Argon-dominated plasma beam generated by filtered vacuum arc and its substrate etching

A new technique to etch a substrate as a pre-treatment prior to functional film deposition was developed using a filtered vacuum arc plasma. An Ar-dominated plasma beam was generated from filtered carbon arc plasma by introducing appropriate flow rate of Ar gas in a T-shape filtered arc deposition (T-FAD) system. The radiation spectra emitted from the filtered plasma beam in front of a substrate table were measured. The substrate was etched by the Ar-dominated plasma beam. The principal results are summarized as follows. At a high flow rate of Ar gas (50 ml/min), when the bias was applied to the substrate, the plasma was attracted toward the substrate table and the substrate was well etched without film formation on the substrate. Super hard alloy (WC), bearing steel (SUJ2), and Si wafer were etched by the Ar-dominated plasma beam. The etching rate was dependent on the kind of substrate. The roughness of the substrate increased, when the etching rate was high. A pulse bias etched the substrate without roughening the substrate surface excessively.     

Piezoelectric evaluation of ion beam etched Pb(Zr,Ti)O3 thin films by piezoresponse force microscopy

The evolution of piezoelectric properties of Pb(Zr,Ti)O₃ (PZT) thin films after ion beam etching have been investigated at the nanoscale level by piezoelectric force microscopy. A comparison of the piezoelectric properties on etched and unetched films is realized. Piezoelectric contrasts imaging evidences a modification of the domain architecture at the film surface. Local piezoelectric hysteresis loops measurements on grains indicate that the coercive voltage for switching is much higher for the etched films (2.3 V) compared to the unetched ones (1.0 V) while the average piezoelectric activity is slightly lower. The results are explained in terms of grain-damaging during etching and domain-wall pinning.     

Synchrotron radiation photoelectron spectroscopy and near-edge X-ray absorption fine structure study on oxidative etching of diamond-like carbon films by hyperthermal atomic oxygen

Surface structural changes of a hydrogenated diamond-like carbon (DLC) film exposed to a hyperthermal atomic oxygen beam were investigated by Rutherford backscattering spectroscopy (RBS), synchrotron radiation photoelectron spectroscopy (SR-PES), and near-edge X-ray absorption fine structure (NEXAFS). It was confirmed that the DLC surface was oxidized and etched by high-energy collisions of atomic oxygen. RBS and real-time mass-loss data showed a linear relationship between etching and atomic oxygen fluence. SR-PES data suggested that the oxide layer was restricted to the topmost surface of the DLC film. NEXAFS data were interpreted to mean that the sp² structure at the DLC surface was selectively etched by collisions with hyperthermal atomic oxygen, and an sp³-rich region remained at the topmost DLC surface. The formation of an sp³-rich layer at the DLC surface led to surface roughening and a reduced erosion yield relative to the pristine DLC surface.     

Localized dissolution electrochemistry at surface irregularities of pipeline steel

The localized electrochemical dissolution behavior at surface irregularities, including scratch, mechanically induced hole and corrosion pit, on pipeline steel was investigated in both near-neutral pH and high pH solutions by scanning vibrating micro-electrode and localized electrochemical impedance spectroscopy measurements. In near-neutral pH solution, the localized dissolution behavior at surface irregularities is dependent of their geometrical depth, which is critical to development of a local electrochemical condition to support the further localized dissolution. Therefore, surface irregularities exceeding a certain depth provide potential sites to initiate stress corrosion cracks in near-neutral pH solution. The strong passivating capability of high pH solution would result in the formation of oxide film over the whole electrode surface to “equalize” the electrochemical activity at irregularities to the intact area. Therefore, the irregularities would not result in localized dissolution electrochemistry. Consequently, localized corrosion and crack initiation are not anticipated to initiate from the geometrical irregularities in high pH solution. However, corrosion pits generating due to passive film breakdown could support the high local dissolution kinetics in high pH solution, providing potential sites for crack initiation. The effects of hydrogen-charging on anodic dissolution at regularities depend on the defect geometry and the solution pH.     

A novel optical technique for the estimation of porosity in porous silicon thin films

Porous silicon (por-Si) can be produced when silicon single crystals are submerged in fluoride solutions and irradiated with laser light. The shape of the por-Si film is determined by the laser beam intensity profile. When laser light is reflected from a Gaussian-shaped film, a divergent beam, which exhibits ring patterns, is observed. The rings are formed by a combination of optical interference and Fresnel diffraction. The size of the pattern is determined by the shape and depth of the film interfaces as well as the index of refraction of the film. The index of the film is determined by the porosity and the index of the fluid that fills the pores. We explore the application of measurements of the reflected beam patterns to the determination of porosity for por-Si thin films. We report the first direct estimation of the porosity of photochemically produced porous silicon. Porosities of 70-95% are found for n-type Si(111) etched in 48% HF with 633-nm illumination. Having demonstrated the success of this technique, we discuss improvements and extensions that can be made.     

