Thermal Nanoimprint Lithography Research Articles

Replicated biopolymer pattern on PLLA-Ag basis with an excellent antibacterial response

The design of functional micro or nanostructured surfaces is undergoing extensive research for their intriguing multifunctional properties and for large variety of potential applications in biomedical field (tissue engineering or cell adhesion), electronics, optics or microfluidics. Such nanosized topographies can be easily fabricated by various lithography techniques and can be also further reinforced by synergic effect by combining aforementioned structures along materials with already outstanding antibacterial properties. In this work we fabricated novel micro/nanostructured substrates using soft lithography replication method and subsequent thermal nanoimprint lithography method, creating nanostructured films based on poly (l-lactic acid) (PLLA) fortified by thin silver films deposited by PVD. Main nanoscale patterns were fabricated by replicating surface patterns of optical discs (CDs and DVDs), which proved to be easy, fast and inexpensive method for creating relatively large area patterned surfaces. Their antimicrobial activity was examined in vitro against the bacteria Escherichia coli and Staphylococcus epidermidis strains. The results demonstrated that nanopatterned films actually improved the conditions for bacterial growth compared to pristine PLLA films, the novelty is based on formation of Ag nanoparticles on the surface/and in bulk, while silver nanoparticle enhanced and nanopatterned films exhibited excellent antibacterial activity against both bacterial strains, with circa 80 % efficacy in 4 h and complete bactericidal effect in span of 24 h.

Research on the influence of stamping materials on resist flow and the residual layer in thermal nanoimprint lithography

AbstractVarious stamp materials can significantly affect the filling quality of nanoimprint lithography (NIL). The effects of different stamp materials on the imprinting process were investigated from the angles of residual layer (RL) thickness, contact pressure, and filling proportion. The selection of various stamp materials affects the thickness and uniformity of the RL. Soft stamps (PDMS, PU) leave a thin but uneven RL distribution, while the RL imprinted by hard stamps (Si, Ni) is thicker but more uniform. The contact pressure using soft stamps is relatively more evenly distributed than hard stamps. The uneven distribution of contact pressure leads to poor cavity‐filling proportion, especially for hard stamps. This study offers guidance for choosing proper nanoimprint stamp materials for different NIL applications.

The implementation of thermal and UV nanoimprint lithography for selective area epitaxy

Semiconductor nanowires (NWs) in horizontal configuration could provide a path for scalable NW-based devices. Bottom–up large-scale manufacturing of these nanostructures by selective area epitaxy (SAE) relies on precise nanopatterning of various shapes on the growth masks. Electron beam lithography offers an extraordinary accuracy suited for the purpose. However, this technique is not economically viable for large production as it has a low throughput and requires high investment and operational costs. Nanoimprint lithography (NIL) has the potential to reduce fabrication time and costs significantly while requiring less sophisticated equipment. In this work, we utilize both thermal and UV NIL for patterning substrates for SAE, elucidating the advantages and disadvantages of each lithography technique. We demonstrate the epitaxial growth of Ge and GaAs NWs on these substrates, where we observe high-quality mono-crystalline structures. Even though both processes can produce small uniform structures suitable for SAE, our results show that UV NIL proves to be superior and enables reliable and efficient patterning of sub-100 nm mask features at the wafer scale.

Thermal Nanoimprint Lithography-A Review of the Process, Mold Fabrication, and Material.

Micro- and nanopatterns perform unique functions and have attracted attention in various industrial fields, such as electronic devices, microfluidics, biotechnology, optics, sensors, and smart and anti-adhesion surfaces. To put fine-patterned products to practical use, low-cost patterning technology is necessary. Nanoimprint lithography (NIL) is a promising technique for high-throughput nanopattern fabrication. In particular, thermal nanoimprint lithography (T-NIL) has the advantage of employing flexible materials and eliminating chemicals and solvents. Moreover, T-NIL is particularly suitable for compostable and recyclable materials, especially when applying biobased materials for use in optics and electronics. These attributes make T-NIL an eco-friendly process. However, the processing time of normal T-NIL is longer than that of ultraviolet (UV) NIL using a UV-curable resin because the T-NIL process requires heating and cooling time. Therefore, many studies focus on improving the throughput of T-NIL. Specifically, a T-NIL process based on a roll-to-roll web system shows promise for next-generation nanopatterning techniques because it enables large-area applications with the capability to process webs several meters in width. In this review, the T-NIL process, roll mold fabrication techniques, and various materials are introduced. Moreover, metal pattern transfer techniques using a combination of nanotransfer printing, T-NIL, and a reverse offset are introduced.

