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JOURNAL OF APPLIED PHYSICS 102, 043113 2007

Optical characterization of Nd3+- and Er3+-doped lead-indium-phosphate glasses


Tasa B. Brito, M. V. D. Vermelho, E. A. Gouveia, and M. T. de Araujo
Instituto de Fsica, Universidade Federal de Alagoas, UFAL, Macei, AL, 57072/970, Brazil

I. Guedes
Departamento de Fsica, Universidade Federal do Cear, Caixa Postal 6030, Campus do PICI, Fortaleza, CE, Brazil

C.-K. Loong
Intense Pulsed Neutron Source Division, Argonne National Laboratory, Argonne, Illinois 60439-4814

L. A. Boatner
Center for Radiation Detection Materials and Systems, Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6056

Received 30 March 2007; accepted 1 June 2007; published online 31 August 2007 In this work, JuddOfelt analysis is applied to rare-earth-doped lead-indium-phosphate glasses RE-PbInPO4, where RE= Er3+ and Nd3+ in order to evaluate their potential as both glass laser systems and amplier materials. The phenomenological JuddOfelt parameters 2 , 4 , and 6 are determined for both rare-earth ions together with their quality factors and compared with the equivalent parameters for several other host glasses. The spontaneous emission probabilities and the lifetimes of the Nd3+ 4F3/2 laser transitions are determined and analyzed as a function of the optical quality factor. For Nd3+-PbInPO4, glass uorescence emission 890, 1058, and 1330 nm lines are observed. Highly efcient infrared-to-visible frequency up-conversion at 530, 550, and 670 nm as well as an intense infrared uorescence emission 1540 nm is observed in Er3+-doped PbIn PO4 glasses pumped using 800 nm radiation excitation. 2007 American Institute of Physics. DOI: 10.1063/1.2756705
I. INTRODUCTION

Novel materials suitable for the development of new solid-state laser-active media as well as infrared-to-visible converters continue to be of considerable scientic and technological interest, and photonic devices for high-density optical storage, optoelectronics, or medical diagnostics that exploit green light sources via frequency up-conversion are currently widely investigated.13 The potential of incoherent infrared broadband uorescence in applications such as optical gyroscopes, or in the optical communication systems, e.g., multiplexing devices, is also signicant.4 By exploiting the inhomogeneous broadening that is manifested as relatively large widths of the emission and absorption lines, both Er3+ and Nd3+ ions have also been used for tunable and ultrafast laser medium. In addition to the rare-earth ion characteristics, the glass host matrices also play a fundamental role in determining the performance of photonic devices since the stimulated emission characteristics of a trivalent rare-earth ion depend on the surrounding host matrix in which the ions are incorporated. The surrounding ligand eld can have a considerable inuence on the optical absorption cross-section, stimulated emission cross-section and uorescence decay, and the quantum efciency of the system.5 There are numerous known inorganic glass-forming systems that provide suitable hosts for laser ions, and the spectroscopic properties of rare-earth ions in many different glasses have been investigated as described in recent surveys of trivalent rare-earth ions in
0021-8979/2007/102 4 /043113/7/$23.00

tellurides,6 silicates,7 phosphates.8 The desire to increase the thermomechanical, as well as radiative, properties of glasses has resulted in the development of a number of high-quality laser phosphate glasses. Although binary PbO-P2O5 glasses near the metaphosphate composition are somewhat susceptible to aqueous corrosion and crystallization at low temperatures,911 their chemical durability can be enhanced dramatically by adding a third metal-oxide component. Moreover, the resulting ternary glasses may exhibit unique properties that are desirable for a variety of novel applications. Accordingly, new glass systems based on ternary lead indiumphosphate Pb-In- PO4 compositions have previously been developed, and the physical, chemical, and optical characteristics of these materials make them good candidates for optical devices in both the visible and infrared spectral region. Further, these hosts readily dissolve the rare earths, and their resistance to radiation-induced browning has led to the development of a Pm3+ laser in a Pb-In- PO4 host.12 The high refractive index 1.75 1.83 in the visible region and optical quality of this glass system has also been exploited in high-numerical-aperture optical ber fabrication. The subject phosphate glass preparation temperatures are relatively low 900 1000 C , and the chemical durabilradiation are ity and resistance to both weathering and good. Their low attenuation transmission window ranges from 350 nm up to the infrared absorption beyond 2800 nm.10 Due to this interesting combination of optical and other characteristics, in the present work we have investigated the
2007 American Institute of Physics

