DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: A Versatile Thin-Film Deposition Method for Multidimensional Semiconducting Bismuth Halides

Abstract

Despite the significant progress in fabricating hybrid organic-inorganic lead halide perovskite solar cells, their toxicity and low stability remain as major drawbacks, thereby hindering large-scale commercialization. Given the isoelectronic nature of lead(II) and bismuth(III) ions, potentially stable and non-toxic alternatives for efficient light absorption in thin-film photovoltaic (PV) devices may be found among bismuth-based halide semiconductors. However, high-quality polycrystalline films of many of these systems have not been demonstrated. In this work, we present a versatile and facile two-step co-evaporation approach to fabricate A3Bi2I9 (A = Cs, Rb) and AgBi2I7 polycrystalline films with smooth, pin-hole-free morphology and average grain size of > 200 nm. The process involves an initial two-source evaporation step (involving CsI, RbI or AgI, and BiI3 sources), followed by an annealing step under BiI3 vapor. The structural, optical and electrical characteristics of the resulting thin films are studied by X-ray diffraction, optical spectroscopy, X-ray/UV photoelectron spectroscopy and scanning electron microscopy.

Authors:
 [1];  [2];  [3];  [4];  [5];  [5];  [4];  [6]; ORCiD logo [7]
  1. Duke Univ., Durham, NC (United States). Dept. of Mechanical Engineering and Materials Science; Univ. of Duisburg-Essen (Germany). Inst. for Materials Science and Center for Nanointegration Duisburg-Essen (CENIDE)
  2. Duke Univ., Durham, NC (United States). Dept. of Mechanical Engineering and Materials Science
  3. Duke Univ., Durham, NC (United States). Dept. of Mechanical Engineering and Materials Science; Dalhousie Univ., Halifax, Nova Scotia (Canada). Dept. of Physics and Atmospheric Science
  4. North Carolina State Univ., Raleigh, NC (United States). Dept. of Materials Science and Engineering
  5. Dalhousie Univ., Halifax, Nova Scotia (Canada). Dept. of Physics and Atmospheric Science
  6. Univ. of Duisburg-Essen (Germany). Inst. for Materials Science and Center for Nanointegration Duisburg-Essen (CENIDE)
  7. Duke Univ., Durham, NC (United States)
Publication Date:
Research Org.:
Duke Univ., Durham, NC (United States); Univ. of North Carolina, Chapel Hill, NC (United States); North Carolina State Univ., Raleigh, NC (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); National Science Foundation (NSF); Leitmarktwettbewerb NRW (European Union); Natural Sciences and Engineering Research Council of Canada (NSERC)
OSTI Identifier:
1593836
Grant/Contract Number:  
EE0006712; DMR-1709294; EFRE-0800120; NW-1-1-040h; RGPIN-298170- 2014; ECCS-1542015
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 10; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Khazaee, Maryam, Sardashti, Kasra, Sun, Jon-Paul, Zhou, Hanhan, Clegg, Charlotte, Hill, Ian G., Jones, Jacob L., Lupascu, Doru C., and Mitzi, David B. A Versatile Thin-Film Deposition Method for Multidimensional Semiconducting Bismuth Halides. United States: N. p., 2018. Web. doi:10.1021/acs.chemmater.8b01341.
Khazaee, Maryam, Sardashti, Kasra, Sun, Jon-Paul, Zhou, Hanhan, Clegg, Charlotte, Hill, Ian G., Jones, Jacob L., Lupascu, Doru C., & Mitzi, David B. A Versatile Thin-Film Deposition Method for Multidimensional Semiconducting Bismuth Halides. United States. https://doi.org/10.1021/acs.chemmater.8b01341
Khazaee, Maryam, Sardashti, Kasra, Sun, Jon-Paul, Zhou, Hanhan, Clegg, Charlotte, Hill, Ian G., Jones, Jacob L., Lupascu, Doru C., and Mitzi, David B. Mon . "A Versatile Thin-Film Deposition Method for Multidimensional Semiconducting Bismuth Halides". United States. https://doi.org/10.1021/acs.chemmater.8b01341. https://www.osti.gov/servlets/purl/1593836.
@article{osti_1593836,
title = {A Versatile Thin-Film Deposition Method for Multidimensional Semiconducting Bismuth Halides},
author = {Khazaee, Maryam and Sardashti, Kasra and Sun, Jon-Paul and Zhou, Hanhan and Clegg, Charlotte and Hill, Ian G. and Jones, Jacob L. and Lupascu, Doru C. and Mitzi, David B.},
abstractNote = {Despite the significant progress in fabricating hybrid organic-inorganic lead halide perovskite solar cells, their toxicity and low stability remain as major drawbacks, thereby hindering large-scale commercialization. Given the isoelectronic nature of lead(II) and bismuth(III) ions, potentially stable and non-toxic alternatives for efficient light absorption in thin-film photovoltaic (PV) devices may be found among bismuth-based halide semiconductors. However, high-quality polycrystalline films of many of these systems have not been demonstrated. In this work, we present a versatile and facile two-step co-evaporation approach to fabricate A3Bi2I9 (A = Cs, Rb) and AgBi2I7 polycrystalline films with smooth, pin-hole-free morphology and average grain size of > 200 nm. The process involves an initial two-source evaporation step (involving CsI, RbI or AgI, and BiI3 sources), followed by an annealing step under BiI3 vapor. The structural, optical and electrical characteristics of the resulting thin films are studied by X-ray diffraction, optical spectroscopy, X-ray/UV photoelectron spectroscopy and scanning electron microscopy.},
doi = {10.1021/acs.chemmater.8b01341},
journal = {Chemistry of Materials},
number = 10,
volume = 30,
place = {United States},
year = {2018},
month = {4}
}

