Magnetic characterization of ZnO doped with vanadium

The magnetic properties of vanadium doped ZnO nanorods formed by different growth methods were examined. The samples under investigation were either grown by metallorganic vapour-phase epitaxy (MOVPE) with in situ incorporation of the V atoms or by aqueous chemical growth (ACG) in combination with an ion-implantation process. The V concentration for all samples was less than 2 at.%.Field-cooled SQUID measurements only reveal a weak ferromagnetic signal still in a very sensitive measuring range. However, the MFM micrographs obtained at room temperature show a clear magnetic contrast and complex structures, the images are in good agreement with the phase images expected for vertically aligned magnetic dipoles. This is a strong indication for a ferromagnetic behaviour at room temperature.     

Co掺杂的ZnO稀磁半导体块体的退火热处理研究

采用固相反应法制备了Zn_0.95Co_0.05O块体样品,并对其进行了不同方式的退火处理.实验表明在锌气氛中500℃退火的样品表现出铁磁性,而在真空中退火的样品却没有磁性,进一步,在锌气氛中1100℃退火的样品虽然表现出铁磁性,但其铁磁性来源于样品在锌气氛中1100℃退火过程中产生了1%左右的Co金属团簇杂质相.另外,在低温时所有样品都表现出较大的正磁电阻,认为正磁电阻效应是由于s-d电子交换相互作用引起的自旋劈裂造成的,而高场时出现的负磁电阻效应则可能归因于磁场 关键词： Co掺杂ZnO X射线衍射 铁磁性 磁电阻     

Correlation between the structural and optical properties of Co doped ZnO thin films prepared at different film thickness

Cobalt doped zinc oxide (ZnO:Co) thin films were deposited on glass substrates by ultrasonic spray technique decomposition of Zinc acetate dihydrate and cobalt acetate tetrahydrate in an ethanol solution with film thickness. All films are polycrystalline with a hexagonal wurtzite-type structure with a preferential orientation according to the direction (0 0 2), with the maximum crystallite size was found of 59.42 nm at 569 nm. The average transmittance of all films is about 65–95% measured by UV–vis analyzer. The band gap energy increased from 3.08 to 3.32 eV with increasing the film thickness from 192 to 569 nm. The increase of the electrical conductivity with increases in the film thickness to maximum value of 9.27 (Ω cm)⁻¹ can be explained by the increase in carrier concentration and displacement of the electrons of the films. The correlation between the band gap and crystal structure suggests that the band gap energy of Co doped ZnO is influenced by the crystallite size and the mean strain.     

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     

Comparison of ferromagnetism in n- and p-type magnetic semiconductor thin films of ZnCoO

Both n- and p-type diluted magnetic semiconductor ZnCoO are made by magnetron co-sputtering with, respectively, dopants of Al and dual dopants of Al and N. The two sputtering targets are compound ZnCoO with 5% weight of Co and pure metal Al. Sputtering gases for n- and p-type films are pure Ar and N₂, respectively. These films are magnetic at room temperature and possess free electron- and hole-concentration of 5.34×10²⁰ and 5.27×10¹³ cm⁻³. Only the n-type film exhibits anomalous Hall-effect signals. Magnetic properties of these two types of films are compared and discussed based on measurements of microstructure and magneto-transport properties.     

Surface‐enhanced Raman scattering of molecules adsorbed on Co‐doped ZnO nanoparticles

