Cu掺杂氧化锌薄膜的发光特性研究

通过射频反应溅射法在Si（111）衬底上制备了不同Cu掺杂量的ZnO薄膜.室温下测量了样品的光致发光（PL）谱，所有样品的PL谱中均观察到435?nm左右的蓝光发光带，该发光带的强度与Cu掺杂量和溅射功率有关.当溅射功率为150?W，Cu掺杂量为2.5%时，ZnO薄膜的PL谱中出现了较强的蓝光双峰，而溅射功率为100?W，Cu掺杂量为1.5%时，出现了位于437nm（2.84eV）处较强的蓝光峰，后者的取向性较好.还研究了掺杂量和溅射功率对发光特性的影响，并对样品的蓝光发光机制进行了探讨. 关键词： ZnO薄膜 Cu掺杂 光致发光谱 射频反应共溅射     

超声处理对ZnO薄膜光致发光特性的影响

对于结晶状态好的ZnO薄膜，测量了其光致发光(PL)光谱，发射光谱中只发现了峰值波长约389 nm的近紫外光.样品进行超声处理后，发射谱中不仅观察到近紫外峰，又观察到波长约508 nm的绿光峰.绿光峰的强度比近紫外光的强度强得多，且近紫外峰红移.进一步的热处理使绿光峰大大增强.超声处理改变了ZnO薄膜的质量和结晶状态，使晶格中产生氧空位.处理过程中的热效应使得薄膜晶格振动加剧.当晶格振动加剧到一定程度，晶格中的氧脱离格点形成氧空位.510 nm左右的绿色发光峰是ZnO晶体中的氧空位产生的.薄膜的温度越高， 关键词： ZnO薄膜 超声 光致发光     

退火对多晶ZnO薄膜结构与发光特性的影响

用射频反应溅射法在Si（111）衬底上制备了C轴取向的多晶ZnO薄膜，通过不同温度的退火处理，研究了退火对多晶ZnO薄膜结构和发光特性的影响.由x射线衍射得知，随退火温度的升高，晶粒逐渐变大，薄膜中压应力由大变小至出现张应力.光致发光测量发现，样品在430nm附近有一光致发光峰, 峰的强度随退火温度升高而减弱，联合样品电阻率随退火温度升高而逐渐变大的测量及能级图，推测出ZnO薄膜中的蓝光发射主要来源于锌填隙原子缺陷能级与价带顶能级间的跃迁. 关键词： ZnO薄膜 退火 光致发光 射频反应溅射     

Co与Cu掺杂ZnO薄膜的制备与光致发光研究

采用溶胶-凝胶旋涂法在玻璃衬底上制备了Co, Cu单掺杂及Co,Cu共掺杂ZnO薄膜.用金相显微镜观察了Co与Cu掺杂对ZnO薄膜形貌的影响.X射线衍射（XRD）研究揭示所有ZnO薄膜样品都存在（002）择优取向,在Cu单掺的ZnO薄膜中晶粒尺寸最大.对所有样品的室温光致发光测量都观察到较强的蓝光双峰发射和较弱的绿光发射,其中长波长的蓝光峰和绿光峰都能够通过掺杂进行控制.对不同掺杂源的ZnO薄膜发光性能进行了分析,认为蓝光峰来源于电子由导带底到锌空位能级的跃迁及锌填隙到价带顶的跃迁,绿光峰是由于掺杂造成的 关键词： ZnO薄膜 溶胶-凝胶 Co Cu掺杂 光致发光     

磁控溅射制备ZnO薄膜的受激发射特性的研究

用射频磁控反应溅射法在二氧化硅衬底上制备ZnO薄膜。得到了在不同温度下ZnO薄膜的吸收与光致发光。观测到了纵光学波 (LO)声子吸收峰与自由激子吸收峰 ;室温 (30 0K)下 ,PL谱中仅有自由激子发光峰。这些结果证实了ZnO薄膜具有较高的质量。探讨了变温ZnO薄膜的发光特性。研究了ZnO薄膜的受激发射特性。     

