Nanosphere Lithography Method Research Articles

(Invited) Plasmonic Nanofabrication of Chiral Nanodisk Ensembles

Chiral plasmonic nanostructures attract attention because those could be applied to enantioselective chemical sensors, optical isolators, light sources for circularly polarized light (CPL), metasurfaces, and metamaterials. In many cases, chiral plasmonic nanostructures are fabricated by a top-down method such as electron beam lithography (EBL). Since EBL is time-consuming and expensive, we have developed photoelectrochemical methods in which a site-selective reaction is driven by optical near field generated around anisotropic metal nanoparticles under right- or left-CPL. As anisotropic metal precursors for preparation of chiral nanoparticles, we have used gold or silver nanocuboids, nanorods, nanocubes, and triangular or hexagonal nanoplates so far.1-5 In the present work we demonstrate that laterally isotopic, circular nanodisks can also be used as precursors for the preparation of chiral nanostructures.We prepared ensembles of circular gold nanodisks on a glass plate by a nanosphere lithography method. A glass plate was coated with a gold thin film, and an array of polystyrene spheres (500 nm diameter) was prepared on the gold film. The polystyrene spheres were etched by oxygen plasma, and the exposed gold film was etched by argon ion milling. As a result, an ensemble of gold nanodisks (~200 nm diameter) was obtained. Each nanodisk was capped with a polystyrene cone, and the cap was removed by sonication in toluene if necessary. We used both capped and uncapped nanodisk ensembles. The ensemble was irradiated with visible right- or left-CPL in the presence of silver ions and sodium citrate. The obtained Au-Ag nanostructures exhibited circular dichroism (CPL), indicating that the nanostructures have chirality. Initial deposition at arbitrary site may break the geometric symmetry, resulting in the growth into chiral structures. Saito, K.; Tatsuma, T. Nano Lett. 2018, 18, 3209–3212.Morisawa, K.; Ishida, T.; Tatsuma, T. ACS Nano 2020, 14, 3603–3609.Shimomura, K.; Nakane, Y.; Ishida, T.; Tatsuma, T. Appl. Phys. Lett. 2023, 122, 151109.Homma, T.; Sawada, N.; Ishida, T.; Tatsuma, T. ChemNanoMat 2023, 9, e202300096.Ishida, T.; Isawa, A.; Kuroki, S.; Kameoka, Y.; Tatsuma, T. Appl. Phys. Lett. 2023, 123, 061111.

Tunable polarization control with self-assembled arrays of anisotropic plasmonic coaxial nanocavities

Polarization control with nanostructures having a tunable design and allowing inexpensive large-scale fabrication is important for many nanophotonic applications. For this purpose, we developed and experimentally demonstrated nanostructured plasmonic surfaces based on hexagonal arrays of anisotropic coaxial nanocavities, which can be fabricated by a low-cost self-assembled nanosphere lithography method. Their high polarization sensitivity is achieved by engineering anisotropy of the coaxial nanocavities, while the optical response is enhanced by the excitation of surface plasmon resonances. Particularly, varying the geometrical parameters of the coaxial nanocavities, namely the height and tilt angle of their central core nanoellipsoids, the plasmonic resonance wavelengths as well as the polarization-selective behavior can be individually tuned in the entire visible and near-infrared spectral regions, which makes such nanostructures good candidates for the implementation of polarization-controlled optical switches and polarization-tunable filters. Moreover, the developed nanostructures demonstrate sensitivity up to 1335 nm/RIU in refractive index sensing.

Investigation of perfect narrow-band absorber in silicon nano hole array

In this paper, we proposed a triple layer structure consisting of the bottom silver layer, thin silicon oxide space layer, and ultrathin semiconductor silicon film with nano hole array achieving three absorption peaks with narrow band. The absorption spectrum can be easily controlled by adjusting the structural parameters including the radius and period of the nano hole array, and the maximal absorption can reach 99.0% and the narrowest full width of half maximum can reach about 6.5 nm in theory. We also clarified the physical mechanism of the proposed structure in details by finite-difference time-domain simulation, in which the three narrow band perfect adsorption peaks can be attributed to electric dipole resonance, magnetic dipole resonance and plasmonic resonance respectively. At the same time, we used a low-cost nanosphere lithography method to fabricate the proposed nano hole array in large area. In experiment, the absorption peak of the proposed triple layer structure can reach up to 98.3% and the narrowest full width of half maximum can reach up to about 10.1 nm. The highest quality factor Q can reach up to 98.4. This work can open a new avenue for high-quality factor narrow band perfect absorption using ultrathin semiconductor film and benefit for many fields such as infrared sensors, plasmonic filters, and hyperspectral imaging.

