Optical Materials 12 (1999) 467±471

Dy3‡-doped stabilized GeGaS glasses for 1.3 lm optical ®ber

ampli®ers
Y. Guimond a, J.L. Adam a,*
, A.M. Jurdyc b, J. Mugnier b, B. Jacquier b,
X.H. Zhang a
a
Laboratoire des Verres et C
eramiques, UMR-CNRS 6512, Universite de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France
b
Laboratoire de Physico-Chimie des Mat
eriaux Luminescents, UMR-CNRS 5620, Universit e Claude Bernard,
43 Bd du 11 novembre 1918, 69622 Villeurbanne Cedex, France
Received 30 April 1998; accepted 30 October 1998

Abstract
Dy3‡ -doped stabilized-GeGaS sul®de glasses are synthesized and characterized. When antimony is added to GeGaS,
the glass shows very weak crystallization upon heating as compared to standard compositions. Because of the low
phonon energy inherent in sul®de glasses, the 1.3 lm emission of Dy3‡ ions can be observed. This transition is char-
acterized in terms of emission cross-section and quantum eciency. Ó 1999 Elsevier Science B.V. All rights reserved.

Keywords: Sul®de glasses; Low phonon; Dysprosium; 1.3 lm; Optical ampli®er

1. Introduction 370 cmÿ1 ), these GeGaSbS glasses are character-

Glasses with low phonon energy (LPE) are of
prime importance for the realization of ecient
optical ®ber ampli®ers for the second telecommu-
nication window. 1.3 lm emission has already
been observed in LPE sul®de glasses doped with
either Pr3‡ or Dy3‡ ions [1±4]. However, real ap-
plications necessitate glasses with excellent thermal
stability in order to develop optical ®bers with
reasonable loss. This has not been achieved yet
with usual germanium±gallium sul®de glasses.
In this paper, we show the spectroscopic prop-
erties of Dy3‡ ions in a novel germanium±gal-
liumbased sul®de glass stabilized by addition of
antimony. Besides low phonon energy (typically
*
Corresponding author. Tel.: +33 2 99286262; fax: +33 2
99286262/1600; e-mail: jean-luc.adam@univ-rennes.fr
0925-3467/99/$ ± see front matter Ó 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 5 - 3 4 6 7 ( 9 8 ) 0 0 0 7 7 - 9
ized by an excellent resistance to moisture, rela-
tively high glass transition temperatures (around
300°C), and a very weak crystallization peak (with
10°C minÿ1 heating rate). On the contrary, stan-
dard GeGaS glasses show strong crystallization
around 520°C±540°C, which dramatically impairs
their potential for optical ®ber drawing.
2. Experimental procedures
Stabilized GeGaSbS glass samples were pre-
pared by weighing pure elements (5±6 N) in a dry
glove box. Then, the mixture was placed in a fused
silica ampoule and pumped under vacuum for a
few hours. At this stage, the tube was sealed,
heated in a rocking furnace at 1000°C for 6 h, and
cooled down to room temperature. About 3 mm-
thick glass plates containing 0.05, 0.1, 0.2, 0.5 and
468 Y. Guimond et al. / Optical Materials 12 (1999) 467±471

