Effect of indium incorporation in Zn1−xCoxO thin films

In the present paper, the preliminary investigations of a series of ZnO thin films co-doped with indium and cobalt with an objective to elucidate the correlation, if any, between the carrier concentration and the induced room temperature ferromagnetism (RTFM), are presented. The single-phasic (Zn_99.5In_0.5)_1−xCo_xO thin films are deposited by spray pyrolysis. The substitution of Zn²⁺ by Co²⁺ has been established by optical transmission analysis of these films. The films are ferromagnetic at room temperature; and the magnetization has higher value for indium and cobalt co-doped thin film as compared with Zn0₉₀Co_0.1O thin film (having no indium).     

Effect of Mg doping and substrate temperature on the properties of pulsed laser deposited epitaxial Zn1?xMgxO thin films

In this paper, we report on the pulsed laser deposition of epitaxial (0002) oriented Zn_1−x Mg _x O thin films onto (0001) sapphire substrate in O₂ ambient at different deposition temperatures. Pulsed laser deposited Zn_1−x Mg _x O films showed (0002) oriented hexagonal wurtzite structure up to 34% of Mg concentration. The bandgap of Zn_1−x Mg _x O thin films is successfully tuned from 3.3 to 4.2 eV by adjusting the Mg concentration x=0.0 to x=0.34. Pulsed laser deposited Zn_1−x Mg _x O thin films were characterized by XRD, AFM, SEM, PL and UV–VIS spectrometer. We have also studied the effect of deposition temperature on to the structure, surface morphology and optical properties of Zn_1−x Mg _x O thin films.     

Magnetic properties of Er-doped ZnO films prepared by reactive magnetron sputtering

All Zn_1−x Er _x O (x=0.04, 0.05, and 0.17) films deposited on glass substrates by radio-frequency reactive magnetron sputtering exhibit the mixture of ferromagnetic and paramagnetic phases at room temperature. The estimated magnetic moment per Er ion decreases with the increase of Er concentration. The temperature dependence of the magnetization indicates that there is no intermetallic ErZn buried in the films. The ferromagnetism is attributed to the Er ions substitution for Zn²⁺ in ZnO lattices, and it can be interpreted by the bound-magnetic-polaron model.     

Zn-interstitial-enhanced ferromagnetism in Cu-doped ZnO films

Copper-doped ZnO (ZnO:Cu) films exhibiting room-temperature (RT) ferromagnetism were prepared by filtered cathodic vacuum arc (FCVA) technique. The ZnO:Cu films deposited at RT showed the strongest magnetic moment of 0.40 μ_B/Cu as compared with the samples prepared at elevated temperatures. The observed strong ferromagnetism in the RT-deposited ZnO:Cu films could be partly associated with Zn-interstitial defects. The degradation of magnetic moment in the ZnO:Cu prepared at high temperatures and annealed at elevated temperatures might be attributed to the out-diffusion of Zn interstitials to the ZnO lattice.     

Synthesis and magnetic properties of Ni-doped zinc oxide powders

Polycrystalline Zn_1−xNi_xO diluted magnetic semiconductors have been successfully synthesized by an auto-combustion method. X-ray diffraction measurements indicated that the 5 at% Ni-doped ZnO had the pure wurtzite structure. Refinements of cell parameters from powder diffraction data revealed that the cell parameters of Zn_0.95Ni_0.05O were a little bit larger than ZnO. Transmission electron microscopy observation showed that the as-synthesized powders were of the size ∼60 nm. Magnetic investigations showed that the nanocystalline Zn_0.95Ni_0.05O possessed room temperature ferromagnetism with the saturation magnetic moment of 0.1 emu/g (0.29 μ_B/Ni²⁺).     