Investigation of Photonic-Crystal-Structured p-GaN Nanorods Fabricated by Polystyrene Nanosphere Lithography Method to Improve the Light Extraction Efficiency of InGaN/GaN Green Light-Emitting Diodes

We fabricated the photonic-crystal-structured p-GaN (PC-structured p-GaN) nanorods using the modified polystyrene nanosphere (PS NS) lithography method for InGaN/GaN green light-emitting diodes (LEDs) to enhance the light extraction efficiency (LEE). A modified PS NS lithography method including two-times spin-coating processes and the post-spin-coating heating treatment was used to obtain a self-assembly close-packed PS NS array of monolayer as a mask and then a partially dry etching process was applied to PS NS, SiO2, and p-GaN to form PC-structured p-GaN nanorods on the InGaN/GaN green LEDs. The light output intensity and LEE of InGaN/GaN green LEDs with the PC-structured p-GaN nanorods depend on the period, diameter, and height of PC-structured p-GaN nanorods. RSoft FullWAVE software based on the three-dimension finite-difference time-domain (FDTD) algorithm was used to calculate the LEE of InGaN/GaN green LEDs with PC-structured p-GaN nanorods of the varied period, diameter, and height. The optimal period, diameter, and height of PC-structured p-GaN nanorods are 150, 350, and 110 nm. The InGaN/GaN green LEDs with optimal PC-structured p-GaN nanorods exhibit an enhancement of 41% of emission intensity under the driving current of 20 mA as compared to conventional LED.

Fabrication of a honeycomb-like bimetallic SERS substrate for the detection of triphenyltin chloride.

Triphenyltin chloride (TPhT) is an organotin compound that causes intensive toxicological risk to the environment and humans. A detection method with high sensitivity and stability is therefore desired to better detect TPhT. In this study, a novel SERS substrate was prepared by sputtering an ultra-thin Au layer on a honeycomb-like silver nanoarray fabricated via the nanosphere lithography method. The ultra-thin Au layer was formed by sputtering the intermittent Au nanoparticles on the silver nanoarray, resulting in bimetallic coupling with dramatically increased hotspots and extremely high SERS enhancement with an analytical enhancement factor (AEF) of 6.08 × 109 using Rhodamine 6G (R6G) as the probe molecule. Based on density functional theory (DFT) simulations, the Raman characteristic peaks of TPhT at 999 cm-1 and 655 cm-1 were selected for TPhT detection. The AEF of the SERS substrate HC5-AgAu was calculated to be 3.38 × 106 with the detection concentration of TPhT down to 10-10 M. The as-prepared honeycomb-like silver-gold bimetallic SERS substrate demonstrated great stability and sensitivity for TPhT detection, which might also be applied in monitoring many other environmental pollutants.

Optimization of SERS Sensing With Micro-Lensed Optical Fibers and Au Nano-Film

We present the fabrication and characterization of optical fiber reflection probes based on surface-enhanced Raman scattering (SERS) and micro-lensed multimode fibers. For the SERS substrate, a nano-sphere lithography method is used. Comparison of SERS measurements with three different fiber probe configurations is presented. The proposed optimized structure shows a five times increase in SERS signal for dried Rhodamine 6G (R6G) and two times for aqueous R6G in comparison to a standard reflection configuration. Measurements of different concentrations of R6G in a water solution with an limit of detection (LOD) equal to 10−7 M are demonstrated.

Hexagonal arrays of gold triangles as plasmonic tweezers.

We present theoretical and experimental studies of the plasmonic properties of hexagonal arrays of gold triangles, fabricated by angle-resolved nanosphere lithography method. Our numerical and experimental results both show that a change in the angle of gold deposition affects the size and the distance between the triangles, leading to a controlled shift in their absorption and scattering spectra. We calculate the force exerted on the polystyrene particles of 650 nm radii numerically while passing above the hexagonal arrays. Simulation results show that the presented hexagonal arrays of gold triangles can operate as efficient plasmonic tweezers with a controllable operating wavelength and high trap strength, owing to the additive interaction of the neighboring triangles. Moreover, we apply the realized plasmonic nanostructures in a conventional optical tweezers configuration and show that the optical tweezers stiffness can be effectively modulated by the plasmonic forces, at the IR wavelength of 1064 nm.

