可溶性钒氧酞菁在不同介质中的吸收光谱研究

研究了四丙基取代钒氧酞菁（Ｐｒ４ＶＯＰｃ）在不同介质中的吸收光谱。Ｐｒ４ＶＯＰｃ分子在不同介质中的吸收光谱差别很大：在稀溶液中以分子的单体吸收为主（λｍａｘ＝７０７ｎｍ），在浓溶液和ＰＭＭＡ薄膜中由于形成平行排列结构的二聚体而使分子单体的吸收峰发生蓝移（λｍａｘ＝６６０ｎｍ），在蒸发膜中则由于形成斜交结构的二聚体使得分子单体的吸收峰发生分裂形成红移和蓝移峰（λｍａｘ＝７２０ｎｍ，６６０ｎｍ），在溶液沉积的固态薄膜中由于形成结晶相Ｉ而表现出强烈的近红外吸收（λｍａｘ＝８２６．９ｎｍ）。造成这种差别的原因是四个丙基的引入加大了ＶＯＰｃ分子的空间位阻效应。通过热处理或溶剂蒸汽处理，可以使Ｐｒ４ＶＯＰｃ蒸发膜转变成具有强近红外吸收的结晶相Ｉ；而只有通过溶剂蒸汽处理才能使ＰＭＭＡ介质中的Ｐｒ４ＶＯＰｃ转变成结晶相ＩＩ。     

Vanadyl phthalocyanine: An organic material for optical data recording

Vanadyl Phthalocyanine (VOPc) is a stable organic dye which absorbs in the spectral range of currently available injection lasers. The applicability for high density optical storage of single, double and triple layer structures containing a thin film of this dye, is investigated. It is concluded that if VOPc is used in combination with a tellurium film, some power reduction relative to single Te films can be achieved.     

基于SSCVD方法的a-b轴取向ZnO薄膜制备

以Zn₄(OH)₂(O₂CCH₃)₆·2H₂O为单一固相有机源,采用单源化学气相沉积法(Single sour cechem icalvapor deposition,SSCVD)在Si(100)衬底上制备ZnO薄膜,用X射线衍射(XRD)、原子力显微镜(AFM)分析ZnO薄膜样品的晶体结构和微观形貌,并用X射线光电子能谱(XPS)对薄膜的锌氧化学计量比进行了分析。研究结果表明:在非平衡条件下所得到的ZnO薄膜沿a-b轴取向生长,基片温度对ZnO薄膜生长过程影响较大,随着基片温度的升高,薄膜呈现c轴生长趋势;晶粒成柱状、尺寸均匀、膜层结构致密;薄膜样品中n_Zn:n_O=0.985。     

溶剂处理对Pr4VOPc染料掺杂聚合物薄膜光谱的影响

制备了Ｐｒ４ＶＯＰｃ染料掺掺杂的聚合物ＰＭＭＡ（ＤＩＰ）薄膜。Ｐｒ４ＶＯＰｃ在染料掺杂聚合物薄膜形成阶段形成玻璃态Ⅰ，经有机溶剂蒸汽处理后，Ｐｒ４ＶＯＰｃ形成了热力学更稳定的相Ⅱ。     

Weakly bound buffer layers: A versatile template for metallic nano-clusters growth and film patterning on solid surfaces

Buffer layers composed of weakly bound atoms or molecules on solid surfaces are discussed as a versatile platform for size controlled growth of nano-clusters and for patterning of thin metallic films. Metallic nano-crystals can be prepared and their size and density be controlled by varying the film thickness. Cold metallic or oxide clusters, softly land and deposit on solid substrates via the Buffer Layer Assisted Growth (BLAG) method. Their final structure, therefore, reflects purely the interaction with the substrate with no kinetic constraints that may play a role in direct deposition methods of hot atoms. The nature of the buffer film, being a rare gas or a molecular film, can somewhat affect the shape of clusters as well. Applying laser ablation techniques, these weakly bound films were demonstrated to assist in patterning of metallic films. It operates on practically any cold, flat solid substrate that absorbs the laser light. Parallel stripes at sub-micron width, millimeter long, were obtained experimentally, with line width determined by the ablating laser power. The versatility of these weakly bound films in manipulating the structure of metallic particles and thin films is discussed in its wider potential scope.     

