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August 1994

PT~CAL
-

Optical Materials 3 (1994) 187203

ELSEVIER

Tellurite glass: a new candidate for fiber devices


J.S.

Wang, E.M. Vogel

1,

E. Snitzer

Rutgers University, Fiber Optics Materials Research Program, Piscataway, NJ 08855, USA

Abstract
The physical properties of R

20-ZnO-TeO2 glasses have been studied for their feasibility for fiber drawing and rare earth doping. A telluriteglass3~,
fiber
with
less athan
1 dB/m
has been
by the rod-in-tube
method.
The spectroscopic
properties of
Nd3~,
Er3~,
nd Tm3~)
inloss
tellurite
glass made
are discussed
and compared
with silica,
fluoride and chalcogenide
rare earthions (Pr
glasses.

1. Introduction
The first glass laser was obtained in a barium silicate glass [1]. This result initiated a new application
for glass. It is clearly evident that silicate glass has
been most extensively studied as a laser host because
ofits excellent glass stability, chemical durability, and
good fluorescence properties. However, with the
widespread use of optical components for telecommunications, sensors and medical applications, new
glass hosts have emerged for special usage. They indude the less common oxides, halides and chalcogenide glasses. Furthermore, with the success of fiber
technology for optical communication, a variety of
research efforts have been undertaken in glass and
glass fibers. This diversity includes new applications,
such as the use of ultraviolet-induced photo-refractive gratings, and new glass families, particularly,
those that can be fabricated into fiber waveguides with
low loss. One of the very important advantages of
glass is its ability to be fabricated into a fiber with
ultra low light attenuation. This also made fiber optic
telecommunication possible and growing.
Recently there has been considerable attention
_______

Belicore, Morristown, NJ 07960, USA.

given to optical fiber amplifiers which were first

demonstrated in neodymium-doped glass fiber in


1965 on a pulse basis [2] and later with CW pumping by a laser diode [3]. However, the results did not
attract much attention until the mid- 1980s when
work with an erbium amplifier showed useful gains
of40 dB or more when pumped with single mode laser
diodes of 30 mW or less [4].
While erbium-doped fiber amplifiers operating at
the 1.5 jim windows are commercially available now,
the majority of already-installed telecommunications fibers are optimized for the 1.3 jim window. Because changing the fiber fort the 1.55 jim window
would be costly, 1.3 jim amplifiers have attracted so
much attention.
Nd3 + and Pr3 + are two active rare earth ions that
have been investigated as potential candidates in a
variety of glass hosts since each has emission bands
near 1.3 jim. Recently, another rare earth ion, Dy3
in chalcogenide glass emitting at 1.3 jim with reasonable quantum efficiency based on lifetime measurements also has been demonstrated [5]. A praseodymium-doped fluoride fiber amplifier announced in
1991 [6] comes closest to a practical 1.3 jim fiber
amplifier to date. Apeak gain of 38.2 dB with around
1.31 jim was obtained with a launched pump power

0925-3467/94/$07.00 1994 Elsevier Science By. All rights reserved


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~,

.1.5. Wang et al. / Optical Materials 3 (1994) 18 7203

188

of 300 mW [7]. The high pump power required is

due to the low quantum efficiency (3%) of this praseodymium-doped fluoride glass. More recently,
Dejneka et al. [8] has found another fluoride glass
host for Pr3 based on Pb-In-Ga-Zn-F [9], to have
longer measured lifetime. The fluorescence rate of
Pr3~in La-Ga-S glass has also been reported [10],
although there has been no report to date on their
~,

fiberization.
Although many fiber lasers and fiber amplifiers

have been studied for both silica-based and fluoridebased glasses, the former suffer, in some cases, from
their inherent high phonon energy and the latter from
their poor glass stability and chemical durability. On
the other hand, chalcogenide glasses have not been
much studied. One of the major difficulties is their
low solubilities for rare earths. However, Wei et al.
[11] have recently demonstrated that the Ge-Ga-S
based glasses can be made with only a yellow tint and
with a high rare earth solubility.
Tellurite glasses combine the attributes of (i) a

amplifiers at long wavelength are possible in oxide


glasses, for example, Pr3 + at 1.3 jim. A detail discussion is given in section 3.3.2.1. It is also believed that

tellurite glasses could have better glass stability and


chemical durability than halide glasses [12], better
glass stability than chalcogenides, and better compatibility with other oxide glasses than the nonoxide

glasses. Another interesting fact is the degree of


covalence among the four glass family, as given in
Table 1, decreases in the order: Chalcogenide> Tellurite> Silica> Fluoride glasses, which di-

rectly affects the wavelength of the transition peak.


Although tellurites have been known for some time
as stable glass formers and selected properties of some
rare earth ions in tellurite glasses have been reported
[13,14], their utility has not been extended to fiber
optics where advantage could be taken of their non-

linear properties and the desirable fluorescence properties associated with their low energy phonon spectrum and high indices of refraction. Our goal is to
fabricate active tellurite glass fiber devices based on

reasonably wide transmission region (0.355 jim),


versus only 0.23 jim for silicate glasses, (ii) good
glass stability and corrosion resistance, which pres-

the laser action of rare earth ions in tellurite glass and/


or on the nonlinear properties of tellurite glasses.
Some recent work was done to the searching the glass

ent difficulties in fluoride glasses, (iii) a relatively


low phonon energy among oxide glass formers, and
(iv) high refractive index and high nonlinear refractive index, which are generally low in both fluoride

compositions [15] and investigating the spectroscopic properties of various rare earth ions in tellurite glasses [16]. In this paper, the emphasis is placed
on the material properties of the TeO
2-based glasses
and fibers, and the unique spectroscopic properties
in the near infrared for fiber laser oscillators and
amplifiers.

and silicate glasses. A comparison of the selected optical properties among tellurite, silica, fluoride and
chalcogenide glasses is shown in Table 1. The high
nonlinear refractive index and the low phonon energy make the tellurite glass fibers uniquely suitable
for nonlinear and laser applications. For example, the
lower phonon energy results in a lower nonradiative
transition rate between adjacent rare earth energy
levels, leading to fluorescence and laser emission from
additional energy levels that are not possible for silicate glasses. The longest fluorescent wavelengthsthat
could be observed are about 2.8 jim, 2.2 jim, 4.4 jim,
and 7.4 jim for tellurite, silica, fluoride and chalcogenide glasses, respectively. This is due to difference
in the highest phonon energy for different glass hosts,
as shown in Table 2.
With lower phonon energy, Te02-based glasses intrinsically could have higher quantum efficiencies and
could provide more fluorescent emissions than silica-basedglasses. This implies that new fiber laser and

2. Experimental procedure
2.1. Preparation ofbulk glass
High-purity commercial oxides (99.999% and
99.99% pure) were used as the starting materials.
Powders of these materials, weighed to conform to
the oxide molar percentages as indicated in the text,
were mixed and than transferred to a gold crucible.
The crucible was heated to 8000 C in a resistance furnace, and held in an air atmosphere for 2 hours. Melts
were cast into preheated cylindrical brass molds and
allowed to cool to room temperature. Samples 0.51
cm long were cut from these glasses, and the faces were
polished to a 0.5 jim finish.

