Fabrication of elliptical nanorings with highly tunable and multiple plasmonic resonances

Herein, a new and facile patterning method is demonstrated for the scalable fabrication of gold elliptical rings (ERs) in a controlled manner over large areas. In this method, well-ordered hexagonally arrayed polystyrene (PS) rings, fabricated by colloidal lithography, were used as masters to generate poly(dimethylsiloxane) (PDMS) stamps with circular apertures. The stamps were then stretched and utilized as molds for creating elliptical PS rings by a capillary filling process. Through subsequent reactive ion etching and chemical wet-etching, the elliptical PS rings could be readily transferred into an underlying gold film, leading to the formation of gold ERs. Since the aspect ratio (AR) of the elliptical PS rings could be controlled by varying the applied strain during the capillary filling process, gold ERs with different ARs could be fabricated in a scalable manner. The optical properties of the gold ERs were characterized by UV-vis/NIR and IR extinction measurements. The ERs exhibited only odd modes of polarization-dependent plasmonic resonances at normal incidence. The experiments and corresponding theoretical studies illustrated that all resonant modes could be tuned across a broad spectral range from the visible to the mid infrared (550-4700 nm) by simply varying the AR of the ERs. Moreover, the experimental data were confirmed by COMSOL simulations.     

Soft lithographic printing of patterns of stretched DNA and DNA/electronic polymer wires by surface-energy modification and transfer

Aligned and stretched lambda DNA is directed to specific locations on solid substrates. Surface-energy modification of glass substrates by using patterned polydimethylsiloxane (PDMS) stamps is used to direct DNA onto the surface-energy-modified micrometer-scale pattern through molecular combing. As an alternative, patterned and nonpatterned PDMS stamps modified with polymethylmethacrylate (PMMA) are utilized to direct the stretched DNA to the desired location and the results are compared. The DNA is elongated through molecular combing on the stamp and transfer printed onto the surfaces. PMMA-modified stamps show a more defined length of the stretched DNA, as compared to bare PDMS stamps. A combination of these two methods is also demonstrated. As an application example, transfer printing of DNA decorated with a semiconducting conjugated polyelectrolyte is shown. The resulting patterned localization of stretched DNA can be utilized for functional nanodevice structures, as well as for biological applications.     

Maskless projection lithography for the fast and flexible generation of grayscale protein patterns

Protein patterns of different shapes and densities are useful tools for studies of cell behavior and to create biomaterials that induce specific cellular responses. Up to now the dominant techniques for creating protein patterns are mostly based on serial writing processes or require templates such as photomasks or elastomer stamps. Only a few of these techniques permit the creation of grayscale patterns. Herein, the development of a lithography system using a digital mirror device which allows fast patterning of proteins by immobilizing fluorescently labeled molecules via photobleaching is reported. Grayscale patterns of biotin with pixel sizes in the range of 2.5 μm are generated within 10 s of exposure on an area of about 5 mm(2) . This maskless projection lithography method permits the rapid and inexpensive generation of protein patterns definable by any user-defined grayscale digital image on substrate areas in the mm(2) to cm(2) range.     

Rapid prototyping of 2D structures with feature sizes larger than 8 microm

This paper extends rapid prototyping for several types of lithography to the 8-25-microm size range, using transparency photomasks prepared by photoplotting. It discusses the technical improvement in photomask quality achieved by photoplotting, compared to the currently used image setting, and demonstrates differences in the resolution that can be obtained with photomasks with features in the 8-100-microm size range. These high-resolution photomasks were used to microfabricate microelectrodes, microlenses, and stamps for microcontact printing, following methods described previously.     

玻璃基底上的蛋白质微接触压印图型化

研究了一种将胶原Ⅰ型蛋白通过微接触压印技术图型化于玻璃基底表面的方法.采用标准光刻工艺制备印章母版,并运用反应离子刻蚀设备对印章表面进行氧等离子体处理,以期改善印章表面亲水性能.将涂敷了胶原Ⅰ型蛋白,并经返潮处理的印章以50 g/cm^2大小的力与玻璃表面接触10 s,得到蛋白质微图型.结果表明,采用反应离子刻蚀技术能显著改善聚二甲基硅氧烷（PDMS）印章表面的亲水性.表面亲水性得到改善的PDMS印章,在经过湿盒返潮后,再进行微接触压印得到的蛋白质微图型其质量得到显著提高.     

