Efficient Near-Infrared Quantum Cutting in Tm3＋/yb3＋ Codoped LiYF4 Single Crystals for Solar Photovoltaic

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

非真空密闭条件下的Ce3＋：LiYF4晶体生长

本文报道了氟化物激光晶体Ce3+∶LiYF4的坩埚下降法生长工艺。以高纯氟化物LiF、YF3和CeF3为初始试剂,按照LiF∶YF3∶CeF3=51.5∶47.5∶1.0的物质的量比配料,经高温氟化处理合成严格无水的Ce3+∶LiYF4多晶料。将Ce3+∶LiYF4多晶料密封于铂坩埚中,添加少量聚四氟乙烯粉末,可避免氟化物熔体的氧化与挥发,从而在非真空条件下实现Ce3+∶LiYF4晶体的坩埚下降法生长,成功生长出尺寸达28 mm×70 mm的无色透明完整单晶。采用XRD、差热/热重分析、透射光谱和荧光光谱对Ce3+∶LiYF4单晶基本性质的进行表征。结果表明,该晶体在320~3000 nm区域内的光透过率达90%以上,晶体在297 nm处有一强吸收峰;荧光光谱显示晶体在紫外光区310nm、325 nm处有两个强发射峰。

Optimum fluorescence emission around 1.8μm for LiYF_4 single crystals of various Tm^(3+)-doping concentrations

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.

2.0-μm emission and energy transfer of Ho^(3+)/Yb^(3+) co-doped LiYF_4 single crystal excited by 980 nm

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.

Er^(3+):LiYF_4单晶生长与光谱特性

采用坩埚下降法在非真空密闭条件下生长出尺寸为φ9mm×68mm的1mol%Er3+:LiYF4单晶材料,测试了样品的折射率、透过光谱、吸收光谱、以及在980nm和792nm激光泵浦下的近红外和中红外荧光光谱.应用Judd-Ofelt理论计算了Er3+离子在LiYF4晶体材料中的强度参数(Ωt,t=2,4,6)、能级跃迁振子强度(fcal)、自发辐射跃迁几率(A)、荧光分支比(β)、辐射寿命(τrad)等光谱参数,讨论了其近红外和中红外的荧光特性.结果表明,在980nm和792nm激光泵浦下观察到了1.5μm近红外荧光和3.0μm中红外荧光,分别对应于Er3+:4I13/2→4I15/2和4I11/2→4I13/2跃迁,并分析了3.0μm中红外荧光强度较弱的可能原因.

Ho^(3+):LiYF_4晶体的中红外发光特性

用坩埚下降法制备了Ho3+离子掺杂的LiYF4单晶。测定了Ho3+:LiYF4晶体的偏振吸收光谱。应用Judd-Ofelt理论分别计算了Ho3+:LiYF4晶体中Ho3+离子的有效强度参数Ω2,4,6、能级跃迁振子强度fexp和fcal、自发辐射跃迁几率A、荧光分支比β、辐射寿命τrad等光谱参数。测定了样品在640 nm光激发下的红外发射光谱,观测到由Ho3+离子的5I6→5I7跃迁所致的2.8～3μm中红外发光,以及在1.2μm(5I6→5I8)和2.0μm(5I7→5I8)处较强的荧光。Ho3+:LiYF4单晶样品的吸收峰线宽较宽,计算得到1.2μm和2.0μm的峰值发射截面分别达到0.20×10-20cm2和0.51×10-20cm2,同时测定了1 191 nm(5I6→5I8)和2 059 nm(5I7→5I8)发射的荧光寿命。研究结果表明:Ho3+:LiYF4晶体在2.0～3μm波段的中红外激光器中有较大的应用前景。

坩锅下降法生长Nd～(3+)∶LiYF_4单晶及其光谱性能研究

以LiF∶YF3∶NdF3=51.5∶47.5∶1为原料摩尔比,在50～60℃/cm固液界面温度梯度下,采用密封的坩埚下降法制备了尺寸为φ10 mm×50 mm的高质量Nd3+掺杂LiYF4单晶,并对产物的物相结构和光谱性能进行表征。结果表明,Nd3+在807 nm处的最大吸收系数α=1.96 cm-1,吸收跃迁截面为0.973×10-20cm2。在808 nm LD激发下,测定了样品的荧光光谱和及最强荧光峰1050 nm(4F3/2→4I11/2)的荧光寿命(～451.0μs),并计算得到1050nm的最大受激发射跃迁截面为1.60×10-19cm2。

Pr^(3+)掺杂的LaF_3纳米微晶/氟氧化物玻璃陶瓷的VUV光谱

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+.