J.S. Wanget al. / Optical Materials 3(1994) 187203

189

Table 1
A comparison ofselected properties for tellurite, silica, fluoride and chalcogenide glasses.
Property
Optical properties (typical values)
Refractive index (n)
Abbenumber(v)
2/W)
Nonlinearrefractive index (n
Transmission range (ism) 2, m
Highest phonon energy (cm)
Longest fluorescent wavelength (i.tm)
Bandgap(eV)
Acousto-optical figure of merit,
p2n6/rv3 (10_li ~3/g)
Physical properties (typical values)
Glass transition (Tg, 0 C)
Thermalexpansion(107C)
Density (g/cm3)
Dielectric constant (~)
Fiberloss

Tellurite

Silica

Fluoride

Chalcogenide

1.82.3
1020
2.5x i0~
0.45.0
800
2.8
~3
24

1.46
80

1.5
60110

2.83

0.22.5
1000
2.2
~l0
119

0.27.0
500
4.4

1000
5
2.2
4.0
0.2 dB/km
(1.5 ~m)
ionic-covalent
<l0~

300
150
5.0

300
120-170
5.5
1335

Bonding
Solubilityinwater

covalent-ionic
<102

Table 2
Highest phonon energy (hw) for various glasses [48,49].
Glasses

hw [cm-]

Borate
Phosphate
Silicate
Germanate
Tellurite
Fluoride

13501480
11001350
10001100
800975
600850
500600

Chalcogenide

l020

l0_21

higher
0.816
300
7.4
13

300
140
4.51

1525 dB/km
(1.52.75 ~m)
ionic
soluble

0.4 dB/km
6.5 ~tm
covalent

The fluorescence spectra were obtained at 90 degrees to the incident pump beam, so that there would
be a minimum interference of the pump with the
measurements. Fluorescent lifetimes were measured
on glasses using a similar experimental setup. The
fluorescent intensity decay was sensed by a detector
.

200300

located 90with respect to the pumping light. To ensure detection of only the fluorescent intensity, appropriate band pass filters were placed in front of the
detector. The lifetime measurements were made with

175

a chopper between the light source and the spectrom-

LaBr
3

2.2. Fluorescence and lifetime


The main excitation source used for fluorescence
and lifetime measurements was a Schwartz Electro
Optic Ti-sapphire laser pumped with a Coherent 200
10 W argon ion laser. The tunability of the Ti-sapphire laser ranged from 700 nm to 1130 nm by use of
four sets of mirrors for the short, midrange, long, or
extra-long-band wavelength sub-ranges. The other
source used for long wavelength pumping was a filtered 20 jis pulsed xenon flash lamp. Depending on
the wavelength of the signal, Ge PIN diode, Si photodiode, or liquid nitrogen-cooled InSb detectors were
used to detect the signals.

eterdetector combination.
3 at 1.3For
jim,short
it waslifetimes,
essentialsuch
that
as
obtained
from
Pr
the chopper wheel be placed in the focal plane of a
microscope objective and a second lens used to illuminate the sample. The chopper wheel then was able
to cut the beam on or off by displacement of only 5
jim which could be done in approximately 5 jis. A
Tektronix Model 41 05A console/monitor coupled
with a 4041 microcomputer was used to store the lifetime acquisition and manipulation program and control a Tektronix Model 7854 oscilloscope. The fluorescent intensity decay was thus recorded, digitized
and time averaged sequentially in a Tektronix Model
7854 oscilloscope. The decay trace and three e-folding times [17] were visualized directly on the oscil-

190

J.S. Wang et al. / Optical Materials 3 (1994) 18 7203

loscope screen. Six hundred scans were routinely averaged in making the measurements.

3. Results and discussion


3.1. Material aspects oftellurite glass andfiber

2.3. Preform preparation andfiber drawing


The melting procedure for making a core for a preform is similar to the preparation ofbulk glass. A suetion method was employed to make the tube for the
cladding. Then the rod-in-tube technique was employed for fabricating fiber. In orderto achieve a single mode fiber, a double rod-in-tube draw had to be
performed because the ratio of core radius to cladding wall thickness was not small enough.
2.4. Thermal study
Thermal analysis was employed to determine the
effect ofglass composition on glass stability. Samples
weighing 10 to 20 mg were sealed in aluminium pans
and heated at a rate of 10C/mm from 250 to 550C
in a either Perkin-Elmer DSC7 or DSC4. Because of
the temperature limitation of aluminium pans, DTA
was used to determine the liquids temperature (T1),
glass transition temperature (Tg) and crystallization
onset temperature (Tx) for high temperature glasses.
2.5. Viscosity measurement

A Theta Instruments parallel plate viscometer was


utilized to establish the temperature needed to achieve
the appropriate viscosity for fiber drawing [18].
Samples 35 mm thick were prepared with flat and
parallel faces and heated at a rate of 1 C/minfrom
200C to a point where the samples had decreased in
thickness to below 0.5 mm.
2.6. UV- VIS absorption measurement
Absorption spectra were obtained using a Perkin
Elmer UV/VIS/NIR Lamda 9 double beam spectrophotometer. The glass cylinder was usually scanned
from 3200 nm to 300 nm in air at ambient temperature after running a background with air as a reference. Instrumental parameters were set as follows:
absorbance mode, slit width 0.8 nm, scan speed 60
nm/mm and response time 0.5 s, which has good
enough resolution for glass samples.

To qualify tellurite glass as a practical fiber device,


the glass must posses gooddoping solubility with various rare earth ions. It also must have enough glass
stability for drawing fibers. It should be good enough
for different core-cladding configuration redrawings
without sacrificing the glass stability. Additionally,
glass fibers should have good chemical durability,
good mechanical strength, and reasonable optical loss.
In fact, the need for low loss fiber always imposes requirements for ultra-highpurity starting materials and
very clean processes during fiber fabrication.
The selection of glass composition for fiber fabrication is a very important task and is often a compromise among many factors. A brief evolution of glass
composition development in the early stage of this
study is given in Table 3. While glasses with BaO or
WO3 modifiers have good durability and rare earth
solubility, they appear yellow in color. With alkali
oxides present, the glasses have poor chemical durability. ZnO-TeO2 glass has a short wavelength UV
edge and good durability but low rare earth solubility. To solve this drawback, the addition of sodium
oxide in the ZnO-Te02 glasses significantly improves
the rare earth solubility (see Table 3) without affecting the other two properties. Later, it was observed
that Na2O could be replaced by other monovalent
ions, such as Li20, K2O, Rb20, Cs20, or Ag20, without deteriorating the UV edge, chemical durability,
and rare earth solubility. Thus, for the R2O-ZnO-Te02
system, R can be Li, Na, K, Rb, Cs, or Ag or combinations thereof. Also, the relative amounts of these
constituents can be varied over a wide range without
seriously affecting glass stability. Therefore, a wide
range of compositions can be achieved to match specific needs in the R20-ZnO-Te02 family.