Growth and photoluminescence properties of inclined ZnO and ZnCoO thin films on SrTiO₃（110） substrates

ZnO thin film growth prefers different orientations on the etched and unetched SrTiO 3(STO)(110) substrates.Inclined ZnO and cobalt-doped ZnO(ZnCoO) thin films are grown on unetched STO(110) substrates using oxygen plasma assisted molecular beam epitaxy,with the c-axis 42 inclined from the normal STO(110) surface.The growth geometries are ZnCoO[100]//STO[110] and ZnCoO[111]//STO[001].The low temperature photoluminescence spectra of the inclined ZnO and ZnCoO films are dominated by D 0 X emissions associated with A 0 X emissions,and the characteristic emissions for the 2 E(2G)→ 4A2(4F) transition of Co 2+ dopants and the relevant phonon-participated emissions are observed in the ZnCoO film,indicating the incorporation of Co 2+ ions at the lattice positions of the Zn 2+ ions.The c-axis inclined ZnCoO film shows ferromagnetic properties at room temperature     

Highly regular nanometer-sized hexagonal pipes in 6H-SiC(0001)

An array of troughs was prepared on a 6H-SiC(0001) surface using focused ion beam (FIB) patterning. Troughs were etched with various ion doses and close-to-circular voids of increasing depths for larger ion doses were obtained. The samples were then etched in a hot-wall reactor at a hydrogen partial pressure of 13 mbar at 1800 °C. The resulting morphological reorganizations have been studied by scanning electron and atomic force microscopy. Very regular hexagonal voids with facets oriented perpendicular to the surface were obtained after hydrogen etching. The voids were surrounded by regular secondary facets of lower inclination. Whereas the depth of the voids increases with ion dose, the void diameter and facet sizes stay constant. This effect is explained by surface diffusion during hydrogen etching. The FIB technique in combination with hydrogen etching allows the preparation of very regular surface patterns and highly ordered wells and tubes for nanometer-sized sieves and photonic crystals. PACS 47.70.Fw; 68.37.-d; 68.37.Hk; 68.37.Ps; 81.65.Cf     

A surface sensitive optical method for the evaluation of processed ZnO: exploitation of LO phonon interaction

We report on a surface property of bulk ZnO crystals and an optical method to evaluate it. Bulk ZnO crystals have a damaged surface layer due to chemomechanical polishing. We prepared the ZnO crystals by etching, and evaluated the improvement of the surface by high-resolution X-ray diffraction (XRD) and photoluminescence (PL). In PL measurements, the relative intensity of the first order longitudinal optical phonon replica of free exciton (FX-1LO) to second order process (FX-2LO) was compared. The relative intensity becomes weak with increasing etched depth and finally saturates at the etched depth of 5 μm. This result agrees well with XRD results.     

Studies of CdTe surfaces with secondary ion mass spectrometry,rutherford backscattering and ellipsometry

The composition and the stability of chemically etched, mechanically polished and oxidized surfaces of single crystals of cadmium-telluride were studied by secondary ion mass spectroscopy (SIMS), Rutherford backscattering (RBS) and ellipsometry. CdTe surfaces etched using a solution of bromine in methanol were found to be enriched in cadmium but a film, identified to be an oxide of tellurium, was observed to grow on it at room temperature and in air. The thickness of this film increased over long periods of timet linearly versus lnt. Mechanically polished samples and also chemically etched surfaces which were oxidized in a solution of hydrogen peroxide in amoniac were found to be stable.     

氧回旋离子束刻蚀化学气相沉积金刚石膜

利用非对称磁镜场电子回旋共振等离子体产生的氧回旋离子束刻蚀了化学气相沉积金刚石膜,研究了工作气压和磁电加热电压对金刚石样品附近的离子温度和密度的影响,并分析了金刚石膜的刻蚀和机械抛光效果。结果表明:当工作气压为0.03 Pa,磁电加热电压为200 V时,离子温度和密度最大,分别为7.38 eV和 23.81010 cm-3 。在此优化条件下刻蚀金刚石膜4 h后,其表面粗糙度由刻蚀前的3.525 m降为2.512 m,机械抛光15 min后,表面粗糙度降低为0.517 m,即金刚石膜经离子束刻蚀后可显著提高机械抛光效率。     

The measurement of slope using shearography

This paper presents an optical method which is based on speckle-shearing interferometry for the measurement of the slope at any point of an object. The object under study is illuminated by an expanded laser beam and its image is recorded on a photographic plate placed at the image plane of an image-shearing camera. A second exposure on the photographic film is made after the light source is moved slightly. The resulting photograph yields a fringe pattern which represents lines of constant displacement gradients. Theory of the method as well as some experimental results are presented.     

