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Title: Energy band structure of CuInS 2 and optical spectra of CuInS 2 nanocrystals

Abstract

Using first principles calculations we describe the energy band structure of bulk CuInS2. The energy band parameters for the multiband effective mass approximation that describes the band edges of this semiconductor are obtained by fitting them to the first principles spectra. Within the multiband effective mass approximation we develop a theoretical description for the structure of band-edge levels and optical properties of the CuInS2 nanocrystals. For the nanocrystals of spherical shape, the optical transitions are weakly allowed between the electron and hole ground states due to the tetragonal symmetry of the crystal lattice, resulting in a large Stokes shift of photoluminescence up to 300 meV in the smallest nanocrystals. In conclusion, this theory of the band-edge optical transitions in CuInS2 NCs can be applied to spherical NCs made of other chalcopyrite compounds.

Authors:
 [1];  [2];  [2]
  1. George Mason Univ., Fairfax, VA (United States)
  2. Naval Research Lab. (NRL), Washington, DC (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Advanced Solar Photophysics (CASP)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1371348
Alternate Identifier(s):
OSTI ID: 1203806
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review. B, Condensed Matter and Materials Physics
Additional Journal Information:
Journal Volume: 92; Journal Issue: 3; Related Information: CASP partners with Los Alamos National Laboratory (lead); University of California, Irvine; University of Colorado; Colorado School of Mines; George Mason University; Los Alamos National Laboratory; University of Minnesota; National Renewable Energy Laboratory; Journal ID: ISSN 1098-0121
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; solar (photovoltaic); solar (fuels); solid state lighting; bio-inspired; electrodes - solar; defects; charge transport; materials and chemistry by design; optics; synthesis (novel materials); synthesis (scalable processing)

Citation Formats

Shabaev, A., Mehl, M. J., and Efros, Al. L. Energy band structure of CuInS2 and optical spectra of CuInS2 nanocrystals. United States: N. p., 2015. Web. doi:10.1103/PhysRevB.92.035431.
Shabaev, A., Mehl, M. J., & Efros, Al. L. Energy band structure of CuInS2 and optical spectra of CuInS2 nanocrystals. United States. https://doi.org/10.1103/PhysRevB.92.035431
Shabaev, A., Mehl, M. J., and Efros, Al. L. Mon . "Energy band structure of CuInS2 and optical spectra of CuInS2 nanocrystals". United States. https://doi.org/10.1103/PhysRevB.92.035431. https://www.osti.gov/servlets/purl/1371348.
@article{osti_1371348,
title = {Energy band structure of CuInS2 and optical spectra of CuInS2 nanocrystals},
author = {Shabaev, A. and Mehl, M. J. and Efros, Al. L.},
abstractNote = {Using first principles calculations we describe the energy band structure of bulk CuInS2. The energy band parameters for the multiband effective mass approximation that describes the band edges of this semiconductor are obtained by fitting them to the first principles spectra. Within the multiband effective mass approximation we develop a theoretical description for the structure of band-edge levels and optical properties of the CuInS2 nanocrystals. For the nanocrystals of spherical shape, the optical transitions are weakly allowed between the electron and hole ground states due to the tetragonal symmetry of the crystal lattice, resulting in a large Stokes shift of photoluminescence up to 300 meV in the smallest nanocrystals. In conclusion, this theory of the band-edge optical transitions in CuInS2 NCs can be applied to spherical NCs made of other chalcopyrite compounds.},
doi = {10.1103/PhysRevB.92.035431},
journal = {Physical Review. B, Condensed Matter and Materials Physics},
number = 3,
volume = 92,
place = {United States},
year = {Mon Jul 27 00:00:00 EDT 2015},
month = {Mon Jul 27 00:00:00 EDT 2015}
}

Journal Article:

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Cited by: 66 works
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Works referenced in this record:

Ternary I−III−VI Quantum Dots Luminescent in the Red to Near-Infrared
journal, July 2008

