氧空位对Co掺杂TiO2稀磁半导体中杂质 分布和磁交换的影响

本文使用基于密度泛函理论的第一性原理方法研究了Co掺杂TiO₂稀磁半导体中氧空位对体系能量和磁性的影响. 通过对总能量的计算发现当引入氧空位后近邻杂质体系能量高于均匀掺杂体系, 同时氧空位易在Co近邻位置富集. 进而发现氧空位的存在及其占位可以影响Co离子间的磁交换, 近邻Co离子体系下氧空位的引入使Co离子间的铁磁耦合减弱; 非近邻Co离子体系下, 底面氧空位使Co离子间呈反铁磁耦合而顶点氧空位使Co离子间呈铁磁耦合. 总之, 氧空位的存在对Co掺杂TiO₂材料的能量及磁性都有较大影响.     

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.     

二氧化铈基稀磁氧化物的第一性原理研究

基于第一性原理的计算方法研究了纯CeO_2、Co掺杂CeO_2和同时引入氧空位Vo和Co掺杂的CeO_2稀磁半导体体系.通过计算体系的能带结构和态密度,探讨了该体系磁性产生的机制.计算发现,纯CeO_2体系不具有磁性;没有氧空位Vo的Co掺杂CeO_2体系中,Co离子之间通过O原子发生超交换反铁磁耦合,体系无铁磁性;当氧空位Vo和Co离子同时存在于CeO_2体系中时,Co离子之间通过氧空位Vo发生铁磁耦合,该体系表现出铁磁性能.另外,由氧空位Vo诱导的Co离子之间的铁磁耦合不仅发生在紧邻的两个Co离子,而且可以扩展到几个原子距离的长度.计算结果证明了氧空位Vo诱导铁磁性耦合机制.本文工作将为CeO_2基稀磁半导体体系制备与磁学性质的研究提供支持.     

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。     

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     

Effect of defects on room-temperature ferromagnetism in Co and Na co-doped ZnO

The role of defects in the room temperature ferromagnetism of the Co–ZnO based diluted magnetic semiconductor (DMS) was investigated by co-doping the DMS with Na. The structure characterizations indicate that both Na and Co ions enter into the ZnO lattice without the formation of secondary phase. The oxygen vacancy of ZnCoNaO increased while the carrier concentration decreased compared with that of ZnCoO, leading to the enhancement of the ferromagnetic property in the ZnCoNaO. The observed ferromagnetism introduced by Na ions is attributed to the exchange interaction via the electron trapped oxygen vacancies coupled with the magnetic Co ions.     

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.     

Raman scattering investigations on Co-doped ZnO epitaxial films: Local vibration modes and defect associated ferromagnetism

Raman scattering spectroscopy has been performed on high quality Co-doped ZnO epitaxial films, which were grown on Al₂O₃ (0001) by oxygen-plasma assisted molecular beam epitaxy. Raman measurements revealed two local vibration modes (LVMs) at 723 and 699 cm⁻¹ due to the substitution of Co²⁺ in wurtzite ZnO lattice. The LVM at 723 cm⁻¹ is found to be an elemental sensitive vibration mode for Co substitution. The LVM at 699 cm⁻¹ can be attributed to enrichment of Co²⁺ bound with oxygen vacancy, the cobalt–oxygen vacancy–cobalt complexes, in Zn_1−xCo_xO films associated with ferromagnetism. The intensity of LVM at 699 cm⁻¹, as well as saturated magnetization, enhanced after the vacuum annealing and depressed after oxygen annealing.     

First-principle study of magnetism in Co-doped SnO2

The effects of Co dopants and oxygen vacancies on the electronic structure and magnetic properties of the Co-doped SnO₂ are studied by the first-principle calculations in full-potential linearized augmented plane wave formalism within generalized gradient approximations. The Co atoms favorably substitute on neighboring sites of the metal sublattice. Without oxygen vacancies, the Co atoms are at low spin state independent of concentration and distribution of Co atoms, and only the magnetic coupling between nearest-neighbor Co atoms is ferromagnetic through direct exchange and super-exchange interaction. Oxygen vacancies tend to locate near the Co atoms. Their presence strongly increases the local magnetic moments of Co atoms, which depend sensitively on the concentration and distribution of Co atoms. Moreover, oxygen vacancies can induce the long-range ferromagnetic coupling between well-separated Co atoms through the spin-split impurity band exchange mechanism. Thus the room temperature ferromagnetism observed experimentally in the Co-doped SnO₂ may originate from the combination of short-range direct exchange and super-exchange interaction and the long-range spin-split impurity band exchange model.     

