Copper Vacancies and Heavy Holes in the Two-Dimensional Semiconductor KCu3–xSe2
Abstract
The two-dimensional material KCu3–xSe2 was synthesized using both a K2Se3 flux and directly from the elements. It crystallizes in the CsAg3S2 structure (monoclinic space group C2/m with a = 15.417(3) Å, b = 4.0742(8) Å, c = 8.3190(17) Å, and β = 112.94(3)°), and single-crystal refinement revealed infinite copper-deficient [Cu3–xSe2]– layers separated by K+ ions. Thermal analysis indicated that KCu3–xSe2 melts congruently at ~755 °C. UV–vis spectroscopy showed an optical band gap of ~1.35 eV that is direct in nature, as confirmed by electronic structure calculations. Electronic transport measurements on single crystals yielded an in-plane resistivity of ~6 × 10–1 Ω cm at 300 K that has a complex temperature dependence. The results of Seebeck coefficient measurements were consistent with a doped p-type semiconductor (S = +214 μV K–1 at 300 K), with doping being attributed to copper vacancies. Transport is dominated by low-mobility (on the order of 1 cm2 V–1 s–1) holes caused by relatively flat valence bands with substantial Cu 3d character and a significant concentration of Cu ion vacancy defects (p ~ 1019 cm–3) in this material. In conclusion, electronic band structure calculations showed that electrons should be significantly more mobile in this structure type.
- Authors:
-
[1];
[3]
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Leibniz Institute for Solid State and Materials Research (IFW), Dresden (Germany)
- Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); German Research Foundation (DFG)
- OSTI Identifier:
- 1393193
- Grant/Contract Number:
- AC02-06CH11357; STU 695/1-1
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 29; Journal Issue: 14; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Rettie, Alexander J. E., Sturza, Mihai, Malliakas, Christos D., Botana, Antia S., Chung, Duck Young, and Kanatzidis, Mercouri G. Copper Vacancies and Heavy Holes in the Two-Dimensional Semiconductor KCu3–xSe2. United States: N. p., 2017.
Web. doi:10.1021/acs.chemmater.7b02117.
Rettie, Alexander J. E., Sturza, Mihai, Malliakas, Christos D., Botana, Antia S., Chung, Duck Young, & Kanatzidis, Mercouri G. Copper Vacancies and Heavy Holes in the Two-Dimensional Semiconductor KCu3–xSe2. United States. https://doi.org/10.1021/acs.chemmater.7b02117
Rettie, Alexander J. E., Sturza, Mihai, Malliakas, Christos D., Botana, Antia S., Chung, Duck Young, and Kanatzidis, Mercouri G. Wed .
"Copper Vacancies and Heavy Holes in the Two-Dimensional Semiconductor KCu3–xSe2". United States. https://doi.org/10.1021/acs.chemmater.7b02117. https://www.osti.gov/servlets/purl/1393193.
@article{osti_1393193,
title = {Copper Vacancies and Heavy Holes in the Two-Dimensional Semiconductor KCu3–xSe2},
author = {Rettie, Alexander J. E. and Sturza, Mihai and Malliakas, Christos D. and Botana, Antia S. and Chung, Duck Young and Kanatzidis, Mercouri G.},
abstractNote = {The two-dimensional material KCu3–xSe2 was synthesized using both a K2Se3 flux and directly from the elements. It crystallizes in the CsAg3S2 structure (monoclinic space group C2/m with a = 15.417(3) Å, b = 4.0742(8) Å, c = 8.3190(17) Å, and β = 112.94(3)°), and single-crystal refinement revealed infinite copper-deficient [Cu3–xSe2]– layers separated by K+ ions. Thermal analysis indicated that KCu3–xSe2 melts congruently at ~755 °C. UV–vis spectroscopy showed an optical band gap of ~1.35 eV that is direct in nature, as confirmed by electronic structure calculations. Electronic transport measurements on single crystals yielded an in-plane resistivity of ~6 × 10–1 Ω cm at 300 K that has a complex temperature dependence. The results of Seebeck coefficient measurements were consistent with a doped p-type semiconductor (S = +214 μV K–1 at 300 K), with doping being attributed to copper vacancies. Transport is dominated by low-mobility (on the order of 1 cm2 V–1 s–1) holes caused by relatively flat valence bands with substantial Cu 3d character and a significant concentration of Cu ion vacancy defects (p ~ 1019 cm–3) in this material. In conclusion, electronic band structure calculations showed that electrons should be significantly more mobile in this structure type.},
doi = {10.1021/acs.chemmater.7b02117},
journal = {Chemistry of Materials},
number = 14,
volume = 29,
place = {United States},
year = {Wed Jun 21 00:00:00 EDT 2017},
month = {Wed Jun 21 00:00:00 EDT 2017}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 8 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
CuSe2, a Marcasite Type Superconductor
journal, October 1968
- Hull, G. W.; Hulliger, F.
