. These values are close to the previous
can be estimated by equipartition theorem (Equation 1), report that the evaporation temperature is 310–330 °C for PbI2,
and 445–455 °C for CsI.[36] To calculate the value of Ek by Equa-
i tion  1, the freedom degree of the evaporated particles during
Ek = kBT (1)
2 the co-evaporation processes should be analyzed. Monoatomic
molecules possess 3 degrees of freedom, which are 5 and 6
where kB is the Boltzmann constant, i is the freedom degree for rigid diatomic (one chemical bond) and triatomic (three
of the particle, and T is the molecule temperature of the evap- chemical bonds) molecules, respectively. According to the mass
orated gaseous substance. Here the molecule temperature spectrometry results (Figure  S3, Supporting Information), the
is equivalent to the evaporation temperature of PbI2 and CsI values of Ek for each evaporated substance are listed at Table S1
sources because the energy transferring from the crucible (Supporting Information). The average Ek of CsI and PbI2
to the source material abides by the energy conservation law. are 0.050 and 0.041  eV per atom, respectively (Note  S4, Sup-

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porting Information). This energy and the substrate thermal
energy  will synergistically transfer to the perovskite formation
energy. According to Figure  S2 (Supporting Information), the
black phase appears until the temperature arrives at 80 °C, cor-
responding to 0.030 eV per atom. The total energy of Ek and ET
exceeds the value to cross the reaction potential barrier (ΔE1 or
∆E 1′ ) and drives the formation of CsPbI3 (Figure 3b). There are
two possible paths to obtain the γ-CsPbI3 from the CsI and PbI2
vapor state. As shown in the purple line of Figure 3b, the first
one is α-CsPbI3 formed first because the total energy of Ek and
ET is also higher than the α-CsPbI3 formation energy (310 °C,
corresponding to 0.050  eV per atom) (Note  S4, Supporting
Information), and the α phase will quickly transfer to γ-CsPbI3
because rapid energy consumption instantly inducing the
crystal lattice partially shrinking, similar to the rapid cooling
process in solution method. Another path is directly acquiring
the γ-CsPbI3 (the blue line in Figure 3b) when considering the
energy loss due to the migration of the evaporated molecules
on the substrate.
Although the energy prerequisite is satisfied for forming
γ-CsPbI3, there is a special phenomenon in Figure  S2 (Sup-
porting Information) that the mixed powder fades from light
brown to yellow when the temperature continues increasing
to 100 °C. That is to say, the γ-CsPbI3 is prone to transfer into
δ-CsPbI3 after its formation because the δ phase is thermo-
dynamically preferred over γ phase at low temperatures. First
principle theoretical calculation shows that there is a tran-
sition barrier (ΔE2) ≈0.030  eV per atom during the γ-δ phase
transition process.[37] To judge the occurrence possibility of
the phase transition, the motivation energies need to be ana-
lyzed including the constant substrate thermal energy (ET) and
the exothermic energy (ΔH) of the CsPbI3 formation reaction
(Figure 3c). It has been reported that the enthalpy change of the
γ-CsPbI3 formation reaction is 0.008 eV per atom.[38] Combined
with ET, the minimum energy provided for the phase transition
is 0.036  eV per atom, higher than 0.030  eV per atom of ΔE2.
If considering the remaining kinetic energy harvesting from
the collision of CsI and PbI2 vapor particles, the phase transi-
tion occurrence possibility is further raised, referring that the
obtained γ-CsPbI3 cannot stably exist and finally δ-CsPbI3 must
be generated in the aspect of environmental energy, which is
contrary to our experimental phenomenon of direct thermally
evaporated γ-CsPbI3 film. In other words, there is other reason
for the stabilization of γ-CsPbI3.
2.3. Stabilization Mechanism of Thermally Evaporated
γ-CsPbI3 Film
On the basis of solution methods, rapidly cooling the α phase
or introducing additives can induce lattice stress to stabilize
the γ-CsPbI3 (Figure 1).[14,18] But if the cooling rate is small, the
stress will totally release so that the δ-CsPbI3 spontaneously
forms. For the thermal co-evaporation method, there is neither
quenching process nor additives, so it is necessary to clarify the
stabilization mechanism of the thermally evaporated γ-CsPbI3
film.
