Article

Cite This: Chem. Mater. 2019, 31, 8563−8575 pubs.acs.org/cm

Layered Lead Iodide of [Methylhydrazinium]2PbI4 with a Reduced

Band Gap: Thermochromic Luminescence and Switchable Dielectric
Properties Triggered by Structural Phase Transitions
Mirosław Mączka,*,† Maciej Ptak,† Anna Gągor,† Dagmara Stefańska,† and Adam Sieradzki‡
†
Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box 1410, 50-950 Wrocław 2, Poland
‡
Department of Experimental Physics, Wrocław University of Science and Technology, Wybrzeże Wyspiańskiego 27, 50-370
Wrocław, Poland
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*
S Supporting Information
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ABSTRACT: Layered lead halides offer potential for light-

emitting and photovoltaic devices. Here, we report the synthesis
of two-dimensional (2D) lead iodide with single-octahedra slabs
separated by the smallest organic cation used to date in the
construction of A2PbI4 compounds. This compound, MHy2PbI4,
where MHy+ denotes methylhydrazinium cation, shows exception-
ally short separation of adjacent lead iodide layers and strong N−
H···I hydrogen bonds as well as unusually small interoctahedral
tilting of PbI6 octahedra, leading to exceptionally small band gap of
2.20 eV. Photoluminescence (PL) studies show that this compound exhibits at room temperature two emission bands at 561
and 610 nm related to free exciton and bound exciton. The latter one exhibits blue shift on cooling by around 37 nm in the 80−
300 K range. As a result, PL of MHy2PbI4 changes strongly with temperature from yellowish pink at 300 K to yellow-green at 80
K. MHy2PbI4 undergoes three structural phase transitions. The first phase transition occurs at 320 K, and it does not show any
evident change of Pmmn symmetry. The second phase transition that occurs at 298 K is associated with ordering of the MHy+
cations and change of symmetry to Pccn. This phase transition leads also to pronounced steplike change of dielectric
permittivity. Structural investigation indicates that major reorientation of MHy+ cations and tilts of PbI6 octahedra contribute to
this switchable dielectric property. The third phase transition observed at 262 K (233 K) on cooling (heating) leads to
distortion of the structure to triclinic, space group P1̅. MHy2PbI4 shows a low value of direct current conductivity σDC at low
temperatures, but the conductivity increases rapidly with increasing temperature and reaches 1.02 × 10−7 S m−1 at 298 K. We
also report temperature-dependent Raman scattering of MHy2PbI4. Analysis of Raman data revealed clear shifts and changes in
bandwidths at the phase transitions that provided deeper insight into mechanisms of the structural phase transitions in this
material. An interesting feature of the studied perovskite is also unusually large broadening of many bands on heating the sample
from 80 to 300 K that is much larger than typically observed in A2PbI4 compounds. This behavior proves that lattice dynamic
effects play very important role in MHy2PbI4 and that the nature of organic cation has a great impact on the lattice dynamics of
2D perovskites.

■ INTRODUCTION
Organic−inorganic metal halides have attracted a great interest
in recent years due to their remarkable and tunable properties
that make them very suitable materials for a variety of
applications.1−7 One group constitutes three-dimensional (3D)
perovskites with formula ABX3, where A, B, and X denote
monovalent cation (usually methylammonium (MA), for-
mamidinium (FA), or alkali metal), divalent cation (Pb2+, Sn2+,
or Ge2+), and halogen (Cl−, Br−, I−).1,2,5,7 These compounds
have been rapidly developed for applications as solar cells with
power conversion efficiencies exceeding 20% and as light-
emitting diodes.2,5,7 Although 3D perovskites exhibit out-
standing optoelectronic properties, they exhibit low chemical
stability at ambient conditions.8 One of the strategies for
enhancing chemical stability is decreasing the dimensionality
to two-dimensional (2D).9,10 Intrinsic layered structure is also
advantages for easy fabrication of ultrathin films and
nanocrystalline materials by solution-based method and
mechanical exfoliation.11,12 Unfortunately, such 2D materials
exhibit much smaller power conversion efficiencies than 3D
analogues due to the poor charge transport related to the
presence of isolating organic spacers.3,10 However, 2D hybrids
are very promising materials for applications as photodetectors
and light-emitting diodes due to color tunability and often high
efficiency of photoluminescence (PL).3,6,13 Furthermore, 2D
perovskites have often a notable optical nonlinearity.14
Two-dimensional layered halides are composed of metal
halide layers separated by organic cations. In contrast to 3D
Received: September 13, 2019
Revised: September 24, 2019
Published: September 25, 2019

© 2019 American Chemical Society 8563 DOI: 10.1021/acs.chemmater.9b03775

Chem. Mater. 2019, 31, 8563−8575
Chemistry of Materials
perovskites, use of organic cations with different lengths, sizes,
shapes, and strengths of electrostatic interactions as well as
hydrogen bonds (HBs) with the inorganic layers leads to a
remarkable structural tunability of 2D compounds.13 For
instance, single-octahedra slabs may be flat or corrugated and
the PbX6 octahedra may exhibit different degree of distortion.
It is worth adding that the inorganic layers contribute to the
semiconductor electronic structure, and due to the separation,
they form quantum-like structures with 2D electronic confine-
ment. This leads to the existence of stable excitons at room
temperature (RT) with large binding energy of a few hundreds
of meV, which is an order of magnitude higher compared to
3D lead halide perovskites, as well as to blue shift of band gap
compared to 3D analogues.15−17 The presence of organic
spacers leads also to dielectric confinement that makes the
exciton binding energy even larger.18 Such large exciton
binding energy and large band gaps limit photovoltaic
performance of 2D perovskites. It is, therefore, important to
find materials with lower electronic and dielectric confinement.
