skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Viability of Lead-Free Perovskites with Mixed Chalcogen and Halogen Anions for Photovoltaic Applications

Abstract

We assess the viability for photovoltaic applications of proposed Pb-free perovskites with mixed chalcogen and halogen anions, AB(Ch,X)3 (A = Cs or Ba; B = Sb or Bi; Ch = chalcogen; X = halogen), by examining critical issues such as the structural, electronic/optical properties, and stability through the combination of density-functional theory calculations and solid state reactions. The calculations show that these quaternary Pb-free perovskites are thermodynamically unstable--they are prone to decompose into ternary and/or binary secondary phases or form phases with nonperovskite structures. Solid-state synthesis efforts confirm the theoretically predicted difficulty for preparing these compounds; all attempted reactions do not form the desired perovskite phases with mixed chalcogen and halogen anions under conditions examined. Instead, they form separate binary and ternary compounds. Despite earlier predictions of promising characteristics for these prospective perovskites for photovoltaics, our results suggest that, due to their instability, the Pb-free perovskites with mixed chalcogen and halogen anions may be challenging to form under equilibrium synthetic conditions.

Authors:
 [1];  [2];  [3];  [4];  [2];  [4]
  1. Univ. of Toledo, OH (United States). Wright Center for Photovoltaics Innovation and Commercialization (PVIC); Shanghai Univ., Shanghai (China). Dept. of Physics
  2. Duke Univ., Durham, NC (United States). Dept. of Mechanical Engineering and Materials Science, and Dept. of Chemistry
  3. Univ. of Toledo, OH (United States). Wright Center for Photovoltaics Innovation and Commercialization (PVIC); Wuhan Univ., Wuhan (China). School of Physics and Technology, Center for Electron Microscopy, MOE Key Laboratory of Artificial Micro- and Nano-structures, and Inst. for Advanced Studies
  4. Univ. of Toledo, OH (United States). Wright Center for Photovoltaics Innovation and Commercialization (PVIC)
Publication Date:
Research Org.:
Duke Univ., Durham, NC (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1559761
Grant/Contract Number:  
EE0006712
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 12; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hong, Feng, Saparov, Bayrammurad, Meng, Weiwei, Xiao, Zewen, Mitzi, David B., and Yan, Yanfa. Viability of Lead-Free Perovskites with Mixed Chalcogen and Halogen Anions for Photovoltaic Applications. United States: N. p., 2016. Web. https://doi.org/10.1021/acs.jpcc.6b00920.
Hong, Feng, Saparov, Bayrammurad, Meng, Weiwei, Xiao, Zewen, Mitzi, David B., & Yan, Yanfa. Viability of Lead-Free Perovskites with Mixed Chalcogen and Halogen Anions for Photovoltaic Applications. United States. https://doi.org/10.1021/acs.jpcc.6b00920
Hong, Feng, Saparov, Bayrammurad, Meng, Weiwei, Xiao, Zewen, Mitzi, David B., and Yan, Yanfa. Wed . "Viability of Lead-Free Perovskites with Mixed Chalcogen and Halogen Anions for Photovoltaic Applications". United States. https://doi.org/10.1021/acs.jpcc.6b00920. https://www.osti.gov/servlets/purl/1559761.
@article{osti_1559761,
title = {Viability of Lead-Free Perovskites with Mixed Chalcogen and Halogen Anions for Photovoltaic Applications},
author = {Hong, Feng and Saparov, Bayrammurad and Meng, Weiwei and Xiao, Zewen and Mitzi, David B. and Yan, Yanfa},
abstractNote = {We assess the viability for photovoltaic applications of proposed Pb-free perovskites with mixed chalcogen and halogen anions, AB(Ch,X)3 (A = Cs or Ba; B = Sb or Bi; Ch = chalcogen; X = halogen), by examining critical issues such as the structural, electronic/optical properties, and stability through the combination of density-functional theory calculations and solid state reactions. The calculations show that these quaternary Pb-free perovskites are thermodynamically unstable--they are prone to decompose into ternary and/or binary secondary phases or form phases with nonperovskite structures. Solid-state synthesis efforts confirm the theoretically predicted difficulty for preparing these compounds; all attempted reactions do not form the desired perovskite phases with mixed chalcogen and halogen anions under conditions examined. Instead, they form separate binary and ternary compounds. Despite earlier predictions of promising characteristics for these prospective perovskites for photovoltaics, our results suggest that, due to their instability, the Pb-free perovskites with mixed chalcogen and halogen anions may be challenging to form under equilibrium synthetic conditions.},
doi = {10.1021/acs.jpcc.6b00920},
journal = {Journal of Physical Chemistry. C},
number = 12,
volume = 120,
place = {United States},
year = {2016},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 43 works
Citation information provided by
Web of Science