  • Allen, Peter M.; Bawendi, Moungi G.
  • Journal of the American Chemical Society, Vol. 130, Issue 29
  • DOI: 10.1021/ja8036349

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

Stability Assessment on a 3% Bilayer PbS/ZnO Quantum Dot Heterojunction Solar Cell
journal, August 2010

  • Luther, Joseph M.; Gao, Jianbo; Lloyd, Matthew T.
  • Advanced Materials, Vol. 22, Issue 33, p. 3704-3707
  • DOI: 10.1002/adma.201001148

Emergence of colloidal quantum-dot light-emitting technologies
journal, December 2012

  • Shirasaki, Yasuhiro; Supran, Geoffrey J.; Bawendi, Moungi G.
  • Nature Photonics, Vol. 7, Issue 1
  • DOI: 10.1038/nphoton.2012.328

Highly Luminescent, Size- and Shape-Tunable Copper Indium Selenide Based Colloidal Nanocrystals
journal, August 2013

  • Yarema, Olesya; Bozyigit, Deniz; Rousseau, Ian
  • Chemistry of Materials, Vol. 25, Issue 18
  • DOI: 10.1021/cm402306q

Processes for chalcopyrite-based solar cells
journal, February 2000


Structural, Optical, and Electrical Properties of Self-Assembled Films of PbSe Nanocrystals Treated with 1,2-Ethanedithiol
journal, January 2008

  • Luther, Joseph M.; Law, Matt; Song, Qing
  • ACS Nano, Vol. 2, Issue 2
  • DOI: 10.1021/nn7003348

Landau levels of the C-exciton in CuInSe 2 studied by magneto-transmission
journal, October 2014

  • Yakushev, M. V.; Rodina, A. V.; Shuchalin, G. M.
  • Applied Physics Letters, Vol. 105, Issue 14
  • DOI: 10.1063/1.4897995

The Electronic Structure of Semiconductor Nanocrystals
journal, August 2000


Role of mid-gap states in charge transport and photoconductivity in semiconductor nanocrystal films
journal, September 2011

  • Nagpal, Prashant; Klimov, Victor I.
  • Nature Communications, Vol. 2, Issue 1
  • DOI: 10.1038/ncomms1492

Direct Observation of Cu d Levels in I-III- VI 2 Compounds
journal, October 1972


Quantum Theory of Cyclotron Resonance in Semiconductors: General Theory
journal, May 1956


Efficient Synthesis of Highly Luminescent Copper Indium Sulfide-Based Core/Shell Nanocrystals with Surprisingly Long-Lived Emission
journal, February 2011

  • Li, Liang; Pandey, Anshu; Werder, Donald J.
  • Journal of the American Chemical Society, Vol. 133, Issue 5, p. 1176-1179
  • DOI: 10.1021/ja108261h

Development of CuInSe 2 Nanocrystal and Nanoring Inks for Low-Cost Solar Cells
journal, September 2008

  • Guo, Qijie; Kim, Suk Jun; Kar, Mahaprasad
  • Nano Letters, Vol. 8, Issue 9
  • DOI: 10.1021/nl802042g

Photoreflectance of CuInS2 single crystal prepared by traveling heater method
journal, September 2003


Angular Momentum Theory and Localized States in Solids. Investigation of Shallow Acceptor States in Semiconductors
journal, December 1970


Tuning the Luminescence Properties of Colloidal I–III–VI Semiconductor Nanocrystals for Optoelectronics and Biotechnology Applications
journal, October 2012

  • Zhong, Haizheng; Bai, Zelong; Zou, Bingsuo
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 21, p. 3167-3175
  • DOI: 10.1021/jz301345x

Ternary and quaternary metal chalcogenide nanocrystals: synthesis, properties and applications
journal, January 2013

