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Title: Wide Band Gap Chalcogenide Semiconductors

Journal Article · · Chemical Reviews
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [3]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States). Materials Science Center; Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States). Materials Science Center; Zhengzhou Univ. (China)
  3. National Renewable Energy Lab. (NREL), Golden, CO (United States). Materials Science Center
  4. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Wide band gap semiconductors are essential for today’s electronic devices and energy applications because of their high optical transparency, controllable carrier concentration, and tunable electrical conductivity. The most intensively investigated wide band gap semiconductors are transparent conductive oxides (TCOs), such as tin-doped indium oxide (ITO) and amorphous In–Ga–Zn–O (IGZO), used in displays and solar cells, carbides (e.g., SiC) and nitrides (e.g., GaN) used in power electronics, and emerging halides (e.g., γ-CuI) and 2D electronic materials (e.g., graphene) used in various optoelectronic devices. Compared to these prominent materials families, chalcogen-based (Ch = S, Se, Te) wide band gap semiconductors are less heavily investigated but stand out because of their propensity for p-type doping, high mobilities, high valence band positions (i.e., low ionization potentials), and broad applications in electronic devices such as CdTe solar cells. This manuscript provides a review of wide band gap chalcogenide semiconductors. First, we outline general materials design parameters of high performing transparent semiconductors, as well as the theoretical and experimental underpinnings of the corresponding research methods. We proceed to summarize progress in wide band gap (EG > 2 eV) chalcogenide materials—namely, II–VI MCh binaries, CuMCh2 chalcopyrites, Cu3MCh4 sulvanites, mixed-anion layered CuMCh(O,F), and 2D materials—and discuss computational predictions of potential new candidates in this family, highlighting their optical and electrical properties. Then, we finally review applications—for example, photovoltaic and photoelectrochemical solar cells, transistors, and light emitting diodes—that employ wide band gap chalcogenides as either an active or passive layer. Overall, by examining, categorizing, and discussing prospective directions in wide band gap chalcogenides, this Review aims to inspire continued research on this emerging class of transparent semiconductors and thereby enable future innovations for optoelectronic devices.

Research Organization:
National Renewable Energy Laboratory (NREL), Golden, CO (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
AC36-08GO28308; DGE1106400; DGE175281; AC02-05CH11231
OSTI ID:
1659858
Alternate ID(s):
OSTI ID: 1766490
Report Number(s):
NREL/JA-5K00-74974; MainId:6847; UUID:bfc7d2fb-26de-e911-9c26-ac162d87dfe5; MainAdminID:13520
Journal Information:
Chemical Reviews, Vol. 120, Issue 9; ISSN 0009-2665
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 196 works
Citation information provided by
Web of Science

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Visible-Light-Responsive Chalcogenide Photocatalyst Ba 2 ZnSe 3 : Crystal and Electronic Structure, Thermal, Optical, and Photocatalytic Activity journal November 2016
BeMgZnSe-based ultraviolet lasers journal November 2005
Theoretical Design of the Absorber for Intermediate Band Solar Cells from Group-IV (Si, Ge, and Sn)-Doped AgAlSe 2 journal April 2018
Two-Dimensional Dielectric Nanosheets: Novel Nanoelectronics From Nanocrystal Building Blocks journal October 2011
Synthesis and characterization of copper doped zinc telluride thin films journal January 2005
2D Hybrid Nanostructure of Reduced Graphene Oxide–CdS Nanosheet for Enhanced Photocatalysis journal June 2015
Interfacial layer formations between Cu(In,Ga)Se2 and InxSy layers journal December 2005
