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Quantitative Phase-Change Thermodynamics and Metastability of

Perovskite-Phase Cesium Lead Iodide

Article  in  Journal of Physical Chemistry Letters · March 2017

DOI: 10.1021/acs.jpclett.7b00134

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 Letter

pubs.acs.org/JPCL

Quantitative Phase-Change Thermodynamics and Metastability of

Perovskite-Phase Cesium Lead Iodide
Subham Dastidar,† Christopher J. Hawley,‡ Andrew D. Dillon,† Alejandro D. Gutierrez-Perez,‡
Jonathan E. Spanier,‡ and Aaron T. Fafarman*,†
†
Department of Chemical and Biological Engineering, Drexel University, 3141 Chestnut Street, Philadelphia, Pennsylvania 19104,
United States
‡
Department of Materials Science & Engineering, Drexel University, Philadelphia, Pennsylvania 19104, United States
*
S Supporting Information

ABSTRACT: The perovskite phase of cesium lead iodide (α-CsPbI3 or “black” phase) possesses
favorable optoelectronic properties for photovoltaic applications. However, the stable phase at
room temperature is a nonfunctional “yellow” phase (δ-CsPbI3). Black-phase polycrystalline thin
films are synthesized above 330 °C and rapidly quenched to room temperature, retaining their
phase in a metastable state. Using differential scanning calorimetry, it is shown herein that the
metastable state is maintained in the absence of moisture, up to a temperature of 100 °C, and a
reversible phase-change enthalpy of 14.2 (±0.5) kJ/mol is observed. The presence of
atmospheric moisture hastens the black-to-yellow conversion kinetics without significantly
changing the enthalpy of the transition, indicating a catalytic effect, rather than a change in
equilibrium due to water adduct formation. These results delineate the conditions for trapping
the desired phase and highlight the significant magnitude of the entropic stabilization of this
phase.

apid advances in the field of organic−inorganic hybrid

R perovskites (OHPs) have significantly altered the photo-
voltaic research landscape. These materials boast exciting
photophysical properties and robust, inexpensive fabrication
techniques and reported power conversion efficiencies up to
22%.1 However, OHPs suffer from chemical instability due to
the volatile2 and hygroscopic3,4 nature of the organic
component. Recently, perovskite-phase cesium lead iodide
(CsPbI3) has emerged as an all-inorganic alternative to the
OHPs with strikingly similar optoelectronic properties.5−7
Cesium has also been shown to play a critical role as a
substitutional dopant, imparting enhanced stability to the
recently discovered mixed cation perovskites that form the basis
of the highest performing OHP solar cells to date.8−13
According to the Goldschmidt tolerance factor, an empirical
index of the structural stability of perovskites, cesium is almost
too small to form a stable perovskite with lead iodide,10,14
despite being the largest nonradioactive elemental cation.
Nonetheless, at elevated temperature (>305 °C) CsPbI3 adopts
a cubic perovskite structure with a band gap 1.73 eV,5,6,15,16
known as the “black” phase or α-CsPbI3 (Figure 1a). The
equilibrium phase of CsPbI3 at room temperature is a high-
bandgap, nonperovskite “yellow” phase (δ-CsPbI3) that is
essentially nonfunctional as a photovoltaic material.17 It follows
simply that the yellow δ-phase is enthalpically favored, while
the functional, black α-CsPbI3 is entropically favored, however,
the magnitudes of these competing contributions have been
heretofore unknown.
For practical applications, several strategies are being
explored to form the α-CsPbI3 phase and preserve it in a
metastable state for use as a photovoltaic absorber. Our group
recently demonstrated that chloride doping of CsPbI3, by
codeposition of a mixture of CsPbI3 and CsPbCl3 nanocrystals
and subsequent chemical sintering, improves the phase stability
of the resulting polycrystalline α-CsPbI3.18 Deliberate for-
mation of small crystal grains was associated with improved
metastability in α-CsPbI3 thin films.5 This effect may also be at
play in the demonstration that α-CsPbI3 quantum dots are
stable under ambient conditions.6,19,20 Also, CsPbI3−xBrx mixed
crystals have been shown to be more stable than the pure-phase
CsPbI3.21,22 Developing a quantitative understanding of the
phase-change thermodynamics and kinetics of α-CsPbI3 will be
critical to these ongoing efforts to improve its stability,
particularly in the presence of atmospheric moisture.
Herein, the thermodynamics of the reversible phase
transition between the black and yellow phases of CsPbI3 has
been examined, and the transition enthalpies are reported using
differential scanning calorimetry (DSC). The DSC results show
a narrow endothermic peak around 320 °C and a much wider
exothermic feature around 270 °C, signifying the yellow-to-
black phase conversion and reappearance of the yellow phase,
respectively. The position and breadth of the peaks provide
insights into the kinetics of the phase transition in the regime in
which the perovskite phase is metastable. Both indicators are
measured herein as a function of the rate of heat flow,
demonstrating significant thermal hysteresis, which is, in turn,
Received: January 17, 2017
Accepted: March 3, 2017
Published: March 3, 2017

© 2017 American Chemical Society 1278 DOI: 10.1021/acs.jpclett.7b00134

J. Phys. Chem. Lett. 2017, 8, 1278−1282
The Journal of Physical Chemistry Letters Letter

Figure 1. (a) Crystal structure of black (α) and yellow (δ) phases of CsPbI3 at their thermodynamically stable temperatures. (b) XRD of CsPbI3
drop-cast films in black and yellow phase at room temperature. (c) UV−vis transmittance spectra of a thin film of CsPbI3, displaying complete
transition from black to yellow phase within a period of 75 min after exposing to relative humidity (RH) of 33% at 23 °C. (d) Microscopic images of
a thin film of CsPbI3, showing the generation of a yellow nucleation site, subsequent growth, and complete conversion within 15 min. The images
were taken at 2, 5, 10, and 15 min after the exposure, respectively, at RH 50% and 23 °C.

critical to the formation of a trapped state. In the literature, metastable “parent” black phase (Figure 1d). Subsequently, the
thermal hysteresis is observed in OHPs as well. 23,24 yellow phase continues to grow and eventually converts the
Interestingly, in the formamidinium lead iodide system, it has entire film.
been associated with conformational entropy of the A-site The same general phenomena are observed if metastable
molecular cation,24 whereas there can be no such contribution films are instead subjected to elevated temperature while
from cesium. In the current work, additional calorimetric maintaining an inert nitrogen environment, as shown in Figure
studies with and without moisture make it possible to establish 2. In this experiment, transmittance data are recorded as the
the parameters necessary to kinetically trap the black phase of
CsPbI3 in its metastable form and clarify the deleterious role
played by moisture.
Films and powders are fabricated according to a modified
literature procedure5,25 in which solvent evaporation of a
solution of CsI and PbI2 leads to the formation of the
nonfunctional orthorhombic or “yellow” phase (δ-CsPbI3).
Similar to bulk CsPbI3 crystals16 the polycrystalline samples
undergo phase change above 305 °C and convert into a
photoactive black phase (α-CsPbI3). To maintain the desired α-
CsPbI3 phase the films are cooled rapidly (“quenched”) to
capture the metastable black phase at room temperature. These
steps are performed in the inert atmosphere of a nitrogen
glovebox because otherwise, in the ambient atmosphere, α-
CsPbI3 transforms into δ-CsPbI3 in minutes. For powder
samples, a drop-cast film is scraped off the substrate using a
spatula and then ground to a powder. (Details can be found in
the Supporting Information (SI).) Figure 2. Contour plot of transmittance spectra as a function of
X-ray diffraction measurements are performed for the drop- temperature, taken for a thin film of metastable, black-phase α-CsPbI3.
cast films, indicating that quenched samples, encapsulated in Spectra are taken in 5 °C increments over the course of several hours,
nitrogen and black to the eye, are indeed the metastable, cubic achieving an effective scan rate of <1 °C/min. See text labels for phase
descriptions.
α-phase (Figure 1b, black curve). Samples at equilibrium with
ambient atmosphere and yellow to the eye are the
orthorhombic, nonperovskite δ-phase (Figure 1b, red curve).
The moisture dependence of phase transition is shown in temperature is raised in 5 °C increments over several hours.
Figure 1c, where transmittance spectra (shown as the negative Beginning at room temperature, the initially black films absorb
logarithm of transmittance) are collected over a period of 75 across the visible spectrum. Above 200 °C the metastable phase
min for a thin film of CsPbI3 exposed to a 33% relative transforms to a wide-bandgap structure. This indicates thermal
humidity (RH) nitrogen atmosphere at 23 °C. At the start, the destabilization of the metastable phase, in favor of the
spectrum (black curve) represents black α-CsPbI3 with a equilibrium phase for this temperature range, the yellow δ-
bandgap ∼1.73 eV. In contrast, as the film transforms to yellow phase. Importantly, this phenomenon occurs even in the
δ-phase, a strong absorption feature is observed at 420 nm absence of moisture. Above the phase-transition temperature,
(orange curve). The phase transition proceeds via the the black phase becomes the equilibrium phase and the
formation of a nucleation site of yellow δ-phase in the spectrum transitions back to its original state. To understand
1279 DOI: 10.1021/acs.jpclett.7b00134
J. Phys. Chem. Lett. 2017, 8, 1278−1282
The Journal of Physical Chemistry Letters
spectral changes seen as higher temperatures, we turn to
thermogravimetric analysis (TGA).
TGA analysis reveals (Figure 3, black curve) that the thermal
decomposition of CsPbI3 begins above 400 °C. This is
Figure 3. TGA heating profiles for CsPbI3 and PbI2 in black, and red,
respectively. The weight loss is calculated relative to the weight at the
final temperature of 800 °C, before which both curves exhibit a
plateau.
significantly higher than, for example, MAPbI3, in which the
initial decomposition is governed by the release of HI and
CH3NH2 and begins by ∼300 °C.26 For CsPbI3 the initial mass
loss begins in approximately the same temperature range as
PbI2 sublimation (Figure 3, red curve). The two distinct mass-
loss features in the TGA curve for CsPbI 3 coincide