3.1.1. Viscosity
Since drawing fiber is a process involving a dynamic deformation at high temperature, it is necessary to determine the relationship between viscosity
and temperature in the glass. Fig. 1 shows the viscosity data obtained through the use of the parallel plate
viscometer, which is suitable for measuring viscosities ranging from 1 0~to 1 0~poise. A stable glass is

J.S. Wang eta!. / Optical Materials 3 (1994) 187203

191

Table 3
Properties ofselected tellurite glasses.
(l00x)%Te0

2+x%X

X=

UVedge (nm)

Durability (H20)

Rareearth
solubility

good
good
poor
good
good
good

good
good
good
poor
good
good

(mol%)

15%BaO
30%W03
1015% alkali oxides
28%ZnO
20%ZnO+5%Na20
20% ZnO+5% K20

487
458
370
373
370
365

CAta5 cm

Temperature

~
.4

10000~
9.000

384

W03-Te02
374
364

354

(C)

Temperature (C)

~ Na20-ZnO
I
334 Te02
_______
324
314

8000

8~7

-o

10.000

7000

677

Na2O.SI~,,,J

4
7.000

13000

577

____

6.000
1.5

____

____

____

____

________

,,,IZBLAL

________

4000

,..,...,,..........

1.54

Na20-zno ?2

1.58
1.62
1 000/T(K(

1 66

1.7

Fig. 1. The viscosity versus temperature ofWO3-TeO2 and Na20ZnO-Te02 glasses.

characterized by rapid but smooth changes in viscosity in the entire region from 102 to 1014 poise. A vis
cous flow curve exhibiting a discontinuity or unsmooth variation may be attributed to structure
change, perhaps devitrification, in the glass.
The temperature dependence of the viscosity is
shown for Na20-ZnO-Te02, Na20-SiO2, and ZBLAN
glasses in Fig. 2. There are two important parameters
we can derive from viscosity-temperature curve: (i)
the temperature corresponding to fiber drawing viscosity and (ii) the slope of te viscosity-temperature
curve in the low temperature region. Hu et al. [19]
have proposed that glasses with a flat viscosity-ternperature curve are more resistant to crystallization
than glasses with steep one in the low temperature
range. Although the viscosity required for the fiber
drawing in the silicate glass is around 10~poise, it
could be slightly higher, around 1 ~ to 1065 poise,
for the fluoride and tellurite glasses.
The temperature dependence of the viscosity can
be roughly represented by the exponential equation

08

1,2

16

1 000/T)K)

Fig. 2. The viscosity-temperature behavior of tellurite (center),


silicate (left), and fluoride (right) glasses (ZBLAL=ZrF4-BaF2LaF3-AIF3-LiF).

1~=1~oexp(E~/RT)
,

(1)

where i~is the viscosity and E~the activation energy


for viscous flow. This Arrhenius-type relation rarely
holds for polymeric melts over a wide temperature
range, such as glass, because of depolymerization with
increasing temperature. However, the linearity of the
data in Fig. 2 with 1 / T indicates that the viscosity
obeys the Arrhenius equation (1) at both the high
and low temperature regions, but not in the intermediate temperature region. The curve-fitting results for
Na20-ZnO-TeO2, ZBLAN, and Na2O-Si02 are given
in Table 4. A high activation energy for viscous flow
is indicative of a very steep viscosity-temperature
profile, which shortens the working-temperature
range. Additionally, the activation energy difference
between the low and high temperature regions mdicates the differences in the glass deformation structure Silicate glass exhibit~only a small difference, tellurite glass some difference, and ZBLAN a large

192

.1.5. Wang et al. / Optical Materials 3 (1994) 187203

Table 4
Fitting parameters for Eq. (1) in variousglasses.
Glass
ii=,~oexp(E~/RT)

High temperature region

Na
W020-ZnO-Te02
3-Te02
ZBLAN
Na20-Si02

1.6x10
l.6x i0~
5
4.4x 10~2
6.5X10

Low temperature region

E,, (kcal/mole)

lo

33.6

i.4X 1021

E~(kcal/mole)

41.4
31.8
37.6

l.3x 1021
6.2x108
8.9x i0~~

7.9
1.9
49
103.6

30.

difference. This imposes great processing difficulty for


ZBLAN glasses. Attempting to reduce the activation

_-

25.

mote%Na
20

energy for viscous flow, or to keep it constant during


temperature changes, was a major research effort in
fluoride glasses [20].
The curve fitting results (derived from Fig. 1) for
WO3-Te02 glasses are also listed in Table 4. They all
show a certain degree of glass structurevariation with
the temperature changes.

20

15.

~,

to mole%Nu20

0
200

3.1.2. Thermal analysis


To investigate the glass stability, we used a differential scanning calorimeter (DSC) and a differential
thermal analyzer (DTA). The purpose ofusing DTA
instead of DSC is to measure the liquidus temperature of glasses, because the maximum temperature
employed in DSC is around 550Cif an aluminium
pan was not replaced with the gold sample holder. The
glass transition temperature (T5), crystallization onset temperature (Tx), and liquidus temperature (T1)
are important information in the thermal analysis.
The glass transition temperature, which corresponds
to a viscosity of 10i2_ 1013 P, was defined as the ternperature region in which the behavior of the material
changes from solid-like to liquid-like [21]. The crystallization temperature indicates the region in which
the glass viscosity is sufficiently low to permit rapid
crystal growth. It can be defined as the extrapolated
onset of the first crystallization exotherm. The quantity of T~ 7~has been frequently used as a rough
measure ofglass stability. To achieve a large working
range during operations such as preform preparation
for fiber drawing, it is desirable to have (T~ Tg) as
large as possible [22]. Typical DTA traces are illustrated in Fig. 3 for the Na2O-ZnO-TeO2 glasses.
Table 5 lists T5, T~and (T~ Is) for some tellurite
glasses studied. Since doping with rare earth ions is

mule%Na20

10

250

300

350

400

450

500

550

600

650

700

Temperature (C)

Fig. 3. DTA traces of ZnO-Te02 glasses with various concentrations of Na20.

one of our objectives, it is natural to study the effects


of rare earth oxide on glass composition. Although
P205-Te02 glass has a very large (Tx Tg), Er2O3 addition decreases its stability from 147Cdown to
101 C. A similar effect has been observed for 28ZnO72TeO2 glass.
For 5Na2O-2OZnO-75TeO2 glass, the (Tx 1s), i.e.
glass stability, increases with Er203 doping. Table 6
shows the effect of rare earth doping (using Pr2O3,
Er2O3, Tm203, and Yb2O3) on the glass stability. It
is clear that all four rare earths improve the glass stability for the 5Na2O-2OZnO-75TeO2 family. As we
can see, the increases in (T~ Tg) mainly result from
the increase in the crystallization temperature (Tx).
This suggests that the rare earth doping inhibits crystal formation. The dependence of (T~ Tg) with
Er203 concentration has been investigated, as shown
in Table 6. The experimental results indicate that the
glass stability increases (3.9 wt% Er2O3) and then
decreases with increasing Er2O3 concentration. However, even with 7.5 wt% Er2O3 doping, the glass stability does not decrease in comparison with the base
glass.

