Optical Materials 57 (2016) 236e242

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Optical Materials
journal homepage: www.elsevier.com/locate/optmat

2 mm emission properties and hydroxy groups quenching

of Tm3þ in germanate-tellurite glass
Muzhi Cai, Yu Lu, Ruijie Cao, Ying Tian, Shiqing Xu, Junjie Zhang*
College of Materials Science and Engineering, China Jiliang University, Hangzhou, 310018, China

a r t i c l e i n f o a b s t r a c t

Article history: Tm3þ activated germanate-tellurite glasses with good thermal stability and anti-crystallization ability
Received 10 January 2016 were prepared. Efficient 2 mm fluorescence was observed in the optimal concentration Tm3þ doped glass
Received in revised form and the corresponding radiative properties were investigated. For Tm3þ: 3F4 / 3H6 transition, high
22 February 2016
spontaneous radiative transition probability (260.75 s1) and large emission cross section
Accepted 31 March 2016
(7.66  1021 cm2) were obtained from the prepared glass. According to Dexter's and Forster's theory,
Available online 12 May 2016
energy transfer microscopic parameters were computed to elucidate the observed 2 mm emissions in
detail. Besides, the effect of hydroxy groups quenching was also quantificationally investigated based on
Keywords:
2 mm laser
simplified rate equations. Results demonstrate that the optimal concentration Tm3þ doped germanate-
Optical materials tellurite glass possessing excellent spectroscopic properties might be an attractive candidate for 2 mm
Germanate-tellurite glasses laser or amplifier.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction attention of many researchers in recent decade. The heavy metal

Lasers around 2 mm are attractive due to it is located in the
strong liquid water absorption band and the 1.5e1.9 mm high at-
mospheric transmission window. Laser around 2 mm has been used
for widely applications containing medical scalpels in surgery,
remote sensing of atmospheric CO2, N2O and H2O, coherent laser
ladar, and infrared countermeasures [1,2]. Fiber lasers are desirable
owing to its compact structure, low heat effect, high electro-optical
conversion efficiency, good beam quality and so on [3]. Especially in
medical field, fiber lasers can be used in some application that
limiting other solid-state laser such as arthroscopy and urology
surgery [4].
Tm3þ is a suitable candidate to obtain 2 mm laser because its
efficient absorption of the 800 nm excitation beam through the
3
H6 / 3H4 transition, which overlaps with the emission band of the
commercially available AlGaAs laser diodes. A quantum efficiency
can be achieved to 200% because of the cross-relaxation (CR) en-
ergy transfer (3H6 þ 3H4 / 3F4 þ 3F4) between Tm3þ ions [5]. Till
now, Tm3þ: 1.85 mm laser output has been realized in various glass
host [6e9]. Among those glasses host, the heavy metal oxide
glasses including germanate and tellurite glass have attracted
* Corresponding author.
E-mail address: jjzhang@cjlu.edu.cn (J. Zhang).
oxide glasses have better thermal stability, chemical durability and
mechanical strength than fluoride glass, and lower phonon energy
which is good for spontaneous radiative transition than silicate
glass. In 2010, a femtosecond mode-locked Tm-doped germanate
fiber laser was achieved with output wavelength at 2.05 mm [10]. Its
slope efficiency and output power is as high as 50% and 190 mW,
respectively. An output power of 280 mW with a slope efficiency of
76% laser has been obtained in Tm-doped tellurite fiber in 2008 [9].
So, germanate and tellurite glass has a great potential to achieve
2 mm lasers.
Compare with tellurite glass, germanate glass has better thermal
stability but higher phonon energy. Fortunately, the germanate-
tellurite glass can take good advantage of both germanate and
tellurite glass, which could be a promising material in realizing
2 mm lasers. However, few researches have been focused on the
detailed mechanism of 1.8 mm in germanate-tellurite glass. In order
to develop Tm-doped germanate-tellurite glasses or fibers for ap-
plications in 2 mm laser, the identification of the optimum Tm3þ
concentration and hydroxy groups quenching the mid-infrared
emissions should be considered. In this work, a series of different
concentrations of Tm3þ doped germanate-tellurite glasses have
been prepared, and the optimal concentration has been found.
Moreover, the energy transfer between Tm3þ ions and to hydroxyl
groups have been quantificationally calculated. The results suggests
that the 1.25 mol% Tm3þ concentration doped germanate-tellurite