Structural and optical properties of (Ag,Cu)(In,Ga)Se 2 polycrystalline thin film alloys journal June 2014
Structural chemistry of Ba2CdS3, Ba2CdSe3, BaCdS2, BaCu2S2 and BaCu2Se2 journal January 1974
Characterization of CuAlS2 Films Grown by Molecular Beam Epitaxy journal October 1992
High electron mobility, quantum Hall effect and anomalous optical response in atomically thin InSe journal November 2016
CuGaS 2 –ZnS p–n nanoheterostructures: a promising visible light photo-catalyst for water-splitting hydrogen production journal January 2016
Heterogeneous photocatalyst materials for water splitting journal January 2009
AgSCN micro/nanostructures: Facile sonochemical synthesis, characterization, and photoluminescence properties journal September 2014
Metastability and reliability of CdTe solar cells journal March 2018
Band alignment at β-In2S3/TCO interface journal July 2002
Transmission spectra of some transition metal dichalcogenides. II. Group VIA: trigonal prismatic coordination journal December 1972
Recent developments in the Inorganic Crystal Structure Database: theoretical crystal structure data and related features journal September 2019
First-Principles Investigation of Half-metallic Ferromagnetism in V-doped BeS, BeSe, and BeTe journal November 2013
Hopping conduction in gallium selenide single crystals journal November 1969
Electrical properties of cadmium and Zinc doped CuAlS2 journal July 1988
Optical properties of undoped and co-doped CuGa1−XAlXSe2 single crystals journal November 1993
High-efficiency Silicon Heterojunction Solar Cells: A Review journal January 2012
Carrier Scattering in Metals and Semiconductors journal January 1988
n-ZnO nanorods/p-CuSCN heterojunction light-emitting diodes fabricated by electrochemical method journal July 2010
Progress, Challenges, and Opportunities in Two-Dimensional Materials Beyond Graphene journal March 2013
Emitter/absorber interface of CdTe solar cells journal June 2016
Hierarchical microarchitectures of AgGa1−xInxS2: Long chain alcohol assisted synthesis, band gap tailoring and photocatalytic activities of hydrogen generation journal August 2013
CuZnS hole contacts on monocrystalline CdTe solar cells
  • Becker, Jacob J.; Xu, Xiaojie; Woods-Robinson, Rachel
  • 2017 IEEE 44th Photovoltaic Specialists Conference (PVSC), 2017 IEEE 44th Photovoltaic Specialist Conference (PVSC) https://doi.org/10.1109/PVSC.2017.8366221
conference June 2017
The circular economy journal March 2016
Perovskite solar cells with CuSCN hole extraction layers yield stabilized efficiencies greater than 20% journal September 2017
Fundamental Optical Absorption in the IIA-VIB Compounds journal February 1959
Phase correlations in the CuAlSe2-CuAlTe2 system journal July 2005
Thermodynamic limit for synthesis of metastable inorganic materials journal April 2018
Epitaxial Growth of ZnMgSSe on GaAs Substrate by Molecular Beam Epitaxy journal September 1991
Growth of high mobility n ‐type CdTe by photoassisted molecular beam epitaxy journal October 1986
Growth and characterization of tin disulfide (SnS2) thin film deposited by successive ionic layer adsorption and reaction (SILAR) technique journal June 2007
Mobility engineering and a metal–insulator transition in monolayer MoS2 journal June 2013
Unbiased Sunlight-Driven Artificial Photosynthesis of Carbon Monoxide from CO 2 Using a ZnTe-Based Photocathode and a Perovskite Solar Cell in Tandem journal July 2016
p -type conductivity in wide-band-gap BaCuQF (Q=S,Se) journal April 2003
Atomically thin two-dimensional materials as hole extraction layers in organolead halide perovskite photovoltaic cells journal July 2016
Growth of MgTe and Cd1−xMgxTe thin films by molecular beam epitaxy journal August 1993
Band gap engineering, band edge emission, and p -type conductivity in wide-gap LaCuOS1−xSex oxychalcogenides journal April 2002
Honeycomb Carbon: A Review of Graphene journal January 2010
