电化学微/纳加工分辨率的影响因素及对策

The etching resolution of electrochemical fabrication technique is influenced significantly by the diffusion layer of the etchant. It has been shown that a fast etching rate can achieve higher etching resolution due to so-called heterogeneous scavenging effect, while a lower etching rate will result in rather lower etching resolution. For the latter case, the confined etchant layer technique(CELT) has been employed to improve the etching resolution. i. e., a certain redox couple which can consume the etchant homogeneously and rapidly was added to the solution. The homogeneous scavenging effect confined the etchant within a narrow layer around the electrode surface and much improved etching resolution was achieved. Using the CELT and a needle-shaped microelectrode, an etching spot of several micro-meters was obtained at silicon wafer surface.     

Tip current/positioning close-loop mode of scanning electrochemical microscopy for electrochemical micromachining

Scanning electrochemical microscopy (SECM) has been approved as a prospective electrochemical micromachining (ECMM) technique soon after its birth. However, it still remains challenge for SECM to fabricate arbitrary three-dimensional (3D) microstructures because of the limitation of positioning system. To solve this problem, we proposed a tip current signal/positioning close-loop mode in which the tip current signal is fed back to the positioning system in order to program the motion trial of SECM tip. Both the triedge-cone and sinusoidal microstructures were obtained by the close-loop positioning mode. The static-state etching process was demonstrated not to be disturbed by the slow motion rate of SECM tip. The unique positioning mode would be significant for both ECMM and electrochemical imaging.     

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.     

金属铜表面的三维齿状图形的化学微加工

金属铜表面的三维齿状图形的化学微加工;约束刻蚀剂层技术(CELT);化学刻蚀     

镍表面三维微图形的复制加工

运用约束刻蚀剂层技术(CELT)在金属镍(Ni)表面实现三维微图形加工,以规整的三维齿状微结构作模板,获得可有效CELT加工的化学刻蚀和捕捉体系,在Ni表面得到了与齿状结构互补的三维微结构并应用扫描电子显微镜(SEM)和原子力显微镜(AFM)表征刻蚀图案,证实CELT可用于金属表面Ni的三维微图形刻蚀加工．     

金属的电化学微区刻蚀方法

本文概述了现行的金属微区刻蚀方法并详细地介绍几种电化学刻蚀方法 ,比较了掩膜法、扫描电化学显微镜法、约束刻蚀剂层法、电化学扫描隧道显微镜法和超短电位脉冲法各自的特点 .从加工精度 (能否进行微米和纳米级加工 )、加工效率 (工序复杂程度 ,能否批量制造或复制 )、可用范围 (主要是能否加工复杂三维立体结构 )等各项因素进行了综合分析 ,结果表明 ,各种加工方法各有其优缺点 ,从总的效果来看 ,约束刻蚀剂层技术在微加工方面具有较大优势     

约束刻蚀剂层技术对金属铝的微结构加工研究

采用约束刻蚀剂层技术, 以亚硝酸钠为先驱物, 通过电化学氧化产生刻蚀剂(硝酸)刻蚀铝, 并以NaOH为捕捉剂, 在电极模板上形成约束刻蚀剂层. 在金属铝表面加工出梯型槽微结构, 加工分辨率约为500 nm. 通过测量表面氢离子浓度, 对捕捉剂的约束效果进行了分析.     

The effect of NDGA-modified etchant on the enzymatic degradation resistance and mechanical properties of collagen matrix

Bio-modified etchant can significantly improve the biostability of demineralized dentin collagen matrix, which validates the concept of etch-andcrosslink in dentin bonding.     

When Mesoporous Silica Meets the Alkaline Polyelectrolyte: A Controllable Synthesis of Functional and Hollow Nanostructures with a Porous Shell

An efficient and environment friendly surface‐protected etching method by using mesoporous silica as a template and alkaline polyelectrolyte as both the protecting and etching agent was developed to prepare a SiO₂ nanotube with a porous shell. The polyelectrolytes attached to the template not only create a localized alkaline environment, but also effectively protect the silica surface, whereas the mesopore channels accelerate the diffusion of etchant throughout the template, all of which facilitate the formation of hollow structures in a fully controllable way. By tuning the etching power and protecting ability of the polyelectrolyte, the rigidity and porosity of products can be precisely manipulated. It is inspiring that various alkaline polyelectrolytes including polypeptide and dextran derivative can be used for the etching process, so that the porous and hollow nanostructures are born with positively charged and biocompatible surface as well as abundant amino groups for further coupling, which make them potential capsules for drug delivery and probes for imaging and detection. The protective etching process can also be extended to the preparation of yolk‐shell super structures with functional cores, or porous nanoparticle assemblies with their individual characteristics maintained.     

