Effect of temperature on pulsed laser deposition of ZnO films

ZnO thin films have been deposited on Si(1 1 1) substrates at different substrate temperature by pulsed laser deposition (PLD) of ZnO target in oxygen atmosphere. An Nd:YAG pulsed laser with a wavelength of 1064 nm was used as laser source. The influences of the deposition temperature on the thickness, crystallinity, surface morphology and optical properties of ZnO films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), selected area electron diffraction (SAED), photoluminescence (PL) spectrum and infrared spectrum. The results show that in our experimental conditions, the ZnO thin films deposited at 400 °C have the best surface morphology and crystalline quality. And the PL spectrum with the strongest ultraviolet (UV) peak and blue peak is observed in this condition.     

石英衬底上Au缓冲层对ZnO薄膜微结构的影响

采用单源化学气相沉积(SSCVD)法,在石英衬底上以Au为缓冲层,Zn4(OH)2(O2CCH3)6.2H2O为固相源制备ZnO薄膜。SEM和XRD测试ZnO薄膜的微结构,结果表明:相对于SiO2衬底上生长的ZnO薄膜,Au/SiO2衬底上生长的ZnO薄膜具有较好的结晶质量和表面平整度;对制备ZnO薄膜的衬底温度进行了工艺优化,结果表明:500℃时制备的ZnO薄膜颗粒大小均匀,结晶质量较好;通过荧光光谱仪对Au/SiO2衬底上的ZnO薄膜进行光致发光(PL)谱测试,ZnO薄膜在400nm出现紫光发射峰,而没有出现与缺陷相关的深能级发射峰,表明ZnO薄膜具有较好的结晶质量。     

Effects of the sputtering time of ZnO buffer layer on the quality of GaN thin films

ZnO thin films with different thickness (the sputtering time of ZnO buffer layers was 10 min, 15 min, 20 min, and 25 min, respectively) were first prepared on Si substrates using radio frequency magnetron sputtering system and then the samples were annealed at 900 °C in oxygen ambient. Subsequently, a GaN epilayer about 500 nm thick was deposited on ZnO buffer layer. The GaN/ZnO films were annealed in NH₃ ambient at 950 °C. X-ray diffraction (XRD), atom force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) were used to analyze the structure, morphology, composition and optical properties of GaN films. The results show that their properties are investigated particularly as a function of the sputtering time of ZnO layers. For the better growth of GaN films, the optimal sputtering time is 15 min.     

低温缓冲层对氧化锌薄膜质量的影响

利用金属有机化学气相沉积(MOCVD)法,在Si衬底上外延生长ZnO薄膜。为了改善氧化锌薄膜的质量,首先在Si衬底上生长低温ZnO缓冲层,然后再生长高质量的ZnO薄膜。通过XRD、SEM、光致发光(PL)光谱的实验研究,发现低温ZnO缓冲层可有效降低ZnO薄膜和Si衬底之间的晶格失配以及因热膨胀系数不同引起的晶格畸变。利用低温缓冲层生长的ZnO薄膜的(002)面衍射峰的强度要比直接在Si上生长的ZnO薄膜样品的高,并且衍射峰的半高宽也由0.21°减小到0.18°,同时有低温缓冲层的样品室温下的光致发光峰也有了明显的增高。这说明利用低温缓冲层生长的ZnO薄膜的结晶质量和光学性质都得到了明显改善。     

Ti缓冲层及退火处理对Si(111)基片上生长的ZnO薄膜结构和发光特性的影响

采用反应磁控溅射法在Si（111）基片上制备了带有Ti缓冲层的高c轴取向ZnO薄膜.通过X射线衍射分析和光致荧光光谱测量,研究了Ti缓冲层厚度和退火处理对ZnO薄膜结晶质量和光致荧光特性的影响.研究结果表明,Ti缓冲层的引入可以有效改善Si基片上ZnO薄膜的发光性能,但缓冲层存在一个最佳的厚度.薄膜应力是影响ZnO薄膜紫外荧光发射性能的重要因素,较小的残余应力对ZnO薄膜的紫外荧光发射是有利的,残余应力的存在可以改变ZnO薄膜紫外荧光发射能量.随着退火温度的增加,薄膜中的张应力增大,导致带隙宽度减小以及激子复合跃迁峰逐渐向低能方向移动. 关键词： ZnO薄膜 缓冲层 退火处理 应力分析     

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.     

