ELSEVIER

Journal of Non-Crystalline

Solids 191(1995)

339-345

EXAFS of germanium in glasses of the GeO,-TeO,

system

Akiyoshi Osaka a7*, Qiu Jianrong b71,Yoshinari Miura b, Takeshi Yao

a Department of Bioengineering Science, Faculty of Engineering, Okayama University, 3-l-l Tsushima Naka, Okayama-shi 700, Japan
b Department of Environmental Materials, Faculty of Environmental Science and Technology, Okayama University, 2-1 -I Tsushima Naka,
Okayama-shi 700, Japan
Department of Materials Chemistry, Faculty of Engineering, Kyoto Universily, Yoshida, Sakyo-ku, Kyoto 606-01, Japan
Received 4 March 1993; revised manuscript

received 15 March 1995

Abstract
Extended
X-ray absorption
fine structure
(EXAFS) near the Ge K-edge in glasses of the GeO,-TeOz system was
measured. The results were analyzed with both the GeO,-GeO, two-shell model and the GeO, single-shell model. Since the
two-shell model gave a better fit of the measured EXAFS it was concluded that the germanate anomaly should be interpreted
by the convention, namely, the formation of GeO, units. The fraction of the GeO, units decreased from 0.46 to 0.266 as the
GeO, content increased from 12 to 68 mol%.

1. Introduction
Maxima or minima appeared in properties versus
composition curves for glasses in several germanate
systems such as R,O-GeO, (R = L, Na) [1,2] and
GeO,-P,O, [3]. They are known as the germanate
anomaly and have been explained by an increase in
coordination number of Ge atoms from four to six:
GeO, + GeO,, although Henderson and Fleet [4]
recently attributed the anomaly to the formation of a
Ge,O, group. Most of those studies were concerned
with glasses containing a network-modifying oxide,
and thus Henderson and Fleet [4] were able to propose such a ring group that involved non-bridging
bonds.

Corresponding author. Tel: + 81-862 52 1111. Telefax: + 81862 52 7889. E-mail: osaka@cc.okayama-u.ac.jp.
Present address: Yamamura Glass Co., Nishinomiya, Hyogo
663 Japan.
0022-3093/95/$09.50
0 1995 Elsevier Science B.V. All rights reserved
SSDI 0022-3093(95)00317-7

What happens, then, for the glasses consisting of

two network-forming oxides in which a non-bridging
bond is unlikely to be formed? Shimizugawa et al.
[3a] reported elongated Ge-0 distances for the
glasses in the GeO,-P,O,
system and attributed
them to the formation of GeO, units. Huang et al. [51
proposed that Ge atoms remain four-coordinated in
the GeO,-SiO, system. Ahmad et al. [6] studied
electron hopping, band gaps and infrared spectra of
glasses of the GeO,-TeO, system but gave no insight into the structural aspect. Dimitriev et al. [7]
derived radial distribution functions (RDF) for the
glasses from their X-ray diffraction. They interpreted
the monotonic shift of the first peak corresponding to
the Ge-0 and Te-0 bonds as showing that a germanate network was transformed into a tellurite one
as the TeO, content increased. Although the coordination of Ge atoms might depend on the second
oxide, it seems unchanged for the glasses in those
two systems, SiO,-GeO, and TeO,-GeO,. Despite

340

A. Osaka et al. /Journal

of Non-Crystalline

those previous studies, the germanate anomaly is not

yet fully understand in those glasses. Moreover, Te
atoms can change coordination in glass, hence the
glasses in the GeO,-TeO,
system might have a
more complicated constitution than supposed. It is
therefore interesting to examine the glass constitution around Ge atoms in the GeO,-TeO, system.
In the present study we have measured the extended X-ray absorption fine structure (EXAFS) of
Ge in glasses of the GeO,-TeO, system. EXAFS
gives direct information on Ge-0 bond length. We
analyzed the EXAFS with a single-shell model taking only GeO, units into account. A two-shell analysis was also conducted which assumed the presence
of both GeO, and GeO, units as well as the simple
crystal-chemical principle that a longer bond length
was associated with the GeO, units. The fraction,
N,, of six-coordinated Ge atoms was derived from
the latter analysis. The possibility of the three Ge-0
membered-rings (Ge,O, groups) in the network was
examined, and whether it was preferential to the
conventional interpretation of the germanate anomaly
is discussed.

