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

Title: Influence of defects and dopants on the photovoltaic performance of Bi2S3: First-principles insights

Abstract

Bi2S3 has attracted extensive attention recently as a light-absorber, sensitizer or electron acceptor material in various solar cells. Using first-principles calculations, we find that the photovoltaic efficiency of Bi2S3 solar cells is limited by its intrinsic point defects, i.e., both S vacancy and S interstitial can have high concentration and produce deep defect levels in the bandgap, leading to non-radiative recombination of electron–hole carriers and reduced minority carrier lifetime. Unexpectedly most of the intrinsic defects in Bi2S3, including even the S interstitial, act as donor defects, explaining the observed n-type conductivity and also causing the high p-type conductivity impossible thermodynamically. Doping in Bi2S3 by a series of extrinsic elements is studied, showing that most of the dopant elements such as Cu, Br and Cl make the material even more n-type and only Pb doping makes it weakly p-type. Based on this, we propose that the surface region of n-type Bi2S3 nanocrystals in p-PbS/n-Bi2S3 nano-heterojunction solar cells may be type-inverted into p-type due to Pb doping, with a buried p–n junction formed in the Bi2S3 nanocrystals, which provides a new explanation to the longer carrier lifetime and higher efficiency. Lastly, considering the relatively low conduction band and high n-type conductivity, wemore » predict that Cu, Br and Cl doped Bi2S3 may be an ideal n-type electron acceptor or counter electrode material, while the performance of Bi2S3 as a light-absorber or sensitizer material is intrinsically limited.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]
  1. East China Normal Univ., Shanghai (China)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. East China Normal Univ., Shanghai (China); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1351779
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 13; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Han, Dan, Du, Mao -Hua, Dai, Chen -Min, Sun, Deyan, and Chen, Shiyou. Influence of defects and dopants on the photovoltaic performance of Bi2S3: First-principles insights. United States: N. p., 2017. Web. doi:10.1039/C6TA10377D.
Han, Dan, Du, Mao -Hua, Dai, Chen -Min, Sun, Deyan, & Chen, Shiyou. Influence of defects and dopants on the photovoltaic performance of Bi2S3: First-principles insights. United States. doi:10.1039/C6TA10377D.
Han, Dan, Du, Mao -Hua, Dai, Chen -Min, Sun, Deyan, and Chen, Shiyou. Thu . "Influence of defects and dopants on the photovoltaic performance of Bi2S3: First-principles insights". United States. doi:10.1039/C6TA10377D. https://www.osti.gov/servlets/purl/1351779.
@article{osti_1351779,
title = {Influence of defects and dopants on the photovoltaic performance of Bi2S3: First-principles insights},
author = {Han, Dan and Du, Mao -Hua and Dai, Chen -Min and Sun, Deyan and Chen, Shiyou},
abstractNote = {Bi2S3 has attracted extensive attention recently as a light-absorber, sensitizer or electron acceptor material in various solar cells. Using first-principles calculations, we find that the photovoltaic efficiency of Bi2S3 solar cells is limited by its intrinsic point defects, i.e., both S vacancy and S interstitial can have high concentration and produce deep defect levels in the bandgap, leading to non-radiative recombination of electron–hole carriers and reduced minority carrier lifetime. Unexpectedly most of the intrinsic defects in Bi2S3, including even the S interstitial, act as donor defects, explaining the observed n-type conductivity and also causing the high p-type conductivity impossible thermodynamically. Doping in Bi2S3 by a series of extrinsic elements is studied, showing that most of the dopant elements such as Cu, Br and Cl make the material even more n-type and only Pb doping makes it weakly p-type. Based on this, we propose that the surface region of n-type Bi2S3 nanocrystals in p-PbS/n-Bi2S3 nano-heterojunction solar cells may be type-inverted into p-type due to Pb doping, with a buried p–n junction formed in the Bi2S3 nanocrystals, which provides a new explanation to the longer carrier lifetime and higher efficiency. Lastly, considering the relatively low conduction band and high n-type conductivity, we predict that Cu, Br and Cl doped Bi2S3 may be an ideal n-type electron acceptor or counter electrode material, while the performance of Bi2S3 as a light-absorber or sensitizer material is intrinsically limited.},
doi = {10.1039/C6TA10377D},
journal = {Journal of Materials Chemistry. A},
number = 13,
volume = 5,
place = {United States},
year = {2017},
month = {2}
}

