JOURNAL OF APPLIED PHYSICS 106, 113111 2009

Quantum efciencies and thermo-optical properties of Er3+-, Nd3+-, and Pr3+-single doped lead-indium-phosphate glasses
E. A. F. Santos,1 W. F. Silva,1 M. T. de Arajo,1 M. V. D. Vermelho,1 I. Guedes,2 C.-K. Loong,3 L. A. Boatner,4 and C. Jacinto1,a
1 2

Instituto de Fsica, Universidade Federal de Alagoas, 57072-970 Alagoas, Brazil Departamento de Fsica, Universidade Federal do Cear, 60455-970 Cear, Brazil 3 School of Physics and Engineering, Sun Yat-Sen University, Guangzhou 510275, China 4 ORNL Center for Radiation Detection Materials and Systems, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6056, USA

Received 27 August 2009; accepted 9 November 2009; published online 15 December 2009 The experimental determination of thermal and optical properties, such as the uorescence quantum and temperature coefcient of the optical path length change ds / dT have been a efciency challenging task. In this work, mode-mismatched thermal lens and spectroscopic measurements were performed using Er3+-, Nd3+-, and Pr3+-doped lead-indium-phosphate glasses to obtain the thermal diffusivity and conductivity, ds / dT, the thermal loading nonradiative quantum efciency , and . The experimental difculties associated with obtaining for systems with several emitting levels, such as Er3+-doped materials were overcome. A discussion of the implications of the small values obtained for Er3+- and Pr3+-doped glass is presented. 2009 American Institute of Physics. doi:10.1063/1.3271345
I. INTRODUCTION

Glasses continue to attract a high level of research and development interest due to their ease of fabrication and their ability to be tailored for specic applications. For example, glasses are currently used as diode-pumped high-power solid state laser hosts, sensors, optical ampliers, optical switchers, infrared-to-visible converters, protection systems, sealed hosts for radioactive materials, etc.14 The characterization of glasses for practical applications includes the investigation of their thermal and optical properties.5,6 One of the most important glass optical paramdened as eters is the uorescence quantum efciency the ratio between the number of radiative deexcitations and the total number of deexcitations of an energy state in a given system.7 The determination of this parameter has been a challenging task, particularly in solids, with several conicting results that are extant in the prior literature.58 For systems with a single emitter level, such as the majority of Nd3+-doped materials, the thermal lens TL technique has been developed as a powerful tool for determining .59 For media with several emitting levels, however, the experimental determination of is not straightforward.10 Accordingly, there are only a few reports of the experimental determination of for systems with various emitter levels,10,11 and many of these associated values were obtained using simplied models, i.e., obtained with models similar to those used in systems with a single emitter level.1113 Regarding the thermo-optical properties of glasses, the thermal diffusivity, the thermal conductivity, and the temperature coefcient of the optical path length change ds / dT are all important parameters. Among these, ds / dT presents
a

additional difcult to determine experimentally and its value depends strongly on the experimental conguration employed.5,1416 Jacinto et al.5,79,14 have previously described the difculty in obtaining both and ds / dT. We have recently reported the optical characteristics of the rare-earth doped lead-indium-phosphate glasses: RE3+ : PbInPO4 RE= Nd and Er .17 Optical absorption and emission spectra and a JuddOfelt JO 18,19 analysis of the data were presented. The previous results indicated that these systems are good candidates for photonics applications. In this previous work, however, optical properties such as the nonradiative and radiative quantum efciencies were not experimentally quantied, and the thermal parameters were not determined. In the present work, we report the results of extended characterization studies of glasses of the form: RE3+ : PbInPO4 RE= Nd, Er, and Pr .17 Here both the modemismatched TL technique and spectroscopic measurements were used to obtain the thermal diffusivity and conductivity, ds / dT, the nonradiative quantum efciency, and .
II. EXPERIMENTAL

Author to whom correspondence should be addressed. Electronic mail: cjacinto@if.ufal.br.

