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。     

The Effects of Thermal Treatments on Microstructure Phosphorus-Doped ZnO Layers Grown by Thermal Evaporation

The ZnO films doped with 3 wt% phosphorus (P) were produced by activating phosphorus doped ZnO (ZnO:P) thin films in oxygen (O₂) ambient at 600°C for 30, 60, 90 and 120 min, respectively. As-deposited films doped with phosphorus are highly conductive and n type. All the films showed p-type conduction after annealing, in an O₂ ambient atmosphere. The activation energies of the phosphorus dopant in the p-type ZnO under O₂ ambient gases indicate that phosphorus substitution on the O site yielded a deep level in the gap. With a further increase of the annealed durations, the crystalline quality of the ZnO:P sample is degraded. The best p-type ZnO:P film deposited at 600°C for 30 min shows a resistivity of 1.85 Ω cm and a relatively high hole concentration of 5.1 × 10¹⁷cm^–3 at room temperature. The films exhibit a polycrystalline hexagonal wurtzite structure without preferred orientation. The mean grain sizes are calculated to be about 60, 72, 78, 85 and 90 nm for the p-type ZnO films prepared at 600°C for 30, 60, 90 and 120 min, respectively. Room temperature photoluminescence (PL) spectra of the ZnO film exhibit two emission bands — paramount excitonic ultraviolet (UV) emission and weak deep level visible emission. The excellent emission from the film annealed at 600°C for 30 min is attributed to the good crystalline quality of the p-type ZnO film and the low rate of formation of intrinsic defects at such short duration. The visible emission consists of two components in the green range.     

退火温度对ZnO薄膜结构和发光特性的影响

采用反应射频磁控溅射法在 Si(100)基片上制备了高c轴择优取向的ZnO薄膜，研究了退火温度对ZnO薄膜的晶粒尺度、应力状态、成分和发光光谱的影响，探讨了ZnO薄膜的紫外发光光谱和可见发光光谱与薄膜的微观状态之间的关系.研究结果显示,在600—1000℃退火温度范围内，退火对薄膜的织构取向的影响较小，但薄膜的应力状态和成分有比较明显的变化.室温下光致发光光谱分析发现，薄膜的近紫外光谱特征与薄膜的晶粒尺度和缺陷状态之间存在着明显的对应关系；而近紫外光谱随退火温度升高所呈现的整体峰位红移是各激子峰相对比例变 关键词： ZnO薄膜 退火 光致发光 射频反应磁控溅射 可见光发射     

Structure and properties of ZnO films grown on Si substrates with low temperature buffer layers

Zinc oxide (ZnO) thin films were grown on Si (1 0 0) substrates by pulsed laser deposition (PLD) using two-step epitaxial growth method. Low temperature buffer layer (LTBL) was initially deposited in order to obtain high quality ZnO thin film; the as-deposited films were then annealed in air at 700 °C. The effects of LTBL and annealing treatment on the structural and luminescent properties of ZnO thin film were investigated. It was found that tensile strain was remarkably relaxed by employing LTBL and the band-gap redshifted, correspondingly. The shift value was larger than that calculated from band-gap theories. After annealing treatment, it was found that the annealing temperature with 700 °C has little influence on strains of ZnO films with LTBLs other than directly deposited film in our experiments. Interestingly, the different behaviors in terms of the shift of ultraviolet (UV) emission after annealing between films with and without buffer were observed, and a tentative explanation was given in this paper.     

Post-annealing influence on properties of N-In codoped ZnO thin films prepared by ion beam enhanced deposition method

N-In codoped ZnO thin films were prepared by ion beam enhanced deposition method (IBED) and were annealed in nitrogen and oxygen ambient after deposition. The influence of post-annealing on structure, electrical and optical properties of thin films were investigated. As-deposited and all post-annealed samples showed preferential orientation along (0 0 2) plane. Electrical property studies indicated that the as-deposited ZnO film showed p-type with a sheet resistance of 67.5 kΩ. For ZnO films annealed in nitrogen with the annealing temperature increasing from 400 to 800 °C, the conduction type of the ZnO film changed from p-type to n-type. However, for samples annealed in oxygen the resistance increased sharply even at a low annealing temperature of 400 °C and the conduction type did not change. Room temperature PL spectra of samples annealed in N₂ and in O₂ showed UV peak located at 381 and 356 nm, respectively.     

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.     

