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     

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.     

分子束外延PbTe单晶薄膜的反常拉曼光谱研究

采用分子束外延(MBE)方法在BaF₂(111)衬底上生长了高质量的PbTe单晶薄膜， 拉曼光谱测量观察到了表面氧化物的振动模、布里渊区中心(q≈0)纵光学(LO)声子振动模以 及声子-等离子激元耦合模振动.随着显微拉曼光谱仪激光光斑聚焦深度的改变，各拉曼散射 峰的峰位、积分强度、半高宽等都表现出不同的变化趋势. 随着激光光斑聚焦位置从样品表 面上方3μm处变化到表面下方3μm处，PbTe外延薄膜的LO声子频率从119cm^-1移 动到124cm^{-1关键词： PbTe外延薄膜 拉曼散射 纵光学声子}     

Structural characterization of supported nanocrystalline ZnO thin films prepared by dip-coating

Nanocrystalline ZnO thin films prepared by the sol-gel dip-coating technique were characterized by grazing incidence X-ray diffraction (GIXD), atomic force microscopy (AFM), X-ray reflectivity (XR) and grazing incidence small-angle X-ray scattering (GISAXS). The structures of several thin films subjected to (i) isochronous annealing at 350, 450 and 550 °C, and (ii) isothermal annealing at 450 °C during different time periods, were characterized. The studied thin films are composed of ZnO nanocrystals as revealed by analysing several GIXD patterns, from which their average sizes were determined. Thin film thickness and roughness were determined from quantitative analyses of AFM images and XR patterns. The analysis of XR patterns also yielded the average density of the studied films. Our GISAXS study indicates that the studied ZnO thin films contain nanopores with an ellipsoidal shape, and flattened along the direction normal to the substrate surface. The thin film annealed at the highest temperature, T = 550 °C, exhibits higher density and lower thickness and nanoporosity volume fraction, than those annealed at 350 and 450 °C. These results indicate that thermal annealing at the highest temperature (550 °C) induces a noticeable compaction effect on the structure of the studied thin films.     

Observation of regular defects formed on the surface of PbTe thin films grown by molecular beam epitaxy

Regular shape defects on the surface of PbTe thin films grown by molecular beam epitaxy (MBE) were studied by scanning electron microscope (SEM). Two types of regular shape defects were observed on Te-rich PbTe films grown at substrate temperature T ≥ 235 °C with a beam flux ratio of Te to PbTe (R_f) to be 0.5 and at 280 °C with a R_f ≥ 0.4, which include cuboids and triangular pyramids. The formation mechanism of the observed regular shape defects is interpreted as following: They are the outcome of fast growth rate along {1 0 0} crystal planes that have the lowest surface energy and the enclosure of the {1 0 0} crystal planes. The formation of the regular shape defects in the growth of PbTe needs appropriate substrate temperature and Te-rich ambience. However, when R_f is decreased low enough to make the films slightly Pb-rich, triangular pits that originate from the insufficient glide of the threading dislocations along the main 〈1 1 0〉 {1 0 0} glide system of PbTe in Cottrell atmosphere, will be the main feature on the film surface.     

Annealing effects on electrical and optical properties of ZnO thin films synthesized by the electrochemical method

Microstructural and electrical properties of potentiostatically electrodeposited ZnO thin films from an aqueous bath were investigated after annealing at different temperatures in Ar and 5% H₂/Ar atmospheres. It is confirmed that the bandgap energy of ZnO thin films decreased with annealing from 3.42 to 3.27-3.29 eV by calculating the wavelength of the absorption region. The annealing at temperatures as low as 200 °C decreased the sheet resistance of ZnO thin films because of the extinction of Zn(OH)₂ in the atmosphere. In addition, the sheet resistance of ZnO thin films decreased by annealing in a 5% H₂ atmosphere, which caused an increase of carrier concentration by hydrogen reduction.     