According to the energy dispersive X-ray spectroscopy
(EDS) data in Table  S4 (Supporting Information), the Cs/Pb
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ratio is 1.10 rather than the standard stoichiometric ratio of
1, suggesting that the fabricated γ-CsPbI3 film is with a Cs-
rich composition. Becker et  al. briefly mentioned that the
CsI-rich perovskite film possesses a small crystal grain size
(100–200 nm), which can lower the surface energy of γ-CsPbI3
to make it stabilizer than δ phase at low temperature.[31] As
shown in Figure  5b, the crystal grains of thermally evapo-
rated γ-CsPbI3 film exhibits a rod-like growth mode with an
average grain size of 96 nm. Relative to the solution-processed
CsPbI3 film (>  500  nm, Figure  S1d, Supporting Informa-
tion), the grain size is extremely small. It has been reported
that H2O incorporation varying the crystal size can change
surface free energy and endow γ-CsPbI3 with intrinsic ther-
modynamic stability.[39] Similarly, CsPbI3 quantum dot solar
cells always stabilize γ phase governed by the quantum con-
finement effect.[16] These studies inspire us that the size effect
inducing the internal energy variation of perovskite gives the
possibility for γ-CsPbI3 stabilization. Hence, the Gibbs free
energy difference (ΔG) consisting of the bulk free energy dif-
ference ( ∆Gb = Gbδ − Gbγ ) and the surface free energy difference
( ∆Gs = Gsδ − Gsγ ) is introduced to evaluate which phase is ther-
modynamically preferred for the CsPbI3 film. ΔG is rewritten
as Equation 2,
∆G = ∆Gb + ∆Gs (2)
The former ΔGb is 20.9  kJ  mol−1 as reported.[39] The latter
ΔGs is related to the surface area and the specific surface energy
(Esurf, eV  cm−2, more details are given in Note  S5, Supporting
Information). To simplify the calculation, we consider the grain
shape is cubic. It is notable that other shape is also accept-
able, but the calculation is more complex. The ΔGs is given by
Equation 3,
∆Gs = S δ E surf
δ
− S γ E surf
γ
(3)
where Sδ and Sγ are the total surface area of unit mole of δ- and
γ-CsPbI3. They can be expressed by Equation 4,
6r 2VN A 6VN A
S δ (γ ) = nS δg (γ ) = = (4)
Nr 3 Nr
where Sg is the surface area for a crystal grain, n is the number
of crystal grains within unit mole of CsPbI3, V is the unit cell
volume (Table  S3, Supporting Information), N is the number
of CsPbI3 molecule within a unit crystal cell, NA is the Avog-
adro constant and r is the average size of crystal grains. The
calculated relationship curve between ΔG and r is displayed in
Figure 4a. Larger G-value represents that the material structure
is more labile. As a result, the γ-CsPbI3 is more thermodynami-
cally stable than δ-CsPbI3 when ΔG value is positive. The crit-
ical crystal size (r*) is 101  nm, higher than the average crystal
grain size (96  nm) of the thermal-evaporated CsPbI3 film. It
reveals the reason for the stable existence of γ-CsPbI3 rather
than δ-CsPbI3 (Figure 4b).
In essence, crystal grain size is determined by the nuclear
density. Figure  S5 (Supporting Information) demonstrates
that the nuclear density is 9.80 × 1013 m−2 at r* of 101 nm. For
thermal evaporation, the evaporation rate of material sources
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Figure 4.  a) Gibbs free energy difference between γ and δ phases varies with the crystal grain size. b) Schematic illustration of the CsPbI3 phase related
to the average crystal grain size.
(F) and the substrate temperature (T) collectively adjust the
nuclear density (N) according to the following relationship:[40]
Fp
N∝ (5)
Dq
where D is the surface diffusion coefficient. Obviously, N is
proportional to the evaporation rate and reciprocal to the diffu-
sion coefficient. This parameter depends on the site-to-site hop-
ping rate of the absorbed particle (vs) and the effective hopping
distance between sites (l), which is D  = l2 vs. The relationship
between the versus and temperature satisfies Arrhenius for-
mula. Thus, the D is exponentially related to the temperature,
 E 
D = l 2v s ∝ exp  − s  (6)
 kBT 
where Es is the potential-energy barrier from site to site and kB
is the Boltzmann constant. As demonstrated in Equations  5
and  6, T and F can largely influence the nuclear density. We
respectively regulated their values to realize the controllability
of the size effect that induces γ-CsPbI3 stabilization. When
the evaporation rates of PbI2 and CsI are 0.75 and 0.95 Å s−1
respectively, to select proper temperature to fabricate the
γ-CsPbI3, Figure  S6a (Supporting Information) compares
the films formed under five temperatures and shows the
high substrate temperature cannot obtain the black phase.