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

Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Bismuth chalcohalides and oxyhalides as optoelectronic materials
journal, March 2016


Structural and Electronic Properties of Semiconductor-Sensitized Solar-Cell Interfaces
journal, September 2011

  • Patrick, Christopher E.; Giustino, Feliciano
  • Advanced Functional Materials, Vol. 21, Issue 24
  • DOI: 10.1002/adfm.201101103

Transport Properties of Bi 2 S 3 and the Ternary Bismuth Sulfides KBi 6.33 S 10 and K 2 Bi 8 S 13
journal, July 1997

  • Chen, Baoxing; Uher, Ctirad; Iordanidis, Lykourgos
  • Chemistry of Materials, Vol. 9, Issue 7
  • DOI: 10.1021/cm970033m

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

Principles of Chemical Bonding and Band Gap Engineering in Hybrid Organic–Inorganic Halide Perovskites
journal, February 2015

  • Walsh, Aron
  • The Journal of Physical Chemistry C, Vol. 119, Issue 11
  • DOI: 10.1021/jp512420b

Solution-Processed Heterojunction Solar Cells Based on p-type PbS Quantum Dots and n-type Bi2S3 Nanocrystals
journal, July 2011

  • Rath, Arup K.; Bernechea, Maria; Martinez, Luis
  • Advanced Materials, Vol. 23, Issue 32
  • DOI: 10.1002/adma.201101399

Thermoelectric Properties of (Bi1−x Sb x )2S3 with Orthorhombic Structure
journal, September 2013


Physical vapor deposition of Bi2S3 as absorber material in thin film photovoltaics
journal, May 2013


Rapid thermal evaporation of Bi2S3 layer for thin film photovoltaics
journal, March 2016


Copper-alloyed ZnS as a p-type transparent conducting material
journal, August 2012

  • Diamond, Anthony M.; Corbellini, Luca; Balasubramaniam, K. R.
  • physica status solidi (a), Vol. 209, Issue 11
  • DOI: 10.1002/pssa.201228181

Perovskite Solar Cells Shine in the “Valley of the Sun”
journal, April 2016


Topotactically Grown Bismuth Sulfide Network Film on Substrate as Low-Cost Counter Electrodes for Quantum Dot-Sensitized Solar Cells
journal, March 2014

  • Yu, Haijing; Bao, Huili; Zhao, Ke
  • The Journal of Physical Chemistry C, Vol. 118, Issue 30
  • DOI: 10.1021/jp4125217

Analysis of a Bismuth Sulfide/Silicon Junction for Building Thin Film Solar Cells
journal, January 2011

  • Becerra, D.; Nair, M. T. S.; Nair, P. K.
  • Journal of The Electrochemical Society, Vol. 158, Issue 7
  • DOI: 10.1149/1.3591045

Band-Edge Tuning in Self-Assembled Layers of Bi 2 S 3 Nanoparticles Used To Photosensitize Nanocrystalline TiO 2
journal, August 2003

  • Peter, Laurence M.; Wijayantha, K. G. Upul; Riley, D. Jason
  • The Journal of Physical Chemistry B, Vol. 107, Issue 33
  • DOI: 10.1021/jp030334l

Relativistic electronic structure and band alignment of BiSI and BiSeI: candidate photovoltaic materials
journal, January 2016

  • Ganose, Alex M.; Butler, Keith T.; Walsh, Aron
  • Journal of Materials Chemistry A, Vol. 4, Issue 6
  • DOI: 10.1039/C5TA09612J

Synthesis and transport properties of AgBi3S5 ternary sulfide compound
journal, May 2013


Solution-processed inorganic bulk nano-heterojunctions and their application to solar cells
journal, July 2012


