First-principles study on electronic and magnetic properties of Cu-doped CdS

Based on the full-potential linearized augmented plane wave (FLAPW) method, the electronic structures and magnetic properties in Cu-doped CdS diluted magnetic semiconductors (DMSs) have been investigated. The results indicate that Cu-doped CdS systems show half-metallic character with a total magnetic moment of 1.0 μ_B per supercell. In the case of two Cu atoms substituting for Cd atoms, the long-range ferromagnetism is observed, which results from Cu(3d)-S(3p)-Cd-S(3p)-Cu(3d) coupling chain. The estimated Curie temperature of Cu-doped CdS is predicted to be 400 K, higher than room temperature. These results suggest that Cu-doped CdS may be a promising half-metallic ferromagnetic material for practical applications in electronics and spintronics.     

N空位对Cu掺杂AlN电磁性质的影响的第一性原理研究

利用基于密度泛函理论的平面波超软赝势法研究了N空位对Cu掺杂AlN的电子结构和磁学性质的影响。结果表明,与Cu最近邻的N原子更易失去形成N空位。N空位的引入减小了Cu掺杂AlN体系的半金属能隙;减弱了Cu及其近邻N原子的自旋极化的强度以及Cu3d与N2p轨道间的杂化,因而减小了体系的半金属铁磁性。因此,制备Cu掺杂AlN稀磁半导体时应尽可能地避免产生N空位。     

Ferromagnetism in Cu-doped ZnSe semiconducting quantum dots

The projection of integrating optical, magnetic and electronic functionalities into a single material have aggravated passionate attention in mounting wide band gap diluted magnetic semiconductor (DMS) in the midst of room temperature ferromagnetism. We report the evidence of ferromagnetism in Cu-doped ZnSe quantum dots (QDs) below room temperature, grown from a single source precursor by lyothermal method with the sizes of approximately 3.2–5.14 nm. QDs mainly exhibit paramagnetic behavior between 80 and 300 K, with a weak ferromagnetic/anti-ferromagnetic exchange at lower temperature as observed by superconducting quantum interference device (SQUID) magnetometer. From the Curie–Weiss behavior of the susceptibility, Curie temperature (T _c) of Cu-doped ZnSe sample has been evaluated. From EPR, we obtain the Lande-g factor in the Zeeman interaction term as 2.060. Photoluminescence and EPR measurements support and confirm the view that Cu²⁺ substitutes for Zn²⁺ in Cu-doped ZnSe quantum dots.     

The structure and magnetic properties of Cu-doped ZnO prepared by sol-gel method

The Cu-doped ZnO and pure ZnO powders were synthesized by sol-gel method. The structural properties of the samples were investigated by X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy. All the results confirmed that copper ions were well incorporated into the ZnO lattices by substituting Zn sites without changing the wurtzite structure and no secondary phase existed in Cu-doped ZnO nanoparticles. The Zn_0.97Cu_0.03O nanoparticles exhibited ferromagnetism at room temperature, as established by the vibrating sample magnetometer analysis.     

Cu、Ag和Au掺杂AlN的电磁性质的第一性原理研究

采用基于密度泛函理论（DFT）的平面波超软赝势法,研究了Cu、Ag、Au掺杂AlN的晶格常数、磁矩、能带结构和态密度。电子结构表明,Cu、Ag、Au的掺杂使在带隙中引入了由杂质原子的d态与近邻N原子的2p态杂化而成的杂质带,都为p型掺杂,增强了体系的导电性。Cu掺杂AlN具有半金属铁磁性,半金属能隙为0.442eV,理论上可实现100%的自旋载流子注入;Ag掺杂AlN具有很弱的半金属铁磁性;而Au掺杂AlN不具有半金属铁磁性。因此,与Ag、Au相比,Cu更适合用来制作AlN基稀磁半导体。     

Disorder induced ferromagnetism in the Cu-doped molybdate SrMo1−xCuxO3 (0≤x≤0.20)

The effect of Cu-doping at Mo-site on structural, magnetic, electrical transport and specific heat properties in molybdates SrMo_1−xCu_xO₃ (0≤x≤0.2) has been investigated. The Cu-doping at Mo-site does not change the space group of the samples, but decreases the structural parameter a monotonously. The magnetic properties change from Pauli-paramagnetism for x=0 to exchange-enhanced Pauli-paramagnetism for x=0.05 and 0.10, and then ferromagnetism for x=0.15 and 0.20. All samples exhibit metallic-like transport behavior in the whole temperature range studied. The magnitude of resistivity increases initially to x=0.10 and then decreases with increasing Cu-doping concentration. The results are discussed according to the electron localization due to the disorder effect induced by the random distribution of Cu at Mo site in the samples. In addition, the temperature dependence of specific heat for the Cu-doped sample has also been studied.     