http://dx.doi.org/10.1016/j.optmat.2016.03.055
0925-3467/© 2016 Elsevier B.V. All rights reserved.
 M. Cai et al. / Optical Materials 57 (2016) 236e242
glass with oxygen bubbling during melting is a promising material
for 2 mm lasers application.
2. Experiments
The Tm3þ doped germanateetellurite having chemical compo-
sition (mol%) 75(GeO2þTeO2)(20x)(K2O þ Nb2O5)
4.25La2O3xTm2O3(x ¼ 0.25, 0.5, 0.75, 1.0, 1.25, 1.5) were prepared
by traditional melt-quenching method with high purity reagent as
raw materials donated as GTT1-GTT6, respectively. Moreover, the
composition of x ¼ 1.25(GTT5) was prepared with oxygen bubbling
during melting donated as GTT5O. Before melting the powders in a
SiC-resistance electric furnace, the molar masses were weighted,
mixed and dried. The mixtures were homogenized and melted at
1200  C in a covered alumina crucible in furnace. The homogeneous
melt was poured onto a preheated brass mould and annealed for
several hours around 450  C in a muffle furnace, and then allowed
to cool slowly inside the furnace by turning the power supply off.
The two-face polished sample has plate shape with
10  10  1 mm3 for optical measurements.
The refractive index of the host glass was measured by the prism
minimum deviation method at four wavelengths, 633, 1311and
1539 nm, and they are 1.7411, 1.7351, and 1.7295, respectively. The
resolution of the instrument is ±0.5  104. The standard deviation
in refractive index at different points of the same glass is around
±1  104. The refractive index dispersion curve was calculated by
Cauchy's formula n(l) ¼ aþb/l2þc/l4, where a, b and c are found to
be 1.71, 5.055  104 and 1.54  1010 respectively. The density of
the glass was measured by Archimedes method using distilled
water as buoyancy liquid at room temperature. As a part of struc-
tural investigation on the glasses, thermal relaxation properties
were measured using a differential scanning calorimeter (DSC). The
characteristic temperatures were performed with a NETZSCH STA
409 PC/PG under Ar atmosphere at the heating rate of 10 K/min.
The structure of glass was analyzed using Raman spectra, which
were measured with a FT Raman spectrophotometer (Nicolet
MODULE) in the spectra range 100e1000 cm1. The analysis of
Tm3þ ions absorption was carried out using a Perkin-Elmer-Lambda
900UV/VIS/NIR spectrophotometer in the range of 350e2200 nm.
X-ray diffraction patterns (XRD) were recorded from glass powders
in a Bruker D2 PHASER Diffractometer with Cu Ka radiation
(l ¼ 0.154 nm). Photoluminescence spectra in the ranges of
1700e2000 nm were determined via a combined fluorescence
lifetime and steady state spectrometer (FLSP 980) (Edingburg Co.,
England), which was detected with a liquid-nitrogen-cooled PbS
detector using an 808 nm laser diode (LD) as an excitation source.
The same experimental conditions for different samples were
maintained so as to get comparable results. All the measurements
were performed at ambient temperature.
3. Results and discussion
3.1. Thermal stability
The differential scanning calorimeter (Netzsch) curves were
measured for characteristic temperatures (temperature of glass
transition Tg, temperature of onset crystallization Tx, and temper-
ature of peak crystallization Tp) as shown in Fig. 1(a). As an
important factor for laser glass, Tg of the prepared samples (550  C)
is higher than that of germanate-tellurite glass (431  C) [11] and
comparable to germanate-tellurite glasses (550  C) [12](582  C)
[13], which gives glass good thermal stability to resist thermal
damage at high pumping intensities. Glass optical fibers are
currently drawn from preforms, which means that the glass crosses
twice the thermal range of instability: first on cooling for preform
237
manufacturing and then on reheating for fiber drawing. Hence, the