J.S. Wanget al. / Optical Materials 3(1994) 187203

193

Table 5
The Tg, T~and (T~ Tg) of tellurite glasses.
Glass(Mole%)
l0%P

205-90%Te02
10% P205-90% Te02-l wt% Er203
28%ZnO-72% Te02
28%ZnO-72% Te02-1 wt% Er203
5% Na20-20% ZnO-75% Te02
5% Na20-20% ZnO-75% Te02- 1 wt% Er203
15%W03-85%Te02
15%WO3-85%Te02-0.5w1%Er203
1l%BaO-89%Te02
10%BaO-20%ZnO-70%Te02
6%Na20-94%Te02

Tg(C)

T~(C)

TxTg

347
330
324
330
299
304
343
357
325
339
294

494
431
420
425
417
432
467
505
468
495
338

147
101
96
95
118
128
124
148
143
156
44

Table 6
The Tg, T~and (T. Tg) of rare earth doped tellurite glasses.
Glass(Mole%)

Tg(C)

T~(C)

T~T~

5%Na20-20%ZnO-75%Te02
+lwt%Pr203
+lwt%Er203
+lwtkTm2O3
+lwt%Yb203

299
302
304
298
303

417
452
432
424
430

118
150
128
126
127

5% Na~O-20%ZnO-75% Te02
5% Na~O-20%ZnO-75% Te02-1 wt% Er203
5% Na20-20% ZnO-75% Te02-3.9 wt% Er203
5% Na20-20% ZnO-75% TeO2-7.5 wt% Er203

299
304
311
324

417
432
447
443

118
128
136
119

To illustrate the effects ofNa2O addition on T, T~,


T1 and glass stability in ZnO-Te02 glasses, DTA traces
are given in Fig. 3. Comparing the three traces (0
mole%, 5 mole% and 10 mol% Na20), one can condude the following:
The crystallization temperature (Tx) increases
very slightly with increasing Na2O concentration.
The glass transition (Tg) temperature decreases.
Therefore, with unchanged T~and decreased 7s, the
magnitude of (Tx Tg) definitely increases so that
glass stability increases.
The liquidus temperature (T1) decreases and also
becomes broad.
DTA curves of x wt% Nd2O3 in 5Na2O-2OZnO75TeO2 glasses (x=0.05 wt%, 1.4%, 2.7%, and 6.7
wt%) are illustrated in Fig. 4. The effects of Nd203
concentration on Tg, T~,and T1 are clear. With increasing Nd203 concentration,
the crystallization temperature increases;

6 7w1% Nd 0
I

25
20

2 7w1% Nd203

15

1 4wt% Nd203

/\

O5~%Nd 0

/\

200

. .

Temperature )~C)

Fig. 4. DTA traces of 5Na2O-2OZnO-75TeO2 glasses with various


concentrations ofNd203.

the intensity of the crystallization exotherm is


reduced;
the glass transition temperature only slightly increases; and
the liquidus temperature increases slightly.

194

J.S. Wang eta!. / Optical Materials 3(1994) 18 7203

According to Hrubys criterion:


HR(T T )/(T T)

~2

where HR (Hrubys Ratio) is a measure of glass stability. The closer T1 is to T~(the maximum ofexotherm), the better is the glass stability. Nd2O3 addition
not only increases (Ti Tg) but also decreases
(T1 T~)for 5Na2O-2OZnO-7 5TeO2 glasses, both of
which are favorable to improving glass stability. Note
the different roles of Nd203 and Na2O play in increasing glass stability. The former may participate
in prohibiting crystalline formation whereas the latter act mainly as network breaking agents to decrease
the liquidus and glass transition temperatures.

3.2. Tellurite glassfiber


3.2.1. Fiber loss
To estimate the intrinsic minimum loss of tellurite
glass fiber, the V curve is generated by the following
equations [23]:
4

a0=A0(l/..t )+B0exp(B1/).)+C0exp(C1/A),
(3

,~

where A0, B0, B1, C0 and C1 are constants. The first


term indicates a loss that is due to light scatteringfrom
microscopic density and composition fluctuations in
the material. These effects decrease rapidly with increasing wavelength. The second and third terms describe, respectively, losses due to ultraviolet absorption from the electronic band edge (Urbach tail) and
infrared edge losses arising from multiphonon absorption. With an assumption ofa single component
of tellurite glass, the first term could be calculated by
the following equation, as described in Ref. [23].
~ 3 8 2Q1 p
8 31 2
03~
n p
-~~r
~,n 1,~2~I~
~
,,

,,~

where n is the refractive index of glass, p is the average photoelastic


constant,
/3 is the temperature
isothermal cornpressibility,
Tg is the
glass transition
and
k is Boltzmanns constant.
The second and third terms of Eq. (3) are used to
fit the experimental data on the UV and infrared
spectra of fibers, bulks and film. The fitting parameters for the tellurite, fluoride and chalcogenide glasses
are listed in Table 7. The projected minimum loss of
the tellurite glass fiber is calculated to be around
3.6 x 1 0~dB/km and the minimum loss wavelength

to be 3.02 jim, which are both comparable to the


fluorideglass. Butthelossisaboutoneorderofmagnitude better than the chalcogenide glass. The V curve
for the tellurite glass is given in Fig. 5. With OH
absorption present at 3.33 and 2.86 jim, the predicted minimum loss would be shifted to 1.8 x 1 0_2
dB/km at 1.9 jim. However, the measured minimum
loss for fiber is about 0.9 dB/m at 1.35 jim. The high
loss are probably due to the starting powder impurities, crucible contamination, and melting in air. The
fundamental lattice vibration of tellurite glass, observed in thin film samples, is 690 cm~,as shown in
Fig. 5.
Presently, we are using the (i) rod and tube method
and (ii) suction technique for preform fabrication.
The result is a fiber geometry with core diameter 5
jim (core composition Nd203-l.5Bi2O3-6Na2O1 5.5ZnO-77TeO2) and overall fiberdiameter 125 jim
(cladding composition 5Na2O-2OZnO-75TeO2).
Tellurite glass fibers with losses less than 1 dB/m have
been achieved. The loss spectra are shown in Fig. 6.
Tellurite glass fibers with 1.4% fracture strain, measured by the two point bending test, have been obtamed, as listed in Table 8. However, many techniques have also been developed to introduce rare
earth ions in the core of the fiber, i.e., solution doping [24], chelate vapor deposition [25], aerosol
doping [26], the sol-gel method [27], and the powder-in-tube method [28].
3.3. Spectroscopic properties of rare earth in tellurite
glass
In contrast to silicate, borate, fluorophosphate and
fluoride glasses, which have been investigated extensively as laser glasses, tellurite glasses have not recerred much attention. Among the many lasing
wavelength of 3~
rare
ions,has
only
one
rare earth
at earth
1.06 jim)
been
reported
in a
transition
(Nd
bulk
tellurite
glass [29].
.

