The metal-insulator transition and the phase transition in metal-ammonia solutions

The ground state of impurity metal (sodium) atoms in liquid ammonia close to the solvated state of the free electrons is considered. It is shown that the critical solubility point lying on the metal side of the metal-insulator transition is determined by the Coulomb interaction between the ions and electrons in the overlapping impurity states, classically accessible spheres of which form an infinite percolation cluster. The percolation conductivity via the impurity states is estimated. The estimate agrees with the experimental data near the critical solubility point. Zh. éksp. Teor. Fiz. 111, 938–948 (March 1997)     

Electronic structure of bivalent copper off-center complexes in SrF<Subscript>2</Subscript> crystals from data of EPR and ENDOR spectroscopy

The electronic structure of bivalent copper off-center complexes in SrF₂ crystals is calculated from experimental data obtained earlier by electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy. The electronic structure parameters characterizing the unpaired-electron density in the vicinity of the nucleus of a copper impurity ion are determined, and the parameters of covalent bonds between an impurity copper ion and three groups of the fluorine ions nearest to this impurity are calculated. It is demonstrated that states of the ground electron configuration of the bivalent copper impurity complex involve an admixture of excited electron configurations due to electron transfer from the ligand to 4s and 4p unfilled shells of the copper ion.     

Size effects in photoexcitation of triplet states of ammonium tetraphenylborate

This paper reports on the results of complex investigations of photoexcited states of ammonium tetraphenylborate, which are characterized by self-sensitized luminescence. It has been established that the excitation by UV light at 77 K leads to the formation of stable triplet states due to the capture of electrons on electron traps. The EPR and luminescence excitation spectra exhibit the formation of a set of triplet states with different distances between electrons and holes. The performed investigations give grounds to affirm that, in bulk samples, cations in the structure of ammonium tetraphenylborate are electron traps. When the size of the ammonium tetraphenylborate sample is changed to 6 and 3 nm, the capture of excited electrons on sorbed oxygen molecules becomes dominant. In this case, the appearance of the spectrum of O₂⁻ anion radicals has been detected by the EPR method. The proposed interpretation of the observed effects has been confirmed by the thermoluminescence data on the recombination of electron-hole pairs, which correlate with a change in the intensity of the EPR spectra during annealing.     

EPR studies of highly pure,pure and doped chromium oxide powders

Abstract

EPR absorption measurements on ‘pure’, highly pure and A1₂O₃ doped Cr₂O₃ powder have been made. The EPR absorption in the ‘pure’ powders obtained below Ntel temperature is shown to be due to background magnetic impurities present in the powders and not due to superparamagnetism as suggested by earlier authors. No EPR absorption could be observed below Nkl temperature in highly pure powders (total background impurity concentration less than 5 ppm). ‘Pure’ powders or highly pure powders mixed with A1₂O₃ powder and annealed at high temperatures showed a symmetrical EPR absorption line at room temperature. The shape and the g value of this line are practically the same as those obtained for Cr³⁺ ions in Cr₂O₃ above Nee1 temperature or in other nonmagnetic crystals. It is concluded from these results that the impurities diffuse into Cr₂O₃ powder, the antiferro-magnetic coupling between some of the Cr³⁺ ions is broken and these Cr³⁺ ions become paramagnetic, even when the bulk of the material is in antiferromagnetic state. The variation of half-width of EPR lines with impurity concentration shows that the dipolar coupling between Cr³⁺ ions decreases with the increase in impurity concentration and when the impurity concentration is high the Néel temperature seems to shift to lower temperatures. A longer heat treatment of the ‘pure’ B powder resulted in the production of shining metal particles in the powder. The EPR of this powder showed excessive increase in the intensity of EPR absorption when the temperature of the powder was raised to a value just above the Néel temperature. A comparison of these reuslts with the work of earlier authors suggests that the shinning metal particles are those of chromium metal and are responsible for this increase in EPR absorption.     

2S12 state ions in inorganic luminescent materials

Selected examples of impurity ions with one unpaired electron in an unfilled shell are Pb³⁺ ions in II–IV compounds (ZnO, ZnSe, ZnTe), Pb³⁺ in CaWO₄,F centres in alkali halides and Ag⁰ and Au⁰ atoms in radiophotoluminescent (RPL) glasses. Comparative studies of EPR, luminescence, thermoluminescence and related phenomena were performed on systems with ²S_{$\text{1}\text{2}$} state ions as central ions and systematically varying ligand ions in the temperature range from 1.6°K to 450°K. Luminescence bands attributed to internal transitions ²P_{$\text{3}\text{2}$,$\text{1}\text{2}$}→²S_{$\text{1}\text{2}$} ground state are reported especially with respect to the corresponding EPR data. All data are summarized in a molecular orbital model for the luminescence complex.     

