Electron paramagnetic resonance and luminescence of chromium in calcium germanate crystals

The luminescence of Ca₂GeO₄: Cr⁴⁺ single crystals at wavelengths in the range of 1.3 μm upon excitation with a 1-μ m semiconductor laser is investigated in the temperature range up to 573 K. At T<110 K, the Ca₂GeO₄: Cr⁴⁺ crystals are characterized by the electron paramagnetic resonance, which is attributed to the Cr⁴⁺ ions substituted for Ge⁴⁺ ions. The components of the g tensor and its principal axes are determined. It is revealed that the Cr⁴⁺ impurity centers in calcium germanate affect the crystal symmetry to a lesser degree compared to Cr⁴⁺ ions in forsterite. The observed deviation of the temperature dependence of the electron paramagnetic resonance from the Curie law is explained by the transition to the excited state with a low activation energy, as is the case in impurity 3d ions in diamond-like semiconductors. The inference is made that the giant effective degeneracy multiplicity of the excited state is associated with the initiation of soft phonon modes in the crystal upon excitation of the defect.     

Forsterite nano glass-ceramics doped with Cr<Superscript>4+</Superscript> ions for fiber lasers and amplifiers

Forsterite nano glass-ceramics doped with tetravalent chromium ions is synthesized, and the spectral and luminescence properties of this material are investigated. A technique for measuring the absolute quantum yield of Cr⁴⁺ luminescence is proposed and implemented experimentally. The luminescence spectra and the absolute quantum yield of Cr⁴⁺ luminescence of the forsterite nano glass-ceramics are compared with those of the forsterite single crystal and calcium aluminate glass doped with tetravalent chromium ions.     

The electronic structure and photoluminescence properties of Ca2GeO4:Eu in ultraviolet and vacuum ultraviolet region

Ca₂GeO₄:Eu³⁺ phosphors were synthesized by the solid state method. The ultraviolet and vacuum ultraviolet excited photoluminescence properties were investigated in detail. It revealed that the emission of Ca₂GeO₄:Eu³⁺ comprised two parts: the red emission of Eu³⁺ and host defect emission in 330-550 nm. Ca₂GeO₄:Eu³⁺ presented intense excitation intensity at 163-200 and 466 nm, which suggested the potential applications in plasma display panels and light emitting diodes. The excitation spectra were studied to identify the photoluminescence mechanisms of Ca₂GeO₄:Eu³⁺. First principles calculation within the local density approximation of the density functional theory was applied to calculate the electronic structure and linear optical properties of Ca₂GeO₄.     

Ca2GeO4 ∶Eu3+ 的电子结构和紫外-真空紫外发光特性的研究

采用高温固相法合成了发光材料Ca₂GeO₄ ∶Eu³⁺ ,并详细研究了其紫外-真空紫外发光特性. 发现并解释了Eu³⁺ 离子在空气中的自还原以及在不同波长激发下的颜色转换现象. Ca₂GeO₄ ∶Eu³⁺ 在163—230和301,466 nm处具有强激发带,表明Ca₂GeO₄ ∶Eu³⁺ 关键词： 2GeO₄ ∶Eu³⁺')" href="#">Ca₂GeO₄ ∶Eu³⁺ 光致发光机理 空气中自还原 颜色转换     

Luminescence of Cr<Superscript>3+</Superscript> impurity ions in Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript> nanocrystals and clusters embedded in lithium germanate glasses

The properties of Cr³⁺-doped Li₂Ge₇O₁₅ (LGO) lithium germanate nanocrystals produced in lithium germanate glasses under isothermal heating were studied. The samples were characterized by x-ray diffraction and small-angle scattering, as well as by transmission electron microscopy. The luminescence spectra of the impurity chromium measured in lithium germanate glasses containing LGO crystals revealed transitions in Cr³⁺ ions residing in the glass phase and in LGO crystallites starting from extremely small clusters. This provided the possibility of following the process of crystallization of the lithium germanate glass from Cr³⁺ luminescence spectra. The effects observed in the Cr³⁺ luminescence spectrum revealed a ferroelectric phase transition in LGO nanocrystals embedded in the glass.     

