MBE生长ZnO薄膜的结构和光学特性的研究

用等离子体源辅助分子束外延(P-MBE)方法在蓝宝石(0001)面上生长出了高质量的ZnO薄膜,并对其结构和发光特性进行了研究。在XRD中只观察到ZnO薄膜的(0002)衍射峰,其半高宽(FWHM)值为0.18°;而在共振Raman散射光谱中观测到1LO(579cm-1)和2LO(1152cm-1)两个峰位,这些结果表明ZnO薄膜具有单一c轴取向和高质量的纤维锌矿晶体结构。在吸收光谱中观测到自由激子吸收和激子-LO声子吸收峰,这表明在ZnO薄膜中激子稳定的存在于室温,并且两峰之间能量间隔为71.2meV,与文献上报道的ZnO纵向光学声子能量(71meV)相符。室温下在光致发光光谱(PL)中仅观测到位于376nm处的自由激子发光峰,而没有观测到与缺陷相关的深能级发射峰,表明ZnO薄膜具有较高的质量和低的缺陷密度。     

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     

ZnO薄膜的性质对水热生长ZnO纳米线阵列的影响

用水热法在ZnO薄膜上制备了直径、密度及取向可控的ZnO纳米线阵列。ZnO薄膜是通过原子层沉积(ALD)方法制备并在不同温度下退火处理得到的,退火温度对ZnO薄膜的晶粒尺寸、结晶质量和缺陷性质有很大的影响。而ZnO薄膜的性质对随后生长的ZnO纳米线的直径、密度及取向能起到调节控制的作用。通过扫描电子显微镜(SEM)、X射线衍射(XRD)仪和光致发光(PL)测试对ZnO薄膜和ZnO纳米线进行了表征。最后得到的垂直取向的ZnO纳米线阵列适合在发光二极管和太阳能电池等领域使用。     

氧气压强对PLD制备MgZnO薄膜光学性质的影响(英文)

使用准分子脉冲激光沉积(PLD)方法在Si(100)基片上制备了高度c轴取向的MgZnO薄膜。分别使用SEM、XRD、XPS、PL谱和吸收谱表征了薄膜的形貌、结构、成分和光学性质。实验发现氧气压强对MgZnO薄膜的结构和光学性质有重要影响。当氧气压强由5 Pa增大到45 Pa时,薄膜的PL谱紫外峰蓝移了86meV,表明氧气压强的增大提高了MgZnO薄膜中Mg的溶解度。在15 Pa氧气压强下制备的薄膜显示了独特、均匀的六角纳米柱状结构,其PL谱展示了优异的发光特性,具有比其他制备条件下超强的紫外发射和微弱的可见发光。500~600 nm范围内的绿光发射,我们讨论其机理可能源于深能级中与氧相关的缺陷。使用PLD得到纳米柱状结构表明:优化制备条件,可望使用PLD制备ZnO纳米阵列的外延衬底;可使用PLD技术开发基于ZnO纳米结构的高效发光器件。     

ZnO薄膜的分子束外延生长及性能

利用分子束外延(MBE)和氧等离子体源辅助MBE方法分别在Si(100)、GaAs(100)和蓝宝石Al2O3(0001)衬底上用Zn、ZnS或以一定Zn-O化学计量比作缓冲层,改变衬底生长温度和氧压,并在氧气氛下,进行原位退火处理,得到ZnO薄膜。依据X射线衍射(XRD)图,表明样品的结晶性能尚好,且呈c轴择优取向;实验结果表明在不同衬底上生长的ZnO薄膜,由于晶格失配度不同,其衍射峰也有区别。用原子力显微镜(AFM)观测薄膜的表面形貌,为晶粒尺寸约几十纳米的ZnO纳米晶,且ZnO晶粒呈六边形柱状垂直于衬底的表面。采用掠入射X射线反射率法测膜厚。在360nm激发下,样品的发光光谱是峰值为410,510nm的双峰谱,是与样品表面氧缺陷有关的深能级发光。     

