V. Alberts et al., Material properties and growth mechanism of CuInSe2 prepared by H2Se treatment of metallic alloys, J MAT S-M E, 10(7), 1999, pp. 469-474
A fundamental understanding of the mechanism of growth of CuInSe2 is essent
ial for the production of device quality material. In this contribution, th
e growth kinetics of thin film CuInSe2 are investigated in the special case
of H2Se/Ar treated copper-indium metallic alloys. A systematic study was c
onducted in which the evolution of surface morphologies by scanning electro
n microscopy (SEM), formation of crystalline X-ray diffraction (XRD) and va
riation in film composition, energy dispersive spectrometry (EDS) were eval
uated during various stages of selenization. SEM and XRD studies revealed a
dramatic improvement in crystalline quality with increasing selenization t
emperature. SEM studies indicated a substantial increase in grain size (0.2
mu m --> 1 mu m) when the reaction temperature was increased from 150 degr
ees C to 450 degrees C. XRD studies revealed the presence of mostly binary
phases (i.e. Cu11In9, InSe, In6Se7 and CuSe) at selenization temperatures u
p to 250 degrees C. CuInSe2 was found to be the dominant phase at 350 degre
es C and the film was almost completely converted to single phase material
at 450 degrees C. The composition of the selenized films remained virtually
unchanged in the temperature range between 150 degrees C and 350 degrees C
. However, reaction of the metallic alloys to H2Se/Ar at temperatures aroun
d 450 degrees C resulted in a significant loss of indium from the films and
subsequently to an increase in the Cu/In atomic ratio. The variation in cr
ystalline quality of the films during various stages of selenization was al
so clearly reflected by low temperature photoluminescence (PL) studies. Vir
tually no PL response was detected from samples selenized at low temperatur
es below 350 degrees C, compared to rather strong emissions from samples se
lenized at higher temperatures around 450 degrees C. Furthermore, a signifi
cant difference in PL response was detected from samples selenized at 350 d
egrees C and 450 degrees C, respectively. Comparative studies indicated the
presence of a free-to-bound transition (at 0.992 eV) only in the case of s
amples selenized at 450 degrees C, which indicated that these specific poin
t defects (V-ln) are created at high selenization temperatures. This observ
ation is consistent with EDS results, indicating a substantial loss of In f
rom samples selenized in this high temperature range. PL spectra from sampl
es selenized at 350 degrees C were also characterized by a broad peak close
to the band gap value, which was attributed to the presence of point defec
ts associated with In-rich secondary phases. The improvement in crystalline
quality with increased selenization temperatures and reaction periods was
also clearly reflected by the reduction in the FWHM values of the PL peaks.
The information gained from this study played an important role in the pro
duction of high quality films in our laboratories.