激光、激光技术 激光应用 激光化学

O644.18 2006032084激光化学液相次序选择腐蚀新方法=A new order-selec-tive etching method in laser induced wet-chemical etching[刊,中]/刘霖(电子科技大学光电信息学院.四川,成都(610054)) ,叶玉堂…∥中国激光.—2006 ,33(1) .—49-52提出了一种激光诱导液相腐蚀新方法—次序选择腐蚀法。次序选择腐蚀是指在激光化学液相腐蚀中,腐蚀溶剂不是混合后同时作用于基片,而是按照溶剂的性能,分先后对基片进行腐蚀。实质是是采用微处理(表面处理)再进行混合液相激光辅助下的腐蚀。理论分析和实验结果都表明,与国内外研究普遍采用的混合溶剂…     

两步退火法对硫化铅薄膜光电性能的影响

采用先低温O₂气氛退火,后高温N₂气氛退火的两步退火法工艺,探究了两步退火法对化学浴沉积(CBD)制备的多晶硫化铅(PbS)薄膜光电性能的影响。结果表明,相比于一步退火法,两步退火法所得的PbS薄膜具有较大的晶粒尺寸、较少的晶界和良好的光电性能。在两步退火法中,当第二步退火时间为80 min时,PbS薄膜的响应度为2.33 A·W^-1,比探测率为1.18×10¹⁰ cm·H^1/2·W^-1,与一步退火法相比分别提高了259%和236%,即两步退火法可以在传统一步退火法的基础上进一步提高PbS红外光电探测器的性能。     

紫外激光诱导近化学计量比钽酸锂晶体铁电畴反转

对紫外激光诱导近化学计量比钽酸锂晶体铁电畴反转进行了实验研究。波长为351 nm的连续紫外激光被聚焦在近化学计量比钽酸锂晶体的-z表面,同时沿与晶体自发极化相反的方向施加均匀外电场。实验证实紫外激光辐照可以有效地降低晶体畴反转所需的矫顽电场,采用数字全息干涉测量技术检测证实在激光辐照区域实现局域畴反转。研究表明采用紫外激光诱导可以实现对近化学计量比钽酸锂晶体铁电畴反转的局域控制。提出了物理机理的理论分析,认为外电场和激光辐照场的共同作用在晶体内部产生高浓度、大尺寸的缺陷结构,缺陷一定程度上降低畴体成核和畴壁运动所需要克服的退极化能和畴壁能,实现激光诱导畴反转。     

晶体取向对定向凝固枝晶生长的影响

采用类金属透明模型合金丁二腈-1.0 wt%乙醇(SCN-1.0 wt% Eth)合金, 考察了晶体取向对定向凝固过程中晶粒的平界面失稳孕育时间、枝晶形态演化以及枝晶一次间距的影响. 结果表明, 随着枝晶择优生长方向与温度梯度方向夹角的增大, 晶粒的平界面失稳孕育时间增加, 界面的稳定性增强; 对于不同晶体取向的枝晶形态演化, 枝晶择优生长方向与温度梯度方向夹角越大, 枝晶二次臂不对称生长越严重, 同时, 具有生长优势的枝晶二次臂对相邻枝晶的生长的抑制越强烈; 至于不同晶体取向的枝晶一次间距, 随着枝晶择优生长方向与温度梯度方向夹角的增大, 枝晶一次间距增大. 关键词： 定向凝固 平界面失稳 枝晶间距 晶体取向     

虹吸动态化学腐蚀法制备近场光学显微镜光纤探针的研究

基于虹吸原理 ,设计了一种动态化学腐蚀法的简易装置 ,用于制备近场光学显微镜光纤探针。在一般化学腐蚀法的基础上 ,通过改变虹吸管中水的流向和流速来有效地控制探针锥角和锥长 ,制备出多种形貌的光纤探针。与传统的静态化学腐蚀法相比 ,该法具有重复性高、探针形貌可控、操作方便、实验费用低廉、制备的探针表面光滑等优点。利用该装置 ,成功地制备出针尖尺寸 5 0～ 30 0nm ,针尖锥角在 16°～ 6 5°之间可调的光纤探针。同时 ,选择适当的液位差 ,通过一步腐蚀法制备出针尖尺寸小于 5 0nm ,针尖锥角 12 5°的双锥角光纤探针。并对可能的腐蚀机理进行了探讨。     

