Large-area Patterning Research Articles

Transformation from nano-ripples to nano-triangle arrays and their orientation control on titanium surfaces by using orthogonally polarized femtosecond laser double-pulse sequences

One-dimensional and two-dimensional laser-induced periodic structures (nano-ripples and nano-triangle arrays) are fabricated on titanium surfaces by direct scanning with orthogonally polarized and equal-energy femtosecond laser double-pulse sequences (OP pulses). Clear and regular nano-ripples and nano-triangle arrays are formed when the laser fluence is slightly higher than the ablation threshold of titanium and the time delay is approximately 2 ps or shorter. By changing only the scanning speed, we achieve the transformation from nano-ripples to nano-triangle arrays. The orientation of nano-ripples and that of one of the three sides of nano-triangle arrays are always perpendicular to the scanning direction rather than the laser polarization. The mechanism underlying this phenomenon is as follows. First, the nano-ripples are formed due to periodic energy deposition along the direction of surface waves (surface plasmon polaritons; SPPs), which is along the scanning direction during the scan process. Subsequently, the preformed nano-ripples irradiated with subsequent laser pulses undergo hexagonal convection flow and are transformed into nano-triangle arrays. The preformed nano-ripples perpendicular to the scanning direction have a positioning effect on the formation of nano-triangle arrays, as verified in two-step fast scan experiments. Large-area patterning of nano-triangle arrays producing three-directional structural color is demonstrated in this paper.

Metal-Assisted Electrochemical Nanoimprinting of Porous and Solid Silicon Wafers.

Metal-assisted electrochemical imprinting (Mac-Imprint) is a combination of metal-assisted chemical etching (MACE) and nanoimprint lithography that is capable of direct patterning 3D micro- and nanoscale features in monocrystalline group IV (e.g., Si) and III-V (e.g., GaAs) semiconductors without the need of sacrificial templates and lithographical steps. During this process, a reusable stamp coated with a noble metal catalyst is brought in contact with a Si wafer in the presence of a hydrofluoric acid (HF) and hydrogen peroxide (H2O2) mixture, which leads to the selective etching of Si at the metal-semiconductor contact interface. In this protocol, we discuss the stamp and substrate preparation methods applied in two Mac-Imprint configurations: (1) Porous Si Mac-Imprint with a solid catalyst; and (2) Solid Si Mac-Imprint with a porous catalyst. This process is high throughput and is capable of centimeter-scale parallel patterning with sub-20 nm resolution. It also provides low defect density and large area patterning in a single operation and bypasses the need for dry etching such as deep reactive ion etching (DRIE).

An atom passing through a hole in a dielectric membrane: impact of dispersion forces on mask-based matter-wave lithography

Fast, large area patterning of arbitrary structures down to the nanometre scale is of great interest for a range of applications including the semiconductor industry, quantum electronics, nanophotonics and others. It was recently proposed that nanometre-resolution mask lithography can be realised by sending metastable helium atoms through a binary holography mask consisting of a pattern of holes. However, these first calculations were done using a simple scalar wave approach, which did not consider the dispersion force interaction between the atoms and the mask material. To access the true potential of the idea, it is necessary to access how this interaction affects the atoms. Here we present a theoretical study of the dispersion force interaction between an atom and a dielectric membrane with a hole. We look at metastable and ground state helium, using experimentally realistic wavelengths (0.05–1 nm) and membrane thicknesses (5–50 nm). We find that the effective hole radius is reduced by around 1–7 nm for metastable helium and 0.5–3.5 nm for ground-state helium. As expected, the reduction is largest for thick membranes and slow atoms.

Organic ultrathin nanostructure arrays: materials, methods and applications.

