Fabrication of Flexible and Transparent Metal Mesh Electrodes Using Surface Energy-Directed Assembly Process for Touch Screen Panels and Heaters.

Transparent conductive electrodes (TCEs) are indispensable components of various optoelectronic devices such as displays, touch screen panels, solar cells, and smart windows. To date, the fabrication processes for metal mesh-based TCEs are either costly or having limited resolution and throughput. Here, a two-step surface energy-directed assembly (SEDA) process to efficiently fabricate high resolution silver meshes is introduced. The two-step SEDA process turns from assembly on a functionalized substrate with hydrophilic mesh patterns into assembly on a functionalized substrate with stripe patterns. During the SEDA process, a three-phase contact line pins on the hydrophilic pattern regions while recedes on the hydrophobic non-pattern regions, ensuring that the assembly process can be achieved with excellent selectivity. The necessity of using the two-step SEDA process rather than a one-step SEDA process is demonstrated by both experimental results and theoretical analysis. Utilizing the two-step SEDA process, silver meshes with a line width down to 2 µm are assembled on both rigid and flexible substrates. The thickness of the silver meshes can be tuned by varying the withdraw speed and the assembly times. The assembled silver meshes exhibit excellent optoelectronic properties (sheet resistance of 1.79 Ω/□, optical transmittance of ≈92%, and a FoM value of 2465) as well as excellent mechanical stability. The applications of the assembled silver meshes in touch screen panels and thermal heaters are demonstrated, implying the potential of using the two-step SEDA process for the fabrication of TCEs for optoelectronic applications.

Directed Assembly of Nanomaterials for Making Nanoscale Devices and Structures: Mechanisms and Applications.

Nanofabrication has been utilized to manufacture one-, two-, and three-dimensional functional nanostructures for applications such as electronics, sensors, and photonic devices. Although conventional silicon-based nanofabrication (top-down approach) has developed into a technique with extremely high precision and integration density, nanofabrication based on directed assembly (bottom-up approach) is attracting more interest recently owing to its low cost and the advantages of additive manufacturing. Directed assembly is a process that utilizes external fields to directly interact with nanoelements (nanoparticles, 2D nanomaterials, nanotubes, nanowires, etc.) and drive the nanoelements to site-selectively assemble in patterned areas on substrates to form functional structures. Directed assembly processes can be divided into four different categories depending on the external fields: electric field-directed assembly, fluidic flow-directed assembly, magnetic field-directed assembly, and optical field-directed assembly. In this review, we summarize recent progress utilizing these four processes and address how these directed assembly processes harness the external fields, the underlying mechanism of how the external fields interact with the nanoelements, and the advantages and drawbacks of utilizing each method. Finally, we discuss applications made using directed assembly and provide a perspective on the future developments and challenges.

High-Rate Printing of Micro/Nanoscale Patterns Using Interfacial Convective Assembly.

Printing of electronics has been receiving increasing attention from academia and industry over the recent years. However, commonly used printing techniques have limited resolution of micro- or sub-microscale. Here, a directed-assembly-based printing technique, interfacial convective assembly, is reported, which utilizes a substrate-heating-induced solutal Marangoni convective flow to drive particles toward patterned substrates and then uses van der Waals interactions as well as geometrical confinement to trap the particles in the pattern areas. The influence of various assembly parameters including type of mixing solvent, substrate temperature, particle concentration, and assembly time is investigated. The results show successful assembly of various nanoparticles in patterns of different shapes with a high resolution down to 25 nm. In addition, the assembly only takes a few minutes, which is two orders of magnitude faster than conventional convective assembly. Small-sized (diameter below 5 nm) nanoparticles tend to coalesce during the assembly process and form sintered structures. The fabricated silver nanorods show single-crystal structure with a low resistivity of 8.58 × 10-5 Ω cm. With high versatility, high resolution, and high throughput, the interfacial convective assembly opens remarkable opportunities for printing next generation nanoelectronics and sensors.

Solution-processed organic field-effect transistors using directed assembled carbon nanotubes and 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT).

