Phonon density of states of CdI2 deduced fro,the fine structure of the 3A2g → 1Eg electronic transition of CdI2:Ni2+

The absorption and MCD spectra of the ³A_2g → ¹E_g transition of CdI₂:Ni²⁺ at about 12,500 cm^?1 have been measured. The unusual vibronic fine structure is explained by the coupling of the phonons of the CdI₂ lattice to the electronic states of Ni²⁺. The dispersion curves for the acoustical and optical branches in the Brillouin Zone of CdI₂ are deduced.     

Absorption and emission spectra of yttria-stabilized zirconia and magnesium oxide

We have investigated the luminescence and absorption spectra of doped and undoped ZrO₂-Y₂O₃ and MgO crystals at room- and low temperatures. The crystals used are partly doped with the transition metals Ni, Co, Cr and the rare earth Pr. The emission spectra were obtained under laser excitation at different wavelengths. The observed optical emission and absorption bands of the MgO crystals doped with Ni, Co and Cr correspond to transitions between spin-orbit split crystal field levels of the transition metals. Luminescence and absorption bands of undoped yttria-stabilized zirconia (YSZ) crystals are due to color centers, absorption bands of the doped YSZ correspond to the well known transitions of the Ni²⁺, Co²⁺ and Pr³⁺ ions, respectively. The emission spectra of the doped YSZ obtained under various laser excitations can be explained by an energy transfer process between the color center and the doping materials. The influence of annealing on the absorption and emission of Pr³⁺/Pr⁴⁺ is investigated.     

Recombination processes in europium-doped cadmium iodide crystals

Results of comprehensive research into optical and luminescent-kinetic characteristics of europium-doped cadmium iodide crystals excited by nitrogen laser radiation, α-particles, and x-rays are presented. Crystals under study have been grown by the Bridgman–Stockbarger method. The doping EuCl₃ admixture was introduced into the charge in quantities of about 0.05 and 1.0 mol%. Impurity absorption detected in the near-edge region of the crystals is interpreted as part of the Eu²⁺ ion long-wavelength band associated with f–d-transitions. The cation impurity and matrix defects in CdI₂:Eu²⁺ crystals create complex centers responsible for emission with a maximum in the 580–600-nm region. The short component in the luminescence decay kinetics of weakly-doped crystal excited by α-particles and x-ray photons is due to the exciton emission characteristic of CdI₂. The slow component in the scintillation pulse results from recombination of charge carriers followed by creation of exciton-like states on the defect-impurity centers. Laser or x-ray excitation induces light-sum accumulation on the trapping levels at a depth of 0.2–0.6 eV that is mainly related to matrix microdefects. Trapping centers associated with the chlorine impurity are observed in the heavily-doped crystal. Photostimulated luminescence at 85 K arising at the electron stage of the recombination process is caused by recombination of electrons released from F-type centers with holes localized near the activator. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 3, pp. 358–364, May–June, 2009.     

Calculations of physical properties of pure and doped crystals: Ab initio and semi-empirical methods in application to YAlO3:Ce and TiO2

In this paper we demonstrate that two independent methods of calculations (DFT based ab initio and semi-empirical crystal field theory) can be used to form a complementary picture of the optical and electronic properties of the doped host and impurity ion. The crystals considered in the present paper are: (i) YAlO₃:Ce³⁺ and (ii) two dominant phases of TiO₂—rutile and anatase. As an example, detailed calculations of the band structure and crystal field energy level scheme of YAlO₃:Ce³⁺ are reported. From the analysis of the band structure and density of states, the character of the YAlO₃ energetic bands and positions of the Ce impurity energy levels were established. It was also shown how the ab initio methods can be used for calculations of the structural properties of solids under elevated pressure. Taking the two dominant phases of TiO₂ as an example, it was demonstrated how the elastic properties can be extracted from the calculated unit cell’s volume at different pressures. Particular attention was paid to the microscopic effects of crystal field, which were evidenced by the pressure-induced changes of the structure and shape of distribution of the Ti 3d electrons density of states. It was demonstrated how the difference in crystal structure of the anatase and rutile phases leads to remarkable difference in microscopic crystal field effects, which was explained by different Ti-O distances in both phases. In addition, the pressure dependence of the band gaps for anatase and rutile was investigated. It was shown that the hydrostatic pressure leads to the band gap narrowing in anatase and band gap widening in rutile, with pressure coefficients +0.00681 eV/GPa for rutile and −0.0088 eV/GPa for anatase.     