Distributed Feedback Lasers by Thermal Nanoimprint of Perovskites Using Gelatin Gratings.

To date, thermal nanoimprint lithography (NIL) for patterning hybrid perovskites has always involved an intricate etching step of a hard stamp material or its master. Here, we demonstrate for the first time the successful nanopatterning of a perovskite film by NIL with a low-cost polymeric stamp. The stamp consists of a dichromated gelatin grating structured by holographic lithography. The one-dimensional grating is imprinted into a perovskite film at 95 °C and 90 MPa for 10 min, resulting in a high quality second-order distributed feedback (DFB) laser. The laser exhibits an excellent performance with a threshold of 81 μJ/cm2, a line width of 0.32 nm, and a pronounced linear polarization. This novel approach enables cost-effective fabrication of high-quality DFB lasers compatible with different perovskite compositions and photonic nanostructures for a wide range of applications.

Toward the Scalable Fabrication of Fully Bio-Based Antimicrobial and UVB-Blocking Transparent Polylactic Acid Films That Incorporate Natural Coatings and Nanopatterns.

Microbial transmissions via membrane surface and single-use plastic-induced pollution are two urgent societal problems. This research introduces a scalable fabrication strategy for fully biobased antibacterial and ultraviolet-B block polylactic acid (PLA) films integrating natural coatings and nanopatterns via ultrasonic atomization spray coating and thermal nanoimprinting lithography (TNIL) techniques, respectively. Tannic acid (TA) and gallic acid (GA) were formulated prior to TNIL using anode aluminum oxide template. Results reveal that TA and GA inks display intense adsorption in the UVB region. Plasma increases the hydrophilicity of PLA films for fast spreading of ink droplets. Micron-sized pillars observed on film confirm the successful structural replication. TA-coated PLA films display higher transparency than GA-coated ones. Nanopatterned PLA films have a modest antibacterial resistance of c. 45% against Escherichia coli. TA/GA coatings, however, impart PLA films with a bacterial reduction rate of over 80%. The integration of a TA or GA coating with nanopatterns further promotes the antibacterial rate up to 98%. The cytocompatibility of TA and GA demonstrates that the engineered film can potentially be applied as food packaging. Finally, a continuous mass production strategy is proposed along with an outline of the associated challenges and costs. This study provides a scalable strategy to the sustainable development of eco-benign and functional films.

Fabrication of ITO diffraction grating structure for infrared plasmonics by thermal nanoimprint lithography

Fabrication of ITO diffraction grating structure for infrared plasmonics by thermal nanoimprint lithography

Dual functional anode for organic light-emitting devices by directly imprinted nanostructured ultrathin Au film

The ultrathin metal film with excellent electrical conductivity and high visible-band transmittance has attracted considerable attention as a transparent electrode for the organic light-emitting devices (OLEDs). However, the deficient surface morphology and poor continuity of low thickness evaporated metal films and the surface plasmon-polaritons (SPPs) mode induced energy loss still seriously limit the actual efficiency of OLEDs. In this work, the thermal nanoimprint lithography has been further modified and directly applied to fabricate nanostructures onto the ultrathin Au film. During the imprinting process, the surface smoothness and conductivity of the Au film are obviously optimized with the formation of nanostructures. After integrating proper nanostructures into OLEDs, the photons that trapped by SPPs mode within the device were effectively out-coupled. The current efficiency and luminance have been enhanced 45.3% and 18.1%, respectively. Furthermore, the emitting properties of the OLEDs were also modified by the nanostructures, and the directional transmission capability of output light was significantly improved.

