Directed assembly of conducting polymers on sub-micron templates by electrical fields

Patterning of conducting polymer into sub-micron patterns over large areas at high rate and low cost is significant for commercial manufacturing of novel devices. Electrophoretic and dielectrophoretic assembly provide an easily scaled approach with high fabrication rates. In this work, electrophoretic and dielectrophoretic assembly were used to assemble polyaniline (PANi) into multiscale sub-micron size patterns in less than 1 min. The process was controlled by assembly time, amplitude, and frequency of the electric field. Dielectrophoretic assembly is preferable for manufacturing as it reduces damage to the templates used to control the assembly. Using this method, sub-micron patterns with dimensions of the assembled PANi down to 100 nm were fabricated over large areas in short times. The assembled PANi was further transferred to other flexible polymer substrates by a thermoforming process, providing a fast, easily controlled and promising approach for fabrication of nanoscale devices.     

Fabrication of flexible polymer dispersed liquid crystal films using conducting polymer thin films as the driving electrodes

Conducting polymers exhibit good mechanical and interfacial compatibility with plastic substrates. We prepared an optimized coating formulation based on poly(3,4-ethylenedioxythiophene) (PEDOT) and 3-(trimethoxysilyl)propyl acrylate and fabricated a transparent electrode on poly(ethylene terephthalate) (PET) substrate. The surface resistances and transmittance of the prepared thin films were 500-600 Ω/□ and 87% at 500 nm, respectively. To evaluate the performance of the conducting polymer electrode, we fabricated a five-layer flexible polymer-dispersed liquid crystal (PDLC) device as a PET-PEDOT-PDLC-PEDOT-PET flexible film. The prepared PDLC device exhibited a low driving voltage (15 VAC), high contrast ratio (60:1), and high transmittance in the ON state (60%), characteristics that are comparable with those of conventional PDLC film based on indium tin oxide electrodes. The fabrication of conducting polymer thin films as the driving electrodes in this study showed that such films can be used as a substitute for an indium tin oxide electrode, which further enhances the flexibility of PDLC film.     

Fabrication of flexible transparent conductive films from long double-walled carbon nanotubes

The fabrication of flexible transparent conducting films (TCFs) is important for the development of the next-generation flexible devices. In this study, we used double-walled carbon nanotubes (DWCNTs) as the starting material and described a fabrication method of flexible TCFs. We have determined in a quantitative way that the key factors are the length and the dispersion states of the DWCNTs as well as the weight-ratios of dispersant polymer/DWCNTs. By controlling such factors, we have readily fabricated a flexible highly transparent (94% transmittance) and conductive (surface resistivity = 320 Ω sq⁻¹) DWCNT film without adding any chemical doping that is often used to reduce the surface resistivity. By applying a wet coating, we have succeeded in the fabrication of large-scale conducting transparent DWCNT films based on the role-to-role method.     

Inherently reproducible fabrication of plasmonic nanoparticle arrays for SERS by combining nanoimprint and copolymer lithography

We present an inherently reproducible route to realizing high-performance SERS substrates by exploiting a high-throughput top-down/bottom-up fabrication scheme. The fabrication route employs self-assembly of amphiphilic copolymers to create high-resolution molds for nanoimprint lithography (NIL) spanning entire 100 mm Si wafers. The nanoporous polymer templates obtained upon NIL are subjected to galvanic displacement reactions to create gold nanorod arrays. Nanorods are subsequently converted to nanodiscs by thermal annealing. The nanodiscs were found to perform as robust SERS substrates as compared with the nanorods. The SERS performance of these substrates and its generality for catering to diverse molecules is demonstrated through the excellent Raman peak resolution and intensity for three different molecules, exhibiting different interaction modes on surface. Numerical simulations using FDTD shows plasmonic coupling between the particles and also brings out the influence due to size distribution. The approach combines distinct advantages of high-precision and repeatability offered by NIL with low-cost fabrication of high-resolution NIL molds by copolymer self-assembly.     