Role of intrinsic defects and impurities in forming the optical characteristics of ZnWO4 and CdWO4 crystals

We analyze the optical characteristics of crystals within the framework of a model representation that presupposes the entry of the background impurity of iron ions in two valence states, Fe³⁺ and Fe²⁺, into regular lattice nodes. The spectral manifestation of intrinsic defects of vacancy-type structure depending on the conditions of crystal growth and heat treatment is comprehensively investigated. With allowance for the specific features of the technology applied, we have tested the technique suggested in scientific periodicals for bleaching ZnWO₄ and CdWO₄ crystals by doping with nonisovalent ions, in particular, with Sb and Ag impurities. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 2, pp. 211–216, March–April, 2000. The work was carried out with support from INTAS-UKRAINE within the framework of the project INTAS-UA-95-0166.     

High-energy frenkel cation exciton and specific features of its self-trapping in the CdI<Subscript>2</Subscript>-PbI<Subscript>2</Subscript> crystal system

It has been shown using atomic-force microscopy that the PbI₂ impurity is embedded in the CdI₂ crystal lattice in the form of nanocrystalline inclusions. The model of a high-energy cation exciton related to the ³ P ₂ state of a free Pb²⁺ ion has been considered for the impurity absorption (excitation) band at 3.23 eV. The resonance narrow photoluminescence bands with the split absorption band at 3.12 and 3.20 eV have been compared with the emission of a free Frenkel exciton. It has been demonstrated that, in the temperature range 25–45 K, there arises a self-trapped exciton state, and the main role in its formation is played by the bending vibrations of the CdI₂ crystal lattice. The potential barrier separating the self-trapped state from the free exciton is 23 meV. The photoluminescence band at 2.4 eV is assigned to the emission of the self-trapped high-energy cation exciton of PbI₂ in the CdI₂ crystal lattice.     

An experimental and theoretical study of Ni impurity centers in Ba<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>TiO<Subscript>3</Subscript>

The local environment and the charge state of a nickel impurity in cubic Ba_0.8Sr_0.2TiO₃ are studied by XAFS spectroscopy. According to the XANES data, the mean Ni charge state is ~2.5+. An analysis of the EXAFS spectra and their comparison with the results of first-principle calculations of the defect geometry suggest that Ni²⁺ ions are in a high-spin state at the B sites of the perovskite structure and the difference of charges of Ni²⁺ and Ti⁴⁺ is mainly compensated by distant oxygen vacancies. In addition, a considerable amount of nickel in the sample is in a second phase BaNiO_{3 ? δ}. The measurements of the lattice parameter show a decrease in the unit cell volume upon doping, which can indicate the existence of a small amount of Ni⁴⁺ ions at the B site.     

Structural,optical and dielectric properties of Ni substituted NdFeO3

Present study reports the structural, optical and dielectric properties of Ni substituted NdFe_1−xNi_xO₃ (0 ≤ x ≤ 0.5) compounds prepared through the ceramic method. X-ray diffraction (XRD) confirmed an orthorhombic crystal structure of all the samples. Both unit cell volume and grain size were found to decrease with an increase in Ni concentration. Morphological study by Scanning electron microscope (SEM) shows less porosity with Ni substitution in present system. From UV–vis spectroscopy, the optical band gap was found to increase with Ni doping. This observed behavior was explained on the basis of reduction in crystallite size, unit cell volume and its impact on the crystal field potential of the system after Ni substitution. The dielectric properties (?′ and tanδ) as a function of frequency or temperature, and the ac electrical conductivity (σ_ac) as a function of frequency have been studied. Hopping of charge carriers between Fe²⁺ → Fe³⁺ ions and Ni²⁺ → Ni³⁺ ions are held responsible for both electrical and dielectric dispersion in the system. Wide optical band gap and a very high dielectric constant of these materials promote them to be a suitable candidate for memory based devices in electronic industry.     