Introducing surface functionality on thermoformed polymeric films

We present a fabrication process for the production of 3-dimensional micro-structured polymeric films. The microstructures are fabricated in a single step using thermal nanoimprint lithography as patterning technique. The micro-structured polymer films are then transformed into a 3D shape by means of a plug-assisted thermoforming process, while keeping the functionality of the micro-patterned areas. The preserved functionality is characterized by water contact angle measurements, while the deformation of the micro-structured topographies due to the thermoforming process is analyzed using confocal microscopy and Digital Image Correlation (DIC) techniques. This combined fabrication process represents a promising solution to complement in-mold decoration approaches, enabling the production of new functional surfaces. As the microstructures are fabricated by means of a mechanical modification of the surface, without the need of chemical treatments or coatings, the presented technique represents a promising, simple and green solution, suitable for the industrial fabrication of 3D nonplanar shaped functional surfaces. • A method to produce 3-dimensional micro-structured polymeric films by combination of nanoimprint lithography and thermoforming is presented • The surface microstructures defined by Nanoimprint Lithography induce surface hydrophobicity which is maintained after the thermoforming process. The microstructures defined by nanoimprint induce surface hydrophobicity which is maintained after the thermoforming process. • The strain induced by the thermoforming process deforms the microstructure, affecting the functional properties. • This combined process complement in-mold decoration approaches with the introduction of new functional surfaces.

Thermal nanoimprint lithography of sodium hyaluronate solutions with gas permeable inorganic hybrid mold for cosmetic and pharmaceutical applications

Gas-permeable inorganic hybrid mold that hybridized the surface layer of TiO2–SiO2 gas-permeable polymer using the sol–gel method and the lower layer of porous maraging steel by a metal three-dimensional printer was developed for fluid function materials containing high concentrations of water and volatile solvents. Thermal nanoimprint lithography was used to fabricate the advanced high-resolution needle patterning of sodium hyaluronate containing volatile solvents to broaden the application area of fluid function materials such as cosmetics and pharmaceuticals.

Reversible Photo-Induced Reshaping of Imprinted Microstructures Using a Low Molecular Azo Dye.

A blend of low molecular azo glass (AZOPD) and polystyrene (PS) were used for the systematic investigation of photo-induced stretching and recovery of nanoimprinted structures. For this purpose, light and heat was used as recovery stimuli. The AZOPD/PS microstructures, fabricated with thermal nanoimprint lithography (tNIL), comprises three different shapes (circles, crosses and squares) and various concentrations of AZOPD fractions. The results show a concentration-dependent reshaping. Particularly the sample with 43 w-% of the AZOPD fraction have shown the best controllable recovery for the used parameters. A possible explanation for shape recovery might be the stabilizing effect of the PS-matrix.

Fluidic operation of a polymer-based nanosensor chip for analysing single molecules.

Most medical diagnostic tests are expensive, involve slow turnaround times from centralized laboratories and require highly specialized equipment with seasoned technicians to carry out the assay. To facilitate realization of precision medicine at the point of care, we have developed a mixed-scale nanosensor chip featuring high surface area pillar arrays where solid-phase reactions can be performed to detect and identify nucleic acid targets found in diseased patients. Products formed can be identified and detected using a polymer nanofluidic channel. To guide delivery of this platform, we discuss the operation of various components of the device and simulations (COMSOL) used to guide the design by investigating parameters such as pillar array loading, and hydrodynamic and electrokinetic flows. The fabrication of the nanosensor is discussed, which was performed using a silicon (Si) master patterned with a combination of focused ion beam milling and photolithography with deep reactive ion etching. The mixed-scale patterns were transferred into a thermoplastic via thermal nanoimprint lithography, which facilitated fabrication of the nanosensor chip making it appropriate for in vitro diagnostics. The results from COMSOL were experimentally verified for hydrodynamic flow using Rhodamine B as a fluorescent tracer and electrokinetic flow using single fluorescently labelled oligonucleotides (single-stranded DNAs, ssDNAs).