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.     

Chiral-selective etching effects on carbon nanotube growth at edge carbon atoms

Chemical vapor deposition (CVD) utilizing metal cluster nanoparticle catalysts is commonly used to synthesize carbon nanotubes (CNT), with oxygen-containing species such as water or alcohol included in the feedstock for enhanced yield. However, the etching effect of these additives on the growth mechanism has rarely been investigated, despite evidence suggesting that etching potentially affects the chirality distribution of product CNTs. We used quantum chemical methods to study how water-based etchant radicals (OH and H) may enhance the chiral selectivity during CVD growth using CNT cap models. Chemical reactivities of the caps with the etchant radicals were evaluated using density functional theory (DFT). It was found that the reactivities on the cap edges correlate with the chirality of the caps. These results suggest that proper selection of etchant species can provide opportunities for selective chirality control of the product CNTs. © 2018 Wiley Periodicals, Inc.     

用规整膜板对砷化镓的三维微结构图形加工刻蚀

以微齿轮图形结构作为规整模板 ,用约束刻蚀剂层技术对GaAs样品表面进行了加工刻蚀 .在有捕捉剂H3AsO3存在的情况下 ,规则微齿轮图形能够很好地在样品表面复制 .刻蚀结果与没有捕捉剂存在时的刻蚀结果做了比较 .另外还测试了不同方法制得膜板的性能 ,初步探讨了电化学模板的制作工艺 .     

金纳米棒的生长及与FeCl_3的作用

采用三氯化铁选择性刻蚀法获得了预定长径比的金纳米棒.相比于晶种生长法,三氯化铁选择性刻蚀法可以更加简便快捷地调控金纳米棒形貌.以三氯化铁为刻蚀剂的刻蚀反应优先发生在金纳米棒尖端,这是因为金纳米棒尖端反应活性更高且表面活性剂钝化作用更弱.通过控制刻蚀反应时间及刻蚀剂浓度,可以精确调控金纳米棒的长径比.实验结果表明,增加刻蚀剂浓度、卤素离子浓度以及升高反应温度可以加快刻蚀反应速率.进一步讨论了金属离子的刻蚀作用机理.     

Diffusion in ternary aqueous systems containing human serum albumin and precipitants of different classes

The mutual diffusion coefficients for two aqueous ternary systems, both containing a protein, human serum albumin (HSA, component 1), were measured. The first system contained a neutral polymer, polyethylene glycol (PEG, component 2), and the second an "organic solvent", 2-methyl-2,4-pentanediol (MPD, component 3). Both PEG and MPD are used as co-precipitants in HSA crystallization protocols. Measurements were performed at constant protein concentration, with increasing precipitant content. The results obtained for the two systems were discussed and compared. In both cases, the two main diffusion coefficients, relative to the motion of the protein and of the precipitant under their own concentration gradient, can be interpreted in terms of non-specific volume interactions between the solutes. Particularly, it was showed that any possible direct HSA-MPD interaction may not have a significant effect on the values of these two diffusion coefficients. Differences arise between the cross precipitant's diffusion coefficients, relative to the motion of the precipitant under the protein concentration gradient, D(i1) with i = 2, 3. In the case of PEG, the D(21) trend vs. c(2) can be simply interpreted in terms of an "exclude volume" effect. In contrast, in the case of MPD, the D(31)vs. c(3) trend seems to indicate a more complex mechanism of transport. Because the cross precipitant's diffusion coefficient plays an important role in the crystallization process, the implication of the observed difference on the crystallization procedure was also discussed.     

Fabrication of nanostructured silicon by metal-assisted etching and its effects on matrix-free laser desorption/ionization mass spectrometry

A matrix-free, high sensitivity, nanostructured silicon surface assisted laser desorption/ionization mass spectrometry (LDI-MS) method fabricated by metal-assisted etching was investigated. Effects of key process parameters, such as etching time, substrate resistance and etchant composition, on the nanostructured silicon formation and its LDI-MS efficiency were studied. The results show that the nanostructured silicon pore depth and size increase with etching time, while MS ion intensity increases with etching time to 300 s then decreases until 600 s for both low resistance (0.001–0.02 Ω cm) and high resistance (1–100 Ω cm) silicon substrates. The nanostructured silicon surface morphologies were found to directly affect the LDI-MS signal ion intensity. By characterizing the nanostructured silicon surface roughness using atomic force microscopy (AFM) and sample absorption efficiency using fluorescence microscopy, it was further demonstrated that the nanostructured silicon surface roughness was highly correlated to the LDI-MS performance.     

