Fabrication of a carbon-nanotube-based field-effect transistor by microcontact printing

The fabrication of a field-effect transistor with both channel material and source and drain electrodes made from carbon nanotubes (CNTs) through patterned deposition of CNT films by microcontact printing is described. Surfactant-dispersed single-walled CNTs are first separated into semiconducting and metallic fractions by gel filtration. The semiconducting and metallic CNTs are then sequentially transferred by dendrimer-coated polydimethylsiloxane stamps onto dendrimer-coated silicon wafers following a printing protocol optimized for this purpose. The resulting CNT micropatterns are visualized by atomic force microscopy. Semiconducting as well as metallic CNTs preserve their characteristic electronic properties within the transferred films. A device composed of a rather thick (ca. 5 nm) and densely patterned film of metallic CNTs cross-printed on top of a thinner (ca. 1.5 nm) and less dense film of semiconducting CNTs shows the typical properties of a field-effect transistor with the metallic CNT stripes as electrodes, the semiconductive CNT stripes as channel material, and the silicon substrate as gate electrode.     

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.     

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.     

Micropatterning of Ag and Au nanoparticles by microcontact printing and block copolymer micelles

Micropatterns of gold and silver nanoparticles were successfully obtained by combining microcontact printing and poly(2-vinylpyridine)-block-poly(cyclohexyl metharylate) (P2VP-b-PCHMA) diblock copolymer micelles with metal precursors. The metal ions were incorporated into poly(2-vinylpyridine) blocks and located into the core area of micelles. Then the metal-loaded micellar solutions were used as inks which were spin coated as thin layers onto polydimethylsiloxane stamps and transferred onto the substrates by stamping. Different morphologies of micellar aggregates were formed on the substrates depending on the stamp morphologies, and single layers of nanoparticles in the micropattern were obtained by the reducing process.     

The Janus‐SAM Approach for the Flexible Functionalization of Gold and Titanium Oxide Surfaces

A novel approach is developed to address the requirement of multiple stamps and inks for microcontact printing (µCP) onto different substrate surfaces. This approach relies on µCP one divalent molecule, which is able to form Janus self‐assembled monolayers (JSAMs) with a labile cleavable centre, thus providing a facile method for the chemical derivatization of different substrate surfaces. This study presents an answer to the challenges presented within a highly versatile application, µCP. N‐(3‐diethylphosphatoxy)propyl‐11‐mercaptoundecanamide is used for the first time as an ink for µCP onto both gold and titanium oxide surfaces, utilizing the same polydimethylsiloxane stamp. Following printing, the JSAMs are enzymatically treated on these two different substrates to reveal different functional groups. The newly formed surfaces are subjected to additional surface reactions and used for the chemisorption of bovine serum albumin. At each stage, these JSAMs are characterized by X‐ray photoelectron spectroscopy and dynamic water‐contact‐angle measurements. Confocal laser scanning microscopy is used for the characterization of the adsorbed proteins.     

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.     

Wafer scale synthesis of dense aligned arrays of single-walled carbon nanotubes

Here we present an easy one-step approach to pattern uniform catalyst lines for the growth of dense, aligned parallel arrays of single-walled carbon nanotubes (SWNTs) on quartz wafers by using photolithography or polydimethylsiloxane (PDMS) stamp microcontact printing (μCP). By directly doping an FeCl₃/methanol solution into Shipley 1827 photoresist or polyvinylpyrrolidone (PVP), various catalyst lines can be well-patterned on a wafer scale. In addition, during the chemical vapor deposition (CVD) growth of SWNTs the polymer layers play a very important role in the formation of mono-dispersed nanoparticles. This universal and efficient method for the patterning growth of SWNTs arrays on a surface is compatible with the microelectronics industry, thus enabling of the fabrication highly integrated circuits of SWNTs.     

基于微接触印刷法的PbS微图案的制备

以聚二甲基硅氧(PDMS)弹性体为印模,十八烷基三氯硅烷(OTS)为"墨水",采用微接触印刷法分别在平整的玻璃基片表面和弯曲的玻璃棒表面进行印刷操作,将印刷后的基片浸入到PbS化学浴液中沉积得到微图案化的PbS薄膜.交叉印刷和光学显微观察结果表明,所沉积的PbS微图案边界清晰规整,并且PbS会选择性沉积在基片表面没有被OTS覆盖的区域.     

