An ultraviolet-curable mold for sub-100-nm lithography

We describe a novel UV-curable mold that is stiff enough for replicating dense sub-100-nm features even with a high aspect ratio. It also allows for flexibility when the mold is prepared on a flexible support such that large area replication can be accomplished. The composite material of the mold is inert to chemicals and solvents. The surface energy is made low with a small amount of releasing agent such that the mold can be removed easily and cleanly after patterning. In addition, the material allows self-replication of the mold. These unique features of the mold material should make the mold quite useful for various patterning purposes.     

Microscale patterning of organic films on carbon surfaces using electrochemistry and soft lithography

We have demonstrated three simple strategies employing poly(dimethylsiloxane) (PDMS) molds for patterning carbon surfaces with two different modifiers in an 18 microm line pattern. The PDMS molds are patterned with microfluidic channels (approximately 22 microm wide and 49 microm deep) and form a reversible, conformal seal to the pyrolyzed photoresist film (PPF) and modified PPF surfaces. Modifiers are electrochemically grafted to the PPF surface by the reduction of aryl diazonium salts and the oxidation of primary amines. For the fill-in patterning approach, the first modifier is electrografted to the PPF surface exposed within the microchannels, and in a second grafting step after removal of the PDMS mold, the second modifier fills in the remaining surface. The selective conversion strategy involves electrografting a continuous film of the modifier to the PPF surface, sealing the PDMS mold to the modified surface and carrying out an irreversible electrochemical reaction of the modifier exposed within the microchannels. In the build-up patterning approach, the PDMS mold is sealed to the modified PPF surface, and a chemical coupling reaction is effected in the microchannels to build up the pattern. The patterns are characterized using SEM, optical microscopy, the formation of condensation figures, and SEM imaging after the assembly of Au nanoparticles.     

Microscale features and surface chemical functionality patterned by electron beam lithography: a novel route to poly(dimethylsiloxane) (PDMS) stamp fabrication

Poly(dimethylsiloxane) (PDMS) has become a ubiquitous material for microcontact printing, yet there are few methods available to pattern a completed PDMS stamp in a single step. It is shown here that electron beam lithography (EBL) is effective in writing patterns directly onto cured PDMS stamps, thus overcoming the need for multiple patterning steps. Not only does this method allow the modification of an existing lithographic pattern, but new 3D features such as cones, pits, and channels can also be fabricated. EBL can also be used to fabricate PDMS masks for photolithography whereby 1:1 pattern transfer into a photoresist is achieved. Additionally, direct EBL writing of surface chemical features has been achieved using a PDMS stamp coated with a self-assembled monolayer. An electrostatic mechanism appears to be operative in the EBL patterning process, as supported by calculations, thermogravimetric analysis, time-of-flight secondary ion mass spectroscopy, optical and atomic force microscopy, and chemical functionalization assays.     

细胞图案化技术及其在胚胎干细胞研究中的应用

图案化技术的不断创新及在细胞领域研究中的应用使细胞图案化技术成为研究和控制细胞行为的有效实验工具.该技术结合微纳米制备、电化学、表面化学和光化学等手段与方法塑造和细胞相关的物理化学参量,如形貌、粗糙度、亲疏水性等,动态地控制细胞的粘附、脱附、迁移、分化及细胞间相互作用,为细胞生物学研究提供一个崭新的技术平台.本文从细胞...     

Fabrication of microfluidic chip using micro‐hot embossing with micro electrical discharge machining mold

This study develops an improved method for generating aluminum mold inserts used in the replication of polymer‐based microfluidic chip. Since molding masters that are suitable for microfluidic chip replication must have features whose dimensions are of the order of tens to hundreds of microns, micro electrical discharge machining is employed herein to fabricate an aluminum mold insert of a microfluidic chip. The width and depth of the aluminum mold insert for the microfluidic chip are 61.50 and 49.61 µm, respectively. The surface roughness values of the microchannel and the sample reservoir in aluminum mold insert for the microfluidic chip are 53.9 and 34.3 nm, respectively. PMMA material is adopted as the molded microfluidic chip that is produced by micro‐hot embossing molding. The PMMA material can replicate the microchannel and sample reservoir very well when the aluminum mold insert is used in micro‐hot embossing molding. The results indicate that the most important parameter in the replication of molded microfluidic chip is the embossing pressure, which is also the most important parameter in determining the surface roughness of the molded microfluidic chip. Copyright © 2010 John Wiley & Sons, Ltd.     