Microthermoforming of flexible, not-buried hollow microstructures for chip-based life sciences applications

A new method is presented for the manufacturing of flexible, not buried and thin-walled hollow microstructures from polymer films. This low-cost method seems to be especially suited for the fabrication of plastic microstructures for fluidic one-way applications in the field of life sciences. It is based on a thermoforming process adapted to microstructure technology and is called 'microthermoforming'. Inside a hot embossing press, a heated thin thermoplastic film is formed into the evacuated microcavities of a plate-shaped metal mould using a compressed gas. The film may be heat-sealed on to a thicker plastic film substrate inside the same press without demoulding the thermoformed film. To demonstrate the performance of the new manufacturing method, flexible capillary electrophoresis and cell culture chips from polystyrene, polycarbonate and a cyclo-olefin polymer with 16 and 625 parallel microstructures each, respectively, have been fabricated.     

Durable diamond-like carbon templates for UV nanoimprint lithography

The interaction between resist and template during the separation process after nanoimprint lithography (NIL) can cause the formation of defects and damage to the templates and resist patterns. To alleviate these problems, fluorinated self-assembled monolayers (F-SAMs, i.e.?tridecafluoro-1,1,2,2,tetrahydrooctyl trichlorosilane or FDTS) have been employed as template release coatings. However, we find that the FDTS coating undergoes irreversible degradation after only 10 cycles of UV nanoimprint processes with SU-8 resist. The degradation includes a 28% reduction in surface F atoms and significant increases in the surface roughness. In this paper, diamond-like carbon (DLC) films were investigated as an alternative material not only for coating but also for direct fabrication of nanoimprint templates. DLC films deposited on quartz templates in a plasma enhanced chemical vapor deposition system are shown to have better chemical and physical stability than FDTS. After the same 10 cycles of UV nanoimprints, the surface composition as well as the roughness of DLC films were found to be unchanged. The adhesion energy between the DLC surface and SU-8 is found to be smaller than that of FDTS despite the slightly higher total surface energy of DLC. DLC templates with 40?nm features were fabricated using e-beam lithography followed by Cr lift-off and reactive ion etching. UV nanoimprinting using the directly patterned DLC templates in SU-8 resist demonstrates good pattern transfer fidelity and easy template-resist separation. These results indicate that DLC is a promising material for fabricating durable templates for UV nanoimprint lithography.     

Novel gold-capped nanopillars imprinted on a polymer film for highly sensitive plasmonic biosensing

Herein, a nanoporous alumina was fabricated to use as a mold in transforming nanopillar structures onto a thin film polymer by thermal nanoimprint lithography (NIL). The size of the pores was successfully controlled by varying the applied voltages and etching time. These nanoporous structures were transferred to the Cyclo-olefin polymer (COP) film surface from the porous mold by a thermal nanoimprinting process. A plasmonic substrate was fabricated by sputtering a thin layer of gold onto this nanopillar polymer structure, and the refractive index response in a variety of media was evaluated. Finally, the biosensing capacity of this novel plasmonic substrate was verified by analysis of Human immunoglobulin and achieved a minimum detection limit of 1.0 ng/mL. With the advantages of mass production with consistent reproducibility stemming from the nanoimprint fabrication process, our gold-capped polymeric pillars are ready for the transition from academic interest into commercialization systems for practical use in diagnostic applications.     

Advances in piezoelectric thin films for acoustic biosensors,acoustofluidics and lab-on-chip applications

Recently, piezoelectric thin films including zinc oxide (ZnO) and aluminium nitride (AlN) have found a broad range of lab-on-chip applications such as biosensing, particle/cell concentrating, sorting/patterning, pumping, mixing, nebulisation and jetting. Integrated acoustic wave sensing/microfluidic devices have been fabricated by depositing these piezoelectric films onto a number of substrates such as silicon, ceramics, diamond, quartz, glass, and more recently also polymer, metallic foils and bendable glass/silicon for making flexible devices. Such thin film acoustic wave devices have great potential for implementing integrated, disposable, or bendable/flexible lab-on-a-chip devices into various sensing and actuating applications. This paper discusses the recent development in engineering high performance piezoelectric thin films, and highlights the critical issues such as film deposition, MEMS processing techniques, control of deposition/processing parametres, film texture, doping, dispersion effects, film stress, multilayer design, electrode materials/designs and substrate selections. Finally, advances in using thin film devices for lab-on-chip applications are summarised and future development trends are identified.     

