Thin Solid Films, 161 (1988) 139 147
PREPARATION AND CHARACTERIZATION 139
EFFECT OF DEPOSITION RATE ON STRUCTURE AND PROPERTIES
OF As2S 3 FILM
KOTO WHITE
Materials Laboratory, Wright-Patterson AFB, OH 45433 (U.S.A.)
BINOD KUMAR
University of Dayton Research Institute, Dayton, OH 45469 (U.S.A.)
AMARENDRA K. RAI
Universal Energy System, Dayton, OH 45432 (U.S.A.)
(Received November 25, 1986; revised November 9, 1987; accepted November 24, 1987)
Thin films of glassy As2S 3 were prepared by physical vapor deposition at
deposition rates ranging from 15/~ s 1to 300/~ s- ~. The refractive index of the films
was determined by a spectrophotometry and stylus technique. The films were
characterized by X-ray diffraction, energy dispersive X-ray analysis, differential
scanning calorimetry and transmission electron microscopy. The result was
interpreted in terms of variation in stoichiometry and structure.
1. INTRODUCTION
Arsenic trisulfide (As253) glass has been widely used in IR optical devices
because of its good transparency in the wavelength region from 0.7 ~tm to 11.0 lam,
and because of its excellent resistance against devitrification, moisture and corrosive
chemicals. The vapor-deposited films of As2S3-based compositions, which have
been used mainly as optical coatings, have found new applications in electronics,
electro-optics and optical information storage in recent yearst-4.
In general, the physical and structural properties of vapor-deposited films are
greatly different from those of the corresponding bulks and are affected by
deposition conditions such as the deposition rate, residual gas pressure, type and
temperature of substrates, and the angle and velocity of incident vapor 5-1 o. Apling,
Leadbetter and coworkerst 1-~3 examined the structural dissimilarity between bulk
and thin film As2S3 and As2Se3, using a hot-stage X-ray diffraction technique. The
first diffraction peaks for both compounds were found to be sharper and more
intense in as-deposited films reflecting an enhanced longer range order, and their
intensities decreased and approached that of the bulk on annealing. This was
explained by the possible existence of As--As bonds and a sheet-like open structure
in as-deposited films. This speculation was supported by an arsenic-rich stoichiome-
try in their films and a considerable fragmentation of As2S 3 into S 2 and As4S4
during the evaporation process, as detected by mass spectroscopy 12,14 Nemanich
and coworkersl 5,16, from extended X-ray absorption edge fine structure and Raman
spectroscopic results, and Tohge et al.17, through IR spectroscopy, suggested that all
the As--As bonds may be incorporated as S2As--AsS 2 units, as in As4S 4 molecules,
0040-6090/88/$3.50 © Elsevier Sequoia/Printed in The Netherlands