Polyelectrolyte brushes as efficient ultrathin platforms for site-selective copper electroless deposition

Ion-exchange in surface-initiated polyelectrolyte brushes provides a versatile route to the formation of catalytically active surfaces for electroless deposition of Cu. The advantage of this procedure is the covalent anchoring of the catalyst support layer, eliminating delamination of the metal film, even when deposited onto PDMS substrates. Furthermore, by tuning the concentration of PdCl4(2-) ions in the brushes, the rate of deposition and hence the thickness of the overall film can be controlled easily.     

Direct patterning of copper on polyimide using ion exchangeable surface templates generated by site-selective surface modification

We demonstrate site-selective chemical surface modification by dispensing potassium hydroxide solution onto polyimide, which confines source metallic ions that can subsequently be used in resist- and mask-free fabrication of copper circuit patterns. Metallization can be achieved by a wet chemical method, providing control over metal/polymer interfacial structures. Because the approach is compatible with other existing printing technologies and much simpler than conventional lithography-based methods, we propose that the present surface template method may be of general application in fabrication of metallized polymers as well as in development of integrated circuits with a variety of electronic circuit elements.     

Hollow capsule processing through colloidal templating and self-assembly

Hollow capsules of nanometer to micrometer dimensions constitute an important class of materials that are employed in diverse technological applications, ranging from the delivery of encapsulated products for cosmetic and medicinal purposes to their use as light-weight composite materials and as fillers with low dielectric constant in electronic components. Hollow capsules comprising polymer, glass, metal, and ceramic are nowadays routinely produced by using various chemical and physicochemical methods. The current article focuses on a recent novel and versatile technique, based on a combination of colloidal templating and self-assembly processes, developed for synthesizing uniform hollow capsules of a broad range of materials. The strategy outlined readily affords control over the size, shape, composition, and wall thickness of the hollow capsules.     

pH and ionic strength responsive photonic polymers fabricated by using colloidal crystal templating

In this paper, monodispersed silica particles were synthesized using tetraethoxysiliane hydrolyzing in ethanol by a Stöber–Fink–Bobn method and then self-assembled on cleaning glass slides to form silica colloidal crystals. After photopolymerization of methacrylic acid mixing with ethylene glycol dimethylacrylate and hydrofluoric acid etching, the pH-responsive polymers were obtained with highly 3D-ordered macroporous structures templated by silica colloidal crystals. These polymers films can swell or deswell in response to external stimuli, causing a change of Bragg diffraction to read pH or ionic strength of various solutions by optical signals or electrochemical signals. As an application, they can be used as chemical sensors to detect pH or ionic strength variation of environment.     

Crystallization of colloidal crystal on hydrogel surface

A dip-coating method to fabricate wet and dry type of colloidal crystal films was developed. The wet type of colloidal crystal film was fabricated by lifting an agarose-hydrogel-coated substrate out of an aqueous suspension containing monodisperse polymer spheres and the dry type of colloidal crystal film was derived by following desiccation of the wet film. Monodisperse spheres formed ordered structures in the both type of the films, which contributed sharp reflection peaks. Brilliant colors were observed when the reflection peaks fell in the visible region. Formation mechanism of the colloidal crystal and their optical properties were discussed.     

Photocatalytic patterning of monolayers for the site-selective deposition of quantum dots onto TiO2 surfaces

A novel photochemical mechanism is reported for the site-selective deposition of quantum dots onto nanocrystalline TiO2 films. The patterning mechanism involves the combination of surfactant-mediated self-assembly and monolayer photolithography. In the self-assembly process, CdS and CdSe quantum dots were attached to TiO2 surfaces through bifunctional mercaptoalkanoic acid (MAA) linkers. MAAs were adsorbed to the TiO2 surface as the deprotonated carboxylates, primarily through monodentate coordination to Ti4+ sites. CdSe quantum dots were bound to the terminal thiol groups of surface-adsorbed MAAs, with a surface adduct formation constant, Kad, of (2.1 +/- 0.7) x 104 M-1. The color and optical density of the quantum dot-functionalized TiO2 films were tunable. Monolayer photopatterning involved the TiO2-catalyzed oxidative degradation of surface-adsorbed mercaptohexadecanoic acid (MHDA). A mechanism is proposed wherein MHDA degradation occurs through both oxidative decarboxylation and the formation of interchain disulfides. These MHDA photodegradation processes regulate the extent to which CdSe quantum dots adsorb onto the TiO2 surface. Illumination through a photomask yielded optically patterned, quantum dot-functionalized TiO2 films that were characterized by scanning electron microscopy and energy-dispersive X-ray analysis.     

