Functional antibody immobilization on 3-dimensional polymeric surfaces generated by reactive ion etching

Reactive ion etching (RIE) was used to pattern antibodies onto the surfaces of polymer substrates. A low pressure, inductively coupled oxygen plasma was used to anisotropically etch 25-30 mum deep features into poly(methyl methacrylate) (PMMA), Zeonex, and polycarbonate (PC). Scanning electron microscopy and contact angle measurements show that the resulting surfaces exhibit significant microroughness and enhanced hydrophilicity. Fourier transform infrared spectroscopy suggests that, in addition to enhanced surface area, chemical modifications may contribute to antibody immobilization. Polyclonal antibodies preferentially bind to the etched areas in RIE-patterned PMMA and Zeonex substrates but localize in unetched regions of RIE-patterned PC surfaces. Simple immunoassays were performed to demonstrate a potential application for RIE-modified polymer surfaces. Antibodies specific for the capture of fluorescently labeled cholera toxin, S. aureus enterotoxin B, and B. anthracis protective antigen were immobilized onto etched PMMA surfaces and shown to specifically capture their labeled antigen from solution. This work demonstrates a potentially useful fabrication methodology for constructing antibody microarrays on plastic substrates.     

Surface modification of a liquid‐crystalline polymer for copper metallization

The effects of different surface modifications on the adhesion of copper to a liquid‐crystalline polymer (LCP) were investigated with X‐ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy, contact‐angle measurements, and pull tests. High pull‐strength values were achieved when copper was sputter‐deposited onto plasma and reactive‐ion‐etching (RIE)‐pretreated LCP surfaces. The values were comparable to the reference pull strengths obtained with laminated copper on the LCP. The adhesion was relatively insensitive to the employed feed gas in the pretreatments. The surface characterizations revealed that for RIE and plasma treatments, the enhanced adhesion was attributable to the synergistic effects of the increased surface roughness and polar component of the surface free energy of the polymer. However, if the electroless copper deposition was performed on RIE‐ or plasma‐treated surfaces, very poor adhesion was measured. Good adhesion between the LCP substrate and electrolessly deposited copper was achieved only in the case of wet‐chemical surface roughening as a result of the creation of a sufficient number of mechanical interlocking sites, together with a significant loss of oxygen functionalities, on the surface. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 623–636, 2003     

Etching characteristics of GaN by plasma chemical vaporization machining

A high‐quality bulk gallium nitride (GaN) substrate, which is suitable for high‐quality homoepitaxial growth, is indispensable for realizing high‐performance GaN devices. With improvement in the quality of the bulk GaN substrate, the removal of subsurface damage induced during surface polishing has become increasingly necessary. To remove the subsurface damage from the bulk GaN substrate, a chemical finishing method that does not produce further damage is required. We applied plasma chemical vaporization machining (CVM) to remove the subsurface damage from the bulk GaN substrate. In this study, we investigated the etching characteristics of GaN by plasma CVM applying atmospheric pressure Cl₂/He plasma. The maximum removal rate in the depth direction by plasma CVM was 9100 nm/min, which is seven times greater than that of reactive ion etching (RIE). The activation energy in plasma CVM was estimated to be 2.1 kcal/mol, which is 1.75 times greater than that in RIE. It is supposed that some of the energy required for the removal reaction in RIE is supplied by ion bombardment, but plasma CVM depends on only a chemical reaction without high‐energy ion collision. This result suggests that plasma CVM is a finishing method that causes less subsurface damage than RIE. Copyright © 2008 John Wiley & Sons, Ltd.     

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     

Characterization and Wettability of ZnO Film Prepared by Chemical Etching Method

ZnO thin films were prepared by a chemical etching method and their wettability was investigated. The structure and surface composition structure were characterized by means of scanning electron microscopy, X-ray photoelectronic spectrometry(XPS), X-ray diffraction(XRD) and Raman spectrometry. These analyses reveal that the etched films were large-scale micro-nanohierarchical structures composed of a Zn core and a ZnO coating. Superhydrophobic surfaces with water contact angles of over 150o were obtained by n-octadecanethiol(ODT) modification. The XPS and Raman results indicate that ODT molecules were bound to the ZnO surface with the S head group by forming Zn-S bond.     

