Structural and photoluminescence studies on europium-doped lithium tetraborate(Eu:Li_2B_4O_7) single crystal grown by microtube Czochralski(μT-Cz) technique

Rare earth europium(Eu(3+))-doped lithium tetraborate(Eu:Li_2B_4O_7) crystal is grown from its stoichiometric melt by microtube Czochralski pulling technique(μT-Cz) for the first time. The grown crystals are subjected to powder x-ray diffraction(PXRD) analysis which reveals the tetragonal crystal structure of the crystals. UV–vis–NIR spectral analysis is carried out to study the optical characteristics of the grown crystals. The crystal is transparent in the entire visible region, and the lower cutoff is observed to be at 304 nm. The existence of BO_3 and BO_4 bonding structure and the molecular associations are analyzed by Fourier transform infrared(FTIR) spectroscopy. The results of excitation and emission-photoluminescence spectra of europium ion incorporated in lithium tetraborate(LTB) single crystal reveal that the observations of peaks at 258,297, and 318 nm in the excitation spectra and peaks at 579, 591, 597, 613, and 651 nm are observed in the emission spectra.The chromaticity coordinates are calculated from the emission spectra, and the emission intensity of the grown crystal is characterized through a CIE 1931(Commission International d'Eclairage) color chromaticity diagram.     

V-doped MgAl6O10:novel luminescence substrate for phosphor-free UV-white LEDs

V-doped MgAl6O10 is grown by the conventional Czochralski method. The crystal structure and the cell parameters are analyzed through X-ray diffraction experiments. The absorption and emission spectra are investigated. Under pumping at 324 nm, the emission spectra of V-doped MgAl6O10 obtain two emission peaks at the wavelengths of 471 and 570 nm. Two emission bands of the spectra combine to produce a spectrum that is perceived as white by the naked eye. Therefore, V-doped MgAl6O10 single crystal can be applied as substrate for phosphor-free ultraviolet (UV)-white light-emitting diodes (LEDs).     

Ce~(3+)ion-doped α-NaYF_4 single crystal for UV laser

A Ce~(3+)tion-doped α-Na YF_4 single crystal of high quality is grown successfully by an improved flux Bridgman method under the conditions of taking the chemical raw composition of Na F:KF:YF_3:CeF_3 in the molar ratio of30∶18∶48∶4, where the KF is shown to be an effective assistant flux. The x ray diffraction, absorption spectra,excitation spectra, and emission spectra of the Ce~(3+)t-doped α-Na YF_4 single crystal are measured to investigate the phase and optical properties of the single crystals. The absorption spectrum of the Ce~(3+)t:α-Na YF_4 shows a strong band that peaks at the wavelength of 300 nm. The emission spectrum of the Ce~(3+)t:α-Na YF_4 emits an intense ultraviolet(UV) band at the wavelength of 332 nm under the excitation of 300 nm light. Two separated luminous bands of 330 and 350 nm, which correspond to the transitions 5d → 2F25∕2and 5d → F7∕2, can be obtained by Gauss fitting. The strong emission intensity at the UV band and the excellent optical transmission in the range of UV wavelengths indicate that Ce~(3+)t:α-Na YF_4 single crystals can be considered as a promising material for UV lasers.     

Intensities and spectral features of the ~4I_(13/2)-~4I_(15/2) potential laser transition of Er~(3+) centers in CaF_2-CeF_3 disordered crystal

A CaF_2-CeF_3 disordered crystal containing 1.06% of Er~(3+) ions was grown by the temperature gradient technique.Optical absorption and emission spectra recorded at room temperature and at 10 K, luminescence decay curve recorded at room temperature, and extended x-ray-absorption fine structure spectra were analyzed with an intention to assess the laser potential related to the ~4I_(13/2)→~4I_(15/2) transition of Er~(3+). In addition, the thermal diffusivity of the crystal was measured at room temperature. The analysis of room-temperature spectra revealed that the ~4I_(13/2) emission is long-lived with a radiative lifetime value of 5.5 ms, peak emission cross section of 0.73 × 10~(-20) cm~2, and large spectral width pointing at the tunability of the emission wavelength in the region stretching from approximately 1480 nm to 1630 nm. The energies of the crystal field components for the ground and excited multiplets determined from low-temperature absorption and emission spectra made it possible to predict successfully the spectral position and shape of the room-temperature ~4I_(13/2)→~4I_(15/2) emission band. Based on the correlation of the optical spectra and dynamics of the luminescence decay, it was concluded that in contrast to Yb~(3+) ions in heavily doped CaF_2 erbium ions in the CaF_2-CeF_3 crystal reside in numerous sites with dissimilar relaxation rates.     

