Effects of temperature and atmosphere on the magnetic properties of Co-doped ZnO rods

Co-doped ZnO (Zn_0.95Co_0.05O) rods are fabricated by co-precipitation method at different temperatures and atmospheres. X-ray diffraction, Energy dispersive X-ray spectroscopy and Raman results indicate that the samples were crystalline with wurtzite structure and no metallic Co or other secondary phases were found. Raman results indicate that the Co-doped ZnO powders annealed at different temperatures have different oxygen vacancy concentrations. The oxygen vacancies play an important role in the magnetic origin for diluted magnetic semiconductors. At low oxygen vacancy concentration, room temperature ferromagnetism is presented in Co-doped ZnO rods, and the ferromagnetism increases with the increment of oxygen vacancy concentration. But at very high oxygen vacancy concentration, large paramagnetic or antiferromagnetic effects are observed in Co-doped ZnO rods due to the ferromagnetic-antiferromagnetic competition. In addition, the sample annealed in Ar gas has better magnetic properties than that annealed in air, which indicates that O₂ plays an important role. Therefore, the ferromagnetism is affected by the amounts of structural defects, which depend sensitively on atmosphere and annealing temperature.     

Magnetic behavior of nanocrystalline powders of Co-doped ZnO diluted magnetic semiconductors synthesized by polymerizable precursor method

This paper reports the first synthesis of nanocrystalline powders of Co-doped ZnO (i.e. Zn_0.9Co_0.1O) diluted magnetic semiconductor by a polymerizable precursor method using nitrate salts of Zn and Co and a mixed solution of citric acid and ethylene glycol as a chelating agent and reaction medium, respectively. The polymeric precursors were characterized by TG-DTA to determine the thermal decomposition and crystallization temperature which was found to be at 723 K. The precursors were calcined at different temperatures of 773, 873, 973, and 1073 K for 1 h to obtain nanocrystalline powders. The morphology and crystalline size of the calcined particles were evaluated by SEM, TEM and Scherrer's equation. The average particle sizes calcined at 773, 873, 973, and 1073 K for 1 h were, respectively, 20, 60, 80, 150 nm, obtained from TEM. The XRD and Fourier transmission infrared (FT-IR) results indicated that the synthesized Zn_0.9Co_0.1O powders have the pure 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⁺. Room temperature magnetization results revealed a ferromagnetic behavior for the Zn_0.9Co_0.1O powders. Although the specific magnetization seemed to change with the particle size but there was no clear dependency since the largest magnetization was observed in the powders calcined at 873 K (60 nm). Instead, the specific magnetization appeared to show a trend of dependency on the lattice constant c of the wurtzite unit cell.     

H-impurity induced high-temperature ferromagnetism in Co-doped ZnO

Through first-principles total-energy calculations, the effect of H-impurity on the magnetic properties of Co-doped ZnO is studied. Instead of an antibonding location, a bond-centered location of Co-O is the most stable location for isolated H in Co-doped ZnO with a strong bond with oxygen which results in the Co neighbor displaced from the host site to form a Co dimer with the other Co. At the most stable position, due to the strong hybridization between the H-impurity states and the Co 3d-t_2g minority spin states at the Fermi level in the gap, H-impurity can mediate a strong short-ranged and long-ranged ferromagnetic spin-spin interaction between neighboring Co atoms. Results based on first-principles total-energy calculations show that H-impurity is a very effective agent that can make Co-doped ZnO process high-temperature ferromagnetism.     

Influence of defects on magnetism of Co-doped ZnO

Two kinds of Zn_0.97Co_0.03O powders were prepared by precursor thermal decomposition under different conditions. One grown at low temperature has a positive Curie-Weiss temperature Θ, while the other grown at high temperature has a negative Θ. Both of them contain oxygen vacancies. There are more shallow donors in the former than those in the latter. It is proposed that coexistence of oxygen vacancies and shallow donors is necessary to induce ferromagnetic coupling between Co ions.     