CF4气氛中生长Re：LiM(Re=Tm,Ce;M=Lu,Y)F4晶体

本文在CF4气氛中以提拉法成功地生长出高质量的掺入Tm3+、Ce3+的LiLuF4和LiYF4晶体,对比了Ar和CF4气氛中生长的LiYF4晶体的红外光谱特性,讨论了CF4气氛对LiM(M=Y,Lu)F4晶体生长的影响。同时测试了Tm3+、Ce3+在LiLuF4和LiYF4晶体中的有效分凝系数,从离子半径和晶胞畸变的角度,讨论了Tm3+、Ce3+在LiLuF4和LiYF4晶体中有效分凝系数差别的产生原因。

LiYF_4晶体中Ho^(3+)离子真空紫外吸收光谱的理论解析

运用配位场理论方法获得了Ho3+离子低自旋4f95d组态的谱项和J-光谱多重态,根据电偶极跃迁选律合理地解析了LiYF4晶体中Ho3+离子在真空紫外区(120～160 nm)的吸收光谱,4个主要的吸收峰分别被归属为从基态(5I8)到Ho3+离子的低自旋4f95d组态的自旋允许跃迁。

双波长二极管合束端面抽运掺镨氟化钇锂单纵模360nm紫外激光器

报道了一种双波长半导体激光二极管(LD)合束端面抽运掺镨氟化钇锂晶体(Pr^(3+):LiYF_4)全固态、单纵模360nm紫外激光器.该激光器采用V形折叠腔结构,利用反射式体布拉格光栅作为波长选择反射镜来压缩光谱线宽,与法布里-珀罗(F-P)标准具组合构成窄带滤波器进行单纵模的有效选取,通过Ⅰ类位相匹配切割的倍频晶体三硼酸锂对腔内720nm基频光进行倍频.在444nmLD输出功率为1200mW和469nmLD输出功率为1400mW时,合束抽运获得了功率为112mW的连续单纵模360nm紫外激光稳定输出,光-光转换效率为4.3%.测量结果表明,边摸抑制比大于60dB,4h功率均方根值稳定性优于0.5%,1h频率漂移小于220MHz,激光振幅噪声小于0.5%.

Yb^(3+)∶LiYF_4激光晶体的生长与光谱性能

报道了氟化物激光晶体Yb3+∶LiYF4的单晶生长与光谱性能。按照n(LiF)∶n(YF3)∶n(YbF3)=51.5∶47.5∶1.0制备配合料,经干燥HF气氛下的固相烧结合成制备出无水Yb3+∶LiYF4多晶料;采用非真空密闭条件下的坩埚下降法成功生长出系列12 mm尺寸的透明完整Yb3+∶LiYF4单晶。采用化学分析和光谱测量表征了所生长单晶的掺杂浓度和光谱性能,结果表明,Yb3+离子已成功掺杂进入基质晶体,其有效分凝系数估算为0.455;此单晶在较宽波长范围内具有良好光学透过性,在896 nm波长激发光作用下,该单晶具有930~1 030 nm波长范围的荧光发射,其荧光衰减寿命为1 888μs。

Dy^(3+)-doped LiYF_4 crystals for UV-excited white light-emitting diodes

A Dy3＋-doped LiYF4 single crystal capable of generating white light by simultaneous blue and yellow light emission of phosphorescent centers is produced. Chromaticity coordinates and photoluminescence intensity vary with excitation wavelength. Under 350, 365, and 388 nm excitation, the crystal shows excellent white light emission. The most efficient wavelength for white light is 388 nm. The CIE coordina.tes are x=0.316 and y =0.321, and the color temperature （Tc） is 6 368 K. These results indicate that the studied crystal is a potential candidate for ultraviolet light-excited white light-emitting diodes.

Optical Spectra and Gain Properties of Ho^(3+)/Pr^(3+)Co-doped LiYF_4 Crystal

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 the Ho3＋：5/6 level. The Ho3＋/pr3＋：LiYF4 crystal may be a potential media for 2.9 μm mid-infrared laser.

Refractive Index Change and Color Center Formation in LiYF_4 Crystal Induced by a Femtosecond Laser

The refractive index change and color centers formation in LiYF4 crystal at room temperature are induced by a femtosecond laser irradiation. A mechanism for refractive index change and color centers formation is proposed.