Electrical and optical properties of ZnO films grown by molecular beam epitaxy

Zinc oxide (ZnO) films have been grown on sapphire by molecular beam epitaxy (MBE), and it is found that the grain size of the ZnO films increased with increasing the growth temperature. Photoluminescence (PL) study shows that the intensity ratio of near-band-edge emission to deep-level-related emission (NBE/DL) of the ZnO is significantly enhanced with increasing the growth temperature, and the dependence of the carrier mobility on the growth temperature shows very similar trend, which implies that there is a community factor that determines the optical and electrical properties of ZnO, and this factor is suggested to be the grain boundary. The results obtained in this paper reveal that by reducing the grain boundaries, ZnO films with high optical and electrical properties may be acquired.     

溶胶凝胶旋转涂敷技术制备ZnO:In薄膜的结构特性

采用溶胶凝胶法,结合旋转涂敷技术在石英衬底上制备了210—240nm厚度的ZnO∶In薄膜.使用掠角入射X射线衍射(GI_XRD)、常规X射线衍射、傅里叶变换红外光谱、原子力显微镜、光致发光谱以及不同入射角GI_XRD谱(α=1,2,3和5°)等手段,对不同掺杂浓度的ZnO∶In薄膜进行了结构分析.发现ZnO∶In薄膜内部是由大尺寸(002)晶向的无应力ZnO晶粒堆积而成,而薄膜表面主要是小尺寸的(002)和(103)晶粒,并且适量的In掺杂能有效改善ZnO薄膜内部的晶体结构特性. 关键词： ZnO∶In薄膜 晶体结构 掠角入射X射线衍射 溶胶凝胶法     

Nucleation control for ZnO nanorods grown by catalyst-driven molecular beam epitaxy

We report a study of the annealing temperature and time on Ag catalyst size and density for subsequent growth of ZnO nanorods by catalyst-driven molecular beam epitaxy (MBE). Two different substrates (SiO₂ and SiN_X) for the Ag deposition were used and the thickness of the Ag held constant at 25 Å. Annealing between 600 and 800 °C produced Ag cluster sizes in the range 8-30 nm diameter on SiO₂ and 10-65 nm on SiN_X with a cluster density from 100 to 2500 mm⁻² for SiO₂ and 30 to 1900 mm⁻² for SiN_X. ZnO nanorods grown on these clusters show single-crystal, wurtzite-phase nature and strong band-edge photoluminescence at 380 nm. The nanorods can also be grown selectively on lithographically-patterned dielectric stripes with Ag clusters formed on top by e-beam evaporation and annealing.     

Influence of polarity inversion on the electrical properties of Ga‐doped ZnO thin films

This study investigates how polarity inversion influences the relationship between the electrical properties of heavily Ga‐doped ZnO (GZO) films deposited by RF magnetron sputtering and their thickness. The electrical properties observed in very thin films are correlated with a change of polarity from O‐polar to Zn‐polar face upon increasing the film thickness based on results of valence band spectra measured by X‐ray photoelectron spectroscopy. It is found that the electrical properties of very thin GZO films deposited on Zn‐polar ZnO templates are significantly improved compared to those deposited on O‐polar face. A low resistivity of 2.62 × 10^–4 Ω cm, high Hall mobility of 26.9 cm²/V s, and high carrier concentration of 8.87 × 10²⁰ cm^–3 being achieved with 30 nm‐thick GZO films using Zn‐polar ZnO templates on a glass substrate. In contrast, the resistivity of 30 nm‐thick GZO films on bare glass that shows more likely O‐polar is very poor about 1.44 × 10^–3 Ω cm with mobility and carrier concentration are only 11.9 cm²/V s and 3.64 × 10²⁰ cm^–3, respectively. It is therefore proposed that polarity inversion plays an important role in determining the electrical properties of extremely thin GZO films. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Fe3O4/MgO(100)薄膜的激光分子束外延与磁电学性能

 采用激光分子束外延方法,以烧结α-Fe₂O₃/为靶材,在MgO（100）基底上制备了Fe₃O₄薄膜。通过反射高能电子衍射原位观察了薄膜生长前后的表面结构,结果表明所生长的Fe₃O₄薄膜表面平整。经显微激光拉曼光谱和X光电子能谱分析证实所得薄膜表面成分为纯相Fe₃O₄。磁电学性能采用多功能物性系统测量,结果表明：当温度降至100 K附近时,薄膜电阻率有较大增加,Verwey相转变的范围变宽而且不明显,说明反向晶粒边界的存在;在7 160 kA·m^-1的磁场下,室温磁电阻达到-6.9%,在80和150 K温度下磁电阻分别达到-10.5%和-16.1%;薄膜的室温饱和磁化强度约为260 kA·m^-1,其矫顽磁场约为202 kA·m^-1。     

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.     

