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.

Preparation of multilayer periodic nanopatterned WO3-based photoanode by reverse nanoimprinting for water splitting.

Photoelectrochemical (PEC) water splitting has been studied extensively as an environmentally friendly technology for hydrogen production using solar energy. WO3is considered a promising semiconducting material for photoanodes due to its high electron mobility, good hole diffusion length, and chemical stability. Periodic nanostructures of WO3have been investigated for enhancing the PEC performance of WO3-based photoanodes. In this study, facile fabrication of periodic nanostructures of WO3was achieved using reverse nanoimprint lithography, and the multilayer stacking of nanopatterned WO3film was also confirmed. The multilayer nanopatterned WO3films were used as photoanodes for PEC water splitting. The performance of the fabricated photoanode in PEC was 2 times higher than that of planar WO3film due to its higher light absorbance and lower charge transfer resistance.

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.

Scalable and enhanced triboelectric output power generation by surface functionalized nanoimprint patterns.

We report nanoimprint lithographic submicron surface patterning for scalable output power generation and performance enhancement in triboelectric nanogenerators (TENGs). Specifically, one contact surface of a TENG is nanoimprinted with polyurethane acrylate (PUA) lines in different pitches and the counter contact surface is coated with perfluoropolyether (PFPE). The results show that a TENG with 200 nm pitch PUA lines exhibits voltage and current up to ∼430 V and ∼55 µA cm(-2), generating about a sixfold higher output power than that with a flat PUA surface at an applied force of 0.3 MPa. In addition, scalable output power was obtained by adjusting line pitches. Further enhancement in output power was also demonstrated by chemically functionalizing the PUA line patterns with poly (diallyldimethylammonium chloride) (PDDA). The PDDA functionalization boosted voltage and current up to ∼500 V and ∼100 µA cm(-2), respectively, which corresponds to ∼50% power density enhancement. The approach introduced here is a simple, effective, scalable and reproducible way to fabricate TENGs.

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.

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.

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.

Solvent-assisted optimal BaTiO3 nanoparticles-polymer composite cluster formation for high performance piezoelectric nanogenerators.

We report on an optimal BaTiO3-P(VDF-HFP) composite thin-film formation process for high performance piezoelectric nanogenerators (NGs). By examining different solvent ratios in a solvent-assisted composite thin film formation process, the BTO nanoparticle (NPs) clustering and related performance enhancements were carefully investigated. Using the optimal process, the fabricated BTO NGs exhibited an excelling output power performance. Under a compressive force of ∼0.23 MPa normal to the surface, the measured open-circuit output voltage and short-circuit current were over 110 V and 22 µA, respectively, with a corresponding peak output power density of 0.48 Wcm(-3). Our results clearly demonstrate the effectiveness of a solvent-assisted BTO cluster formation process for fabricating high performance piezoelectric energy harvesting devices.

Wavelength-selective infrared Salisbury screen absorber.

Experimental long wavelength infrared spectral response characterization of a narrowband Salisbury screen absorber suitable for use in microbolometer focal plane arrays is presented. We have demonstrated a microfabricated germanium dielectric support structure layer that replaces the usual silicon nitride structural layer in microbolometers. The fabricated Salisbury screen absorber consists of a chromium resistive sheet as an absorber layer above a germanium dielectric/air-gap/interference structure. In order to produce wavelength-selective narrowband absorption, the general design rules for the germanium dielectric supported Salisbury screen show that the thickness of the air gap should be a half wavelength thick and the optical thickness of the germanium layer a quarter dielectric wavelength thick.

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.

Multiple-Route Exciton Recombination Dynamics and Improved Stability of Perovskite Quantum Dots by Plasmonic Photonic Crystal.

We have studied the excited-state exciton recombination dynamics of perovskite quantum dots (QDs) through time-resolved photoluminescence (PL), PL blinking, PL intensity-dependent lifetime modulation, and long-term photostability tests. The various spectroscopic characterizations elucidate that the perovskite QDs have multiple intrinsic exciton recombination routes even in a single QD, i.e., exciton, biexciton, and positive/negative trions, which are dissimilarly contributed to ON and OFF state emissions. We also find that the enhanced radiative recombination from placing green QDs on a photonic Ag nanotip array induces notably improved long-term PL stability. We consider that the accelerated radiative recombination of QDs by strong coupling with the plasmonics of the photonic Ag nanotip array, while eliminating nonradiative pathways, is proven to be a critical factor for improved long-term stability.