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.     

EPR and optical spectra of Ni2+-VAg in silver chloride and silver bromide

The optical absorption and EPR spectra of Ni²⁺-V_Ag centres in the AgCl:Ni²⁺ and AgBr:Ni²⁺ systems have been investigated theoretically on the basis of the complete energy matrices including the electron–electron repulsion interaction, the ligand field interaction, the spin–orbit coupling interaction, and Zeeman interaction. Because the charge compensation forms a silver ion vacancy (V_Ag) which makes the attractive force acted on the each ligand ion different, it was determined that the Ni–X (X = Cl, Br) distance next to V_Ag is shorter than others for both AgCl:Ni²⁺ and AgBr:Ni²⁺ systems in the tetragonal symmetry. Besides, it was found that the local lattice structure of (NiX₆)^4? clusters in AgCl and AgBr crystals exhibit a compression distortion. This compression distortion may be ascribed to the fact that the Ni²⁺ ion has a smaller ionic radius and more effective charge than the Ag⁺ ion.     

Thermo- and photostimulated processes of polarization and depolarization in CdI<Subscript>2</Subscript>: Ag

Currents of thermogradient polarization and depolarization of an electret state that arises in a photochromic crystal CdI₂: Ag during one-side cooling of the sample in the dark from 325 to 90 K in the presence of a temperature gradient directed along the crystallographic axis C ₆ have been found. At 90 K, the crystal polarized in the thermogradient electromotive force field is characterized by the photosensitivity in the near-edge, impurity, and infrared spectral regions. It is revealed that the electret state in the CdI₂: Ag crystal is also formed at room temperature during photolysis under irradiation of the samples by integrated light from a xenon lamp. Models of photosensitive centers formed upon doping of the CdI₂ crystal from the melt by the Ag⁺ impurity and during the occurrence of thermo- and photostimulated chemical reactions are proposed. The mechanism of the photochromic effect, including the change in the charge state of silver impurity ions, is considered.     

Structural, spectroscopic and crystal field analyses of Ni2+ and?Co2+ doped Zn2SiO4 powders

In this paper we presented structural and spectroscopic study of zinc silicate powder samples doped with divalent nickel and cobalt ions. Results of the Rietveld structural refinement, combined with optical spectroscopic study and theoretical crystal field calculations, are presented and discussed. X-ray diffraction studies were performed to establish reliable structure of the doped samples; in this way the interionic distances and chemical bond angles in Zn₂SiO₄:Co²⁺ and Zn₂SiO₄:Ni²⁺ were calculated and are reported for the first time. The room temperature reflection spectra of the prepared samples were measured in a spectral region from 4000 to 50000 cm^?1. The exchange charge model of crystal field has been applied to analyze the experimental spectra and assign all observed details in the spectra to the corresponding electronic transitions between the Co²⁺ and Ni²⁺ crystal field energy levels. The only input information for the model calculation was the experimentally obtained structural data, which were used for the calculations of the crystal field parameters with subsequent diagonalization of the crystal field Hamiltonian for both ions. Agreement between the calculated and experimentally detected energy levels of impurity ions was good. On the basis of the crystallographic and crystal field studies it was established that there exists a systematic trend of preferential occupation of one out of two possible crystallographic sites (namely, Zn2) for both impurity ions.     

EPR and optical spectroscopy of Yb<Superscript>3+</Superscript> ions in CaF<Subscript>2</Subscript>: an analysis of the structure of tetragonal centers

CaF₂ crystals doped with Yb³⁺ ions have been studied by electron paramagnetic resonance (EPR) and optical spectroscopy. EPR spectra of paramagnetic centers (PCs) for cubic (T_c) and tetragonal (T_tet) symmetries were identified. Empirical energy level diagrams were established and crystal field parameters were determined. Information on the CaF₂∶Yb³⁺ phonon spectra was obtained from the electron-vibrational structure of the optical spectra. The crystal field parameters were used to analyze the crystal lattice distortions in the vicinity of the Yb³⁺ ion. Within the framework of a superposition model, it is established that four F⁻ ions located symmetrically with respect to the fourfold axis from the side of the ion-compensator approach the impurity ion and deviate from the PC axis. The second set of four fluorine ions also approaches the Yb³⁺ ion and the PC axis. The ion-compensator F⁻ also approaches considerably the impurity ion.     

