Wide Band Gap CuGa(S,Se)2 Thin Films on Transparent Conductive Fluorinated Tin Oxide Substrates as Photocathode Candidates for Tandem Water Splitting Devices
Abstract
Theaim of this report was to explore the potential of CuGa(S,Se)2 thin films as wide-EG top cell absorbers for photoelectrochemical (PEC) water splitting. A synthesis was developed on fluorinated tin oxide (FTO) photocathodes by converting copper-rich co-evaporated CuGaSe2 into CuGa(S,Se)2 via a post-deposition annealing. We found it necessary to first anneal CuGaSe2 at low-temperature in sulfur then at high-temperature in nitrogen to preserve the transparency and conductivity of the FTO. Using this two-step synthesis, we fabricated a 1.72eV CuGa(S,Se)2 photocathode with a saturation current density and photocurrent onset potential of 10mA/cm2 and -0.20V vs. RHE, respectively. Yet we found that the PEC performance and sub-EG transmittance, worsened with increasing copper content. Using flatband potential measurements and the Gerischer model, we show that divergences in PEC performance of CuGa(S,Se)2 photocathodes can be explained by differences in conduction band minimums and Fermi levels. We also explain that sub-EG transmittance is likely hampered by a defect band 100-400 meV below EC. Additional external quantum efficiency measurements of a high-efficiency 1.1 eV Cu(In,Ga)Se2 photovoltaic driver, while shaded by the CuGa(S,Se)2 photocathode, yielded a short-circuit current density of 4.14 mA/cm2 revealing that CuGa(S,Se)2 reflects promise as a top cell for PEC water splitting.
- Authors:
-
- 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 (HFTO)
- OSTI Identifier:
- 1570461
- Grant/Contract Number:
- EE0006670
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 122; Journal Issue: 26; 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
DeAngelis, Alexander D., Horsley, Kimberly, and Gaillard, Nicolas. Wide Band Gap CuGa(S,Se)2 Thin Films on Transparent Conductive Fluorinated Tin Oxide Substrates as Photocathode Candidates for Tandem Water Splitting Devices. United States: N. p., 2018.
Web. doi:10.1021/acs.jpcc.8b02915.
DeAngelis, Alexander D., Horsley, Kimberly, & Gaillard, Nicolas. Wide Band Gap CuGa(S,Se)2 Thin Films on Transparent Conductive Fluorinated Tin Oxide Substrates as Photocathode Candidates for Tandem Water Splitting Devices. United States. https://doi.org/10.1021/acs.jpcc.8b02915
DeAngelis, Alexander D., Horsley, Kimberly, and Gaillard, Nicolas. Sun .
"Wide Band Gap CuGa(S,Se)2 Thin Films on Transparent Conductive Fluorinated Tin Oxide Substrates as Photocathode Candidates for Tandem Water Splitting Devices". United States. https://doi.org/10.1021/acs.jpcc.8b02915. https://www.osti.gov/servlets/purl/1570461.