Enhancement of Antiviral Effect of Plastic Film against SARS-CoV-2: Combining Nanomaterials and Nanopatterns with Scalability for Mass Manufacturing.

Direct contact with contaminated surfaces in frequently accessed areas is a confirmed transmission mode of SARS-CoV-2. To address this challenge, we have developed novel plastic films with enhanced effectiveness for deactivating the SARS-CoV-2 by means of nanomaterials combined with nanopatterns. Results prove that these functionalized films are able to deactivate SARS-CoV-2 by up to 2 orders of magnitude within the first hour compared to untreated films, thus reducing the likelihood of transmission. Nanopatterns can enhance the antiviral effectiveness by increasing the contact area between nanoparticles and virus. Significantly, the established process also considers the issue of scalability for mass manufacturing. A low-cost process for nanostructured antiviral films integrating ultrasonic atomization spray coating and thermal nanoimprinting lithography is proposed. A further in-depth investigation should consider the size, spacing, and shape of nanopillars, the type and concentration of nanoparticles, and the scale-up and integration of these processes with manufacturing for optimal antiviral effectiveness.

Nanoimprinting for high-throughput replication of geometrically precise pillars in fused silica to regulate cell behavior

Developing high-throughput nanopatterning techniques that also allow for precise control over the dimensions of the fabricated features is essential for the study of cell-nanopattern interactions. Here, we developed a process that fulfills both of these criteria. Firstly, we used electron-beam lithography (EBL) to fabricate precisely controlled arrays of submicron pillars with varying values of interspacing on a large area of fused silica. Two types of etching procedures with two different systems were developed to etch the fused silica and create the final desired height. We then studied the interactions of preosteoblasts (MC3T3-E1) with these pillars. Varying interspacing was observed to significantly affect the morphological characteristics of the cell, the organization of actin fibers, and the formation of focal adhesions. The expression of osteopontin (OPN) significantly increased on the patterns, indicating the potential of the pillars for inducing osteogenic differentiation. The EBL pillars were thereafter used as master molds in two subsequent processing steps, namely soft lithography and thermal nanoimprint lithography for high-fidelity replication of the pillars on the substrates of interest. The molding parameters were optimized to maximize the fidelity of the generated patterns and minimize the wear and tear of the master mold. Comparing the replicated feature with those present on the original mold confirmed that the geometry and dimensions of the replicated pillars closely resemble those of the original ones. The method proposed in this study, therefore, enables the precise fabrication of submicron- and nanopatterns on a wide variety of materials that are relevant for systematic cell studies. Statement of significanceSubmicron pillars with specific dimensions on the bone implants have been proven to be effective in controlling cell behaviors. Nowadays, numerous methods have been proposed to produce bio-instructive submicron-topographies. However, most of these techniques are suffering from being low-throughput, low-precision, and expensive. Here, we developed a high-throughput nanopatterning technique that allows for control over the dimensions of the features for the study of cell-nanotopography interactions. Assessing the adaptation of preosteoblast cells showed the potential of the pillars for inducing osteogenic differentiation. Afterward, the pillars were used for high-fidelity replication of the bio-instructive features on the substrates of interest. The results show the advantages of nanoimprint lithography as a unique technique for the patterning of large areas of bio-instructive surfaces.

