对比分析三角Pr~(3+)中心在CsCdBr_3和GdCl_3晶体中的能级分裂

以Racah的群表示论和Slater的波函数理论为基础,分别建立了4f2组态离子Pr~(3+)在三角晶体场C3v和C3h中的91×91完全能量矩阵,并对Pr~(3+)离子掺杂在卤化物CsCdBr_3和GdCl_3中的Stark能级做了计算与分析.结果显示计算值与实验值吻合很好,表明在分析由稀土离子掺杂体系的能级分裂时,完全能量矩阵方法是有效的方法.此外,将两种具有不同点群对称的体系的能级分裂情况作了比较,结果显示六阶晶体场参量对能级分裂的影响是不能忽略的,而且CsCdBr_3:Pr~(3+)和GdCl_3:Pr~(3+)将产生不同程度的畸变.     

掺入Ni~(2+)和V~(3+)对α-Al_2O_3晶体光谱精细结构、晶体局域结构和零场分裂参量的影响

应用晶体场理论和不可约张量算符方法构造了3d2/3d8态离子在C3v对称晶场中包含自旋-轨道相互作用、自旋-自旋相互作用、自旋-其它轨道相互作用和其它轨道-其它轨道相互作用四种微观磁效应的45阶可完全对角化的能量哈密顿矩阵.利用该矩阵,计算了V3+∶α-Al2O3和Ni2+∶α-Al2O3晶体的光谱精细结构、晶体局域结构和零场分裂参量,研究了掺入两种互补态离子Ni2+和V3+对同种晶体的光谱精细结构、晶体局域结构和零场分裂参量的影响,理论计算值和实验值相符.研究发现:掺杂没有改变晶体的光谱精细结构和能级分裂条数,但改变了能级间距;掺杂也没有改变晶体的对称性,但使晶体局域结构发生了一定程度的畸变;Ni2+∶α-Al2O3晶体局域结构的伸长畸变量大于V3+∶α-Al2O3晶体,键角的变化量小于V3+∶α-Al2O3晶体.     

YAlO3晶体中pr3+的4f2能级

YAlO3∶pr3+是一种受到广泛关注的发光体系,本文根据文献中给出的YAlO3∶pr3+晶体中Pr3+的晶体场能级,从Nd3+离子的晶体场参数和Pr3+的准自由离子参数出发,采用f-shell计算软件包对pr3+的能级参数进行了研究,并对获得的参数进行了讨论.用拟合获得的参数计算了pr3+的4f2电子构型的所有能级.     

晶体场理论引论(四)

晶体场中能级分裂的计算--行列式波函数方法(4-1)用微扰法计算晶体场中能级分裂的示例 用简并微扰法计算晶体场中自由离子能级的分裂时,晶体场哈密顿量作为微扰,自由离子波函数为基,求出矩阵元,解久期方程,求出一级能量修正值即晶体场中能级的分裂,同时可求出自由离子基函数的线性组合作为零级近似波函数.下面以3d1组态的能级为例.     

掺入Mg2+对CsNiCl3晶体的基态能级、零场分裂参量及Jahn-Teller效应的影响

应用不可约张量理论构造了三角对称晶场中3d2/3d8态离子的45阶可完全对角化的微扰哈密顿矩阵,在考虑了以前工作中被忽略的自旋-自旋耦合作用的基础上计算了CsNiCl3晶体和CsNiCl3:Mg2+晶体的基态能级、晶体结构、零场分裂参量和Jahn-Teller效应,研究了掺入Mg2+对CsNiCl3晶体的光谱、零场分裂参量及Jahn-Teller效应的影响和自旋单重态对基态能级的贡献,发现掺杂使得晶体结构产生畸变,从而改变晶体光谱的精细结构和零场分裂参量,不改变Jahn-Teller效应的分裂规律但改变分裂的大小.     

YGG:Cr3+低温常压下的能谱和g因子的理论计算

采用对角化由强场方案和无耦合的三角基建立的三角畸变八面体场中的d3离子完全能量矩阵,对YGG:Cr3+在低温常压下的能谱及波函数进行了拟合计算,并分析了各参数对部分能级的影响,定量地显示了能级分裂的影响因素.同时,使用对角化完全能量矩阵所获得的基态波函数,进一步计算了YGG:Cr3+的基态g因子.各项计算结果均与实验符合很好.     

