Dynamic Evolution of 2D Layers within Perovskite Nanocrystals via Salt Pair Extraction and Reinsertion
Abstract
Metal halide perovskite (MHP) semiconductors exhibit unprecedented optoelectronic properties coupled with low formation energies that enable scalable, cost-efficient solution processing. The low formation energies additionally facilitate dynamic transformation of the chemical composition and crystal structure of the MHP material. In this work, we show that CsBr salt is selectively extracted from CsPbBr3 nanocrystals (NCs) to yield PbBr2 NCs. The PbBr2 NCs are then exposed to different glacial acetic acid ABr salt solutions to generate a variety of emissive compounds with the generic structure A'2An-1PbnBr3n-1X'2, where A = cesium (Cs+), methylammonium (MA+), formamidinium (FA+); A' = A or H+; X' = Br- or acetate (CH3COO-); and n is the number of lead halide layers, where n = 1, 2, 3, ...8. We systematically vary the ratios of PbBr2/ABr/CH3COOH and show that certain ratios result in isolable single-phase APbBr3 NCs - an effective A-site cation exchange from the parent CsPbBr3 NCs. Importantly, time-resolved photoluminescence (PL) spectroscopy shows the dynamic evolution of many additional species as evidenced by blue-shifted emission peaks from 2.85-2.49 eV for MA+-based structures. We assign these species to n = 1, 2, 3, 4, and 5 quasi-two-dimensional network (2DN) sheets, in which CH3COO- anions and Br- anions compete formore »
- Authors:
-
[3];
[1]
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Florida, Gainesville, FL (United States)
- National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Southern Illinois, Carbondale, IL (United States)
- Publication Date:
- Research Org.:
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1456865
- Report Number(s):
- NREL/JA-5900-70903
Journal ID: ISSN 1932-7447
- Grant/Contract Number:
- AC36-08GO28308
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 122; Journal Issue: 25; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 14 SOLAR ENERGY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; layered perovskite; perovskite nanocrystal; two-dimensional semiconductors; two-dimensional network; cation exchange; quantum confinement
Citation Formats
Wheeler, Lance M., Anderson, Nicholas C., Bliss, Taylor S., Hautzinger, Matthew P., and Neale, Nathan R. Dynamic Evolution of 2D Layers within Perovskite Nanocrystals via Salt Pair Extraction and Reinsertion. United States: N. p., 2018.
Web. doi:10.1021/acs.jpcc.8b01164.
Wheeler, Lance M., Anderson, Nicholas C., Bliss, Taylor S., Hautzinger, Matthew P., & Neale, Nathan R. Dynamic Evolution of 2D Layers within Perovskite Nanocrystals via Salt Pair Extraction and Reinsertion. United States. https://doi.org/10.1021/acs.jpcc.8b01164
Wheeler, Lance M., Anderson, Nicholas C., Bliss, Taylor S., Hautzinger, Matthew P., and Neale, Nathan R. Sat .
"Dynamic Evolution of 2D Layers within Perovskite Nanocrystals via Salt Pair Extraction and Reinsertion". United States. https://doi.org/10.1021/acs.jpcc.8b01164. https://www.osti.gov/servlets/purl/1456865.