approximately with literature values for the temperatures at
which pure PbI2 and CsI reach an appreciable vapor pressure
(arbitrarily defined as 200 Pa), at 493 and 762 °C,
respectively.27 This analysis allows us to assign the spectral
changes above 450 °C in Figure 2 to the formation of residual
CsI, coinciding with the loss of PbI2. We speculate that the
broadly absorbing material observed in the temperature range
between 420 to 450 °C is due to a PbI2-depleted intermediate
that forms transiently. As a consequence of the high-
temperature threshold for sublimation, it is possible to directly
measure the reversible enthalpies of phase changes using DSC.
To quantify the free-energy landscape of the CsPbI3 crystal
phases we employed DSC. Aluminum DSC crucibles are filled
with powder samples, and except where otherwise noted,
crimped inside a N2-filled glovebox to control the composition
of the head space of the crucible. The yellow sample is obtained
by exposing a black-phase powder sample to moist ambient
(22−23 °C, RH 20−40%) and subsequently transferring it back
into the glovebox prior to sealing the crucible. The heating and
cooling curves are obtained sequentially by heating the sample
from 20 to 350 °C and then cooling it back to the starting
point. Figure 4 represents the DSC thermograms for both black
and yellow samples at a 2 °C/min scan rate. While the yellow
sample, being the stable phase, shows no sign of thermal
activity at temperatures below 200 °C, the quenched black
sample undergoes an exothermic change (i.e., positive heat flow
out of the sample) between 90 and 150 °C, magnified in the
inset to Figure 4. The negative enthalpy of change indicates
that the rise in temperature provides enough thermal energy to
overcome the energy barrier and allows the metastable black
phase to convert into a stable yellow phase. We speculate that
the relatively greater range of metastability (>200 °C) observed
in Figure 2 is due to the formation of smaller grain sizes5 in
spincast films in comparison with powders made by
dropcasting. As temperature continues to rise, at 321 °C both
samples shown in Figure 4 exhibit a strong narrow endothermic
1280
Letter
Figure 4. DSC curves for the CsPbI3 powders, sealed under N2
atmosphere, heating at 2 °C/min. The “black” and “yellow” labels
indicate the starting phase of the powders (α-CsPbI3 and δ-CsPbI3,
respectively). The curves are offset for clarity. The inset shows an
expanded and baseline-corrected view of the temperature range where
the quenched metastable black phase transforms to a stable yellow
phase. The arrows indicate the direction of heating/cooling.
peak due to the yellow-to-black phase transition. On cooling,
the existence of a broad exothermic feature centered about 277
°C signifies the reemergence of the yellow phase. The
asymmetry of the exothermic peak could be due to the
presence of some transient intermediate crystal structure, as
attributed in previous studies of MAPbI3.23,26
The enthalpy changes of the forward and the reverse phase
transition can be quantified by measuring the area under the
exothermic or endothermic features. From DSC analysis (see
Table 1) the transition enthalpies are calculated to be 14.2
(±0.5) kJ/mol for both types of samples and for both
exothermic and endothermic peaks. We have executed three
consecutive scanning cycles for the same sample and found that
the individual peaks overlap and the transition energies are
identical within the experimental certainty (Figure S1). This
repeatability confirms the reversibility of the phase transitions
and the absence of significant material losses, either to
evaporation or chemical reaction with the crucible walls. To
the best of our knowledge this represents the first measurement
of this energy difference, and as such it can form a valuable
benchmark for first-principles calculations of stability. The large
magnitude of this enthalpy is interesting from two perspectives:
First, it demonstrates that the observed metastability of the
black phase at room temperature persists despite a significant
driving force to convert to yellow (>5kBT per formula unit at
room temperature, where kB is the Boltzmann constant);
second, it highlights the fact that the entropic favorability of the
black phase must be quite substantial to reverse the relative
stability of the two phases at the moderate phase-transition
temperature of ∼300 °C.
To draw further insight from calorimetry, we note that
although the phase transition is reversible, the exothermic and
endothermic peak centers are not aligned and there is a
considerable amount of thermal hysteresis. To understand how
the rate of temperature change and atmospheric moisture affect
the phase change kinetics and particularly the kinetic trapping
of desired black phase, DSC analysis is performed at a higher
temperature ramp rate (10 °C/min). At the faster scan rate, we
see qualitatively similar behavior to that shown in Figure 4 but
with substantial differences in the transition peak locations,
peak width, and onset temperature of the phase change (Figure
S2; see also Table 1). The exothermic peak corresponding to
the destabilization of the quenched black-phase sample now
DOI: 10.1021/acs.jpclett.7b00134
J. Phys. Chem. Lett. 2017, 8, 1278−1282
The Journal of Physical Chemistry Letters Letter