Organic ultrathin semiconductor nanostructures have attracted continuous attention in recent years owing to their excellent charge transport capability, favorable flexibility, solution-processability and adjustable photoelectric properties, providing opportunities for next-generation optoelectronic applications. For integrated electronics, organic ultrathin nanostructures need to be prepared as large-area patterns with precise alignment and high crystallinity to achieve organic electronic devices with high performance and high throughput. However, the fabrication of organic ultrathin nanostructure arrays still remains challenging due to uncontrollable growth along the height direction in solution processes. In this review, we first introduce the properties, assembly methods and applications of four typical organic ultrathin nanostructures, including small molecules, polymers, and other organic–inorganic hybrid materials. Five categories of representative solution-processing techniques for patterning organic micro- and nanostructures are summarized and discussed. Finally, challenges and perspectives in the controllable preparation of organic ultrathin arrays and potential applications are featured on the basis of their current development.

State-and-Evolution Detection Models: A Framework for Continuously Monitoring Landscape Pattern Change

Detecting the evolution of large-area landscape patterns using long-term remote-sensing images is helpful in supporting research on the relationship between landscape patterns and ecological processes, as well as the development of ecological process simulations and spatiotemporal interaction models. However, detection methods have generally been developed as separate applications, each with a separate type of landscape pattern change; remote-sensing images are acquired at epochal timesteps. Consequently, in practical applications, many omission changes for some types of pattern changes and inaccurate evolution time are presented in the detected map. In this article, state-and-evolution detection models (SEDMs) are promoted to obtain complete information about the evolution of landscape patterns based on yearly land cover data. In the proposed framework, we first define the major categories of landscape pattern changes to comprehensively reveal the characteristics of landscape pattern changes associated with real change cases. Next, a morphological rule-based pattern recognition approach is proposed for quantitative discrimination among these categories. This approach is then applied in annual land cover data to continuously detect landscape pattern evolution processes and evolution time. Finally, the detected evolution time in different evolution processes is applied to measure the timestep between two disparate types. The performances of the SEDMs are presented by Landsat-derived land cover evolution in Shanxi, China. The detected results are indirectly verified by the land cover conversion matrix and connect index, indicating strong robustness and generalization ability of the SEDMs.

Large area patterning of ultra-high thermal-stable structural colors in transparent solids

Large area patterning of ultra-high thermal-stable structural colors in transparent solids

Automated SEM Image Analysis of the Sphere Diameter, Sphere-Sphere Separation, and Opening Size Distributions of Nanosphere Lithography Masks.

Colloidal nanosphere monolayers—used as a lithography mask for site-controlled material deposition or removal—offer the possibility of cost-effective patterning of large surface areas. In the present study, an automated analysis of scanning electron microscopy (SEM) images is described, which enables the recognition of the individual nanospheres in densely packed monolayers in order to perform a statistical quantification of the sphere size, mask opening size, and sphere-sphere separation distributions. Search algorithms based on Fourier transformation, cross-correlation, multiple-angle intensity profiling, and sphere edge point detection techniques allow for a sphere detection efficiency of at least 99.8%, even in the case of considerable sphere size variations. While the sphere positions and diameters are determined by fitting circles to the spheres edge points, the openings between sphere triples are detected by intensity thresholding. For the analyzed polystyrene sphere monolayers with sphere sizes between 220 and 600 nm and a diameter spread of around 3% coefficients of variation of 6.8–8.1% for the opening size are found. By correlating the mentioned size distributions, it is shown that, in this case, the dominant contribution to the opening size variation stems from nanometer-scale positional variations of the spheres.

Fabrication of Large Area, Ordered Nanoporous Structures on Various Substrates for Potential Electro-Optic Applications

Nanoporous structures have attracted great attention in electronics, sensor and storage devices, and photonics because of their large surface area, large volume to surface ratio, and potential for high-sensitivity sensor applications. Normally, electron or ion beam patterning can be used for nanopores fabrication by direct writing. However, direct writing is a rather expensive and time-consuming method due to its serial nature. Therefore, it may not translate to a preferred manufacturing process. In this research, a perfectly ordered large-area periodic pattern in an area of approximately 1 cm2 has been successfully fabricated on various substrates including glass, silicon, and polydimethylsiloxane, using a two-step process comprising visible light-based multibeam interference lithography and subsequent pattern transfer processes of reactive ion etching and nanomolding. Additionally, the multibeam interference lithography templated anodized aluminum oxide process has been described. Since the fabrication area in multibeam interference lithography can be extended by using a larger beam size, it is highly cost effective and manufacturable. Furthermore, although not described here, an electrodeposition process can be utilized as a pattern transfer process. This large-area perfectly ordered nanopore array will be very useful for high-density electronic memory and photonic bandgap and metamaterial applications.

