EPR diagnostics of laser materials based on ZnSe crystals doped with transition elements

The electron paramagnetic resonance (EPR) spectra observed in laser materials based on zinc selenide (ZnSe) crystals doped with transition elements have been analyzed and identified. It has been shown that, in addition to working impurities (Cr²⁺, Co²⁺, or Fe²⁺), the diffusion layer exhibits EPR spectra of accompanying impurities due to the diffusion of transition elements (chromium, cobalt, or iron) used in the preparation of active materials for quantum electronics (lasers, switches) operating in the mid-infrared range. EPR diagnostics of these impurities can be used in the development of appropriate regimes for minimizing concentrations of accompanying impurities that adversely affect the performance characteristics of laser materials. It has been found that, during the diffusion of transition metals, ions of the accompanying impurity Mn²⁺, which is characterized by extremely informative EPR spectra, are embedded in the crystal lattice. It has been proposed to use these ions as ideal markers to control, on the electronic level, the crystal structure of the active diffusion layer.     

Pb2+ Defects in perovskite-like KMgF3 crystals

Abstract

The physical properties of Pb²⁺ impurities in the perovskite-like lattice of KMgF₃ are very similar to those of (ns)² ions in alkali halides. The impurity inhomogeneous distribution leads to high dopant levels in the bottom region of the crystals, with a segregation coefficient equal to 0. 020. The optical features of the 336 nm emission support its attribution to luminescence of Pb²⁺ ions from the relaxed excited B state.     

Tuning the bottleneck effect in Ag metallic host doped with magnetic Gd and non-magnetic Sb ions

The Ag metallic host doped with Gd and Sb is an excellent model system to study the bottleneck effect associated to the conduction-electron (c-e) spin-flip scattering mechanism. Electron spin resonance of Gd³⁺ in both, Ag-(Gd doped)- and Ag-(Gd and Sb doped)-systems, reveal the presence of bottleneck which can be tuned by the amount of Gd and Sb impurities. The increase of the Gd concentration leads to a c-e spin-flip relaxation rate to the magnetic Gd³⁺ ions larger than that to the lattice, favoring the bottleneck regime. Whereas the effect of the non-magnetic impurities (Sb ions) is to increase, via spin–orbit scattering, the spin-flip relaxation rate of the c-e to the lattice, weakening the bottleneck regime.     

Dislocation nucleation and precipitation of impurity in calcium-doped NaCl-KCl crystals

In calcium-doped mixed NaCl-KCl crystals, Ca²⁺ ion sites were selectively sensed by a suitable etchant. Different impurity substructures, viz. arrays, close-networks, unevenly distributed clusters were formed by the dopant ions in the lattice. Non-uniform distributions of the impurity ions in the lattice does not nucleate dislocations. Non-structural impurities like precipitates were found to take different forms, viz. elongated rods, rectangular forms, with different orientations. Dislocations showed strong preference for the nucleation of the precipitates. The nucleation of the precipitates at sites other than those of dislocations is discussed.     

Characterization of ZnO:Co particles prepared by hydrothermal method for room temperature magnetism

ZnO based diluted magnetic semiconductor particles (ZnO:Co) have been grown using a hydrothermal method with good crystallinity. The atomic percentage of Co presented in the specimen is about 0.01. Based on the x-ray diffraction and high-resolution transition electron, Co is found to be incorporated into ZnO lattice without evidence of obvious Co precipitates. However, from photoluminescence (PL) spectra in the range of 1.94 -3.45 eV, a strong broad emission centered around 600 nm (2.07 eV) in the visible range as well as a relatively weak peak at 2.81 eV are observed, indicating the presence of Co impurities. Moreover, intrinsic emissions such as D^OX suggest that at least some Co have been doped into ZnO lattice, substituting for Zn²⁺ ions. The PL results further confirm the substitution of Zn²⁺ ions by Co, which leads to the changes of the electronic band structures. Magnetism could be realized at room temperature for the ZnO:Co nanoparticles under our experimental conditions although with low coercivity. The field-cooled and zero-field-cooled curves can be explained as a result of competition between the ferromagnetic and the antiferromagnetic ordering in the ZnO:Co nanoparticles. Combining the results from PL and magnetism characterization, it is reasonable to think that both doped Co in the ZnO lattice and Co impurities contribute to magnetism in ZnO:Co nanoparticles at room temperature.     