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     

蓝光ZnO薄膜的特性研究

采用反应溅射法在n型硅（100）衬底上制备了ZnO薄膜,分别用X射线衍射仪、原子力显微镜和荧光分光光度计对样品的结构、表面形貌和光致发光特性进行了表征。X射线衍射结果表明,实验中制备出了应变小的c轴择优取向的ZnO薄膜;原子力显微镜观察表明,薄膜表面平整,颗粒大小约为50nm,为柱状结构,颗粒垂直于硅衬底表面生长;在室温光致发光（PL）谱中观察到了波长位于434nm处的较窄的强蓝光发射峰,该蓝光峰的半峰全宽约为50meV。对蓝光峰的发光机制进行了讨论,并推断出该蓝光峰来源于电子从Zn填隙缺陷能级向价带顶跃迁。     

Fe,Co共掺杂ZnO薄膜结构及发光特性研究

采用溶胶凝胶法在玻璃衬底上制备了Fe,Co共掺Zn0.9FexCo0.1-xO(x=0,0.03,0.05,0.07)系列薄膜.通过扫描电镜(SEM)、X射线衍射(XRD)、X射线光电子谱(XPS)和光致发光(PL)谱对薄膜样品的表面形貌、晶体结构、成分和光学性能进行了研究.XRD结果表明所有ZnO薄膜样品都呈六方纤锌矿结构,在样品中没有观察到与Fe和Co相关的团簇,氧化物及其他杂相的衍射峰,表明共掺杂改善了Fe或Co在ZnO的分散性.XPS测试结果揭示样品中Co离子的价态为+2价;Fe离子的价态为+2价和+3价共存,但Fe相对浓度的增大导致Fe3+含量增加.所有样品的室温光致发光谱(PL)均观察到紫外发光峰和蓝光双峰,其中Fe,Co共掺ZnO薄膜的紫外发光峰较本征ZnO出现蓝移,蓝光双峰峰位没有变化,但发光强度有所减弱;而掺杂ZnO薄膜的绿光发光峰几乎消失.最后,结合微结构和成分分析对薄膜样品的发光机理进行了讨论.     

反应溅射氧化锌薄膜的结构特点及性质

以金属Zn(纯度为99.99%)作为靶材,采用离子束反应溅射法在玻璃衬底上溅射沉积了一系列ZnO薄膜样品。通过对薄膜样品X射线衍射(XRD)谱的分析,发现尽管溅射条件不同,但是ZnO薄膜只沿(0002)晶面取向生长。衬底温度和溅射气体的氧分压对薄膜沿c轴取向生长有影响,其中衬底温度的影响较明显。溅射过程中发现衬底温度为360℃最适合(0002)晶面的生长,在此温度下溅射获得了完全沿c轴取向生长且衍射峰最强的ZnO薄膜。室温下测量了ZnO薄膜的发射光谱,发现薄膜在紫外区(364nm附近)、蓝绿区(470nm附近)有较强的发光峰,在紫光区(398nm附近)、蓝光区(452nm附近)和红外区(722nm附近)有较弱的发光峰。ZnO薄膜在空气中退火,对薄膜的结构、发光和电学性质都有一定影响。合适的退火温度可以促进薄膜沿c轴的取向生长;退火后ZnO多晶薄膜的晶粒比未退火的略大;退火使部分发光峰的位置发生偏移并使薄膜的发光强度增强;退火使薄膜的电阻率显著增大,薄膜的电阻率随氧分压的增大而增大。     