EPR study of the impurity paramagnetic centres in (CaO−Ga2O3−GeO2) glasses

The X-band EPR spectra of Cr³⁺, Mn²⁺, and Fe³⁺ impurity ions in glasses of (CaO?Ga₂O₃?GeO₂) system are investigated in the 77÷300 K temperature range. The experimental data analysis yields the following results: (i) Impurity chromium ions are incorporated into the (CaO?Ga₂O₃?GeO₂) glasses network in Cr³⁺ (3d³,⁴F_3/2) paramagnetic valence state only and occupy the strong distorted oxygen coordinated octahedral sites. (ii) For all activated and non-activated (CaO?Ga₂O₃?GeO₂) glasses the iron impurity is present at concentration roughly 0.01 wt.%. Isotropic EPR signals atg _eff=4.29 andg _eff=2.00 are assigned to Fe³⁺ (3d⁵,⁶S_5/2) ions in the sites with strong rhombic distortion and in the sites with nearly cubic symmetry respectively. (iii) The manganese EPR spectrum in (CaO?Ga₂O₃?GeO₂) glasses is weakly dependent on temperature, doping procedure as well as manganese concentration. EPR spectra of impurity manganese ions in glasses with Ca₃Ga₂Ge₃O₁₂ and Ca₃Ga₂Ge₄O₁₄ compositions are virtually identical and belong to Mn²⁺ (3d⁵,⁶S_5/2) ions. Impurity manganese ions are incorporated into the (CaO?Ga₂O₃?GeO₂) glass network as isolated Mn²⁺ centres and clusters of Mn²⁺ ions.     

Nanocrystalline BaTiO3, doped with Eu and Cr: Fluorescence spectroscopy and spontaneous ordering effects

The results of optical studies of Cr³⁺ and Eu³⁺ ions doped nanocrystalline ferroelectric BaTiO₃ produced by the sol-gel process (particle size 20-40 nm) are reported. The Cr³⁺ impurity ions ²E-⁴A₂ (R-lines) fluorescence spectra in BaTiO₃ revealed significant differences from that reported in literature for the bulk material. At least three types of Cr³⁺ centers were found in the spectra. The temperature dependence of optical second harmonic generation in nanocrystalline BaTiO₃: Eu³⁺ shows a strong hysteresis in C_4v-O_h ferroelectric phase transition region, which was explained by the ordering effects in the system of electric dipole moments of dipole nanocrystals. The temperature dependencies of radiative lifetime of Eu³⁺⁵D₀ excited level reveal some hysteresis too. The possibility of influence of the ordering in the system of BaTiO₃:Eu³⁺ nanocrystals on the effective index of refraction of the medium and thus on the Eu³⁺⁵D₀ radiative lifetime, due to the local field effects is discussed.     

Excited state absorption measurements and laser potential of Cr4+ doped Ca2GeO4

4+ doped Ca₂GeO₄ in the 450–2000 nm spectral region at room temperature are presented. Weak ESA bands due to the transition are observed between 1200 and 2000 nm and stronger ESA bands due to peak below 1200 nm. The overlap of the ESA band with the emission which extends from 1100 to about 1600 nm will significantly affect the laser performance of Cr⁴⁺ doped Ca₂GeO₄. The effective peak stimulated emission cross section at 1350 nm in E∥b polarization is only about 3×10^-20 cm². However, our results indicate that tunable laser action between 1300 and 1500 nm should, in principle, be possible. Received: 28 October 1996     

Determination of the charge state of chromium in Cr:Bi<Subscript>12</Subscript>GeO<Subscript>20</Subscript> single crystals by spectral luminescence methods

The valence state and structural localization of Cr ions in Cr:Bi₁₂GeO₂₀ single crystals grown by the Czochralski method in air and annealed in argon or UV-irradiated have been determined in the spectral luminescence study. It is established that chromium is in the state of tetrahedrally coordinated Cr⁴⁺ ions in the samples studied. Octahedrally coordinated Cr²⁺ and Cr³⁺ ions and tetrahedrally coordinated Cr⁵⁺ ions were not revealed.     