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

Citation Metrics:
Cited by: 19 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Compositional engineering of perovskite materials for high-performance solar cells
journal, January 2015

  • Jeon, Nam Joong; Noh, Jun Hong; Yang, Woon Seok
  • Nature, Vol. 517, Issue 7535
  • DOI: 10.1038/nature14133

A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells
journal, January 2016


High Charge Carrier Mobilities and Lifetimes in Organolead Trihalide Perovskites
journal, December 2013

  • Wehrenfennig, Christian; Eperon, Giles E.; Johnston, Michael B.
  • Advanced Materials, Vol. 26, Issue 10
  • DOI: 10.1002/adma.201305172

Organometal Halide Perovskite Solar Cell Materials Rationalized: Ultrafast Charge Generation, High and Microsecond-Long Balanced Mobilities, and Slow Recombination
journal, February 2014

  • Ponseca, Carlito S.; Savenije, Tom J.; Abdellah, Mohamed
  • Journal of the American Chemical Society, Vol. 136, Issue 14
  • DOI: 10.1021/ja412583t

Charge Carriers in Hybrid Organic–Inorganic Lead Halide Perovskites Might Be Protected as Large Polarons
journal, November 2015


Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber
journal, October 2013

  • Stranks, S. D.; Eperon, G. E.; Grancini, G.
  • Science, Vol. 342, Issue 6156, p. 341-344
  • DOI: 10.1126/science.1243982

Long-Range Balanced Electron- and Hole-Transport Lengths in Organic-Inorganic CH3NH3PbI3
journal, October 2013


Organometallic Halide Perovskites: Sharp Optical Absorption Edge and Its Relation to Photovoltaic Performance
journal, March 2014

  • De Wolf, Stefaan; Holovsky, Jakub; Moon, Soo-Jin
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 6
  • DOI: 10.1021/jz500279b

Toxicity of organometal halide perovskite solar cells
journal, February 2016

  • Babayigit, Aslihan; Ethirajan, Anitha; Muller, Marc
  • Nature Materials, Vol. 15, Issue 3
  • DOI: 10.1038/nmat4572

Carbon Nanotube/Polymer Composites as a Highly Stable Hole Collection Layer in Perovskite Solar Cells
journal, September 2014

  • Habisreutinger, Severin N.; Leijtens, Tomas; Eperon, Giles E.
  • Nano Letters, Vol. 14, Issue 10, p. 5561-5568
  • DOI: 10.1021/nl501982b

Kinetics of Ion Transport in Perovskite Active Layers and Its Implications for Active Layer Stability
journal, September 2015

  • Bag, Monojit; Renna, Lawrence A.; Adhikari, Ramesh Y.
  • Journal of the American Chemical Society, Vol. 137, Issue 40
  • DOI: 10.1021/jacs.5b08535

The Role of Oxygen in the Degradation of Methylammonium Lead Trihalide Perovskite Photoactive Layers
journal, May 2015