退火对ZnO薄膜光学特性的影响

用射频磁控溅射法在蓝宝石衬底上制备出ZnO薄膜,通过X射线衍射(XRD)、扫描电镜(SEM)和光致发光(PL)谱等研究了退火温度对ZnO薄膜结构和光学性质的影响。测量结果显示,所制备的ZnO薄膜为六角纤锌矿结构,具有沿c轴的择优取向;随着退火温度的升高,(002)XRD峰强度和平均晶粒尺寸增大,(002)XRD峰半高宽(FWHM)减小,光致发光紫外峰强度增强。结果证明,用射频磁控溅射法通过适当控制退火温度可得到高质量ZnO薄膜。     

分子束外延生长的ZnO压电薄膜及其声表面波器件特性

用RF-MBE在蓝宝石(0001)衬底上引入MgO和低温ZnO双缓冲层生长了ZnO薄膜,并制备了声表面波器件。在ZnO薄膜中,仅观测到(0002)面的XRD,且衍射峰增强,半高宽减小,表明ZnO薄膜c轴取向性更好,晶体结构更优。室温下自由激子吸收峰更尖锐和吸收边更陡峭以及仅观测到自由激子发光,且发光线宽变窄、发光强度变大,表明ZnO薄膜缺陷密度减小,薄膜质量提高。测得该ZnO压电薄膜的电阻率高达4×10⁷ Ω·cm,其声表面波的速度高达5 010 m/s。     

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.     

不同衬底温度下PLD法制备的氧化锌薄膜的特性

利用GCR-170型脉冲激光器Nd:YAG的三次谐波(355nm),以蓝宝石Al2O3(0001)为衬底,在不同温度下采用脉冲激光沉积法制备了ZnO薄膜.通过原子力显微镜、Raman谱、光致发光谱、红外透射谱、霍尔效应和表面粗糙度分析仪对制备的ZnO薄膜进行了测试.分析了在不同衬底温度下薄膜的表面形貌、光学特性,同时进行了薄膜结构和厚度的测试.研究表明:衬底温度对ZnO薄膜的表面形貌、光学特性、结构特性都是重要的工艺参量,尤其在500℃时沉积的ZnO薄膜致密均匀,并表现出较强的紫外发射峰.     

有序ZnO纳米阵列的制备及其光学特性

纳米球刻蚀技术和磁控溅射方法在普通玻璃衬底上制备有序氧化锌(ZnO)纳米阵列。利用扫描电子显微镜对样品表面形貌进行了观测,并对样品进行荧光(PL)光谱测试。结果表明,相比于普通ZnO薄膜,ZnO纳米阵列的有序结构可以提高在紫外区域的发光性能,减少蓝绿光的发射缺陷。研究了不同ZnO纳米阵列粒径大小和不同ZnO纳米阵列的厚度对其光学性质的影响。溅射时间30min的有序ZnO纳米阵列样品的质量和结晶状态较好,随着聚苯乙烯(PS)纳米球粒径的减小,样品吸收峰和荧光光谱均发生"蓝移"。     

石墨烯对ZnO微米棒光学特性的影响

采用化学气相沉积(CVD)方法制备了具有良好结晶质量和(002)择优取向的ZnO微米棒。在此基础上,选取单根ZnO微米棒,将其部分搁置于单层石墨烯表面。光致发光(PL)谱结果表明,石墨烯不仅增强了ZnO微米棒的紫外发光强度,同时也对光场在ZnO微米棒中的分布有很大的限域作用。分析认为这是由于石墨烯的表面等离子效应引起了ZnO微米棒与石墨烯之间的光-物质相互作用导致的。在拉曼(Raman)光谱中,石墨烯对ZnO微米棒的E2(L)声子振动模和E2(H)声子振动模的强度具有明显的减弱效应,这进一步证明二者之间存在光子的传输和电荷的转移,从而导致其晶格振动受到抑制。     

Optical Field Confinement Enhanced Single ZnO Microrod UV Photodetector

ZnO mirorods are synthesized using the vapor phase transport method, and the magnetron sputtering is used to decorate the Al nanoparticles(NPs) on a single ZnO microrod. The micro-PL and I-V responses are measured before and after the decoration of Al NPs. The FDTD stimulation is also carried out to demonstrate the optical field distribution around the decoration of Al NPs on the surface of a ZnO microrod. Due to an implementation of Al NPs, the ZnO microrod exhibits an improved photoresponse behavior. In addition, Al NPs induced localized surface plasmons(LSPs) as well as improved optical field confinement can be ascribed to an enhancement of ultraviolet(UV) response. This research provides a method for improving the responsivity of photodetectors.     

