scalable-solution-processed-fabrication-strategy-for-high-performance

Scalable Solution-processed Fabrication Strategy for High-performance, Flexible, Transparent Electrodes with Embedded Metal Mesh

Here, the authors report the embedded metal-mesh transparent electrode (EMTE), a new transparent electrode (TE) with a metal mesh completely embedded in a ...

University of Hong Kong

Single-walled carbon nanotubes (SWCNTs) have been shown to exhibit excellent electrical properties, such as ballistic transport over several hundred nanometers at room temperature. Field-effect transistors (FETs) made from individual tubes show dc performance specifications rivaling those of state-of-the-art silicon devices. An important next step is the fabrication of integrated circuits on SWCNTs to study the high-frequency ac capabilities of SWCNTs. We built a five-stage ring oscillator that comprises, in total, 12 FETs side by side along the length of an individual carbon nanotube. A complementary metal-oxide semiconductor-type architecture was achieved by adjusting the gate work functions of the individual p-type and n-type FETs used.

An integrated logic circuit assembled on a single carbon nanotube.

This work details a method to make efficacious field-effect transistors from monolayers of polycyclic aromatic hydrocarbons that are able to sense and respond to their chemical environment. The molecules used in this study are functionalized so that they assemble laterally into columns and attach themselves to the silicon oxide surface of a silicon wafer. To measure the electrical properties of these monolayers, we use ultrasmall point contacts that are separated by only a few nanometers as the source and drain electrodes. These contacts are formed through an oxidative cutting of an individual metallic single-walled carbon nanotube that is held between macroscopic metal leads. The molecules assemble in the gap and form transistors with large current modulation and high gate efficiency. Because these devices are formed from an individual stack of molecules, their electrical properties change significantly when exposed to electron-deficient molecules such as tetracyanoquinodimethane (TCNQ), forming the basis for new types of environmental and molecular sensors.

Chemoresponsive monolayer transistors.

This study details a new derivative of the contorted HBCs that self-organizes into one-dimensional, single-crystalline fibers. X-ray diffraction, transmission electron microscopy, and electron diffraction studies show that they have an orthorhombic unit cell with dimensions of 5.8 nm x 4.5 nm x 0.45 nm. Each fiber is composed of a few thousands columns. A method is put forth that utilizes elastomer stamps to manipulate and position isolated fibers in organic field effect transistors.

Transferring self-assembled, nanoscale cables into electrical devices.

Encoding molecular-wire formation within nanoscale sockets.

We report the fabrication of devices in which one single-walled carbon nanotube spans a barrier between two fluid reservoirs, enabling direct electrical measurement of ion transport through the tube. A fraction of the tubes pass anomalously high ionic currents. Electrophoretic transport of small single-stranded DNA oligomers through these tubes is marked by large transient increases in ion current and was confirmed by polymerase chain reaction analysis. Each current pulse contains about 10(7) charges, an enormous amplification of the translocated charge. Carbon nanotubes simplify the construction of nanopores, permit new types of electrical measurements, and may open avenues for control of DNA translocation.

Translocation of single-stranded DNA through single-walled carbon nanotubes.

This work investigated the thermoelectric properties of thin silicon membranes that have been decorated with high density of nanoscopic holes. These "holey silicon" (HS) structures were fabricated by either nanosphere or block-copolymer lithography, both of which are scalable for practical device application. By reducing the pitch of the hexagonal holey pattern down to 55 nm with 35% porosity, the thermal conductivity of HS is consistently reduced by 2 orders of magnitude and approaches the amorphous limit. With a ZT value of ∼0.4 at room temperature, the thermoelectric performance of HS is comparable with the best value recorded in silicon nanowire system.

Holey silicon as an efficient thermoelectric material.

We have constructed devices in which the interior of a single-walled carbon nanotube (SWCNT) field-effect transistor acts as a nanofluidic channel that connects two fluid reservoirs, permitting measurement of the electronic properties of the SWCNT as it is wetted by an analyte. Wetting of the inside of the SWCNT by water turns the transistor on, while wetting of the outside has little effect. These observations are consistent with theoretical simulations that show that internal water both generates a large dipole electric field, causing charge polarization of the tube and metal electrodes, and shifts the valence band of the SWCNT, while external water has little effect. This finding may provide a new method to investigate water behavior at nanoscale. This also opens a new avenue for building sensors in which the SWCNT simultaneously functions as a concentrator, nanopore, and extremely sensitive electronic detector, exploiting the enhanced sensitivity of the interior surface.