The electronic and optical properties of Cu doped CdI2

Based on the density functional pseudopotential method, the electronic structures and the optical properties of CdI₂ doped with Cu are investigated in detail. The calculation results indicate that the defect of Cu(Cd) exists steadily with a certain solubility. For the Cu doped CdI₂, the new highly localized impurity bands induced by Cu 3d states lie just across the Fermi energy at the top of the valence band. The doping of Cu induces reduction of band gap of CdI₂; red shifts are revealed in both the imaginary part of dielectric function and the absorption spectra corresponding to the change in band gaps. Moreover, the study of the reflection spectrum and the loss function shows that the doped Cu is responsible for the increased reflection peak intensity and the red shift of the plasma resonant frequency of CdI₂.     

Comparative first-principle analysis of un-doped and V3+-doped α-ZnAl2S4 spinel

The experimental and theoretical studies of the optical properties of pure α-ZnAl₂S₄ and α-ZnAl₂S₄:V³⁺ crystals were carried out. The ab initio and crystal field calculations of the structural and optical properties of α-ZnAl₂S₄:V³⁺ were compared with the corresponding experimental data. It was shown that the lowest vanadium 3d states are located at about 1.36 eV above the valence band's top. The complete energy level scheme of the α-ZnAl₂S₄:V³⁺ system, which includes the host's electronic band structure and impurity ion's energy levels, was suggested on the basis of the performed calculations.     

First principles studies on the electronic structures of LiMxFe1-xPO4 （M = Co, Ni and Rh）

The local crystal structures and electronic structures of LiMxFe1-xPO4 （M = Co, Ni, Rh） are studied through first-principles calculations. The lattice constants and unit cell volumes are smaller for the Co and Ni doped materials than for pure LiFePO4, while larger than for the Rh doped material. The local structures around M atoms in the doped materials are studied in details. The total density of states （DOS） and atomic projected DOS （PDOS） are all calculated and analysed in detail. The results give a reasonable prediction to the improvement of electronic conductivity through Fe-site doping in LiFePO4 material.     

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.     

First principles analysis of the MgAl2O4:Ni absorption spectrum

Analysis of the energy-level scheme and absorption spectrum of the Ni²⁺ ion in MgAl₂O₄ was performed. The recently developed first-principles approach to the analysis of the absorption spectra of impurity ions in crystals based on the discrete variational multi-electron (DV-ME) method [K. Ogasawara, et al., Phys. Rev. B 64 (2001) 115413) was used in the calculations. The method is based on the numerical solution of the Dirac equation; no phenomenological parameters are used in the calculations. As a result, complete energy-level scheme of Ni²⁺ and its absorption spectra were calculated, assigned and compared with experimental data on the ground and excited state absorption spectra. Numerical contributions of all possible electron configurations into the calculated energy states were determined. By performing analysis of the molecular orbitals population, numerical contributions of the oxygen 2p- and 2s-orbitals into the 3d molecular orbitals were determined.     

Lattice dynamics of ZnSe x S1 − x semiconductor crystals

Recently ultrabroadband infrared solid state lasers based on a new vibronic material Cr²⁺:ZnSe _x S_1–x were demonstrated [1–3]. Cr²⁺ ion substitutes the metal ion (tetrahedral sites), the crystal field of the solid solution is responsible for large inhomogeneous broadening of Cr²⁺ electron states. The crystal field can be reconstructed by investigation of lattice dynamics — optical phonon parameters and dielectric function in IR. We paid special attention to investigation of vibrational and infrared spectroscopic properties of ZnSe _x S_{1 ? x} crystals. A very interesting and somewhat unexpected result of these studies was the existence in the crystals of effective S-Se dipoles, which generate an additional deep dynamically charged level in the forbidden gap of the semiconductors. The results of the first-principles calculations of both the phonon structure and the electron localization in ZnSe _x S_1–x crystals as well as acceptor levels in Cr²⁺: ZnSe crystal are discussed.     

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.