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 vacuum ultraviolet (VUV) spectroscopic properties of praseodymium (Pr3+, 1at%) doped LaF3 nanocrystals/glass at room temperature and 20 K are reported. Two types of Pr3+ ions, those in LaF3 nanocrystals and those ...The vacuum ultraviolet (VUV) spectroscopic properties of praseodymium (Pr3+, 1at%) doped LaF3 nanocrystals/glass at room temperature and 20 K are reported. Two types of Pr3+ ions, those in LaF3 nanocrystals and those in the glass host, were excited to 4f 5d band by VUV using synchrotron radiation as an excitation source, and emissions of 1S0 → 1D2 (336 nm), 1S0 → 1I6 (397 nm ) of Pr3+ in the nanocrystals and emissions of 4f 5d → 3HJ, 3FJ of Pr3+ in the glass appeared at the same time. But unlike in the bulk sample crystals, emission of 3P0 → 3HJ, 3FJ as the second step of the quantum splitting (QS) of Pr3+ in the LaF3 nanocrystals was not observed at room temperature, which could be explained that Pr3+ ions in the glass absorbed the energy of 3P0 → 3H4 of Pr3+ in the nanocrystals. Two types of excitation spectra monitoring different emissions were also measured, so it could be observed that the lowest energy of 4f 5d band of Pr3+ in the nanocrystals was about 53 500 cm-1 (186 nm) and in the glass about 33 800 cm-1(295 nm), respectively. These emission and excitation spectra were contrasted to those of bulk sample crystals LaF3∶Pr3+.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
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 vacuum ultraviolet (VUV) spectroscopic properties of praseodymium (Pr3+, 1at%) doped LaF3 nanocrystals/glass at room temperature and 20 K are reported. Two types of Pr3+ ions, those in LaF3 nanocrystals and those in the glass host, were excited to 4f 5d band by VUV using synchrotron radiation as an excitation source, and emissions of 1S0 → 1D2 (336 nm), 1S0 → 1I6 (397 nm ) of Pr3+ in the nanocrystals and emissions of 4f 5d → 3HJ, 3FJ of Pr3+ in the glass appeared at the same time. But unlike in the bulk sample crystals, emission of 3P0 → 3HJ, 3FJ as the second step of the quantum splitting (QS) of Pr3+ in the LaF3 nanocrystals was not observed at room temperature, which could be explained that Pr3+ ions in the glass absorbed the energy of 3P0 → 3H4 of Pr3+ in the nanocrystals. Two types of excitation spectra monitoring different emissions were also measured, so it could be observed that the lowest energy of 4f 5d band of Pr3+ in the nanocrystals was about 53 500 cm-1 (186 nm) and in the glass about 33 800 cm-1(295 nm), respectively. These emission and excitation spectra were contrasted to those of bulk sample crystals LaF3∶Pr3+.
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.