Micron and submicron patterning of dicyanopyrazine-linked porphyrin molecules using micro-contact printing and Langmuir-Blodgett assembly

We describe a method to conveniently fabricate micron- and submicron-sized patterns of well-ordered and densely-packed dicyanopyrazine-linked porphyrin (4-TDCPP) molecules by using micro-contact printing (micro-CP) in conjunction with Langmuir-Blodgett (LB) deposition. SEM and AFM images reveal that the sizes and shapes of the 4-TDCPP patterns are well-matched with the geometric features of the polydimethylsiloxane (PDMS) stamps used for micro-CP. Fluorescence images show strong, red emission from the 4-TDCPP patterns. However, the thicknesses of the 4-TDCPP patterns transferred onto a silicon substrate by micro-CP are not the same, even though the same amount of 4-TDCPP layers are deposited on the surface of PDMS stamps in the LB process. The thicknesses of the 10 microm line, 2 microm dot and 300 nm line patterns of 10-layered 4-TDCPP molecules are 34.6, 26.7 and 5.9 nm, respectively. These differences may be due to variations in adhesion forces between the silicon substrate and 4-TDCPP on PDMS stamps having different size patterns. Larger patterns have greater contact areas compared to smaller patterns. This phenomenon can cause stronger adhesion forces, resulting in greater pattern thickness.     

Bond-detach lithography: a method for micro/nanolithography by precision PDMS patterning

We have discovered a micro/nanopatterning technique based on the patterning of a PDMS membrane/film, which involves bonding a PDMS structure/stamp (that has the desired patterns) to a PDMS film. The technique, which we call "bond-detach lithography", was demonstrated (in conjunction with other microfabrication techniques) by transferring several micro- and nanoscale patterns onto a variety of substrates. Bond-detach lithography is a parallel process technique in which a master mold can be used many times, and is particularly simple and inexpensive.     

Controllable and Facile Fabrication of Gold Nanostructures for Selective Metal‐Assisted Etching of Silicon

A method with the combination of organic‐vapor‐assisted polymer swelling and nanotransfer printing (nTP) is used to manufacture desirable patterns consisting of gold nano‐clusters on silicon wafers for Au‐assisted etching of silicon. This method remarkably benefits to the size control and regional selection of the deposited Au. By tuning the thickness of the Au films deposited on the polydimethylsiloxane (PDMS) stamps, along with the swelling of PDMS stamps in acetone atmosphere, the Au films are cracked into diverse nanostructures. These nanostructures are covalently transferred onto silicon substrates in a large scale and enable to accelerate the chemical etching of silicon. The etched areas are composed of porous structures which can be readily distinguished from the surroundings on optical microscope. PDMS stamps and the Au clusters provide the control over the feature of the etched areas and the porous silicon, respectively. The silicon surfaces with patterned porous features offer a platform for exploiting new functional templates, for example, they present a diversity of antireflective and fluorescent performance.     

Printed circuit technology for fabrication of plastic-based microfluidic devices

One of the primary advantages of using plastic-based substrates for microfluidic systems is the ease with which devices can be fabricated with minimal dependence on specialized laboratory equipment. These devices are often produced using soft lithography techniques to cast replicas of a rigid mold or master incorporating a negative image of the desired surface structures. Conventional photolithographic micromachining processes are typically used to construct these masters in either thick photoresist, etched silicon, or etched glass substrates. The speed at which new masters can be produced using these techniques, however, can be relatively slow and often limits the rate at which new device designs can be built and tested. In this paper, we show that inexpensive photosensitized copper clad circuit board substrates can be employed to produce master molds using conventional printed circuit technology. This process offers the benefits of parallel fabrication associated with photolithography without the need for cleanroom facilities, thereby providing a degree of speed and simplicity that allows microfluidic master molds with well-defined and reproducible structural features to be constructed in approximately 30 min in any laboratory. Precise control of channel heights ranging from 15 to 120 microm can be easily achieved through selection of the appropriate copper layer thickness, and channel widths as small as 50 microm can be reproducibly obtained. We use these masters to produce a variety of plastic-based microfluidic channel networks and demonstrate their suitability for DNA electrophoresis and microfluidic mixing studies.     

