p-type ZnO thin films grown by RF plasma beam assisted Pulsed Laser Deposition

The high exciton binding energy and band gap energy of ZnO thin films open the prospect of fabricating semiconductor lasers in the ultraviolet spectral range. A prerequisite for laser diode fabrication is highly p-doped ZnO which was not reproducibly obtained up to now. Without intentional doping ZnO exhibits n-type conduction. ZnO thin films have been obtained by radio-frequency assisted pulsed laser deposition. A metallic Zn target was used for ablation in an oxygen and nitrogen RF discharge. The electrical and morphological properties of the films grown on Si were studied by Atomic Force Microscopy (AFM), X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), optical absorption and Hall Effect measurements for different ratios between the nitrogen and oxygen content. The AFM images of the as-grown ZnO films reveal high quality surfaces with low values for the surface roughness and a sharp distribution of grains sizes as an effect of the RF discharge. The XRD patterns for all samples exhibit only (002) and (004) peaks indicating that the c-axis is always oriented normal to the substrate surface. The films present p-type conductivity with different carrier concentration and mobility depending on the nitrogen/oxygen ratio.     

氧分压对PLD制备ZnO薄膜结构和发光性质的影响

采用脉冲激光沉积(PLD)技术,在Si(100)衬底上制备出高度c轴取向的ZnO薄膜。通过X射线衍射(XRD)谱,扫描电镜(SEM)和室温光致发光(PL)光谱的测量,研究了生长气氛压强的改变对薄膜结构和光致发光的影响。实验结果表明,当氧压从10Pa升高到100Pa时ZnO(002)衍射峰的半峰全宽(FWHM)增大。可以认为这是由于较高的氧压下,到达衬底表面的离子动能减小。这样部分离子没有足够的能量迁移到生长较快的(002)面,c轴取向变差,导致(002)衍射峰的强度降低,半峰全宽增大。随着氧压增大,紫外发光强度增强。这可能是氧压变大,薄膜的化学配比升高,说明化学配比对UV发光的影响要大于薄膜微结构的影响。改变氧气压强对薄膜的表面形貌也有较大的影响。     

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     

Antimicrobial ZnO Nanoparticle–Doped Polyvinyl Alcohol/Pluronic Blends as Active Food Packaging Films

Today, plastic waste has been highlighted as one of the greatest threats to the environment. These environmental concerns and the increased necessity for safe food packaging have inspired scientists to focus on the development of active biodegradable materials. Herein, a novel poly(vinyl alcohol)/pluronic/ZnO nanocomposite film (PVA/PLUR/ZnO) is introduced as an active packaging material with enhanced antimicrobial activity. Gamma irradiation is used as a “green” route to prepare ZnO nanoparticles via a polymer pyrolysis method. The as-prepared ecofriendly ZnO nanoparticles are characterized and incorporated into the PVA/PLUR matrix in different concentrations. Transmission electron microscopy and dynamic light scattering measurements prove that ZnO nanoparticles have a mean particle size of 30 nm with a spherical-like morphology. Morphological and structural characterization confirm the successful incorporation of ZnO into the PVA/PLUR matrix, which in turn enhances the thermal and barrier properties of PVA/PLUR/ZnO nanocomposite films. On the other hand, the opacity of blends is increased. The PVA/PLUR/ZnO composites exhibit broad-spectrum antimicrobial activity against Gram-positive, Gram-negative bacterial pathogens, and fungi, and the activity increases with increasing concentrations of ZnO nanoparticles. These results introduce PVA/PLUR/ZnO films as effective antimicrobial materials for active food-packaging applications.     

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.     