Save / Share:

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
  • DOI: 10.1021/ja809598r

Efficient planar heterojunction perovskite solar cells by vapour deposition
journal, September 2013

  • Liu, Mingzhen; Johnston, Michael B.; Snaith, Henry J.
  • Nature, Vol. 501, Issue 7467, p. 395-398
  • DOI: 10.1038/nature12509

The emergence of perovskite solar cells
journal, July 2014

  • Green, Martin A.; Ho-Baillie, Anita; Snaith, Henry J.
  • Nature Photonics, Vol. 8, Issue 7, p. 506-514
  • DOI: 10.1038/nphoton.2014.134

Perovskites: The Emergence of a New Era for Low-Cost, High-Efficiency Solar Cells
journal, October 2013

  • Snaith, Henry J.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 21, p. 3623-3630
  • DOI: 10.1021/jz4020162

Sequential deposition as a route to high-performance perovskite-sensitized solar cells
journal, July 2013

  • Burschka, Julian; Pellet, Norman; Moon, Soo-Jin
  • Nature, Vol. 499, Issue 7458, p. 316-319
  • DOI: 10.1038/nature12340

Interface engineering of highly efficient perovskite solar cells
journal, July 2014


High-performance photovoltaic perovskite layers fabricated through intramolecular exchange
journal, May 2015


Overcoming ultraviolet light instability of sensitized TiO2 with meso-superstructured organometal tri-halide perovskite solar cells
journal, December 2013

  • Leijtens, Tomas; Eperon, Giles E.; Pathak, Sandeep
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3885

Chemical Management for Colorful, Efficient, and Stable Inorganic–Organic Hybrid Nanostructured Solar Cells
journal, March 2013

  • Noh, Jun Hong; Im, Sang Hyuk; Heo, Jin Hyuck
  • Nano Letters, Vol. 13, Issue 4, p. 1764-1769
  • DOI: 10.1021/nl400349b

Transformation of the Excited State and Photovoltaic Efficiency of CH 3 NH 3 PbI 3 Perovskite upon Controlled Exposure to Humidified Air
journal, January 2015

  • Christians, Jeffrey A.; Miranda Herrera, Pierre A.; Kamat, Prashant V.
  • Journal of the American Chemical Society, Vol. 137, Issue 4
  • DOI: 10.1021/ja511132a

Unique Properties of Halide Perovskites as Possible Origins of the Superior Solar Cell Performance
journal, May 2014


Superior Photovoltaic Properties of Lead Halide Perovskites: Insights from First-Principles Theory
journal, February 2015

  • Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa
  • The Journal of Physical Chemistry C, Vol. 119, Issue 10
  • DOI: 10.1021/jp512077m

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
  • DOI: 10.1021/ja5033259

Lead-free organic–inorganic tin halide perovskites for photovoltaic applications
journal, January 2014

  • Noel, Nakita K.; Stranks, Samuel D.; Abate, Antonio
  • Energy Environ. Sci., Vol. 7, Issue 9
  • DOI: 10.1039/C4EE01076K

Lead-free solid-state organic–inorganic halide perovskite solar cells
journal, May 2014

  • Hao, Feng; Stoumpos, Constantinos C.; Cao, Duyen Hanh
  • Nature Photonics, Vol. 8, Issue 6
  • DOI: 10.1038/nphoton.2014.82

Lead Replacement in CH 3 NH 3 PbI 3 Perovskites
journal, August 2015

  • Wang, Kan; Liang, Ziqi; Wang, Xinqiang
  • Advanced Electronic Materials, Vol. 1, Issue 10
  • DOI: 10.1002/aelm.201500089

Thin-Film Preparation and Characterization of Cs 3 Sb 2 I 9 : A Lead-Free Layered Perovskite Semiconductor
journal, August 2015


Bismuth Based Hybrid Perovskites A 3 Bi 2 I 9 (A: Methylammonium or Cesium) for Solar Cell Application
journal, September 2015

  • Park, Byung-Wook; Philippe, Bertrand; Zhang, Xiaoliang
  • Advanced Materials, Vol. 27, Issue 43
  • DOI: 10.1002/adma.201501978

Crystal and Electronic Structures of Complex Bismuth Iodides A 3 Bi 2 I 9 ( A = K, Rb, Cs) Related to Perovskite: Aiding the Rational Design of Photovoltaics
journal, October 2015


Chalcogenide Perovskites for Photovoltaics
journal, December 2014

  • Sun, Yi-Yang; Agiorgousis, Michael L.; Zhang, Peihong
  • Nano Letters, Vol. 15, Issue 1
  • DOI: 10.1021/nl504046x

Ferroelectric materials for solar energy conversion: photoferroics revisited
journal, January 2015