- Nature, Vol. 220, Issue 5164
Superconducting properties of CuS2−xSex under high pressure
journal, November 2000
- Takano, Yoshihiko; Uchiyama, Naoaki; Ogawa, Shinji
- Physica C: Superconductivity, Vol. 341-348
Superionics: crystal structures and conduction processes
journal, June 2004
- Hull, Stephen
- Reports on Progress in Physics, Vol. 67, Issue 7
Phase transitions in copper chalcogenides: I. The copper-selenium system
journal, January 1971
- Stevels, A. L. N.; Jellinek, F.
- Recueil des Travaux Chimiques des Pays-Bas, Vol. 90, Issue 3
Phase transitions in copper chalcogenides II. The tellurides Cu3-x Te2 and CuTe
journal, January 1971
- Stevels, A. L. N.; Wiegers, G. A.
- Recueil des Travaux Chimiques des Pays-Bas, Vol. 90, Issue 4
Vacancy Ordering as the Cause for the Electrical Resistivity Anomalies and Superlattice Modulations inACu7−xS4(A=Tl, K, Rb)
journal, November 1997
- Lee, K. -S.; Seo, D. -K.; Whangbo, M. -H.
- Journal of Solid State Chemistry, Vol. 134, Issue 1
Na 3 Cu 4 S 4 -ein Thiocuprat mit unverknüpften 1 ∞ [Cu 4 S 4 ] -Ketten / Na 3 Cu 4 S 4 -a Thiocuprate with Isolated 1 ∞ [Cu 4 S 4 ]-Chains
journal, March 1979
- Burschka, Christian
- Zeitschrift für Naturforschung B, Vol. 34, Issue 3
In situ studies of a platform for metastable inorganic crystal growth and materials discovery
journal, July 2014
- Shoemaker, D. P.; Hu, Y. -J.; Chung, D. Y.
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 30
KCu 3 S 2 , ein neues Thiocuprat / KCu 3 S 2 , a New Thiocuprate
journal, January 1977
- Burschka, Christian; Bronger, Welf
- Zeitschrift für Naturforschung B, Vol. 32, Issue 1
Zur kenntnis von Na2Cu4S3 und KCu3Te2
journal, October 1981
- Savelsberg, G.; Schäfer, H.
- Materials Research Bulletin, Vol. 16, Issue 10
Zur Kristallstruktur der Thiocuprate K 3 Cu 8 S 6 und Rb 3 Cu 8 S 6 / On the Crystal Structure of the Thiocuprates K 3 Cu 8 S 6 and Rb 3 Cu 8 S 6
journal, May 1979
- Burschka, Christian
- Zeitschrift für Naturforschung B, Vol. 34, Issue 5
Tern�re Selenide des Kupfers
journal, January 1979
- Schils, H.; Bronger, W.
- Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 456, Issue 1
Physical Properties and Successive Phase Transitions in Quasi-One-Dimensional Sulfides ACu7S4 (A = Tl, K, Rb)
journal, March 1995
- Ohtani, T.; Ogura, J.; Yoshihara, H.
- Journal of Solid State Chemistry, Vol. 115, Issue 2
NaCu 6 Se 4 : A Layered Compound with Mixed Valency and Metallic Properties
journal, October 2014
- Sturza, Mihai; Malliakas, Christos D.; Bugaris, Daniel E.
- Inorganic Chemistry, Vol. 53, Issue 22
Mixed-Valent NaCu 4 Se 3 : A Two-Dimensional Metal
journal, May 2016
- Sturza, Mihai; Bugaris, Daniel E.; Malliakas, Christos D.