脉冲激光沉积方法制备ZnO薄膜生长参量对发光特性的影响

用脉冲激光沉积（PLD）方法在Si（111）衬底上制备了ZnO薄膜。以325nmHe-Cd激光器为光源对薄膜进行了荧光光谱分析,用X射线衍射仪（XRD）和原子力显微镜（AFM）分别对薄膜的结构和形貌进行了分析。脉冲激光沉积方法的主要生长参量为氧压、激光重复频率、生长温度和激光能量。通过控制这些参量变量,研究了这些参量对ZnO薄膜发光特性的影响,得到了用于紫外发光的ZnO薄膜生长的优化条件：发现在温度为650℃左右、氧压50Pa左右、频率5Hz左右的范围内能得到半峰全宽较窄,强度较大的紫外发光峰。分析认为紫外峰主要是由激子辐射复合发光形成的,绿光带主要和Ozn的存在密切相关,氧空位是蓝光发射的重要原因。     

XRD study on the effect of the deposition condition on pulsed laser deposition of ZnO films

Using a pulsed laser deposition (PLD) process on a ZnO target in an oxygen atmosphere, thin films of this material have been deposited on Si(111) substrates. An Nd: YAG pulsed laser with a wavelength of 1064 nm was used as the laser source. The influences of the deposition temperature, laser energy, annealing temperature and focus lens position on the crystallinity of ZnO films were analyzed by X-ray diffraction. The results show that the ZnO thin films obtained at the deposition temperature of 400°C and the laser energy of 250 mJ have the best crystalline quality in our experimental conditions. The ZnO thin films fabricated at substrate temperature 400°C were annealed at the temperatures from 400°C to 800°C in an atmosphere of N₂. The results show that crystalline quality has been improved by annealing, the optimum temperature being 600°C. The position of the focusing lens has a strong influence on pulsed laser deposition of the ZnO thin films and the optimum position is 59.5 cm from the target surface for optics with a focal length of 70 cm.      

Crystalline structure and morphological properties of undoped and Sn doped ZnO thin films

Undoped and tin (Sn) doped ZnO thin films have been prepared by spray pyrolysis method. Effect of Sn dopant on the crystalline structure and morphological properties of ZnO thin films has been investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) method. XRD patterns confirm that the films have polycrystalline nature. While undoped ZnO film has (101) as the preferred orientation, Sn doped ZnO thin films have (002) as the preferred orientation. Grain sizes, lattice parameters and texture coefficient values of the films were determined. Microstructure was analyzed by SEM and the influence of the doping concentration in the microstructure of the films is investigated.     

不同溶胶体系对纳米氧化锌发光特性的影响

采用溶胶-凝胶工艺制备ZnO纳米粉体,研究了两种不同溶剂下制备的纳米ZnO的荧光特性。实验结果表明两种氧化锌样品有相同的晶型和能带结构,其紫外发光相似,但其带间的可见发射表现出了巨大差异,其原因在于两溶剂的极性不同导致两体系凝胶、烧结的微过程不同,从而使两种ZnO样品的表面态结构和布局发生变化。     

氧气后处理对氧化锌薄膜紫外发射性质的影响

为了提高ZnO光发射效率和制备p型ZnO,对热处理的氧分压对薄膜的结构、形貌、光致光发射和ZnO/Si异质结的Ⅰ-Ⅴ特性的影响进行了研究.用直流反应溅射法在p型硅衬底上生长ZnO薄膜形成n-ZnO/P-Si异质结.在1000℃下用不同比例的氧和氨热处理,我们发现,在纯氮气中得到的样品有强的紫外发射(390nm),随氧气比例增大,紫外增强,同时绿光也产生并随之增强.但过大的氧分压反而产生多的受主缺陷,使越来越多的激发能量转移到发射能量低的绿光中心,从而使紫外减弱.在纯氧和无氧条件下热处理的俄歇谱表明纯氧下氧过量,而无氧下锌大大过量.ZnO/p-Si异质结的Ⅰ-Ⅴ特性表明,无氧热处理表现为典型的n-ZnO/p-Si异质结;而在纯氧气氛中处理后所得Ⅰ-Ⅴ曲线反向,这表明在高氧压下受主缺陷的产生,表明ZnO薄膜有可能由于高氧压热处理由n型转为p型.     

