Micrometer and nanometer-scale parallel patterning of ceramic and organic–inorganic hybrid materials

This review gives an overview of the progress made in recent years in the development of low-cost parallel patterning techniques for ceramic materials, silica, and organic–inorganic silsesquioxane-based hybrids from wet-chemical solutions and suspensions on the micrometer and nanometer-scale. The emphasis of the discussion is placed on the application of soft-lithographic methods, but photolithography-aided patterning methods for oxide film growth are also discussed. In general, moulding-based patterning approaches and surface modification-based patterning approaches can be distinguished. Lateral resolutions well below 100 nm have been accomplished with some of these methods, but the fabrication of high-aspect ratio patterns remains a challenge.     

Versatility of photoalignment techniques: From nematics to a wide range of functional materials

Alignment methods of nematic liquid crystals (LCs) by surface photoreactions on substrate surfaces were initially proposed around 1990, and the photoalignment technology of nematic LCs has recently been integrated into the LC device fabrication industry due to its profitable features. Accumulated efforts in this field have revealed that applications of photoalignment processes are not limited to conventional nematic LCs but that a variety of functional materials can also be manipulated according to this principle. Target materials have now been extended to thermotropic smectic LCs, discotic LCs, LC polymers, block copolymers, gel networks, conjugated polymers, and organic semiconductors and lyotropic systems including chromonic LCs and inorganic–organic mesostructured hybrids. Through these photochemical approaches, many types of photopatterning for both topographical and orientational modulations have become feasible. This article reviews photoalignment processes applied to a wide range of materials, surveying relatively recent work. Some important related alignment and patterning processes are also introduced to clarify the significance of these photoalignment techniques.     

Light-emitting devices for wearable flexible displays

Light-emitting devices have potential applications in functional and 'intelligent' textiles and clothing. Much research work has been conducted on electroluminescent devices based on small organic molecules and polymers due to their potential application in new generation displays. An overview is presented of progress in the development of organic and polymer light-emitting devices. The fabrication processes, materials and methods of improving their performance are reviewed. Attention is given to the potential application of flexible displays and the patterning method for producing a full colour display. Analytical methods are also discussed.     

Ordering in thin films of block copolymers: Fundamentals to potential applications

The ordering of block copolymers in thin films is reviewed, starting from the fundamental principles and extending to recent promising developments as templates for nanolithography which may find important applications in the semiconductor industry. Ordering in supported thin films of symmetric and asymmetric AB diblock and ABA triblock copolymers is discussed, along with that of more complex materials such as ABC triblocks and liquid crystalline block copolymers. Techniques to prepare thin films, and to characterise ordering within them, are summarized. Several methods to align block copolymer nanostructures, important in several applications are outlined. A number of potential applications in nanolithography, production of porous materials, templating, and patterning of organic and inorganic materials are then presented. The influence of crystallization on the morphology of a block copolymer film is briefly discussed, as are structures in grafted block copolymer films.     

Methods for Nano/Micropatterning of Substrates: Toward Stem Cells Differentiation

Micro- and nanoengineering of materials offer novel technologies and serve as an interface between material sciences and biomedical nanotechnology. Various techniques are used for the engineering of polymers, and it allows the precise orientation of biomolecules with designed nanoregions in a substrate, with defined sizes and continuity offering well featured substrate topographies. Methods such as the electron beam lithography coupled with microcontact printing have been applied for the fabrication of high resolution surface features that are smaller than the size of a cell. This review elaborates more deeply on the different methods used for the fabrication of patterned surfaces such as the photolithography, electron beam lithography, microcontact printing, soft lithography, capillary force lithography, and patterning of electrospun fibers. The nanoengineered substrates may have the ability to influence the differentiation of stem cells to specific lineages and here we survey a few details on the influence of surface topology and its potential for tissue regeneration.     

