Defect-induced band-edge reconstruction of a bismuth-halide double perovskite for visible-light absorption
Abstract
Halide double perovskites have recently been developed as less toxic analogs of the lead perovskite solar-cell absorbers APbX3(A = monovalent cation; X = Br or I). However, all known halide double perovskites have large bandgaps that afford weak visible-light absorption. The first halide double perovskite evaluated as an absorber, Cs2AgBiBr6(1), has a bandgap of 1.95 eV. Here, we show that dilute alloying decreases 1's bandgap by ca. 0.5 eV. Importantly, time-resolved photoconductivity measurements reveal long-lived carriers with microsecond lifetimes in the alloyed material, which is very promising for photovoltaic applications. The alloyed perovskite described herein is the first double perovskite to show comparable bandgap energy and carrier lifetime to those of (CH3NH3)PbI3. By describing how energy- and symmetry-matched impurity orbitals, at low concentrations, dramatically alter 1's band edges, we open a potential pathway for the large and diverse family of halide double perovskites to compete with APbX3absorbers.
- Authors:
-
- Stanford Univ., Stanford, CA (United States). Dept. of Chemistry
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of California, Berkeley, CA (United States). Dept. of Physics
- Delft Univ. of Technology, Delft (The Netherlands). Dept. of Chemical Engineering and Optoelectronic Materials Section; Materials Innovation Institute (M2i), Delft (The Netherlands)
- Stanford Univ., Stanford, CA (United States). Dept. of Chemistry; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
- Delft Univ. of Technology, Delft (The Netherlands). Dept. of Chemical Engineering and Optoelectronic Materials Section
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of California, Berkeley, CA (United States). Dept. of Physics; Kavli Energy NanoScience, Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab. (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; Sloan Foundation; Alexander von Humboldt Foundation; Netherlands Organization for Scientific Research (NWO); National Science Foundation (NSF)
- OSTI Identifier:
- 1360903
- Alternate Identifier(s):
- OSTI ID: 1458491
- Grant/Contract Number:
- AC02-76SF00515; AC02-05CH11231; DGE-1147470; F71.4.15562a
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 139; Journal Issue: 14; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Slavney, Adam H., Leppert, Linn, Bartesaghi, Davide, Gold-Parker, Aryeh, Toney, Michael F., Savenije, Tom J., Neaton, Jeffrey B., and Karunadasa, Hemamala I. Defect-induced band-edge reconstruction of a bismuth-halide double perovskite for visible-light absorption. United States: N. p., 2017.
Web. doi:10.1021/jacs.7b01629.
Slavney, Adam H., Leppert, Linn, Bartesaghi, Davide, Gold-Parker, Aryeh, Toney, Michael F., Savenije, Tom J., Neaton, Jeffrey B., & Karunadasa, Hemamala I. Defect-induced band-edge reconstruction of a bismuth-halide double perovskite for visible-light absorption. United States. https://doi.org/10.1021/jacs.7b01629
Slavney, Adam H., Leppert, Linn, Bartesaghi, Davide, Gold-Parker, Aryeh, Toney, Michael F., Savenije, Tom J., Neaton, Jeffrey B., and Karunadasa, Hemamala I. Wed .
"Defect-induced band-edge reconstruction of a bismuth-halide double perovskite for visible-light absorption". United States. https://doi.org/10.1021/jacs.7b01629. https://www.osti.gov/servlets/purl/1360903.
@article{osti_1360903,
title = {Defect-induced band-edge reconstruction of a bismuth-halide double perovskite for visible-light absorption},
author = {Slavney, Adam H. and Leppert, Linn and Bartesaghi, Davide and Gold-Parker, Aryeh and Toney, Michael F. and Savenije, Tom J. and Neaton, Jeffrey B. and Karunadasa, Hemamala I.},
abstractNote = {Halide double perovskites have recently been developed as less toxic analogs of the lead perovskite solar-cell absorbers APbX3(A = monovalent cation; X = Br or I). However, all known halide double perovskites have large bandgaps that afford weak visible-light absorption. The first halide double perovskite evaluated as an absorber, Cs2AgBiBr6(1), has a bandgap of 1.95 eV. Here, we show that dilute alloying decreases 1's bandgap by ca. 0.5 eV. Importantly, time-resolved photoconductivity measurements reveal long-lived carriers with microsecond lifetimes in the alloyed material, which is very promising for photovoltaic applications. The alloyed perovskite described herein is the first double perovskite to show comparable bandgap energy and carrier lifetime to those of (CH3NH3)PbI3. By describing how energy- and symmetry-matched impurity orbitals, at low concentrations, dramatically alter 1's band edges, we open a potential pathway for the large and diverse family of halide double perovskites to compete with APbX3absorbers.},
doi = {10.1021/jacs.7b01629},
journal = {Journal of the American Chemical Society},
number = 14,
volume = 139,
place = {United States},
year = {Wed Mar 29 00:00:00 EDT 2017},
month = {Wed Mar 29 00:00:00 EDT 2017}
}
Web of Science
Works referenced in this record:
Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells
journal, May 2009
- Kojima, Akihiro; Teshima, Kenjiro; Shirai, Yasuo
- Journal of the American Chemical Society, Vol. 131, Issue 17, p. 6050-6051
Metal halide perovskites for energy applications
journal, May 2016
- Zhang, Wei; Eperon, Giles E.; Snaith, Henry J.