102, 043113-1

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J. Appl. Phys. 102, 043113 2007

spectroscopic properties of Nd3+ and Er3+ ions in Pb-In- PO4 glasses in order to facilitate future photonic device development. Specically, the absorption rare-earth spectra have been analyzed on the basis of the JuddOfelt theory, which is a standard tool for calculating the parityforbidden electric dipole radiative rates between various levels of both ions in this glass host. The three phenomenologi= 2, 4, and 6 were detercal intensity parameters mined, by performing a least-squares t of the calculated and observed absorption line intensities. The ions concentrations used in the JuddOfelt theory were determined through stoichiometric calculation considering nominal rare-earth doping concentrations 1.0 wt % Nd2O3 and Er2O3, respectively . These parameters were used to determine the spontaneous emission probabilities and branching ratios of the energy levels.

f exp =

mc2 e 2N 0

d ,

where is the absorption coefcient, is the energy cm1 of the transition, and N0 is the density of the ions cm3 . The measured line strength is used to calculate the by solving a set of equations for the intensity parameters corresponding transitions between initial S , L J and terminal S , L J manifolds expressed by15 f theo JJ = 8 2mc 3h 2J + 1 e2 Sed JJ + nSmd JJ , 2

II. EXPERIMENTAL

The rare-earth-doped lead-indium-phosphate glasses 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 either Er2O3 or Nd2O3 at rare-earth oxide doping levels of 1 4 wt %. The mixture was then heated to 1100 C, held at that 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. Room-temperature optical absorption spectra in the visible and near-infrared regions were measured using a white light source LS-1 tungsten halogen lamp Ocean Optics Inc. . Room-temperature uorescence spectra were recorded using the 800 nm line of a Ti:sapphire laser as the excitation source. The uorescence signal was collected by a berbundle and dispersed in a 64 cm single-grating monochromator with a resolution of 0.5 nm. The light was detected using an S-20 uncooled photomultiplier tube or photodetectors Si, Ge, and PbS in conjunction with a lock-in amplier and microcomputer for data acquisition. The lifetime measurements were performed by passing the laser beam through a telescope and then focusing it into a chopper for phasesensitive detection.

where = n2 + 2 2 / 9n is a factor for the effective eld at the well-localized center in a medium of isotropic refractive index n and Sed and Smd are the electric dipole and magnetic dipole line strengths, respectively. All the spectra of rareearth ions arise from intraconguration transitions within the 4f shell16 which are forbidden by the parity rule of electric dipole transitions. However, ions incorporated in a host matrix can experience a non-centro symmetric crystal eld interaction. This interaction admixes the states of opposite parity, thereby relaxing the parity restrictions.17 Their contribution is then given by Sed JJ = e2 SL J U SL J
2

The selection rules for the electric dipole contribution Sed from the f-conguration mixing include l = l, S = 0, L , and J 6. However, the magnetic dipole transitions are parity allowed between states of f nand obey the selection rules S = L = 0, J = 0, and 1 but not 0 0 transitions . Its contribution is given by the equation Smd JJ = eh 8 2mc
2