Electronic sensitivity of carbon nanotubes to internal water wetting.

Semiconductor nanowires are promising for photovoltaic applications, but, so far, nanowire-based solar cells have had lower efficiencies than planar cells made from the same materials, even allowing for the generally lower light absorption of nanowires. It is not clear, therefore, if the benefits of the nanowire structure, including better charge collection and transport and the possibility of enhanced absorption through light trapping, can outweigh the reductions in performance caused by recombination at the surface of the nanowires and at p-n junctions. Here, we fabricate core-shell nanowire solar cells with open-circuit voltage and fill factor values superior to those reported for equivalent planar cells, and an energy conversion efficiency of ∼5.4%, which is comparable to that of equivalent planar cells despite low light absorption levels. The device is made using a low-temperature solution-based cation exchange reaction that creates a heteroepitaxial junction between a single-crystalline CdS core and single-crystalline Cu2S shell. We integrate multiple cells on single nanowires in both series and parallel configurations for high output voltages and currents, respectively. The ability to produce efficient nanowire-based solar cells with a solution-based process and Earth-abundant elements could significantly reduce fabrication costs relative to existing high-temperature bulk material approaches.

Solution-processed core-shell nanowires for efficient photovoltaic cells.

Gallium phosphide (GaP) nanowire photocathodes synthesized using a surfactant-free solution-liquid-solid (SLS) method were investigated for their photoelectrochemical evolution of hydrogen. Zinc as a p-type dopant was introduced into the nanowires during synthesis to optimize the photocathode's response. Investigation of the electrical properties of Zn-doped GaP nanowires confirmed their p-type conductivity. After optimization of the nanowire diameter and Zn doping concentration, higher absorbed photon-to-current efficiency (APCE) over the spectrum was achieved. The versatility of the SLS synthesis and the capability to control the electrical properties suggest that our approach could be generalized to other III-V and II-VI semiconductors.

Zn-doped p-type gallium phosphide nanowire photocathodes from a surfactant-free solution synthesis.

Artificial photosynthesis, the biomimetic approach to converting sunlight's energy directly into chemical fuels, aims to imitate nature by using an integrated system of nanostructures, each of which plays a specific role in the sunlight-to-fuel conversion process. Here we describe a fully integrated system of nanoscale photoelectrodes assembled from inorganic nanowires for direct solar water splitting. Similar to the photosynthetic system in a chloroplast, the artificial photosynthetic system comprises two semiconductor light absorbers with large surface area, an interfacial layer for charge transport, and spatially separated cocatalysts to facilitate the water reduction and oxidation. Under simulated sunlight, a 0.12% solar-to-fuel conversion efficiency is achieved, which is comparable to that of natural photosynthesis. The result demonstrates the possibility of integrating material components into a functional system that mimics the nanoscopic integration in chloroplasts. It also provides a conceptual blueprint of modular design that allows incorporation of newly discovered components for improved performance.

A fully integrated nanosystem of semiconductor nanowires for direct solar water splitting.

Block copolymer patterned holey silicon (HS) was successfully integrated into a microdevice for simultaneous measurements of Seebeck coefficient, electrical conductivity, and thermal conductivity of the same HS microribbon. These fully integrated HS microdevices provided excellent platforms for the systematic investigation of thermoelectric transport properties tailored by the dimensions of the periodic hole array, that is, neck and pitch size, and the doping concentrations. Specifically, thermoelectric transport properties of HS with a neck size in the range of 16-34 nm and a fixed pitch size of 60 nm were characterized, and a clear neck size dependency was shown in the doping range of 3.1 × 10(18) to 6.5 × 10(19) cm(-3). At 300 K, thermal conductivity as low as 1.8 ± 0.2 W/mK was found in HS with a neck size of 16 nm, while optimized zT values were shown in HS with a neck size of 24 nm. The controllable effects of holey array dimensions and doping concentrations on HS thermoelectric performance could aid in improving the understanding of the phonon scattering process in a holey structure and also in facilitating the development of silicon-based thermoelectric devices.