An NMR Analysis of Transitions in FexNbxV2-2xO4

The first order semiconductor - metall phase transition with the lattice symmetry change from monoclinic to tetragonal and the conductivity jump of several orders of magnitude is observed in pure vanadium dioxide and the dioxide doped by varios impurities [I]. Transition temperature T_t for pure VO₂ is 68°C and depends on the impurity. For example, the impurities which enter the insulating phase as pentavalent ions Nb⁵⁺ [2] give rise to a decrease in metal-semiconductor transition temperature at low concentrations and the trivalent ions Cr³⁺, Fe³⁺ [3,4] lead to an increase in T_t. In the latter case three different monoclinic phases are stabilized at a temperature below T_t. It has been already shown [5] that for double doping of vanadium dioxide by pentavalent Nb⁵⁺ and trivalent Fe³⁺ or Cr³⁺ ions three semiconductor phases exist (M_I, M₂, M₃) but the transition temperature decreases as the impurity concentration increases.     

激光上转换玻璃陶瓷材料中稀土杂质Yb^3＋和Tm^3＋局域行为

对红光上转换玻璃陶资ＰｂＦ２＋ＷＯ３＋ＧｅＯ２以及ＰｂＦ２＋ＷＯ３＋ＧｅＦ３＋ＴｍＦ３材料中的微晶相进行了喇曼光谱研究,获得了光谱表明ＰｂＦ２＋ＷＯ３＋ＧｅＯ２＋ＹｂＦ３＋ＴｍＦ３中的微晶是由ＰｂＦ：Ｙｂ＾３＋、Ｔｍ＾３＋构成的,其中Ｙｂ＾３＋和Ｔｍ＾３＋替代部分Ｐｂ＾２＋的格位而形成了荷正电的局域杂质中心。这些局域杂质中心导致了ＰｂＦ２＋ＷＯ３＋ＧｅＯ２＋ＹｂＦ３＋ＴｍＦ３中局域电场的形成。除了     

ESR-analysis of the chalcopyrite structure: CuGaS2:Fe3+

The electron spin resonance spectrum of Fe³⁺ impurity ions in the ternary semiconductor CuGaS₂ has been analysed. The two magnetically inequivalent metal sites in the chalcopyrite lattice could be distinguished via fourth order terms in the spin Hamiltonian. No serious deviations from stoichiometry could be detected in transport-grown crystals. It was found that traces of iron impurities lead to strong absorption in the visible and near infrared spectral region.     

Ground state valency and spin configuration of the Ni ions in nickelates

The ab initio self-interaction-corrected local-spin-density approximation is used to study the electronic structure of both stoichiometric and nonstoichiometric nickelates. From total energy considerations it emerges that, in their ground state, both LiNiO2 and NaNiO2 are insulators, with the Ni ion in the Ni3+ low-spin state (t(2g)(6)e(g)(1)) configuration. It is established that a substitution of a number of Li/Na atoms by divalent impurities drives an equivalent number of Ni ions in the NiO2 layers from the Jahn-Teller (JT)-active trivalent low-spin state to the JT-inactive divalent state. We describe how the observed considerable differences between LiNiO2 and NaNiO2 can be explained through the creation of Ni2+ impurities in LiNiO2. The indications are that the random distribution of the Ni2+ impurities might be responsible for the destruction of the long-range orbital ordering in LiNiO2.     

Electron paramegnetic detection of ionic motional effects in the super ionic conductor β-sodium gallate

The EPR spectra of Cu²⁺, Mn²⁺ and Eu²⁺, incorporated into the conducting mirror planes of β-sodium gallate, have been studied. For all three impurities, the EPR spectra at or near room temperature show pronounced relaxation effects caused by the motion of the ions. From the relaxation effects the correlation time of the motion is found to be of the order of 10^-11 sec. This time corresponds to a residence time for the paramagnetic ion at a lattice site in the conducting plane. From this time and the thermal activation energy an attempt frequency of 10¹² Hz is determined.     

Inhomogeneous lattice distortions in the Zn0.99Cd0.01Se crystal

The structural state of a Zn_0.99Cd_0.01Se crystal at temperatures of 78 and 300 K has been investigated using thermal neutron diffraction. It has been found that the diffraction patterns of the crystal contain diffuse scattering regions in the vicinity of the basic structure reflections, which are independent of temperature. It has been shown that the effects of diffuse scattering are caused by transverse displacements of lattice atoms, which are induced by impurities of the Cd²⁺ ions whose sizes substantially exceed the sizes of the Zn²⁺ ions. The obtained results have been used to construct a picture of the influence of cadmium ions on the structural state of the crystal under study.     