  • Aldakov, Dmitry; Lefrançois, Aurélie; Reiss, Peter
  • Journal of Materials Chemistry C, Vol. 1, Issue 24
  • DOI: 10.1039/c3tc30273c

p d Hybridization of the Valence Bands of I-III- VI 2 Compounds
journal, June 1972


Efficient CuInSe 2 /CdS solar cells
journal, July 1975

  • Shay, J. L.; Wagner, Sigurd; Kasper, H. M.
  • Applied Physics Letters, Vol. 27, Issue 2
  • DOI: 10.1063/1.88372

Band structure of CdGeAs 2 near the fundamental gap
journal, April 2002


Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965


Excited states of the A free exciton in CuInS2
journal, March 2008

  • Yakushev, M. V.; Martin, R. W.; Mudryi, A. V.
  • Applied Physics Letters, Vol. 92, Issue 11
  • DOI: 10.1063/1.2896301

Simple yet Versatile Synthesis of CuInSe x S 2– x Quantum Dots for Sunlight Harvesting
journal, May 2014

  • McDaniel, Hunter; Koposov, Alexey Y.; Draguta, Sergiu
  • The Journal of Physical Chemistry C, Vol. 118, Issue 30
  • DOI: 10.1021/jp5004903

Diamagnetic shifts of free excitons in CuInS2 in magnetic fields
journal, January 2009

  • Yakushev, M. V.; Martin, R. W.; Mudryi, A. V.
  • Applied Physics Letters, Vol. 94, Issue 4
  • DOI: 10.1063/1.3077022

Anisotropy of effective masses in CuInSe 2
journal, December 2012

  • Yakushev, M. V.; Luckert, F.; Rodina, A. V.
  • Applied Physics Letters, Vol. 101, Issue 26
  • DOI: 10.1063/1.4773480

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

PbSe Quantum Dot Solar Cells with More than 6% Efficiency Fabricated in Ambient Atmosphere
journal, September 2014

  • Zhang, Jianbing; Gao, Jianbo; Church, Carena P.
  • Nano Letters, Vol. 14, Issue 10
  • DOI: 10.1021/nl503085v

New world record efficiency for Cu(In,Ga)Se2 thin-film solar cells beyond 20%
journal, January 2011

  • Jackson, Philip; Hariskos, Dimitrios; Lotter, Erwin
  • Progress in Photovoltaics: Research and Applications, Vol. 19, Issue 7
  • DOI: 10.1002/pip.1078

Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006

  • Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.
  • The Journal of Chemical Physics, Vol. 125, Issue 22
  • DOI: 10.1063/1.2404663

Ab initio molecular dynamics for open-shell transition metals
journal, November 1993


Electron and hole conductivity in CuInS2
journal, January 1976


Highly efficient Cu(In,Ga)Se2 solar cells grown on flexible polymer films
journal, September 2011

  • Chirilă, Adrian; Buecheler, Stephan; Pianezzi, Fabian
  • Nature Materials, Vol. 10, Issue 11
  • DOI: 10.1038/nmat3122

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


n-Type Transition Metal Oxide as a Hole Extraction Layer in PbS Quantum Dot Solar Cells
journal, August 2011

  • Gao, Jianbo; Perkins, Craig L.; Luther, Joseph M.
  • Nano Letters, Vol. 11, Issue 8, p. 3263-3266
  • DOI: 10.1021/nl2015729

Synthesis of CuInS 2 , CuInSe 2 , and Cu(In x Ga 1- x )Se 2 (CIGS) Nanocrystal “Inks” for Printable Photovoltaics
journal, December 2008

  • Panthani, Matthew G.; Akhavan, Vahid; Goodfellow, Brian
  • Journal of the American Chemical Society, Vol. 130, Issue 49
  • DOI: 10.1021/ja805845q

Energy of excitons in CuInS2 single crystals
journal, January 2006

  • Yakushev, M. V.; Mudryi, A. V.; Victorov, I. V.
  • Applied Physics Letters, Vol. 88, Issue 1
  • DOI: 10.1063/1.2152114