The rare-earth-doped lead-indium-phosphate glasses investigated here were prepared by rst using phosphoric acid to precipitate PbHPO4 lead hydrogen phosphate from a lead-nitrate solution. Upon heating, this compound decomposes to form lead pyrophosphate Pb2P2O7 that then combines with In2O3 to form the lead-indium-phosphate glass composition. In forming the glass, 30 g of PbHPO4 and 1.75 g of In2O3 were placed in a Pt crucible along with Er2O3, Pr2O3, or Nd2O3 at rare-earth oxide doping level of 1.0 wt %. The mixture was heated to 1100 C, held at this temperature for 34 h, and the glass melt was then poured into a boron nitride mold. This procedure was followed by an annealing step that was carried out in air at 450 C for 45 h.
2009 American Institute of Physics

0021-8979/2009/106 11 /113111/6/$25.00

106, 113111-1

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Optical absorption spectra in the visible and nearinfrared regions were measured using a white light source LS LS-1 tungsten halogen lamp Ocean Optics, Inc. . Fluorescence spectra were recorded using the 488 Er3+ and Pr3+ and 514.5 nm Nd3+ lines of an Ar+ laser as the excitation source. The uorescence signal was collected by a ber-bundle and dispersed in a 64 cm single-grating monochromator with a resolution of 0.1 nm. The light was detected using an S-20 uncooled photomultiplier tube or photodetectors i.e., Si, Ge, or PbS in conjunction with a lock-in amplier and microcomputer for data acquisition. The lifetime measurements were performed by rst passing the laser beam through a telescope and then focusing it into a chopper for phase-sensitive detection. The 4F3/2 Nd3+ level lifetime measurement was recorded by detecting the 1064 nm emission with a duty cycle of 1 ms, while the 4I13/2 Er3+ level lifetime was recorded by detecting the 1540 nm emission with a duty cycle of 10 ms. The TL technique was employed to quantify the heat generation, , and the thermo-optical properties. The TL effect is caused by the deposition of heat via nonradiative decay processes after the laser energy is absorbed by the sample. In this situation, a transverse temperature gradient is established, thereby generating a ds / dT that creates a lenslike optical element. In the dual beam mode-mismatched conguration,5,20 the propagation of a probe laser beam through this TL results in a variation of its on-axis intensity I t , which can be calculated using diffraction integral theory.21 In the transient regime, an analytical expression can be obtained for the probe beam intensity,5,20 which is given by I t =I 0 1 2 mV 2 1 + 2 m + V2 tc/2t + 1 + 2 m + V2
2

Normalized TL signal

1.08 1.06 1.04 1.02 1.00 0

Nd :PbIn(PO4)

3+

Experimental data Theoretical fiting

Pexc = 180 mW
50 100 150 200

Time ( ms )

FIG. 1. Typical transient TL signal for Nd3+ : PbInPO4 glasses. The sample was excited using the 514.5 nm line of an Ar+ ion laser operating at 180 mW. The 632.8 nm line of a HeNe laser operating at 3 mW was used as the probe beam. The solid curve is the best t obtained using Eq. 1 .

rameter is approximately the phase difference of the probe beam at r = 0 and r = 2we induced by TL, and it is given by = Pabs ds , K p dT 3

where p is the probe beam wavelength, Pabs is the absorbed pump power, and is the fraction of absorbed energy converted into heat, which is also called the absolute nonradiative quantum efciency or fractional thermal loading. In the present work, it is useful to redene Eq. 3 as a normalized phase shift = Pabs =C , 4

where C = K p 1ds / dT is a constant that depends only on the host matrix characteristics and the probe beam wavelength.
III. RESULTS AND DISCUSSION

atan 2

, 1

A. Nd3+ : PbInPO4

with m= wp we
2

V=

Z1 when Zc Zc

Z2 ,

where Zc is the confocal distance of the probe beam, Z1 is the distance between the probe beam waist and the sample, Z2 is the distance between the sample and the photodiode, w p is the probe beam radius at the sample, we is the excitation laser beam radius at the sample position, and I 0 = I t when t or is zero. The temporal evolution of the TL signal depends on the characteristic TL signal time tc , which is related to the thermal diffusivity by D = w2 / 4tc; the thermal e conductivity K is given by K = c pD, where is the density and c p is the specic heat. Thus, a t of the experimental data using Eq. 1 provides both D and . The TL studies were carried out using the 488 Er3+ and Pr3+ doped samples and 514.5 nm Nd3+ doped sample as excitation wavelengths and 632.8 nm as the probe beam. The beam radii at the sample position were 40, 41, and 212 m for the wavelengths of 488, 514.5, and 632.8 nm, respectively. The pa-

