Optical and EPR spectroscopy of manganese ions in Sr3Ga2Ge4O14 crystals

Results of investigations of the spectroscopic properties of manganese-activated single crystals of Sr₃Ga₂Ge₄O₁₄ by the methods of optical and EPR spectroscopy are reported. It is shown that magnagese activator ions form substitutional centers Mn³⁺ and Mn²⁺ in 1a-octahedral positions of the Sr₃Ga₂Ge₄O₁₄ lattice. Changes in the opticla properties of Sr₃Ga₂Ge₄O₁₄: Mn after vacuum thermal annealing are attributed to charge transfer of some of the manganese ions (Mn³⁺→Mn²⁺). The relationship between the spectroscopical properties of Mn²⁺ ions and the crystallochemical structure of the system are discussed. I. Franko L’vov State University, 50, Dragomanov St., L’vov, 290005, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 779–783, November–December, 1997.     

Theoretical explanation of optical absorption spectra and covalent effect of Ni2+ ions in octahedral sites of Ca3Sc2Ge3O12 crystal

The optical absorption spectra (d-d transition bands) and covalent effect of Ni²⁺ ions in octahedral sites of Ca₃Sc₂Ge₃O₁₂ crystal have been investigated by the full energy matrix based on the two spin–orbit coupling parameters model. The bond length of octahedral site is R_i?=?2.19 Å, which can be determined by the cubic crystal-field parameter and optical spectral data. The lattice distortion of the Ni²⁺ center in Ca₃Sc₂Ge₃O₁₂ crystal is also obtained from the calculations. In addition, the result has shown that the covalent effect of Ni²⁺ ion in the octahedral site of Ga₃Sc₂Ge₃O₁₂ is obvious and cannot be ignored. The calculated d-d transition bands agree well with that of the experimental findings, suggesting that the present methods can explain reasonably the optical spectral data and covalent effect of 3d⁸ ions in octahedral lattices.     

Radiation-Induced Paramagnetic Centers in the Glasses Of CaO-Ga2O3-GeO2 System

The X-band (v ? 9.4 GHz) ESR spectra of the UV-, X-, and γ-irradiated glasses of CaO-Ga₂O₃-GeO₂ system with compositions similar to Ca₃Ga₂Ge₃O₁₂, Ca₃Ga₂Ge₄O₁₄, and Ca₃Ga₂O₆ crystals have been investigated at 300 and 77 K. It was shown that X- and γ-irradiation of the Ge-contained glasses induce simultaneously electron and hole paramagnetic centers, stable at room temperature. The UV-irradiation of Ge-contained glasses leads to the generation of stable centers of electron type, whereas the X- and γ-irradiation of glasses with Ca₃Ga₂O₆ composition induces stable hole centers, exclusively. The electron centers are assigned to E′ (Ge) centers with different local environments. ESR spectrum of hole centers is ascribed to O^? centers, localized on non-bridging oxygen of the glass network. The E′ (Ge) and O^? centers show high thermal stability in the CaO-Ga₂O₃-GeO₂ glass network. The obtained ESR spectra are described by spin Hamiltonian with g-factor of axial and rhombic symmetry for the E′ (Ge) and O^? centers, respectively. The nature, electron structure and some formation peculiarities of the radiation defects in CaO-Ga₂O₃-GeO₂ glasses are discussed in comparison with other glasses as well as Ca₃Ga₂Ge₃O₁₂ and Ca₃Ga₂Ge₄O₁₄ crystals.     

