Observation of `hyperfine multistage transition' at the 320 K phase transition in CsPbCl3

Tozaki, Ken–ichi; Ishii, Chiaki; Kojima, Akira; Yoshimura, Yukio; Izuhara, O.; Yamada, Kozo; Iwasaki, Hiroshi; Noda, Yasutoshi; Harada, J.

doi:10.1016/s0375-9601(99)00680-5

Cited by 11 publications

(6 citation statements)

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“…[ 27 ] are strongly different with all the rest of published experimental results ([ 12 ] and refs therein). The red shift reported in Figure 6 a–c highlights a change in the band gap energy, which is possibly related to the phase transitions that are reported for CsPbCl 3 in the T range (300–330 K) [ 13 , 14 , 15 , 16 ]. Quite remarkable is also the observation (see Figure 6 c) of a similar red shift at room temperature when the excitation density is changed, the generated electron–hole pair density in the range 10 17 –10 20 cm −3 , and the absence of shift in the temperature range around 315 K where phase transitions are reported for CsPbCl 3 .…”

Section: Discussionmentioning

confidence: 76%

“…By an exponential fit of the Urbach tail, we evaluate the Urbach energy E U . The dependence of E U on the temperature is shown in Figure 11 b where the red arrows indicate the temperatures where the phase transitions are reported in the literature [ 13 , 16 , 21 , 30 ]. A flattening in the Urbach energy is found in a restricted temperature interval around each phase transition: such behavior represents a significant deviation from what was found and expected, considering the origin of the Urbach tail in halide perovskites related to the dynamic disorder induced by the lattice vibration [ 26 ].…”

Section: Discussionmentioning

confidence: 99%

“…Of course, the values of T at which transition from monoclinic-tetragonal-cubic lattice occurs depend on the specific kind of perovskite. For CsPbCl 3 bulk samples, a few phase transitions have been reported by several authors using different techniques (Raman spectra, X-ray diffraction studies, heat flow) in the temperature range 310–320 K [ 14 , 15 , 16 , 17 ]. In this work, we investigate the correlation between the structural phase transition and the optical/electrical characteristics of CsPbCl 3 thin films realized by RF magnetron sputtering.…”

Section: Introductionmentioning

confidence: 99%

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Electrical and Optical Characterization of CsPbCl3 Films around the High-Temperature Phase Transitions

et al. 2022

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Large-area CsPbCl3 films in the range 0.1–1.5 μm have been grown by radio frequency (RF)-magnetron sputtering on glass substrates by means of a one-step procedure. Three structural phase transitions have been detected, which are associated with hysteresis behavior in the electrical current when measured as a function of temperature in the range 295–330 K. Similarly, photoluminescence (PL) experiments in the same temperature range bring evidence of a non-monotonic shift of the PL peak. Detailed electrical characterizations evidenced how phase transitions are not influencing detrimentally the electrical transport properties of the films. In particular, the activation energy (0.6–0.8 eV) extracted from the temperature-dependent film resistivity does not appear to be correlated with phase changes. A non-linear trend of the photoconductivity response as a function of a ultra violet (UV) 365 nm light emitting diode (LED) power has been interpreted considering the presence of an exponential tail of intragap defects. Thermally stimulated currents after exposure with the same LED measured from room temperature up to 370 K showed no evidence of trapping effects due to intragap states on the electrical transport properties at room temperature of the films. As a consequence, measured photocurrents at room temperature appear to be well reproducible and stable in time, which are attractive features for possible future applications in photodetection.

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Section: Discussionmentioning

confidence: 76%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electrical and Optical Characterization of CsPbCl3 Films around the High-Temperature Phase Transitions

et al. 2022

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“…Indeed, a perovskite-like structure is observed at room temperature only for CsPbCl 3 and CsPbBr 3 . They were shown to possess relatively weak orthorhombic distortions, which are released upon heating. − Thus, both CsPbCl 3 and CsPbBr 3 are cubic perovskites at above 320 and 403 K, respectively. − The values of heat of transition from the orthorhombic to cubic phase still remain somewhat uncertain since those reported by different authors range from 0.229 to 0.795 kJ·mol –1 for CsPbCl 3 ,, and lie almost in the same range for CsPbBr 3 . , However, it is clear that such heat effects, corresponding to the weak distortions of the perovskite structure due to rotations of octahedra and atomic displacements, are, expectedly, quite lowless than 1 kJ·mol –1 . ,,,, At the same time, the δ phase of CsPbI 3 , which is the one stable at room temperature, is not a perovskite phase. ,, It transforms into cubic perovskite at temperatures higher than ≈593 K. ,,, The enthalpy values of this transition, reported by Dastidar et al, 14.2 ± 0.5 kJ·mol –1 , and Wang et al, 14.10 ± 0.24 kJ·mol –1 , are in good agreement with each other and are significantly larger than the transition enthalpies of chloride and bromide.…”

