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.     

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.     

Mn掺杂ZnO稀磁半导体材料的制备和磁性研究

采用共沉淀方法制备了名义组分为Zn_1-xMn_xO(x=0.001,0.005,0.007,0.01)的Mn掺杂的ZnO基稀磁半导体材料,并研究了在大气气氛下经过不同温度退火后样品的结构和磁性的变化.结果表明：样品在600℃的大气条件下退火后, 仍为单一的六方纤锌矿结构的ZnO颗粒材料;当样品经过800℃退火后,Mn掺杂量为0.007,0.01的样品中除了ZnO纤锌矿结构外还观察到ZnMnO₃第二相的存在.磁性测量表明,大气条件下600℃退火后的样品,呈现出室温铁磁性;而800℃退火后的样品,其室温铁磁性显著减弱,并表现为明显的顺磁性.结合对样品的光致发光谱的分析,认为合成样品的室温铁磁性是由于Mn离子对ZnO中的Zn离子的替代形成的. 关键词： ZnO 掺杂 稀磁半导体 铁磁性     

Microstructural and magnetic properties of Ax:Zn1-xO (A=Mn,Gd and Mn/Gd) nanocrystals

We report the microstructural and magnetic properties of transition (3d) and rare earth (4f) metal substituted into the A_x:Zn_1?xO (A=Mn, Gd and Mn/Gd) nanocrystal samples synthesized by solgel method. The structural properties and morphology of all samples have been analysed using X-ray diffraction (XRD) method and scanning electron microscopy. The impurity phase in the XRD patterns for all samples is not seen, except (Mn/Gd):ZnO sample where a very weak secondary phase of Gd₂O₃ is observed. Due to the large mismatch of the ionic radii between Mn²⁺ and Gd³⁺ ions, the strain inside the matrix increases, unlike the crystallite size decreases with the substitution of Mn and Gd into ZnO system. A couple of additional vibration modes due to the dopant have been observed in Raman spectrum. The magnetic properties have been studied by vibrating sample magnetometer. The magnetic hysteresis shows that Mn:ZnO and Gd:ZnO have soft ferromagnetic (FM) behaviour, whereas (Mn/Gd):ZnO has strong FM behaviour at room temperature (RT). The enhancement of ferromagnetism (FM) in (Mn/Gd):ZnO sample might be related to short-range FM coupling between Mn²⁺ and Gd³⁺ ions via defects potential and/or strain-induced FM coupling due to the expansion lattice by doping. The experimental results indicate that RTFM can be achieved by co-substitution of 3d and 4f metals in ZnO which can be used in spintronics applications.     

No room temperature ferromagnetism in Mn over-doped Zn1−xMnxO (x>0.02)

Mn-doped ZnO samples having composition Zn_1−xMn_xO (x=0.02, 0.04 and 0.05) were synthesized by solid state reaction technique with varying concentration of Mn from 0.02 to 0.05. Evidence of room temperature ferromagnetism was observed only in the composition Zn_0.98Mn_0.02O sintered at 500 °C. Our XRD pattern confirms the presence of Mn₃O₄ impurity phase in all the Zn_1−xMn_xO samples with the exception of Zn_0.98Mn_0.02O. We emphasize that the appearance of Mn₃O₄ phase in the system forbids the exchange type of interaction between the Mn ions and suppresses the ferromagnetism in all the Mn over-doped Zn_1−xMn_xO (x>0.02) system. SEM microstructure study also supports the interruption of exchange type of interaction inside the system with the increase in Mn concentration in the sample. Interestingly, for this particular composition, Zn_0.98Mn_0.02O sintered at 500 °C, glassy ferromagnetism type of transition is observed at low temperature. This type of transition is attributed to the formation of the oxides of Mn clusters at low temperature.     

On the structural analysis and magnetic behavior of heavily doped Zn1−xMnxO nanopowders synthesized by wet chemistry method

Nanocrystalline Zn_1−xMn_xO(x=0−0.1) powders are prepared by polymeric precursor method and their structural and magnetic properties carefully studied. X-ray diffraction studies and Raman spectroscopy reveal that Mn²⁺ ions have substituted the Zn²⁺ ion without changing the würtzite structure of pristine ZnO up to Mn concentrations x≤0.05. The presence of a secondary phase, related to the solubility of Mn in ZnO is evident for higher Mn-doping concentrations. The negative value obtained for the Curie–Weiss temperature indicates that the interactions between the Mn ions are predominantly antiferromagnetic. Thus, no bulk ferromagnetism is evident in any of the studied samples.     