@article{osti_1456865,
title = {Dynamic Evolution of 2D Layers within Perovskite Nanocrystals via Salt Pair Extraction and Reinsertion},
author = {Wheeler, Lance M. and Anderson, Nicholas C. and Bliss, Taylor S. and Hautzinger, Matthew P. and Neale, Nathan R.},
abstractNote = {Metal halide perovskite (MHP) semiconductors exhibit unprecedented optoelectronic properties coupled with low formation energies that enable scalable, cost-efficient solution processing. The low formation energies additionally facilitate dynamic transformation of the chemical composition and crystal structure of the MHP material. In this work, we show that CsBr salt is selectively extracted from CsPbBr3 nanocrystals (NCs) to yield PbBr2 NCs. The PbBr2 NCs are then exposed to different glacial acetic acid ABr salt solutions to generate a variety of emissive compounds with the generic structure A'2An-1PbnBr3n-1X'2, where A = cesium (Cs+), methylammonium (MA+), formamidinium (FA+); A' = A or H+; X' = Br- or acetate (CH3COO-); and n is the number of lead halide layers, where n = 1, 2, 3, ...8. We systematically vary the ratios of PbBr2/ABr/CH3COOH and show that certain ratios result in isolable single-phase APbBr3 NCs - an effective A-site cation exchange from the parent CsPbBr3 NCs. Importantly, time-resolved photoluminescence (PL) spectroscopy shows the dynamic evolution of many additional species as evidenced by blue-shifted emission peaks from 2.85-2.49 eV for MA+-based structures. We assign these species to n = 1, 2, 3, 4, and 5 quasi-two-dimensional network (2DN) sheets, in which CH3COO- anions and Br- anions compete for the c-axis X' sites separating haloplumbate(II) layers within the A'2An-1PbnBr3n-1X'2 NCs. Finally, we demonstrate the degree of CH3COO- incorporation, and thus the 2DN layer thickness and PL energy, is controlled in the early reaction times by kinetic factors. After a longer time (3 h), thermodynamic forces dictated by Le Chatelier's principle tune the structure in A'2An-1PbnBr3n-1X'2 NCs from exclusively n = 1 to n = 8 depending on the PbBr2/ABr/CH3COOH ratio.},
doi = {10.1021/acs.jpcc.8b01164},
journal = {Journal of Physical Chemistry. C},
number = 25,
volume = 122,
place = {United States},
year = {2018},
month = {4}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 7 works
Citation information provided by
Web of Science
Web of Science
Figures / Tables:
Scheme1.: Transformations of MHP NCs Based on CsBr Salt Extraction from CsPbBr3 NCs to Form PbBr2 NCs that Are Re-formed into A′2An−1PbnBr3n−1X′2 NCs via A′X′ Additiona
All figures and tables
(5 total)
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Metal halide perovskites for energy applications
journal, May 2016
- Zhang, Wei; Eperon, Giles E.; Snaith, Henry J.
- Nature Energy, Vol. 1, Issue 6
Tailored interfaces of unencapsulated perovskite solar cells for >1,000 hour operational stability
journal, January 2018
- Christians, Jeffrey A.; Schulz, Philip; Tinkham, Jonathan S.
- Nature Energy, Vol. 3, Issue 1
Iodide management in formamidinium-lead-halide–based perovskite layers for efficient solar cells
journal, June 2017
- Yang, Woon Seok; Park, Byung-Wook; Jung, Eui Hyuk
- Science, Vol. 356, Issue 6345
Enhanced mobility CsPbI 3 quantum dot arrays for record-efficiency, high-voltage photovoltaic cells
journal, October 2017
- Sanehira, Erin M.; Marshall, Ashley R.; Christians, Jeffrey A.
- Science Advances, Vol. 3, Issue 10
Low-threshold amplified spontaneous emission and lasing from colloidal nanocrystals of caesium lead halide perovskites
journal, August 2015
- Yakunin, Sergii; Protesescu, Loredana; Krieg, Franziska
- Nature Communications, Vol. 6, Issue 1
Bright triplet excitons in caesium lead halide perovskites
journal, January 2018
- Becker, Michael A.; Vaxenburg, Roman; Nedelcu, Georgian
- Nature, Vol. 553, Issue 7687
Controlled Alloying of the Core–Shell Interface in CdSe/CdS Quantum Dots for Suppression of Auger Recombination
journal, April 2013
- Bae, Wan Ki; Padilha, Lazaro A.; Park, Young-Shin
- ACS Nano, Vol. 7, Issue 4
Highly Luminescent Phase-Stable CsPbI 3 Perovskite Quantum Dots Achieving Near 100% Absolute Photoluminescence Quantum Yield
journal, September 2017
- Liu, Feng; Zhang, Yaohong; Ding, Chao
- ACS Nano, Vol. 11, Issue 10
Essentially Trap-Free CsPbBr 3 Colloidal Nanocrystals by Postsynthetic Thiocyanate Surface Treatment
journal, May 2017
- Koscher, Brent A.; Swabeck, Joseph K.; Bronstein, Noah D.
