Effect of thermal treatment on room-temperature ferromagnetism in Co-doped ZnO powders

The Co-doped ZnO powders were synthesized by sol-gel method, and treated at different temperatures (673-873 K) in the presence or absence of NH₃ atmosphere for 0.5 and 2 h, respectively. X-ray diffraction (XRD) and vibrating sample magnetometer (VSM) show that better crystal structure can cause larger ferromagnetism and the second phase (Co₃O₄) is the reason for saturation magnetization decrease of the sample sintered at higher temperature in air. XPS and nuclear magnetic resonance (NMR) prove the existence of Co²⁺ ions in the Zn_0.9Co_0.1O and the absence of Co clusters, indicating intrinsic ferromagnetism of the samples treated in air. However, strong ferromagnetism of the samples annealed in NH₃ is ascribed to cobalt nitride formed during annealing.     

Role of donor defects in stabilizing room temperature ferromagnetism in (Mn, Co) co-doped ZnO nanoparticles

We report the effects of co-doping ZnO with Co and Mn in an n-type environment on ferromagnetism (FM). Two sets of samples, Zn(0.95-x)Co(0.04)Mn(x)O (0.000 ≤ x ≤ 0.02) and Zn(0.95-y)Co(y)Mn(0.04)O (0.000 ≤ y ≤ 0.02), were synthesized by the chemical route with oxygen vacancies introduced via annealing in a forming gas (reducing the atmosphere). In addition to the magnetization, the particles were characterized by x-ray diffraction, diffuse reflectance spectroscopy and x-ray absorption near-edge emission spectroscopy. The Co and Mn ions were determined to be in the + 2 state in a tetrahedral symmetry, with no evidence of metallic Co or Mn. We find that while a purely Mn-doped sample exhibits weak FM at room temperature, the general effect of Mn as a co-dopant with Co, in an n-type environment, is to decrease the moment strongly. All of our results can be systematically explained within the context of defect mediated FM in these wide bandgap semiconductors, where the coincidence of the spin-split-impurity (defect) band states and the 3d states leads to the development of a net moment alongside the formation of spin polarons.     

Nature of room-temperature ferromagnetism from undoped ZnO nanoparticles

ZnO nanoparticles were synthesized by a sol–gel calcination process following being annealed in air at 400, 600, 800 and 1000°C. X-ray diffraction pattern and X-ray photoelectron spectroscopy show that all the samples present a typical wurtzite structure and no other impurity phases are observed. Room-temperature ferromagnetism from all the samples is confirmed by the vibrating sample magnetometer measurements, which shows that the RTFM decreases with the annealing temperature increasing from 400 to 800°C, and then became larger for the sample annealed at 1000°C. According to the Raman scattering spectra and electron paramagnetic resonance, the RTFM of samples annealed at 600, 800 and 1000°C might be related to the oxygen vacancy related defects. However, the RTFM from the sample annealed at 400°C, presenting nearly the same value as that of the sample annealed at 1000°C, could originate with the interstitial zinc defects associated with XPS and photoluminescence analyses.     

Structure and room-temperature ferromagnetism of Co-doped ZnO DMS films

Co-doped ZnO diluted magnetic semiconductor films were prepared on Si(100) substrates by magnetron sputtering system and the Co content varies from 0.01 to 0.15. The X-ray diffraction results showed ZnO of the wurtzite structure. The ferromagnetism was observed at room temperature. The X-ray near-edge absorption spectroscopy revealed that Co substitutes for Zn²⁺ ions in the valence of +2 state in the Co-doped ZnO films.     

Hydrogen shallow donors in Co-doped ZnO showing room-temperature ferromagnetism

Room-temperature ferromagnetism has been identified in sol–gel-prepared Co-doped ZnO (ZnCoO), hydrogen being incorporated by a linear polymer polyvinyl pyrrolidone. The magnetic order was investigated by the X-ray photoemission and magnetization measurements in view of the interstitial hydrogen being coupled with Co²⁺. The electron paramagnetic resonance measurements revealed that hydrogens not contributing to the magnetic order occupy the shallow donor levels in the hydrogenated ZnCoO system.     