Structural, compositional and magnetic characterization of bulk V2O5 doped ZnO system

This paper investigates the structural, compositional and magnetic properties of vanadium doped ZnO bulk samples prepared by solid state reaction technique. The Rietveld refinement analysis for XRD results of samples showed small change in lattice parameters for 3 and 5% vanadium doped ZnO samples indicating the substitution of Zn²⁺ ions by vanadium ions in ZnO lattice. Raman spectroscopy reveals the change in ZnO modes positions due to vanadium doping. The appearance of E₁ and E₂ modes showed that the wurtzite structure of ZnO is still maintained after doping of vanadium oxide. XPS analysis confirms the presence of the different elements and oxidation states of vanadium ions. M-H curves obtained from VSM showed weak ferromagnetism in the samples. The observation of ferromagnetic behavior indicates the formation of ZnVO phase with V²⁺ ion substitution in the ZnO lattice. XPS scans of the etched bulk samples confirmed the 2+ oxidation state of vanadium ions in our samples explaining the origin of ferromagnetism.     

Enhancement of initial permeability due to Mn substitution in polycrystalline Ni0.50−xMnxZn0.50Fe2O4

The structural and magnetic properties of Mn substituted Ni_0.50−xMn_xZn_0.50Fe₂O₄ (where x=0.00, 0.10 and 0.20) sintered at various temperatures have been investigated thoroughly. The lattice parameter, average grain size and initial permeability increase with Mn substitution. Both bulk density and initial permeability increase with increasing sintering temperature from 1250 to 1300 °C and above 1300 °C they decrease. The Ni_0.30Mn_0.20Zn_0.50Fe₂O₄ sintered at 1300 °C shows the highest relative quality factor and highest initial permeability among the studied samples. The initial permeability strongly depends on average grain size and intragranular porosity. From the magnetization as a function of applied magnetic field, M(H), it is clear that at room temperature all samples are in ferrimagnetic state. The number of Bohr magneton, n(μ_B), and Neel temperature, T_N, decrease with increasing Mn substitution. It is found that Mn substitution in Ni_0.50−xMn_xZn_0.50Fe₂O₄ (where x=0.20) decreases the Neel temperature by 25% but increases the initial permeability by 76%. Possible explanation for the observed characteristics of microstructure, initial permeability, DC magnetization and Neel temperature of the studied samples are discussed.     

退火对Mn和N共掺杂的Zn0.88Mn0.12O:N薄膜特性的影响

以NH₃为掺N源,采用电子束反应蒸发技术生长了Mn和N共掺杂的Zn_1-xMn_xO:N薄膜,生长温度为300℃,然后在O₂气氛中400℃退火0.5 h.X射线衍射测量表明,Zn_0.88Mn_0.12O(Mn掺杂)薄膜或Zn_0.88Mn_0.12O:N(Mn和N共掺杂)薄膜仍具有单一晶相纤锌矿结构,未检测到杂质相 关键词： ZnO薄膜 Mn和N共掺杂 电学特性 磁特性     

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.     

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     

Optical properties of oxide magnetic ZnO, Zn0.95Mn0.05O and Cu2O nanopowders

ZnO, Zn_0.95Mn_0.05O and Cu₂O nanocrystals are synthesized. Excitonic lines in absorption spectra of these materials are detected. In photoluminescence and photoluminescence excitation spectra of Zn_0.95Mn_0.05O the dangling bond hybrid (DBH) state is found. It has splitted out from the top of the valence band due to the hybridization between d-states of the Mn impurity and the p-states of oxygen.     