Inelastic magnetic neutron scattering from inner filled shells of impurity atoms in metals

The differential cross section of inelastic magnetic neutron scattering by paired electrons of inner filled s ² shells of impurity atoms in metals is first derived taking into account single electron excitations from the inner shell of the impurity to the free states of the metal. The energy-angle distributions of the scattered neutrons are calculated depending on the effective electronic mass near the Fermi surface.     

Electron spin resonance in amorphous Si and Ge doped with Mn

ESR signal with hyperfine structure due to Mn and that due to dangling bonds are observed. From the magnitude of the hyperfine structure constant, Mn is considered to locate within voids without making a covalent bond with the host atom in the form of Mn²⁺. The intensity of the ESR signal due to dangling bonds decreases with the increase of that due to Mn, so it is likely that electrons are transfered from Mn to dangling bonds and their unpaired electrons are paired up.     

Magnetic 4d systems studied by implanted ions

By application of the perturbed -ray distribution method following heavy-ion reactions and recoil implantation techniques, we have found an experimental way of producing and investigating magnetic 4d states in metals. Strong 4d magnetism has been found for 4d ions in alkali metal hosts and in Pd hosts. In alkali metals, 4d ions reflect the phenomena of well-defined ionic ground states, orbital magnetism, mixed valence, and crystal field splittings smaller than theLS coupling. Magnetic 4d states in alkali metals cannot be described by one-electron approaches based on Anderson-type models, but requires an analysis in terms of many electron ionic configurations exhibiting basic features common to the physics of stable and unstable f stales in metals. In contrast, the local moment formation of 4d and 3d ions in Pd is governed by inter-atomic interactions of the magnetic d states with host d-band electrons, giving rise to spin magnetic behavior of the 4d impurity and to strong spin polarizations of the 4d electrons of the Pd host. Thus, the magnetism and electronic structure of 4d ions in metals exhibit qualitative differences in alkali metal hosts compared to Pd. The existence of magnetic 4d systems strongly depends on the 4d ion species and the host matrix, and on spin fluctuation rates or the corresponding Kondo temperatures. The results can be directly compared to theoretical work and also to the magnetic behavior of 3d ions in sp metal hosts and in hosts with d-band electrons.     

The effect of interstitial hydrogen on the electronic structure of Fe-Pd alloys

The electronic structure and bonding in Fe-Pd alloys were computed using a tight binding method. Two phases have been identified for these alloys, a high temperature fcc and a low temperature fct structure. The hydrogen absorption turns out to be a favorable process in both structures. The hydrogen at tetrahedral interstitial site for the fct structure is 2.2 eV more stable than that impurity atom located at an octahedral interstitial site in the fcc structure.The density of states curves show a peak below the d metal band which is made up mostly of hydrogen based states (>50% H_1s) while the metal contribution includes mainly s and p orbitals.In the fcc structure, both Fe-H and Pd-H bonds are developed while the Fe-Pd interface shows antibonding filled states near the Fermi level. When the fct phase is considered, the Fe-H overlap population (OP) decreases, while the Pd-H remains similar to the previous case. The Fe-Fe OP decreases and the Pd-Pd bonds are almost unaltered. The interfacial Fe-Pd bonds are almost unaffected by hydrogen. The band structure of the hydrogenated alloys in the fcc and fct phases were also computed.     

Electron paramagnetic resonance and optical spectroscopy of K3Na(CrO4)2 ferroelastics activated by MnO 4 2− molecular impurity ions

Crystals of a proper ferroelastic K₃Na(CrO₄)₂ containing molecular impurity ions MnO ₄ ^2? are studied using electron paramagnetic resonance (EPR) and optical spectroscopy. The EPR spectrum of the Mn⁶⁺ ion contained in the molecular impurity ion MnO ₄ ^2? is identified at low temperatures (T ≤ 20 K). The intensity of this spectrum decreases unusually fast as the temperature increases. A broad IR luminescence band with a vibronic structure well resolved at a temperature of 8 K is revealed. Theoretical treatment of the Mn⁶⁺ ion involved in the molecular impurity ions MnO ₄ ^2? of the K₃Na(CrO₄)₂ ferroelastic crystal suggests that an important role in this case is played by the pseudo-Jahn-Teller. The pseudo-Jahn-Teller effect offers an explanation for the appearance of a fine structure in the vibronic replicas in the luminescence spectrum, on the one hand, and accounts for the fast decrease in the intensity of the EPR spectrum of K₃Na(CrO₄)₂: MnO ₄ ^2? with increasing temperature, on the other.     

