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Title: Density-functional theory computer simulations of CZTS0.25Se0.75 alloy phase diagrams

Abstract

Here, density-functional theory simulations of CZTS, CZTSe, and CZTS0.25Se0.75 photovoltaic compounds have been performed to investigate the stability of the CZTS0.25Se0.75 alloy vs. decomposition into CZTS, CZTSe, and other secondary compounds. The Gibbs energy for vibrational contributions was estimated by calculating phonon spectra and thermodynamic properties at finite temperatures. It was demonstrated that the CZTS0.25Se0.75 alloy is stabilized not by enthalpy of formation but primarily by the mixing contributions to the Gibbs energy. The Gibbs energy gains/losses for several decomposition reactions were calculated as a function of temperature with/without intermixing and vibration contributions to the Gibbs energy. A set of phase diagrams was built in the multidimensional space of chemical potentials at 300 K and 900 K temperatures to demonstrate alloy stability and boundary compounds at various chemical conditions. It demonstrated for CZTS0.25Se0.75 that the chemical potentials for stability differ between typical processing temperature (~900 K) and operating temperature (300 K). This implies that as cooling progresses, the flux/concentration of S should be increased in MBE growth to maintain the CZTS0.25Se0.75 in a thermodynamically stable state to minimize phase decomposition.

Authors:
 [1];  [1];  [2];  [3];  [1]
  1. Univ. of California, San Diego, CA (United States). Dept. of Chemistry and Biochemistry
  2. International Business Machines Corp. (IBM), Yorktown Heights, NY (United States). Thomas J. Watson Research Center
  3. Duke Univ., Durham, NC (United States). Dept. of Mechanical Engineering and Materials Science
Publication Date:
Research Org.:
International Business Machines Corp. (IBM), Yorktown Heights, NY (United States). Thomas J. Watson Research Center
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1467855
Alternate Identifier(s):
OSTI ID: 1287751
Grant/Contract Number:  
EE0006334
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 6; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 14 SOLAR ENERGY; decomposition reactions; phonons; solar cells; density functional theory; zinc; entropy; Gibbs free energy; II-VI semiconductors; phase diagrams; chemical potential

Citation Formats

Chagarov, E., Sardashti, K., Haight, R., Mitzi, D. B., and Kummel, A. C. Density-functional theory computer simulations of CZTS0.25Se0.75 alloy phase diagrams. United States: N. p., 2016. Web. doi:10.1063/1.4959591.
Chagarov, E., Sardashti, K., Haight, R., Mitzi, D. B., & Kummel, A. C. Density-functional theory computer simulations of CZTS0.25Se0.75 alloy phase diagrams. United States. doi:10.1063/1.4959591.
Chagarov, E., Sardashti, K., Haight, R., Mitzi, D. B., and Kummel, A. C. Tue . "Density-functional theory computer simulations of CZTS0.25Se0.75 alloy phase diagrams". United States. doi:10.1063/1.4959591. https://www.osti.gov/servlets/purl/1467855.
@article{osti_1467855,
title = {Density-functional theory computer simulations of CZTS0.25Se0.75 alloy phase diagrams},
author = {Chagarov, E. and Sardashti, K. and Haight, R. and Mitzi, D. B. and Kummel, A. C.},
abstractNote = {Here, density-functional theory simulations of CZTS, CZTSe, and CZTS0.25Se0.75 photovoltaic compounds have been performed to investigate the stability of the CZTS0.25Se0.75 alloy vs. decomposition into CZTS, CZTSe, and other secondary compounds. The Gibbs energy for vibrational contributions was estimated by calculating phonon spectra and thermodynamic properties at finite temperatures. It was demonstrated that the CZTS0.25Se0.75 alloy is stabilized not by enthalpy of formation but primarily by the mixing contributions to the Gibbs energy. The Gibbs energy gains/losses for several decomposition reactions were calculated as a function of temperature with/without intermixing and vibration contributions to the Gibbs energy. A set of phase diagrams was built in the multidimensional space of chemical potentials at 300 K and 900 K temperatures to demonstrate alloy stability and boundary compounds at various chemical conditions. It demonstrated for CZTS0.25Se0.75 that the chemical potentials for stability differ between typical processing temperature (~900 K) and operating temperature (300 K). This implies that as cooling progresses, the flux/concentration of S should be increased in MBE growth to maintain the CZTS0.25Se0.75 in a thermodynamically stable state to minimize phase decomposition.},
doi = {10.1063/1.4959591},
journal = {Journal of Chemical Physics},
number = 6,
volume = 145,
place = {United States},
year = {2016},
month = {8}
}

