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Journal of Non-Crystalline Solids 210 1997.

130135

Raman spectra and thermal analysis of a new


leadtelluriumgermanate glass system
Zhengda Pan ) , Steven H. Morgan
Center for Photonic Materials and Deices, Physics Department, Fisk Uniersity, Nashille, TN 37208, USA
Received 7 June 1996; revised 28 August 1996

Abstract
Differential scanning calorimetry DSC. and Raman scattering studies of a new glass system, leadtelluriumgermanate
glasses in the form of 90 y x .GeO 2 P x TeO 2 P 27PbOP 10CaO with x s 0, 10, 20, 30, and 40, are reported. The glass
samples were fabricated using a conventional melt-quenching method. The Raman spectra and possible glass structures are
discussed for different TeO 2 contents. The results indicate that increasing TeO 2 content up to 40 mol% in the glass system
decreases the glass transition temperature and melting temperature, and suppresses the crystallization tendency in the fiber
pulling temperature range. The leadtelluriumgermanate glass, GTPC, possesses a larger refractive index and a smaller
maximum phonon energy than that of a leadgermanate glass, 63GeO 2 P 27PbOP 10CaO, and shows a better thermal
stability compared to a tellurite glass, 75TeO 2 P 20ZnOP 5Na 2 O TZN.. These improved properties could be beneficial for
fabricating rare-earth doped fiber devices.

1. Introduction
The properties and structures of leadgermanate
and tellurite based glasses have been the subject of
several recent investigations w15x. Germanate and
tellurite based glasses generally have better mechanical strength, chemical durability, and thermal stability than fluoride based glasses, and therefore are
more promising than halide glasses for practical use
as long optical fibers. The smaller maximum vibrational energy 750 to 850 cmy1 . of germanate and
tellurite glasses compared to that of silicate ; 1150
cmy1 . glasses, results in a smaller multiphonon decay rate of doped rare-earth ions, compared to that in
silicate based glasses w14x.
)

Corresponding author. Tel.: q1-615 329 8537; fax: q1-615


329 8634; e-mail: zpan@dubois.fisk.edu.

GeO 2 has long been recognized as a good glass


former w6x. GeO 2 based glasses exhibit better infrared IR. transmission than SiO 2 based glasses due
to the larger size and the heavier mass of germanium
when compared to that of silicon. Leadgermanate
based glass systems have been previously reported
having a large glass forming region while maintaining a high infrared transmittance w7,8x. A specific
glass of the composition 63GeO 2 27PbO10CaO
GPC. was noted to have less OHy contamination,
but crystallized in the fiber pulling temperature range
w2x.
TeO 2 is not able to form a glass itself, but it
forms glasses with modifying oxides w9x. Tellurite
glasses have a wide transmission region 0.35 to 5
mm., the lowest maximum phonon energy among
the common oxide glasses, and a large refractive
index, compared to both silicate and fluoride glasses

0022-3093r97r$17.00 Copyright q 1997 Elsevier Science B.V. All rights reserved.


