Conductive Nanofiber Web Film with Polydimethylsiloxane Sidewalls Selectively Coated through a Plasma Process for High Performance Flexible Transparent Electrodes.

Transparent electrodes are commonly used in various applications, such as solar cells, touch screens, smart windows, wearable electronic devices, and rollable flexible displays. Currently, indium tin oxide (ITO) is widely used as a transparent electrode material. However, ITO is not suitable for next-generation transparent electrodes that require flexibility; therefore, alternative nanomaterials, such as carbon nanotubes, conductive polymers, and metal nanowires, are being studied. However, these nanomaterials have poor mechanical strength and limited substrate availability. In this study, we developed a high-performance transparent electrode web film fabrication process based on conductive nanofibers, in which metal nanofibers are semiembedded in polydimethylsiloxane (PDMS). The mechanical strength of the conductive nanofibers was improved through the PDMS coating on the entire surface of the film, and the semiembedded structure of the nanofibers was realized using the reactive ion etching (RIE) process. In this study, we confirmed through transparency/conductivity analysis and bending, cycle, and taping tests that the transparent electrode fabricated using our approach has excellent mechanical strength and conductivity. Finally, the transparent electrode fabricated using our method can be widely applied as a next-generation transparent electrode because the process is easy and simple and requires inexpensive equipment and materials.

Effective Approach for Fabricating Highly Precise High-Curvature Structural Patterns via Air-Bubble Induction.

Developing a new master mold-based patterning technology that can be used to accurately, precisely, and uniformly create large-area micropatterns while controlling the micropatterns of curved structures is essential for promoting innovative developments in various application fields. This study develops a new top-down lithographic process that can effectively produce structural patterns with high curvatures by growing isolated microbubbles in the master pattern holes. The isolated air-pocket lithography (IAL) we developed is based on the controlled behavior of micrometer-sized air pockets trapped between the grooves of the master pattern and the curable polymer. We successfully fabricated a concave array polydimethylsiloxane (PDMS) film and a convex array polymer film. In addition, the IAL mechanism was proven by confirming the expansion process of micrometer-sized air pockets trapped between the deep groove of the silicon master pattern and the PDMS coating film by using optical microscopy images. We successfully obtained complex three-dimensional structural patterns containing both 3D hollow spherical concave and ring-shaped two-dimensional convex patterns. This simple, fast, and effective high-curvature patterning technique is expected to provide innovative solutions for future applications such as nanoelectronics, optical devices, displays, and photovoltaics.

Hierarchical Self-Assembly of Perylene Diimide (PDI) Crystals.

Controlling molecular self-assembly of organic semiconductors is a key factor in enhancing the performance of organic electronics and optoelectronics. However, unlike various p-type organic semiconductors, it has proven elusive to control molecular self-assembly with about tens of nm dimensions using n-type organic semiconductors including perylene diimide (PDI), which is the most promising alternative to fullerene derivatives, without using an additional synthetic method or additives, thus far. Here, we developed a simple self-assembling method for the hierarchical self-assembly of PDI crystals with nanometer-to-micrometer scale features using pristine PDI-C8 without using an additional synthetic method or additive. Interestingly, we observed crystalline and optical properties of self-assembled PDI crystals depending on their size and structural features. In addition, we fabricated p-n junctions composed of PDI and poly(3-hexylthiophene) (P3HT), where the p-n junctions had coassembled and blended nanomorphologies, and confirmed that coassembled nanomorphologies enabled more effective energy transfer than the blended nanomorphologies.

Recent Progress in Simple and Cost-Effective Top-Down Lithography for ≈10 nm Scale Nanopatterns: From Edge Lithography to Secondary Sputtering Lithography.

