The crystalline structure,conductivity and optical properties of Co-doped ZnO thin films

Transparent conductive Co-doped ZnO thin films were deposited by ultrasonic spray technique. Conditions of preparation have been optimized to get good quality. A set of cobalt (Co)-doped ZnO (between 0 and 3 wt%) thin films were grown on glass substrate at 350 °C. The thin films were annealed at 500 °C for improvement of the physical properties. Nanocrystalline films with hexagonal wurtzite structure and a strong (0 0 2) preferred orientation were obtained. The maximum value of grain size G = 63.99 nm is attained with undoped ZnO film. The optical transmissions spectra showed that both the undoped and doped ZnO films have transparency within the visible wavelength region. The band gap energy decreased after doping from 3.367 to 3.319 eV when Co concentration increased from 0 to 2 wt% with slight increase of electrical conductivity of the films from 7.71 to 8.33 (Ω cm)⁻¹. The best estimated structure, optical and electrical results are achieved in Co-doped ZnO film with 2 wt%.     

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.     

Giant temperature coefficient of resistance in Co-doped ZnO thin films

A novel high-performance thermistor material based on Co-doped ZnO thin films is presented. The films were deposited by the pulsed laser deposition technique on Si (111) single-crystal substrates. The structural and electronic transport properties were correlated as a function of parameters such as substrate temperature and Co-doped content for Zn_1?x Co _x O (x=0.005,0.05,0.10 and 0.15) to prepare these films. The Zn_1?x Co _x O films were deposited at various substrate temperatures between 20 and 280 °C. A value of 20 %/K for the negative temperature coefficient of resistance (TCR) with a wide range near room temperature was obtained. It was found that both TCR vs. temperature behavior and TCR value were strongly affected by cobalt doping level and substrate temperature. In addition, a maximal TCR value of over 20 %?K^?1 having a resistivity value of 3.6 Ω?cm was observed in a Zn_0.9Co_0.1O film near 260 °C, which was deposited at 120 °C and shown to be amorphous by X-ray diffraction. The result proved that the optimal Co concentration could help us to achieve giant TCR in Co-doped ZnO films. Meanwhile, the resistivities of the films ranged from 0.4 to 270 Ω?cm. A Co-doped ZnO/Si film is a strong candidate of thermometric materials for non-cooling and high-performance bolometric applications.     

Study on field-emission characteristics of electrodeposited Co-doped ZnO thin films

Co-doped ZnO films were fabricated using electrodeposition method on the ITO substrates. The structure of the Co-doped ZnO films was analyzed by X-ray diffraction and scanning electron microscope. The field-emission characteristics of the prepared Co-doped ZnO films were examined using diode structure in a vacuum chamber. The examined results indicate that the Co-doping cause the turn-on field increasing by increasing the concentration of the Co-dopant, probably due to the band gap changing, which could attributed to the sp-d exchange interactions between the band electrons and the localized d electrons of the Co²⁺ ions substituting Zn ions in the films.     

Reactivity of ZnO: Impact of polarity and nanostructure

The effects of atomic hydrogen and nitrogen produced by remote r.f. H₂ and N₂ plasmas on the structure, morphology, and optical and electrical properties of Zn- and O-polar ZnO crystals and on ZnO thin films grown by metal–organic chemical vapour deposition (MOCVD) have been studied. It is found that the Zn-polar form is highly reactive with atomic hydrogen, while the O-polar form is almost inert. This difference in reactivity allows one to discern the O-polarity of the (0001) oriented ZnO thin films grown by MOCVD. A decrease of the resistivity of the grain-like MOCVD films is found upon atomic hydrogen treatment. Conversely, atomic nitrogen treatment results in p-type doping of the ZnO film and in an improvement of the surface morphology and microstructure.     

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.     

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。     

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.     

Photosensitivity of nanocrystalline ZnO films grown by PLD

We have studied the properties of ZnO thin films grown by laser ablation of ZnO targets on (0 0 0 1) sapphire (Al₂O₃), under substrate temperatures around 400 °C. The films were characterized by different methods including X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and atomic force microscopy (AFM). XPS analysis revealed that the films are oxygen deficient, and XRD analysis with θ-2θ scans and rocking curves indicate that the ZnO thin films are highly c-axis oriented. All the films are ultraviolet (UV) sensitive. Sensitivity is maximum for the films deposited at lower temperature. The films deposited at higher temperatures show crystallite sizes of typically 500 nm, a high dark current and minimum photoresponse. In all films we observe persistent photoconductivity decay. More densely packed crystallites and a faster decay in photocurrent is observed for films deposited at lower temperature.     