Room-Temperature Ferromagnetism in Zn1-xMnxO Thin Films Deposited by Pulsed Laser Deposition

Zn1-xMnxO （x = O.Olq3.1） thin films with a Curie temperature above 300K are deposited on Al2O3 （0001） substrates by pulsed laser deposition. X-ray diffraction （XRD）, ultraviolet （UV）-visible transmission and Raman spectroscopy are employed to characterize the microstructural properties of these films. Room temperature ferromagnetism is observed by superconducting quantum interference device （SQUID）. The results indicate that Mn doping introduces the incorporation of Mn^2＋ ions into the ZnO host matrix and the insertion of Mn^2＋ ions increases the lattice defects, which is correlated with the ferromagnetism of the obtained films. The doping concentration is also proven to be a crucial factor for obtaining highly ferromagnetic Zn1-xMnxO films.     

Raman spectroscopy of Cu doping in Zn1−xCoxO diluted magnetic semiconductor

The room‐temperature ferromagnetism and the Raman spectroscopy of the Cu‐doped Zn_1−xCo_xO powders prepared by the sol–gel method are reported. The x‐ray diffraction (XRD) data confirmed that the wurtzite structure of ZnO is maintained for ZnO doped with Co below 10 at%. The magnetization–field curves measured at room temperature demonstrated that all Co‐doped ZnO powders were paramagnetic. Ferromagnetic ordering is observed for the samples doped with Cu in Zn_0.98Co_0.02O and strongly depends on the concentration of Cu. The relative strength of the second‐order LO peak to the first‐order one in the Raman spectra, which is related to the carrier concentration, of the Cu‐doped Zn_0.98Co_0.02O powder is strongly correlated with the saturation magnetic moment of the system. This seems to be in favor of the Ruderman‐Kittel‐Kasuya‐Yosida (RKKY) or double exchange mechanism of the ferromagnetism in this system. Copyright © 2009 John Wiley & Sons, Ltd.     

Growth and physical properties of sol–gel derived Co doped ZnO thin film

Zn_1−xCo_xO films were grown on glass by sol–gel spin coating process. The Zn_1−xCo_xO thin films with 10 at.% Co were highly c-axis oriented. The electrical resistivity of the films at 10 at.% Co had the lowest value due to the highest c-axis orientation. XPS and AGM analyses indicated that Co metal clusters weren’t formed, and the ferromagnetism was appeared at room temperature. The characteristics of the electrical resistivity and room temperature ferromagnetism of sol–gel derived Zn_1−xCo_xO films suggest a potential application to dilute magnetic semiconductor devices.     

Structural,optical and magnetic properties of Cu and V co-doped ZnO nanoparticles

Zn_0.98−xCu_xV_0.02O (x=0, 0.01, 0.02 and 0.03) samples were synthesized by the sol–gel technology to dope up to 3% Cu in ZnO. Investigations of structural, optical and magnetic properties of the samples have been done. The results of X-ray diffraction (XRD), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS) indicated that the V and Cu ions were incorporated into the crystal lattices of ZnO. With Cu doping concentration increasing up to 2 at%, the XRD results showed that all diffraction peaks corresponded to the wurtzite structure of ZnO. Photoluminescence (PL) measurements showed that Zn_0.98−xCu_xV_0.02O powders exhibited that the position of the ultraviolet (UV) emission peak of the samples showed an obvious red-shift and the green emission peak enhanced significantly with Cu doping in ZnVO nanoparticle. Magnetic measurements indicated that room temperature ferromagnetism (RTFM) of Zn_0.98−xCu_xV_0.02O was an intrinsic property when Cu concentration was less than 3 at%. The saturation magnetization (M_s) of Zn_0.98−xCu_xV_0.02O (x=0, 0.01 and 0.02) increased with the increase of the Cu concentration.     

Zn1-xCoxO稀磁半导体薄膜的结构及其磁性研究

利用X射线吸收精细结构、X射线衍射和磁性测量等技术研究脉冲激光气相沉积法制备的Zn_1-xCo_xO (x＝0.01,0.02)稀磁半导体薄膜的结构和磁性.磁性测量结果表明Zn₁-xCo_xO样品都具有室温铁磁性.X射线衍射结果显示其薄膜样品具有结晶良好的纤锌矿结构.荧光X射线吸收精细结构测试结果表明,脉冲激光气相沉积法制备的样品中的Co离子全部进入ZnO晶格中替代了部分Zn的格点位置,生成单一相的Zn_1-xCo_xO 稀磁半导体.通过对X射线吸收近边结构谱的分析,确定Zn_1-xCo_xO薄膜中存在O空位,表明Co离子与O空位的相互作用是诱导Zn_1-xCo_xO产生室温铁磁性的主要原因. 关键词： 1-xCo_xO稀磁半导体')" href="#">Zn_1-xCo_xO稀磁半导体 X射线吸收精细结构谱 脉冲激光气相沉积法     

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.     