SL J L + 2S S L J

The values of the reduced matrix elements U 2 and L + 2S 2 were calculated by Carnall et al.18 and Weber.19 The calculations of the parameters were performed minimizing the root mean square rms deviation of the measured and calculated oscillator strength, respectively,
p i i f meas f theor rms = i=1 2

p3

III. RESULTS AND DISCUSSION A. Spectral intensities and JuddOfelt Theory


13,14

where p is the number of absorption bands, and 3 indicates the number of tting parameters. From the phenomenologi, we calculate the radiative transition rates cal parameters of all of the excited states of interest through the relation20 AR JJ = 64 4 3h 2J + 1 Sed JJ + n3Smd JJ . 6

The JuddOfelt parameters = 2, 4, and 6 can be determined by obtaining the experimental ground state oscillator strengths of the absorption transitions via an integration of the absorption coefcients for each band according to the following equation:

The emission branching ratio for transitions originating from an initial manifold i can be obtained from the radiative transition probabilities using the following equation:

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J. Appl. Phys. 102, 043113 2007 TABLE II. Radiative transition rates and Branching ratios of the 4F3/2 level of Nd3+ in Pb-In- PO4 glass. Average energy cm1 5 370.8 8 030.1 9 238.4 11 431.4 AR s1 4.19 105.90 414.59 384.40 Branching ratio % 0.5 11.6 45.6 42.3

F3/2
4 4

I15/2 I13/2 4 I11/2 4 I9/2

FIG. 1. Ground state absorption of Nd3+ ions in Pb-In- PO4 glass at room temperature.

AJJ

i, j

i, j A j JJ

= AJJ

i, j

R,

where

i R=1/

i, j jAJJ

is the radiative lifetime.

B. Characterization of Nd3+-doped Pb-In-PO4 1. Absorption spectrum

The typical room-temperature ground-state absorption spectrum of Nd3+-PbInPO4 glasses in the wavelength range from 400 to 900 nm is shown in Fig. 1. The bands are assigned as absorptions from the 4I9/2 ground state to the 4F3/2, 4 F5/2 + 4H9/2, 4F7/2 + 4S3/2, 4F9/2, 4H11/2, 4G5/2 + 2G7/2, 4G7/2 + 2G9/2, 4G9/2 + 2D3/2 + 4G11/2, and 2 P1/2 + 2D5/2 levels.The measured and calculated oscillator strengths are summarized in Table I. The good agreement between theoretical and experimental values is evident through its oscillator strength ratios as also shown in Table I. The three phenomenological JuddOfelt parameters determined for Nd3+ ions in lead20 cm2, indium-phosphate glass are 2 = 1.33 10 4 20 2 20 2 = 2.17 10 cm , and 6 = 2.44 10 cm yielding an oscillator strength standard deviation of around 0.4 107. For Nd3+ ions, the 4F3/2 manifold is the only excited J manifold that does not relax predominantly by a multiphonon process. This level uoresces in four bands ascribed to 4 F3/2 4I9/2 890 nm , 4F3/2 4I11/2 1058 nm , 4F3/2 4 4 4 I13/2 1330 nm , and F3/2 I15/2 1800 nm . The
TABLE I. Experimental and calculated Nd3+ oscillator strengths in units of 106 in Pb-In- PO4 glass. Average wavelength nm 874.78 802.40 745.48 685.25 628.83 582.46 521.08 469.86 436.51