Laser-assisted etching of diamonds in air and in liquid media

2 O, (CH₃)₂SO). Diamond samples are virtually transparent at this wavelength, and the coupling of laser radiation to diamond is via the formation of a thin graphitized layer at the diamond surface. The etching rate in liquid media is slightly higher than in air at otherwise equal conditions and is as high as 50 μm/s for etching with a scanning laser beam. Raman spectra measurements carried out on diamond samples etched in air show the presence of glassy carbon on the surface, whereas for samples etched in a liquid the diamond peak at 1332 cm^-1 dominates with significantly lower intensity of the glassy carbon peak. Electroless copper deposition on the laser-etched features is studied to compare the catalytic activity of the diamond surface etched in air with that etched in liquids. Possible mechanisms responsible for the observed difference both in the structure of the etched area and in the electroless Cu deposition onto the surface etched in various media (air or liquids) are discussed. Received: 2 August 1996/Accepted: 7 January 1997     

Al_(0.17)Ga_(0.83)As/GaAs(001)薄膜退火过程的热力学分析

在As_4束流等效压强为1.2×10~(-3)Pa、退火60 min条件下改变退火温度,对Al_(0.17)Ga_(0.83)As/GaAs薄膜表面平坦化的条件进行了探讨.定量分析了薄膜表面坑、岛与平台的覆盖率和台阶-平台间薄膜粗糙度随退火温度变化的规律,得到最合适的退火温度为545℃(±1℃);根据退火模型发现退火温度的改变会影响参与熟化的原子的数量,熟化原子比θ正比于退火温度,即θ∝Τ.退火温度540℃条件下退火约60 min,薄膜表面达到基本平坦,推测此时0.20θ0.25;退火温度为545℃时,推测退火时间约为55-60 min.本实验得到的结论可以为生长平坦的Al_(0.17)Ga_(0.83)As/GaAs薄膜提供理论与实验指导.     

多晶硅表面陷阱坑形貌对表面光反射率的影响

利用光学傅里叶变换研究多晶硅绒面微结构形貌与反射率之间的关系。理论分析表明:多晶硅绒面反射率与表面微结构形貌、单位面积上陷阱坑数量有关。如绒面由V字型槽或坑构成,则绒面反射率比较高;如多晶硅表面上密集布满U字形坑或槽、内表面绒面化,这种结构构成的绒面反射率低。实验上用不同比例的酸液刻蚀多晶体表面,用扫描电镜(SEM)观察多晶硅表面SEM图,测量了其表面反射率,分析表面结构形貌与反射率的关系。实验结果与理论分析相吻合。     

Crystal dissolution kinetics and Gibbs free energy

The dependence of dissolution rates on the difference of Gibbs free energy is of critical importance for our understanding of crystal dissolution, reactive flow models and their applications to a variety of environmentally related problems. Here, we review experimental data generated with mineral powders and single crystals to develop a better understanding of apparent inconsistencies between otherwise internally consistent data sets. Additional information from direct surface observations and measurements with vertical scanning interferometry (VSI) and atomic force microscopy (AFM) of albite dissolution at 25, 150 and 185 °C may shed new light on this old but unsolved question. Our discussion is based on the importance of etch pit development, its ΔG dependence, and the pits’ role as a source for steps and step movement in the dissolution process. Results indicate that reaction history may be of critical importance in determining the overall reaction mechanism and its rate. Different rates are observed for systems having otherwise identical ΔG_r acquired from increasing versus decreasing disequilibrium positions.

In this context, we finally discuss the validity of the common application of transition state theory (TST) to elementary and overall reactions governing the dissolution process. In this discussion of crystal dissolution, we contrast TST applications with a stochastic, many-body treatment that has led to the development of a stepwave model. This discussion also focuses on the controversy caused by the rivalry between surface adsorption models and a probabilistic model that seeks to incorporate the full three-dimensional crystal structure.     

CVD金刚石中的氮对等离子体刻蚀的影响

采用非对称磁镜场电子回旋共振等离子体分别对沉积过程中掺氮和未掺氮的化学气相沉积金刚石膜进行了刻蚀研究, 结果表明: 掺氮制备的金刚石膜的刻蚀主要集中在晶棱处, 经过4h刻蚀后其表面粗糙度由刻蚀前的4.761 μm下降至3.701 μm, 刻蚀对金刚石膜的表面粗糙度的影响较小; 而未掺氮制备的金刚石膜的刻蚀表现为晶面的均匀刻蚀, 晶粒坍塌,刻蚀4h后其表面粗糙度由刻蚀前的3.061 μm下降至1.083 μm. 刻蚀导致表面粗糙度显著降低. 上述差别的主要原因在于金刚石膜沉积过程中掺氮导致氮缺陷在金刚石晶棱处富集, 晶棱处电子发射加强, 引导离子向晶棱运动并产生刻蚀, 从而加剧晶棱的刻蚀. 而未掺氮金刚石膜,其缺陷相对较少且分布较均匀 ,刻蚀时整体呈现为 (111) 晶面被均匀刻蚀继而晶粒坍塌的现象. 关键词： 掺氮 金刚石膜 刻蚀 非对称磁镜场     