Combinatorial approach to the fabrication of organic thin films

We demonstrate combinatorial approach in investigation of organic thin film fabrication. “Combinatorial substrate screening”, which is the deposition onto several kinds of substrates simultaneously, is useful to choose suitable substrate for organic thin film growth. “Combinatorial thickness-gradient films” can be fabricated using a moving mask which travels from an edge to another edge of substrate continuously during the deposition. The combinatorial thickness-gradient film can be regarded as the library for time evolution of film growth during the deposition. This mapping can serve as a powerful method for the research of growth of thin film in an initial stage. Besides, combinatorial thickness-gradient film can be utilized for the examination of a buffer layer effect. These techniques enable us to quickly optimize for the fabrication of high-quality organic thin films.     

Effect of Substrate Bias on Microstructures of Zirconia Thin Films Deposited by Cathodic Vacuum Arc

Zirconium oxide （Zr02） thin films are deposited at room temperature by cathodic arc at substrate biases of 0 V, -60 V and -120 V, respectively. The crystal structure, composition, morphology, and deposition rate of the as-deposited thin films are systematically investigated by x-ray diffraction, x-ray photoelectron spectroscopy （XPS） as well as scanning electron microscopy. The results show that the crystal structure, morphology and deposition rate of the films all are dependant on substrate bias. With the increase of bias voltage from 0 V to -120 V, the zirconium oxide thin film grown on silicon wafer first exhibits monoclinic lattice and tetragonal lattice, further evolves monoclinic phase with the preferred orientation along the （-111） and （-222） directions at -60 V and finally along nearly one observed preferred （002） direction under -120 V. In addition, the variations of morphology with bias voltage are correlated to changes of the film structure. The results of XPS demonstrate that Zr elements are almost oxidized completely in the films achieved under -120 V bias.     

Morphological and optical properties of titanyl phthalocyanine films deposited by supersonic molecular beam epitaxy (SuMBE)

We studied the growth and properties of titanyl phthalocyanine (TiOPc) thin films made by supersonic molecular beam epitaxy (SuMBE). Interesting differences in the growth properties on amorphous (quartz) and crystalline (mica) substrates were found, indicating that SuMBE gives rise to an epitaxy of disc-like organic molecules on crystalline substrates. The combined control of the kinetic energy of the molecules in the supersonic beam specific to SuMBE and of the substrate temperature during deposition are the key parameters used to determine the final properties of the films. We show that SuMBE is a well-suited epitaxy method for the deposition of relatively large organic molecules, leading to layers of thin organic (single-)crystals with lateral dimensions in the micrometer range. By SuMBE we can control the growth of different polymorphs of TiOPc. We found and studied two ways to produce films of red and infrared absorbing phase II TiOPc, which is of interest for applications in organic solar cells.     

Fabrication of ZnO thin films by femtosecond pulsed laser deposition

The growth of ZnO thin films on sapphire substrate using the femtosecond PLD technique is reported. The effect of substrate temperature and oxygen pressure on the structural properties of the films was studied. Highly c-axis oriented ZnO films can be grown on sapphire substrates under vacuum conditions using the femtosecond PLD process. There is an optimum substrate temperature for the pulsed laser deposition of ZnO film that enhances the thermodynamic stability and allows the formation of well-crystallized thin films. The crystal quality of the films can be further improved by increasing the deposition time and introducing oxygen during the pulsed laser deposition process.     

Perpendicularly oriented barium ferrite thin films with low microwave loss,prepared by pulsed laser deposition

Barium ferrite(Ba M) thin films are deposited on platinum coated silicon wafers by pulsed laser deposition(PLD).The effects of deposition substrate temperature on the microstructure,magnetic and microwave properties of Ba M thin films are investigated in detail.It is found that microstructure,magnetic and microwave properties of Ba M thin film are very sensitive to deposition substrate temperature,and excellent Ba M thin film is obtained when deposition temperature is 910℃ and oxygen pressure is 300 m Torr(1 Torr = 1.3332×10~2Pa).X-ray diffraction patterns and atomic force microscopy images show that the best thin film has perpendicular orientation and hexagonal morphology,and the crystallographic alignment degree can be calculated to be 0.94.Hysteresis loops reveal that the squareness ratio(M_r/M_s) is as high as 0.93,the saturated magnetization is 4004 Gs(1 Gs = 10~4T),and the anisotropy field is 16.5 kOe(1 Oe = 79.5775 A·m~(-1)).Ferromagnetic resonance measurements reveal that the gyromagnetic ratio is 2.8 GHz/kOe,and the ferromagnetic resonance linewith is108 Oe at 50 GHz,which means that this thin film has low microwave loss.These properties make the Ba M thin films have potential applications in microwave devices.     