main radiative transitions for Nd3+ ions occur from the 4F3/2 level providing the commercial laser wavelengths at 1330 and 1058 nm. The branching ratios, as well as the radiative lifetime, are critical parameters to the laser designer, because they characterize the possibility of attaining stimulated emission from any specic transition. The respective radiative transition and the branching ratio from the 4F3/2 level for the Nd3+ ions in the leadindiumphosphate glass are reported in Table II. As the reduced matrix elements 4F3/2 U 2 4I j are null for the Nd3+ 4F3/2 transitions 18 its 2 will not affect the stimulated emission parameters. This makes the intensity parameters 4 and 6 more relevant than the 2 parameter for the determination of optical properties such as the branching ratios. Thus, the four branching ratios related to the 4F3/2 level can be expressed in terms of the quality factor QF = 4 / 6 and its dependence as shown in Fig. 2. Extrapolation of the data shows that the maximum 1060 nm branching ratio tends to 0.66 when QF approaches zero. At this limit, the 1330 nm branching ratio reaches a value of 0.18. From Fig. 2, we also conclude that the smaller the value of the optical quality, the more efcient is the 1330 nm transition. The 1058 nm line is less sensitive than the transition at 1330 nm to the factor quality variation. As a matter of comparison, in Table III we list the JuddOfelt parameters along with the optical quality factor for different glasses. The signicantly different JuddOfelt parameters in Refs. 1517 are not surprising in view of the different structure of the glass hosts. Regarding the comparison between the present Pb-In- PO4 glass and the In-free lead-phosphate glass,21 a previous neutron-diffraction characterization of the Incontaining glass indicated that the structural environment around the In atoms is more compact than that for the Pb

4 4

I9/2

Ftheor 106 1.764 17 5.536 97 5.698 82 0.440 33 0.126 27 11.994 86 4.138 15 2.096 06 0.586 93

Fmeas 106 1.826 67 5.949 77 5.513 56 0.415 27 0.089 44 11.982 35 4.343 24 1.159 12 0.485 99

Ratio Ftheor / Fmeas 1.0 1.1 1.0 0.9 0.7 1.0 1.0 0.6 0.8

F3/2 F5/2 + 2H11/2 4 F7/2 + 4S3/2 4 F9/2 2 H11/2 4 G5/2 + 2G7/2 4 G7/2 + 2G9/2 4 G9/2 + 2D3/2 + 4G11/2 2 P1/2 + 2D5/2
4

FIG. 2. Predicted branching rations of the 4F3/2 level of Nd3+ in Pb-In- PO4 as a function of the optical quality factor.

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Brito et al. TABLE III. Phenomenological Nd3+ Judd-Ofelt parameters for different glasses.
2 4 6

J. Appl. Phys. 102, 043113 2007

Host Pb-In- PO4 Phosphate Fluoroborophosphate Fluorophosphate

1020cm2 1.33 3.42 2.57 2.90

1020cm2 2.17 4.09 4.40 5.00

1020cm2 2.44 4.35 5.99 7.27

QF /

Reference This work 20 15 16

0.89 0.94 0.73 0.68

atoms, showing a shorter mean In-O nearest distance and a higher coordination number with O. Therefore, qualitatively, the different JuddOfelt parameters may reect the modied structure of the Pb-In- PO4 glass with respect to the In-free counterpart.
2. Emission spectrum

population of the metastable level according the relation: Nd1 4F3/2 + Nd2 4I9/2 Nd1 4I15/2 + Nd2 4I15/2 when both ions undergo nonradiative relaxation to the ground state. The second route, Nd1 4F3/2 + Nd2 4F3/2 Nd1 4I13/2 4 + Nd2 G7/2 , is also responsible for a reduction in the uorescence around the 1320 nm band.
C. Characterization of Er3+-doped PbInPO4 1. Absorption spectrum

The typical room-temperature uorescence spectrum of the Nd3+-Pb-In-PO4 glass pumped by a Ti:sapphire laser tuned to 800 nm is shown in Fig. 3. The three bands observed here result from the following transitions: 4F3/2 4I9/2, 4F3/2 4I11/2, and 4F3/2 4I13/2. We were not able to observe the 4F3/2 4I15/2 transition, probably due to its low intensity. Owing to its importance as a high-power and highenergy laser line, the 4F3/2 4I11/2 1058 nm emission is probably the most thoroughly characterized transition for both glass and crystalline hosts. However, the transition at 1330 nm has also been extensively investigated. These bands provide four-level laser operation at room temperature. Fluoride, uorophosphate, and borate glasses have the highest values of 4F3/2 4I13/2 branching ratios, whereas the values for some silicate compositions are extremely low. The peak of the 4F3/2 4I13/2 transition varies signicantly with host composition, following the usual trend of the more covalent glasses that emit at longer wavelengths. For Nd3+ ions, the 4F3/2 radiative lifetime is inversely proportional to a linear combination of 4 and 6 . The radiative lifetime determined through the JuddOfelt analysis is 1090 s, and this value is in reasonable agreement with the measured lifetime, 600 s, if concentration quenching is taken into account. The two main crossrelaxation routes for Nd3+ are very efcient processes for depopulating the 4F3/2 level. The rst route reduces the