The development of a simple and cost-effective method for fabricating ≈10 nm scale nanopatterns over large areas is an important issue, owing to the performance enhancement such patterning brings to various applications including sensors, semiconductors, and flexible transparent electrodes. Although nanoimprinting, extreme ultraviolet, electron beams, and scanning probe litho-graphy are candidates for developing such nanopatterns, they are limited to complicated procedures with low throughput and high startup cost, which are difficult to use in various academic and industry fields. Recently, several easy and cost-effective lithographic approaches have been reported to produce ≈10 nm scale patterns without defects over large areas. This includes a method of reducing the size using the narrow edge of a pattern, which has been attracting attention for the past several decades. More recently, secondary sputtering lithography using an ion-bombardment technique was reported as a new method to create high-resolution and high-aspect-ratio structures. Recent progress in simple and cost-effective top-down lithography for ≈10 nm scale nanopatterns via edge and secondary sputtering techniques is reviewed. The principles, technical advances, and applications are demonstrated. Finally, the future direction of edge and secondary sputtering lithography research toward issues to be resolved to broaden applications is discussed.

Polyelemental Nanolithography via Plasma Ion Bombardment: From Fabrication to Superior H2 Sensing Application.

The development of complex nanostructures containing a homo- and heteromixture of two or more metals is a considerable challenge in nanotechnology. However, previous approaches are considerably limited to the number of combinations of metals depending on the compatibility of elements, and to the complex shape control of the nanostructure. In this study, a significant step is taken toward resolving these limitations via the utilization of a low-energy argon-ion bombardment. The multilayer films are etched and re-sputtered on the sidewall of the pre-pattern, which is a secondary sputtering phenomenon. In contrast to the precursor mixing method, most metallic combinations can be fabricated. The degree of mixing is tuned by the control of the sequence and thickness of multilayers. In addition, the feature shape and dimensions are controlled by changing the pre-pattern or by controlling the ion-beam angle. Using this method, the shortest response time (2 s to 1% H2 ) in comparison with those of Pd-based H2 sensors reported previously and a limit of detection below 1 parts per million (ppm) for Pd/Au and Pd/Pt bimetallic line arrays are achieved. This study is expected to realize a family of polyelements that can be used in various applications.

Correction: A three-dimensional metal grid mesh as a practical alternative to ITO.

Correction for 'A three-dimensional metal grid mesh as a practical alternative to ITO' by Sungwoo Jang et al., Nanoscale, 2016, 8, 14257-14263.

Universal Nanopatterning Technique Combining Secondary Sputtering with Nanoscale Electroplating for Fabricating Size-Controllable Ultrahigh-Resolution Nanostructures.

Here, we describe a next-generation lithographic technique for fabricating ultrahigh-resolution nanostructures. This technique makes use of the secondary sputtering phenomenon of plasma ion etching and of nanoscale electroplating to finely control the resolution of the fabricated structures from ten nanometers to hundreds of nanometers from a single microsized master pattern. In contrast to previously described techniques that incorporate a recently developed secondary sputtering lithography (SSL) patterning approach, which could only yield 10 nm-resolution structures, in the current technique, we used an improved SSL approach to produce various-sized, high-resolution structures. Additionally, this improved SSL approach was used to fabricate size-controllable 3D patterns on various types of substrates, in particular, a silicon wafer, transparent glass, and flexible polycarbonate (PC) film. Thus, this method can serve as a new-concept patterning method for the efficient mass production of ultrahigh-resolution nanostructures.

Fabrication of three-dimensional hybrid nanostructure-embedded ITO and its application as a transparent electrode for high-efficiency solution processable organic photovoltaic devices.

Well-aligned, high-resolution (10 nm), three-dimensional (3D) hybrid nanostructures consisting of patterned cylinders and Au islands were fabricated on ITO substrates using an ion bombardment process and a tilted deposition process. The fabricated 3D hybrid nanostructure-embedded ITO maintained its excellent electrical and optical properties after applying a surface-structuring process. The solution processable organic photovoltaic device (SP-OPV) employing a 3D hybrid nanostructure-embedded ITO as the anode displayed a 10% enhancement in the photovoltaic performance compared to the photovoltaic device prepared using a flat ITO electrode, due to the improved charge collection (extraction and transport) efficiency as well as light absorbance by the photo-active layer.