Although the corresponding thermal energy is enough for the
black phase formation (Figure S6b, Supporting Information),
the crystal grain size increases at the same time, causing the
instability of the film. There is a report about the in situ ther-
mally evaporated CsPbI3 phase during increasing the sub-
strate temperature.[32] It indicates that when the temperature
is higher than 310 °C, α phase can in situ form. However, it
lacks the quick cooling process when taken out of the evapo-
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ration chamber, thus the α-δ phase transition happens. Based
on this, we chose substrate temperatures lower than 80 °C
to guarantee the γ-CsPbI3 formation. Figure  5a–c shows the
morphologies of the evaporated-CsPbI3 films deposited at dif-
ferent in situ substrate temperatures. It is obvious that the
crystal grain size increases as the temperature increases.
The statistic histogram distribution of crystal grain sizes in
Figure 5d–f gives quantitative values. The average size ranges
from 59 to 136  nm when the temperature changes from
34 to 70 °C. Bigger than r*, the enlarged crystal at 70 °C leads
to the phase non-stability. This is verified by the partially
faded CsPbI3 film under 70 °C (insert of Figure  5c) while
the colors of the CsPbI3 films made at lower temperatures
(34 and 50 °C) are black. In addition, the peak marked by red
in Figure S7a (Supporting Information) shows the appearance
of δ phase at 70 °C, further causing the poor light absorp-
tion of the film in Figure  S7b,c (Supporting Information).
Although the film fabricated at 34 °C does not show yellow
phase, there is a great deal of pinholes in the 34 °C-prepared
CsPbI3 film, leading to more intrinsic defects and non-radi-
ative recombination when they are assembled into solar cell
devices. Therefore, the most suitable in-situ substrate tem-
perature during the fabrication process is 50 °C because the
nuclear density and the film compactness should attain a com-
promise. Figure S8 (Supporting Information) provides a com-
parison of the evaporated-CsPbI3 films prepared at different
deposition rates under a substrate temperature of 50 °C,
and higher rates contribute to smaller crystal size and larger
nuclear density, identical with the above results, further con-
firming the correctness of Equations 5 and 6. Also, Figure S9
(Supporting Information) indicates the lower or higher
evaporation rates cannot benefit the film crystallization and
absorption ability, thus the best evaporation rate for PbI2 and
CsI are 0.75 and 0.95 Å s−1, respectively.
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Figure 5.  The SEM images of the thermally evaporated γ-CsPbI3 films prepared at the substrate temperature of a) 34 °C, b) 50 °C, and c) 70 °C, respec-
tively. d–f) Statistic histogram distribution of crystal grain sizes at the corresponding substrate temperature.
2.4. Performance of the Thermally Evaporated
γ-CsPbI3 Solar Cell
To evaluate the photovoltaic property of the thermal-evaporated
γ-CsPbI3 film, we fabricated the solar cell based on the film
without any post-treatment. The energy diagram of the corre-
sponding planar heterojunction device is shown in Figure  6a
with the structure of ITO/PTAA/CsPbI3/LiF/C60/Ag (ITO:
indium tin oxides, PTAA: Poly[bis(4-phenyl)(2,4,6-triMethyl-
phenyl)aMine]). Besides, Figure  6 gives the current density-
voltage (J--V) curve for the photovoltaic device. The values of
open-circuit voltage (Voc), short-circuit current density (Jsc),
fill factor (FF), and power conservation efficiency (PCE) are
0.971  V, 18.15  mA  cm−2, 0.723 and 12.75%, respectively. This
demonstrated performance is much higher than the sequen-
tial deposited CsPbI3 solar cell, and can be parallel with the
co-evaporated CsPbI3 devices in other reports (Table  S5, Sup-
porting Information). A small hysteresis shown in Figure S10a
(Supporting Information) may be caused by the imperfect inter-
face. This is also proved by the EQE curve (Figure  S10b, Sup-
porting Information) where the light absorption is insufficient,
suggesting defects at the buried interface. Therefore, the inter-
face improvement for the thermally evaporated γ-CsPbI3 solar
cell needs further study. Figure S10c (Supporting Information)
Figure 6.  a) The energy band diagram and b) The J–V curve for the photovoltaic device based on the thermal-evaporated γ-CsPbI3 film.
Adv. Funct. Mater. 2023, 33, 2214414
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gives the steady-state photocurrent (16.89 mA cm−2) and output
efficiency (12.47%). To evaluate the device repeatability, a sta-
tistical distribution of efficiencies for sixteen devices is shown
in Figure  S10d (Supporting Information) and the average effi-
ciency is 10.9%. Also, the absorption spectra varying with time
in Figure S11 (Supporting Information) shows the film stability
in nitrogen and ambient atmosphere. The film can be pre-
served for 70 min in air with the temperature of ≈18 °C and the
relative humidity of 25%. Also, the light absorption of the film
is not attenuated after being placed in nitrogen for 168 h. Even
for 1560 h, the film can still keep γ phase due to no shift for the
absorption edge. In the future research, the film crystallization
adjustment, interface defect passivation, and environmental
stability improvement of thermal-evaporated γ-CsPbI3 solar
cells should be paid more attention to for better-performance
single-junction and tandem photovoltaics.