  • Butler, Keith T.; Frost, Jarvist M.; Walsh, Aron
  • Energy & Environmental Science, Vol. 8, Issue 3
  • DOI: 10.1039/C4EE03523B

Discovering lead-free perovskite solar materials with a split-anion approach
journal, January 2016


Projector augmented-wave method
journal, December 1994


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


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
  • DOI: 10.1103/PhysRevLett.77.3865

Hybrid functionals based on a screened Coulomb potential
journal, May 2003

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1564060

The Perdew–Burke–Ernzerhof exchange-correlation functional applied to the G2-1 test set using a plane-wave basis set
journal, June 2005

  • Paier, Joachim; Hirschl, Robin; Marsman, Martijn
  • The Journal of Chemical Physics, Vol. 122, Issue 23
  • DOI: 10.1063/1.1926272

Crystal Structures of Bismuth Tellurohalides BiTeX (X = Cl, Br, I) from X-Ray Powder Diffraction Data
journal, February 1995

  • Shevelkov, A. V.; Dikarev, E. V.; Shpanchenko, R. V.
  • Journal of Solid State Chemistry, Vol. 114, Issue 2
  • DOI: 10.1006/jssc.1995.1058

Preparation and basic physical properties of BiTeI single crystals
journal, November 1978

  • Dich, Nguyêñ Tât; Lošťák, P.; Horák, J.
  • Czechoslovak Journal of Physics, Vol. 28, Issue 11
  • DOI: 10.1007/BF01599969

Untersuchungen zum quasibinären System Bi2Se3/BiI3
journal, November 1998


Homologous Silver Bismuth Chalcogenide Halides(N, x)P. I. Syntheses and Crystal Structures of the(0, 1)P Compound AgBi2S2Cl3 and of Three Members of the(1, x)P Solid Solution Series Ag2xBi4—2xS6—4xBr4x
journal, August 2004

  • Poudeu Poudeu, Pierre Ferdinand; Söhnel, Tilo; Ruck, Michael
  • Zeitschrift für anorganische und allgemeine Chemie, Vol. 630, Issue 89
  • DOI: 10.1002/zaac.200400131

Strong positive and negative deviations from Vegard's rule: X-ray powder investigations of the three quasi-binary phase systems BiS X 1 −  x Y x ( X , Y = Cl, Br, I)
journal, March 2014

  • Schultz, Peter; Keller, Egbert
  • Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 70, Issue 2
  • DOI: 10.1107/S2052520614000766

A high temperature variety of BiOF
journal, September 1983


New Dion−Jacobson-Type Layered Perovskite Oxyfluorides, ASrNb 2 O 6 F (A = Li, Na, and Rb)
journal, March 2001

  • Choy, Jin-Ho; Kim, Jong-Young; Kim, Seung-Joo
  • Chemistry of Materials, Vol. 13, Issue 3
  • DOI: 10.1021/cm000673g

New rare-earth double-layered-perovskite oxyfluorides, RbLnTiNbO6F (Ln = La, Pr, Nd)
journal, January 2002


Anion order in perovskite oxynitrides
journal, November 2010

  • Yang, Minghui; Oró-Solé, Judith; Rodgers, Jennifer A.
  • Nature Chemistry, Vol. 3, Issue 1
  • DOI: 10.1038/nchem.908

Thermally Robust Anion-Chain Order in Oxynitride Perovskites
journal, December 2013

  • Clark, Lucy; Oró-Solé, Judith; Knight, Kevin S.
  • Chemistry of Materials, Vol. 25, Issue 24
  • DOI: 10.1021/cm4037132

Unusual defect physics in CH 3 NH 3 PbI 3 perovskite solar cell absorber
journal, February 2014

  • Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa
  • Applied Physics Letters, Vol. 104, Issue 6
  • DOI: 10.1063/1.4864778

Cation Ordering in the Sillén X1-Type Oxychloride, BaBiO2Cl
journal, June 1995

  • Kennard, Mark A.; Darriet, Jacques; Grannec, Jean
  • Journal of Solid State Chemistry, Vol. 117, Issue 1
  • DOI: 10.1006/jssc.1995.1263

A reinvestigation of quaternary layered bismuth oxyhalides of the Sillén X1 type
journal, November 2003


Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976


Neutron diffraction investigation of the Ba1−xBixF2+x solid solution
journal, April 1992


    Works referencing / citing this record:

    Silver Bismuth Sulfoiodide Solar Cells: Tuning Optoelectronic Properties by Sulfide Modification for Enhanced Photovoltaic Performance
    journal, December 2018


    From Lead Halide Perovskites to Lead‐Free Metal Halide Perovskites and Perovskite Derivatives
    journal, January 2019


    Chalcogenide Materials and Derivatives for Photovoltaic Applications
    journal, September 2019