Maskless multiple-beam laser lithography for large-area nanostructure/microstructure fabrication

This paper reports a maskless multiple-beam laser lithography technique for large-area nanostructure/microstructure fabrication. This lithography technique can flexibly generate arbitrary nanostructures/microstructures over a large area at a high speed. The feature size of the nanostructures/microstructures can be controlled by exposure time and moving speed of the nanostage. Functional predesigned patterns, including split-ring resonator metamaterials for terahertz waves, can be obtained. More complicated structures can be made by single- and double-exposure schemes to make hybrid nanostructures/microstructures and tune surface plasmonic resonance properties. Meanwhile, microstructures with large height to lateral dimension ratios (2.5D microstructures) fabricated on silicon substrates can be used as mold tools for soft lithography. This technology shows its unique capacity to create various nanostructures/microstructures for extensive applications.     

Facile patterning of reduced graphene oxide film into microelectrode array for highly sensitive sensing

In this study, we develop a new technique to fabricate a reduced graphene oxide (rGO)-based microelectrode array (MEA) with low-cost soft lithography. To prepare patterned rGO, a polydimethylsiloxane (PDMS) mold with an array of microwells on its surface is fabricated using soft lithography, and GO is assembled on an indium tin oxide (ITO) electrode with a layer-by-layer method. The rGO pattern is formed by closely contacting the assembled GO film onto the ITO electrode with the PDMS mold filled with hydrazine solution in the microwells to selectively reduce the localized GO into the rGO. The MEA with patterned rGO as the microelectrode is characterized with Kelvin probe force microscopy (KFM), atomic force microscopy (AFM), and cyclic voltammetry (CV) with ferricyanide in aqueous solution as the redox probe. The KFM and AFM results demonstrate that each rGO pattern prepared under the present conditions is 3 μm in diameter, which is close to that of the PDMS mold we use. The CV results show that the rGO patterned onto the ITO exhibits a sigmoid-shaped voltammogram up to 200 mVs(-1) with a microampere level current response, suggesting that the rGO-based electrode fabricated with soft lithography behalves like a MEA. To demonstrate the potential electroanalytical application of the rGO-based MEA, prussian blue (PB) is electrodeposited onto the rGO-based MEA to form the PB/rGO-based MEA. Electrochemical studies on the formed PB/rGO-based MEA reveal that MEA shows a lower detection limit and a larger current density for the detection of H(2)O(2), as compared with the macroscopic rGO electrode. The method demonstrated here provides a simple and low-cost strategy for the fabrication of graphene-based MEA that are useful for electroanalytical applications.     

Replication of a thin polydimethylsiloxane stamp and its application to dual-nanoimprint lithography for 3D hybrid nano/micropatterns

This paper presents the fabrication of a thin and flexible polydimethylsiloxane (PDMS) stamp with a thickness of a few tens of um and its application to nanoimprint lithography (NIL). The PDMS material generally has a low elastic modulus and high adhesive characteristics. Therefore, after being treated, the thin PDMS stamp is easily deformed and torn, adhering to itself and other materials. This paper introduces the use of a metal ring around the flange of a thin PDMS stamp to assist with the handling of this material. A PDMS stamp with a motheye pattern in nanometer scale was inserted between a substrate and a microstamp with concave patterns in micrometer scale. Subsequently, three-dimensional (3D) hybrid nano/micropatterns were fabricated by pressing these two stamps and curing the resist. The fabricated hybrid patterns were measured and verified in both the microscale and nanoscale. The process, termed "dual NIL," can be applied to the fabrication of optical components or bio-sensors that require repetitive nanopatterns on micropatterns.     