Transition‐metal‐doped semiconductor nanoparticles (NPs) have been well studied for their optical and catalytic properties but seldom studied by surface‐enhanced Raman scattering (SERS). In this paper, transition‐metal‐doped semiconductor NPs are investigated for their SERS property. Four groups of Co‐doped (0.5, 1, 3, and 5%) ZnO (Co ZnO) NPs and pure ZnO NPs were synthesized and studied. When 4‐mercaptobenzoic acid was used as probing molecule, significant SERS signals were obtained on all the five samples. Moreover, it is very interesting to observe a relationship between the Co‐doping concentration and enhancement of the SERS signals. SERS intensities first increase with doping concentration (up to 1%), and then decrease with further increase in doping concentration (up to 5%). Charge transfer (CT) is considered to be the main contribution to this phenomenon. Different CT ratios from substrates to molecules seem to induce different intensities of the SERS signals. In our experiments, the crystalline defects of Co ZnO NPs caused by the Co dopant affect the CT ratios. A possible mechanism of CT from the valance band of Co ZnO NPs to the lower unoccupied molecular orbital of the molecules via energy of the surface states is suggested. X‐ray photoelectron spectra, UV vis spectra, and Raman spectra were used to characterize the structure and defects in Co ZnO NPs. Copyright © 2011 John Wiley & Sons, Ltd.     

Magnetism in Cr doped ZnO: Density-functional theory studies

We investigate the magnetism in wurtzite and zinc-blende Zn_0.875Cr_0.125O (wz- and zb-Zn_0.875Cr_0.125O) using the density-functional theory calculations. We demonstrate that the delta-doping structures are more energetically favorable than the homogeneous-doping ones. The delta-doping structure of zb-Zn_0.875Cr_0.125O shows robust ground state ferromagnetism (FM) with ferromagnetic stabilization energy of 575 meV/Cr-Cr pair, while delta-doping structure of wz-Zn_0.875Cr_0.125O shows weak ground state anti-FM. We discuss the magnetic coupling in Zn_1−xCr_xO, and the origin of FM in zb-Zn_1−xCr_xO using a crystal field model. Finally, we anticipate the potential spintronics applications of the zb-Zn_1−xCr_xO.     

铁磁性锰氧化物掺杂的ZnO压敏电阻性能研究

利用通常的电子陶瓷制备工艺制备了铁磁性锰氧化物La_07Sr_03MnO₃掺杂的ZnO陶瓷. 晶界处存在La_07Sr_03MnO₃(LSMO)和LaMnO₃(LMO)两种杂相. 样品中绝缘相LMO的含量显著影响着样品的电学性能. 掺杂后的样品仍具有一定的铁磁性. 在样品上施加磁场后,样品电阻值增加,表现为正磁电阻性质. 正磁电阻的出现,是由于磁场的存在 关键词： ZnO 压敏电阻 锰氧化物 正磁电阻     

Structural and optical properties of cobalt doped ZnO nanocrystals

Zn_1−xCo_xO nanocrystals with nominal Co doping concentrations of x = 0–0.1 were synthesized through a simple solution route followed by a calcining process. The doping effects on the structural, morphological and optical properties were investigated by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman, absorption and luminescence spectroscopy. The results indicated that a small amount of Co ions were incorporated into ZnO lattice structure, whereas the secondary phase of Co₃O₄ was segregated and precipitated at high Co doping concentrations, the solid solubility of Co ions in ZnO nanocrystals could be lower than 0.05. The spectra related to transitions within the tetrahedral Co²⁺ ions in the ZnO host crystal were observed in absorption and luminescence spectra.     

Structural, optical and electronic properties of P doped p-type ZnO thin film

P doped ZnO films were grown on quartz by radio frequency-magnetron sputtering method using a ZnO target mixed with 1.5 at% P₂O₅ in the atmosphere of Ar and O₂ mixing gas. The as-grown P doped ZnO film showed n-type conductivity, which was converted to p-type after 800 °C annealing in Ar gas. The P doped ZnO has a resistivity of 20.5 Ω cm (p∼2.0×10¹⁷ cm⁻³) and a Hall mobility of 2.1 cm² V⁻¹ s⁻¹. XRD measurement indicated that both the as-grown and the annealed P doped ZnO films had a preferred (0 0 2) orientation. XPS study agreed with the model that the P_Zn-2V_Zn acceptor complex was responsible for the p-type conductivity as found in the annealed P-doped ZnO. Temperature-dependent photoluminescence (PL) spectrum showed that the dominant band is located at 3.312 eV, which was attributed to the free electronic radiative transition to neutral acceptor level (FA) in ZnO. The P_Zn-2V_Zn acceptor complex level was estimated to be at E_V=122 meV.     

