Effect of annealing temperature on structure, magnetic properties and optical characteristics in Zn0.97Cr0.03O nanoparticles

The Cr-doped zinc oxide (Zn_0.97Cr_0.03O) nanoparticles were successfully synthesized by sol-gel method. The relationship between the annealing temperature (400 °C, 450 °C, 500 °C and 600 °C) and the structure, magnetic properties and the optical characteristics of the produced samples was studied. The results indicate that Cr (Cr³⁺) ions at least partially substitute Zn (Zn²⁺) ions successfully. Energy dispersive spectroscopy (EDS) measurement showed the existence of Cr ion in the Cr-doped ZnO. The samples sintered in air under the temperature of 450 °C had single wurtzite ZnO structure with prominent ferromagnetism at room temperature, while in samples sintered in air at 500 °C, a second phase-ZnCr₂O₄ was observed and the samples were not saturated in the field of 10000 Oe. This indicated that they were mixtures of ferromagnetic materials and paramagnetic materials. Compared with the results of the photoluminescence (PL) spectra, it was reasonably concluded that the ferromagnetism observed in the studied samples was originated from the doping of Cr in the lattice of ZnO crystallites.     

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.     

Room-temperature ferromagnetism in lightly Cr-doped ZnO nanoparticles

Zn_1−x Cr _x O (0≤x≤0.15) nanoparticles were synthesized by an auto-combustion method and characterized by x-ray diffraction and Raman scattering techniques. The solubility limit for Cr in ZnO was determined as x≈0.03. Room-temperature ferromagnetism (RT-FM) was observed in lightly Cr-doped ZnO nanoparticles with x=0.01 and 0.02. Raman scattering spectra of the lightly Cr-doped and Co-doped ZnO were studied and compared. The enhancement of both the magnetization and the intensity of Raman scattering peak associated with donor defects (Zn_i and/or V_O) and carriers indicates that light Cr doping in ZnO could be an effective way to achieve pronounced RT-FM and the ferromagnetism is closely related to the dopant-donor hybridization besides the ferromagnetic Cr–O–Cr superexchange interactions.     

Comment on “Effect of annealing temperature on structure, magnetic properties and optical characteristics in Zn0.97Cr0.03O nanoparticles” by Liu et al., [Appl. Surf. Sci. 256 (2010) 3559]

The authors of a recent paper (Appl. Surf. Sci. 256 (2010) 3559) studied the effect of annealing temperature on structural, magnetic and optical properties in Cr-doped zinc oxide (Zn_0.97Cr_0.03O) nanoparticles synthesized by sol-gel method. The authors have verified that Cr ions, in 3+ valence state, substitute the Zn ions in the ZnO lattice. They concluded that the ferromagnetism observed in the samples is an intrinsic property of the Cr-doped ZnO. However, we noticed an unusual point in this article. The Cr 2p XPS spectrum shown by them is against the general trend of the 2p XPS spectra of the transition metals. In this light, we re-measured the high-resolution 2p XPS spectrum of Cr for a 3% Cr-doped ZnO sample that is entirely different than theirs. The spectrum presented by them therefore demands proper interpretations or it might mislead the researchers in this developing field.     

A threshold of Vo/Vo to room temperature ferromagnetism of hydrogenated Mn doped ZnO nanoparticles

Hydrogenated Mn doped Zn_1−xMn_xO (x = 0.03, 0.04, 0.08) nanoparticles were prepared by co-precipitation method. With the increase of Mn ions concentration, the magnetization of the hydrogenated Zn_1−xMn_xO increased. Photoluminescence spectra of samples annealed in Ar and H₂ respectively were performed and the visible bands were fitted with Gaussian analysis. It is concluded that the sharp magnetization enhancement could be attributed to the long-rang interaction between bound-magnetic-polarons led by the singly charged oxygen vacancy (Vo⁺).     

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.     

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.     

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.     

Room temperature ferromagnetism in Ni-doped ZnO films

Zn_1−xNi_xO (x = 0.02, 0.03, 0.04, 0.05, 0.07) films were prepared using magnetron sputtering. X-ray diffraction indicates that all samples have a wurtzite structure with c-axis orientation. X-ray photoelectron spectroscopy results reveal that the Ni ion is in a +2 charge state in these films. Magnetization measurements indicate that all samples have room temperature ferromagnetism. In order to elucidate the origin of the ferromagnetism, Zn_0.97Ni_0.03O films were grown under different atmospheric ratios of argon to oxygen. The results show that as the fraction of oxygen in the atmosphere decreases, both the saturation magnetization and the number of oxygen vacancies increase, confirming that the ferromagnetism is correlated with the oxygen vacancy level.     

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).     

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.     

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.     