Gigahertz acoustic vibrations of Ga-doped ZnO nanoparticle array

In this work, we present an experimental study on the acoustic vibrations of ZnO nanoparticles array with different concentration of Ga dopings by using femtosecond pump-probe technique. The Ga-doped ZnO (GZO) nano-triangle particles with the sizes of 190, 232 and 348 nm are fabricated by nanosphere lithography and pulsed laser deposition method. The result indicates that the frequency of acoustic vibrations of GZO nanoparticles decrease as the Ga-concentration is increased. Importantly, the vibration period of the GZO nanoparticles at the same Ga doping concentration show a nonlinear increase as the nanoparticle size is increased, which is different from the common linear dependency in undoped ZnO nanoparticles. It may be attributed to the crystal structure distortion and elastic characteristics variation due to Ga doping, and the elastic modulus at 7.3% Ga doping is decreased by 30%–60% for GZO nanoparticles with different sizes. The study can be very helpful for evaluating the crystal structure distortion and elastic characteristics of doped nano-materials with optical methods. Besides, it can offer a complementary method of thermal management in ZnO based optoelectronic devices.

Enhanced photoelectrochemical water splitting of BiVO4 photonic crystal photoanode by decorating with MoS2 nanosheets

Bismuth vanadate (BiVO4) has been considered as one of the promising Photoelectrochemical (PEC) photoanode materials. However, the performances remain poorly rated due to inefficient carrier separation, short carrier diffusion length, and sluggish water oxidation kinetics. Herein, a photoanode consisting of MoS2 nanosheet coating on the three-dimensional ordered BiVO4 inverse opal is fabricated by a facile combination of nanosphere lithography and hydrothermal methods. By taking advantage of the photonic crystal and two-dimensional material, the optimized MoS2/BiVO4 inverse opal photoanode exhibits a 560% improvement of the photocurrent density and threefold enhancement of the incident photon-to-current efficiency than that of the pristine BiVO4 film photoanode. Systematic studies reveal that the excellent PEC activity should be attributed to enhanced light harvesting and charge separation efficiency.

Fabrication of highly ordered 2D metallic arrays with disc-in-hole binary nanostructures via a newly developed nanosphere lithography

2D metallic arrays with binary nanostructures derived from a nanosphere lithography (NSL) method have been rarely reported. Here, we demonstrate a novel NSL strategy to fabricate highly ordered 2D gold arrays with disc-in-hole binary (DIHB) nanostructures in large scale by employing a sacrificing layer combined with a three-step lift-off process. The structural parameters of the resultant DIHB arrays, such as periodicity, hole diameter, disc diameter and thicknesses can be facilely controlled by tuning the nanospheres size, etching condition, deposition angle and duration, respectively. Due to the intimate interactions between two subcomponents, the DIHB arrays exhibit both an extraordinary high surface-enhanced Raman scattering enhancement factor up to 5 × 108 and a low sheet resistance down to 1.7 Ω/sq. Moreover, the DIHB array can also be used as a metal catalyzed chemical etching catalytic pattern to create vertically-aligned Si nano-tube arrays for anti-reflectance application. This strategy provides a universal route for synthesizing other diverse binary nanostructures with controlled morphology, and thus expands the applications of the NSL to prepare ordered nanostructures with multi-function.

Effects of doping concentration on the surface plasmonic resonances and optical nonlinearities in AGZO nano-triangle arrays

Al and Ga co-doped ZnO (AGZO) nano-triangle arrays have been fabricated by nanosphere lithography and pulsed laser deposition methods. By changing the doping concentrations, the surface plasmonic resonance (SPR) peaks of the nano-triangle arrays were tuned in the infrared range from 2.4 to 3.6 $$\upmu$$ m. The SPR peaks show blue shift with Al dopant increasing. The nonlinear optical properties of the AGZO nano-triangle arrays were investigated by Z-scan method with femtosecond laser. The results show that the nonlinear optical properties of the nano-triangle arrays could be tuned by adjusting Al doping concentration. And the AGZO nano-triangle arrays show nonlinear optical properties suitable for applications on all-optical switching.