Pure UV photoluminescence from ZnO thin film by thermal retardation and using an amorphous SiO2 buffer layer

ZnO/SiO₂ thin films were fabricated on Si substrates by E-beam evaporation with thermal retardation. The as-prepared films were annealed for 2 h every 100 °C in the temperature range 400-800 °C under ambient air. The structural and optical properties were investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL). The XRD analysis indicated that all ZnO thin films had a highly preferred orientation with the c-axis perpendicular to the substrate. From AFM images (AFM scan size is 1 μm×1 μm), the RMS roughnesses of the films were 3.82, 5.18, 3.65, 3.40 and 13.2 nm, respectively. PL measurements indicated that UV luminescence at only 374 nm was observed for all samples. The optical quality of the ZnO film was increased by thermal retardation and by using an amorphous SiO₂ buffer layer.     

Fabrication and characteristics of a surface acoustic wave UV sensor based on ZnO thin films grown on a polycrystalline 3C-SiC buffer layer

Zinc oxide (ZnO) thin films were deposited onto a polycrystalline (poly) 3C-SiC buffer layer for surface acoustic wave (SAW) ultraviolet (UV) sensing using a magnetron sputtering system. X-ray diffraction (XRD) and photoluminescence (PL) spectra showed that the ZnO film grown on 3C-SiC/Si had a dominant c-axis orientation, a lower residual stress, and higher intensity of luminescence at 380 nm of ZnO thin film. The SAW resonator UV detector were fabricated on ZnO/Si structures with a 3C-SiC buffer layer. The SAW resonator exposed under UV illumination had a linear response with sensitivity of 85 Hz/(μW/cm²) in ZnO/3C-SiC/Si structures, as compared to 25 Hz/(μW/cm²) in ZnO/Si structures with UV intensity varied until 600 μW/cm².     

Structural and optical properties of nanocrystalline ZnO thin films synthesized by the citrate precursor route

Nanocrystalline zinc oxide (ZnO) thin films have been deposited by spin-coating polymeric precursors synthesized by the citrate precursor route using ethylene glycol and citric acid as chelating agents. The ZnO thin films were annealed in air at different temperatures for 10 min. The films were characterized by different structural and optical techniques, including X-ray diffraction (XRD), atomic force microscopy (AFM), optical transmission spectroscopy, and photoluminescence (PL). The thermal decomposition of polymeric precursor was studied by thermogravimetric analysis (TGA). XRD analysis with grazing incidence and rocking curves indicate that the ZnO films are polycrystalline with preferential orientation along the c-axis direction with a full-width at half-maximum (FWHM) of 0.31° for 600 °C-annealed samples. On annealing, the texturing in films increased along with a decrease in FWHM. AFM micrographs illustrate that the ZnO films are crack-free with well-dispersed homogeneous and uniformly distributed spherical morphology. The synthesized ZnO thin films have transparency >85% in the visible region exhibiting band edge at 375 nm, which becomes sharper with anneal. Room temperature PL spectra of these films show strong ultraviolet (UV) emission around 392 nm with an increase in intensity with annealing temperature, attributed to grain growth. Deconvolution of the PL spectra reveals that there is coupling of free excitons with higher orders of longitudinal optical (LO) phonon replicas leading to a broad asymmetric near-band-edge peak.     

Preparation and investigation of optical, structural, and morphological properties of nanostructured ZnO:Mn thin films

Nanostructured ZnO:Mn thin films have been prepared by sol–gel dip coating method. The content of Mn in the sol was varied from 0 to 12 wt%. The effect of Mn concentration on the optical, structural, and morphological properties of ZnO thin films were studied by using Fourier Transform Infrared (FTIR), UV–visible and photoluminescence (PL) spectroscopy, X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). XRD results showed that the films have hexagonal wurtzite structure at lower content of Mn. The diffraction peaks corresponding to ZnO disappeared and two diffraction peaks of MnO₂ and Mn₃O₄ appeared at the highest value of doping concentration (viz., 12 wt%). SEM results revealed that the surface smoothness of the films improved at higher content of Mn. The optical band gap of the films decreased from 3.89 to 3.15 eV when the Mn concentration increased from 0 to 12 wt%. The PL spectra of the films showed the characteristic peaks linked to band-to-band, green and yellow emissions. Besides, the PL intensity of the samples decreased with increase in Mn concentration.     