Simultaneous Thermoelectric Property Measurement and Incoherent Phonon Transport in Holey Silicon.

Photoelectrochemistry is one of several promising approaches for the realization of efficient solar-to-fuel conversion. Recent work has shown that photoelectrodes made of semiconductor nano-/microwire arrays can have better photoelectrochemical performance than their planar counterparts because of their unique properties, such as high surface area. Although considerable research effort has focused on studying wire arrays, the inhomogeneity in the geometry, doping, defects and catalyst loading present in such arrays can obscure the link between these properties and the photoelectrochemical performance of the wires, and correlating performance with the specific properties of individual wires is difficult because of ensemble averaging. Here, we show that a single-nanowire-based photoelectrode platform can be used to reliably probe the current-voltage (I-V) characteristics of individual nanowires. We find that the photovoltage output of ensemble array samples can be limited by poorly performing individual wires, which highlights the importance of improving nanowire homogeneity within an array. Furthermore, the platform allows the flux of photogenerated electrons to be quantified as a function of the lengths and diameters of individual nanowires, and we find that the flux over the entire nanowire surface (7-30 electrons nm(-2) s(-1)) is significantly reduced as compared with that of a planar analogue (∼1,200 electrons nm(-2) s(-1)). Such characterization of the photogenerated carrier flux at the semiconductor/electrolyte interface is essential for designing nanowire photoelectrodes that match the activity of their loaded electrocatalysts.

Single-nanowire photoelectrochemistry.

A new structure of flexible transparent electrodes is reported, featuring a metal mesh fully embedded and mechanically anchored in a flexible substrate, and a cost-effective solution-based fabrication strategy for this new transparent electrode. The embedded nature of the metal-mesh electrodes provides a series of advantages, including surface smoothness that is crucial for device fabrication, mechanical stability under high bending stress, strong adhesion to the substrate with excellent flexibility, and favorable resistance against moisture, oxygen, and chemicals. The novel fabrication process replaces vacuum-based metal deposition with an electrodeposition process and is potentially suitable for high-throughput, large-volume, and low-cost production. In particular, this strategy enables fabrication of a high-aspect-ratio (thickness to linewidth) metal mesh, substantially improving conductivity without considerably sacrificing transparency. Various prototype flexible transparent electrodes are demonstrated with transmittance higher than 90% and sheet resistance below 1 ohm sq(-1) , as well as extremely high figures of merit up to 1.5 × 10(4) , which are among the highest reported values in recent studies. Finally using our embedded metal-mesh electrode, a flexible transparent thin-film heater is demonstrated with a low power density requirement, rapid response time, and a low operating voltage.

High-Performance Flexible Transparent Electrode with an Embedded Metal Mesh Fabricated by Cost-Effective Solution Process.

Phototaxis is commonly observed in motile photosynthetic microorganisms. For example, green algae are capable of swimming towards a light source (positive phototaxis) to receive more energy for photosynthesis, or away from a light source (negative phototaxis) to avoid radiation damage or to hide from predators. Recently, with the aim of applying nanoscale machinery to biomedical applications, various inorganic nanomotors based on different propulsion mechanisms have been demonstrated. The only method to control the direction of motion of these self-propelled micro/nanomotors is to incorporate a ferromagnetic material into their structure and use an external magnetic field for steering. Here, we show an artificial microswimmer that can sense and orient to the illumination direction of an external light source. Our microswimmer is a Janus nanotree containing a nanostructured photocathode and photoanode at opposite ends that release cations and anions, respectively, propelling the microswimmer by self-electrophoresis. Using chemical modifications, we can control the zeta potential of the photoanode and program the microswimmer to exhibit either positive or negative phototaxis. Finally, we show that a school of microswimmers mimics the collective phototactic behaviour of green algae in solution.

Programmable artificial phototactic microswimmer.