Achieving low-cost fabrication of organic field-effect transistors (OFETs) has long been pursued in the semiconductor industry. Solution-based process allows the fabrication of OFETs cost-effective because of its merit of vacuum-free and room temperature operation. Here, we show a facile and scalable fabrication of solution-processed OFETs using carbon nanotube (CNT) as source/drain electrodes and 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) as semiconducting layer on silicon as well as on flexible and transparent polyethylene terephthalate (PET) substrates. The CNT electrodes and the C8-BTBT film are fabricated using a dip coating-based directed assembly process, and two dip coating parameters, the pulling speed and the solution concentration, are carefully chosen so that the thickness of the C8-BTBT film is close to that of the CNT electrodes. The fabricated OFET devices show typical p-channel behavior. Low-cost, ease of processing, wafer level scalability and good compatibility with various substrates make the fabrication process presented in this paper well suited for next-generation electronics and sensors.

Assembly of Highly Aligned Carbon Nanotubes Using an Electro-Fluidic Assembly Process.

Carbon nanotubes (CNTs) are promising building blocks for emerging wearable electronics and sensors due to their outstanding electrical and mechanical properties. However, the practical applications of the CNTs face challenges of efficiently and precisely placing them at the desired location with controlled orientation and density. Here, we introduce an electro-fluidic assembly process to assemble highly aligned and densely packed CNTs selectively on a substrate with patterned wetted areas at a high rate. An electric field is applied during the electro-fluidic assembly process, which drives the CNTs close to the patterned regions and shortens the assembly time. Meanwhile, the electric field orientates the CNTs perpendicular to the substrate and anchors one end of the CNTs onto the substrate. When pulling the substrate out of the CNT suspension, the capillary force at the air-water-substrate interface stretches the free end of the CNTs and aligns the CNTs along the pulling direction. By adjusting two governing parameters, the direct current voltage and the pulling speed, we have demonstrated well aligned CNTs assembled in patterns with widths from 1 to 100 µm and lengths from 20 to 120 µm at a rate 20 times higher than a fluidic assembly process. The aligned CNTs show improved electrical conductivity compared with the random networks and prove possibility for strain detection. Precise and reproducible control of the orientation and the placement of the CNTs opens up their practical application in the next-generation electronics and sensors.

Measuring Bone Biomarker Alkaline Phosphatase with Wafer-Scale Nanowell Array Electrodes.

Biosensors that can analyze a single drop of biological fluid can overcome limitations such as extraction volume from humans or animals, ethical problems, time, and cost. In this work, we have developed a highly sensitive electrochemical (EC) biosensor based on a nanowell array (NWA) for the detection of alkaline phosphatase (ALP), a serum indicator of bone formation. The size of the electrode is 2 × 1 mm2 and has over 10 million nanowells (400 nm diameter) arranged uniformly on the electrode surface. For detecting ALP, anti-ALP was immobilized and oriented on the NWA surface using a self-assembled monolayer and protein G. EC impedance spectroscopy (EIS) was used to determine the amount of ALP in 10 µL of sample. The impedance was calibrated with ALP concentration. The NWA has a linear dynamic range from 1 pg/mL to 100 ng/mL with a limit of detection (LOD) at 12 pg/mL. We used the sensor to measure the ALP in real mouse serum from 4, 10, and 20 weeks old mice and compared the results to the standard photometric assay. This work demonstrates the potential of EC NWA sensors to analyze a single drop of a real body fluid sample and to be developed for broad applications.

Scalable Directed Assembly of Highly Crystalline 2,7-Dioctyl[1]benzothieno[3,2- b][1]benzothiophene (C8-BTBT) Films.

Assembly of organic semiconductors with ordered crystal structure has been actively pursued for electronics applications such as organic field-effect transistors (OFETs). Among various film deposition methods, solution-based film growth from small molecule semiconductors is preferable because of its low material and energy consumption, low cost, and scalability. Here, we show scalable and controllable directed assembly of highly crystalline 2,7-dioctyl[1]benzothieno[3,2- b][1]benzothiophene (C8-BTBT) films via a dip-coating process. Self-aligned stripe patterns with tunable thickness and morphology over a centimeter scale are obtained by adjusting two governing parameters: the pulling speed of a substrate and the solution concentration. OFETs are fabricated using the C8-BTBT films assembled at various conditions. A field-effect hole mobility up to 3.99 cm2 V-1 s-1 is obtained. Owing to the highly scalable crystalline film formation, the dip-coating directed assembly process could be a great candidate for manufacturing next-generation electronics. Meanwhile, the film formation mechanism discussed in this paper could provide a general guideline to prepare other organic semiconducting films from small molecule solutions.

Directed assembly-based printing of homogeneous and hybrid nanorods using dielectrophoresis.