For lead halide hybrids containing flat single-octahedra layers,
the electronic confinement can be reduced by decreasing the
organic cation length. For instance, studies of 2D A2PbI4(100)
perovskites with A = benzylammonium, 2-phenethylammo-
nium (PEA), and 4-phenyl-1-butylammonium cations showed
that decrease of the organic cation length leads to shift of the
band gap from 2.40 to 2.34 eV.13 The electronic confinement
is also affected by distortion of the PbX6 layer, i.e., it decreases
with decreasing distortion.19,20 For instance, it was shown that
weakly distorted (100) GAMAPbI4 and CsGAPbI4 perovskites
(GA and MA denote guanidinium and methylammonium
cations, respectively) have smaller band gaps, i.e., 2.27 and 2.35
eV,20,21 than strongly distorted (110) GA2PbI4, FAGAPbI4, or
ImEAPbI4 analogues (FA = formamidinium and ImEA =
imidazolium ethylammonium) that showed band gap of 2.45−
2.54 eV.22−24 Reduction of the dielectric confinement can be
achieved by using high-dielectric-permittivity organic compo-
nents.25 It was shown that lead iodide containing ethanolamine
(EA) with high dielectric permittivity of 37 has strongly
reduced dielectric confinement and the exciton binding energy
20 times smaller compared to conventional 2D perovskites.25
As a result, EA 2 PbI 4 is expected to have improved
optoelectronic properties, especially for solar cells and
photodetectors.25
In addition to band gap tunability, A2PbX4 compounds with
well-separated inorganic layers often exhibit strong excitonic
PL even at room temperature.13,26,27 When structural
distortion is weak, such PL bands related to free exciton
(FE) are narrow and the Stokes shift is small.13,24,26,27 When
structural distortion is important, red-shifted PL bands may
appear. For instance, two bands were observed for cystamine-
based lead iodide. The narrow band at 522 nm overlapping
with the excitonic absorption feature was attributed to FE,
while the broader one at 554 nm was attributed to bound
exciton (BE).28 Situation may become much more compli-
cated in the case of 2D perovskites with short separation of
inorganic layers due to reduced quantum and dielectric
confinement. For instance, narrow excitonic PL with a few
nanometers Stokes shifts was reported at 558 and 550 nm for
(100) perovskites 3AMPPbI4 [3AMP = 3-(aminomethyl)-
piperidinium] and GAMAPbI4, respectively, but this PL was
weak at room temperature.20,27 (100) perovskite EA2PbI4 also
revealed excitonic PL with very small Stokes shift, but due to
extremely reduced dielectric confinement, this PL was absent
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at RT and appeared below 170 K.25 Another representative of
(100) perovskites, CsGAPbI4, showed an asymmetric band at
77 K with maximum near 535 nm and small Stokes shift.21
This PL was not measurable at RT. Interestingly, this
compound showed also a weaker and very broad band with
maximum near 730 nm. Such broad PL bands with large
Stokes shifts appear often for compounds exhibiting large
degree of octahedral distortion, especially for (110) com-
pounds, and they are usually attributed to self-trapped
excitons.21−23,25,29−34 Regarding (110) iodides with short
separation of inorganic layers, GA2PbI4 showed broad PL at
598 nm (100 nm Stokes shift) while PL of FAGAPbI4 (FA =
formamidinium) consisted of a few bands in the 600−700 nm
range (Stokes shift, 90−190 nm).22,23 It is worth adding that
broad PL is attractive for applications since it may lead to
white emission.29−35
Apart of differences in structural connectivity and distortion,
PL and optoelectronic properties can also be affected by the
dynamic of the organic cations.36−38 It is therefore of great
interest to perform temperature-dependent studies of hybrid
halides, especially those undergoing order−disorder phase
transitions, using various experimental methods that have
different probing length scales and sensitivities. One of such
methods sensitive to the order−disorder phenomena, defects,
and local symmetry changes is Raman spectroscopy.17,38−40
Literature data show that employment of small organic
cations in the synthesis of 2D lead halides may result in
discovery of novel materials with promising functional
properties. FA+ cation with ionic radius of 253 pm is small
enough to stabilize 3D perovskite structure (tolerance factor,
TF = 0.99, only slightly smaller than 1), while GA+ with ionic
radii 278 pm is large enough to stabilize 2D A2PbI4 structure
(TF = 1.04).1,22,41,42 There are four other organic ions with
ionic radii between FM+ and GA+, i.e., imidazolium (IM+, 258
pm), methylhydrazinium (MHy+, 264 pm), dimethylammo-
nium (DMA+, 272 pm), and ethylammonium (EtA+, 274
pm).1,43 EtA+, DMA+, and IM+ form iodides of APbI3
composition, but 2D compounds of A2PbI4 compositions are
not known.44−46 MHy+ have not been yet employed in
construction of any lead halide hybrid. We have decided,
therefore, to undertake efforts to prepare novel lead iodide
containing MHy+ cations. It is worth emphasizing that there
are only a few organic−inorganic hybrid perovskites containing
methylhydrazinium cations, i.e., methylhydrazinium metal
formates that were shown to exhibit ferroelectric and
multiferroic properties.43,47,48 We will show that this small
and high-dielectric-permittivity organic cation of 2249 can be
employed in the synthesis of 2D layered perovskite of formula
MHy2PbI4. This compound undergoes three structural phase
transitions, shows small band gap, and exhibits PL as well as
switchable dielectric behavior near 300 K. It also shows
pronounced temperature dependence of PL and Raman bands.
We discuss the origin of this behavior and mechanism of the
phase transitions.
■
EXPERIMENTAL SECTION
Synthesis. PbI2 (99%, Sigma-Aldrich), methylhydrazine (98%,
Sigma-Aldrich), hydroiodic acid (57 wt % in H2O, 99.95% Sigma-
Aldrich), methylacetate (99.5%, Sigma-Aldrich), and ethanol (95%,
Sigma-Aldrich) were commercially available and used without further
purification. Single crystals were grown using antisolvent vapor-
assisted crystallization, in which the appropriate antisolvent is slowly
diffused into a solution containing the crystal precursors. The crystal
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precursor was prepared by adding 3 mmol PbI2 to a solution 7. The triclinic phase was heavily twinned with overlapping diffraction
containing 9 mmol methylhydrazine dissolved in 6 mL of HI. The peaks from at least three domains. The model of the structure was
clear solution obtained after stirring for 15 min was placed into a glass obtained from one dominating domain indexing ∼50% of diffracted
vial, which was placed in a second larger glass vial containing ethanol intensities. This resulted in disturbed intensities and high (max ∼ 4 e
and methylacetate in 1:1 ratio. The lid of the outer vial was A−3) residual densities around heavy atoms and negative anisotropic
thoroughly sealed, but the lid of the inner vial was loosened to allow displacement parameters of the organic part. Thus, all C and N atoms
diffusion of the ethanol and methylacetate into the precursor solution. were refined using the isotropic displacement parameters.
Red platelets were harvested after 4 days, filtered from the mother Raman and IR Studies. Temperature-dependent Raman spectra
liquid, and dried at room temperature. A good match of their powder on a single crystal were measured using a Renishaw InVia Raman
X-ray diffraction (XRD) patterns with the calculated ones based on spectrometer equipped with a confocal DM 2500 Leica optical
the single-crystal data (Figure S1, Supporting Information) confirmed microscope and a thermoelectrically cooled CCD as a detector.
the phase purity of the bulk sample. Additional measurements of low-wavenumber modes (down to 5
Differential Scanning Calorimetry (DSC) and Thermogravi- cm−1) were performed on the same instrument using an eclipse filter.
metric Analysis (TGA) Measurements. Heat capacity was Since excitation with an argon laser operating at 488 or 514 nm
measured using a Mettler Toledo DSC-1 calorimeter with high resulted in a very strong luminescence background, a diode laser
resolution of 0.4 μW. Nitrogen was used as a purging gas, and the operating at 830 nm was used for Raman studies. The temperature
heating and cooling rate was 5 K min−1. The sample weight was 26.11 was controlled using Linkam cryostat cell. The spectral resolution was
mg. The excess heat capacity associated with the phase transitions was 2 cm−1.
evaluated by subtraction from the data the baseline representing
variation in the absence of the phase transitions. TGA study was
performed in the temperature range 300−1073 K using PerkinElmer
TGA 4000. The sample weight was ca. 23.4 mg, and the heating speed
■ RESULTS AND DISCUSSION
DSC and TGA. The DSC measurements show the presence
was 10 K min−1. Pure nitrogen gas as an atmosphere was used. of three heat anomalies at T1 = 320 K (318 K), T2 = 299 K
X-ray Powder Diffraction. Powder XRD pattern was obtained on (295 K), and T3 = 262 K (233 K) during heating (cooling)
an X’Pert PRO X-ray diffraction system equipped with a PIXcel (Figures 1 and S2). Strongly symmetric shapes of these
ultrafast line detector and Soller slits for Cu Kα1 radiation (λ =
1.54056 Å). The powders were measured in the reflection mode, and
the X-ray tube settings were 30 mA and 40 kV.