- Nature Energy, Vol. 1, Issue 6
Lead Poisoning
journal, February 2004
- Needleman, Herbert
- Annual Review of Medicine, Vol. 55, Issue 1
Toxicity of organometal halide perovskite solar cells
journal, February 2016
- Babayigit, Aslihan; Ethirajan, Anitha; Muller, Marc
- Nature Materials, Vol. 15, Issue 3
Chemical Approaches to Addressing the Instability and Toxicity of Lead–Halide Perovskite Absorbers
journal, August 2016
- Slavney, Adam H.; Smaha, Rebecca W.; Smith, Ian C.
- Inorganic Chemistry, Vol. 56, Issue 1
A Bismuth-Halide Double Perovskite with Long Carrier Recombination Lifetime for Photovoltaic Applications
journal, February 2016
- Slavney, Adam H.; Hu, Te; Lindenberg, Aaron M.
- Journal of the American Chemical Society, Vol. 138, Issue 7
Cs 2 AgBiX 6 (X = Br, Cl): New Visible Light Absorbing, Lead-Free Halide Perovskite Semiconductors
journal, February 2016
- McClure, Eric T.; Ball, Molly R.; Windl, Wolfgang
- Chemistry of Materials, Vol. 28, Issue 5
Lead-Free Halide Double Perovskites via Heterovalent Substitution of Noble Metals
journal, March 2016
- Volonakis, George; Filip, Marina R.; Haghighirad, Amir Abbas
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 7
The synthesis, structure and electronic properties of a lead-free hybrid inorganic–organic double perovskite (MA) 2 KBiCl 6 (MA = methylammonium)
journal, January 2016
- Wei, Fengxia; Deng, Zeyu; Sun, Shijing
- Materials Horizons, Vol. 3, Issue 4
Exploring the properties of lead-free hybrid double perovskites using a combined computational-experimental approach
journal, January 2016
- Deng, Zeyu; Wei, Fengxia; Sun, Shijing
- Journal of Materials Chemistry A, Vol. 4, Issue 31
Cs 2 InAgCl 6 : A New Lead-Free Halide Double Perovskite with Direct Band Gap
journal, January 2017
- Volonakis, George; Haghighirad, Amir Abbas; Milot, Rebecca L.
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 4
Hybrid perovskites for photovoltaics: Insights from first principles
journal, March 2014
- Filippetti, A.; Mattoni, A.
- Physical Review B, Vol. 89, Issue 12
XANES Studies of Thallium Compounds and Valence States and Local Environment of Thallium in Some of its Superconducting Cuprates
journal, January 2005
- Agarwal, Arvind; Vishnoi, A. N.
- Physica Scripta
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Revealing the Dynamics of Charge Carriers in Polymer:Fullerene Blends Using Photoinduced Time-Resolved Microwave Conductivity
journal, October 2013
- Savenije, Tom J.; Ferguson, Andrew J.; Kopidakis, Nikos
- The Journal of Physical Chemistry C, Vol. 117, Issue 46
Charge Carrier Lifetimes Exceeding 15 μs in Methylammonium Lead Iodide Single Crystals
journal, February 2016
- Bi, Yu; Hutter, Eline M.; Fang, Yanjun
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 5
Relativistic quasiparticle self-consistent electronic structure of hybrid halide perovskite photovoltaic absorbers
journal, April 2014
- Brivio, Federico; Butler, Keith T.; Walsh, Aron
- Physical Review B, Vol. 89, Issue 15
Red Shift of Photoluminescence and Absorption in Dilute GaAsN Alloy Layers
journal, July 1992
- Weyers, Markus; Sato, Michio; Ando, Hiroaki
- Japanese Journal of Applied Physics, Vol. 31, Issue Part 2, No. 7A
New Visible Light Absorbing Materials for Solar Fuels, Ga(Sb x )N 1− x
journal, February 2014
- Sunkara, Swathi; Vendra, Venkat Kalyan; Jasinski, Jacek Bogdan
- Advanced Materials, Vol. 26, Issue 18
Anomalous Band Gap Behavior in Mixed Sn and Pb Perovskites Enables Broadening of Absorption Spectrum in Solar Cells
journal, May 2014
- Hao, Feng; Stoumpos, Constantinos C.; Chang, Robert P. H.
