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Structural and Electronic Properties of Cu3InSe4

Department of Physics, University of South Florida, Tampa, FL 33620, USA
Materials Measurement Science Division, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA
ChemMatCARS, University of Chicago, Argonne, IL 60439, USA
Author to whom correspondence should be addressed.
Crystals 2022, 12(9), 1310;
Received: 12 August 2022 / Revised: 9 September 2022 / Accepted: 11 September 2022 / Published: 17 September 2022
(This article belongs to the Section Crystal Engineering)


Single crystals of a new ternary chalcogenide Cu3InSe4 were obtained by induction melting, allowing for a complete investigation of the crystal structure by employing high-resolution single-crystal synchrotron X-ray diffraction. Cu3InSe4 crystallizes in a cubic structure, space group P 4 ¯ 3 m , with lattice constant 5.7504(2) Å and a density of 5.426 g/cm3. There are three unique crystallographic sites in the unit cell, with each cation bonded to four Se atoms in a tetrahedral geometry. Electron localization function calculations were employed in investigating the chemical bonding nature and first-principle electronic structure calculations are also presented. The results are discussed in light of the ongoing interest in exploring the structural and electronic properties of new chalcogenide materials.

1. Introduction

Multinary metal chalcogenides consisting of primarily earth-abundant, low-cost, and non-toxic constituents exhibit physical properties that can be tuned via composition, specific bonding scheme, lattice defects or disorder, and have been investigated for a variety of different applications of interest including thermoelectrics [1,2,3,4,5,6], photovoltaics [7,8,9,10], superconductivity [11,12,13], and as potential topological insulators [14,15]. The interest in ternary Cu-based compositions has recently intensified in pursuit of commercially viable solar cells [16,17,18] and thermoelectrics [19,20,21,22]. The ternary Cu-In-Se system is of particular interest [23], with a number of compounds possible along the Cu2Se-InSe3 tie-line [24,25] such as CuInSe2 [26,27], Cu3In5Se9 [28], Cu7In19Se32 [23], CuIn5Se8 [25], Cu2In4Se7 [29] and CuIn3Se5 [30]. The crystal structure of CuInSe2 was reported to be either tetragonal with space group I 4 ¯ 2 m [31,32] or cubic, F 4 ¯ 3 m [23,33], where the latter structure can be considered as two interpenetrating face-centered cubic sub-lattices. In the case of Cu3MSe4, where M is V, Ta, Nb or Sb, both cubic [34,35] and tetragonal [36,37] structure types were reported.
To the best of our knowledge, the synthesis and crystal structure of Cu3InSe4 has not been previously reported. Wei et al. [38] predicted Cu3InSe4 to be metallic, with “holes in the valence band”, however structural information and details of the electronic structure were not reported. Therefore, we have undertaken to synthesize and investigate the crystal structure and electronic properties of Cu3InSe4. We employed high-resolution single crystal synchrotron measurements to determine the structure of this previously unascertained ternary compound. The structural features and bonding were investigated in detail, including analyses of calculated electron localization, and the electronic properties were obtained using density functional theory. Our results are compared to that of other ternary chalcogenides.

2. Materials and Methods

Single crystals of Cu3InSe4 were initially obtained in an attempt to prepare CuFe2InSe4, resulting in FeSe as well as the shiny metallic ternary chalcogenide crystals identified as Cu3InSe4. This procedure was repeated with a stoichiometric ratio of the starting high-purity elements, Cu powder (99.9 % purity, Alfa Aesar, Thermo Fisher Scientific, Ward Hill, MA, USA), In shot (99.99 % purity, Alfa Aesar, Thermo Fisher Scientific, Ward Hill, MA, USA) and Se ingot (99.999 % purity, Alfa Aesar, Thermo Fisher Scientific, Ward Hill, MA, USA) [39]. The elements were placed in a silica ampoule and vacuum-sealed inside a quartz tube, then melted via a water-cooled 3-coil induction (Superior Induction, SI-7KWHF) furnace resulting in an agglomeration of gray Cu3InSe4 crystals.
Single-crystal synchrotron measurements were carried out at NSF’s ChemMatCARS, Sector 15 of the Advanced Photon Source, Argonne National Laboratory. Data were collected using a Huber 3-circle diffractometer (Huber diffraction, Lancaster, CA, USA) equipped with a Pilatus3X 2M detector (Dectris USA Inc., Philadelphia, PA, USA) using an Oxford Cryojet (American Laboratory Trading, East Lyme, CT, USA). The ω-angle was set at −180°, κ-angle was set at 0° and 30°, with ϕ-angle scanned over the range of 360° using the shutterless mode of the detector. Data integration was performed with the Bruker APEX 3 suite software. The reduction of the data was obtained with the SAINT v.8.38A and SADABS v.2016 programs (Bruker AXS Inc., Madison, WI, USA) that are included in the APEX suite. The structure was solved directly and refined by the full-matrix least-squares method.
Ab initio calculations based on density functional theory, plane-waves basis set, and pseudopotentials were carried out using the Quantum Espresso software package [40]. Projector-augmented waves (PAW) pseudopotentials [41], the generalized gradient approximation of Perdew-Burke-Ernzehof [42,43] plus Hubbard correction [44] (GGA-PBE + U) exchange-correlation functional were applied. A U parameter of 4 eV for the cations was used based on previous studies on Cu-based chalcogenide materials [45,46] that provide for good agreement between calculated and experimental structure values. For the pseudopotentials, Cu 3d104s1, In 4d105s25p1 and Se 4s24p4 valence configurations were considered. For self-consistent field (SCF) calculations, a k-point mesh of 6 × 6 × 6 was applied to sample the Brillouin zone. The kinetic energy cutoff for wavefunctions and charge density was set to 70 Ry and 300 Ry, respectively, and an energy convergence threshold of 10−7 eV was utilized. The electron localization function (ELF) distribution was analyzed and visualized using VESTA v.3.5.8 software [47].
CCDC 2172956 contains the supplementary crystallographic data. These data can be obtained free of charge via, accessed on 10 September 2022, (or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44 1223 336033; E-mail: [email protected]).