Table 1. Phase-Transition Enthalpies of CsPbI3 Powders under Varied Conditions

exothermic endothermic
phase/atmosphere rate (°C/min) peak (°C) fwhm (°C)a |ΔH| (kJ/mol) |ΔS| (J/K·mol)b peak (°C) fwhm (°C) |ΔH| (kJ/mol) |ΔS| (J/K ·mol)b
black − N2 10 256.7 14.6 15.1 29 324.5 3.8 13.8 23
2 278.7 6.6 14.4 27 321.7 2.3 14.0 24
yellow − N2 10 259.9 19.4 15.0 28 325.3 3.6 13.8 23
2 275.1 6.5 14.6 27 321.8 2.2 13.9 23
yellow − air 10 267.6 8.9 14.6 27 325.8 3.7 14.0 23
2 281.8 4.5 14.2 26 323.1 2.0 13.7 23
a
fwhm: full width at half-maximum. bApproximate entropy values were calculated from ΔG = ΔH − TΔS using the temperature at the transition
peak.

extends over a temperature range of 110−185 °C. To facilitate
the comparison for different scanning rates, the ordinate (y
axis) is transformed to heat capacity rather than heat flow.
Figure 5 exhibits a significant shift toward lower onset
Figure 5. Effect of cooling rate and moisture on phase transition. The
exothermic transition for yellow phase δ-CsPbI3 powders, sealed either
under N2 atmosphere (red curves) or in moist atmosphere (blue
curves) at cooling rate of 2 °C/min (solid lines) and 10 °C/min
(dashed lines), respectively. Arrow indicates temperature scanning
direction.
temperature and increased breadth of the transition feature
with faster cooling. At all temperatures below the phase-
transition temperature, the yellow phase is thermodynamically
favored, yet the system is kinetically trapped in the black phase
over the temperature interval defined by the magnitude of the
hysteresis, which itself depends on the cooling rate. At the limit
of the extremely fast cooling (>200 °C/min) used to quench
the samples in the metastable black phase, the system is
depleted of the thermal energy it would require to overcome
the activation barrier on the time scale of observation. Thus the
system becomes frozen in a metastable state. It is interesting to
note here that only small hysteresis values (1 to 2 °C) have
been previously reported for MAPbI3 for the tetragonal to cubic
phase transition, and even those have been ascribed to presence
of moisture.23
It is known that moisture has the effect of destabilizing the
metastable black phase of CsPbI3; however, to identify the
mechanistic role of moisture in the phase transition, DSC
analysis is repeated in the presence of moisture. Figure 5
depicts the exothermic transition during the cooling cycle for
yellow phase δ-CsPbI3 with and without a humid atmosphere.
increased sharpness of the peaks at either scan rate. At 2 °C/
min, in the presence of water molecules, the reappearance of
the yellow phase from the black phase (Figure S3b) appears 4
to 5 °C before the transition temperatures in a dry atmosphere.
Most importantly, however, the enthalpy of the phase change is
the same with or without water molecules present, and no new
distinct enthalpic features are observed anywhere else in the