Room temperature ferromagnetic pure ZnO

Pure ZnO films were prepared by pulsed laser deposition on oxidized Si substrates under different oxygen pressure and substrate temperature. Clear room temperature ferromagnetism has been observed in the ZnO film prepared under high vacuum and room temperature. The observation of anomalous Hall effect confirms the intrinsic nature of the ferromagnetism. The photoluminescence and X-ray photoelectron spectroscopy spectra show the high concentration of oxygen vacancies in the ferromagnetic ZnO film. Our results clearly demonstrate the ferromagnetic contribution of the oxygen vacancies mediated by the spin polarized electrons hopping between discrete states in pure ZnO.     

氧空位对钴掺杂氧化锌半导体磁性能的影响

从实验和理论上阐述了氧空位对Co掺杂ZnO半导体磁性能的影响.采用磁控溅射法在不同的氧分压下制备了Zn_095Co_005O薄膜,研究了氧分压对薄膜磁性能的影响.实验结果表明,高真空条件下制备的Zn_095Co_005O薄膜具有室温铁磁性,提高氧分压后制备的薄膜铁磁性逐渐消失.第一性原理计算表明,在Co掺杂ZnO体系中引入氧空位有利于降低铁磁态的能量,铁磁态的稳定性与氧空位和Co之间的距离密切相关. 关键词： Co掺杂ZnO 稀磁半导体 第一性原理计算 氧空位缺陷     

磁控溅射法制备钴掺杂氧化锌薄膜室温磁学性质

钴掺杂氧化锌是室温稀磁半导体的重要候选材料,其磁学特性和钴掺杂浓度、显微结构及光学性质密切相关。磁控溅射具有成本低、易于大面积沉积高质量薄膜等特点,是广受关注的稀磁半导体薄膜制备方法。利用磁控溅射方法制备了不同浓度的钴掺杂氧化锌薄膜,并对其显微结构、光学性质和磁学特性进行了系统分析。结果表明：当掺杂原子分数在8%以内时,钴掺杂氧化锌薄膜保持单一的铅锌矿晶体结构,钴元素完全溶解在氧化锌晶格之中;薄膜在可见光区域有很高的透射率,但在567, 615和659 nm处有明显吸收峰,这些吸收峰源于Co2+处于O2-形成的四面体晶体场中的特征d-d跃迁。磁学特性测试结果表明钴掺杂氧化锌薄膜具有室温铁磁性,且钴的掺杂浓度对薄膜的磁学特性有重要影响。结合薄膜结构、光学和电学性质分析,实验中观察到的室温铁磁性应源于钴掺杂氧化锌薄膜的本征属性,其铁磁耦合机理可由束缚磁极化子模型进行解释。     

Co掺杂ZnO薄膜的结构和磁学性能

研究了用单束脉冲激光沉积法制备的Co掺杂ZnO薄膜的结构和磁学性能。XRD表征结果表明制备的薄膜是具有沿c轴择优取向的纤锌矿点阵结构。然而,进一步的高分辨电子显微镜结果显示整个样品上的晶体取向并不完全相同。很难说明形成了单晶。结果分析表明Co占据了部分Zn的格点,并对电子结构产生了影响。室温下观察到了磁滞回线,显示掺杂Co可以实现ZnO的磁性翻转,但磁性比较小。该薄膜与我们以前用双束脉冲激光沉积法制备的Co掺杂ZnO薄膜具有相似的性能,提示我们其内部的机制可能相似。     

A simple synthesis and magnetic behavior of nanocrystalline Zn0.9Co0.1O powders by using Zn and Co acetates and polyvinyl pyrrolidone as precursors

This paper reports the synthesis of nanocrystalline powders of Co-doped ZnO (i.e. Zn_0.9Co_0.1O (ZCO)) diluted magnetic semiconductor by a simple method using acetate salts of Zn and Co, and polyvinyl pyrrolidone as precursors. The morphology and crystalline size of the synthesized powders were evaluated by scanning electron microscopy and transmission electron microscopy (TEM). The ZCO powders consist of both nanoparticles with particle sizes of ∼50–100 nm and nanorods with diameters of ∼100–200 and ∼200–500 nm in length. The X-ray diffraction and TEM results indicated that the synthesized ZCO powders had the pure wurtzite structure without any significant change in the structure affected by Co substitution. Optical absorption measurements showed absorption bands indicating the presence of Co ions in substitution of Zn ions. Room-temperature magnetization results revealed a paramagnetic behavior for the ZCO precursor (as grown sample) and a ferromagnetic behavior for the ZCO powders calcined in air at 873 K for 1 h.     

