Room temperature magnetic properties of ZnO nanostructured films

The ZnO nanorod array films have been epitaxially deposited on indium tin oxide (ITO) glass along 〈0001〉 direction. It is found that the film is grown in a two-step process including nanoparticle film nucleation and oriented rod growth. The as-prepared ZnO film shows a dominant diamagnetic signal and a weak ferromagnetic signal at room temperature. The room temperature ferromagnetism deteriorated by annealing in air or N₂. The photoluminescent spectra revealed that the intensity of ZnO defect band decreases after annealing. Thus, the decreased ferromagnetism is likely to have resulted from the decrease of oxygen vacancies and defects in the as-prepared film. Moreover, ZnO deposited at various times showed that defects located at or near the interface between the substrate and the film play a major role in ferromagnetism. It suggests that ferromagnetism can be tuned by changing the defects in ZnO.     

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.     

Influence of reducing anneal on the ferromagnetism in single crystalline Co-doped ZnO thin films

This paper reports that the high-quality Co-doped ZnO single crystalline films have been grown on $a$-plane sapphire substrates by using molecular-beam epitaxy. The as-grown films show high resistivity and non-ferromagnetism at room temperature, while they become good conductive and ferromagnetic after annealing in the reducing atmosphere either in the presence or absence of Zn vapour. The x-ray absorption studies indicate that all Co ions in these samples actually substituted into the ZnO lattice without formatting any detectable secondary phase. Compared with weak ferromagnetism (0.16~$\mu _{\rm B}$/Co$^{2 + })$ in the Zn6110M, 7550P, 7280E, 7870Dhttp://cpb.iphy.ac.cn/CN/10.1088/1674-1056/19/5/056101https://cpb.iphy.ac.cn/CN/article/downloadArticleFile.do?attachType=PDF&id=111756Co-doped ZnO, diluted magnetic semiconductors, x-ray absorption fine structure, single crystalline thin filmsProject partially supported by National Science Foundation of China (Grant No.~10804017), National Science Foundation of Jiangsu Province of China (Grant No.~BK2007118), Research Fund for the Doctoral Program of Higher Education of China (Grant No.~20070286037), Cyanine-Project Foundation of Jiangsu Province of China (Grant No.~1107020060), Foundation for Climax Talents Plan in Six-Big Fields of Jiangsu Province of China (Grant No.~1107020070) and New Century Excellent Talents in University (NCET-05-0452).This paper reports that the high-quality Co-doped ZnO single crystalline films have been grown on $a$-plane sapphire substrates by using molecular-beam epitaxy. The as-grown films show high resistivity and non-ferromagnetism at room temperature, while they become good conductive and ferromagnetic after annealing in the reducing atmosphere either in the presence or absence of Zn vapour. The x-ray absorption studies indicate that all Co ions in these samples actually substituted into the ZnO lattice without formatting any detectable secondary phase. Compared with weak ferromagnetism (0.16~$\mu _{\rm B}$/Co$^{2 + })$ in the Zn$_{0.95}$Co$_{0.05}$O single crystalline film with reducing annealing in the absence of Zn vapour, the films annealed in the reducing atmosphere with Zn vapour are found to have much stronger ferromagnetism (0.65~$\mu _{\rm B}$/Co$^{2 + })$ at room temperature. This experimental studies clearly indicate that Zn interstitials are more effective than oxygen vacancies to activate the high-temperature ferromagnetism in Co-doped ZnO films, and the corresponding ferromagnetic mechanism is discussed.Co-doped;ZnO;diluted;magnetic;semiconductors;x-ray;absorption;fine;structure;single;crystalline;thin;filmsThis paper reports that the high-quality Co-doped ZnO single crystalline films have been grown on a-plane sapphire substrates by using molecular-beam epitaxy.The as-grown films show high resistivity and non-ferromagnetism at room temperature,while they become more conductive and ferromagnetic after annealing in the reducing atmosphere either in the presence or absence of Zn vapour.The x-ray absorption studies indicate that all Co ions in these samples actually substituted into the ZnO lattice without formatting any detectable secondary phase.Compared with weak ferromagnetism(0.16 μB/Co2+) in the Zn0.95Co0.05O single crystalline film with reducing annealing in the absence of Zn vapour,the films annealed in the reducing atmosphere with Zn vapour are found to have much stronger ferromagnetism(0.65 μB/Co2+) at room temperature.This experimental studies clearly indicate that Zn interstitials are more effective than oxygen vacancies to activate the high-temperature ferromagnetism in Co-doped ZnO films,and the corresponding ferromagnetic mechanism is discussed.     

Ferromagnetism in carbon-doped In2O3 thin films

Carbon-doped In₂O₃ thin films exhibiting ferromagnetism at room temperature were prepared on Si (100) substrates by the rf-magnetron co-sputtering technique. The effects of carbon concentration as well as oxygen atmosphere on the ferromagnetic property of the thin films were investigated. The saturated magnetizations of thin films varied from 1.23 to 4.86 emu/cm³ with different carbon concentrations. The ferromagnetic signal was found stronger in samples with higher oxygen vacancy concentrations. In addition, deposition temperature and different types of substrates also affect the ferromagnetic properties of carbon-doped In₂O₃ thin films. This may be related to the oxygen vacancies in the thin film system. The experiment suggests that oxygen vacancies play an important role in introducing ferromagnetism in thin films.     