Enhanced photoluminescence of Sm/Bi co-doped Gd2O3 phosphors by combustion synthesis

Gd₂O₃:Sm³⁺ and Gd₂O₃:Sm³⁺,Bi³⁺ powders were prepared by a combustion method. Their structures were determined using X-ray diffraction. UV-visible absorption and photoluminescence spectra were investigated for Gd₂O₃:Sm³⁺ and Gd₂O₃:Sm³⁺,Bi³⁺ at different annealing temperatures and different doping concentrations. The emission spectra of all samples presented the characteristic emission narrow lines arising from the ⁴G_5/2→⁶H_J transitions (J=5/2, 7/2, and 9/2) of Sm³⁺ ions upon excitation with UV irradiation. The emission intensity of Sm³⁺ ions was largely enhanced with introducing Bi³⁺ ions into Gd₂O₃:Sm³⁺ and the maximum occurred at a Bi³⁺ concentration of 0.5 mol%. The relevant mechanisms were discussed with the sensitization theory by Dexter and the aggregation behavior of Bi³⁺ ions.     

EPR Spectra of Cr3+ Ions in Sr3Ga2Ge4O14:Cr Single Crystals

The results of investigations of chromiumdoped Sr₃Ga₂Ge₄O₁₄ single crystals by the EPRspectroscopy method are presented. It is shown that activating chromium ions form Cr³⁺ Ga³⁺ (Ge⁴⁺) substitution centers in the 1aoctahedral positions of the lattice of Sr₃Ga₂Ge₄O₁₄. Depending on the combination of occupation of the 3ftetrahedral positions of the first cationic coordination sphere by Ga³⁺ and Ge⁴⁺ ions, Cr³⁺ centers of two types are formed. Their individual magnetic spectra are characterized by axial and rhombic symmetry. The magnetic multiplicity of the axialsymmetry spectrum is equal to unity. There exist rhombicsymmetry centers of two types differing in the orientation of the principal magnetic axes and the value of the spinHamiltonian parameter E. The magnetic multiplicity of the individual magnetic spectra of rhombic centers of each type is equal to three. The detected EPR spectra of Cr³⁺ ions have been described by the spin Hamiltonian of rhombic symmetry. Its parameters and their spread have been determined.     

Sol-gel synthesis, structural and optical properties of rare earth ions (Sm or Dy) activated Ca3Ga2Si3O12 powder phosphors

Structural, morphological and optical properties of rare earth ions (RE³⁺=Sm³⁺ or Dy³⁺) activated Ca₃Ga₂Si₃O₁₂ (CaGaSi) phosphors synthesized by the sol-gel method are reported. XRD results confirmed the cubic phase structure of RE³⁺:CaGaSi phosphors. From the SEM images of RE³⁺:CaGaSi phosphors, it is observed that the particles are agglomerated. Photoluminescence spectra of Sm³⁺:CaGaSi phosphors have shown bright orange red emission at 598 nm (⁴G_5/2→⁶H_7/2) with an excitation wavelength of λ_exci=401 nm. In the case of Dy³⁺:CaGaSi phosphors bright yellow emission has been observed at 574 nm (⁴F_9/2→ ⁶H_13/2) with λ_exci=451 nm. From the PL spectral results, the rare earth ion concentration of CaGaSi phosphors is optimized.     

Energy transfers between Sm and Eu in YPO4, LaP5O14 and LaP3O9 phosphates. Potential quantum cutters for red emitting phosphors

This work concerns the studies of energy transfers between Sm³⁺ and Eu³⁺ ions in some phosphates as new luminescent materials emitting in the orange-red color. The choose of ions is based on the possibility of quantum cutting process and the matrices are selected according to the 5d bands position of Sm³⁺ ion. The Sm³⁺ and Eu³⁺ doped YPO₄, LaP₅O₁₄ and LaP₃O₉ are synthesized and spectroscopic studies in ultraviolet and vacuum ultraviolet ranges have been achieved.     

Synthesis and Sm/Sm doping effects on photoluminescence properties of Sr4Al14O25

Complete and partial samarium reduction was achieved under strong reducing atmosphere by solid-state and combustion synthesis of Sr_3.96Sm_0.04Al₁₄O₂₅. Dependence of different fluxing agents on the formation of various strontium aluminates was examined. The samples were investigated by X-ray powder diffraction, temperature dependent luminescence decay and photoluminescence measurements. Excitation with UV radiation resulted in sharp and well resolved emission lines of samarium ions. Distinct temperature behavior for Sm²⁺ and Sm³⁺ were detected in the range of 100-500 K. Estimated emission thermal quenching values (TQ_1/2) for divalent samarium were approximately 270 K while for trivalent state around 660 K. Measured luminescence decay values of Sm²⁺ are substantially lower than for Sm³⁺,≈1.7 and ≈2.7 ms, respectively. The spectral feature of Sm²⁺ emission spectrum indicates that dopant occupies low symmetry site in Sr₄Al₁₄O₂₅ compound.     