In Ref. 17, the uorescence emission spectra of Nd3+and Er3+-doped PbInPO4 glasses were obtained under excitation at 800 nm. Here, we have used the 514.5 and 488 nm lines to excite the Nd3+- and Er3+-doped PbInPO4, respectively, and the results were similar to those obtained previously using the different excitation wavelength. Figure 1 shows a representative TL transient for Nd3+ : PbInPO4 glass under an excitation wavelength of 514.5 nm and a laser power of 180 mW. The TL and luminescence measurements were carried out with the same excitation wavelength and excitation power level, to detect the heat generation under similar conditions. The solid line shows the t using Eq. 1 that gives the values for tc and . From tc, D was calculated. For all of the samples D = 2.0 0.2 103 cm2 / s. This D is an average value obtained for the three samples used in this work Er3+ : PbInPO4, Pr3+ : PbInPO4, and Nd3+ : PbInPO4 . To obtain more accurate values of D and , several TL signals taken using different excitation powers Pexc were recorded. The measurements were carried out in a low-power pump rad to avoid saturation and energy transfer regime

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0.20 0.16

was conrmed through the luminescence spectrum obtained from 400 to 2000 nm, Fig. 3 b , which reports only the region from 850 to 1500 nm. In this case, the parameter in Eq. 4 is simply given by Eq. 5 =1
Nd 3+ Pr :PbIn(PO ) 4 3+ Er
0 70 140 210 280
3+

- (rad)

0.12
exc em

0.08 0.04 0.00

Pump Power (mW)

FIG. 2. TL phase shift vs excitation power for Nd3+-, Pr3+-, and Er3+-doped PbInPO4 glasses. The samples were excited with the 488 nm Pr3+ and Er3+ and 514.5 nm Nd3+ lines of an Ar+ ion laser. The 632.8 nm line of a HeNe laser operating at 3 mW was used as the probe beam.

upconversion effects that are very common in Nd3+- and Er3+-doped materials.2225 The accurate determination of is important, since this parameter will subsequently be used to quantify and . Figure 2 shows the linear dependence of versus Pexc for the three investigated samples. For Nd3+-doped materials the emission bands usually result from the 4F3/2 state as shown in Fig. 3. This information

(a)
20
2

D 5/2
4 4

D 3/2 + G 9/2 + G 11/2

2

15

G 7/2 + G 9/2 2 H 11/2 4 F 9/2 F 2 F 5/2 + H 9/2 7/2 4 F 3/2

4

10

I 15/2
4

5 I 13/2
4

I 11/2
4

I 9/2

Nd
4

3+
4

25

F 3/2

I11/2

(b)
Nd 3+ :PbInPO 4
exc = 514 nm

Intensity ( a.u. )

20 15 10 5
4

where exc and em are the excitation and the average emission wavelengths, respectively. The main problem in obtaining and then using the TL technique lies in the fact that ds / dT or Csee Eq. 4 is usually unknown. Recently, a new TL approach for the simultaneous determination of and C for compounds containing Nd3+ or Yb3+ ions was reported.7,9 In this so-called normalized lifetime approach, one measures the TL phase shifts and lifetimes of a glass matrix with different doping levels. The constant C and therefore ds / dT can also be obtained by carrying out TL measurements using an undoped sample with = 0 = 1 .5,7 Nevertheless, undoped samples normally present a low optical absorption coefcient that makes the calculation of Pabs and then of = / Pabs more difcult. Since neither undoped sample nor samples with different concentrations of the same ion were available here, as an alternative approach, we obtain =Wrad / Wexp for the 4F3/2 Nd3+ emitting level using the JO theory18,19 and luminescence decay measurements to determine the radiative Wrad = 1 / rad = 3745.3 s1 and the experimental Wexp = 1 / exp = 4201.7 s1 decay rates, respectively. After obtaining = 0.89, was calculated and Nd using Eq. 5 . By substituting the values of = 2.27 0.04 W1 into Eq. 4 , we obtain the constant C = 3.98 0.07 W1. The density of the PbInPO4 samples = 5.3 g / cm3 was measured using the Archimedes method. In order to obtain the thermal conductivity, the specic heats were approximated from the DulongPetit relation.26 The c p = 0.402 J / g K value was found for all samples within 3% of accuracy. From the values of D, , and c p we then calculate K = 4.3 0.4 103 W / cm K and using the C relation see Eq. 4 , ds / dT = 1.07 0.02 106 K1. It is worth noting that the C and ds / dT values are characteristic parameters of the glass matrix. This information is important because the constant C will subsequently be used in the analysis of the Pr3+- and Er3+-doped samples. The values found for D, K, ds / dT, and C are close to those reported for Kigres Q-98 and Q-100 phosphate glasses7 that are considered to be athermal laser materials, and the values are slightly smaller than those reported for uorozirconate ZBLAN and aluminosilicate LSCAS glasses.5 The value of is also similar to the values found for phosphate and silicate glasses with similar Nd3+ concentrations.5,7,14
B. Pr3+ : PbInPO4