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.     

NH3等离子体后处理Co掺杂ZnO的薄膜结构及磁学性能

通过电化学沉积方法成功生长了Co掺杂ZnO的薄膜,但并没有实现室温下的铁磁性.通过NH3等离子体的后处理,导致有一部分N原子进入了ZnO晶格替代了一部分O格位,从而在ZnO中产生空穴.在空穴间接交换作用下,ZnCoO薄膜中产生了被束缚的磁极子,产生了室温下的铁磁性.     

Vacancy-induced room-temperature ferromagnetism in ZnO rods synthesized by Ni-doped solution and hydrothermal method

Pure ZnO and Ni-doped ZnO rods have been prepared by hydrothermal method at a temperature of 120 °C. The morphological, structural, magnetic and optical properties of the as-prepared rods were investigated by means of field emission scanning electron microscopy, X-ray diffraction, vibrating sample magnetometer and photoluminescence. All the samples are radial-grown hexagon rods with diameter from 470 to 720 nm and length of 4-6 μm. X-ray diffraction shows that the rods have single crystalline wurtzite structure without other impurity phases. The pure ZnO rods and Ni-doped ZnO rods have ferromagnetism at room temperature, and the special saturation magnetization deduces with the increasing diameter of rods. These results reveal that the saturation magnetization of the ZnO rods depends on the surface-to-volume ratio of rods rather than the Ni doping concentrations. The photoluminescence spectra studies show the same diameter dependences of oxygen vacancies as that of magnetization, which demonstrates that oxygen vacancies at surface of rods play an important role in introducing ferromagnetism. The annealing in rich oxygen and reducing atmospheres confirms this argument further.     

Observation of magnetic domains in undoped ZnO grains at room temperature

The present study reports the room temperature ferromagnetism in undoped ZnO thin films grown by PVD method. The 500 nm film with small (90 nm) ZnO grains possess isolated magnetic domains with coercivity of 520 Oe. However, long range magnetic ordering with smaller coercivity of 230 Oe is observed for 1000 nm film. The long range ordering is caused by the reduction in domain wall pinning effect due to the presence of bigger (270 nm) ZnO grains. PL measurements show that these grains are semiconducting in nature. Results presented here suggest that oxygen vacancies at the surface may be responsible for the observed ferromagnetism.     

Defects in room-temperature ferromagnetic Cu-doped ZnO films probed by x-ray absorption spectroscopy

We report a comprehensive study of the defects in room-temperature ferromagnetic (RTFM) Cu-doped ZnO thin films using x-ray absorption spectroscopy. The films are doped with 2 at.% Cu, and are prepared by reactive magnetron sputtering (RMS) and pulsed laser deposition (PLD), respectively. The results reveal unambiguously that atomic point defects exist in these RTFM thin films. The valence states of the Cu ions in both films are 2(+). In the film prepared by PLD, the oxygen vacancies (V(O)) form around both Zn ions and Cu ions in the hexagonal wurtzite structure. Upon annealing of the film in O(2), the V(O) population reduces and so does the RTFM. In the film prepared by RMS, the V(O)s around Cu ions are not detected, and the V(O) population around Zn ions is also smaller than in the PLD-prepared film. However, zinc vacancies (V(Zn)) are evidenced. Given the low doping level of spin-carrying Cu ions, these results provide strong support for defect-mediated ferromagnetism in Cu-doped ZnO thin films.     

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.     

Multiferroic ZnO obtained by substituting oxygen with nitrogen

N-doped ZnO films were prepared in nitrogen plasma by pulsed laser deposition.Clear room temperature ferro-magnetism has been observed in the film prepared at a substrate temperature of 500 C.The structural characterizations of X-ray diffraction,Raman,and X-ray photoelectron spectroscopy confirm the substitution of O by N in ZnO,which has been considered to be the origin of the observed ferromagnetism.Furthermore,ferroelectricity has been observed at room temperature by piezoelectric force microscopy,indicating the potential multiferroic applications.     

Room temperature ferromagnetism in Tb doped ZnO nanocrystalline films

Nanocrystalline Tb doped ZnO films have been prepared by ion-beam sputtering technology. Magnetic property shows that the films are ferromagnetic and the Curie Temperature (T_c) is over room temperature. Structure property investigation indicates that no secondary phase is found in all the films, which suggests that the ferromagnetism is caused by the incorporation of Tb into ZnO lattice. The saturation magnetization of the films are about 0.38 μb/Tb. Electrical property investigation proves that the carriers of the films are strongly localized, which suggests that the ferromagnetism in the film may be caused by the defects in the films.     

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.     