Preparation and characterization of Mg-doped ZnO thin films by sol-gel method

Undoped and Mg-doped ZnO thin films were deposited on Si(1 0 0) and quartz substrates by the sol-gel method. The thin films were annealed at 873 K for 60 min. Microstructure, surface topography and optical properties of the thin films have been measured by X-ray diffraction (XRD), atomic force microscope (AFM), UV-vis spectrophotometer, and fluorophotometer (FL), respectively. The XRD results show that the polycrystalline with hexagonal wurtzite structure are observed for the ZnO thin film with Mg:Zn = 0.0, 0.02, and 0.04, while a secondary phase of MgO is evolved for the thin film with Mg:Zn = 0.08. The ZnO:Mg-2% thin film exhibits high c-axis preferred orientation. AFM studies reveal that rms roughness of the thin films changes from 7.89 nm to 16.9 nm with increasing Mg concentrations. PL spectra show that the UV-violet emission band around 386-402 nm and the blue emission peak about 460 nm are observed. The optical band gap calculated from absorption spectra and the resistivity of the ZnO thin films increase with increasing Mg concentration. In addition, the effects of Mg concentrations on microstructure, surface topography, PL spectra and electrical properties are discussed.     

Effect of ZnO sacrificial layer thickness on the structure and optical properties of GaN nanoparticles prepared by RF magnetron sputtering

GaN nanoparticles were prepared on sapphire (0001) substrates with ZnO sacrificial layers by self assembly of Ga₂O₃ films in their reaction with NH₃. ZnO sacrificial layers with different thicknesses and Ga₂O₃ films were deposited on sapphire substrates in turn by a radio frequency (RF) magnetron sputtering system. Nitridation of the Ga₂O₃ films was then carried out in a quartz tube furnace. The effect of ZnO sacrificial layer thickness on the structure and optical properties of nanoparticles prepared by RF magnetron sputtering were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and photoluminescence (PL). GaN nanoparticles with ZnO sacrificial layers of different thicknesses possess hexagonal wurtzite crystal structure and have a preferred orientation with c axis perpendicular to the sapphire substrates. XRD, SEM, and AFM results reveal that the better-crystallinity, uniform, and well-dispersed GaN nanoparticles (～30 nm) without agglomeration were obtained with a ZnO sacrificial layer 300-nm thick. The PL result reveals that the optical properties of the GaN nanoparticles are improved with a ZnO sacrificial layer 300-nm thick. Therefore, we suggest that a ZnO sacrificial layer 300-nm thick is the most suitable condition for obtaining better-quality GaN nanoparticles with good luminescence performance. Moreover, the mechanism of the formation of GaN nanoparticles with ZnO sacrificial layers is also discussed.     

Comparison of ZnO thin films grown on a polycrystalline 3C-SiC buffer layer by RF magnetron sputtering and a sol-gel method

Zinc oxide (ZnO) thin films were deposited on a polycrystalline (poly) 3C-SiC buffer layer using RF magnetron sputtering and a sol-gel method. The post-deposition annealing was performed on ZnO thin films prepared using both methods. The formation of ZnO piezoelectric thin films with less residual stress was due to a close lattice mismatch of the ZnO and SiC layers as obtained by the sputtering method. Nanocrystalline, porous ZnO film prepared using the sol-gel method showed strong ultraviolet UV emission at a wavelength of 380 nm. The 3C-SiC buffer layer improved the optical and piezoelectric properties of the ZnO film produced by the two deposition methods. Moreover, the different structures of the ZnO films on the 3C-SiC intermediate layer caused by the different deposition techniques were also considered and discussed.     