Energy ( 10 cm )

-1

em = 1.064 m

F 3/2

I 9/2

em = 1.34 m
4

exc = 514 nm

em = 890 nm

F 3/2

I13/2
1450

0 850

W avelength ( nm )

1050

1250

FIG. 3. a Simplied energy level diagram for Nd3+ : PbInPO4 glasses showing absorption at 514.5 nm upward arrow , emission lines downward arrows , and multiphonon relaxation waving arrows . b Roomtemperature uorescence spectra of Nd3+ : PbInPO4 glass excited at 514.5 nm.

In the case of Pr3+-doped materials, there are only a few reports of the experimental and theoretical values of . For these systems, the JO theory can usually not be applied because the 4f5d states lie below or overlap with the 4f states. Nevertheless, some authors have recently presented experifor the mental results for . Quimby et al.27 measured

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(a)
20

P2 3 P0,1
1

490 nm

530 nm

606 nm

645 nm

10 5 0

488 nm

726 nm

15

D2

1 3

G4
3

F3,4

F2 H6 3 H5
3

7 6
(1)

Pr
(3)

3+

H4

and 1D2 levels at 1350 and 1500 nm, respectively. Excited state absorption at 488 nm from the 3P0 level can also be neglected, since it lies on a nonexisting state at 4 104 cm1. Therefore, in this case, the Pr3+ : PbInPO4 glass behaves as a single emitter level system with an average emission wavelength of 600 nm. The thermal load or nonradiative quantum yield Pr = 0.55 0.02 for the Pr3+ : PbInPO4 glass was obtained using the Pr = Pr / Pabs and C values Eq. 4 . The value of = 0.55 0.02 for the 3P0 level that is directly obtained from Eq. 5 is large when compared with the value of = 0.31 obtained for a SrAl12O19 crystal with a small Pr3+ concentration 0.1% .29 However, it is still signicantly smaller than 100%. Possible explanations for the small value of include the following: i Multiphonon relaxation. The energy difference between the 3P0 and 1D2 levels demands only the participation of 4 or 5 host phonons. In fact, in Ref. 29 the authors found a value = 0.68 for a highly diluted sample, indicating the presence of multiphonon relaxation. Concentration quenching. This effect was observed by Huang et al.29 in low concentration samples from 0.005% to 0.1% . Since our sample contains 1 wt % Pr3+ ions, this effect is also likely to occur. Thermal excitation of the 1I6 and 3P1 levels. The energy gaps between the 3P0 level and these two levels are very small, i.e., they can be populated at room value of the 3P0 level. temperature, reducing the However, this possibility could be low as exemplied in the following section on the Er3+ ion that has been studied as a temperature sensor.36

Energy (10 cm )

-3

-1

(b)
Pr 3+ :PbInPO 4
exc = 488 nm
ii
(4) (2) (5)

Intensity (a.u.)

5 4 3 2 1 0 500

iii
Wavelength ( nm )
550 600 650 700 750 800

FIG. 4. a Simplied energy level diagram for Pr3+ : PbInPO4 glasses showing absorption at 488 nm upward arrow , emission lines downward arrows , and multiphonon relaxation waving arrows . b Room-temperature uorescence spectra of Pr3+ : PbInPO4 glass excited at 488 nm.