Section: Resultsmentioning

confidence: 99%

Formation Thermodynamics, Stability, and Decomposition Pathways of CsPbX₃ (X = Cl, Br, I) Photovoltaic Materials

et al. 2020

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Standard enthalpies of formation of CsPbX3 (X = Cl, Br, I) perovskites from halides and from elements at 298 K were measured using solution calorimetry. Intrinsic and extrinsic stabilities of CsPbX3 halides were analyzed and compared with those of CH3NH3PbX3. The main difference between the stabilities of CsPbX3 and CH3NH3PbX3 halides was found to stem from the different chemical natures of cesium and methylammonium cations. Indeed, the enthalpies of formation of CsPbX3 from binary constituent halides, Δf H°hal, are only slightly more negative than those of CH3NH3PbX3. Small values of Δf H°hal imply that the entropic contribution to the Gibbs free energy of the formation of CsPbX3 and CH3NH3PbX3 is significant and, hence, of utmost importance for understanding the intrinsic stability of these compounds and their analogues. Regarding the extrinsic stability, the presence of gaseous O2, H2O, and CO2 was shown to be crucial for the stability of the iodide, CsPbI3, for which several decomposition reactions, exergonic at 298 K, were identified. At the same time, chloride, CsPbCl3, and bromide, CsPbBr3, are much less sensitive to these chemical agents. However, liquid water should degrade all of the CsPbX3 halides.

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“…We have shown that BaTiO 3 reveals an inevitable transient process with a nearly quasi-static temperature change. It is thought that the cooling process with an infinitesimally small temperature change shows more complicated features than the simple heating process for crystals of three components such as BaTiO 3 and CsPbCl 3 [8,9]. A new feature of the 403 K transition in BaTiO 3 has been determined by the present measurements.…”

Section: Discussionmentioning

confidence: 65%

Simultaneous Measurements of Thermal, Electrical, and Acoustic Properties of BaTiO3 – New Feature of 403 K Phase Transition

et al. 2005

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In order to obtain useful information on the transient process of phase transitions in ferroelectrics by various methods including calorimetry, the "mK-stabilized cell" of a small size has been developed. It is based on the heat flux differential scanning calorimeter (DSC) and has a temperature stability better than 1 mK. The "cell" can be used to change the temperature under nearly quasi-static conditions by an infinitesimally small rate not only on heating but also on cooling while passing through the transition points. It enables simultaneous measurements of endothermic heat and exothermic heat along with dielectric constants, displacement currents, etc. with a high degree of temperature resolution. X-ray diffraction measurements for sensing thermal anomalies are also possible by a minor modification of the "cell." Precise and simultaneous measurements of thermal, electrical, and acoustic properties were carried out at the 403 K phase transition in BaTiO 3 single crystal grown by the top-seeded solution growth method. It has been clarified that the exothermic heat at the transition on cooling has more useful information than the endothermic heat on heating; in the cooling process two thermal anomalies occur separately at T 1 and T 2 although the transition is in a narrow temperature range. It is recognized from other methods that the nature of the 1 1964 Kojima et al.transition on cooling is not of a single but of multiple steps. Resonant ultrasonic measurements using the "cell" were carried out, after developing a new excitation method. The sample does not have a simple softening approaching the transition point on cooling but has different elastic moduli for the two thermal anomalies at T 1 and T 2 . The dielectric constant also has an intermediate constant value between T 1 and T 2 . The crystal structure in the room temperature phase below the transition point has been determined by X-ray diffraction. In this region, tetragonal and monoclinic structures coordinating with each other exist.

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Observation of `hyperfine multistage transition' at the 320 K phase transition in CsPbCl3

Cited by 11 publications

References 16 publications

Electrical and Optical Characterization of CsPbCl3 Films around the High-Temperature Phase Transitions

Electrical and Optical Characterization of CsPbCl3 Films around the High-Temperature Phase Transitions

Formation Thermodynamics, Stability, and Decomposition Pathways of CsPbX₃ (X = Cl, Br, I) Photovoltaic Materials

Simultaneous Measurements of Thermal, Electrical, and Acoustic Properties of BaTiO3 – New Feature of 403 K Phase Transition

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Observation of `hyperfine multistage transition' at the 320 K phase transition in CsPbCl3

Cited by 11 publications

References 16 publications

Electrical and Optical Characterization of CsPbCl3 Films around the High-Temperature Phase Transitions

Electrical and Optical Characterization of CsPbCl3 Films around the High-Temperature Phase Transitions

Formation Thermodynamics, Stability, and Decomposition Pathways of CsPbX3 (X = Cl, Br, I) Photovoltaic Materials

Simultaneous Measurements of Thermal, Electrical, and Acoustic Properties of BaTiO3 – New Feature of 403 K Phase Transition

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Formation Thermodynamics, Stability, and Decomposition Pathways of CsPbX₃ (X = Cl, Br, I) Photovoltaic Materials