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.     

Difference in magnetic properties between Co-doped ZnO powder and thin film

This paper reports that the Zn掺钴;氧化锌粉末;氧化锌薄膜;磁性差异;晶体取向ZnO, Co-doped, crystalline orientation, magnetismProject supported by the Shanghai Nanotechnology Promotion Center (Grant No~0452nm071).2006-09-152006-11-29This paper reports that the Zn0.95Co0.05O polycrystalline powder and thin film were prepared by sol-gel technique under the similar preparation conditions. The former does not show typical ferromagnetic behaviour, while the latter exhibits obvious ferromagnetic properties at 5 K and room temperature. The UV-vis spectra and x-ray absorption spectra show that Co2＋ ions are homogeneously incorporated into ZnO lattice without forming secondary phases.The distinct difference between film and powder sample is the c-axis （002） preferential orientation indicated by the x-ray diffraction pattern and field emission scanning electron microscopy measurement, which may be the reason why Zn0.95Co0.05O film shows ferromagnetic behaviour.     

Effect of oxygen vacancy defect on the magnetic properties of Co-doped ZnO

The influence of oxygen vacancy on the magnetism of Co-doped ZnO has been investigated by the first-principles calculations.It is suggested that oxygen vacancy and its location play crucial roles on the magnetic properties of Co-doped ZnO.The exchange coupling mechanism should account for the magnetism in Co-doped ZnO with oxygen vacancy and the oxygen vacancy is likely to be close to the Co atom.The oxygen vacancy (doping electrons) might be available for carrier mediation but is localized with a certain length and can strengthen the ferromagnetic exchange interaction between Co atoms.     

Study of the magnetic and structural properties of Mn-, Fe-, and Co-doped ZnO powder

A study of the magnetic and structural properties of Zn_1−xM_xO powder (where x=0 or 0.01, and M=Mn, Fe or Co) produced by the proteic sol–gel process was undertaken. The sample crystal structure was analyzed by XRD and magnetic measurements were carried out in a SQUID magnetometer. Of the XRD analysis, all samples had hexagonal wurtzite crystal structure with P63mc space group, and no secondary phase was observed. It is observed of the M(H) measures at 2 K, that the Co- and Mn-doped ZnO displayed saturation magnetizations (M_s) of approximately 2 and 3.2 emu/g, respectively, and no remanence (M_r) was observed, indicating a superparamagnetic behavior in these samples. However, the Fe-doped sample showed a ferromagnetic behavior with M_s∼0.34 emu/g, M_r∼0.05 emu/g, and coercivity (H_c)∼1090 Oe. Already at room temperature, the M(H) measurements reveal a purely paramagnetic behavior for Mn- and Fe-doped ZnO, indicating that the Curie temperature (T_c) is below 300 K. However, a weak superparamagnetic behavior was observed in the Co-doped sample, indicating that T_c>300 K.     

Co掺杂ZnO薄膜的局域结构和电荷转移特性研究

采用磁束缚电感耦合等离子体溅射沉积法在不同的氧气分压下制备了Zn_0.95Co_0.05O和Zn_0.94Co_0.05Al_0.01O薄膜.利用X射线吸收精细结构技术对薄膜O-K,Co-K和Co-L边进行了局域结构研究,结果表明：Co²⁺取代了四配位晶体场中的Zn²⁺而未改变ZnO的六方纤锌矿结构,高真空条件下制备的薄膜 关键词： Co掺杂ZnO 稀磁半导体 X射线吸收精细结构 共振非弹性X射线散射     

Co掺杂闪锌矿ZnO的磁性和光学性质

采用自旋极化密度泛函理论方法对Co掺杂闪锌矿ZnO的能带结构、态密度、磁学和光学属性进行了研究.计算结果显示:Co掺杂闪锌矿ZnO的基态是反铁磁态,具有金属性特征;而铁磁态具有半金属性特征.铁磁耦合在费米能级附近出现了明显的自旋劈裂现象,表现出明显的不对称性和强烈的Co 3d和O 2p杂化效应.磁矩主要来源于Co 3d轨道电子以及部分近邻耦合的O 2p轨道电子,大小与Co原子的掺杂位置有关.光学性质计算结果显示,Co掺杂闪锌矿ZnO在可见光范围内都有较强的光吸收能力,吸收峰在高能区发生了红移现象.理论计算结果表明,Co掺杂闪锌矿ZnO或许是一种优异的磁光材料.     