脉冲激光沉积法在多孔铝衬底上生长的ZnO薄膜的结构与光学性质

ZnO是一种性质优良很有前途的紫外光电子器件材料,多孔铝是一种良好的模板型衬底,试图将二者结合起来以制备出一种全新的光电功能材料。制备了三种不同孔径多孔铝衬底,采用脉冲激光沉积法,在真空背景下,在多孔铝衬底上生长了氧化锌薄膜。利用扫描电子显微镜、X射线衍射和光致荧光对样品进行了测试和分析。研究表明:利用不同孔径的多孔铝衬底生长的氧化锌薄膜的结构和光学性质差异很大。样品A的光致发光主要是394nm的紫外发射和498nm的蓝绿光发射;样品B的光致发光主要是417nm的紫光发射和466nm蓝光发射;样品C的光致发光主要是415nm的紫光发射和495nm的蓝绿光发射。由于薄膜是富锌的,随着在空气中氧化的进行,光谱发生变化。利用固体能带理论对光谱进行了全面的分析。     

Influence of Al-doping on the structure and optical properties of ZnO films

Al-doped ZnO (ZnO:Al) thin films with c-axis preferred orientation were deposited on glass substrates using the radio frequency reactive magnetron sputtering technique. The effect of Al concentrations on the microstructure and the luminescence properties of the ZnO:Al thin films were studied by atomic force microscopy (AFM), X-ray diffraction (XRD), and fluorescence spectrophotometer. The results showed that the crystallization of the films was promoted by appropriate Al concentrations; the photoluminescence spectra (PL) of the samples were measured at room temperature. Strong blue peak located at 437 nm (2.84 eV) and two weak green peaks located at about 492 nm (2.53 eV) and 524 nm (2.37 eV) were observed from the PL spectra of the four samples. The origin of these emissions was discussed. In addition, absorption and transmittance properties of the samples were researched by UV spectrophotometer; the UV absorption edge shifted to a shorter wavelength first as Al was incorporated, and then to a longer wavelength with the increasing Al concentrations. The optical band gaps calculated based on the quantum confinement model are in good agreement with the experimental values.     

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.     

The Al-doping and post-annealing treatment effects on the structural and optical properties of ZnO:Al thin films deposited on Si substrate

Al-doped ZnO (ZnO:Al) thin films with different Al contents were deposited on Si substrates using the radio frequency reactive magnetron sputtering technique. X-ray diffraction (XRD) measurements showed that the crystallinity of the films was promoted by appropriate Al content (0.75 wt.%). Then the ZnO:Al film with Al content of 0.75 wt.% was annealed in vacuum at different temperatures. XRD patterns revealed that the residual compressive stress decreased at higher annealing temperatures. While the surface roughness of the ZnO:Al film annealed at 300 °C became smoother, those of the ZnO:Al films annealed at 600 and 750 °C became rougher. The photoluminescence (PL) measurements at room temperature revealed a violet, two blue and a green emission. The origin of these emissions was discussed and the mechanism of violet and blue emission of ZnO:Al thin films were suggested. We concluded that the defect centers are mainly ascribed to antisite oxygen and interstitial Zn in annealed (in vacuum) ZnO:Al films.     

两步溶液法制备亚微米ZnO棒阵列及其退火后的发光

通过改变溶液浓度、酸碱度等生长条件,用两步化学溶液沉积法在玻璃衬底上制备出有序排列的亚微米级ZnO棒阵列,棒的截面呈正六边形,直径约为200~500nm。测量了样品的XRD谱和扫描电镜像,证明这些样品都是六方纤锌矿结构的ZnO单晶,且以[002]方向择优生长。将样品退火前后的PL光谱进行比较分析,发现退火后样品的发射光谱中紫外峰消失而长波段的红色发光峰红移并且增强(峰位由630nm左右移到720nm),而其激发光谱中的室温激子激发峰也增强。当退火时间增加到6h后,出现了由430nm的蓝峰和505nm绿峰组成的宽谱带蓝绿色发射。并对发光机理进行了讨论。     

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.     

