Polarization and local disorder effects on the properties of -doped , or Na and or Mo, crystalline tunable laser hosts
Mauricio Rico, Antonio Méndez-Blas, Vladimir Volkov, María Ángeles Monge, Concepción Cascales, Carlos Zaldo, Andreas Kling, and María Teresa Fernández-Díaz
Mauricio Rico,1
Antonio Méndez-Blas,1
Vladimir Volkov,1
María Ángeles Monge,1
Concepción Cascales,1
Carlos Zaldo,1
Andreas Kling,2
and María Teresa Fernández-Díaz3
1Consejo Superior de Investigaciones Científicas, Instituto de Ciencia de Materiales de Madrid, c/Sor Juana Inés de la Cruz 3, Madrid 28049, Spain
2Instituto Tecnológico e Nuclear, Estrada Nacional No. 10. 2686-953 Sacavém and Centro de Física Nuclear da Universidade de Lisboa, Avenida Professor Gama Pinto 2, Lisbon 1649-003, Portugal
3Institut Laue Langevin, ILL Boîte Postale 156X, Grenoble 38042, France
Mauricio Rico, Antonio Méndez-Blas, Vladimir Volkov, María Ángeles Monge, Concepción Cascales, Carlos Zaldo, Andreas Kling, and María Teresa Fernández-Díaz, "Polarization and local disorder effects on the properties of Er3+-doped XBi(YO4)2, X=Li or Na and Y=W or Mo, crystalline tunable laser hosts," J. Opt. Soc. Am. B 23, 2066-2078 (2006)
Pure and Er-doped , (NBW), , and crystals have been grown by the Czochralski method. The three crystal hosts have similar structural and optical properties. The noncentrosymmetric space group (No. 82) crystallographic structure has been established through single-crystal x-ray and neutron (for NBW only) diffraction. energy levels were determined experimentally and simulated in the symmetry through a crystal-field analysis. With this background, the large spectroscopic bandwidths observed were ascribed to the presence of two and sites for and to different short-range and distributions around both sites. The radiative properties of are described by the Judd–Ofelt theory achieving branching ratios and radiative lifetimes for transitions useful as laser channels. The laser channel shows a peak emission cross-section
and a quantum efficiency to 0.74. The laser emission is envisaged to be tunable by .
José M. Cano-Torres, María Dolores Serrano, Carlos Zaldo, Mauricio Rico, Xavier Mateos, Junhai Liu, Uwe Griebner, Valentin Petrov, Francisco José Valle, Miguel Galán, and Gregorio Viera J. Opt. Soc. Am. B 23(12) 2494-2502 (2006)
Andreas Schmidt, Simon Rivier, Valentin Petrov, Uwe Griebner, Xiumei Han, José María Cano-Torres, Alberto García-Cortés, María Dolores Serrano, Concepción Cascales, and Carlos Zaldo J. Opt. Soc. Am. B 25(8) 1341-1349 (2008)
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XRD wavelength 0.71073 (Å).
Neutron diffraction (ND) wavelength 0.84 (Å).
XRD absorption correction SADABS.
ND absorption correction DATAP.
Refinement method: full matrix least squares on .
Atomic coordinates . is defined as one third of the trace of the orthogonalized tensor.
Occupancy factor for the indicated site. They were refined with no restrains between and sites.
Positive anisotropic thermal displacements for all atoms have been obtained and are available from the authors.
Italics indicate results from neutron D9-ILL, Grenoble data.
Table 4
Selected Bond Lengths (Å) for Pure NBW, NBM, and LBM and Er-Doped NBW Crystalsa
.
Distances corresponding to results from the neutron diffraction refinement.