Surface-anisotropic polystyrene spheres by electroless deposition

Surfaces of sulfate-terminated polystyrene microspheres are anisotropically modified with silver nanoparticles covering 20-50% of the sphere surface using electroless deposition. A PDMS templating method is employed. Silver nanoparticles are found to deposit uniformly onto the exposed sphere surfaces. The deposition is diffusion-controlled and the nanoparticles adhere strongly to the polystyrene particles despite extensive exposure to ultrasonication. Silver content is confirmed by EDAX analysis. The final silver coverage is controlled via the PDMS pre-curing conditions.     

Formation of microstructured silicon surfaces by electrochemical etching using colloidal crystal as mask

Silicon disk arrays and silicon pillar arrays with a close-packed configuration having an ordered periodicity were fabricated by the electrochemical etching of a silicon substrate through colloidal crystals used as a mask. The colloidal crystals were directly prepared by the self-assembly of polystyrene particles on a silicon substrate. The transfer of a two-dimensional hexagonal array of colloidal crystals to the silicon substrate could be achieved by the selective electrochemical etching of the exposed silicon surfaces, which were located in interspaces among adjacent particles. The diameter of the tip of the silicon pillars could be controlled easily by changing the anodization conditions, such as current density and period of electrochemical etching.     

Rapid fabrication of large-area colloidal crystal monolayers by a vortical surface method

We have developed a simple approach for rapidly fabricating large-scale colloidal crystal arrays on substrates. Latex particles were first assembled into a close-packed monolayer on a vortical water surface; the monolayer was then transferred onto substrates by a withdrawer. Such an assembly method is conceptually similar to the Langmuir-Blodgett (L-B) methods for film deposition but does not require an L-B trough. The samples exhibit a large-scale periodic feature based on optical microscopy and scanning electron microscopy observations and diffract the laser beam, acting as crystals. This newly developed technique is timesaving, widely accessible, and applicable to large particles (up to 2 microm). It promises to be useful in nanofabrication.     

Submicron scale patterning in sintered silica colloidal crystal films using a focused ion beam

Focused ion beam milling is used to fabricate micron and submicron scale patterns in sintered silica colloidal crystal films. Rectangular cavities with both solid and porous boundaries, fluidic channels, and isolation of a small number of packed spheres are patterned. The ion beam can pattern sintered films of individual submicron size spheres and create patterns that cover up to 40 mum in less than 15 min. The experiments in this work indicate that the amount of redeposited material on the surface of a milled cavity determines whether the surface will be porous or solid. FIB direct patterning has applications in colloidal crystal based lithography, integrated photonic devices, optofluidic devices, and micrototal-analytical systems.     

Chemical vapour deposition on silicon: In situ surface studies

The decomposition of Fe(CO)₅ to produce Fe films on Si(100) has been examined in situ using Auger electron spectroscopy. Processes occurring during pyrolytic, UV photolytic and electron beam deposition are determined. The nature of the surface films produced by these different methods is compared and contrasted.     

Epitaxial single crystal surface patterning and study of physical and chemical environmental effects on crystal growth

For designing the responsive polymer brushes, and tuning the local and chemical surface responses to the external stimuli, the epitaxial single crystals were patterned by combination of bared surfaces of poly(ethylene glycol) (PEG) substrate, polymer homo-brushes constructed from poly(ethylene glycol)-b-polystyrene (PEG-b-PS) as well as poly(ethylene glycol)-b-poly(methyl methacrylate) (PEG-b-PMMA), and PEG-b-PS/PEG-b-PMMA mixed-brush channels. To achieve this target, various single crystals and epitaxial structures grown from dilute solutions through self-seeding approach were utilized as seeds to fabricate the next channels. The characteristics and morphologies of different channels were detectable by atomic force microscopy (AFM). The influence of chemical (solvent quality and interaction of substrate with different brushes) and physical (presence of brushes from another type in their vicinity) environments on crystallization was studied. Due to the effect of chemical environment, the PS brushes hampered the growth of PEG crystals at M _n ^PS?=?10,000 g/mol. However, the PMMA brushes allowed PEG crystals to grow completely at M _n ^PMMA =13,100 g/mol, and indicated their hindrance at higher molecular weights (here, M _n ^PMMA?=?17,100 g/mol). It was feasible to neutralize the mentioned hindrance through fabricating the channels with brushes having the highest hindrance (M _n ^PS?=?14,800 g/mol and M _n ^PMMA?=?17,100 g/mol), and altering the physical environment from homo- to mixed-brush morphology. The characteristics (thickness, tethering density, and domain size) of developed channels from a certain material, in all arrangements and in various channels were in good agreement with those of corresponding non-epitaxial single crystals grown under the same conditions.     