Influence of Al~(3+) doping on the energy levels and thermal property of the 3.5MgO·0.5MgF_2·GeO_2:Mn~(4+) red-emitting phosphor

A series of Al3+-doped 3.5MgO·0.5MgF2·GeO2:Mn4+red-emitting phosphors is synthesized by high temperature solid-state reaction. The broad excitation band at 300 nm–380 nm, resulting from the4A2→4T1transition of Mn4+,exhibits a blue shift with the increase of Al2O3 content. The observation of the decreased Mn4+–O2-distance is explained by the crystal field theory. The temperature-dependent photoluminescence spectra with various amounts of Al2O3 content are comparatively measured and the calculation shows that the activation energy increases up to 0.41 eV at the Al2O3 content of 0.1 mol. The maximum phonon densities of state for these samples are calculated from Raman spectra and they are correlated with the thermal properties.     

Spectroscopic properties of thulium ions in bismuth silicate glass

A new type of bismuth silicate glass (Bi2O3-SiO2-ZnO-Al2O3-La2O3) doped with Tm2O3 is prepared by melt-quenching method. The thermal stability of the glass is examined by differential scanning calorimetry. No crystallization peak is found. Using the absorption and emission spectra, the absorption and emission cross-sections are calculated. Their maximum data are 2.9×10-21cm2 at 1663 nm and 4.7×10-21cm2 at 1826 nm, respectively. Using the Judd-Ofelt theory, the radiation transition probabilities and radiative lifetimes are obtained. The extended overlap integral method is applied to analyze energy transfer process among the Tm3+ ions. The transfer constants of cross-relaxation and energy migration among the Tm3+ ions at the 3H4 level are 7.60×10-40 and 14.98×10-40 cm6 /s, respectively. The critical transfer radius for cross-relaxation is 0.99 nm. The cross relaxation process is easy to realize and is favorable for obtaining ～2-μm laser.     

Spectroscopic investigation of a new crystal： Nd^3＋,Yb^3＋：YVO4

The absorption and emission spectra of the YVO4 single crystal co-doped with 1 at.% Nd^3＋ and 1 at.% Yb^3＋ are investigated. The efficient Nd^3＋ → Yb^3＋ energy transfer and the back transfer （Yb^3＋ → Nd^3＋） are observed at room temperature. The fluorescence lifetime of the 4F3/2 level of Nd^3＋ in Nd,Yb：YVO4 is measured under 808 nm laser light excitation. The efficiency of Nd^3＋ → Yb^3＋ energy transfer in YVO4 is determined to be about 34%.     

Influence of Gamma-Ray Irradiation on Absorption and Fluorescent Spectra of Nd：YAG and Yb：YAG Laser Crystals

We investigate the influence of gamma-ray irradiation on the absorption and fluorescent spectra of Nd^3＋：Y3A15 O12 （Nd： YAG） and Yb^3＋ ： Y3A15 O12 （Yb： YAG） crystals grown by the Czochralski method. Two additional absorption （AA） bands induced by gamma-ray irradiation appear at 255nm and 340nm. The former is contributed due to Fe^3＋ impurity, the latter is due to Fe^2＋ ions and F-type colour centres. The intensity of the excitation and emission spectra as well as the fluorescent lifetime of Nd：YAG crystal decrease after the irradiation of 100 Mrad gamma-ray. In contrast, the same dose irradiation does not impair the fluorescent properties of Yb：YAG crystal. These results indicate that Yb： YA G crystal possesses the advantage over Nd： YA G crystal that has better reliability for applications in harsh radiant environment.     