Passively Q-switched self-frequency doubling Nd:Ca4GdO(BO3)3 laser with Cr:YAG saturable absorber

Nd³⁺ : Ca₄GdO(BO₃)₃, known as Nd : GdCOB, is a new self-frequency doubling laser crystal. Using Cr⁴⁺ : YAG as passive Q-switch, we have realized the Q-switched laser running at 0.53 μm with an Nd : GdCOB crystal. Meanwhile, the pulse width, the single pulse energy and the repetition rate under different small-signal transmission of Cr⁴⁺ : YAG and different pump conditions are measured and the numerical solutions of the coupling wave rate equations agree with the experimental results.     

Reversible photochromic effects in doped single crystals of bismuth germanium (Bi12GeO20) and bismuth silicon oxide (Bi12SiO20)

Absorption of Bi₁₂GeO₂₀ and Bi₁₂SiO₂₀ single crystals doped with Mn and Cr were investigated before and after illumination with visible light. Pronounced photochromic effects were found. The effects are explained in terms of light induced charge transfer Mn⁴⁺→Mn⁵⁺ and Cr³⁺→Cr²⁺.     

Ultrafast laser pulses generated from the chromium-doped cunyite laser

Femtosecond pulses were generated from a Cr⁴⁺: Cunyite laser using a combination of a broadband semiconductor saturable absorber mirror (SESAM), chirped mirrors, and passive mode locking. The astigmatically compensated asymmetric X-cavity with a 4.5-mm-long Cr⁴⁺:Ca₂GeO₄ sample was operated with a 2.5% output coupler. Dispersion compensation was achieved using chirped mirrors. During self-starting mode-locked operation, pulses as short as 365 fs were generated at a pulse repetition rate of 100 MHz with output power of 70 mW and a spectral bandwidth of 5.2 nm at the center wavelength of 1432 nm.     

Fluorine deficient layer at the surface of transparent glass-ceramics with CaF2 nanocrystals

Optically transparent glass-ceramics with CaF₂ nanocrystals (diameter: ～30 nm) for 25CaF₂–5CaO–20Al₂O₃–50SiO₂ were fabricated using a conventional glass crystallization method in an electric furnace in air and the dispersion state of CaF₂ nanocrystals at the surface was examined from transmission electron microscope observations combined with focused ion beam sample preparations. It was demonstrated that a fluorine deficient layer of about 150–200 nm is formed during the heating at temperatures above the glass transition temperature in the surface region and thus CaF₂ nanocrystals are not present in the surface region. The reason for the formation of such fluorine deficient layers is due to the removal of some fluorine from the surface of bulk glass during heating. The present study gives new information on the crystal growth behavior of fluoride nanocrystals in oxyfluoride glass-ceramics.     

Cr3+:Al2O3透明多晶陶瓷光谱特性分析

对透光性良好的Cr³⁺:Al₂O₃透明多晶陶瓷的光谱性能 进行了研究，其吸收光谱中吸收峰与单晶红宝石相一致，按吸收光谱和Tanabe-Sugano能级 图，算出其晶场强度参数D_q及Racah参数B分别为1792cm^-1， 689cm ^-1，D_q/B=2.6，陶瓷中Cr³⁺离子所处格位的晶体场强 比单晶弱一些，但Cr³⁺:Al₂O₃透明陶瓷仍属于强场晶 体材料；当Cr³⁺掺杂浓度到达0.8wt%时，陶瓷的发射谱仍保持较好的R线发射 ；随Cr³⁺掺杂浓度的增大，激发峰位发生“红移”.在Cr³⁺:Al₂O₃透明多晶陶瓷的荧光谱上，发现一个波长为670nm的发射峰，经激发 谱确认为Cr³⁺的发射峰. 关键词： 氧化铝 透明陶瓷 离子格位 光谱性质     

Thermal stability and spectroscopic properties of Er-doped lead fluorogermanate glasses

The thermal characterization and spectroscopic properties of Er³⁺-doped 0.6GeO₂-(0.4-x)PbO-xPbF₂ glasses were investigated experimentally. With the replacement of PbO by PbF₂ the thermal stability of glasses is improved and the infrared fluorescence intensity at 1530 nm is increased. The Judd-Ofelt intensity parameters, radiative transition rates, and fluorescence lifetimes of the excited ⁴I_13/2 level of Er³⁺ ions were calculated from Judd-Ofelt theory. The asymmetric ligand field around Er³⁺ ions resulted from the incorporation of PbF₂ into germanate glasses, broadens the infrared emission spectra at 1530 nm. Upconversion luminescence in the investigated glasses was observed at room temperature under the excitation of 976 nm laser diode. The glass 0.6GeO₂-0.3PbO-0.1PbF₂ exhibits the maximum upconversion emission intensity, while no frequency upconversion luminescence was observed in the 0.6GeO₂-0.4PbO glass. The quadratic dependence of the green and red emissions on excitation power indicates that two-photon absorption contributes to the visible emission under the 976-nm excitation.     

