Highly sensitive and label-free protein immunoassay-based biosensor comprising infrared metamaterial absorber inducing strong coupling.

A mid-infrared label-free immunoassay-based biosensor is an effective device to help identify and quantify biomolecules. This biosensor employs a surface-enhanced infrared absorption spectroscopy, which is a highly potent sensing technique for detecting minute quantities of analytes. In this study, a biosensor was constructed using a metamaterial absorber, which facilitated strong coupling effects. For maximum coupling effect, it is necessary to enhance the near-field intensity and the spatial and spectral overlap between the optical cavity resonance and the vibrational mode of the analyte. Due to significant peak splitting, conventional baseline correction methods fail to adequately analyze such a coupling system. Therefore, we employed a coupled harmonic oscillation model to analyze the spectral distortion resulting from the peak splitting induced by the strong coupling effect. The proposed biosensor with a thrombin-binding aptamer-based immunoassay could achieve a limit of detection of 267.4 pM, paving the way for more efficient protein detection in clinical practice.

Synergistically designed antireflective cover for improving wide-angle photovoltaic efficiencies.

We demonstrated that a well-designed nanopatterned cover improves photovoltaic efficiency across a wide range of incident angles (θ). A nanopatterned cover was created using an integrated ray-wave optics simulation to maximize the light absorption of the surface-textured Si photovoltaic device. A hexagonally arranged nanocone array with a 300 nm pitch was formed into a polymer using nanoimprinting, and the nanostructured polymer was then attached to a glass cover with an index-matching adhesive. Angle-resolved current density-voltage measurements on Si photovoltaic devices showed that the nanopatterned glass cover yielded a 2-13% enhancement in power conversion efficiency at θ = 0-60°, which accounted for its broadband antireflective feature. We performed all-season-perspective simulations based on the results of the integrated ray-wave optics simulations and solar altitude database of South Korea, which validated the sustainability of the developed nanopatterned cover during significant seasonal fluctuations.

Enhancement of refractive index sensing for an infrared plasmonic metamaterial absorber with a nanogap.

An infrared plasmonic metamaterial absorber with a nanogap was numerically and experimentally investigated as a refractive index sensor. We experimentally demonstrated large enhancements of both sensitivity (approximately 1091 nm/refractive index unit) and figure of merit (FOM*; approximately 273) owing to the nanogap formation in the metamaterial absorber to achieve perfect absorption (99%). The refractive index sensing platform was fabricated by producible nanoimprint lithography and isotropic dry etching processes to have a large area and low cost while providing a practical solution for high-performance plasmonic biosensors.

Quasi-3D Plasmonic Nanowell Array for Molecular Enrichment and SERS-Based Detection.

We report on a quasi-three-dimensional (3D) plasmonic nanowell array with high structural uniformity for molecular detection. The quasi-3D plasmonic nanowell array was composed of periodic hexagonal Au nanowells whose surface is densely covered with gold nanoparticles (Au NPs), separated by an ultrathin dielectric interlayer. The uniform array of the Au nanowells was fabricated by nanoimprint lithography and deposition of Au thin film. A self-assembled monolayer (SAM) of perfluorodecanethiol (PFDT) was coated on the Au surface, on which Au was further deposited. Interestingly, the PFDT-coated Au nanowells were fully covered with Au NPs with an ultra-high density of 375 µm-2 rather than a smooth film due to the anti-wetting property of the low-energy surface. The plasmonic nanogaps formed among the high-density Au NPs led to a strong near-field enhancement via coupled localized surface plasmon resonance and produced a uniform surface-enhanced Raman spectroscopy (SERS) response with a small relative standard deviation of 5.3%. Importantly, the highly uniform nanostructure, featured by the nanoimprint lithography and 3D growth of densely-packed Au NPs, minimizes the spatial variation of Raman intensity, potentially providing quantitative analysis. Moreover, analyte molecules were highly concentrated and selectively deposited in nanowells when a water droplet containing the analyte was evaporated on the plasmonic substrate. The analyte formed a relatively thick overcoat in the nanowells near the triple line due to the coffee-ring effects. Combining 3D plasmonic nanowell substrates with molecular enrichments, highly sensitive detection of lactic acid was demonstrated. Given its combination of high sensitivity and signal uniformity, the quasi-3D plasmonic nanowell substrate is expected to provide a superior molecular detection platform for biosensing applications.

