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Title: Copper Vacancies and Heavy Holes in the Two-Dimensional Semiconductor KCu 3–xSe 2

The two-dimensional material KCu 3–xSe 2 was synthesized using both a K 2Se 3 flux and directly from the elements. It crystallizes in the CsAg 3S 2 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 [Cu 3–xSe 2]– layers separated by K + ions. Thermal analysis indicated that KCu 3–xSe 2 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 cm 2 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 ~ 10 19 cm –3) in this material. In conclusion,more » electronic band structure calculations showed that electrons should be significantly more mobile in this structure type.« less
ORCiD logo [1] ;  [2] ;  [3] ;  [1] ;  [1] ; ORCiD logo [3]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Leibniz Institute for Solid State and Materials Research (IFW), Dresden (Germany)
  3. Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357; STU 695/1-1
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 14; Journal ID: ISSN 0897-4756
American Chemical Society (ACS)
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); German Research Foundation (DFG)
Country of Publication:
United States
OSTI Identifier: