The Effects of KCN Etching on Cu-Rich Epitaxial CuInSe₂ Thin Films

Abstract

A series of Cu-rich CuInSe₂ epitaxial thin films were grown by molecular beam epitaxy on GaAs(00l) substrates from elemental sources at a growth temperature of 450 °C. All samples were grown with an excess of Cu. Electron microprobe analysis (EPMA) indicated a Cu/In ratio of about 2.1–2.6 in the as-grown films. Additionally, the Se / (In+Cu) ratio was observed to be ~0.95 indicating that the films were slightly Se poor. These Cu-rich samples were etched in a KCN solution for periods ranging from 30 seconds to 3 minutes. EPMA measurements indicated that the bulk Cu/In ratio was reduced to ~0.92 in all films regardless of etching time. Atomic force microscopy (AFM) was used to characterize the topology of each sample before and after etching. These measurements indicated that the precipitates present on the as-grown films were removed and large nearly isotropic holes were etched into the sample to a depth of over 1000 Å even for etching times as short as 30 seconds. The samples were also evaluated both before and after etching using a Phillips MRD diffractometer with parallel beam optics and a 18,000 watt Cu rotating anode X-ray source in the chalcopyrite [001], [101], and [112] directions. A peak was observed at ~15 degrees in the [001] scan after etching consistant with the presence of the ordered vacancy compound, CuIn₃Se₅. Additionally the integrated intensity ratios of the chalcopyrite (202) reflection to the chalcopyrite (101) reflection ∞(f_Cu-f_In)² along the [101] direction indicated the presence of a near-surface region containing cation sublattice disorder that was subsequently removed by the etching process.