1 at.% Dy3‡ were obtained. Also, an undoped

GeGaSbS glass prism with 10 ´ 10 mm2 faces was
fabricated.
Thermal analyses were carried out for single
glass chips, about 50 mg, in sealed aluminum pans.
The measurements were performed by means of a
Setaram 92 di€erential scanning calorimeter
(DSC) with 10°C minÿ1 heating rate.
Refractive indices were measured by two inde-
pendent methods: ®rst, by the prism-coupling
method with a rutile prism optically coupled to a
GeGaSbS glass plate and, second, by the minimum
deviation method applied directly to the GeGaSbS
prism. Both the measurements were carried out
with 632.8 nm light from an He±Ne laser.
For Dy3‡ emission measurements, continuous
excitation in the infrared was obtained with a
Coherent CW ring titanium±sapphire laser (2 GHz
linewidth) pumped by a Coherent 310 argon ion
laser. Fluorescence at 90°C was analyzed through
a Jobin±Yvon double monochromator (HR320).
Laser light was modulated through a mechanical
chopper and the output signal of a germanium
photodiode (ADC, 403 L, Low Speed), cooled to
liquid nitrogen temperature, was fed into a lock-in
ampli®er. The ¯uorescence data were corrected by
Fig. 1. DSC curves for: (a) Ge25 Ga5 S70 , (b) 80GeS2 ±20Ga2 S3 ,
the response of the detection system obtained with
and (c) GeGaSbS sul®de glasses. (Note the large Y-scale for
a calibrated standard lamp. Ge25 Ga5 S70 glass.)
Selective pulsed laser excitation was used for
lifetime measurements. The visible beam of a
pulsed dye laser pumped by an Nd : YAG from transition temperatures are 333°C, 432°C and
BM Industry was shifted towards the infrared 305°C and the crystallization temperatures are
range by stimulated Raman scattering through an 506°C, 513°C and 494°C, respectively. Our results
H2 cell and delivers pulses of about 10 ns duration for the two standard glasses are in good agreement
and 0.04 cmÿ1 spectral width. The ¯uorescence with previously reported data [5,6]. The tempera-
was then analyzed with a Jobin±Yvon mono- ture di€erence between crystallization and glass
chromator (H25) and a high speed germanium transition is the largest for GeGaSbS glass with a
photodiode (ADC, 403 HS, High Speed) cooled to value of 189°C, to be compared with 81°C and
liquid nitrogen temperature. The ¯uorescence time 173°C for standard glasses. In addition, the crys-
evolution was then recorded with a Lecroy 9410 tallization peak is signi®cantly less intense for the
digital oscilloscope. antimony containing glass, as shown in Fig. 1.
Thus, GeGaSbS glass is, by far, the most stable
material.
3. Results From an optical point of view, GeGaSbS is
transparent from 0.6 lm in the visible to 11 lm in
The results of thermal analysis are shown in the infrared. As expected, it shows a high refrac-
Fig. 1 for standard Ge25 Ga5 S70 and 80 GeS2 , 20 tive index as reported in Table 1. We ®rst mea-
Ga2 S3 glasses, and for GeGaSbS glass. The glass sured the refractive index of a GeGaSbS glass
 Y. Guimond et al. / Optical Materials 12 (1999) 467±471
Table 1
Refractive index of GeGaSbS glass at 632.8 nm
Method nmeas naver
Prism coupling 2.3658 2.3657 (‹5 ´ 10ÿ4 )
2.3657
2.3655
Minimum deviation 2.368 (‹2 ´ 10ÿ3 ) ±
plate by means of the prism-coupling technique [7].
These measurements were performed three times,
with a very good reproducibility, leading to a
mean refractive index of 2.3657 ‹ 5 ´ 10ÿ4 at
632.8 nm. This result was con®rmed by direct
measurement using the minimum deviation tech-
nique with a GeGaSbS prism. The refractive index
was found to be 2.368 ‹ 2 ´ 10ÿ3 which is in good
agreement with the previous measurements.
The absorption spectrum of Dy3‡ ions (0.5
at.%) is shown in Fig. 2. Despite the limited
transparency of sul®de glasses in the visible, as
many as seven optical transitions are observed.
The experimental oscillator strengths are given in
Table 2, together with the average peak positions.
For the 6 H13=2 absorption, the magnetic dipole
contribution was calculated (54 ´ 10ÿ8 ) and then
subtracted from the total oscillator strength. The
remainder is the experimental electric dipole os-
cillator strength. With seven absorption bands, the
Judd±Ofelt (J±O) theory can be applied eciently
to this new rare earth-host system. The main steps
of the procedure can be found in Ref. [8]. By em-
ploying a least-squares ®tting of calculated and
experimental oscillator strengths, the following set
of J±O parameters is determined: X2 ˆ 9.49,
Fig. 2. Absorption spectrum of Dy 3‡
ions (0.5 at.%) in Ge-
GaSbS glass.
469
X4 ˆ 2.29, X6 ˆ 1.79, in 10ÿ20 cm2 units. In these
measurements, a constant refractive index of
2.3657 is used, and the number of Dy3‡ ions per
cm3 of glass is equal to 1.90 ´ 1020 (0.5 at.%-doped
sample). Because of a higher refractive index, the
J±O parameters are lower in GeGaSbS than in
standard glasses (a constant refractive index of
2.15 was used in Ref. [1,4]). The high value of X2 ,
as compared to ¯uoride glasses (X2 ˆ 3.22 ´ 10ÿ20
in ZBLA glass [9]) is due to the more covalent
nature of chemical bondings in sul®de glasses.
Radiative properties of Dy3‡ ions in GeGaSbS
glass are calculated by means of the J±O parame-
ters. The results for the 1.3 lm emission, which
originates from two overlapping levels, 6 F11=2 and
6
H9=2 , are given in Table 3. Assuming that the
energy gap between the two levels is negligible, the
e€ective emission rate is calculated from the indi-
vidual radiative rates Arad ˆ 1=srad †, according to
the following equation [8]
   