3.3.1. Nonradiative relaxation


Since the role of multiphonon electron-lattice relaxation is so critical in determining the efficiency of
fluorescence, studies of the multiphonon nonradiative rate in various hosts have been reported
[9,30,31]. They have shown that when the phonon
occupation number is smaller than 1 and coupling

J.S. Wang eta!. / Optical Materials 3 (1994) 18 7203

195

Table 7
Fitting parameters for Eq. (3) in various glasses.
Glass [Ref.]

Rayleigh scattering
loss (dB/km)
4

Te0

2 [this work]

0.29/A

5i0

2 [50]
BaF
2-GdF3-ZrF4[23]
GeS
3 [23]

Ultraviolet absorption
loss (dB/km)

Infra-red absorption
loss (dB/km)

Projected minimum
loss (dB/km)
(atA [jim])

6.47x l06
exp(9.84/A)

5.75x 1015

3.5x l0~

exp(

3.4x 1011

2.56x10
exp(6.76/A)
5.26x l0~
exp(15.2/A)

exp(31.4/A)
2.82xl06
exp(163/A)
5.63X 1012
exp(l64/A)

0.70/A
4
0.112/A
4
3.97/A

126.67/A)

(3.02 jim)
l.2xl0~
(1.55 jim)
l.1x103
(3.44 jim)
1.1 X 102
(4.54 jim)

16
Fundamental Lattice Vibratiorr

Table 8
Comparison of fiber strengths of various glasses in two-point
b d

12

OH Absorption
8

1k

Film

_______________

~~Ik

.4

2,
3
Log(Wavelength, 5m(

0.2

10

30

Fig. 5. The projected loss spectrum and measured minimum loss


for Na
20-ZnO-Te02 glass fiber; Eq. (3) was employed to fit the
experimental data on UV and infrared spectra of fibers, bulks,
and film. Curve 1: electronic edge; Curve 2: infrared edge with
OH presence; Curve 3: infrared edge without OH presence;
and Curve 4: Rayleigh scattering.

Fracture strain

Tellurite glass

Silica

Fluoride glass

(%)

fiber
1.4%

fiber
67%

fiber
0.42%

with the phonon is weak, the internal multiphonon


relaxation transition probability, Wm~,can be given
by
Wmi.t = /3[ n (w, T) + 1 ] exp ( azS.E)

(5)

where /3 is a constant characteristic of the host material, LiE is the energy gap between two successive 1evels, and a is expressed by
a=(hw)_i(ln
p
l
\. g(n+l)

3500
.3000
E
~25OO

__---

~ 2000

iooo

~
.~

~ma=

500

_~

~__

0
1000

1100

1200
1300
1400
Wavelength )nm)

1500

(hw)~ln(e)

(6)

where g is the electronphonon coupling constant (~


is the coupling constant), hw is the energy of the
phonon which contributes predominantly to the relaxation process,pis the numberofphonons emitted
intheprocess,namelyp=AE/hw,andnisthephonon
occupation number defined through the Bose-Emstein equation as

-~7;;~

~z~

1500

1600

Fig. 6. The absorption spectraof tellurite glass fibers. Core: Nd2O31 .5Bi2O3-6Na2O-l 5.5ZnO-77TeO2. Cladding: 5Na2O-2OZnO75TeO2. (a) Core diameter 45 jim, fiber OD 85 jim. (b) Core
diameter 5 jim, fiber OD 155 jim.

n = [exp(hw/kT)

1]

(7)

a, /3 and e are dependent on the host but independent


of the specific electronic level of the rare earth from
which the decay occurs.

J.S. Wang et al. / Optical Materials 3 (1994)187203

196

From the equations above, it is clear that for a given


glass the probability of non-radiative relaxation between two electronic levels decreases with increases
in the energy gap AE and in the number of phonons
required to bridge the gap, provided that there is no

pulling possible. Their high index is also desirable,


since it increases the local field correction at the rare
earth site, leading to large radiative transition probabilities [32]. The fluorescence spectrum of a PrSh~
doped Te02 glass, pumped at 1.02 jim, is shown in

significant change in the value of e. Table 9 presents


typical values for various glasses [48,49]. Therefore,
the nonradiative transition rate decreases in the
sequence: Phosphate> Silicate> Germanate> Tellurite> Fluoride> Chalcogenide. Tellurite glasses
have the lowest nonradiative transition rate among
oxide glasses. In the case of 5Na2O-2OZnO-75TeO2,
the highest phonon energy is about 690 cmi, based
on infrared measurements of glass film. It is interesting to note that while chalcogenides have the lowest
nonradiative
rate, their
coupling
constants
one
order
of magnitude
higher
than heavy
metalareoxide
glasses.

Fig. 7. The peak fluorescence appears at 1.33 jim and


the bandwidth is around 90 nm. Table ] 0 summarizes the Judd-Ofelt parameters as well as calculated
and measured lifetime values. The fluorescent lifetime calculated from Judd-Ofelt parameters is 460 jis
and the measured lifetime is 22 jis. Therefore, the radiative quantum efficiency is expected to be around
4%. The e-folding times obtained from fluorescence
measurements suggest that the quantum efficiency of
tellurite glasses
is comparable
that [6].
of the first re3~in ZBLAN
fluoridetoglass
ported
Pr way of increasing the performance ofthese
Another
glasses is by codoping with another rare earth ion in
order to improve absorption of the pump. The fluorescent spectrum of a Yb3~-codopedPr3~tellurite
glass is also shown in Fig. 7. The spectrum demonstrates reasonably efficient energy transfer from the
2F
3~to the G
3~so that the
312 level
ofYb of the Pr3 4level
weak
absorption
level ofPr
does not limit the
pump efficiency. In ZBLAN it was shown by Ohishi
et a!. [33] that direct pumping of Pr34 alone is more
efficient than pumping by energy transfer from Yb3 4.
To utilize this advantage, long lengths of
Pr34 : ZBLAN fiber are required. Given the high
background optical loss for the tellurites, Yb34-Pr34
codoping may be favored because a given inversion
(and gain) can be obtained in a shorter length fiber.
Fig. 8 presents the comparison of fluorescence spectra of tellurite, fluoride and chalcogenide glass hosts
doped with Pr3~.The emission bandwidth in tellurite glass is the smallest, around 88 nm. However, the
peak emission has been shifted from 1.32 jim in

3.3.2. Spectroscopic properties ofPr~,Nd3t Ho3~,


Er3~,and Tm3~in tellurite glasses
In this section, the spectroscopic properties of Pr3
Nd3~,Ho3~,Er3~,and Tm3~in tellurite glasses will
be discussed. At particular, a comparison of the selected properties for different glasses are listed,
~,