纳米孔氮化镓材料的制备和研究

介绍了一种在氮化镓外延片表面制备得到孔径为纳米量级的多孔结构的工艺.用电化学方法制备出孔径为纳米量级的多孔阳极氧化铝模板作为掩模,经过电感耦合等离子体(ICP)刻蚀制备得到纳米孔氮化镓材料.孔的大小和孔间距可以通过改变阳极氧化条件来控制,改变刻蚀时间可以控制孔深.刻蚀所用气体为氯气和惰性气体的混合物.扫描电镜照片显示,掩模图形能够很好地转移到GaN材料上.刻蚀后的材料经光荧光谱(PL Spectra)谱和Raman散射谱测试,显示出良好的光学特性,并在一定程度上释放了应力.     

Direct nanofabrication and transmission electron microscopy on a suite of easy-to-prepare ultrathin film substrates

A high-yield, easy to master method for preparing electron transparent metal, oxide, and carbon ultrathin film substrates suitable for direct nano/micro-fabrication and transmission electron microscopy (TEM) is presented. To demonstrate the versatility of these substrates for fabrication processes, we use e-beam lithography, self-assembled colloidal and protein templates, and microcontact printing to create patterned masks for subsequent electrodeposition of two dimensional and three dimensional structures. The electrodeposited structures range in scale from a few nanometers to a few micrometers in characteristic dimensions. Because fabrication occurs directly on ultrathin films, TEM analysis of the resulting materials and buried interfaces is straightforward without any destructive sample preparation. We show that all the normal TEM analytical methods (imaging, diffraction, electron and X-ray spectroscopies) are compatible with the fabricated structures and the thin film substrates. These electron transparent substrates have largely rendered the need for TEM sample preparation on fabricated structures obsolete in our lab.     

Fabrication of nano-sized metal patterns on flexible polyethylene-terephthalate substrate using bi-layer nanoimprint lithography

Polymer films are widely used as a substrate for displays and for solar cells since they are cheap, transparent and flexible, and their material properties are easy to design. Polyethylene-terephthalate (PET) is especially useful for various applications requiring transparency, flexibility and good thermal and chemical resistance.In this study, nano-sized metal patterns were fabricated on flexible PET film by using nanoimprint lithography (NIL). Water-soluble poly-vinyl alcohol (PVA) resin was used as a planarization and sacrificial layer for the lift-off process, as it does not damage the PET films and can easily be etched off by using oxygen plasma. NIL was used to fabricate the nano-sized patterns on the non-planar or flexible substrate. Finally, a nano-sized metal pattern was successfully formed by depositing the metal layer over the imprinted resist patterns and applying the lift-off process, which is economic and environmentally friendly, to the PET films.     

Graphene oxide thin films for flexible nonvolatile memory applications

There has been strong demand for novel nonvolatile memory technology for low-cost, large-area, and low-power flexible electronics applications. Resistive memories based on metal oxide thin films have been extensively studied for application as next-generation nonvolatile memory devices. However, although the metal oxide based resistive memories have several advantages, such as good scalability, low-power consumption, and fast switching speed, their application to large-area flexible substrates has been limited due to their material characteristics and necessity of a high-temperature fabrication process. As a promising nonvolatile memory technology for large-area flexible applications, we present a graphene oxide based memory that can be easily fabricated using a room temperature spin-casting method on flexible substrates and has reliable memory performance in terms of retention and endurance. The microscopic origin of the bipolar resistive switching behavior was elucidated and is attributed to rupture and formation of conducting filaments at the top amorphous interface layer formed between the graphene oxide film and the top Al metal electrode, via high-resolution transmission electron microscopy and in situ X-ray photoemission spectroscopy. This work provides an important step for developing understanding of the fundamental physics of bipolar resistive switching in graphene oxide films, for the application to future flexible electronics.     