anti-crystallization ability is a vital requirement for glass. The DT
(Tx -Tg) has been frequently used as a rough indicator of the glass
formation ability or glass stability against crystallization, and large
DT is beneficial to the fiber drawing [10]. However, the Tx can hardly
be observed during 300e800  C as shown in Fig. 1(a). So, we
guessed that the prepared glass has a great anti-crystallization
ability. To validate the assumption, the prepared glass was put in
the furnace increasing the temperature to 800  C in 90 min, and
then allowed to cool slowly inside the furnace by turning the power
supply off. It is found that the prepared glass has been melted and
kept transparent. Moreover, the melted glass was pulverized to
perform X-ray diffraction measurements. The X-ray diffraction
measurements shown the typical glassy state as illustrated in
Fig. 1(b), which demonstrated that the prepared glasses indeed
have a great anti-crystallization ability that are good for fiber
drawing.
3.2. Absorption spectra and J-O analysis
The absorption spectra were obtained at room temperature over
a wavelength region of 300e3300 nm. The absorption spectra of
the prepared samples at room temperature is shown in Fig. 2, and
the absorption bands centered corresponding to the transitions
from the 3H6 ground state to the exited stated of 3F4 (1694 nm), 3H5
(1208 nm), 3H4 (792 nm), 3F2 þ 3F3 (686 nm) and 1G4 (492 nm),
respectively. The transitions to energy levels higher than 1G4 are
not observed because of the intrinsic band gap absorption of host
glass. In order to investigate the local environment around Tm3þ
ions, J-O intensity parameters have been calculated by fitting the
experimental and calculated oscillator strengths based on absorp-
tion spectra and J-O theory [14,15]. The detailed calculation pro-
cedures have been well described elsewhere [16].
Table 1 compares the JuddeOfelt parameters of Tm3þ ions in
silica, germanate, tellurite, fluoride and the prepared glasses. The
U2 parameter is closely related to the hypersensitive transitions
which is related to the covalency parameter through nephelauxetic
effect and it is attributed to the increasing polarizability of the li-
gands around the rare earth ions [17]. A high polarizability of ox-
ygen at the rare earth site mainly owe to a large field strength. It can
be seen that the polarizability of oxygen at the Tm3þ ions site of the
prepared germanate-tellurite glass is higher than those of other
glasses except germanate glass. By the crystal field parameter, the
asymmetry of the rare earth sites can affect the value of U2 as well
[18]. Meanwhile, compare with U2, U6 depends less on the envi-
ronment but is more dependent on the overlap integrals of the 4f
and 5d orbits [19].
Table 2 gives the radiative transition rates, branching ratios,
radiative transition probability and lifetime of different transitions
from Tm3þ. It can be found that the radiative transition probability
of the Tm3þ:3F4 is calculated to be 260.75 s1. The high radiative
transition probability may provide a good opportunity for glass to
obtain laser actions. The root-mean-square error drms is
0.26  106.
3.3. Fluorescence spectra and stimulated emission cross-section
The fluorescence spectra during 1700e2200 nm of the glass
samples doped with different Tm2O3 concentrations were
measured pumped at 808 nm as shown in Fig. 3. With increasing
Tm2O3 concentration, the intensity of 1.8 mm emission increased
firstly then slightly decreased, and the maximum fluorescence peak
intensity for the prepared germanate-tellurite glass is observed
around 1.25 mol.% Tm2O3(GTT5). Hence, the optimal 1.8 mm fluo-
rescence spectra are selected to calculate emission cross sections in
238 M. Cai et al. / Optical Materials 57 (2016) 236e242

