Experimental and theoretical study of stable and metastable phases in sputtered CuInS${_2}$

TL;DR

This study combines theoretical calculations and experimental synthesis to investigate stable and metastable phases in CuInS₂ thin films, revealing new polymorphs and emphasizing the importance of precise composition control.

Contribution

It provides a comprehensive analysis of CIS polymorphs, including the first observation of wurtzite CIS in sputtered films, and highlights the stabilization of metastable phases by off-stoichiometry.

Findings

Multiple CIS structures identified with overlapping XRD/Raman features

Wurtzite CIS observed for the first time in sputtered films

Metastable polymorphs stabilized by off-stoichiometry

Abstract

The chalcopyrite Cu(In,Ga)S${_2}$ has gained renewed interest in recent years due to the potential application in tandem solar cells. In this contribution, a combined theoretical and experimental approach is applied to investigate stable and metastable phases forming in CuInS${_2}$ (CIS) thin films. Ab initio calculations are performed to obtain formation energies, X-ray diffraction patterns, and Raman spectra of CIS polytypes and related compounds. Multiple CIS structures with zinc-blende and wurtzite-derived lattices are identified and their XRD/Raman patterns are shown to contain overlapping features, which could lead to misidentification. Thin films with compositions from Cu-rich to Cu-poor are synthesized with a two-step approach based on sputtering from binary targets followed by high-temperature sulfurization. It is discovered that several CIS polymorphs are formed when growing the material with this approach. In the Cu-poor material, wurtzite CIS is observed for the first time in sputtered thin films along with chalcopyrite CIS and CuAu-ordered CIS. Once the wurtzite CIS phase has formed, it is difficult to convert into the stable chalcopyrite polymorph. CuIn${_5}$S${_8}$ and NaInS${_2}$ accommodating In-excess are found alongside the CIS polymorphs. It is argued that the metastable polymorphs are stabilized by off-stoichiometry of the precursors, hence tight composition control is required.