Optical Tunneling Mediated Sub-Skin-Depth High Emissivity Tungsten Radiators.

Tailoring the spectrum of thermal radiation at high temperatures is a central issue in the study of thermal radiation harnessed energy resources. Although bulk metals with periodic cavities incorporated into their surfaces provide high emissivity, they require a complicated micron metal etch, thereby precluding reliable, continuous operation. Here, we report thermally stable, highly emissive, ultrathin (<20 nm) tungsten (W) radiators that were prepared in a scalable and cost-effective route. Alumina/W/alumina multiwalled, submicron cavity arrays were fabricated sequentially using nanoimprinting lithography, thin film deposition, and calcination processes. To highlight the practical importance of high-temperature radiators, we developed a thermophotovoltaic (TPV) system equipped with fabricated W radiators and low-bandgap GaSb photovoltaic cells. The TPV system produced electric power reliably during repeated temperature cycling between 500 and 1200 K; the power density at 1200 K was fixed to be approximately 1.0 W/cm2. The temperature-dependent electric power was quantitatively reproduced using a one-dimensional energy conversion model. The symmetric configuration of alumina/W/alumina multiwall together with the presence of a void inside each cavity alleviated thermal stress, which was responsible for the stable TPV performance. The short-current-density (JSC) of developed TPV system was augmented significantly by decreasing the W thickness below its skin depth. A 17 nm thick W radiator yielded a 32% enhancement in JSC compared to a 123 nm thick W radiator. Electromagnetic analysis indicated that subskin-depth W cavity arrays led to suppressed surface reflection due to the mitigated screening effect of free electrons, thereby enhancing the absorption of light within each W wall. Such optical tunneling-mediated absorption or radiation was valid for any metal material and morphology (e.g., planar or patterned).

Dual nanotransfer printing for complementary plasmonic biosensors.

One of the main challenges in the widespread utilization of localized plasmon resonance-based biosensors is the fabrication of large-area and low-cost plasmonic nanostructures. In this work, we fabricated large-area and low-cost complementary plasmonic biosensors such as nanohole and nanodisk arrays using dual nanotransfer printing (NTP) with a single metal deposition and a single reusable mold. The suspended nanohole arrays and the suspended nanodisk arrays were fabricated using the subsequent dry etching process. We confirmed a maximum enhancement in bulk sensitivity in experiments and simulations by controlling the vertical and lateral etching depths of the dielectric layer underneath the gold (Au) nanohole and nanodisk arrays. Furthermore, we show that the surface sensitivity evaluated by atomic layer deposition of aluminum oxide increased because appropriate vertical and lateral etching depths allow the target analyte to access the additional near-field formed at the bottom of the Au nanostructure. The dual NTP method provides a practical solution for the realization of large-area and low-cost label-free plasmonic biosensing systems, with a reduction in complexity and cost of the fabrication process of complementary plasmonic structures and metasurfaces.

Spontaneous Additive Nanopatterning from Solution Route Using Selective Wetting.

Nanopatterns of functional materials have successfully led innovations in a wide range of fields, but further exploration of their full potential has often been limited because of complex and cost-inefficient patterning processes. We here propose an additive nanopatterning process of functional materials from solution route using selective wetting phenomenon. The proposed process can produce nanopatterns as narrow as 150 nm with high yield over large area at ultrahigh process speed, that is, the speed of solution dragging, of up to ca. 4.6 m·min-1. The process is highly versatile that it can utilize a wide range of solution materials, control vertical structures including pattern thickness and multistacks, and produce nanopatterns on various substrates with emerging form factors such as foldability and disposability. The solution patterning in nanoscale by selective wetting is enabled by corresponding surface energy patterns in high contrast that are achieved by one-step imprinting onto hydrophobic/hydrophilic bilayers. The mechanisms and control parameters for the solution patterning are revealed by fluid-dynamic simulation. With the aforementioned advantages, we demonstrate 25 400 pixel-per-inch light-emitting pixel arrays and a plasmonic color filter of 10 cm × 10 cm area on a plastic substrate as potential applications.

Shape-Controlled 3D Periodic Metal Nanostructures Fabricated via Nanowelding.

