锑化镓的光助微刻蚀及其表面氧化物的研究

用电化学和光电化学方法研究锑化镓表面的腐蚀以及锑化镓表面氧化膜的生成和溶解，锑化镓电极在一定电势下生成的氧化膜，用俄歇能谱证明，其主要成分为难溶的氧化锑，此氧化膜的存在抑制了锑化镓的进一步腐蚀，同时亦使锑化镓的半导体光电化学性能大为减弱，通过激光微刻蚀及电子显微镜的观察，在刻蚀剂中添加酒石酸，柠檬酸和氢氟酸等试剂，可使刻蚀形得改善，实验研究了锑化镓的平带电势的测定。     

不同类型GaAs上应用约束刻蚀剂层技术进行电化学微加工

应用约束刻蚀剂层技术(CELT)对GaAs进行电化学微加工. 研究了刻蚀溶液体系中各组成的浓度比例、GaAs类型、掺杂以及阳极腐蚀过程对GaAs刻蚀加工过程的影响. 循环伏安实验表明, Br-可以通过电化学反应生成Br2作为刻蚀剂, L-胱氨酸可作为有效的捕捉剂. CELT中刻蚀剂层被紧紧束缚于模板表面, 模板和工件之间的距离小于刻蚀剂层的厚度时, 刻蚀剂可以对GaAs进行加工. 利用表面具有微凸半球阵列的导电模板, 可以在不同类型GaAs上加工得到微孔阵列. 实验结果表明: 在相同刻蚀条件下, GaAs的加工分辨率与刻蚀体系中各组分的浓度比例有关, 刻蚀结构的尺寸随着刻蚀剂与捕捉剂浓度比的增加而增大; 在加工过程中, p-GaAs相对于n-GaAs和无掺杂GaAs受到阳极氧化过程的影响较为显著, p-GaAs表面易生成氧化物层, 影响电化学微加工过程. X射线光电子能谱(XPS)和极化曲线实验也证明了这一点.     

等离子体聚合法修饰半导体光电极的研究——聚丙烯腈/n-GaAs,n-GaP电极

用导电聚合物修饰光电化学体系中的半导体电极,对于抑制电极的光腐蚀、改善电极特性及赋予其催化功能有明显的效果.在制备聚合物薄膜的几种方法中,等离子体聚合可得到高度交联、均匀、化学稳定性好的超薄膜,且成膜工序简单,已引起重视并取得初步应用。等离子体聚合法修饰导体电极国内外均有报道,但在修饰半导体电极方面的研究甚少。本文探讨了用这种方法在n-GaAs、n-GaP电极上制备聚丙烯腈(PAN)薄膜,并进行     

利用H3PO4液层侧面红外热像研究YBCO高温超导薄膜的激光辅助刻蚀特性

利用红外热像实时监测系统,获取钇钡铜氧激光辅助化学刻蚀中H₃PO₄液层的侧面红外热像,研究了其溶液温度分布与热对流特性,并对红外监测数据与钇钡铜氧薄膜激光化学刻蚀特性的关系进行了分析.主要实验结论包括:红外灰度图可真实反映溶液的温度分布和热对流情况,为激光化学刻蚀的热环境分析提供有价值的红外监测数据;通过任意时刻钇钡铜氧表面生成热流所到达高度的分布情况和该时刻的红外灰度图,分析出钇钡铜氧薄膜表面各区域的腐蚀启动先后和刻蚀程度差异等重要信息,为钇钡铜氧及其它材料的激光化学刻蚀特性的实时监测提供了一种新的技术手段.     

热诱导金属/聚合物膜系图案化控制的研究

近年来 ,在简单体系上形成复杂规则的图案已引起诸多学者的注意 ,其中以聚合物为母体的体系发展了模板、局部紫外照射和激光诱导等一系列技术 ,从而得到可控的表面图案[1～ 6] .本文用激光刻蚀法对溅射在聚合物膜上的金属薄膜进行处理 ,在热诱导情况下使金属 /聚合物膜系表面产生了规则的图案 .薄膜热应力的可控释放作用和激光刻蚀造成的区域局限作用被认为是诱导这种可控图案产生的两种基本要素 .通过控制激光刻蚀区域 ,可控制薄膜表面形貌变化 ,从而实现可控的图案化设计 .1　实验部分1.1　原料及仪器　聚苯乙烯 (PS) :北京燕山石油化工…     

