离子色谱法测定蚀刻槽废氢氟酸中的六氟硅酸

建立了一种新的检测蚀刻槽废氢氟酸中六氟硅酸的离子色谱方法。色谱柱为Metrosep A Supp 7阴离子交换柱,流动相为3.2 mmol/L碳酸钠-1.0 mmol/L碳酸氢钠,流速为0.7 mL/min。六氟硅酸经过抑制型电导检测器后进行衍生化反应,在360 nm波长下用紫外检测器检测。六氟硅酸的线性范围为2.4~120 mg/L,相关系数r²大于0.999,定量限为0.24 mg/L,平均加标回收率为97.2%。本方法还可以同时利用电导检测器检测废氢氟酸中的氢氟酸、醋酸、盐酸、硝酸、磷酸和硫酸的含量。该方法快速、准确,适用于蚀刻槽液中六氟硅酸的检测。     

Untersuchungen zur atomspektroskopischen spurenanalyse in AIIIBV-halbleiter-mikroproben—III: Untersuchungen zur schichtabtrennung und zur spurenanalyse in dünnen GaAs schichten

Three methods for stripping thin layers of GaAs have been compared with regard to depth of layer and reproducibility. They are (1) chemical etching with methanolic bromine solution, (2) mechanical separation with a microtome, (3) chemical etching after a preliminary amperostatic anodic oxidation. Conditions were optimized. The depth of strip was 0.4 μm for chemical etching, 1 μm for the mechanical separation and 0.02 μm for the anodic oxidation method. Thus the anodic oxidation is specially suitable for profile analysis, and the mechanical method for investigation of thicker layers; chemical etching lies between them. The trace elements in the micro samples thus obtained were determined by d.c. are atomic-emission spectrography (AES) and atomic-absorption spectrometry with electrothermal atomization in a graphite tube (AAS). The absolute and relative detection limits of AAS for the 0.1–0.2 mg micro samples were on average better by an order of magnitude than those of AES. The advantage of AES lies in the possibility of simultaneous determination of several elements. in der Möglichkeit der Simultanbestimmung mehrerer Elemente.     

Online process control of acidic texturisation baths with ion chromatography

Etching of silicon with mixtures of hydrofluoric acid and nitric acid is a widely used process in silicon solar cell fabrication. One precondition for an optimized usage of the acidic etching baths is the exact knowledge of the chemical bath composition. In this paper, we investigated a fast and online-capable method for the total analysis of all bath constituents by ion chromatography. The chromatographical system consists of a low-volume injection valve, which injects the concentrated samples directly into the KOH-based eluent. After separation and detection of nitrate and fluoride, a post-column derivatization with sodium molybdate is applied to detect the hexafluorosilicic acid, which enriches in the texturisation bath during the etching process. The results of the presented approach are discussed and compared with already published chromatographical and titration methods found in literature.     

Metal-assisted photochemical etching of gallium nitride using electrodeposited noble metal nanoparticles as catalysts

Porous gallium nitride (PGaN) layers were fabricated by metal-assisted photochemical etching (MaPCE) using electrodeposited platinum nanoparticles (PtNPs) or gold nanoparticles (AuNPs) as catalysts. After identification of a suitable negative potential and appropriate cyclic voltammetry (CV) conditions, high-density PtNPs or AuNPs were deposited onto a planar GaN substrate. Based on the concrete numerical values of energy levels, the generation, transfer and consumption of electrons and holes, and the assumption that localized galvanic cells are formed, an etching mechanism was proposed which may provide theoretical guidance for future work on etching of GaN and other semiconductor materials.     

Chemical stability of ZnO nanostructures in simulated physiological environments and its application in determining polar directions

The in vitro chemical stability and etching of ZnO nanostructures in simulated physiological solution (SPS) were studied using electron microscopy. Calcium hydrogen phosphate thin layers were observed to be uniformly deposited on the surfaces of ZnO nanomaterials in SPS. Electron diffraction and high-resolution transmission electron microscopy revealed that the calcium hydrogen phosphate layers were amorphous and had excellent interfacial contact with the nanocrystals. ZnO nanostructures fabricated by thermal evaporation were found to survive much longer in SPS than those fabricated using a hydrothermal solution method. The shapes of the voids formed in the ZnO nanostructures by the etching in SPS can be used to deduce the polar directions of ZnO nanostructures.     

