Structural, electronic, and magnetic properties of Co-doped ZnO

Density functional theory based calculations have been carried out to study structural, electronic, and magnetic properties of Zn1-xCoxO (x = 0, 0.25, 0.50, 0.75) in the zinc-blende phase, and the generalized gradient approximation proposed by Wu and Cohen has been used. Our calculated lattice constants decrease while the bulk moduli increase with the increase of Co 2+ concentration. The calculated spin polarized band structures show the metallic behavior of Co-doped ZnO for both the up and the down spin cases with various doping concentrations. Moreover, the electron population is found to shift from the Zn-O bond to the Co-O bond with the increase of Co 2+ concentration. The total magnetic moment, the interstitial magnetic moment, the valence and the conduction band edge spin splitting energies, and the exchange constants decrease, while the local magnetic moments of Zn, Co, O, the exchange spin splitting energies, and crystal field splitting energies increase with the increase of dopant concentration.     

The magnetic moments of (vg 9/2)-levels in odd Zn isotopes

^69m,71mZn have been implanted with an isotope separator on-line into a cold iron host matrix. Nuclear magnetic resonance of the low-temperature oriented isotopes has been observed. The resonance frequencies for zero external magnetic field are v_L(^69mZnFe@#@) =36.814(35) MHz andv _L (^71mZnFe)=33.47(19) MHz. From these the magnetic moments of the 9/2⁺ iosmeric states have been derived as μ(^69mZn)=(?)1.138(18) n.m. andμ(^71mZn)=(?)1.035(18) n.m. The experimentally known magnetic moments of (vg _9/2)-levels in odd zinc isotopes are compared to theoretical estimates.     

Laser cooling and isotope-shift measurement of Zn<Superscript>+</Superscript> with 202-nm ultraviolet coherent light

We have laser-cooled all even isotopes of Zn⁺ ions confined in a linear radio-frequency ion trap, and measuredoptical isotope shifts in the 4s ² S _1/2-4p ² P _3/2 transition. Tunable continuous-wave coherent light near 202 nm was generated for this experiment by means of frequency conversion of light from diode and solid-state lasers. The measured isotope shifts are as follows: ⁶⁶Zn⁺-⁶⁴Zn⁺, 0.676(6) GHz; ⁶⁸Zn⁺-⁶⁶Zn⁺, 0.670(4) GHz; and ⁷⁰Zn⁺-⁶⁸Zn⁺, 0.568(10) GHz. In all cases, the transition line of the heavier isotope was observed at the higher frequency. The mass and the field shifts were estimated using a King plot. This is the first isotope-shift measurement in the transition involving the ground (4s ² S _1/2) state of Zn⁺ ions. Received: 18 July 2002 / Revised version: 20 October 2002 / Published online: 5 February 2003 RID="*" ID="*"Corresponding author. Fax: +81-42/327-6694, E-mail: matubara@crl.go.jp Present address: Communications Research Laboratory, 4-2-1 Nukui-Kitamachi, Koganei, Tokyo 184-8795, Japan     

Theoretical study of the magnetic interaction of Cr-doped ZnO with and without vacancies

First-principles density-functional theory (DFT) calculations have been performed to study the magnetic properties of ZnO:Cr with and without vacancies. The results indicate that the doping of Cr in ZnO induces obvious spin polarization around the Fermi level and a total magnetic moment of 3.77μ_B. The ferromagnetism (FM) exchange interaction between Cr atoms is short-ranged and decreases with increasing Cr separation distance. It is suggested that the FM state is not stable with low concentration of Cr. The presence of O vacancies can make the half-metallic FM state of the system more stable, so that higher Curie temperature ferromagnetism may be expected. Nevertheless, Zn vacancies can result in the FM stability decreasing slightly. The calculated formation energy shows that V_Zn+Cr_Zn complex forms spontaneously under O-rich conditions. However, under Zn-rich conditions, the complex of V_O+Cr_Zn forms more easily. Thus, ZnO doped with Cr may exhibit a concentration of vacancies that influence the magnetic properties.     

High-resolution67Zn-Mössbauer study of oxide spinels

We report on first experiments to investigate the electronic structure in the normal spinels ZnAl₂O₄ and ZnFe₂O₄ and in the inverse spinels Zn₂SnO₄ and Zn₂TiO₄ using the high-resolution⁶⁷Zn-Mössbauer spectroscopy. The electric field gradient for⁶⁷Zn at the B (octahedral) site in ZnAl₂O₄ is negative, whereas the A (tetrahedral) site remains essentially cubic, however, with a more positive center shift. ZnFe₂O₄ orders antiferromagnetically at ≈10K. Due to superexchange a magnetic field is observed at⁶⁷Zn. In the inverse spinels short range order leads to only few (Zn,Sn) and (Zn,Ti) configurations at the octahedral sites. The s-electron densities at the⁶⁷Zn sites are distinct and cover a surprisingly broad range for Zn₂TiO₄. This strongly suggests that d-electrons of Ti play an essential role in the chemical bond of this compound.     

