Solid State Communications, Vol. 9, pp. 159—161, 1971. Pergamon Press.

Printed in Great Britain

MOTIONAL EFFECTS IN THE TRAPPED-HOLE CENTER IN SMOKY QUARTZ

R. Schnadt* and A. R~uber

Institut für Angewandte Festkörperphysik, D78 Freiburg, Germany

(Received 11 November 1970 by E. Moliwo)

The thermal broadening of the ESR spectrum of the trapped-hole

center in smoky quartz was investigated between 40 and 200°K.The
activation energy for the hole hopping process responsible was deter-
mined, W = (70 ±1O)meV. This value is in order of magnitude agree-
ment with those inferred from dielectric and anelastic loss measure-
ments.

AFTER EXPOSURE to ionizing radiation, quartz g,. g. 2~lO2

single crystals generally exhibit a characteristic 2.109

electron spin resonance (ESR) spectrum. This •

arises
four oxygen
from aligands
defect around
electron
a substitutional
trapped at one alu-
of the ~ao~ QUARTZ POWDER
CRYSTALLINE
minium ion in the a —SiO2 lattice.1’2 The ESR
spectrum rapidly broadens beyond detection above b
77°K.We want to show that this line broadening
is likely to arise from a thermally activated hop-
ping of the defect electron among the different
oxygen ligands around the aluminum impurity. In
such a process, the hole can lose its phase mem- C

ory and the ESR signals will be broadened.

Since the defect charge, associated with the d 5 “~
hopping hole represents an electric dipole, di-
electric losses are expected to occur in X-irradiated 912 0Hz
quartz. The same mechanism should also cause

anelastic losses in the piezoelectric quartz crys-

tal. H

In electron spin resonance, the influence of

~I\~7ICLASS
the hopping process on the line-width is pronounced,
as shown in Fig. 1. Here the ESR spectra of crys-
talline quartz powder and of silica glass, both FIG. 1. ESR spectra of the trapped-hole center in
X-irradiated
silica glass crystalline quartz powder and inprin-
X-irradiated, are compared, both taken at 77 and at 77 and 300°K.The indicated
cipal values of the g-tensor were taken from refer-
* Present address: IBM. Laboratorien, D703 ence 2 and are those for the ground state of the
Böblingen, Germany center.

159
160 TRAPPED-HOLE CENTER IN SMOKY QUARTZ Vol. 9, No. 2

300°K. Fig. lb reproduces the typical powder I (°K)

spectrum at 77°K. The principal values of the 20 1~0 1~0 ~0 6p 1.0
27 100
g-tensor are indicated and the characteristic Al
hyperfine splitting of about 30 G can be ident-
ified.2 Fig. la shows that at 300°K the lines of
the aluminum center in X-irradiated crystalline
quartz.2 A sample of silica glass was prepared by
melting an aluminum-doped synthetic quartz sample 10
which was subsequently X-irradiated. Fig. lc and
ld show that in this silica glass sample an ESR
spectrum, exhibiting a certain similarity with the
powder spectrum at 77°K(Fig. lb), appears at
both temperatures. We want to assign this spectrum I
to the aluminum center in silica glass. In the .2 ____________

