Depressed Phase Transitions and Thermally Persistent Local Distortions in CsPbBr3 Quantum Dots
Abstract
The optoelectronic properties of CsPbX3 quantum dots (where X = Cl, Br, or I) are influenced by both their local and average structures. Variable-temperature synchrotron X-ray diffraction measurements of CsPbBr3 quantum dots show that the temperatures for both the orthorhombic-to-tetragonal (50 °C < Tγ-β < 59 °C) and tetragonal-to-cubic (108 °C < Tβ-α < 117 °C) phase transitions of the average structure are depressed relative to their temperatures in bulk CsPbBr3. Simultaneously, pair distribution function (PDF) analysis of syn-chrotron X-ray total scattering measurements indicate that the local crystal structure of the quantum dots is best described as ortho-rhombically distorted over the temperature range of 22 °C < T < 160 °C, with only small changes in the magnitude of the distortion occurring during the observed changes in the average structure. Here, taken together these results suggest that phase transitions in CsPbBr3 quantum dots are order-disorder, involving the gradual ordering of individually coherent domains that cannot be attributed to changes in the surface area or to ferroelectric phenomena.
- Authors:
-
- Univ. of Southern California, Los Angeles, CA (United States)
- Publication Date:
- Research Org.:
- Univ. of Southern California, Los Angeles, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1582648
- Grant/Contract Number:
- SC0006812; FG02-11ER4682; AC02-06CH11357; DMR 1720256
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 30; Journal Issue: 19; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Cottingham, Patrick, and Brutchey, Richard L. Depressed Phase Transitions and Thermally Persistent Local Distortions in CsPbBr3 Quantum Dots. United States: N. p., 2018.
Web. doi:10.1021/acs.chemmater.8b02295.
Cottingham, Patrick, & Brutchey, Richard L. Depressed Phase Transitions and Thermally Persistent Local Distortions in CsPbBr3 Quantum Dots. United States. https://doi.org/10.1021/acs.chemmater.8b02295
Cottingham, Patrick, and Brutchey, Richard L. Sat .
"Depressed Phase Transitions and Thermally Persistent Local Distortions in CsPbBr3 Quantum Dots". United States. https://doi.org/10.1021/acs.chemmater.8b02295. https://www.osti.gov/servlets/purl/1582648.
@article{osti_1582648,
title = {Depressed Phase Transitions and Thermally Persistent Local Distortions in CsPbBr3 Quantum Dots},
author = {Cottingham, Patrick and Brutchey, Richard L.},
abstractNote = {The optoelectronic properties of CsPbX3 quantum dots (where X = Cl, Br, or I) are influenced by both their local and average structures. Variable-temperature synchrotron X-ray diffraction measurements of CsPbBr3 quantum dots show that the temperatures for both the orthorhombic-to-tetragonal (50 °C < Tγ-β < 59 °C) and tetragonal-to-cubic (108 °C < Tβ-α < 117 °C) phase transitions of the average structure are depressed relative to their temperatures in bulk CsPbBr3. Simultaneously, pair distribution function (PDF) analysis of syn-chrotron X-ray total scattering measurements indicate that the local crystal structure of the quantum dots is best described as ortho-rhombically distorted over the temperature range of 22 °C < T < 160 °C, with only small changes in the magnitude of the distortion occurring during the observed changes in the average structure. Here, taken together these results suggest that phase transitions in CsPbBr3 quantum dots are order-disorder, involving the gradual ordering of individually coherent domains that cannot be attributed to changes in the surface area or to ferroelectric phenomena.},
doi = {10.1021/acs.chemmater.8b02295},
journal = {Chemistry of Materials},
number = 19,
volume = 30,
place = {United States},
year = {Sat Sep 08 00:00:00 EDT 2018},
month = {Sat Sep 08 00:00:00 EDT 2018}
}
Web of Science
Works referenced in this record:
Nanocrystals of Cesium Lead Halide Perovskites (CsPbX 3 , X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut
journal, February 2015
- Protesescu, Loredana; Yakunin, Sergii; Bodnarchuk, Maryna I.
- Nano Letters, Vol. 15, Issue 6
Colloidal lead halide perovskite nanocrystals: synthesis, optical properties and applications
journal, November 2016
- Huang, He; Polavarapu, Lakshminarayana; Sichert, Jasmina A.
