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Title: Sustainable p-type copper selenide solar material with ultra-large absorption coefficient

Abstract

Earth-abundant solar absorber materials with large optical absorption coefficients in the visible enable the fabrication of low-cost high-efficiency single and multi-junction thin-film solar cells. Here, we report a new p-type semiconductor, Cu 4TiSe 4 (CTSe), featuring indirect (1.15 eV) and direct (1.34 eV) band gaps in the optimal range for solar absorber materials. CTSe crystallizes in a new noncentrosymmetric cubic structure (space group F$$\bar{4}$$3c) in which CuSe 4 tetrahedra share edges and corners to form octahedral anionic clusters, [Cu 4Se 4] 4-, which in turn share corners to build the three-dimensional framework, with Ti 4+ ions located at tetrahedral interstices within the channels. The unique crystal structure and the Ti 3d orbital character of the conduction band of CTSe give rise to near-optimal band gap values and ultra-large absorption coefficients (larger than 10 5 cm -1) throughout the visible range, which are promising for scalable low-cost high-efficiency CTSe-based thin-film solar cells.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [2];  [1];  [1];  [1]; ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Department of Materials Science and Engineering, University of Michigan, Ann Arbor, USA
  2. Department of Electrical Engineering and Computer Science, University of Michigan, Ann Arbor, USA
Publication Date:
Research Org.:
Univ. of Michigan, Ann Arbor, MI (United States); Univ. of California, Riverside, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1439769
Alternate Identifier(s):
OSTI ID: 1505219
Grant/Contract Number:  
SC0008574; AC02-05CH11231
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 9 Journal Issue: 24; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; 14 SOLAR ENERGY

Citation Formats

Chen, Erica M., Williams, Logan, Olvera, Alan, Zhang, Cheng, Zhang, Mingfei, Shi, Guangsha, Heron, John T., Qi, Liang, Guo, L. Jay, Kioupakis, Emmanouil, and Poudeu, Pierre F. P. Sustainable p-type copper selenide solar material with ultra-large absorption coefficient. United Kingdom: N. p., 2018. Web. doi:10.1039/C8SC00873F.
Chen, Erica M., Williams, Logan, Olvera, Alan, Zhang, Cheng, Zhang, Mingfei, Shi, Guangsha, Heron, John T., Qi, Liang, Guo, L. Jay, Kioupakis, Emmanouil, & Poudeu, Pierre F. P. Sustainable p-type copper selenide solar material with ultra-large absorption coefficient. United Kingdom. doi:10.1039/C8SC00873F.
Chen, Erica M., Williams, Logan, Olvera, Alan, Zhang, Cheng, Zhang, Mingfei, Shi, Guangsha, Heron, John T., Qi, Liang, Guo, L. Jay, Kioupakis, Emmanouil, and Poudeu, Pierre F. P. Mon . "Sustainable p-type copper selenide solar material with ultra-large absorption coefficient". United Kingdom. doi:10.1039/C8SC00873F.
@article{osti_1439769,
title = {Sustainable p-type copper selenide solar material with ultra-large absorption coefficient},
author = {Chen, Erica M. and Williams, Logan and Olvera, Alan and Zhang, Cheng and Zhang, Mingfei and Shi, Guangsha and Heron, John T. and Qi, Liang and Guo, L. Jay and Kioupakis, Emmanouil and Poudeu, Pierre F. P.},
abstractNote = {Earth-abundant solar absorber materials with large optical absorption coefficients in the visible enable the fabrication of low-cost high-efficiency single and multi-junction thin-film solar cells. Here, we report a new p-type semiconductor, Cu4TiSe4 (CTSe), featuring indirect (1.15 eV) and direct (1.34 eV) band gaps in the optimal range for solar absorber materials. CTSe crystallizes in a new noncentrosymmetric cubic structure (space group F$\bar{4}$3c) in which CuSe4 tetrahedra share edges and corners to form octahedral anionic clusters, [Cu4Se4]4-, which in turn share corners to build the three-dimensional framework, with Ti4+ ions located at tetrahedral interstices within the channels. The unique crystal structure and the Ti 3d orbital character of the conduction band of CTSe give rise to near-optimal band gap values and ultra-large absorption coefficients (larger than 105 cm-1) throughout the visible range, which are promising for scalable low-cost high-efficiency CTSe-based thin-film solar cells.},
doi = {10.1039/C8SC00873F},
journal = {Chemical Science},
number = 24,
volume = 9,
place = {United Kingdom},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C8SC00873F

