Low-temperature growth of ZnO epitaxial films by metal organic chemical vapor deposition

ZnO films were grown on Al₂O₃ (0001) substrates by metal organic chemical vapor deposition at temperatures of T_g=150300 °C. Epitaxial growth was obtained for T_g200 °C. The in-plane orientation of the ZnO unit cells was found to change from a no-twist one with respect to that of the substrate at T_g=200 °C to a 30°-twist one at T_g=300 °C. Absorption and photoluminescence were observed from the film grown at 150 °C, although there was no evidence of epitaxial growth. Films grown at T_g200 °C exhibited smoother surfaces. Moreover, all the films grown at T_g=150300 °C revealed acceptor-related emission peaks, indicating the incorporation of acceptors into the films. PACS 81.15.Gh; 78.55.Et; 78.66.Hf     

The role of a ZnO buffer layer in the growth of ZnO thin film on Al2O3 substrate

A ZnO buffer layer and ZnO thin film have been deposited by the pulsed laser deposition technique at the temperatures of 200 C and 400 C, respectively. Structural, electrical and optical properties of ZnO thin films grown on sapphire (Al₂O₃) substrate with 1, 5, and 9 nm thick ZnO buffer layers were investigated. A minute shift of the (101) peak was observed which indicates that the lattice parameter was changed by varying the thickness of the buffer layer. High resolution transmission electron microscopy (TEM) was used to investigate the thickness of the ZnO buffer layer and the interface involving a thin ZnO buffer between the film and substrate. Selected area electron diffraction (SAED) patterns show high quality hexagonal ZnO thin film with 30 in-plane rotation with respect to the sapphire substrate. The use of the buffer can reduce the lattice mismatch between the ZnO thin film and sapphire substrate; therefore, the lattice constant of ZnO thin film grown on sapphire substrate became similar to that of bulk ZnO with increasing thickness of the buffer layer.     

Structural and luminescent characteristics of non-stoichiometric ZnO films by various sputtering and annealing temperatures

ZnO thin films were prepared by reactive RF magnetron sputtering at various deposition temperatures. They were annealed in oxygen ambient at various annealing temperatures. The microstructures and photoluminescence characteristics of ZnO films were investigated. The grain size of the ZnO thin film that was deposited at room temperature (RT) after annealing exceeded that of the film that was deposited at . Excess Zn atoms were considered to be present in the ZnO film that was deposited at RT, so the film was non-stoichiometric ZnO. No visible emission of either of the ZnO films deposited at the two temperatures was observed before annealing. Following annealing at high temperature, the green emission from the ZnO film that was deposited at RT was stronger than that of the film that was deposited at . The relationship between the non-stoichiometry of the thin film and the visible emission was discussed. The luminescent centers that correspond to green emission are defects; the concentration of defects was higher in the ZnO thin film that was deposited at RT than in the film that was deposited at .     

Inclined ZnO thin films produced by pulsed-laser deposition

ZnO thin films with a uniformly inclined structure are grown by pulsed-laser deposition on SrTiO₃. The c-axis of ZnO films is inclined by an angle =20±0.5° and =42±0.5° against the surface normal of 25° miscut (100) SrTiO₃ and (110) SrTiO₃ single crystal substrates, respectively. The inclined structure is due to epitaxial growth of hexagonal ZnO on cubic SrTiO₃ as evidenced by X-ray diffraction and high-resolution transmission electron microscopy investigations. The range of deposition parameters (substrate temperature, oxygen background pressure) to achieve epitaxial growth is determined. The inclined films are smooth with an rms surface roughness of 1.5 nm for layer thicknesses up to 700 nm. PACS 61.10.-i; 68.37.-d; 81.15.Fg     

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.     

Fabrication of transparent and flexible carbon‐doped ZnO field emission display on plastic substrate

Transparent and flexible carbon doped ZnO (C:ZnO) field emission device was successfully fabricated on an arylite substrate. Excellent adhesion of deposited C:ZnO on the flexible substrate was achieved with low sputtering power and Ar flow rate. In the fabricated device, nanostructured C:ZnO and as‐deposited thin films were used as field emitter and phosphor screen, respectively. The C:ZnO thin film showed a transparency of about 80% at 550 nm wavelength and average sheet resistance of 1.96 kΩ/□. The C:ZnO phosphor screen emitted red light during the field emission measurement, correlating the dominant cathodoluminescence peak at 646 nm. Thus, a promising transparent and flexible field emission display can be realized with C:ZnO based material.

Transparent and flexible C:ZnO film phosphor screen (anode) and nanocone emitters (cathode) for field emission device.     