Density of states in the impurity d band and inelastic electron scattering by a system of mixed-valence iron ions in HgSe: Fe crystals

The resistivity and the Hall coefficient of HgSe: Fe crystals with various iron content are experimentally studied in the temperature range 1.3≤T≤300 K and in magnetic fields up to 60 kOe. The temperature dependences of the density and mobility of conduction electrons in these crystals are determined. The influence of spatial charge ordering in the system of mixed-valence iron ions on impurity states in HgSe: Fe crystals is considered. The density of states in the impurity d band is theoretically analyzed, and inelastic electron scattering in which bi-and trivalent iron ions are recharged is discussed. It is shown that the experimentally detected features in the dependence of the density and mobility of electrons on temperature and iron impurity content can be explained by the influence of Coulomb correlations in the mixed-valence iron ion system on the structure of the impurity d band.

     

Defects and impurities in nanodiamonds: EPR, NMR and TEM study

EPR, ¹³C NMR and TEM study of ultradisperse diamond (UDD) samples is reported. The compounds show a high concentration of paramagnetic centers (up to 10²⁰ spin/g), which are due to structural defects (dangling C-C bonds) on the diamond cluster surface. The anomalous reduction in the spin-lattice relaxation time of ¹³C (from several hours in natural diamond to ∼150 ms in UDD clusters) is attributed to the interaction between the unpaired electrons of the paramagnetic centers and nuclear spins. ¹³C NMR line-width reflects the fact that the structure of the UDD surface is distorted in comparison to the ‘bulk’ diamond structure.     

Two- and three-photon excitation of Gd in CaAl12O19

We have employed two-photon excitation to study the higher energy levels of Gd³⁺ ions in CaAl₁₂O₁₉ and we compare the results with those obtained using conventional UV excitation techniques. Under two-photon excitation, the luminescence intensity exhibits an unusual temporal behavior, a very long build-up followed by a decrease by orders of magnitude, ascribed to a recombination-assisted luminescence excitation mechanism assuming photo-ionization of Gd³⁺ ions and trapping of free electrons on deep traps.

We also find that the two-photon excitation spectra contain an additional broadening contribution which can be attributed to homogeneous broadening of excitation levels caused by excited state absorption into the conduction band. We believe that this may be a general phenomenon whenever participating photons produce ionization of impurity ions from metastable excited states. The phenomenon can manifest itself also in two-photon ionization spectral hole burning and in up-conversion processes (in the latter case, the homogeneous broadening can be caused by an intra-ion excited-state absorption).     

On reasons for the hysteresis of melting and crystallization of nanoparticles

The specific features of the EPR spectra of Tm³⁺ impurity ions in synthetic forsterite have been studied by continuous-wave EPR spectroscopy in the frequency range of 270–310 GHz at a temperature of 4.2 K in weak magnetic fields. Narrow resonance signals unrelated to the modulation of the resonance conditions of EPR under the modulation of the external magnetic field have been discovered in measurements at frequencies corresponding to the zero field splitting between the ground and first excited singlet electron states of Tm³⁺ ions in zero magnetic field. The origin of these narrow lines is discussed.     

Influence of the form of structure factor on the mobility of nondegenerate two-dimensional electrons

The temperature dependences of the mobility of nondegenerate two-dimensional electrons in scattering by a correlated distribution of impurity ions in Al _x Ga_{1 ? x} As/GaAs heterostructures have been investigated. The cases where the influence of the first maximum of the structure factor on the scattering of electrons begins to dominate with increasing temperature have been considered. It has been found that the mobility of two-dimensional electrons decreases with increasing correlations in the spatial distribution of impurity ions. The influence exerted by the correlations and the width of the spacer layer on this effect has been analyzed.     

New high-energy luminescence bands from Co2+ in ZnSe

Three sharp absorption features in the energy range 2.36–2.55 eV have been detected in the transmission spectrum of Co-diffused ZnSe, and a number of luminescence transitions originating from the lowest of these states at 2.361 eV have been observed. Photoluminescence excitation spectra prove that these are high energy excited states of the Co²⁺_Zn impurity, a conclusion confirmed by comparison of measured and predicted luminescence energies. This represents the first identification of luminescence branching from a higher excited state of a transition metal ion in any semiconductor. The sharp, weakly phonon-coupled transitions involve either intra-impurity excitation or transitions from the impurity to localised states split off from a minimum in the conduction band. The implications of these observations for the mechanism of host-impurity energy transfer and for the nature of the excited state wavefunctions are discussed.     

