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Title: Assessing the role of hydrogen in Fermi-level pinning in chalcopyrite and kesterite solar absorbers from first-principles calculations

Abstract

Understanding the impact of impurities in solar absorbers is critical to engineering high-performance in devices, particularly over extended periods of time. Here we use hybrid functional calculations to explore the role of hydrogen interstitial (Hi) defects on the electronic properties of a number of attractive solar absorbers within the chalcopyrite and kesterite families to identify how this common impurity may influence device performance. Our results identify that Hi can inhibit the highly p-type conditions desirable for several higher-band gap absorbers and that H incorporation could detrimentally affect the open-circuit voltage (Voc) and limit device efficiencies. Moreover, we discover that Hi can drive the Fermi level away from the valence band edge enough to lead to n-type conductivity in a number of chalcopyrite and kesterite absorbers, particularly those containing Ag rather than Cu. We find these results can lead to interfacial Fermi-level pinning that can qualitatively explain observed performance in high-Ga content CIGSe solar cells that exhibit saturation in the Voc with increasing band gap. Our results suggest that compositional grading rather than bulk alloying, such as by creating In-rich surfaces, may be a better strategy to favorably engineering improved thin-film photovoltaics with larger-band gap absorbers.

Authors:
 [1];  [1];  [1];  [2];  [2];  [2]
+ Show Author Affiliations
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. Univ. of Hawaii, Honolulu, HI (United States)
Publication Date:
Research Org.:
Univ. of Hawaii, Honolulu, HI (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office
OSTI Identifier:
1570463
Grant/Contract Number:  
EE0006670; AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Applied Physics
Additional Journal Information:
Journal Volume: 123; Journal Issue: 16; Journal ID: ISSN 0021-8979
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN

Citation Formats

Varley, J. B., Lordi, V., Ogitsu, T., Deangelis, A., Horsley, K., and Gaillard, N. Assessing the role of hydrogen in Fermi-level pinning in chalcopyrite and kesterite solar absorbers from first-principles calculations. United States: N. p., 2018. Web. doi:10.1063/1.5006272.
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Varley, J. B., Lordi, V., Ogitsu, T., Deangelis, A., Horsley, K., & Gaillard, N. Assessing the role of hydrogen in Fermi-level pinning in chalcopyrite and kesterite solar absorbers from first-principles calculations. United States. https://doi.org/10.1063/1.5006272
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Varley, J. B., Lordi, V., Ogitsu, T., Deangelis, A., Horsley, K., and Gaillard, N. Wed . "Assessing the role of hydrogen in Fermi-level pinning in chalcopyrite and kesterite solar absorbers from first-principles calculations". United States. https://doi.org/10.1063/1.5006272. https://www.osti.gov/servlets/purl/1570463.
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@article{osti_1570463,
title = {Assessing the role of hydrogen in Fermi-level pinning in chalcopyrite and kesterite solar absorbers from first-principles calculations},
author = {Varley, J. B. and Lordi, V. and Ogitsu, T. and Deangelis, A. and Horsley, K. and Gaillard, N.},
abstractNote = {Understanding the impact of impurities in solar absorbers is critical to engineering high-performance in devices, particularly over extended periods of time. Here we use hybrid functional calculations to explore the role of hydrogen interstitial (Hi) defects on the electronic properties of a number of attractive solar absorbers within the chalcopyrite and kesterite families to identify how this common impurity may influence device performance. Our results identify that Hi can inhibit the highly p-type conditions desirable for several higher-band gap absorbers and that H incorporation could detrimentally affect the open-circuit voltage (Voc) and limit device efficiencies. Moreover, we discover that Hi can drive the Fermi level away from the valence band edge enough to lead to n-type conductivity in a number of chalcopyrite and kesterite absorbers, particularly those containing Ag rather than Cu. We find these results can lead to interfacial Fermi-level pinning that can qualitatively explain observed performance in high-Ga content CIGSe solar cells that exhibit saturation in the Voc with increasing band gap. Our results suggest that compositional grading rather than bulk alloying, such as by creating In-rich surfaces, may be a better strategy to favorably engineering improved thin-film photovoltaics with larger-band gap absorbers.},
doi = {10.1063/1.5006272},
journal = {Journal of Applied Physics},
number = 16,
volume = 123,
place = {United States},
year = {Wed Mar 07 00:00:00 EST 2018},
month = {Wed Mar 07 00:00:00 EST 2018}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1063/1.5006272
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Cited by: 10 works
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Figures / Tables:

FIG. 1 FIG. 1: Formation energies of Hi defects in (a) CuInSe2 and (b) CuGaSe2. Only the lowest energy charge states are included; Hi acts exclusively as a shallow donor in CISe but is amphoteric in CGSe, having a transition level (+/-) at 1.15 eV above the VBM ( ~0.5 eV belowmore » the CBM). Schematic representations of the H$^{+}_{i}$ and H$^{-}_{i}$ configurations are included in (c), (d), and (e) as described in the text. Group Ⅰ atoms are blue, Group Ⅵ atoms are orange, and Group Ⅲ are green.« less
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Works referenced in this record:

Hydrogen in Semiconductors
journal, August 2006

Engineering of interface band bending and defects elimination via a Ag-graded active layer for efficient (Cu,Ag) 2 ZnSn(S,Se) 4 solar cells
journal, January 2017

  • Qi, Ya-Fang; Kou, Dong-Xing; Zhou, Wen-Hui
  • Energy & Environmental Science, Vol. 10, Issue 11
  • DOI: 10.1039/C7EE01405H

Hydrogenated cation vacancies in semiconducting oxides
journal, August 2011

Energy band alignment in chalcogenide thin film solar cells from photoelectron spectroscopy
journal, March 2015