Dielectric Properties. The complex impedance (Z*) measure-
ments were done using a Novocontrol Alpha analyzer. The complex
dielectric permittivity (ε*), electric modulus (M*), and alternating
current (AC) and direct current (DC) conductivities (σ) have been
evaluated from the measured complex impedance. The platelike single
crystal of 3.1 × 1.7 mm2 with thickness 0.4 with crystallographic
orientation perpendicular to the (001) cleavage plane (notation for
the Pmmn phase) was used. The silver paste was coated on both
parallel surfaces of the sample to ensure a good electrical contact. A
sinusoidal voltage with amplitude of 1 V and frequency in the range
101−106 Hz was applied across the sample. The temperature was
controlled by the Novocontrol Quattro system, by using a nitrogen
gas cryostat. The measurements were taken every 1 K in the
temperature range of 140−350 K. The temperature stability of the
samples was better than 0.1 K. Owing to the shape of the sample
crystal, measurements in other crystallographic directions were not
possible. We have, therefore, performed additional dielectric measure-
ments for pellet with a diameter of 6 mm and thickness of 0.4 mm
made of well-dried sample.
Optical Studies. RT diffuse reflectance spectrum of the powdered
sample was measured using the Varian Cary 5E UV−vis−NIR
spectrophotometer. Temperature-dependent emission spectra under
405 nm excitation line from a diode laser were measured with the Figure 1. Change in (a) Cp and (b) S related to the phase transitions
Hamamatsu photonic multichannel analyzer PMA-12 equipped with a in the heating (red) and cooling (blue) runs.
BT-CCD linear image sensor. The temperature of the sample was
controlled using Linkam THMS 600 heating/freezing stage. The
quantum efficiency was measured on Hamamatsu Absolute PL
anomalies, sharp changes of entropy, and large thermal
quantum yields (QYs) measurement system C9920-02G. To record hysteresis (especially the lowest-temperature phase transition
time-resolved PL spectra and decay times, a femtosecond laser at T3) point to the first-order character of these phase
(Coherent Model Libra) was used as an excitation source. transitions. The associated changes in enthalpy ΔH and
Single-Crystal X-ray Diffraction. Single-crystal X-ray diffraction entropy ΔS were estimated to be, respectively, ∼120 J mol−1
was collected at Xcalibur diffractometer operating with Atlas charge- and ∼0.41 J mol−1 K−1 for the phase transition at T1, ∼744 J
coupled device (CCD) detector and Mo Kα radiation. In all phases, mol−1 and ∼2.65 J mol−1 K−1 for the phase transition at T2,
empirical absorption correction using spherical harmonics, imple- and ∼56 J mol−1 and ∼0.23 J mol−1 K−1 for the phase
mented in SCALE3 ABSPACK scaling algorithm, was done using transition at T3 (average values).
CrysAlis PRO 1.171.38.46 (Rigaku Oxford Diffraction, 2015). The
According to our X-ray diffraction data, the MHy+ cations
structures were solved using SHELXT 2014/5 and refined in
SHELXL2018/3. Due to the disorder of MHy+ in phases I, II, and show 3-fold disorder above T2 and complete order below T3.
III, the displacement parameters of split nitrogen atoms were refined In the intermediate phase III, only one of three MHy+ ions
isotopically, additionally not all hydrogen atoms were incorporated in shows 2-fold disorder. Thus, the total change in entropy at T2
the model. In the last phase, phase IV, all hydrogen atoms were and T3 is expected to be R ln 3 = 9.13 J mol−1 K−1. The large
included from geometry; terminal NH2 groups were refined with afix (small) experimental value of ΔS at T2 (T3) is consistent with
8565 DOI: 10.1021/acs.chemmater.9b03775
Chem. Mater. 2019, 31, 8563−8575
Chemistry of Materials
Figure 2. (a) Details of the crystal structure of phase I, T = 330 K. The MHy+ cation is disordered over three positions. Possible N−H···I hydrogen
bonds are marked as dashed lines. (b) Tilting of PbI64− octahedra in subsequent phases, as seen along the b axis. (c) Temperature changes of the
interlayer distance between the lead iodide sheets. (d) Details of the crystal structure in the triclinic LT polymorph, T = 100 K, P1̅. All MHy+ ions
are ordered and interact with the inorganic substructure via N−H···I HBs and intermolecular N−H···N HB interactions. Only 12 independent
molecules from the asymmetric unit are drawn for the picture clarity.
large (small) change in disorder of MHy+ cations. However,
the total change in entropy (∼2.88 J mol−1 K−1) is smaller than
expected. As discussed in the literature, some residual entropy
is always left over if a phase transition has some relaxor
character.50 Thus, our results showing less-than-expected
entropy change indicate that much residual entropy is left
over, implying relaxor character of the phase transition.
The anomaly at T1 leads to small changes in entropy,
suggesting weak contribution of an order−disorder mechanism
to this phase transition.
The thermogravimetric plot indicates that MHy2PbI4 starts
to decompose at about 480 K (Figure S3). In this plot, a
weight loss of about 44% takes place between 480 and 660 K,
corresponding to release of methylhydrazinium iodide (the
calculated value is 43.1%). On further heating, PbI2 starts to
sublimate, and this process ends near 900 K. The
decomposition temperature of MHy2PbI4 falls within the
range typically observed for A2PbI4 iodides (558 K for n-
butylammonium, 51 543 K for EA 2 PbI 4 , 52 478 K for
[NH3(CH2)4NH3]PbI4 and [NH3(CH2)6NH3]PbI4,53 and
528 K for FAGAPbI4).23
Single Crystal X-ray Diffraction. To obtain information
on symmetries of the observed phases, we employed X-ray
diffraction method. The crystals of MHy2PbI4 possess four
different polymorphs depending on the temperature: two high-
temperature (HT) phases II and I, room-temperature phase III
expanding down to 233 K on cooling, and low-temperature
(LT) polymorph IV, below. Phases II and I are isostructural
and adopt orthorhombic Pmmn symmetry with the unit cell
volume near 770 Å3 (Table S1). The phase transition to phase
III leads to a substantial increase of the unit cell volume to
4575 Å3 because of a tripling of b and doubling of c lattice
parameters. The symmetry of phase III remains orthorhombic,
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and the space group changes to Pccn. The last phase transition
to phase IV introduces small triclinic distortion of the large
unit cell. The triclinic angles are very close to 90° nevertheless,
the splitting of diffraction peaks clearly confirms this drastic
symmetry reduction. Figure S4 shows the reconstruction of the
reciprocal space before and after the transition to phase IV.