Printing nano and microscale three-dimensional (3D) structures using directed assembly of nanoparticles has many potential applications in electronics, photonics and biotechnology. This paper presents a reproducible and scalable 3D dielectrophoresis assembly process for printing homogeneous silica and hybrid silica/gold nanorods from silica and gold nanoparticles. The nanoparticles are assembled into patterned vias under a dielectrophoretic force generated by an alternating current (AC) field, and then completely fused in situ to form nanorods. The assembly process is governed by the applied AC voltage amplitude and frequency, pattern geometry, and assembly time. Here, we find out that complete assembly of nanorods is not possible without applying both dielectrophoresis and electrophoresis. Therefore, a direct current offset voltage is used to add an additional electrophoretic force to the assembly process. The assembly can be precisely controlled to print silica nanorods with diameters from 20-200 nm and spacing from 500 nm to 2 µm. The assembled nanorods have good uniformity in diameter and height over a millimeter scale. Besides homogeneous silica nanorods, hybrid silica/gold nanorods are also assembled by sequentially assembling silica and gold nanoparticles. The precision of the assembly process is further demonstrated by assembling a single particle on top of each nanorod to demonstrate an additional level of functionalization. The assembled hybrid silica/gold nanorods have potential to be used for metamaterial applications that require nanoscale structures as well as for plasmonic sensors for biosensing applications.

Polypyrrole Films with Micro/Nanosphere Shapes for Electrodes of High-Performance Supercapacitors.

We demonstrate a simple and efficient one-step procedure for synthesizing a solid state polypyrrole (PPy) thin film for supercapacitor applications using alternating current impedance spectroscopy. By controlling the frequency and amplitude we were able to create unique PPy nano/microstructures with a particular morphology of the loop. Our PPy micro/nanosphere shows extremely high capacitance of 568 F/g, which is close to the theoretical value of 620 F/g and 20-100% higher than that of other reported PPy electrodes. Most of all, this material presents high capacitance and significantly improved electrochemical stability without pulverization of its structure, demonstrating 77% retention of the capacitance value even after 10 000 charge/discharge cycles. These results are a consequence of the larger surface area and adequate porosity generated due to the balance between the nano/micro PPy loops. This created porous structure also allows the favored penetration of electrolyte and high ion mobility within the polymer and prevents the mechanical failure of the physical structure during volume variation associated with the insertion/deinsertion of ions upon cycling.

High-Rate Assembly of Nanomaterials on Insulating Surfaces Using Electro-Fluidic Directed Assembly.

Conductive or semiconducting nanomaterials-based applications such as electronics and sensors often require direct placement of such nanomaterials on insulating surfaces. Most fluidic-based directed assembly techniques on insulating surfaces utilize capillary force and evaporation but are diffusion limited and slow. Electrophoretic-based assembly, on the other hand, is fast but can only be utilized for assembly on a conductive surface. Here, we present a directed assembly technique that enables rapid assembly of nanomaterials on insulating surfaces. The approach leverages and combines fluidic and electrophoretic assembly by applying the electric field through an insulating surface via a conductive film underneath. The approach (called electro-fluidic) yields an assembly process that is 2 orders of magnitude faster compared to fluidic assembly. By understanding the forces on the assembly process, we have demonstrated the controlled assembly of various types of nanomaterials that are conducting, semiconducting, and insulating including nanoparticles and single-walled carbon nanotubes on insulating rigid and flexible substrates. The presented approach shows great promise for making practical devices in miniaturized sensors and flexible electronics.

Novel Nanoprinting for Oral Delivery of Poorly Soluble Drugs.

Many of the newly developed drugs for cancer, and some of those for cardiovascular disease, are poorly soluble in water and cannot be taken orally. This can be overcome by employing a new and effective delivery system utilizing nanotechnology. We present a new method for oral preparation of poorly soluble drugs that entails assembling (printing) drug-loaded polymeric micelles into sub-100 nm orally acceptable nanorods (NRs). Due to their small size, these NRs will have a high permeability through cells and thus should transport through the intestine to allow for drug delivery in the blood. These NRs drugs are expected to penetrate tumors more efficiently and much faster than individual nanoparticles and may also be useful for drug delivery to atherosclerotic plaque. This should lead to better bioavailability of the drug with reduced toxicity and side effects. Currently used micellar formulations are administered intravenously, which is invasive and could be toxic due to high doses and interaction with normal healthy tissues. Oral drug administration is the easiest and most desirable way to deliver most drugs, including those that are poorly soluble.

High-rate nanoscale offset printing process using directed assembly and transfer of nanomaterials.