Catalyst-free synthesis of novel brush-shaped ZnO particles by a simple oxidation in air

Brush-shaped ZnO particles were synthesized by controlling the growth time in the direct melt oxidation process of Al-Zn mixture in air at atmospheric pressure. Particles with two kinds of structures were formed. One was consisted of nanowires grown along [0 0 0 1] direction at the six corners and the center of (0 0 0 1) basal plane on hexagonal ZnO microrod. The other was constructed by nanobelts between the corner-nanowires as well as nanowires at the corners on ZnO microrod. The structural configuration that the nanowires and the nanobelts have a well coherent orientation alignment with the base microrod implies that the brush-shaped ZnO is single crystal. Room temperature PL spectrum of the brush-shaped ZnO particles displayed predominant green emission with a wavelength of 510 nm.     

Cu ions induced reorientation of crystallite in ZnO nano/micro rod arrays thin films

Undoped and Cu doped ZnO nano/microrod arrays (N/MRAs) films were grown on seeded glass substrates by chemical bath deposition technique. The structural and morphological characterizations (X-ray diffraction and scanning electron microscopy) clearly illustrate that the pure ZnO N/MRAs has well-defined hexagonal prismatic cross-sectional crystallographic facets and its crystallographic plane is more vertically grown along (002) crystallographic direction. The horizontally aligned (100) crystallographic plane is induced at 20% Cu doping level. Morphological structure of ZnO N/MRAs changed into nanoplates/microballs with increasing of Cu doping level. Hexagonal crystal structure of undoped and Cu doped ZnO N/MRAs is then confirmed by µ-Raman scattering. Energy band gaps are found to be decreased with Cu doping and reached a minimum of 3.04 eV when doping level is 20%. The defect related peak intensity is suppressed in ZnO N/MRAs by Cu doping.     

High-quality CdS quantum dots sensitized ZnO nanotube array films for superior photoelectrochemical performance

The surface characteristics of ZnO were synthetically optimized by a self-designed simultaneous etching and W-doping hydrothermal method utilizing as-prepared ZnO nanorod (NR) array films as the template. Benefiting from the etching and regrowth process and the different structural stabilities of the various faces of ZnO NRs, the uniquely etched and W-doped ZnO (EWZ) nanotube (NT) array films with larger surface area, more active sites and better energy band structure were used to improve the photoelectrochemical (PEC) performance and the loading quality of CdS quantum dots (QDs). On the basis of their better surface characteristics, the CdS QDs were uniformly loaded on EWZ NT array film with a good coverage ratio and interface connection; this effectively improved the light-harvesting ability, charge transportation and separation as well as charge injection efficiency during the PEC reaction. Therefore, all the CdS QD-sensitized EWZ NT array films exhibited significantly enhanced PEC performance. The CdS/EWZ-7 composite films exhibited the optimal photocurrent density with a value of 12 mA· cm^-2, 2.5 times higher than that of conventional CdS/ZnO-7 composite films under the same sensitization times with CdS QDs. The corresponding etching and optimizing mechanisms were also discussed.     

Synthesis and photoelectric characterization of semiconductor CdSe microrod array by a simple electrochemical synthesis method

It is reported here that the microrod array of CdSe on indium doped tin oxide coated conducting glass (ITO) substrate has been developed by a simple electrochemical synthesis method. The electrodeposition of CdSe was also investigated by cyclic voltammetric technique. The sample was characterized by XRD, EDX, FESEM and UV-vis spectroscopic. The X-ray diffraction investigation demonstrates that the CdSe microrod is a uniform hexagonal CdSe crystal. EDX shows that the high purity CdSe is obtained. Field emission scanning electron microscope (FESEM) results show that the microrods’ length, diameter, and direction of growth are nearly uniform and perpendicular to the ITO substrate. UV-vis absorption spectrum study shows the presence of direct transition with the band gap energy 2.13 eV. Photoelectrochemical solar cells are constructed using CdSe microrod array as the photocathode in polysulphide electrolyte and their power output characteristics are studied.     

