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Title: Low-Temperature Surface Preparation and Epitaxial Growth of ZnS and Cu 2ZnSnS 4 on ZnS(110) and GaP(100)

Abstract

Here we give a summary of the low-temperature preparation methods of ZnS(110) and GaP(100) crystals for epitaxial growth of ZnS and Cu 2ZnSnS 4 (CZTS) via molecular beam epitaxy. Substrates were prepared for epitaxial growth by means of room-temperature aqueous surface treatments and subsequent ultra-high vacuum transfer to the deposition system. Epitaxial growth of ZnS was successful at 500 K on both ZnS(110) and GaP(100) as only single domains were observed with electron backscatter diffraction; furthermore, transmission electron microscopy measurements confirmed an epitaxial interface. Epitaxial growth of CZTS was successful on ZnS at 700 K. However, epitaxial growth was not possible on GaP at 700 K due to Ga xS y formation, which significantly degraded the quality of the GaP crystal surface. Although CZTS was grown epitaxially on ZnS, growth of multiple crystallographic domains remains a problem that could inherently limit the viability of epitaxial CZTS for model system studies.

Authors:
 [1];  [2];  [1]; ORCiD logo [1];  [1]
  1. National Renewable Energy Laboratory (NREL), Golden, CO (United States)
  2. Univ. of Florida, Gainesville, FL (United States). Dept. of Chemical Engineering
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Solar Energy Technologies Office (EE-4S); National Science Foundation (NSF)
OSTI Identifier:
1393378
Report Number(s):
NREL/JA-5K00-68184
Journal ID: ISSN 0022-0248
Grant/Contract Number:
AC36-08GO28308; CHE-1230929
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Crystal Growth
Additional Journal Information:
Journal Volume: 478; Journal ID: ISSN 0022-0248
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 36 MATERIALS SCIENCE; sulfides; molecular beam epitaxy; zinc compounds; solar cells; semiconducting quaternary alloys