Wrinkled interfaces: Taking advantage of surface instabilities to pattern polymer surfaces

The generation of nano-microstructured polymer film surfaces has been a challenge during the last decades. Advances in the fabrication of structured polymer surfaces to obtain micro and nano patterns have been accomplished following two different approaches, i.e., by adapting techniques, such as molding (embossing) or nano/microimprinting or by developing novel techniques including laser ablation, soft lithography or laser scanning among others. Thus, higher resolution capabilities are directly related with technological advances. In contrast to the use of highly sophisticated tools required by the above mentioned techniques, surface instabilities produced by different mechanisms take advantage of the inherent properties of polymers to induce particular surface patterns. Some of the surface instabilities are well known since decades but novel and old known instability mechanisms have been only recently extended their use to pattern polymer surfaces. This recent interest relies on the rich and complex patterns obtained as a result of self-organizing processes that are rather difficult if not impossible to fabricate by using traditional patterning techniques.Among the approaches to obtain patterned interfaces by means of surface instabilities the formation of wrinkles is the most explored method and will be the center of this review. The fabrication approaches employed to induce wrinkle formation and the possibilities to fine tune the amplitude and period of the wrinkles, the functionality and their final morphology are thoroughly described. Finally, an overview about the main applications in which buckled interfaces have been already employed or may have an impact in the near future is provided. Their use as templates, as flexible electronics, as supports with controlled wettability and/or adhesion or for biorelated applications are few of the fields in which the unique characteristics of wrinkled interfaces play distinguishing role.     

Large-area nanoscale patterning: chemistry meets fabrication

This Account describes a new paradigm for large-area nanoscale patterning that combines bottom-up and top-down approaches, merging chemistry with fabrication. This hybrid strategy uses simple nanofabrication techniques to control the alignment, size, shape, and periodicity of nanopatterns and chemical methods to control their materials properties and crystallinity. These tools are highly flexible and can create surface-patterned nanostructures with unusual properties and free-standing nanostructures that are multifunctional and monodisperse. The unprecedented scientific and technological opportunities enabled by nanoscale patterning over wafer-sized areas are discussed.     

Additive fabrication and the mechanisms of nucleation and growth in chemical vapor deposition processes

In this Account, we present several representative studies of thin-film growth by chemical vapor deposition, with particular emphasis given to elucidating the mechanistic, energetic, and structural aspects of nucleation and growth. These understandings have allowed us to develop new methods to deposit patterned, as opposed to blanket, thin films. We show how such procedures can be exploited to effect the directed assembly (i.e., the additive fabrication) of a device architecture.     

Fabrication of ultra-fine nanostructures using edge transfer printing

The exploration of new methods and techniques for application in diverse fields, such as photonics, microfluidics, biotechnology and flexible electronics is of increasing scientific and technical interest for multiple uses over distance of 10-100 nm. This article discusses edge transfer printing--a series of unconventional methods derived from soft lithography for nanofabrication. It possesses the advantages of easy fabrication, low-cost and great serviceability. In this paper, we show how to produce exposed edges and use various materials for edge transfer printing, while nanoskiving, nanotransfer edge printing and tunable cracking for nanogaps are introduced. Besides this, different functional materials, such as metals, inorganic semiconductors and polymers, as well as localised heating and charge patterning, are described here as unconventional "inks" for printing. Edge transfer printing, which can effectively produce sub-100 nm scale ultra-fine structures, has broad applications, including metallic nanowires as nanoelectrodes, semiconductor nanowires for chemical sensors, heterostructures of organic semiconductors, plasmonic devices and so forth.     