Effects of aluminum doping and substrate temperature on zinc oxide thin films grown by pulsed laser deposition

Aluminum-doped zinc oxide (AZO) thin films have been deposited on amorphous fused silica substrates by pulsed laser ablation of a Zn:Al metallic targets. We varied the film growth condition such as the substrate temperature and Al concentrations. The films were deposited at substrate temperatures ranging from 20 to 600°C with oxygen partial pressure of 1 torr. The characteristics of the deposited films were examined by analyzing their photoluminescence (PL), X-ray diffraction (XRD), and UV–visible spectra. It is observed that the optical bandgap energy of the deposited films increased with the increase of Al concentration and substrate temperature. Besides, the PL peak energy shifted to blue and the Stokes shift became larger as the Al content increased.     

退火对ZnO薄膜的结构和光学性质的影响

采用射频磁控溅射法在Si衬底上制备了高c轴择优取向的ZnO薄膜,研究了退火对ZnO薄膜的晶粒尺度和发光光谱的影响。XRD结果显示退火可以改善ZnO薄膜的结构特性,PL谱结果显示退火对ZnO薄膜的发光强度产生很大影响。     

The structure and optical properties of SiC film on Si (111) substrate with a ZnO buffer layer by RF-magnetron sputtering technique

We have fabricated a multiply layer SiC/ZnO on Si substrates using the RF-magnetron sputtering technique with the targets of a single crystalline SiC and a polycrystalline ZnO. The as-deposited films were annealed in the temperature range of 600–1000 °C under nitrogen ambient. We have observed a strong ultraviolet (UV) emission (370 nm) from the as-deposited SiC/ZnO film and an intense violet emission (412 nm) from the film annealed at high temperature (1000 °C) under nitrogen ambient. The SiC film quality and the PL intensities are considered to be strongly dependent on the crystalline quality of the ZnO buffer layer. With the increase of the annealing temperature, the crystalline quality of the ZnO buffer layer is improved, resulting in the improvement of the SiC film quality and the increase of the PL intensities. The thin films have been characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) to provide the evidences of photoluminescence (PL). We suggest that the UV emission could be attributed to the nanocrystal silicon particles, that the 395 nm band is related to ZnO buffer layer and has a great relation to the crystalline quality of the ZnO film, and that the violet emission is associated with the emission luminescence from 6H-SiC, which bears on the SiC film quality. The obtained results are expected to have important applications in modern optoelectronic devices.     

SiC缓冲层对Si表面生长的 ZnO薄膜结构和光电性能的改善

用脉冲激光沉积(PLD)技术制备了ZnO/SiC/Si和 ZnO/Si薄膜并制成了紫外探测器。利用X射线衍射(XRD),光致发光(PL)谱,I-V曲线和光电响应谱对薄膜的结构和光电性能进行了研究。实验结果表明:SiC缓冲层改善了ZnO薄膜的结晶质量和光电性能,其原因可能是SiC作为柔性衬底能够减少ZnO与Si 之间大的晶格失配和热失配导致的界面缺陷和界面态。     

Thickness effect on the evolution of morphology and optical properties of ZnO films

N-Al co-doped ZnO films with various thicknesses were deposited on glass substrates by ultrasonic spray pyrolysis (USP). The crystalline microstructure, morphology, distribution of elements and photoluminescence properties of ZnO films were characterized by X-ray diffraction (XRD), field emission scanning microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS) and photoluminescence (PL) spectroscopy. The XRD and FESEM results show that with the increase of film thickness the grain size increases and the grain shape changes from regular hexagonal sheet-like to wedge-shaped, even pyramidal. The PL spectra illustrate that there is an obvious red-shift for the emission center from ultraviolet to blue region, and the intensities of defects emissions increase with the increase of thickness. In addition, the electrical properties are proved to be strongly affected by film thickness.     

Fabrication of Mg-doped ZnO thin films by laser ablation of Zn:Mg target

Mg-doped ZnO thin films were fabricated by laser ablation of Zn:Mg targets consisting of Mg metallic strips and Zn disk in oxygen atmosphere with a goal to facilitate convenient control of Mg contents in the films. The characteristics of the deposited films were examined by analyzing their photoluminescence (PL), X-ray diffraction and X-ray photoelectron spectroscopy (XPS) spectra. Mg contents as analyzed by XPS indicate that the target composition is fairly transferred to the deposited films. The wurtzite structure of ZnO was conserved even for the highly doped ZnO films and there was no Mg- or MgO-related XRD peaks. With increase in the Mg content, the bandgap and PL peak energy shifted to blue and the Stokes shift became larger.