G4 3H5 transition of a Pr3+-doped sulde glass by analyzing uorescence ratios, and they showed that the resulting value of was in good agreement with that obtained using the integrating sphere technique. An alternative procedure was recently proposed by Wang et al.28 that is based on a two-step excitation and the difference of the integrated spectral intensities. They measured for the Pr3+ 1S0 state that has recently attracted attention due to potential applications can be higher than in quantum cutting.29 In this case, 100%.30,31 Although measuring a uorescence signal is simple, the emission usually depends on the excitation wavelength,29 the effects of sample size and ion concentration excited state absorption, reabsorption, radiation trapping, etc. .3235 These constitute drawbacks for the use of uorescence-based techniques. Figure 4 b shows the emission spectrum of the Pr3+ : PbInPO4 glass under excitation at 488 nm 3H4 3P0,1 . The peaks labeled 1 through 5 correspond to the 3 P0 3H4, 3H5, 3H6, 3F2, and 3F4 transitions, respectively, as displayed in the simplied energy level diagram shown in Fig. 4 a . Since the splitting between the Stark levels 3P0, 3 P1, and 3P2 is small see Fig. 4 , it is reasonable to assume that depopulations of the levels above 3P0 are dominated by multiphonon relaxation, i.e., all radiative emissions originate from the 3P0 level. No emission was observed from the 1G4
1

C. Er3+ : PbInPO4

Under excitation at 488 nm the Er3+ : PbInPO4 glass system has several emitting levels, as shown in Figs. 5 a and 5 b . This makes an analysis of the TL data more difcult. In this case, Eq. 5 is no longer valid, and a valid relation for should depend on exc and the uorescence quantum efciencies of the emitting levels. The heat generated per unit of time and unit volume, based on the level diagram presented in Fig. 5 a is given by H = Rp h
exc mp mp E40 n0 + W43 n4E43 + W32 n3E32 mp mp + W21 n2E21 + W10 n1E10 ,

where Eij is the energy gap between the levels i and j, R p is the pump rate, Wmp is the multiphonon decay rate between ij the ith and jth levels, h exc is the excitation energy, and ni is the population of the ith level. The heat generation, Er, can be evaluated through the relation = H / R pnoEexc. The population dynamics, for excitation at 488 nm are described by the following system of rate equations:
mp n1 = W21 n2 A1n1 , mp n2 = W32 n3 A2n2 ,

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25

(a)
4

Energy (103 cm-1)

20 15 10 670 nm 5 0 1550 nm 530 nm 550 nm

4 F7/2 3 4S3/2; 2H11/2 2 4F9/2

4 4 4

F5/2; F3/2

I9/2

I11/2

1 I13/2
4

Er
(b)

3+
3+

0 I15/2

Normalized Intensity (a.u.)

1.0 0.8 0.6 0.4 0.2 0.0 450

Er :PbInPO 4
exc=488 nm

Eq. 3 , the unknown parameters in Eq. 8 are exactly 1 and 3. The experimental lifetime of the 4I13/2 level exp = 2.57 ms is easily obtained because it is scaled in the millisecond range. By knowing that rad = 1 / Wrad = 6.58 ms for the 4I13/2 level,17 we calculate 1 = 0.39. Thus, using Er, 1, and all of the ij, the uorescence quantum efciency of level 3 levels 4S3/2 + 2H11/2 was found to be 3 = 0.23 by using Eq. 8 . It is important to emphasize that experimental values of for Er3+ levels are rare. They have been generally obtained using the JO theory and luminescence decay measurements. Muoz et al.11 obtained a value of 3 = 0.20 for a 2% Er3+-doped lithium niobate crystal using a method based on a photoacoustic technique and luminescence signals produced after pulsed laser excitation. This value was, however, slightly above that obtained from the JO theory and luminescence decay measurements. The authors explained and corrected their experimental value by considering the mixing of the 4S3/2 level with the upper lying 2H11/2 level. So, an effective radiative transition probability was introduced taking into account the two levels
eff Wrad T = 1 g1Wrade E/kT 2 + g2Wrad 1 g1Wrade E/kT