A novel method for fabricating 3D metallic nanostructures to be used in polarized color filters based on nanoimprint lithography, electron-beam evaporation, and nanowelding is proposed. The shape of the nanostructures can be controlled by adjusting the temperature for the nanowelding process. Ag nanowires deposited on polymer patterns are accumulated by the nanowelding process to build up diverse 3D nanostructures. The morphologies of the fabricated 3D nanostructures are analyzed using scanning electron microscopy, atomic force microscopy, and focused ion beam; the heating temperature is varied from 90 to 130 °C in steps of 10 °C. In order to analyze the recrystallization phenomenon after welding, transmission electron microscopy is utilized. The 3D metallic nanostructure has different morphologies and optical properties corresponding to welding temperature conditions and accumulated layer thicknesses. Based on preliminary experimental results, the process parameters are optimized and a polarized color filter is fabricated. Optical characteristics of the filter are evaluated using polarizer and spectrometer. Through this work, it is shown that the proposed method is an effective way to realize various 3D metallic nanostructures for special optical properties, therefore the method based on nanowelding can be utilized in fabrication of functional metamaterials, optical filters, biosensors, and others.

Covalent bonding-assisted nanotransfer lithography for the fabrication of plasmonic nano-optical elements.

Many high-resolution patterning techniques have been developed to realize nano- and microscale applications of electric devices, sensors, and transistors. However, conventional patterning methods based on photo or e-beam lithography are not employed to fabricate optical elements of high aspect ratio and a sub-100 nm scale due to the limit of resolution, high costs and low throughput. In this study, covalent bonding-assisted nanotransfer lithography (CBNL) was proposed to fabricate various structures of high resolution and high aspect ratio at low cost by a robust and fast chemical reaction. The proposed process is based on the formation of covalent bonds between silicon of adhesive layers on a substrate and oxygen of the deposited material on the polymer stamp. The covalent bond is strong enough to detach multiple layers from the stamp for a large area without defects. The obtained nanostructures can be used for direct application or as a hard mask for etching. Two nano-optical applications were demonstrated in this study, i.e., a meta-surface and a wire-grid polarizer. A perfect absorption meta-surface was generated by transferring subwavelength hole arrays onto a substrate without any post-processing procedures. In addition, a wire-grid polarizer with high aspect ratio (1 : 3) and 50 nm line width was prepared by the nano-transfer of materials, which were used as a hard mask for etching. Therefore, CBNL provides a means of achieving large-area nano-optical elements with a simple roll-to-plate process at low cost.

Infrared broadband metasurface absorber for reducing the thermal mass of a microbolometer.

We demonstrate an infrared broadband metasurface absorber that is suitable for increasing the response speed of a microbolometer by reducing its thermal mass. A large fraction of holes are made in a periodic pattern on a thin lossy metal layer characterised with a non-dispersive effective surface impedance. This can be used as a non-resonant metasurface that can be integrated with a Salisbury screen absorber to construct an absorbing membrane for a microbolometer that can significantly reduce the thermal mass while maintaining high infrared broadband absorption in the long wavelength infrared (LWIR) band. The non-dispersive effective surface impedance can be matched to the free space by optimising the surface resistance of the thin lossy metal layer depending on the size of the patterned holes by using a dc approximation method. In experiments a high broadband absorption was maintained even when the fill factor of the absorbing area was reduced to 28% (hole area: 72%), and it was theoretically maintained even when the fill factor of the absorbing area was reduced to 19% (hole area: 81%). Therefore, a metasurface with a non-dispersive effective surface impedance is a promising solution for reducing the thermal mass of infrared microbolometer pixels.

Fabrication of high aspect ratio nanogrid transparent electrodes via capillary assembly of Ag nanoparticles.

In this report, we describe the fabrication of periodic Ag nanogrid electrodes by capillary assembly of silver nanoparticles (AgNPs) along patterned nanogrid templates. By assembling the AgNPs into these high-aspect-ratio nanogrid patterns, we can obtain high-aspect-ratio nanogratings, which can overcome the inherent trade-off between the optical transmittance and the sheet resistance of transparent electrodes. The junction resistance between the AgNPs is effectively reduced by photochemical welding and post-annealing. The fabricated high-aspect-ratio nanogrid structure with a line width of 150 nm and a height of 450 nm has a sheet resistance of 15.2 Ω sq(-1) and an optical transmittance of 85.4%.

Controlled Patterning of Vertical Silicon Structures Using Polymer Lithography and Wet Chemical Etching.