The Bragg peak profiles are the convolution of at least three
maxima from dominating domains. As the symmetry reduction
to monoclinic would result in maximum two domain states, the
structure of phase IV was resolved in the triclinic system of P1̅
space group.
The crystal structure of all phases is built of the inorganic 2D
perovskite substructure, which can be derived from 3D
perovskites by slicing of the lattice along (100) crystallographic
planes.23,54 The PbI64− octahedra share four corners and
expand as layers in b and c directions. Thus, in all octahedra,
there are two apical iodides and four bridging ones. The a
direction corresponds to the interlayer distance, which is equal
to a/2. The presence of n-glide plane results in the (1/2, 1/2,
0) translation of neighboring layers. The MHy+ ions are
located between the planes and interact with them via an
extended system of N−H···I HB interactions and intra-
molecular N−H···N HBs. In phases I and II, all cations are
disordered within three positions, which are related to the
rotations of molecules along the long axis (Figure 2a). With
temperature lowering, the movements gradually cease. In phase
III, only one of the three MHy+ cations is disordered over two
sites; in phase IV, all cations are ordered.
In phases I and II, the lead iodide sheets consist of only
slightly tilted octahedra. There are two distinct bridging angles
Pb(1)−I(1)−Pb(1) of 171° and Pb(1)−I(3)−Pb(1) of 180°.
The I(1)−Pb(1)−I(1) angle, where I(1) is an apical iodide,
equals 179° (Tables 1 and S2). The high symmetry of the
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Table 1. Distortion Parameters Resulting from the Single-Crystal X-ray Structures of MHy2PbI4 Perovskite in Subsequent
Polymorphic Phases
phase T (K) Pb−I−Pb direction maxa θtilt 180 − θin 180 − θout max Δd max σ2
−6
I 330 [001] 180 0 0 6.8 × 10 5.6
[010] 170.7(1) 9.3 0
II 305 [001] 180 0 0 1.3 × 10−5 8.8
[010] 170.3(1) 9.7 0
III 280 [001] 166.87(1) 13.13 0.24 1.4 × 10−4 11.9
[010] 170.99(1) 1.55 7.92
IV 100 [001] 163.43(1) 16.50 1.69 3.9 × 10−4 18.1
[010] 166.49(1) 2.53 13.47
a
Maximum distortion parameters are given because the structures of LT phases contain two (phase III) and six (phase IV) inequivalent [PbI6]4−
octahedra. Δdbond length distortion; σ2octahedral angle variance.56

Figure 3. (a) Photograph of MHy2PbI4 single crystals showing orientation of the crystallographic axes in notation for phase I (space group Pmmn).
(b−e) Details of the Raman spectra at different temperatures in a heating run for z(xx + xy)z polarization.

individual octahedra (C2v) may result from the lack of
preference in directional bonding due to the temperature-
induced dynamic distribution of NH2 and NH2+ donor groups.
The presence of HBs has a strong impact on the position of
iodide ligands.55 Those iodides, which act as acceptors for the
hydrogen atoms, shift from the ideal linear placements between
the lead atoms. The II−III phase transition brings distortions
within the lead iodide layers and the changes in the cations
distribution. The unit cell expands in both b and c directions
accommodating the distortions arising from the interoctahe-
dral tilting. Figure 2 illustrates the tilting of the PbI64−
octahedra in subsequent phases and the temperature changes
of interlayer distance. The local structural distortions result in
two inequivalent PbI64− octahedra of lower symmetry, C2 and
C1 in phase III. The number of inequivalent cations increases
to three, of which every third is disordered over two possible
sites with 0.7/0.3 ratio at 280 K. Figure S5 illustrates the
selected details of the structure of phase III.
During the last phase transition, the interoctahedral
distortions increase and the local octahedral symmetry
decreases. The triclinic unit cell accommodates 6 inequivalent
PbI64− octahedra of C1 symmetry and 12 ordered cations. The
octahedral distortion parameters (Table 1) increase with the
temperature lowering, as it is expected from the symmetry
reduction. The values and the differences between the phases
are, however, rather small, indicating only slight deviations
from the ideal octahedral coordination. The main modifica-
tions between the phases concern the variations in the
interoctahedral tilting, which changes from 180 to max
163.43(1)° (for Pb−I−Pb along the [001]) and from
8567
170.7(1) to 166.49(1)° (along the [010] direction) (Tables
1 and S4).
Phase IV is entirely ordered, Figure 2d, and all 24
inequivalent iodides act as acceptors in HB interactions
(Table S5). Additionally, the structure is stabilized by N−
H···N intermolecular HBs with terminal N atoms serving as
donors and acceptors for the hydrogen atoms and in-chain
NH2 groups being hydrogen atoms donors.
It is important to compare structural data of A2PbI4(100)
perovskites with short separation of inorganic layers. According
to literature data, the distances between layers are 9.288,
9.4129, 9.9003, 10.2261, 10.2263, and 10.4999 Å for
CsGAPbI4, GAMAPbI4, PyrEAPbI4 (PyrEA = pyridinium
ethylammonium), 3AMPPbI 4 , EA 2 PbI 4 , and 4AMPPbI 4
[4AMP = 4-(aminomethyl)piperydinium], respectively
(Table S6).20,21,24,25,27 For MHy2PbI4, this value is 9.3635 Å
(at 305 K, Table S1), i.e., smaller value is observed only for
mixed-cation CsGAPbI4. For CsGAPbI4, GAMAPbI4, Pyr-
EAPbI4, 3AMPPbI4, EA2PbI4, and 4AMPPbI4 compounds, the
Pb−I−Pb angles are 149.74 + 165.19, 159.04 + 180.0, 159−
174, 163.39−168.83, 159.93 + 161.06, and 154.2−154.59°,
respectively (Table S6).20,21,24,25,27 Significant deviation from
180° is also observed for many A2PbI4(100) perovskites with
large separation between inorganic layers, such as NBT2PbI4
(NBT = n-butylammonium) and PEA2PbI4 (Table S6).57,58
Thus, MHy2PbI4 shows the smallest deviation of the Pb−I−Pb
angles from 180°, and this deviation is observed for phases I
and II only along the [010] direction.
Regarding phase transitions, they have been reported for a
number of A2PbI4(100) perovskites with large separation
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Chemistry of Materials
between inorganic layers due to the presence of bulky organic
cations containing organic rings or alkyl chains.57,59−61 The
mechanism of these transitions was related mainly to dynamic
rotational disordering of the NH3 head group or melting of the
chains.59,61 Among (100) iodide perovskites with short
separation between inorganic layers, phase transition was
reported only for EA2PbI4, but the structure of the HT phase
was not solved.52 As discussed above, phase transitions in
MHy2PbI4 are associated with rotational disordering of the
whole MHy+ cations associated with tilts and distortion of PbI6
octahedral units.