Epitaxial Properties of Co-Doped ZnO Thin Films Grown by Plasma Assisted Molecular Beam Epitaxy

High quality Co-doped ZnO thin films are grown on single crystalline Al2O3（0001） and ZnO（0001） substrates by oxygen plasma assisted molecular beam epitaxy at a relatively lower substrate temperature of 450℃. The epitaxial conditions are examined with in-situ reflection high energy electron diffraction （RHEED） and ex-situ high resolution x-ray diffraction （HRXRD）. The epitaxial thin films are single crystal at film thickness smaller than 500nm and nominal concentration of Co dopant up to 20%. It is indicated that the Co cation is incorporated into the ZnO matrix as Co^2＋ substituting Zn^2＋ ions. Atomic force microscopy shows smooth surfaces with rms roughness of 1.9 nm. Room-temperature magnetization measurements reveal that the Co-doped ZnO thin films are ferromagnetic with Curie temperatures Tc above room temperature.     

Effects of oxygen vacancy location on the electronic structure and spin density of Co-doped rutile TiO₂ dilute magnetic semiconductors

According to density functional theory (DFT) using the plane wave base and pseudo-potential, we investigate the effects of the specific location of oxygen vacancy (VO) in a (Ti,Co)O 6 distorted octahedron on the spin density and magnetic properties of Co-doped rutile TiO2 dilute magnetic semiconductors. Our calculations suggest that the V O location has a significant influence on the magnetic moment of individual Co cations. In the case where two Co atoms are separated far away from each other, when the V O is located at the equatorial site of a Co-contained octahedron, the ground state of the two Co cations is d6 (t3 2g ↑, t 3 2g ↓) without any magnetic moment. However, if the V O is located at the apical site, these two Co sites have different ground states and magnetic moments. The spin densities are also observed to be modified by the exchange coupling between the Co cations and the location of V O . Some positive spin polarization is induced around the adjacent O ions.     

Optical study of D–D neutron irradiation-induced defects in Co- and Cu-doped ZnO wafers

Room-temperature photoluminescence and optical transmittance spectroscopy of Co-doped (1×10¹⁴,5×10¹⁶, and 1×10¹⁷ cm^-2) and Cu-doped (5×10¹⁶ cm^-2) ZnO wafers irradiated by D-D neutrons (fluence of 2.9×10¹⁰ cm^-2) have been investigated. After irradiation, the Co or Cu metal and oxide clusters in doped ZnO wafers are dissolved, and the würtzite structure of ZnO substrate for each sample remains unchanged and keeps in high c-axis preferential orientation. The degree of irradiation-induced crystal disorder reflected from absorption band tail parameter (E₀) is far greater for doped ZnO than undoped one. Under the same doping concentration, the Cu-doped ZnO wafer has much higher irradiation-induced disorder than the Co-doped one. Photoluminescence measurements indicate that the introduction rate of both zinc vacancy and zinc interstitial is much higher for the doped ZnO wafer with high doping level than the undoped one. In addition, both crystal lattice distortion and defect complexes are suggested to be formed in doped ZnO wafers. Consequently, the Co- or Cu-doped ZnO wafer (especially with high doping level) exhibits very low radiation hardness compared with the undoped one, and the Cu-doped ZnO wafer is much less radiation-hard than the Co-doped one.     

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。     

Structure and room-temperature ferromagnetism of Co-doped ZnO DMS films

Co-doped ZnO diluted magnetic semiconductor films were prepared on Si(100) substrates by magnetron sputtering system and the Co content varies from 0.01 to 0.15. The X-ray diffraction results showed ZnO of the wurtzite structure. The ferromagnetism was observed at room temperature. The X-ray near-edge absorption spectroscopy revealed that Co substitutes for Zn²⁺ ions in the valence of +2 state in the Co-doped ZnO films.     

退火氛围对掺杂ZnO薄膜磁性的影响

采用直流磁控反应共溅法制备了非磁性元素Al和磁性元素Co掺杂的ZnO薄膜, 样品原位真空退火后再空气退火处理. 利用X射线衍射仪(XRD) 和物理性能测量仪(PPMS) 对薄膜的结构和磁性进行了表征. XRD和PPMS结果表明, 不同的退火氛围对掺杂薄膜的结构和磁性有着很大的影响. 真空退火的Al掺杂ZnO薄膜没有观察到铁磁性, 而空气退火的样品却显示出明显的室温铁磁性, 铁磁性的来源与空气退火后导致Al和ZnO基体间电荷转移增强有关. 而对于Co掺杂ZnO薄膜, 真空退火后再空气退火, 室温铁磁性明显减弱. 其磁性变化与Co离子和ZnO基体间电荷转移导致磁性增强和间隙Co原子被氧化导致磁性减弱有关.     

