Downconversion （DC） with emission of two near-infrared photons about 1000 nm for each blue photon absorbed was obtained in thulium （Tm3＋） and ytterbium （Yb3＋） codoped yt- trium lithium fluoride （LiYF4） singl...Downconversion （DC） with emission of two near-infrared photons about 1000 nm for each blue photon absorbed was obtained in thulium （Tm3＋） and ytterbium （Yb3＋） codoped yt- trium lithium fluoride （LiYF4） single crystals grown by an improved Bridgman method. The luminescent properties of the crystals were measured through photoluminescence excitation, emission spectra and decay curves. Luminescence between 960 and 1050 nm from yb3＋： 2Fs/2--＋2FT/2 transition, which was originated from the DC from Tm3＋ ions to Yb3＋ ions, was observed under the excitation of blue photon at 465 nm. Moreover, the energy transfer processes were studied based on the Inokuti-Hirayama model, and the results indicated that the energy transfer from Tm3＋ to Yb3＋ was an electric dipole-dipole interaction. The max- imum quantum cutting efficiency approached with 0.49mo1% Tm3＋ and 5.99mo1% Yb3＋. increasing the energy efficiency of crystalline energy part of the solar spectrum. up to 167.5% in LiYF4 single crystal codoped Application of this crystal has prospects for Si solar cells by photon doubling of the high展开更多
The electronic structures of LiYF4：Ce^3＋ and LiYF4 crystal simulated by an embedded （in a microcrystal containing 1938 ions） cluster CeY4Li8F24, and Y5LisF24 respectively, were computed by the ab initio self-consi...The electronic structures of LiYF4：Ce^3＋ and LiYF4 crystal simulated by an embedded （in a microcrystal containing 1938 ions） cluster CeY4Li8F24, and Y5LisF24 respectively, were computed by the ab initio self-consistent relativistic DV-Xa （discrete variational Xa） method. The ground-state calculation showed that only the lowest 5d level Ed of Ce^3＋ ion lies around the BCB （bottom of the conduction band） while the lowest 4f levels is 2.5 eV lower than BCB. The CB states consist of 4d of Y mixed with 5d of Ce, even for the wavefunctions （WFS） with energy Ed under BCB there are still 24% of Y-4d and 9% of F-2p as components. So, they are not pure crystal-field states at all. Furthermore, transition state （TS） calculation was performed to obtain the 4f→5d transition energies Efd, to improve the previous calculation performed by Andriessen et al, in which a small CeF8 cluster embedded in an array of point charge was used and the results of ground-state calculation were roughly used to compare with the observed 4f→5 d transition energies. The ionic radius of Ce^3＋ is larger than that of y^3＋ , so we had also modeled approximately the lattice relaxation. As results, the CeY4Li8F24 cluster with 4.56 % outward relaxation （of the nearest-neighbor and next nearest-neighbor eight fluorines） has the lowest total energy and gave satisfactory 4f→5d energies Efd, but the ground-state calculated Ed is 0.68 eV higher than BCB. For another cluster with 7.36% outward relaxation the Ed is 0.43 eV lower than BCB, which makes the observation of fine structure （including zero-phonon line） of the lowest 5 d band understandable easier, but the splits between the transition energies Efd were not as good as the former. Therefore, we consider the relaxation is some how around 4. 56% -7.36% outward, not as large as 10% proposed by Andriessen et al.展开更多
Pr^（3＋）-doped transparent oxyfluoride glass-ceramic containing tetragonal LiYF_4 nanocrystals has been synthesized by melting-quenching method and subsequent thermal treatment and spectroscopic properties of Pr^（...Pr^（3＋）-doped transparent oxyfluoride glass-ceramic containing tetragonal LiYF_4 nanocrystals has been synthesized by melting-quenching method and subsequent thermal treatment and spectroscopic properties of Pr^（3＋） ions were investigated. The crystalline phase and microstructure of the LiYF_4 nanocrystals were studied by X-ray diffraction（XRD） and transmission electron microscopy（TEM）, respectively. Compared with those of Pr^（3＋）-doped glass（Pr^（3＋）：PG）, the sharp absorption and emission bands of Pr^（3＋）-doped glass-ceramic（Pr^（3＋）：GC） reveal parts of Pr^（3＋） ions are incorporated into LiYF_4 nanocrystals. The peak absorption cross-section at 443 nm（~3H_4 → ~3P_2） adds to 110% and the full width at half maximum（FWHM） for the band around 443 nm reduces from 22 to 14 nm after crystallization. The fluorescence lifetime of the ~3P_0 multiplet of Pr^（3＋） ions increases from 5.35 to 11.14 μs after crystallization. The results indicate that this glass-ceramic is promising to be a visible laser material.展开更多