Functional Asymmetry-Enabled Self-Adhesive Film via Phase Separation of Binary Polymer Mixtures for Soft Bio-Integrated Electronics.

Biocompatible adhesive films are important for many applications (e.g., wearable devices, implantable devices, and attachable sensors). In particular, achieving self-adhesion on one side of a film with biocompatible materials is a compelling goal in adhesion science. Herein, we report a simple and easy manufacturing process using water-soluble hyaluronic acid (HA) that allows adhesiveness on only one side using binary polymer mixtures based on a phase-separation strategy with an elastomer. HA influx allows for the entangled polymer chains of the elastomer to spontaneously deform, permitting tunable mechanical elasticity, conformability, and adhesion. The proposed adhesive film enables the transfer of nanopatterning and the attachment of various surfaces without the use of additional chemicals. In addition, the film can be used for measuring epidermal biopotential and for skin fixation of drug devices. Therefore, the developed facile asymmetric adhesion can block the interferences of other materials on the unnecessary adhesion side, providing considerable potential for the development of functional, multifunctional, and smart bioadhesives.

Ultrasensitive Molecule Detection Based on Infrared Metamaterial Absorber with Vertical Nanogap.

Surface-enhanced infrared absorption (SEIRA) spectroscopy is a powerful methodology for sensing and identifying small quantities of analyte molecules via coupling between molecular vibrations and an enhanced near-field induced in engineered structures. A metamaterial absorber (MA) is proposed as an efficient SEIRA platform; however, its efficiency is limited because it requires the appropriate insulator thickness and has a limited accessible area for sensing. SEIRA spectroscopy is proposed using an MA with a 10 nm thick vertical nanogap, and a record-high reflection difference SEIRA signal of 36% is experimentally achieved using a 1-octadecanethiol monolayer target molecule. Theoretical and experimental comparative studies are conducted using MAs with three different vertical nanogaps. The MAs with a vertical nanogap are processed using nanoimprint lithography and isotropic dry etching, which allow cost-effective large-area patterning and mass production. The proposed structure may provide promising routes for ultrasensitive sensing and detection applications.

Fano Metamaterials on Nanopedestals for Plasmon-Enhanced Infrared Spectroscopy.

We report a sensing platform for surface-enhanced infrared absorption (SEIRA) spectroscopy, based on Fano metamaterials (FMMs) on dielectric nanopedestals. FMMs consist of two parallel gold (Au) nanorod antennas, with a small horizontal coupler attached to one of the nanorod antenna. When placed on SiO2 dielectric nanopedestals, which exhibit strong field enhancements caused by the interference between subradiant and superradiant plasmonic resonances, they provide the highly enhanced E-field intensities formed near the Au nanoantenna, which can provide more enhanced molecular detection signals. Here, the sensing characteristics of FMMs on nanopedestals structure was confirmed by comparison with FMMs on an unetched SiO2 substrate as a control sample. The control FMMs and the FMMs on nanopedestals were carefully designed to excite Fano resonance near the target 1-octadecanethiol (ODT) fingerprint vibrations. The FMMs were fabricated by using nanoimprint lithography and the nanopedestal structures were formed by isotropic dry-etching. The experimental reflection spectra containing the enhanced absorption signals of the ODT monolayer molecules was analyzed using temporal coupled-mode theory. The FMMs on nanopedestals achieved over 7% of reflection difference signal, which was 1.7 times higher signal than the one from the control FMMs. Based on the FMMs on nanopedestal structures proposed in this study, it may be widely applied to future spectroscopy and sensor applications requiring ultrasensitive detection capability.

An ultraviolet and electric field activated photopolymer-ferroelectric nanoparticle composite for the performance enhancement of triboelectric nanogenerators.