ZnO/Zn界面对纳米ZnO薄膜光学性质的影响

采用氧等离子体辅助电子束蒸发金属Zn后低温退火的方法制备纳米ZnO薄膜。利用X射线衍射(XRD)谱、拉曼(Raman)谱、X射线光电子能谱(XPS)以及光致发光(PL)谱等手段,分析了退火温度及ZnO/Zn界面对样品的结构和发光性质的影响。Raman结果表明随着退火温度的升高,界面模式(Es)振动减弱并向低波数方向移动。当退火温度为400℃时,界面振动消失,Zn全部转化成具有六方纤锌矿结构的ZnO,得到化学配比的纳米ZnO薄膜。PL谱表明,经400℃退火处理的样品紫外发射最强,发光性质最好。     

非掺杂ZnO薄膜中紫外与绿色发光中心

用直流反应溅射方法在硅衬底上淀积了ZnO薄膜,测量它们的光致发光(PL)光谱,观察到两个发光峰,峰值能量分别为3.18(紫外峰,UV)和2.38eV(绿峰).样品用不同温度分别在氧气、氮气和空气中热处理后,测量了PL光谱中绿峰和紫外峰强度随热处理温度和气氛的变化,同时比较了用FP-LMT方法计算的ZnO中几种本征缺陷的能级位置.根据实验和能级计算的结果,推测出ZnO薄膜中的紫外峰与ZnO带边激子跃迁有关,而绿色发光主要来源于导带底到氧错位缺陷(O_Zn)能级的跃迁,而不是通常认为的氧空 关键词： ZnO薄膜 热处理 光致发光光谱 缺陷能级     

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.     

LP-MOCVD异质外延ZnO薄膜中的应力及对缺陷的影响

利用低压金属有机化学气相淀积(LP-MOCVD)在Si基片上外延生长ZnO薄膜，制备了两类样品 ：一类是在Si上直接外延ZnO，另一类是在Si上通过SiC过渡层来外延ZnO.根据两类样品的拉 曼光谱、x射线衍射、原子力显微图和光致发光的结果，表明ZnO外延薄膜中的张应力对薄膜 的结晶状况有着重要的影响，使用SiC过渡层能够有效缓解ZnO薄膜中的张应力，减小缺陷浓 度，提高ZnO外延层的质量；然后根据缺陷的形成机制进一步提出，对于ZnO/Si，其中较大 的张应力导致了高浓度的非辐射复合缺陷的形成，使得样品的紫外和绿峰的发射强度均大大 降低；对于ZnO/SiC/Si，其中较小的张应力导致ZnO薄膜中主要形成氧替位缺陷O_{Zn，从而使发光中的绿峰增强. 关键词： ZnO薄膜 应力 缺陷 拉曼光谱}     

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.     

Initial study on the structure and photoluminescence properties of SiC films doped with Al

SiC films doped with aluminum (Al) were prepared by the rf-magnetron sputtering technique on p-Si substrates with a composite target of a single crystalline SiC containing several Al pieces on the surface. The as-deposited films were annealed in the temperature range of 400-800 °C under nitrogen ambient. The thin films have been characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The results show that the introduction of Al into films hinders crystalline formation process. And with the increase of annealing temperature, more Si particles are formed in the films, which strongly affect the optical absorption properties. The photoluminescence (PL) spectra of the samples show two peaks at 370 nm and 412 nm. The intensities of the PL peaks are evidently improved after Al doped. We attribute the origin of the two PL peaks to a kind of Si-related defect centres. 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。     

Effects of sic buffer layer on the optical properties of ZnO films grown on Si (1 1 1) substrates

ZnO films have been grown by a sol-gel process on Si (1 1 1) substrates with and without SiC buffer layers. The influence of SiC buffer layer on the optical properties of ZnO films grown on Si (1 1 1) substrates was investigated. The intensity of the E₂ (high) phonon peak in the micro-Raman spectrum of ZnO film with the SiC buffer layer is stronger than that of the sample without the SiC buffer layer, and the breadth of E₂ (high) phonon peak of ZnO film with the SiC buffer layer is narrower than that of the sample without the SiC buffer layer. These results indicated that the crystalline quality of the sample with the SiC buffer layer is better than that of the sample without the SiC buffer layer. In photoluminescence spectra, the intensity of free exciton emission from ZnO films with the SiC buffer was much stronger than that from ZnO film without the SiC buffer layer, while the intensity of deep level emission from sample with the SiC buffer layer was about half of that of sample without the SiC buffer layer. The results indicate the SiC buffer layer improves optical qualities of ZnO films on Si (1 1 1) substrates.     

Optical properties of ZnO thin films on SiO2 substrates deposited by radio frequency magnetron sputtering

The optical properties of both the annealed and as-deposited ZnO thin films by radio frequency (RF)magnetron sputtering on SiO2 substrates were studied. In the annealed films, two pronounced well defined exciton absorption peaks for the A and B excitons were obtained in the absorption spectra, a strong free exciton emission without deep-level emissions was observed in the photoluminescence (PL) spectra at room temperature. It was found that annealing the films in oxygen dramatically improved the optical properties and the quality of the films.     