PII S 0 0 2 2 - 3 0 9 3 9 6 . 0 0 6 0 3 - 5

Z. Pan, S.H. Morganr Journal of Non-Crystalline Solids 210 (1997) 130135

w3x. The large refractive index and the small phonon


energy are desirable for radiative transitions of rareearth ions w1x. The PbOTeO 2 GeO 2 glass was first
reported as a low-loss infrared transmitting glass
w10x. Few studies on PbOTeO 2 GeO 2 glasses have
been reported. One recent article reports on the
third-order non-linearity of PbOTeO 2 GeO 2
glasses, where GeO 2 was added to improve the glass
forming ability and thermal stability w11x.
In this article, we report on the thermal properties,
refractive index, and Raman spectra of a new lead
telluriumgermanate glass system in the form of
63 y x .GeO 2 P x TeO 2 P 27PbOP 10CaO with different TeO 2 content, x. Based on the glass properties
studied, we propose a new glass composition, lead
telluriumgermanate glass, GTPC, as a possible candidate material for rare-earth doped fiber devices.
2. Experiment
Glasses were prepared from anhydrous oxide
powders of GeO 2 , PbO, and TeO 2 , and anhydrous
carbonate powder of CaCO 3 . The PbO and CaCO 3
were common reagent grade, GeO 2 was of 99.9999%
purity Eagle Picher Research Lab., and TeO 2 was
of 99.99% purity Alfa, Johnson Matthey.. The glass
compositions were in the form of 63 y x .GeO 2 P
x TeO 2 P 27PbOP 10CaO with x s 0, 10, 20, 30, and
40. The CaO was added to reduce the OHy contamination w2x. The batch powders of 30 g were thoroughly mixed, and melted in fused silica crucibles in
a temperature range of 780 to 11008C. The liquids
were held for 1.5 h and cast onto a copper plate and
pressed by another copper plate from the top, forming a glass plate about 2 mm in thickness. The
glasses were subsequently annealed just below the
glass transition temperatures for 50 min and then
cooled to room temperature in the furnace.
The Raman spectra were taken using a right angle
scattering geometry on a double-grating spectrometer
Spex Model 1403. with a cooled photomultiplier
RCA3134. and photon-counting system. The excitation source of Raman measurements was an argon
ion laser Coherent Innova 90. operating at 514.5 nm
and 50 mW. Both parallel polarized HH. and cross
polarized HV. spectra were recorded.
The refractive index, n, was measured using an
ellipsometer type 43603-200E, Rudolph Research..

131

The thermal properties were analyzed by differential


scanning calorimetry DSC. on a scanning calorimeter PerkinElmer DSC-4.. A glass sample, about 60
mg, was heated at a rate of 108Crmin, from room
temperature to 6008C. The sample pans used were
matched pans made of stainless steel.

3. Results
3.1. DSC results
Fig. 1 shows the DSC curves for leadtellurium
germanate glasses with different TeO 2 contents. The
glass transition temperature, Tg , gradually decreased
with increasing TeO 2 content. The 63GeO 2 P 27PbO
P 10CaO GPC. sample has a sharp exothermal peak
at 5718C, indicating a strong crystallization. With
increasing TeO 2 content, the exothermal peak is
gradually suppressed. For samples with 30 mol%
TeO 2 , there is no exothermal peak in the temperature
region up to 5908C, but there is a bump near 6008C
which is close to the glass melting point. For samples with 40 mol% TeO 2 , there is a broad bump
around 5608C, which may indicate some crystalliza-

Fig. 1. DSC curves of 67y x .GeO 2 P x TeO 2 P27PbOP10CaO


glasses.

Z. Pan, S.H. Morganr Journal of Non-Crystalline Solids 210 (1997) 130135

132

Table 1
Thermal properties and refractive index of 63y x .GeO 2 P x TeO 2
P27PbOP10CaO glasses with different TeO 2 content x
Properties

xs0

x s10

x s 20

x s 30

x s 40

Tg C.
Tx C.
Tm C.
.
n 5461 A

505
560
;940

470
560

420
570

385
no
;600

365
no
;610

1.79

1.82

1.86

1.91

1.95

Tg : glass transition temperature, Tx : crystallization onset temperature, Tm : glass melting temperature, n: refractive index.

tion tendency. The melting temperatures were tested


by placing samples in an electric furnace, gradually
increasing the temperature to the point that the sample becomes liquid. The melting temperature Tm
decreases from about 9408C for GPC glass without
TeO 2 . to near 6008C for glasses with 30 mol% to 40
mol% TeO 2 . Table 1 lists the measured thermal
properties and refractive index of glasses with different TeO 2 content.
3.2. Raman spectra
Figs. 2 and 3 illustrate the parallel-polarized and
cross-polarized Raman spectra of leadtellurium
germanate glasses with different TeO 2 content, x,

Fig. 3. Cross-polarized Raman spectra of 67y x .GeO 2 P x TeO 2 P


27PbOP10CaO glasses.

respectively. These spectra are composed of three


spectral regions: Low-frequency region F 250
cmy1 .; intermediate region 250 to 600 cmy1 .; and
high-frequency region ) 600 cmy1 .. The Raman
spectrum of GPC sample agrees well with the reported spectrum of the same composition in a previous study w4x. With increasing TeO 2 content and
decreasing GeO 2 content, the evolution of Raman
spectra show the following features: i. The high
frequency Raman band decreases in frequency from
820 to 750 cmy1 . and increases in intensity; ii.
intermediate bands at 430 and 525 cmy1 decrease in
intensity, while a weak band at 330 cmy1 grows;
iii. a polarized shoulder at the high frequency side
of the low-frequency band grows. These spectral
features reflect the structure change of the samples
when tellurium oxide content increases.
4. Discussion
4.1. Thermal analysis

Fig. 2. Parallel-polarized Raman spectra of 67y x .GeO 2 P x TeO 2


P27PbOP10CaO glasses.