New approach for fabricating hybrid-structured metal mesh films for flexible transparent electrodes by the combination of electrospinning and metal deposition.

In this study, hybrid-structured metal mesh (HMM) films as potential flexible transparent electrodes, composed of aligned micro-sized metal fibers integrated into random network of metal nanofibers, were fabricated by the combination of electrospinning and metal deposition. These naturally fiber-bridged HMMs, with a gold layer thickness of 85 nm, exhibited a high transmittance of around 90% and a sheet resistance of approximately 10 Ω sq-1, as well as favorable mechanical stability under bending stress. These results demonstrate that the approach employed herein is a simple, highly efficient, and facile process for fabricating, uniform, interconnected fiber networks with potential for producing high-performance flexible transparent electrodes.

Complex High-Aspect-Ratio Metal Nanostructures by Secondary Sputtering Combined with Block Copolymer Self-Assembly.

High-resolution (10 nm), high-areal density, high-aspect ratio (>5), and morphologically complex nanopatterns are fabricated from a single conventional block copolymer (BCP) structure with a 70 nm scale resolution and an aspect ratio of 1, through the secondary-sputtering phenomenon during the Ar-ion-bombardment process. This approach provides a foundation for the design of new routes to BCP lithography.

A three-dimensional metal grid mesh as a practical alternative to ITO.

The development of a practical alternative to indium tin oxide (ITO) is one of the most important issues in flexible optoelectronics. In spite of recent progress in this field, existing approaches to prepare transparent electrodes do not satisfy all of their essential requirements. Here, we present a new substrate-embedded tall (∼350 nm) and thin (∼30 nm) three-dimensional (3D) metal grid mesh structure with a large area, which is prepared via secondary sputtering. This structure satisfies most of the essential requirements of transparent electrodes for practical applications in future opto-electronics: excellent optoelectronic performance (a sheet resistance of 9.8 Ω□(-1) with a transmittance of 85.2%), high stretchability (no significant change in resistance for applied strains <15%), a sub-micrometer mesh period, a flat surface (a root mean square roughness of approximately 5 nm), no haze (approximately 0.5%), and strong adhesion to polymer substrates (it survives attempted detachment with 3M Scotch tape). Such outstanding properties are attributed to the unique substrate-embedded 3D structure of the electrode, which can be obtained with a high aspect ratio and in high resolution over large areas with a simple process. As a demonstration of its suitability for practical applications, our transparent electrode was successfully tested in a flexible touch screen panel. We believe that our approach opens up new practical applications in wearable electronics.

High-Resolution p-Type Metal Oxide Semiconductor Nanowire Array as an Ultrasensitive Sensor for Volatile Organic Compounds.

The development of high-performance volatile organic compound (VOC) sensor based on a p-type metal oxide semiconductor (MOS) is one of the important topics in gas sensor research because of its unique sensing characteristics, namely, rapid recovery kinetics, low temperature dependence, high humidity or thermal stability, and high potential for p-n junction applications. Despite intensive efforts made in this area, the applications of such sensors are hindered because of drawbacks related to the low sensitivity and slow response or long recovery time of p-type MOSs. In this study, the VOC sensing performance of a p-type MOS was significantly enhanced by forming a patterned p-type polycrystalline MOS with an ultrathin, high-aspect-ratio (∼25) structure (∼14 nm thickness) composed of ultrasmall grains (∼5 nm size). A high-resolution polycrystalline p-type MOS nanowire array with a grain size of ∼5 nm was fabricated by secondary sputtering via Ar(+) bombardment. Various p-type nanowire arrays of CuO, NiO, and Cr2O3 were easily fabricated by simply changing the sputtering material. The VOC sensor thus fabricated exhibited higher sensitivity (ΔR/Ra = 30 at 1 ppm hexane using NiO channels), as well as faster response or shorter recovery time (∼30 s) than that of previously reported p-type MOS sensors. This result is attributed to the high resolution and small grain size of p-type MOSs, which lead to overlap of fully charged zones; as a result, electrical properties are predominantly determined by surface states. Our new approach may be used as a route for producing high-resolution MOSs with particle sizes of ∼5 nm within a highly ordered, tall nanowire array structure.