The electronic structures of LiYF4：Ce^3＋ and LiYF4 crystal simulated by an embedded （in a microcrystal containing 1938 ions） cluster CeY4Li8F24, and Y5LisF24 respectively, were computed by the ab initio self-consi...The electronic structures of LiYF4：Ce^3＋ and LiYF4 crystal simulated by an embedded （in a microcrystal containing 1938 ions） cluster CeY4Li8F24, and Y5LisF24 respectively, were computed by the ab initio self-consistent relativistic DV-Xa （discrete variational Xa） method. The ground-state calculation showed that only the lowest 5d level Ed of Ce^3＋ ion lies around the BCB （bottom of the conduction band） while the lowest 4f levels is 2.5 eV lower than BCB. The CB states consist of 4d of Y mixed with 5d of Ce, even for the wavefunctions （WFS） with energy Ed under BCB there are still 24% of Y-4d and 9% of F-2p as components. So, they are not pure crystal-field states at all. Furthermore, transition state （TS） calculation was performed to obtain the 4f→5d transition energies Efd, to improve the previous calculation performed by Andriessen et al, in which a small CeF8 cluster embedded in an array of point charge was used and the results of ground-state calculation were roughly used to compare with the observed 4f→5 d transition energies. The ionic radius of Ce^3＋ is larger than that of y^3＋ , so we had also modeled approximately the lattice relaxation. As results, the CeY4Li8F24 cluster with 4.56 % outward relaxation （of the nearest-neighbor and next nearest-neighbor eight fluorines） has the lowest total energy and gave satisfactory 4f→5d energies Efd, but the ground-state calculated Ed is 0.68 eV higher than BCB. For another cluster with 7.36% outward relaxation the Ed is 0.43 eV lower than BCB, which makes the observation of fine structure （including zero-phonon line） of the lowest 5 d band understandable easier, but the splits between the transition energies Efd were not as good as the former. Therefore, we consider the relaxation is some how around 4. 56% -7.36% outward, not as large as 10% proposed by Andriessen et al.展开更多
In this paper, optical spectra of LiYF4 single crystals doped with Tm3＋ ions of various concentrations are reported. The emission intensity at 1.8 ktm first increases with increasing Tm3＋ concentration, and reaches ...In this paper, optical spectra of LiYF4 single crystals doped with Tm3＋ ions of various concentrations are reported. The emission intensity at 1.8 ktm first increases with increasing Tm3＋ concentration, and reaches a maximum value when the concentration of Tm3＋ is about 1.28 mol%, then it decreases rapidly as the concentration of Tm3＋ further increases to 3.49 mol%. The emission lifetime at 1.8 p.m also shows a similar tendency to the emission intensity. The maximum lifetime of 1.8 μm is measured to be 17.68 ms for the sample doped with Tm3＋ of 1.28 mol%. The emission cross section of 3F4 level is calculated. The maximum reaches 3.76 × 10 -21 cm2 at 1909 nm. The cross relaxation （3H6, 3H4 →3 F4, 3F4） between Tm3＋ ions and the concentration quenching effect are mainly attributed to the change of emission with Tm3＋ concentration. The largest quantum efficiency between Tm3＋ ions is estimated to be ,-147% from the measured lifetime and calculated radiative lifetime. All the results suggest that the Tm3＋/LiYF4 single crystal may have potential applications in 2 μm mid-infrared lasers.展开更多
Ho3＋/yb3＋ co-doped LiYF4 single crystals with various Yb3＋ concentrations and ,-~ 0.98 mol% Ho3＋ concentration are grown by the Bridgman method under the conditions of taking LiF and YF3 as raw materials and a tem...Ho3＋/yb3＋ co-doped LiYF4 single crystals with various Yb3＋ concentrations and ,-~ 0.98 mol% Ho3＋ concentration are grown by the Bridgman method under the conditions of taking LiF and YF3 as raw materials and a temperature gradient （40 ~C/cm-50 ~C/cm） for the solid-liquid interface. The luminescent performances of the crystals are investigated through emission spectra, infrared transmittance spectrum, emission cross section, and decay curves under excitation by 980 nm. Compared with the Ho3＋ single-doped LiYF4 crystal, the Ho3＋/yb3＋ co-doped tiYf4 single crystal has an obviously enhanced emission band from 1850 nm to 2150 nm observed when excited by a 980-nm diode laser. The energy transfer from Yb3＋ to Ho3＋ and the optimum fluorescence emission around 2.0 p-m of Ho3＋ ions are investigated. The maximum emission cross section of the above sample at 2.0 p.m is calculated to be 1.08 × 10-20 cm2 for the LiYF4 single crystal of 1-mol% Ho3＋ and 6-mo1% Yb3＋ according to the measured absorption spectrum. The high energy transfer efficiency of 88.9% from Yb3＋ to Ho3＋ ion in the sample co-doped by Ho3＋ （1 mol%） and Yb3＋ （8 tool%） demonstrates that the Yb3＋ ions can efficiently sensitize the Ho3＋ ions.展开更多