Interfacial Oxygen Vacancies as a Potential Cause of Hysteresis in Perovskite Solar Cells
journal, January 2016


Acceptor Levels in p -Type Cu 2 O : Rationalizing Theory and Experiment
journal, August 2009


Bi 2 S 3 nanowire networks as electron acceptor layers in solution-processed hybrid solar cells
journal, January 2015

  • Whittaker-Brooks, Luisa; Gao, Jia; Hailey, Anna K.
  • J. Mater. Chem. C, Vol. 3, Issue 11
  • DOI: 10.1039/C4TC02534B

Assessment of correction methods for the band-gap problem and for finite-size effects in supercell defect calculations: Case studies for ZnO and GaAs
journal, December 2008


Materials interface engineering for solution-processed photovoltaics
journal, August 2012

  • Graetzel, Michael; Janssen, René A. J.; Mitzi, David B.
  • Nature, Vol. 488, Issue 7411
  • DOI: 10.1038/nature11476

Tellurium-Free Thermoelectric: The Anisotropic n-Type Semiconductor Bi2S3
journal, March 2012

  • Biswas, Kanishka; Zhao, Li-Dong; Kanatzidis, Mercouri G.
  • Advanced Energy Materials, Vol. 2, Issue 6
  • DOI: 10.1002/aenm.201100775

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


Improvement in PbS-based Hybrid Bulk-Heterojunction Solar Cells through Band Alignment via Bismuth Doping in the Nanocrystals
journal, April 2015

  • Saha, Sudip K.; Bera, Abhijit; Pal, Amlan J.
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 16
  • DOI: 10.1021/acsami.5b01521

Influence of interface modification on the performance of polymer/Bi2S3 nanorods bulk heterojunction solar cells
journal, November 2010


Optoelectronic properties of chemically deposited Bi2S3 thin films and the photovoltaic performance of Bi2S3/P3OT solar cells
journal, April 2012


Doping asymmetry in wide-bandgap semiconductors: Origins and solutions
journal, April 2008


Theoretical and experimental investigations of the thermoelectric properties of Bi 2 S 3
journal, March 2015

  • Chmielowski, Radoslaw; Péré, Daniel; Bera, Chandan
  • Journal of Applied Physics, Vol. 117, Issue 12
  • DOI: 10.1063/1.4916528

Toward Antimony Selenide Sensitized Solar Cells: Efficient Charge Photogeneration at spiro -OMeTAD/Sb 2 Se 3 /Metal Oxide Heterojunctions
journal, May 2012

  • Guijarro, Néstor; Lutz, Thierry; Lana-Villarreal, Teresa
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 10
  • DOI: 10.1021/jz3004365

Solution-Processed Antimony Selenide Heterojunction Solar Cells
journal, February 2014


Native point defects in ZnO
journal, October 2007


Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965


Synthesis, optical and photovoltaic properties of bismuth sulfide nanorods
journal, January 2012

  • Liao, Hsueh-Chung; Wu, Ming-Chung; Jao, Meng-Huan
  • CrystEngComm, Vol. 14, Issue 10
  • DOI: 10.1039/c2ce06154f

Compositional dependence of structural and electronic properties of Cu 2 ZnSn(S,Se) 4 alloys for thin film solar cells
journal, March 2011


Dynamic random access memory devices based on bismuth sulfide nanoplates prepared from a single source precursor
journal, January 2013

  • Liu, Gao-Yan; Xu, Ling-Yun; Zhou, Feng
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 27
  • DOI: 10.1039/c3cp50700a

Chemical trends of defect formation and doping limit in II-VI semiconductors: The case of CdTe
journal, October 2002


Near IR-Sensitive, Non-toxic, Polymer/Nanocrystal Solar Cells Employing Bi2S3 as the Electron Acceptor
journal, September 2011

  • Martinez, Luis; Bernechea, Maria; de Arquer, F. Pelayo García
  • Advanced Energy Materials, Vol. 1, Issue 6
  • DOI: 10.1002/aenm.201100441

Thermodynamic Oxidation and Reduction Potentials of Photocatalytic Semiconductors in Aqueous Solution
journal, September 2012