石英衬底上GaN薄膜沉积及其光学性能的研究

GaN薄膜材料广泛应用于发光二极管(LED),激光二极管(LD)等光电器件。但是GaN基器件的制备与应用以及器件推广很大一部分取决于其器件的价格,常用的方式是在单晶蓝宝石衬底上沉积制备GaN薄膜样品,单晶蓝宝石衬底晶向择优,可以制备出高质量的GaN薄膜样品,但是单晶蓝宝石衬底价格昂贵,一定程度上限制了其GaN基器件推广使用。如何在廉价衬底上直接沉积高质量的GaN薄膜,满足器件的要求成为研究热点。石英玻璃价格廉价,但是属于非晶体,没有择优晶向取向,很难制备出高质量薄膜样品。本研究采用等离子体增强金属有机物化学气相沉积系统在非晶普通石英衬底上改变氮气反应源流量低温制备GaN薄膜材料。制备之后采用反射高能电子衍射谱、X射线衍射光谱、室温透射光谱和光致光谱对制备的薄膜进行系统的测试分析。其结果表明：在氮气流量适当的沉积参数条件下,所制备的薄膜具有高C轴的择优取向,良好的结晶质量以及优异的光学性能。     

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利用微波电子回旋共振等离子体增强型化学气相沉积(ECR-PECVD)采用一步法直接在K9玻璃上低温沉积制备了多晶硅薄膜.研究了不同实验参数对薄膜沉积的影响,采用X射线衍射(XRD)、拉曼光谱、扫描电子显微镜(SEM)等实验分析方法对不同条件下制备的样品进行了晶体结构和表面形貌分析,并讨论了多晶硅薄膜沉积的最佳条件.实验结果表明,玻璃衬底上多晶硅薄膜呈柱状生长,并有一定厚度的非晶孵化层;较高氢气比例和衬底温度有利于结晶,薄膜的结晶率达到了62％;晶粒团簇的最大尺寸约为500nm.     

退火处理对YMnO3薄膜的结构和荧光性能的影响

室温下,采用脉冲激光沉积方法在Si(100)衬底上制备了YMnO3薄膜,并对其进行了不同温度的退火处理。采用X射线衍射和荧光光谱分析方法对薄膜的结构和荧光特性进行了研究。结果表明:通过退火处理,可以得到正交相和六方相共存的多晶态YMnO3薄膜,并且随着退火温度的升高,两相的比例发生变化,由正交相为主转变为六方相为主。YMnO3薄膜样品的荧光发射峰集中在波长430～620nm范围内,可能是由Mn3 离子从5T2到5E之间的能级跃迁所引起的。其荧光强度随着退火温度的升高逐渐增强,但峰位基本保持不变,说明薄膜结构的改变对Mn3 离子的能级跃迁几率有明显的影响,对能级位置的影响不大;而且荧光光谱还显示在同一薄膜中各个荧光峰的相对强度随着退火温度的变化不大。     

显微拉曼研究外延生长的BaTiO_(3-x)薄膜的结构相变与结构动力学(英文)

我们用显微拉曼、卢瑟福背散射谱、X射线散射和非对称摇摆等实验手段研究了在1 0 - 2 到1 0 - 5帕氧气压下用激光分子束外延技术生长的BaTiO3-x薄膜的结构动力学特性。测量结果表明生长氧压越低,晶格常数c和c/a越大,晶格常数a稍微减小,晶胞体积变大。随着生长氧压的减小,薄膜中氧含量减小。在3 0×1 0 - 5帕氧气压下生长的薄膜中氧缺陷可达0 48,但是样品的四方相结构可以很好的维持。显微拉曼研究进一步确定了样品都是四方相结构。另外,在BaTiO2 52 薄膜的拉曼光谱中发现高频段有两个新峰,其可能是由于氧缺陷导致的二级拉曼散射引起的。随着生长氧压的减小,拉曼峰向低频移动,表明薄膜中的应力减小。同时,拉曼峰变宽,这可能是由于氧缺陷导致的结构畸变引起的。由于在薄膜中存在二维张应力,BaTiO3单晶样品中的结构相变特征在我们的样品中从78到5 5 0K的温度范围内不存在。     

Internal stresses and stability of the tetragonal phase in zirconia thin layers deposited by OMCVD

