Abstract
CuInS2 nanocrystals were synthesized by thermal decomposition of the molecular precursor [(Me3P)3Cu(SC2H4S)In(i)Pr2] in the presence of oleylamine in dioctyl phthalate. According to X-ray diffraction patterns, the as-synthesized CuInS2 nanocrystals crystallize in the wurtzite type structure. High-resolution transmission electron images and selected area electron diffraction patterns reveal a nanodomain structure. The individual domains are approximately 5-10 nm in size and characterized by short-range cation ordering, which assuming hypothetical long-range order, corresponds to an orthorhombic superstructure (space group Pmc21, a = 4.09 ± 0.01 Å, b = 7.16 ± 0.02 Å and c = 6.56 ± 0.03 Å). The domains are separated by twin and antiphase boundaries.
Highlights
The ternary compounds CuME2 (M = Ga, In; E = S, Se) are semiconductors with a direct band gap ranging from 1.0 (CuInSe2) to 2.5 eV (CuGaS2)[1] and high absorption coefficients (∼104 cm−1).[2]
41, 43 a Modification observed in bulk single crystals. b Modification observed in nanocrystalline materials. c Binsma et al assumed this hightemperature modification to be wurtzite type (WZ). d Space group Pmc21. e A range of cation-ordered wurtzite-like structures. f Modification observed at a pressure of 53 GPa. g Modification observed at a pressure of 7.6 GPa. h Modification observed at a pressure above 15.9 GPa
2.1 Synthesis The molecular precursor complex [(Me3P)3Cu(SC2H4S)IniPr2] (1), consisting of a tris(trimethylphosphino)-copper(I) unit coordinated to a sulfur atom of a iPr2In(S2C2H4) group with a chelating 1,2-ethanedithiolate ligand, as shown in Fig. 1, was mixed with oleylamine (OLA) in dioctyl phthalate (DOP)
Summary
One orthorhombic structure was identified as the hightemperature phase of bulk single crystal AgInS2 (ht-AgInS2, space group Pna21),[23] see Table 1. These structures retain the tetrahedral coordination existing in the chalcopyrite and cubic zinc-blende modifications. In this work the synthesis of nanocrystalline CuInS2 by thermal decomposition of a molecular single-source precursor is reported The aim of these attempts was to produce “inks”, which might be used to deposit ternary light-absorbing CuInS2 thin films by direct liquid coating methods.[45,46] A systematic analysis of selected area electron diffraction (SAED) patterns and high-resolution transmission electron microscopy (HRTEM). 41, 43 a Modification observed in bulk single crystals. b Modification observed in nanocrystalline materials. c Binsma et al assumed this hightemperature modification to be WZ. d Space group Pmc21. e A range of cation-ordered wurtzite-like structures. f Modification observed at a pressure of 53 GPa (space group Cmcm). g Modification observed at a pressure of 7.6 GPa. h Modification observed at a pressure above 15.9 GPa
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