Luminescence behavior of Tb ions in transparent glass and glass-ceramics containing CaF2 nanocrystals

Transparent glass-ceramics have been fabricated by heat treatment with 1.0 mol% Tb₂O₃-doped 45SiO₂-20Al₂O₃-10CaO-25CaF₂ aluminosilicate glass. The precipitated crystalline phase in the glass-ceramics is CaF₂ nanocrystals with a size of 15-27 nm and dispersed in the amorphous phase. Both photo- and radioluminescence measurements show that the increase of Tb³⁺ 545 nm line intensity by a factor of 4 and 3.5 is obtained in glass-ceramics with respect to the as-made glass, respectively.     

Enhanced Green Emission from Er<Subscript>2</Subscript>WO<Subscript>6</Subscript> Nanocrystals Embedded Composite Tellurite Glasses

A series of tungsten-tellurite glasses activated with different concentrations (0–1.5 mol %) of Er³⁺ has been synthesized. The structural properties of the best luminescent sample and the optical properties of its Er³⁺ ions, are studied both immediate after its preparation as well as after its ageing. On ageing the glass suffers structural reorganization and generates Er₂WO₆—nanocrystals in the matrix, which greatly enhances the normal and upconversion green luminescence efficiency of Er³⁺. The nanocrystal aided enhancement of normal and upconversion luminescence of Er³⁺ of the glass has been attributed to the crystal field effects of the new environment of Er³⁺ in the nanocrystals. A phenomenon of preferential enhancement of red upconversion luminescence at the cost of green upconversion luminescence of Er³⁺ at its higher concentrations in the glass has been observed and the related photo-physics is proposed. The material shows the prospect of being used as NIR solar concentrator.     

Eu3+离子在微晶玻璃研究中的探针作用

制备出单掺Eu³⁺离子的氟氧化物玻璃陶瓷系列样品，利用Eu³⁺离子作为荧光探针，通过热处理前后Eu³⁺离子发射光谱中电偶极子跃迁与磁偶极子跃迁强度比值的变化表征在玻璃材料中微晶是否形成，分析了Eu³⁺离子荧光发射谱中电偶极子跃迁与晶体场对称性的关系，进一步表征了稀土离子所处微晶晶格场的变化. 关键词： 微晶玻璃 探针 3+离子')" href="#">Eu³⁺离子     

Structural and spectroscopic studies of Lu2O3/Eu nanocrystallites embedded in SiO2 sol-gel ceramics

Preparation and optical properties of Lu₂O₃/Eu³⁺ nanocrystals embedded in silica gel glass are described. The structure of the obtained ceramics was determined by XRD and transmission electron microscopy. It was found that with increasing sintering temperature the Lu₂O₃/Eu³⁺ nanocrystallites underwent transformation into monoclinic Lu₂Si₂O₇ nanocrystallites. The fluorescence properties were investigated as a function of thermal treatment of the samples. It was found that after sintering at 1250 °C the fluorescence lifetime increased to 1.5 ms at room temperature. The material studied in this work exhibits a very high intensity of fluorescence with potentials for display application.     

Light induced charge transfer processes in Cr doped Bi12GeO20 and Bi12SiO20 single crystals

Optical absorption and ESR spectra of Bi₁₂GeO₂₀ doped with Cr were measured before and after illumination with visible light. It was found that Cr⁴⁺ ions in tetrahedral position are responsible for light induced ESR and optical spectra. The g-factor of the center is 1.945 ± 0.002. Crystal field parameters for the Cr⁴⁺ center are D_q = 820 cm^?1 and B = 429cm^?1. The photochromic effect is explained in terms of a Cr⁵⁺?Cr⁴⁺ charge transfer process.