退火及超声处理对ZnO薄膜结构和发光特性的影响

 利用对向靶射频磁控溅射系统在Si（100）衬底上制备了ZnO薄膜，并对其进行了退火和超声处理。采用XRD,AFM和光致发光谱对其结构、表面形貌和性能进行了分析。结果表明：沉积态ZnO薄膜（002）择优取向稍差,尺寸较小,表面粗糙度较大。随退火温度的升高，颗粒粒径增大，样品的取向性和结晶度都明显变好，应力状态由压应力转变为张应力,粗糙度降低。超声处理缓解了薄膜中的张应力，晶粒尺寸更趋增大;用波长为280 nm的激发光激发薄膜时，沉积态薄膜无发光峰存在;随着退火温度升高，出现了一个378 nm的紫外峰和一个398 nm的紫峰;紫外峰峰值强度随退火温度升高不断增强，而紫峰的峰位随退火温度升高基本不发生变化，峰值强度增强;700 ℃退火后的薄膜经超声处理后，发光谱中出现了峰值波长为519 nm的绿色发光带。     

Growth of hierarchical based ZnO micro/nanostructured films and their tunable wettability behavior

Hierarchical zinc oxide (ZnO) micro/nanostructured thin films were grown onto as-prepared and different annealed ZnO seed layer films by a simple two step chemical process. A cost effective successive ionic layer adsorption and reaction (SILAR) method was employed to grow the seed layer films at optimal temperature (80 °C) and secondly, different hierarchical based ZnO structured thin films were deposited over the seed layered films by chemical bath deposition (CBD). The influence of seed layer on the structural, surface morphological, optical and wettability behavior of the ZnO thin films were systematically investigated. The XRD analysis confirms the high crystalline nature of both the seed layer and corresponding ZnO micro/nanostructured films with a perfect hexagonal structure oriented along (0 0 2) direction. The surface morphology revels a complex and orientated hierarchical based ZnO structured films with diverse shapes from plates to hexagonal rod-like crystal to tube-like structure and even much more complex needle-like shapes during secondary nucleation, by changing the seed layer conditions. The water contact angle (WCA) measurements on hierarchical ZnO structured films are completely examined to study its surface wettability behavior for its suitability in future self-cleaning application. Photoluminescence (PL) spectra of the ZnO structured film exhibit UV and visible emissions in the range of 420-500 nm. The present approach demonstrates its potential for low-temperature, large-scale, controlled synthesis of crystalline hierarchical ZnO nanostructures films.     

ZnO-Si不同退火条件对生长ZnSe薄膜的影响

研究了作为缓冲层的ZnO薄膜在不同的退火时间、退火温度下退火对Si衬底上生长ZnSe膜质量的影响。当溅射有ZnO膜的Si(111)衬底的退火条件变化时，从X射线衍射谱（XRD）和光致发光谱（PL）中可见，ZnSe(111)膜的晶体质量有较大的变化。变温的PL谱表明，Si衬底上生长的具有ZnO缓冲层的ZnSe膜的近带边发射峰起源于自由激子发射。     

高浓度Er/Yb共掺ZnO薄膜的结构及室温光致发光特性

采用射频磁控溅射方法制备了Er/Yb共掺ZnO薄膜,研究了退火处理对高浓度Er/Yb共掺ZnO薄膜的结构演化和光致发光(PL)特性的影响。X射线衍射分析结果表明:Er/Yb掺杂导致ZnO薄膜的晶粒细化及择优取向性消失,ZnO晶粒随退火温度的增加而逐渐长大。900℃退火时,出现Er3 、Yb3 偏析,退火温度高于1000℃时,薄膜与基体间发生了界面反应,1200℃时,ZnO完全转变为Zn2SiO4相。光致发光测量结果表明:高于900℃退火处理后,Er/Yb共掺ZnO薄膜在1540 nm附近具有明显的光致发光,发光强度在退火温度为1050℃时达到最大值;光致发光光谱呈现典型的晶体基质中Er3 离子发光光谱所具有的明锐多峰结构特征。此外,探讨了薄膜结构演化及其对光致发光光谱的影响。     

Excellent UV absorption in spin-coated thin films of oleic acid modified zinc oxide nanorods embedded in Polyvinyl alcohol

The aim of the study is to investigate the optical properties of spin-coated, highly transparent nanocomposite films of oleic acid modified ZnO (Zinc oxide) nanorods embedded in Polyvinyl alcohol (PVA) matrix. Pristine and oleic acid (OA) modified ZnO nanorods have been prepared by wet chemical synthesis and are characterized by X-ray diffraction, FESEM, TEM and FT–IR spectroscopy techniques. The optical properties of ZnO/PVA films are studied using UV–visible absorption and Photoluminescence (PL) spectroscopy. The results show that the optical absorption of the films in the UV region is quite high and more than 95% absorption is observed in films prepared from OA modified ZnO nanorods. The excellent UV absorption at around 300 nm offers prospects of applications of these films as efficient UV filters in this wavelength region. The PL spectrum of pristine ZnO nanorods shows almost white light emission whereas OA modified ZnO nanorods have a more intense peak centered in the blue region. The PL emission of OA modified ZnO/PVA film shows appreciable increase in intensity compared to the film obtained with pristine ZnO. The surface modification of ZnO by the polymer matrix removes defect states within ZnO and facilitates sharp near band edge PL emission at 364 nm.