3. Results

The crystallographic data and structural refinement results are shown in Table 1. Cu3InSe4 crystallizes in the cubic space group P 4 ¯ 3 m (No. 215) with cell parameter a = 5.7504(2) Å, Z = 1 and density = 5.426 g/cm3. The atomic coordinates and equivalent isotropic displacement parameters, Ueq, are shown in Table 2. The anisotropic displacement parameters are presented in Table 3. As shown in Figure 1, the structure consists of CuSe4 (Cu-Se distance of 2.4622(4) Å) and InSe4 (In-Se distance of 2.5775(13) Å) tetrahedra connected by corner-sharing Se atoms. Selenium is surrounded by three Cu atoms and by an In atom, as shown in Figure 1a. The CuSe4 and InSe4 tetrahedra are illustrated in Figure 1b. The tetrahedron about the In site is a regular tetrahedron with Se-In-Se angles of 109.471(11)°, while that of Cu is somewhat distorted with Se-Cu-Se angles ranging from 105.63(6)° to 111.42(3)°. The Cu-Se distance (2.4622(4) Å) is similar to that reported for sulvanite and adamantine compounds [36,48,49], while the In-Se distance (2.5775(13) Å) is similar to that for CuInSe2 (2.591 Å) [49] and LiInSe2 (2.57 Å) [50]. It is important to note that the structure of Cu3InSe4 is related to that of sulvanites Cu3XQ4 (X = V, Nb, Ta; Q = S, Se, Te) [19,51,52]; however, the Cu atoms occupy different Wyckoff sites in these two different ternary chalcogenides thus resulting in corner sharing and edge sharing tetrahedra for Cu3InSe4 and Cu3XQ4, respectively.
The electron density distribution was investigated by calculating the ELF, revealing the ionic nature of the bonding in Cu3InSe4, as shown in Figure 2. Figure 2 shows the calculated ELF along the (110) plane. ELF values of 0.0, 0.5 and 1.0 represent fully delocalized, electron-gas-like pair probability and perfect localization, respectively [53]. The atomic core regions of the cations have localization domains with ELF values close to unity and low ELF values away from these regions. This suggests electrons transfer from both Cu and In atoms to adjacent Se atoms, indicating ionic bonding. In comparing the Cu3XSe4 compounds [54] with Cu3InSe4, the X-Se bonds in the former show a higher degree of covalency as compared with the primarily ionic character for In-Se in Cu3InSe4.
The oxidation states of Cu, In and Se are 1+, 3+ and 2−, respectively, resulting in 30 electrons per formula unit, or two fewer than required for the tetrahedral bonds in Cu3InSe4 thus resulting in p-type metallic behavior. Our detailed structural analyses allow for an investigation of the electronic structure of Cu3InSe4 by calculating the energy band structure and density of states (DOS). As shown in Figure 3, the Fermi level, Ef, crosses the valence band in multiple regions, thus, Cu3InSe4 is a p-type metal [46,55], confirming the simple charge imbalance argument. This is also in agreement with the early conjecture [38], and corroborated by our room temperature conductivity measurements indicating metallic conduction [56]. The orbital-projected DOS indicates that the valence band maximum has contributions mainly from the Cu 3d and Se 4p orbitals, while the conduction band maximum is mainly composed of In 5s and Se 4p and minor contributions from Cu 3d4s4p, In 5p and Se 4s orbitals. The orbital interactions between the CuSe4 tetrahedra therefore play a dominant role in the metallic conductivity of Cu3InSe4. It is instructive to compare the electronic structure of Cu3InSe4 to that of Cu3XSe4 in light of the fact that the crystal structure of Cu3InSe4 is not isostructural to that of the later compositions. Specifically, for the case of the Cu3XSe4 compositions [19,57,58], an energy gap opens between the valence and conduction bands in these materials. These compositions are therefore semiconductors and are being investigated for thermoelectric [19,20] and photovoltaic [59,60] applications, whereas in the case of Cu3InSe4 Ef falls relatively deep in the valence band and will therefore not be of interest for such applications.