Mold design rules for residual layer-free patterning in thermal imprint lithography

We present the mold design rules for assuring residual layer-free patterning in thermal imprint processes. Using simple relations for mass balance, structural stability, and work of adhesion, we derive the conditions with respect to the given single or multigeometrical feature of the mold, which are compared with simple thermal imprint experiments using soft imprint molds. Our analysis could serve as a guideline for designing the optimum mold geometry and selecting mold material in residual layer-free thermal imprint processes.     

Directed immobilization of protein-coated nanospheres to nanometer-scale patterns fabricated by electron beam lithography of poly(ethylene glycol) self-assembled monolayers

Controlling the spatial organization of biomolecules on solid supports with high resolution is important for a wide range of scientific and technological problems. Here we report a study of electron beam lithography (EBL) patterning of a self-assembled monolayer (SAM) of the amide-containing poly(ethylene glycol) (PEG) thiol CH(3)O(CH(2)CH(2)O)(17)NHCO(CH(2))(2)SH on Au and demonstrate the patterning of biomolecular features with dimensions approaching 40 nm. The electron dose dependence of feature size and pattern resolution is studied in detail by atomic force microscopy (AFM), which reveals two distinct patterning mechanisms. At low doses, the pattern formation occurs by SAM ablation in a self-developing process where the feature size is directly dose-dependent. At higher doses, electron beam-induced deposition of material, so-called contamination writing, is seen in the ablated areas of the SAM. The balance between these two mechanisms is shown to depend on the geometry of the pattern. The patterned SAMs were backfilled with fluorescent 40-nm spheres coated with NeutrAvidin. These protein-coated spheres adhered to exposed areas in the SAM with high selectivity. This direct writing approach for patterning bioactive surfaces is a fast and efficient way to produce patterns with a resolution approaching that of single proteins.     

Development and research for applying innovative magnetic soft mold imprinting techniques in microstructure component manufacturing

The present study employs an innovative technique, which uses PDMS soft mold, blended with magnetic powder as the transmission and imprinting methods, and integrates features from soft micromolding PMMA, an electro‐magnetically controlled, well‐proportioned, pressing technique in order to study how to create microlens arrays through a magnetic soft mold imprinting resist technique. Thus, it renders nanometer imprinting applications, and its technology, more developed and mature. The research findings revealed that, PDMS, blended with magnetic powder, can accurately recast and duplicate nanometer microstructures. Under well‐proportioned magnetic pressing, controlled by an electro‐magnetic disk, it can effectively fill and shape resist microstructures. The composite material of PDMS, with added magnetic iron powder, can effectively improve mechanical strength properties of pure PDMS soft mold, which is easily transformed for imprinting. Meanwhile, owing to the unique features of PDMS soft mold, conformal contact with the base material is possible; therefore, the effective imprinting area and the duplicated representation are significantly improved. In addition, as magnetic PDMS soft mold is easily produced and fast in recasting, the costs can be effectively reduced. In addition, due to features such as low surface free energy and a tendency not to stick to resist in imprinting, the soft mold is evenly controlled by the electro‐magnetic disk for imprinting duplication, highlighting the advantages of microstructure imprinting procedures. Copyright © 2008 John Wiley & Sons, Ltd.     

Surface patterning and its application in wetting/dewetting studies

Recent advances in microfabrication have allowed one to pattern the surface of a solid substrate with patches of different wettabilities on the micrometer-sized scale. These textured surfaces provide a well-characterized model system for studying the wetting and dewetting behaviors of liquids on heterogeneous surfaces. They also present a well-defined template to direct the self-organization of liquids on the surfaces of solid substrates, and to form patterned microstructures of various materials without using expensive, clean-room facilities. As demonstrated in a number of studies, the three-dimensional morphologies of the liquid microstructures could be easily controlled by changing the two-dimensional features patterned on the surface of a solid substrate. These demonstrations suggest that microfabrication based on surface patterning and selective wetting or dewetting will offer immediate advantages in applications such as fabrication of microreactor arrays and microfluidic devices, where a liquid (or solution) is the primary material to be patterned.     