Tuning response amplitude in nanoimprinted thermoresponsive polymer blend

AbstractWe demonstrate the potential of thermoresponsive poly N‐(isopropylacrylamide) (PNIPAM) based surfaces in achieving a low‐energy approach to modulate surface wetting for applications such as fog harvesting and anti‐fogging. Alternative to grafting methods, we use a two‐step approach for tuning the response amplitude. First, we blend PNIPAM with a chemically non‐reactive poly (vinylidene fluoride), PVDF (1/3, 1/1, 3/1 by weight). Second, thermal nanoimprint lithography is used to create micro (3, 5, 10, and 20 μm) and nano‐scale (100 and 200 nm) pillars. Nano‐patterned surfaces show a response amplitude of ~30°–50° compared to ~15°–30°, observed for the micro‐patterned surface. X‐ray photo‐electron spectroscopy and energy dispersive X‐ray analysis confirms the reduction of polyvinylidene fluoride phase domains and enrichment of PNIPAM on the nano‐patterned surface. A real‐time dynamic mist condensation study showed that the nano‐patterned blend exhibited a lower temperature range (34/41°C) for on/off (wetting/drying) state compared to an unpatterned blend (37/50°C).

One-step fabrication of high refractive index inorganic nanostructures

Direct printing of spin-on functional films is probably the most efficient method to develop low-cost novel photonic nanodevices, such as diffraction gratings, planar waveguides, nano- lasers, and antireflective coatings. For these applications high refractive index transparent materials are demanded; however, this class of materials generally requires inorganic oxides, well known for their hardness, typical of ceramic materials, and so incompatible with a soft character of printable resins. Herein, inorganic high refractive index TiO2 micro- and nano- structures, with unusual depth up to 600 nm and aspect ratio larger than 5, are obtained by combining thermal nanoimprint lithography (NIL) with UV curing. To achieve printed patterns, a hybrid organic-inorganic spin-on film is deposited at low-temperature by sol–gel processing. Two distinct bottom-up synthetic approaches are used, called in situ and ex situ, using titanium isopropoxide (90%) or TiO2 anatase nanoparticles (70%), respectively, and adding a silica sol modified by organic moieties. The two syntheses were optimized to obtain, after patterning by thermal imprint, amorphous or crystalline titania crack-free micro- and nano- patterns for in situ and ex situ, respectively. The further UV irradiation converts imprinted films to totally inorganic patterns, through the titania photocatalytic effect, allowing refractive indexes up to 1.82 at 632 nm to be achieved. This novel strategy of combining thermal imprint with UV exposure allows inorganic deep patterns to be fabricated without a calcination step, which is generally needed for inorganic resists processing. Eventually, a thermal treatment only at 300 °C can be applied to achieve a final refractive index of 2 at 632 nm.Direct printing of spin-on TiO2 high refractive index (1.82 @632 nm) transparent films, with depth up to 600 nm, aspect ratio larger than 5 and without lateral shrinkage are obtained combining thermal Nanoimprint Lithography (NIL) with UV curing.

Development of the Soaking Method for Manufacturing Polymer Electrolyte Fuel Cells with a High-Aspect-Ratio Microstructure