镍电极在硼砂-硼酸缓冲溶液中的钝化和点蚀

近年来交流阻抗技术用于研究局部腐蚀,尤其在点蚀方面,引起了很大兴趣。Mansfeld等人和Oltra等人都提出了电极在点蚀时的等效电路.有关镍电极在Cl~-存在时的点蚀研究有过许多报导,但是至今尚未见到用交流阻抗技术研究Ni电极的点蚀.本文用交流阻抗技术对Ni电极在Na_2SO_4硼砂-硼酸缓冲溶液(pH8.4)中的钝化行为和Cl~-存在时的点蚀行为进行了研究,探讨了钝化和点蚀的规律和机理。     

图案化TiO2薄膜的制备技术

本文综述了图案化TiO2薄膜的制备技术,按图案的生成方式可分为图案的直接生成,掩膜复制法,硬质模板复制法三大类。可以通过针尖写蚀法、电子书写蚀法、激光写蚀法、自组装法、光电化学法直接制备图案。掩膜复制法包括光刻胶法、自组装膜法、光敏凝胶膜法等。硬质模板法也称软刻蚀技术,分为复制微模塑、转移微模塑、毛细管微模塑、微接触印刷法、光-盖印印刷等技术。对每类方法的优缺点作了适当评述,对今后图案化TiO2薄膜制备的研究方向提出了一些建议。     

激光在电化学中的应用（Ⅰ）

本文是激光在电化学中应用的综述第一部分,简要介绍激光电化学的特点、历史和有关实验装置;综述激光在电沉积、电聚合、电极材料改性、表面刻蚀、电化学吸脱附、控制电化学反应、光电化学开关与信息存储等方面的应用。     

n-GaAs(100)、Si(111)表面修饰卟啉分子的光致界面电荷转移特性的研究

利用表面光电压谱研究了四碘化四-(4-三甲胺苯基)卟啉(TTMAPPIH₂)修饰n-GaAS(100)和n-Si(111)半导体表面的光致界面电荷转移特性,结果表明,n-GaAs(100)表面修饰TTMAPPIH₂分子的光致界面电荷转移效率远比n-Si(111)表面修饰的高,并且发现在该卟啉分子的非吸收区也有明显的光致界面电荷转移现象,而与n-Si(111)间则没有这种转移特性。用电化学测量和UV光谱确定了TTMAPPIH₂相对于n-GaAs(100)、n-si(111)的能级位置关系,对TTMAPPIH₂分子与n-GaAs(100)和n-Si(111)间的不同光致界面电荷转移特性进行了解释。     

含氟水溶液中电化学刻蚀氟化WO3薄膜电极增强可见光光电化学性能

报道了在含氟的酸性水溶液中, 对电沉积制备的WO3薄膜电极进行电化学刻蚀, 并采用光电化学、扫描电子显微镜(SEM)、X射线衍射(XRD)、光电子能谱(XPS)、紫外-可见漫反射光谱、光致发光(PL)等方法对电极进行了表征. 结果表明, 刻蚀使电极比表面积增大, 质量减少, 重要的是可使电极表面状态发生变化. 在相同催化剂质量和比表面积的条件下, 这种变化显著提高了WO3薄膜电极在可见光和紫外-可见光照下的光电转换性能. 机理研究表明, 电极光电化学性能提高可归因于刻蚀使电极表面发生氟化, 光生载流子表面复合中心数目减少, 平带电位负移. 刻蚀对电极的吸光性质和晶体结构等未检测出明显变化. 氟化电极在酸性中具有良好的光电化学稳定性.     

A comparative study on electrochemical micromachining of n-GaAs and p-Si by using confined etchant layer technique