The typical room-temperature ground-state absorption spectrum of Er3+-Pb-In- PO4 glasses in the wavelength range from 400 to 1650 nm is shown in Fig. 4. The bands are assigned as absorptions from the 4I15/2 ground state to the 4 I13/2, 4I11/2, 4I9/2, 4F9/2, 4S3/2, 2H11/2, 4F7/2, and 4F5/2 + 4F3/2 levels. Owing to the negligible contribution of the overlapping absorption bands 4F5/2 + 4F3/2 and the uncertainty in their measurement, they were not considered in the calculation of the intensity parameters. The measured and calculated oscillator strengths are summarized in Table IV, and there is good agreement between the theoretical and experimental values. The three phenomenological JuddOfelt parameters 20 cm2, were determined as: 2 = 11.24 10 4 = 4.17 20 2 20 2 10 cm , and 6 = 1.61 10 cm resulting an oscillator strength standard deviation of 0.8 107. The spectroscopic quality factor, in Er3+-doped 4 / 6, Pb-In- PO4 glass is found to be 2.59; this value is somewhat high if compared to the values obtained for Er3+ in other glasses. The JuddOfelt intensity parameters were applied to determinations of the electric dipole Aed , magnetic dipole radiative Amd , and branching ratios corresponding to all possible transitions from the upper manifold states starting in the 4 F5/2 level down to the 4I13/2 level. The results are summa-

FIG. 3. Typical infrared uorescence of Nd

3+

in Pb-In- PO4 .

FIG. 4. Ground state absorption of Er3+ ions in Pb-In- PO4 glass at room temperature.

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J. Appl. Phys. 102, 043113 2007 TABLE V. Predicted electric dipole Aed , dipole magnetic Amd . Radiative of Er3+ in Pb-In- PO4 glass. transition rate, and branching ratios State energy cm1 Aed s1 Amd s1 Branching ratio %

TABLE IV. Experimental and calculated Er3+ oscillator strengths in unit of 106 in Pb-In- PO4 glass. Average wavelength nm 1514.73 974.50 818.50 656.88 544.75 522.58 489.20 Ftheor 106 3.519 45 1.473 06 1.266 63 7.309 64 1.074 35 31.415 09 5.589 20 Fmeas 106 4.680 96 1.910 74 1.101 76 7.672 15 1.093 10 31.396 94 4.518 76 Ratio Ftheor / Fmeas 1.3 1.3 0.9 1.0 1.0 1.0 0.8

I15/2
4 4

Transitions
R = 0.47 ms F5/2 4F7/2 2H11/2 4S3/2 4F9/2 4I9/2 4I11/2 4I13/2 4I15/2 R = 0.29 ms 4 F7/2 2H11/2 4S3/2 4F9/2 4I9/2 4I11/2 4I13/2 4I15/2 R = 0.09 ms 2 H11/2 4S3/2 4F9/2 4I9/2 4I11/2 4I13/2 4I15/2 R = 0.70 ms 4 S3/2 4F9/2 4I9/2 4I11/2 4I13/2 4I15/2 = 0.51 ms R 4 F9/2 4I9/2 4I11/2 4I13/2 4I15/2 = 4.20 ms R 4 I9/2 4I11/2 4I13/2 4I15/2 = 5.80 ms R 4 I11/2 4I13/2 4I15/2 = 6.30 ms R 4 I13/2 4I15/2 4