Citation Formats

Harvey, Steven P, Wilson, Samual, Moutinho, Helio R, Norman, Andrew, and Teeter, Glenn R. Low-Temperature Surface Preparation and Epitaxial Growth of ZnS and Cu2ZnSnS4 on ZnS(110) and GaP(100). United States: N. p., 2017. Web. doi:10.1016/j.jcrysgro.2017.08.018.
Harvey, Steven P, Wilson, Samual, Moutinho, Helio R, Norman, Andrew, & Teeter, Glenn R. Low-Temperature Surface Preparation and Epitaxial Growth of ZnS and Cu2ZnSnS4 on ZnS(110) and GaP(100). United States. doi:10.1016/j.jcrysgro.2017.08.018.
Harvey, Steven P, Wilson, Samual, Moutinho, Helio R, Norman, Andrew, and Teeter, Glenn R. Sat . "Low-Temperature Surface Preparation and Epitaxial Growth of ZnS and Cu2ZnSnS4 on ZnS(110) and GaP(100)". United States. doi:10.1016/j.jcrysgro.2017.08.018.
@article{osti_1393378,
title = {Low-Temperature Surface Preparation and Epitaxial Growth of ZnS and Cu2ZnSnS4 on ZnS(110) and GaP(100)},
author = {Harvey, Steven P and Wilson, Samual and Moutinho, Helio R and Norman, Andrew and Teeter, Glenn R},
abstractNote = {Here we give a summary of the low-temperature preparation methods of ZnS(110) and GaP(100) crystals for epitaxial growth of ZnS and Cu2ZnSnS4 (CZTS) via molecular beam epitaxy. Substrates were prepared for epitaxial growth by means of room-temperature aqueous surface treatments and subsequent ultra-high vacuum transfer to the deposition system. Epitaxial growth of ZnS was successful at 500 K on both ZnS(110) and GaP(100) as only single domains were observed with electron backscatter diffraction; furthermore, transmission electron microscopy measurements confirmed an epitaxial interface. Epitaxial growth of CZTS was successful on ZnS at 700 K. However, epitaxial growth was not possible on GaP at 700 K due to GaxSy formation, which significantly degraded the quality of the GaP crystal surface. Although CZTS was grown epitaxially on ZnS, growth of multiple crystallographic domains remains a problem that could inherently limit the viability of epitaxial CZTS for model system studies.},
doi = {10.1016/j.jcrysgro.2017.08.018},
journal = {Journal of Crystal Growth},
number = ,
volume = 478,
place = {United States},
year = {Sat Aug 12 00:00:00 EDT 2017},
month = {Sat Aug 12 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
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  • Presented here are results of x-ray photoelectron spectroscopy (XPS) on multilayers of metal-sulfide binaries ZnS, SnS2, and Cu2S grown by atomic layer deposition (ALD) on Si substrates, and of Cu2ZnSnS4 (CZTS) formed upon 450 °C annealing of the parent multilayer ZnS/SnS2/Cu2S. Survey and detailed spectral analysis of the multilayer ZnS/SnS2/Cu2S are presented step-wise, as each layer was sequentially added by ALD. The set of data is finalized with spectra of the resulting alloy CZTS. XPS analyses indicate significant mixing between SnS2 and Cu2S, which favors CZTS formation within the ALD approach.
  • A key requirement for large-scale deployment of photovoltaic technologies is the development of highly functional materials with controllable opto-electronic properties. In this work, we report on the room-temperature synthesis of disordered alloys of the Earth-abundant, tetrahedrally coordinated semiconductors Cu 2SnS 3, Cu 2ZnSnS 4 (CZTS), and ZnS as (Cu 2SnS 3) 1-x(ZnS) x. The resulting disordered semiconductors are found to have continuously and independently tunable optical and electronic properties. Quasi-isovalent alloying on the cation sublattice allows the optical band gap to be varied continuously from 1.1 eV to 2.8 eV. Aliovalent alloying leads to independent control of carrier concentration overmore » at least three orders of magnitude. A conceptual framework describing these disordered materials is presented, in which the structural disorder, constrained by local tetrahedral coordination of both anions and cations, leads to the observed high degree of tunability of the opto-electronic properties. These materials are not only independently interesting, but the developed framework also applies to the opto-electronic properties of kesterite CZTS materials as well as provides a basis for the development of new semiconductors.« less
  • To explore the possibility of Cu{sub 2}ZnSnS{sub 4} (CZTS)/Si based tandem solar cells, the heteroepitaxy of tetragonal Cu{sub 2}ZnSnS{sub 4} thin films on single crystalline cubic Si (111) wafers with 4° miscut is obtained by molecular beam epitaxy. The X-ray θ-2θ scan and selected area diffraction patterns of the CZTS thin films and Si substrates, and the high resolution transmission electron microscopy image of the CZTS/Si interface region demonstrate that the CZTS thin films are epitaxially grown on the Si substrates. A CZTS/Si P-N junction is formed and shows photovoltaic responses, indicating the promising application of epitaxial CZTS thin filmsmore » on Si.« less
  • Cited by 4
  • Cu{sub 2}ZnSnS{sub 4} (CZTS) is a promising semiconductor material for ecological cost effective thin film Photovoltaic (PV) devices. As it contains earth abundant and non-toxic elements, it has the advantages over commercially available CIGS and CdTe thin film PV devices. In the present work, the pure phase Cu{sub 2}ZnSnS{sub 4} particles were successfully synthesised with microwave irradiation. The morphology and phase study was carried out for the samples prepared with two different sulphur precursors viz. thiourea and thioacetamide (TAA). CZTS particles with thiourea as sulphur precursor are more crystalline than CZTS particles with TAA. The band gap of 1.654 eVmore » and 1.713 eV were calculated for the samples prepared with thiourea and TAA respectively.« less