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.

Electrospun fibrous membrane reinforced hydrogels with preferable mechanical and tribological performance as cartilage substitutes.

Hydrogels have attracted much attention as cartilage substitutes due to their human tissue-like characteristics. However, developing cartilage substitutes require the combination of high mechanical strength and low friction. Despite great success in tough hydrogels, this combination was hardly realized. Inspired by the natural cartilage, electrospun fibrous membrane reinforced hydrogels with superior mechanical properties and low friction coefficient were designed using electrospinning, freeze-thawing, and annealing techniques. An ordered fibrous membrane was first constructed by electrospinning, in which the tensile strength and modulus have been improved successfully. Then the PVA/PAA/GO hydrogel was modified layer-by-layer by the multilayer ordered electrospun membrane of PVA/PAA/GO. The ordered fibrous membrane significantly enhanced the mechanical strength and friction properties in a manner that mimicked the collagen fibrils in the cartilage. When the number of the membranes was 4, the mechanical properties of the fibrous membrane reinforced hydrogel is maximized, which can be compared to natural cartilage, which can achieve a tensile strength of 13.7 ± 1.5 MPa, tensile modulus of 27.5 ± 3.2 MPa, compressive strength of 12.32 ± 1.35 MPa, compressive modulus of 20.35 ± 2.50 MPa. The ordered fibrous membrane endows the hydrogel with a higher tearing energy of 39.16 ± 4.05 KJ m-2, which is the 5 times that of pure hydrogel (7.74 ± 0.86 KJ m-2). In addition, the friction coefficient of the fibrous membrane reinforced hydrogel is as low as 0.039, 2 times smaller than that of the hydrogel without addition of the fibrous membrane. Therefore, such hydrogels had excellent mechanical properties and tribological properties, which could be widely used in tissue engineering such as in cartilage replacement.

Bilayer Hydrogels with Low Friction and High Load-Bearing Capacity by Mimicking the Oriented Hierarchical Structure of Cartilage.

Natural articular cartilages exhibit extraordinary lubricating properties and excellent load-bearing capacity based on their penetrated surface lubricated biomacromolecules and gradient-oriented hierarchical structure. Hydrogels are considered as the most promising cartilage replacement materials due to their excellent flexibility, good biocompatibility, and low friction coefficient. However, the construction of high-strength, low-friction hydrogels to mimic cartilage is still a great challenge. Here, inspired by the structure and functions of natural articular cartilage, anisotropic hydrogels with horizontal and vertical orientation structure were constructed layer by layer and bonded with each other, successfully developing a bilayer oriented heterogeneous hydrogel with a high load-bearing capacity, low friction, and excellent fatigue resistance. The bilayer hydrogel exhibited a high compressive strength of 5.21 ± 0.45 MPa and a compressive modulus of 4.06 ± 0.31 MPa due to the enhancement mechanism of the anisotropic structure within the bottom anisotropic hydrogel. Moreover, based on the synergistic effect of the high load-bearing capacity of the bottom layer and the lubrication of the surface layer, the bilayer hydrogel possesses excellent biotribological properties in hard/soft (0.032) and soft/soft (0.028) contact, which is close to that of natural cartilage. It is worth noting that the bilayer oriented heterogeneous hydrogel is able to withstand repeated loading without fatigue crack. Therefore, this work could open up a new avenue for constructing cartilage-like materials with both high strength and low friction.

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.

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.

Reducing adhesion force by means of atomic layer deposition of ZnO films with nanoscale surface roughness.

Adhesion is a big concern for the design of Si-based microelectromechanical devices. A ZnO film with nanoscale surface roughness is a promising candidate to decrease adhesion as the protective coating. In this study, the adhesion force of ZnO films prepared by atomic layer deposition (ALD) on a Si (100) substrate was studied. The root-mean-square (RMS) roughness of the ZnO films was in the range of 0.7-4.28 nm, and the contact angle of water was in the range of 85-88°. The adhesion force was measured by atomic force microscopy (AFM) at both low (12%) and high (60%) relative humidities. The results show that the adhesion force decreases as the surface roughness increases. A low adhesion force at high RMS roughness is attributed to the large asperities on the film, and a large adhesion force at high humidity is attributed to the large capillary force. The experimental adhesion force was compared to the force calculated using the Rabinovich model. Although the theoretical value underestimates the experimental value, the proportion of the two components of the adhesion force is clearly shown. At the low humidity, the van der Waals force component differs not greatly with the capillary force component, while at the high humidity, the capillary force component becomes dominant.