Effects of RF power on BZN thin‐film etching in SF6/Ar using surface analysis

Reactive ion etching (RIE) was used to etch bismuth zinc niobate (BZN) films in SF₆/ Ar plasma as a function of radio frequency (RF) power. Within the RF power range of choice, the etch rate of BZN films increases with increasing RF power. However, when RF power exceeds 200 W, the etch rate of films appears to increase at a slower rate. The structural properties of the BZN films before and after etching were characterized using X‐ray diffraction. As‐deposited film shows a cubic pyrochlore structure with preferential (222) plane orientation, but all the films etched at different reactive ion etching powers exhibit preferential (400) plane orientation. With increasing RF power, the ZnF₂ phase becomes evident. Also, the film surfaces before and after etching were analysed using XPS. Metal fluorides were found to remain on the surface, resulting in varying relative atomic percentages with RF power. Zn‐rich surfaces were formed because low‐volatile ZnF₂ residues were difficult to remove. Bi and Nb can be removed easily through chemical reactions because of their high volatility, whereas Bi–F and Nb–F, which were thought to be present in the form of a metal oxyfluoride, can still be detected using the narrow scan spectra. RF power has an effect on etch reaction through different plasma densities and particle energies, thus resulting in varying compositions and element chemical binding states. RF power also has an effect on the removal of residues. The minimum value of F atomic concentration is achieved at 150 W. Copyright © 2011 John Wiley & Sons, Ltd.     

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．     

Evaluation of the surface free energy of spin‐coated photodefinable epoxy

The surface free energy of crosslinked photodefinable epoxy (PDE) was evaluated from the advancing contact angles measured by the sessile drop method. Poly(tetrafluoroethylene) (PTFE) was used as a reference material in the evaluation of the surface free energies by various models. Pure water, diiodomethane, formamide, ethylene glycol, diethylene glycol, glycerol, 1‐bromonaphthalene, decane, and tetradecane were used as the probing liquids. The surface free energies for PDE and PTFE were calculated to be 43.6 and 21.2 mJ/m², respectively. The contact‐angle measurements indicated the isotropy of the PDE surface with respect to the surface free energy. The PDE coating was further characterized with scanning electron microscopy and atomic force microscopy. The PDE surface was treated chemically and by reactive ion etching (RIE) to determine their impact on the wettability and adhesion. The treatments resulted in decreased contact angles between the crosslinked PDE surface and water as the polarity of the surface increased from about 9% to 18 and 43% by the chemical and RIE treatments, respectively. On the contrary, the surface free energy of the treated PDEs, as calculated by the geometric mean model, did not change markedly (to 47.4 and 41.8 mJ/m² by the chemical and RIE treatments, respectively). Consequently, the contact angles of diiodomethane and the PDE solution on the treated surfaces did not decrease noticeably. The stud‐pull test showed improved adhesion strength for PDE that was left less crosslinked and, therefore, had residual affinity against the sequential PDE layer. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2137–2149, 2002     

Combined analysis methods for investigating titanium and nickel surface contamination after plasma deep etching

Plasma etching techniques can result in damage and contamination of materials, which, if not removed, can interfere with further processing. Therefore, characterisation of the etched surface is necessary to understand the basic mechanisms involved in the etching process and enable process control and cleaning procedures to be developed. A detailed investigation by means of the combined use of scanning electron microscopy coupled with energy-dispersive X-ray spectrometry (SEM/EDS), X-ray photoelectron spectroscopy (XPS) and optical microscopy (OM) has been carried out on deep titanium trenches etched by plasma. This innovative approach has provided a further insight into the microchemical structure of the surface contamination layer on both the titanium and the nickel hard mask surfaces. The described experiments were conducted on 25 to 100-μm wide trenches, first etched in bulk titanium by an optimised Cl₂/SF₆/O₂-based inductively coupled plasma process, through an electroplated nickel hard mask. The results allow to identify chlorine, fluorine and carbon as the main contaminating agents of the nickel mask and to associate three oxidation states around the etched trenches highlighting certain specific aspects related to the passivation mechanism. These observations reinforce the scientific relevance of the combined use of complementary optical and imaging analytical techniques.     

Effect of AA2024‐T3 surface pretreatment on the physicochemical properties and the anticorrosion performance of poly(γ‐glycidoxypropyltrimethoxysilane) sol‐gel coating