- Journal of the American Chemical Society, Vol. 139, Issue 19
Near-Unity Photoluminescence Quantum Yield in CsPbBr 3 Nanocrystal Solid-State Films via Postsynthesis Treatment with Lead Bromide
journal, September 2017
- Di Stasio, Francesco; Christodoulou, Sotirios; Huo, Nengjie
- Chemistry of Materials, Vol. 29, Issue 18
Quantum dot-induced phase stabilization of -CsPbI3 perovskite for high-efficiency photovoltaics
journal, October 2016
- Swarnkar, A.; Marshall, A. R.; Sanehira, E. M.
- Science, Vol. 354, Issue 6308
Structural and chemical evolution of methylammonium lead halide perovskites during thermal processing from solution
journal, January 2016
- Nenon, David P.; Christians, Jeffrey A.; Wheeler, Lance M.
- Energy & Environmental Science, Vol. 9, Issue 6
Switchable photovoltaic windows enabled by reversible photothermal complex dissociation from methylammonium lead iodide
journal, November 2017
- Wheeler, Lance M.; Moore, David T.; Ihly, Rachelle
- Nature Communications, Vol. 8, Issue 1
Fast Anion-Exchange in Highly Luminescent Nanocrystals of Cesium Lead Halide Perovskites (CsPbX 3 , X = Cl, Br, I)
journal, July 2015
- Nedelcu, Georgian; Protesescu, Loredana; Yakunin, Sergii
- Nano Letters, Vol. 15, Issue 8
Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions
journal, August 2015
- Akkerman, Quinten A.; D’Innocenzo, Valerio; Accornero, Sara
- Journal of the American Chemical Society, Vol. 137, Issue 32
Anion charge storage through oxygen intercalation in LaMnO3 perovskite pseudocapacitor electrodes
journal, June 2014
- Mefford, J. Tyler; Hardin, William G.; Dai, Sheng
- Nature Materials, Vol. 13, Issue 7
B-Site Metal Cation Exchange in Halide Perovskites
journal, April 2017
- Eperon, Giles E.; Ginger, David S.
- ACS Energy Letters, Vol. 2, Issue 5
Highly Emissive Divalent-Ion-Doped Colloidal CsPb 1– x M x Br 3 Perovskite Nanocrystals through Cation Exchange
journal, March 2017
- van der Stam, Ward; Geuchies, Jaco J.; Altantzis, Thomas
- Journal of the American Chemical Society, Vol. 139, Issue 11
Postsynthetic, Reversible Cation Exchange between Pb 2+ and Mn 2+ in Cesium Lead Chloride Perovskite Nanocrystals
journal, September 2017
- Gao, Di; Qiao, Bo; Xu, Zheng
- The Journal of Physical Chemistry C, Vol. 121, Issue 37
Stabilizing Perovskite Structures by Tuning Tolerance Factor: Formation of Formamidinium and Cesium Lead Iodide Solid-State Alloys
journal, December 2015
- Li, Zhen; Yang, Mengjin; Park, Ji-Sang
- Chemistry of Materials, Vol. 28, Issue 1
Cation exchange for thin film lead iodide perovskite interconversion
journal, January 2016
- Eperon, Giles E.; Beck, Clara E.; Snaith, Henry J.
- Materials Horizons, Vol. 3, Issue 1
Synthesis of formamidinium lead halide perovskite nanocrystals through solid–liquid–solid cation exchange
journal, January 2017
- Hills-Kimball, K.; Nagaoka, Y.; Cao, C.