电沉积种子层化学控制生长氧化锌纳米棒和纳米管

采用水溶液法在电沉积的ZnO种子层上制备了高度取向的ZnO纳米棒阵列,并通过碱溶液化学腐蚀法获得了ZnO纳米管。对ZnO纳米棒和纳米管的溶液生长和腐蚀过程进行了分析。结果表明,种子层的结构和性能对ZnO纳米棒有着重要的影响,在-700 mV电位下沉积的种子层薄膜均匀性好,生长的纳米棒密度大、与基底垂直性好;碱溶液对纳米棒的腐蚀具有选择性,通过控制腐蚀液的浓度和时间,可获得中空的ZnO纳米管。     

Microstructure analysis of a carbon-carbon composite using argon ion etching.

The microstructure of carbon-carbon composites obtained by chemical vapor infiltration of a carbon fiber felt was comparatively studied by reflection light microscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), and laser scanning confocal microscopy (LSCM). Ar+ ion etching was used to reveal and distinguish structural units of the pyrolytic carbon matrix. Mechanically polished samples, polished and subsequently ion etched samples, and fractured samples were compared. The values of surface roughness and surface height after polishing or after polishing and subsequent etching determined by AFM and LSCM correlate well with the degree of texture of the matrix layers obtained by polarized light microscopy and selected area electron diffraction. The carbon matrix is composed of structural units or "cells," which contain a carbon fiber and a sequence of several differently textured layers around each fiber. Within high-textured layers columnar grains are well recognizable using polarized reflection light microscopy and confocal microscopy. The size of depressions within high-textured carbon layers found by AFM after ion etching correlates well with the size of differently tilted domains detected by both TEM and SEM.     

Microstructuring of solid-supported lipid layers using SAM pattern generation by scanning electrochemical microscopy and the chemical lens

To prepare patterns of adsorption sites for alkanethiols with high lateral resolution, we used the scanning electrochemical microscopy (SECM) to etch masks into uniform layers of nickel coated on gold surfaces. The patterning of the nickel mask was accomplished in aqueous solutions by electrogenerating nitric acid out of nitrite at an ultramicroelectrode. Due to the sluggish kinetics of nickel etching in acidic media, the pattern generated by a 10-microm tip was about 50-microm wide, depending on the duration of the etching. As an alternative, applying the principle of the chemical lens by adding potassium hydroxide as a scavenger, the size of the adsorption sites had been reduced to 4 microm, independent of the duration of etching. In a follow-up step, monolayers of 11-mercaptoundecanoic acid were formed on the exposed gold areas of the surface by self-assembly. Fluorescent liposomes containing tetramethylrhodamine-labeled phospholipids were used to create solid-supported lipid layers (SSLLs). These fluorescent liposomes showed a selective binding affinity to the self-assembled monolayers (SAMs) modified areas, but not to the nickel surface. The patterns generated were imaged by the SECM itself, as well as by optical and fluorescence microscopy.     

Intercalation-etching of graphene on Pt(111) in H_2 and O_2 observed by in-situ low energy electron microscopy

Graphene layers are often exposed to gaseous environments in their synthesis and application processes, and interactions of graphene surfaces with molecules particularly H_2 and O_2 are of great importance in their physico-chemical properties. In this work, etching of graphene overlayers on Pt(111) in H_2 and O_2 atmospheres were investigated by in-situ low energy electron microscopy. Significant graphene etching was observed in 10~(-5) Torr H_2 above 1023 K, which occurs simultaneously at graphene island edges and interiors with a determined reaction barrier at 5.7 eV. The similar etching phenomena were found in 10.7 Torr O_2 above 973 K, while only island edges were reacted between 823 and 923 K. We suggest that etching of graphene edges is facilitated by Pt-aided hydrogenation or oxidation of edge carbon atoms while intercalation-etching is attributed to etching at the interiors at high temperatures. The different findings with etching in O_2 and H_2 depend on competitive adsorption, desorption, and diffusion processes of O and H atoms on Pt surface, as well as intercalation at the graphene/Pt interface.     