Nanoimprinted and Anodized Templates for Large-Scale and Low-Cost Nanopatterning.

Nanopatterning to fabricate advanced nanostructured materials is a widely employed technology in a broad spectrum of applications going from spintronics and nanoelectronics to nanophotonics. This work reports on an easy route for nanopatterning making use of ordered porous templates with geometries ranging from straight lines to square, triangular or rhombohedral lattices, to be employed for the designed growth of sputtered materials with engineered properties. The procedure is based on large-scale nanoimprinting using patterned low-cost commercial disks, as 1-D grating stamps, followed by a single electrochemical process that allows one to obtain 1-D ordered porous anodic templates. Multiple imprinting steps at different angles enable more complex 2-D patterned templates. Subsequently, sputtering facilitates the growth of ferromagnetic antidot thin films (e.g., from 20 to 100 nm Co thick layers) with designed symmetries. This technique constitutes a non-expensive method for massive mold production and pattern generation avoiding standard lithographical techniques. In addition, it overcomes current challenges of the two-stage electrochemical porous anodic alumina templates: (i) allowing the patterning of large areas with high ordering and/or complex antidot geometries, and (ii) being less-time consuming.

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.

Large-area surface-patterned Li metal anodes fabricated using large, flexible patterning stamps for Li metal secondary batteries

The use of surface-patterned lithium (Li) metal has been proposed as a promising strategy for inhibiting the formation of Li dendrites during repeated Li plating/stripping processes. Nevertheless, the conventional Li metal patterning process is complex, expensive, incompatible with mass production, and incapable of producing finely controlled patterns on the Li metal surface. A large, flexible patterning stamp capable of large-area patterns is developed using a silicon (Si) wafer-based chemical etching process, and its effect on the electrochemical performance of a Li metal anode is investigated. The newly developed stamps have 5,000% larger patterning area compared to the conventional stainless-steel stamps. Furthermore, when compared to conventional surface-patterned Li metal fabricated with conventional stainless-steel stamps (SP-LM), the surface-patterned Li metal fabricated with large and flexible patterning stamps (LAP-LM) demonstrates improved electrochemical performance and stable morphological properties. As a result, the LAP-LM is able to retain up to 85.2% of its initial discharge capacity (85.9 mAh g −1 ) after 200 cycles at 3C (3.96 mA cm −2 ), while the SP-LM shows a severe capacity decay after 150 cycles (94.0 mAh g −1 and 13.0 mAh g −1 at the 150th cycle and 200th cycle, respectively). • A large, flexible patterning stamp capable of large-area patterns was developed. • The newly developed stamps achieved 5,000% larger patterning area for Li metal. • The new large-area stamp produced stable morphological properties for Li metal. • The new large-area stamp showed significantly improved electrochemical properties.

Multi-Wavelength Optical Patterning for Multiscale Materials Design

Laser interferometry is a consolidated technique for materials structuring, enabling single step and large area patterning. Here we report the investigation of the morphological modification encoded on a thin film of a photosensitive material by the light interference pattern obtained from a laser operating in multiline mode. Four lines with equal intensity are retained, with the same p linear polarization. An azopolymer is exploited as medium for the holographic recording. Optical microscopy and profilometer measurements analyze the modification induced in the bulk and on the surface of the irradiated area. We show that the intensity profile of the interference patterns of two laser beams is the one obtained assuming each line of the laser as an independent oscillator of given intensity and wavelength, and how these light structures are faithfully replicated in the material bulk and on the topography of the free surface. Patterns at different length scales are achievable in a single step, that can be traced back to both interference fringes and wave envelopes. The proposed multi-wavelength holographic patterning provides a simple tool to generate complex light structures, able to perform multiscale modifications of photoresponsive materials

3D MOF Nanoarchitecture Membrane via Ultrafast Laser Nanoforging.