3.3.2.1. Spectroscopic properties ofPr3 4


One approach to achievinggain at 1.3 jim is to use
Pr34~in a host with lower phonon energy than silicate
glasses. Glass hosts with lower characteristic phonon
energies are expected to provide an environment with
considerably lower non-radiative decay rates, which
is more favorable for 1.3 jim emission in Pr34-doped
glass.
Tellurite glasses are being investigated because they
combine the desired lower phonon energies with
thermal and mechanical properties which make fiber
Table 9
Typical nonradiative parameters for different glass hosts [49]
Glass

fl(s~)

a(cm)

hw(cm~)

Phosphate
Silicate
Germinate
Tellurite
Fluoride
Chalcogenide

5.4x 1012

4.7X

1.4x1012
3.4x101
6.3x lOb
l.88x10
lxlO6

l0~
4.7x103
4.9xl03

1200
1100
900

0.0037
0.0057
0.013

47x l0~

700

0.037

10~
2.9x103

500
350

0.056
0.36

5.77X

J.S. Wangeta!. /
12

Optical Materials 3

..---

trend: silicate (32 nm) > tellurite (27nm) > phossult implies that tellurite glass has less multiple-sites
34 and/or less crystal field splitbroadening
for Nd
phate
(21silicate
nm)
> fluoroberyllate (19 nm). This reting
than
glass. TheJudd-Ofelt parameters and
calculated lifetimes for the 4F
312 level are listed in Table 11. Again, the more covalent the glass, the greater
spectroscopic and laser properties among various
is its radiative transition rate. The comparisons of

Ibi

610.
6

197

(1994) 18 7203

2
~
1200

1250

3H

1300

13521400

Wavelength nm)

1450

1500

34 in (a) 5Na

Fig. 7. G4. 5 fluorescence


spectra of5Na
Pr
2O34-codoped
2OZnO-75TeO2 glass, (b) Yb
2O-2OZnO-75TeO2
glass.

fluoride glass to 1.33 jim in tellurite and chalcogenide glasses due to the nephalauxetic effect. As
Jrgensen et al. [34] described, the Q2 parameter is
strongly affected by covalent chemical bonding and
the Q4 and Q6 parameters are related to the rigidity
of the medium in which the ions are situated. Therefore, a large Q2 indicates a greater degree of covalency and longer emission wavelength, as indicated
in Table 11 and Table 12.
34
3.3.2.
2. Spectroscopic
ofNd1.3 jim amplifiAlthough
our goal isproperties
to optimize
cation, we began with the 1.06 jim characterization
ofNd34-doped tellurite glass, since numerous results
on both materials and devices with Nd3 + operating
at 1.06 jim are widely available. A comparison of
4F
41
312e 1112 emission among several typical glasses,
including Na2O-Te02 glass, is shown in Fig. 9. Their
emission peak wavelengths are quite different: 1046
nm for fluoroberyllate, 1052 nm for phosphate, 1062
nm for silicate, and 1065 nm for tellurite glasses. Additionally, their emission full widths at half maximum height are also different with the following
Table 10
TheJudd-Ofelt parameters, calculated and measuredlifetimes,
Glass
Q
(pm2)
(pm2)
2 2)
24
Q6
(pm
ZnNaTe
8.7
9.1
8.7
ZBLAN
1.4
4.2
4.9
LaGaS
9.8
2.8
5.5

glasses are given in Table 12. The laser wavelengths


varies from 1.306 jim in fluorides to 1.34 jim in silidates, and in tellurite and chalcogenide glasses to 1.37
jim. Generally speaking, tellurite and chalcogenide
glasses have larger absorption and emission cross sections in comparison with other oxide and halide
glasses.
Neodymium-doped tellurite glass appears to be a
less promising material for 1.3 jim applications because the excited state absorption eliminates gain in
much of the target wavelength region, and there is a
+ in Te0
red3shift
of this emission. The 1.3 jim transition for
Nd
2 glasses has not been studied very much.
It is conceivable that tellurite glasses lower the ESA
and/or shift it toward shorter wavelengths.
3.3.2.3. Spectroscopic properties ofEr3 ~
Erbium doped glasses were first investigated for
eye-safe range finders, but more recently have received a great deal of attention as fiber amplifiers for
the
1.55 jim telecommunications window
[35,36,37,38].
The Judd-Ofelt parameters [39,40] and radiative
lifetimes for the transitions 41i3,2_e2Iis,2 and
Iii/2_6115/2 for R20-Te02 glass with about 1 wt%
Er2O3 dopant (where R20 = Li20, Na20, K20, Rb2O,
Cs20) and for Na2O-ZnO-Te02 glass with 1 wt%
Er203 have been reported [16]. The fluorescence
spectra of the ~Ii3,2e~Ii5,2
transition for Na2O-ZnO3Hg transition.

emission cross sections, and branching ratios ofPr~for G4e


(jis)
T

(jis)
i,,,~

ratio
Branching

(cm2)
~x
1021

Ref.

460
3240
500

22
110
300

63%
64%

8.7
3.48
10.5

[this work]
[6]
[10]

J.S. Wang eta!. / Optical Materials 3 (1994) 18 7203

198

the lifetime of the

Fluoride
0.8

~P

show any decrease but then dropped by SOlo at 2.87


Tellurite

0.6

..

0,2
0

1200

1500

12501300135014001450
Wavelength (nrc)

Fig. 8. The G

did not

.~

0,4

I13/2e~Iis,2transition

Chalcoge ide

as sensitive to Er2O3 concentration as it is in the


Na2O-Si02
mole% [16].glasses.
However, the decrease in lifetime is not
The absorption and emission cross sections, and
their difference are shown in Fig. 12 and Fig. 13 for
silicate and tellurite glasses, respectively [16]. For the
tellurite glass, the difference
haswavelength
larger val2) spectrum
at the short
ues (0.3
0.2xand
l0_20
cm width for the fluorescent
side
ofthetopeak
a wider

3H

4e 5 fluorescent spectra ofPr~in 5Na2O-20ZnO75TeO2, chalcogenide and fluoride glasses.


Table 11
Typical valuesof Judd-Ofelt parameters and calculated lifetimes
ofNd04 forfluorescence from the 4F
312 level in fluoride, silicate,
tellurite and chalcogenide glasses.
Glass

2
GLS

( Ii 5/2~ 9/2) to ESA ( L 3/2~ H1 I/2) in silicate glass

24
(pm2)

Q6
(pm2)

Tmnan
(ms)

and tellurite glass are 0.34 and 1.23, respectively. The


lineconsidered,
be
shapes of these
but based
absorption
on the total
spectra
transition
also have
probto

(pm
2.0
4.5

4.0
3.0

4.5
3.0

0.5
0.4

abilities there appears to be a three-fold improvement for tellurite glasses against the detrimental ESA

5.8
6.65

4.9
4.39

5.8
4.67

0.14
0.1

at 0.8 jim pumping. The ratios of (~Ii3,2~II5,2)


fluorescence to (41i3/2_2I9/2) ESA for silicate and tellurite glasses are 4.6 and 3.5, respectively, which are
comparable.
The three e-folding lifetime dependencies on glass
composition are given in Table 13. The three e-folding lifetime is very dependent on the glass modifiers.
It varied from 2.6 ms to 7.8 ms. For comparison, Fig.