The transparence comparison of Ga- and Al-doped ZnO thin films

The Ga-doped ZnO (GZO) and Al-doped ZnO (AZO) thin films were grown on quartz glass substrates by pulsed laser deposition under different oxygen partial pressures (PO₂). The transparent performances of films versus properties of structure and conductivity were discussed. With the increase of PO₂, the transmittance of both GZO films and AZO films increased to maximum and then decreased which were in according with the change of crystallization quality. The transmittance of GZO films was higher than that of AZO films, which were not dominated by the impurity ions induced by doping. AFM images and surface roughness mean square coefficients showed that the surfaces of GZO films were smoother than that of AZO films, which were due to the dopant Ga acting as the surfactant and smoothed the GZO films surface.     

Electrical and optical properties of Sb-doped ZnO thin films synthesized by sol–gel method

Sb-doped ZnO thin films with different values of Sb content （from 0 to 1.1 at.%） are deposited by the sol-gel dip- coating method under different sol concentrations. The effects of Sb-doping content, sol concentration, and annealing ambient on the structural, optical, and electrical properties of ZnO films are investigated. The results of the X-ray diffraction and ultraviolet-visible spectroscopy （UV-VIS） spectrophotometer indicate that each of all the films retains the wurtzite ZnO structure and possesses a preferred orientation along the c axis, with high transmittance （〉 90%） in the visible range. The Hall effect measurements show that the vacuum annealed thin films synthesized in the sol concentration of 0.75 mol/L each have an adjustable n-type electrical conductivity by varying Sb-doping density, and the photoluminescence （PL） spectra revealed that the defect emission （around 450 nm） is predominant. However, the thin films prepared by the sol with a concentration of 0.25 mol/L, despite their poor conductivity, have priority in ultraviolet emission, and the PL peak position shows first a blue-shift and then a red-shift with the increase of the Sb doping content.     

ZnO：Sb薄膜的光致发光及拉曼特性研究

利用射频磁控溅射法（MS．RF）在玻璃基片上制备了不同掺杂浓度的ZnO：Sb薄膜．借助X射线衍射仪（XRD）、透射光谱、光致发光谱（PL）和拉曼散射光谱（Raman）等手段研究了Sb掺杂浓度对ZnO薄膜的微结构、光致发光和拉曼特性的影响．结果表明：所有样品均呈现ZnO六角纤锌矿结构且具有高度C轴择优取向;在Sb掺杂ZnO薄膜的拉曼光谱中观察到位于532cm^-1的振动模式,结合XRD分析认为此峰归因于Sb替代Zn位且与0成键的局域振动模式（LVMSb--O）;光致发光谱测试发现,仅在ZnO：Sb薄膜中观察到位于3．11eV附近的紫光发射峰,结合拉曼光谱分析认为此峰与XbZn-O复合体缺陷相关．     

Structural and photoluminescent properties of ZnO films deposited by radio frequency reactive sputtering

Zinc oxide films with c-axis preferred orientation were deposited on silicon (100) substrates by radio frequency (RF) reactive sputtering. The properties of the sam- ples were characterized by X-ray diffractometer, X-ray photoelectron spectroscopy and fluorescent-spectrophotometer. The effect of sputtering power and substrate temperature on the structural and photoluminescent (PL) properties of the ZnO films was investigated. The results indicated that when the sputtering power is 100 W and the substrate temperature is 300-400℃, it is suitable for the growth of high c-axis orientation and small strain ZnO films. A violet peak at about 380 nm and a blue band at about 430 nm were observed in the room temperature photolumines- cence spectra, and the origin of blue emission was investigated.     

