Structural Polymorphism in “Kesterite” Cu2ZnSnS4 : Raman Spectroscopy and First-Principles Calculations Analysis

Dimitrievska, Mirjana; Boero, Federica; Litvinchuk, Alexander P.; Delsante, Simona; Borzone, Gabriella; Perez-Rodriguez, Alejandro; Izquierdo-Roca, Victor

doi:10.1021/acs.inorgchem.6b03008

Title: Structural Polymorphism in “Kesterite” Cu₂ZnSnS₄ : Raman Spectroscopy and First-Principles Calculations Analysis

Journal Article · Mon Mar 06 00:00:00 EST 2017 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.6b03008· OSTI ID:1348152

^[1]; Boero, Federica ^[2]; Litvinchuk, Alexander P. ^[3]; Delsante, Simona ^[2]; Borzone, Gabriella ^[2]; Perez-Rodriguez, Alejandro ^[4]; Izquierdo-Roca, Victor ^[5]

National Renewable Energy Lab. (NREL), Golden, CO (United States); National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research; Catalonia Inst. for Energy Research (IREC), Jardins de les Dones de Negre (Barcelona)
Univ. of Genoa (Italy). Dept. of Chemistry and Industrial Chemistry
Univ. of Houston, TX (United States). Texas Center for Superconductivity and Dept. of Physics
Catalonia Inst. for Energy Research (IREC), Jardins de les Dones de Negre (Barcelona); Univ. of Barcelona (Spain). Inst. of Nanoscience and Nanotechnology (IN2UB)
Catalonia Inst. for Energy Research (IREC), Jardins de les Dones de Negre (Barcelona)

This work presents detailed structural and vibrational characterization of different Cu₂ZnSnS₄ (CZTS) polymorphs (space groups: I$$\bar{4}$$, P$$\bar{4}$$2c, and P$$\bar{4}$$2m), using Raman spectroscopy and first-principles calculations. Multiwavelength Raman measurements on bulk crystalline CZTS samples permitted determination of the vibrational modes of each polymorph structure, with frequencies matching well with the results obtained from simulations. Lastly, the results present Raman spectra fingerprints as well as experimental references for the different polymorph modifications.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1348152

Report Number(s):: NREL/JA-5900-68155

Journal Information:: Inorganic Chemistry, Vol. 56, Issue 6; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 72 works

Citation information provided by
Web of Science

References (44)