488 nm

525

600

675

1450

1500

1550

1600

+ g2

Wavelength ( nm )
FIG. 5. a Simplied energy level diagram for Er3+ : PbInPO4 glasses showing absorption at 488 nm upward arrow , emission lines downward arrows , and multiphonon relaxation waving arrows . b Room-temperature uorescence spectra of Er3+ : PbInPO4 glass excited at 488 nm.
mp n3 = W43 n4 A3n3 , mp n4 = R pn0 W43 n4 ,

where Ai is the radiative decay rate of the ith level. Due to thermal coupling between the 4S3/2 and 2H11/2 levels, they were considered as a single level level 3 in Eq. 7 . Interactions between Er3+ ions were neglected in Eq. 7 since this Er3+ concentration can be considered to be low. This is further justied by the observation of the low-intensity band at 670 nm 100 times weaker than the green emissions that is related to the emission of Er3+ that involves energy transfer.37 Thus, the radiative emission from level 2 can be neglected. All of the remaining excited states have negligibly small contributions to the luminescence spectrum, decaying nonradiatively to the lower-lying levels. From the steadystate solution of Eq. 7 , we nd the following equation for Er:
Er =

i where gi and Wrad are, respectively, the degeneracy and radiative rates of the levels 1 2H11/2 and 2 4S3/2 , E is the energy separation between these levels, k is the Boltzmann constant, and T is the absolute temperature. By using Eq. 9 , eff Muoz et al.11 obtained, at room temperature, a Wrad that was 2 4 40% higher than Wrad that of the isolated S3/2 level . From the absorption spectrum, our system exhibits a value of E 824 cm1 so that these two levels are, in principle, thermally coupled at room temperature. From Eq. 9 and the 1 2 values of Wrad = 1428.6 s1 and Wrad = 1960.8 s1 obtained eff 2 from the JO analysis, we found Wrad 300 K Wrad, and at 400 K they differ by 3%. Thus, the value of 3 = 0.23 can be attributed exclusively to the 4S3/2 level. This value is nearly twice that obtained for the case of 2% Er3+-doped lithium niobate from 0.11 to 0.16 .11

IV. SUMMARY AND CONCLUSIONS

exc 30

+ 1

exc 3 31

+ 1

exc 1 10

where i is the uorescence quantum efciency of the ith level and ij is the wavelength of the i j transition. Note that, if 1 or 3 is zero, Eq. 8 reduces to the standard expression obtained for a system with only one emitting state: Er = 1 3 exc / 30 or Er = 1 1 exc / 10. Since Er = 0.70 0.02 was obtained from Er = Er / Pabs and C with

In summary, the TL technique and luminescence measurements were used to quantify the thermal and optical properties of RE3+ : PbInPO4 glasses. These results show that the thermal properties of the RE3+ : PbInPO4 glasses are comparable to those of commercial laser glasses such as the athermal phosphates. For the case of Nd3+ : PbInPO4, the value of = 0.89 is also comparable to the values reported for the uoride ZBLAN, = 0.99 and phosphate Q-98, = 0.90 commercial glasses. For Pr3+ : PbInPO4 the value of = 0.55 for the 3P0 level is higher than that in the case of Pr3+ : SrAl12O19 single-crystal bers = 0.31 , but it is still far from the ideal = 1 value. The primary reasons for the reduced value of are: multiphonon relaxation, concentration quenching, and thermal excitation. It is important to emphasize that to the best of our knowledge, this is the rst time that has been obtained for Pr3+ levels using the TL technique.

