晶体(ZnKPO_4·6H_2O)∶VO~(2+)的自旋哈密顿参数及局域结构

基于晶体场理论和电荷转移机制,采用双旋-轨耦合参量模型的3d~1离子在D_(4h)对称的晶场中自旋哈密顿参量的高阶微扰公式和晶场能级公式,计算了(ZnKPO_4·6H_2O)∶VO~(2+)晶体的光吸收谱和自旋哈密顿参量。本文不仅考虑了晶场机制,同时也考虑了电荷转移机制。计算结果与实验数据是一致的。说明电荷转移机制对(ZnKPO_4·6H_2O)∶VO~(2+)晶体的自旋哈密顿参量的结果有不可忽略的作用。     

ThSiO4：V^4＋晶体的光谱及EPR参量的理论研究

基于晶体场理论,采用3d1离子在D2d对称中的晶场能级公式和EPR参量高阶微扰公式,计算了ThSiO4:V4 晶体的光谱和电子顺磁共振(EPR)参量g因子g//,g⊥和超精细结构常数A//,A⊥.计算结果与实验发现很好吻合.由于晶体中顺磁杂质中心的EPR参量与其缺陷结构密切相关,本计算还获得了V4 杂质中心缺陷结构的信息.对上述结果进行了讨论.     

ZrSiO4∶Ti3+晶体的电子顺磁共振参量理论研究

基于离子簇模型,采用d1在四角伸长四面体对称中电子顺磁共振(EPR)参量的高阶微扰公式,计算了ZrSiO4 晶体中处于Si4+位的四角Ti3+中心的EPR参量(g因子g//,g⊥和超精细结构常数A因子A//,A⊥).由于配体O2-与中心金属离子Ti3+的旋轨耦合系数大小相近,在这些公式中同时考虑了配体p、s轨道及旋轨耦合作用对EPR参量的贡献.公式里的能级分裂由叠模型和杂质中心的局部结构确定.研究发现,掺杂后形成的四面体团簇[TiO4]5-相对母体产生了约0.3°的角度畸变.计算所得的EPR理论值与实验值符合的很好.     

Cu2+在晶体K2Cd(SO4)2·6H2O中的电子顺磁共振参量及局部结构的理论研究

在晶体场理论的基础上,由重叠模型建立了杂质中心结构参数与电子顺磁共振(EPR)参量之间的定量关系;利用3d9离子正交(D2h)伸长八面体对称EPR参量的高阶微扰公式计算了K2Cd(SO4)2·6H2O∶Cu2+的g因子gi(i=x,y,z)和超精细结构常数Ai.研究表明,K2Cd(SO4)2·6H2O晶体中络离子[Cu(H2O)6]2+的Cu2-H2O键长分别为Rx≈0.181 nm,Ry≈0.199 nm,Rz≈0.232 nm,局域结构为沿C4轴方向呈正交伸长八面体(D2h)结构.所得EPR参量理论计算与实验符合较好,并对上述结果进行了讨论.     

SrCl2∶Ag2+晶体局部结构及电子顺磁共振参量的理论研究

基于离子簇模型,采用d9离子在四角伸长八面体对称中电子顺磁共振(EPR)参量的高阶微扰公式,计算了SrCl2中四角Ag2+中心的EPR参量(g因子g//,g⊥和超精细结构常数A因子A//,A⊥).由于体系的共价性及配体Cl-较大的旋轨耦合系数,在这些公式中同时考虑了配体轨道及旋轨耦合作用对EPR参量的贡献.公式里的能级分裂由重叠模型和杂质中心的局部结构确定.研究发现,掺杂后由于尺寸失配,杂质Ag2+沿着C4轴有一个很大的非中心位移,到最近邻的Cl-平面距离约为0.060 nm.计算所得的EPR理论值与与实验值符合的很好.     

