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.

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.

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.

All-Solution-Processed Electronics with Sub-Microscale Resolution and Nanoscale Fidelity Fabricated Via a Humidity-Controlled, Surface Energy-Directed Assembly Process.

Solution-based processes have received considerable attention in the fabrication of electronics and sensors owing to their merits of being low-cost, vacuum-free, and simple in equipment. However, the current solution-based processes either lack patterning capability or have low resolution (tens of micrometers) and low pattern fidelity in terms of line edge roughness (LER, several micrometers). Here, we present a surface energy-directed assembly (SEDA) process to fabricate metal oxide patterns with up to 2 orders of magnitude improvement in resolution (800 nm) and LER (16 nm). Experiment results show that high pattern fidelity can be achieved only at low relative humidities of below 30%. The reason for this phenomenon lies in negligible water condensation on the solution droplet. Employing the SEDA process, all-solution-processed metal oxide thin film transistors (TFTs) are fabricated by using indium oxide as channel layers, indium tin oxide as source/drain electrodes and gate electrodes, and aluminum oxide as gate dielectrics. TFT-based logic gate circuits, including NOT, NOR, NAND, and AND are fabricated as well, demonstrating the applicability of the SEDA process in fabricating large area functional electronics.

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.

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.

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.

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.

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.

A molybdenum disulfide/carbon nanotube heterogeneous complementary inverter.

We report a simple, bottom-up/top-down approach for integrating drastically different nanoscale building blocks to form a heterogeneous complementary inverter circuit based on layered molybdenum disulfide and carbon nanotube (CNT) bundles. The fabricated CNT/MoS(2) inverter is composed of n-type molybdenum disulfide (MOS(2)) and p-type CNT transistors, with a high voltage gain of 1.3. The CNT channels are fabricated using directed assembly while the layered molybdenum disulfide channels are fabricated by mechanical exfoliation. This bottom-up fabrication approach for integrating various nanoscale elements with unique characteristics provides an alternative cost-effective methodology to complementary metal-oxide-semiconductors, laying the foundation for the realization of high performance logic circuits.

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.

Size-selective template-assisted electrophoretic assembly of nanoparticles for biosensing applications.

The precise, size-selective assembly of nanoparticles gives rise to many applications where the assembly of nano building blocks with different biological or chemical functionalizations is necessary. We introduce a simple, fast, reproducible-directed assembly technique that enables a complete sorting of nanoparticles with single-particle resolution. Nanoparticles are size-selectively assembled into prefabricated via arrays using a sequential template-directed electrophoretic assembly method. Polystyrene latex (PSL) nanoparticles with diameters ranging from 200 to 50 nm are selectively assembled into vias comparable to nanoparticle diameter. We investigate the effects of particle size and via size on the sorting efficiency. We show that complete sorting can be achieved when the size of the vias is close to the diameter of the nanoparticles and the size distribution of the chosen nanoparticles does not overlap. The results also show that it is necessary to keep the electric field on during the insertion and removal of the template. To elucidate the versatility and nil effects that the electrophoresis assembly technique has on the assembled nanoparticle characteristics, we have assembled cancer-specific monoclonal antibody-2C5-coated nanoparticles and have also shown that they can successfully measure low concentrations of the nucleosome (NS) antigen.

Modulating the performance of carbon nanotube field-effect transistors via Rose Bengal molecular doping.

A simple, reliable, and large scale ambient environment doping method for carbon nanotubes is a highly desirable approach for modulating the performance of nanotube based electronics. One of the major challenges is doping carbon nanotubes to simultaneously offer a large shift in threshold voltage and an improved subthreshold swing. In this paper, we report on modulating the performance of carbon nanotube field-effect transistors (CNTFETs) by rationally selecting doping molecules. We demonstrated that Rose Bengal sodium salt (RB-Na) molecular doping can effectively shift the threshold voltage (ΔVth) of CNTFETs up to ∼6 V, decrease the subthreshold swing down to 130 mV/decade, and increase the effective field-effect mobility to 5 cm2 V(-1) s(-1). It is also shown that CNTFETs doped with Rose Bengal lactone (RBL) show a smaller variation in ΔVth (∼2 V) and subthreshold swing than those doped by RB-Na, which can be attributed to the difference in their molecular structures. The observed right-shift of the threshold voltage is attributed to the positive charge doping of the nanotube conduction channel from Rose Bengal molecules. The resultant lowering of the subthreshold swing is due to the reduced Schottky barrier at the CNT/metal/molecule interface. This room temperature chemical doping approach provides an efficient, simple, and cost-effective method to fabricate highly reliable and high-performance nanotube transistors for future nanotube based electronics.