2)

Q2

Fluoride
Silicate
BaO-TeO

spectrum on the long wavelength side (1.531.62


jim), which could make wider34-doped
bandwidth
lasersfiber
posactive
sible. Oneat 0.8
pumping
problem
jim is excited
with Erstate absorption (ESA)
[40]. The Judd-Ofelt calculated ratios of GSA

TeO2 glasses with various amounts of Er2O3 dopant


(mole% Er203=0.055, 1.085 and 7.513) are shown
in Fig. 10. They are similar for high and low concentration. As shown in Fig. 11, up to 1.46 mol% Er2O3,

3 4 in tellurite glasses ascompared to other glasses.


Table 12
Spectroscopic and laser properties of Nd
Glass
Transition Laser
Abs. coef.
wavelength
at 806 nm
(nm)
(cm)
PBLA

~I,i,2

ED2

~I,3,2
~I,i,2

ZnTe

~I,3,2
~Ibb,2
113/2

GLS

111/2

113/2

1039
1306
1060
1340
1060
1340
1077
1370

3.57
1.27
4.73
14.5

PBLA 34PbF
2-24ZnF2-35GaF3-2A1F3-3YF3-2NdF3 (mole%) [51].
ED2 60SiO2-27.5Li2O-lOCaO-2.5A12O3-0. 1 6CeO2-2.0 I 2wt%Nd2O3 [17].
ZnTe 35ZnO-65TeO2-2 wt%Nd203 [51].
GLS 3Ga2S3-0.85LaS3-O.1 5Nd2S3 [52].

AA

o~<l0_20

(nm)

(cm2)

33.0
65.0
27.8
64.4
29.0
73.0

2.75
0.85
2.9
0.72
3.6
0.76
7.95
3.60

.1.5. Wanget al. lOptical Materials 3(1994)187203

199

1,2
0.8-

I:

j:~

08

_____

1020

1040

1060
1080
Wavelength (nm(

1100

Absorption

Emission

1120
011ev

4F
41, 1/2 fluorescence spectrum ofNd3 in differFig. 9. The
ent glasses at 5,2-.
295K;fluoroberyllate (A), phosphate (x); silicate () [30]; and tellurite glasses.

1500

1600

Wavelength

1700
-

(crc)

Fig. 12. Absorption cross section, emission cross section andtheir


difference for Er
203 in Al203-Si02 glass.

1.212

1430

1480

1530
1580
Wavelength (nm)

1630

1680

3 at 0.055 mole% (1),


1.08510.mole%
(2) and 7.513spectra
mole%of(3)
Fig.
The fluorescence
Er Er
203.

04
1400

1500

1600

Wavelength

1700

(nnli

Fig. 13. Absorption cross section, emission cross section and their
difference for Er203 and 5Na2O-2OZnO-75TeO2 glass.

________

5.

~Silicate
\~

_______

_______

________

________

emission spectra as a function of composition [41],

________

Tellarite~
_______

almost all spectra in the tellurite glasses are similar in

emission widths, number of main maxima, and


structure details. They are slightly different in the intensity ratio. In fact, the possibility of rare earth ions
entering in the Te02 network [40] was proposed to

-_______

ii

6
Er 0, vrvi hr

. .

Fig. 11. Lifetimes for the Ii3/2~ 115/2 transition at 1.54 jim as a
function of the Er203 concentration in Na20-2SiO2 [41] and
5Na2O-2OZnO-75TeO2 glasses.

14 presents the fluorescence spectra ofEr3~in tellurite, silicate and fluoride glasses. It indicates the sensitivity of fluorescence spectra on hosts, not only in
the fluorescence
wavelength buthave
alsobeen
the peak
width.
More thanpeak
50 compositions
prepared and their emission spectra were investigated.
A few typical samples are shown in Fig. 15. Unlike in
the silicate glasses, which show a great variety of

explain the smaller dependence on the glass modifiers. Note that the emission width in most tellurite
glasses is wider than in silicate based glasses.
3.3.2.4. Spectroscopic
Tm~4
34,properties
Nd34 andof
Pr34,
thulium (III)
Er earth ion, which has been intenionInisaddition
anothertorare
sively studied for use in optical amplifiers [41,421.
Both 2.3 jim (3H
3H
3F
3H
4~
5)and 1.88forjimchemical
( 4e sen6)
3
are attractive
emissions
in Tm
sing,
medical
and atmosphere transmission applications, and the 1.47 jim emission is near the third telecommunication window ofsilica fiber. Additionally,
Tm34 has a strong absorption band around 0.79 jim

200

J.S. Wang et al. / Optical Materials 3 (1994) 18 7203

Table 13
3 on glass composition.
Lifetime dependence of ~I,3,2~I,5f2
transition of Er
Composition (mole%);
Er
203 (wl%)
e, (ms)
(l00x)%Te02+x%;X=

e2 (ms)

e3 (ms)

PbO-B203-W03-La203
l5%B203
5%Nb205
lO%P2O5
l0%Ge02
25%W03
15%TiO2

0,99
1.29
1.15
0.1
1.22
1,19
1.65

2.64
3.08
3.91
4,03
4.10
5.29
5.74

2.59
3,13
4.15
4.49
4.22
6.14
5.88

2.64
3.22
4.42
5.05
4.42
6.51
6.08

7%La2O3

1.03

6.25

6.66

7.03

l0%Na20-lO%TiO2
18%Bi2O3
10%Bi203-l0%Ti02

1.29
1.42
1.04

6.45
6.98
7.15

6.45
7,13
8,06

6.49
7.37
9.03

30% BaO

1.16

7.88

7.37

7.62

12-

rozirconate fiber lasers [42] have been reported, as


we described previously, the former suffer from in-

~~

0.8.

herent high phonon energy and the latter from their


poor glass stability and chemical durability. The lowest phonon energy of Te02 glass is around 600 cm

,,,,,,,,,,,

06
~ 54.

______

______

______

______

______

02-

01420 ~

1470

1~0

I ..

1670

1620~-,..

lb

3 in tellurite (x

), silicate

Fig.
(A) 14.
andThe
fluoride
fluorescence
glasses spectra
(0). of Er
1 4

______

_______

which is less than Si02 glass (1100 cm ) but larger


3Hit is3H
than fluoride glass (500 cm i)~ Since
necessary
to have 5 and 6 phonons to bridge the 4 5 (4500
3F
3H
cm) andwe 4~
cm~)transitions,
respectively,
expect 6(5300
Te02 glass
will provide much
jim
andquantum
1.88 jim.efficiencies than Si02 glass at 1.47
higher
For 1.47 jim lasing action to occur, it is necessary
to quench the relatively long-lived lower laser level to
eliminate the self-terminating behavior of -thulium.