High-rate nanoscale offset printing using a newly developed reusable template enables the assembly of nanomaterials into nanostructures followed by their transfer onto a flexible substrate in a few minutes. The developed template can potentially be reused more than 100 times in the offset printing process without any additional functionalization. This approach provides a new way for the printing of flexible devices with nanoscale patterns.

Life cycle impacts and benefits of a carbon nanotube-enabled chemical gas sensor.

As for any emerging technology, it is critical to assess potential life cycle impacts prior to widespread adoption to prevent future unintended consequences. The subject of this life cycle study is a carbon nanotube-enabled chemical gas sensor, which is a highly complex, low nanomaterial-concentration application with the potential to impart significant human health benefits upon implementation. Thus, the net lifecycle trade-offs are quantified using an impact-benefit ratio (IBR) approach proposed herein, where an IBR < 1 indicates that the downstream benefits outweigh the upstream impacts. The cradle-to-gate assessment results indicate that the midpoint impacts associated with producing CNTs are marginal compared with those associated with the other manufacturing stages. The cumulative upstream impacts are further aggregated to units of disability-adjusted life years (DALYs) using ReCiPe end point analysis method and quantitatively compared with the potential downstream DALY benefits, as lives saved, during the use phase. The approach presented in this study provides a guiding framework and quantitative method intended to encourage the development of nanoenabled products that have the potential to realize a net environmental, health, or societal benefit.

3-D perpendicular assembly of single walled carbon nanotubes for complimentary metal oxide semiconductor interconnects.

Due to their superior electrical properties such as high current density and ballistic transport, carbon nanotubes (CNT) are considered as a potential candidate for future Very Large Scale Integration (VLSI) interconnects. However, direct incorporation of CNTs into Complimentary Metal Oxide Semiconductor (CMOS) architecture by conventional chemical vapor deposition (CVD) growth method is problematic since it requires high temperatures that might damage insulators and doped semiconductors in the underlying CMOS circuits. In this paper, we present a directed assembly method to assemble aligned CNTs into pre-patterned vias and perpendicular to the substrate. A dynamic electric field with a static offset is applied to provide the force needed for directing the SWNT assembly. It is also shown that by adjusting assembly parameters the density of the assembled CNTs can be significantly enhanced. This highly scalable directed assembly method is conducted at room temperature and pressure and is accomplished in a few minutes. I-V characterization of the assembled CNTs was conducted using a Zyvex nanomanipulator in a scanning electron microscope (SEM) and the measured value of the resistance is found to be 270 komega s.

Three-dimensional crystalline and homogeneous metallic nanostructures using directed assembly of nanoparticles.

Directed assembly of nano building blocks offers a versatile route to the creation of complex nanostructures with unique properties. Bottom-up directed assembly of nanoparticles have been considered as one of the best approaches to fabricate such functional and novel nanostructures. However, there is a dearth of studies on making crystalline, solid, and homogeneous nanostructures. This requires a fundamental understanding of the forces driving the assembly of nanoparticles and precise control of these forces to enable the formation of desired nanostructures. Here, we demonstrate that colloidal nanoparticles can be assembled and simultaneously fused into 3-D solid nanostructures in a single step using externally applied electric field. By understanding the influence of various assembly parameters, we showed the fabrication of 3-D metallic materials with complex geometries such as nanopillars, nanoboxes, and nanorings with feature sizes as small as 25 nm in less than a minute. The fabricated gold nanopillars have a polycrystalline nature, have an electrical resistivity that is lower than or equivalent to electroplated gold, and support strong plasmonic resonances. We also demonstrate that the fabrication process is versatile, as fast as electroplating, and scalable to the millimeter scale. These results indicate that the presented approach will facilitate fabrication of novel 3-D nanomaterials (homogeneous or hybrid) in an aqueous solution at room temperature and pressure, while addressing many of the manufacturing challenges in semiconductor nanoelectronics and nanophotonics.

Acceleration of poly(L-lactide) degradation by TiO2 nanoparticles in sunlight.

Poly(L-lactide) (PLA) is known to eventually be degraded into water and carbon dioxide by the microorganisms of the natural world. Titanium dioxide (TiO2) has been used in the biomedical and bioengineering fields as a photocatalyst. The purpose of this research project is to evaluate the influence of TiO2 added to PLA films both before and after irradiation of the films with sunlight. The PLA-TiO2 films were prepared by the addition of TiO2 (size: > 100 nm) nanoparticles to PLA. The surface changes of the PLA film were investigated before and after the films were exposed to sunlight. Tiny holes were observed in the PLA film without TiO2 nanoparticles after irradiation with sunlight, whereas large pits formed in the PLA-TiO2 films. It is suggested that PLA was degraded by the ultraviolet rays in sunlight. In addition, the decomposition speed was thought to be enhanced by the addition of TiO2, which acted as a catalyst.