Effect of the oxygen pressure on the microstructure and optical properties of ZnO films prepared by laser molecular beam epitaxy

A series of ZnO films were prepared on the Si (1 0 0) or glass substrate at 773 K under various oxygen pressures by using a laser molecular beam epitaxy system. The microstructure and optical properties were investigated through the X-ray diffraction, Raman spectrometer, scanning electron microscope, ultraviolet–visible spectrophotometer and spectrofluorophotometer. The results showed that ZnO thin film prepared at 1 Pa oxygen pressure displayed the best crystalinity and all ZnO films formed a columnar structure. Meanwhile, all ZnO films exhibited an abrupt absorption edge near the wavelength of 380 nm in transmission spectra. With increasing the oxygen pressure, the transmission intensity changed non-monotonically and reached a maximum of above 80% at 1 Pa oxygen pressure, based on which the band gaps of all ZnO films were calculated to be about 3.259–3.315 eV. Photoluminescence spectra indicated that there occurred no emission peak at a low oxygen pressure of 10⁻⁵ Pa. With the increment of the oxygen pressure, there occurred a UV emission peak of 378 nm, a weak violet emission peak of 405 nm and a wide green emission band centered at 520 nm. As the oxygen pressure increased further, the position of UV emission peak remained and its intensity changed non-monotonically and reached a maximum at 1 Pa. Meanwhile the intensity of green emission band increased monotonically with increasing the oxygen pressure. In addition, it was also found that the intensity of UV emission peak decreased as the measuring temperature shifted from 80 to 300 K. The analyses indicated that the UV emission peak originated from the combination of free excitons and the green emission band originated from the energy level jump from conduction band to O_Zn defect.     

Effect of substrate temperature on the morphology, structural and optical properties of Zn1−xCoxO thin films

Zn_1−xCo_xO thin films with c-axis preferred orientation were deposited on sapphire (0 0 0 1) by pulsed laser deposition (PLD) technique at different substrate temperatures in an oxygen-deficient ambient. The effect of substrate temperature on the microstructure, morphology and the optical properties of the Zn_1−xCo_xO thin films was studied by means of X-ray diffraction (XRD), atomic force microscopy (AFM), UV-visible-NIR spectrophotometer, fluorescence spectrophotometer. The results showed that the crystallization of the films was promoted as substrate temperature rose. The structure of the samples was not distorted by the Co incorporating into ZnO lattice. The surface roughness of all samples decreased as substrate temperature increased. The Co concentration in the film was higher than in the target. Emission peak near band edge emission of ZnO from the PL spectra of the all samples was quenched because the dopant complexes acted as non-radiative centers. While three emission bands located at 409 nm (3.03 eV), 496 nm (2.5 eV) and 513 nm (2.4 eV) were, respectively, observed from the PL spectra of the four samples. The three emission bands were in relation to Zn interstitials, Zn vacancies and the complex of V_O and Zn_i (V_OZn_i). The quantity of the Zn interstitials maintained invariable basically, while the quantity of the V_OZn_i slightly decreased as substrate temperature increased.     

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.     

Influence of annealing temperature on the photoluminescence property of ZnO thin film covered by TiO2 nanoparticles

In this work, ZnO thin films covered by TiO₂ nanoparticles (labeled as TiO₂-ZnO thin films) were prepared by electron beam evaporation. The influence of annealing temperature on the photoluminescence property of the samples was studied. The structures and surface morphologies of the samples were analyzed by X-ray diffraction (XRD) and atomic force microscope, respectively. The photoluminescence was used to investigate the fluorescent properties of the samples. The measurement results show that the ultraviolet emission of ZnO thin films is largely enhanced after they are covered by TiO₂ nanoparticles, while the green emission is suppressed. However, when the annealing temperature is relatively high (≥500 °C), the intensity of ultraviolet emission drops off and a violet emission peak along with a blue emission peak appears. This is probably connected with the atomic interdiffusion between TiO₂ nanoparticles and ZnO thin film. Therefore, selecting a suitable annealing temperature is a key factor for obtaining the most efficient ultraviolet emission from TiO₂-ZnO thin films.