Nanoskiving: a new method to produce arrays of nanostructures

This Account reviews nanoskiving--a new technique that combines thin-film deposition of metal on a topographically contoured substrate with sectioning using an ultramicrotome--as a method of fabricating nanostructures that could replace conventional top-down techniques in selected applications. Photolithography and scanning beam lithography, conventional top-down techniques to generate nanoscale structures and nanostructured materials, are useful, versatile, and highly developed, but they also have limitations: high capital and operating costs, limited availability of the facilities required to use them, an inability to fabricate structures on nonplanar surfaces, and restrictions on certain classes of materials. Nanoscience and nanotechnology would benefit from new, low-cost techniques to fabricate electrically and optically functional structures with dimensions of tens of nanometers, even if (or perhaps especially if) these techniques have a different range of application than does photolithography or scanning beam lithography. Nanoskiving provides a simple and convenient procedure to produce arrays of structures with cross-sectional dimensions in the 30-nm regime. The dimensions of the structures are determined by (i) the thickness of the deposited thin film (tens of nanometers), (ii) the topography (submicrometer, using soft lithography) of the surface onto which the thin film is deposited, and (iii) the thickness of the section cut by the microtome (> or =30 nm by ultramicrotomy). The ability to control the dimensions of nanostructures, combined with the ability to manipulate and position them, enables the fabrication of nanostructures with geometries that are difficult to prepare by other methods. The nanostructures produced by nanoskiving are embedded in a thin epoxy matrix. These epoxy slabs, although fragile, have sufficient mechanical strength to be manipulated and positioned; this mechanical integrity allows the nanostructures to be stacked in layers, draped over curved surfaces, and suspended across gaps, while retaining the in-plane geometry of the nanostructures embedded in the epoxy. After removal of the polymer matrix by plasma oxidation, these structures generate suspended and draped nanostructures and nanostructures on curved surfaces. Two classes of applications, in optics and in electronics, demonstrate the utility of nanostructures fabricated by nanoskiving. This technique will be of primary interest to researchers who wish to generate simple nanostructures, singly or in arrays, more simply and quickly than can be accomplished in the clean-room. It is easily accessible to those not trained in top-down procedures for fabrication and those with limited or no access to the equipment and facilities needed for photolithography or scanning-beam fabrication. This Account discusses a new fabrication method (nanoskiving) that produces arrays of metal nanostructures. The defining process in nanoskiving is cutting slabs from a polymeric matrix containing embedded, more extended metal structures.     

Direct selective growth of ZnO nanowire arrays from inkjet-printed zinc acetate precursor on a heated substrate

Inkjet printing of functional materials has drawn tremendous interest as an alternative to the conventional photolithography-based microelectronics fabrication process development. We introduce direct selective nanowire array growth by inkjet printing of Zn acetate precursor ink patterning and subsequent hydrothermal ZnO local growth without nozzle clogging problem which frequently happens in nanoparticle inkjet printing. The proposed process can directly grow ZnO nanowires in any arbitrary patterned shape, and it is basically very fast, low cost, environmentally benign, and low temperature. Therefore, Zn acetate precursor inkjet printing-based direct nanowire local growth is expected to give extremely high flexibility in nanomaterial patterning for high-performance electronics fabrication especially at the development stage. As a proof of concept of the proposed method, ZnO nanowire network-based field effect transistors and ultraviolet photo-detectors were demonstrated by direct patterned grown ZnO nanowires as active layer.     

Nanocrystallized Organic Thin Films as Effective Light Outcoupling Layers for Organic Light-Emitting Diodes

Light outcoupling from organic light-emitting diodes (OLEDs) is essential for developing energy-saving displays and efficient lighting sources. Nanocrystallized organic thin films exhibiting scattering features have been considered as effective light extractors for OLEDs. This paper reviews recent advancements in nanocrystallized thin films and their applications in OLEDs. Due to the advantages of easy preparation and OLED compatibility, nanocrystallized organic thin films can integrate with OLEDs as external or internal light extractors easily. Significant light enhancement has been achieved. The fabrication methods and mechanisms of light enhancement are discussed.     

Monolayer-Mediated Deposition of Tantalum(V) Oxide Thin Film Structures from Solution Precursors