Structural and electrochemical characterization of Ce0.85Ca0.05Sm0.1O1.9 oxide ion electrolyte with Sr-doped LaMnO3 and SmCoO3 cathodes

This paper reports on the electrochemical properties and chemical stability of a recently developed Ca²⁺ and Sm³⁺-doped oxide ion conducting electrolyte, Ce_0.85Ca_0.05Sm_0.1O_1.9 (CCS), employed in an intermediate temperature solid oxide fuel cell (IT-SOFC) using conventional Sm_0.5Sr_0.5CoO₃ (SSC) and La_0.8Sr_0.2MnO₃ (LSM) cathodes in air at elevated temperatures. The materials were prepared by conventional solid-state reactions using their corresponding metal oxides and salts in the temperature range of 1,200–1,450 °C in air. Powder X-ray diffraction (PXRD) and impedance spectroscopy were employed for phase formation, chemical compatibility, and electrochemical characterization. PXRD studies on 1:1 weight ratio of heat-treated (1,000 °C for 3 days) mixtures of SSC or LSM and CCS revealed the presence of fluorite-type and perovskite-like phases. The area-specific resistance (ASR) value in air was lower for SSC cathodes (4.3–0.15 Ω cm²) compared to those of LSM (407–11 Ω cm²) over the investigated temperature range of 600–800 °C. As expected, a significant increase in ASR was observed in Ar as compared to air.     

Emission analysis of Pr and Tm: Ca2Gd2W3O14 phosphors

5 mol% of Pr³⁺ and Tm³⁺ ions activated calcium gadolinium tungstate (Ca₂Gd₂W₃O₁₄₎ phosphors were synthesized by traditional solid state reaction method. Crystalline phase structure was identified from the X-ray diffraction (XRD) profiles. From the scanning electron microscopy (SEM) images, we have observed the agglomeration of the particles, and average grain size is around 40-300 nm. Using the energy dispersive X-ray analysis (EDAX) and Fourier transform infrared (FTIR) spectra, identified the elements and functional groups present in the prepared phosphors. The emission spectrum of Pr³⁺: Ca₂Gd₂W₃O₁₄ powder phosphors have shown an intense red emission at 615 nm with the excitation wavelength λ_exci=450 nm and thus these red color emitting powder phosphors are used as one of the components in the preparation of WLEDs. The excitation spectrum of Tm³⁺: Ca₂Gd₂W₃O₁₄ powder phosphor has shown a ligand to metal charge transfer (W-O) band (LMCT) within the WO₄²⁻ group. Emission spectrum of Tm³⁺: Ca₂Gd₂W₃O₁₄ phosphors have shown blue emissions at 453 nm (¹D₂→³F₄).     

Spectral properties of Nd-doped Sr3Ga2Ge4O14 crystal

Neodymium doped strontium gallogermanate crystals were grown successfully by the Bridgman technique. The linear thermal expansion coefficients for the c- and a-axes were measured as 5.8 × 10⁻⁶ °C⁻¹ and 6.5 × 10⁻⁶ °C⁻¹. Absorption spectra, and fluorescence spectra, as well as fluorescence decay curves of Nd³⁺-doped Sr₃Ga₂Ge₄O₁₄ crystal, have been recorded at room temperature and used to calculate the absorption and stimulated emission cross-sections. Based on the Judd-Ofelt theory, three intensity parameters were obtained. The luminescent quantum efficiency of the ⁴F_3/2 level was determined to be approximately 73.8% for this material. Compared with other Nd³⁺-doped laser crystals, Nd³⁺-doped Sr₃Ga₂Ge₄O₁₄ crystal displays special laser properties due to its disorder structure.     

