Solid State Communications 151 (2011) 1459–1462
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Solid State Communications
journal homepage: www.elsevier.com/locate/ssc
Magnetic resonance study of arsenic bonding sites in ternary
chalcogenide glasses
E. Mammadov
a,*
, D. Bobela
b
, A. Reyes
c
, S. Mehdiyeva
a
, P.C. Taylor
b
a
Institute of Physics, National Academy of Sciences, Baku, AZ 1143, Azerbaijan
b
Physics Department, Colorado School of Mines, Golden, CO 80401, USA
c
National High Magnetic Field Laboratory, Tallahassee, FL 32310, USA
article info
Article history:
Received 21 February 2011
Received in revised form
12 May 2011
Accepted 28 June 2011
by R. Phillips
Available online 5 July 2011
Keywords:
A. Disordered systems
A. Semiconductors
E. Nuclear resonances
abstract
75
As NQR and high-field NMR experiments have been performed on Ge
x
As
y
Se
1-x-y
glasses. Evolution of As
bonding structure from arsenic sites with axially symmetric distribution of the electric field gradient (EFG)
to highly asymmetric As surroundings has been revealed. Arsenic atoms form pyramidal structural units in
Ge
2
As
2
Se
7
with no evidence of significant concentration of homopolar bonds. In Ge
2
As
2
Se
5
most of arsenic
atoms form structural units with two As–As bonds per atom and asymmetric EFG distribution. Arsenic
bondings become more complicated in Ge
0.33
As
0.12
Se
0.55
where all arsenic sites are highly distorted. The
combination of NQR and NMR data provide valuable information on arsenic bonding dynamics in these
glasses.
© 2011 Elsevier Ltd. All rights reserved.
1. Introduction
Ternary chalcogenide glasses are of interest for several im-
portant applications such as phase-change memory devices, ac-
tive and passive media for optoelectronics, waveguides etc [1,2].
Glasses of Ge–As–Se (GAS) system have extensively been studied
for rare-earth-doped optical fiber amplifiers [3,4]. However, due to
lack of understanding of their local structure improvement of de-
vice parameters and development of new materials is mainly based
on a trial-and-error approach. Application of scattering techniques
to reveal information on the local structural arrangement in these
materials is hindered due to absence of long-range atomic order.
The problem is further complicated in ternary systems as a com-
positional disorder is introduced in addition to the structural dis-
order. Nuclear magnetic resonance (NMR) and nuclear quadrupole
resonance (NQR) techniques provide direct information on asym-
metry of nearest-neighbor surrounding of an atom absent from
scattering techniques and have been proved as a powerful tool for
study of the local structure in disordered solids [5,6].
The local structure of chalcogenide glasses is often described
using the 8-N rule when coordination of atoms is determined by
number of covalent bonds formed to maintain a closed shell of
*
Corresponding author.
E-mail addresses: mammadov_eldar@hotmail.com,
emammadov@physics.ab.az (E. Mammadov).
eight electrons with N being the corresponding group number
of each atom [7]. On the other hand, bondings in these glasses
are formed with preference of heteropolar bonds with highest
bond energy being formed first [8]. Thus, in the GAS system
Ge–Se and As–Se bonds are the most probable. To satisfy all their
bonding requirements four-fold coordinated Ge and three-fold
coordinated As atoms form tetrahedral and pyramidal structural
units, respectively, cross-linking Se-chains [7].
We present results of combined NQR and high-field NMR
studies of arsenic local bonding structure in GAS glasses.
2. Experimental procedure
Glasses for NMR and NQR experiments have been synthesized
from high purity (6N ) constituent elements by rocking the melts at
900 °C overnight and quenching in ice water. Powdered samples
of different compositions as Ge
0.05
As
0.1
Se
0.85
, Ge
0.15
As
0.1
Se
0.75
,
Ge
0.18
As
0.18
Se
0.63
(Ge
2
As
2
Se
7
), Ge
0.22
As
0.22
Se
0.55
(Ge
2
As
2
Se
5
),
and Ge
0.33
As
0.12
Se
0.55
were prepared.
NQR and NMR measurements were performed at liquid nitro-
gen temperature. The spin-echo technique with 90°–180° pulse se-
quence was utilized for both experiments using 90° pulse widths
as 5 and 4 μs, respectively. Intensity of the NQR echo signal was
obtained by averaging over 2000 scans for each data point. A stan-
dard NMR probe with a coil made of copper wire has been utilized
to obtain spin-echo signal in NMR measurements. Since the echo
amplitude for the samples was very small a special pulse setting
0038-1098/$ – see front matter © 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ssc.2011.06.040