1. IntroductionPolymer electrolyte fuel cells (PEFCs) are one of the major devices utilizing hydrogen. Owing to its small size and capacity of low-temperature operation, PEFCs are used in practical applications such as fuel cell vehicles.The power generation efficiency of PEFC is relatively low. Heinzmann et al. suggested that the main cause of low efficiency is the chemical reactions at the cathode [1]. Therefore, having a large triple phase boundary (TPB), where an oxygen reduction reaction occurs, is crucial. Bea et al. reported that the performance of PEFCs was improved by introducing micro-patterns on the surface of a Nafion membrane [2]. Organizing a high-aspect-ratio microstructure on its surface is more effective for increasing the size of the TPB.In the powder molding field, a typical problem exists: particles in solution form bridge structures because Van der Waals forces are dominant at the micrometer scale. Thus, fabricating a high-aspect-ratio microstructure on the surface of a Nafion membrane is challenging.2. ExperimentLine-and-space patterns with three different dimensions—width/spacing/height of 1/1/2 μm, respectively—were introduced onto the cathode surface via thermal nanoimprint lithography (120 °C; 5 MPa). The catalyst ink was prepared using Pt/C (TEC10V50E, Tanaka Kikinzoku Kogyo K.K.), deionized water, and 10 wt.% ionomer solution. Two samples (samples A and B) were fabricated by spraying the catalyst ink on the micro-patterned surface with a 1-cm2 mask attached at 80 °C and 30 °C, respectively. Moreover, the time between one push and another was controlled at 5 s and 0.5 s, respectively. The same amount of catalyst ink was sprayed on both samples under the same relative pressure (0.1 MPa).After drying, the cross-sections of both samples were investigated using scanning electron microscopy (SEM).3. Results and discussionFigure 1 shows the appearance of each sample immediately after spraying. As shown in Figure 1 (a), the ink on sample A had already dried, whereas, as shown in Figure 1 (b), the Nafion membrane of sample B was soaked in the ink. Figure 2 shows the SEM images of the cross-sections of both samples. As shown in Figure 2 (a), the catalyst layer formed a bridge structure in sample A. On the contrary, as shown in Figure 2 (b), the catalyst layer goes deep into the spaces of line-and-space patterns without forming a bridge structure in sample B.Figure 3 shows the mechanism of bridge structure formation. Water accounted for 99 wt.% of the catalyst ink; therefore, the ink is incompatible with the water-repellent Nafion membrane. The reason for forming a bridge structure when normally sprayed as sample A can be that water, which is a solvent, rapidly evaporates before the catalyst ink enters the spaces of line-and-space patterns. On the contrary, the reason for preventing bridge structure from forming when soaking can be that water evaporates after the catalyst ink goes deep into the spaces.4. ConclusionsBy using the original soaking method, a high-aspect-ratio microstructure was successfully arranged in the cathode without the formation of a bridge structure. When a cell is manufactured, the surface of its cathode with micro patterns will first be soaked and dried as the process of making sample B. Subsequently, catalyst ink was normally sprayed on both the cathode and anode surfaces as much as needed. Optimization of the soaking process parameters is required to manufacture a higher-aspect-ratio microstructure and to increase the size of the TPB.

Enhanced Mechanical and Thermal Resistances of Nanoimprinted Antireflective Moth‐Eye Surfaces Based on Poly Vinylidene Fluoride/TiO2 Surface Nanocomposites

Herein, the fabrication of bioinspired moth‐eye antireflective (AR) films based on surface nanocomposites of poly vinylidene fluoride (PVDF) and TiO2 nanoparticles produced in a single thermal nanoimprint lithography step is described. The incorporation of nanoparticles enhances the mechanical and thermal stability of the AR topography as demonstrated by nanoindentation tests and in situ temperature‐dependent grazing incidence X‐ray scattering measurements using synchrotron radiation. The effect of thermal annealing and UV radiation on the degradation in the optical performance and durability of the AR films is also evaluated in weathering tests. Improving the thermal and mechanical behavior as well as the long‐term durability of nanoimprinted polymer AR films will significantly expand their potential for implementation in solar devices.

Controllable fabrication of polymeric nanowires by NIL technique and self-assembled AAO template for SERS application

A controllable strategy to fabricate the polymeric nanowires with high throughput and low cost is developed by using the thermal nanoimprint lithography (NIL) technique and self-assembled anodic aluminum oxide (AAO) template. The length of polymeric nanowires can be controlled by adjusting the duration of thermal NIL. A fill mechanism of thermoplastic intermediate polymer stamp (IPS) polymer pressed into the AAO nanopores is closely studied. The as-prepared IPS polymeric nanowire-based Surface-Enhanced Raman Scattering (SERS)-active substrate exhibits a remarkable reproducibility. The effective adsorption of the R6G as probe molecule near to hotspots generated at 3D vertically aligned polymeric nanowire SERS active substrates shows extraordinary enhancement of Raman signal with an enhancement factor (EF) of 105–106. The present strategy is of great guiding significance to broaden the use of thermal NIL technique and AAO template for the fabrication of other nanomaterials, especially for the flexible and transparent polymer-based nanomaterials.

Proposal of hybrid deep learning systems for process and material design in thermal nanoimprint lithography

Proposal of hybrid deep learning systems for process and material design in thermal nanoimprint lithography