thermogram. By contrast, in OHPs, irreversible enthalpic
features in the thermogram have been observed and
hypothesized to originate from H2O desorption.23 In computa-
tional studies of moisture-induced instability of OHPs, the
emphasis has been on the energetics of complex formation
between the perovskite and H2O.28,29 For the present results,
no such H2O adducts are evidenced, and the observed effect
can be explained simply as a transitory stabilization of the
transition state, with no effect on the equilibrium enthalpies of
the two phases.
The enthalpy and the temperature of the reversible phase
transition between the functional perovskite α-phase of CsPbI3
and the nonfunctional yellow δ-phase was measured as a
function of atmosphere, heating rate, and sample history. The
black α-phase is intrinsically unstable at room temperature,
even in a moisture-free atmosphere. Only above 321 °C is it
spontaneously formed from the δ-phase. In the absence of
moisture, the α-phase can be rapidly cooled or “quenched” to
form a metastable functional material at room temperature,
which remains metastable for significant periods of time, up to
∼100 °C. Moisture, which was previously known to destabilize
the α-phase, is shown here to play a primarily catalytic role,
lowering the kinetic barrier to the phase transition without
impacting the enthalpy significantly. CsPbI3 shows promise as
an all-inorganic alternative to the hybrid halide perovskite
photovoltaic materials; however, to realize this potential,
methods such as those demonstrated herein will be critical to
understand the phase stability of α-CsPbI3 and related halide
perovskites.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpclett.7b00134.
Experimental procedures, additional DSC plots, and
method for baseline correction and Gaussian fitting for
transition peaks. (PDF)

■
To achieve a humid environment, a yellow phase CsPbI3
powder sample is sealed in a DSC crucible in open atmosphere
AUTHOR INFORMATION
(22 to 23 °C, RH = 40%). The striking differences between the
N2- (red curve) and air- (blue curve) filled samples are the Corresponding Author
earlier transition onsets (i.e., at higher temperature) and the *E-mail: fafarman@drexel.edu.
1281 DOI: 10.1021/acs.jpclett.7b00134
J. Phys. Chem. Lett. 2017, 8, 1278−1282
 The Journal of Physical Chemistry Letters
ORCID
Subham Dastidar: 0000-0002-3025-4787
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
S.D. and A.T.F. acknowledge funding from CBET-1604293.
A.D.D. acknowledges funding from CMMI-1463412. C.J.H.,
A.D.G.-P., and J.E.S. acknowledge support from ONR under
N00014-14-1-0761. The TGA was performed in Prof. Giuseppe
R. Palmese’s lab. We thank Weichun Huang from Prof.
Christopher Li’s group for helping with the DSC measurement.
■
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DOI: 10.1021/acs.jpclett.7b00134
J. Phys. Chem. Lett. 2017, 8, 1278−1282