Colloidal lithographic nanopatterning via reactive ion etching

We report here a novel colloidal lithographic approach to the fabrication of nonspherical colloidal particle arrays with a long-range order by selective reactive ion etching (RIE) of multilayered spherical colloidal particles. First, layered colloidal crystals with different crystal structures (or orientations) were self-organized onto substrates. Then, during the RIE, the upper layer in the colloidal multilayer acted as a mask for the lower layer and the resulting anisotropic etching created nonspherical particle arrays and new patterns. The new patterns have shapes that are different from the original as a result of the relative shadowing of the RIE process by the top layer and the lower layers. The shape and size of the particles and patterns were dependent on the crystal orientation relative to the etchant flow, the number of colloidal layers, and the RIE conditions. The various colloidal patterns can be used as masks for two-dimensional (2-D) nanopatterns. In addition, the resulting nonspherical particles can be used as novel building blocks for colloidal photonic crystals.     

Complex solid state physical investigations of metal layers on plastics

Several plastics were coated with different metal layers. Different plasma etching methods of plastics were used before deposition of metal layers. The adhesion strength depends on etching methods. With XPS it was shown that different bonds between C-C, C-H, C-Cl and C-O are existing. With X-ray diffraction methods it was found that decreasing peak intensities depend on increasing adhesion strengths.     

Layer-by-layer analysis of A4B6 thin-film heterostructures using inductively coupled plasma atomic fluorescence spectrometry (ICP-AFS)

The technique of layer-by-layer analysis of semiconductive A₄B₆ heterostructures using electrochemical etching and inductively coupled plasma atomic fluorescence spectrometry (ICP AFS) is developed. The Norr etching solution and electrochemical oxidation with subsequent dissolution of oxidized layers in acid were used to remove layers of 0.5 to several microns thickness. Pb_1?xEu_xTe/PbTe and Pb_1?xEu_xSe/PbSe heterostructures were analyzed. The Eu content in removed layers was determined by ICP-AFS. The data on Eu depth profiles were used for the evaluation of the Eu diffusion coefficient in this heterostructures to predict the changes of properties along the depth of the structure. The technique can be applied to the analysis of semiconductive heterostructures with different admixtures.     

Layer-by-layer analysis of A4B6 thin-film heterostructures using inductively coupled plasma atomic fluorescence spectrometry (ICP-AFS)

The technique of layer-by-layer analysis of semiconductive A₄B₆ heterostructures using electrochemical etching and inductively coupled plasma atomic fluorescence spectrometry (ICP AFS) is developed. The Norr etching solution and electrochemical oxidation with subsequent dissolution of oxidized layers in acid were used to remove layers of 0.5 to several microns thickness. Pb_1–xEu_xTe/PbTe and Pb_1–xEu_xSe/PbSe heterostructures were analyzed. The Eu content in removed layers was determined by ICP-AFS. The data on Eu depth profiles were used for the evaluation of the Eu diffusion coefficient in this heterostructures to predict the changes of properties along the depth of the structure. The technique can be applied to the analysis of semiconductive heterostructures with different admixtures.     

