P−T phase diagram for ferromagnetic semiconductor CdCr2Se42

The P?T phase diagram associated with the ferromagnetic semiconductor CdCr₂Se₄ was determined between 600 and 964°C for the first time from the P_{Se2(or Cd)} ? T diagram for the stability of the compound disclosed by annealing experiments under controlled Se₂ and Cd vapor pressures, and from the phase equilibria in the CdSeCrSeSe system examined by usual annealing experiments. The following characteristic features are also clarified. (1) The maximum temperature for the stability of CdCr₂Se₄ is about 900°C. (2) CdCr₂Se₄ dissolves into Se melt and is in equilibrium with the Se-rich melt which has a CdSe content in excess of CdSe·Cr₂Se₃. The solubility decreases rapidly as temperature falls from 900 to 860°C. (3) Cr₂Se₃ is the only compound in the CrSe system in equilibrium with CdCr₂Se₄ above about 860°C. Both Cr₃Se₄ and Cr₂Se₃ exist below this temperature. (4) The P_Se2 range for the stability of CdCr₂Se₄ is estimated as a measure of the concentration ranges of native defects due to nonstoichiometry. It increases as temperature decreases and is about 5 × 10⁹ at 600°C.     

Heat capacity and thermal expansion of CdCr2Se4 and CdCr2S4

The thermodynamic properties of the spinel ferromagnetic compounds CdCr₂Se₄ and CdCr₂S₄ have been investigated by making heat capacity and thermal expansion measurements on single crystals. For both compounds, the ferromagnetic transition is marked by λ-type thermal anomalies, and the results provide a pressure dependence of the transition temperatures that is in agreement with direct measurements. Below the transition, CdCr₂S₄ shows an anomalous heat-capacity contribution and negative thermal expansion, which are in contrast to the conventional behavior found in CdCr₂Se₄.     

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     

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⁺.     

Cr4+在Al2O3多晶体中的光谱性能研究

采用传统无压烧结工艺制备Cr:Al₂O₃透明多晶陶瓷.测定了其退火前后的吸收光谱和荧光光谱，发现在Al₂O₃六配位的八面体结构中，Cr⁴⁺的荧光发射也处在1100—1600nm波段的红外区间，荧光发射峰位于1223nm附近，类似Cr⁴⁺在四面体中的发光行为.同时由于氧化铝晶格常数较小，晶体场强较强，使Cr⁴⁺:Al₂O_{3< 关键词： 4+')" href="#">Cr⁴⁺ 2}O₃透明陶瓷')" href="#">Cr:Al₂O₃透明陶瓷 光谱性质 八面体     

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     

Antiferromagnetism and spin-glass transition in the FeInxCr2−xSe4 series of selenides

The magnetic behavior of the FeIn_xCr_2−xSe₄ system (with x=0.0, 0.2 and 0.4) has been investigated by magnetic and Mössbauer spectroscopy. Hyperfine parameters indicate that iron is in the Fe²⁺ oxidation state, with a minor (∼9%) Fe³⁺ fraction, located at different layers in the structure. Low-field magnetization curves as a function of temperature showed that the antiferromagnetic (AFM) order temperature is T_N=208(2) K for FeCr₂Se₄ and decreases to 174(3) K for FeIn_0.4Cr_1.6Se₄. The effective magnetic moment μ_eff decreases with increasing In contents, and shows agreement with the expected values from the contribution of Fe²⁺ (⁵D) and Cr³⁺ (⁴F) electronic states. A second, low-temperature transition is observed at T_G∼13 K, which has been assigned to the onset of a glassy state.     

Comparative analysis of crystal field effects and energy level scheme of six-fold coordinated Cr ion in the pyrochlores, Y2B2O7 (B=Ti, Sn)

The electronic energy levels of the six-fold coordinated Cr⁴⁺ ion in the pyrochlores Y₂B₂O₇ (B=Sn⁴⁺, Ti⁴⁺), have been computed using the exchange charge model of crystal field theory. The calculated Cr⁴⁺ energy levels and their trigonal splitting are in good agreement with experimental spectra. Calculations of the crystal field parameters show that the higher crystal field strength in Y₂Sn₂O₇ (in comparison with Y₂Ti₂O₇) arises from increased orbital overlap effects between the Cr⁴⁺ ion and the nearest oxygen ions, which are located at the 48f crystallographic position of the pyrochlore lattice. The increased overlap in Y₂Sn₂O₇ occurs despite the fact that the Cr⁴⁺-O^2- bond distance in Y₂Sn₂O₇ is longer than in Y₂Ti₂O₇. This is attributed to a lack of hybridization (covalent bonding) between the filled 2p orbital of oxygen ion occupying the 48f site of the pyrochlore lattice and the filled Sn⁴⁺ 4d¹⁰ orbital. As a result, a stronger crystal field is experienced by Cr⁴⁺ ions in Y₂Sn₂O₇, even if the Cr⁴⁺-O²⁻ distances are greater in this case, when compared to those in Y₂Ti₂O₇.     