文摘Downconversion （DC） with emission of two near-infrared photons about 1000 nm for each blue photon absorbed was obtained in thulium （Tm3＋） and ytterbium （Yb3＋） codoped yt- trium lithium fluoride （LiYF4） single crystals grown by an improved Bridgman method. The luminescent properties of the crystals were measured through photoluminescence excitation, emission spectra and decay curves. Luminescence between 960 and 1050 nm from yb3＋： 2Fs/2--＋2FT/2 transition, which was originated from the DC from Tm3＋ ions to Yb3＋ ions, was observed under the excitation of blue photon at 465 nm. Moreover, the energy transfer processes were studied based on the Inokuti-Hirayama model, and the results indicated that the energy transfer from Tm3＋ to Yb3＋ was an electric dipole-dipole interaction. The max- imum quantum cutting efficiency approached with 0.49mo1% Tm3＋ and 5.99mo1% Yb3＋. increasing the energy efficiency of crystalline energy part of the solar spectrum. up to 167.5% in LiYF4 single crystal codoped Application of this crystal has prospects for Si solar cells by photon doubling of the high
文摘The electronic structures of LiYF4：Ce^3＋ and LiYF4 crystal simulated by an embedded （in a microcrystal containing 1938 ions） cluster CeY4Li8F24, and Y5LisF24 respectively, were computed by the ab initio self-consistent relativistic DV-Xa （discrete variational Xa） method. The ground-state calculation showed that only the lowest 5d level Ed of Ce^3＋ ion lies around the BCB （bottom of the conduction band） while the lowest 4f levels is 2.5 eV lower than BCB. The CB states consist of 4d of Y mixed with 5d of Ce, even for the wavefunctions （WFS） with energy Ed under BCB there are still 24% of Y-4d and 9% of F-2p as components. So, they are not pure crystal-field states at all. Furthermore, transition state （TS） calculation was performed to obtain the 4f→5d transition energies Efd, to improve the previous calculation performed by Andriessen et al, in which a small CeF8 cluster embedded in an array of point charge was used and the results of ground-state calculation were roughly used to compare with the observed 4f→5 d transition energies. The ionic radius of Ce^3＋ is larger than that of y^3＋ , so we had also modeled approximately the lattice relaxation. As results, the CeY4Li8F24 cluster with 4.56 % outward relaxation （of the nearest-neighbor and next nearest-neighbor eight fluorines） has the lowest total energy and gave satisfactory 4f→5d energies Efd, but the ground-state calculated Ed is 0.68 eV higher than BCB. For another cluster with 7.36% outward relaxation the Ed is 0.43 eV lower than BCB, which makes the observation of fine structure （including zero-phonon line） of the lowest 5 d band understandable easier, but the splits between the transition energies Efd were not as good as the former. Therefore, we consider the relaxation is some how around 4. 56% -7.36% outward, not as large as 10% proposed by Andriessen et al.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB20000000)
文摘Pr^（3＋）-doped transparent oxyfluoride glass-ceramic containing tetragonal LiYF_4 nanocrystals has been synthesized by melting-quenching method and subsequent thermal treatment and spectroscopic properties of Pr^（3＋） ions were investigated. The crystalline phase and microstructure of the LiYF_4 nanocrystals were studied by X-ray diffraction（XRD） and transmission electron microscopy（TEM）, respectively. Compared with those of Pr^（3＋）-doped glass（Pr^（3＋）：PG）, the sharp absorption and emission bands of Pr^（3＋）-doped glass-ceramic（Pr^（3＋）：GC） reveal parts of Pr^（3＋） ions are incorporated into LiYF_4 nanocrystals. The peak absorption cross-section at 443 nm（~3H_4 → ~3P_2） adds to 110% and the full width at half maximum（FWHM） for the band around 443 nm reduces from 22 to 14 nm after crystallization. The fluorescence lifetime of the ~3P_0 multiplet of Pr^（3＋） ions increases from 5.35 to 11.14 μs after crystallization. The results indicate that this glass-ceramic is promising to be a visible laser material.