- Journal of the American Chemical Society, Vol. 136, Issue 22
Heterovalent Dopant Incorporation for Bandgap and Type Engineering of Perovskite Crystals
journal, January 2016
- Abdelhady, Ahmed L.; Saidaminov, Makhsud I.; Murali, Banavoth
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 2
Works referencing / citing this record:
Nb-doped amorphous titanium oxide compact layer for formamidinium-based high efficiency perovskite solar cells by low-temperature fabrication
journal, January 2018
- Numata, Youhei; Ishikawa, Ryo; Sanehira, Yoshitaka
- Journal of Materials Chemistry A, Vol. 6, Issue 20
Perovskite Solar Absorbers: Materials by Design
journal, March 2018
- Xu, Qiaoling; Yang, Dongwen; Lv, Jian
- Small Methods, Vol. 2, Issue 5
Long Electron-Hole Diffusion Length in High-Quality Lead-Free Double Perovskite Films
journal, March 2018
- Ning, Weihua; Wang, Feng; Wu, Bo
- Advanced Materials, Vol. 30, Issue 20
Investigation of the Mn dopant-enhanced photoluminescence performance of lead-free Cs 2 AgInCl 6 double perovskite crystals
journal, January 2020
- Wu, Wentiao; Cong, Wei-Yan; Guan, ChengBo
- Physical Chemistry Chemical Physics, Vol. 22, Issue 4
Structural, elastic, electronic and optical properties of lead-free halide double perovskite Cs 2 AgBiX 6 (X = Cl, Br, and I)
journal, September 2019
- Tripathi, Madhvendra Nath; Saha, Aditi; Singh, Santosh
- Materials Research Express, Vol. 6, Issue 11
Bandgap Engineering of Lead-Free Double Perovskite Cs 2 AgBiBr 6 through Trivalent Metal Alloying
journal, June 2017
- Du, Ke-zhao; Meng, Weiwei; Wang, Xiaoming
- Angewandte Chemie International Edition, Vol. 56, Issue 28
Perovskite solar cells: must lead be replaced – and can it be done?
journal, May 2018
- Zhang, Qi; Hao, Feng; Li, Jianbao
- Science and Technology of Advanced Materials, Vol. 19, Issue 1
Single-Source Vapor-Deposited Cs2AgBiBr6 Thin Films for Lead-Free Perovskite Solar Cells
journal, December 2019
- Fan, Ping; Peng, Huan-Xin; Zheng, Zhuang-Hao
- Nanomaterials, Vol. 9, Issue 12
Small-Band-Gap Halide Double Perovskites
journal, August 2018
- Slavney, Adam H.; Leppert, Linn; Saldivar Valdes, Abraham
- Angewandte Chemie International Edition, Vol. 57, Issue 39
Recent Progress and Development in Inorganic Halide Perovskite Quantum Dots for Photoelectrochemical Applications
journal, October 2019
- Liang, Junhui; Chen, Da; Yao, Xin
- Small, Vol. 16, Issue 15
Synthesis and Photocatalytic Application of Stable Lead-Free Cs 2 AgBiBr 6 Perovskite Nanocrystals
journal, January 2018
- Zhou, Lei; Xu, Yang-Fan; Chen, Bai-Xue
- Small, Vol. 14, Issue 11
Extending lead-free hybrid photovoltaic materials to new structures: thiazolium, aminothiazolium and imidazolium iodobismuthates
journal, January 2018
- Li, Tianyue; Wang, Qifei; Nichol, Gary S.