- Inorganic Chemistry, Vol. 55, Issue 10
NaBa 2 Cu 3 S 5 : A Doped p-Type Degenerate Semiconductor
journal, June 2013
- Sturza, Mihai; Han, Fei; Shoemaker, Daniel P.
- Inorganic Chemistry, Vol. 52, Issue 12
The Cu−Se (Copper-Selenium) system
journal, December 1981
- Chakrabarti, D. J.; Laughlin, D. E.
- Bulletin of Alloy Phase Diagrams, Vol. 2, Issue 3
On the Electrochemically Grown Quasi-One-Dimensional KCu 7- x S 4 Series (0 ⩽ x ⩽ 0.34): Nonstoichiometry, Superlattice, and Unusual Phase Transitions
journal, October 1998
- Li, He; Mackay, Richard; Hwu, Shiou-Jyh
- Chemistry of Materials, Vol. 10, Issue 10
Influence of the cation disordering on the electronic conductivity of superionic copper selenide
journal, June 1982
- Vucic, Z.; Horvatic, V.; Ogorelec, Z.
- Journal of Physics C: Solid State Physics, Vol. 15, Issue 16
Materials Discovery by Flux Crystal Growth: Quaternary and Higher Order Oxides
journal, January 2012
- Bugaris, Daniel E.; zur Loye, Hans-Conrad
- Angewandte Chemie International Edition, Vol. 51, Issue 16
Discovery-Synthesis, Design, and Prediction of Chalcogenide Phases
journal, March 2017
- Kanatzidis, Mercouri G.
- Inorganic Chemistry, Vol. 56, Issue 6
Phase transitions and transport properties of complex copper chalcogenides
journal, March 2003
- Jacyna-Onyszkiewicz, I.; Sidowski, M.; Starodub, V.
- physica status solidi (a), Vol. 196, Issue 1
Transport and Magnetic Studies of New Mixed-Valence Compounds: K 3 Cu 8 Se 6 , KCu 3 Se 2 , K 3 Cu 8 Te 6 and BaCuS 3-x
journal, February 1997
- Jacyna-Onyszkiewicz, I.; Sidowski, M.; Starodub, W.
- Acta Physica Polonica A, Vol. 91, Issue 2
Electronic properties and superlattice formation in the semimetal
journal, November 1976
- Di Salvo, F. J.; Moncton, D. E.; Waszczak, J. V.
- Physical Review B, Vol. 14, Issue 10
A short history of SHELX
journal, December 2007
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
Crystallographic Computing System JANA2006: General features
journal, January 2014
- Petříček, Václav; Dušek, Michal; Palatinus, Lukáš
- Zeitschrift für Kristallographie - Crystalline Materials, Vol. 229, Issue 5
Recent advances in magnetic structure determination by neutron powder diffraction
journal, October 1993
- Rodríguez-Carvajal, Juan
- Physica B: Condensed Matter, Vol. 192, Issue 1-2
An alternative way of linearizing the augmented plane-wave method
journal, March 2000
- Sjöstedt, E.; Nordström, L.; Singh, D. J.
- Solid State Communications, Vol. 114, Issue 1
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
Band theory and Mott insulators: Hubbard U instead of Stoner I
journal, July 1991
- Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K.
- Physical Review B, Vol. 44, Issue 3, p. 943-954
Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992
- Perdew, John P.; Wang, Yue
- Physical Review B, Vol. 45, Issue 23, p. 13244-13249
BoltzTraP. A code for calculating band-structure dependent quantities
journal, July 2006
- Madsen, Georg K. H.; Singh, David J.
- Computer Physics Communications, Vol. 175, Issue 1
Ternäre selenide des silbers
journal, July 1978
- Bronger, W.; Eyck, J.; Schils, H.
- Journal of the Less Common Metals, Vol. 60, Issue 1
�ber die Struktur von CsAg3S2 und RbAg3S2
journal, April 1977
- Burschka, C.; Bronger, W.
- Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 430, Issue 1
Crystal structure of Cu2Se
journal, January 2011
- Gulay, Lubomir; Daszkiewicz, Marek; Strok, Oksana
- Chemistry of Metals and Alloys, Vol. 4, Issue 3/4
Crystal Structure of Umangite, Cu3Se2
journal, April 1966
- Morimoto, N.; Koto, K.