Influence of Fe-doping on the structural,optical and magnetic properties of ZnO nanoparticles

Zn_1–xFe_xO (x=0–0.05) nanoparticles were synthesized without a catalyst by a two-step method. Fe was doped into ZnO by a source of metallic Fe sheets in a solid–liquid system at 80 °C, and the Zn_1−xFe_xO nanoparticles were obtained by annealing at 300 °C. X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy were used to characterize the structural properties of the as-grown Zn_1−xFe_xO. The optical properties were determined by Infrared and Ultraviolet–visible spectroscopy. The results confirm that the crystallinity of the ZnO is deteriorated due to Fe-doping. XPS results show that there is a mixture of Fe⁰⁺ and the Fe³⁺ in the representative Zn_0.95Fe_0.05O sample. The optical band gap of Zn_1−xFe_xO is enhanced with increasing of Fe-doping. Room temperature ferromagnetism was observed in all the Fe-doped ZnO samples.     

An alternative approach to investigate the origin of p-type conductivity in arsenic doped ZnO

P-type conductivity in MOCVD grown ZnO was obtained by directional thermal diffusion of arsenic from semi-insulating GaAs substrate. The films were single crystalline in nature and oriented along (002) direction. Ab initio calculations in the framework of density functional theory have been carried out with different chemical states of arsenic in ZnO. Present calculations suggested As_Zn–2V_Zn defect is a shallow acceptor and results in ferromagnetism in ZnO. The magnetic measurements of the samples indeed showed ferromagnetic ordering at room temperature. X-ray photoelectron spectra confirmed the presence of As_Zn and V_Zn. The core level chemical shift in binding energy of As_Zn indicated the formation of As_Zn–2V_Zn. Diffused arsenic substitutes zinc atom and creates additional zinc vacancies. The zinc vacancies, surrounding the oxygen atoms, result in unpaired O 2p electrons which in turn induce ferromagnetism in the samples.     

Influence of annealing temperature on structural, optical and magnetic properties of Zn0.95Cu0.02Cr0.03O powders

Zn_0.95Cu_0.02Cr_0.03O powders have been synthesized by the sol-gel method and sintered in argon atmosphere under different temperatures. The structural, optical and magnetic properties of the powders were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) and vibrating sample magnetometer (VSM). The XRD results demonstrated that Cr and Cu ions are incorporated into ZnO successfully when annealing temperatures were 600 and 700 °C. But when the samples were annealed at 500 °C, the crystallinity of the samples was not very good. However, when the annealing temperature was increased to 800 °C, the secondary phase of Cu and ZnCr₂O₄ appeared in the samples. The PL spectra revealed that the position of the ultraviolet (UV) emission peak of the samples showed a blue shift and the green emission peak enhanced significantly with the annealing temperature increasing from 600 to 700 °C. Magnetic measurements indicated that the room temperature ferromagnetism of Zn_0.95Cu_0.02Cr_0.03O was intrinsic in nature. In addition, the saturation magnetization (Ms) increased from 0.0078 to 0.0088 emu/g with the annealing temperature increased from 600 to 700 °C.     

Structural, magnetic and transport properties of Ni-doped ZnO films

In this work, Ni-doped ZnO (Zn_1−xNi_xO, x=0, 0.03, 0.06, 0.11) films were prepared using magnetron sputtering. X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), temperature dependence electrical resistance, Hall and magnetic measurements were utilized in order to study the properties of the Ni-doped ZnO films. XRD and XAS results indicate that all the samples have a ZnO wurtzite structure and Ni atoms incorporated into ZnO host matrix without forming any secondary phase. The Hall and electrical resistance measurements revealed that the resistivity increased by Ni doping, and all the Ni-doped ZnO films exhibited n-type semiconducting behavior. The magnetic measurements showed that for the samples with x=0.06 and 0.11 are room-temperature ferromagnetic having a saturation magnetization of 0.33 and 0.39 μ_B/Ni, respectively. The bound-magnetic-polaron mediated exchange is proposed to be the possible mechanism for the room-temperature ferromagnetism in this work.     

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.     

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     

Ferromagnetism of MnxLiyZn1−x−yO films

We had prepared Mn-doped ZnO and Li, Mn codoped-ZnO films with different concentrations using spin coating method. Crystal structure and magnetic measurements demonstrate that the impurity phases (ZnMnO₃) are not contributed to room temperature ferromagnetism and the ferromagnetism in Mn-doped ZnO film is intrinsic. Interesting, saturated magnetization decreases with Mn or Li concentration increase, showing that some antiferromagnetism exists in the samples with high Mn or Li concentration. In addition, Mn_0.05Zn_0.95O film annealed in vaccum shows larger ferromagnetism than the as-prepared sample and more oxygen vacancies induced by annealing in reducing atmosphere enhance ferromagnetism, which supports the bound magnetic polaron model on the origin of room temperature ferromagnetism.     

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.