Patterning NHS-terminated SAMs on germanium

Here we report a simple, robust approach to patterning functional SAMs on germanium. The protocol relies on catalytic soft-lithographic pattern transfer from an elastomeric stamp bearing pendant immobilized sulfonic acid moieties to an NHS-functionalized bilayer molecular system comprising a primary ordered alkyl monolayer and a reactive ester secondary overlayer. The catalytic polyurethane-acrylate stamp was used to form micrometer-scale features of chemically distinct SAMs on germanium. The methodology represents the first example of patterned SAMs on germanium, a semiconductor material.     

Interfacial chemistries for nanoscale transfer printing

We describe a patterning technique that uses self-assembled monolayers and other surface chemistries for guiding the transfer of material from relief features on a stamp to a substrate. This purely additive contact printing technique is capable of nanometer resolution. Pattern transfer is fast and it occurs at ambient conditions. We illustrate the versatility of this method by printing single-layer metal patterns with feature sizes from a few tens of microns to a few tens of nanometers. We also demonstrate its use for patterning, in a single step, metal/dielectric/metal multilayers for functional thin film capacitors on plastic substrates.     

Cell patterning using a template of microstructured organosilane layer fabricated by vacuum ultraviolet light lithography

Micropatterning techniques have become increasingly important in cellular biology. Cell patterning is achieved by various methods. Photolithography is one of the most popular methods, and several light sources (e.g., excimer lasers and mercury lamps) are used for that purpose. Vacuum ultraviolet (VUV) light that can be produced by an excimer lamp is advantageous for fabricating material patterns, since it can decompose organic materials directly and efficiently without photoresist or photosensitive materials. Despite the advantages, applications of VUV light to pattern biological materials are few. We have investigated cell patterning by using a template of a microstructured organosilane layer fabricated by VUV lithography. We first made a template of a microstructured organosilane layer by VUV lithography. Cell adhesive materials (poly(d-lysine) and polyethyleneimine) were chemically immobilized on the organosilane template, producing a cell adhesive material pattern. Primary rat cardiac and neuronal cells were successfully patterned by culturing them on the pattern substrate. Long-term culturing was attained for up to two weeks for cardiac cells and two months for cortex cells. We have discussed the reproducibility of cell patterning and made suggestions to improve it.     

Large-area patterning of coinage-metal thin films using decal transfer lithography

We describe two new procedures that appear to hold significant promise as means for patterning thin-film microstructures of the coinage metals (Cu, Ag, Au). A feature central to both is the modification of their surfaces to promote the adhesive transfer of PDMS thin-film microstructures, a material suitable for use as resist layers in large-area patterning, using Decal Transfer Lithography (DTL). The present work provides a significant extension of the capabilities of DTL patterning, providing general protocols that can be used to transfer decal resists to essentially any substrate surface. The first method involves the functionalization of a surface, specifically those of gold and silver films with a thiol-terminated silane coupling agent, (mercaptopropyl)trimethoxysilane. This self-assembled monolayer, when hydrolyzed to its silanol form, provides a robust adhesion-promoting layer suitable for use in DTL patterning. The second method exploits the surface chemistry provided by the deposition of a nanoscale silicon dioxide thin-film capping layer using e-beam evaporation. This procedure provides an exceptional method for patterning large-area, thin-film microstructures of Cu-one compatible with micrometer-scale design rules-that are essentially defect free. Both surface modification strategies enable high-quality poly(dimethylsiloxane) decal transfers, and as the current work shows, these structures are suitable for large-area micrometer-sized patterning of gold, silver, and copper thin films via both wet-etching and lift-off procedures.     

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.     

Preparation of Barium Titanate with Patterned Microstructure by a Novel Electrophoretic Deposition Method

In order to prepare barium titanate (BaTiO₃) with patterned microstructure, a novel electrophoretic method that uses a partially hydrolyzed highly concentrated solution of barium and titanium alkoxides was developed. By using electron beam lithography, a micro-patterned mold, that is a mold with an array of air holes of 250 nm arranged in a triangular lattice with a lattice constant of 500 nm was prepared on a Pt/Ti/SiO₂/Si substrate. Electrophoretic deposition of BaTiO₃ gel was carried out by negatively biasing the Pt/Ti/SiO₂/Si substrate as cathode which had the resist mold on the surface. Removal of the resist mold left a gel material with a patterned structure that was transferred from the pattern of the mold. The gel material was confirmed by ICP-AES to have nearly the stoichiometric composition of BaTiO₃, that is, a composition in which Ba:Ti = 1:1 in molar ratio.     