- NPG Asia Materials, Vol. 8, Issue 11
Structural and electronic properties of organo-halide lead perovskites: a combined IR-spectroscopy and ab initio molecular dynamics investigation
journal, January 2014
- Mosconi, Edoardo; Quarti, Claudio; Ivanovska, Tanja
- Phys. Chem. Chem. Phys., Vol. 16, Issue 30
Structural and optical properties of methylammonium lead iodide across the tetragonal to cubic phase transition: implications for perovskite solar cells
journal, January 2016
- Quarti, Claudio; Mosconi, Edoardo; Ball, James M.
- Energy & Environmental Science, Vol. 9, Issue 1
Temperature-dependent photoluminescence of inorganic perovskite nanocrystal films
journal, January 2016
- Li, Jiaming; Yuan, Xi; Jing, Pengtao
- RSC Advances, Vol. 6, Issue 82
High-Temperature Photoluminescence of CsPbX 3 (X = Cl, Br, I) Nanocrystals
journal, March 2017
- Diroll, Benjamin T.; Nedelcu, Georgian; Kovalenko, Maksym V.
- Advanced Functional Materials, Vol. 27, Issue 21
Crystal Growth of the Perovskite Semiconductor CsPbBr 3 : A New Material for High-Energy Radiation Detection
journal, June 2013
- Stoumpos, Constantinos C.; Malliakas, Christos D.; Peters, John A.
- Crystal Growth & Design, Vol. 13, Issue 7
On the crystal structure of colloidally prepared CsPbBr 3 quantum dots
journal, January 2016
- Cottingham, Patrick; Brutchey, Richard L.
- Chemical Communications, Vol. 52, Issue 30
Melting in Semiconductor Nanocrystals
journal, June 1992
- Goldstein, A. N.; Echer, C. M.; Alivisatos, A. P.
- Science, Vol. 256, Issue 5062, p. 1425-1427
Size Dependence of a First Order Solid-Solid Phase Transition: The Wurtzite to Rock Salt Transformation in CdSe Nanocrystals
journal, July 1994
- Tolbert, S. H.; Alivisatos, A. P.
- Science, Vol. 265, Issue 5170
Size-induced transition-temperature reduction in nanoparticles of ZnS
journal, October 1999
- Qadri, S. B.; Skelton, E. F.; Hsu, D.
- Physical Review B, Vol. 60, Issue 13
Size Dependence of a Temperature-Induced Solid–Solid Phase Transition in Copper(I) Sulfide
journal, September 2011
- Rivest, Jessy B.; Fong, Lam-Kiu; Jain, Prashant K.
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 19
Solution-Based Synthesis and Characterization of Cu 2 ZnSnS 4 Nanocrystals
journal, September 2009
- Riha, Shannon C.; Parkinson, Bruce A.; Prieto, Amy L.
- Journal of the American Chemical Society, Vol. 131, Issue 34
Colloidal CsPbBr 3 Perovskite Nanocrystals: Luminescence beyond Traditional Quantum Dots
journal, November 2015
- Swarnkar, Abhishek; Chulliyil, Ramya; Ravi, Vikash Kumar
- Angewandte Chemie International Edition, Vol. 54, Issue 51
Coherent Nanotwins and Dynamic Disorder in Cesium Lead Halide Perovskite Nanocrystals
journal, April 2017
- Bertolotti, Federica; Protesescu, Loredana; Kovalenko, Maksym V.
- ACS Nano, Vol. 11, Issue 4
Compositionally Dependent Phase Identity of Colloidal CsPbBr 3– x I x Quantum Dots
journal, October 2016
- Cottingham, Patrick; Brutchey, Richard L.
- Chemistry of Materials, Vol. 28, Issue 21
Perspectives on the Physical Chemistry of Semiconductor Nanocrystals
journal, January 1996
- Alivisatos, A. P.
- The Journal of Physical Chemistry, Vol. 100, Issue 31
High-Pressure Structural Transformations in Semiconductor Nanocrystals
journal, October 1995
- Tolbert, Sarah H.; Alivisatos, A. P.