Magnetic field effect on the critical EPR-dynamics of the cubic ferromagnets CdCr2Se4 and CdCr2S4

We present measurements of the critical behaviour of the EPR linewidths at frequencies 9.21 and 35.5 GHz. In the exchange critical region above T_c (4πx ? 1) the strong field dependence of the linewidths is observed, even when the field variation of susceptibility x is small. This phenomenon is explained by the spin diffusion effect on the linewidth. The spin diffusion coefficients D for CdCr₂Se₄ and CdCr₂S₄ are determined from the linewidths data. The temperature dependence D is found to be consistent with the predictions of the dynamical scaling theory.     

Spectroscopic characteristic and energy levels of Cr in Cr:KAl(MoO4)2 crystal

This paper reports polarized spectral properties and energy levels of Cr³⁺ in KAl(MoO₄)₂ crystal. The absorption and emission cross sections are estimated as 3.72×10^-20 cm² at 669 nm and 2.74×10^-20 cm^-2 at 823 nm for σ-polarization, respectively. The energy levels of Cr³⁺ ion in KAl(MoO₄)₂ crystal were calculated based on the Tanabe-Sugano theory. It is suggested that Cr³⁺ ions occupy at an intermediate crystal field site in Cr³⁺:KAl(MoO₄)₂.     

BeAl2O4:Cr3+的晶场能级

金绿宝石中镜对称格位上Cr³⁺(Ⅱ)离子的⁴T₂,⁴T₁和²E能级与该材料的激光运转有关。⁴T₂和⁴T₁能级各分裂成三个子能级。为从偏振吸收谱上确定BeAl₂O₄:Cr³⁺的能级图,本文计算了⁴T₂和⁴T₁的分裂,找到了对谱方法,得到了表征能级分裂的参量K_{1和K2的值。最后给出了以低点群不可约表示标号的、BeAl2O4:Cr³⁺(Ⅱ)的晶场能级图。 关键词：}     

High pressure optical study of KTbP2Se6

We have observed a pressure induced phase transition in KTbP₂Se₆ at about 9.2 GPa which was accompanied by a discontinuous jump of the absorption edge of about 0.5 eV into the red. We have proposed that the high pressure phase is due to charge transfer from the selenium to the phosphorous accompanied by the formation of a Se-Se bond. In order to exclude a model which involves a 4f-5d charge transfer in Tb, leading to the intervalence charge transfer from Tb³⁺P⁴⁺-Tb⁴⁺P³⁺,we have measured the pressure dependence of the luminescence of the crystal field split levels of the Tb-ion. A comparison of the pressure dependence of the luminescence spectra of KTb(MoO₄)₂ and KTbP₂Se₆ shows that such a charge transfer does not occur in KTbP₂Se₆.     

Resonant Raman scattering of CdCr2Se4

The scattering cross section of the Raman-active phonons at 156 cm^?1 (Eg) and 169 cm^?1 (F2g) in the ferromagnetic semiconductor CdCr₂Se₄ (T_c=130 K) has been measured as a function of incident photon energy between 1.55 and 2.81 eV, both in the ferromagnetic and paramagnetic phases. The resonance curve peaks sharply near 2 eV and shows a broadening for temperatures below the Curie point. The relative line intensities change significantly with photon energy. The results show that the concept of spin-dependent Raman scattering in the ferromagnetic spinels has to be revised in terms of exchange-splitting-induced resonant Raman scattering.     

Preparation and characterization of ternary magnetic semiconductors

Summary Crystal growth processes, the characterization of properties and the application prospects for ternary magnetic semiconductors (TMS) are reviewed. The regulation of the TMS properties can be achieved either by composition change while growing crystals or by further thermal treatment. The compounds CdCr₂Se₄, CdCr₂S₄, Cu _y Cr₂Se_4−z Br _x have been selected for discussion. Paper presented at the ?V International Conference on Ternary and Multinary Compounds?, held in Cagliari, September 14–16, 1982.     