不同溶胶体系对纳米氧化锌发光特性的影响

采用溶胶-凝胶方法制备ZnO纳米粉体,研究了两种不同溶剂下制备的纳米ZnO的荧光特性。结果表明两种氧化锌有相同的晶型和能带结构,其紫外发光相似,但其带间的可见发射表现出了巨大差异,其原因在于两溶剂的极性不同导致两体系凝胶、烧结的微过程不同,从而使两ZnO样品的表面态结构和布局发生变化。     

Effects of oxygen pressures on pulsed laser deposition of ZnO films

Zinc oxide (ZnO) thin films on Si (1 1 1) substrates were deposited by pulsed laser ablation of ZnO target at different oxygen pressures. A pulsed Nd:YAG laser with wavelength of 1064 nm was used as laser source. The deposited thin films have been characterized by X-ray diffraction (XRD), Atomic force microscopy (AFM), and Raman spectroscopy. XRD measurements indicate that the ZnO thin films deposited at the oxygen pressure of 1.3 Pa have the best crystalline quality. AFM results show that the surface roughness of ZnO film increases with the increase of oxygen pressure. The Raman results indicate that oxygen ambient plays an important role in removing defects due to excess zinc.     

不同基体刚性偶氮化合物光致光学各向异性及其唯象模拟

在不同刚性的聚合物基体聚甲基丙烯酸甲酯（PMMA）、聚乙烯咔唑（PVK）和聚苯乙烯（PS）薄膜基体中掺入相同质量分数（均为0．003）的分散红13（DRl3）偶氮染料。以线偏振连续Ar^＋激光（514nm）作为控制光,连续He-Ne激光（632．8nm）作为信号光考察了具有相同厚度的三种样品在相同控制光功率（15mW）下的光致双折射效应。实验发现刚性较大的聚乙烯咔唑基体样品的双折射效应最小,刚性最小的聚苯乙烯基体样品的双折射效应最大。在偶氮生色团光致异构的四能级模型基础上,建立一新的唯象的模型。在模型中引入描述聚合物基体刚性的参量s,通过数值计算描述了不同基体刚性参量s对偶氮生色团光致异构取向的影响。计算结果表明,基体的刚性越大,样品的光致双折射效应越小,定性地解释了实验现象。     

高分子网络凝胶法制备ZnO超细粉体及其光学性能

采用高分子网络凝胶法制备球形ZnO超细粉体。通过聚乙烯醇(PVA)亚浓溶液交联网络的空间位阻作用,经过烧结,获得了具有球形形貌的粒径为1~3μm的ZnO粉体颗粒。利用X射线衍射(XRD)、扫描电镜(SEM)分析了不同PVA浓度以及退火温度对产物形貌、结构的影响,发现在PVA溶液浓度为5%,并且经500℃热处理所形成的ZnO球形颗粒最为均匀规整。研究了球形ZnO粉体的光致发光性能,室温下经325nm波长激发,观察到两个中心波长分别位于407,468nm的微弱的荧光发射带,在合适温度下,在385nm处还出现了较强的紫外峰。PL光谱表明,退火温度对ZnO的光致发光影响较大,随着退火温度升高,由于表面缺陷和结晶性能发生变化,407nm处发射峰逐渐减弱消失,而紫外发光先增强后减弱,经500℃热处理样品的紫外发光性能达到最佳。     

Effect of excimer laser annealing on the properties of ZnO thin film prepared by sol-gel method

Pristine ZnO thin films have been deposited with zinc acetate [Zn(CH₃COO)₂], mono-ethanolamine (stabilizer), and isopropanol solutions by sol-gel method. After deposition, pristine ZnO thin films have been irradiated by excimer laser (λ = 248, KrF) source with energy density of 50 mJ/cm² for 30 sec. The effect of excimer laser annealing on the optical and structural properties of ZnO thin films are investigated by photoluminescence and field emission scanning electron microscope. As-grown ZnO thin films show a huge peak of visible region and a wide full width at half maximum (FWHM) of UV region due to low quality with amorphous ZnO thin films. After KrF excimer laser annealing, ZnO thin films show intense near-band-edge (NBE) emission and weak deep-level emission. The optically improved pristine ZnO thin films have demonstrated that excimer laser annealing is novel treatment process at room temperature.     