高应变率加载下FCC金属晶体取向对孔洞增长的影响

采用率相关的晶体塑性本构模型研究了冲击荷载作用下晶体取向对面心立方金属内部孔洞增长的影响。利用VUMAT子程序,将率相关晶体塑性本构模型嵌入ABAQUS有限元软件中,分析了单晶晶内孔洞、双晶晶界孔洞和三角晶界孔洞的增长行为,结果显示：孔洞的变形模式与晶体取向、晶界位置（冲击加载方向与晶界的相对方位）、加载方向相关,晶体的滑移线模型与晶界位置之间的关系可以反映孔洞增长方向。对于晶内孔洞,加载方向越接近[011],孔洞开始增长变形时间越晚,但孔洞的总体增长变形越大;加载方向越接近[111],孔洞开始增长变形时间越早,但孔洞的总体增长变形越小。对于晶界处孔洞,晶界位置影响孔洞的部分变形,但不会影响总体变形。晶体受冲击之后,若孔洞增长方向沿晶内,则晶界会促进孔洞沿晶内增长;若增长方向沿晶界,则晶界会促进孔洞沿晶界方向增长,抑制其向晶内增长。     

动态化学腐蚀法制备大锥角近场光纤探针

基于液压传递原理,设计出一种用动态化学腐蚀法制备大锥角近场光纤探针的装置.实验结果表明,在传统的化学腐蚀法制备光纤探针的过程中,通过控制腐蚀液液面的上升速度,可以有效地控制探针针尖的形状以及锥角的大小.在此基础上,还论述了分步控制光纤与腐蚀液液面的相对位移的方法在大锥角光纤探针的制备中所具有的独特优越性.利用所制备的大锥角近场光纤探针在扫描近场光学显微镜上对直径为200nm的小球进行探测,其力学像证实该探针具有较高的形貌分辨率(约为50nm). 关键词： 动态化学腐蚀法 大锥角 近场光纤探针     

晶体相场法研究应力状态及晶体取向对微裂纹尖端扩展行为的影响

采用晶体相场模拟研究了单向拉伸作用下初始应力状态、晶体取向角度对单晶材料内部微裂纹尖端扩展行为的影响, 以(111)晶面上的预制中心裂纹为研究对象探讨了微裂纹尖端扩展行为的纳观机理, 结果表明: 微裂纹的扩展行为主要发生在<011>(111)滑移系上, 扩展行为与扩展方向与材料所处的初始应力状态及晶体取向紧密相关. 预拉伸应力状态将首先诱发微裂纹尖端生成滑移位错, 进而导致晶面解理而实现微裂纹尖端沿[011]晶向扩展, 扩展到一定程度后由于位错塞积, 应力集中, 使裂纹扩展方向沿另一滑移方向[101], 并形成锯齿形边缘; 预剪切应力状态下, 微裂纹尖端首先在[101]晶向解理扩展, 并诱发位错产生, 形成空洞聚集型长大的二次裂纹, 形成了明显的剪切带; 预偏变形状态下微裂纹尖端则直接以晶面解理形式[101]在上进行扩展, 直至断裂失效; 微裂纹尖端扩展行为随晶体取向不同而不同, 较小的取向角度会在裂纹尖端形成滑移位错, 诱发空位而形成二次裂纹, 而较大的取向角下的裂纹尖端则以直接解理扩展为主, 扩展方向与拉伸方向几近垂直.     

碳纳米管受限空间对共轭高分子聚(9,9-二辛基芴-2,7-二基)链段运动行为的影响

在纳米受限空间中,高分子往往会表现出与本体状态不同的性质,如异常的链段运动特性及晶相间转变行为等,这些性质对于研究和开发新型高分子材料具有重要的意义,因此针对受限环境下高分子的物理化学特性研究也一直是高分子界关注的焦点.本文通过化学气相沉积法制备垂直取向排列的多壁碳纳米管阵列,借助溶剂润湿–收缩法获得规整的高密度阵列结构,其取向排列的碳纳米管间隙形成了准一维的纳米受限空间,尺寸在5—50 nm尺度下可调.进一步将共轭高分子聚(9,9-二辛基芴-2,7-二基)(PFO)填充到碳管间隙的纳米空间中,制备PFO与取向多壁碳纳米管阵列复合膜.结果发现在碳纳米管形成的纳米受限空间中,PFO的链段热运动行为与本征态PFO薄膜相比受到了明显的抑制,不同晶型间转变速度大大减缓,提高了构象的热稳定性,同时取向排列的碳纳米管对PFO分子链取向排列分布具有明显的诱导作用,有利于获得高性能的PFO晶体.这种高密度取向排列的碳纳米管阵列结构未来可以用于制备优良发光性能及高稳定性的PFO光电器件.     

