磁控溅射ZnO薄膜的成核机制及表面形貌演化动力学研究

利用原子力显微镜分析了ZnO薄膜在具有本征氧化层的Si(100)和Si(111)基片上的表面形貌 随沉积时间的演化. 通过对薄膜生长形貌的动力学标度表征，研究了射频反应磁控溅射条件 下，ZnO薄膜的成核过程及生长动力学行为. 研究发现，ZnO在基片表面的成核过程可分为初 期成核阶段、低速率成核阶段和二次成核阶段. 对于Si(100)基片，三个成核阶段的生长指 数分别为β₁=1.04，β₂=0.25±0.01，β₃=0.74；对 于Si(11 关键词： ZnO薄膜 磁控溅射 生长动力学 成核机制     

Si(001)基片上反应射频磁控溅射ZnO薄膜的两步生长方法

利用反应射频磁控溅射技术，采用两步生长方法制备了ZnO薄膜，探讨了基片刻蚀时间和低温过渡层沉积时间对ZnO薄膜生长行为的影响.研究结果表明，低温ZnO过渡层的沉积时间所导致的薄膜表面形貌的变化与过渡层在Si(001)表面的覆盖度有关.当低温过渡层尚未完全覆盖基片表面时，ZnO薄膜的表面岛尺度较小、表面粗糙度较大，薄膜应力较大；当低温过渡层完全覆盖Si(001)基片后，ZnO薄膜的表面岛尺度较大、表面粗糙度较小，薄膜应力较小.基片刻蚀时间对薄膜表面形貌的影响与低温过渡层的成核密度有关.随着刻蚀时间的增加，ZnO薄膜的表面粗糙度逐渐下降，表面形貌自仿射结构的关联长度逐渐减小. 关键词： ZnO薄膜 反应射频磁控溅射 两步生长 形貌分析     

温度对ZnO/Al2O3(0001)界面的吸附、扩散及生长初期模式的影响

构建了一个ZnO沉积在α-Al₂O₃(0001)表面生长初期的模型，采用基于密度泛函理论的平面波超软赝势法进行了动力学模拟.发现在400，600和800℃的条件下界面原子有不同的扩散能力，因此温度对ZnO/α-Al₂O₃(0001)表面界面结构以及ZnO薄膜生长初期模式有决定性的影响.在整个ZnO吸附生长过程中，O原子的扩散系数大于Zn原子的扩散系数，O原子的层间扩散对薄膜的均匀生长起着重要作用.进一步从理论计算上证实了ZnO在蓝宝石(0001)上两种生长模式的存在，400℃左右生长模式主要是Zn螺旋扭曲生长，具有Zn六角平面对称特征，且有利于Zn原子位于最外表面.600℃左右呈现为比较规则的层状生长，且有利于O原子位于最外表面.模拟观察到在ZnO薄膜临近Al₂O₃基片表面处，Zn的空位缺陷明显多于O的空位缺陷. 关键词： 扩散 薄膜生长 2O₃(0001)')" href="#">α-Al₂O₃(0001) ZnO     

工作气压对磁控溅射ZnO薄膜结晶特性及生长行为的影响

采用射频反应磁控溅射方法，在Si(001)基片上制备了具有高c轴择优取向的ZnO薄膜.利用原子力显微镜、X射线衍射、透射电子显微镜和透射光谱分析技术，对不同工作气压下合成的ZnO薄膜的表面形貌、微观结构和光学性能进行表征，研究了工作气压对ZnO薄膜的结晶性能以及生长行为的影响.研究结果显示：对于Ar/O₂流量比例接近1∶1的固定比值下，ZnO薄膜的生长行为主要取决于成膜空间中氧的密度，临界工作气压介于0.5—1.0 Pa之间.当工作气压小于临界值时，ZnO薄膜的成核密度较高，且随工作气压的变化明显，ZnO的生长行为受控于氧的密度，属于氧支配的薄膜生长；当工作气压大于临界值以后，ZnO薄膜的成核密度基本保持不变，Zn原子的数量决定薄膜的生长速率；在0.1—5.0 Pa的工作气压范围内，均可获得高度c轴取向的ZnO薄膜，但工作气压的变化改变着ZnO晶粒之间的界面特征和取向关系.随着工作气压的增加，ZnO晶粒之间的界面失配缺陷减少，但平面织构特征逐渐消失，三叉晶界的空洞逐渐扩大，薄膜的密度下降，折射率减小. 关键词： ZnO薄膜 磁控溅射 表面形貌 微观结构 光学性能     

