The use of Pr3+co-doping for great enhancement of mid-infrared(mid-IR) emissions at 2.9 μm and 2.4 μm is investigated in the Ho3+/Pr3+co-doped LiYF4 crystals.With the introduction of Pr3+ions,the fluorescence lifetime of Ho3+:5I7 level is 2.15 ms for Ho3+/Pr3+co-doped crystal,and the lifetime for Ho3+singly doped crystal is 17.70 ms,while the lifetime of Ho3+:5I6 level decreases slightly from 2.11 ms for Ho3+:LiYF4 to 1.83 ms for Ho3+/Pr3+:LiYF4.It is also demonstrated that the introduction of Pr3+greatly increases the mid-infrared emission of Ho3+:5I6 →5I7 which depopulates the Ho3+:5I7 level,while it has little influence on the Ho3+:5I6 level,which is beneficial for greater population inversion and laser operation.The analysis on the decay curves of the 2.0 μm emissions in the framework of the Inokuti-Hirayama model indicates that the energy transfer from Ho3+to Pr3+is mainly from electric dipole-dipole interaction.The calculated efficiency of energy transfer from Ho3+:5I7 to Pr3+:3F2 level is 87.53% for Ho3+/Pr3+(1.02%/0.22%) co-doped sample.Our results suggest that the Ho3+/Pr3+co-doped LiYF4 single crystals may have potential applications in mid-IR lasers.
The LiYF4 single crystals singly doped Ho3＋ and co-doped Ho3＋, Pr3＋ ions were grown by a modified Bridgman method. The Judd-Ofelt strength parameters （Ω2, Ω4, Ω6） of No3＋ were calculated according to the absorption spectra and the Judd-Ofelt theory, by which the radiative transition probabilities （A）, fluorescence branching ratios （β） and radiative lifetime （τ rad） were obtained. The radiative lifetimes of 5/6 and 5/7 levels in Ho3＋ （1 mol%）：LiYF4 are 10.89 and 20.19 ms, respectively, while 9.77 and 18.50 ms in Ho3＋/pr3＋ doped crystals. Hence, the τ rad of 5/7 level decreases significantly by introduction of Pr3＋ into Ho3＋：LiYF4 crystal which is beneficial to the emission of 2.9 μm. The maximum emission cross section of Ho3＋：LiYF4 crystal located at 2.05 μm calculated by McCumber theory is 0.51 ×10-20 cm2 which is compared with other crystals. The maximum emission cross section at 2948 nm in Ho3＋/pr3＋ co-doped LiYF4 crystal obtained by Fuchtbauer- Ladenburg theory is 0.68 × 10-20 cm2, and is larger than the value of 0.53 × 10-20 cm2 in Ho3＋ singly doped LiYF4 crystal. Based on the absorption and emission cross section spectra, the gain cross section spectra were calculated. In the Ho3- ions singly doped LiYF4 crystal, the gain cross sections for 2.05 μm infrared emission becomes positive once the population inversion level reaches 30%. It means that the pump threshold for obtaining 2.05 μm laser is probably lower which is an advantage for Ho3＋-doped LiYF4 2.05 μm infrared lasers. The calculated gain cross section for 2.9 μm mid-infrared emission does not become positive until the population inversion level reaches 40% in Ho3＋/pr3＋：LiYF4 crystal, but 50% in Ho3＋ singly doped LiYF4 crystal, indicating that a low pumping threshold is achieved for the H03＋：5/6 → 5/7 laser operation with the introduction of Pr3＋ ions. It was also demonstrated that Pr3＋ ion can deplete rapidly the lower laser Ho3＋：5/7 level and has influence on t
A high-quality Cr 3＋：CdWO4 single crystal at a size of approximatelyΦ25×80 mm is grown using the Bridgman method with CdO,WO3,and Cr2O3 as raw materials and their molar ratio of 100：100：0.5.The temperature gradient of solid-liquid interface at growth is approximately 50？C/cm and the growth rate is 0.05 mm/h.The X-ray diffraction（XRD）,absorption,excitation,and emission spectra of different parts of the as-grown and O2-annealed crystals are investigated.Two strong broad optical absorption bands of about 472 and 708 nm are observed,and they are associated with the transitions 4 A2→ 4 T1 and 4 A2→ 4 T2.The weak 4 T2→ 2 E transition（the R-line）at 632 nm is also observed.The crystal-field parameter Dq and the Racah parameters B and C are estimated to be 1 412.4,776.8,and 3 427.6 cm？ 1,respectively,according to the absorption spectra and crystal-splitting theory.A broadband fluorescence at about 1 000 nm due to 4 T2→ 4 A2 transition is produced by exciting the samples at 675 nm.After being annealed in an O2 atmosphere,the crystals become more transparent,while the effective light absorption of Cr 3＋ ions is evidently enhanced and the emission intensity is also strengthened due to the reduction of oxygen vacancies in the CdWO4 crystal after annealing.
Mid-infrared（MIR） emissions of 2.4 and 3.5 μm from Tm3＋：LiYF4 single crystals attributed to3H4 →3H5 and3H5 →3F4 transitions as well as MIR emissions of 4.2,4.3,and 4.5 μm from Nd3＋：LiYF4 lasers attributed to4I15/2 →4I13/2,4I13/2 →4I11/2,and4I11/2 →4I9/2 transitions,respectively,are observed.LiYF4 single crystals possess high transmittance of over 85% in the 2.5-6 μm range.The large emission crosssections of Tm-doped crystals at 2.4 μm（1.9×10-20cm2） and Nd-doped crystals at 4.2 μm（0.84×10-20 cm2） as well as the high rare-earth doping concentrations,excellent optical transmission,and chemicalphysical properties of the resultant samples indicate that Nd3＋and Tm3＋singly doped crystals may be promising materials for application in MIR lasers.