3. Conclusions
In summary, we prepared γ-CsPbI3 films through co-evap-
oration and presented the growth kinetics process for the γ
phase. The kinetic energies of material sources and the sub-
strate thermal energy synergistically provide the formation
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potential energy of γ-CsPbI3, but the γ-δ phase transition can
happen under the influence of the reaction exothermic energy
and substrate thermal energy. It is proved that the size effect is
the actual stabilizing factor for the γ phase due to the reduced
Gibbs free energy. The obtained thermally evaporated γ-CsPbI3
achieved a p-i-n device efficiency of 12.75% at 50 °C, making
an efficiency breakthrough on the thermally evaporated CsPbI3
photovoltaics without the assistance from additives or high
temperature (Table S5, Supporting Information). Based on the
film growth mechanism, it is possible to fabricate thermally
evaporated β-CsPbI3 film with some additives. Also, this explo-
ration can deepen the understanding of the current co-evapora-
tion and pave the way for perovskite-based tandem solar cells.
4. Experimental Section
Chemicals: All materials were used without further purification.
Lead iodide (PbI2, 99.999%) and cesium iodide (CsI. 99.999%)
were purchased from Liaoning Youxuan Tech. Poly[bis(4-phenyl)
(2,4,6-triMethylphenyl)aMine] (PTAA) and fullerene (C60, 99.5%) were
purchased from P-OLED(Shanghai) Technology CO., LTD.
γ-CsPbI3 Film Preparation: The perovskite film was prepared by
co-evaporation PbI2 and CsI (QHV-R96, ShenYang QiHui Vacuum
Technology Co., LTD). Keep the two material sources directly opposite.
After the vacuum pressure was lower than 3  ×  10−4  Pa, switch on the
substrate temperature to 50 °C. By adjusting the current to change the
heating power, the PbI2 and CsI were vaporized. When the evaporation
rates were 0.13 and 0.1  nmol (cm2  s)−1 respectively, open the substrate
shutter to begin deposition. Until the thickness summation of the two
sources was 400  nm, the deposition ceased and the γ-CsPbI3 film was
obtained.
Device Fabrication: The ITO substrates were washed by detergent,
ultrapure water, acetone, and ethanol in turn. After treatment by O2
plasma for 10  min, the substrates were transferred into N2 glove box.
PTAA solution was spinning-coated on ITO substrates at the speed of
3000 rpm for 40 s, following an annealing process at 100 °C for 10 min.
Then the ITO/PTAA substrates were taken into vacuum chamber for the
CsPbI3 preparation. The deposition process was described as above.
When the perovskite film deposition finished, 1  nm LiF, 20  nm C60,
and 80 nm Ag were successively evaporated on the sample surface. The
active area of the device was 9 mm2.
Characterizations: The SEM images were obtained through the field-
emission scanning electron microscope (Gemini 500, Carl Zeiss).
The XRD patterns were acquired from the X-ray diffraction equipment
(x’pert3 powder, PANalytical B.V.). All the characterizations were
carried out with the ITO/CsPbI3 film, except quartz glass/CsPbI3 film
for the PL measurement. The PL spectra were detected through laser
confocal Raman spectrometer (LabRAM HR800, Horiba JobinYvon). A
programmable Keithley 2400 source meter under was used to test the
J–V curves of the photovoltaic device at the illumination of AM 1.5G
(100 mW cm−2).
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
C.D. and D.Y.L. contributed equally to this work. All the works were
supported by the National Natural Science Foundation of China
(62174064, 61904058, 61725401, 62004075), Hubei Province Natural
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Science Foundation (2021CFB373), the Innovation Project of Optics
Valley Laboratory (Grant No. OVL2021BG008), Queen Mary University
of London – Huazhong University of Science and Technology Strategic
Partnership Research Funding and the Fundamental Research Funds
for the Central Universities (2021XXJS028). We also appreciate the
measurement support from Die & Mould Technology and the Analytical
and Testing Center of Huazhong University of Science and Technology,
Prof. Zewen Xiao at Huazhong University of Science and Technology,
and Jinchao Wei at Institute of Chemistry, Chinese Academy of Sciences.
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
The data that support the findings of this study are available in the
supplementary material of this article.
Keywords
CsPbI3, growth mechanisms, solar cells, thermal evaporation
Received: December 9, 2022
Revised: February 14, 2023
Published online: April 2, 2023
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