用特征矩阵法研究一维激光全息光子晶体的禁带特性

介质中传播方向相反的2束激光干涉可形成具有一维周期结构的体积全息图,而这种全息图可以看作一维光子晶体,称为一维激光全息图光子晶体,用特征矩阵法研究了一维激光全息图光子晶体的透射谱中的禁带随入射角、记录波长、介质折射率、折射率调制度的变化规律。结果表明：当入射角变大,激光波长、介质折射率及介质折射率调制度变小时, 禁带的位置向短波方向移动, 禁带宽度减小。     

Formation of three‐dimensional GaAs microstructures by combination of wet and metal‐assisted chemical etching

Previously, plasma‐enhanced dry etching has been used to generate three‐dimensional GaAs semiconductor structures, however, dry etching induces surface damages that degrade optical properties. Here, we demonstrate the fabrication method forming various types of GaAs microstructures through the combination etching process using the wet‐chemical solution. In this method, a gold (Au)‐pattern is employed as an etching mask to facilitate not only the typical wet etching but also the metal‐assisted chemical etching (MacEtch). High‐aspect‐ratio, tapered GaAs micropillars are produced by using [HF]:[H₂O₂]:[EtOH] as an etching solution, and their taper angle can be tuned by changing the molar ratio of the etching solution. In addition, GaAs microholes are formed when UV light is illuminated during the etching process. Since the wet etching process is free of the surface damage compared to the dry etching process, the GaAs microstructures demonstrated to be well formed here are promising for the applications of III–V optoelectronic devices such as solar cells, laser diodes, and photonic crystal devices. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

一种简单高效的制备硅纳米孔阵结构的方法

本文介绍了一种简单高效的制备硅纳米孔阵结构的方法. 利用激光干涉光刻技术, 结合干法和湿法刻蚀工艺, 直接将光刻胶点阵刻蚀为硅纳米孔阵结构, 省去了图形反转工艺中的金属蒸镀和光刻胶剥离等必要步骤, 在2英寸的硅 (001) 衬底上制备了高度有序的二维纳米孔阵结构. 利用干法刻蚀产生的氟碳有机聚合物作为湿法刻蚀的掩膜, 以及在干法刻蚀时对样品进行轻微的过刻蚀, 使SiO₂点阵图形下形成一层很薄的硅台面, 是本方法的两个关键工艺步骤. 扫描电子显微镜图片结果表明制备的孔阵图形大小均匀, 尺寸可控, 孔阵周期为450 nm, 方孔大小为200–280 nm. 关键词： 激光干涉光刻 纳米阵列 刻蚀 氟碳有机聚合物     

超声波辅助酸蚀提高熔石英损伤阈值

为了提高熔石英元件表面抗激光损伤阈值,利用超声波辅助HF酸研究平滑光学元件表面缺陷形貌和去除刻蚀后残留物效果,通过扫描电子显微镜电镜和原子力显微镜记录表面形貌结构,以及单脉冲激光辐照测试抗损伤阈值确定实验参数。研究表明,超声波场的引入能催化HF酸的刻蚀速率、提高钝化效果并且更易剥离嵌入的亚μm级杂质粒子。经过实验测试,获得了熔石英类元件相匹配的超声辅助HF酸刻蚀实验参数,研究结果对应用超声波辅助HF酸研究熔石英表面抗激光损伤有重要意义。     

太阳电池中新腐蚀液实现纳米黑硅表面的一步腐蚀制备

通过引入添加剂,调节腐蚀溶液的pH值,实现了一步法制备黑硅表面. 在取得低表面反射率的同时,减小了黑硅层的腐蚀深度,对于16 min腐蚀的黑硅层,其表面加权平均反射率可达5%(300～1200 nm),但腐蚀深仅约为200 nm. 减小腐蚀深度能够降低黑硅太阳电池的表面复合速率,从而提高太阳电池性能,尤其是开路电压及填充因子. 以新腐蚀液制备的黑硅为衬底,在常规太阳电池产线上制备大面积p-Si黑硅太阳电池,实现了15.63%的转换效率,具有高的开路电压(624.32 mV)和填充因子(77.88%),改进了大面积黑硅太阳电池的性能.     

Fabrication of 3D microfluidic structures inside glass by femtosecond laser micromachining

Femtosecond lasers have opened up new avenues in materials processing due to their unique characteristics of ultrashort pulse widths and extremely high peak intensities. One of the most important features of femtosecond laser processing is that a femtosecond laser beam can induce strong absorption in even transparent materials due to nonlinear multiphoton absorption. This makes it possible to directly create three-dimensional (3D) microfluidic structures in glass that are of great use for fabrication of biochips. For fabrication of the 3D microfluidic structures, two technical approaches are being attempted. One of them employs femtosecond laser-induced internal modification of glass followed by wet chemical etching using an acid solution (Femtosecond laser-assisted wet chemical etching), while the other one performs femtosecond laser 3D ablation of the glass in distilled water (liquid-assisted femtosecond laser drilling). This paper provides a review on these two techniques for fabrication of 3D micro and nanofluidic structures in glass based on our development and experimental results.     