Additive Manufacturing of SiOC,SiC, and Si3N4 Ceramic 3D Microstructures

Herein, the fabrication of hard ceramic SiOC 3D microstructures by precursor synthesis, laser lithography, and pyrolysis combination is proposed. Precursors are hybrid organosilicon materials prepared via sol–gel method using trimethoxymethylsilane and 3-(trimethoxysilyl)propyl methacrylate, which has an acrylate functional group enabling laser photopolymerization process. Hard 3D ceramic structures (hardness up to ≈15 GPa, reduced elastic modulus ≈105 GPa) from soft organometallic derivatives are obtained after high-temperature pyrolysis under nitrogen atmosphere. The advantage of the proposed method is the absence of shrinkage defects leading to a uniform repetitive decrease in the volume of printed microstructures. In contrast to slurry-based printing technology, the proposed method is focused on homogeneous monolithic molecular resins resulting in visual smooth surfaces of prepared microstructures. Moreover, the printing resolution of the proposed method is substantially improved through the absence of predispersed ceramic microparticles in mixtures, which is a necessary element in a slurry-based technology.     

Microcontact printing of living bacteria arrays with cellular resolution

Arrays of living bacteria were printed on agarose substrate with cellular resolution using elastomeric stamps with a high aspect ratio generated by reverse in situ lithography (RISL). The printed bacteria reproduced the original stamp patterns with high fidelity and continued growing as in bulk culture. This methodology provides a simple route to any desired bacterial spatial 2D distribution and may be applied to screening as well as to studies of bacteria phenotypic variability, population dynamics, and ecosystem evolution.     

纳米光子结构软膜紫外光固化纳米压印

紫外光固化纳米压印是实现纳米结构批量复制的一种新技术．其特点是低成本和高分辨，而且可以达到极高的套刻精度．为了得到大面积图案的均匀复制，可用聚二甲基硅氧烷（PDMS）制备透光的压印软模板．其母版图案可由高分辨率电子柬曝光和反应离子刻蚀的方法在硅片基底上获得，然后用浇注的方法将图案转移到PDMS上．本实验特别发展了紫外光固化纳米压印适用于软膜压印的双层膜图型转移技术．该双层膜由廉价的光胶和聚甲基丙烯酸甲脂（PMMA）构成．对光胶层的压印可用普通的光学曝光仪实现．然后再将图案用反应离子刻蚀的方法转移到PMMA层中．为了证明方案的可行性，在两种不同材料的半导体基片上压印了三角晶格的光子晶体和准晶结构的图案，并用剥离的方法将它们转移到金属薄膜上，最后成功地进行了硅片刻蚀实验．相信这一纳米制做方法对大面积纳米光子结构和光学集成芯片的制造是普遍适用的．     

Fabrication of topologically complex three-dimensional microfluidic systems in PDMS by rapid prototyping

This paper describes a procedure for making topologically complex three-dimensional microfluidic channel systems in poly(dimethylsiloxane) (PDMS). This procedure is called the "membrane sandwich" method to suggest the structure of the final system: a thin membrane having channel structures molded on each face (and with connections between the faces) sandwiched between two thicker, flat slabs that provide structural support. Two "masters" are fabricated by rapid prototyping using two-level photolithography and replica molding. They are aligned face to face, under pressure, with PDMS prepolymer between them. The PDMS is cured thermally. The masters have complementary alignment tracks, so registration is straightforward. The resulting, thin PDMS membrane can be transferred and sealed to another membrane or slab of PDMS by a sequence of steps in which the two masters are removed one at a time; these steps take place without distortion of the features. This method can fabricate a membrane containing a channel that crosses over and under itself, but does not intersect itself and, therefore, can be fabricated in the form of any knot. It follows that this method can generate topologically complex microfluidic systems; this capability is demonstrated by the fabrication of a "basketweave" structure. By filling the channels and removing the membrane, complex microstructures can be made. Stacking and sealing more than one membrane allows even more complicated geometries than are possible in one membrane. A square coiled channel that surrounds, but does not connect to, a straight channel illustrates this type of complexity.     