Citation Metrics:
Cited by: 1 work
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Figures / Tables:

Figure 1 Figure 1: Crystal structure of CTSe projected along [001]. (a) A ball-and-stick representation showing the 3D connectivity between metal tetra- hedra, MSe4; (b) an alternate polyhedral representation highlighting octahedral building blocks of [Cu4Se4]4- anionic clusters. The [Cu4Se4]4- anionic clusters form two interpenetrated face centered cubic (fcc) lattices (yellow and purplemore » denote the two sublattices) to generate a 3D structure that is topologically similar to a double perovskite, with Ti4+ ions located at tetrahedral sites within the channels; (c) [Cu4Se4]4- anionic cluster consisting of a Cu-centered hexanuclear octahedral [Cu]6 cluster capped by Se atoms on four of the eight triangular faces; (d) TiSe4 tetrahedron shares only corners with Cu(1)Se4 tetrahedra; (e) environment of Cu(1) and Cu(2) and their connectivity within the [Cu4Se4]4- anionic cluster. Cu(2)Se4 tetrahedron share all edges with Cu(1)Se4 tetrahedra, Cu(1)Se4 tetrahedra exclusively share corners with each other and Cu(2) Se4 tetrahedra are isolated from each other; (f) TiSe4 tetrahedron shares only corners with Cu(2)Se4 tetrahedra and TiSe4 tetrahedra are isolated from each other.« less

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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

Metal-halide perovskites for photovoltaic and light-emitting devices
journal, May 2015

  • Stranks, Samuel D.; Snaith, Henry J.
  • Nature Nanotechnology, Vol. 10, Issue 5
  • DOI: 10.1038/nnano.2015.90

Cu 2 ZnSnSe 4 Thin-Film Solar Cells by Thermal Co-evaporation with 11.6% Efficiency and Improved Minority Carrier Diffusion Length
journal, December 2014

  • Lee, Yun Seog; Gershon, Talia; Gunawan, Oki
  • Advanced Energy Materials, Vol. 5, Issue 7
  • DOI: 10.1002/aenm.201401372

Low-temperature processed meso-superstructured to thin-film perovskite solar cells
journal, January 2013

  • Ball, James M.; Lee, Michael M.; Hey, Andrew
  • Energy & Environmental Science, Vol. 6, Issue 6
  • DOI: 10.1039/c3ee40810h

Projector augmented-wave method
journal, December 1994


Lattice instabilities in metallic elements
journal, June 2012

  • Grimvall, Göran; Magyari-Köpe, Blanka; Ozoliņš, Vidvuds
  • Reviews of Modern Physics, Vol. 84, Issue 2
  • DOI: 10.1103/RevModPhys.84.945

wannier90: A tool for obtaining maximally-localised Wannier functions
journal, May 2008

  • Mostofi, Arash A.; Yates, Jonathan R.; Lee, Young-Su
  • Computer Physics Communications, Vol. 178, Issue 9
  • DOI: 10.1016/j.cpc.2007.11.016

Ab Initio Calculation of Excitonic Effects in the Optical Spectra of Semiconductors
journal, May 1998


Interface engineering of highly efficient perovskite solar cells
journal, July 2014


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


Structural investigation of the Cu2Se–In2Se3–Ga2Se3 phase diagram, X-ray photoemission and optical properties of the Cu1−z(In0.5Ga0.5)1+z/3Se2 compounds
journal, October 2010

  • Souilah, M.; Lafond, A.; Guillot-Deudon, C.
  • Journal of Solid State Chemistry, Vol. 183, Issue 10
  • DOI: 10.1016/j.jssc.2010.08.014

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

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

Optical Properties and Electronic Structure of Amorphous Germanium
journal, January 1966


Ab initiomolecular dynamics for liquid metals
journal, January 1993


An Ultrathin, Smooth, and Low-Loss Al-Doped Ag Film and Its Application as a Transparent Electrode in Organic Photovoltaics
journal, June 2014