Enhanced ferromagnetic properties of ZnO: Cu tuned by HPHT

A series of Cu-doped ZnO ceramics were synthesized from pre-prepared Cu-doped ZnO nanocrystals using a cubic anvil high pressure apparatus under various pressure and temperature conditions. The structures, vibrational spectra and magnetic properties were investigated in detail. The results indicated that the enhancement of ferromagnetism had been achieved for the sample tuned by proper pressure and temperature (5 GPa, 500 °C). The ferromagnetism returned again to the primary state once the tuning temperature was raised up to 800 °C. Compared with those of the samples prepared at ambient pressure, the magnetic properties of the samples tuned by HPHT method had been improved greatly.     

Ferromagnetic behavior of high-purity ZnO nanoparticles

ZnO nanoparticles with the wurtzite structure were prepared by chemical methods at low temperature in aqueous solution. The size of the nanoparticles is in the range from about 10 to 30 nm. Ferromagnetic properties were observed from 2 K to room temperature and above. Magnetization versus temperature, M(T), and isothermal M(H) measurements were obtained. The coercive field clearly shows ferromagnetism above room temperature. An exchange bias was observed, and we related this behavior to the core-shell structure present in the samples. The chemical synthesis, structure, and defects in the bulk related to oxygen vacancies are the main factors for the observed magnetic behavior.     

ZnO-Fe3O4 composite prepared by sol-gel method with H2 deoxidation

Fe doped ZnO powder samples (Fe/Zn=0.05 and 0.1) were prepared by sol-gel method with H₂ deoxidation at 450 ^°C for several hours or just heated in air at the same temperature. It was showed by vibrating sample magnetometer (VSM) that samples heat treated in H₂ could show strong ferromagnetism at room temperature while samples treated in air only show very weak magnetism. XRD using Co kα X-ray revealed that the samples heated in H₂ were not pure phase but like a granular system and the magnetism mainly results from Fe₃O₄ in samples while samples heated in air showed pure ZnO phase. Our work indicated that H₂ deoxidation treatment may be an effective technique to fabricate such magnetic semiconductor-like materials with Curie temperature higher than room temperature.     

Defect induced ferromagnetism in carbon-doped ZnO thin films

We report on room temperature ferromagnetism in C-doped ZnO thin films prepared by electron beam evaporation. Magnetization, Hall effect, X-ray photoemission spectroscopy (XPS) and X-ray diffraction studies have been conducted to investigate the source and nature of ferromagnetism in C-doped ZnO. The samples were observed to have n-type conduction with the carrier concentration increasing with C doping. XPS does not give any evidence for C substituted at the O site, and is more consistent with the formation of C-O bonds and with the presence of C primarily in the +4 state. It is suggested that the ferromagnetism originates in the development of Zn vacancies that are stabilized due to the incorporation of C in a high valence state (C⁴⁺).     

Synthesis,structural, optical and magnetic properties of Cu-doped ZnO nanorods prepared by a simple direct thermal decomposition route

Cu-doped ZnO nanorods (i.e. Cu = 1.75, 3.55, 5.17 and 6.39 at.%) have been successfully synthesized by simple, direct, thermal decomposition of zinc and copper acetates in air at 300 °C for 6 h. The prepared samples were characterized by X-ray diffraction (XRD) and transmission electron microscopy. The XRD results indicate that the 1.75 at.% Cu-doped ZnO sample has a pure phase with the ZnO wurtzite structure, while the impurity phases are detected with increasing Cu concentrations. It was found that the doping of Cu results in a reduction of the preparation temperature. The optical properties of the samples were also investigated by UV–visible spectroscopy and photoluminescence measurements. The results show that the Cu doping causes the change in energy-band structures and effectively adjusts the intensity of the luminescence properties of ZnO nanorods. X-ray photoelectron spectroscopy analysis implies that there are some oxygen vacancies in the samples and also indicates that all the doped samples are associated with the mixture of Cu ion states (Cu²⁺ and Cu¹⁺/Cu⁰). Magnetic measurements by vibrating sample magnetometry indicate that undoped ZnO is diamagnetic, whereas all of the Cu-doped ZnO samples exhibit room temperature ferromagnetic behavior. We suggest that Cu substitution and density of oxygen vacancies (V _o) may play a major role in the room temperature magnetism of the Cu-doped ZnO samples.     