Enhanced optical and field emission properties of CTAB-assisted hydrothermal grown ZnO nanorods

We have developed a simple N-cetyl-N,N,N-trimethyl ammonium bromide (CTAB)-assisted hydrothermal route for the production of ZnO one-dimensional (1D) nanostructures on zinc foil at reaction temperature of 160 °C. With the increase of CTAB concentration, the one-dimensional structures change from microrod to a mixture of nano- and microrod and finally to nanorods. X-ray diffraction studies confirmed the proper phase formation of the grown nanostructures. The room temperature photoluminescence spectra showed that ZnO nanostructures prepared with increased CTAB concentration exhibited enhanced band edge UV emission and also blue shift of the emission peak. All the samples show no defect related green emission. Field emission property of the 1D structures has been investigated in detail. By tuning the CTAB concentration, the field emission property was optimized. The nanorods synthesized with high CTAB showed turn-on and threshold fields of 3.2 and 5 V/μm, respectively, which are comparable to the values for vapour phase synthesized high field emitting ZnO nanostructures.     

Controlling the size and alignment of ZnO microrods using ZnO thin film templates deposited by pulsed laser ablation

The production of dense arrays of well aligned ZnO nano- and microrods with a controllable distribution of diameters is demonstrated. The rods were grown using a hydrothermal method, on pre-deposited ZnO thin films exhibiting a range of different grain sizes. These template ZnO thin films were deposited by pulsed laser ablation, at 193 nm, in a low background pressure of O₂; average grain sizes ranged from 10 nm (room temperature deposition) to 50 nm when deposited at a substrate temperature (T_sub) of 500 °C. The morphology of the ZnO microrod arrays grown onto these ZnO thin films was found to depend on the T_sub used during film deposition. Increasing T_sub resulted in a lower density of larger nanorods, with a more pronounced [0001] alignment. The diameters of the rods produced are typically an order of magnitude greater than the grain size of the template ZnO film. Thus the rods cannot be a direct continuation of the grain structure of the template films. Rather, we suggest that the rod diameter is controlled by the density of sites at which the initial nucleation occurs, which is expected to be higher on the smaller grain size films deposited at lower temperatures. The factor controlling the final size of the rods is thus the available free space into which they can grow, which is smaller at the higher nucleation densities. The increased extent of [0001] texturing of the thin film templates deposited at higher T_sub is proposed as the reason for the improved [0001] alignment of rods grown on these templates. PACS 81.07.De; 81.10.Dn; 52.38.Mf     

Facilitating epitaxial growth of ZnO films on patterned GaN layers: A solution-concentration-induced successive lateral growth mechanism

The hydrothermal epitaxy of ZnO films on a patterned GaN layer with a honeycomb etching hole array is demonstrated. Through m-planes of the GaN layer exposed on the vertical walls of the etching holes, highly crystalline ZnO films via multiple lateral growth stages can be realized. It is found that higher concentrations of zinc nitrate hexahydrate (ZNH) and hexamethylenetetramine (HMT) in hydrothermal solution yield a larger number of ZnO molecules to speed up ZnO growth during the initial stage of hydrothermal growth, also create secondary crystals and initialize further lateral growth stages to bridge neighboring ZnO prisms after smooth surfaces formed on the m-plane of a ZnO prism. A successive lateral growth mechanism that strongly depends on ZNH and HMT concentrations in the hydrothermal solution is proposed and discussed.     

Photocatalytic performance of ZnO:Fe array films under sunlight irradiation

ZnO:Fe array thin films were prepared by the hydrothermal method using the sol-gel grown film as a seed layer. The samples were characterized by X-ray diffraction (XRD), ultraviolet/visible absorption spectra (UV-vis) and scanning electron microscopy (SEM). The photocatalytic activities of the prepared samples were investigated for the photodegradation of methylene blue (MB) under sunlight irradiation. The results show that the lattice constant a and the cell volume of ZnO:Fe film increase due to the substitution of Fe for Zn. The absorption edge of Fe-doped ZnO displays a red shift with a significant absorption between 600 and 700 nm. The ZnO:Fe array film is composed of disk particles with uniformity and compactness. Doping Fe ions enhances the photodegradation rate of ZnO array film for MB. 1.5% Fe doped ZnO sample exhibits the highest activity under irradiation time of 4 h. Its degradation rate increases about 1.6 times compared to the undoped ZnO.