silica glass specLra there is no paramagnetic

absorption in the region of g
1 = 2.061, see Fig.
ic and id. This can be explained by the stätisti-
cal distortion of the oxygen tetrahedra in the .1
silica glass. From the 2discussion of the
it is apparent thatg-shifts
the 10 15 19~~
20(°K)~ 25
of theg-shift,
large aluminumg,,center
is caused by the small difference
of two large crystal field energies. Therefore g
1
is very sensitive to lattice distortions. FIG. 2. Temperature dependence of the ESR line-
width of the trapped-hole center in X-irradiated
The differehce in the temperature dependence crystalline quartz, measured at 9GHz. The dotted
line is an xetrapolation in order to determine the
of the ESR line-width of the aluminum center in
activation energy.
crystalline quartz and silica glass originate from
their different relaxation behavior. In the perfect
lattice there are four possible oxygen sites around pattern can no longer be resolved and therefore
a substitutional aluminum2 and
ion.thermally
These positions
activated L\.H is obtained
splitting of 30Gbyfrom
subtracting
the spreadthe
of total
the entire
hyperfine
are pairwise
hopping equivalent
among them will be likely. In silica glass, spectrum. Figure 2 shows that these data are
however, the local statistical distortions make well fitted by the relation:
all the ligand sites non-equivalent and only one
of the oxygen ions is able to capture the hole H = const . exp ( — + z\H
0,
whereas the others are energetically unfavorable. kT)
Therefore, in crystalline quartz the thermally
activated hopping of the spin among the equivalent where W is the activation energy for the hopping
oxygen sites forms an effective relaxation process, and AH0 is the low-temperature inhomogeneous
which is not present in silica glass. line-width, caused by dipole—dipole interaction
and by statistical stress and electrical fields in
To get more insight into the broadening mech- the quartz crystal. The data shown in Fig. 2 yield
anism, we have measured the ESR line-width AR an activation energy W = (70 ±10) meV and
for X-irradiated quartz crystals from 40 to 200°K, AH0 = 0.5G.
with the magnetic field oriented parallel to the
c-axis of the crystal. At the latter temperature the As m~ntioned above, the hopping of the hole
lines were broadened beyond detection. At low among the different oxygen sites around a given
temperatures the hyperfine pattern is well resolved, aluminum ion should cause dielectric losses.
therefore the line broadening due to hopping is Therefore comparison of the ESR data is indicated
taken as the width of an individual hyperfine with the results of dielectric relaxation measure-
line. With increasing temperature the hyperfine ments in X-irradiated quartz crystals. Very recently,
Vol. 9, No. 2 TRAPPED-HOLE CENTER IN SMOKY QUARTZ 161

3 obtained in the temperature
De Vos and Volger
region of 100.—170°Ka similar activation energy
W = (85 ±5) meV for the relaxation time of the
dielectric loss. Since this type of dielectric loss
is not present in silica glass,4 there is a close
correspondence between the two experiments.
Apparently the temperature dependence of the
ESR line-width and the dielectric loss are caused
by the same mechanism, i.e. the hopping of the
hole.
anism for ultrasonic relaxation: King5 has measured
the Q-value of X-irradiated quartz crystal resonators
and obtained an activation energy W = 100meV
from the analysis of the temperature dependence
of the ultrasonic relaxation time.
In conclusion, we note that the different mani-
festations of the hopping motion give strong sup-
port for the model on which the present investi-
gation is based.

Acknowledgements — We wish to thank Mr. K.

Additional evidence for the hopping of the
hole comes from an ultrasonic measurement. The
reorientation of the elastic moment, which is
associated with the hopping motion, forms a mech-
Sambeth for .designing the variable temperature
equipment. We would like to acknowledge Dr.. B.
Dischler, Dr. 0. Schirmer and Dr. J. Schneider
for many helpful discussions.

REFERENCES
1. GRIFFITHS J.H.E., OWEN J. and WARD I.M., Defects in crystalline solids; report of Bristol confer-
ence p.81. Physical Society, London (1954).
2. SCHNADT R. and SCHNEIDER J., Phys. kondens. liaterie 11, 19 (1970).
3. de VOS W.J. and VOLGER J., Physica 47, 13 (1970).
4. VOLGER J. and STEVELS J.M., Philips Res. Rep. 11, 79 (1956).
5. KING J.C., Bell System Techn. J. 38, 573 (1959).

Es wurde zwischen 40 und 200°Kdie thermische Verbreiterung des

ESR-Spektrums des Zentrums untersucht, das sich durch Einfang
eines Loches in Rauchquarz bildet. Es wurde die Aktivierungsenergie
W = (70 ±10) meV bestimmt für den Platzwechsel des Loches, der
die Verbreiterung verursacht. Dieser Wert stimmt gröBenordnungsmäBig
mit denen überein, die sich aus der Messung dielektrischer und ane-
lastischer Verluste ergeben.