Fig. 1. (a) DSC curve for germanate-tellurite glass with heating rate of 10 K/min. (b) X-ray diffraction patterns for the secondary melted glass.

probability. lI(l) is the emission spectrum, and n and c are the

refractive index and light speed in value, respectively. Moreover,
Based on emission cross section, sem(l), absorption cross section
(sabs(l)) can be obtained by Refs. [25],
  
Zl hc 1 1
sem ðlÞ ¼ sabs ðlÞ   exp   (2)
Zu kT lZL l

where Zl and Zu are the partition functions for the lower and the
upper levels involved in the considered optical transition, respec-
tively. T is the temperature (here is 300 K), k is the Boltzmann
constant and lZL is the wavelength for the transition between the
lower Stark sublevels of the emitting multiplets and the lower Stark
sublevels of the receiving multiplets.
According to Eqs. (1) and (2), the absorption and emission cross
sections are determined as depicted in the inset in Fig. 3. It can be
seen that the peak absorption and emission cross sections at 1.8 mm
are 6.39  1021 cm2 and 7.66  1021 cm2, respectively. Higher
Fig. 2. Absorption spectra of GTT glasses. emission cross section is extremely useful for better laser actions
[26]. The emission cross sections in the prepared glass is higher
than those of silicate glass (3.7  1021 cm2) [27], germanate glass
Table 1 (4.92  1021 cm2) [28] and fluoride glass (2.4  1021 cm2) [29],
Comparison of JuddeOfelt parameters of different Tm3þ-doped glasses. but lower than the germanate-tellurite glass (13.01  1021 cm2)
Glass U2 U4 U6 Reference [12]. The product of sem  trad is another important parameter to
1020 cm2
evaluate the gain performances of prepared samples,
29.41  1021 cm2ms, which is larger than that of tellurite glass
GTT5 4.25 0.84 0.97 This work
(16.37  1021 cm2ms) [30]. However, it is interesting that the
Silica 3.7 2.3 0.6 [20]
Germanate 8.13 2.32 1.92 [21] measured lifetime of 1.85 mm emission of the prepared glass
Tellurite 3.20 2.01 1.83 [22] (671 ms), which is more appropriate to evaluate the emission
ZBLAN 2.7 1.59 1.09 [23] properties of laser glass, is larger than that of the germanate-tel-
lurite glass (482.2 ms) [12]. To explain this interesting finding, the
energy transfer processes have been detailed as well.
order to estimate the gain property in this wavelength region. The
emission cross-section were subsequently calculated by the 3.4. Energy transfer of Tm3þ ions and energy transfer to hydroxyls
following FuchtbauereLadenburg equation [24].
It is known that the contents of OH groups have an influence
l4 Arad Z lIðlÞ on mid-infrared fluorescence since residual hydroxyl groups in
sem ¼  (1)
glasses can act as the fluorescence-quenching center. To investigate
8pcn2
lIðlÞdl the hydroxyl groups decreasing the 1.85 mm fluorescence, the
GTT5O has been prepared to make a comparison between GTT5
where l is the wavelength. Arad is the spontaneous transition because oxygen bubbling during melting can effectively remove the
 M. Cai et al. / Optical Materials 57 (2016) 236e242 239

Table 2
The electric and magnetic dipole line strengths, radiative transition probability, branching ratio and radiative lifetime of Tm3þ in the germanate-tellurite glass.
P
S,L,J S0 ,L0 ,J0 Wavelength (nm) Sed  1021cm2 Smd  1021cm2 Arad (S1) b (%) trad (ms)
3 3
F4 H6 1687 32.52 260.75 100.00% 3.84
3 3
H5 H6 1210 12.7 4.074 304.04 99.28% 3.27
3
F4 4279 5.446 2.19 0.72%
3 3
H4 H6 792 15.67 1214.54 90.53% 0.75
3
F4 1493 8.470 97.99 7.30%
3
H5 2293 4.716 4.062 29.07 2.17%
3 3
F3 H6 684 10.81 1672.57 76.07% 0.45
3
F4 1150 1.745 2.538 145.90 6.64%
3
H5 1573 29.63 376.47 17.12%
3
H4 5016 9.344 3.66 0.17%
3 3
F2 H6 641 2.513 661.26 38.26% 0.58
3
F4 1034 13.00 815.52 47.19%
3
H5 1363 8.151 223.01 12.90%
3
H4 3362 15.51 28.28 1.64%
3
F3 10,196 0.7899 2.507 0.23 0.01%
1 3
G4 H6 470 2.696 999.86 45.27% 0.45
3
F4 652 0.9101 126.69 5.74%
3
H5 769 8.815 747.64 33.85%
3
H4 1156 11.03 274.75 12.44%
3
F3 1502 4.331 49.19 2.23%
3
F2 1762 1.481 10.43 0.47%

hydroxyl groups in oxide glass. Fig. 4 shows the infrared trans-

mission spectra of GTT5 and GTT5O, and the GTT5O evidently has a
higher transmittance during 2700e4500 nm, especially ~3 mm
which is mainly caused by hydroxyl groups. Moreover, the ab-
sorption spectra of GTT5 and GTT5O show that the GTT5O has a
lower absorption around 3 mm as shown in the inset in Fig. 4.
The content of OH groups in the prepared glass is expressed by
the absorption coefficient of the OH vibration band at 3 mm which
is given by Ref. [31].