掺入Mg2+对CsNiCl3晶体的基态能级、零场分裂参量及Jahn-Teller效应的影响

应用不可约张量理论构造了三角对称晶场中3d²/3d^８态离子的45阶可完全对角化的微扰哈密顿矩阵，在考虑了以前工作中被忽略的自旋-自旋耦合作用的基础上计算了CsNiCl₃晶体和CsNiCl₃:Mg²⁺晶体的基态能级、晶体结构、零场分裂参量和Jahn-Teller效应，研究了掺入Mg²⁺对CsNiCl₃晶体的光谱、零场分裂参量及Jahn-Teller效应的影响和自旋单重态对基态能级的贡献，发现掺杂使得晶体结构产生畸变，从而改变晶体光谱的精细结构和零场分裂参量，不改变Jahn-Teller效应的分裂规律但改变分裂的大小. 关键词： 基态能级 掺杂 零场分裂 自旋-自旋耦合     

Cr3+∶MgAl2O4晶体的基态能级分裂及Jahn-Teller效应*

构造了3d3/3d7离子在三角对称晶场中考虑自旋-轨道相互作用,自旋-自旋相互作用和自旋-其它轨道相互作用的120阶微扰哈密顿矩阵.利用完全对角化该矩阵的方法计算了Cr3+∶MgAl2O4晶体的基态能级、零场分裂参量,理论计算值与实验值相符合.定量研究了自旋二重态对基态能级的贡献,证明该贡献是不可忽略的.定量研究了自旋-轨道相互作用、自旋-自旋相互作用和自旋-其它轨道相互作用对Cr3+∶MgAl2O4晶体的光谱精细结构和零场分裂参量的影响,发现自旋-轨道和自旋-自旋相互作用对基态能级和零场分裂参量的影响的程度和方式是不同的,自旋-其它轨道相互作用的影响也是不可忽略的.通过理论计算值和实验值的比较,证实了在Cr3+∶MgAl2O4晶体中Jahn-Teller效应的存在,解释了该晶体的光谱精细结构的成因.     

MnFe2O4晶体的基态能级和零场分裂参量

由不可约张量理论构成一个3d4/3d6离子三角(C3V)对称的晶体场和自旋-轨道相互作用哈密顿矩阵,由这个晶体场和自旋-轨道相互作用哈密顿矩阵被完全对角化后能够求出MnFe2O4晶体中的Fe2+离子的电子顺磁共振零场分裂参量D和F-a,计算了低自旋态(3L态)对电子顺磁共振零场分裂参量(D,F-a)的贡献.结果显示低自旋3L态对电子顺磁共振的零场分裂参量的贡献是较强的.理论计算的结果与实验值是相符的.     

掺入Ni2+和V3+对α-Al2O3晶体光谱精细结构、晶体局域结构和零场分裂参量的影响

应用晶体场理论和不可约张量算符方法构造了3d2/3d8态离子在C3v对称晶场中包含自旋-轨道相互作用、自旋-自旋相互作用、自旋-其它轨道相互作用和其它轨道-其它轨道相互作用四种微观磁效应的45阶可完全对角化的能量哈密顿矩阵.利用该矩阵,计算了V³⁺∶α-Al₂O₃和Ni²⁺∶α-Al₂O₃晶体的光谱精细结构、晶体局域结构和零场分裂参量,研究了掺入两种互补态离子Ni²⁺和V³⁺对同种晶体的光谱精细结构、晶体局域结构和零场分裂参量的影响,理论计算值和实验值相符.研究发现：掺杂没有改变晶体的光谱精细结构和能级分裂条数,但改变了能级间距|掺杂也没有改变晶体的对称性,但使晶体局域结构发生了一定程度的畸变| Ni²⁺∶α-Al₂O₃晶体局域结构的伸长畸变量大于V³⁺∶α-Al₂O₃晶体,键角的变化量小于V³⁺∶α-Al₂O₃晶体.     