  • Chen, Shiyou; Wang, Lin-Wang
  • Chemistry of Materials, Vol. 24, Issue 18
  • DOI: 10.1021/cm302533s

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

Structural and electronic properties of CuSbS2 and CuBiS2: potential absorber materials for thin-film solar cells
journal, January 2012

  • Dufton, Jesse T. R.; Walsh, Aron; Panchmatia, Pooja M.
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 20
  • DOI: 10.1039/c2cp40916j

Electrochemical atomic layer deposition of Bi2S3/Sb2S3 quantum dots co-sensitized TiO2 nanorods solar cells
journal, March 2016


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


Preparation and electrical properties of Bi 2 S 3 whiskers
journal, July 1995

  • Mizoguchi, H.; Hosono, H.; Ueda, N.
  • Journal of Applied Physics, Vol. 78, Issue 2
  • DOI: 10.1063/1.360315

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

Chemical potential dependence of defect formation energies in GaAs: Application to Ga self-diffusion
journal, October 1991


Linker free synthesis of TiO2/Bi2S3 heterostructure towards solar cell application: Facile chemical routes
journal, February 2015

  • Salunkhe, D. B.; Dubal, D. P.; Sali, J. V.
  • Materials Science in Semiconductor Processing, Vol. 30
  • DOI: 10.1016/j.mssp.2014.10.024

Inhomogeneous Electron Gas
journal, November 1964


Intrinsic n -type versus p -type doping asymmetry and the defect physics of ZnO
journal, January 2001


Overcoming the doping bottleneck in semiconductors
journal, August 2004


Engineering Solar Cell Absorbers by Exploring the Band Alignment and Defect Disparity: The Case of Cu- and Ag-Based Kesterite Compounds
journal, October 2015

  • Yuan, Zhen-Kun; Chen, Shiyou; Xiang, Hongjun
  • Advanced Functional Materials, Vol. 25, Issue 43
  • DOI: 10.1002/adfm.201502272

Improved performance and stability in quantum dot solar cells through band alignment engineering
journal, May 2014

  • Chuang, Chia-Hao M.; Brown, Patrick R.; Bulović, Vladimir
  • Nature Materials, Vol. 13, Issue 8, p. 796-801
  • DOI: 10.1038/nmat3984

Ground State of the Electron Gas by a Stochastic Method
journal, August 1980


Perovskite Solar Cells: From Materials to Devices
journal, October 2014


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

Enhanced thermoelectric performance of chloride doped bismuth sulfide prepared by mechanical alloying and spark plasma sintering
journal, February 2014


Classification of Lattice Defects in the Kesterite Cu 2 ZnSnS 4 and Cu 2 ZnSnSe 4 Earth-Abundant Solar Cell Absorbers
journal, February 2013


Assembly of one-dimensional nanorods into Bi2S3 films with enhanced thermoelectric transport properties
journal, March 2007

  • Liufu, Sheng-Cong; Chen, Li-Dong; Yao, Qin
  • Applied Physics Letters, Vol. 90, Issue 11
  • DOI: 10.1063/1.2712504

Nanostructured Bi2−xCuxS3 bulk materials with enhanced thermoelectric performance
journal, January 2012

  • Ge, Zhen-Hua; Zhang, Bo-Ping; Liu, Yong
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 13
  • DOI: 10.1039/c2cp23955h

    Works referencing / citing this record:

    Crystal structure design and multiband physical properties of quaternary sulfide Ba 5 Bi 2 Co 2 S 10 for optoelectronic conversion
    journal, January 2019

    • Bu, Kejun; Zhang, Xian; Huang, Jian
    • Chemical Communications, Vol. 55, Issue 33
    • DOI: 10.1039/c9cc00794f

    Crystal structure design and multiband physical properties of quaternary sulfide Ba 5 Bi 2 Co 2 S 10 for optoelectronic conversion
    journal, January 2019

    • Bu, Kejun; Zhang, Xian; Huang, Jian
    • Chemical Communications, Vol. 55, Issue 33
    • DOI: 10.1039/c9cc00794f