Tuning stamp surface energy for soft lithography of polar molecules to fabricate bioactive small-molecule microarrays

Soft-lithography-based techniques are widely used to fabricate microarrays. Here, the use of microcontact insertion printing is described, a soft-lithography method specifically developed for patterning at the dilute scales necessary for highly selective biorecognition. By carefully tuning the polar surface energy of polymeric stamps, problems associated with patterning hydrophilic tether molecules inserted into hydrophilic host self-assembled monolayers (SAMs) are surmounted. Both prefunctionalized tethers and on-chip functionalization of SAMs patterned by microcontact insertion printing enable the fabrication of small-molecule microarrays. Substrates patterned with the neurotransmitter precursor 5-hydroxytryptophan selectively capture a number of different types of membrane-associated receptor proteins, which are native binding partners evolved to recognize free serotonin. These advances provide new avenues for chemically patterning small molecules and fabricating small molecule microarrays with highly specific molecular recognition capabilities.     

Easy Fabrication of Electrically Insulating Nanogaps by Transfer Printing

An easy and cost‐effective method to reproducibly fabricate nanogaps over a large area is introduced. Gold is evaporated on low‐aspect‐ratio polydimethylsiloxane (PDMS) stamps at an angle of 60°. Afterwards, the stamp is brought into contact with a silicon/silicon dioxide substrate and subsequently peeled at rates varying from 1 to 3 mm s^?1, resulting in the fabrication of nanogaps between two gold electrodes. The fabrication of insulating nanogaps with a width down to 50 nm is demonstrated.     

Patterning Hydrophobic Surfaces by Negative Microcontact Printing and Its Applications

Here, a negative microcontact printing method is developed to form hydrophilic polydopamine (PDA) patterns with micrometer resolution on hydrophobic including perfluorinated surfaces. In the process of the negative microcontact printing, a uniform PDA thin film is first formed on the hydrophobic surface. An activated polydimethylsiloxane (PDMS) stamp is then placed in contact with the PDA‐coated hydrophobic surface. Taking advantage of the difference in the surface energy between the hydrophobic surface and the stamp, PDA is removed from the contact area after the stamp release. As a result, a PDA pattern complementary to the stamp is obtained on the hydrophobic surface. By using the negative microcontact printing, arrays of liquid droplets and single cells are reliably formed on perfluorinated surfaces. Microlens array with tunable focal length for imaging studies is further created based on the droplet array. The negative microcontact printing method is expected to be widely applicable in high‐throughput chemical and biological screening and analysis.     

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.     

Directed collagen patterning on gold-coated silicon substrates via micro-contact printing

The ability to create biologically functional systems from non-biological materials has importance in the arena of tissue engineering and medical device implantation. Directing the immobilization of proteins to specified regions on a substrate has attracted a lot of attention as one potential approach. Functionalization of the surface of gold-coated silicon wafers was accomplished by micro-contact printing a hydrophilic (or hydrophobic) self-assembled monolayer (SAM) atop the gold coating using poly(dimethylsiloxane) (PDMS) stamps. Afterwards, the substrate was soaked in a solution of hydrophobic (or hydrophilic) surfactant molecules which filled in the un-stamped area. The intention was to use carbodiimide coupling to attach fluorescently labeled collagen to COOH-terminated (hydrophilic) regions of the substrate. However, even in the presence of the reagents for this reaction, the collagen preferred to assemble on the hydrophobic regions. The results suggest that micro-contact printing may provide a simple mechanism for patterning collagen onto surfaces simply using selective adsorption. This might be useful for examining directed cell interactions, or to enhance the biocompatibility of inorganic materials used as substrates in tissue engineering or devices that are to be implanted into the body.     

Multiwalled carbon-nanotube-functionalized microelectrode arrays fabricated by microcontact printing: platform for studying chemical and electrical neuronal signaling

A facile method is proposed for the deposition of multiwalled carbon nanotube (MWCNT) layers onto microelectrode arrays by means of a microcontact printing technique, leading to the fabrication of MEAs characterized by well defined electrical and morphological properties. Using polydimethyl siloxane stamps, produced from different mold designs, a flexibility of printing is achieved that provides access to microscale, nanostructured electrodes. The thickness of MWCNT layers can be exactly predetermined by evaluating the concentration of the MWCNT solution employed in the process. The electrode morphology is further characterized using laser scanning and scanning electron microscopy. Next, by means of impedance spectroscopy analysis, the MWCNT-electrode contact resistance and MWCNT film resistance is measured, while electrochemical impedance spectroscopy is used to estimate the obtained electrode-electrolyte interface. Structural and electrochemical properties make these electrodes suitable for electrical stimulation and recording of neurons and electrochemical detection of dopamine. MWCNT-functionalized electrodes show the ability to detect micromolar amounts of dopamine with a sensitivity of 19 nA μm(-1) . In combination with their biosensing properties, preliminary electrophysiological measurements show that MWCNT microelectrodes have recording properties superior to those of commercial TiN microelectrodes when detecting neuronal electrical activity under long-term cell-culture conditions. MWCNT-functionalized microelectrode arrays fabricated by microcontact printing represent a versatile and multipurpose platform for cell-culture monitoring.     