4. Conclusions

Single crystals of a new ternary chalcogenide Cu3InSe4 were obtained by induction melting, and the structural and electronic properties are reported for the first time. Cu3InSe4 forms in a cubic crystal structure that consists of CuSe4 and InSe4 tetrahedra connected by corner sharing Se atoms. Electron localization function analyses indicated partially ionic bonding between the cations and Se atoms, with highly delocalized electrons in the regions between cation and selenium. Electronic structure calculations reveal this ternary chalcogenide to be metallic. Given that ternary chalcogenide compounds are of interest for potential thermoelectric and optoelectronic applications, our findings will be useful for investigations on new materials for applications of interest. The results and analyses in this work add to our understanding of the structural and electronic properties of ternary chalcogenides.

Author Contributions

Conceptualization, G.S.N.; methodology, O.P.O.; data curation, O.P.O., W.W.-N., T.C. and Y.-S.C.; formal analysis, O.P.O., W.W.-N., T.C. and Y.-S.C.; writing—original draft preparation, O.P.O.; writing—review and editing, G.S.N.; visualization, O.P.O.; supervision, G.S.N. All authors have read and agreed to the published version of the manuscript.


This work was supported, in part, by the National Science Foundation, Grant No. DMR-1748188. W.W.-N., T.C. and Y.-S.C. gratefully acknowledge NSF’s ChemMatCARS Sector 15 which is supported by the Divisions of Chemistry (CHE) and Materials Research (DMR), National Science Foundation, under grant number NSF/CHE- 1834750. Use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357.

Data Availability Statement

Not applicable.


The contribution of all authors is gratefully acknowledged.

Conflicts of Interest

The authors declare no conflict of interest.


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Figure 1. Schematic illustrating the crystal structure of Cu3InSe4 showing the (a) unit cell and (b) stacking of the CuSe4 (red) and InSe4 (gray) tetrahedra.
Figure 1. Schematic illustrating the crystal structure of Cu3InSe4 showing the (a) unit cell and (b) stacking of the CuSe4 (red) and InSe4 (gray) tetrahedra.
Crystals 12 01310 g001
Figure 2. ELF calculated along the (110) plane.
Figure 2. ELF calculated along the (110) plane.
Crystals 12 01310 g002
Figure 3. Calculated energy band structure and orbital-projected DOS.
Figure 3. Calculated energy band structure and orbital-projected DOS.
Crystals 12 01310 g003
Table 1. Crystal data and structure refinement results.
Table 1. Crystal data and structure refinement results.
Empirical formula Cu3InSe4
Formula weight 621.32
Temperature 100(2) K
Wavelength 0.49594 Å
Crystal system Cubic
Space group P 4 ¯ 3 m (No. 215)
Unit cell dimensiona = 5.7504(2)
Volume190.15(2) Å3
Density (calculated)5.426 mg/m3
Absorption coefficient11.36 mm−1
Crystal size30 × 20 × 10 µm3
Theta range for data collection2.283 to 26.223°
Reflections collected2237
Independent reflections251 [R(int) = 0.0945]
Goodness-of-fit on F21.190
Final R indices [I > 2σ(I)]R1 = 0.0375, wR2 = 0.0886
R indices (all data)R1 = 0.0403, wR2 = 0.0908
Table 2. Atomic coordinates and equivalent isotropic displacement parameters (Å2). Ueq is defined as one third of the trace of the orthogonalized Uij tensor.
Table 2. Atomic coordinates and equivalent isotropic displacement parameters (Å2). Ueq is defined as one third of the trace of the orthogonalized Uij tensor.
Table 3. Anisotropic displacement parameters (Å2). The anisotropic displacement factor exponent takes the form: −2π2[h2a*2U11 + … + 2hka*b*U12].
Table 3. Anisotropic displacement parameters (Å2). The anisotropic displacement factor exponent takes the form: −2π2[h2a*2U11 + … + 2hka*b*U12].
In0.010(1) 0.010(1)0.010(1) 00 0
Se0.011(1) 0.011(1)0.011(1) −0.002(1)−0.002(1) −0.002(1)
Cu0.007(1) 0.007(1)0.006(1) 00 0
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Ojo, O.P.; Wong-Ng, W.; Chang, T.; Chen, Y.-S.; Nolas, G.S. Structural and Electronic Properties of Cu3InSe4. Crystals 2022, 12, 1310.

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Ojo OP, Wong-Ng W, Chang T, Chen Y-S, Nolas GS. Structural and Electronic Properties of Cu3InSe4. Crystals. 2022; 12(9):1310.

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Ojo, Oluwagbemiga P., Winnie Wong-Ng, Tieyan Chang, Yu-Sheng Chen, and George S. Nolas. 2022. "Structural and Electronic Properties of Cu3InSe4" Crystals 12, no. 9: 1310.

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