Inhomogeneous Electron Gas
journal, November 1964


Electrical Properties, Optical Properties, and Band Structure of CuGa S 2 and CuIn S 2
journal, October 1971


Efficient Spray-Coated Colloidal Quantum Dot Solar Cells
journal, November 2014

  • Kramer, Illan J.; Minor, James C.; Moreno-Bautista, Gabriel
  • Advanced Materials, Vol. 27, Issue 1
  • DOI: 10.1002/adma.201403281

Improved performance and stability in quantum dot solar cells through band alignment engineering
journal, May 2014

  • Chuang, Chia-Hao M.; Brown, Patrick R.; Bulović, Vladimir
  • Nature Materials, Vol. 13, Issue 8, p. 796-801
  • DOI: 10.1038/nmat3984

Luminescence of CuInS2
journal, June 1982


Theory of the band-gap anomaly in AB C 2 chalcopyrite semiconductors
journal, February 1984


An integrated approach to realizing high-performance liquid-junction quantum dot sensitized solar cells
journal, December 2013

  • McDaniel, Hunter; Fuke, Nobuhiro; Makarov, Nikolay S.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3887

Absorption and intensity-dependent photoluminescence measurements on CdSe quantum dots: assignment of the first electronic transitions
journal, January 1993

  • Ekimov, A. I.; Kudryavtsev, I. A.; Efros, Al. L.
  • Journal of the Optical Society of America B, Vol. 10, Issue 1
  • DOI: 10.1364/JOSAB.10.000100

Engineered CuInSe x S 2– x Quantum Dots for Sensitized Solar Cells
journal, January 2013

  • McDaniel, Hunter; Fuke, Nobuhiro; Pietryga, Jeffrey M.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 3
  • DOI: 10.1021/jz302067r

Exciton binding energies in chalcopyrite semiconductors
journal, February 2012


ESR and x-ray analysis of the ternary semiconductors CuAlS2, CuInS2 and AgGaS2
journal, March 1973


Electron and hole conductivity in CuInS2
journal, October 1975


Works referencing / citing this record:

Evidence for the Band‐Edge Exciton of CuInS 2 Nanocrystals Enables Record Efficient Large‐Area Luminescent Solar Concentrators
journal, November 2019

  • Anand, Abhinav; Zaffalon, Matteo L.; Gariano, Graziella
  • Advanced Functional Materials, Vol. 30, Issue 4
  • DOI: 10.1002/adfm.201906629

Near-Infrared, Heavy Metal-Free Colloidal “Giant” Core/Shell Quantum Dots
journal, September 2017

  • Tong, Xin; Kong, Xiang-Tian; Zhou, Yufeng
  • Advanced Energy Materials, Vol. 8, Issue 2
  • DOI: 10.1002/aenm.201701432

Rational Construction of Z‐Scheme CuInS 2 /Au/g‐C 3 N 4 Heterostructure: Experimental Results and Theoretical Calculation
journal, October 2019


Prospects of Colloidal Copper Chalcogenide Nanocrystals
journal, February 2016

  • van der Stam, Ward; Berends, Anne C.; de Mello Donega, Celso
  • ChemPhysChem, Vol. 17, Issue 5
  • DOI: 10.1002/cphc.201500976

Electronic energy band parameters of CuInS e 2 : Landau levels in magnetotransmission spectra
journal, December 2019


Investigation of AgInS2/ZnS Quantum Dots by Magnetic Circular Dichroism Spectroscopy
journal, November 2019

  • Gromova, Yulia; Sokolova, Anastasiia; Kurshanov, Danil
  • Materials, Vol. 12, Issue 21
  • DOI: 10.3390/ma12213616

Prospects of Colloidal Copper Chalcogenide Nanocrystals
journal, February 2016

  • van der Stam, Ward; Berends, Anne C.; de Mello Donega, Celso
  • ChemPhysChem, Vol. 17, Issue 5
  • DOI: 10.1002/cphc.201600094