Integration of oxide thin films with semiconductor substrates is a critical technology for a variety of microelectronic memory and circuit applications. Patterned oxide thin film devices are typically formed by uniform deposition followed by postdeposition ion-beam or chemical etching in a controlled environment. This paper reports details of an ambient atmosphere technique which allows selective deposition of dielectric oxide thin layers without postdeposition etching. In this method, substrate surfaces are selectively functionalized with hydrophobic self-assembled monolayers of octadecyltrichlorosilane by microcontact printing (μ-CP). Sol-gel deposition of ceramic oxides on these functionalized substrates, followed by mild, nonabrasive polishing, yields high-quality, patterned oxide thin layers only on the unfunctionalized regions. A variety of micrometer-scale dielectric oxide devices have been fabricated by this process, with lateral resolutions as fine as 4 μm. In this paper, we describe the solution chemistry, evolution of microstructure, and electrical properties of Ta₂O₅ thin films, as well as the stress-related mechanism which enables selective de-adhesion and resultant patterning. Selectively deposited, 80-120 nm thick Ta₂O₅ thin film capacitors were crystallized on platinized silicon at 700-800°C, and had dielectric constants of 18-25 depending upon the processing conditions, with 1 V leakage current densities as low as 2 × 10⁻⁸ A/cm². The ability to selectively deposit Ta₂O₅ and other electrical ceramics (such as LiNbO₃ and PbTiO₃) on a variety of technologically important substrate materials suggests broad potential for integrated circuit and hybrid microelectronics applications.     

Additively patterned ferroelectric thin films with vertical sidewalls

The functional properties of electroceramic thin films can be degraded by subtractive patterning techniques used for microelectromechanical (MEMS) applications. This work explores an alternative deposition technique, where lead zirconate titanate (PZT) liquid precursors are printed onto substrates in a desired geometry from stamp wells (rather than stamp protrusions). Printing from wells significantly increased sidewall angles (from ~1 to >35 degrees) relative to printing solutions from stamp protrusions. Arrays of PZT features were printed, characterized, and compared to continuous PZT thin films of similar thickness. Three‐hundred‐nanometer‐thick printed PZT features exhibit a permittivity of 730 and a loss tangent of 0.022. The features showed remanent polarizations of 26 μC/cm², and coercive fields of 95 kV/cm. The piezoelectric response of the features produced an e_31,f of ?5.2 C/m². This technique was also used to print directly atop prepatterned substrates. Optimization of printing parameters yielded patterned films with 90° sidewalls. Lateral feature sizes ranged from hundreds of micrometers down to one micrometer. In addition, several device designs were prepatterned onto silicon on insulator (SOI) wafers (Si/SiO₂/Si with thicknesses of 0.35/1/500 μm). The top patterned silicon was released from the underlying material, and PZT was directly printed and crystallized on the free‐standing structures.     

Nanometer‐thick patterned conductive films prepared through the self‐synthesis of polythiophene derivatives

The development of flexible electronics requires the patterning of conductive and active semiconductor films. Although inorganic materials such as indium tin oxide and metal nanoparticles have high conductivity and transparency, their poor interfacial adhesion with organic layers, lack of flexibility, high weight and high capital costs are drawbacks. In contrast, organic conducting polymers have great potential for use in commercial flexible electronic applications because of their low production costs, environmental stability and acceptable conductivities. A UV‐curable photoresist containing hydroxyl groups was prepared from a mixture of a photoinitiator, epoxy‐acrylate resin, hydroxyethyl methacrylate and tripropylene glycol diacrylate. Patterns having line widths/spaces of 100/100 µm and 10/5 µm were fabricated on a poly(ethylene terephthalate) (PET) substrate using lithography techniques. (3‐Methyl‐3,4‐dihydro‐2H‐thieno[3,4‐b]dioxepin‐3‐yl)methanol (ProDOT‐OH) was self‐synthesized through urethane linkages onto the surface of the patterned photoresist on the PET film, which was then dipped into a solution of another monomer, 3‐thienylethoxybutanesulfonate (TEBS), and initiator and polymerized in situ to form conductive poly(ProDOT‐OH‐co‐TEBS) films covering the surface of the patterned resist. The optimal conductivity of the poly(ProDOT‐OH‐co‐TEBS) films was ca 90 S cm^?1 with an optical transparency of ca 70%. A new bottom‐up technique has been developed for the preparation of patterned organic transparent conductive films: self‐synthesis of the monomer using urethane‐forming reactions and subsequent in situ polymerization. The conductivity of the films can be controlled by the polymerization reaction time and the resolution of the pattern. These conductive patterned films might be applicable to the manufacture of industrial touch panels or chemical/biological sensors. Copyright © 2009 Society of Chemical Industry     