Clear glasses were formed for 63 y x .GeO 2 P


x TeO 2 P 27PbOP 10CaO system with x s 0, 10, 20,
30 and 40. These glasses appear to be of good
optical quality, with no visual evidence of devitrifi-

Z. Pan, S.H. Morganr Journal of Non-Crystalline Solids 210 (1997) 130135

cation, however, attempts to make glass with 50


mol% TeO 2 were unsuccessful because of phase
separation.
The DSC results show that substitution of GeO 2
with TeO 2 decreases the glass transition temperature,
Tg , and melting temperature, Tm . The Tg decreased
from 5058C for sample GPC to 3658C for a sample
with 40 mol% TeO 2 . The corresponding melting
temperature decreased from circa 9408C to near
6008C. The Tg and Tm values of GPC samples are
consistent with that reported in a previous study w2x.
Our DSC curve of a GPC sample shows an exothermal peak at 5718C with a crystallization onset temperature Tx s 5608C. With increase of TeO 2 content,
this exothermal peak shifts to higher temperatures
and is gradually suppressed. No exothermal maxima,
therefore no crystallizations were observed for glass
with 30 mol% TeO 2 up to 5908C. A criterion,
Hrubys ratio, has been frequently used to measure
glass stability w12,13x. Hrubys ratio involves the
glass transition temperature Tg , the melting temperature Tm , and the crystallization onset temperature Tx ,
and has been defined as w12x
KG s

Tx y Tg
Tm y Tx

According to this formula, the larger the difference,


Tx y Tg , and the smaller the temperature interval,
Tm y Tx , the stronger is the inhibition to processes of
nucleation and crystallization, and consequently the
greater the glass forming tendency for the system. In
our leadtelluriumgermanate glass system, a higher
TeO 2 content up to 40 mol%. decreases Tm and Tg
Tg and Tm are approximately related by 2r3 rule.
and increases Tx , both lead to an increase in Hrubys
ratio. These results indicate that incorporation of
TeO 2 into the leadgermanate glass network improved the glass thermal stability. The improved
glass stability is desirable to achieve a large working
range during operations such as preform preparation
for fiber drawing w2,3x. The optimized TeO 2 content
in the 63 y x .GeO 2 P x TeO 2 P 27PbOP 10CaO system is 30 mol%. This new glass is labeled GTPC.
We also compared our GTPC glass to a tellurite
glass 75TeO 2 P 20ZnOP 5Na 2 O TZN. which was
previously reported as a new candidate for fiber
devices and had a glass transition temperature at

133

2998C and a crystallization onset temperature at


4178C, which gives a working range Tx y Tg . s
1188C w3x. The GTPC glass has a much larger working range ) 2008C. without crystallization, therefore shows a better thermal stability than TZN glass.
We found that the TZN glass and binary leadtellurite glasses have a tendency to crystallize during
the conventional melting-quench process.
4.2. Raman scattering and glass structure
The low-frequency F 250 cmy1 . Raman scattering is attributed to the collective modes of local
structures and heavy metal vibrational modes w14
16x. There is almost no change with increasing TeO 2
content for the depolarized component Fig. 3., which
has been attributed to the collective modes of local
structures w15x. However, the polarized component
Fig. 2. has changed, the intensity near 90 cmy1 has
decreased while a shoulder at the high frequency
side ; 130 cmy1 . has grown with the increase of
TeO 2 content. The polarized band near 130 cmy1 is
attributed to the PbO symmetric stretching modes
in PbO4 pyramids while the component at near 90
cmy1 is due to the vibration of PbO bonds with a
more ionic bonding nature w1416x. Our lowfrequency Raman results therefore suggest that the
bonding strength between lead cation and oxygen
anion has been enhanced in GTPC glass as compared
to GPC glass.
Raman scattering in the intermediate region 300
to 580 cmy1 . has generally been attributed to the
deformation vibrational modes of glass network
structure with bridged oxygen w1720x. The Raman
bands at 430 to 525 cmy1 are attributed to the bond
rocking modes of the glass network units with bridged
anion i.e., bridged GeOGe in germanate glass.
w17x. In a glass structure with mixed glass formers,
the connection between structure units could be
non-symmetric bridged oxygens andror non-bridged
oxygens. Previous studies w7,21x have indicated that,
with increased non-symmetric bridged oxygens
andror non-bridged oxygens in glass network, the
Raman scattering increases in the high frequency
region and decreases in the intermediate region,
which is consistent with our observed Raman scattering features. The weak band at 330 cmy1 from