Table 5
Observed at and Calculated for an Average Site Energy Levels of in LBM Single Crystala
‖
‖
σ
0
8
0
σ
18 349
18 350
13
2
σπ
18
8
0
σπ
18 409
18 413
20
11
33
41
5
54
58
3
σ
19 063
19 071
12
2
208
209
4
σπ
19 081
19 096
14
6
251
242
7
σπ
19 129
19 142
13
10
292
286
14
σ
19 199
19 192
7
310
313
20
σπ
19 215
19 204
18
8
σ
19 225
19 210
7
σπ
6527
6524
6
3
σ
6538
6524
9
3
σπ
20 462
20 451
14
3
σ
6576
6574
9
4
σ
20 474
20 468
14
7
σπ
6646
6640
18
4
σ
20 533
20 545
15
8
σ
6675
6666
10
σπ
20 566
20 567
28
15
σπ
6691
6694
23
9
σ
6710
6714
26
15
σ
22 149
22 142
13
5
σ
22 170
22 158
13
3
σπ
10 199
10 184
5
3
σπ
22 194
22 193
16
9
σ
10 202
10 194
7
5
σ
10 217
10 240
10
5
σ
22 506
22 503
21
4
σπ
10 232
10 260
10
6
σπ
22 547
22 549
28
12
σ
10 254
10 269
10
σπ
10 286
10 282
18
11
σπ
24 466
24 450
14
3
σ
24 534
24 544
15
1
σπ
12 352
12 342
11
3
σπ
24 567
24 568
15
10
σ
—
12 448
1
σπ
24 660
24 661
20
5
σ
—
12 483
13
σπ
12 518
12 504
20
3
σπ
12 594
12 598
17
13
σπ
15 226
15 227
13
1
σ
15 252
15 263
13
10
σπ
15 266
15 267
18
1
σπ
15 328
15 336
16
8
σ
15 379
15 392
22
13
‖ and IR indicate the OA observed polarization character and corresponding irreducible representation of the transition, respectively. is the observed OA FWHM linewidth. is the energy separation simulated using SOM CF parameters (Ref. 28) for the nonequivalent and sites in the host.
Table 6
Phenomenological FI and CF Parameters for in LBM Single Crystala
Italic values are CF parameters calculated using the SOM model (Ref. 28) with previously determined and crystal data (; effective charge for ). Values in parentheses refer to estimate standard deviations in the indicated parameter. Values in square brackets were not allowed to freely vary in the parameter fitting. . .
The CF strength parameter and are defined as . ; 1 is the number of levels and p is the number of parameters.
Table 7
Average Wavelength , Integrated OA Cross Section , Averaged Experimental ED Oscillator Strength , and Calculated ED Oscillator Strength , for , Multiplets of in NBW, NBM, and LBM.a
The fit quality obtained with the JO parameter sets is described by .
Magnetic dipole contributions, , were evaluated and discounted as follows: NBW ( and ), NBM and ), and LBM and ).
Table 8
ED and MD Transition Probabilities, and ; Branching Ratios, β; Radiative, , and Experimental, , Lifetimes of in NBM Calculated from the Seta
Only transitions with are shown. experimental , and lifetimes of Er in NBM crystals doped with the lowest concentration available experimental lifetimes of Er in NBW and LBM are also included.
Tables (8)
Table 1
Er Concentration [Er] and Segregation Coefficient S of the Crystals Used in This Work
Crystal
mol.%
mol.%
S
NBW:
0.02
0.03
1.5
0.02
0.44
1.47
3.3
0.92
0.88
3.85
4.3
2.41
NBM:
0.16
1.2
7.5
0.75
0.33
1.68
5.1
1.05
0.73
3.45
4.7
2.15
LBM:
0.03
0.11
3.7
0.07
0.16
0.88
5.5
0.56
0.3
1.22
4.0
0.78
Table 2
Assessment of the Distortion from Individual Scan Intensity Measurements versus Background Intensity EB
X-Ray Reflections Forbidden in
NBW
NBM
LBM
, l even
Table 3
Crystal Data at 296(2) K and Structure Refinement details of , W, and Er-doped NBW
XRD wavelength 0.71073 (Å).