Doping CuSCN films for enhancement of conductivity: Application in dye-sensitized solid-state solar cells journal March 2005
Vertically oriented MoS 2 and WS 2 nanosheets directly grown on carbon cloth as efficient and stable 3-dimensional hydrogen-evolving cathodes journal January 2015
Deposition and characterization of highly p-type antimony doped ZnTe thin films journal February 2009
Electrical Conductivities of Alkaline Earth Sulfides journal January 1981
The Preparation and Paramagnetic Susceptibility of β-MnSe journal December 1972
Single crystal synthesis and electrical properties of CdSnO3, Cd2SnO4, In2TeO6 and Cdln2O4 journal January 1977
Tin Disulfide—An Emerging Layered Metal Dichalcogenide Semiconductor: Materials Properties and Device Characteristics journal September 2014
Room‐Temperature Electrical Properties of Ten I‐III‐VI 2 Semiconductors journal May 1972
Zinc‐blende MnTe: Epilayers and quantum well structures journal November 1989
Spray pyrolytic deposition and characterization of SnS and SnS 2 thin films journal April 2000
Electrical and optical properties of as-grown TlInS2, TlGaSe2 and TlGaS2 single crystals journal January 1992
Surface morphology and ionization potentials of polar semiconductors: The case of GaAs journal January 2004
High Performance and Bendable Few-Layered InSe Photodetectors with Broad Spectral Response journal April 2014
Review of carbon nanotube nanoelectronics and macroelectronics journal May 2014
Recent developments in RF sputtered cadmium stannate films journal September 1996
Thin-film transistors based on p-type Cu2O thin films produced at room temperature journal May 2010
New and Old Concepts in Thermoelectric Materials journal November 2009
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation journal July 2013
Semiconducting properties of silver thiocyanate journal April 1983
Controlled Synthesis of Ultrathin 2D β‐In 2 S 3 with Broadband Photoresponse by Chemical Vapor Deposition journal August 2017
Characterization of 2D As2S3 crystal by Raman spectroscopy journal January 2018
Blue‐green laser diodes journal September 1991
PyCDT: A Python toolkit for modeling point defects in semiconductors and insulators journal May 2018
Growth and electrical properties of AgGaS2 thin films journal January 1984
p-Type electrical conduction and wide optical band gap in Mg-doped CuAlS2 journal June 2008
Growth of CuGaS 2 Single Crystals by Chemical Vapor Transport and Characterization journal April 2007
Descriptor-Based Approach for the Prediction of Cation Vacancy Formation Energies and Transition Levels journal October 2017
Some electrical properties of AgGaS 2 journal August 1974
Photoluminescence Studies in CuAlS 2 Crystals journal August 1992
Sulfide perovskites for solar energy conversion applications: computational screening and synthesis of the selected compound LaYS 3 journal January 2017
Surface sensing behavior and band edge properties of AgAlS 2 : Experimental observations in optical, chemical, and thermoreflectance spectroscopy journal June 2012
H 2 Evolution from Aqueous Potassium Sulfite Solutions under Visible Light Irradiation over a Novel Sulfide Photocatalyst NaInS 2 with a Layered Structure journal September 2002
A study of Ag/Ag2S and Ag/AgSCN electrodes: coulometric production of sulphide and thiocyanate ions journal January 1967
Semiconductors: Data Handbook book January 2004
A phenomenological model for systematization and prediction of doping limits in II–VI and I–III–VI2 compounds journal March 1998
Efficient silicon solar cells with dopant-free asymmetric heterocontacts journal January 2016
Performances of Liquid-Exfoliated Transition Metal Dichalcogenides as Hole Injection Layers in Organic Light-Emitting Diodes journal June 2015
p-type transparent conductor: Zn-doped CuAlS2 journal February 2007
Properties and characterization of Cu3SbS3 nanowires synthesized by solvothermal route journal June 2008