Spectral dependence of nonlinear absorption in ordered silver metallic nanoprism arrays

Ordered metallic nanoprism arrays have been proposed as novel and versatile systems for the observation of nonlinear effects such as nonlinear absorption. The study of the effect of the local field reinforcement on the fast optical third order nonlinear response around the Surface Plasmon Resonance is of great interest for many plasmonic applications. In this work, silver nanoprism arrays have been synthesized by the nanosphere lithography method. A low repetition rate tunable picosecond laser source was used to study the irradiance and wavelength dependence of the nonlinear absorption properties around the dipolar and quadrupolar resonances of the nanoarray with the use of the z-scan technique. The irradiance dependence of the on-resonance nonlinearity was studied, and a spectral region where nonlinear absorption is negligible was identified. This is important for the possible application of these materials in optical information processing devices.

Effect of the Fabrication Parameters of the Nanosphere Lithography Method on the Properties of the Deposited Au-Ag Nanoparticle Arrays.

The nanosphere lithography (NSL) method can be developed to deposit the Au-Ag triangle hexagonal nanoparticle arrays for the generation of localized surface plasmon resonance. Previously, we have found that the parameters used to form the NSL masks and the physical methods required to deposit the Au-Ag thin films had large effects on the geometry properties of the nanoparticle arrays. Considering this, the different parameters used to grow the Au-Ag triangle hexagonal nanoparticle arrays were investigated. A single-layer NSL mask was formed by using self-assembly nano-scale polystyrene (PS) nanospheres with an average radius of 265 nm. At first, the concentration of the nano-scale PS nanospheres in the solution was set at 6 wt %. Two coating methods, drop-coating and spin-coating, were used to coat the nano-scale PS nanospheres as a single-layer NSL mask. From the observations of scanning electronic microscopy (SEM), we found that the matrixes of the PS nanosphere masks fabricated by using the drop-coating method were more uniform and exhibited a smaller gap than those fabricated by the spin-coating method. Next, the drop-coating method was used to form the single-layer NSL mask and the concentration of nano-scale PS nanospheres in a solution that was changed from 4 to 10 wt %, for further study. The SEM images showed that when the concentrations of PS nanospheres in the solution were 6 and 8 wt %, the matrixes of the PS nanosphere masks were more uniform than those of 4 and 10 wt %. The effects of the one-side lifting angle of substrates and the vaporization temperature for the solvent of one-layer self-assembly PS nanosphere thin films, were also investigated. Finally, the concentration of the nano-scale PS nanospheres in the solution was set at 8 wt % to form the PS nanosphere masks by the drop-coating method. Three different physical deposition methods, including thermal evaporation, radio-frequency magnetron sputtering, and e-gun deposition, were used to deposit the Au-Ag triangle hexagonal periodic nanoparticle arrays. The SEM images showed that as the single-layer PS nanosphere mask was well controlled, the thermal evaporation could deposit the Au-Ag triangle hexagonal nanoparticle arrays with a higher quality than the other two methods.

Local-field enhancement of optical nonlinearities in the AGZO nano-triangle array

Enhancement of the third order optical nonlinearities in Ga and Al co-doped ZnO (AGZO) nano-triangle array was investigated by performing a Z-scan method with a femtosecond laser (800 nm, 40 fs). The AGZO nano-triangle array was fabricated on silica substrates by nanosphere lithography (NSL) method, showing a surface plasmon resonance (SPR) peak around 3 μm. The two photon absorption (TPA) coefficient and nonlinear refractive index of the AGZO nano-triangle array were determined to be 340 cm/GW and 3.22 × 10−2 cm2/GW under an excitation intensity of 26 GW/cm2. It shows a 3.4-fold enhancement of the nonlinear refraction in the AGZO array with respect to that in the AGZO film, which attributes to the local field enhancement effect. The finite-difference time-domain (FDTD) simulation was in agreement with the experimental results. It indicates that the AGZO nano-triangle arrays have potential applications for nonlinear optical devices like all-optical switching, optical limiting and other types of signal processing.

Superimposed Arrays of Nanoprisms for Multispectral Molecular Plasmonics

Molecular plasmonics relies on the development of conductive nanostructures to yield large local electromagnetic enhancement enabling the detection of molecules located in their vicinity. Although various spectroscopic techniques benefit from such enhancement, performing different spectroscopic measurements on the same platform remains a challenge. As such, the rational design of structures capable of enhancement effects over a large spectral range, particularly from the visible to the mid-infrared, is of great interest. Herein, we have developed a series of metallic patterns, consisting of superimposed arrays of gold nanoprisms, that have the potential for surface-enhanced Raman spectroscopy (SERS), surface-enhanced fluorescence (SEF), and surface-enhanced infrared absorption (SEIRA). We first demonstrate that a modified version of the nanosphere lithography method can be used to fabricate such platforms. Patterns with selected sizes can further be produced by electron-beam lithography with virtually no ...