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Works referenced in this record:

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

Thin film solar cell with 8.4% power conversion efficiency using an earth-abundant Cu 2 ZnSnS 4 absorber : Cu
journal, November 2011

  • Shin, Byungha; Gunawan, Oki; Zhu, Yu
  • Progress in Photovoltaics: Research and Applications, Vol. 21, Issue 1
  • DOI: 10.1002/pip.1174

Efficient hybrid density functional calculations in solids: Assessment of the Heyd–Scuseria–Ernzerhof screened Coulomb hybrid functional
journal, July 2004

  • Heyd, Jochen; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 121, Issue 3, p. 1187-1192
  • DOI: 10.1063/1.1760074

Structural and elemental characterization of high efficiency Cu2ZnSnS4 solar cells
journal, January 2011

  • Wang, Kejia; Shin, Byungha; Reuter, Kathleen B.
  • Applied Physics Letters, Vol. 98, Issue 5
  • DOI: 10.1063/1.3543621

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

Crystal and electronic band structure of Cu2ZnSnX4 (X=S and Se) photovoltaic absorbers: First-principles insights
journal, January 2009

  • Chen, Shiyou; Gong, X. G.; Walsh, Aron
  • Applied Physics Letters, Vol. 94, Issue 4
  • DOI: 10.1063/1.3074499

Ab initio thermodynamic model of Cu 2 ZnSnS 4
journal, January 2014

  • Jackson, Adam J.; Walsh, Aron
  • J. Mater. Chem. A, Vol. 2, Issue 21
  • DOI: 10.1039/C4TA00892H

Photovoltaic manufacturing: Present status, future prospects, and research needs
journal, May 2011

  • Wolden, Colin A.; Kurtin, Juanita; Baxter, Jason B.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 29, Issue 3
  • DOI: 10.1116/1.3569757

The crystal structure of kesterite type compounds: A neutron and X-ray diffraction study
journal, June 2011


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


Phase equilibria in the Cu2S–ZnS–SnS2 system
journal, April 2004


High-Efficiency Solar Cell with Earth-Abundant Liquid-Processed Absorber
journal, May 2010

  • Todorov, Teodor K.; Reuter, Kathleen B.; Mitzi, David B.
  • Advanced Materials, Vol. 22, Issue 20, p. E156-E159
  • DOI: 10.1002/adma.200904155

Prospects and performance limitations for Cu-Zn-Sn-S-Se photovoltaic technology
journal, July 2013

  • Mitzi, D. B.; Gunawan, O.; Todorov, T. K.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 371, Issue 1996, Article No. 20110432
  • DOI: 10.1098/rsta.2011.0432

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

A Strategy to Stabilize Kesterite CZTS for High-Performance Solar Cells
journal, April 2015


Low band gap liquid-processed CZTSe solar cell with 10.1% efficiency
journal, January 2012

  • Bag, Santanu; Gunawan, Oki; Gokmen, Tayfun
  • Energy & Environmental Science, Vol. 5, Issue 5
  • DOI: 10.1039/c2ee00056c

Chemical Insights into the Instability of Cu 2 ZnSnS 4 Films during Annealing
journal, October 2011