Electrical and Photonic Functions Originating from Low-Dimensional Structures in Wide-Gap Semiconductors LnCuOCh (Ln=lanthanide, Ch=chalcogen): A Review journal January 2005
Photoelectronic properties of Cu3PS4 and Cu3PS3Se single crystals journal August 1983
High-Performance Monolayer WS 2 Field-Effect Transistors on High-κ Dielectrics journal August 2015
Formation of MoO x barrier layer under atmospheric based condition to control MoSe 2 formation in CIGS thin film solar cell journal July 2018
Transparent Conducting Oxides for Photovoltaics: Manipulation of Fermi Level, Work Function and Energy Band Alignment journal November 2010
The sol-gel process journal January 1990
Structural, morphological and optical properties of CuAlS2 films deposited by spray pyrolysis method journal March 2008
Group-IV (Si, Ge, and Sn)-doped AgAlTe 2 for intermediate band solar cell from first-principles study journal May 2017
Cuprous iodide: A p-type transparent semiconductor, history, and novel applications: Cuprous iodide journal August 2013
The effect of substrate temperature on the structural, optical and electrical properties of vacuum deposited ZnTe thin films journal August 2009
Photoelectrochemical properties of CdX (X=S, Se, Te) films electrodeposited from aqueous and non-aqueous baths journal February 2001
Electronic and Defect Structures of CuSCN journal April 2010
Study of structural and optical properties of quaternary CuxAg1-xAlS2 thin films journal October 2016
Charge transport in layer semiconductors journal January 1976
Growth of In2S3 thin films by atomic layer epitaxy journal December 1994
High-mobility thin-film transistor with amorphous InGaZnO4 channel fabricated by room temperature rf-magnetron sputtering journal September 2006
Electronic structure of GaSe, GaS, InSe and GaTe journal November 1979
Electrical properties of β-BaCu2S2 journal December 2004
Electrochemical Stability of Metastable Materials journal November 2017
Correcting density functional theory for accurate predictions of compound enthalpies of formation: Fitted elemental-phase reference energies journal March 2012
Inorganic hole conductor-based lead halide perovskite solar cells with 12.4% conversion efficiency journal May 2014
Thermal Stability of CuSCN Hole Conductor-Based Perovskite Solar Cells journal September 2016
Tunable properties of wide-band gap p-type BaCu(Ch1−xChx′)F (Ch = S, Se, Te) thin-film solid solutions journal July 2010
CuInS 2 and CuGaS 2 thin films grown by modulated flux deposition with various Cu contents journal August 2006
Transparent p -type conducting BaCu2S2 films journal June 2002
Studies of sputtered ZnTe films as interlayer for the CdTe thin film solar cell journal June 2005
p -type doping with N and Li acceptors of ZnS grown by metalorganic vapor phase epitaxy journal March 2000
Electrical properties of La2S3-doped calcium sulfide solid electrolyte journal February 1981
Preparation and Characterization of Cu(Al, Ga)(S, Se) 2 Penternary Alloys journal January 1993
Synthesis, structure, and optical properties of the new lanthanum copper oxysulfide La3CuO2S3 journal May 2003
Tuning the optical, electronic and thermal properties of Cu 3 NbS 4−x Se x through chemical substitution journal January 2017
Low-temperature conductivity in CuGaS2 single crystals journal April 2015
Low and small resistance hole-injection barrier for NPB realized by wide-gap p-type degenerate semiconductor, LaCuOSe:Mg journal October 2008
Electrical properties of CuGaS 2 single crystals journal December 1974
Annealing effect of Cu2TeAu contact to evaporated CdTe film on photovoltaic properties of CdS/CdTe solar cell journal January 1998
Synthesis and Photoluminescence of Cd-doped α-MnS Nanowires journal September 2006
Synthesis and characterization of sol-gel derived Mn2+ doped In2S3 nanocrystallites embedded in a silica matrix journal July 2006
Enhanced photocatalytic activity and stability of interstitial Ga-doped CdS: Combination of experiment and calculation journal April 2014