Spin-polarized room temperature ferromagnetism in co-doped ZnO synthesized by electrodeposition

We have investigated the structural, optical and magnetic properties of Zn_0.90Co_0.10O, synthesized by the method of two electrode electrodeposition. X-ray diffraction measurement confirms the evolution of a single-phase polycrystalline hcp Wurtzite structure. Co-2p core-level XPS confirms that Co is present in mixed 2+ and 3+ states. The Fourier Transform Infrared (FTIR) spectrum findings substantiate the fact that a single-phase Hexagonal Wurtzite ZnO Crystal Structure has evolved. The SEM micrograph of the sample reveals smooth and dispersed morphology consisting of fine particles. The U-V visible NIR and PL spectroscopy measurements substantiate the fact that Co²⁺ has substituted Zn²⁺ in the matrix of ZnO which agrees with XRD findings. The sample shows good optical property and reveals a blue shift. It seems that the material is a potential candidate to be used as UV sensors. Room Temperature Intrinsic Ferromagnetism has been confirmed by VSM measurement.     

Defect-induced reversible ferromagnetism in hydrogenated ZnO:Co

Through simple hydrogen annealing treatment, we observed robust inducement of room temperature ferromagnetism (RTFM) in ZnO:Co (5%) pellets. The hydrogen mediated magnetic transition is accompanied by electronic structure plus bonding modifications with no structural deviations or creation of secondary phases, as evidenced by XRD and photoemission investigations. Our findings reveal a route correlation of oxygen vacancies with the observed RTFM. In particular, we systematically investigated the time controlled re-heating consequences on hydrogenated sample. The H-induced RTFM and subsequent modifications viz. electronic structure, transport properties and bonding effect gradually retrace back upon evaporating the hydrogen.     

Vacancy-induced room-temperature ferromagnetism in ZnO rods synthesized by Ni-doped solution and hydrothermal method

Pure ZnO and Ni-doped ZnO rods have been prepared by hydrothermal method at a temperature of 120 °C. The morphological, structural, magnetic and optical properties of the as-prepared rods were investigated by means of field emission scanning electron microscopy, X-ray diffraction, vibrating sample magnetometer and photoluminescence. All the samples are radial-grown hexagon rods with diameter from 470 to 720 nm and length of 4-6 μm. X-ray diffraction shows that the rods have single crystalline wurtzite structure without other impurity phases. The pure ZnO rods and Ni-doped ZnO rods have ferromagnetism at room temperature, and the special saturation magnetization deduces with the increasing diameter of rods. These results reveal that the saturation magnetization of the ZnO rods depends on the surface-to-volume ratio of rods rather than the Ni doping concentrations. The photoluminescence spectra studies show the same diameter dependences of oxygen vacancies as that of magnetization, which demonstrates that oxygen vacancies at surface of rods play an important role in introducing ferromagnetism. The annealing in rich oxygen and reducing atmospheres confirms this argument further.     

Mn和N共掺ZnO稀磁半导体薄膜的研究

使用对Zn₂N₃:Mn薄膜热氧化的方法成功制备了高含N量的Mn和N共掺ZnO的稀磁半导体薄膜.在没有N离子共掺的情况下,ZnO:Mn薄膜的铁磁性非常微弱;如果进行N离子的共掺杂,就会发现ZnO:Mn薄膜在室温下表现出非常明显的铁磁性,饱和离子磁矩为0.23 μ_B—0.61 μ_B.这说明N的共掺激发了ZnO:Mn薄膜中的室温铁磁性,也就是受主的共掺引起的空穴有利于ZnO中二价Mn离子的铁磁性耦合,这和最近的相关理论研究符合很好. 关键词： 磁性半导体 受主掺杂 空穴媒介的铁磁性     