An electrically driven jetting technique for diverse high-resolution surface structures of nanometre hydroxyapatite crystals

Nanometre hydroxyapatite (nHA) coated metallic materials have been successfully used for bone tissue implantation for several decades now due to its sound biological and mechanical properties. The microstructure and surface topography of the implant material are well-known to play a crucial role in influencing cellular responses to implants and bone tissue regeneration ultimately. Recently, a novel jet-based patterning technique, template-assisted electrohydrodynamic atomisation (TAEA) spraying, has been devised to prepare depositions with defined surface topography for guiding the cellular response. In this study, an improvement investigation of this patterning process was carried out to precisely control the nHA surface structure in terms of geographies and dimensions via an angular needle jetting during the patterning process. More importantly, the mechanism of such improvement of the TAEA patterning technique was also discussed and uncovered. A range of diverse nHA surface structures with high-resolution was therefore achieved, which paves the way for the research of the new generation implant materials with defined cellular response.     

Microstencils for the patterning of nontraditional materials

A microfabrication technique that uses a photolithographically patterned film as a microstencil has been developed. This microstencil has a bilayer structure comprised of parylene and SU-8 films with thicknesses from 4 to 100 microm. The parylene layer enables the microstencil to be mechanically peeled from hydrophilic substrates. Since no chemicals are required to release the microstencil, this technique can be used to pattern chemically and biologically sensitive materials. The amount of material deposited can be automatically controlled by the height of the SU-8 structures or externally controlled by spin coating or other thin film deposition techniques. This patterning method is very versatile and has been used to pattern features as small as 25 by 25 microm on silicon, glass, and polymer substrates. As an initial demonstration, we have patterned wax, cells, proteins, sol, and CYTOP.     

Protein recording material: photorecord/erasable protein array using a UV-eliminative linker

Protein patterning on solid surfaces is a topic of significant importance in the fields of biosensors, diagnostic assays, cell adhesion technologies, and biochip microarrays. In this letter, we have established a novel, rapid method for the fabrication of a "protein recording material", which enables us to spatiotemporally regulate the recording, reading, and erasing of a fluorescent protein array as information by a photochemical technique. A photolinker that we synthesized here was used to control the protein array spatiotemporally. The recording process was almost completed after 1 min of photoirradiation to read a clear pattern consisting of a specific protein-ligand complex with high spatiotemporal resolution. The erasing of the protein array was then achieved by photoirradiation onto the entire patterned surface.     

Micro patterning of active proteins with perforated PDMS sheets (PDMS sieve)

We propose a novel technique for patterning active proteins on a glass substrate using a perforated polydimethylsiloxane (PDMS) sheet-sieve. The sieve, which has tapering holes, is fabricated by spin-coating PDMS on a pyramidal-shaped mold. By means of this sieve, FITC (fluorescent isothiocyanate, bovine)-albumin was successfully spotted in a 5 x 5 microm(2) area in an array. The patterned spots were perfectly isolated, which eliminates the problem of non-specific binding of proteins to undesired areas. To show that proteins maintained their activity after the patterning, we used F(1)-ATPase biomolecular motors; their activity can easily be verified by observing their rotary motion after patterning. Selective patterning with three kinds of fluorescent micro beads indicated the possibility of patterning of different proteins on the same substrate by using the sieve.     

Polydimethylsiloxane–graphene oxide composite improving performance by ion beam irradiation

A hybrid film consisting of graphene oxide covered with poly(dimethylsiloxane) was prepared via spin coater and followed by thermal annealing to improve the bond strength of the polymerized systems. Direct patterning on both graphene oxide and hybrid graphene oxide–poly(dimethylsiloxane) foils by ion microbeam was performed to induce localized reduction in the ion irradiated material. It is well established that the ion irradiation of graphene oxide induces modifications in its electrical, mechanical, and optical properties and disorder in the carbon crystal structure and defect production. The presence of poly(dimethylsiloxane) can be useful as it confers flexibility to the produced pattern and oxygen permeability from the graphene oxide surface. Rutherford backscattered spectroscopy and elastic recoil detection analysis were performed to evaluate the compositional changes in the composite. Atomic force microscopy studied the pattern fidelity. The electrical conductivity of the hybrid material was used to evaluate the changes induced during the proton irradiation of the material.