  • Aristidou, Nicholas; Sanchez-Molina, Irene; Chotchuangchutchaval, Thana
  • Angewandte Chemie International Edition, Vol. 54, Issue 28
  • DOI: 10.1002/anie.201503153

Formamidinium lead trihalide: a broadly tunable perovskite for efficient planar heterojunction solar cells
journal, January 2014

  • Eperon, Giles E.; Stranks, Samuel D.; Menelaou, Christopher
  • Energy & Environmental Science, Vol. 7, Issue 3
  • DOI: 10.1039/c3ee43822h

Cesium Lead Halide Perovskites with Improved Stability for Tandem Solar Cells
journal, February 2016

  • Beal, Rachel E.; Slotcavage, Daniel J.; Leijtens, Tomas
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 5
  • DOI: 10.1021/acs.jpclett.6b00002

Stabilizing Perovskite Structures by Tuning Tolerance Factor: Formation of Formamidinium and Cesium Lead Iodide Solid-State Alloys
journal, December 2015


Incorporation of rubidium cations into perovskite solar cells improves photovoltaic performance
journal, September 2016


Hybrid Germanium Iodide Perovskite Semiconductors: Active Lone Pairs, Structural Distortions, Direct and Indirect Energy Gaps, and Strong Nonlinear Optical Properties
journal, May 2015

  • Stoumpos, Constantinos C.; Frazer, Laszlo; Clark, Daniel J.
  • Journal of the American Chemical Society, Vol. 137, Issue 21
  • DOI: 10.1021/jacs.5b01025

Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties
journal, July 2013

  • Stoumpos, Constantinos C.; Malliakas, Christos D.; Kanatzidis, Mercouri G.
  • Inorganic Chemistry, Vol. 52, Issue 15, p. 9019-9038
  • DOI: 10.1021/ic401215x

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

Evidence for the direct population of solid-state bands by non-bonding electron pairs in compounds of the type CsM II X3(M II = Ge, Sn, Pb; X = Cl, Br, I)
journal, January 1995

  • Clark, Stephen J.; Donaldson, John D.; Harvey, Josephine A.
  • Journal of Materials Chemistry, Vol. 5, Issue 11
  • DOI: 10.1039/jm9950501813

Thin-Film Deposition and Characterization of a Sn-Deficient Perovskite Derivative Cs 2 SnI 6
journal, March 2016


Synthesis, Crystal Structure, and Optical and Thermal Properties of (C4H9NH3)2MI4 (M = Ge, Sn, Pb)
journal, January 1996

  • Mitzi, David B.
  • Chemistry of Materials, Vol. 8, Issue 3, p. 791-800
  • DOI: 10.1021/cm9505097

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

Effect of Electron Transporting Layer on Bismuth-Based Lead-Free Perovskite (CH 3 NH 3 ) 3 Bi 2 I 9 for Photovoltaic Applications
journal, June 2016

  • Singh, Trilok; Kulkarni, Ashish; Ikegami, Masashi
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 23
  • DOI: 10.1021/acsami.6b02843

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


Bismuth Iodide Perovskite Materials for Solar Cell Applications: Electronic Structure, Optical Transitions, and Directional Charge Transport
journal, December 2016

  • Pazoki, Meysam; Johansson, Malin B.; Zhu, Huimin
  • The Journal of Physical Chemistry C, Vol. 120, Issue 51
  • DOI: 10.1021/acs.jpcc.6b11745

Strong Electron–Phonon Coupling and Self-Trapped Excitons in the Defect Halide Perovskites A 3 M 2 I 9 (A = Cs, Rb; M = Bi, Sb)
journal, April 2017


Cs 2 AgBiX 6 (X = Br, Cl): New Visible Light Absorbing, Lead-Free Halide Perovskite Semiconductors
journal, February 2016


Silver bismuth iodides in various compositions as potential Pb-free light absorbers for hybrid solar cells
journal, January 2018

  • Jung, Ki Woo; Sohn, Mi Rae; Lee, Hye Min
  • Sustainable Energy & Fuels, Vol. 2, Issue 1
  • DOI: 10.1039/C7SE00477J

Pure Cubic-Phase Hybrid Iodobismuthates AgBi 2 I 7 for Thin-Film Photovoltaics
journal, June 2016

  • Kim, Younghoon; Yang, Zhenyu; Jain, Ankit
  • Angewandte Chemie International Edition, Vol. 55, Issue 33
  • DOI: 10.1002/anie.201603608