Investigation of the growth and optical properties of a Co~(2+)-doped Na_5Lu_9F_(32) single crystal

A 0.1 mol.% CoF_2-doped Na_5Lu_9F_(32)single crystal with high quality in the size of ～φ10 mm×100 mm was grown by the Bridgman method. Three peaks located at 504, 544, and 688 nm and a broad band in the range of 1200–1600 nm centered at 1472 nm were observed in the absorption spectra. The absorption peak position suggests cobalt ions in the divalent state in the grown crystal. Moreover, the cobalt ions are confirmed to locate in the distorted cubic crystal structure. Upon excitation of 500 nm light, a sharp emission peak at 747 nm ascribed to the ~2T_2(H_1) →~4A_2(F) transition was observed for the crystal. The Co~(2+)-doped Na_5Lu_9F_(32)crystal shows a potentially promising material for the application of a passively Q-switched laser operating in the near-infrared range.     

Growth and spectroscopic characteristics of Nd-doped PbWO₄ crystal

Nd-doped PbWO4 crystals are grown by using the modified Bridgman method.The spectroscopic properties of the crystals are investigated.The changes of the absorption band at 350 nm are discussed for samples annealed at 740℃ and 1040℃.The radiative lifetime of the 4 F 3/2 level is calculated by using the Judd-Ofelt theory according to the absorption spectrum of 0.5 at.% Nd-doped PbWO 4 crystal.The spontaneous Raman scattering properties of the crystals are analysed.     

Tm3+掺杂CdWO4单晶的发光特性

用坩埚下降法生长获得了尺寸为φ25 mm×90 mm、Tm₂O₃初始掺杂摩尔分数为0.5%的CdWO₄单晶。晶体的颜色由上部血红色逐渐加深至下部的黑褐色。对不同部位的晶体薄片进行800 ℃的氧化处理,测定了处理前后不同部位的吸收光谱和FTIR红外光谱。经氧气退火处理后,由于氧空位缺陷减少,晶体的颜色明显变淡。在吸收光谱中观测到421,684,805 nm的吸收带。其中421 nm的吸收峰随退火温度的升高而逐步减弱,经800 ℃处理后基本消失。在808 nm激光二极管激发下,观察到中心波长为1.5 μm和1.8 μm的荧光发射,分别对应于Tm³⁺的³H₄→³F₄,³F₄→³H₆的能级跃迁。     

掺Co钨酸镉单晶体的坩埚下降生长及光谱特性

应用坩埚下降法,采用70℃.cm-1的固液界面温度梯度与0.50 mm.h-1生长速度,生长出了初始Co掺杂摩尔百分浓度为0.5 mol%、尺寸为Ф25 mm×120 mm的钨酸镉单晶体。晶体呈透明深蓝色。用XRD表征了获得的晶体。观测到518,564和655 nm三个可见波段吸收带以及发光中心1 863 nm(1 323～2 220 nm)的超宽吸收带。可见波段的吸收归属于Co2+在八面晶格场中4T1(4F)→4A2(4F),4T1(4F)→4T1(4P)跃迁叠加,而红外波段的宽带吸收则为八面体场Co2+的4T1(4F)→4T2(4F)能级跃起所致。从吸收特性表明,Co离子掺杂于畸变的氧八面体中,呈现+2价态。根据吸收光谱计算出晶格场参数Dq=990 cm-1,Racah参数BC=726.3 cm-1。在520 nm波长光的激发下,观察到778 nm波段的荧光发射,归属于八面体晶格场中Co2+的4T1(4P)→4T1(4F)能级的跃迁。从吸收与荧光强度的变化推断:沿着晶体生长方向,Co2+浓度逐渐增加,有效分凝系数小于1。     

水热法祖母绿激光晶体的光谱性质研究

报道了温差水热法生长的祖母绿激光晶体(Cr3+:Be3Al2Si6O18)的光学参量特点.通过对祖母绿晶体的吸收光谱和荧光光谱的测量,计算了晶体场强度Dq、Racah参量B和C, Dq/B≈2.3,说明了祖母绿晶体中的Cr3+离子处于中等晶场.室温下的荧光光谱特点显示4T2→4A2的跃迁为700～840nm的宽带辐射跃迁.此外该晶体的有效声子能量h－ω=409.6cm－1,Huang-Rhys因子S=3.5较小,说明祖母绿的电-声子耦合作用较弱.     