ESR study of the ferrimagnetic spinel selenide CuCr2Se4

Ferrimagnetic spinel selenide CuCr₂Se₄ has been investigated by the electron spin resonance (ESR) spectroscopy. Experimental results reveal that ESR signals originate from the localized d-shell electrons of Cr³⁺ ions. In addition, the ESR linewidth ΔH _PP increases linearly with decreasing temperature. It is suggested that the spin-orbit coupling may be one of the contributions to the broadening of ΔH _PP . Our ESR results support the model of the ferrimagnetic hybridization between localized 3d ³ electrons of Cr³⁺ with delocalized holes of Se 4p band.     

Magnetic resonance study of the magnetic structures of Rb2MnxCr1−xCl4, a random mixture of a ferromagnet and an antiferromagnet

We have studied samples of Rb₂Mn_xCr_1?xCl₄ with various concentrations x by magnetic resonance in the millimeter wave range. This mixed crystal system is of interest because of completing exchange interactions, in addition to competing anisotropies. One of the end members (Rb₂MnCl₄) is an easy-axis antiferromagnet while the other (Rb₂CrCl₄) is an easy-plane ferromagnet. Our experiments have been performed for different configurations in order to obtain information about the magnetic structure of the mixed crystal in the corresponding concentration range. On the Mn-rich site, this structure changes already at about 5% Cr²⁺ from an easy-axis antiferromagnet to an easy-plane antiferromagnet. With further increasing Cr²⁺ concentration, our results indicate an increasing ferromagnetic component which finally (Cr²⁺ concentration more than 60%, x ? 0.4) leads to a predominantly ferromagnetic order on the Cr-rich side.     

Crystal field analysis of energy level structure of the Cr2O3 antiferromagnet

A detailed analysis of the energy level structure of the six-fold coordinated Cr³⁺ ion in the chromium oxide Cr₂O₃ is performed using the exchange charge model of the crystal field theory. Parameters of the crystal field acting on the Cr³⁺ optical electrons are calculated from the crystal structure data for the [CrO₆]⁹⁻ impurity center. The energy levels obtained are compared with the experimental absorption spectra for the considered crystal; a good agreement with experimental data is demonstrated. One possible explanation for the ultraviolet p₁ absorption band is proposed based on the results of crystal field calculations.     

Spectroscopic and crystal field studies of (Ce,Gd)Sc3 (BO3)4:Cr crystals

Complex spectroscopic studies of (Ce,Gd)Sc₃(BO₃)₄:Cr³⁺ (CSB:Cr³⁺) crystals (crystal growth, absorption and luminescence spectroscopy, crystal field calculations, analysis of the radiative and non-radiative decays) are presented. The main results of the paper include calculations of crystal field parameters and energy level scheme for Cr³⁺ at distorted octahedral Sc³⁺ sites, evaluation of the Huang-Rhys factor, effective phonon frequency, zero-phonon line energy, and parameters of radiative and non-radiative decays. Comparison with experimental results and other literature data is discussed. A very unusual value of the frequency factor (related to the non-radiative processes) is explained as being due to heterodesmic nature of chemical bonds in the CSB crystal. Cr³⁺-doped CSB crystals (with Cr³⁺ concentration 5.1×10¹⁹ cm⁻³ or 1%) are suggested as promising candidates for potential applications as active media for solid state lasers.     

Deviation from Kittel's magnetic resonance formula near Tc of CdCr2Se4

Approaching the Curie temperature of the cubic ferromagnet CdCr₂Se₄ from above, the g-factor increasingly shifts from the value predicted by Kittel's formula. In the exchange critical region (susceptibility χ ?1) the g-shift is consistent with δg/g ≈ χ² following from the complex self-energy.     

Spin-dependent phonon Raman scattering in CdCr2Se4

Influences of ferromagnetic ordering on the phonon Raman scattering are studied for CdCr₂Se₄ through the intensity measurements of Raman spectra between 25 and 300 K with various wavelengths of excitation light (488.0–676.4 nm). Spin-dependent enhancements of Raman cross section are observed for optical phonon lines D(168 cm^?1) and F(238 cm^?1) with excitation wavelengths of about 630 and 550 nm, respectively. This kind of phenomenon in spinel-type chalcogen chromites seems to originate in spin-dependent intermediate interactions in the excited states of specific electronic transitions with which the incident or scattered light is resonant.