Nanoporous structures on ZnO thin films

Porous structures were formed on ZnO thin films which were grown by an electrochemical deposition (ECD) method. The growth processes were carried out in a solution of dimethylsulfoxide (DMSO) zinc perchlorate, Zn(ClO₄)₂, at 120 ^°C on indium tin oxide (ITO) substrates. Optical and structural characterizations of electrochemically grown ZnO thin films have shown that the films possess high (0002) c$c$-axis orientation, high nucleation, high intensity and low FWHM of UV emission at the band edge region and a sharp UV absorption edge. Nanoporous structures were formed via self-assembled monolayers (SAMs) of hexanethiol (C₆SH) and dodecanethiol (C₁₂SH). Scanning electron microscope (SEM) measurements showed that while a nanoporous structure (pore radius 20 nm) is formed on the ZnO thin films by hexanathiol solution, a macroporous structure (pore radius 360 nm) is formed by dodecanethiol solution. No significant variation is observed in X-ray diffraction (XRD) measurements on the ZnO thin films after pore formation. However, photoluminescence (PL) measurements showed that green emission is observed as the dominant emission for the macroporous structures, while no variation is observed for the thin film nanoporous ZnO sample.     

CVD两步法生长ZnO薄膜及其光致发光特性

用CVD两步法在常压下于p型Si(100)衬底上沉积出具有较好择优取向的多晶ZnO薄膜。在325nm波长的光激发下,室温下可观察到显著的紫外光发射(峰值波长381nm)。高温退火后氧空位缺陷浓度增加,出现了一个450~600nm的绿光发光带,发光峰值在510nm。作为比较,用一步法生长的ZnO薄膜结晶质量稍差。在其PL谱中不仅有峰值波长389nm的紫外发射而且还出现了一个很强的蓝光发光中心(峰值波长437nm),退火后同样产生绿光发光带。对这两种绿光发光带的发光机制进行了研究,认为前者源于VO,而后者与O_Zn有密切的关系。     

Effect of substrate and annealing on the structural and optical properties of ZnO:Al films

ZnO:Al thin films with c-axis preferred orientation were deposited on glass and Si substrates using RF magnetron sputtering technique. The effect of substrate on the structural and optical properties of ZnO:Al films were investigated. The results showed a strong blue peak from glass-substrate ZnO:Al film whose intensity became weak when deposited on Si substrate. However, the full width at half maxima (FWHM) of the Si-substrate ZnO:Al (0 0 2) peaks decreased evidently and the grain size increased. Finally, we discussed the influence of annealing temperature on the structural and optical properties of Si-substrate ZnO:Al films. After annealing, the crystal quality of Si-substrate ZnO:Al thin films was markedly improved and the intensity of blue peak (∼445 nm) increased noticeably. This observation may indicate that the visible emission properties of the ZnO:Al films are dependent more on the film crystallinity than on the film stoichiometry.     

Growth behaviour of ZnO thin films and nanowires on SrTiO3 substrates

We report on comparative investigations of ZnO thin films and nanowires grown on SrTiO₃ (STO) single crystal substrates. Using pulsed laser deposition technique, we could grow ZnO thin films with ()- and (0001)-orientations on (100)- and (110)-orientated STO substrates, respectively. ZnO nanowires, grown by vapour condensation method with Au catalyst layers, did not show preferential alignment on either of the STO substrates. When the ZnO(0001)/STO(110) film was used as seed layer, we obtained dense and vertically aligned nanowires. Whereas, few and inclined nanowires were grown on the ZnO()/STO(100) film. We discuss possible origins to cause all the observations.     

Effects of deposition temperature on the structural and morphological properties of thin ZnO films fabricated by pulsed laser deposition

ZnO thin films were grown on Si(1 0 0) substrates using pulsed laser deposition in O₂ gas ambient (10 Pa) and at different substrate temperatures (25, 150, 300 and 400 °C). The influence of the substrate temperature on the structural and morphological properties of the films was investigated using XRD, AFM and SEM. At substrate temperature of T=150 °C, a good quality ZnO film was fabricated that exhibits an average grain size of 15.1 nm with an average RMS roughness of 3.4 nm. The refractive index and the thickness of the thin films determined by the ellipsometry data are also presented and discussed.     

Deposition of NiFe(200) and NiFe(111) textured films onto Si/SiO<Subscript>2</Subscript> substrates by DC magnetron sputtering

The effect of substrate temperature T_sub and bias voltage U_bias on the texture of NiFe films with thickness d ～ 30–340 nm deposited by DC magnetron sputtering onto Si(111)/SiO₂ substrates under working gas pressure ～ 0.2 Pa has been investigated. It has been demonstrated that films grown at room substrate temperature have the (111) texture that is refined under a negative bias voltage. The deposition of films onto a grounded (U_bias ～ 0) substrate heated to T_sub ～ 440–640 K results in the formation of textured NiFe(200) films.     

Particulate assisted growth of ZnO nanorods and microrods by pulsed laser deposition

Zinc oxide (ZnO) thin films were deposited on the gallium nitride (GaN) and sapphire (Al₂O₃) substrates by pulsed laser deposition (PLD) without using any metal catalyst. The experiment was carried out at three different laser wavelengths of Nd:YAG laser (λ = 1064 nm, λ = 532 nm) and KrF excimer laser (λ = 248 nm). The ZnO films grown at λ = 532 nm revealed the presence of ZnO nanorods and microrods. The diameter of the rods varies from 250 nm to 2 μm and the length varies between 9 and 22 μm. The scanning electron microscopy (SEM) images of the rods revealed the absence of frozen balls at the tip of the ZnO rods. The growth of ZnO rods has been explained by vapor-solid (V-S) mechanism. The origin of growth of ZnO rods has been attributed to the ejection of micrometric and sub-micrometric sized particulates from the ZnO target. The ZnO films grown at λ = 1064 nm and λ = 248 nm do not show the rod like morphology. X-ray photoelectron spectroscopy (XPS) has not shown the presence of any impurity except zinc and oxygen.     