Highly Stable and Stretchable Conductive Films through Thermal‐Radiation‐Assisted Metal Encapsulation

Stretchable conductors are the basic units of advanced flexible electronic devices, such as skin‐like sensors, stretchable batteries and soft actuators. Current fabrication strategies are mainly focused on the stretchability of the conductor with less emphasis on the huge mismatch of the conductive material and polymeric substrate, which results in stability issues during long‐term use. Thermal‐radiation‐assisted metal encapsulation is reported to construct an interlocking layer between polydimethylsiloxane (PDMS) and gold by employing a semipolymerized PDMS substrate to encapsulate the gold clusters/atoms during thermal deposition. The stability of the stretchable conductor is significantly enhanced based on the interlocking effect of metal and polymer, with high interfacial adhesion (>2 MPa) and cyclic stability (>10 000 cycles). Also, the conductor exhibits superior properties such as high stretchability (>130%) and large active surface area (>5:1 effective surface area/geometrical area). It is noted that this method can be easily used to fabricate such a stretchable conductor in a wafer‐scale format through a one‐step process. As a proof of concept, both long‐term implantation in an animal model to monitor intramuscular electric signals and on human skin for detection of biosignals are demonstrated. This design approach brings about a new perspective on the exploration of stretchable conductors for biomedical applications.     

Revealing the dependence of cell spreading kinetics on its spreading morphology using microcontact printed fibronectin patterns

Since the dawn of in vitro cell cultures, how cells interact and proliferate within a given external environment has always been an important issue in the study of cell biology. It is now well known that mammalian cells typically exhibit a three-phase sigmoid spreading on encountering a substrate. To further this understanding, we examined the influence of cell shape towards the second rapid expansion phase of spreading. Specifically, 3T3 fibroblasts were seeded onto silicon elastomer films made from polydimethylsiloxane (PDMS), and micro-contact printed with fibronectin stripes of various dimensions. PDMS is adopted in our study for its biocompatibility, its ease in producing very smooth surfaces, and in the fabrication of micro-contact printing stamps. The substrate patterns are compared with respect to their influence on cell spreading over time. Our studies reveal, during the early rapid expansion phase, 3T3 fibroblasts are found to spread radially following a law; meanwhile, they proliferated in a lengthwise fashion on the striped patterns, following a law. We account for the observed differences in kinetics through a simple geometric analysis which predicted similar trends. In particular, a t² law for radial spreading cells, and a t¹ law for lengthwise spreading cells.     

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．     

Organization of nanoparticles on hard substrates using block copolymer films as templates

We present a technique for the organization of pre-synthesized nanoparticles on hard substrates, using block copolymer films as sacrificial templates. A thin block copolymer film is dip-coated on the substrate of interest and the sample is exposed to a solution containing nanoparticles. Spontaneous preferential adsorption of the nanoparticles on one phase of the block copolymer film results in their lateral organization. An oxygen plasma etch is used to remove the polymer film; the nanoparticles end up organized on the substrate. We demonstrate that this is a general approach for the patterning of inorganic nanoparticles on hard substrates, showing the organization of metal and semiconductor nanoparticles having different chemistries at the particle/solvent and solvent/polymer interfaces. The nanoparticle patterns that we present have typical periodicities in the nanometer scale. In some cases, microcontact printing is used to create a double length scale of organization, on the micrometer and on the nanometer level. The characteristic periodicity of the template is studied with respect to the nanoparticle size in order to optimize the organization. Finally, we describe how to extend this technique for the production of continuous gold nanowires on hard substrates. We expect that the flexibility of this approach and the degree of control that can be obtained over nanoparticle organization should make it a powerful tool for nanoscale fabrication.     

Prototyping of masks, masters, and stamps/molds for soft lithography using an office printer and photographic reduction

This paper describes a practical method for the fabrication of photomasks, masters, and stamps/molds used in soft lithography that minimizes the need for specialized equipment. In this method, CAD files are first printed onto paper using an office printer with resolution of 600 dots/in. Photographic reduction of these printed patterns transfers the images onto 35-mm film or microfiche. These photographic films can be used, after development, as photomasks in 1:1 contact photolithography. With the resulting photoresist masters, it is straightforward to fabricate poly(dimethylsiloxane) (PDMS) stamps/molds for soft lithography. This process can generate microstructures as small as 15 microm; the overall time to go from CAD file to PDMS stamp is 4-24 h. Although access to equipment-spin coater and ultraviolet exposure tool-normally found in the clean room is still required, the cost of the photomask itself is small, and the time required to go from concept to device is short. A comparison between this method and all other methods that generate film-type photomasks has been performed using test patterns of lines, squares, and circles. Three microstructures have also been fabricated to demonstrate the utility of this method in practical applications.     

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.