The formation of submonolayer thorium coatings on a silicon oxide surface by electrochemical deposition

Data are reported on the mechanisms of the formation of submonolayer coatings based on thorium oxide on the surface of Si(111) single crystal with natural oxide as a result of electrochemical deposition. It is experimentally shown that the deposition of thorium atoms from an acetone solution of Th(NO₃)₄ onto the surface of natural silicon oxide leads to the formation of defects in the thin silicon oxide layer, which is accompanied by the deposition of thorium nanoclusters onto a pure silicon surface. The observed effects have been qualitatively explained assuming the breakdown of natural silicon oxide due to the presence of an electrical double layer in the near-surface region of the cathode.     

Biomimetic creation of hierarchical surface structures by combining colloidal self-assembly and Au sputter deposition

Surfaces of hexagonally packed silica spheres have been functionalized with silanes containing different hydrocarbon or fluorocarbon chains. The resulting chemical and physical structures were studied to establish the effect of surface hydrophobicity on the measured contact angles on the rough surfaces. The results were used to assess the effects of surface modifications on the parameters in the Cassie equation. To achieve superhydrophobicity via a biomimetic approach, we created two-scale structures by first forming hexagonally packed SiO2 spheres, followed by Au deposition on the spheres and heat treatment to form Au nanoparticles on sphere surfaces. Contact angles over 160 degrees were achieved. This work provides improved understanding of the effect of the surface roughness and solid surface fraction on superhydrophobicity.     

Characterization of silicon wafers through deposition of self-assembled monolayers

AFM imaging of the adsorption of self-assembled octadecylsiloxane (ODS) monolayers has been utilized for probing surface properties of silicon wafers. It has been found that both growth rate of the organic films and island size of sub-monolayer films are influenced by the doping level of the wafers as well as by the surface finishing step during wafer production. Generally, higher doping levels led to lower adsorption rates and smaller islands. Variation of the sample pretreatment used for surface finishing of similarly doped wafers led only to significant changes of the island size, but not of the surface coverage. The results presented open up a valuable perspective for characterizing the surface homogeneity of silicon wafers which is an important parameter for monitoring-wafers in semiconductor industry. Received: 26 June 2000 / Revised: 26 July 2000 / Accepted: 1 August 2000     

Characterization of silicon wafers through deposition of self-assembled monolayers

AFM imaging of the adsorption of self-assembled octadecylsiloxane (ODS) monolayers has been utilized for probing surface properties of silicon wafers. It has been found that both growth rate of the organic films and island size of sub-monolayer films are influenced by the doping level of the wafers as well as by the surface finishing step during wafer production. Generally, higher doping levels led to lower adsorption rates and smaller islands. Variation of the sample pretreatment used for surface finishing of similarly doped wafers led only to significant changes of the island size, but not of the surface coverage. The results presented open up a valuable perspective for characterizing the surface homogeneity of silicon wafers which is an important parameter for monitoring-wafers in semiconductor industry. Received: 26 June 2000 / Revised: 26 July 2000 / Accepted: 1 August 2000     

Copper nanoparticles seeded functionalized‐PVC plastic surface for electroless nickel deposition

A novel and facile activation process for electroless nickel deposition was developed. The semi‐interpenetrating polymer network hydrogel biofilm was used to functionalize the inert poly(vinyl chloride) (PVC) surface, and then Cu nanoparticles, which can initial the subsequent electroless nickel deposition successfully seeded on the functionalized‐PVC surface. The samples were characterized by scanning electron microscopy, X‐ray photoelectron spectroscopy, X‐ray diffraction, and transmission electron microscopy. The results show that the hydrogel film provided the PVC surface with amino groups and Cu nanoparticles of 20–50 nm in size could be functioned as the catalytic nuclei for the subsequent electroless metal deposition on PVC plastic. It can be concluded that the novel Cu activation was effective for the nickel deposition on PVC surface, because of more chemisorption sites for Cu nanoparticles generated on PVC surface. Copyright © 2013 John Wiley & Sons, Ltd.     

Electrohydrodynamic flow and colloidal patterning near inhomogeneities on electrodes

Current density inhomogeneities on electrodes (of physical, chemical, or optical origin) induce long-range electrohydrodynamic fluid motion directed toward the regions of higher current density. Here, we analyze the flow and its implications for the orderly arrangement of colloidal particles as effected by this flow on patterned electrodes. A scaling analysis indicates that the flow velocity is proportional to the product of the applied voltage and the difference in current density between adjacent regions on the electrode. Exact analytical solutions for the streamlines are derived for the case of a spatially periodic perturbation in current density along the electrode. Particularly simple asymptotic expressions are obtained in the limits of thin double layers and either large or small perturbation wavelengths. Calculations of the streamlines are in good agreement with particle velocimetry experiments near a mechanically generated inhomogeneity (a "scratch") that generates a current density larger than that of the unmodified electrode. We demonstrate that proper placement of scratches on an electrode yields desired patterns of colloidal particles.