Photoassisted etching of silicon dioxide films

Theoretical approaches to resolving the problem of photoassisted etching of silicon dioxide as the most widely used protective layer in microelectronics are presented. A model of donor-acceptor interaction providing for the desolvation of the F^? ion involved in SiO₂ photoetching is proposed. The etchant compositions were optimized, and the effect of the most important factors on the etching process was examined. It has been shown that the maximal photoetching rate is 0.42 μm/min and the chemical contribution to etching is small, being about 0.02 μm/min.     

Why is copper locally etched by scanning electrochemical microscopy?

The etching of thin copper films by scanning electrochemical microscopy (SECM) was investigated. It is not trivial that locally injected charge by an oxidized mediator will lead to dissolution of copper as the charge can easily be dissipated by lateral charge propagation. We studied the effect of different parameters, such as thickness of the Cu film and concentration of the mediator, on the efficiency of etching. The feedback current is the sum of three charge transfer contributions: diffusion of mediator species, chemical reaction on the surface and lateral charge propagation across the copper film. We have introduced an approach for isolating the lateral contribution and studied the parameters affecting the fate of the locally injected charge. We found that etching becomes effective once the lateral contribution cannot dissipate the locally injected charge. This occurs as the concentration of the etchant increases or the film thickness decreases. Measuring the steady-state current above Cu films with different thickness, allowed estimating the potential difference across the Cu area underneath the tip. We conclude that driving local processes, such as etching, depends on creating a mechanism which maintains the injected charge focused.     

Oxidative dissolution of copper and zinc metal in carbon dioxide with tert-butyl peracetate and a beta-diketone chelating agent

A series of beta-diketone ligands, R(1)COCH(2)COR(2) [tmhdH (R(1) = R(2) = C(CH(3))(3)); tfacH (R(1) = CF(3); R(2) = CH(3)); hfacH (R(1) = R(2) = CF(3))], in combination with tert-butyl peracetate (t-BuPA), have been investigated as etchant solutions for dissolution of copper metal into carbon dioxide solvent. Copper removal in CO(2) increases in the order tfacH < tmhdH < hfacH. A study of the reactions of the hfacH/t-BuPA etchant solution with metallic copper and zinc was conducted in three solvents: scCO(2) (supercrical CO(2)); hexanes; CD(2)Cl(2). The etchant solution/metallic zinc reaction produced a diamagnetic Zn(II) complex, which allowed NMR identification of the t-BuPA decomposition products as tert-butyl alcohol and acetic acid. Gravimetric analysis of the amount of zinc consumed, together with NMR studies, confirmed the 1:1:2 Zn:t-BuPA:hfacH reaction stoichiometry, showing t-BuPA to be an overall two-electron oxidant for Zn(0). The metal-containing products of the copper and zinc reactions were characterized by elemental analysis, IR spectroscopy, and, as appropriate, NMR spectroscopy and single-crystal X-ray diffraction [trans-M(hfac)(2)(H(2)O)(CH(3)CO(2)H) (1, M = Cu; 2, M = Zn)]. On the basis of the experimental results, a working model of the oxidative dissolution reaction is proposed, which delineates the key chemical variables in the etching reaction. These t-BuPA/hfacH etchant solutions may find application in a CO(2)-based chemical mechanical planarization (CMP) process.     

Influence of Variant Electrolyte in Electrochemical Micromachining of Micro Holes in SMA Using Taguchi Optimization

Russian Journal of Electrochemistry - Electrochemical micromachining (ECMM) is one of the commercially successful modern machining processes used in various manufacturing industries. Nitinol, a...     

Structural and mechanical studies on modified reused tyres composites

Reused tyres powder was used as reinforcement in HDPE-reused tyre composites. In order to improve the compatibility between both components, several pre-treatments performed over the rubber tyres were applied: sulphuric acid etching, use of a silane coupling agent and chlorination with trichloroisocyanuric acid (TCI). Mechanical properties of the resulting materials (e.g. tensile strength, Young’s Modulus, toughness and elongation at break) were studied and compared. Chemical modifications on the surface of reused tyres were monitored by FTIR and physical modifications and behaviour to fracture were followed by means of SEM. The influence of rubber pre-treatment was assessed by comparing the results of treated and untreated composites with those for neat HDPE. Reused tyre rubber, added to the HDPE in small quantities, acts as a filler, improving the stiffness and providing a more brittle behaviour. Pre-treatment with TCI gave poor results in terms of mechanical properties obtaining lower values than neat HDPE in some cases and always worst properties than sulphuric or silane coupling agent. Treatments with H₂SO₄ and silane coupling agent improve the ability of rubber to interact with the HDPE, increasing the material’s stiffness and its tensile strength. Sulphuric acid modificates chemical and physically the particles’ surface improving mainly mechanical adhesion, whereas silane acts as a compatibilizer developing chemical matrix-reinforcement interactions.