薄膜外延生长的计算机模拟

以Cu膜为例，用Monte-Carlo算法模拟了薄膜生长的随机过程，并提出了更加完善的模型.在合理选择原子间相互作用计算方法的基础上，考虑了原子的吸附、在生长表面的迁移及迁移所引起的近邻原子连带效应、从生长表面的脱附等过程.模拟计算了薄膜的早期成核情况以及表面粗糙度和相对密度.结果表明，随着衬底温度的升高或入射率的降低，沉积在衬底上的原子逐步由离散型分布向聚集状态过渡形成一些岛核，并且逐步由二维岛核向三维岛核过渡.在一定的原子入射率下，存在三个优化温度，成核率最高时的最大成核温度Tn、薄膜的表面粗糙度最低 关键词： Monte-Carlo算法 计算机模拟 薄膜生长     

Pd,Ge薄膜体系中的分形晶化行为

利用透射电子显微镜（ＴＥＭ）对有化合物生成（Ｐｄ₂Ｇｅ和ＰｄＧｅ等）的Ｐｄ，Ｇｅ薄膜体系中的分形晶化行为进行了系统研究实验结果和分析表明：在各种退火温度条件下，Ｐｄ－Ｇｅ共蒸膜都难以发生分形晶化，Ｐｄ／ａ－Ｇｅ双层膜较ａ－Ｇｅ／Ｐｄ双层膜更容易导致分形结构的产生Ｚ化合物Ｐｄ₂Ｇｅ和ＰｄＧｅ的形成对薄膜中的分形晶化有明显的抑制作用，体系中能否出现分形结构，取决于非晶Ｇｅ的成核生长和Ｐｄ，Ｇｅ化学反应两种过程的相互竟争． 关键词：     

衬底表面覆盖对薄膜成核和生长的影响

在薄膜生长的成核阶段,稳定聚集体将逐渐覆盖衬底表面．同时,薄膜的生长将发生在被覆盖的衬底部分,而成核则发生在未被覆盖的部分．本文研究了衬底表面被覆盖的程度对薄膜成核和生长的影响,对广泛应用的薄膜理论,给出一些修正公式．结果表明,成核速率正比于衬底表面未被覆盖面积的平方．而薄膜理论认为成核速率是时间常量,似显得粗糙． 关键词：     

离子注入Zn的Si(001)基片热氧化制备纳米ZnO团簇及其生长行为研究

采用离子注入技术将Zn离子注入Si（001）基片,并在大气环境下加热氧化制备了ZnO纳米团簇.利用电子探针、薄膜X射线衍射仪、原子力显微镜和透射电子显微镜,对注入和热氧化后的薄膜成分、表面形貌和微观结构进行表征,探讨了热氧化温度以及注入剂量对纳米ZnO团簇的成核过程及生长行为的影响.结果表明,Zn离子注入到Si基片表面后形成了Zn纳米团簇,热氧化过程中Zn离子向表面扩散,在表面SiO₂非晶层和Si基片多晶区的界面处形成纳米团簇.热氧化温度是影响ZnO纳米团簇结晶质量的一个重要参数.随着热氧化温度的升高,金属Zn的衍射峰强度逐渐变弱并消失,而ZnO的（101）衍射峰强度逐渐增强.当热氧化温度高于800 ℃以后,ZnO与SiO₂之间开始发生化学反应形成Zn₂SiO₄. 关键词： ZnO纳米团簇 离子注入 微观结构 形貌分析     