  • Scragg, Jonathan J.; Ericson, Tove; Kubart, Tomas
  • Chemistry of Materials, Vol. 23, Issue 20
  • DOI: 10.1021/cm202379s

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Band tailing and efficiency limitation in kesterite solar cells
journal, September 2013

  • Gokmen, Tayfun; Gunawan, Oki; Todorov, Teodor K.
  • Applied Physics Letters, Vol. 103, Issue 10
  • DOI: 10.1063/1.4820250

The path towards a high-performance solution-processed kesterite solar cell
journal, June 2011

  • Mitzi, David B.; Gunawan, Oki; Todorov, Teodor K.
  • Solar Energy Materials and Solar Cells, Vol. 95, Issue 6, p. 1421-1436
  • DOI: 10.1016/j.solmat.2010.11.028

A low-temperature order-disorder transition in Cu 2 ZnSnS 4 thin films
journal, January 2014

  • Scragg, Jonathan J. S.; Choubrac, Léo; Lafond, Alain
  • Applied Physics Letters, Vol. 104, Issue 4
  • DOI: 10.1063/1.4863685

Investigating the Role of Grain Boundaries in CZTS and CZTSSe Thin Film Solar Cells with Scanning Probe Microscopy
journal, January 2012

  • Li, Joel B.; Chawla, Vardaan; Clemens, Bruce M.
  • Advanced Materials, Vol. 24, Issue 6
  • DOI: 10.1002/adma.201103470

Materials Availability Expands the Opportunity for Large-Scale Photovoltaics Deployment
journal, March 2009

  • Wadia, Cyrus; Alivisatos, A. Paul; Kammen, Daniel M.
  • Environmental Science & Technology, Vol. 43, Issue 6
  • DOI: 10.1021/es8019534

Device Characteristics of CZTSSe Thin-Film Solar Cells with 12.6% Efficiency
journal, November 2013

  • Wang, Wei; Winkler, Mark T.; Gunawan, Oki
  • Advanced Energy Materials, Vol. 4, Issue 7, Article No. 1301465
  • DOI: 10.1002/aenm.201301465

Electronic and elemental properties of the Cu 2 ZnSn(S,Se) 4 surface and grain boundaries
journal, January 2014

  • Haight, Richard; Shao, Xiaoyan; Wang, Wei
  • Applied Physics Letters, Vol. 104, Issue 3
  • DOI: 10.1063/1.4862791

Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]
journal, February 1997


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


Theoretical limits on the stability of single-phase kesterite-Cu2ZnSnS4
journal, January 2015

  • Sarker, Pranab; Al-Jassim, Mowafak M.; Huda, Muhammad N.
  • Journal of Applied Physics, Vol. 117, Issue 3
  • DOI: 10.1063/1.4906065

Development of thin film solar cell based on Cu2ZnSnS4 thin films
journal, January 2001

  • Katagiri, Hironori; Saitoh, Kotoe; Washio, Tsukasa
  • Solar Energy Materials and Solar Cells, Vol. 65, Issue 1-4
  • DOI: 10.1016/S0927-0248(00)00088-X

In-depth resolved Raman scattering analysis for the identification of secondary phases: Characterization of Cu2ZnSnS4 layers for solar cell applications
journal, May 2011

  • Fontané, X.; Calvo-Barrio, L.; Izquierdo-Roca, V.
  • Applied Physics Letters, Vol. 98, Issue 18
  • DOI: 10.1063/1.3587614

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


First principles phonon calculations in materials science
journal, November 2015


Investigation of combinatorial coevaporated thin film Cu 2 ZnSnS 4 (II): Beneficial cation arrangement in Cu-rich growth
journal, May 2014

  • Lund, E. A.; Du, H.; Hlaing OO, W. M.
  • Journal of Applied Physics, Vol. 115, Issue 17
  • DOI: 10.1063/1.4871665