@article{osti_1570461,
title = {Wide Band Gap CuGa(S,Se)2 Thin Films on Transparent Conductive Fluorinated Tin Oxide Substrates as Photocathode Candidates for Tandem Water Splitting Devices},
author = {DeAngelis, Alexander D. and Horsley, Kimberly and Gaillard, Nicolas},
abstractNote = {Theaim of this report was to explore the potential of CuGa(S,Se)2 thin films as wide-EG top cell absorbers for photoelectrochemical (PEC) water splitting. A synthesis was developed on fluorinated tin oxide (FTO) photocathodes by converting copper-rich co-evaporated CuGaSe2 into CuGa(S,Se)2 via a post-deposition annealing. We found it necessary to first anneal CuGaSe2 at low-temperature in sulfur then at high-temperature in nitrogen to preserve the transparency and conductivity of the FTO. Using this two-step synthesis, we fabricated a 1.72eV CuGa(S,Se)2 photocathode with a saturation current density and photocurrent onset potential of 10mA/cm2 and -0.20V vs. RHE, respectively. Yet we found that the PEC performance and sub-EG transmittance, worsened with increasing copper content. Using flatband potential measurements and the Gerischer model, we show that divergences in PEC performance of CuGa(S,Se)2 photocathodes can be explained by differences in conduction band minimums and Fermi levels. We also explain that sub-EG transmittance is likely hampered by a defect band 100-400 meV below EC. Additional external quantum efficiency measurements of a high-efficiency 1.1 eV Cu(In,Ga)Se2 photovoltaic driver, while shaded by the CuGa(S,Se)2 photocathode, yielded a short-circuit current density of 4.14 mA/cm2 revealing that CuGa(S,Se)2 reflects promise as a top cell for PEC water splitting.},
doi = {10.1021/acs.jpcc.8b02915},
journal = {Journal of Physical Chemistry. C},
number = 26,
volume = 122,
place = {United States},
year = {Sun Jun 03 00:00:00 EDT 2018},
month = {Sun Jun 03 00:00:00 EDT 2018}
}
Web of Science
Figures / Tables:
Works referenced in this record:
Basic concepts of photoelectrochemical solar energy conversion systems
journal, February 2012
- Fiechter, S.; Bogdanoff, P.; Bak, T.
- Advances in Applied Ceramics, Vol. 111, Issue 1-2
Photocatalytic Water Splitting—The Untamed Dream: A Review of Recent Advances
journal, July 2016
- Jafari, Tahereh; Moharreri, Ehsan; Amin, Alireza
- Molecules, Vol. 21, Issue 7
Electrochemical Stability of p-GaInP[sub 2] in Aqueous Electrolytes Toward Photoelectrochemical Water Splitting
journal, January 1998
- Khaselev, Oscar
- Journal of The Electrochemical Society, Vol. 145, Issue 10
Effects of heavy alkali elements in Cu(In,Ga)Se 2 solar cells with efficiencies up to 22.6%
journal, July 2016
- Jackson, Philip; Wuerz, Roland; Hariskos, Dimitrios
- physica status solidi (RRL) - Rapid Research Letters, Vol. 10, Issue 8
Determination of the band gap depth profile of the penternary Cu(In(1−X)GaX)(SYSe(1−Y))2 chalcopyrite from its composition gradient
journal, October 2004
- Bär, M.; Bohne, W.; Röhrich, J.
- Journal of Applied Physics, Vol. 96, Issue 7
Efficiency of Splitting Water with Semiconducting Photoelectrodes
journal, January 1984
- Weber, Michael F.
- Journal of The Electrochemical Society, Vol. 131, Issue 6
Modeling Practical Performance Limits of Photoelectrochemical Water Splitting Based on the Current State of Materials Research
journal, April 2014
- Seitz, Linsey C.; Chen, Zhebo; Forman, Arnold J.
- ChemSusChem, Vol. 7, Issue 5
An analysis of the optimal band gaps of light absorbers in integrated tandem photoelectrochemical water-splitting systems
journal, January 2013
- Hu, Shu; Xiang, Chengxiang; Haussener, Sophia
- Energy & Environmental Science, Vol. 6, Issue 10
Photoelectrolysis of water using thin copper gallium diselenide electrodes
journal, September 2008
- Marsen, Bjorn; Cole, Brian; Miller, Eric L.