Combined AFM nano-machining and reactive ion etching to fabricate high aspect ratio structures

In this paper, a new combined method of sub-micron high aspect ratio structure fabrication is developed which can be used for production of nano imprint template. The process includes atomic force microscope (AFM) scratch nano-machining and reactive ion etching (RIE) fabrication. First, 40 nm aluminum film was deposited on the silicon substrate by magnetron sputtering, and then sub-micron grooves were fabricated on the aluminum film by nano scratch using AFM diamond tip. As aluminum film is a good mask for etching silicon, high aspect ratio structures were finally fabricated by RIE process. The fabricated structures were studied by SEM, which shows that the grooves are about 400 nm in width and 5 microm in depth. To obtain sub-micron scale groove structures on the aluminum film, experiments of nanomachining on aluminum films under various machining conditions were conducted. The depths of the grooves fabricated using different scratch loads were also studied by the AFM. The result shows that the material properties of the film/substrate are elastic-plastic following nearly a bilinear law with isotropic strain hardening. Combined AFM nanomachining and RIE process provides a relative lower cost nano fabrication technique than traditional e-beam lithography, and it has a good prospect in nano imprint template fabrication.     

Large-scale ultraflat nanopatterned surfaces without template residues

Ultraflat surfaces are required for many studies of single molecules, and the need for both a wide choice of surface materials and the ability to pattern these surfaces has led to the development of different template-stripping approaches. The fabrication of nanopatterned ultraflat surfaces is particularly challenging, because more than one material is present in the surface. We demonstrate a new template-stripping strategy that allows us to fabricate large-area nanopatterned surfaces, solving the problem of incomplete template removal by introducing a sacrificial carbon layer and a sandwich structure for the template. The thin residual carbon film transferred from the template is removed from the nanopatterned surface by dry etching, as demonstrated by x-ray photoelectron spectroscopy and, for metal nanoparticles embedded in a glass surface, by a shift in the absorption of the localized surface plasmon resonance. We show that gold nanoparticles in a glass surface can be selectively functionalized with thiols yielding about 2?nm height increase. Atomic force microscopy and localized surface plasmon resonance spectroscopy both indicate that the nanoparticle shape is preserved well.     

Fabrication of Covalently Crosslinked and Amine-Reactive Microcapsules by Reactive Layer-by-Layer Assembly of Azlactone-Containing Polymer Multilayers on Sacrificial Microparticle Templates

We report on the fabrication of covalently crosslinked and amine-reactive hollow microcapsules using 'reactive' layer-by-layer assembly to deposit thin polymer films on sacrificial microparticle templates. Our approach is based on the alternating deposition of layers of a synthetic polyamine and a polymer containing reactive azlactone functionality. Multilayered films composed of branched poly(ethylene imine) (BPEI) and poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) were fabricated layer-by-layer on the surfaces of calcium carbonate and glass microparticle templates. After fabrication, these films contained residual azlactone functionality that was accessible for reaction with amine-containing molecules. Dissolution of the calcium carbonate or glass cores using aqueous ethylenediamine tetraacetic acid (EDTA) or hydrofluoric acid (HF), respectively, led to the formation of hollow polymer microcapsules. These microcapsules were robust enough to encapsulate and retain a model macromolecule (FITC-dextran) and were stable for at least 22 hours in high ionic strength environments, in low and high pH solutions, and in several common organic solvents. Significant differences in the behaviors of capsules fabricated on CaCO(3) and glass cores were observed and characterized using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Whereas capsules fabricated on CaCO(3) templates collapsed upon drying, capsules fabricated on glass templates remained rigid and spherical. Characterization using EDS suggested that this latter behavior results, at least in part, from the presence of insoluble metal fluoride salts that are trapped or precipitate within the walls of capsules after etching of the glass cores using HF. Our results demonstrate that the assembly of BPEI/PVDMA films on sacrificial templates can be used to fabricate reactive microcapsules of potential use in a wide range of fields, including catalysis, drug and gene delivery, imaging, and biomedical research.     