DMDMH镀液体系中金的电沉积

在以1,3-二羟甲基-5,5′-二甲基乙内酰脲(DMDMH)为配位剂的镀液体系中研究了金的电沉积工艺和电结晶行为。循环伏安曲线测试中,在-0.88 V附近出现了金的阴极还原峰,在一定的正向电势扫描区间内没有阳极氧化峰出现。计时电流法研究表明,金在玻碳电极上的电结晶过程符合三维连续成核生长模式。SEM和AFM观察表明,在DMDMH体系中获得的镀金层比DMH体系获得的镀金层结晶更为细小,平整性更好。XRD测试表明,在两种镀液体系中获得的镀金层都沿着(111)晶面择优生长。DMDMH镀液体系稳定性能良好。     

Comparative characterisation by atomic force microscopy and ellipsometry of soft and solid thin films

Ellipsometry and atomic force microscopy (AFM) were used to study the film thickness and the surface roughness of both ‘soft’ and solid thin films. ‘Soft’ polymer thin films of polystyrene and poly(styrene–ethylene/butylene–styrene) block copolymer were prepared by spin‐coating onto planar silicon wafers. Ellipsometric parameters were fitted by the Cauchy approach using a two‐layer model with planar boundaries between the layers. The smooth surfaces of the prepared polymer films were confirmed by AFM. There is good agreement between AFM and ellipsometry in the 80–130 nm thickness range. Semiconductor surfaces (Si) obtained by anisotropic chemical etching were investigated as an example of a randomly rough surface. To define roughness parameters by ellipsometry, the top rough layers were treated as thin films according to the Bruggeman effective medium approximation (BEMA). Surface roughness values measured by AFM and ellipsometry show the same tendency of increasing roughness with increased etching time, although AFM results depend on the used window size. The combined use of both methods appears to offer the most comprehensive route to quantitative surface roughness characterisation of solid films. Copyright © 2007 John Wiley & Sons, Ltd.     

Effect of the shear layer on the etching behavior of 6060 aluminum extrusion alloys

The occurrence of preferential grain etching (PGE) during alkaline etching of aluminum extrusion alloys from the 6XXX series is often linked to the presence of certain impurity elements such as zinc, causing an undesired etching appearance. In the presented work, an additional culprit in this context is identified, which has not been investigated yet. A clear relation between PGE and the presence of a subsurface shear layer is identified for extruded Al 6060 alloys containing 0.02 and 0.06 wt% Zn. This shear layer can be distinguished from the bulk of the metal by its difference in crystallographic texture as visualized by electron backscatter diffraction (EBSD). For the Zn enriched alloy, the <111>//ND grains are etched away faster than grains with other orientations, resulting in the grainy appearance typical for PGE. Independent of the Zn content in the alloy, once the shear layer is removed and <111>//ND grains are practically absent on the new surface, the depths variations caused by preferential etching disappear. Instead, the surface of the alloy is attacked uniformly by the caustic etch bath.     

Positive microcontact printing with mercaptoalkyloligo(ethylene glycol)s

The soft lithographic replication of patterns with a low filling ratio by microcontact printing (microCP) is problematic due to the poor mechanical stability of common elastomeric stamps. A recently described strategy to avoid this problem employs a modified patterning method, positive microcontact printing ((+)microCP), in which a stamp with a mechanically more stable inverted relief pattern is used. In contrast to conventional negative microCP ((-)microCP), in the contact areas a self-assembled monolayer (SAM) is printed of a "positive ink", which provides only minor etch protection, whereas the noncontacted areas are subsequently covered with a different, etch-resistant SAM, prior to development by chemical etching. With the aim to identify novel, highly versatile positive inks, the patterning of gold by (+)microCP with mercaptoalkyloligo(ethylene glycol)s (MAOEGs), the subsequent adsorption of octadecanethiol (ODT), and the final development by wet chemical etching have now been studied. A polydisperse mixture of mercaptoundecylocta(ethylene glycol) derivatives was found to provide the best patterning results. The surface spreading of the positive ink during stamping, the exchange of printed MAOEGs with ODT, and the choice of the right etching bath were identified as key parameters that influence the achievable pattern resolution and contrast. Due to the modular composition of functionalized alkyloligo(ethylene glycol) derivatives, (+)microCP with these positive inks has the potential for easy adaptation to a variety of materials and development conditions.     