134

Z. Pan, S.H. Morganr Journal of Non-Crystalline Solids 210 (1997) 130135

GTPC samples has been assigned to symmetric


bending vibration of TeO 32y units w19x.
The Raman scattering in the high-frequency region ) 600 cmy1 . has been attributed to the stretching vibrational modes of the glass network former
w1720x. The Raman spectrum of the GPC sample
agrees well with the reported spectrum of the same
composition in a previous study w4x. Lead oxide
enters the glass as an intermediate between a network former and a network modifier, increases the
number of non-bridging oxygens in the glass network, and weakens the GeO bond w1,15x. As a
result, the GeO stretching band shifted to 820
cmy1 , less than that of the pure GeO 2 glass which
has a maximum phonon band around 860 cmy1 w17x.
The Raman spectrum of tellurite glasses has two
high frequency bands at 745 and 665 cmy1 w11x.
These two Raman bands are well understood. The
665 cmy1 band is from the TeO stretching vibration of TeO4 trigonal bipyramids tbp. units while
the 745 cmy1 band is attributed to that of TeO 3
trigonal pyramids tp. units w11,20x. It has been
suggested that the relative intensities of the Raman
bands assigned to tbp and tp units stand for the
fractions of these two units in glass w22x. The Raman
spectra of our GTPC samples with 30 to 40 mol%
TeO 2 show a strong high-energy phonon band peaked
at 750 cmy1 . The Raman band from GeO stretching vibration was red-shifted and merged under the
high-frequency side of the broad 750 cmy1 band,
and a small shoulder at 665 cmy1 appears at the
low-frequency side which is from TeO4 tbp units.
The large intensity ratio of I 750.rI 665. indicates
that tellurium oxide is mostly in the form of tp units
in the GTPC sample. Previous studies suggest that
these tp units are in the O 1r2Te5O.Oy or
O 2r2Te5Oy configurations w19,20,22x. These features of the Raman spectra suggest that a mixed
tellurium oxide and germanium oxide glass network
has been formed in GTPC sample, where the tellurium oxide is mostly in the tp units and germanium
oxide in the distorted tetrahedral units w23x. The
interconnections could be the non-symmetric bridged
oxygens andror non-bridged oxygens. The position
of the highest-phonon band is important because the
multiphonon decay of rare-earth ions in a glass
depends on the maximum-phonon energy of the host
glass w24,25x. Our Raman spectra indicate that the

maximum-phonon band in GTPC sample is at 750


cmy1 , smaller than the 820 cmy1 in GPC sample.
We also measured the infrared reflectance spectrum
of GTPC sample, the maximum infrared band peaked
at 650 cmy1 with a shoulder extending to about 750
cmy1 . Because the rate of multiphonon decay is
sensitive to the maximum vibrational energy of the
glass, a smaller multiphonon decay rate of rare-earth
ions in GTPC glass compared to GPC glass is therefore expected.