不同晶化工艺对非晶PZT纳米薄膜形核取向生长机理的影响

射频磁控溅射法室温下在Pt/Ti/SiO2/Si上制备非晶Pb(Zr048Ti052)O3薄膜，非晶PZT薄膜分别经常规炉退火(CFA)处理和快速热退火(RTA)处理晶化为（100），（111）不同择优取向的多晶薄膜. 采用x射线衍射测定了薄膜相组分、择优取向度；用原子力显微镜和压电响应力显微镜观察了薄膜表面形貌，以及对应区域由自发极化形成的铁电畴像，观察了不同取向薄膜的电畴分布特征. 结果表明，RTA晶化过程钙钛矿结构PZT结晶主要以PZT/Pt界面处的PtPb化合物为成核点异质形核并类似外延的结晶生长，沿界面结晶速率远大于垂直膜面结晶速率，而CFA晶化样品成核发生在膜内杂质缺陷处，以同质成核为主. 不同的成核机理导致了不同晶面择优取向生长. 关键词： PZT薄膜 结晶 形核 力显微技术     

GaAs(001)衬底上分子束外延生长立方和六方GaN薄膜

采用分子束外延方法在GaAs(001)衬底上生长出了03微米厚的GaN薄膜,X射线双晶衍射和室温光荧光测试结果表明,采用GaAs氮化表面作为成核层可获得高纯度立方GaN薄膜而采用AlAs氮化表面作为成核层可获得高纯度六方GaN薄膜.这一研究结果表明在GaAs衬底上生长GaN薄膜的相结构可以通过选择不同的成核层来控制. 关键词：     

Controlling the orientation of ZnO nanorod arrays using TiO<Subscript>2</Subscript> thin film templates dip-coated by sol–gel

The oriented ZnO nanorod arrays have been synthesized on a silicon wafer that coated with TiO₂ films by aqueous chemical method. The morphologies, phase structure and the photoluminescence (PL) properties of the as-obtained product were investigated by field-emission scanning electron microscopy (FE-SEM), X-ray diffractometer (XRD), transmission electron microscope (TEM) and PL spectrum. The nanorods were about 100 nm in diameter and more than 1 μm in length, which possessed wurtzite structure with a c axis growth direction. The room-temperature PL measurement of the nanorod arrays showed strong ultraviolet emission. The effect of the crystal structure and the thickness of TiO₂ films on the morphologies of ZnO nanostructures were investigated. It was found that the rutile TiO₂ films were appropriate to the oriented growth of ZnO nanorod arrays in comparison with anatase TiO₂ films. Moreover, flakelike ZnO nanostructures were obtained with increasing the thickness of anatase TiO₂ films.     

Controllable vertical growth onto anatase TiO2 nanoparticle films of ZnO nanorod arrays and their photoluminescence and superhydrophilic characteristics

Well-aligned ZnO nanorod arrays have been successfully fabricated directly on anatase TiO₂ nanoparticle films via low-temperature hydrothermal processes. The effects of the reactive time, temperature and reactant concentration on the growth of the as-prepared ZnO crystals are investigated in detail, and the possible mechanisms of crystal ZnO nanorod growth are also suggested. The results show that the low reactant concentration is in favor of the increase in the aspect ratio of crystal ZnO nanorods with weak orientation, while the long reactive time and high reactant concentration are useful to prepare well-aligned crystal ZnO nanorod arrays. Interestingly, the typically constructed composite films exhibit superhydrophilic characteristic without UV irradiation. Moreover, a strong near-ultraviolet PL band centering at about 385 nm and a weak green PL band centering at about 525 nm can appear at the room temperature.     