- Solar Energy Materials and Solar Cells, Vol. 92, Issue 9
Photosplitting of Water from Wide-Gap Cu(In,Ga)S 2 Thin Films Modified with a CdS Layer and Pt Nanoparticles for a High-Onset-Potential Photocathode
journal, April 2015
- Septina, Wilman; , Gunawan; Ikeda, Shigeru
- The Journal of Physical Chemistry C, Vol. 119, Issue 16, p. 8576-8583
CuInGaS 2 photocathodes treated with SbX 3 (X = Cl, I): the effect of the halide on solar water splitting performance
journal, December 2016
- Guijarro, Néstor; Prévot, Mathieu S.; Johnson, Melissa
- Journal of Physics D: Applied Physics, Vol. 50, Issue 4
Photoelectrochemical water splitting using Cu(In,Al)Se2 photoelectrodes developed via selenization of sputtered Cu–In–Al metal precursors
journal, July 2016
- Cheng, Kong-Wei; Hinaro, Kei; Antony, Mini Pothanadu
- Solar Energy Materials and Solar Cells, Vol. 151
Chalcopyrite Thin Film Materials for Photoelectrochemical Hydrogen Evolution from Water under Sunlight
journal, July 2015
- Kaneko, Hiroyuki; Minegishi, Tsutomu; Domen, Kazunari
- Coatings, Vol. 5, Issue 3
Synthesis of the solution-processed wide band-gap chalcopyrite CuGa(S,Se) 2 thin film and its application to photovoltaics
journal, January 2017
- Park, Gi Soon; Park, Se Jin; Jeong, Jae Seung
- Thin Solid Films, Vol. 621
Effects of residual copper selenide on CuInGaSe2 solar cells
journal, February 2011
- Hsieh, Tung-Po; Chuang, Chia-Chih; Wu, Chung-Shin
- Solid-State Electronics, Vol. 56, Issue 1
Photoelectrochemical Water Splitting
book, January 2013
- Chen, Zhebo; Dinh, Huyen N.; Miller, Eric
- SpringerBriefs in Energy
Band gap energies of bulk, thin-film, and epitaxial layers of CuInSe2 and CuGaSe2
journal, April 1998
- Chichibu, S.; Mizutani, T.; Murakami, K.
- Journal of Applied Physics, Vol. 83, Issue 7
Optical properties of laser-evaporated CuGaSe2 films near and above the fundamental absorption edge
journal, October 1994
- Kindyak, V. V.; Kindyak, A. S.; Gremenok, V. F.
- Thin Solid Films, Vol. 250, Issue 1-2
Photoluminescence of CuGaS2 epitaxial layers grown by metalorganic vapor phase epitaxy
journal, April 2000
- Shirakata, Sho; Chichibu, Shigefusa
- Journal of Applied Physics, Vol. 87, Issue 8
Optical properties of epitaxial CuGaS2 layers on Si(111)
journal, September 2003
- Eberhardt, J.; Metzner, H.; Hahn, Th.
- Journal of Physics and Chemistry of Solids, Vol. 64, Issue 9-10
Formation and analysis of graded CuIn(Se1−ySy)2 films
journal, May 2001
- Engelmann, M.; McCandless, B. E.; Birkmire, R. W.
- Thin Solid Films, Vol. 387, Issue 1-2
Preparation and characterization of CuInS2 thin films completely converted from CuInSe2 by sulfurization
journal, June 2005
- Liu, C. P.; Tseng, B. H.
- Thin Solid Films, Vol. 480-481, p. 50-54
Post-Deposition Sulfur Incorporation into CuInSe 2 Thin Films
journal, January 2001
- Titus, Jochen; Schock, Hans-Werner; Birkmire, Robert W.
- MRS Proceedings, Vol. 668
Surface sulfurization studies of Cu(InGa)Se2 thin film
journal, March 2006
- Singh, Udai P.; Shafarman, William N.; Birkmire, Robert W.
- Solar Energy Materials and Solar Cells, Vol. 90, Issue 5
Studies on sulfur diffusion into Cu(In,Ga)Se2 thin films
journal, March 2000
- Ba?ol, B. M.; Halani, A.; Leidholm, C.
- Progress in Photovoltaics: Research and Applications, Vol. 8, Issue 2
Band gap engineering in polycrystalline Cu(In,Ga)(Se,S)2 chalcopyrite thin films
journal, March 2004
- Alberts, V.
