脉冲激光沉积法制备VO_2热致变色薄膜研究进展

基于半导体和金属间的相变特性,伴随着温度、电场、压力的变化,具有相关智能特性的VO_2薄膜材料具有较大的应用潜力.本文主要阐述脉冲激光沉积技术在制备金属氧化物方面的物理过程和技术特点,详细介绍脉冲激光沉积制备VO_2薄膜材料的工艺参数和国内外研究进展,并与几种常规制备方法进行对比,给出脉冲激光沉积掺杂对VO_2薄膜材料特性的影响,以及采用脉冲激光沉积制备VO_2纳米材料,讨论了脉冲激光沉积制备具有智能特性的VO_2薄膜材料存在的问题和发展方向.     

蓝宝石衬底上VO_2薄膜的PLD外延生长

采用脉冲激光沉积技术,在c面蓝宝石衬底上制备出了VO_2薄膜。利用X射线衍射、Raman光谱、原子力显微镜对生长的样品的结构和表面形貌进行了表征;利用霍尔效应测试仪和紫外-可见-红外光分光光度计分别测试薄膜的方块电阻和透过率。结果表明:在蓝宝石衬底上生长出了结晶性能良好的VO_2薄膜;相变前后其方块电阻变化高达4个数量级,红外透过率的变化高达56%。VO_2薄膜表现出了良好的金属-绝缘转变特性。     

激光化学刻蚀YBCO高温超导薄膜进程中电流与红外特性

利用自行研制的电流与红外实时监测系统,研究了YBCO高温超导薄膜激光辅助化学刻蚀进程中溶液腐蚀电流与红外辐射的变化规律,为YBCO激光化学刻蚀技术中激光功率选择,腐蚀液配比,温度控制以及刻蚀时间的掌握提供了重要的实验依据.主要研究结论包括:YBCO薄膜激光化学刻蚀中溶液腐蚀电流初始值较大,增长速率相对稳定,观察到"陡降峰"的出现,并与无激光辐照下的溶液腐蚀电流变化曲线进行对比,分析了可能的原因;通过对腐蚀溶液的侧面红外实时监测,观察化学热的生成及其对流情况,发现激光辐照使YBCO薄膜刻蚀速率加快,而且除激光化学作用外,腐蚀液自身温度升高也是导致刻蚀速率加快的重要因素.     

纳秒激光辐照对类金刚石薄膜的损伤及改性

利用Nd:YAG纳秒激光(波长分别为355、532和1 064 nm)辐照由电子束蒸发技术制备的类金刚石(DLC)薄膜,通过光学显微镜、光学轮廓仪和拉曼光谱仪等分析了辐照后的薄膜样品,结果表明:不同波长的单脉冲激光辐照时,DLC膜的激光损伤阈值不同;同一波长的多脉冲激光辐照时,损伤阈值低于单脉冲辐照阈值;脉冲激光辐照对DLC膜具有改性作用,受辐照薄膜区域表层发生了石墨化、剥落和气化效应,致使DLC膜表面出现了隆起和弹坑,隆起高度和弹坑深度与激光能量密度大小和脉冲个数有关.     

晶格畸变对VO_2相变温度的影响

采用高功率脉冲磁控溅射在石英玻璃基片上成功制备了具有明显金属-绝缘体转变特性的多晶VO_2薄膜,其最低相变温度仅为32℃。X射线衍射结果表明沉积薄膜的晶体结构均为存在明显晶格畸变的VO_2(M),且薄膜(011)晶面间距越接近相变后VO_2(R)(110)晶面的晶面间距,相变温度越低。根据试验结果,利用从头算分子动力学分别对VO_2金属-绝缘体相变过程的晶体结构与态密度演化规律进行了研究。结果表明:随计算温度升高,不同(011)晶面间距绝缘态超胞的晶体结构均逐渐由VO_2(M)向VO_2(R)转变,同时伴随着禁带宽度的逐渐降低,最终转变为费米能级完全被电子占据的金属态;初始VO_2(M)超胞(011)面的晶面间距与相变后VO_2(R)(110)面的晶面间距之差越小,费米能级附近的禁带宽度也越小,这可能是导致VO_2金属-绝缘体转变温度降低的本质物理原因。     