脉冲激光沉积法(PLD)生长Co掺杂ZnO薄膜及其磁学性能

采用脉冲激光沉积(PLD)法在单晶Si(100)及石英衬底上生长Co掺杂ZnO薄膜,并且比较了不同生长条件下薄膜的性能。实验观察到了700℃、0.02Pa氧压气氛下生长的Co掺杂ZnO薄膜显示室温磁滞回线。采用XRD、SEM等手段对Co掺杂ZnO薄膜的晶体结构及微观形貌进行了分析,得到的ZnO薄膜具有高度的c轴择优取向,结构比较致密,表面平整度较高,并且没有发现Co的相关分相,初步表明Co有效地掺入了ZnO的晶格当中。霍尔测试表明Co掺杂ZnO薄膜样品保持了半导体的电学性能,电阻率为0.04Ω·cm左右,载流子浓度约为1018/cm3,迁移率都在18.7cm2/V·s以上。实验结果表明材料保持了ZnO半导体的性能,并具有室温铁磁性。     

Room-temperature anomalous Hall effect and magnetroresistance in (Ga, Co)-codoped ZnO diluted magnetic semiconductor films

This paper reports that the(Ga,Co)-codoped ZnO thin films have been grown by inductively coupled plasma enhanced physical vapour deposition.Room-temperature ferromagnetism is observed for the as-grown thin films.The x-ray absorption fine structure characterization reveals that Co 2+ and Ga 3+ ions substitute for Zn 2+ ions in the ZnO lattice and exclude the possibility of extrinsic ferromagnetism origin.The ferromagnetic(Ga,Co)-codoped ZnO thin films exhibit carrier concentration dependent anomalous Hall effect and positive magnetoresistance at room temperature.The mechanism of anomalous Hall effect and magneto-transport in ferromagnetic ZnO-based diluted magnetic semiconductors is discussed.     

Ferromagnetism and microstructure in Fe-implanted ZnO

Fe ions were implanted into ZnO single crystals with multiple energies between 50 and 380 keV up to a total fluence of 12.5×10¹⁷ cm⁻². The crystal quality of Fe⁺ implanted ZnO was investigated by X-ray diffraction 2θ scans and ω-rocking curve measurements. The appearance of Fe related diffraction peaks after C annealing of the implanted sample indicates possibly formation of Fe nanoparticles. Superconducting quantum interference device measurements revealed ferromagnetic behavior below 250 K for both the as-implanted and post-annealed ZnO. Photoluminescence and Raman scattering as well as X-ray rocking curve measurements all indicate introduction of structural defects after Fe implantation. Some of the defects act as nonradiative recombination centers, and suppress the visible and ultraviolet (UV) emission in ZnO. These defects also break the Raman selection rule, and lead to the activation of some silent phonon modes. Annealing of the implanted sample at C causes partial recovery of the defects, however, the X-ray diffraction results of the anneal ZnO show even an improvement of the crystal quality compared with the un-implanted one. This could be attributed to the recovery of the grown-in defects in ZnO.     

Structural, optical and magnetic properties of Cr doped ZnO microrods prepared by spray pyrolysis method

A series of Cr-doped ZnO micro-rod arrays were fabricated by a spray pyrolysis method. X-ray diffraction patterns of the samples showed that the undoped and Cr-doped ZnO microrods exhibit hexagonal crystal structure. Surface morphology analysis of the samples has revealed that pure ZnO sample has a hexagonal microrod morphology. From X-ray photoelectron spectroscopy studies, the Cr 2p3/2 binding energy is found to be 577.3 eV indicating that the electron binding energy of the Cr in ZnO is almost the same as the binding energy of Cr³⁺ states in Cr₂O₃. The optical band gap E_g decreases slightly from 3.26 to 3.15 eV with the increase of actual Cr molar fraction from x = 0.00 to 0.046 in ZnO. Photoluminescence studies at 10 K show that the incorporation of chromium leads to a relative increase of deep level band intensity. It was also observed that Cr doped samples clearly showed ferromagnetic behavior; however, 2.5 at.% Cr doped ZnO showed remnant magnetization higher than that of 1.1 at.% and 4.6 at.% Cr doped samples, while 4.6 at.% Cr doped ZnO samples had a coercive field higher than the other dopings.     