- Journal of Materials Chemistry C, Vol. 5, Issue 23
Intercalation Behavior of n -Alkylamines into a Protonated Form of a Layered Perovskite Derived from Aurivillius Phase Bi 2 SrTa 2 O 9
journal, February 2003
- Tsunoda, Yu; Sugimoto, Wataru; Sugahara, Yoshiyuki
- Chemistry of Materials, Vol. 15, Issue 3
Organic-inorganic electronics
journal, January 2001
- Mitzi, D. B.; Chondroudis, K.; Kagan, C. R.
- IBM Journal of Research and Development, Vol. 45, Issue 1
Ligand-Stabilized Reduced-Dimensionality Perovskites
journal, February 2016
- Quan, Li Na; Yuan, Mingjian; Comin, Riccardo
- Journal of the American Chemical Society, Vol. 138, Issue 8
Conducting Layered Organic-inorganic Halides Containing <110>-Oriented Perovskite Sheets
journal, March 1995
- Mitzi, D. B.; Wang, S.; Feild, C. A.
- Science, Vol. 267, Issue 5203, p. 1473-1476
Layered organic–inorganic hybrid perovskites: structure, optical properties, film preparation, patterning and templating engineering
journal, January 2010
- Cheng, Ziyong; Lin, Jun
- CrystEngComm, Vol. 12, Issue 10
Ligand Mediated Transformation of Cesium Lead Bromide Perovskite Nanocrystals to Lead Depleted Cs 4 PbBr 6 Nanocrystals
journal, April 2017
- Liu, Zeke; Bekenstein, Yehonadav; Ye, Xingchen
- Journal of the American Chemical Society, Vol. 139, Issue 15
Postsynthesis Transformation of Insulating Cs 4 PbBr 6 Nanocrystals into Bright Perovskite CsPbBr 3 through Physical and Chemical Extraction of CsBr
journal, September 2017
- Palazon, Francisco; Urso, Carmine; De Trizio, Luca
- ACS Energy Letters, Vol. 2, Issue 10
Structure-Tuned Lead Halide Perovskite Nanocrystals
journal, November 2015
- Hassan, Yasser; Song, Yin; Pensack, Ryan D.
- Advanced Materials, Vol. 28, Issue 3
Ligand Assisted Transformation of Cubic CsPbBr 3 Nanocrystals into Two-Dimensional CsPb 2 Br 5 Nanosheets
journal, November 2017
- Balakrishnan, Subila K.; Kamat, Prashant V.
- Chemistry of Materials, Vol. 30, Issue 1
Colloidal CsX (X = Cl, Br, I) Nanocrystals and Their Transformation to CsPbX 3 Nanocrystals by Cation Exchange
journal, December 2017
- Shamsi, Javad; Dang, Zhiya; Ijaz, Palvasha
- Chemistry of Materials, Vol. 30, Issue 1
Nucleation, Growth, and Structural Transformations of Perovskite Nanocrystals
journal, January 2017
- Udayabhaskararao, Thumu; Kazes, Miri; Houben, Lothar
- Chemistry of Materials, Vol. 29, Issue 3
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
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
Die Kristallstruktur von Bleibromid PbBr 2
journal, October 1933
- Nieuwenkamp, W.; Bijvoet, J. M.
- Zeitschrift für Kristallographie - Crystalline Materials, Vol. 84, Issue 1-6
Highly Dynamic Ligand Binding and Light Absorption Coefficient of Cesium Lead Bromide Perovskite Nanocrystals
journal, January 2016
- De Roo, Jonathan; Ibáñez, Maria; Geiregat, Pieter
- ACS Nano, Vol. 10, Issue 2
All-Inorganic Germanium Nanocrystal Films by Cationic Ligand Exchange
journal, January 2016
- Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.