Neutron diffraction (ND) wavelength 0.84 (Å).
XRD absorption correction SADABS.
ND absorption correction DATAP.
Refinement method: full matrix least squares on .
Atomic coordinates . is defined as one third of the trace of the orthogonalized tensor.
Occupancy factor for the indicated site. They were refined with no restrains between and sites.
Positive anisotropic thermal displacements for all atoms have been obtained and are available from the authors.
Italics indicate results from neutron D9-ILL, Grenoble data.
Table 4
Selected Bond Lengths (Å) for Pure NBW, NBM, and LBM and Er-Doped NBW Crystalsa
.
Distances corresponding to results from the neutron diffraction refinement.
Table 5
Observed at and Calculated for an Average Site Energy Levels of in LBM Single Crystala
‖
‖
σ
0
8
0
σ
18 349
18 350
13
2
σπ
18
8
0
σπ
18 409
18 413
20
11
33
41
5
54
58
3
σ
19 063
19 071
12
2
208
209
4
σπ
19 081
19 096
14
6
251
242
7
σπ
19 129
19 142
13
10
292
286
14
σ
19 199
19 192
7
310
313
20
σπ
19 215
19 204
18
8
σ
19 225
19 210
7
σπ
6527
6524
6
3
σ
6538
6524
9
3
σπ
20 462
20 451
14
3
σ
6576
6574
9
4
σ
20 474
20 468
14
7
σπ
6646
6640
18
4
σ
20 533
20 545
15
8
σ
6675
6666
10
σπ
20 566
20 567
28
15
σπ
6691
6694
23
9
σ
6710
6714
26
15
σ
22 149
22 142
13
5
σ
22 170
22 158
13
3
σπ
10 199
10 184
5
3
σπ
22 194
22 193
16
9
σ
10 202
10 194
7
5
σ
10 217
10 240
10
5
σ
22 506
22 503
21
4
σπ
10 232
10 260
10
6
σπ
22 547
22 549
28
12
σ
10 254
10 269
10
σπ
10 286
10 282
18
11
σπ
24 466
24 450
14
3
σ
24 534
24 544
15
1
σπ
12 352
12 342
11
3
σπ
24 567
24 568
15
10
σ
—
12 448
1
σπ
24 660
24 661
20
5
σ
—
12 483
13
σπ
12 518
12 504
20
3
σπ
12 594
12 598
17
13
σπ
15 226
15 227
13
1
σ
15 252
15 263
13
10
σπ
15 266
15 267
18
1
σπ
15 328
15 336
16
8
σ
15 379
15 392
22
13
‖ and IR indicate the OA observed polarization character and corresponding irreducible representation of the transition, respectively. is the observed OA FWHM linewidth. is the energy separation simulated using SOM CF parameters (Ref. 28) for the nonequivalent and sites in the host.
Table 6
Phenomenological FI and CF Parameters for in LBM Single Crystala
Italic values are CF parameters calculated using the SOM model (Ref. 28) with previously determined and crystal data (; effective charge for ). Values in parentheses refer to estimate standard deviations in the indicated parameter. Values in square brackets were not allowed to freely vary in the parameter fitting. . .
The CF strength parameter and are defined as . ; 1 is the number of levels and p is the number of parameters.
Table 7
Average Wavelength , Integrated OA Cross Section , Averaged Experimental ED Oscillator Strength , and Calculated ED Oscillator Strength , for , Multiplets of in NBW, NBM, and LBM.a
The fit quality obtained with the JO parameter sets is described by .
Magnetic dipole contributions, , were evaluated and discounted as follows: NBW ( and ), NBM and ), and LBM and ).
Table 8
ED and MD Transition Probabilities, and ; Branching Ratios, β; Radiative, , and Experimental, , Lifetimes of in NBM Calculated from the Seta
Only transitions with are shown. experimental , and lifetimes of Er in NBM crystals doped with the lowest concentration available experimental lifetimes of Er in NBW and LBM are also included.