Epitaxial Lift‐Off of Centimeter‐Scaled Spinel Ferrite Oxide Thin Films for Flexible Electronics

Mechanical flexibility of electronic devices has attracted much attention from research due to the great demand in practical applications and rich commercial value. Integration of functional oxide materials in flexible polymer materials has proven an effective way to achieve flexibility of functional electronic devices. However, the chemical and mechanical incompatibilities at the interfaces of dissimilar materials make it still a big challenge to synthesize high‐quality single‐crystalline oxide thin film directly on flexible polymer substrates. This study reports an improved method that is employed to successfully transfer a centimeter‐scaled single‐crystalline LiFe₅O₈ thin film on polyimide substrate. Structural characterizations show that the transferred films have essentially no difference in comparison with the as‐grown films with respect to the microstructure. In particular, the transferred LiFe₅O₈ films exhibit excellent magnetic properties under various mechanical bending statuses and show excellent fatigue properties during the bending cycle tests. These results demonstrate that the improved transfer method provides an effective way to compose single‐crystalline functional oxide thin films onto flexible substrates for applications in flexible and wearable electronics.     

Piezoresistive polysilicon film obtained by low-temperature aluminum-induced crystallization

A low-temperature deposition process employing aluminum-induced crystallization has been developed for fabrication of piezoresistive polycrystalline silicon (polysilicon) films on low cost and flexible polyimide substrates for force and pressure sensing applications. To test the piezoresistive properties of the polysilicon films, prototype pressure sensors were fabricated on surface-micromachined silicon nitride (Si₃N₄) diaphragms, in a half-Wheatstone bridge configuration. Characterization of the pressure sensor was performed using atomic force microscope in contact mode with a specially modified probe-tip. Low pressure values ranging from 5 kPa to 45 kPa were achieved by this method. The resistance change was found to be − 0.1% to 0.5% and 0.07% to 0.3% for polysilicon films obtained at 500 °C and 400 °C, respectively, for the applied pressure range.     

A hybrid mask-mould lithography scheme and its application in nanoscale organic thin film transistors

Nanoimprint lithography (NIL) has stimulated great interest in both academic research and industrial development due to its high resolution, high throughput and low cost advantages. Though NIL has been demonstrated to be very successful in replicating nanoscale features, it also has its limitations as a general lithography technique. Its fundamental moulding characteristics (i.e.?physically displacing polymer materials) frequently lead to pattern defects when replicating arbitrary patterns, especially patterns with broad size distribution. To solve this problem, we have developed a combined nanoimprint and photolithography technique that uses a hybrid mould to achieve good pattern definitions. In this work, we applied this technique to fabricate finger-shaped nanoelectrodes, and demonstrated nanoscale pentacene organic thin film transistors (OTFTs). Methods of the hybrid mask-mould (HMM) fabrication and results on the device electrical characteristics are provided. With combined advantages of both photolithography and NIL, and the applicability to general nanoscale device and system fabrication, this method can become a valuable choice for low cost mass production of micro-?and nanoscale structures, devices and systems.     

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.     

嵌段共聚物自组装模板--构造纳米结构的一种新方法

纳米结构的构造在整个纳米科技中有着特殊重要的意义．如何低成本、大规模地实现纳米结构材料的控制合成与组装一直是纳米加工中的热点问题．高分子嵌段共聚物分子结构独特，包含着热力学不相容的不同高分子嵌段，并由化学键相连．通过控制外界条件，嵌段共聚物可以自组装成高度规则的超分子结构，特征尺寸为10nln～100nm．以嵌段共聚物膜自组装相分离图案为模板，或把这种图案复制到其它材料上，通过刻蚀等技术可以制备纳米结构模板，再经纳米铸造得到相应结构的纳米材料和纳米器件，文中主要介绍嵌段共聚物自组装模板的原理、模板图案的调控方法和模板应用，并详细阐述了各自的发展状况。