The confined etchant layer technique has been applied to achieve effective three-dimensional (3D) micromachining on n-GaAs and p-Si. This technique operates via an indirect electrochemical process and is a maskless, low-cost technique for microfabrication of arbitrary 3D structures in a single step. Br(2) was electrogenerated at the mold surface and used as an efficient etchant for n-GaAs and p-Si; l-cystine was used as a scavenger, for both substrates. The resolution of the fabricated microstructure depended strongly on the composition of the electrolyte, and especially on the concentration ratio of l-cystine to Br(-). A well-defined, polished Pt microcylindrical electrode was employed to examine the deviation of the size of the etched spots from the real diameter of the microelectrode. The thickness of the confined etchant layer can be estimated, and thus the composition of the electrolyte can be optimized for better etching precision. The etched patterns were approximately negative copies of the mold, and the precision of duplication could reach the micrometer level for p-Si and the submicrometer level for n-GaAs. Although the same etchant (Br(2)) and scavenger (l-cystine) were used in the etching solutions for GaAs and Si, the etching process, or mechanism, is completely different in the two cases. Compared with the fast etching process on GaAs in an etching solution with a concentration ratio of 3:1 of l-cystine to Br(-), the concentration ratio needs to be 50:1 for etching of Si. For the micromachining of Si, the addition of a cationic surfactant (cetyltrimethylammonium chloride, CTACl) is necessary to reduce the surface tension of the substrate and hence reduce the influence of evolution of the byproduct H(2). The function of the surfactant CTACl in comparison with an anionic surfactant (sodium dodecyl sulfate) was studied in contact-angle experiments and micromachining experiments and then is discussed in detail.     

n-GaAs为基的光电化学电池输出特性

GaAs 的禁带宽度为1.428eV,而且是直接跃迁,是光电化学电池中很好的电极材料.一些作者研究了 n-GaAs 为基的光电化学电池^[1,2].本文讨论了光强,化学刻蚀、氧化还原对浓度及离子修饰对 n-GaAs 光电化学电池输出特性的影响.所用的电极为低阻 n-GaAs[(100)面],N_D=5.1×10¹⁷cm^-3,试验前通高纯氮20分钟.测光强用的辐照计经上海计量局校正,其它测试方法同前文^[3].     

Studies on Optimal Gas Supply For a Maskless Etching System with Micro- Discharge Plasma Operated at Atmospheric Pressure

An optimal gas supply method for the micro discharge plasma generated along a quartz glass electrode, which was useful for the maskless fabrication of electrode grooves for surface electrodes on solar cells, was examined. We here constructed an electrode system with gas inlet and outlet holes. The gas supply directly to the plasma region contributed to reduce byproducts on the surface being etched, and then it was confirmed that the uniform etching was achieved in the case where the micro-discharge plasma locally produced at the etching area.     

An agar-microchamber cell-cultivation system: flexible change of microchamber shapes during cultivation by photo-thermal etching

A new type of cell-cultivation system based on photo-thermal etching has been developed for the on-chip cultivation of living cells using an agarose microchamber array. The method can be used to flexibly change the chamber structure by photo-thermal etching, even during the cultivation of cells, depending upon the progress in cell growth. We used an infrared (1064 nm) focused laser beam as a heat source to melt and remove agar gel at the heated spot on a thin chromium layer. The melting of the agar occurred just near the chromium thin layer, and the size of the photo-thermally etched area depended almost linearly on the power of the irradiated laser beam from 2 microm to 50 microm. Thus by using photo-thermal etching with adequate laser power we could easily fabricate narrow tunnel-shaped channels between the microchambers at the bottom of the agar-layer even during cell cultivation. After 48 h of cultivation of nerve cells, the nerve cells in two adjacent chambers made fiber connections through the fabricated narrow tunnel-shaped channels. These results suggest that photo-thermal etching occurred only in the area where an absorbing material was used, which means that it is possible to photo-thermally etch lines without damaging the cells in the microchambers. The results also suggest that the agar-microchamber cell cultivation system in combination with photo-thermal etching can potentially be used for the next stage of single cell cultivation including the real-time control of the interaction of cells during cell cultivation.     

Chemical and structural changes of quartz surfaces due to structuring by laser-induced backside wet etching

Various physical and chemical processes which are involved in laser-induced backside wet etching are investigated. The surface of quartz etched by the laser-induced backside wet etching using a XeCl excimer laser at various fluences is analyzed by Raman microscopy, X-ray photoelectron spectroscopy and fiber-tip attenuated total-reflection Fourier-transform infrared spectroscopy. The investigations reveal the formation of a high amount of amorphous carbon deposits at low laser fluences, which strongly adhere to the quartz surface. Combining X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy reveals that the quartz is also chemically and structurally modified due to a loss of oxygen and by a change of the quartz polymorph at intermediate and high laser fluences. These modification and their differences for different fluences are explained by the etching mechanisms itself, i.e. different magnitudes of temperature and pressure jumps. The results show clearly which conditions for etching must be applied to machine high-quality structures, e.g. micro-optical elements in quartz.     