Copper-doped AlN polycrystalline powders: A class of room-temperature ferromagnetic materials

Cu-doped AlN polycrystalline samples were synthesized by a solid-state reaction. X-ray diffraction analysis revealed the hexagonal structure of the doped samples. Photoluminescence measurements reveal the substitution of Cu for Al in the AlN lattice. Clear hysteresis loops are observed in the M-H curves for the samples at 300 K, revealing room temperature ferromagnetism of the samples. Our experimental results verify that room temperature ferromagnetism is an intrinsic property of Cu-doped AlN.     

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.     

单晶和孪晶的Zn0.96Co0.04O稀磁半导体薄膜的制备与研究

采用分子束外延技术分别在不同晶面的蓝宝石（sapphire Al₂O₃）基片上制备了沿c轴生长的Zn_0.96Co_0.04O稀磁半导体薄膜.发现在Al₂O₃（1120）晶面（a面）上薄膜是二维层状外延生长的高质量单晶薄膜,而在Al₂O₃（0001）晶面（c面）上薄膜却具有有趣的孪晶结构,部分区域相互之间有一个30°的面内转动来减少和基片之间的失配度.在孪晶薄膜中存在的这些相互旋转形成的区域界面上会引起载流子强烈的散射作用,导致载流子迁移率的下降和平均自由程的缩短.利用X射线吸收精细结构技术证明了无论单晶还是孪晶的Zn_0.96Co_0.04O薄膜中所有的Co都以+2价替代进入了ZnO的晶格,而没有形成任何杂相.而对其磁性研究发现,孪晶的薄膜样品比高质量的单晶薄膜样品具有大得多的饱和磁矩.这充分说明孪晶薄膜中的铁磁性来源与缺陷有关.我们还对铁磁性耦合机制进行了探讨. 关键词： Co掺杂ZnO 稀磁半导体 X射线吸收精细结构 单晶和孪晶薄膜     

水热法制备Co掺杂ZnO纳米棒及其光学性能

采用水热法在石英衬底上以Zn(CH3COO)2.2H2O和Co(NO3)2.6H2O水溶液为源溶液,以C6H12N4(HMT)溶液作为催化剂,在较低温度下制备了Co掺杂的ZnO纳米棒。采用X射线衍射(XRD)和扫描电子显微镜(SEM)对所生长ZnO纳米棒的晶体结构和表面形貌进行了表征,考察了Co掺杂对ZnO纳米棒微观结构和对发光性能影响的机制。结果表明:Co掺杂的ZnO纳米棒呈六方纤锌矿结构,具有沿(002)面择优生长特性,Co掺杂使ZnO纳米棒的直径变细;同时室温光致发光(PL)谱检测显示Co掺杂ZnO纳米棒具有很强的近带边紫外发光峰,而与深能级相关的缺陷发光峰则很弱。本研究采用水热法在石英衬底上于较低温度下生长出了具有较高光学质量的Co掺杂ZnO纳米棒。     

ZnCoO稀磁半导体的室温磁性

采用固相反应法，将ZnO和Co₂O₃粉末按不同的成分配比混合，制备了稀磁半导体Zn_1-xCo_xO (x=0.02,0.06,0.10)材料.并使用H₂气氛退火技术对样品进行了处理，得到了具有室温铁磁性的掺Co氧化锌稀磁半导体.利用全自动X射线衍射仪、X射线光电子能谱仪、高分辨透射电子显微镜和超导量子干涉器件磁强计对样品的结构、晶粒的尺寸、微观形貌以及磁性等进行了测量和标度. 关键词： 稀磁半导体 氧化锌 掺杂 固相反应法