Spectral properties of Tm,Ho:LiYF_4 laser crystal

The LiYF4 single crystal codoped with thulium and holmium ions was successfully grown by the Cz method. The optimal technical parameters obtained were as follows： the pulling rate was 0.16 mm/h; the rotation speed was 3 rpm; the cooling rate was 15 °C/h. The result of XRD curve showed that as-grown Tm,Ho：LiYF4 laser crystal belonged to the monoclinic system with scheelite-type structure and space group I41/a. The cell parameters calculated were： a=0.52160 nm, c=1.09841 nm and Z=4. Absorption and fluorescence spectra of Tm,Ho：LiYF4 laser crystal at room temperature were measured and analysed. The absorption cross section, FWHM and absorption coefficient at 779.3 nm calculated were 7.44×10–21 cm2, 8.7 nm and 2.23 cm–1, respectively. An intensive fluorescence emission peak appeared near 2045 nm. The emission cross section and fluorescence lifetime were 0.87×10–20 cm2 and 10.8 ms, respectively. The ratio of Tm–Ho transfer to its back-transfer process was 10.6.

Tm^(3+) and Nd^(3+) singly doped LiYF_4 single crystals with 3-5 μm mid-infrared luminescence

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.

Simulation of f-d transition using the extended crystal-field model:parameter dependent study for Er^(3+) in various hosts

The 4f-5d transitions of Er3+ ions doped in crystals were widely studi ed due to their potential applications in quantum cutting phosphors and VUV lase rs,etc.The theory to do the calculations of 4f-5d transitions and various rela ted aspects,such as the ways to determining various parameters,were summarized .The impacts of various interactions on the spectra were also demonstrated clea rly with Er3+ ions in crystals CaF2 and LiYF4.Predicted results were compared w ith measured spectra.

亚晶格能量团簇构建及晶场调控对四方LiYF4:RE上转换发光机制的影响研究

四方LiYF4是一种与六方NaYF4相当的稀土上转换发光基质材料,由于相对优异的短波上转换发光特性,近年受到业界的相当关注,但对产生这一优异特性的原因还未见报道.经研究发现,四方LiYF4具有六边环状亚晶格结构,每5个间距小于0.4 nm的近邻三价阳离子形成一个团簇,稀土离子间的能量传递容易在团簇内或六边形环内环绕传递.基于它的这一亚晶格结构特征,本工作通过引入不同量敏化剂Yb^3+和掺杂离子Sc^3+和Hf^4+,考察不同激活离子Er^3+、Ho^3+和Tm^3+与敏化离子Yb^3+构建亚晶格能量团簇以及异质离子Sc^3+和Hf^4+掺杂晶场调控对稀土离子上转换发光性能的影响机制.发现不同稀土离子与Yb^3+存在不同的能级匹配,导致不同概率的无辐射交叉弛豫行为,当引入适量的Yb^3+时,可分别构建1Er-2Yb、1Ho-2Yb和1Tm-4Yb亚晶格能量团簇,实现最佳的上转换发光性能;当6 mol%Sc^3+和4mol%Hf^4+引入时,可有效调控晶场的不对称性;掺杂后,5个近邻三价离子的团簇结构中,只有3个近邻Yb^3+离子,无法同时实现Er^3+离子的4F5/2和Sc^3+的2G7/2或Hf^4+的4Fo5/2激发态的双光子合作上转换电子布居,导致Sc^3+或Hf^4+成为荧光猝灭中心, Sc^3+掺杂晶场调控最大仅提升50%的荧光强度, Hf^4+掺杂没有提升反而降低Er3+离子的上转换发光强度,不同于它们掺杂六方NaYF4:Er/Yb那样扮演储能离子角色,显著提升Er^3+离子的短波上转换发光强度.本研究揭示了在六边环状亚晶格基质结构中不同稀土离子与敏化剂Yb^3+的敏化上转换发光机制,以及基质结构特征对掺杂晶场调控行为的影响机制,可为设计和制备高性能上转换发光材料提供借鉴.

Crystal-field analyses for trivalent lanthanide ions in LiYF_4

Based on the completely parametric crystal-field model, the energy level parameters, including free-ion parameters and crystal-field parameters, obtained by fitting the experimental energy level data sets of Ln^（3＋） in LiYF_4 were systematically analyzed. The results revealed that the regular variation trends of the major parameters at relatively low site symmetry still existed. The g factors of ground states were calculated using the parameters obtained from least-squares fitting. The results for Ce^（3＋）, Nd^（3＋）, Sm^（3＋）, Dy^（3＋） and Yb^（3＋） were in good agreement with experiment, while those of Er^（3＋） deviated from experiment dramatically. Further study showed that the g factors depended strongly on B_4~6, and a slightly different B_4~6 value of -580cm^（-1） led to g factors agreeing well with the experimental values.