I13/2 I11/2 4 I9/2 4 F9/2 4 S3/2 2 H11/2 4 F7/2

1 211 1 306 2 084 5 218 8 224 10 180 13 840 204 442 95 874 4 007 7 013 8 969 12 629 19 231 779 3 912 6 919 8 874 12 534 19 136 3 134 6 140 8 095 11 755 18 357 3 006 4 962 8 622 15 224 1 956 5 616 12 217 3 660 10 262 6 602

0.4936 0.2794 0.2329 57.8678 82.8868 118.2627 953.8500 915.7514 0.0005 0.0019 3.8720 86.7471 201.9850 587.1515 2 545.0822 0.0250 34.1571 128.5503 96.8402 163.1484 10 230.1824 0.4441 67.2859 30.4942 365.3299 965.8702 6.0384 55.6256 92.1965 1 807.8029 0.6275 33.1384 201.7598 18.1668 137.9436 98.6038

0.6825

2.7 3.9 5.6 44.8 43.0

rized in Table V. At the bottom of each manifold result, is the predicted radiative lifetime of the excited state at room temperature is shown. One remarkable feature of the 4I13/2 4I15/2 transition is the magnetic dipole contribution. Its contribution to the radiative transition rate is 37%. The at emission spectra 1530 nm needed by the wavelength division multiplexing devices require electric dipole contribution relatively higher than the magnetic one. According to the JuddOfelt Theory, the electric dipole cross section is strongly dependent on the ligand eld, whereas the magnetic dipole does not. Thus, inhomogeneous broadening owing to the amorphous structure as well as the sensitivity of the local elds should be used to improve this glass quality. Table VI summarizes the JuddOfelt parameters for the Pb-In- PO4 glass along with the optical quality factors for different glasses as reported in the literature.
2. Emission spectra

50.1364

0.1 2.5 5.9 17.1 74.3

0.3 1.2 0.9 1.5 96.0

4.7 2.1 25.6 67.6 0.3 2.8 4.7 92.2 3.8782 0.3 14.1 85.7 11.6 88.4 100.0

Figures 5 a and 5 b show the room-temperature emission spectrum in the ranges of 450700 nm and 14001650 nm for Er3+-doped Pb-In-PO4 glasses as excited by 800 nm laser light, respectively. From Fig. 5 a we observe three distinct emission bands centered at 525, 550, and 660 nm. The green uorescence emission could easily be seen by the naked eye. This indicates an efcient up-conversion process in this glass and it also reects the inuence of the low maximum phonon energy of the Pb-In- PO4 glass ~1070 cm1 which prevents de-excitation from the excited-state through a nonradiative phonon-assisted relaxation. The Er3+ ion is initially excited by a single 800 nm photon from the 4I15/2 ground state to the 4I9/2 state, from which it decays to the 4I11/2 state due to a multiphonon relaxation process. The same ion absorbs a second 800 nm photon and is promoted to the 4F3/2 and 4F5/2 states. The ion decays to the 2H11/2 state, and the 2H11/2 4I15/2 transition produces the 525 nm emission. Due to multiphonon relaxation processes, the Er3+ ion 2H11/2 state can also decay to the 4S3/2 state and the subsequent 4S3/2 4I15/2 transition produces the 550 nm emission. The inset in Fig. 5 a shows a plot of the log Isign log Ipump value for the green lines. In n frequency up-conversion processes, Isign Ipumpwhere Isign is the up-conversion emission intensity, Ipump is the infrared excitation intensity, and n is number of infrared photon absorbed per visible photon emitted. We obtain n = 1.6 and 2.0 for the lines at 525 and 550 nm, respectively, which indicates