气相输运法制备ZnO薄膜(英文)

运用气相输运技术在不同的衬底上制备ZnO薄膜,同时对这些ZnO薄膜的表面形貌、晶体结构和光学特性进行表征。在扫描电子显微镜图像上可以看到,相比没有镀金的Si衬底,ZnO纳米颗粒在镀金的Si衬底上的生长尺寸较大。X射线衍射测试结果表明,在Si(111)和Si(100)衬底上生长的ZnO薄膜显示出不同的六角纤锌矿结构的衍射峰,但没有出现立方闪锌矿ZnO结构的衍射峰。在镀金的Si衬底上,ZnO薄膜生长取向主要为c轴方向。此外,所有ZnO样品的光致发光谱上均只出现一个狭窄且强的紫外峰,约在389 nm(3.19 eV)波长处。     

氧分压对磁控溅射制备ZnO薄膜的结构及光学特性的影响

采用射频反应磁控溅射法在玻璃衬底上成功制备出具有c轴高择优取向的ZnO薄膜,利用X射线衍射及紫外-可见吸收和透射光谱研究了氧分压变化对ZnO薄膜的微观结构及光吸收特性的影响。结果表明,当工作气压恒定时,用射频反应磁控溅射制备的ZnO薄膜的生长行为主要取决于成膜空间中氧的密度,合适的氧分压能够提高ZnO薄膜的结晶质量;薄膜在可见光区的平均透过率达到90%以上,且随着氧分压的增大,薄膜的光学带隙发生了一定程度的变化。采用量子限域模型对薄膜的光学带隙作了相应的理论计算,计算结果与对样品吸收谱所作的拟合结果符合较好,二者的变化趋势完全一致,表明ZnO纳米晶粒较小时,薄膜光学带隙的变化与量子限域效应有很大关系。     

ZnO薄膜受激发射特性的研究

氧化锌薄膜因其大的激子结合能和强的光发射、激光阈值低和能在高温下工作等优点而成为制备短波长激光、发光二极管等光电子器件的有希望材料。采用激光分子束外延 (L MBE)方法制备了ZnO薄膜。在室温下 ,测量了样品的吸收光谱 ,以及不同光泵浦强度下的发射光谱。从光谱图中可以看出该材料有很好的质量。研究了ZnO薄膜的受激发射特性及机理 ;测量了发射光强与泵浦光强之间的关系 ;比较了较高激发密度下的受激发射、自发发射和激光脉冲的时间特性 ,这些都证实了该发射是受激发射。     

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.     

Characterization and aging effect study of nitrogen-doped ZnO nanofilm

The influence of sputtering and annealing conditions and aging effect on properties of sputtered ZnO:N thin films were investigated. Achieved results confirmed a planar growth of nitrogen-doped ZnO film with a high uniform and smooth surface morphology. Incorporation of nitrogen in the ZnO films made new Raman shifts. X-ray diffraction spectra showed only the ZnO (0 0 2) diffraction peak, which was slightly shifted toward lower angels, compared to pure ZnO, which is the result of incorporating nitrogen in the ZnO films. The amount of this shift was proportional to N concentration. In addition, annealed samples showed better crystallinity with lower shift due to dramatically reduction of N atoms during the annealing. The Hall effect measurements exhibited p-type behaviour on annealed ZnO:N thin films while the un-annealed samples showed n-type conductivity. Aging effect studies demonstrated that the N content of thin films decreased dramatically as time passed. The reduction of N concentration in annealed samples was lower than un-annealed ones after 6 months.