Electronic structure and ferromagnetism of polycrystalline Zn1−xCoxO (0≤x≤0.15)

The electronic structure of polycrystalline ferromagnetic Zn_1−xCo_xO (0.05≤x≤0.15) and the oxidation state of Co in it, have been investigated. The Co-doped polycrystalline samples are synthesized by a combustion method and are ferromagnetic at room temperature. XPS and optical absorption studies show evidence for Co²⁺ ions in the tetrahedral symmetry, indicating substitution of Co²⁺ in the ZnO lattice. However, powder XRD and electron diffraction data show the presence of Co metal in the samples. This give evidence to the fact that some Co²⁺ ion are incorporated in the ZnO lattice which gives changes in the electronic structure whereas ferromagnetism comes from the Co metal impurities present in the samples.     

Soliton Lattice in Trans-Polyacetylene with Random Site-Type impurities

In order to understand the effect of disorder of impurities in doped trans-polyacetylene, we investigate the electronic states of trans-PA with random site-type impurities, especially, taken into account the Coulomb interaction between impurity ions. The randomness of impurity ions can obviously affect the electronic structures of trans-PA chain for the intermediate doping regime (y ≈ 4~8%). With increasing doping level, this in turn leads to widen the soliton band and narrow the band gap. Moreover, the upper gap will appear a maximum at the critical doping level (y ≈ 6%). In addition, when the doping concentration is larger than 12%, the random distribution of impurities tends to be uniform because of being concerned with the Coulomb interaction between ions. Meanwhile, the order parameter configuration indicates that it will appear soliton lattice.     

Some crystalline field effects in metals

We discuss different physical effects which are caused by the crystalline electric field splitting of rare earth ions in metals. Thus, the rare earth ions may be impurities dissolved in a metallic matrix or they may form a regular lattice. In the former case we distinguish between the cases of a normal conducting and a superconducting matrix. The influence of the crystalline field splitting on the properties of the conduction electrons is calculated. In the case of a normal matrix anomalous behaviour of the thermoelectric power is found due to the impurity levels. If the matrix is superconducting large deviations result from the theory of Abrikosov and Gorkov which describes the influence of non-split magnetic impurities on superconductivity. A comparison of the theory with available experiments is presented.

For the case that the rare earth ions form a regular lattice we discuss various aspects of the collective excitations in the paramagnetic state. Special attention is paid to the soft mode problem of exchange induced ferromagnets. Furthermore we discuss the influence of impurities on the excitation spectrum (localized modes, resonant modes etc.) and on the magnetic ordering temperature.     

EPR characterization of Mn impurity ions in PbWO4 single crystals

The electron paramagnetic resonance (EPR) properties of the Mn²⁺ ions in PbWO₄ single crystals grown by the Czochralski method have been investigated in the X-band microwave frequency, at T=20 K. The angular dependence of the EPR line positions obtained by rotating the magnetic field in the main crystallographic planes shows that the local symmetry at the Mn²⁺ impurity ions is tetragonal, strongly suggesting that the Mn²⁺ ions substitute for the Pb²⁺ lattice cations, without charge compensation. The resulting spin Hamiltonian parameters compare well with the corresponding values for the Mn²⁺ ions in other isomorphous tungstates. The observed strong angular variation of the EPR linewidth has been quantitatively described considering a random distribution of lattice strains.     

A close correlation between induced ferromagnetism and oxygen deficiency in Fe doped In2O3

We report on the reversible manipulation of room temperature ferromagnetism in Fe (5%) doped In₂O₃ polycrystalline magnetic semiconductor. The X-ray diffraction and photoemission measurements confirm that the Fe ions are well incorporated into the lattice, substituting the In³⁺ ions. The magnetization measurements show that the host In₂O₃ has a diamagnetic ground state, while it shows weak ferromagnetism at 300 K upon Fe doping. The as-prepared sample was then sequentially annealed in hydrogen, air, vacuum and finally in air. The ferromagnetic signal shoots up by hydrogenation as well as vacuum annealing and bounces back upon re-annealing the samples in air. The sequence of ferromagnetism shows a close inter-relationship with the behavior of oxygen vacancies (V_o). The Fe ions tend to a transform from 3+ to 2+ state during the giant ferromagnetic induction, as revealed by photoemission spectroscopy. A careful characterization of the structure, purity, magnetic, and transport properties confirms that the ferromagnetism is due to neither impurities nor clusters but directly related to the oxygen vacancies. The ferromagnetism can be reversibly controlled by these vacancies while a parallel variation of carrier concentration, as revealed by resistance measurements, appears to be a side effect of the oxygen vacancy variation.     