分子束外延Mn4N单晶薄膜的反常霍尔效应研究

Mn₄N是立方相的反钙钛矿型晶体,具有显著的亚铁磁性和反常霍尔效应.该文利用等离子辅助分子束外延在MgO(100)衬底上生长厚度为40 nm的Mn₄N(100)单晶薄膜,通过X射线衍射θ扫描和φ扫描,证实外延层的结构符合Mn₄N单晶的空间结构特征;化学态测试结果表明Mn₄N(100)薄膜内部存在Mn⁰、Mn²⁺和Mn⁴⁺等几种价态,其实际化学式为Mn_3.6N,薄膜中存在富余的N元素;电学测试数据表明Mn₄N(100)薄膜具有以电子为载流子的反常霍尔效应(在正磁场中得到负的霍尔电阻率),正常霍尔效应的贡献约占千分之六,其反常霍尔电阻率随着测试温度升高5 K～350 K单调增大,说明温度升高导致电子散射现象加剧.通过对测试数据分析可以推断,在5 K～50 K和50 K～75 K温度范围,反常霍尔效应的来源可分别归结为电子斜散射机制和电子边跳机制.在75 K～350 K这一温度范围内,反常霍尔效应...     

Effects of sapphire substrates surface treatment on the ZnO thin films grown by magnetron sputtering

The surface treatment effects of sapphire substrate on the ZnO thin films grown by magnetron sputtering were studied. The sapphire substrates properties have been investigated by means of atomic force microscopy (AFM) and X-ray diffraction rocking curves (XRCs). The results show that sapphire substrate surfaces have the best quality by CMP with subsequent chemical etching. The surface treatment effects of sapphire substrate on the ZnO thin films were examined by X-ray diffraction (XRD) and photoluminescence (PL) measurements. Results show that the intensity of (0 0 2) diffraction peak of ZnO thin films on sapphire substrates treated by CMP with subsequent chemical etching was strongest, FWHM of (0 0 2) diffraction peak is the narrowest and the intensity of UV peak of PL spectrum is strongest, indicating surface treatment on sapphire substrate preparation may improve ZnO thin films crystal quality and photoluminescent property.     

Structure distortion,optical and electrical properties of ZnO thin films co-doped with Al and Sb by sol-gel spin coating

ZnO thin films co-doped with Al and Sb with different concentrations and a fixed molar ratio of AlCl 3 to SbCl 3 at 1:2, are prepared by a sol-gel spin-coating method on glass annealed at 550°C for 2 h in air. The x-ray diffraction results confirm that the ZnO thin films co-doped with Al and Sb are of wurtzite hexagonal ZnO with a very small distortion, and the biaxial stresses are 1.03×10 8 , 3.26×10 8 , 5.23×10 8 , and 6.97×10 8 Pa, corresponding to those of the ZnO thin films co-doped with Al and Sb in concentrations of 1.5, 3.0, 4.5, 6.0 at% respectively. The optical properties reveal that the ZnO thin films co-doped with Al and Sb have obviously enhanced transmittance in the visible region. The electrical properties show that ZnO thin film co-doped with Al and Sb in a concentration of 1.5 at% has a lowest resistivity of 2.5Ω·cm.     

Structural and electrical properties of lithium manganese oxide thin films grown by pulsed laser deposition

LiMn₂O₄ thin films were deposited by reactive pulsed laser deposition technique and studied the microstructural and electrical properties of the films. The LiMn₂O₄ thin films deposited in an oxygen partial pressure of 100 mTorr and at a substrate temperature of 573 K from a lithium rich target were found to be nearly stoichiometric. The films exhibited predominantly (111) orientation representing the cubic spinel structure with Fd3m symmetry. The intensity of (111) peak increased and a slight shift in the peak position was observed with the increase of substrate temperature. The lattice parameter increased from 8.117 to 8.2417 Å with the increase of substrate temperature from 573 to 873 K. The electrical conductivity of the films is observed to be a strong function of temperature. The evaluated activation energy for the films deposited at 873 K is 0.64 eV.