Radiation-induced paramagnetic centers in Ca3Ga2Ge4O14 crystals

Studies of EPR spectra, additional optical absorption, and the kinetics of buildup and decay of radiation-induced paramagnetic centers in compositionally disordered crystals of trigonal Ca-gallogermanate are reported. The parameters of the spin-Hamiltonian describing the observed room-temperature EPR spectra are determined. It is established that the radiation-induced paramagnetic centers in Ca₃Ga₂Ge₄O₁₄ crystals are O⁻ centers in common 6g sites stabilized by the Ge⁴⁺ vacancy in tetrahedral 2d sites. Fiz. Tverd. Tela (St. Petersburg) 39, 1044–1049 (June 1997)     

Er3+及Er3+/Yb3+掺杂ZrO2-Al2O3的制备及发光性质

采用共沉淀法制备了纳米晶ZrO₂-Al₂O₃∶Er³⁺发光粉体.所制备的粉体室温下具有Er3+离子特征荧光发射,主发射在绿光,其中位于547 nm、560 nm的绿光最强,并得出稀土离子与基质之间有能量传递.对不同煅烧温度下的样品研究表明:因不同温度下所制得的样品晶相不同.研究了纳米晶ZrO2-Al2O3∶Er3+及ZrO₂-Al₂O₃∶Er³⁺/Yb³⁺的上转换发光,并分析了上转换的跃迁机制.发现ZrO₂-Al₂O₃∶Er³⁺的绿光为双光子过程,而ZrO₂-Al₂O₃∶Er³⁺、Yb³⁺的上转换光谱中,红光和绿光也为双光子过程,而极弱的蓝光为三光子过程.讨论了Er³⁺的浓度猝灭现象.最适宜掺杂浓度的原子分数为2%（Er³⁺/Zr⁴⁺）.     

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.     

Luminescent characteristics of LiCaBo3:M (M=Eu, Sm, Tb, Ce, Dy) phosphor for white LED

LiCaBO₃:M (M=Eu³⁺, Sm³⁺, Tb³⁺, Ce³⁺, Dy³⁺) phosphors were synthesized by a normal solid-state reaction using CaCO₃, H₃BO₃, Li₂CO₃, Na₂CO₃, K₂CO₃, Eu₂O₃, Sm₂O₃, Tb₄O₇, CeO₂ and Dy₂O₃ as starting materials. The emission and excitation spectra were measured by a SHIMADZU RF-540 UV spectrophotometer. And the results show that these phosphors can be excited effectively by near-ultraviolet light-emitting diodes (UVLED), and emit red, green and blue light. Consequently, these phosphors are promising phosphors for white light-emitting diodes (LEDs). Under the condition of doping charge compensation Li⁺, Na⁺ and K⁺, the luminescence intensities of these phosphors were increased.     

Absorption and EPR spectra of Cr3+ ions in a LaBeAl11O19 crystal

Electron spectra of optical absorption and EPR of Cr³⁺ ions in a LaBeAl₁₁O₁₉ crystal are investigated. It is shown that the Cr³⁺ ions occupy, three different octahedral positions of Al³⁺ in the LaBeAl₁₁O₁₉ structure, namely, 12k, 2a, and 4f₂; the ratio of their intensitites is 1∶2∶30, respectively. Parameters of the Cr³⁺ centers are determined and its is shown that the optical absorption spectra in the visible region are practically determined by the Cr³⁺ (III) occupying the 4f₂-positions. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 2, pp. 275–277, March–April, 1999.     