晶体zinc 1-malate trihydrate∶Cu~(2+)的自旋哈密顿参量及局部结构的理论研究

在晶体场理论的基础上,利用四角对称3d9离子自旋哈密顿参量高阶微扰公式计算了Zinc 1-malate trihydrate:Cu2+的g因子(g//,g⊥)和超精细结构常数(A//,A⊥)。结果表明,由于Jahn-Teller效应,Zinc 1-malate trihydrate:Cu2+晶体中配体氧八面体沿C4轴方向伸长约0.0033 nm,络离子[CuO6]10-的键长R//≈0.2157 nm,R⊥≈0.2058 nm;局域结构沿C4轴方向呈伸长八面体结构。所得EPR参量理论计算与实验符合较好,并对上述结果进行了讨论。     

Study on the Local Structure Phase Transition, Spectral Fine Structure and EPR Spectra of RbCdF3∶Ni2+ Crystals

本文采用半自洽场(semi-SCF) 3d轨道模型和μ-K-α模型,利用完全对角化方法,建立了Oh、D4h对称晶体场局部结构参数与光谱精细结构、EPR谱之间的定量关系,统一解释了RbCdF3∶ Ni2晶体的光谱精细结构和EPR谱.所得理论结果与实验值符合很好.     

YAG:V2+激光材料晶格畸变及其EPR参量研究

利用Newman的晶场叠加模型,建立了晶体微观结构与电子顺磁共振(EPR)参量之间的定量关系.采用全组态完全对角化方法,对YAG:V2+晶体的局域晶格畸变及其EPR参量进行了系统的研究,结果表明:V2+离子掺入YAG晶体后,V2+离子的局域结构产生压缩三角晶格畸变,沿[111]晶轴方向V2+离子上方的三个O2-配体与下方的三个O2-配体均偏离[111]轴1.96°,从而成功地解释了YAG:V2+晶体的EPR参量.同时研究也表明,SS与SOO磁相互作用对EPR参量的贡献不可忽略.     

RbCdF3:Ni2+晶体结构相变、光谱精细结构和EPR谱的研究

本文采用半自洽场(semi-SCF)3d轨道模型和μ-κ-α模型,利用完全对角化方法,建立了Oh、D4h对称晶体场局部结构参数与光谱精细结构、EPR谱之间的定量关系,统一解释了RbCdF3∶Ni2+晶体的光谱精细结构和EPR谱。所得理论结果与实验值符合很好。     

Ni(IO_3)_2·2H_2O晶体的局部结构、吸收光谱和漫反射光谱的研究

采用半自洽场(semi-SCF)d轨道模型和点电荷模型,利用完全对角化方法,建立了D4h对称晶体场中晶体的局部结构与光谱之间的定量关系,统一解释了Ni(IO3)2.2H2O晶体的局部结构、吸收光谱和漫反射光谱的实验值,预测了Ni(IO3)2.2H2O晶体的光谱精细结构和电子顺磁共振(EPR)谱(零场分裂D和顺磁g因子)。所得理论结果与实验值符合得很好。     

CdX2(X=Cl、Br):Ni2+晶体的吸收光谱和EPR谱的统一解释

本文考虑3d电子和轨道局域性差异和配体旋-轨耦合作用的影响,在晶体场理论和电子顺磁共振理论基础上,采用d轨道模型,推导出了3d2/d8电子组态在D3d对称下的广义能量矩阵,利用双共价因子双旋-轨耦合EPR谱高阶微扰公式,统一解释了CdX2(X=Cl、Br):Ni2+晶体的吸收光谱和EPR谱.     

Paramagnetic germanium-related centers induced by energetic radiation in optical fibers and preforms

We investigated the creation processes of Ge-related paramagnetic point defects in silica fibers and preforms, doped with different amounts of germanium, and X-ray irradiated at several radiation doses. Different paramagnetic defect species, like GeE′, Ge(1) and Ge(2), were revealed by electron paramagnetic resonance measurements and their concentration was studied as a function of the irradiation dose. The comparison with the optical absorption spectra points out the main role of Ge(1) on the optical transmission loss of fibers in the UV region.     