Enhanced ferromagnetism in nano-sized Zn0.95Mn0.05O grains

The present work reports ferromagnetism by doping magnetic Mn atoms in the diamagnetic ZnO matrix and the ferromagnetism has been extended up to 640 K in nano-grained Zn_0.95Mn_0.05O samples. The bulk and nano-grained samples were stabilized in hexagonal crystal structure with space group p63mc. The grain size and lattice strain of the samples were estimated from room temperature XRD spectrum. Surface morphology of the samples was examined at room temperature using SEM picture and EDX spectrum. The ferromagnetism of the bulk material shows enhancement in nano-grained samples, which was mainly due to the solution of Mn atoms into the lattice sites of ZnO by mechanical milling. The enhancement of magnetic moment and ferromagnetic ordering temperature with reduction in grain size has been understood in terms of the core-shell structure and existing theoretical models. The present work also demonstrated the role of surface spin disorder on the enhancement of ferromagnetism in Zn_0.95Mn_0.05O nanograins.     

Observation of room temperature ferromagnetism in pure La2O3 nanoparticles

In this paper, we report the observation of intrinsic room temperature ferromagnetism in pure La₂O₃ nanoparticles. Magnetism measurement indicates that all of the samples exhibit room temperature ferromagnetism and the saturation magnetization for the samples decreases with the increase in annealing temperature from 700 to 1,000 °C. X-ray photoelectron spectroscopy identifies the presence of oxygen vacancies in the La₂O₃ nanoparticles. The fitting results of the O 1s spectrum indicate that the variation of the oxygen vacancy concentration is in complete agreement with the change of the saturation magnetization. It is also found that the saturation magnetization of the La₂O₃ nanoparticles can be tuned by post-annealing in argon or oxygen atmosphere. These results suggest that the oxygen vacancies are largely responsible for the room temperature ferromagnetism in pure La₂O₃ nanoparticles.     

Magnetic and optical properties of epitaxial n-type Cu-doped ZnO thin films deposited on sapphire substrates

In this paper, we report on pulsed laser deposition of n-type Cu-doped ZnO thin films on c-plane sapphire substrates at 700°C. XRD and HRTEM were employed to study the epitaxial growth relationship between the Zn_1−x Cu _x O film and sapphire substrate. Absorption measurements showed excitonic nature of the thin films and a decrease in the bandgap energy with increased Cu concentration was observed. Such as-deposited films showed room temperature ferromagnetism with Curie temperature (T _c ) at around 320 K. The moment per Cu atom decreases as the Cu concentration increases. The largest magnetic moment about 0.81μ _B /Cu atom was observed for Zn_0.95Cu_0.05O thin films. The presence of any magnetic second phase was ruled out and the ferromagnetism was attributed to Cu ions substituted directly into the ZnO lattice.     

Ferromagnetism in MnxGe1−x films prepared by magnetron sputtering

Mn_xGe_1−x thin films were prepared by magnetron sputtering with a substrate temperature of 673 K and subsequently annealed at 873 K. The X-ray diffraction (XRD) measurements showed that all samples had a single Ge cubic structure. No films showed clear magnetic domain structure under a magnetic force microscope (MFM). Atom force microscope (AFM) measurements showed that the films had an uniform particle size distribution, and a columnar growth pattern. X-ray photoelectron spectroscopy (XPS) measurements indicated that the valences of both Mn and Ge atoms increase with the Mn concentration. The resistance decreased with increasing temperature, suggesting that the films were typical semiconductors. Magnetic measurements carried out using a Physical Property Measurement System (PPMS) showed that all samples exhibited ferromagnetism at room temperature. There was a small concentration of Mn₁₁Ge₈ in the films, but the ferromagnetism was mainly induced by Mn substitution for Ge site.     

Room-temperature ferromagnetism in Zn1−xMnxO

In view of recent controversies on above room-temperature ferromagnetism (RTFM) in transition-metal-doped ZnO, the present paper aims to shed some light on the origin of ferromagnetism by investigating annealing effects on structure and magnetism for polycrystalline Zn_1−xMn_xO powder samples prepared by solid-state reaction method and annealed in air at different temperatures. Magnetic measurements indicate that the samples are ferromagnetic at room temperature (RTFM). Room temperature ferromagnetism has been observed in the sample annealed at a low temperature of 500 °C with a saturated magnetization (M_s) of 0.159 emu/g and a coercive force of 89 Oe. A reduction in RTFM is clearly observed in the sample annealed at 600 °C. Furthermore, the saturation magnetic moment decreases with an increase in grain size, suggesting that ferromagnetism is due to defects and/or oxygen vacancy confined to the surface of the grains. The experimental results indicate that the ferromagnetism observed in Zn_1−xMn_xO samples is intrinsic rather than associated with secondary phases.     