- Annual Review of Physical Chemistry, Vol. 46, Issue 1
Pressure-Induced Structural and Optical Properties of Inorganic Halide Perovskite CsPbBr 3
journal, July 2017
- Zhang, Long; Zeng, Qingxin; Wang, Kai
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 16
Pressure Effects on Structure and Optical Properties in Cesium Lead Bromide Perovskite Nanocrystals
journal, July 2017
- Xiao, Guanjun; Cao, Ye; Qi, Guangyu
- Journal of the American Chemical Society, Vol. 139, Issue 29
Size effect on the ferroelectric phase transition in ultrafine particles
journal, April 1988
- Ishikawa, Kenji; Yoshikawa, Kazutoshi; Okada, Nagaya
- Physical Review B, Vol. 37, Issue 10
Dependence of the Crystal Structure on Particle Size in Barium Titanate
journal, August 1989
- Uchino, Kenji; Sadanaga, Eiji; Hirose, Terukiyo
- Journal of the American Ceramic Society, Vol. 72, Issue 8
Size-dependent phase transition in methylammonium lead iodide perovskite microplate crystals
journal, April 2016
- Li, Dehui; Wang, Gongming; Cheng, Hung-Chieh
- Nature Communications, Vol. 7, Issue 1
Inhibition of a structural phase transition in one-dimensional organometal halide perovskite nanorods grown inside porous silicon nanotube templates
journal, February 2017
- Arad-Vosk, N.; Rozenfeld, N.; Gonzalez-Rodriguez, R.
- Physical Review B, Vol. 95, Issue 8
The Impact of Phase Retention on the Structural and Optoelectronic Properties of Metal Halide Perovskites
journal, October 2016
- Osherov, Anna; Hutter, Eline M.; Galkowski, Krzysztof
- Advanced Materials, Vol. 28, Issue 48
Size-Dependent Polar Ordering in Colloidal GeTe Nanocrystals
journal, March 2011
- Polking, Mark J.; Urban, Jeffrey J.; Milliron, Delia J.
- Nano Letters, Vol. 11, Issue 3
Applications of an amorphous silicon-based area detector for high-resolution, high-sensitivity and fast time-resolved pair distribution function measurements
journal, May 2007
- Chupas, Peter J.; Chapman, Karena W.; Lee, Peter L.
- Journal of Applied Crystallography, Vol. 40, Issue 3
Spontaneous Octahedral Tilting in the Cubic Inorganic Cesium Halide Perovskites CsSnX 3 and CsPbX 3 (X = F, Cl, Br, I)
journal, September 2017
- Yang, Ruo Xi; Skelton, Jonathan M.; da Silva, E. Lora
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 19
EXPGUI , a graphical user interface for GSAS
journal, April 2001
- Toby, Brian H.
- Journal of Applied Crystallography, Vol. 34, Issue 2
PDFgetX3 : a rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions
journal, March 2013
- Juhás, P.; Davis, T.; Farrow, C. L.
- Journal of Applied Crystallography, Vol. 46, Issue 2
PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals
journal, July 2007
- Farrow, C. L.; Juhas, P.; Liu, J. W.
- Journal of Physics: Condensed Matter, Vol. 19, Issue 33
Works referencing / citing this record:
Electronic structure of CsPbBr 3−x Cl x perovskites: synthesis, experimental characterization, and DFT simulations
journal, January 2019
- Liashenko, Tatiana G.; Cherotchenko, Evgeniia D.; Pushkarev, Anatoly P.
- Physical Chemistry Chemical Physics, Vol. 21, Issue 35
Photoinduced, reversible phase transitions in all-inorganic perovskite nanocrystals
journal, January 2019
- Kirschner, Matthew S.; Diroll, Benjamin T.; Guo, Peijun
- Nature Communications, Vol. 10, Issue 1
Dual phases of crystalline and electronic structures in the nanocrystalline perovskite CsPbBr3
journal, November 2019
- Whitcher, T. J.; Gomes, L. C.; Zhao, D.
- NPG Asia Materials, Vol. 11, Issue 1
Low-energy paths for octahedral tilting in inorganic halide perovskites
journal, March 2019
- Klarbring, Johan
- Physical Review B, Vol. 99, Issue 10
Low energy paths for octahedral tilting in inorganic halide perovskites
text, January 2018
- Klarbring, Johan
- arXiv
Composition, Size, and Surface Functionalization dependent Optical Properties of Lead Bromide Perovskite Nanocrystals
text, January 2020
- Ijaz, Palvasha; Imran, Muhammad; Soares, Márcio M.
- arXiv