Effects of ArF excimer irradiation on single energy and multi energy Ge ion implanted silica

Some of the effects of ArF excimer irradiation on the optical bands produced by single energy (4 MeV) and multi energy (highest energy 4 MeV) Ge implantations in silica (Type III) have been determined. Ge ions were implanted at 4 MeV with nominal doses of 1.25, 2.5 and 5.0×10¹⁵ ions/cm². A second series of samples was made using implant energies ranging from 4 to 0.7 MeV. The doses at each energy were varied to maintain an approximate constant implant species concentration with the total number of ions implanted being 10×10¹⁵ and 5×10¹⁵ cm⁻² for concentrations of 0.042 and 0.021 at.%, respectively. The optical absorption was measured from 2.8 to 6.5 eV. The absorption of samples was then measured after 6.4 eV ArF excimer radiation with a fluence of 44 mJ/cm² per pulse for pulse totals of 3, 11 and 31. We fit the observed spectra for the as-implanted samples and the samples after each ArF exposure to the minimum number of bands attributed to intrinsic states in SiO₂ required to fit the data within ±2%. The magnitude and response of these absorption bands to the ArF irradiation was a function of dose and implant conditions.     

EPR and Optical Absorption Studies of Radiation-Induced Radicals in Biphenyl Single Crystals

Biphenyl single crystals irradiated with γ rays at liquid nitrogen temperature have been investigated by electron paramagnetic resonance and optical absorption experiments. EPR spectra at room temperature exhibit a triplet characteristic separated by 39 gauss and each line of the triplet further splits to a triplet. The main triplet has been interpreted as being caused by hydrogen added biphenyl radicals. The splitting of each line of the main triplet is consistent with the calculated splittings of 2-hydro-biphenyl radicals and 4-hydro-biphenyl radicals. The presence of 3-hydro-biphenyl radicals could not be judged from the EPR spectra due to the broadness of the lines. In the optical absorption spectra at low temperature, obtained with the light polarized to the a-, b- and c'-axes of the crystals, nine bands were detected. Transition energies were calculated using SCF-C1 molecular orbital theory for the three kinds of the hydrogen added biphenyl radicals. By comparing the experimental spectra with the theoretical transitions of the three kinds of radicals, the bands at 666 nm and 424 nm have been assigned to the transitions of 2-hydro-biphenyl radicals, the 660 nm band to that of 3-hydro-biphenyl radicals, and the bands at 604 nm and 598 nm to the ones of 4-hydro-biphenyl radicals. The decays of these radicals at room temperature are very similar and upon annealing a new absorption band appears at 462 nm.     

EPR and Optical Absorption Studies of γ-irradiated Pyrene Single Crystals

Pyrene single crystals irradiated with γ rays at room temperature have been investigated by electron paramagnetic resonance and optical absorption experiments. EPR spectra exhibit a triplet characteristic and each line of the triplet shows characteristic features with rotations of the crystals in a magnetic field. From analyses of these spectra the presence of two kinds of hydrogen added pyrene radicals, 3-H₂-pyrene and 2-H₂-pyrene radicals, is concluded. In the optical absorption spectrum nine main absorption bands have been detected. These absorption bands are compared with the theoretically calculated transition energies with SCF-CI molecular orbital calculations for 3-H₂-pyrene and 2-H₂-pyrene radicals. Reasonable correspondences are obtained between theoretical values and the experimental spectrum.     

EPR and optical spectra of gamma-irradiated sodium-silicate glasses containing copper oxide

The effects of an addition of CuO on the intrinsic and induced EPR and optical absorption spectra of γ-irradiated sodium-silicate glasses melted under different redox conditions are studied. It is shown that the CuO impurity blocks the formation of radiation-induced centers associated with the intrinsic defects of glass matrix. A new paramagnetic centre appears in the sodium-silicate glasses containing CuO after γ-irradiation. This center is the hole trapped at the Cu¹⁺ ion, and its spectral parameters are different from ones of the Cu²⁺ ions obtained by chemical oxidation of copper.     