Band energy diagram of CdTe thin film solar cells journal February 2002
Transparent conducting oxide semiconductors for transparent electrodes journal March 2005
High Mobility in a Stable Transparent Perovskite Oxide journal May 2012
Attempts of Homo p-n Junction Formation in ZnS by Impurity Co-Doping with Vapor Phase Epitaxy journal January 2002
Optical Nonlinearity in Cu 2 CdSnS 4 and α/β-Cu 2 ZnSiS 4 : Diamond-like Semiconductors with High Laser-Damage Thresholds journal July 2014
Properties of transparent conducting oxides formed from CdO and ZnO alloyed with SnO2 and In2O3
  • Wu, X.; Coutts, T. J.; Mulligan, W. P.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 15, Issue 3 https://doi.org/10.1116/1.580429
journal May 1997
High-mobility ultrathin semiconducting films prepared by spin coating journal March 2004
Tailoring the electronic and elastic properties by varying the composition of the CuGa 1− x Al x S 2 chalcopyrite semiconductor journal June 2013
Preparation and Photoelectrochemistry of Semiconducting WS 2 Thin Films journal April 1997
Large-scale pattern growth of graphene films for stretchable transparent electrodes journal January 2009
Electron reflector to enhance photovoltaic efficiency: application to thin-film CdTe solar cells: Proposed Electron Reflector for CdTe Solar Cells journal August 2011
p-Type Characteristics of Cu-Doped CdS Thin Films journal April 1992
Nanostructured electrochromic smart windows: traditional materials and NIR-selective plasmonic nanocrystals journal January 2014
Colloidal Synthesis of Non-Equilibrium Wurtzite-Type MnSe journal May 2010
Degenerate electrical conductive and excitonic photoluminescence properties of epitaxial films of wide gap p-type layered oxychalcogenides, LnCuOCh (Ln=La, Pr and Nd; Ch=S or Se) journal September 2004
Tunable electronic and dielectric behavior of GaS and GaSe monolayers journal January 2013
Enhancement in the physical properties of spray deposited nanostructured ternary PbMgS thin films towards optoelectronic applications journal January 2016
Wide gap p-type degenerate semiconductor: Mg-doped LaCuOSe journal December 2003
Cd free buffer layers for solar cells conference January 2001
Defect Tolerant Semiconductors for Solar Energy Conversion journal March 2014
Molecular beam epitaxy journal March 2002
Ab initio study of carrier mobility of few-layer InSe journal February 2016
Preparation and characterization of ZnS/CdS bi-layer for CdTe solar cell application journal December 2013
First-principles study of band alignments in the p-type hosts Ba M 2 X 2 ( M = Cu, Ag; X = S, Se) journal March 2014
Transport and Deformation-Potential Theory for Many-Valley Semiconductors with Anisotropic Scattering journal February 1956
The electronic structure of sulvanite structured semiconductors Cu 3 MCh 4 (M = V, Nb, Ta; Ch = S, Se, Te): prospects for optoelectronic applications journal January 2015
Electrical properties and phase transitions of TlCu3S2 and BaCu2S2 journal April 2001
Electronic properties of BaCuChF (Ch=S,Se,Te) surfaces and BaCuSeF/ZnPc interfaces journal May 2010
Zinc-Stabilized Manganese Telluride with Wurtzite Crystal Structure journal July 2018
Defect physics of CuGaS 2 journal May 2010
First-principles study on the electronic properties of BaCu2S2 journal November 2010
Optical properties and applications of chalcogenide glasses: a review journal November 2003
Ionic conductivity of solid calcium sulfide at 650 to 1000° C journal April 1974
Electric field-induced hole transport in copper(i) thiocyanate (CuSCN) thin-films processed from solution at room temperature journal January 2013
Improvement of Electrical Characteristics and Stability of Amorphous Indium Gallium Zinc Oxide Thin Film Transistors Using Nitrocellulose Passivation Layer journal April 2017
Transparent conductors as solar energy materials: A panoramic review journal October 2007
Ternary chalcogenides C s 2 Z n 3 S e 4 and C s 2 Z n 3 T e 4 : Potential p -type transparent conducting materials journal November 2014