Raman and IR Studies. Further information on the
mechanism of the phase transitions and lattice dynamics can be
obtained by analyzing temperature-dependent Raman spectra.
Orientation of the single crystal is shown in Figure 3a, and
nonresonant Raman spectra are presented in Figures 3b−e, 4,
Figure 4. Details of the low-wavenumber Raman spectra at different
temperatures in a heating run for (a) z(xx + xy)z and (b) z(yy + yx)z
polarization configurations.
and S6−S8. The observed Raman modes and their assignment
are listened in Table S7. Former studies of lead halide
perovskites showed that lattice modes are observed below 300
cm−1, and the most intense Raman bands can be attributed to
vibrations involving Pb2+ and I− ions.38,60,62,63 In particular, the
Pb−I stretching modes were observed in the 70−110 cm−1
range, while modes below 80 cm−1 were attributed to
librational and deformational modes of PbI6 octahedra.60−63
We assign, therefore, the strong bands at 120, 112, and 90
cm−1 as well as very strong bands at 34, 27, and 13 cm−1 (at
370 K, Figures 3, 4, and S6−S8) to the Pb−I stretching and
PbI6 librational modes, respectively. One should also expect to
observe translational and librational modes of MHy+ ions.
These modes are overlapped by much stronger ones
corresponding to the Pb−I stretching modes and are not
resolved at 370 K. However, some weak bands appear at 80 K
in the 123−195 cm−1 range and at 302 cm−1 (Table S7) that
can be most likely attributed to translational and librational
modes of MHy+. The remaining weak- and medium-intensity
bands observed above 200 cm−1 can be attributed to internal
vibrations of MHy+ cation. Assignment of these modes to
respective motions of atoms can be proposed based on our
previous Raman and IR studies of methylhydrazinium metal
formates and theoretical data reported for methylhydra-
zine.43,64,65
Thermal evolution of the Raman spectra, presented in
Figures 3, 4, and S6−S8, shows that when temperature
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decreases, the Raman spectra exhibit weak changes down to
300 K. Detailed analysis of Raman wavenumbers and full width
at half-maximum (FWHM) values as a function of temperature
shows, however, clear anomalies at T1 (Figure S9). First, some
bands exhibit weak discontinuous shifts at T1. The shifts are
negligible for the Pb−I stretching and PbI6 librational modes,
but clear shifts up to 1.6 cm−1 are observed for the 1358 and
1322 cm−1 τ(NH2) modes (Figure S9a). Furthermore, the
δ(NH2) band at 1574 cm−1 splits into two bands. Second, the
δ(NH2) band narrows at T1 (Figure S9b). These changes
indicate that the phase transition at T1 is associated with subtle
reorganization of MHy+ cations, which is too small to lead to
any clear distortion of the inorganic layers and space group
change.
The phase transition at T2 is very clearly observed when the
temperature decreases from 300 to 295 K. First, the PbI6
librational bands observed at 15.8 and 33.4 cm−1 split into 13.0
+ 19.8 and 29.3 + 40.8 cm−1 bands (Figures 4a and S9a),
respectively. Second, the ρ(NH2) band shifts from 857.1 to
855.3 cm−1. Furthermore, a new band appears at 866 cm−1.
Weak upshifts are also observed for the τ(NH2) modes from
1322.5 and 1357.9 cm−1 to 1324.6 and 1359.4 cm−1, and for
the τ(CH3) mode, from 337.1 to 339.1 cm−1 (Figure S9a).
Third, the 339.1 and 1357.9 cm−1 modes exhibit decrease of
FWHM values from 65.4 and 20.8 cm−1 to 52.0 and 18.2 cm−1
(Figure S9b). The observed narrowing, splitting, and shift of
bands are consistent with the first-order character of the phase
transition at T2, ordering of MHy+ cations, tilts of PbI6
octahedra, and increase of the formula units in the unit cell.
On further decrease of temperature, the Pb−I stretching
modes observed at 110.1 and 88.5 cm−1 (at 295 K) exhibit
softening to 106.1 and 83.1 cm−1 (at 260 K), followed by
abrupt shift to 97.1 and 80.7 cm−1, respectively, at 250 K.
Furthermore, a new band appears at 250 K at 76.1 cm−1.
Interestingly, librations of PbI6 octahedra do not show any
significant changes in the 295−250 K range (Figure S9a).
Softening is also observed for the δ(CNN) mode, which shifts
from 442.6 cm−1 at 295 K to 442.0 cm−1 at 260 cm−1 and
437.9 cm−1 at 250 K. The δ(NH2), νas(CNN), and νs(CNN)
modes also exhibit significant shifts (see changes near 1580,
1090, and 885 cm−1 in Figure S9a). FWHM values show weak
anomalies at T3. It is worth noting that the bands are still broad
at 250 K, indicating significant motional freedom of MHy+
cations. However, all bands related to internal vibrations of
MHy+ cations show pronounced narrowing on cooling to 80 K.
The fact that the L(PbI6) modes are barely affected whereas
large anomalies are observed for the Pb−I stretching modes
indicates that the phase transition at T3 is associated with
significant distortion of the PbI6 octahedra, whereas tilts of
these octahedra seem to be weakly affected. The distortion of
the inorganic layers is certainly associated with changes of the
interaction strength between MHy+ and I− ions, and changes
in the C−N−N bond angle, as evidenced by the wavenumber
shifts observed for the δ(NH2), δ(CNN), νs(CNN), and
νas(CNN) modes.
In summary, Raman data show that when going from 80 to
370 K, the largest broadening is observed for the τ(CH3),
ρ(NH2), and δ(NH2) modes. This behavior proves that
dynamics of MHy+ cations plays a very important role in this
perovskite. However, significant broadening is also observed
for the lattice modes, and this behavior can be attributed to
softness of the structure and interactions of the organic layers
with inorganic layers mediated by the HBs. Such dynamic
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Chemistry of Materials Article

disorder was shown to play an important role in the

optoelectronic and photovoltaic properties of these perov-
skites.36,38,66 It was especially large for 3D perovskites that
were even regarded as phonon glass materials.17 Regarding
A2PbX4 2D analogues, only a few temperature-dependent
lattice dynamics studies were reported to date, i.e., non-
resonant Raman scattering spectra were analyzed for
(FC6H4C2H4NH3)2PbI4 in the 300−600 cm−1 range and
300−380 K as well as PEA2PbI4 and NBT2PbI4 in the 65−250
cm−1 range and 15−295 K.61,63 No information on temper-
ature dependence of Raman modes below 65 cm−1 was
reported, although a few such modes have been observed
recently at 15 K in PEA2PbI4 and NBT2PbI4 by high-resolution
resonant impulsive stimulated Raman spectroscopy.38 Our
results on MHy2PbI4 show the presence of a few modes below
40 cm−1. They also show pronounced broadening of both
intramolecular MHy+ modes and modes related to inorganic
layers. This broadening is much more pronounced for
MHy2PbI4 compared to PEA2PbI4 and NBT2PbI4. For
instance, the 119 cm−1 band shows increase of FWHM from Figure 5. (a) Dielectric permittivity, (b) dielectric loss, (c) real part,
9.8 cm−1 at 80 K to 25.8 cm−1 at 300 K, whereas for PEA2PbI4 and (d) imaginary part of electric modulus spectra as a function of
and NBT2PbI4, the FWHM values were less than 15 cm−1 for temperature in MHy2PbI4 single crystal. The representative curves are
the Pb−I stretching modes. Broadening of the τ(CH3) mode is plotted in frequency decades between 1 Hz and 1 MHz. The vertical
also larger (FWHM, 5.1 cm−1 at 80 K and 65.4 cm−1 at 300 K) lines correspond to the phase-transition temperatures obtained from
compared to the broadening of the torsional mode in the DSC measurements.