VO2（M）控温包装薄膜制备的研究进展

二氧化钒(VO_2)纳米颗粒具有多种晶型结构,其单斜型半导体M相(VO_2(M))在接近室温时具有完全可逆的相转变性质,相变为四方金红石金属R相,从而引起光学性能的急剧变化,因而VO_2(M)可作为良好的阻热材料应用于控温包装薄膜领域。综述了VO_2(M)纳米颗粒和控温包装薄膜的制备方法,展望了VO_2(M)控温包装薄膜的研究方向。VO_2(M)纳米颗粒的传统制备方法有一步水热法和热分解法等,近年来也出现了新型制备方法,如籽晶诱导法和火焰燃烧法等;控温包装薄膜主要的制备方法为气相法和液相法。根据不同产品的温度需求,通过改变原料种类、温度及掺杂元素等工艺参数调节VO_2(M)纳米颗粒的相变温度,可制备出不同相变温度的VO_2控温包装薄膜。VO_2(M)控温包装薄膜作为一种高新科技产物,可以有效调控商品运输和储藏过程中包装内氛围,具有广阔的应用前景。     

浸渍法VO_2薄膜的相变

本文以VO(i-OC_2H_5)_3为原料采用溶胶-凝胶浸渍法在三种不同基片上制备了凝胶薄膜,通过真空热处理得到了 VO_2薄膜。由于 VO_2在67℃左右产生热诱导半导体-金属可逆相变,红外区域透过率在加热前后可变化45%,采用红外光谱及 X 射线衍射法分析了 VO_2薄膜的结构。     

二氧化钒薄膜智能窗的研究进展

二氧化钒具有良好的半导体-金属相变特性,在常温下,二氧化钒的晶体结构为单斜晶系结构(M相),随着温度的升高达到相变温度,二氧化钒的晶型变成四方晶红石结构(R相),当温度降低到相变温度时,二氧化钒的晶型又变回单斜晶系结构(M相)。这种典型可逆热色特征,使二氧化钒成为当前建筑用智能窗材料的最佳选择。综述了近些年来制备VO_2薄膜的几种常用方法,并针对VO_2薄膜在热色智能窗应用方面存在的主要问题,从掺杂和复合薄膜结构两方面总结了提高VO_2薄膜性能的改进工艺,为推进VO_2薄膜智能窗的进一步研究提供了依据。     

VO2薄膜相变温度调节方法及机理

VO_2是一种相变温度为68℃(接近室温)的热致相变材料,具有十分广泛的潜在应用价值。但68℃相较于环境温度仍显得较高,而且不同的应用环境对相变温度有不同的需求,因此针对VO_2薄膜相变温度调节问题的研究很有必要。详细介绍了元素掺杂、引入离子液体、氢化处理、界面应力调节等相变温度调节方法并阐述了其各自相变温度调节机理,同时比较了这几种方法的优缺点,并对未来研究方向作出展望,为今后VO2薄膜的制备与应用研究提供了重要参考。     

激光作用下GeS2非晶半导体薄膜的性能及结构变化

采用514.5石nm波长的氩离子激光器,结合X射线衍射分析（XRD）、红外光谱分析（IR）、扫描电镜分析（SEM）和透射光谱分析,研究了GeS₂非晶半导体薄膜在激光辐照后的性能及结构变化.实验结果发现,经热处理和激光辐照后,薄膜的光学吸收边均移向短波长处,并且随着辐照激光强度和辐照时间的增加而增加,这种平移在退火薄膜中是可逆的.SEM结果分析表明,薄膜在激光辐照后有晶相出现,且随着辐照激光强度的增加,晶相更多.     

Nonlinear optical investigations on Al doping ratio in ZnO thin film under pulsed Nd:YAG laser irradiation

In the present study, it has been reported on the effect of Al doping on linear and nonlinear optical properties of ZnO thin films synthesized by spray pyrolysis method. The structural properties of ZnO thin films with different Al doping levels (0–4 wt%) were analyzed using X-ray diffraction (XRD). The results obtained from XRD analysis indicated that the grain size decreased as the Al doping value increased. The UV–Vis diffused refraction spectroscopy was used for calculation of band gap. The optical band gap of Al-doped ZnO (AZO) thin films is increased from 3.26 to 3.31 eV with increasing the Al content from 0 to 4 wt%. The measurements of nonlinear optical properties of AZO thin films have been performed using a nanosecond Nd:YAG pulse laser at 532 nm by the Z-scan technique. The undoped ZnO thin film exhibits reverse saturation absorption (RSA) whereas the AZO thin films exhibit saturation absorption (SA) that shows RSA to SA process with adding Al to ZnO structure under laser irradiation. On the other hand, all the films showed a self-defocusing phenomenon because the photons of laser stay on below the absorption edge of the ZnO and AZO films. The third-order nonlinear optical susceptibility, χ⁽³⁾, of AZO thin films, was varied from of the order of 10^?5–10^?4 esu. The results suggest that AZO thin films may be promising candidates for nonlinear optical applications.     