Observation of novel coexistence of Kondo effect and room temperature magnetism in AlN/Al/AlN trilayer thin film

In this work for the first time, we are reporting the unusual observation of the Kondo effect with the coexistence of room temperature ferromagnetism in AlN/Al/AlN trilayer thin film. The grown film shows resistivity minimum at a temperature of ∼48K, which shifts to the lower temperature on the application of magnetic fields. After considering various possibilities for an upturn in resistivity, we found that the Kondo scattering is responsible for upturn at low temperature. The simultaneous presence of ferromagnetism and Kondo scattering is explained by spatial variation of nitrogen vacancy defects from the film surface to the Al sandwich layer. Furthermore, magneto-transport properties of the film measured at different temperature exhibits both negative and positive components described by localized magnetic moment model for the spin scattering of carriers and two-band model, respectively. This work provides insight into the novel co-existence of ferromagnetism and Kondo effect in crystalline AlN.     

Electronic structures and magnetic properties in Cu-doped two-dimensional dichalcogenides

We explore the electronic structures and magnetic properties in Cu-doped MX₂ (=MoS₂, MoSe₂, MoTe₂, and WS₂) based on density functional theory. A Cu dopant leads to a net moment of 5.0 or 1.0 μ_B in MX₂, which mainly depend on the size of crystal-field splitting relative to that of the spin splitting. No magnetism is observed in Cu-doped MoTe₂. The local distortion around the Cu atom reduces the total magnetic moment in two-Cu-doped MX₂. The magnetic coupling between the nearest neighboring Cu atoms is ferromagnetic for all the cases, but they demonstrate various magnetic ground states with the increasing distance between Cu atoms: the Cu-doped MoS₂ and WS₂ exhibit anti-ferromagnetic and nonmagnetic ground state, respectively. A long-range ferromagnetic or ferrimagnetic coupling is attributed to double-exchange interaction in Cu-doped MoSe₂. Half-metallic ferromagnetism with Curie temperature above room temperature in Cu-doped MoSe₂ provides a useful guidance to engineer the magnetic properties of MoSe₂ in experiments.     

First-principles study on the origin of ferromagnetism in n-type Cu-doped ZnO

Based on the density functional calculations with the GGA+U correction, we elucidate the origin of the experimentally reported ferromagnetism in n-type Cu-doped ZnO. Pure Cu-doped ZnO shows the unoccupied 3d states in the gap introduced by Cu, resulting in the insulating ground state and weak magnetic exchange interactions, in contrast to the half-metallic ground state and high ferromagnetic stability predicted by the calculations without U correction. However, the electron traps induced by Cu in n-type Cu-doped ZnO may lead to the partial occupancy of the Cu gap states, which stabilize the ferromagnetic ordering between two Cu atoms.     

Determination of kinetic parameters of thermally stimulated luminescence of Cu-doped BaSO4

Studies of thermally stimulated luminescence (TSL) of doped BaSO₄ with Cu activator have been carried out. The polycrystalline sample of Cu-doped BaSO₄ is prepared by recrystallisation method. The characterization and elemental analysis of BaSO₄:Cu compound are carried out by X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDX). The compound has orthorhombic structure at room temperature. The TSL studies of Cu-doped BaSO₄ sample show two glow peaks at 160 and 227 °C. Comparison of TL intensity of the most intensive glow peak of Cu- and Mn-doped BaSO₄ compounds with that of undoped BaSO₄ shows that addition of Cu and Mn impurity in BaSO₄ compound enhances the TL intensity by about 9 and 3 times, respectively. Among the studied samples, namely undoped, Cu- and Mn-doped BaSO₄, Cu-doped BaSO₄ is found to be the most sensitive. The trap parameters namely order of kinetics (b), activation energy (E), frequency factor (s) and Balarin parameter (γ) associated with the most intensive glow peak, i.e. the 227 °C glow peak of BaSO₄:Cu phosphor were determined by using isothermal decay method and glow curve shape (Chen's) method and these parameters are in good agreement.