6 6
1 g 1 A rad F11=2 ‡ g 2 A rad H 9=2
Aeff ˆ ˆ ; 1†
seff g1 ‡ g 2
where g1 and g2 are the respective degeneracies of
the levels.
Thus, the e€ective spontaneous emission rate is
found to be 2641 sÿ1 , and the e€ective lifetime is
379 ls, which is apparently higher than the life-
times reported for standard GeGaS sul®de glasses
[1,4]. This point will be discussed in the next sec-
tion.
The 1.3 lm emission for the 0.1 at.% Dy3‡
sample, expressed in terms of emission cross-sec-
tion, is displayed in Fig. 3. The cross-section was
determined from the measured emission spectra
and the calculated branching ratio and radiative
lifetime using a formula derived from McCumber
[10] usually referred to as the Ladenburg±Fu-
chtbauer method [11]
1 Ic k†
re k† ˆ b=srad †k4 R
8pc0 n 2 Ic dk
1 k4
ˆ b=s rad † ; 2†
8pc0 n2 Dkeff
where c0 is the velocity of light in vacuum, n the
refractive index and I(k) the ¯uorescence intensity
(i.e. number of photons per wavelength interval).
470 Y. Guimond et al. / Optical Materials 12 (1999) 467±471

Table 2
Average absorption wavelengths, measured and calculated electric-dipole oscillator strengths (f) for Dy3‡ ions in GeGaSbS glass.
Transitions are from the 6 H15=2 ground state to the levels indicated
Level k (nm) fmeas (10ÿ8 ) fcalc (10ÿ8 ) Deviation (10ÿ8 )
6
F3=2 764 24 26 ÿ2
6
F5=2 814 138 139 ÿ1
6
F7=2 917 321 318 3
6
F9=2 ‡ 6 H7=2 1112 438 442 ÿ4
6
F11=2 ‡ 6 H9=2 1302 1633 1635 ÿ2
6
H11=2 1718 216 224 ÿ8
6
H13=2 2868 307 288 19
drms ˆ 10 ´ 10ÿ8 .

Table 3
Electric-dipole spontaneous emission rates, radiative and e€ective lifetimes, and e€ective branching ratios for emissions from the 6 F11=2
(6 H9=2 ) levels of Dy3‡ in GeGaSbS glass
Transition k (lm) Aed (sÿ1 ) srad (ls) seff (ls) beff
6
ÿ

F11=2 ÿ6 H9=2
! 6 H11=2 5.38 a
11 (26) 219 (3106) 379 0.007
6 6
F11=2 ÿ H9=2
! 6 H13=2 2.38 a
320 (114) 0.086
6
F11=2 6 H9=2 ! 6 H15=2 1.34 4243 (182) 0.907
a
Wavelengths determined from absorption data.