Fine structure and isotope shift of the 3s4d 3 D-3s3p 3 P, 3s5d 3 D-3s3p 3 P and 3p 2 3 P-3s3p 3 P Transitions of MgI

Summary We report the measurements of the³ D(3s4d)-³ P(3s3p)³ D(3s5d)-³ P(3s3p), and³ P(3p ²)-³ P(3s3p) transition frequency of MgI, the fine-structure separation and isotope shift between²⁴Mg and²⁶Mg. The measurements have been performed in a metastable atomic beam; a good agreement is found for data already existing in the literature. The accuracy of the measurements reported in this paper is mainly limited by the Doppler broadening of theI ₂ transitions used as a reference and by the precision in the knowledge of the related wavelengths.     

The gas phase infrared band contours of s-triazine and s-triazine-d3: The fundamentals of C3N3H3 and C3N3D3 and some overtone and combination bands of C3N3H3

The systematic application of band contour techniques to account for most of the observed features of the ir spectra of s-triazine and s-triazine-d₃ have been made as well as a critique as to the limitations of such methods. The experimental and computer methods used to study the gas phase infrared band contours of s-triazine and s-triazine-d₃ are out-lined. Contours of the five E′ fundamentals of s-triazine have been recorded under moderate resolution and analyzed to give the Coriolis constants $\text{ζ}{}_{\mathrm{i}}{}^{\mathrm{z}}$, i = 6–10. The effects of l-resonance are very apparent for ν₈ and ν₉, in the form of holes in the Q branches of these bands. Under the highest resolution available, ν₆ and ν₁₀ also show l-resonance effects. Values of the l-doubling constants $\text{q}{}_{\mathrm{i}}{}^{\mathrm{(+)}}$ were obtained for these four fundamentals. One of the parallel A₂″ fundamentals of C₃H₃N₃ (ν₁₂) has also been studied. It lies close to ν₁₀(E′) and an A × E type of second-order Coriolis resonance may be the cause of the intensity enhancement observed in the inner wings of the ν₁₂ and ν₁₀ bands. Hot bands of the type (ν_i + nν₁₄ ? nν₁₄) have been observed in the contours of ν₈, ν₁₀, and ν₁₂. This is felt to be responsible for the large difference between our observed zeta sum (?1.30) and the theoretical sum (?1.00).The gas phase infrared band contours of the five E′ and 2A₂″ fundamentals of C₃N₃D₃ have also been recorded under moderate resolution. From P-R separations and by computer simulation of the contours, values of the Coriolis constants $\text{ζ}{}_{\mathrm{i}}{}^{\mathrm{z}}$ have been obtained for the E′ modes. The effects of l-resonance have been observed for ν₈(E′) and ν₁₀(E′) and values of the l-doubling constants $\text{q}{}_{\mathrm{i}}{}^{\mathrm{(+)}}$ have been estimated. An extensive series of hot bands of the type (ν₁₂ + nν₁₄ ? nν₁₄) has been observed in the contour of the ν₁₂ (A₂″) fundamental. The mass effect on the Coriolis constants has been discussed.Infrared band contours of the overtone 2ν₇ and seven degenerate E′ combination bands of C₃N₃H₃ have been recorded under moderate resolution. Analysis of these contours using the P-R separation method and computer simulation of the contours has given values of $\text{ζ}{}_{\mathrm{<mtext>eff</mtext>}}{}^{\mathrm{z}}$ for these bands. Fermi resonance between 2ν₇ and ν₆ has been analyzed. The importance of considering both the observed contour as well as the observed frequency when assigning higher tone bands is illustrated.     

LaGaO3:RE3+(RE3+=Eu3+,Ho3+)的光谱

本文用固态反应合成了钙钛矿型的LaGaO3和LaGaO3:RE3+(RE3+=Eu3+,Ho3+)荧光体,并观察了物相随不同的激活离子浓度的变化。测量了化合物在室温下的反射光谱,激发光谱和荧光光谱。研究了Eu3+的D0→7F2和Ho3+的5S2→5I8的荧光强度与激活离子浓度的关系,发现了浓度猝灭,并得到了最大荧光强度的浓度值。     