- Science, Vol. 152, Issue 3720
Significance tests on the crystallographic R factor
journal, May 1965
- Hamilton, W. C.
- Acta Crystallographica, Vol. 18, Issue 3
X-ray scattering study of charge-density waves in
journal, April 1987
- Fleming, R. M.; Haar, L. W. ter; DiSalvo, F. J.
- Physical Review B, Vol. 35, Issue 10
Synthesis, crystal structure and low-temperature X-ray investigations of K3Cu8Se6
journal, September 1998
- Näther, C.; Röhnert, D.; Bensch, W.
- European Journal of Solid State and Inorganic Chemistry, Vol. 35, Issue 8-9
Accelerating materials development for photoelectrochemical hydrogen production: Standards for methods, definitions, and reporting protocols
journal, January 2010
- Chen, Zhebo; Jaramillo, Thomas F.; Deutsch, Todd G.
- Journal of Materials Research, Vol. 25, Issue 1
Tabulated values of the Shockley–Queisser limit for single junction solar cells
journal, June 2016
- Rühle, Sven
- Solar Energy, Vol. 130
n-Type KCu 3 S 2 microbelts: optical, electrical, and optoelectronic properties
journal, January 2014
- Wu, Chunyan; Wang, Wenjian; Wang, Xingang
- RSC Adv., Vol. 4, Issue 103
Charge-density waves and superlattices in the metallic layered transition metal dichalcogenides
journal, March 1975
- Wilson, J. A.; Di Salvo, F. J.; Mahajan, S.
- Advances in Physics, Vol. 24, Issue 2
Divergence in the Behavior of the Charge Density Wave in RE Te 3 ( RE = Rare-Earth Element) with Temperature and RE Element
journal, October 2006
- Malliakas, Christos D.; Kanatzidis, Mercouri G.
- Journal of the American Chemical Society, Vol. 128, Issue 39
Charge Density Waves in the Square Nets of Tellurium of AMRE Te 4 ( A = K, Na; M = Cu, Ag; RE = La, Ce)
journal, September 2007
- Malliakas, Christos D.; Kanatzidis, Mercouri G.
- Journal of the American Chemical Society, Vol. 129, Issue 35
Large magnetoresistance in non-magnetic silver chalcogenides
journal, November 1997
- Xu, R.; Husmann, A.; Rosenbaum, T. F.
- Nature, Vol. 390, Issue 6655
Megagauss sensors
journal, May 2002
- Husmann, A.; Betts, J. B.; Boebinger, G. S.
- Nature, Vol. 417, Issue 6887
Nonelectronic origin of superlattice modulations and resistivity anomalies in ternary copper sulfides
journal, March 1992
- Whangbo, M. -H.; Canadell, E.
- Solid State Communications, Vol. 81, Issue 11
Charge density wave fluctuations, heavy electrons, and superconductivity in KNi S
journal, January 2013
- Neilson, James R.; McQueen, Tyrel M.; Llobet, Anna
- Physical Review B, Vol. 87, Issue 4
Mixed-valence-driven heavy-fermion behavior and superconductivity in KNi Se
journal, August 2012
- Neilson, James R.; Llobet, Anna; Stier, Andreas V.
- Physical Review B, Vol. 86, Issue 5
Combined Charge Carrier Transport and Photoelectrochemical Characterization of BiVO 4 Single Crystals: Intrinsic Behavior of a Complex Metal Oxide
journal, July 2013
- Rettie, Alexander J. E.; Lee, Heung Chan; Marshall, Luke G.
- Journal of the American Chemical Society, Vol. 135, Issue 30
Origins of the -type nature and cation deficiency in and related materials
journal, July 2007
- Raebiger, Hannes; Lany, Stephan; Zunger, Alex
- Physical Review B, Vol. 76, Issue 4
Defect physics of the chalcopyrite semiconductor
journal, April 1998
- Zhang, S. B.; Wei, Su-Huai; Zunger, Alex
- Physical Review B, Vol. 57, Issue 16
Works referencing / citing this record:
Low temperature thermoelectric and magnetoresistive properties of Tl 2 Cu 3 FeQ 4 (Q = S, Se, Te)
journal, January 2018
- Aswathy, Vijayakumar Sajitha; Sankar, Cheriyedath Raj
- Inorganic Chemistry Frontiers, Vol. 5, Issue 7