Study on the ferromagnetism in Co and N doped ZnO thin films

Present investigation reports the structural, optical and magnetic properties of co-doping of Co and N ions in ZnO samples, prepared by two distinct methods. In the first method, samples are synthesized by Sol–gel technique in which the Co and N are co-doped simultaneously during the growth process itself. In the second case, N ions are implanted in the Co doped ZnO thin films grown by Pulsed Laser Deposition (PLD). Structural studies showed that the nitrogen implantation on Co doped ZnO samples developed compressive stress in the films. X-ray photoelectron spectroscopy confirmed the doping of Co and N in ZnO matrix. In the Resonant Raman scattering multiple LO phonons up to fifth order are observed in the (Co, N) co-doped ZnO. Photoluminescence spectra showed that there is reduction in the bandgap due to the presence of Co in the lattice and also the presence of Zn vacancies in the films. All samples showed ferromagnetic behavior at room temperature. The magnetic moment observed in the implanted films is found to be varied with the different dosages of the implanted N ions. First principle calculations have been carried out to study the possible magnetic interaction in the co-doped system. Present study shows that the ferromagnetic interaction is due to the hybridization between N 2p and Co 3d states in the (Co, N) co-doped ZnO and is very sensitive to the geometrical configurations of dopants and the vacancy in the ZnO host lattice.     

Enhanced room temperature ferromagnetism and photoluminescence behavior of Cu-doped ZnO co-doped with Mn

Cu, Mn co-doped ZnO nanoparticles were successfully synthesized by the sol–gel technique. XRD pattern described that Mn-doping did not affect the hexagonal wurtzite structure of the samples and no secondary phases were found. The reduced crystallite size at Mn=2% is due to the suppression of grain surface growth by foreign impurity. The enhancement of crystal size after Mn=2% is due to the expansion of lattice volume produced by the distortion around the dopant ion. The better dielectric constant and conductivity noticed at Mn=2% are explained by charge carrier density and crystallite size. The suppression of broad UV band by Mn-doping is discussed based on the generation of non-radiative recombination centers. Hysteresis loop showed the clear room temperature ferromagnetism in all the samples and the magnetization increased with Mn-doping. Better electrical and magnetic behavior of Zn_0.94Cu_0.04Mn_0.02O sample is suggested for effective opto-magnetic devices.     

Infrared emissivities of Mn,Co co-doped ZnO powders

<正>Infrared emissivities of Zn_0.99-xMn_0.01Co_xO（x=0.00,0.01,0.03,0.05） powders synthesized at different calcination temperatures by solid-state reaction are investigated.Their phases,morphologies,UV absorption spectra,and infrared emissivities are studied by XRD,SEM,UV spectrophotometer,and an IR-2 dual-band infrared emissometer in a range of 8μm-14μm.Doped ZnO still has a wurtzite structure,and no peaks of other phases originating from impurities are detected.The optical band-gap decreases as the Co content and calcination temperature ascend,and of which the smallest optical band gap is 2.19 eV.The lowest infrared emissivity,0.754,is observed in Zn_0.98Mn_0.01Co_0.01O with the increase in Co concentration.The infrared emissivity experiences fluctuations as the calcination temperature increases,and its minimum value is 0.762 at 1100℃.     

Doping dependent room-temperature ferromagnetism and structural properties of dilute magnetic semiconductor ZnO:Cu nanorods

Copper doped ZnO nanoparticles were synthesized by the chemical technique based on the hydrothermal method. The crystallite structure, morphology and size were determined by X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM) for different doping percentages of Cu²⁺ (1-10%). TEM/SEM images showed formation of uniform nanorods, the aspect ratio of which varied with doping percentage of Cu²⁺. The wurtzite structure of ZnO gradually degrades with the increasing Cu²⁺ doping concentration and an additional CuO associated diffraction peak was observed above 8% of Cu²⁺ doping. The change in magnetic behavior of the nanoparticles of ZnO with varying Cu²⁺ doping concentrations was investigated using a vibrating sample magnetometer (VSM). Initially these nanoparticles showed strong room-temperature ferromagnetic behavior, however at higher doping percentage of copper the ferromagnetic behavior was suppressed and paramagnetic nature was enhanced.     

Magnetic anisotropy of Co2+ as signature of intrinsic ferromagnetism in ZnO:Co

We report on the magnetic properties of thoroughly characterized Zn(1-x)Co(x)O epitaxial thin films, with low Co concentration, x = 0.003-0.005. Magnetic and EPR measurements, combined with crystal field theory, reveal that isolated Co2+ ions in ZnO possess a strong single ion anisotropy which leads to an "easy plane" ferromagnetic state when the ferromagnetic Co-Co interaction is considered. We suggest that the peculiarities of the magnetization process of this state can be viewed as a signature of intrinsic ferromagnetism in ZnO:Co materials.     