γ射线辐照与O2退火对Bi∶CdWO4单晶体光谱性能的影响

用500和800℃,在氧气下,对掺Bi钨酸镉晶体进行热退火处理,测定了处理后晶体的吸收光谱与发射光谱。随退火处理温度的升高晶体的吸收强度降低,吸收边带发生蓝移。在373与980nm的光激发下,分别观察到发光中心为528nm的CdWO4晶体本征发光与发光中心为1 078nm的Bi 5+发光。晶体样品通过高温氧气处理,发光中心为528nm的荧光带强度增强,但发光中心为1 078nm的荧光带强度变弱。这可能是由于氧退火使Bi 5+转化成Bi 3+所致。经退火处理后,晶体的颜色逐渐变浅,透光率明显提高,这是由于晶体中氧空位减少所致。经γ射线辐照处理后,528nm处的发光增强,而1 078nm处的发光减弱,这可能是由于γ射线辐照后导致Bi 5+变成Bi 3+。     

大尺寸掺钛铝酸铍(Ti~(3+):BeAl_2O_4)激光晶体的提拉法生长

应用提拉法技术,采用BeO:Al2O3:Ti2O3摩尔比=100:99.85:0.15的化学组分配比,以及选用合适的固液界面温度梯度与生长速度等优化工艺条件,成功地生长出了T3+离子掺杂、无气泡、无云层和核心、尺寸≈Ф60mm×85mm的粉红色Ti3+:BeAl2O4大尺寸晶体。测定了Ti3+:BeAl2O4晶体的激发与荧光光谱。沿着晶体生长方向,晶体的颜色变深。在激发光谱中观测到了502 nm与567nm的激发峰,在发射光谱中观察到了发光中心为710nm的宽带荧光。两激发峰与Ti3+离子的2T2→2E能级跃迁有关,710nm的荧光峰是由振动能级2E→2T2产生的。从不同部位晶体的吸收强度和颜色变化可得到Ti3+离子在BeAl2O4晶体中的有效分凝系数小于1。     

Ca4LaNbMo4O20:Pr3+荧光粉的发光性质

采用高温固相法成功制备出荧光粉Ca₄LaNbMo₄O₂₀:Pr³⁺,通过X射线衍射分析了样品的结构,其结构与CaMoO₄结构相似。在Ca₄LaNbMo₄O₂₀:Pr³⁺的激发光谱中出现了NbO₄^3-和MoO₄^2-的电荷迁移(CTS)吸收和Pr³⁺离子的4f→4f5d激发跃迁,以及Pr³⁺-金属离子的价间电荷迁移(IVCT)吸收;另外在420~520 nm处,还观测到属于Pr³⁺离子的典型f-f激发跃迁。发射光谱中,在452 nm激发下,主要出现绿光和红光两种发射,其峰值位于490 nm和607 nm处,分别是Pr³⁺的³P₀→³H₄和¹D₂→³H₄的跃迁作用;在紫外287 nm激发下出现NbO₄^3-和MoO₄^2-发射和Pr³⁺离子的4f5d→4f跃迁宽带,以及Pr³⁺离子的4f→4f发射峰。     