2. Experimental
2.1. Samples
Homogeneous glasses of compositions xGe0, (100 - x)TeO, (x in mol%) were prepared in the
range 10 < x Q 60 (batch) by a conventional meltquench technique. Batches from four-9 grade GeO,
and reagent grade TeO, were placed in Pt crucibles
and melted in an electric furnace for 30 min in air.
a-TeO, was precipitated at quenching the melts with
x < 10, and the melts with x > 65 were separated
into two phases: one was transparent vitreous phase
deep yellow in color and the other was a grayish
phase including quartz-type GeO, crystals. Homogeneous glasses were all chemically analyzed by inductively coupled plasma (ICP) spectroscopy within uncertainties of f 0.1 in x.
As-received quartz type GeO, (h-GeO,) of four-9
grade served as one of the two standard materials for
the phasf shift correction. Fe lattice constants, a =
4.9892 A and c = 5.6508 A, were obtained through
the standard procedure provided in a X-ray diffrac-

Solids 191 (1995) 339-345

tometer (Rigaku RINT System). They were similar

to those giveonin JCPDS 36-1463 (a = 4.9850 A and
c = 5.6480 A). The atomic positions, after Smith and
Isaacs [8], gave the average Ge-0 distance 1.7391 A
(= (1.7371 + 1.7412)/2) which agreed with that in
vitreous GeO, [2,9]. The rutile-type GeO, (t-GeO,)
as the other standard was prepared by calcining a
mixture of GeO, + O.OlLi,CO, (mol) at 1430C for
24 h. The lattice constants obtained were a = 4.3974
A and c = 2.8627 A, similar to a = 4.3963 A and
c = 2.8626 A of JCPDS 35-729. Thus the average
Ge-0 distance was 1.8824 A ( = (4 X 1.8724 + 2 X
1.9024)/6) due to the atomic positions after Baur
and Khan [lo]. Those two average Ge-0 distances
are similar to the Ge-0 distances reported for the
GeO, and GeO, groups in the glasses of the systems
Li,O-GeO,
[2], Na,O-GeO, [ll] or GeO,-P,O,
[31.
2.2. Ge K-edge EXAFS

Details of the measurement, formulation and analysis were already reported in the previous papers
[12,13], so only an outline of the analysis procedure
is presented here. The normalized modulation, x (k)
(EXAFS), in an X-ray absorption spectrum is expressed as the sum of the modulation of the jth shell,
xj(k), in the neighbor of the absorber ion:
Xck) = CXjCk)9

(1)

xj(k)=~lf,Iexp(-2~2k2)
I
Xexp( -2Rj/A)

sin(2kRj + Sj).

(2)

Here, k is the momentum of the photoelectron, nj is

the number of ions in the jth shell, Rj is the distance
from the absorber ion to the jth shell, fi is the
backscattering amplitude, aj2 is the variance in R,,
and 4 is the phase shift depending on the combination of the absorber ion and scattering ion. These
equations were applied to both single- and two-shell
models. X-ray absorption spectra near the Ge K-edge
were measured for pulverized samples at the High
Intensity X-ray Laboratory of Kyoto University. An
X-ray spectrometer (Rigaku Model RU-1000)
equipped with a LaB, filament [14] and a rotating
MO anode was operated at 50 kV and 600 mA. Fig. 1

A. Osaka et al. /Journal of Non-Crystalline Solids 191 (1995) 339-345

341

11.0

ll.2

11.4

IA

11.6

Energy WV)
Fig. 1. X-ray absorption spectra near Ge K-edge for the glasses in
the GeO, -TeO, system.

shows the X-ray absorption spectra of the glasses.