Effect of the content of hydrogen fluoride in an etchant on the formation of nanopores in silicon during electrolytic etching

The effect of the HF content on the formation of nanopores in silicon during electrochemical etching was studied. Nanoporous silicon layers were established to be formed only when hydrogen fluoride content in etchants (initial HF content: 49 wt %) was higher than 10–12 vol %. The mass and charge balance of the electrolytic etching of silicon was calculated, and the change in charge number of reaction (effective silicon valence) was determined depending on the HF content. The obtained data were used to propose a silicon etching model with the formation of SiF₄ and nanoporous silicon (where nanopores were formed due to the action of predominantly (HF₂)^? ions).     

Low temperature plasma for the preparation of crater walls for compositional depth profiling of thin inorganic multilayers

An indirect, compositional depth profiling of an inorganic multilayer system using a helium low temperature plasma (LTP) containing 0.2% (v/v) SF₆ was evaluated. A model multilayer system consisting of four 10 nm layers of silicon separated by four 50 nm layers of tungsten was plasma‐etched for (10, 20, 30) s at substrate temperatures of (50, 75, and 100) °C to obtain crater walls with exposed silicon layers that were then visualized using time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) to determine plasma‐etching conditions that produced optimum depth resolutions. At a substrate temperature of 100 °C and an etch time of 10 s, the FWHM of the second, third, and fourth Si layers were (6.4, 10.9, and 12.5) nm, respectively, while the 1/e decay lengths were (2.5, 3.7, and 3.9) nm, matching those obtained from a SIMS depth profile. Though artifacts remain that contribute to degraded depth resolutions, a few experimental parameters have been identified that could be used to reduce their contributions. Further studies are needed, but as long as the artifacts can be controlled, plasma etching was found to be an effective method for preparing samples for compositional depth profiling of both organic and inorganic films, which could pave the way for an indirect depth profile analysis of inorganic–organic hybrid structures that have recently evolved into innovative next‐generation materials. Copyright © 2016 John Wiley & Sons, Ltd.     

Photoassisted tuning of silicon nanocrystal photoluminescence

Silicon is a rather inefficient light emitter due to the indirect band gap electronic structure, requiring a phonon to balance the electron momentum during the interband transition. Fortunately, momentum requirements are relaxed in the 1-5 nm diameter Si crystals as a result of quantum confinement effects, and bright photoluminescence (PL) in the UV-vis range is achieved. Photoluminescent Si nanocrystals along with the C- and SiC-based nanoparticles are considered bioinert and may lead to the development of biocompatible and smaller probes than the well-known metal chalcogenide-based quantum dots. Published Si nanocrystal production procedures typically do not allow for the fine control of the particle size. An accepted way to make the H-terminated Si nanocrystals consists of anodic Si wafer etching with the subsequent breakup of the porous film in an ultrasound bath. Resulting H-termination provides a useful platform for further chemical derivatization and conjugation to biomolecules. However, a rather polydisperse mixture is produced following the ultrasonic treatment, leading to the distributed band gap energies and the extent of surface passivation. From the technological point of view, a homogeneous nanoparticle size mixture is highly desirable. In this study, we offer an efficient way to reduce the H-terminated Si nanocrystal diameter and narrow size distribution through photocatalyzed dissolution in a HF/HNO3 acid mixture. Si particles were produced using the lateral etching of a Si wafer in a HF/EtOH/H2O bath followed by sonication in deaerated methanol. Initial suspensions exhibited broad photoluminescence in the red spectral region. Photoassisted etching was carried out by adding the HF/HNO3 acid mixture to the suspension and exposing it to a 340 nm light. Photoluminescence and absorbance spectra, measured during dissolution, show the gradual particle size decrease as confirmed by the photoluminescence blue shift. The simultaneous narrowing of the photoluminescence spectral bandwidth suggests that the dissolution rate varies with the particle size. We show that the Si nanoparticle dissolution rate depends on the amount of light adsorbed by the particle and accounts for the etching rate variation with the particle size. Significant improvement in the PL quantum yield is observed during the acid treatment, suggesting improvement in the dangling bond passivation.