Dynamic optical limiting experiments on vanadium dioxide and vanadium pentoxide thin films irradiated by a laser beam

Vanadium dioxide (VO2) and vanadium pentoxide (V2O5) thin films are irradiated by a near-infrared continuous-wave laser beam and the dynamic optical limiting performance is measured. The temperature varying with time of the films induced by a laser beam is also recorded by an IR thermal sensor. Under the irradiation of a laser beam with an intensity of 255 W/cm2 and a spot diameter of 2 mm, the laser beam transmittance of the VO2 film decreases from 47% before phase transition to 28% after phase transition, and the response time is approximately 200 ms; the laser beam transmittance of the V2O5 film decreases from 51% before phase transition to 24% after phase transition, and the response time is approximately 40 ms. The optical limiting is realized by this laser heating-induced phase transition.     

Manipulation of cell membrane using carbon nanotube scaffold as a photoresponsive stimuli generator

We describe, for the first time, the perforation of the cell membrane in the targeted single cell based on the nanosecond pulsed near-infrared (NIR) laser irradiation of a thin film of carbon nanotubes that act as an effective photon absorber as well as stimuli generator. When the power of NIR laser is over 17.5 μJ/pulse, the cell membrane after irradiation is irreversibly disrupted and results in cell death. In sharp contrast, the perforation of the cell membrane occurs at suitable laser power (～15 μJ/pulse) without involving cell termination.     

Novel approach to the fabrication of Au/silica core-shell nanostructures based on nanosecond laser irradiation of thin Au films on Si

We demonstrate the possibility of producing Au/SiO(2) core-shell nanoparticles by nanosecond laser irradiation of thin (5 and 20 nm) Au films on Si. The Au/Si eutectic reaction and dewetting process caused by the fast melting and solidification dynamics induced by the nanosecond laser irradiations are investigated as the origin of the formation of core-shell nanoparticles. Using several microscopic techniques (Rutherford backscattering spectrometry, scanning electron microscopy, atomic force microscopy, transmission electron microscopy, and energy filtered transmission electron microscopy) the formation and evolution of the core-shell structures are investigated as a function of the laser fluence in the 500-1500 mJ cm(-2) range for both film thicknesses. In particular, the mean height and diameter and surface density evolution of the core-shell structures are quantified and correlated to the laser fluence and Au film thickness.     

Analysis of thermal effect on transparent conductive oxide thin films ablated by UV laser

Transparent conductive oxide thin films are applied to many computer, communication and consumer electronics products including thin film transistor liquid crystal displays, organic light emitting diodes, solar cells, mobile phones, and digital cameras. The laser direct write patterning of the indium tin oxide (ITO) thin film processing technique produces a heat affected zone that has an enormous effect on the electro-optical efficiency of transparent conductive oxide films. This is because direct laser writing patterning in thermal machining process can create debris and micro-cracks in the substrate. Therefore, this study establishes the ultraviolet (UV) laser ablation of temperature model on the polycarbonate and soda-lime glass substrates using the finite element analysis software ANSYS, and measures the temperature field based on the laser micro-patterning process. The meshing model determines the structure of the pre-processors and parameters were set with ANSYS parameter design language. This study also simulates the Gaussian distribution laser irradiation on the pre-processor structure. A UV laser processing system made micro-patterning on ITO thin films to analyze which conditions damaged the substrates. Comparing the simulation and experiment results reveals the minimum laser ablation threshold of the ITO thin films with the melting and vaporization temperatures. Simulation results show that the temperature distribution on PC and soda-lime glass substrates after laser irradiation of 1.05 μs with a laser output power of 0.07 W produces temperatures of approximately 52 °C, 54 °C and 345°Cand 205 °C at the laser output power of 0.46 W. The experiment results show that the patterning region is similar to the simulation results, and the lower laser power does not damage the substrates.     