Modelling polycrystalline semiconductor solar cells
journal, February 2000

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

Projector augmented-wave method
journal, December 1994

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

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

The absolute electrode potential: an explanatory note (Recommendations 1986)
journal, January 1986

Wide bandgap Cu(In,Ga)Se 2 solar cells with improved energy conversion efficiency : Wide bandgap Cu(In,Ga)Se
journal, June 2012

  • Contreras, Miguel A.; Mansfield, Lorelle M.; Egaas, Brian
  • Progress in Photovoltaics: Research and Applications, Vol. 20, Issue 7
  • DOI: 10.1002/pip.2244

Electrical properties of point defects in CdS and ZnS
journal, September 2013

  • Varley, J. B.; Lordi, V.
  • Applied Physics Letters, Vol. 103, Issue 10
  • DOI: 10.1063/1.4819492

Hydrogen states in CuInSe2—a μSR study
journal, December 2003

Electronic properties of Cu(In,Ga)Se 2 heterojunction solar cells-recent achievements, current understanding, and future challenges
journal, August 1999

  • Rau, U.; Schock, H. W.
  • Applied Physics A: Materials Science & Processing, Vol. 69, Issue 2
  • DOI: 10.1007/s003390050984

The absolute potential of the standard hydrogen electrode: a new estimate
journal, September 1985

  • Reiss, Howard; Heller, Adam
  • The Journal of Physical Chemistry, Vol. 89, Issue 20
  • DOI: 10.1021/j100266a013

XPS study of OH impurity in solution processed CdS thin films
journal, February 2017

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

Standard hydrogen electrode and potential of zero charge in density functional calculations
journal, September 2011

  • Tripkovic, Vladimir; Björketun, Mårten E.; Skúlason, Egill
  • Physical Review B, Vol. 84, Issue 11
  • DOI: 10.1103/PhysRevB.84.115452

Modeling Practical Performance Limits of Photoelectrochemical Water Splitting Based on the Current State of Materials Research
journal, April 2014

Ionization potentials of (112) and (11 2 ¯ ) facet surfaces of CuInSe 2 and CuGaSe 2
journal, December 2012

First-principles calculations for point defects in solids
journal, March 2014

  • Freysoldt, Christoph; Grabowski, Blazej; Hickel, Tilmann
  • Reviews of Modern Physics, Vol. 86, Issue 1
  • DOI: 10.1103/RevModPhys.86.253

Understanding defect-related issues limiting efficiency of CIGS solar cells
journal, August 2009

  • Igalson, Małgorzata; Zabierowski, Paweł; Prządo, Daniel
  • Solar Energy Materials and Solar Cells, Vol. 93, Issue 8
  • DOI: 10.1016/j.solmat.2009.01.022

Hydrogen in CuInSe2
journal, September 2003

Origin of Reduced Efficiency in Cu(In,Ga)Se$_2$ Solar Cells With High Ga Concentration: Alloy Solubility Versus Intrinsic Defects
journal, January 2014

Cd doping at PVD-CdS/CuInGaSe2 heterojunctions
journal, May 2017

Intrinsic limitations to the doping of wide-gap semiconductors
journal, January 2001

Intermixing and Formation of Cu-Rich Secondary Phases at Sputtered CdS/CuInGaSe 2 Heterojunctions
journal, September 2016

Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)]
journal, June 2006

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 124, Issue 21
  • DOI: 10.1063/1.2204597

Band offsets and optical bowings of chalcopyrites and Zn‐based II‐VI alloys
journal, September 1995

  • Wei, Su‐Huai; Zunger, Alex
  • Journal of Applied Physics, Vol. 78, Issue 6
  • DOI: 10.1063/1.359901

Descriptor-Based Approach for the Prediction of Cation Vacancy Formation Energies and Transition Levels
journal, October 2017

  • Varley, Joel B.; Samanta, Amit; Lordi, Vincenzo
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 20
  • DOI: 10.1021/acs.jpclett.7b02333

Technical and economic feasibility of centralized facilities for solar hydrogen production via photocatalysis and photoelectrochemistry
journal, January 2013

  • Pinaud, Blaise A.; Benck, Jesse D.; Seitz, Linsey C.
  • Energy & Environmental Science, Vol. 6, Issue 7
  • DOI: 10.1039/c3ee40831k

Impact of a RbF Postdeposition Treatment on the Electronic Structure of the CdS/Cu(In,Ga)Se 2 Heterojunction in High-Efficiency Thin-Film Solar Cells
journal, September 2017

Prospects of wide-gap chalcopyrites for thin film photovoltaic modules
journal, December 1997

n -type doping and passivation of CuInSe 2 and CuGaSe 2 by hydrogen
journal, August 2003

Hydrogen passivation of shallow-acceptor impurities in p -type GaAs
journal, January 1986

Hydrogenated vacancies and hidden hydrogen in SrTiO 3
journal, February 2014

Universal alignment of hydrogen levels in semiconductors, insulators and solutions
journal, June 2003

Exploring Cd-Zn-O-S alloys for improved buffer layers in thin-film photovoltaics
journal, July 2017

Band alignment of semiconductors from density-functional theory and many-body perturbation theory
journal, October 2014

Intrinsic point defects in CuInSe 2 and CuGaSe 2 as seen via screened-exchange hybrid density functional theory
journal, June 2013

Fermi-level stabilization energy in group III nitrides
journal, April 2005

High-resolution X-ray luminescence extension imaging
journal, February 2021

Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect
journal, February 2020

Hydrogen in Semiconductors
conference, January 2003

  • Stavola, Michael
  • HYDROGEN IN MATERIALS & VACUUM SYSTEMS: First International Workshop on Hydrogen in Materials and Vacuum Systems, AIP Conference Proceedings
  • DOI: 10.1063/1.1597353
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