______

Otherwise, the advantage of four level laser system in

1.2

thulium will be lost. Codopingwith terbium


[44] and holmium [45] for thulium in the fluoride
glasses has been demonstrated. The results indicated
that holmium codoping decreased the lifetime of the
lower laser level by nearly two orders of magnitude
with much less effect on the upper laser level. Therefore, Ho3 was selected for quenching the lower laser
level ofTm3 emitting at 1.47 jim.
In order to obtain an efficient system, it is always
trivalent

21 08
______

06
04

4)(
~

/ I
7,I
/

______

______

______

______

~-~

-.,~

0 ~
1430

N~

0.2

~
~

1480

1530
1580
Wavelength (om)

1630

1680

Fig. 15. The fluorescence spectra of Er3~in R

necessary to keep the doping concentration below a

20-ZnO-Te02
glasses, R=Rb (l),Li (2), Cs (3),K(4), and Na (5).

certain value, which depends on the host and the

3H
3F
( 6e 4) which is a convenient pumping wavelength for 3-doped
A1GaAs semiconductor
diode
Alsilica fiber lasers
[43]lasers.
and fluothough Tm

quenching mechanisms. This phenomena, so-called


concentration quenching, is caused by the strong
coupling
amongonactive
ions themselves.
The
tration effects
the lifetimes
of 3F
3Hconcen4 and 4 levels

J.S. Wang et aL / Optical Materials 3 (1994) 18 7203

of Tm3~and Tm3-Ho34-codoped barium tellurite


glasses have been reported recently [46]. It has shown
that for 1.47 jim emission in the 1 lBaO-89TeO
2 glass,
Ho2O3 is a very efficient co-dopant to eliminate
3F population in the long-lived lower laser level ( 4) without decreasing the upper laser level population. For
example, 3F
up to 0.8 wt% Ho203 can be added to reduce the
3H 4 lifetime 83% with only a 5% reduction
in the 4 lifetime, and the upper limit ofthe thulium
concentration is around 0.4 wt% in order to avoid
concentration quenching via the two-for-one process
(see Figs. 2a and 2b in Ref. [46]). Moreover, since
tellurite glasses have lower phonon energies in comparison with silicate glasses, tellurite glass as a host
could
improve3).
the efficiency for lasing at ].88 jim
3F 3H
( Fig.
4 166, illustrates
Tm
the emission spectra of Tm3 +

from
It
is clear
3H that the
3F dependencies on the concentration
creased
4 of
and
the
4 levels
0.2,as
0.4,
the0.8
concentration
and 1.6 wt%was
[46].
in34in
theorder
3H
3F
of Tm
4 and 4 emission intensities
are
3H
in opposite directions, that is, the relative 4 emission intensity decreases
3F with increasing Tm2O3 concentration,
theto the
4 emission
intensity
increases.
The
reason but
is due
existence
of a cross-relaxation process occurring between 3H 3F
4-+ 4 and
3H 3F
4. This3Fprocess results in two ions remaining
in 6.
the excited
tion of the 3H 4 state at the expense of the popula4 state and is usually referred to as the
two-for-one conversion,
illustrated in Fig.
16. Fig.
3asconcentration
increases
in
1 7 shows
the
order 0,that
0.2,the
0.4,Ho
0.8 and 1.6 wt% [46], while the
Tm3 concentration is held at 0.2 wt%. All peaks are
normalized with respect to the 1.47 jim peak. It is
clear that 1.8 jim Tm3 emission decreased remarkedly due to the increase ofthe Ho
2O3 concentra__________________________________

________________________________
1300

1400

1500

1600
1700 1800
Wavelength nm)

1900

2000

2100

3 at various concentrations in

BaO-Te0
Fig. 16. Emission spectra of Tm
2 glasses (1=0.2, 2=0.4, 3=0.8, 4= 1.6 wt% Tm203)
[46].

201

1
0,9
0,8
~O,7
.06
-~ 0.5
0 0.4

0,2
01300 1400

1500 1600 1700 1800 1900 2000 2100 2200 2300


Wavelength
nm) wt% Tm
3 (0.2

Fig. 17. Emission spectra of Tm


203) codoping
with various concentrations of Ho203 in BaO-Te02 glasses (1=0,
2=0.2,3=0.4,4=0.8,5=1.6 wt% Ho203) [46].
__________

Silicate ~

09

__________
_______

__________

~Tellu6te

Emission

0.6

______

83
__________

1300

__________

__________

1600 Wavelength (cm) 1900

3F 3H 2200
Fig. 18 The3
absorption
andand
emission
in tellurite
silicatespectra
glasses.ofthe 4 6 transition ofTm

tion, but 1.47 jim emission slightly3decreased.


This3is
(3F
due to energy transfer from Tm
4) 3
to Ho
emis(5J~),This led to an apparent increase ofHo
sion at 2.05 jim. Fig. 18 shows the overlap
ab3 + atof3Fthe 3H
sorption
andItsemission
Tm 117 nm,
4and6
transitions.
red shiftspectra
is large,ofabout
the emission linewidth is wide, around 234 nm, both
ofwhich are a little bit less than that of silicate glasses
with a red shift of 136 nm and an emission width of
260 nm [47], as shown in Fig. 18. This result makes
3 a good candidate for a tunable fiber laser source
Tm
around 1.9 jim. Additionally, the emission peak
wavelength has been shifted to a longer wavelength
in tellurite glass which is favorable for air transmission applications. Moreover, the strong two-for-one
process with a concentration optimization could further improve the 1.9 jim emission. Although this is
as three level system (3F 3H
4 6 transitions), it will not
be a serious problem with a strong pumping source
available, e.g. AlGaAs. Note that in a three level sys
tern the branching ratio is always one (as shown in
Table 14) while in four level system the branching
ratio is usually considerably less than one.

202

J.S, Wang eta!. / Optical Materials 3 (1994) 18 7203

Table 14
Judd-Ofelt parameters, Q2= 5.7 0.4,

Q4=

1.40.3,

Q6=

3 in BaO-Te0

1.6 0.1, and selected transitions of Tm

2 glass.
tr~d~abivn,
J.tS

)~(emission), nm
1800
2300
1470
800

Transition
3F 3H
3H4 3H6
3H,,3F
4 5
3H 3H4
4 6

4. Conclusions
Tellurite glasses possess (i) a reasonably wide
transmission region (0.355 jim), (ii) good glass
stability and corrosion resistance, (iii) a relatively low
phonon energy spectrum among oxide glass formers,
and (iv) high linear and nonlinear refractive indices.
We have studied the glass formation and properties
of rare earth ion doped tellurite glasses. Glass cornpositions based on Na20-ZnO-TeO2 showed excellent properties in terms of UV edge, chemical durability, rare earth solubility, stability, viscosity and
fiberization. Tellurite glass fiber with a loss less than
1 dB/m has been achieved by using the rod-in-tube
fabrication method. As compared with silicates, rare
earth elements in tellurite glass generally have lower
nonradiative decay rates, larger values of the radiative cross section (or transition strength), shorter
fluorescent lifetimes, and a red shift of the radiative
transitions. The emission spectra seem less sensitive
to glass modifiers
in tellurite glass than in silicate
3, Er3.
glass, i.e. Nd
Acknowledgement
The authors gratefully acknowledge the support of
the Fiber Optic Materials Research Program at Rutgers and the New Jersey Commission on Science and
Technology.

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