Collapse behavior and forces of multistack nanolines.

Two types of multistack nanolines (MNLs), Si-substrate (Si)/siliconoxynitride (SiON)/amorphous Si (a-Si)/ SiO(2) and Si/ SiO(2) /polycrystalline Si (poly-Si)/ SiO(2) were used to measure the collapse force and to investigate their collapse behavior by an atomic force microscope (AFM). The Si/SiON/a-Si/ SiO(2) MNL showed a larger length of fragment in the collapse patterns at a smaller collapse force. The Si/ SiO(2) /poly-Si/ SiO(2) MNL, however, demonstrated a smaller length of fragment at a higher applied collapse force. The collapse forces increased by the square of the linewidth in both Si/SiON/a-Si/ SiO(2) and Si/SiO(2) /poly-Si/ SiO(2) MNLs. Once an AFM tip touches an Si/SiON/a-Si/ SiO(2) line, which is a softer MNL, it was delaminated first at the Si/SiON interface. One end of the delaminated line was first broken and then the other end was bent until it was broken. A harder MNL, Si/ SiO(2) /poly-Si/ SiO(2), however, was broken at two ends simultaneously after the delamination occurred at the Si/ SiO(2) /poly-Si interface. The different collapse behaviors were attributed to the magnitude of adhesion forces at the stack material interfaces and the mechanical strength of MNLs.

DNA-decorated carbon-nanotube-based chemical sensors on complementary metal oxide semiconductor circuitry.

We present integration of single-stranded DNA (ss-DNA)-decorated single-walled carbon nanotubes (SWNTs) onto complementary metal oxide semiconductor (CMOS) circuitry as nanoscale chemical sensors. SWNTs were assembled onto CMOS circuitry via a low voltage dielectrophoretic (DEP) process. Besides, bare SWNTs are reported to be sensitive to various chemicals, and functionalization of SWNTs with biomolecular complexes further enhances the sensing specificity and sensitivity. After decorating ss-DNA on SWNTs, we have found that the sensing response of the gas sensor was enhanced (up to approximately 300% and approximately 250% for methanol vapor and isopropanol alcohol vapor, respectively) compared with bare SWNTs. The SWNTs coupled with ss-DNA and their integration on CMOS circuitry demonstrates a step towards realizing ultra-sensitive electronic nose applications.

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.

Mechanism of very large scale assembly of SWNTs in template guided fluidic assembly process.

Very large scale patterned single-walled carbon nanotube (SWNT) networks were fabricated using a newly developed template guided fluidic assembly process. A mechanism for SWNT assembly and their control is described here. To maximize the directed assembly efficiency of SWNTs toward a wafer level SWNT deposition, Si or SiO(2) substrate was pretreated with precisely controlled SF(6), O(2), and Ar plasma. Chemical and physical properties of the surface were characterized using several surface characterization techniques to investigate and control the mechanism of SWNT assembly. We found that hydrophilic chemical groups such as hydroxides were created on the silicon or silicon oxide surface through the controlled plasma treatment and fluidic SWNT dip-coating process. Also we found that nanoscale rough surface structures formed during the plasma treatment significantly increased the number of dangling bonds and hydroxide functional groups on the surface. These combined chemical and physical enhancements that attract SWNTs in the aqueous solution enable us to build highly organized and very large scale SWNT network architectures effectively in various dimensions and geometries.

Directed assembly of high density single-walled carbon nanotube patterns on flexible polymer substrates.

We report an effective technique for the controlled assembly of single-walled carbon nanotubes (SWNTs) and demonstrate organized high density network architectures on soft polymeric substrates. We utilize the surface energy differential between a plasma treated (hydrophilic) parylene-C surface and a photoresist (hydrophobic) surface to create microscale patterns of SWNT networks on a 10 microm thick parylene-C substrate. The large scale fabrication of patterned SWNT structures presented is achieved by performing site-selective fluidic assembly of SWNTs. Electrically continuous nanotube network micro-arrays as small as 4 microm wide that are up to 1500 microm long with controlled separation have been fabricated by dissolving the photoresist after assembly. Electrical and mechanical characterization of nanotube networks on the flexible substrate in both static and dynamic modes indicates that the structure can handle both compressive and tensile deformations with no hysteresis. The technology presented has immediate applications in making thin film transistors, interconnects and sensors on flexible substrates.

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.