Studies of the physical properties of Co, Cu codoped ZnO powders

Zn_0.95−xCo_0.05Cu_xO powders have been synthesized by the sol-gel method and the structural, magnetic and electrical properties of the powders have been investigated. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) indicate that the Co ions do not change the ZnO wurtzite structure. Magnetic measurements indicate that Co doping can induce room temperature (RT) ferromagnetism and the addition of Cu to the powders further increases the magnetic moment per Co ion. The effects of the introduction of Cu as an acceptor dopant in the host matrix are further studied using resistance measurements. It is demonstrated experimentally that acceptor doping plays an important role in realizing dominant ferromagnetic ordering in Co doped ZnO powders.     

Mn–AlInN: a new diluted magnetic semiconductor

Mn ions have been incorporated into MOCVD grown Al_1−x In _x N/GaN thin films by ion implantation to achieve the room temperature ferromagnetism in the samples. Magnetic characterizations revealed the presence of two ferromagnetic transitions: one has Curie points at ∼260 K and the other above room temperature. In-diffusion of indium caused by the Mn implantation leads to the partition of AlInN epilayer into two diluted magnetic semiconductor sub-layers depending on the Mn concentration. The Curie temperature of 260 K is assigned to the layer having lower concentration, whereas T _c above room temperature is assumed to be associated to the layer having higher Mn concentration.     

Structure and magnetic properties of Zn<Subscript>0.9</Subscript>Co<Subscript>0.1</Subscript>O nanorods synthesized by a simple sol–gel method using metal acetylacetonate and poly(vinyl alcohol)

Room-temperature ferromagnetism was observed in Zn_0.9Co_0.1O nanorods with diameters and lengths of ∼100–200 nm and ∼200–1000 nm, respectively. Nanorods were synthesized by a simple sol–gel method using metal acetylacetonate powders of Zn and Co and poly(vinyl alcohol) gel. The XRD, FT-IR and SAED analyses indicated that the nanorods calcined at 873–1073 K have the pure ZnO wurtzite structure without any significant change in the structure affected by Co substitution. Optical absorption measurements showed absorption bands indicating the presence of Co²⁺ in substitution of Zn²⁺. The specific magnetization of the nanorods appeared to increase with a decrease in the lattice constant c of the wurtzite unit cell with the highest value being at 873 K calcination temperature. This magnetic behavior is similar to that of Zn_0.9Co_0.1O nanoparticles prepared by polymerizable precursor method. We suggest that this behavior might be related to hexagonal c-axis being favorable direction of magnetization in Co-doped ZnO and the 873 K (energy of 75 meV) being close to the exciton/donor binding energy of ZnO.     

Influence of annealing temperature on structural, optical and magnetic properties of Mn-doped ZnO thin films prepared by sol-gel method

Thin films of Zn_1−xMn_xO (x=0.01) diluted magnetic semiconductor were prepared on Si (1 0 0) substrates by the sol-gel method. The influence of annealing temperature on the structural, optical and magnetic properties was studied by X-ray diffraction (XRD), atom force microscopy (AFM), photoluminescence (PL) and SQUID magnetometer (MPMS, Quantum Design). The XRD spectrum shows that all the films are single crystalline with (0 0 2) preferential orientation along c-axis, indicating there are not any secondary phases. The atomic force microscopy images show the surfaces morphologies change greatly with an increase in annealing temperature. PL spectra reveal that the films marginally shift the near band-edge (NBE) position due to stress. The magnetic measurements of the films using SQUID clearly indicate the room temperature ferromagnetic behavior, and the Curie temperature of the samples is above room temperature. X-ray photoelectron spectroscopy (XPS) patterns suggest that Mn²⁺ ions were successfully incorporated into the lattice position of Zn²⁺ ions in ZnO host. It is also found that the post-annealing treatment can affect the ferromagnetic behavior of the films effectively.     