Zirconia thin films were deposited by OMCVD (organo-metallic chemical vapour deposition) at various temperatures and oxygen partial pressures on a AISI 301 stainless steel substrate with Zr(thd)₄ as precursor. The as deposited 250 nm thin zirconia films presented a structure consisting of two phases: the expected monoclinic one and also an unexpected tetragonal phase. According to the literature, the stabilization of the tetragonal phase (metastable in massive zirconia) can be related to the crystallite size and/or to the generated internal compressive stresses.To analyze the effect of internal and external stresses on the thin film behaviour, in-situ tensile experiments were performed at room temperature and at high temperature (500 °C).Depending on the process parameters, phase transformations and damage evolution of the films were observed. Our results, associated to XRD (X-ray diffraction) analyses, used to determine phase ratios and residual stresses within the films, before and after the mechanical experiments, are discussed with respect to their microstructural changes.     

Al(001)表面上沉积Ti薄膜的分子动力学模拟

采用分子动力学模拟方法,研究了Ti原子连续沉积于Al(001)表面上的薄膜生长过程,分析了入射能量为0.1、5 eV和衬底温度为300、700 K时的界面结合及微观结构.模拟结果表明,增加入射能量和衬底温度,使Ti薄膜的表面越光滑;通过径向分布函数和键对分析技术对薄膜微观结构进行分析,发现衬底温度时薄膜微观结构影响较大,温度300 K及以下时,Ti薄膜主要是FCC结构,随着温度升高,FCC结构成分减少,无序结构成分增加,而入射能量则对薄膜微观结构没有明显影响.     

Morphology and gas sensitivity of erbium di-phthalocyanine thin films

Studies have been made of the application of certain phthalocyanine films in the detection of toxic gases such as chlorine. Consideration has been given to preparation parameters such as deposition conditions (evaporation rate, ambient pressure, post deposition annealing) together with varying central metal atoms within the phthalocyanine molecule. Particular studies have been made concerning the relationship between elevated substrate temperature deposition, the molecular structure and the corresponding sensitivity of the films to gases. The present results are considered within the context of the development of an economically viable selective thin film gas sensor.     

Spectroscopic and Morphological Properties of Divinylbenzoxazolylbiphenyl Thin Films

The thin organic films based on 4,4′-bis-[(Z)-1-(1,3-benzoxazol-2-yl-2-ethenyl)]biphenyl and its partly fluorinated derivatives are studied. Absorption, luminescence, and excitation spectra, luminescence decay and film morphology were found to depend sensitively on the changes in molecule structure, nature and temperature of the substrate, as well as the thermovacuum deposition rate, being the origins of bad reproducibility of the optical properties of such films. Molecular aggregation with chromophore dipoles arranged parallel to each other has been observed in absorption and luminescence spectra. The fluorescence characteristics can be explained by the combination of radiation of aggregated and non-aggregated molecules. The main characteristics of the molecules under study are calculated using DFT approach. The unusual behaviour of photodegradation in fluorinated film is found.     

Effects of deposition temperature and thickness on the structural properties of thermal evaporated bismuth thin films

Bismuth (Bi) thin films of different thicknesses were deposited onto Si(1 0 0) substrate at various substrate temperatures by thermal evaporation technique. Influences of thickness and deposition temperature on the film morphologies, microstructure, and topographies were investigated. A columnar growth of hexahedron-like grains with bimodal particle size distribution was observed at high deposition temperature. The columnar growth and the presence of large grains induce the Bi films to have large surface roughness as evidenced by atomic force microscopy (AFM). The dependence of the crystalline orientation on the substrate temperature was analyzed by X-ray diffraction (XRD), which shows that the Bi films have completely randomly oriented polycrystalline structure with a rhombohedral phase at high deposition temperature (200 °C) and were strongly textured with preferred orientation at low deposition temperatures (30 and 100 °C).     

红荧烯薄膜生长及稳定性的研究

利用原子力显微镜研究了二氧化硅衬底上红荧烯薄膜的生长及稳定性。在较低沉积速率下,较低衬底温度时,红荧烯分子有充足的扩散时间,利于薄膜的横向生长,形成连续性、均匀性较好的薄膜。快速蒸镀及较高衬底温度使红荧烯薄膜转变为纵向生长模式,形成团粒状岛。横向生长的红荧烯薄膜在退火和空气中表现为亚稳特性,随着退火温度的升高和空气中放置时间的延长,红荧烯分子会自发地进行质量传输,发生纵向转移,转变为团粒状岛。获得了二氧化硅界面上红荧烯薄膜的生长及亚稳定机制模型。研究结果证明红荧烯分子与二氧化硅界面之间的作用力小于红荧烯分子间的作用力。