Great influence of the oxygen vacancies on the ferromagnetism in the Co-doped ZnO films

The ZCO (Co-doped ZnO) films were prepared by using submolecule-doping technique, where the magnetic sputtering of Co and ZnO were alternatively performed onto silicon substrates. The prepared ZCO films were then annealed at different temperatures, and the dependence of the ferromagnetism on annealing temperature was studied. It is found that the saturation magnetization of our samples decreases with the increase of annealing temperature. This behavior is possibly due to the decrease of oxygen vacancies with the increase of the annealing temperature.     

Monte Carlo simulations of donor band exchange in (Zn,Co)O

We present results of a Monte Carlo study over the ferromagnetism of Co-doped ZnO. The magnetic interaction has the form of the donor impurity band exchange model, where the Co magnetic moments are exchange coupled to band electrons. These are assumed to occupy large hydrogenic orbitals and originate from shallow intrinsic ZnO defects. A number of parameters of this model remain uncertain and here we investigate the dependence of the Curie temperature on the strength of the magnetic coupling. We find an unusual concave upward shape in the magnetization curves consistent with other Monte Carlo studies for dilute systems and we predict high temperature ferromagnetism for sufficiently strong coupling.     

Studies on structural and magnetic properties of Co-doped pyramidal ZnO nanorods synthesized by solution growth technique

Large-area arrays of highly oriented Co-doped ZnO nanorods with pyramidal hexagonal structure are grown on silica substrates by wet chemical decomposition of zinc–amino complex in an aqueous medium. In case of undoped ZnO with an equi-molar ratio of Zn²⁺/hexamethylenetetramine (HMT), highly crystalline nanorods were obtained, whereas for Co-doped ZnO, good quality nanorods were formed at a higher Zn²⁺/HMT molar ratio of 4:1. Scanning electron microscope (SEM) studies show the growth of hexagonal-shaped nanorods in a direction nearly perpendicular to the substrate surface with a tip size of ～50 nm and aspect ratio around 10. The XRD studies show the formation of hexagonal phase pure ZnO with c-axis preferred orientation. The doping of Co ions in ZnO nanorods was confirmed by observation of absorption bands at 658, 617 and 566 nm in the UV–vis spectra of the samples. The optical studies also suggest Co ions to be present both in +2 and +3 oxidation states. From the photoluminescence studies, a defect-related emission is observed in an undoped sample of ZnO at 567 nm. This emission is significantly quenched in Co-doped ZnO samples. Further, the Co-doped nanorods have been found to show ferromagnetic behavior at room temperature from vibrating sample magnetometer (VSM) studies.     

Highly sensitive breath sensor based on sonochemically synthesized cobalt-doped zinc oxide spherical beads

In this study, we introduce cobalt (Co)-doped zinc oxide (ZnO) spherical beads (SBs), synthesized using a sonochemical process, and their utilization for an acetone sensor that can be applied to an exhalation diagnostic device. The sonochemically synthezied Co-doped ZnO SBs were polycrystalline phases with sizes of several hundred nanometers formed by the aggregation of ZnO nanocrystals. As the Co doping concentration increased, the amount of substitutionally doped Co²⁺ in the ZnO nanocrystals increased, and we observed that the fraction of Co³⁺ in the Co-doped ZnO SBs increased while the fraction of oxygen vacancies decreased. At an optimal Co-doping concentration of 2 wt%, the sensor operating temperature decreased from 300 to 250 °C, response to 1 ppm acetone improved from 3.3 to 7.9, and minimum acetone detection concentration was measured at 43 ppb (response, 1.75). These enhancements are attributed to the catalytic role of Co³⁺ in acetone oxidation. Finally, a sensor fabricated using 2 wt% Co-doped ZnO SBs was installed in a commercially available exhalation diagnostic device to successfully measure the concentration of acetone in 1 ml of exhaled air from a healthy adult, returning a value of 0.44 ppm.     

Effects of oxygen vacancies on the room-temperature ferromagnetism of Co-doped polycrystalline CeO2

Pure and Co-doped single-phase CeO₂ crystals were synthesized by a solid-state reaction method. Samples of different oxygen vacancy concentration were studied, including (1) as-sintered crystals, (2) powders ground from the same crystal, and (3) a cold-pressed pellet from the ground powder that was unannealed and annealed at 800 °C. By analyzing the magnetic behaviors, surface/volume ratio and O vacancy concentration, the effects of oxygen vacancies on the room-temperature ferromagnetism (RT-FM) of Co-doped CeO₂ were systematically investigated. The results confirm that the RT-FM observed in Co-doped CeO₂ has a direct relationship with the oxygen vacancy concentration, and support the oxygen vacancy mediated FM mechanism.