The current status and future prospects of kesterite solar cells: a brief review: Kesterite solar cells Liu, Xiaolei; Feng, Yu; Cui, Hongtao Progress in Photovoltaics: Research and Applications, Vol. 24, Issue 6 https://doi.org/10.1002/pip.2741	journal	January 2016
Cu2ZnSnS4 thin film solar cells Katagiri, Hironori Thin Solid Films, Vol. 480-481 https://doi.org/10.1016/j.tsf.2004.11.024	journal	June 2005
Photovoltaic manufacturing: Present status, future prospects, and research needs Wolden, Colin A.; Kurtin, Juanita; Baxter, Jason B. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 29, Issue 3 https://doi.org/10.1116/1.3569757	journal	May 2011
Towards sustainable materials for solar energy conversion: Preparation and photoelectrochemical characterization of Cu2ZnSnS4 Scragg, Jonathan J.; Dale, Phillip J.; Peter, Laurence M. Electrochemistry Communications, Vol. 10, Issue 4 https://doi.org/10.1016/j.elecom.2008.02.008	journal	April 2008
Thin film solar cell with 8.4% power conversion efficiency using an earth-abundant Cu ₂ ZnSnS ₄ absorber : Cu Shin, Byungha; Gunawan, Oki; Zhu, Yu Progress in Photovoltaics: Research and Applications, Vol. 21, Issue 1 https://doi.org/10.1002/pip.1174	journal	November 2011
Atom-probe tomographic study of interfaces of Cu ₂ ZnSnS ₄ photovoltaic cells Tajima, S.; Asahi, R.; Isheim, D. Applied Physics Letters, Vol. 105, Issue 9 https://doi.org/10.1063/1.4894858	journal	September 2014
Loss mechanisms in hydrazine-processed Cu2ZnSn(Se,S)4 solar cells Gunawan, Oki; Todorov, Teodor K.; Mitzi, David B. Applied Physics Letters, Vol. 97, Issue 23 https://doi.org/10.1063/1.3522884	journal	December 2010
Semi-empirical device model for Cu ₂ ZnSn(S,Se) ₄ solar cells Gokmen, Tayfun; Gunawan, Oki; Mitzi, David B. Applied Physics Letters, Vol. 105, Issue 3 https://doi.org/10.1063/1.4890844	journal	July 2014
Compositional paradigms in multinary compound systems for photovoltaic applications: a case study of kesterites Fairbrother, Andrew; Dimitrievska, Mirjana; Sánchez, Yudania Journal of Materials Chemistry A, Vol. 3, Issue 18 https://doi.org/10.1039/C5TA02000J	journal	January 2015
The path towards a high-performance solution-processed kesterite solar cell Mitzi, David B.; Gunawan, Oki; Todorov, Teodor K. Solar Energy Materials and Solar Cells, Vol. 95, Issue 6, p. 1421-1436 https://doi.org/10.1016/j.solmat.2010.11.028	journal	June 2011
Secondary phase and Cu substitutional defect dynamics in kesterite solar cells: Impact on optoelectronic properties Dimitrievska, Mirjana; Fairbrother, Andrew; Saucedo, Edgardo Solar Energy Materials and Solar Cells, Vol. 149 https://doi.org/10.1016/j.solmat.2016.01.029	journal	May 2016
Systematic compositional changes and their influence on lattice and optoelectronic properties of Cu2ZnSnSe4 kesterite solar cells Márquez, J.; Neuschitzer, M.; Dimitrievska, M. Solar Energy Materials and Solar Cells, Vol. 144 https://doi.org/10.1016/j.solmat.2015.10.004	journal	January 2016
Cu-Zn disorder and band gap fluctuations in Cu ₂ ZnSn(S,Se) ₄ : Theoretical and experimental investigations (Phys. Status Solidi B 2/2016) Scragg, Jonathan J. S.; Larsen, Jes K.; Kumar, Mukesh physica status solidi (b), Vol. 253, Issue 2 https://doi.org/10.1002/pssb.201670508	journal	February 2016
Study on Phase Formation Mechanism of Non- and Near-Stoichiometric Cu ₂ ZnSn(S,Se) ₄ Film Prepared by Selenization of Cu–Sn–Zn–S Precursors Yin, Xuesong; Tang, Chunhua; Sun, Linfeng Chemistry of Materials, Vol. 26, Issue 6 https://doi.org/10.1021/cm403423e	journal	March 2014
Growth mechanisms of co-evaporated kesterite: a comparison of Cu-rich and Zn-rich composition paths: Growth mechanisms of co-evaporated kesterite Hsu, Wan-Ching; Repins, Ingrid; Beall, Carolyn Progress in Photovoltaics: Research and Applications, Vol. 22, Issue 1 https://doi.org/10.1002/pip.2296	journal	January 2013
Crystal and electronic band structure of Cu2ZnSnX4 (X=S and Se) photovoltaic absorbers: First-principles insights Chen, Shiyou; Gong, X. G.; Walsh, Aron Applied Physics Letters, Vol. 94, Issue 4 https://doi.org/10.1063/1.3074499	journal	January 2009
First-principles investigation of the structural, dynamical, and dielectric properties of kesterite, stannite, and PMCA phases of ${Cu}_{2} {ZnSnS}_{4}$ Ramkumar, S. Poyyapakkam; Gillet, Y.; Miglio, A. Physical Review B, Vol. 94, Issue 22 https://doi.org/10.1103/PhysRevB.94.224302	journal	December 2016
Imaging and phase identification of Cu ₂ ZnSnS ₄ thin films using confocal Raman spectroscopy Cheng, A. -J.; Manno, M.; Khare, A. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 29, Issue 5 https://doi.org/10.1116/1.3625249	journal	September 2011
Wurtzite-derived polytypes of kesterite and stannite quaternary chalcogenide semiconductors Chen, Shiyou; Walsh, Aron; Luo, Ye Physical Review B, Vol. 82, Issue 19 https://doi.org/10.1103/PhysRevB.82.195203	journal	November 2010
A low-temperature order-disorder transition in Cu ₂ ZnSnS ₄ thin films Scragg, Jonathan J. S.; Choubrac, Léo; Lafond, Alain Applied Physics Letters, Vol. 104, Issue 4 https://doi.org/10.1063/1.4863685	journal	January 2014
Raman scattering crystalline assessment of polycrystalline Cu2ZnSnS4 thin films for sustainable photovoltaic technologies: Phonon confinement model Dimitrievska, M.; Fairbrother, A.; Pérez-Rodríguez, A. Acta Materialia, Vol. 70 https://doi.org/10.1016/j.actamat.2014.02.035	journal	May 2014