Direct kinetic correlation of carriers and ferromagnetism in Co2+: ZnO

The hypothesis that high-Curie-temperature ferromagnetism in cobalt-doped ZnO (Co2+: ZnO) is mediated by charge carriers was tested by controlled introduction and removal of the shallow donor interstitial zinc. Using oriented epitaxial Co2+: ZnO films grown by chemical vapor deposition, kinetics measurements demonstrate a direct correlation between the oxidative quenching of ferromagnetism and the diffusion and oxidation of interstitial zinc. These results demonstrate controlled systematic variation of a key parameter involved in the ferromagnetism of Co2+: ZnO and, in the process, unambiguously reveal this ferromagnetism to be dependent upon charge carriers. The distinction between defect-bound and free carriers in Co2+: ZnO is discussed.     

Effect of annealing atmosphere on ferromagnetism in Mn doped ZnO films

This paper reports that Zn_0.97Mn_0.03O thin films have been prepared by radio-frequency sputtering technology followed by rapid thermal processing in nitrogen and oxygen ambient respectively. Magnetic property investigation indicates that the films are ferromagnetic and that the Curie temperature (T_c) is over room temperature. It is observed that the saturation magnetization of the films increases after annealing in nitrogen ambience but decreases after annealing in oxygen. Room temperature photoluminescence spectra indicate that the amount of defects in the films differs after annealing in the different ambiences. This suggests that the ferromagnetism in Zn_0.97Mn_0.03O films is strongly related to the defects in the films.     

Co掺杂的ZnO室温铁磁半导体材料制备与磁性和光学特性研究

采用溶胶-凝胶法制备出具有室温铁磁性的Co掺杂的ZnO稀磁半导体材料. 通过对样品的结构、磁性和发光特性的研究发现,样品具有室温铁磁性,并发现其铁磁性源于磁性离子对ZnO中Zn离子的取代. 对不同温度制备的样品的磁性以及其发光特性的变化研究发现,样品的铁磁性与样品中锌间隙位（Zn_i）缺陷的密度有关. 关键词： ZnO 稀磁半导体 铁磁性     

Room-temperature ferromagnetism in carbon-doped ZnO

We report ferromagnetism in carbon-doped ZnO. Our first-principles calculations based on density functional theory predicted a magnetic moment of 2.02 mu(B) per carbon when carbon substitutes oxygen in ZnO, and an ferromagnetic coupling among magnetic moments of the carbon dopants. The theoretical prediction was confirmed experimentally. C-doped ZnO films deposited by pulsed-laser deposition showed ferromagnetism with Curie temperatures higher than 400 K. The measured magnetic moment based on the content of carbide in the films [(1.5-3.0) mu(B) per carbon] was in agreement with the theoretical prediction. The magnetism is due to the Zn-C system in the ZnO environment.     

Preparation and characterization of room-temperature ferromagnetism GaMnN based on ion implantation

This paper reports the fabrication of GaMnN ferromagnetic semiconductor on GaN substrate by high-dose Mn ion implantation. Both the structural and optical properties for Mn+-implanted GaN material were studied by X-ray diffraction, Raman scattering and photolumi-nescence. The results reveal that the implanted manganese incorporates on Ga site and GaMnN ternary phase is formed in the substrate. The magnetic behavior has been characterized by superconducting quantum interference device. The material shows room-temperature ferromagnet-ism. The temperature-dependent magnetization indicates different mechanism for ferromagnetism in Mn+-implanted GaN.     

退火温度对N+注入ZnO:Mn薄膜结构及室温铁磁性的影响

采用射频磁控溅射法在石英玻璃衬底上制备了ZnO:Mn薄膜, 结合N⁺ 注入获得Mn-N共掺ZnO薄膜, 进而研究了退火温度对其结构及室温铁磁性的影响. 结果表明, 退火后ZnO:(Mn, N) 薄膜中Mn²⁺和N^3-均处于ZnO晶格位, 没有杂质相生成. 退火温度的升高 有助于修复N⁺注入引起的晶格损伤, 同时也会让N逸出薄膜, 导致受主(N_O)浓度降低. 室温铁磁性存在于ZnO:(Mn, N)薄膜中, 其强弱受N_O浓度的影响, 铁磁性起源可采用束缚磁极化子模型进行解释.