In order to improve their performance for various applications, a facile method for the wafer-scale fabrication of micro/nano-patterned vertical silicon (Si) structures such as silicon nanowires (SiNWs), silicon nanorods (SiNRs), and porous silicon (p-Si) was developed. The method is based on the combination of lithography techniques (photolithography, thermal nano-imprint lithography, nanosphere lithography) and wet chemical etching (electro-chemical etching, metal-assisted chemical etching) processes. Micro-patterned p-Si with various pore diameters from 30 nm to 1.2 um were fabricated via electro-chemical etching. Micro/nano-patterned Si microstructures, nanorods, and nanowires were also successfully fabricated by changing the thickness of the metal layer of 5 nm or 20 nm in the metal-assisted chemical etching process. This study also investigated the effect of the etching time and patterning on the etched SiNWs length. This method provides advantages of simplicity, speed, large-scale production, easy size and shape manipulation, and low cost.

A facile patterning of silver nanowires using a magnetic printing method.

Patterning of metal nanowires (NWs) is vital for the fabrication of NW-based, high-performance devices such as sensors, transparent conducting electrodes, and optoelectronics. However, the majority of existing patterning methods require complex and expensive technologies. For this reason, we report for the first time a facile and quick patterning method of silver (Ag) NWs using a magnetic printing method. We successfully demonstrated a patterned AgNW grid structure ona flexible substrate as transparent electrodes. The flexible AgNW grid electrode exhibited optical and electrical properties comparable to those of commercial transparent conducting electrodes.We believe our work will be broadly applicable to other NW-based devices such as sensors,energy storage devices, meta devices, nanoscale electronics, and optoelectronics.

13.2% efficiency Si nanowire/PEDOT:PSS hybrid solar cell using a transfer-imprinted Au mesh electrode.

In recent years, inorganic/organic hybrid solar cell concept has received growing attention for alternative energy solution because of the potential for facile and low-cost fabrication and high efficiency. Here, we report highly efficient hybrid solar cells based on silicon nanowires (SiNWs) and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) ( PEDOT: PSS) using transfer-imprinted metal mesh front electrodes. Such a structure increases the optical absorption and shortens the carrier transport distance, thus, it greatly increases the charge carrier collection efficiency. Compared with hybrid cells formed using indium tin oxide (ITO) electrodes, we find an increase in power conversion efficiency from 5.95% to 13.2%, which is attributed to improvements in both the electrical and optical properties of the Au mesh electrode. Our fabrication strategy for metal mesh electrode is suitable for the large-scale fabrication of flexible transparent electrodes, paving the way towards low-cost, high-efficiency, flexible solar cells.

Rapid Low-Temperature 3D Integration of Silicon Nanowires on Flexible Substrates.

The vertical integration of 1D nanostructures onto the 2D substrates has the potential to offer significant performance gains to flexible electronic devices due to high integration density, large surface area, and improved light absorption and trapping. A simple, rapid, and low temperature transfer bonding method has been developed for this purpose. Ultrasonic vibration is used to achieve a low temperature bonding within a few seconds, resulting in a polymer-matrix-free, electrically conducting vertical assembly of silicon nanowires (SiNWs) with a graphene/PET substrate. The microscopic structure, and mechanical and electrical characteristics of the interface between the transferred SiNW array and graphene layer are subsequently investigated, revealing that this creates a mechanically robust and electrically Ohmic contact. This newly developed ultrasonic transfer bonding technique is also found to be readily adaptable for diverse substrates of both metal and polymer. It is therefore considered as a valuable technique for integrating 1D vertical nanostructures onto the 2D flexible substrates for flexible photovoltaics, energy storage, and water splitting systems.

Interior-architectured ZnO nanostructure for enhanced electrical conductivity via stepwise fabrication process.

Fabrication of ZnO nanostructure via direct patterning based on sol-gel process has advantages of low-cost, vacuum-free, and rapid process and producibility on flexible or non-uniform substrates. Recently, it has been applied in light-emitting devices and advanced nanopatterning. However, application as an electrically conducting layer processed at low temperature has been limited by its high resistivity due to interior structure. In this paper, we report interior-architecturing of sol-gel-based ZnO nanostructure for the enhanced electrical conductivity. Stepwise fabrication process combining the nanoimprint lithography (NIL) process with an additional growth process was newly applied. Changes in morphology, interior structure, and electrical characteristics of the fabricated ZnO nanolines were analyzed. It was shown that filling structural voids in ZnO nanolines with nanocrystalline ZnO contributed to reducing electrical resistivity. Both rigid and flexible substrates were adopted for the device implementation, and the robustness of ZnO nanostructure on flexible substrate was verified. Interior-architecturing of ZnO nanostructure lends itself well to the tunability of morphological, electrical, and optical characteristics of nanopatterned inorganic materials with the large-area, low-cost, and low-temperature producibility.