Density-functional theory computer simulations of CZTS0.25Se0.75 alloy phase diagrams
journal, August 2016

  • Chagarov, E.; Sardashti, K.; Haight, R.
  • The Journal of Chemical Physics, Vol. 145, Issue 6
  • DOI: 10.1063/1.4959591

Investigation of combinatorial coevaporated thin film Cu 2 ZnSnS 4 . I. Temperature effect, crystalline phases, morphology, and photoluminescence
journal, May 2014

  • Du, Hui; Yan, Fei; Young, Matthew
  • Journal of Applied Physics, Vol. 115, Issue 17
  • DOI: 10.1063/1.4871664

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


Vibrational spectra and lattice thermal conductivity of kesterite-structured Cu 2 ZnSnS 4 and Cu 2 ZnSnSe 4
journal, April 2015

  • Skelton, Jonathan M.; Jackson, Adam J.; Dimitrievska, Mirjana
  • APL Materials, Vol. 3, Issue 4
  • DOI: 10.1063/1.4917044

Reaction pathways for the formation of Cu2ZnSn(Se,S)4 absorber materials from liquid-phase hydrazine-based precursor inks
journal, January 2012

  • Hsu, Wan-Ching; Bob, Brion; Yang, Wenbing
  • Energy & Environmental Science, Vol. 5, Issue 9
  • DOI: 10.1039/c2ee21529b

Ag2ZnSn(S,Se)4: A highly promising absorber for thin film photovoltaics
journal, March 2016

  • Chagarov, Evgueni; Sardashti, Kasra; Kummel, Andrew C.
  • The Journal of Chemical Physics, Vol. 144, Issue 10, Article No. 104704
  • DOI: 10.1063/1.4943270

Determination of secondary phases in kesterite Cu 2 ZnSnS 4 thin films by x-ray absorption near edge structure analysis
journal, December 2011

  • Just, Justus; Lützenkirchen-Hecht, Dirk; Frahm, Ronald
  • Applied Physics Letters, Vol. 99, Issue 26
  • DOI: 10.1063/1.3671994

Analysis of Atomic and Electronic Structures of Cu 2 ZnSnS 4 Based on First-Principle Calculation
journal, September 2009

  • Ichimura, Masaya; Nakashima, Yuki
  • Japanese Journal of Applied Physics, Vol. 48, Issue 9
  • DOI: 10.1143/JJAP.48.090202

Kesterite Thin-Film Solar Cells: Advances in Materials Modelling of Cu2ZnSnS4
journal, March 2012

  • Walsh, Aron; Chen, Shiyou; Wei, Su-Huai
  • Advanced Energy Materials, Vol. 2, Issue 4
  • DOI: 10.1002/aenm.201100630

Thermodynamic Aspects of the Synthesis of Thin-Film Materials for Solar Cells
journal, April 2012

  • Scragg, Jonathan J.; Dale, Phillip J.; Colombara, Diego
  • ChemPhysChem, Vol. 13, Issue 12
  • DOI: 10.1002/cphc.201200067

Analysis of the Heyd-Scuseria-Ernzerhof density functional parameter space
journal, May 2012

  • Moussa, Jonathan E.; Schultz, Peter A.; Chelikowsky, James R.
  • The Journal of Chemical Physics, Vol. 136, Issue 20
  • DOI: 10.1063/1.4722993

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


First-principles calculations of the ferroelastic transition between rutile-type and CaCl 2 -type SiO 2 at high pressures
journal, October 2008


Intrinsic point defects and complexes in the quaternary kesterite semiconductor Cu 2 ZnSnS 4
journal, June 2010


Detection of a ZnSe secondary phase in coevaporated Cu2ZnSnSe4 thin films
journal, March 2011

  • Redinger, Alex; Hönes, Katja; Fontané, Xavier
  • Applied Physics Letters, Vol. 98, Issue 10
  • DOI: 10.1063/1.3558706