- Nano Letters, Vol. 16, Issue 3
Luminescent and Photoconductive Layered Lead Halide Perovskite Compounds Comprising Mixtures of Cesium and Guanidinium Cations
journal, September 2017
- Nazarenko, Olga; Kotyrba, Martin Robert; Wörle, Michael
- Inorganic Chemistry, Vol. 56, Issue 19
Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design
journal, March 2016
- Saparov, Bayrammurad; Mitzi, David B.
- Chemical Reviews, Vol. 116, Issue 7
Low-Dimensional-Networked Metal Halide Perovskites: The Next Big Thing
journal, March 2017
- Saidaminov, Makhsud I.; Mohammed, Omar F.; Bakr, Osman M.
- ACS Energy Letters, Vol. 2, Issue 4
2D Ruddlesden-Popper Perovskites for Optoelectronics
journal, October 2017
- Chen, Yani; Sun, Yong; Peng, Jiajun
- Advanced Materials, Vol. 30, Issue 2
Between the Sheets: Postsynthetic Transformations in Hybrid Perovskites
journal, February 2017
- Smith, Ian C.; Smith, Matthew D.; Jaffe, Adam
- Chemistry of Materials, Vol. 29, Issue 5
Synthesis, structure and optical properties of different dimensional organic–inorganic perovskites
journal, September 2007
- Li, Yinyan; Zheng, Guoli; Lin, Cuikun
- Solid State Sciences, Vol. 9, Issue 9
Preparation and characterization of layered lead halide compounds
journal, March 1991
- Calabrese, J.; Jones, N. L.; Harlow, R. L.
- Journal of the American Chemical Society, Vol. 113, Issue 6, p. 2328-2330
Spectroscopic studies of (C10H21NH3)2PbI4, (CH3NH3)(C10H21NH3)2Pb2I7, (CH3NH3) PbI3, and similar compounds
journal, April 1993
- Papavassiliou, G. C.; Patsis, A. P.; Lagouvardos, D. J.
- Synthetic Metals, Vol. 57, Issue 1
Preparation and characterization of natural lower dimensional layered perovskite-type compounds
journal, June 2000
- Tabuchi, Y.; Asai, K.; Rikukawa, M.
- Journal of Physics and Chemistry of Solids, Vol. 61, Issue 6
Quantum Size Effect in Organometal Halide Perovskite Nanoplatelets
journal, September 2015
- Sichert, Jasmina A.; Tong, Yu; Mutz, Niklas
- Nano Letters, Vol. 15, Issue 10
Highly Luminescent Colloidal Nanoplates of Perovskite Cesium Lead Halide and Their Oriented Assemblies
journal, December 2015
- Bekenstein, Yehonadav; Koscher, Brent A.; Eaton, Samuel W.
- Journal of the American Chemical Society, Vol. 137, Issue 51
A Mechanistic Study of Phase Transformation in Perovskite Nanocrystals Driven by Ligand Passivation
journal, December 2017
- Udayabhaskararao, Thumu; Houben, Lothar; Cohen, Hagai
- Chemistry of Materials, Vol. 30, Issue 1
Nonmonotonic Size Dependence in the Hole Mobility of Methoxide-Stabilized PbSe Quantum Dot Solids
journal, July 2013
- Scheele, Marcus; Engel, Jesse H.; Ferry, Vivian E.
- ACS Nano, Vol. 7, Issue 8
Works referencing / citing this record:
Metal halide perovskite nanostructures for optoelectronic applications and the study of physical properties
journal, February 2019
- Fu, Yongping; Zhu, Haiming; Chen, Jie
- Nature Reviews Materials, Vol. 4, Issue 3
Tailoring the luminescence of atomic clusters via ligand exchange reaction mediated post synthetic modification
journal, January 2020
- Basu, Srestha; Gayen, Chirantan; Dolai, Santanu
- Physical Chemistry Chemical Physics, Vol. 22, Issue 7
Figures / Tables found in this record:
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.