Enhanced performance and stability of polymer BHJ photovoltaic devices from dry transfer of PEDOT:PSS.

Polymer solar cells with enhanced initial cell performances and long-term stability were fabricated by performing a simple dry transfer of a hole extraction layer [poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)] onto an indium tin oxide (ITO) substrate. Due to the very flat surface of the polyurethane acrylate/polycarbonate (PUA/PC) film, which was used as a mold and resembled the surface of the original substrate (silicon wafer), the transferred layer had a very smooth surface morphology, resulting in enhancement of the interfacial characteristics. The work function of the PEDOT:PSS layer and the morphology of bulk hetero junction (BHJ) layer were tuned by controlling the position of PSS enrichment in the PEDOT:PSS layer using the dry transfer. The power conversion efficiency of PTB7:PC71 BM BHJ device prepared by the dry transfer was 8.06%, which was significantly higher than that of the spin-cast device (7.32%). By avoiding direct contact between the ITO substrate and the PEDOT:PSS solution in the dry transfer system, etching and diffusion of indium in the ITO substrate were greatly reduced, thereby improving the stability.

High-durable AgNi nanomesh film for a transparent conducting electrode.

Uniform metal nanomesh structures are promising candidates that may replace of indium-tin oxide (ITO) in transparent conducting electrodes (TCEs). However, the durability of the uniform metal mesh has not yet been studied. For this reason, a comparative analysis of the durability of TCEs based on pure Ag and AgNi nanomesh, which are fabricated by using simple transfer printing, is performed. The AgNi nanomesh shows high long-term stability to oxidation, heat, and chemicals compared with that of pure Ag nanomesh. This is because of nickel in the AgNi nanomesh. Furthermore, the AgNi nanomesh shows strong adhesion to a transparent substrate and good stability after repeated bending.

Polymer-free Vertical Transfer of Silicon Nanowires and their Application to Energy Storage.

Silicon nanowires (SiNWs) for use as lithium-ion battery (LIB) anode materials have been studied for their one-dimensional (1D) properties and ability to accommodate large volume changes and avoid rapid capacity fading during cycling. Although the vertical transfer of SiNWs from their original substrate onto a conducting electrode is very important, to date, there has been no report of a direct integration method without polymer binders. Here, we propose for the first time a vertical transfer method for SiNWs grown on a Si substrate directly to the current-collecting electrode without using a polymer adhesive for the use as a binder-free LIB anode. The vertical SiNWs produced using a low-cost wafer-scale metal-assisted chemical etching (MaCE) process have been successfully transferred directly to a copper electrode coated with a thin Ag layer by using a simple hot pressing method. When evaluated as an LIB anode without using conventional polymeric binder and a conducting additive, the transferred vertically aligned SiNWs showed a high specific capacity (≈2150 mAh g(-1) ) and excellent rate performance. It is believed that the anode-manufacturing process is simple and fast, thus enabling a large-scale production that is of low-cost, broadly applicable, and provides new avenues for the rational engineering of Si-based electrode materials with enhanced power density and conductivity.

Highly robust silicon nanowire/graphene core-shell electrodes without polymeric binders.

A large theoretical charge storage capacity along with a low discharge working potential renders silicon a promising anode material for high energy density lithium ion batteries. However, up to 400% volume expansion during charge-discharge cycling coupled with a low intrinsic electronic conductivity causes pulverization and fracture, thus inhibiting silicon's widespread use in practical applications. We report herein on a low cost approach to fabricate hybrid silicon nanowire (SiNW)/graphene nanostructures that exhibit enhanced cycle performance with the capability of retaining more than 90% of their initial capacity after 50 cycles. We also demonstrate the use of hot-pressing in the absence of any common polymer binder such as PVDF to bind the hybrid structure to the current collector. The applied heat and pressure ensure strong adhesion between the SiNW/graphene nano-composite and current collector. This facile yet strong binding method is expected to find use in the further development of polymer-binder free anodes for lithium ion batteries.