Influence of compositionally induced defects on the vibrational properties of device grade Cu ₂ ZnSnSe ₄ absorbers for kesterite based solar cells Dimitrievska, Mirjana; Fairbrother, Andrew; Saucedo, Edgardo Applied Physics Letters, Vol. 106, Issue 7 https://doi.org/10.1063/1.4913262	journal	February 2015
Characterization of vibrational and mechanical properties of quaternary compounds Cu $_{2}$ ZnSn $S_{4}$ and Cu $_{2}$ ZnSnSe $_{4}$ in kesterite and stannite structures Gürel, Tanju; Sevik, Cem; Çağın, Tahir Physical Review B, Vol. 84, Issue 20 https://doi.org/10.1103/PhysRevB.84.205201	journal	November 2011
Calculation of the lattice dynamics and Raman spectra of copper zinc tin chalcogenides and comparison to experiments Khare, Ankur; Himmetoglu, Burak; Johnson, Melissa Journal of Applied Physics, Vol. 111, Issue 8 https://doi.org/10.1063/1.4704191	journal	April 2012
Vibrational spectra and lattice thermal conductivity of kesterite-structured Cu ₂ ZnSnS ₄ and Cu ₂ ZnSnSe ₄ Skelton, Jonathan M.; Jackson, Adam J.; Dimitrievska, Mirjana APL Materials, Vol. 3, Issue 4 https://doi.org/10.1063/1.4917044	journal	April 2015
The crystal structure of kesterite type compounds: A neutron and X-ray diffraction study Schorr, Susan Solar Energy Materials and Solar Cells, Vol. 95, Issue 6 https://doi.org/10.1016/j.solmat.2011.01.002	journal	June 2011
A new phase in the Cu–Sn–Zn–S photovoltaic system Boero, F.; Delsante, S.; Colombara, D. Materials Letters, Vol. 145 https://doi.org/10.1016/j.matlet.2015.01.048	journal	April 2015
Raman scattering analysis of the surface chemistry of kesterites: Impact of post-deposition annealing and Cu/Zn reordering on solar cell performance Dimitrievska, Mirjana; Giraldo, Sergio; Pistor, Paul Solar Energy Materials and Solar Cells, Vol. 157 https://doi.org/10.1016/j.solmat.2016.07.009	journal	December 2016
The Materials Science beamline upgrade at the Swiss Light Source Willmott, P. R.; Meister, D.; Leake, S. J. Journal of Synchrotron Radiation, Vol. 20, Issue 5 https://doi.org/10.1107/S0909049513018475	journal	July 2013
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I. Physical Review Letters, Vol. 100, Issue 13 https://doi.org/10.1103/PhysRevLett.100.136406	journal	April 2008
First principles methods using CASTEP Clark, Stewart J.; Segall, Matthew D.; Pickard, Chris J. Zeitschrift für Kristallographie - Crystalline Materials, Vol. 220, Issue 5/6 https://doi.org/10.1524/zkri.220.5.567.65075	journal	January 2005
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
Electronic structure, optical properties, and lattice dynamics of orthorhombic ${Cu}_{2} {CdGeS}_{4}$ and ${Cu}_{2} {CdSiS}_{4}$ semiconductors Litvinchuk, Alexander P.; Dzhagan, Volodymyr M.; Yukhymchuk, Volodymyr O. Physical Review B, Vol. 90, Issue 16 https://doi.org/10.1103/PhysRevB.90.165201	journal	October 2014
Optical phonons in the kesterite Cu ₂ ZnGeS ₄ semiconductor: polarized Raman spectroscopy and first-principle calculations Guc, M.; Litvinchuk, A. P.; Levcenko, S. RSC Advances, Vol. 6, Issue 16 https://doi.org/10.1039/C5RA26844C	journal	January 2016
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011
Bilbao Crystallographic Server. II. Representations of crystallographic point groups and space groups Aroyo, Mois I.; Kirov, Asen; Capillas, Cesar Acta Crystallographica Section A Foundations of Crystallography, Vol. 62, Issue 2 https://doi.org/10.1107/S0108767305040286	journal	March 2006
Bilbao Crystallographic Server: I. Databases and crystallographic computing programs Aroyo, Mois Ilia; Perez-Mato, Juan Manuel; Capillas, Cesar Zeitschrift für Kristallographie - Crystalline Materials, Vol. 221, Issue 1 https://doi.org/10.1524/zkri.2006.221.1.15	journal	January 2006
Multiwavelength excitation Raman scattering study of polycrystalline kesterite Cu ₂ ZnSnS ₄ thin films Dimitrievska, M.; Fairbrother, A.; Fontané, X. Applied Physics Letters, Vol. 104, Issue 2 https://doi.org/10.1063/1.4861593	journal	January 2014
Resonant Raman scattering of ZnS _x Se _1−x solid solutions: the role of S and Se electronic states Dimitrievska, M.; Xie, H.; Jackson, A. J. Physical Chemistry Chemical Physics, Vol. 18, Issue 11 https://doi.org/10.1039/C5CP04498G	journal	January 2016
Development of a Selective Chemical Etch To Improve the Conversion Efficiency of Zn-Rich Cu ₂ ZnSnS ₄ Solar Cells Fairbrother, Andrew; García-Hemme, Eric; Izquierdo-Roca, Victor Journal of the American Chemical Society, Vol. 134, Issue 19 https://doi.org/10.1021/ja301373e	journal	April 2012
Ab initio thermodynamic model of Cu ₂ ZnSnS ₄ Jackson, Adam J.; Walsh, Aron J. Mater. Chem. A, Vol. 2, Issue 21 https://doi.org/10.1039/C4TA00892H	journal	January 2014
Polarized Raman scattering study of kesterite type Cu2ZnSnS4 single crystals Guc, Maxim; Levcenko, Sergiu; Bodnar, Ivan V. Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep19414	journal	January 2016
The vibrational properties study of kesterite Cu2ZnSnS4 single crystals by using polarization dependent Raman spectroscopy Dumcenco, Dumitru; Huang, Ying-Sheng Optical Materials, Vol. 35, Issue 3 https://doi.org/10.1016/j.optmat.2012.09.031	journal	January 2013
${Cu}_{2} {ZnSnS}_{4}$ as a potential photovoltaic material: A hybrid Hartree-Fock density functional theory study Paier, Joachim; Asahi, Ryoji; Nagoya, Akihiro Physical Review B, Vol. 79, Issue 11 https://doi.org/10.1103/PhysRevB.79.115126	journal	March 2009