交流量热法测量SiO2薄膜的热扩散率

介绍了交流量热法测量薄膜热扩散率的原理和系统组建，用脉宽为纳秒级的超短激光脉冲作为热源，测量了Si衬底上厚度为100nm和500nm的SiO2薄膜水平方向上的热扩散率，实验结果表明该结构的热扩散率比SiO2体材料的要小，并且随着SiO2层厚度的减小，热扩散率也减少。     

晶粒尺寸对氧化钒薄膜电学与光学相变特性的影响

采用直流对靶磁控溅射方法制备氧化钒薄膜,通过改变热处理温度获得了具有不同晶粒尺寸的相变特性氧化钒薄膜,对氧化钒薄膜相变过程中电阻和红外光透射率随温度的突变性能进行研究.结果表明:经300℃和360℃热处理后,薄膜内二氧化钒原子分数达到40%,氧化钒薄膜具有绝缘体-金属相变特性,薄膜的晶粒尺寸分别为50nm和100nm;...     

Improvement of physical properties of IGZO thin films prepared by excimer laser annealing of sol–gel derived precursor films

Indium gallium zinc oxide (IGZO) transparent semiconductor thin films were prepared by KrF excimer laser annealing of sol–gel derived precursor films. Each as-coated film was dried at 150 °C in air and then annealed using excimer laser irradiation. The influence of laser irradiation energy density on surface conditions, optical transmittances, and electrical properties of laser annealed IGZO thin films were investigated, and the physical properties of the excimer laser annealed (ELA) and the thermally annealed (TA) thin films were compared. Experimental results showed that two kinds of surface morphology resulted from excimer laser annealing. Irradiation with a lower energy density (≤250 mJ cm⁻²) produced wavy and irregular surfaces, while irradiation with a higher energy density (≥350 mJ cm⁻²) produced flat and dense surfaces consisting of uniform nano-sized amorphous particles. The explanation for the differences in surface features and film quality is that using laser irradiation energy to form IGZO thin films improves the film density and removes organic constituents. The dried IGZO sol–gel films irradiated with a laser energy density of 350 mJ/cm² had the best physical properties of all the ELA IGZO thin films. The mean resistivity of the ELA 350 thin films (4.48 × 10³ Ω cm) was lower than that of TA thin films (1.39 × 10⁴ Ω cm), and the average optical transmittance in the visible range (90.2%) of the ELA 350 thin films was slightly higher than that of TA thin films (89.7%).     

Thin film deposition on plastic substrates using silicon nanoparticles and laser nanoforming

Reduced melting temperature of nanoparticles is utilized to deposit thin polycrystalline silicon (c-Si) films on plastic substrates by using a laser beam without damaging the substrate. An aqueous dispersion of 5 nm silicon nanoparticles was used as precursor. A Nd:YAG (1064 nm wavelength) laser operating in continuous wave (CW) mode was used for thin film formation. Polycrystalline Si films were deposited on flexible as well as rigid plastic substrates in both air and argon ambients. The films were analyzed by optical microscopy for film formation, scanning electron microscopy (SEM) for microstructural features, energy dispersive spectroscopy (EDS) for impurities, X-ray photoelectron spectroscopy (XPS) for composition and bond information of the recrystallized film and Raman spectroscopy for estimating shift from amorphous to more crystalline phase. Raman spectroscopy showed a shift from amorphous to more crystalline phases with increasing both the laser power and irradiation time during laser recrystallization step.     

Optical features of noble-metal-oxide thin films under irradiation of blue laser

The optical reflectance and transmittance of Platinum oxide (PtO(x)) and palladium oxide (PdO(x)) thin films for ultrahigh-density optical storage are investigated using Z-scan technique under irradiation of blue laser (442 nm). The power thresholds of the PtO(x) and PdO(x) decomposition, 3.1 mW and 2.6 mW, are obtained respectively; the PtO(x) (PdO(x)) thin film is reversible and irreversible when input power is less than and more than 3.1 mW (2.6 mW). Deformation analyses by using an atom force microscope (AFM), which is formed in the micro irradiation region of surface on the thin film samples due to decomposition of the PtO(x) or PdO(x) driving the Z-scan, agree well with the Z-scan results. The optical features obtained at 442-nm wavelength are compared with those at 532-nm wavelength, and the threshold difference between the two wavelengths is also analysed in detail based on wavelength-dependent average power density and wavelength-selected absorption of the thin films.