    • Buffiere, Marie; Dhawale, Dattatray S.; El-Mellouhi, Fedwa
    • Energy Technology, Vol. 7, Issue 11
    • DOI: 10.1002/ente.201900819

    Progress in Theoretical Study of Metal Halide Perovskite Solar Cell Materials
    journal, August 2017


    Potential Substitutes for Replacement of Lead in Perovskite Solar Cells: A Review
    journal, July 2019

    • Kour, Ravinder; Arya, Sandeep; Verma, Sonali
    • Global Challenges, Vol. 3, Issue 11
    • DOI: 10.1002/gch2.201900050

    Searching for promising new perovskite-based photovoltaic absorbers: the importance of electronic dimensionality
    journal, January 2017

    • Xiao, Zewen; Meng, Weiwei; Wang, Jianbo
    • Materials Horizons, Vol. 4, Issue 2
    • DOI: 10.1039/c6mh00519e

    Exploring new approaches towards the formability of mixed-ion perovskites by DFT and machine learning
    journal, January 2019

    • Park, Heesoo; Mall, Raghvendra; Alharbi, Fahhad H.
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 3
    • DOI: 10.1039/c8cp06528d

    Mix and Match: Organic and Inorganic Ions in the Perovskite Lattice
    journal, September 2018


    Oxychalcogenide Perovskite Solar Cells: A Multiscale Design Approach
    journal, April 2020

    • Park, Heesoo; Baloch, Ahmer A. B.; Bentria, El Tayeb
    • Energy Technology, Vol. 8, Issue 4
    • DOI: 10.1002/ente.201900766

    Alternative Perovskites for Photovoltaics
    journal, April 2018

    • Jodlowski, AlexanderD.; Rodríguez-Padrón, Daily; Luque, Rafael
    • Advanced Energy Materials, Vol. 8, Issue 21
    • DOI: 10.1002/aenm.201703120

    Perovskite Solar Absorbers: Materials by Design
    journal, March 2018


    Lead-Free Organic-Inorganic Hybrid Perovskites for Photovoltaic Applications: Recent Advances and Perspectives
    journal, February 2017


    Lead-Free Inverted Planar Formamidinium Tin Triiodide Perovskite Solar Cells Achieving Power Conversion Efficiencies up to 6.22%
    journal, August 2016


    Beyond methylammonium lead iodide: prospects for the emergent field of ns 2 containing solar absorbers
    journal, January 2017

    • Ganose, Alex M.; Savory, Christopher N.; Scanlon, David O.
    • Chemical Communications, Vol. 53, Issue 1
    • DOI: 10.1039/c6cc06475b

    Progress on lead-free metal halide perovskites for photovoltaic applications: a review
    journal, March 2017

    • Hoefler, Sebastian F.; Trimmel, Gregor; Rath, Thomas
    • Monatshefte für Chemie - Chemical Monthly, Vol. 148, Issue 5
    • DOI: 10.1007/s00706-017-1933-9

    18% High-Efficiency Air-Processed Perovskite Solar Cells Made in a Humid Atmosphere of 70% RH
    journal, July 2017


    Thermally evaporated methylammonium tin triiodide thin films for lead-free perovskite solar cell fabrication
    journal, January 2016

    • Yu, Yue; Zhao, Dewei; Grice, Corey R.
    • RSC Advances, Vol. 6, Issue 93
    • DOI: 10.1039/c6ra19476a

    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
    • DOI: 10.1002/chem.201705031

    Additive-assisted synthesis and optoelectronic properties of (CH 3 NH 3 ) 4 Bi 6 I 22
    journal, January 2020

    • Sharma, Manila; Yangui, Aymen; Lusson, Alain
    • Inorganic Chemistry Frontiers, Vol. 7, Issue 7
    • DOI: 10.1039/c9qi01574d

    Addressing Toxicity of Lead: Progress and Applications of Low-Toxic Metal Halide Perovskites and Their Derivatives
    journal, March 2017

    • Lyu, Miaoqiang; Yun, Jung-Ho; Chen, Peng
    • Advanced Energy Materials, Vol. 7, Issue 15
    • DOI: 10.1002/aenm.201602512

    Searching for stability at lower dimensions: current trends and future prospects of layered perovskite solar cells
    journal, January 2019

    • Thrithamarassery Gangadharan, Deepak; Ma, Dongling
    • Energy & Environmental Science, Vol. 12, Issue 10
    • DOI: 10.1039/c9ee01591d

    Perovskite Solar Cells with ZnO Electron-Transporting Materials
    journal, November 2017


    Oxychalcogenide Perovskite Solar Cells: A Multiscale Design Approach
    journal, April 2020

    • Park, Heesoo; Baloch, Ahmer A. B.; Bentria, El Tayeb
    • Energy Technology, Vol. 8, Issue 4
    • DOI: 10.1002/ente.202070041