Ga/N高共掺浓度对ZnO导电性能和红移影响的第一性原理研究

采用密度泛函理论框架下的第一性原理平面波超软赝势方法, 建立了未掺杂ZnO单胞和两种不同浓度的Ga/N高共掺ZnO超胞模型, 分别进行了几何结构优化、总态密度分布和能带分布的计算. 研究表明, ZnO高共掺Ga/N的条件下, Ga/N高共掺浓度越大, 导电性能越弱, 并且高掺杂后高能区红移效应显著, 计算得到的结果与实验结果的变化趋势一致. 关键词： Ga/N高共掺ZnO 电导率 红移 第一性原理     

Crystalline structure and morphological properties of undoped and Sn doped ZnO thin films

Undoped and tin (Sn) doped ZnO thin films have been prepared by spray pyrolysis method. Effect of Sn dopant on the crystalline structure and morphological properties of ZnO thin films has been investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) method. XRD patterns confirm that the films have polycrystalline nature. While undoped ZnO film has (101) as the preferred orientation, Sn doped ZnO thin films have (002) as the preferred orientation. Grain sizes, lattice parameters and texture coefficient values of the films were determined. Microstructure was analyzed by SEM and the influence of the doping concentration in the microstructure of the films is investigated.     

First-principles study of ferromagnetism in Ti-doped ZnO with oxygen vacancy

Using first-principles density functional calculations, we have investigated the electronic structures of Ti-doped ZnO (Ti is in 4+ oxidation state) with and without oxygen vacancy. The ferromagnetic property is identified in the presence of oxygen vacancy despite Ti being nonmagnetic in its natural phase. The ferromagnetism originates from the charge transferring from donor derived-defect band to unoccupied Ti-3d states and the hybridization between Ti-3d and O-2p band near the Fermi level. On increasing the oxygen vacancy concentration, a transition from a long-ranged magnetic order to a short-ranged interaction is found and the oxygen vacancies prefer to distribute non-uniformly in Ti-doped ZnO.     

Photoconductivity in metal-semiconductor-metal planar structures with ZnO:Ga and ZnO:Li films

Influence of UV radiation on photoelectric properties of ZnO:Ga and ZnO:Li films prepared by the electron-beam evaporation method was investigated. The photoconductivity was measured, using metal-semiconductor-metal planar structures where metallic aluminum was used as ohmic electrodes. The kinetics of rise and decay of the photoconductivity in these structures was studied. The change of photoconductivity under the action of UV radiation is considered as a result of the photoexcitation-relaxation into the conduction band and photochemical processes of absorption-desorption of oxygen at the film surface. The influence of a MgF₂ protective layer deposited on ZnO:Ga and ZnO:Li films was studied. Measurements of the spatial distribution of the potential between the anode and cathode for determination of the homogeneity of conductivity in the investigated planar structures were performed by the moving probe method.     

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.     

Study of magnetic properties of ZnO nanoparticles codoped with Co and Cu

Here, we report on systematic studies of the magnetic properties of Co and Cu codoped ZnO nanoparticles prepared by sol–gel technique. The effect of hydrogenation and shape on the magnetic properties of Zn_0.93Co_0.05Cu_0.02O nanoparticles is presented. The Zn_0.93Co_0.05Cu_0.02O nanoparticles and well-aligned Zn_0.93Co_0.05Cu_0.02O nanorod array display ferromagnetic behavior at room temperature. Our results demonstrate the influence of shape and hydrogenation on the ferromagnetic properties of Zn_0.93Co_0.05Cu_0.02O nanoparticles at room temperature.