Magnetic and Raman scattering studies of Co-doped ZnO thin films grown by pulsed laser deposition

Phase pure Zn_1?x Co _x O thin films grown by pulsed laser deposition have transmittance greater than 75 % in the visible region. Raman studies confirm the crystalline nature of Zn_1?x Co _x O thin films. Zn_0.95Co_0.05O thin films show room temperature ferromagnetism with saturation magnetization of 0.4μ _B /Co atom. The possible origin of paramagnetism at higher Co doping concentrations can be attributed to the increased nearest-neighbor antiferromagnetic interactions between Co²⁺ ions in ZnO matrix. XPS confirms the substitution of Co²⁺ ions into the ZnO host lattice.     

Room-temperature ferromagnetism of the amorphous Cu-doped ZnO thin films

Amorphous copper-doped ZnO thin films (ZnO:Cu) prepared on glass substrates by the radio-frequency magnetron co-sputtering have been investigated. Magnetic measurements indicated that the amorphous ZnO:Cu thin films were ferromagnetic at room temperature and the saturation magnetization was much higher than that of the polycrystalline films. X-ray diffraction results showed there was no Cu₂O phase in amorphous ZnO:Cu films, which might be the reason for the high magnetic moment of the films. On the other hand, the high saturation magnetization of the amorphous ZnO:Cu films could also attribute to that there was no limit of solid solubility of Cu in amorphous ZnO solvent. The X-ray photoelectron spectroscopy study of the amorphous ZnO:Cu thin films reveal that copper was in Cu²⁺ chemical state.     

Role of vanadium content in ZnO thin films grown by pulsed laser deposition

Vanadium-doped ZnO films (Zn_1−xV_xO, where x = 0.02, 0.03, 0.05 and 0.07), were formed from ceramic targets on c-cut sapphire substrates using pulsed laser deposition at substrate temperature of 600 °C and oxygen pressure of 10 Pa. In order to clarify how the vanadium concentration influences the films’ properties, structural and magnetic investigations were performed. All films crystallised in wurtzite phase and presented a c-axis preferred orientation at low concentrations of vanadium. The results implied that the doping concentration and crystalline microstructure influence strongly the system's magnetic characteristics. Weak ferromagnetism was registered for the film with the lowest doping concentration (2 at.%), which exhibited a ferromagnetic behavior at Curie temperature higher than 300 K. Increasing the vanadium content in the film caused degradation of the magnetic ordering.     

Properties of Cu and V co-doped ZnO nanoparticles annealed in different atmospheres

Zn_0.97Cu_0.01V_0.02O nanoparticles have been successfully prepared by the sol–gel method and sintered at 600 °C in argon and air atmosphere, respectively. The effects of annealing atmosphere on the structural, optical and magnetic properties of the obtained samples were studied. The X-ray diffraction result showed that the Zn_0.97Cu_0.01V_0.02O was single phase with the wurtzite structure of ZnO. The sample annealed in air had much better crystallization. Photoluminescence shows an increase in green emission when annealing in argon. The two Zn_0.97Cu_0.01V_0.02O samples exhibited ferromagnetism at room temperature. The ferromagnetism in this study was itself property of Cu, V co-doped ZnO and not originated from the secondary phase.     

Effect of oxygen annealing on the Mn properties in ZnMnO Films

We studied the influence of thermal annealing in oxygen on the physical properties of MOCVD grown Zn_1−xMn_xO thin layers. Annealing in the 300–1000 °C temperature range modifies both lattice parameters and magnetic properties of the layers. Correlation of the results from X-ray diffraction, EPR studies and Raman spectroscopy indicate a modification of the Mn⁺²-related features in the ZnO matrix.