5. Conclusion
We have presented the DSC and Raman data on a
new leadtelluriumgermanate glass system, 63 y
x .GeO 2 P x TeO 2 P 27PbOP 10CaO with x s 0, 10, 20,
30, and 40. Our results indicate that incorporating
tellurite oxide into the lead germanate oxide network
improves the glass thermal stability and decreases
the maximum phonon energy. The new GTPC glass
showed a better thermal stability than both a lead
germanate glass, GPC, and a tellurite based glass,
TZN, reported previously. The improved thermal
stability is desirable for fiber fabrication. In addition,
a smaller maximum phonon energy and a larger
refractive index are also desirable for reducing multiphonon decay rate and enhancing the radiative transition of rare-earth ions in the host glass, respectively.

Acknowledgements
The authors would like to acknowledge the financial support of NASA through grant NAGW-2925.

References
w1x Z. Pan, S.H. Morgan, K. Dyer, A. Ueda and H. Liu, J. Appl.
Phys. 79 1996. 8906.
w2x J. Wang, J.R. Lincoln, W.S. Brocklesby, R.S. Deol, C.J.
Mackechnie, A. Pearson, A.C. Tropper, D.C. Hanna and
D.N. Payne, J. Appl. Phys. 73 1993. 8066.
w3x J.S. Wang, E.M. Vogel and E. Snitzer, Opt. Mater. 3 1994.
187.
w4x Z. Pan, S.H. Morgan, A. Loper, V. King, B.H. Long and
W.E. Collins, J. Appl. Phys. 77 1995. 4688.
w5x Z. Pan, K. Dyer, A. Loper and S.H. Morgan, in: Synthesis

Z. Pan, S.H. Morganr Journal of Non-Crystalline Solids 210 (1997) 130135

w6x
w7x
w8x
w9x
w10x
w11x

w12x
w13x
w14x

and Application of Lanthanide-Doped Materials, ed. B.G.


Potter, Jr. and A.J. Bruce American Ceramic Society, Westerville, OH, 1996. p. 55.
A. Margaryan and M.A. Piliavin, Germanate Glasses, Artech
House, Boston, MA, 1993. ch. 2.
S.J.L. Ribeiro, J. Dexpert-Ghys, B. Piriou and V.R. Mastelaro, J. Non-Cryst. Solids 159 1993. 213.
A.F. Fray and S. Nielsen, Infrared Phys. 1 1961. 175.
J. Zarzycki, Glasses and the Vitreous State Cambridge, New
York, 1982. ch. 8.
S. Nielsen, W.D. Lawson and A.F. Fray, Infrared Phys. 1
1961. 21.
Y.S. Kim, W.H. Kim and J. Heo, in: Synthesis and Application of Lanthanide-Doped Materials, ed. B.G. Potter Jr. and
A.J. Bruce American Ceramic Society, Westerville, OH,
1996. p. 59.
A. Hruby, Czech. J. Phys. B22 1972. 1187.
A. Feltz, Amorphous Inorganic Materials and Glasses VCH,
New York, 1993. p. 54.
C.A. Worrell and T. Henshall, J. Non-Cryst. Solids 29 1978.
283.

135

w15x Z. Pan, D.O. Henderson and S.H. Morgan, J. Chem. Phys.


101 1994. 1767.
w16x Z. Pan, D.O. Henderson and S.H. Morgan, J. Non-Cryst.
Solids 171 1994. 134.
w17x H. Verweij and J.H.J.M. Buster, J. Non-Cryst. Solids 34
1979. 81.
w18x K.E. Lipinska-Kalita, J. Non-Cryst. Solids 119 1990. 41.
w19x T. Sekiya, N. Mochida, A. Ohtsuka and M. Tonokawa, J.
Non-Cryst. Solids 144 1992. 128.
w20x H. Burger,
K. Kneipp, H. Hobert and W. Vogel, J. Non-Cryst.

Solids 151 1992. 134.


w21x A.E. Miller, K. Nassau, K.B. Lyons and M.E. Lines, J.
Non-Cryst. Solids 99 1988. 289.
w22x Y. Himei, A. Osaka, T. Nanba and Y. Miura, J. Non-Cryst.
Solids 177 1994. 164.
w23x H. Hagiwara and R. Oyamada, J. Phys. Soc. Jpn. 36 1974.
517.
w24x K. Huang, Contemp. Phys. 22 1981. 599.
w25x C.B. Layne, W.H. Lowdermilk and M.J. Weber, Phys. Rev.
B16 1977. 10.

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