High-performance H(2)S detection by redox reactions in semiconducting carbon nanotube-based devices.

Here we report the highly effective detection of hydrogen sulfide (H2S) gas by redox reactions based on single-walled carbon nanotubes (SWCNTs) functionalized with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) as a catalyst and we also discuss the important role of water vapor in the electrical conductivity of SWCNTs during the sensing of H2S molecules. To explore the H2S sensing mechanism, we investigate the adsorption properties of H2S on carbon nanotubes (CNTs) and the effects of the TEMPO functionalization using first-principles density functional theory (DFT) and we summarize current changes of devices resulting from the redox reactions in the presence of H2S. The semiconducting-SWCNT (s-SWCNT) device functionalized with TEMPO shows a very high sensitivity of 420% at 60% humidity, which is 17 times higher than a bare s-SWCNT device under dry conditions. Our results offer promising prospects for personal safety and real-time monitoring of H2S gases with the highest sensitivity and low power consumption and potentially at a low cost.

Wafer-scale nanowell array patterning based electrochemical impedimetric immunosensor.

We have reported that nanowell array (NWA) can enhance electrochemical detection of molecular binding events by controlling the binding sites of the captured molecules. Using NWA biosensor based amperometric analysis, we have detected biological macromolecules such as DNA, protein or aptamers at low concentrations. In this research, we developed an impedimetric immunosensor based on wafer-scale NWA for electrochemical detection of stress-induced-phosphoprotein-1 (STIP-1). In order to develop NWA sensor through the cost-effective combination of high-throughput nanopattern, the NWA electrode was fabricated on Si wafer by krypton-fluoride (KrF) stepper semiconductor process. Finally, 12,500,000 ea nanowell with a 500 nm diameter was fabricated on 4 mm × 2 mm substrate. Next, by using these electrodes, we measured impedance to quantify antigen binding to the immunoaffinity layer. The limit of detection (LOD) of the NWA was improved about 100-fold compared to milli-sized electrodes (4 mm × 2 mm) without an NWA. These results suggest that wafer-scale NWA immunosensor will be useful for biosensing applications because their interface response is appropriate for detecting molecular binding events.

Detection of single nucleotide polymorphisms using a biosensor-containing titanium-well array.

The rapid identification and verification of single nucleotide polymorphisms (SNPs) were demonstrated using a well array sensor containing anti-biofouling titanium (Ti). Probe single-stranded DNA (ssDNA) was immobilized inside a titanium-well array on amine-modified glass surfaces with anti-biofouling behavior via a streptavidin-biotin interaction. Fluorescence intensity changes originating from the hybridization of nucleic acids to protein-bound nucleic acids linked to Alexa Fluor (FL) 647 were observed. The protocol was highly sensitive and reproducible for the detection of DNA hybridization. Significant changes in fluorescence signals were observed when using target DNA with a single base mismatch, indicating that this method is applicable to SNP detection. The microarray technology for the detection of SNPs using anti-biofouling Ti and other methods can be used as a highly sensitive in vitro medical sensor, as highlighted by an increase in genotyping accuracy.

Phospholipase-catalyzed hydrolysis in an artificial cell membrane in the presence of melittin.

Biomimicry involves the use of the structure and function of biological systems as models for the design and engineering of materials and machines. An artificial cell membrane was developed using biomembrane components, and the membrane, formed by a lipid bilayer, was analyzed using surface plasmon resonance (SPR) to monitor hydrolysis by phospholipase (PL). The simultaneous atomic force microscope (AFM) images show that PL catalyzed the nanometer-scale hydrolysis of the artificial lipid biomembranes through enzymatic hydrolysis. In addition, it was confirmed that the combination of PL and melittin allowed the control of enzyme hydrolysis for the degradation of the lipid bilayer. Regarding the expected activating effect of melittin on hydrolysis, no difference with respect to the non-treated lipid membrane was observed in the AFM images. It is assumed that the partitioning of melittin into the membrane might prevent the binding or hydrolysis of Phospholipase A2 (PLA2). This study provides basic knowledge on a new approach for patterning biomimicking lipid membranes on a nano-scale.