This study investigated the dependence of the anticorrosion performance of a poly(γ‐glycidoxypropyltrimethoxysilane) (poly(γ‐GPTMS)) sol‐gel coating on AA2024‐T3 aluminum alloy surface state. Two different AA2024‐T3 surface pretreatment procedures were tested: a degreasing with acetone and a chemical multistep etching process (industrial chemical etching pretreatment). Poly(γ‐GPTMS) coatings were deposited onto both pretreated surfaces using the dip‐coating technique. Surfaces were characterized principally by scanning electron microscopy, X‐ray photoelectron spectroscopy, Fourier transform infrared attenuated total reflectance, contact angles, and roughness measurements. Moreover, for the coated AA2024‐T3 surfaces, a pull‐off test was used to evaluate the poly(γ‐GPTMS) adhesion to the pretreated surface. Bare surface properties depended on the applied pretreatment. The chemically etched surface was the roughest and the most concentrated in hydroxyl groups. In addition, comparatively to the degreased surface, it has a more hydrophobic character. Poly(γ‐GPTMS) coating revealed an uneven nature and a poor adhesion once it was deposited onto the degreased surface. Coatings anticorrosion performances were evaluated using electrochemical impedance spectroscopy measurements (EIS). Electrochemical impedance spectroscopy data proved that the sol‐gel coating applied onto the chemically etched surface had better anticorrosion performance.     

Adsorption of anionic surfactant on porous and non-porous polyethylene terephthalate films

We study the adsorption of anionic surfactant, sodium dodecyl diphenyloxide disulfonate (SDDD) on three types of polyethylene terephthalate substrates from aqueous solutions of SDDD of different concentrations. Neutral electrolyte (KCl) was added to the solutions to vary the ionic strength. The three types of substrates were: (1) original polymer film, (2) etched non-porous film, which was obtained from pristine film by chemical etching and bears negative charge on the surface, (3) etched porous membranes, which were fabricated from pristine film by ion irradiation and subsequent chemical etching. The membranes have negative charge on the flat surface and on the inner pore walls. The comparison of original and etched nonporous films shows that the negative charge on the flat surface has weak effect on adsorption of the anionic surfactant. The comparison of etched non-porous and porous films shows that the SDDD adsorption on the inner walls of pores is much weaker than on flat surface—even in case the pore radius is significantly larger than the Debye length. This “exclusion” effect strongly depends on ionic strength of solution. For the porous films, the effect of the pore size and shape on the anionic surfactant adsorption is presented and discussed.     

Fabrication of 2D photonic crystals using block copolymer patterns on as grown LEDs

Di-block copolymer polystyrene-block-polymethyl methacrylate (PS-b-PMMA) was used to make patterns over a large area of as grown LEDs. The polymer patterns on LEDs surface could be transferred to the underlying p-GaN, the topmost layer of as grown LEDs by both reactive ion etching (RIE) and photo-enhanced chemical (PEC) etching. Removal of remaining polymer chains results in patterned LEDs which shows higher light extraction efficiency. In our experiment, much higher intensity for patterned LEDs in both photoluminescence (PL) and electroluminescence (EL) data plot were found. Similar improvements were found in I-V and L-I curves for patterned LEDs.     

Characterization of Defects in PECVD-SiO2 Coatings on PET by Confocal Microscopy

Thin, transparent ceramic coatings on polymers are effective barriers against gas and vapor transmission. However, they always display some residual permeation, which can be attributed to defects. The main sources of these defects are dust particles on the polymer surface before deposition, and roughness of the polymer surface due to the presence of so-called antiblock particles. The transparency and extreme thinness of the films (d 50 nm) render the detection of defects virtually impossible by optical and even by electron microscopies. However, by using a technique based on reactive ion etching (RIE) in oxygen plasma, we are able to render defects visible, even by optical microscopy at relatively low magnification (100 ×). In the present article we present a confocal microscopy study, which has helped to better understand the effect of RIE at defect sites, as well as the origins of the defects in these coatings.     

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.     

Scanning Probe Microscopy and Spectroscopy of CVD Diamond Films

 The surface morphology and electronic properties of as-deposited CVD diamond films and the diamond films which have been subjected to boron ion implantation or hydrogen plasma etching have been systematically studied by high resolution scanning probe microscopy and spectroscopy techniques. AFM and STM image observations have shown that (a) both the as-deposited CVD diamond films and the boron ion implanted films exhibit similar hillock morphologies on (100) crystal faces and these surface features are formed during the deposition process; (b) boron ion implantation does not cause a discernible increase in surface roughness; (c) atomic flatness can be achieved on crystal faces by hydrogen plasma etching of the film surface. Scanning tunnelling spectroscopy analysis has indicated that (a) the as-deposited diamond films and the hydrogen plasma etched diamond films possess typical p-type semiconductor surface electronic properties; (b) the as-deposited diamond films subjected to boron implantation exhibit surface electronic properties which change from p-type semiconducting behaviour to metallic behaviour; (c) the damage in the boron implanted diamond films is restricted to the surface layers since the electronic properties revert to p-type on depth profiling.     