Investigation of positively charged acceptor states in Si and Ge under uniaxial stress by phonon induced conduction

We use superconducting Al-tunnel junctions as tunable phonon generators in the meV-range to determine ground state splitting at zero stress of positively charged states associated with single acceptors in Si and double acceptors in Ge. From the stress and energy dependence of the conductivity induced by high frequency phonon irradiation of the corresponding two- and three-hole states we find that the splitting is below 0.1 meV for the ground states of Si:B⁺ and Ge:Be⁺, and 1 meV and 1.2 meV for Si:Ga⁺ and Si:Al⁺, respectively. These level separations are comparable to those found previously for the ground states of the corresponding acceptor bound excitons A⁰X. For the deeper acceptors Si:In⁺, Si:Tl⁺, and Ge:Zn⁺ the results are qualitatively different.     

Sb complexes and Zn interstitials in Sb-implanted ZnO epitaxial films

In the present work, post-annealing is adopted to investigate the formation and the correlation of Sb complexes and Zn interstitials in Sb-ion implanted ZnO films, by using Raman scattering technique and electrical characterizations. The damage of Zn sublattice, produced by ion bombardment process is discerned from the unrecovered E2 (L) peak in annealed high Sb+ dose implanted samples. It is suggested that the Zn sublattice may be strongly affected by the introduction of Sb dopant because of the formation of SbZn-2VZn complex acceptor. The appearance of a new peak at 510 cm 1 in the annealed high dose Sb+ implanted samples is speculated to result from (Zn interstitials-O interstitials) Zni-Oi complex, which is in a good accordance with the electrical measurement. The p-type ZnO is difficult to obtain from the Sb+ implantation, however, which can be realized by in-situ Sb doping with proper growth conditions instead.     

Schottky-like anomaly in the low-temperature specific heat of single-crystal NdMnO3

The specific heat of single-crystal NdMnO₃ was investigated from 2 to 20 K under different magnetic fields up to 8 T. All the specific heat data show a Schottky-like anomaly, which becomes more indistinctive as increasing magnetic field. The experiment data were successfully fitted by taking into account factors such as crystal-field splitting, the two-level Schottky anomaly, the lattice vibration, and type-A antiferromagnetic (A-AF) spin waves. It was found that the splitting of the ground state doublet of Nd³⁺ ion increases linearly with magnetic field. The above phenomena can be interpreted in terms of the model of unchanged effective molecular field at Nd³⁺ site caused by the ferromagnetic component of A-AF structure of Mn spins. This ferromagnetic component is likely caused by the GdFeO₃-type octahedron rotation. In addition, it was also found that the magnetic field increases the spin-wave stiffness coefficient, but reduces the Debye temperature.     

Hyperfine field and relaxation effect in Li−Zn−Ti ferrites

⁵⁷Fe Mössbauer effect studies were made on titanium substituted Li?Zn ferrite with composition Li_0.45+0.5tZn_0.1 Ti_t Fe_2.45–1.5tO₄ (t=0.0 to 1.2) at 300K. The Mössbauer spectra for t≤0.4 show two well defined Zeeman sextets corresponding to the Fe³⁺ ions at tetrahedral (A) and octahedral (B) sites. The spectra for t=0.6, 0.8 and 0.9 show relaxation but can still be resolved into 2 sextets. The spectra for t=1.0, 1.2 show strong ferrimagnetic relaxation with the spectra for t=1.2 exhibiting an additional central doublet. The effect of Ti⁴⁺ substitution on the Isomer shift (I.S), Quadrupole splitting (Q.S.) and nuclear magnetic fields of Li?Zn ferrites have been reported in this paper. The I.S. was found to be independent of substitution level t, while the quadrupole splitting was observed to be negligible. The variation of hyperfine field with t has been explained on the basis of superexchange interaction and cation distribution.     