An EXAFS x(k) function was extracted from the
spectrum for each sample. Fig. 2 shows the Fourier
transform, I c& I, of x(k) for the glasses: (a)
11.9Ge0, - 8O.lTeO,, (b) 22.5Ge0,
77.5TeO,, (c)
64.8TeO,, (d) 43.3Ge0,
56.7Te0,
35.2Ge0,
32.2Te0,. The main peaks
and (e) 67.8Ge0,
around 1.5 A correspond to oxygen atoms bonded t:
the Ge atoms. Smaller peaks in t,he range < 1.5 A
and some of the peaks at > 1.5 A are spurious due
to the truncation effect. The peak position shifted
from the true Ge-0 distance to the shorter one
because of the phase shift [15]. The EXAFS function
or the inverse Fourier transform, x,,(k), of the main
peak was so derived using the reference materials
that could give a least-squares fit of the measured
EXAFS function. The ab initio calculated values of
backscattering amplitude [16] were taken for fj in
Eq. (2).
Contributions from the oxygen atoms in the GeO,
and GeO, units, if present, overlap to give the main
peak since the difference in Ge-0 bond length between those two units is not large enough to give
separate peaks. Then the EXAFS function, x,,(k), of
the main peak can be represented as the sum of the
??

??

??

(cl
I

??

Fig. 2. Fourier transform of the EXAFS function for the glasses of

composition (a) 11.9Ge0, * 8O.lTeO,, (b) 22SGe0, - 77STeO,,
(c) 35.2Ge0, - 64.8TeO,, (d) 43.3Ge0, * 56.7Te0, and (e)
67.8Ge0, * 32.2Te0,.

ti

Ii

(d)
Y

b"

(e)
1

342

A. Osaka et al. /Journal

of Non-Crystalline

Solids I91 (1995) 339-345

contributions of the oxygen atoms in the GeO, and

GeO, units, x4(k) and x6(k):
XCIW =(1+6)x4(k)

+N,&W,

(3)

where N6 denotes the assumed fraction of six-coordinated Ge atoms in the total number of Ge:
N6 = [GeO&([GeO,]

+ [GeO,]).

(4)

The parameters involved in Eqs. (2) and (31 were

calculated to give a least-squares fit between the
experimental and calculated values of x&k). In the
fitting procedure, we took the Ge-0 distance, R, as
the variables for the single-shell analysis and N6 for
the two-shell analysis. In the latter case, the Ge-0
distances in the GeO, and GeOg units were taken as
constant, 1.739 A and 1.884 A, respectively. It is
worth noting the standard materials for the phase
shift correction in the two-shell model. The Ge-0
bond length may depend not only on the second
oxide but also on the state of the materials: glass or
crystalline. However small the difference oin bond
length between glass and crystal ( < 0.004 A [2,11]),
the electron density distribution around the bond is
varied, hence the EXAFS is modified. Thus it is
desirable in analyzing EXAFS of glasses at least to
use the Ge-0 bond lengths in the crystals present in
the relevant system so that the phase shift correction
should be optimized. It was therefore fortunate that
Shimizugawa et al. [3a] could employ the Ge-0
distances in 5Ge0, - 3P,O, crystal for the EXAFS
curve fitting analysis for the glasses in the GeO,P,O, system. Unfortunately, no crystalline phases
have been confirmed in the GeO,-TeO, diagram
except for the terminal phases 1171. Thus, for the

1.72 I
0

20

40

60

80

100

GeOa (mol%)

Fig. 4. The Ge-0

analysis.

0,

bond length (A) derived from the single-shell

pure GeO,

glass [2,91.

sake of phase shift correction, we have taken the

Ge-0 distances for the two polymorphs of GeO,.

3. Results
Fig. 3 shows the inverse Fourier transform or
X(/C) k3 for the glass 43.3Ge0, * 56.7Te0,. The
solid line represents the measurement while the broken line represents the fitting by the single-shell
??

(4

6?

4-

2-

"ro
A-2

$4

-6

-6

1011

Wave Number /A-t

(W s 69

2-

f-Y o-i
--2
$4

-6

-6j-1

-et,
0

12

,4

I,

I1

lOll

Wave number/k1

Fig. 3. Results of the parameter fitting of EXAFS using the

single-shell model for 43.3Ge0, - 56.7Te0,.
The solid and broken lines represent the experiment and calculation, respectively.
The fitting was inferior to that in Fig. S(b).

11
1

I,

91011

Wave Number

/A-

Fig. 5. The results of the parameter fitting of EXAFS using the

two-shell model: (a) 22SGe0,
- 77.5Te0, and (b) 43.3Ge0, *
56.7Te0,.
The solid and broken lines represent the experiment
and calculation,
respectively.
Better fitting for 43.3Ge0, 56.7Te0, was achieved than in Fig. 3.