LnðT0 =TÞ
aOH ¼ (3)
d

where d is the sample thickness, T is the transmittance at 3 mm, and

Fig. 3. 1.85 mm luminescence spectra of GTT glasses. The inset is cross section of GTT5.
T0 is the transmittance of the host matrix. The calculated results of
the GTT5 and GTT5O glass is 0.55 and 0.26 cm1, respectively,
which are almost half of the value of germanate glass [20].
To detailedly discuss the energy transfers to hydroxyl groups,
the energy transfer mechanism of Tm3þ have to investigate at first.
Previous studies have reported that the cross-relaxation transfer
process is good for the Tm3þ:1.85 mm emission [27]. The cross
transfer rate can be calculated by the absorption and emission
cross-sections. The extended overlap integral method is widely
used to analyze a dipoleedipole interaction energy transfer pro-
cesses. The microscopic transfer probability can be expressed by

CDA
WDA ðRÞ ¼ (4)
R6

where R is the distance between donor and acceptor, CDA is the

transfer constant defined as follows

R6C
CDA ¼ (5)
tD

where Rc is the critical radius of the interaction and tD is the

intrinsic lifetime of the donor-excited level. For the nonresonant
Fig. 4. Infrared transmission spectra of the germinate-tellurite glass. The insert of
energy transfer process, phonons participate in the process to
figure is the absorption spectra of GTT5 and GTT5O.
balance the energy gap. The transfer constant can be obtained ac-
cording to Eq. (6) [32].
240 M. Cai et al. / Optical Materials 57 (2016) 236e242

D X
∞ Z 
6cglow Sm
CDA ¼ eð2nþ1ÞS0 0
ðn þ 1Þm sDems lþ
m sabs ðlÞdl
A
(6)
ð2pÞ4 n2 gup
D
m¼0
m!

D
where c is the light speed in vacuum, n is the refractive index, glow groups. Therefore, to quantificationally calculated the energy
and gup D is the degeneracy of the lower and upper levels of the transfers to hydroxyl groups, based on the partial energy level di-
donor, respectively. Zu0 is the maximum phonon energy, agram in Fig. 5(c), the rate equations can be elucidated as follows:

n ¼ 1=ðeZu0 =kT  1Þ is the average occupancy of the phonon mode at
T. m is the amount of phonon participating in the energy transfer. S0
þ dn0    
is Huang-Rhys factor (here is 0.31) [33] and lm ¼ 1=ð1=l  mZu0 Þ is ¼ Rn0 þ A20 þ Kmp20 n2 þ A10 þ Kmp10 þ WOH n1
the wavelength with m phonon creation. The energy migration dt
(EM, 3H4þ3H6 / 3H6þ3H4) and crossrelaxation (CR,  WET n0 n2 (9)
3
H4þ3H6 / 3F4þ3F4) processes in GTT5 has been calculated, which
is listed in Table 3. It is worthy noted that GTT5O has a equal result
to GTT5 due to the almost same absorption spectrum around dn1    
1600 nm as shown in the inset in Fig. 4. The EM process is quasi- ¼ A21 þ Kmp21 n2  A10 þ Kmp10 þ WOH n1 þ 2WET n0 n2
dt
resonant, but to achieve the CR process, one phonon is necessary. (10)
Thus, CDD has a much higher value than CDA, here we can use the
hopping model to obtain the energy transfer rate WET,
dn2    
WET ¼ 13ðCDD Þ1=2 ðCDA Þ1=2 Nd (7) ¼ Rn0  A21 þ Kmp21 n2  A20 þ Kmp20 n2  WET n0 n2
dt
(11)
where nd is the concentration of donors. WET can be calculated
according to Eq. (7), and WET is calculated to be 3295  1020 cm3/s where n0, n1, and n3 correspond to the populations at the 3H6, 3F4,
as listed in Table 3. and 3H4 levels, respectively. Kmpij and Aij are the transition rates
Since multiphonon relaxation rate has a substantial impact on because of multiphonon relaxation and spontaneous transition
mid-infrared emission, a low nonradiative decay rate is required to from levels i and j, respectively. WOH is energy transitions from the
achieve strong 2 mm fluorescence. The multiphonon relaxation rate 3
F4 energy levels to OH. WETn0 is the macroscopic cross-relaxation
constant (kmp) from a given excited state can be estimated from the rate and R is the pumping rate. During the calculation, the 3H5 level
energy-gap law [34]. The multiphonon relaxation rate constant is not considered because of the fast relaxation from 3H5 to 3F4. WOH
(kmp) can be defined as, can be calculated from the decay curve of the 3F4 level. The popu-
h ip lation number of 3H4 during decay process can be described as
kmp ðTÞ ¼ beaðDE2Zumax Þ , 1  eZumax =kT (8) follows:

where DE is the energy gap between the emitting level and the
1=t2 ¼ A20 þ Kmp20 þ A21 þ Kmp21  WET n0 (12)
adjacent lower level. a and b are positive-definite constants
depending on glasses. Zumax is the highest phonon energy of the
glass. where p ¼ DE=Zumax is the minimum number of phonons
required to bridge the energy gap DE [35]. In this work, kmp is n2 ¼ n2 ð0Þexpðt=t2 Þ (13)
calculated using the parameters a ¼ 4.6  103 cm, b ¼ 6.1  107 s1 The following equation can be obtained by combining Eqs. (10),
and T ¼ 300 K reported for germanate glass [36]. GTT5O has an (12), and (13),
equal result to GTT5 as well due to the same highest phonon energy
which was shown by the Raman spectra as display in Fig. 5(a). The
multiphonon relaxation rate of 3H4 / 3F4, 3H4 / 3H6 and dn1   
¼ n2 ð0Þ A21 þ Kmp21 þ 2WET n0 expðt=t2 Þ  A10 þ Kmp10
3
F4 / 3H6 transitions are 3.65  103 s1, 5.23  1015 s1 and dt

1.87 s1, respectively. The Tm3þ at the 3H5 energy level can quickly þ WOH n1
relax to 3F4, we assume that the 3H5 energy level is not considered.
(14)
As previously stated, the energy transfer process of Tm3þ and
multiphonon relaxation rate in the GTT5 and GTT5O are the same. Due to the spontaneous transition rates (Aij) are much larger
However, the fluorescence spectrum intensity and lifetime of GTT5 than the multiphonon relaxation rates (Kmpij), hence here we
and GTT5O at 1.85 mm is slightly different as shown in Figs. 5(b) and neglected the Kmpij, and then the population number of Tm3þ in 3F4
6, which can contribute to a part of energy transferring to hydroxyl energy level can be calculated as follows:

Table 3
Energy transfer parameters of the energy migration and cross-relaxation processes.

Energy transfer N (no. Of phonons) (% phonons) Transfer constant (cm6/s) WET (1020 cm3/s)

Tm / Tm (CR) 0,1,2 2.16  1039 3295

3
H4,3H6 / 3F4, 3F4 4.1,95.3,0.6
Tm / Tm (EM) 0,1 18.6  1039
3
H4,3H6 / 3H6,3H4 96.5,3.5
 M. Cai et al. / Optical Materials 57 (2016) 236e242 241

Fig. 5. (a)Raman spectra of GTT5 and GTT5O (b)1.85 mm luminescence spectra of Tm3þ in GTT5 and GTT5O (c) Partial energy diagram of Tm3þ in the glasses.

4. Conclusion

Tm3þ activated germanate-tellurite glasses with good thermal

stability and anti-crystallization ability were prepared. Efficient
2 mm fluorescence was observed when the concentration achieved
1.25 mol%. The corresponding radiative properties were investi-
gated, and high spontaneous radiative transition probability
(260.75 s1) and large emission cross section (7.66  1021 cm2)
were obtained for Tm3þ: 3F4 / 3H6 transition from the GTT5
sample. According to Dexter's and Forster's theory, energy transfer
microscopic parameters were computed to elucidate observed
2 mm emissions in detail. Besides, simplified rate equations have
been established to investigate the effect of hydroxy groups
quenching. Results demonstrate that the 1.25 mol% Tm3þ doped
germanate-tellurite glass with oxygen bubbling during melting
possessing excellent spectroscopic properties might be an attrac-
tive candidate for 2 mm laser or amplifier.

Acknowledge
Fig. 6. Measured 3F4 level decay and fitting curve of GTT5 and GTT5O glass.
This research was financially supported by the Chinese National
Natural Science Foundation (No. 51372235, 51272243, 51472225
and 61308090), Zhejiang Provincial Natural Science Foundation of
China (No.LR14E020003), the International Science & Technology
  Cooperation Program of China (Grant no. 2013DFE63070), and
n ð0ÞðA21 þ 2WET n0 Þ Public Technical International Cooperation project of Science
n1 ¼ n1 ð0Þ  2  expð  ðA10 þ WOH Þ  tÞ
A10 þ WOH  1=t2 Technology Department of Zhejiang Province (2015c340009).
ðA21 þ 2WET n0 Þ  n2 ð0Þ
þ expð  t=t2 Þ
A10 þ WOH  1=t2 References
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