- Dalton Transactions, Vol. 47, Issue 20
Reversible Band Gap Narrowing of Sn-Based Hybrid Perovskite Single Crystal with Excellent Phase Stability
journal, October 2018
- Ju, Dianxing; Zheng, Xiaopeng; Liu, Jialiang
- Angewandte Chemie, Vol. 130, Issue 45
Strongly Coupled Tin-Halide Perovskites to Modulate Light Emission: Tunable 550-640 nm Light Emission (FWHM 36-80 nm) with a Quantum Yield of up to 6.4%
journal, March 2018
- Chen, Min-Yi; Lin, Jin-Tai; Hsu, Chia-Shuo
- Advanced Materials, Vol. 30, Issue 20
Structural and Functional Diversity in Lead‐Free Halide Perovskite Materials
journal, April 2019
- Ning, Weihua; Gao, Feng
- Advanced Materials, Vol. 31, Issue 22
Optoelectronic Properties and Defect Physics of Lead-Free Photovoltaic Absorbers ( )
journal, January 2020
- Kangsabanik, Jiban; Ghorui, Supriti; Aslam, M.
- Physical Review Applied, Vol. 13, Issue 1
The Dawn of Lead-Free Perovskite Solar Cell: Highly Stable Double Perovskite Cs 2 AgBiBr 6 Film
journal, December 2017
- Wu, Cuncun; Zhang, Qiaohui; Liu, Yang
- Advanced Science, Vol. 5, Issue 3
Progress of Lead‐Free Halide Double Perovskites
journal, January 2019
- Igbari, Femi; Wang, Zhao‐Kui; Liao, Liang‐Sheng
- Advanced Energy Materials, Vol. 9, Issue 12
Lead-Free Halide Double Perovskites: A Review of the Structural, Optical, and Stability Properties as Well as Their Viability to Replace Lead Halide Perovskites
journal, August 2018
- Meyer, Edson; Mutukwa, Dorcas; Zingwe, Nyengerai
- Metals, Vol. 8, Issue 9
Low-Bandgap Cs 4 CuSb 2 Cl 12 Layered Double Perovskite: Synthesis, Reversible Thermal Changes, and Magnetic Interaction
journal, July 2018
- Singhal, Nancy; Chakraborty, Rayan; Ghosh, Prasenjit
- Chemistry - An Asian Journal, Vol. 13, Issue 16
Bismuth Halide Perovskite‐Like Materials: Current Opportunities and Challenges
journal, March 2019
- Zhang, Long; Wang, Kai; Zou, Bo
- ChemSusChem, Vol. 12, Issue 8
Chemical Origin of the Stability Difference between Copper(I)- and Silver(I)-Based Halide Double Perovskites
journal, August 2017
- Xiao, Zewen; Du, Ke-Zhao; Meng, Weiwei
- Angewandte Chemie, Vol. 129, Issue 40
The Optical Band-Gap Evolution in Perovskite-Like Hybrid Iodobismuthates Effected by Nuclearity and Dimension: An Experimental and DFT Calculation Study
journal, May 2019
- Jiang, Yu-Xiang; Wang, You-Yu; Song, Li
- Journal of Cluster Science, Vol. 30, Issue 6
Lead‐Free Double Perovskites for Perovskite Solar Cells
journal, August 2019
- Kung, Po-Kai; Li, Ming-Hsien; Lin, Pei-Ying
- Solar RRL, Vol. 4, Issue 2
A Review on Energy Band‐Gap Engineering for Perovskite Photovoltaics
journal, September 2019
- Hu, Zhaosheng; Lin, Zhenhua; Su, Jie
- Solar RRL, Vol. 3, Issue 12
Tunable optical absorption in lead-free perovskite-like hybrids by iodide management
journal, January 2019
- Kou, Bo; Zhang, Weichuan; Ji, Chengmin
- Chemical Communications, Vol. 55, Issue 94
Structurally Stabilizing and Environment Friendly Triggers: Double‐Metallic Lead‐Free Perovskites
journal, May 2019
- Yin, Hang; Xian, Yeming; Zhang, Yongli
- Solar RRL, Vol. 3, Issue 9
Bandgap Optimization of Perovskite Semiconductors for Photovoltaic Applications
journal, January 2018
- Xiao, Zewen; Zhou, Yuanyuan; Hosono, Hideo
- Chemistry - A European Journal, Vol. 24, Issue 10
Submillimeter and lead-free Cs 3 Sb 2 Br 9 perovskite nanoflakes: inverse temperature crystallization growth and application for ultrasensitive photodetectors
journal, January 2019
- Zheng, Zhi; Hu, Qingsong; Zhou, Hongzhi
- Nanoscale Horizons, Vol. 4, Issue 6
From Lead Halide Perovskites to Lead‐Free Metal Halide Perovskites and Perovskite Derivatives
journal, January 2019
- Xiao, Zewen; Song, Zhaoning; Yan, Yanfa
- Advanced Materials, Vol. 31, Issue 47
Alternative Perovskites for Photovoltaics
journal, April 2018
- Jodlowski, AlexanderD.; Rodríguez-Padrón, Daily; Luque, Rafael
- Advanced Energy Materials, Vol. 8, Issue 21
Synthesis, crystal structure, magnetic and electronic properties of the caesium-based transition metal halide Cs 3 Fe 2 Br 9
journal, January 2018
- Wei, Fengxia; Brivio, Federico; Wu, Yue
- Journal of Materials Chemistry C, Vol. 6, Issue 14
Lead-Free Hybrid Perovskite Absorbers for Viable Application: Can We Eat the Cake and Have It too?