氟哌酸1HNMR的测定及过渡金属离子对其影响

氟哌酸^*[即1-乙基-6-氟-4-氧-7-(1-哌嗪)-3-(1,4-二氢化喹啉甲酸]是一种广谱、安全、有效、可供口服的抗感染药。我们测定了它的¹H自旋-晶格弛豫时间T₁及其在Cr³⁺、Mn²⁺、和Fe³⁺等过渡金属离子存在下的T₁值。实验结果表明,在加入过渡金属离子前后,氟哌酸不同位¹H的T₁值发生了一定的变化。据此可揭示过渡金属离子和氟哌酸形成配合物的配位点,从而可确定所形成配合物的结构。     

Cascade-avalanche up-conversion in Tm3+:YLF crystals

New efficient mechanisms of long-wavelength excitation of short-wavelength luminescence in a system of rare-earth impurity ions are proposed. The model studied involves a multilevel system of electronic states of a rare-earth ion interacting with the long-wavelength emission that is in resonance with one or several transitions between the excited levels. The concentration of impurity ions is assumed to be sufficiently high, so that the interionic cross-relaxation and the up-conversion play a significant role. Moreover, the model includes processes similar to photon avalanche, in which the photoinduced excitation of a single ion is converted into lower-level excitations of several ions, each of them reentering the process after photon absorption. Numerical solutions of the system of balance equations for a multilevel system are obtained with calculated and semiempirical parameters of self-quenching and up-conversion. It is shown that, in a system of Tm³⁺ impurity ions, short-wavelength luminescence at λ≥0.29 μm can be efficiently excited by radiation at λ?1.11 or 0.649 μm with a moderate intensity.     

Magnetic Resonance Study of Detonation Nanodiamonds with Surface Chemically Modified by Transition Metal Ions

We report on electron magnetic resonance (EMR) and nuclear magnetic resonance (NMR) study of detonation nanodiamonds (DND) with the surface modified by copper and cobalt ions. The EMR spectrum of the pure DND sample shows an intense singlet originating from broken carbon bonds, while the spectra of copper- and cobalt-modified samples reveal additional signals with g > 2 and pronounced hyperfine structure (for copper). Increase in the Cu/Co concentration causes an increase of the corresponding EMR signals and broadening of the intense carbon-inherited singlet line. Subsequent annealing of the copper-modified samples in a hydrogen gas stream at 550 and 900°C causes narrowing of the singlet line and reduction of the Cu²⁺-related components. Applying the same annealing process to the cobalt-modified samples leads to broadening of the singlet line, reduction of Co²⁺ component and appearance of new intense low-field signals. NMR data correlate well with the EMR findings and yield information on interactions and locations of transition metal ions. ¹³C nuclear spin–lattice relaxation rate R ₁ in pure DND is driven by the interaction of nuclear spins with unpaired electron spins of broken bonds. Chemical modification of the DND surface by Cu and Co causes an increase in the relaxation rate, revealing appearance of paramagnetic Cu²⁺ and Co²⁺ complexes at the DND surface and their interaction with the carbon nuclear spins, both directly and via a coupling of Cu²⁺ and Co²⁺ electrons with those of the broken bonds. The aforementioned annealing of the Cu- and Co-DND results in an inverse process, i.e., a reduction of the relaxation rate, indicating that these complexes are destroyed and metal ions presumably join each other forming copper and cobalt nanoclusters. In the case of Co the nanoclusters are ferromagnetic, which results in the noticeable broadening of the ¹³C NMR lines.     

Transition and rare-earth elements in the SiC and GaN wide-gap semiconductors: Recent EPR studies

EPR studies of transition-element ions in SiC and GaN and of erbium in 6H-SiC are reported. Data are presented on Sc²⁺ ions and scandium acceptors, and chromium and molybdenum ions in various charge states in SiC. A study was made of nickel and manganese in nominally pure GaN grown by the sandwich sublimation method. The first EPR investigation of Er in 6H-SiC is reported. Erbium was identified from the hfs of the EPR spectra. Various possible models of erbium centers in silicon carbides are discussed. Strong room-temperature erbium-ion luminescence was observed. Fiz. Tverd. Tela (St. Petersburg) 41, 865–867 (May 1999)