A. Osaka et al. /Joumal of Non-Crystalline Solids 191 (1995) 339-345

model. The fitting seems to reproduce the measurement inadequately and to be less reliable. Fig. 4
presents the Ge-0 bond length after the single-shell
analysis as a function of the GeO, content, showing
over the entire compositio! range (up to 100% GeO,
content) aochange of 0.6 A that is comparable with
that (0.4 A> for sodium germanate glasses reported
by Ueno et al. [ll]. The results of a fitting calculation with the two-shell analysis are shown in Fig. 5
for the glasses of compositions (a> 22SGe0, 77STe0, and (b) 43.3Ge0, * 56.7Te0,. The calculated inverse Fourier transform represented by the
broken lines reproduce the measured ones represented by the solid line extremely well, and the
fitting is much better than that for the single-shell
model. Table 1 shows the analyzed composition and
the parameters from both analyses: the Ge-0 bond
length from the single-shell model, N., the estimated
standard deviation, and the reliability factor.

4. Discussion
Murthy and Ip [l] found the maximum density at
certain compositions for alkali germanate glasses
whereas Table 1 indicates that the density of the
present glasses decreases monotonically with increase in the GeO, content. Thus we may consider
that the network of the germanium-tellurium oxide
glasses is a simple mixture of TeO, and GeO, units
which constitute the terminal oxides. However, minima or maxima would not necessarily appear in
property versus composition curves even though the

343

oxygen coordination changes for the network-forming cations. In fact, Takahashi et al. [18] suggested
the presence of six-coordinated Si atoms for the
glass in the SiO,-P,O, system though no anomaly
was detected in the property-composition curves.
Another example was that the density of alkali borate glasses increased monotonically with composition 1191 where the oxygen coordination of boron
increased from threefold to fourfold as the alkali
content increased. It is thus possible that the present
glasses should experience a coordination change in
Ge atoms.
The better fit in Fig. 5 than in Fig. 3 and the
smaller value of reliability factor in Table 1 favor the
two-shell model and hence indicate the presence of
GeO, units. The advantages of the two-shell model
over the single-shell model are discussed below. Fig.
4 indicates that the Ge-0 bond length for the GeO,
single-shell model increased with addition of TeO,.
This result might be explained by a similar hypothesis proposed for alkali germanate glasses by Henderson and Fleet [4]: elongation in the Ge-0 bonds due
to addition of an alkali oxide results from the formation of three-membered rings Ge,O, (three tetrahedral. This interpretation is possible since a smaller
Ge-0-Ge
bond angle in GeO, glass (about 130)
may lead to a structure containing a relatively high
number of three-membered rings [9]. That is, the
rings are originally present in the pure GeO, glass if
Henderson and Fleet [4] could detect them with
Raman spectroscopy. Then the addition of an alkali
oxide increases the amount of GeO, units or otherwise forms non-bridging bonds.

Table 1
The Ge-0

bond length in GeO, units due to the single-shell analysis and the fraction, N6, of GeO, units due to the GeO,-GeO, two-shell
analysis for the glasses in the binary GeO,-TeO,
system; the bond length and N6 are parameters of the curve-fitting in the single-shell and
two-shell analyses, respectively (see text)
Density

GeO,
content
(mol%)

(g/cm31

11.9
22.5
35.2
43.3
67.8

5.83
5.31
5.16
4.99
4.64

GeO, single-shell

Ge-0 bond

GeO,-GeOs

model

two-shell model

Rwp

Ns

ESD b

Rwp a

0.447
0.288
0.276
0.204
0.218

0.46
0.41
0.30
0.27
0.26

3.6
2.3
2.2
2.6
2.1

0.261
0.101
0.099
0.114
0.101

length (A)

a Reliability factor.
b Estimated standard

deviation

1.797
1.801
1.779
1.780
1.776

for N6.