Macroscopic alignment of chromonic liquid crystals using patterned substrates.

We demonstrate an efficient technique to align lyotropic chromonic liquid crystals (LCLCs) using secondary sputtering lithography (SSL). Monodomains of LCLCs prepared using SSL maintained their stable alignment for days. A generalization of Berreman's theory was employed to determine the anchoring strength of LCLCs on tessellated surface patterns. The anchoring energy initially increases with the amplitude (A) of the grooves and excellent alignment of LCLCs was observed when the amplitude of the grooves is equal to half its wavelength (λ). We also note that the anchoring energy levels off above qA∼ 3 (where q = 2π/λ), which suggests that increasing qA beyond a certain value does not provide any further advantage for the alignment of LCLCs. This finding provides a useful optimization criterion for the fabrication of the patterned cells to achieve stable monodomain alignment of LCLCs. Our analysis also explains why good alignment of LCLCs has been a difficult task.

Highly Enhanced Fluorescence Signals of Quantum Dot-Polymer Composite Arrays Formed by Hybridization of Ultrathin Plasmonic Au Nanowalls.

Enhancement of the fluorescence intensity of quantum dot (QD)-polymer nanocomposite arrays is an important issue in QD studies because of the significant reduction of fluorescence signals of such arrays due to nonradiative processes in densely packed polymer chains in solid films. In this study, we enhance the fluorescence intensity of such arrays without significantly reducing their optical transparency. Enhanced fluorescence is achieved by hybridizing ultrathin plasmonic Au nanowalls onto the sidewalls of the arrays via single-step patterning and hybridization. The plasmonic Au nanowall induces metal-enhanced fluorescence, resulting in a maximum 7-fold enhancement of the fluorescence signals. We also prepare QD nanostructures of various shapes and sizes by controlling the dry etching time. In the near future, this facile approach can be used for fluorescence enhancement of colloidal QDs with plasmonic hybrid structures. Such structures can be used as optical substrates for imaging applications and for fabrication of QD-LED devices.

Polymer-Layer-Free Alignment for Fast Switching Nematic Liquid Crystals by Multifunctional Nanostructured Substrate.

A novel polymer-layer-free system for liquid-crystal alignment is demonstrated by various shaped indium tin oxide (ITO) patterns. Liquid crystals are aligned along the ITO line pattern and secondary sputtering lithography can change the shape of the ITO line pattern. Different shapes can control the direction and size of the pretilt angle. This effect eliminates defects and reduces the response time.

Well-defined and high resolution Pt nanowire arrays for a high performance hydrogen sensor by a surface scattering phenomenon.

Developing hydrogen (H2) sensors with a high sensitivity, rapid response, long-term stability, and high throughput is one of the critical issues in energy and environmental technology [Hübert et al. Sens. Actuators, B 2011, 157, 329]. To date, H2 sensors have been mainly developed using palladium (Pd) as the channel material because of its high selectivity and strong affinity to the H2 molecule [(Xu et al. Appl. Phys. Lett. 2005, 86, 203104), (Offermans et al. Appl. Phys. Lett. 2009, 94, 223110), (Yang et al. Nano Lett. 2009, 9, 2177), (Yang et al. ACS Nano 2010, 4, 5233), and (Zou et al. Chem. Commun. 2012, 48, 1033)]. Despite significant progress in this area, Pd based H2 sensors suffer from fractures on their structure due to hydrogen adsorption induced volumetric swelling during the α → ß phase transition, leading to poor long-term stability and reliability [(Favier et al. Science 2001, 293, 2227), (Walter et al. Microelectron. Eng. 2002, 61­62, 555), and (Walter et al. Anal. Chem. 2002, 74, 1546)]. In this study, we developed a platinum (Pt) nanostructure based H2 sensor that avoids the stability limitations of Pd based sensors. This sensor exhibited an excellent sensing performance, low limit of detection (LOD, 1 ppm), reproducibility, and good recovery behavior at room temperature. This Pt based H2 sensor relies on a highly periodic, small cross sectional dimension (10­40 nm) and a well-defined configuration of Pt nanowire arrays over a large area. The resistance of the Pt nanowire arrays significantly decreased upon exposure to H2 due to reduced electron scattering in the cross section of the hydrogen adsorbed Pt nanowires, as compared to the oxygen terminated original state. Therefore, these well-defined Pt nanowire arrays prepared using advanced lithographic techniques can facilitate the production of high performance H2 sensors.