6
H7=2 ; 6 F9=2 †. The decays are shown in Fig. 4. For
0.1 and 0.05 at.% Dy3‡ , the decays are identical.
So, we can conclude that there is no luminescence
quenching for these concentrations. For concen-
trations above 0.1%, decays start shortening due to
Dy3‡ ±Dy3‡ interactions. Whatever the Dy3‡ con-
centration is, the decays are markedly non-expo-
nential. It is then necessary to estimate a measured
lifetime. For the lowest concentrations, the ®rst e-
folding time of the decay curve is found to be 33 ls
and the zero-order momentum is equal to 38.5 ls.

Fig. 3. 1.3 lm emission spectrum of Dy3‡ ions in GeGaSbS

glass.

In the present case, the e€ective branching ratio,

beff , and e€ective lifetime, seff , listed in Table 3
must be substituted for b and srad . We assumed
that there is no re-absorption of the emission nei-
ther from the ÿground state
nor from the excited
states. The 6 H9=2 ; 6 F11=2 ! 6 H15=2 emission
band is centered at 1.336 lm and has a bandwidth
of 95 nm.
Lifetime measurements around 1.3 lm were
performed for various Dy3‡ concentrations, ÿ6 with Fig. 4. (6 H9=2 , 6 F11=2 ) decays as a function of Dy3‡ concentra-
pulsed excitation at 1110 nm H15=2 ! tion in GeGaSbS glass.
 Y. Guimond et al. / Optical Materials 12 (1999) 467±471
For the 0.2 and 1 at.% Dy3‡ samples, the ®rst
e-folding time drops to 24.3 and 3.5 ls, respec-
tively. Using those estimations, the total quantum
eciency as usually de®ned by g ˆ smeas =seff is 10%
for the 0.1% doped sample.
4. Discussion
Given the fact that we succeeded in synthesizing
a very stable GeGaSbS glass, it is of prime interest
to compare the performance of Dy3‡ ions in this
glass and in standard sul®de glasses. In the pre-
vious section, we mentioned that our e€ective
lifetime
ÿ6 (379
ls) for the 1.3 lm emission from
H9=2 ; 6 F11=2 was apparently longer than the
lifetime reported for standard sul®de glass [1,4].
Actually, this is due to a di€erent method of cal-
culation. In our case, we used Eq. (1) that ac-
counts for a proportional contribution of the two
levels. In Ref. [1,4], on the contrary, the two con-
tributions were simply added. In the former case,
the e€ective decay time is intermediate between the
two radiative lifetimes, as shown in Table 3. In the
latter, the overall decay is found to be more rapid
than the fast component, which has no physical
meaning to our opinion.
Thus, by means of Eq. ÿ (1), we re-calculated

the
e€ective lifetime for 6 H9=2 ; 6 F11=2 in standard
GeGaS : Dy3‡ glass with the J±O parameters and
refractive index reported in Ref. [1,3]. A value of
417 ls is found, which leads to a quantum e-
ciency of 9% instead of 17% as previously report-
ed. This is to be compared with 10% for our
stabilized GeGaSbS glass.
In the same way, one must also pay attention to
the emission cross-section which must be calcu-
lated from e€ective emission rates or e€ective
branching ratios, as listed in Table 3. If not, the
emission cross-section for the 1.3 lm emission is
overestimated by nearly a factor of 2, as obtained
in Ref. [1]. The use of e€ective emission rates leads
to an estimated value of 2 ´ 10ÿ20 cm2 for con-
471
ventional GeGaS glass, which is similar to the
cross-section of 1.9 ´ 10ÿ20 cm2 obtained in this
work for GeGaSbS glass.
5. Conclusion
In summary, we have investigated the proper-
ties of the 1.3 lm transition of Dy3‡ ions in a novel
generation of GeGaS sul®de glasses. With a
quantum eciency of 10% and a stimulated
emission cross-section of 1.9 ´ 10ÿ20 cm2 , this new
1.3 lm emitting glass compares favorably with
conventional germanium±gallium-based sul®de
glasses if an e€ective radiative lifetime is used for
ÿ

the two overlapping emitting levels 6 F11=2 ; 6 H9=2 .
The newness of this material resides in its ability to
resist devitri®cation (standard thermal analysis
shows very weak crystallization upon heating). It
consequently shows promise for the development
of rare earth-doped optical ®bers with reasonably
low optical attenuation.
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