x
x
x
X
x

1O-3
1O-3
10-3

lo-
10-3

344

A. Osaka ei al. /Journal

of Non-Crystalline Solids 191 (1995) 339-345

The Ge,O, rings involving no non-bridging bonds

coexist with the GeO, units in crystals such as
LiNaGe,O, [20], K,Ge,O, [21] and Rb,Ge,O, [22]
each of which had l/4 in N6. The Ge-0 bond
lengths for the GeO, units and GeO, units in those
crystals are just as long as those for h-GeO, [8] and
t-GeO, [lo], respectively. In consequence, the formation of the three-membered rings is intrinsically
consistent with the formation of GeO, units and
never rules it out for interpreting the germanate
anomaly.
The formation of non-bridging bonds is correlated
to another issue of discussion that Henderson and
Fleet [4] claimed: after the GeO, fraction reaches a
maximum the number fraction of longer bonds should
decrease and the Ge-0 bond length derived from the
RDF hence be shortened. In fact Ueno et al. 1111
reported that the bond length remained constant after
showing a maximum at 20 mol% Na,O in the
sodium germanate glasses. This superficially supports the ring formation model [4]. However, the
constant Ge-0 bond length can alternatively be accounted for in the following way. Suppose the GeO,
units are changed to GeO, units with non-bridging
bonds beyond the composition for the maximum,
e.g., Na,O > 20 mol%. If the bond in the GeO, units
is comparable in length with that in the GeO, counterparts, the first peak of the RDF will not shift and
consequently a constant bond length will beOderived.
Indeed, the bond lengths are 1.82 and 1.85 A for the
GeO, units in Na,GeO, crystal [23], aimmostas long
as those for the GeO, units (1.88 A). Thus the
two-shell model can well explain the experimental
results.
A question may arise of whether the GeO, units
with non-bridging oxygen atoms could appear in the
range of lower alkali contents. The presence of such
GeO, units, however, is inconsistent with the change
in elasticity and molar volume with composition
[24]. Moreover, the non-bridging oxygen atoms are
unlikely to be formed in the present system consisting of two network-forming oxides. Then what about
the charge balance around the six-coordinated germanium? We consider a mechanism similar to that
already proposed [25] for formation of BO, units in
the glasses of the B,O,-TeO, system.
With all these considered, we conclude the presence of six-coordinated Ge atoms and follow the

0-o

60

20

30

Ge0~(lnol%)

Fig. 6. The fractions Ns (Eq. (4)) and T, (Eq. (5)) of the

six-coordinated Ge atoms plotted as functions of the GeOz content.

convention in analyzing the EXAFS data and interpreting the germanate anomaly. From the two-shell
analysis, the fraction, N,, of GeO, units is plotted in
Fig. 6 as a function of the GeO, content. N6 decreases monotonically without a maximum as the
GeO, content increases and is almost constant in the
range > 40 mol% GeO,. Moreover, N6 extrapolates
to about 0.5 when TeO, fully substitutes GeO,. Eq.
(5) gives the fraction, T6, of GeO, in the total
amount of the network-forming cations:
T6 =N,[Ge],

(5)
where N6 is given by Eq. (4) and [Gel represent the
GeO, content in the glass. Fig. 6 shows that Ts
increases up to about 0.18 while N6 decreases as the
GeO, content increases.
Incidentally, note that the conversion of GeO, to
GeO, needs charge-compensating cations like alkali
ions in alkali germanate glasses. The absence of
those cations in the present system leads to such a
structural modification that assumes the formation of
three-coordinated oxygen atoms as proposed in the
GeO,-P,O, system by Shimizugawa et al. [3a] or in
the B,O,-TeO, system by Qiu et al. [25].

5. Summary
Several glasses in the binary GeO,-TeO, system
were prepared and the extended X-ray absorption
fine structure (EXAFS) of the Ge atoms were analyzed with a GeO, and GeO, two-shell model. Formation of Ge,O, three-membered rings was considered unlikely to explain the germanate anomaly. The

A. Osaka et al. /Journal

of Non-Crystalline Solids 191 (1995) 339-345

fitting was carried out with the fixed Ge-0 bond

lengths and employing quartz-type and rutile-type
GeO, as the standard materials for the phase shift
correction. The results showed that the fraction of
six-coordinated Ge atoms decreased from 0.46 to
0.26 as the GeO, content increased from 12 to 68
mol%.

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