Applications of graphitic carbon nitride (g-CN) in photoelectrochemical and optoelectronic devices are still hindered due to the difficulties in synthesis of g-CN films with tunable chemical, physical and catalytic properties. Herein we present a general method to alter the electronic and photoelectrochemical properties of g-CN films by annealing. We found that N atoms can be removed from the g-CN networks after annealing treatment. Assisted by theoretical calculations, we confirm that upon appropriate N removal, the adjacent C atoms will form new C=C π bonds. Detailed calculations demonstrate that the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are located at the structure unit with C=C π bonds and the electrons are more delocalized. Valence band X-ray photoelectron spectroscopy spectra together with optical absorption spectra unveil that the structure changes result in the alteration of the g-CN energy levels and position of band edges. Our results show that the photocurrent density of the annealed g-CN film is doubled compared with the pristine one, thanks to the better charge separation and transport within the film induced by the new C=C π bonds. An ultrathin TiO2 film (2.2 nm) is further deposited on the g-CN film as stabilizer and the photocurrent density is kept at 0.05 mA cm(-2) at 1.23 V versus reversible hydrogen electrode after two-cycle stability assessment. This work enables the applications of g-CN films in many electronic and optoelectronic devices.

C=C π Bond Modified Graphitic Carbon Nitride Films for Enhanced Photoelectrochemical Cell Performance.

Over the last decades, scientists have endeavored to develop nanoscopic machines and envisioned that these tiny machines could be exploited in biomedical applications and novel material fabrication. Here, a visible-/near-infrared light-driven nanomotor based on a single silicon nanowire is reported. The silicon nanomotor harvests energy from light and propels itself by the self-electrophoresis mechanism. Due to the high efficiency, the silicon nanowire can be readily driven by visible and near-infrared illumination at ultralow light intensity (≈3 mW cm(-2) ). The experimental study and numerical simulation also show that the detailed structure around the concentrated reaction center determines the migration behavior of the nanomotor. Importantly, due to the optical resonance inside the silicon nanowire, the spectral response of the nanowire-based nanomotor can be readily modulated by the nanowire's diameter. Compared to other methods, light controlling potentially offers more freedom and flexibility, as light can be modulated not only with its intensity and direction, but also with the frequency and polarities. This nanowire motor demonstrates a step forward to harness the advantages of light, which opens up new opportunities for the realization of many novel functions such as multiple channels communication to nanorobots and controllable self-assembly.

Article	Year
An integrated logic circuit assembled on a single carbon nanotube. Science (New York, N.Y.)\| PubMed ID: 16556834	2006
Chemoresponsive monolayer transistors. Proceedings of the National Academy of Sciences of the United States of America\| PubMed ID: 16855049	2006
Transferring self-assembled, nanoscale cables into electrical devices. Journal of the American Chemical Society\| PubMed ID: 16910663	2006
Encoding molecular-wire formation within nanoscale sockets. Angewandte Chemie (International ed. in English)\| PubMed ID: 17342783	2007
Translocation of single-stranded DNA through single-walled carbon nanotubes. Science (New York, N.Y.)\| PubMed ID: 20044570	2010
Holey silicon as an efficient thermoelectric material. Nano letters\| PubMed ID: 20839780	2010
Electronic sensitivity of carbon nanotubes to internal water wetting. ACS nano\| PubMed ID: 21452854	2011
Solution-processed core-shell nanowires for efficient photovoltaic cells. Nature nanotechnology\| PubMed ID: 21857684	2011
Zn-doped p-type gallium phosphide nanowire photocathodes from a surfactant-free solution synthesis. Nano letters\| PubMed ID: 23025657	2012
A fully integrated nanosystem of semiconductor nanowires for direct solar water splitting. Nano letters\| PubMed ID: 23647159	2013
Simultaneous Thermoelectric Property Measurement and Incoherent Phonon Transport in Holey Silicon. ACS nano\| PubMed ID: 26650117	2016
Single-nanowire photoelectrochemistry. Nature nanotechnology\| PubMed ID: 27018660	2016
High-Performance Flexible Transparent Electrode with an Embedded Metal Mesh Fabricated by Cost-Effective Solution Process. Small (Weinheim an der Bergstrasse, Germany)\| PubMed ID: 27027390	2016
Programmable artificial phototactic microswimmer. Nature nanotechnology\| PubMed ID: 27749832	2016
C=C π Bond Modified Graphitic Carbon Nitride Films for Enhanced Photoelectrochemical Cell Performance. Chemistry, an Asian journal\| PubMed ID: 28272782	2017
A Silicon Nanowire as a Spectrally Tunable Light-Driven Nanomotor. Advanced materials (Deerfield Beach, Fla.)\| PubMed ID: 28599059	2017

Jinyao Tang

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