The effects of core structure on radiative and non-radiative recombinations at metal ion substituents in semiconductors and phosphors

Carrier binding and recombination processes at transition metal (TM) and post-transition metal impurities in solids are reviewed. The presence of low-lying empty core orbitals in these impurities introduces novel binding and recombination phenomena and leads naturally to a classification of impurity centres as ‘simple’ or ‘structured’. ‘Simple’ impurities, generally the main group elements, introduce only effective-mass-like states into the forbidden gap of the host lattice, whereas ‘structured’ impurities show localized atomic-like transitions below the lattice absorption edge. The fact that donor or acceptor centres generated by TM ions in semiconductors are usually deep is discussed with reference to a simple oxidationstate correlation diagram based on the variable chemical valency characteristic of these ions. Many metal ion impurities in solids generate iso-electronic centres however, and evidence is assembled to show how the normally accepted range of iso-electronic centres can be extended to include such impurities. It is emphasized that the formation of bound states at these ‘structured’ cationic iso-electronic centres is fairly common, in contrast to the situation normally found for anionic substituents in semiconductors. A possible explanation for this general property of structured iso-electronic centres is given in terms of the low-lying core levels which they may introduce in the band gap and their enhanced polarizability. Simple arguments then suggest that those centres showing electron ionization thresholds or atomic inter-configurational transitions just below E _g should be hole-attractive, whereas those showing charge transfer transitions should be electron-attractive. It is shown that two kinds of defect Auger recombination (DAR) may be significant for excitons localized at structured impurities. The first involves hole ionization at a deep neutral acceptor, and the conditions which must be met to make this process significant at room temperature are reviewed. The second DAR process involves the transfer of carrier recombination energy to the core electrons of the structured impurity. A simple model developed for this energy transfer process predicts that the coupling between exciton and core states will be larger if the impurity shows strong, broad dipole-allowed transitions quasi-resonant with the lattice absorption edge. Throughout the paper we stress the importance of recombination processes at structured impurities to the problems of phosphor activation and of shunt recombination mechanisms in semiconductor LEDs. In the final sections this general framework of ideas is used to explain the relative cathodoluminescence efficiencies of different rare-earth activators in crystals of Y₃Al₅O₁₂, with good agreement between the theoretical predictions and the experimental observations. Possible evidence for the occurrence of bound exciton states at structured TM impurities is found in the appearance of anomalously weak zero-phonon lines in the near-edge luminescence of GaP crystals prepared under special conditions.     

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.     

Cation distribution in Eu-Sc-Fe garnets

The cation distribution has been studied with ⁵⁷Fe Mössbauer spectroscopy in the garnet system Eu_3?ySc_2+yFe₃O₁₂ with y = 0.0, 0.2 and 0.5. It is shown that the previously proposed cation distribution is not correct. The problem of possible impurities in the investigated system is discussed in detail. Several possible cation distributions are considered compatible with Mössbauer data. Mössbauer results combined with the composition dependence of lattice constants show that the tetrahedral sites are accessible to Sc³⁺ ions. The system studied is a second example of a garnet structure in which Sc³⁺ ions are found at the tetrahedral sites. A small fraction of Sc³⁺ ions for the samples y = 0.2 and 0.5 is also found at the dodecahedral sites.     

彩色金刚石中过渡金属离子的谱学研究

过渡金属镍、钴和铁是高温高压法合成金刚石的常用触媒,已有研究表明：采用镍、钴作触媒所合成的金刚石中存在镍、钴离子,部分天然金刚石含有镍离子;镍、钴离子以替代方式或间隙形式进入金刚石的晶格,并能与杂质氮形成复合体。为了探寻彩色金刚石中过渡金属离子存在的谱学标志,确定镍、钴离子在彩色金刚石中的赋存状态,文章对6颗彩色天然与合成金刚石进行了扫描电镜-能谱、显微红外光谱、光致发光谱、电子顺磁共振谱(EPR)等测试研究。结果表明天然与合成的样品都具有与镍、钴有关的发光中心与EPR结构：包括西澳的蓝灰色天然金刚石中与镍有关的884.6 nm等发光中心,以及天然变色金刚石中与钴有关的发光中心。对各种谱学测试结果的综合分析,得出样品中存在镍、钴离子并与杂质氮形成各种Ni-N或Co-N复合体的结论,其中在天然金刚石中发现钴离子在该领域研究中尚属首次。