Cited By (9)

Green and scalable synthesis of nanocrystalline kuramite Giaccherini, Andrea; Cucinotta, Giuseppe; Martinuzzi, Stefano Beilstein Journal of Nanotechnology, Vol. 10 https://doi.org/10.3762/bjnano.10.202	journal	January 2019
Point defects, compositional fluctuations, and secondary phases in non-stoichiometric kesterites Schorr, Susan; Gurieva, Galina; Guc, Maxim Journal of Physics: Energy, Vol. 2, Issue 1 https://doi.org/10.1088/2515-7655/ab4a25	journal	December 2019
Formation of a phase pure kesterite CZTSe thin films using multisource hybrid physical vapour deposition Simya, O. K.; Geetha Priyadarshini, B.; Balachander, K. Materials Research Express, Vol. 7, Issue 1 https://doi.org/10.1088/2053-1591/ab64ee	journal	January 2020
Homoleptic trimethylsilylchalcogenolato zincates [Zn(ESiMe ₃ ) ₃ ] ⁻ and stannanides [Sn(ESiMe ₃ ) ₃ ] ⁻ (E = S, Se): precursors in solution-based low-temperature binary metal chalcogenide and Cu ₂ ZnSnS ₄ (CZTS) synthesis Guschlbauer, Jannick; Vollgraff, Tobias; Sundermeyer, Jörg Dalton Transactions, Vol. 49, Issue 8 https://doi.org/10.1039/c9dt04144c	journal	January 2020
The effect of stoichiometry on Cu-Zn ordering kinetics in Cu ₂ ZnSnS ₄ thin films Rudisch, Katharina; Davydova, Alexandra; Platzer-Björkman, Charlotte Journal of Applied Physics, Vol. 123, Issue 16 https://doi.org/10.1063/1.5010081	journal	April 2018
Raman characterization of Cu ₂ ZnSnS ₄ nanocrystals: phonon confinement effect and formation of Cu _x S phases Havryliuk, Ye.; Valakh, M. Ya.; Dzhagan, V. RSC Advances, Vol. 8, Issue 54 https://doi.org/10.1039/c8ra05390a	journal	January 2018
Investigation of single phase $C u_{2} ZnS n_{x} S b_{1 - x} S_{4}$ compounds processed by mechanochemical synthesis Neves, F.; Stark, A.; Schell, N. Physical Review Materials, Vol. 2, Issue 7 https://doi.org/10.1103/physrevmaterials.2.075404	journal	July 2018
Raman study of flash-lamp annealed aqueous Cu ₂ ZnSnS ₄ nanocrystals Havryliuk, Yevhenii; Selyshchev, Oleksandr; Valakh, Mykhailo Beilstein Journal of Nanotechnology, Vol. 10 https://doi.org/10.3762/bjnano.10.20	journal	January 2019
Point defects, compositional fluctuations, and secondary phases in non-stoichiometric kesterites Schorr, Susan; Gurieva, Galina; Guc, Maxim Freie Universität Berlin https://doi.org/10.17169/refubium-28526	text	January 2020