Integration of tunable two-dimensional nanostructures on a chip by an improved nanosphere lithography method

By uniform infiltration of a different material into monolayered polystyrene colloidal crystals and by flexibly combining the two materials as etching masks, we demonstrate an improved nanosphere lithography method that possesses the ability to produce a diverse range of tunable nano-patterns in a small area with good reproducibility. The factors that affect the infiltration height and uniformity are characterized and discussed. Annular gap arrays, close-packed ring arrays, and bowl arrays are demonstrated by this method. The geometry size of these nano-patterns can be tuned over the range 10 nm to ∼500 nm with steps of ∼5 nm during the fabrication progress. Formation mechanisms of the close-packed ring arrays are experimentally investigated. Because all the fabrication processes involved in this method are adaptable to sophisticated integrated circuit fabrication techniques, most of the nano-patterns produced by this method could be integrated on thin films, which is desirable for optics integration and array sensing.

Enhanced photoelectrochemical and photocatalytic activity in visible-light-driven Ag/BiVO4 inverse opals

BiVO4 photonic crystal inverse opals (io-BiVO4) with highly dispersed Ag nanoparticles (NPs) were prepared by the nanosphere lithography method combining the pulsed current deposition method. The incorporation of the Ag NPs can significantly improve the photoelectrochemical and photocatalytic activity of BiVO4 inverse opals in the visible light region. The photocurrent density of the Ag/io-BiVO4 sample is 4.7 times higher than that of the disordered sample without the Ag NPs, while the enhancement factor of the corresponding kinetic constant in photocatalytic experiment is approximately 3. The improved photoelectrochemical and photocatalytic activity is benefited from two reasons: one is the enhanced light harvesting owing to the coupling between the slow light and localized surface plasmon resonance effect; the other is the efficient separation of charge carriers due to the Schottky barriers.

Three-dimensional hexagonal GDC interlayer for area enhancement of low-temperature solid oxide fuel cells

A three-dimensional hexagonal gadolinium-doped ceria (GDC) interlayer is fabricated to enhance the cathodic surface area of low-temperature solid oxide fuel cells (LT-SOFCs). By using modified nanosphere lithography method, 3-D nanostructure is successfully fabricated. As a result of the nanostructuring, the 3-D hexagonal GDC interlayer has a 70% increase in cathodic surface area. Electrochemical impedance spectroscopy reveals a 2-fold decrease in the electrode resistance compared with a plane cell, resulting in a current–voltage behavior with a 60% higher peak power density. The superior electrode reaction is attributed to the large surface area (~1.7 times larger) due to the 3-D hexagonal cathodic interlayer. This novel fabrication method can be applied to almost all kinds of LT-SOFC structures, including large-scale and substrate-supported platforms, and thereby it will contribute to commercializing LT-SOFCs.

Fabrication and Photoelectric Properties of Large Area ZnO Nanorod with Au Nanospheres

Novel gold nanospheres top-contact ZnO nanorods arrays were fabricated via combination of self-assemble nanosphere lithography and low-cost hydrothermal chemical method. Gold nanoparticles of different geometries are used to enhance the fluorescent properties of ZnO nanorods based on localized surface plasmonic resonances. The results show that defect-related emission intensity ratio of the ZnO nanorods arrays can be improved up to two orders, and the defect-related emission peak red-shifted from 577 to 623 nm. This improvement is attributed to the enhanced localized surface plasmonic absorption of gold nanoparticles, which implies a promising application in surface plasmonic enhanced spectra.

Nano-honeycomb structured transparent electrode for enhanced light extraction from organic light-emitting diodes

A universal nano-sphere lithography method has been developed to fabricate nano-structured transparent electrode, such as indium tin oxide (ITO), for light extraction from organic light-emitting diodes (OLEDs). Perforated SiO2 film made from a monolayer colloidal crystal of polystyrene spheres and tetraethyl orthosilicate sol-gel is used as a template. Ordered nano-honeycomb pits on the ITO electrode surface are obtained by chemical etching. The proposed method can be utilized to form large-area nano-structured ITO electrode. More than two folds' enhancement in both current efficiency and power efficiency has been achieved in a red phosphorescent OLED which was fabricated on the nano-structured ITO substrate.