Fabrication of sub-20 nm nano-gap structures through the elastomeric nano-stamp assisted secondary sputtering phenomenon.

We describe a highly efficient method for fabricating controllable and reliable sub-20 nm scale nano-gap structures through an elastomeric nano-stamp with an embedded ultra-thin pattern. The stamp consists of ultrahigh resolution (approximately 10 nm) and high aspect ratio (ca. 15) metal nano-structures, which are obtained by secondary sputtering lithography (SSL). The nano-gap structures fabricated in this fashion achieve a high resolution and meet the requirements of minimal cost, high reliability, controllability, reproducibility, and applicability to different materials. Further, we demonstrate that this method enables the fabrication of SERS substrates for detection at the single-molecule level.

Fabrication of 10 nm-scale complex 3D nanopatterns with multiple shapes and components by secondary sputtering phenomenon.

We introduce an advanced ultrahigh-resolution (∼ 15 nm) patterning technique that enables the fabrication of various 3D high aspect ratio multicomponents/shaped nanostructures. This methodology utilizes the repetitive secondary sputtering phenomenon under etching plasma conditions and prepatterned fabrication control. The secondary sputtering phenomenon repetitively generates an angular distribution of target particles during ion-bombardment. This method, advanced repetitive secondary sputtering lithography, provides many strategies to fabricate complex continuous patterns and multilayer/material patterns with 10 nm-scale resolution. To demonstrate the versatility of this method, we show induced vertical alignment of liquid crystals (LCs) on indium-tin-oxide (ITO) grid patterns without any alignment layers. The ITO grid pattern fabricated in this method is found to have not only an alignment capability but also electrode properties without electrical or optical damage.

Fabrication of complex 3-dimensional patterned structures on a ∼10 nm scale from a single master pattern by secondary sputtering lithography.

We describe a highly efficient method for fabricating a variety of complex 3D nano-patterns from a single master pattern using secondary sputtering lithography, which is a 10 nm scale patterning method that we have developed. A rapid etching rate in the bottom part of the PS pillar during the RIE process can produce various nanostructure shapes and the PS residual layer thickness can influence various feature dimensions, due to the controlled RIE time leading to different PS layer thicknesses. This technique provides a highly effective method for producing various complex 3D patterns from a single master pattern. Thus, this method can serve as a new procedure for the cost-effective mass production of complex nanoscale patterns with high resolution.

Cylindrical posts of Ag/SiO2/Au multi-segment layer patterns for highly efficient surface enhanced Raman scattering.

We fabricated a regular array of Ag/SiO2/Au multi-segment cylindrical nanopatterns to create a highly efficient surface enhanced Raman scattering (SERS) active substrate using an advanced soft-nanoimprint lithographic technique. The SERS spectra results for Rhodamine 6G (R6G) molecules on the Ag/SiO2/Au multi-segment nanopatterns show that the highly ordered patterns and interlayer thickness are responsible for enhancing the sensitivity and reproducibility, respectively, The multi-segment nanopattern with a silica interlayer generates significant SERS enhancement (~EF = 1.2 x 106) as compared to that of the bimetallic (Ag/Au) nanopatterns without a dielectric gap (~EF = 1.0 x 104). Further precise control of the interlayer distances between the two metals plays an essential role in enhancing SERS performance for detecting low concentrations of analytes such as fluorescent (Rhodamine 6G) and DNA molecules. Therefore, the highly ordered multi-segment patterns provide great sensitivity and reproducibility of SERS based detection, resulting in a high performance of the SERS substrate.