文摘The electronic structures of LiYF4：Ce^3＋ and LiYF4 crystal simulated by an embedded （in a microcrystal containing 1938 ions） cluster CeY4Li8F24, and Y5LisF24 respectively, were computed by the ab initio self-consistent relativistic DV-Xa （discrete variational Xa） method. The ground-state calculation showed that only the lowest 5d level Ed of Ce^3＋ ion lies around the BCB （bottom of the conduction band） while the lowest 4f levels is 2.5 eV lower than BCB. The CB states consist of 4d of Y mixed with 5d of Ce, even for the wavefunctions （WFS） with energy Ed under BCB there are still 24% of Y-4d and 9% of F-2p as components. So, they are not pure crystal-field states at all. Furthermore, transition state （TS） calculation was performed to obtain the 4f→5d transition energies Efd, to improve the previous calculation performed by Andriessen et al, in which a small CeF8 cluster embedded in an array of point charge was used and the results of ground-state calculation were roughly used to compare with the observed 4f→5 d transition energies. The ionic radius of Ce^3＋ is larger than that of y^3＋ , so we had also modeled approximately the lattice relaxation. As results, the CeY4Li8F24 cluster with 4.56 % outward relaxation （of the nearest-neighbor and next nearest-neighbor eight fluorines） has the lowest total energy and gave satisfactory 4f→5d energies Efd, but the ground-state calculated Ed is 0.68 eV higher than BCB. For another cluster with 7.36% outward relaxation the Ed is 0.43 eV lower than BCB, which makes the observation of fine structure （including zero-phonon line） of the lowest 5 d band understandable easier, but the splits between the transition energies Efd were not as good as the former. Therefore, we consider the relaxation is some how around 4. 56% -7.36% outward, not as large as 10% proposed by Andriessen et al.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51472125 and 51272109)the Natural Science Foundation of Ningbo City,China(Grant No.201401A6105016)K.C.Wong Magna Fund in Ningbo University,China(Grant No.NBUWC001)
文摘In this paper, optical spectra of LiYF4 single crystals doped with Tm3＋ ions of various concentrations are reported. The emission intensity at 1.8 ktm first increases with increasing Tm3＋ concentration, and reaches a maximum value when the concentration of Tm3＋ is about 1.28 mol%, then it decreases rapidly as the concentration of Tm3＋ further increases to 3.49 mol%. The emission lifetime at 1.8 p.m also shows a similar tendency to the emission intensity. The maximum lifetime of 1.8 μm is measured to be 17.68 ms for the sample doped with Tm3＋ of 1.28 mol%. The emission cross section of 3F4 level is calculated. The maximum reaches 3.76 × 10 -21 cm2 at 1909 nm. The cross relaxation （3H6, 3H4 →3 F4, 3F4） between Tm3＋ ions and the concentration quenching effect are mainly attributed to the change of emission with Tm3＋ concentration. The largest quantum efficiency between Tm3＋ ions is estimated to be ,-147% from the measured lifetime and calculated radiative lifetime. All the results suggest that the Tm3＋/LiYF4 single crystal may have potential applications in 2 μm mid-infrared lasers.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51472125 and 51272109)the K.C.Wong Magna Fund in Ningbo University,China(Grant No.NBUWC001)
文摘Ho3＋/yb3＋ co-doped LiYF4 single crystals with various Yb3＋ concentrations and ,-~ 0.98 mol% Ho3＋ concentration are grown by the Bridgman method under the conditions of taking LiF and YF3 as raw materials and a temperature gradient （40 ~C/cm-50 ~C/cm） for the solid-liquid interface. The luminescent performances of the crystals are investigated through emission spectra, infrared transmittance spectrum, emission cross section, and decay curves under excitation by 980 nm. Compared with the Ho3＋ single-doped LiYF4 crystal, the Ho3＋/yb3＋ co-doped tiYf4 single crystal has an obviously enhanced emission band from 1850 nm to 2150 nm observed when excited by a 980-nm diode laser. The energy transfer from Yb3＋ to Ho3＋ and the optimum fluorescence emission around 2.0 p-m of Ho3＋ ions are investigated. The maximum emission cross section of the above sample at 2.0 p.m is calculated to be 1.08 × 10-20 cm2 for the LiYF4 single crystal of 1-mol% Ho3＋ and 6-mo1% Yb3＋ according to the measured absorption spectrum. The high energy transfer efficiency of 88.9% from Yb3＋ to Ho3＋ ion in the sample co-doped by Ho3＋ （1 mol%） and Yb3＋ （8 tool%） demonstrates that the Yb3＋ ions can efficiently sensitize the Ho3＋ ions.