Ho3+掺杂对ZnO薄膜的微观结构和磁性的影响

研究Ho³⁺掺杂对氧化锌半导体材料的微结构和磁学性质影响. 利用热蒸发技术制备了一系列沉积在Si(100)衬底的Zn_1-xHo_xO(x=0.0、0.04、0.05）薄膜. X射线光谱、表面形貌以及磁性的实验结果表明,Ho³⁺掺杂对ZnO薄膜材料的性能影响很大. X射线衍射图显示峰位出现高角度转变并且趋向于(101)取向,在ZnO晶格显示Ho³⁺置换. 扫描电子显微镜和能谱仪对薄膜的表面形貌以及化学     

Defects related room temperature ferromagnetism in p-type (Mn, Li) co-doped ZnO films deposited by reactive magnetron sputtering

We report on the defects related room temperature ferromagnetic characteristics of Zn_0.95-xMn_xLi_0.05O (x = 0.01, 0.03, 0.05 and 0.08) thin films grown on glass substrates using reactive magnetron sputtering. By increasing the Mn content, the films exhibited increases in the c-axis lattice constant, fundamental band gap energy, coercive field and remanent magnetization. Comparison of the structural and magnetic properties of the as-deposited and annealed films indicates that the hole carriers, together with defects concentrations, play an important role in the ferromagnetic origin of Mn and Li co-doped ZnO thin films. The ferromagnetism in films can be described by bound magnetic polaron models with respect to defect-bound carriers.     

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.     

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.     

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.     

Optical properties of Mg0.05Zn0.95O/SiO2 nanocomposite films prepared by sol–gel technique

Mg_0.05Zn_0.95O/SiO₂ nanocomposite films in the molar ratio 25:75 consisting of Mg_0.05Zn_0.95O nanoparticles embedded in a dielectric matrix were prepared by sol–gel technique (spin coating). Optical transmittance, Raman effect and photoluminescence measurements of the composites indicated effective capping of the Mg_0.05Zn_0.95O nanoparticles (radii 1. 61–1.68 nm) in the host showing practically no variation of particle size with the post deposition annealing treatments. The blue shift of the band gap (4.29–4.23 eV) from that of bulk Mg_0.05Zn_0.95O indicated strong carrier confinement for samples annealed at T ≤ 873 K. Highly intense UV emission ( ∼ 4.14 eV) compared to that of defect related emission (2.59 eV) at room temperature was obtained by incorporating 5% Mg in ZnO.     

Synthesis and magnetic properties of Mn doped ZnO nanowires

Mn doped ZnO nanowires have been synthesized using a simple autocombustion method. The as-synthesized Mn doped ZnO nanowires were characterized by X-ray diffraction and transmission electron microscopy. An increase in the hexagonal lattice parameters of ZnO is observed on increasing the Mn concentration. Optical absorption studies show an increment in the band gap with increasing Mn content, and also give evidence for the presence of Mn²⁺ ions in tetrahedral sites. All Zn_1−xMn_xO (0≤x≤0.25) samples are paramagnetic at room temperature. However, a large increase in the magnetization is observed below 50 K. This behavior, along with the negative value of the Weiss constant obtained from the linear fit to the susceptibility data below room temperature, indicate ferrimagnetic behavior. The origin of ferrimagnetism is likely to be either the intrinsic characteristics of the Mn doped samples, or due to some spinel-type impurity phases present in the samples that could not be detected.     

Preparation, structure and ferromagnetic properties of the nanocrystalline Ti1-xMnxO2 thin films grown by radio frequency magnetron co-sputtering

This paper reported that the Mn-doped TiO2 films were prepared by radio frequency （RF） magnetron cosputtering. X-ray diffraction measurements indicate that the samples are easy to form the futile structure, and the sizes of the crystal grains grow big and big as the Mn concentration increases. X-ray photoemlssion spectroscopy measurements and high resolution transmission electron microscope photographs confirm that the manganese ions have been effectively doped into the TiO2 crystal when the Mn concentration is lower than 21%. The magnetic property measurements show that the Ti1-xMnxO2 （x = 0.21） films are ferromagnetic at room temperature, and the saturation magnetization, coercivity, and saturation field are 16.0 emu/cm^3, 167.5 × 80 A/m and 3740 × 80 A/m at room temperature, respectively. The room-temperature ferromagnetism of the films can be attributed to the new futile Ti1-xMnxO2 structure formed by the substitution of Mn^4＋ for Ti^4＋ into the TiO2 crystal .lattice, and could be explained by O vacancy （Vo）-enhanced ferromagnetism model.