X-ray absorption spectroscopic and magnetic characterization of cobalt-doped zinc oxide nanocrystals prepared by the molten-salt method

The local atomic arrangement and electronic structure of the Co-doped Zn_1−xCo_xO nanocrystal have been quantitatively examined along with its magnetic properties. According to our analysis using powder X-ray diffraction, electron microscopy, and Zn K-edge X-ray absorption spectroscopy (XAS), phase-pure wurzite-structured Zn_1−xCo_xO nanocrystals have been successfully synthesized via the molten-salt method. The Co K-edge XAS analysis clearly demonstrates that all the Co²⁺ ions are substituted for the tetrahedral Zn sites of the Wurzite structure with a coordination number of 3.9 and a bond distance of 1.97 Å, ruling out the presence of magnetic impurity phase and Co-metal cluster. Magnetization measurements reveal that the present Zn_1−xCo_xO sample does not show any ferromagnetic transition down to 2 K. In this regard, we can conclude that Co-doped zinc oxide is not ferromagnetic but the previously reported ferromagnetism in this phase would be an extrinsic property.     

Cr<Superscript>3+</Superscript> spectroscopy study in ZnO-codoped and Zn-in-diffused congruent LiNbO<Subscript>3</Subscript>:Cr crystals

This paper reports on the spectroscopy properties, absorption and luminescence, of Cr³⁺ ions in singly doped, ZnO-codoped, and Zn in-diffused LiNbO₃:Cr crystals. In addition to the broad absorption, inter-ionic transitions ascribed to Cr³⁺ ions located in Li⁺ and Nb⁵⁺ sites; [Cr]_Li and [Cr]_Nb centres two absorption bands at higher energy are reported and ascribed to the charge transfer transitions of the Cr³⁺ ions of the two defect centres. The charge transfer transitions are used as optical probe to study the role of the Zn ions in the Zn in-diffused LiNbO₃:Cr samples. It has been observed that the Zn-in-diffused processes created [Cr]_Nb centres in the diffusion zone. The location of the diffused Zn²⁺ ions is considered to be in Li⁺ site, displacing the Cr³⁺ ions from the Li⁺ sites, [Cr]_Li, to the Nb⁵⁺ positions, [Cr]_Nb.     

Hyperfine magnetic field of Zn in iron

Precise hyperfine field value of zinc in iron has been determined by nuclear magnetic resonance on oriented nuclei (NMR/ON): B_hf (ZnFe)=−18.785 (35) T at 7 mK. The relaxation constant of Zn in iron is established C_K=14(3) Ks. The new hyperfine field value of zinc in iron allows a more precise reevaluation of the magnetic moments of^69mZn and^71mZn measured with NMR/ON. and the NICOLE Collaboration, CERN     

Dopant diffusion and segregation in semiconductor heterostructures: Part 1. Zn and Be in III-V compound superlattices

chemical effect on the neutral species; and (ii) a Fermi-level effect on the ionized species, because, in addition to the chemical effect, the solubility of the species also has a dependence on the semiconductor Fermi-level position. For Zn and Be in GaAs and related compounds, their diffusion process is governed by the doubly-positively-charged group III element self-interstitials (I²⁺ _III), whose thermal equilibrium concentration, and hence also the diffusivity of Zn and Be, exhibit also a Fermi-level dependence, i.e., in proportion to p². A heterojunction consists of a space-charge region with an electric field, in which the hole concentration is different from those in the bulk of either of the two layers forming the junction. This local hole concentration influences the local concentrations of I²⁺ _III and of Zn^- or Be^-, which in turn influence the distribution of these ionized acceptor atoms. The process involves diffusion and segregation of holes, I²⁺ _III, Zn^-, or Be^-, and an ionized interstitial acceptor species. The junction electric field also changes with time and position. Received: 20 August 1998/Accepted: 23 September 1998     

Low-temperature study of magnetic ordering in gadolinium orthophosphate

The zero-field heat capacity shows an antiferromagnetic ordering of Gd³⁺ in gadolinium orthophosphate at 0.8 K. The application of the external magnetic field leads to the splitting of the Gd³⁺ ground-state multiplet. The antiferromagnetic ordering becomes gradually suppressed with increasing field, and the loss of the long-range magnetic ordering with a threshold field between 0.2 and 0.5 T is indicated by heat-capacity data. Estimated entropy of the anomaly due to magnetic ordering or the Schottky-type anomaly (above 0.5 T) is close to Rln8 as expected for Gd³⁺ ground-state multiplet. Magnetization measurements above 2 K corroborate this magnetic behaviour.     

Superconductivity induced phonon anomalies in the Raman spectra of Zn and Ni doped YBa2Cu3O7

Here we present Raman spectra of YBa₂(Cu_1–x Zn _x )₃O₇ and YBa₂(Cu_1–x Ni _x )₃O₇ as a function of temperature and Zn or Ni content. The temperature dependence of two modes at 340 and 440 cm^–1 is analyzed. Similarly to the infrared measurements it is found that Zn substantially suppresses the superconductivity induced phonon softening whereas, Ni does not affect much that effect. Moreover, the superconductivity induced phonon stiffening of the 440 cm^–1 mode completely disappeared with the Zn doping. We find this behaviour might support the model where Zn acts effectively as a magnetic pair breaker.     