Microstructures and optical properties of Cu-doped ZnO films prepared by radio frequency reactive magnetron sputtering

Pure and Cu-doped ZnO (ZnO:Cu) thin films were deposited on glass substrates using radio frequency (RF) reactive magnetron sputtering. The effect of substrate temperature on the crystallization behavior and optical properties of the ZnO:Cu films have been studied. The crystal structures, surface morphology and optical properties of the films were systematically investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and a fluorescence spectrophotometer, respectively. The results indicated that ZnO films showed a stronger preferred orientation toward the c-axis and a more uniform grain size after Cu-doping. As for ZnO:Cu films, the full width at half maxima (FWHM) of (0 0 2) diffraction peaks decreased first and then increased, reaching a minimum of about 0.42° at 350 °C and the compressive stress of ZnO:Cu decreased gradually with the increase of substrate temperature. The photoluminescence (PL) spectra measured at room temperature revealed two blue and two green emissions. Intense blue-green luminescence was obtained from the sample deposited at higher substrate temperature. Finally, we discussed the influence of annealing temperature on the structural and optical properties of ZnO:Cu films. The quality of ZnO:Cu film was markedly improved and the intensity of blue peak (∼485 nm) and green peak (∼527 nm) increased noticeably after annealing. The origin of these emissions was discussed.     

以表面等离子体为媒介的ZnO薄膜发光增强特性研究

采用两步法制备Si基Ag/ZnO双层结构薄膜,研究了Ag覆盖层的厚度和生长温度T对ZnO近带边发光强度的影响.对于厚度为100 nm的ZnO薄膜,发现Ag覆盖层的最佳厚度仅为8 nm,此时双层薄膜相对于单层ZnO薄膜的发光增强因子η达到最大值8.1;同时还发现,在最佳Ag层厚度下,生长温度T≥300 ℃时生长Ag所获Ag/ZnO双层薄膜的ZnO发光强度比生长温度T≤200 ℃时生长的双层薄膜样品大一倍以上,η ≈ 18.结合对双层薄膜表 关键词： 表面等离子体共振 复合薄膜     

制备温度对TiO2基膜表面非晶态ZnO薄膜发光特性影响的研究

利用电子束热蒸发镀膜的方式，以高纯度的ZnO和TiO₂颗粒为原料，以Si为基底在有氧的气氛中制备ZnO/TiO₂复合薄膜。研究制备温度对ZnO/TiO₂薄膜的结构以及发光性能的影响。通过拉曼(Raman)谱和X射线衍射(XRD)谱分析了ZnO/TiO₂薄膜的结构，表明所制备的ZnO薄膜为非晶态。用光致发光 (PL) 谱表征了它的发光特性，数据表明在250℃时制备的非晶态ZnO薄膜在波长389nm处具有极强的紫外光发射，在波长431nm处发出很强的紫光，在波长519nm处发出较强的黄绿光。     

ZnO films grown by laser ablation with and without oxygen CVD

In the present work we have studied the properties of zinc oxide (ZnO) thin films grown by laser ablation of ZnO targets under different substrate temperature and background oxygen conditions. The ZnO layers were deposited with a Pulsed Laser Deposition (PLD) system on pre-nitrided (0001) sapphire (Al₂O₃), using the base line of a Nd:YAG laser at 1064 nm. The films were characterized by different structural and optical methods, including X-ray diffraction (XRD), scanning electron microscopy (SEM), optical transmission spectroscopy, and steady-state photoluminescence (PL). XRD analysis with rocking curves and θ–2θ scans indicates preferential growth along the c-axis direction with a full width at half maximum (FWHM) smaller than 1.5. Low-temperature photoluminescence (PL) showed strong excitonic emission near 3.36 eV between 9 and 65 K.     

A simple growth route towards ZnO thin films and nanorods

Highly orientated ZnO thin films and the self-organized ZnO nanorods can be easily prepared by a simple chemical vapor deposition method using zinc acetate as a source material at the growth temperature of 180 and 320 °C, respectively. The ZnO thin films deposited on Si (100) substrate have good crystallite quality with the thickness of 490 nm after annealing in oxygen at 800 °C. The ZnO nanorods grown along the [0001] direction have average diameter of 40 nm with length up to 700 nm. The growth mechanism for ZnO nanorods can be explained by a vapor-solid (VS) mechanism. Photoluminescence (PL) properties of ZnO thin films and self-organized nanorods were investigated. The luminescence mechanism for green band emission was attributed to oxygen vacancies and the surface states related to oxygen vacancy played a significant role in PL spectra of ZnO nanorods.     

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.     

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.