Cr3+掺杂的Cd3Al2Ge3O12光谱特性及晶场参数计算

采用高温固相法合成了Cd₃Al₂Ge₃O₁₂：Cr³⁺多晶材料,利用X射线衍射对其结构进行了分析,通过Cr³⁺的室温吸收光谱、室温和77K发射光谱分别对其光谱特性和晶场参数进行了分析和计算.结果表明：在450 nm的蓝光激发下,Cd₃Al₂Ge₃O₁₂：Cr³⁺室温发 关键词： 3Al₂Ge₃O₁₂：Cr³⁺')" href="#">Cd₃Al₂Ge₃O₁₂：Cr³⁺ 荧光光谱 晶场参数 可调谐激光     

High pressure luminescence study of Sm3+: K–Ba–Al fluorophosphate glass

The luminescence spectra and decay curves for the ⁴G_5/2 level of Sm³⁺ ions in 55.95P₂O₅+14K₂O+6KF+14.95BaO+9Al₂O₃+0.1Sm₂O₃ glass, referred to as PKFBASm01, have been studied as a function of pressure up to 40.5 GPa at room temperature. With the increase in pressure, a continuous red shift of the ⁴G_5/2→⁶H_{9/2, 7/2, 5/2} transitions and a progressive increase in the magnitude of the crystal-field splittings for these transitions are observed. The decay curves for the ⁴G_5/2 level of the Sm³⁺ ions in PKFBASm01 glass are found to exhibit single exponential behavior at ambient pressure and become non-exponential at higher pressures, accompanied by shortening of lifetimes. A generalized Yokoto–Tanimoto model has been used to explain the pressure-induced non-exponential nature of the decay curves.     

Enhanced luminescence of Ca3B2O6:Dy phosphors by Na-codoping for LED applications

The Ca_2.95−yDy_0.05B₂O₆:yNa⁺ (0≤y≤0.20) phosphors were synthesized at 1100 °C in air by the solid-state reaction route. The as-synthesized phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), photoluminescence excitation (PLE), photoluminescence (PL) spectra and thermoluminescence (TL) spectra. The PLE spectra show the excitation peaks from 300 to 400 nm due to the 4f-4f transitions of Dy³⁺. This mercury-free excitation is useful for solid-state lighting and light-emitting diodes (LEDs). The emission of Dy³⁺ ions on 350 nm excitation was observed at 480 nm (blue) due to the ⁴F_9/2→⁶H_15/2 transitions, 575 nm (yellow) due to ⁴F_9/2→⁶H_13/2 transitions and 660 nm (red) due to weak ⁴F_9/2→⁶H_11/2 emissions. The PL results from the investigated Ca_2.95−yDy_0.05B₂O₆:yNa⁺ phosphors show that Dy³⁺ emissions increase with the increase of the Na⁺ codoping ions. The integral intensity of yellow to blue (Y/B) can be tuned by controlling Na⁺ content. By the simulation of white light, the optimal CIE value (0.328, 0.334) can be achieved when the content of Na⁺-codoping ions is y=0.2. The results imply that the Ca_2.95−yDy_0.05B₂O₆:yNa⁺ phosphors could be potentially used as white LEDs.     

Spectroscopic Properties of Er3+/Yb3+-codoped PbO–Bi2O3–Ga2O3–GeO2 Glasses

We investigate the spectroscopic properties of the 1.5-μm emission from the ⁴I_13/2 → ⁴I_15/2 transition of Er³⁺ ions in PbO–Bi₂O₃–Ga₂O₃–GeO₂ glasses for applications in broadband fiber amplifiers. The measured emission peak locates at 1,532 nm with a full width at half-maximum of ∼45 nm. The glasses exhibit a large stimulated emission cross-section of 0.89 × 10⁻²⁰ cm² and a large product of 40.0. Infrared-to-green upconversion occurs simultaneously upon excitation of the 1.5-μm emission with a commercially available 980 nm laser diode. The green-upconversion intensity has a quadratic dependence on incident pump laser power, indicating a two-photon process. Energy transfer processes and nonradiative phonon-assisted decays could account for the population of the ²H_11/2 of Er³⁺. The results indicate the possibility towards the development of lead–bismuth–gallate–germanate based glasses as photonics devices.