NBT2PbI4 observed at 239 cm−1 (FWHM < 25 cm−1). This
behavior proves that the nature of organic cation has a great
higher frequencies, confirming thermally induced activation
impact on the dynamic disorder in 2D lead halide perovskites
process. The observed dipolar process deviates from the
and that this disorder is larger in MHy2PbI4 than in PEA2PbI4
classical Debye behavior. All data were parameterized in the
and NBT2PbI4, and it resembles more that observed in 3D
vicinity of the peak maximum with the use of the single
perovskites. We argue that this difference reflects smaller
Havriliak−Negami function. To describe relaxation dynamics
separation of the inorganic layers and thus stronger coupling
of the observed dipolar processes, we compare the temper-
between the organic moieties and the inorganic perovskite
ature-dependent behavior of its dielectric relaxation times as a
layers mediated by the HBs.
function of 1000/T (see Figure S10c). This relaxation map
Electric Measurements. Since the DSC, X-ray diffraction,
depicts the dynamic properties of this compounds and the
and Raman data revealed the presence of phase transitions, we
characteristic electronic behavior of the investigated structure.
decided to check if these transitions are related with some
The thermal activation of their relaxation time τs spans
dielectric and electric conductivity anomalies. The temperature through almost 4 decades in frequency. In the investigated
dependence of the real ε′ and imaginary ε″ parts of the temperature range, the relaxation times τs exhibit linear
dielectric permittivity is given in Figure 5a,b. Both ε′ and ε″ tendencies versus the inverse temperature. Therefore, the
increase monotonically with increasing temperature and

ij E yz
relaxation times can be modeled using the Arrhenius relation

τ = τ0 expjjj a zzz
exhibit distinct frequency dependence starting from about

250 K, with clear anomalies near 295 and 320 K. The observed
frequency dependence of ε′ and ε″ implies some relaxation
ordering process. Similar behavior was previously noted for a
number of APbI3 and [(CH3)4N]4Pb3Cl10 hybrid perovskites,
but we are not aware of any reports on dielectric dispersion in
A2PbX4 (X = Cl, Br, I) layered perovskites.67−70 To better
visualize the relaxation dynamics and eliminate the contribu-
tion of electrode polarization, the electric modulus M* = 1/ε*
representation was used.71 The temperature-dependent com-
plex electric modulus spectra at various frequencies are shown
in Figure 5c,d. The value of M′ reaches almost a constant value
at lowest temperatures, but it approaches zero at high
temperatures. Each of the temperature dependence of M″
exhibits a well-defined peak. The peak maximum shifts toward
higher temperatures with increasing frequency, indicating the
presence of a structural relaxation.
We also analyzed the frequency-dependent electric modulus
of MHy2PbI4 for several isotherms (Figure S10a,b). The
isothermal complex electric modulus spectra also reveal the
occurrence of dipolar relaxation process above 250 K. As
temperature increases, the modulus peak maxima move toward
8569
j kBT z
k {
where τ0, kB, and Ea are relaxation time at the high temperature
limit, Boltzmann constant, and activation energy, respectively.
Taking into account the X-ray diffraction data, the physical
nature and mechanism of the observed dielectric relaxation
process in MHy2PbI4 can be attributed to the reorientational
motion of MHy+ cations in the structure. No sizable dielectric
relaxation in phase IV corroborates well with well-ordered
MHy+ cations in this phase. With increasing temperature,
thermal motions of MHy+ cations become important and
molecular dipole orientation can be achieved under the applied
AC field, especially in phases II and I, in which MHy+ cations
exhibit rotational disorder. The obtained activation energies
a r e s m a l l e r t h a n r e p o r t e d f o r o n e - d im e n s i o n a l
(triethylpropylammonium)PbI3 for which Ea was 0.65 eV in
the HT phase and 1.09 eV in the LT phase.69 Structural data
allow also to understand temperature dependence of ε′. Due to
the orientational disorder of MHy+ in phase I, the dipole
moment of the cation can easily reorient under AC field
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Chemistry of Materials
leading to weakening of the field, which show the larger
dielectric permittivity and a plateau above 320 K at high
frequencies. In phase IV (III), the cations are ordered (nearly
ordered), leading to small dielectric permittivity in the AC
field. However, the dielectric permittivity increases continu-
ously on heating in phase II, and this behavior suggests gradual
increase in reorientational motions of MHy+ cations. It is
worth adding that the ε′ and ε″ show jumps at 295 K. This
jump is 17.9 for ε′ at 1 Hz, and based on our X-ray diffraction
data, it can be most likely attributed to abrupt change in the tilt
of PbI6 octahedra and orientation of the MHy+ cations.
The AC conductivity at different frequencies and temper-
atures was determined from the dielectric data using the
Jonscher law72
σAC = σDC + Aωn + ε0ε″ω
where σDC corresponds to the frequency-independent direct
current conductivity, A is the temperature-dependent constant,
n is the power exponent representing the degree of interaction
between mobile ions and the surroundings, and ω = 2πf [f
(Hz)] is the angular frequency. The third term defines
dielectric losses related to the dielectric relaxation process,
where ε0 is the vacuum permittivity.
The frequency dependence of the AC conductivity in the
log−log scale is depicted in Figure 6a. It is known that the
Figure 6. Variation of (a) AC conductivity with frequency in the
temperature range 160−340 K and (b) DC conductivity vs
temperature for MHy2PbI4. The dashed line depicts the phase-
transition temperatures obtained from the DSC measurements.
Activation energies in the selected temperature ranges are Ea1 =
0.23 eV; Ea2 = 0.38 eV; Ea3 = 0.26 eV; and Ea4 = 0.06 eV.
mechanism of conductivity can be explained taking into
account the temperature and frequency dependence of n. The
hopping mechanism of conductivity is represented by n close
to 1.72 The variation of the exponent n as a function of
temperature is presented in the inset of Figure 6a. In the
investigated temperature range, the n is equal to 1 at the lowest
temperatures and decreases to almost zero in the HT phase,
which proves that the conductivity mechanism in MHy2PbI4
strongly depends on temperature.