Ferromagnetism induced by oxygen-vacancy complex in (Mn,in) codoped ZnO

Mn doped Zinc oxide (ZnO) thin films were prepared by metal organic chemical vapor deposition (MOCVD) technique. Structural characterizations by X-ray diffraction technique (XRD) and photoluminescence (PL) indicate the crystal quality of ZnO films. PL and Raman show a large fraction of oxygen vacancies (V_O²⁺) are generated by vacuum annealed the film. The enhancement of ferromagnetism in post-annealed (Mn, In) codoped ZnO could result from V_O²⁺ incorporation. The effect of V_O²⁺ on the magnetic properties of (Mn, In) codoped ZnO has been studied by first-principles calculations. It is found that only In donor cannot induce ferromagnetism (FM) in Mn-doped ZnO. Besides, the presence of V_O²⁺ makes the Mn empty 3d-t_2g minority state broadened, and a t_2g-V_O²⁺ hybrid level at the conduction band minimum forms. The presence of V_O²⁺ can lead to strong ferromagnetic coupling with the nearest neighboring Mn cation by BMP model based on defects reveal that the ferromagnetic exchange is mediated by the donor impurity state, which mainly consists of Mn 3d electrons trapped in oxygen vacancies.     

Zn-catalyzed growth processes and ferromagnetism of Mn-doped ZnO nanorods on Si substrate

Well-aligned ZnO nanorods and Mn-doped ZnO nanorods are fabricated on Si (1 0 0) substrate according to the contribution of Zn metal catalysts. Scanning electron microscopy and high-resolution transmission electron microscopy images indicate that the influence of Zn catalyst on the properties of ZnO can be excluded and the growth of ZnO nanorods follows a vapor-liquid-solid and self-catalyzed model. Mn-doped ZnO nanorods show a typical room temperature ferromagnetic characteristic with a saturation magnetization (M_S) of 0.273μ_B/Mn. Cathodoluminescence suggests that the ferromagnetism of Mn-doped ZnO nanorods originates from the Mn²⁺-Mn²⁺ ferromagnetic coupling mediated by oxygen vacancies. This technique provides exciting prospect for the integration of next generation Si-technology-based ZnO spintronic devices.     

Room temperature ferromagnetism in Cu-doped ZnO synthesized from CuO and ZnO nanoparticles

AC susceptibility and ferromagnetic resonance (FMR) measurements indicate that ZnO doped with Cu by a simple sintering process starting from nanoparticles of ZnO and CuO is ferromagnetic above room temperature. FMR measurements above room temperature indicate the ordering temperature to be above 520 K. The observation supports the recent theoretical calculations of Huang et al. which predict ferromagnetism in copper-doped ZnO.     

Fe掺杂ZnO块材样品的结构、形貌及磁性

采用共沉淀法在O2、Air、Ar等不同气氛下制备了名义组分为Zn0.98Fe0.02O的系列块材样品,实验上研究了烧结气氛对样品结构、形貌及磁性质的影响.XRD和SEM结果均显示,在Air和O2气氛中烧结的样品中缺陷较少,具有更好的结晶性.磁测量结果表明,在Air和O2氛中烧结的样品则未表现出明显的磁性特征,而在Ar气氛中烧结的样品在室温下呈现出弱铁磁性行为.样品中的弱铁磁性可能来源于与氧空位有关的束缚磁极化子间的铁磁耦合作用.该样品的HC和MR在低温下表现出反常变化,可能与磁畴壁移动有关.     

高温氧气热处理对TiO_2晶体结构和铁磁性的影响

金红石TiO_2晶体先在真空中进行退火处理,随后在1173 K的氧气中进行不同时间(2 h、5 h、8 h)的热处理.理论上,通过Doppler程序计算了晶体中存在单空位、双空位和间隙O原子时的正电子湮没寿命.实验上,利用正电子湮没寿命谱仪、符合多普勒能谱仪和超导量子干涉仪分别表征了氧气退火后晶体内部的缺陷结构和常温铁磁性.分析结果得出:真空退火晶体的常温铁磁性主要与O空位的存在相关联;而经过氧气退火后,虽然极大地减少了氧空位,但晶体中却产生了大量的Ti双空位,这使得晶体的常温铁磁性有所增加.     

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.     

Defect-mediated ferromagnetism in ZnO:Mn nanorods

In this work, the structural, chemical and magnetic properties of ZnO:Mn nanorods were investigated. Firstly, well-aligned ZnO nanorods with their long axis parallel to the crystalline c-axis were successfully grown by the vapor phase transport technique on Si substrates coated with a ZnO buffer layer. Mn metal was then diffused into these nanorods at different temperatures in vacuum. From SEM results, ZnO:Mn nanorods were observed to have diameters of ～100 nm and lengths of 4 μm. XPS analysis showed that the Mn dopant substituted into the ZnO matrix with a valence state of +2. Magnetic measurements performed at room temperature revealed that undoped ZnO nanorods exhibit ferromagnetic behavior which may be related to oxygen vacancy defect-mediated d ⁰ ferromagnetism. ZnO:Mn samples were seen to show an excess room temperature ferromagnetism that is attributed to the presence of oxygen vacancy defects forming bound magnetic polarons involving Mn.