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J. Appl. Phys. 106, 113111 2009 Solid State Commun. 107, 487 1998 . J. A. Sampaio, S. Gama, M. L. Baesso, and T. Catunda, J. Non-Cryst. Solids 351, 1594 2005 . 13 V. Pilla, E. F. Chillcce, E. Rodriguez, T. Catunda, E. Munin, C. L. Cesar, and L. C. Barbosa, J. Non-Cryst. Solids 352, 3598 2006 . 14 D. N. Messias, C. Jacinto, M. J. V. Bell, and T. Catunda, IEEE J. Quantum Electron. 43, 751 2007 . 15 N. G. C. Astrath, A. Steimacher, J. H. Rohling, A. N. Medina, A. C. Bento, M. L. Baesso, C. Jacinto, T. Catunda, S. M. Lima, and B. Karthikeyan, Opt. Express 16, 21248 2008 . 16 N. G. C. Astrath, M. J. Barboza, A. N. Medina, A. C. Bento, M. L. Baesso, W. F. Silva, C. Jacinto, and T. Catunda, J. Appl. Phys. 106, 073511 2009 . 17 T. B. Brito, M. V. D. Vermelho, E. A. Gouveia, M. T. de Araujo, I. Guedes, C. K. Loong, and L. A. Boatner, J. Appl. Phys. 102, 043113 2007 . 18 B. R. Judd, Phys. Rev. 127, 750 1962 . 19 G. S. Ofelt, J. Chem. Phys. 37, 511 1962 . 20 J. Shen, R. D. Lowe, and R. D. Snook, Chem. Phys. 165, 385 1992 . 21 S. J. Sheldon, L. V. Knight, and J. M. Thorne, Appl. Opt. 21, 1663 1982 . 22 C. Jacinto, S. L. Oliveira, T. Catunda, A. A. Andrade, J. D. Myers, and M. J. Myers, Opt. Express 13, 2040 2005 . 23 C. Jacinto, T. Catunda, D. Jaque, and J. G. Sole, Phys. Rev. B 72, 235111 2005 . 24 D. Khoptyar and B. Jaskorzynska, J. Opt. Soc. Am. B 22, 2091 2005 . 25 C. Jacinto, D. N. Messias, A. A. Andrade, and T. Catunda, J. Opt. Soc. Am. B 26, 1002 2009 . 26 C. Jacinto, C. A. C. Feitosa, V. R. Mastelaro, and T. Catunda, J. NonCryst. Solids 352, 3577 2006 . 27 R. S. Quimby, K. T. Gahagan, B. G. Aitken, and M. A. Newhouse, Opt. Lett. 20, 2021 1995 . 28 X. J. Wang, S. H. Huang, L. Z. Lu, W. M. Yen, A. M. Srivastava, and A. A. Setlur, Appl. Phys. Lett. 79, 2160 2001 . 29 S. H. Huang, X. J. Wang, B. J. Chen, D. Jia, and W. M. Yen, J. Lumin. 102-103, 344 2003 . 30 D. Timmerman, I. Izeddin, P. Stallinga, I. N. Yassievich, and T. Gregorkiewicz, Nat. Photonics 2, 105 2008 . 31 R. T. Wegh, H. Donker, K. D. Oskam, and A. Meijerink, Science 283, 663 1999 . 32 S. X. Dai, J. H. Yang, L. Wen, L. L. Hu, and Z. H. Jiang, J. Lumin. 104, 55 2003 . 33 J. A. Caird, A. J. Ramponi, and P. R. Staver, J. Opt. Soc. Am. B 8, 1391 1991 . 34 D. S. Sumida and T. Y. Fan, Opt. Lett. 19, 1343 1994 . 35 M. Liao, L. Hu, Y. Fang, S. Xu, and Z. Liyan, J. Opt. Soc. Am. B 24, 1498 2007 . 36 P. V. Dos Santos, M. T. de Araujo, A. S. Gouveia-Neto, J. A. M. Neto, and A. S. B. Sombra, IEEE J. Quantum Electron. 35, 395 1999 . 37 C. J. da Silva and M. T. de Araujo, Opt. Mater. 22, 275 2003 .
12

Despite the fact that the Er3+ ion exhibits several emitting levels, a value of 4I13/2 = 0.39 was obtained by using the JO theory and luminescence decay measurements and a value of 4S3/2 = 0.2 by using the TL technique. The 4S3/2 and 2H11/2 levels are thermally coupled with energy gap of 824 cm1. However, we concluded that, at room temperature, this contribution is negligible. Finally, for the 4I13/2 and 4 S3/2 levels, the low values may be primarily due to multiphonon relaxation effects.
ACKNOWLEDGEMENTS

We thank the Brazilian agencies CAPES, CNPq, FINEP, and FAPEAL for nancial support of this work. The research of E.A.F.S. is supported by undergraduate studentships from PIBIC/CNPq and that of F.W.S. by graduate studentships from CAPES. The research was sponsored in part by the Division of Materials Sciences and Engineering, Ofce of Basic Energy Sciences, U.S. Department of Energy under Contract No. DE-AC05-00OR2725 with Oak Ridge National Laboratory managed and operated by UT-Battelle, LLC.
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