Direct-write multiphoton photolithography: a systematic study of the etching behaviors in various commercial polymers

The nonlinear optical processes involved in etching thin polymer films by direct-write multiphoton photolithographic methods (Higgins et al. Appl. Phys. Lett. 2006, 88, 184101) are systematically explored. Power-dependent etching data are obtained for thin films of several commercial polymers, including poly(methyl methacrylate) (PMMA), polystyrene (PS), poly(butyl methacrylate) (PBMA), and poly[2-(3-thienyl)ethyloxy-4-butylsulfonate] (PTEBS). Femtosecond pulses of light from a Ti:sapphire laser are focused to a diffraction limited spot of approximately 570 nm 1/e2 diameter in the films to induce etching. The power dependence of etching in each polymer is used to determine the order of the nonlinear optical process involved. The results for PMMA and PBMA, both of which absorb to the blue of 240 nm, demonstrate that etching involves absorption of several (i.e., 4-6) photons by the polymer, whereas PS, which absorbs wavelengths shorter than 280 nm, is etched by a lower-order process involving fewer (i.e., 3-4) photons. PTEBS, a conducting polymer that absorbs in the visible, is etched by a two-photon process. The results are consistent with an etching mechanism that involves multiphoton-induced depolymerization of the polymer, followed by vaporization of the resulting fragments. The etching resolution is found to be highest for polymers having high glass transition temperatures, low molecular weights, and no visible absorption. Among the polymers examined, low molecular weight PMMA is concluded to be the best polymer for use with this lithographic method. Finally, soft lithography is used to transfer patterns produced in a PMMA film onto poly(dimethylsiloxane), demonstrating a simple means for fabricating submicrometer-scale structures for use in micro- and nanofluidic devices.     

Grayscale patterning of polymer thin films with nanometer precision by direct-write multiphoton photolithography

The fabrication of arbitrary grayscale patterns in poly(ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) thin films is demonstrated. Patterns are formed by ablative direct-write multiphoton lithography using a sample scanning microscope and 870-nm light from a mode-locked Ti:sapphire laser. The surface profiles of all etched samples are characterized by atomic force microscopy. Grayscale patterns are produced by modulating the laser focus during etching. Quantitative models describing the etch depth as a function of laser power and focus are presented and employed to reproducibly control film patterning. PEDOT:PSS is found to be etched by a combination of linear and nonlinear optical processes. Sensitization by PEDOT in the composite is concluded to facilitiate removal of PSS. An ultimate etch depth precision of 1 nm is achieved.     

Ion transport through track etched polypropylene membrane

The transport properties through track etched polypropylene (PP) of 25 μm have been examined. The asymmetric pores in PP have been prepared by track etching technique. The PP membrane was exposed by α-source (₉₅Am²⁴¹). Irradiated PP membrane placed into an electrolyte cell and etched from one side while stopping medium protected other side. The etching is controlled by monitoring the electric current and to be stopped shortly after the breakthrough, which, is observed as a sudden increase in current, indicating that the two chambers of cell are connected through the pores. Asymmetric etching condition allows the preparation of charged pores of conical shape. The resulting conical pores rectify ion current. The voltage current characteristics is strongly non-linear, comparable to that of an electrical diode.     

A problem in etching Pyrex glass capillary columns

Recent attempts to reproduce a literature method for etching of Pyrex glass capillary columns with ?etching ether”? resulted in reduction of the columns to dust through a violent explosion. Although modifications of the method produced etched columns, we found that less than satisfactory results were achieved. Introduction of etching ether by simply coating the column with a thin film of the ether produced an evenly etched column with well defined whiskers. Several observations made during the etching process will also be discussed.     

Comparison of Physical Isolation on Large Active Area Perovskite Solar Cells

To reduce the quadratic scaling of the series resistance(R_s) and sheet resistance(R_st) of the devices, physical isolation of the large area devices into small pieces has been proven to be a reliable and cost-efficient patterning technique. In this paper, we got an interesting result that the physical isolation did not show obvious effect on the photovoltaic performance of perovskite solar cells(PSCs) when fixing the active area. Three different isolation types, unetched ITO, etched ITO, and laser etching whole devices, have been induced to investigate the physical isolation roles. The results show that the electrons and holes could be collected efficiently in active area for all the isolation types. The proposed mechanism illustrates that the nonradiative recombination and recombination of electrons and hole in inactive area do not influence the performance of devices. This work may open a new way for the commercialization of PSCs by reducing the complex process and the etching costs.