journal, November 2017
- Liang, Lusheng; Gao, Peng
- Advanced Science, Vol. 5, Issue 2
Thermochromic Lead‐Free Halide Double Perovskites
journal, March 2019
- Ning, Weihua; Zhao, Xin‐Gang; Klarbring, Johan
- Advanced Functional Materials, Vol. 29, Issue 10
From Pb to Bi: A Promising Family of Pb‐Free Optoelectronic Materials and Devices
journal, April 2020
- Wu, Cuncun; Zhang, Qiaohui; Liu, Ganghong
- Advanced Energy Materials, Vol. 10, Issue 13
Impacts of cation ordering on bandgap dispersion of double perovskites
journal, August 2018
- Kim, Jongseob; Kim, Hyungjun; Chandran, Mahesh
- APL Materials, Vol. 6, Issue 8
Cs 2 AgBiBr 6−x Cl x solid solutions – band gap engineering with halide double perovskites
journal, January 2019
- Gray, Matthew B.; McClure, Eric T.; Woodward, Patrick M.
- Journal of Materials Chemistry C, Vol. 7, Issue 31
Local stress enhanced photocurrent of visible light photo-detection in Cs 2 AgBiBr 6 single crystal
journal, September 2019
- Li, Tong; Wang, Jing; Gao, Ziyan
- Applied Physics Letters, Vol. 115, Issue 13
Inorganic CsPbI 3 Perovskite-Based Solar Cells: A Choice for a Tandem Device
journal, June 2017
- Ahmad, Waqar; Khan, Jahangeer; Niu, Guangda
- Solar RRL, Vol. 1, Issue 7
Rational design of a triiodide-intercalated dielectric-switching hybrid for visible-light absorption
journal, January 2018
- Zhang, Weichuan; Kou, Bo; Peng, Yu
- Journal of Materials Chemistry C, Vol. 6, Issue 45
Bandgap Engineering of Lead-Free Double Perovskite Cs 2 AgBiBr 6 through Trivalent Metal Alloying
journal, June 2017
- Du, Ke-zhao; Meng, Weiwei; Wang, Xiaoming
- Angewandte Chemie, Vol. 129, Issue 28
Small-Band-Gap Halide Double Perovskites
journal, August 2018
- Slavney, Adam H.; Leppert, Linn; Saldivar Valdes, Abraham
- Angewandte Chemie, Vol. 130, Issue 39
A Review on Energy Band‐Gap Engineering for Perovskite Photovoltaics
journal, December 2019
- Hu, Zhaosheng; Lin, Zhenhua; Su, Jie
- Solar RRL, Vol. 3, Issue 12
Reversible Band Gap Narrowing of Sn-Based Hybrid Perovskite Single Crystal with Excellent Phase Stability
journal, October 2018
- Ju, Dianxing; Zheng, Xiaopeng; Liu, Jialiang
- Angewandte Chemie International Edition, Vol. 57, Issue 45
Double Perovskites overtaking the single perovskites : A set of new solar harvesting materials with much higher stability and efficiency
text, January 2018
- Kangsabanik, Jiban; Sugathan, Vipinraj; Yadav, Anuradha
- arXiv
Band-Like Charge Transport in Cs 2 AgBiBr 6 and Mixed Antimony–Bismuth Cs 2 AgBi 1– x Sb x Br 6 Halide Double Perovskites
journal, September 2018
- Hutter, Eline M.; Gélvez-Rueda, María C.; Bartesaghi, Davide
- ACS Omega, Vol. 3, Issue 9
Perovskite solar cells: must lead be replaced – and can it be done?
journal, May 2018
- Zhang, Qi; Hao, Feng; Li, Jianbao
- Science and Technology of Advanced Materials, Vol. 19, Issue 1