Dielectric investigations of solid solutions SrTiO3-KTaO3 and SrTiO3-KNbO3

The temperature dependences of the dielectric constant and dielectric hysteresis loops in ceramic samples of (1 ? x)SrTiO_3?x KNbO₃ and (1 ? x)SrTiO_3?x KTaO₃ (0 ≤ x ≤ 0.3) solid solutions prepared using different heat treatments have been investigated. Phase diagrams of the studied solid solutions have been constructed in the T-x coordinates. It has been shown that, after quenching of samples (spontaneous cooling at room temperature after long-term heating at the sintering temperature of the ceramic samples), the temperature of the induced phase transition increases because of the weakening of random electric fields associated with nonisovalent impurities due to their “frozen” nonequilibrium redistribution. For small concentrations x, strong dielectric relaxation is observed in the temperature range of 150–250 K. A model of relaxing centers, which is based on the local charge compensation of heterovalent impurities, has been proposed.     

Infrared spectra of matrix isolated BH3NH3, BD3ND3, and BH3ND3

The infrared spectra of ammonia-borane, BH₃NH₃, and two of its deuterated isotropic species, BD₃ND₃ and BH₃ND₃, isolated in argon matrix at liquid hydrogen temperature have been measured. Well resolved bands for these three isotopic species have been observed for all the fundamentals. A complete frequency assignment based on C₃v molecular symmetry has been made. A set of force constants have been calculated from the data for the two isotopes BH₃NH₃ and BD₃ND₃ using a valence force field. The agreement between experiment and frequencies calculated from these force constants for the mixed isotopic species, BH₃ND₃, substantiates the present assignment.     

Terahertz Vibrational Modes in CH3NH3PbI3 and CsPbI3 Perovskite Films

JETP Letters - Films of CH3NH3PbI3 organometallic perovskite, which is currently considered as a promising basic material for new-generation solar cells, as well as films containing CsPbI3...     

Ba3La(BO3)3基质中Tb3+的光致发光

以高温固相法合成了Ba3La(BO3)3∶Tb3 发光材料。在254nm紫外光激发下,研究了Ba3La(BO3)3∶Tb3 的激发光谱、发射光谱、发光强度与Tb3 浓度的关系。确定了Ba3La(BO3)3基质中Tb3 的自身浓度猝灭机理;探讨了助熔剂LiCO、敏化剂Ce3 、Bi3 的加入对荧光粉的发光强度的影响。     

Nonhydrogenic exciton spectrum in perovskite CH3NH3PbI3

The excitons in the orthorhombic phase of the perovskite CH₃NH₃PbI₃ are studied using the effective mass approximation. The electron–hole interaction is screened by a distance‐dependent dielectric function, as described by the Haken potential or the Pollmann–Büttner potential. The energy spectrum and the eigenfunctions are calculated for both cases. The results show that the Pollmann–Büttner model, using the corresponding parameters obtained from ab initio calculations, provides better agreement with the experimental results.

     

O_3 fast and simple treatment-enhanced p-doped in Spiro-MeOTAD for CH_3NH_3I vapor-assisted processed CH_3NH_3PbI_3 perovskite solar cells

We demonstrate a simple and fast post-deposition treatment with high process compatibility on the hole transport material(HTM) Spiro-MeOTAD in vapor-assisted solution processed methylammonium lead triiodide(CH_3NH_3PbI_3)-based solar cells. The prepared Co-doped p-type Spiro-MeOTAD films are treated by O_3 at room temperature for 5 min,10 min, and 20 min, respectively, prior to the deposition of the metal electrodes. Compared with the traditional oxidation of Spiro-MeOTAD films overnight in dry air, our fast O_3 treatment of HTM at room temperature only needs just 10 min,and a relative 40.3% increment in the power conversion efficiency is observed with respect to the result of without-treated perovskite solar cells. This improvement of efficiency is mainly attributed to the obvious increase of the fill factor and short-circuit current density, despite a slight decrease in the open-circuit voltage. Ultraviolet photoelectron spectroscopy(UPS) and Hall effect measurement method are employed in our study to determine the changes of properties after O_3 treatment in HTM. It is found that after the HTM is exposed to O_3, its p-type doping level is enhanced. The enhancement of conductivity and Hall mobility of the film, resulting from the improvement in p-doping level of HTM, leads to better performances of perovskite solar cells. Best power conversion efficiencies(PCEs) of 13.05% and 16.39% are achieved with most properly optimized HTM via CH_3NH_3I vapor-assisted method and traditional single-step method respectively.