AgBiI 4 as a Lead-Free Solar Absorber with Potential Application in Photovoltaics
journal, February 2017


Exploring AgBixI3x+1 semiconductor thin films for lead-free perovskite solar cells
journal, March 2018


Photovoltaic Rudorffites: Lead-Free Silver Bismuth Halides Alternative to Hybrid Lead Halide Perovskites
journal, July 2017


Layer-by-Layer Growth of CH 3 NH 3 PbI 3− x Cl x for Highly Efficient Planar Heterojunction Perovskite Solar Cells
journal, December 2014


Electro-optics of perovskite solar cells
journal, December 2014

  • Lin, Qianqian; Armin, Ardalan; Nagiri, Ravi Chandra Raju
  • Nature Photonics, Vol. 9, Issue 2
  • DOI: 10.1038/nphoton.2014.284

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

Perovskite solar cells employing organic charge-transport layers
journal, December 2013


Crystal Structure of AgBi 2 I 7 Thin Films
journal, September 2016

  • Xiao, Zewen; Meng, Weiwei; Mitzi, David B.
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 19
  • DOI: 10.1021/acs.jpclett.6b01834

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


Cesium Titanium(IV) Bromide Thin Films Based Stable Lead-free Perovskite Solar Cells
journal, March 2018


Solvothermale Synthese und Bestimmung der Kristallstrukturen von AgBiI4 und Ag3BiI6
journal, March 2005

  • Oldag, Thorsten; Aussieker, Thomas; Keller, Hans-Lothar
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 631, Issue 4
  • DOI: 10.1002/zaac.200400508

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

Crystal growth and X-ray structure determination of Rb3Bi2I9
journal, January 2000


The Crystal Structure of Cesium Bismuth Iodide, Cs3Bi2I9.
journal, January 1968


Interface energetics in organo-metal halide perovskite-based photovoltaic cells
journal, January 2014

  • Schulz, Philip; Edri, Eran; Kirmayer, Saar
  • Energy & Environmental Science, Vol. 7, Issue 4
  • DOI: 10.1039/c4ee00168k

Electronic structure and photovoltaic application of BiI 3
journal, September 2015

  • Lehner, Anna J.; Wang, Hengbin; Fabini, Douglas H.
  • Applied Physics Letters, Vol. 107, Issue 13
  • DOI: 10.1063/1.4932129

Works referencing / citing this record:

Recent progress of inorganic perovskite solar cells
journal, January 2019

  • Tai, Qidong; Tang, Kai-Chi; Yan, Feng
  • Energy & Environmental Science, Vol. 12, Issue 8
  • DOI: 10.1039/c9ee01479a

Tailoring the film morphology and interface band offset of caesium bismuth iodide-based Pb-free perovskite solar cells
journal, January 2019

  • Khadka, Dhruba B.; Shirai, Yasuhiro; Yanagida, Masatoshi
  • Journal of Materials Chemistry C, Vol. 7, Issue 27
  • DOI: 10.1039/c9tc02181g

Low-dimensional non-toxic A 3 Bi 2 X 9 compounds synthesized by a dry mechanochemical route with tunable visible photoluminescence at room temperature
journal, January 2019

  • El Ajjouri, Yousra; Chirvony, Vladimir S.; Vassilyeva, Natalia
  • Journal of Materials Chemistry C, Vol. 7, Issue 21
  • DOI: 10.1039/c9tc01765h

Dual-source evaporation of silver bismuth iodide films for planar junction solar cells
journal, January 2019

  • Khazaee, Maryam; Sardashti, Kasra; Chung, Ching-Chang
  • Journal of Materials Chemistry A, Vol. 7, Issue 5
  • DOI: 10.1039/c8ta08679f

Perovskite Solar Cells: Can We Go Organic‐Free, Lead‐Free, and Dopant‐Free?
journal, October 2019


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

Performance enhancement of AgBi 2 I 7 solar cells by modulating a solvent-mediated adduct and tuning remnant BiI 3 in one-step crystallization
journal, January 2019

  • Kulkarni, Ashish; Jena, Ajay K.; Ikegami, Masashi
  • Chemical Communications, Vol. 55, Issue 28
  • DOI: 10.1039/c9cc00733d

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
  • DOI: 10.1002/aenm.201902496