Electronic and Optical Properties of Nanoporous Silicon for Solar-Cell Applications
journal, January 2015

  • Shi, Guangsha; Kioupakis, Emmanouil
  • ACS Photonics, Vol. 2, Issue 2
  • DOI: 10.1021/ph5002999

High-efficiency crystalline silicon solar cells: status and perspectives
journal, January 2016

  • Battaglia, Corsin; Cuevas, Andres; De Wolf, Stefaan
  • Energy & Environmental Science, Vol. 9, Issue 5
  • DOI: 10.1039/C5EE03380B

Achievement of More Than 25% Conversion Efficiency With Crystalline Silicon Heterojunction Solar Cell
journal, November 2014


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

Structural analysis of CuInSe2 and CuIn3Se5 at different temperatures with synchrotron radiation
journal, September 2003


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


The internal stability of an elastic solid
journal, December 2000


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

Refractive index and extinction coefficient of CH_3NH_3PbI_3 studied by spectroscopic ellipsometry
journal, December 2014

  • Ziang, Xie; Shifeng, Liu; Laixiang, Qin
  • Optical Materials Express, Vol. 5, Issue 1
  • DOI: 10.1364/OME.5.000029

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Pressure dependence of the elastic moduli in aluminum-rich Al-Li compounds
journal, February 1993


18% Efficiency Cd-Free Cu(In, Ga)Se2 Thin-Film Solar Cells Fabricated Using Chemical Bath Deposition (CBD)-ZnS Buffer Layers
journal, February 2002

  • Nakada, Tokio; Mizutani, Masayuki
  • Japanese Journal of Applied Physics, Vol. 41, Issue Part 2, No. 2B
  • DOI: 10.1143/JJAP.41.L165

Development of CZTS-based thin film solar cells
journal, February 2009

  • Katagiri, Hironori; Jimbo, Kazuo; Maw, Win Shwe
  • Thin Solid Films, Vol. 517, Issue 7, p. 2455-2460
  • DOI: 10.1016/j.tsf.2008.11.002

First principles phonon calculations in materials science
journal, November 2015


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


Electrical and optical properties of CuZnSnS thin films prepared by rf magnetron sputtering process
journal, January 2003


Crystal structure refinement with SHELXL
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053229614024218

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


Dielectric function of Cu(In, Ga)Se 2 -based polycrystalline materials
journal, February 2013

  • Minoura, Shota; Kodera, Keita; Maekawa, Takuji
  • Journal of Applied Physics, Vol. 113, Issue 6
  • DOI: 10.1063/1.4790174

Optical properties of GaAs
journal, March 2013


Efficient planar heterojunction perovskite solar cells by vapour deposition
journal, September 2013

  • Liu, Mingzhen; Johnston, Michael B.; Snaith, Henry J.
  • Nature, Vol. 501, Issue 7467, p. 395-398
  • DOI: 10.1038/nature12509

Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites
journal, October 2012


Electron-Hole Excitations in Semiconductors and Insulators
journal, September 1998


Defect Engineering in Multinary Earth-Abundant Chalcogenide Photovoltaic Materials
journal, January 2017

  • Shin, Donghyeop; Saparov, Bayrammurad; Mitzi, David B.
  • Advanced Energy Materials, Vol. 7, Issue 11
  • DOI: 10.1002/aenm.201602366

Detailed Balance Limit of Efficiency of p‐n Junction Solar Cells
journal, March 1961

  • Shockley, William; Queisser, Hans J.
  • Journal of Applied Physics, Vol. 32, Issue 3, p. 510-519
  • DOI: 10.1063/1.1736034

Lead-free solid-state organic–inorganic halide perovskite solar cells
journal, May 2014

  • Hao, Feng; Stoumpos, Constantinos C.; Cao, Duyen Hanh
  • Nature Photonics, Vol. 8, Issue 6
  • DOI: 10.1038/nphoton.2014.82

Survey of methods to characterize thin absorbing films with Spectroscopic Ellipsometry
journal, September 2008


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


Implementation and performance of the frequency-dependent G W method within the PAW framework
journal, July 2006


    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.