Similar Records

Successive ionic layer adsorption and reaction deposited kesterite Cu{sub 2}ZnSnS{sub 4} nanoflakes counter electrodes for efficient dye-sensitized solar cells

Journal Article · Sat Nov 15 00:00:00 EST 2014 · Materials Research Bulletin · OSTI ID:1348152

Mali, Sawanta S.; Shim, Chang Su

A facile and scalable route to nano-crystallized kesterite Cu{sub 2}ZnSnS{sub 4} fibers via electrospinning/sulfurization

Journal Article · Thu Jan 15 00:00:00 EST 2015 · Materials Research Bulletin · OSTI ID:1348152

Song, Yuanqiang; Liu, Aifang; Mu, Chunhong; +3 more

Depth distribution of secondary phases in kesterite Cu₂ZnSnS₄ by angle-resolved X-ray absorption spectroscopy

Journal Article · Tue Dec 12 00:00:00 EST 2017 · APL Materials · OSTI ID:1348152

Just, J.; Lützenkirchen-Hecht, D.; Müller, O.; +2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
kesterite
polymorphs
structural properties
vibrational properties

Title: Structural Polymorphism in “Kesterite” Cu2ZnSnS4 : Raman Spectroscopy and First-Principles Calculations Analysis

Citation Formats

References (44)

Cited By (9)

Similar Records

Related Subjects

Title: Structural Polymorphism in “Kesterite” Cu₂ZnSnS₄ : Raman Spectroscopy and First-Principles Calculations Analysis