The plot of direct current conductivity σDC versus
temperature is presented in Figure 6b. MHy2PbI4 shows
quite a low values of σDC at low temperatures (1.01 × 10−11 S
m−1 at 160 K), but the conductivity increases rapidly with
increasing temperature and reaches 1.02 × 10−7 S m−1 at 298
K and 3.5 × 10−6 S m−1 at 340 K. A similar RT conductivity of
1.3 × 10−7 S m−1 was observed for other layered A2PbI4
compounds with protonated 1,4-diaminobutane, 1,6-diamino-
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hexane, and 1,8-diaminooctane.53 It is also worth noting that
the conductivity of 2D MHy2PbI4 is an order of magnitude
smaller than that of 3D CH3NH3PbI3 (1.11 × 10−6 S m−1).73
Figure 6 shows that all phase transitions observed in DSC
measurements are also well visible in the temperature
dependence of σDC. The estimated activation energy is 0.06
eV at the lowest temperatures, and it increases to 0.38 eV for
phase II. These values are of the same order of magnitude as
those found for the migration of iodide ion vacancies in
CH3NH3PbI3 and ion migration in 2D BA2MA3Pb4I13, where
BA and MA denote n-butylammonium and methylammonium
cation, respectively.74−76
To check the electrical anisotropy of MHy2PbI4, we have
performed additional measurements for the polycrystalline
sample (pellet). The obtained results, both for dielectric
permittivity and electric modulus, look very similar to those
observed for the single crystal (see Figures S11 and S12),
suggesting small electrical anisotropy. The confirmation of this
assumption is the relaxation map for the pellet sample, which is
very close to that obtained for the single crystal with
comparable value of activation energies (Figure S13).
Optical Properties. Diffuse reflectance spectrum, pre-
sented in Figure S14, shows a band at 561 nm that, in analogy
with other 2D perovskites, can be attributed to excitonic
absorption.24 The excitonic absorption is among the most red-
shifted in the family of A2PbI4(100) layered perovskites. For
instance, other (100) perovskites with short separation of
inorganic layers exhibit the excitonic peaks at 553,21 544,24 and
53652 nm for CsGAPbI4, PyrEAPbI4, and EA2PbI4, respec-
tively, while for NBT2PbI4 and PEA2PbI4 with large separation
of inorganic layers, these peaks were observed at 513 and 517
nm, respectively (Table S6).58,62
The room-temperature diffuse reflectance spectrum was
used to determine the energy band gap (Eg) of MHy2PbI4 with
the Kubelka−Munk relation77
(1 − R )2
F (R ) =
2R
where R denotes reflectance. The graphical analysis of the
energy band gap from UV−vis reflectance transformed to
[F(R)hν]2 and plotted versus hν, which is presented in the
inset to Figure S14. The value of Eg in MHy2PbI4 is estimated
to be 563 nm (2.20 eV). For CsGAPbI4, GAMAPbI4,
PyrEAPbI4, 3AMPPbI4, 4AMPPbI4, and PEA2PbI4, the Eg
values are 2.35,21 2.27,20 2.48,24 2.23,27 2.38,27 and 2.7 eV,58
respectively (Table S6). As can be noted, MHy2PbI4 shows the
smallest energy of Eg among all A2PbI4 layered perovskites.
Interestingly, the band gap of MHy2PbI4 is smaller than the
band gap of CsGAPbI4 analogue, in spite of larger separation
between inorganic layers. According to former reports, smaller
distortion of the structure should lead to red shift of the band
gap.78 Inspection of the crystal structures shows that Pb−I−Pb
angles between the octahedral units are larger for MHy2PbI4
(170.3 and 180° at 305 K, Table 1) than CsGAPbI4 (149.74
and 165.19°).21 Thus, the red shift of Eg for MHy2PbI4
compared to CsGAPbI4 is consistent with more ideal Pb−I−
Pb bond angles.
PL spectra of MHy2PbI4 consist of two bands (Figures 7a
and S15). The P1 band, observed at 561 nm at RT, overlaps
with the excitonic absorption (Figure 7b) and exhibits weak
temperature dependence (Figure 8). Its FWHM is only 21
meV at 80 K (Figure 8). Such minimally Stokes shifted and
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Chemistry of Materials
Figure 7. (a) Temperature-dependent PL spectra measured every 10
K from 80 to 300 K, (b) normalized absorption and emission spectra,
(c) configuration coordinate diagram for FE and BE states, and (d)
temperature dependence of bands’ intensity (contour map).
Figure 8. Temperature dependence of band center positions and
FWHM for FE and BE bands.
narrow PL is characteristic of FE recombination.13,58,62,79 The
second broader band P2 is observed at 610 nm at RT, and this
band exhibits blue shift on cooling (to 573 nm at 80 K). Its
separation from the P1 band is only 12.3 nm (47 meV) at 80
K, but it increases to 49 nm (178 meV) at RT. Additional red-
shifted bands have been observed for many A 2 PbI 4
compounds, and they were usually attributed to bound
excitons,28,34 phonon replicas of the FE,33 and out-of-plane-
oriented magnetic dipole transition.80 Bound excitons were
found red-shifted at RT by around 32 nm for cystamine lead
iodide and 30 nm for PEA2PbI4.28,34 Furthermore, study of
PEA2PbI4 revealed significant blue shift of the BE PL on
cooling.34 The band assigned to phonon replica in trans-2,5-
dimethylpiperazinium lead iodide was red-shifted by 33 nm
and the separation from the FE band changed weakly on
cooling.33 In the case of butylammonium lead iodide, the band
red-shifted by 20 nm was attributed to the out-of-plane-
oriented magnetic dipole transition.80 The strong decrease of
the separation between P1 and P2 bands in MHy2PbI4 is not
consistent with phonon replica, but such behavior as well as
significantly larger width of the P2 band could indicate that this
emission comes from BE states. PL quantum yield (PLQY) of
MHy2PbI4 reaches 0.8% at RT. Such a low value of PLQY at
RT is typical for 2D iodides.33,34 We also studied PL
dependence on excitation intensity. The PL intensity of FE
and BE states increases linearly with excitation power density
from 4.97 to 92.2 mW cm−2 at 80 K (Figure S16). This result
indicates that the broader emission is not associated with any
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Article
permanent lattice defects but is intrinsic feature of the studied
sample.