Synthesis and characterization of MnTe nanocrystals in glass

The first evidence of the growth of MnTe nanocrystals successfully synthesized in a glass matrix (SiO₂–Na₂CO₃–Al₂O₃–B₂O₃) using the fusion method is reported. Measurements of optical absorption, photoluminescence, electronic paramagnetic resonance and atomic force microscopy were carried out in order to characterize the produced nanocrystals.     

Alkaline earth zinc borate glasses doped with Cu2+ ions studied by EPR,optical and IR techniques

Copper ions incorporated into alkaline earth zinc borate glasses 10RO + 30ZnO + 60B₂O₃ (R = Mg, Ca and Sr) and 10SrO + (30 ? x)ZnO + 60B₂O₃ + xCuO (x = 0, 0.1, 0.3, 0.5, and 0.7 wt.%) were characterized by electron paramagnetic resonance (EPR), optical absorption and FTIR techniques. The EPR spectra of all the glass samples exhibit resonance signals characteristic of Cu²⁺ ions. The values of spin-Hamiltonian parameters indicate that the Cu²⁺ ions in alkaline earth zinc borate glasses were present in octahedral sites with tetragonal distortion. The spin concentration (N) participating in resonance was calculated as a function of temperature for strontium zinc borate (SrZB) glass sample containing 0.7 wt.% of Cu²⁺ ions and the activation energy was calculated. From the EPR data, the paramagnetic susceptibility (χ) was calculated at different temperatures and the Curie constant was evaluated from the 1/χ-T graph. The optical absorption spectra of these samples show only one absorption band. The optical band gap energies (E_g) and Urbach energy (ΔE) are calculated from their ultraviolet edges. The FTIR studies show different stretching and bending vibrations of alkaline earth zinc borate glasses.     

Influence of temperature on the microcrystalline structure of thermally evaporated Sb2S3 thin films

Thin films of antimony trisulfide (Sb₂S₃) were prepared by thermal evaporation under vacuum (p=5×10^–5 torr) on glass substrates maintained at various temperatures between 293 K and 523 K. Their microstructural properties have obtained by transmission electron microscopy (TEM). The electron diffraction analysis showed the occurrence of amorphous to polycrystalline transition in the films deposited at higher temperature of substrates (523 K). The polycrystalline thin films were found to have an orthorhombic structure. The interplanar distances and unit‐cell parameters were determined by high‐resolution transmission electron microscopy (HRTEM) and compared with the standard values for Sb₂S₃. The surface morphology of Sb₂S₃ thin films was investigated by scanning electron microscopy (SEM). The optical transmission spectra at normal incidence of Sb₂S₃ thin films have been measured in the spectral range of 400–1400 nm. The analysis of the absorption spectra revealed indirect energy gaps, characterizing of amorphous films, while the polycrystalline films exhibited direct energy gap. From the photon energy dependence of absorption coefficient, the optical band gap energy, E_g, were calculated for each thin films. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Radiation resistance of synthetic sapphire crystal irradiated by low‐energy neutron flux

In this paper, high‐quality sapphire crystal grown by an improved Kyropoulos‐like method, was irradiated by low‐energy neutron (i.e. high proportion of thermal neutron) with various flux (low: 7.5×10¹⁵ n/cm², medium: 7.0×10¹⁶ n/cm² and high: 3.8×10¹⁷ n/cm²). The characteristic features of neutron fluence dependence of radiation‐defect formation process, mainly including its change of the structural and optical properties prior to and after irradiation, were investigated by optical absorption (OA), photoluminescence (PL), electron paramagnetic resonance (EPR) and positron annihilation spectroscopy (PAS). It is found that sapphire crystal exhibits high radiation resistance to low‐energy neutron with low fluence. But with the increase of irradiation fluence, it is still sensitive to neutron irradiation mostly in the UV‐visible spectral range, as irradiation‐induced color centers appear, including F‐type and their aggregate centers. Finally, the formation mechanism of the irradiation defects is also discussed. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)