For the development of high performance triboelectric generators (TENGs), it is required to have facile methods to adjust the triboelectric properties of the friction surfaces. In this work, we present the surface charge density modulation of the photopolymer-ferroelectric nanoparticle composite surface by applying ultraviolet (UV) and electric field. By using the photopolymer, the triboelectric surface property was modulated by exposure to UV. In addition, lithographic surface patterning can be easily adopted to enlarge the frictional surface area as well. Furthermore, the use of the PP allows a facile integration of ferroelectric nanoparticles (NPs) in the form of a nanocomposite structure, which can effectively increase the surface charge density by spontaneous dipole coupling of NPs embedded in the PP layer. As a result, approximately 4-fold higher output power has been achieved by applying this approach. The developed TENGs have also demonstrated superior mechanical durability, generating consistent outputs during 104 cyclic frictional contacts. The approach proposed here is a simple and reliable way to enhance the output performance of TENGs.

Microneedles integrated with a triboelectric nanogenerator: an electrically active drug delivery system.

In this study, a combined system of microneedles and a triboelectric nanogenerator (TENG) has been developed for drug delivery. A triboelectric device, which converts mechanical energy into alternating current (AC), was chosen to replace the electrophoresis (EP) effect. To directly generate triboelectricity from salmon deoxyribonucleic acid (SDNA)-based microneedles, a triboelectric series of SDNA film and chargeable polymers (polyimide and Teflon) was studied. The electrical output of the two charged polymers was compared to find a material that could be highly charged with SDNA. The electrical output was also compared as a function of the concentration of a drug embedded in the SDNA film, and the results confirmed that drug intercalation affected the carrier diffusion. The mechanical strength of the microneedles was assessed by histological analysis of their penetration into porcine cadaver skin. Furthermore, the output voltage of a system incorporating microneedles and TENG in cadaver skin, and in vitro drug release into gelatin were evaluated to examine potential application as an electrically active drug delivery system. The electrical output voltage of this system was ∼95 V. The mechanism of triboelectric perturbation to the skin has also been discussed. The system developed in this work is a new, facile approach toward effective drug delivery that replaces the existing EP method and expands the application of TENGs.

Ferroelectric Zinc Oxide Nanowire Embedded Flexible Sensor for Motion and Temperature Sensing.

We report a simple method to realize multifunctional flexible motion sensor using ferroelectric lithium-doped ZnO-PDMS. The ferroelectric layer enables piezoelectric dynamic sensing and provides additional motion information to more precisely discriminate different motions. The PEDOT:PSS-functionalized AgNWs, working as electrode layers for the piezoelectric sensing layer, resistively detect a change of both movement or temperature. Thus, through the optimal integration of both elements, the sensing limit, accuracy, and functionality can be further expanded. The method introduced here is a simple and effective route to realize a high-performance flexible motion sensor with integrated multifunctionalities.

Flexible Plasmonic Color Filters Fabricated via Nanotransfer Printing with Nanoimprint-Based Planarization.

We investigated the preparation and performance of large-area transmission-type flexible plasmonic color filters (PCFs). These large-area PCFs were fabricated based on a nanotransfer printing (nTP) process that involves nanoimprint-based planarization. This process is a simple surface treatment for easy transfer of a metal to a flexible plastic substrate and formation of patterned aluminum nanodots and nanoholes on a substrate surface with poor roughness. Rabbit-ear structures can form during the nTP process, and this phenomenon was analyzed by numerical simulation. As defects were not detected in a 10 000-round bending test, the PCFs fabricated using this nTP process have excellent mechanical properties.

Three-dimensional plasmonic Ag/TiO2 nanocomposite architectures on flexible substrates for visible-light photocatalytic activity.

In this study, a periodic three-dimensional (3D) Ag/TiO2 nanocomposite architecture of nanowires was fabricated on a flexible substrate to enhance the plasmonic photocatalytic activity of the composite. Layer-by-layer nanofabrication based on nanoimprint lithography, vertical e-beam evaporation, nanotransfer, and nanowelding was applied in a new method to create different 3D Ag/TiO2 nanocomposite architectures. The fabricated samples were characterized by scanning electron microscopy, transmission electron microscopy, focused ion-beam imaging, X-ray photoelectron spectrometry, and UV-visible spectroscopy. The experiment indicated that the 3D nanocomposite architectures could effectively enhance photocatalytic activity in the degradation of methylene blue solution under visible light irradiation. We believe that our method is efficient and stable, which could be applied to various fields, including photocatalysis, solar energy conversion, and biotechnology.

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.