金属-光折变材料复合全息结构对表面等离激元的波前调控

表面等离激元(surface plasmon polaritons, SPPs)控制具有重要意义.表面电磁波全息法是在金属表面设计能有效控制SPP传输的凹槽阵列结构.本文提出一种新的SPP传输的控制方法,利用金属-光折变材料复合全息结构控制SPP传播.在金属表面覆盖一层光折变材料,两束SPP波在光折变材料内干涉生成全息结构,利用此全息结构能够控制SPP的传播.通过时域有限差分法模拟验证,结果显示,通过金属-光折变材料复合全息结构可以有效地控制SPP波束的传输,实现SPP平面波束的单点聚焦、两点聚焦,以及生成零阶和一阶高斯SPP波束.经过优化发现,光折变材料的最佳厚度为3.3μm,最佳折射率调制度为0.06.现有SPP控制器件主要是通过离子束刻蚀,而金属-光折变材料复合全息结构不需要刻蚀,从而扩展了SPP控制的器件的制作方法,为SPPs的全光控制提供了新的思路,使SPP全光控制成为可能,进一步实现了SPP全光开关等功能.     

Structural and optical properties of thin films porous amorphous silicon carbide formed by Ag-assisted photochemical etching

In this work, we present the formation of porous layers on hydrogenated amorphous SiC (a-SiC: H) by Ag-assisted photochemical etching using HF/K₂S₂O₈ solution under UV illumination at 254 nm wavelength. The amorphous films a-SiC: H were elaborated by d.c. magnetron sputtering using a hot pressed polycrystalline 6H-SiC target. Because of the high resistivity of the SiC layer, around 1.6 MΩ cm and in order to facilitate the chemical etching, a thin metallic film of high purity silver (Ag) has been deposited under vacuum onto the thin a-SiC: H layer. The etched surface was characterized by scanning electron microscopy, secondary ion mass spectroscopy, infrared spectroscopy and photoluminescence. The results show that the morphology of etched a-SiC: H surface evolves with etching time. For an etching time of 20 min the surface presents a hemispherical crater, indicating that the porous SiC layer is perforated. Photoluminescence characterization of etched a-SiC: H samples for 20 min shows a high and an intense blue PL, whereas it has been shown that the PL decreases for higher etching time. Finally, a dissolution mechanism of the silicon carbide in 1HF/1K₂S₂O₈ solution has been proposed.     

Coordination chemistry and kinetics of preferential etching on surfaces of TiO2 (rutile)

Fused KHSO₄ can be used as both a polish and a preferential etchant for the {001} surfaces of rutile, depending on the temperature of the system. Polishing occurs at temperatures above 550°C. At temperatures below 550°C, three types of etch pit are observed, two well defined with regular shapes (sides parallel to the <110> and <100> and <130> directions, respectively) and one irregularly shaped. Photochemical deposition of silver [1] onto the crystal surface and subsequent removal (HNO₃) prior to etching causes the irregularly shaped pits to be etched more rapidly than in the case of a surface region that was not predeposited. A chemical reaction mechanism is presented to interpret the observed etching behavior. The crystal structure (i.e. the different ionic composition of different crystallographic planes) and surface chemistry of rutile are considered in the formulation of this mechanism. It is suggested that etchant molecules form surface complexes on the TiO₂ (after dehydration of surface OH groups) through coordination of Ti⁴⁺ via terminal and bridged out-of-plane O^2? positions. Evidence is presented to show that the etching rate-determining reaction is the dissolution of these soluble surface complexes. The observed photochemical effects are explained on the basis of the trapping of photogenerated holes or electrons at certain crystal defects.     

PED沉积La-Sr-Cu-O薄膜表面的有序纳米结构

采用脉冲电子束沉积(PED)技术在Si(100)衬底上生长La_Sr_Cu_O薄膜，在750℃生长温度下获得具有有序纳米结构的表面形貌.采用聚集离子束(FIB)技术对获得的纳米结构进行表征，结果表明，这种有序的纳米结构是由于Si衬底和La_Sr_Cu_O薄膜之间的热膨胀系数和晶格的 失配引起的纳米裂纹.在这些纳米裂纹处，La_Sr_Cu_O成核生长获得独立的纳米线.通过控制 这种有序的纳米结构的生长，这种有序的纳米结构可以用来构造弱连接形成的器件. 关键词： 脉冲电子束沉积 La_Sr_Cu_O薄膜 纳米结构