Figures 7a, 9, and S15 show that intensity of the P1 and P2
bands decreases quickly on heating the sample, indicating that
Figure 9. (a) Temperature-dependent integrated intensities for P1
(FE) and P2 (BE) bands and (b) CIE coordinates of MHy2PbI4 at
different temperatures.
the thermal activation of nonradiative processes is activated at
higher temperatures. A closer inspection of the PL spectra
shows that PL intensity drops by nearly 92% when heating
from 80 to 220 K and to 0.8% at 290 K. Former studies of
EA2PbI4 and PEA2PbI4 showed a drop of about 30% at RT for
the latter compound and to almost zero near 220 K for
EA2PbI4.25 This behavior of MHy2PbI4 is intermediate
between that observed for PEA2PbI4 with strong dielectric
confinement and EA2PbI4 with strongly reduced dielectric
confinement. We can, therefore, suppose that the excitonic
activation energy of MHy2PbI4 is higher than the 13 meV value
found for EA2PbI4 and smaller than 250 meV found for
PEA2PbI4.25 To check this assumption, FE activation energy
has been estimated using temperature dependence of P1 band
intensity and assuming validity of the following equation
I0
I (T ) =
1 + e−Ea / kBT
where I0, Ea, and kB correspond to the emission intensity at low
temperature, activation energy, and Boltzmann constant. From
the fit of the low-temperature experimental data, approximate
activation energy of 59.2 meV was extracted for MHy2PbI4
(Figure S17). As expected, this value is among the smallest
found for A2PbI4 perovskites. It is also smaller than 96.5 meV
found for PyrEAPbI4, which showed a power conversion
efficiency of 1.43%.24 This behavior is consistent with short
separation between the inorganic layers (shorter than for
PyrEAPbI4 and EA2PbI4) and high dielectric constant of
MHy+. It is worth adding that although Ea may not correspond
exactly to the exciton binding energy, its small value suggests
that the exciton binding energy is also small. Indeed, according
to Cheng et al., for A2PbI4 compounds with organic cation
possessing dielectric constant of 22 (like methylhydrazine), the
exciton binding energy should be about 30 meV.25 Thus,
similarly to EA2PbI4, MHy2PbI4 also has significantly reduced
dielectric confinement, is more like a 3D perovskite in
character, and might be promising material for photovoltaic
applications.
PL of MHy2PbI4 is yellowish pink at RT with CIE
coordinate (0.43, 038) (Figure 9b). However, due to
significant shift of P2 band on cooling and different
temperature dependence of its intensity, chromacity exhibits
strong temperature dependence. That is, the color of the PL
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Chemistry of Materials
Figure 10. (a−c) Color maps present intensity of PL and lifetimes of MHy2PbI4 at 80, 193, and 233 K under excitation at 400 nm using
femtoseconds laser. (d−f) PL emission spectra at selected temperatures. (g−i) Emission decay curves for FE and BE bands at given temperatures.
changes with decreasing temperature to yellow-green at 80 K
(0.45, 0.54) (Figure 9b). MHy2PbI4 exhibits, therefore,
thermochromic properties. It is worth adding that significant
changes of the temperature-dependent emission intensity
indicate that this perovskite has high potential for noncontact
temperature sensing. The potential of the metal-organic
frameworks with perovskite-type architecture for noncontact
thermometry has been recently reported by Ptak et al. for
formate-based materials.81
To further understand the origin of PL bands, we have also
performed femtosecond-time-resolved measurements at vari-
ous temperatures (from 80 to 233 K) under 400 nm excitation
line generated by femtoseconds laser. Two bands were
observed (Figures 10 and S18). It can be seen that at 80 K,
the emission at 560 nm decays very quickly (0.37 ns) while
that at 573 nm relaxes more slowly (0.46 ns) (Figures 10g−i,
S19, and S20). Former study of cystamine lead iodide showed
that the decay time was slightly longer for BE (0.81 ns) than
FE emission (0.51 ns).28 On the other hand, the decay times of
the FE and red-shifted band of trans-2,5-dimethylpiperazinium
lead iodide, assigned to phonon replica, were very similar (0.24
nm).33 The same decay times were also reported for the FE
and red-shifted band in butylammonium lead iodide attributed
to out-of-plane-oriented magnetic dipole transition (0.296
ns).80 Thus, decay times of MHy2PbI4 are consistent with
assignment of the P2 band to weakly bound exciton. With
increasing temperature, the decay times of both emissions in
MHy2PbI4 increase to 0.70 ns, i.e., they are significantly longer
than the lifetimes of 3AMPPbI4, 4AMPPbI4, and PEA2PbI4
(0.08, 0.04, and 0.17 ns, respectively).27,82 This indicates
slower carrier combination in MHy2PbI4, which is beneficial
for photovoltaic applications. It is worth adding that the
lifetimes of MHy2PbI4 are comparable to the lifetime of
PyrEAPbI4(100) perovskite (0.41 ns) that has been recently
shown to be promising solar cell material with a power
conversion efficiency of 1.43%.24
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■ CONCLUSIONS
We report the synthesis of 2D lead iodide with single-
octahedra slabs of MHy2PbI4 composition. This compound has
the smallest organic cation among all reported A2PbI4
compounds, and we show that this feature leads to unusual
properties of this material. First, interoctahedral distortion of
the inorganic lattice in MHy2PbI4 is among the smallest among
A2PbI4 perovskites. Due to this feature and high dielectric
constant of organic layers, MHy2PbI4 shows exceptionally
small band gap and is expected to exhibit strongly reduced
dielectric confinement. Second, Raman studies have revealed
that this compound shows significantly higher dynamic
disorder than 2D A2PbI4 analogues with larger organic cations.
Similarity of the dynamic behavior to 3D analogues can be
attributed to small separation between the lead iodide layers
and strong HBs mediated coupling between inorganic and
organic layers. Third, MHy2PbI4 shows two narrower bands in
the 560−610 nm range that exhibit strong change in intensity
in the 80−300 K range. Furthermore, the red-shifted band
exhibits pronounced blue shift on cooling. Thus, MHy2PbI4
shows thermochromic behavior. Fourth, MHy2PbI4 shows
switchable dielectric behavior related to an order−disorder
phase transition at 298 K. It also exhibits ionic conductivity
that is however an order of magnitude smaller than the
conductivity of famous MAPbI3 perovskite.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.chemma-
ter.9b03775.
Crystal data; selected geometrical and hydrogen-bond
parameters for the studied compound at different
temperatures; structural and optical parameters for
selected A2PbI4(100) perovskites; and Raman wave-
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Chem. Mater. 2019, 31, 8563−8575
Chemistry of Materials
numbers together with the proposed assignments
(Tables S1−S7); powder XRD pattern; DSC traces;
TGA plot; reconstruction of hk2 reciprocal layer and 2D
profiles; hydrogen-bond interactions; Raman spectra;
temperature dependence of Raman wavenumbers;
FWHM values and dielectric permittivity; map of
dipolar relaxation process; diffuse reflectance spectrum;
PL spectra; power dependence of PL; temperature-
dependent decay times (Figures S1−S20) (PDF)
CIF files for structures at 100 K (CIF)
CIF files for structures at 280 K (CIF)
CIF files for structures at 305 K (CIF)
CIF files for structures at 330 K (CIF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: m.maczka@int.pan.wroc.pl. Phone: +48-713954161.
Fax: +48-713441029.
ORCID
Mirosław Mączka: 0000-0003-2978-1093
Maciej Ptak: 0000-0002-4639-2367
Adam Sieradzki: 0000-0003-4136-5754
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
■
REFERENCES
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