Surface stress-dependent adhesion to fluorinated polymers

Irradiation of thin commercial sheets of poly(tetrafluoroethylene) (PTFE) or a fluorinated ethylene-propylene copolymer (FEP) yield essentially the same results with mass spectroscopy or x-ray photoelectron spectroscopy (XPS). For both gas phase and surface (ca. 30 Å) products of irradiation, the same product distributions and exposure dependencies are observed. In addition, XPS of chemically etched (with sodium naphthalenide) PTFE and FEP shows the same extent of surface defluorination. In contrast to the more surface-sensitive XPS, Rutherford backscattering spectroscopy of etched PTFE shows that the defluorination extends to depths of ca. 3000 Å, while with etched FEP defluorination extends to only a few hundred Angstroms. Scanning electron microscopy shows the FEP surface to be smooth and featureless both before and after chemical etching, while etched PTFE is characterized by a crazed surface with a high density of unidirectional cracks oriented perpendicular to long macroscopic scratches existing in the virgin surface. Adhesion of Cu to this etched PTFE has previously been shown to be sufficiently strong that failure is a result of near-cohesive failure in the PTFE and not adhesive failure. Conversely, weak adhesion of Cu to etched FEP or to other smooth forms of fluorinated polymers, including polished PTFE, is observed. This correlation of strong adhesion with surface roughness and not with surface chemical changes is consistent with previous suggestions that a major component of adhesion to fluorinated polymers is mechanical interlocking. The differences between FEP and PTFE are discussed in terms of a model involving surface stresses expected from their different methods of manufacture: extrusion from the melt in the case of FEP and skiving from pressed cylinders in the case of PTFE. © 1994 John Wiley & Sons, Inc.     

Dry etching of InGaP and AlInP in CH4/H2/Ar

Electron cyclotron resonance (ECR) plasma etching with additional rf-biasing produces etch rates 2,500 A/min for InGaP and AlInP in CH₄/H₂/Ar. These rates are an order of magnitude or much higher than for reactive ion etching conditions (RIE) carried out in the same reactor. N₂ addition to CH₄/H₂/Ar can enhance the InGaP etch rates at low flow rates, while at higher concentrations it provides an etch-stop reaction. The InGaP and AlInP etched under ECR conditions have somewhat rougher morphologies and different stoichiometries up to 200 Å from the sur face relative to the RIE samples.     

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.     

Study of reactive ion etching of Si and SiO2 for CFxCl4−x gases

A parametric study of the etching of Si and SiO₂ by reactive ion etching (RIE) was carried out to gain a better understanding of the etching mechanisms. The following fluorocarbons (FCs) were used in order to study the effect of the F-to-Cl atom ratio in the parent molecule to the plasma and the etching properties: CF₄, CF₃Cl, CF₂Cl₂, and CFCl₃ (FC-14, FC-13, FC-12, and FC-11 respectively). The Si etch rate uniformity across the wafer as a function of the temperature of the wafer and the Si load, the optical emission as a function of the temperature of the load, the etch rate of SiO₂ as a function of the sheath voltage, and the mass spectra for each of the FCs were measured. The temperature of the wafer and that of the surrounding Si load strongly influence the etch rate of Si, the uniformity of etching, and the optical emission of F, Cl, and CF₂. The activation energy for the etching reaction of Si during CF₄ RIE was measured. The etch rate of Si depends more strongly on the gas composition than on the sheath voltage; it seems to be dominated by ion-assisted chemical etching. The etching of photoresist shifted from chemical etching to ion-assisted chemical etching as a function of the F-to-Cl ratio and the sheath voltage. The etch rate of SiO₂ depended more strongly on the sheath voltage than on the F-to-Cl ratio.     

Etching Characteristics and Mechanisms of TiO2 Thin Films in HBr/Ar and Cl2/Ar Inductively-Coupled Plasmas

The TiO₂ etching characteristics and mechanisms in HBr/Ar and Cl₂/Ar inductively-coupled plasmas were investigated under fixed gas-mixing ratio and bias power conditions. It was found that in both systems, an increase in gas pressure from 4 to 10 mTorr results in a non-monotonic TiO₂ etching rate, while a variation of input power in the range 500–800 W causes a faster-than-linear acceleration of the etching process. Plasma diagnostics performed by Langmuir probes and zero-dimensional plasma modeling provided data on plasma parameters, steady-state densities, and fluxes of the active species on the etched surface. The model-based analysis of the etching mechanism showed that for the given set of processing parameters, the TiO₂ etch kinetics correspond to the transitional regime of ion-assisted chemical reaction in which a chemical-etch pathway dominates.