Effect of substrate temperature on the structural and optical properties of ZnO and Al-doped ZnO thin films prepared by dc magnetron sputtering

ZnO and Al-doped ZnO(ZAO) thin films have been prepared on glass substrates by direct current (dc) magnetron sputtering from 99.99% pure Zn metallic and ZnO:3 wt%Al₂O₃ ceramic targets, the effects of substrate temperature on the crystallization behavior and optical properties of the films have been studied. It shows that the surface morphologies of ZAO films exhibit difference from that of ZnO films, while their preferential crystalline growth orientation revealed by X-ray diffraction remains always the (0 0 2). The optical transmittance and photoluminescence (PL) spectra of both ZnO and ZAO films are obviously influenced by the substrate temperature. All films exhibit a transmittance higher than 86% in the visible region, while the optical transmittance of ZAO films is slightly smaller than that of ZnO films. More significantly, Al-doping leads to a larger optical band gap (E_g) of the films. It is found from the PL measurement that near-band-edge (NBE) emission and deep-level (DL) emission are observed in pure ZnO thin films. However, when Al was doped into thin films, the DL emission of the thin films is depressed. As the substrate temperature increases, the peak of NBE emission has a blueshift to region of higher photon energy, which shows a trend similar to the E_g in optical transmittance measurement.     

Characterization of ZnO:Ga and ZnO:N films prepared by PLD

The thin films of zinc oxide have been produced by the pulse laser deposition method at various levels of gallium and nitrogen doping. To obtain the n-type films we used gallium doping with concentration of gallium from zero up to 5 at %. The dependence of photoluminescence of the epitaxial ZnO:Ga films on the concentration of gallium doping has been studied. An optimum range of the n-type ZnO films doping with gallium has been determined to obtain highly effective films from the viewpoint of realizing p-n transitions. This range, on the one hand, defines the maximal PL amplitude and, on the other hand, specifies the minimal specific resistance that corresponds to an interval of 0.125–1.000 at % Ga. To produce the p-type ZnO:(Ga, N) films, the ZnO targets with the content of GaN from zero up to 2 at % were used. N₂O was used as a buffer gas. A difference is observed in the positions of the peaks of the emission lines of the photoluminescence spectra for the ZnO films, doped with gallium (Ga) and co-doped with gallium and nitrogen (N).     

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.     

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     

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.     

Structural and electrical properties of single crystalline and bi-crystalline ZnO thin films grown by molecular beam epitaxy

C-oriented ZnO epitaxial thin films are grown separately on the a-plane and c-plane sapphire substrates by using a molecular-beam epitaxy technique. In contrast to single crystalline ZnO films grown on a-plane sapphire, the films grown on c-plane sapphire are found to be bi-crystalline; some domains have a 30o rotation to reduce the large mismatch between the film and the substrate. The presence of these rotation domains in the bi-crystalline ZnO thin film causes much more carrier scatterings at the boundaries, leading to much lower mobility and smaller mean free path of the mobile carriers than those of the single crystalline one. In addition, the complex impedance spectra are also studied to identify relaxation mechanisms due to the domains and/or domain boundaries in both the single crystalline and bi-crystalline ZnO thin films.     

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.     

Investigation of electrical and optical properties of ZnO thin films grown with O<Subscript>2</Subscript>/O<Subscript>3</Subscript> gas mixture

The electrical and optical properties of ZnO thin films grown with an O₂/O₃ gas mixture are compared with samples grown with pure oxygen gas. The ZnO films were grown on sapphire(0001) by pulsed laser deposition. The residual background carrier concentration is reduced by using an O₂/O₃ gas mixture as compared to pure molecular oxygen. In particular, a one order of magnitude reduction in residual background carrier density (6.15×10¹⁶ cm^-3) is achieved by using an O₂/O₃ gas mixture. The lower donor defect density is attributed to the generation of acceptor defects compensating for the residual donor defects. Photoluminescence results show that the deep level emission increased and the band edge emission decreased for the ZnO films grown with ozone, as compared to the samples grown with pure oxygen gas. PACS 73.61.Ga; 78.55Et; 81.05 Dz; 81.15.Fg     

Growth of InN thin films on ZnO substrate by plasma-assisted molecular beam epitaxy

We have studied the microstructure property of InN epitaxial films grown on ZnO substrate by plasma-assisted molecular beam epitaxy. We found that the In₂O₃ compound was produced on ZnO substrate and many pits were formed on the InN films when InN was directly grown on ZnO substrate with the N/In flux ratio less than 40. We demonstrated that the quality of InN film was significantly improved when the In₂O₃ layer was used as a buffer to prevent the reaction between In and the ZnO substrate.     

LP-MOCVD异质外延ZnO薄膜中的应力及对缺陷的影响

利用低压金属有机化学气相淀积(LP-MOCVD)在Si基片上外延生长ZnO薄膜，制备了两类样品 ：一类是在Si上直接外延ZnO，另一类是在Si上通过SiC过渡层来外延ZnO.根据两类样品的拉 曼光谱、x射线衍射、原子力显微图和光致发光的结果，表明ZnO外延薄膜中的张应力对薄膜 的结晶状况有着重要的影响，使用SiC过渡层能够有效缓解ZnO薄膜中的张应力，减小缺陷浓 度，提高ZnO外延层的质量；然后根据缺陷的形成机制进一步提出，对于ZnO/Si，其中较大 的张应力导致了高浓度的非辐射复合缺陷的形成，使得样品的紫外和绿峰的发射强度均大大 降低；对于ZnO/SiC/Si，其中较小的张应力导致ZnO薄膜中主要形成氧替位缺陷O_{Zn，从而使发光中的绿峰增强. 关键词： ZnO薄膜 应力 缺陷 拉曼光谱}     

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.