Femtosecond laser assisted etching of quartz: microstructuring from inside

In quartz crystal substrates, microchannels were made by femtosecond laser assisted etching, i.e., irradiation of focused femtosecond laser pulses followed by wet etching. By the use of wet etching, the laser irradiated region was selectively etched out, and a microchannel was formed inside the quartz substrate. The laser irradiated region was found to be amorphous by transmission electron microscopy. Anisotropy in the etching rate inside the quartz was observed. PACS 42.70.Ce; 61.80.Ba; 82.50.-m     

Etching of Sapphire in Supercritical Water at Ultrahigh Temperatures and Pressures under the Conditions of Pulsed Laser Thermoplasmonics

The method of thermoplasmonic laser-induced backside wet etching (TPLIBWE) is applied for effective and well-controlled microstructuring of sapphire. The method is based on the generation of highly absorbing silver nanoparticles in the course of the pulsed-periodic laser irradiation. The silver nanoparticles are formed as a result of the reduction of a water-dissolved precursor, AgNO₃. The process of sapphire etching occurs via the formation of supercritical water at ultrahigh temperatures and pressures (which significantly exceed the critical values for water) and the formation of silver nanoparticles at the sapphire/water interface as a result of the absorption of laser radiation. The mechanism of TPLIBWE is considered and the etching rate, which reaches ~100 nm/pulse, is determined. The formation of aluminum nanoparticles, which indicates a deep destruction of Al₂O₃ as a result of TPLIBWE, is observed.     

Thermal etching of sodium chloride III. Etching of non-cubic surface

Previous work on the thermal etching of (100) surfaces of NaCl single crystals is extended to the other surface orientations by using polycrystalline samples. The results obtained with (110), (111), (520) and (144) surfaces are used to corroborate the correctness of the mechanisms proposed in a previous paper to explain the thermal etching in air of (100) surfaces; it is also shown that these mechanisms are only dependent on crystal structure and not on the surface orientation.When such surfaces were treated with wet silk, concentrated HC1, and Moran's reagent, a very different behaviour was observed for each orientation. The reactivity is very sensitive to crystallographic orientation, being very low in the case of the (144) surface.     

On the Role of Supercritical Water in Laser-Induced Backside Wet Etching of Glass

The features and mechanisms of microcrater formation in optical silicate glass by laser-induced backside wet etching (LIBWE) are determined in a wide range of energy densities (Φ) from 4 to 10³ J/cm² for laser pulses of 5 ns length and 1 kHz repetition rate. The existence of two different mechanisms of laserinduced microcrater formation is revealed: (i) chemical etching in supercritical water (SCW), and (ii) cavitation. At Φ > 10² J/cm² irregular craters of 1–20 μm in depth with rough walls and distinct cracks around microcrater are formed testifying that in such mode (“hard”) laser induced cavitation plays a dominant role in glass removal. At Φ < J/cm² neat glass craters with smooth walls are formed, their size and shape are easily reproducible, cracks are not formed, and the processing area is limited to the laser spot area. In this mode (“soft mode with active cavitation”), a microcirculation of water is stimulated by cavitation without causing undesirable shock breakage. The latter is achieved thanks to the fast removal of glass etching products by microcirculation, and the inflow of “fresh” etchant (SCW) to the glass surface in the vicinity of the formed microcraters. Such mode is optimal for highly controlled laser microstructuring of glass and other optically transparent materials.     

Etching of silicon in fluoride solutions

The development and status of what is commonly called the Gerischer mechanism of silicon etching in fluoride solutions is reviewed. The two most widely used and studied wet etchants of silicon are F^? and OH^?. Their mechanisms of atom removal share many things in common; in particular, chemical passivation by a hydrogen-terminated surface plays an important role in both. Crucially, however, their initiation steps are different, and this leads to important differences in the structures of the materials produced by the etchants. The initiation of etching by F^? is electrochemical in nature, responding to the electronic structure of the Si, and is, therefore, a self-limiting reaction that can produce nanocrystalline porous silicon. Hydroxide etching destroys porous silicon because its initiation step is a catalytic chemical reaction and not a self-limiting process. A number of unanswered questions regarding the dynamics of fluoride etching are highlighted.