LiNbO3:Cr:ZnO晶体生长和光谱特性的研究

采用提拉法从近化学计量比的熔体中生长出尺寸为φ20 mm×50 mm的优质LiNbO3:Cr:ZnO(CZLN)晶体,其光学均匀度为7.59(10-5).进行了吸收和荧光光谱的测定研究.吸收谱测试表明:Cr3 离子在晶体中有2个宽且强的吸收带及1个微弱的吸收线,两宽带中心波长分别为480和660 nm,对应于4A2→4T1和4A2→4T2两个具有相同的总自旋能级之间的跃迁,在4A2→4T2吸收宽带的长波边缘处有个很小的吸收峰,其波长为727nm,对应于4A2→2E(R线)的跃迁.荧光测试表明:当激发波长为660 nm时,CZLN晶体荧光宽带和1个较弱的荧光线峰并存,宽带范围为802～988 nm,峰值波长为871 nm,对应于4T2→2E,4A2的联合能级跃迁,荧光线峰波长约为754 nm,其强度较弱,相应于2E→4A2(零声子线)能级跃迁.计算了晶场强度和Racah参数,其Dq/B=2.72,晶体属于强场介质.研究表明,CZLN晶体具备可调谐激光晶体的基本光谱要求,且有良好的物化性能,可以实现宽频带可调谐激光输出.它又具有较大的倍频系数,有望实现420 nm附近紫外的自倍频激光输出.     

977nm抽运下掺铒碲酸盐基氧卤玻璃的光谱特性

研究了掺铒TeO2-ZnO-PbCl2碲酸盐基氧卤玻璃在977nm激光二极管抽运下的发光和上转换发光特性，结果发现除红外153μm4I13/2→４I15/2发光外（荧光半高宽高达69nm），该玻璃还存在很强的２Ｈ11/2→４I15/2（527nm），４Ｓ3/2→４I15/2（549nm）和４Ｆ９／２→４Ｉ１５／２（666nm）可见上转换发光.应用Judd-Ofelt理论计算得到玻璃强度参数Ωt（t=2，4，6）分别为Ω2=587×10-20cm2，Ω4=208×10-20cm2，Ω6=116×10-20cm2，计算了铒离子跃迁振子强度、自发辐射概率、荧光分支比、荧光寿命等光谱参量.应用McCumber理论计算得153μm处的玻璃受激发射截面可达875×10-21cm2实验结果表明，与硅酸盐玻璃、磷酸盐玻璃、氟化物玻璃等比较，掺铒碲酸盐基氧卤玻璃在宽带掺铒光纤放大器和上转换激光器中有着极大的研究和应用潜力. 关键词： 掺Er3+ 碲酸盐玻璃 氧卤玻璃 Judd-Ofelt理论 光谱性质     

温度梯度法生长的Ce: YAlOZr3高温闪烁晶体的光谱分析

采用温度梯度法生长了熔体掺杂Ce浓度为1at%的YAlO3晶体，对于其吸收光谱、荧光光谱和x射线激发发射谱进行了表征分析.根据吸收光谱提出了一个色心模型，从而成功的解释了为什么刚生长出的晶体为粉红色，而分别经氢气和空气在1400℃退火后均能变为无色的现象和退火以后吸收光谱发生的显著变化.温度梯度法生长的Ce:YAP在330nm处存在着一定程度的自吸收和自激发.光致激发发射谱的发射主峰在368nm，而x射线激发发射谱的主发射峰红移至391nm，这表明在x射线激发下，晶体对发射光的自吸收将会减少.另外在x射线 关键词： 温度梯度法 Ce: YAP 色心 光谱     

铬、钕双掺钆镓石榴石(Cr~(4+),Nd~(3+))∶Gd_3Ga_5O_(12)激光晶体光学性能的研究

用提拉法生长了掺铬、钕的钆镓石榴石(Cr4+,Nd3+∶GGG)自调Q激光晶体。报道了室温下的吸收光谱和荧光光谱特性。分析了Cr离子浓度对光谱性质的影响。比较了Cr4+∶GGG,Nd3+∶GGG和(Cr4+,Nd3+)∶GGG晶体吸收光谱的关系。测量了(Cr4+,Nd3+)∶GGG晶体和Nd3+∶GGG晶体的荧光寿命,它们分别是33μs和250μs。实验表明,(Cr4+,Nd3+)∶GGG晶体是一种非常有潜力的自调Q激光晶体,可以实现大功率激光器的小型化和全固态化。