17.5684

58.9016

that a two-photon process occurs. The difference in the slope of the 525 nm band is associated with the uncertainty in the determination, rather than a saturation-like behavior of the signal. The excellent spectral resolution between the green signals generated by the two thermal-coupled levels and the low intensity of the red uorescence makes this glass a good candidate for the development of thermal optical sensors.7 The emission at 660 nm arises from an energy-transfer ET process. After absorbing one 800 nm photon, the Er3+ ion is excited from the 4I15/2 to the 4I9/2 state. Due to the multiphonon relaxation process, it then decays to either the 4 I11/2 or 4I13/2 state. Therefore, the ET process, promotes the

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Brito et al. TABLE VI. Phenomenological JuddOfelt parameters for different glasses.
2 4 6

J. Appl. Phys. 102, 043113 2007

Host Pb-In- PO4 Phosphate Chloroborophosphate LiBO

1020cm2 11.24 6.28 11.50 3.24

1020cm2 4.17 1.03 3.07 0.92

1020cm2 1.61 1.39 3.69 0.82

QF /

Reference This work 22 23 24

2.59 0.74 0.83 1.12

Er3+ ion to the 4F9/2 state, from which it decays to the 4I15/2 ground state giving rise to the 660 nm emission lines. The infrared uorescence spectrum of the Er3+-doped Pb-In-PO4 glass is shown in Figs. 5 b . A broadband covering the 14701625 nm range is observed. This emission arises from the 4I13/2 to the 4I15/2 transition. The luminescence decay time of the 1540 nm level is 2.8 ms. This value is shorter than the 6.3 ms radiative lifetime predicted from the JuddOfelt calculations, and it indicates that an intense concentration quenching process is taking place.

IV. CONCLUSIONS

Optical characterizations of the rare-earth-doped leadindium-phosphate glasses were carried out in which the JuddOfelt theory was applied to the room-temperature spectra of Nd3+ and Er3+-doped PbIn PO4 glasses. Optical absorption, uorescence emission, frequency up-conversion data, and lifetimes were experimentally obtained and compared with their respective values determined from the Judd Ofelt calculations. Infrared-to-visible frequency upconversion 530, 550, and 670 nm and uorescence emission 1540 nm for Er3+-doped Pb-In- PO4 glasses pumped under 800 nm radiation excitation, were observed. The radiative lifetime and branching ratios of the transitions from the4F5/2, 4F7/2, 2H11/2, 4S3/2, 4F9/2, 4I9/2, 4I11/2, and 4I13/2 to the lower-lying manifold were estimated. The shortest lifetime was assigned to the 2H11/2 as 0.09 ms, and the longest 6.3 ms due to the metastable level 4I13/2. The measured lifetime of this level was estimated as 2.8 ms, indicating strong reduction owing to concentration quenching. Several absorption 750, 800, 870, 1490, and 1600 nm and uorescence emission 890, 1058, and 1330 nm lines in Nd3+-doped Pb-In- PO4 were also observed. The present results indicate that this glass system is characterized by uorescence efciencies at 1060 nm for Nd3+ and at 890 nm for Er3+ ions that can be exploited in both optical laser and amplier applications.25
ACKNOWLEDGMENTS

The nancial support for this research by the PADCT, FUNCAP, PRONEX, FAPEAL, CNPq, and FINEP Brazilian agencies is gratefully acknowledged. One of the authors T.B.B. is supported by an undergraduate studentship from CNPq PIBIC . 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. Work performed at Argonne National Laboratory, managed and operated by the University of Chicago at Argonne, LLC, was supported by the U.S. Department of Energy, Ofce of Science, Ofce of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.
1

FIG. 5. a Visible frequency up-conversion owing to Er3+ ions in Pb-In- PO4 glass pumped at 800 nm. b Normalized infrared uorescence 4 I13/2 to 4I15/2 and absorption 4I15/2 to 4I13/2 owing to Er3+ ions in Pb-In- PO4 glass at room temperature.

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