Band structure and photoemission studies of SnS 2 and SnSe 2 . I. Experimental journal December 1973
(CdSe)ZnS Core−Shell Quantum Dots: Synthesis and Characterization of a Size Series of Highly Luminescent Nanocrystallites journal November 1997
Growth of n- and p-type ZnTe semiconductors by intrinsic doping journal November 2015
Ternary chalcopyrite compounds journal January 1979
Assessing High-Throughput Descriptors for Prediction of Transparent Conductors journal October 2018
Opto-electronic properties and light-emitting device application of widegap layered oxychalcogenides: LaCuO Ch ( Ch = chalcogen) and La 2 CdO 2 Se 2 journal September 2006
Sol–gel derived N-doped ZnO thin films journal October 2009
Inorganic scintillators: today and tomorrow journal December 2002
High-efficiency copper indium gallium diselenide (CIGS) solar cells with indium sulfide buffer layers deposited by atomic layer chemical vapor deposition (ALCVD) journal January 2003
Evidence for grain-boundary-assisted diffusion of sulfur in polycrystalline CdS/CdTe heterojunctions journal November 1999
Efficient creation and convergence of surface slabs journal November 2013
Extraordinary Room-Temperature Photoluminescence in Triangular WS 2 Monolayers journal December 2012
Solution-Processed p-Type Transparent Conducting BaCu 2 S 2 Thin Film journal June 2007
Electronic and optical properties of 2D graphene-like ZnS: DFT calculations journal April 2016
An Empirical, yet Practical Way To Predict the Band Gap in Solids by Using Density Functional Band Structure Calculations journal August 2017
A promising p-type transparent conducting material: Layered oxysulfide [Cu2S2][Sr3Sc2O5] journal December 2007
13.4% efficient thin‐film CdS/CdTe solar cells journal December 1991
Monocrystalline CdTe solar cells with open-circuit voltage over 1 V and efficiency of 17% journal May 2016
Development of rf sputtered, Cu-doped ZnTe for use as a contact interface layer to p-CdTe journal October 1995
Properties of n-type ZnN thin films as channel for transparent thin film transistors journal December 2009
Characteristics of p-type ZnSe Layers Grown by Molecular Beam Epitaxy with Radical Doping journal February 1991
P-type transparent conductors Sr 1−x Na x FCuS and SrF 1−x O x CuS: design, synthesis and physical properties journal January 2006
Applications of CdTe. A review journal January 1977
Material descriptors for predicting thermoelectric performance journal January 2015
Van der Waals heterostructures journal July 2013
Electrical and Optical Properties of Layered Oxysulfides with CuS Layers: Sr−Cu−M−O−S System (M = Zn, Ga, In) journal May 2001
Electronics and optoelectronics of two-dimensional transition metal dichalcogenides journal November 2012
Cadmium sulfide thin-film transistors fabricated by low-temperature chemical-bath deposition journal November 2004
ZnTe and InSb thin-film transistors journal January 1967
CdSe-Sensitized p-CuSCN/Nanowire n-ZnO Heterojunctions journal June 2005
Synthesis and Characterization of V-Doped β-In 2 S 3 Thin Films on FTO Substrates journal December 2016
Preparation and characterization of amorphous manganese sulfide thin films by SILAR method journal August 2007
A Molecular MoS2 Edge Site Mimic for Catalytic Hydrogen Generation journal February 2012
Electrical and optical properties of epitaxial transparent conductive BaCuTeF thin films deposited by pulsed laser deposition journal July 2008
Towards low-cost, environmentally friendly printed chalcopyrite and kesterite solar cells journal January 2014
Excitons and the Absorption Edge of Cadmium Sulfide journal July 1960
Valence band discontinuity at the ZnTe/CdTe interface: Making ohmic contact to P-type CdTe
  • Niles, David W.; Höchst, Hartmut; Rioux, Dennis
  • Photovoltaic advanced research and development project, AIP Conference Proceedings https://doi.org/10.1063/1.42930
conference January 1992