印章特性和印刷压力对微接触印刷工艺的影响

微接触印刷（μCP）是一种能在微纳米尺度上完成表面图案化的技术,主要特点是高效和低成本．研究了μCP过程中印章机械特性和印刷压力对形成的微图案质量的影响．为了进一步分析聚二甲基硅氧烷（PDMS）制作的印章特性,浇注了5种配比的PDMS试样,并进行了单轴拉伸和压缩试验,获得了其应力应变关系．制作了3种配比的表面线型图案印章,实施微接触印刷使其印刷压强在1kPa～1MPa．通过图形化分析对最终的微接触印刷质量进行评估．实验结果表明：最优的压强区间为20～200kPa．较小的压力将会产生印章与基底的间隙,而较大的压力将会导致印章的严重变形．由于质量比为20：1的PDMS印章的弹性模量最小,其在中等压力下的微接触印刷质量最好,而较硬的印章可有效地抵抗印刷中产生的变形．     

Low-cost printing of poly(dimethylsiloxane) barriers to define microchannels in paper

This paper describes the use of a modified x,y-plotter to generate hydrophilic channels by printing a solution of hydrophobic polymer (pol(dimethylsiloxane; PDMS) dissolved in hexanes onto filter paper. The PDMS penetrates the depth of the paper and forms a hydrophobic wall that aqueous solutions cannot cross. The minimum size of printed features is approximately 1 mm; this resolution is adequate for the rapid prototyping of hand-held, visually read, diagnostic assays (and other microfluidic systems) based on paper. After curing the printed PDMS, the paper-based devices can be bent or folded to generate three-dimensional systems of channels. Capillary action pulls aqueous samples into the paper channels. Colorimetric assays for the presence of glucose and protein are demonstrated in the printed devices; spots of Bromothymol Blue distinguished samples with slightly basic pH (8.0) from samples with slightly acidic pH (6.5). The work also describes using printed devices that can be loaded using multipipets and printed flexible, foldable channels in paper over areas larger than 100 cm2.     

Characterization of rapid PDMS casting technique utilizing molding forms fabricated by 3D rapid prototyping technology (RPT)

In this work we characterize a novel possibility for PDMS (PolyDiMethylSiloxane) casting/ micromolding methods with the utilization of molding forms fabricated by a commercially available novel acrylic photopolymer based 3D printing method. The quality and absolute spatial accuracy of 1) different 3D printing modes (‘matt’ vs. ‘glossy’); 2) the molded PDMS structures and 3) the subsequently produced complementary structures made of epoxy resin were investigated. The outcome of these two form transfer technologies were evaluated by the cross sectional analysis of open microfluidic channels (trenches) with various design. Our results reveal the spatial accuracy in terms of real vs. CAD (Computer Aided Design) values for the 3D printed acrylic structures and the limits of their form transfer to PDMS, then to epoxy structures. Additionally the significant differences between the various spatial directions (X, Y, Z) have been characterized, and the conclusion was drawn that the ‘glossy’ printing mode is not appropriate for 3D printing of microfluidic molds.     

Self-organized meso-patterning of soft solids by controlled adhesion: elastic contact lithography

The surface of a soft elastic film becomes unstable and deforms when a rigid flat plate is brought into its contact proximity, without application of any external pressure. These isotropic undulations have a characteristic wavelength, lambda approximately 3H, where H is the film thickness. The wavelength is independent of the adhesive interactions and the mechanical properties of the film. We present here a mini-review of our recent work on techniques of aligning, modulating, and ordering the instability structures by the use of simple 1-D patterned stamps, by changing the stamp-surface separation, by slow shearing of a flat stamp and by confining the instability in soft narrow channels. The generality of the technique for different soft materials is illustrated by patterning cross-linked polydimethylsiloxane (PDMS), aluminum coated PDMS and hydrogels films. Use of a flexible stamp such as a metal foil provides enhanced conformal contact by adhesive forces, which aids large area patterning without critically maintaining a parallel configuration and uniform pressure between the stamp and the film. The technique has the potential to develop into a new soft lithography tool--"Elastic Contact Lithography" suitable for rapid, large area micron and sub-micron self-organized patterning of a variety of soft materials without any special equipments.