Charge compensation on the luminescence properties of ZnWO4:Tb phosphors via hydrothermal synthesis

A phosphor Tb³⁺-doped ZnWO₄ (ZWO:Tb) phosphors were prepared by a hydrothermal method. X-ray powder diffraction (XRD) analysis revealed that the as-obtained sample is pure ZnWO₄ phase. The excitation and emission spectra indicated that the phosphor could be well excited by ultraviolet light (272 nm) and emit blue light at about 491 nm and green light at about 545 nm. Significant energy transfer from WO₄²⁻ groups to Tb³⁺ ions has been observed. Two approaches to charge compensation are investigated: (a) 2Zn²⁺ = Tb³⁺ + M⁺, where M⁺ is a monovalent cation like Li⁺, Na⁺ and K⁺ acting as a charge compensator; (b) 3Zn²⁺ = 2Tb³⁺ + vacancy. Compared with two charge compensation patterns in the ZnWO₄:Tb³⁺, it has been found that ZnWO₄:Tb³⁺ phosphors used Li⁺ as charge compensation show greatly enhanced bluish-green emission under 272 nm excitation.     

The effect of zinc concentration on vacancies jump rate, diffusion coefficient and jump length in Cu-Zn ferrite

Samples with the chemical formula Cu_1−xZn_xFe₂O₄ (x=0.2, 0.4, 0.6, 0.8 and 1) were prepared by the standard ceramic method. The dielectric constant and dielectric loss tangent were studied as a function of vacancy jump rate. The results show that the dielectric constant and dielectric loss tangent decrease with increasing vacancy jump rate. In addition, the electron jump length in the octahedral sites was studied as a function of zinc concentration. The increase in jump length with Zn concentration has been attributed to the substitution of Fe⁺³ for Zn²⁺ at the A-sites, which increases the B-B interaction. The increase of diffusion coefficient with increasing Zn concentration was reinforced by the increase of jump rate.     

Effects of Fe2+ and Zn2+ substitution on the structure and high-pressure stability of MgAl2O4 spinel from DFT calculations

Using density functional theory we show the effects of transition (Fe²⁺) and non-transition (Zn²⁺) divalent cationic substitutions on the following structural parameters: lattice parameters, bond lengths and polyhedral volumes under varying hydrostatic pressures. Fe²⁺ and Zn²⁺ substitutions lead to contrasting modifications of tetrahedral Mg–O bond lengths. Fe²⁺ (50%)increase the tetrahedral Mg–O bond lengths by 0.21%, whereas Zn²⁺ (50%) reduce it by 0.06%.We present the equations of state of Mg spinel with 50% Fe and Zn substitutions as a function of pressure. This study presents the decomposition pressure (P_T) of spinel to periclase (MgO) and corundum (α-Al₂O₃) as a function of Fe and Zn concentrations (x). For pure spinel, P_T=12.1 GPa. Fe²⁺substitution lowers P_T linearly with its concentration as P_T=?12.56x+12.02. But, Zn²⁺ increases P_T non-linearly along a quadratic relation: P_T=42.057x²+14.171x+12.174. We calculated the C₄₄ elastic constant to explain the contrasting effects of Fe and Zn on the decomposition pressure of spinel phase.     

Spectral signatures of hyperfine and isotopic effects and of Tm-Tm pairs in LiYF4:Tm

We report on the high-resolution optical Fourier-transform spectroscopy of the LiYF₄:Tm³⁺ crystals. Splitting of several lines in the optical low-temperature polarized spectra was observed. We show that these splittings are caused by (i) the hyperfine interaction, (ii) the isotopic disorder in the lithium sublattice, and (iii) the interionic interaction between neighboring Tm ions. It is the first observation of the hyperfine splitting in the spectra of the Tm³⁺ ions in crystals. From the experimentally measured hyperfine splitting we evaluate the magnetic field at the thulium nucleus and calculate the magnetic g-factors of the excited crystal-field levels.     

Photon splitting in an ultrastrong magnetic field

We analyze the splitting of a photon with energy ω below the e ⁺ e ⁻ pair-production threshold in an ultrastrong magnetic field. We use the amplitudes found by employing the operator diagrammatic technique. In a field considerably above the critical values the process amplitudes become independent of the field strength. A study of the polarization operator of a photon in an external field of arbitrary strength in the energy range considered in the present investigation shows that there is only one set of polarizations of the initial and final photons for which the splitting amplitude is nonzero. Zh. éksp. Teor. Fiz. 111, 52–62 (January 1997)