- Materials Science and Engineering: B, Vol. 107, Issue 2
Structural, optical, and electrical properties of tin sulfide thin films grown with electron-beam evaporation
journal, September 2015
- Park, Hui Kyung; Jo, Jaeseung; Hong, Hee Kyeung
- Current Applied Physics, Vol. 15, Issue 9
Impact of growth temperature on the properties of SnS film prepared by thermal evaporation and its photovoltaic performance
journal, August 2015
- Kawano, Yu; Chantana, Jakapan; Minemoto, Takashi
- Current Applied Physics, Vol. 15, Issue 8
Electrical properties of spray pyrolytic tin sulfide films
journal, June 2005
- Koteeswara Reddy, N.; Ramakrishna Reddy, K. T.
- Solid-State Electronics, Vol. 49, Issue 6
Structural, optical, and electrical properties of tin sulfide thin films grown by spray pyrolysis
journal, February 2009
- Calixto-Rodriguez, M.; Martinez, H.; Sanchez-Juarez, A.
- Thin Solid Films, Vol. 517, Issue 7
Improved mobility of sol-gel method processed transparent tin sulfide thin films
journal, September 2016
- Sun, Jian; Huang, Yifei; Nie, Sha
- Materials Letters, Vol. 178
Photoelectrochemical studies of copper gallium diselenide films
journal, October 1990
- Kessler, John; Lincot, Daniel; Vedel, Jacques
- Solar Cells, Vol. 29, Issue 4
Investigation of Cu-Deficient Copper Gallium Selenide Thin Film as a Photocathode for Photoelectrochemical Water Splitting
journal, January 2012
- Kim, Jaehong; Minegishi, Tsutomu; Kobota, Jun
- Japanese Journal of Applied Physics, Vol. 51, Issue 1R
Crystallographic and optical properties of CuGa 3 S 5 , CuGa 3 Se 5 and CuIn 3 (S,Se) 5 and CuGa 3 (S,Se) 5 systems
journal, July 2017
- Ueda, Kenta; Maeda, Tsuyoshi; Wada, Takahiro
- Thin Solid Films, Vol. 633
Quasi Fermi level splitting of Cu-rich and Cu-poor Cu(In,Ga)Se 2 absorber layers
journal, August 2016
- Babbe, Finn; Choubrac, Leo; Siebentritt, Susanne
- Applied Physics Letters, Vol. 109, Issue 8
Photoluminescence and sub band gap absorption of CuGaSe2 thin films
journal, February 2002
- Meeder, A.; Fuertes Marrón, D.; Chu, V.
- Thin Solid Films, Vol. 403-404
Revisiting radiative deep-level transitions in CuGaSe 2 by photoluminescence
journal, July 2016
- Spindler, Conrad; Regesch, David; Siebentritt, Susanne
- Applied Physics Letters, Vol. 109, Issue 3
Photoinduced current transient spectroscopy of defect levels in CuInSe 2 and CuGaSe 2 epitaxial and polycrystalline layers
journal, August 2012
- Krysztopa, A.; Igalson, M.; Larsen, J. K.
- Journal of Physics D: Applied Physics, Vol. 45, Issue 33
Defect levels in the epitaxial and polycrystalline CuGaSe 2 by photocurrent and capacitance methods
journal, November 2011
- Krysztopa, Adam; Igalson, Małgorzata; Aida, Yasuhiro
- Journal of Applied Physics, Vol. 110, Issue 10
Works referencing / citing this record:
Efficiency and stability of narrow-gap semiconductor-based photoelectrodes
journal, January 2019
- Zheng, Jianyun; Zhou, Huaijuan; Zou, Yuqin
- Energy & Environmental Science, Vol. 12, Issue 8
Recent Advances and Emerging Trends in Photo-Electrochemical Solar Energy Conversion
journal, November 2018
- Tilley, S. David
- Advanced Energy Materials, Vol. 9, Issue 2
CuGaSe 2 Thin Film Solar Cells: Challenges for Developing Highly Efficient Wide‐Gap Chalcopyrite Photovoltaics
journal, January 2019
- Ishizuka, Shogo
- physica status solidi (a), Vol. 216, Issue 15
Recent Advances and Emerging Trends in Photo-Electrochemical Solar Energy Conversion
text, January 2019
- Tilley, S. David
- Wiley-VCH Verlag