Organic thin film transistors: Materials,processes and devices

For the past ten years, organic materials have been extensively investigated as an electronic material for thin film transistor (TFT) devices. Organic materials offer strong promise in terms of properties, processing and cost effectiveness and they can be used in flat panel displays, imagers, smart cards, inventory tags and large area electronic applications. In this review, we summarize the current status of the organic thin film transistors including substrate materials, electrodes, semiconducting and dielectric layers; organic thin film preparation methods; morphological studies for organic thin films; electrical characterization of gate dielectric layers and semiconducting active layers; and characterization of the OTFTs. Future prospects and investigations required to improve the OTFT performance are also given. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Flattened‐Top Domical Droplet Formed by a Poly(pyrrole) Membrane

Polypyrrole (PPy) is a promising conductive polymer (CP) with electrical versatility, easy synthesis and functionalization, stability, and biocompatibility. Diverse architectures have been adopted to improve PPy performance, but the direct and precise patterning of various architectures remains challenging. Here, the unique formation of a PPy membrane on the air/water interface of a droplet solution containing ammonium persulfate and phytic acid is investigated. When a PPy thin film forms on the air/water interface, the top of the droplet rapidly flattens. The formation procedure and final structure of the PPy thin film are visualized and quantitatively investigated. Unlike the typical globular structure of PPy, the self‐assembled PPy film surface fabricated in this study is very organized and regularly shaped. This well‐ordered membrane may have a very high buckling strength greater than the surface tension of the solution. The proposed precise fabrication method is simple and inexpensive for fabricating patterned functional membranes. These results provide new insight into the fabrication of CP and their applications in various practical electromaterial engineering fields.     

Direct stamping and capillary flow patterning of solution processable piezoelectric polyvinylidene fluoride films

It is well known that the potential applications of polyvinylidene fluoride (PVDF) mainly come from the piezoelectricity and ferroelectricity of its polar β phase. Thus, we have investigated the effect of different preparation conditions namely evaporation temperature, type of solvent and additive to enhance the β crystal structures of PVDF thin film. Subsequently, facile and direct soft lithography technique; direct stamping and capillary flow were employed to demonstrate good pattern transfer of PVDF thin films. The piezoelectricity of the microstructure was characterized using piezoresponse force microscopy (PFM) where fairly good piezoresponse was obtained without further processing procedures i.e., annealing or applied pressure/electric field. As such, our solution processable and direct patterning of PVDF techniques offer facile and promising route to produce arrays of isolated microstructures with improved piezoelectric functionality.     

3D Printing for Tissue Engineering

Tissue engineering aims to fabricate functional tissue for applications in regenerative medicine and drug testing. More recently, 3D printing has shown great promise in tissue fabrication with a structural control from the micro- to the macroscale by using a layer-by-layer approach. Whether through scaffold-based or scaffold-free approaches, the standard for 3D-printed tissue engineering constructs is to provide a biomimetic structural environment that facilitates tissue formation and promotes host tissue integration (e.g., cellular infiltration, vascularization, and active remodeling). This review will cover several approaches that have advanced the field of 3D printing through novel fabrication methods of tissue engineering constructs. It will also discuss the applications of synthetic and natural materials for 3D printing facilitated tissue fabrication.     

Patterning High Explosives at the Nanoscale

For the first time, we have shown that spin coating and Dip pen nanolithography (DPN^TM) are simple methods of preparing energetic materials such as PETN and HMX on the nanoscale, requiring no heating of the energetic material. Nanoscale patterning has been demonstrated by the DPN method while continuous thin films were produced using the spin coating method. Results are presented for preparing continuous PETN thin films of nanometer thickness by the spin coating method and for controlling the architecture of arbitrary nanoscale patterns of PETN and HMX by the DPN method. These methods are simple for patterning energetic materials and can be extended beyond PETN and HMX, opening the door for fundamental studies at the nanoscale.