Morphology transition of ZnO films with DMZn flow rate in MOCVD process

We used a metal-organic chemical vapor deposition (MOCVD) method to grow ZnO films on MgAl₂O₄ (1 1 1) substrate, and succeeded in preparing films with microstructures from well-aligned ZnO nanorods to continuous and dense films by adjusting the ratio of the input rates of oxygen and zinc sources (VI/II). At the growth temperature of 350 °C, the ZnO nanorods were formed under a low flow rate of a zinc precursor. On the other hand, continuous and dense ZnO films were formed under a high flow rate of the zinc precursor. There is a transition zone at medium zinc precursor flow rate, where nanorods transform to dense films. We proved that the height of ZnO nanorods and the thickness of ZnO dense films both increase with zinc flow rate, and are consistent with the mass-transport mechanism for ZnO growth. The XRD spectra of the sample in the transition zone show both (0 0 2) and (1 0 1) peaks, where (1 0 1) peaks are formed only in the transition zone. We consider that there are (0 0 2) and (1 0 1) ZnO grains in the early growth stage of dense ZnO films.     

Effects of crystalline quality on the ultraviolet emission and electrical properties of the ZnO films deposited by magnetron sputtering

The ZnO films were deposited on c-plane sapphire, Si (0 0 1) and MgAl₂O₄ (1 1 1) substrates in pure Ar ambient at different substrate temperatures ranging from 400 to 750 °C by radio frequency magnetron sputtering. X-ray diffraction, photoluminescence and Hall measurements were used to evaluate the growth temperature and the substrate effects on the properties of ZnO films. The results show that the crystalline quality of the ZnO films improves with increasing the temperature up to 600 °C, the crystallinity of the films is degraded as the growth temperature increasing further, and the ZnO film with the best crystalline quality is obtained on sapphire at 600 °C. The intensity of the photoluminescence and the electrical properties strongly depend on the crystalline quality of the ZnO films. The ZnO films with the better crystallinity have the stronger ultraviolet emission, the higher mobility and the lower residual carrier concentration. The effects of crystallinity on light emission and electrical properties, and the possible origin of the n-type conductivity of the undoped ZnO films are also discussed.     

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.     

Growth of vertically aligned one-dimensional ZnO nanowire arrays on sol–gel derived ZnO thin films

Vertically aligned one-dimensional ZnO nanowire arrays have been synthesized by a hydrothermal method on sol–gel derived ZnO films. Sol–gel derived ZnO films and corresponding ZnO nanowire arrays have been characterized by X-ray diffraction and field-emission scanning electron microscopy. The effect of sol–gel derived ZnO film surface on the morphology of ZnO nanowire arrays has been investigated. The authors suggest from our investigation that sol–gel derived ZnO films affect the growth of one-dimensional ZnO nanostructures. Not only crystalline ZnO films but also amorphous ones can act as a scaffold for ZnO nucleus. Tilted ZnO micro-rods are grown on ZnO gel films, whereas vertically aligned ZnO nanowire arrays are grown on nanometer-sized ZnO grains. The average diameter of ZnO nanowire arrays are correlated strongly with the grain size of sol–gel derived ZnO films.     

Surface morphology of ZnO buffer layer and its effects on the growth of GaN films on Si substrates by magnetron sputtering

ZnO thin films were first prepared on Si(111) substrates using a radio frequency magnetron sputtering system. Then the as-grown ZnO films were annealed in oxygen ambient at temperatures of 700, 800, 900, and 1000°C , respectively. The morphologies of ZnO films were studied by an atom force microscope (AFM). Subsequently, GaN epilayers about 500 nm thick were deposited on the ZnO buffer layers. The GaN/ZnO films were annealed in NH₃ ambient at 900°C. The microstructure, morphology and optical properties of GaN films were studied by x-ray diffraction (XRD), AFM, scanning electron microscopy (SEM) and photoluminescence (PL). The results are shown, their properties having been investigated particularly as a function of the ZnO layers. For better growth of the GaN films, the optimal annealing temperature of the ZnO buffer layers was 900°C.     

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.