Metal-organic framework (MOF) crystals are useful in a vast area of applications because of their unique chemical and physical properties. Manufacturing of an integrated MOF membrane with 3D nanoarchitectures on the surface is especially important for their applications. However, as MOF crystals usually exist as powdery crystals, fabrication of their large area, monolithic, and high-resolution patterns is challenging. Here, it is found that isolated MOF nanocrystals could be directly converted to a monolithic MOF film with designed 3D nanoarchitectures/patterns via an ultrafast laser induced nanoforging without binders. During the nanosecond laser shock, the voids among MOF nanocrystals are eliminated due to the surface amorphization effect, which allows the fusing of the MOF nanocrystals on the grain boundaries, leading to the formation of a dense film while preserving the nature of the pristine MOF. The high strain rate by laser enhances formability of MOFs and overcomes their brittleness to generate arbitrary 3D nanoarchitectures with feature sizes down to 100nm and high productivity up to 80 cm2 min-1 . These 3D MOF nanoarchitectures also exhibit boosted mechanical strength up to 100% compared with their powdery particles. This method is facile and low-cost and could potentially be used in various fields, such as devices, separation, and biochemical applications.

Towards achieving a large-area and defect-free nano-line pattern via controlled self-assembly by sequential annealing

Utilizing the controlled self-assembling of a giant surfactant, a bottom-up method for constructing line gratings with sub-10 nm resolution has been developed. Via a simple solvent vapor annealing procedure, the giant surfactant comprised of an oligomeric silsesquioxane (DPOSS) and polystyrene (PS) tail (i.e., DPOSS-PS) has been precisely self-assembled into perpendicularly oriented lamellae structures. A follow-up thermal annealing further significantly promotes the long-range ordering, giving rise to highly oriented and defect-free sub-10 nm line patterns (up to areas of several µm2). The solvent evaporation and thermal annealing process, together with the strong segregation strength (χN) of DPOSS-PS, play crucial roles in the self-orientation and width-reduction of the line patterns. This simple processing of the easy-accessed giant surfactants results in a facile and more economic approach for large-scale nano-sized line grating fabrication.

Large-area patterning of full-color quantum dot arrays beyond 1000 pixels per inch by selective electrophoretic deposition

Colloidal quantum dot (QD) emitters show great promise in the development of next-generation displays. Although various solution-processed techniques have been developed for nanomaterials, high-resolution and uniform patterning technology amicable to manufacturing is still missing. Here, we present large-area, high-resolution, full-color QD patterning utilizing a selective electrophoretic deposition (SEPD) technique. This technique utilizes photolithography combined with SEPD to achieve uniform and fast fabrication, low-cost QD patterning in large-area beyond 1,000 pixels-per-inch. The QD patterns only deposited on selective electrodes with precisely controlled thickness in a large range, which could cater for various optoelectronic devices. The adjustable surface morphology, packing density and refractive index of QD films enable higher efficiency compared to conventional solution-processed methods. We further demonstrate the versatility of our approach to integrate various QDs into large-area arrays of full-color emitting pixels and QLEDs with good performance. The results suggest a manufacture-viable technology for commercialization of QD-based displays.

Dip-Pen Nanolithography(DPN): from Micro/Nano-patterns to Biosensing.

Dip-pen nanolithography is an emerging and attractive surface modification technique that has the capacity to directly and controllably write micro/nano-array patterns on diverse substrates. The superior throughput, resolution, and registration enable DPN an outstanding candidate for biological detection from the molecular level to the cellular level. Herein, we overview the technological evolution of DPN in terms of its advanced derivatives and DPN-enabled versatile sensing patterns featuring multiple compositions and structures for biosensing. Benefitting from uniform, reproducible, and large-area array patterns, DPN-based biosensors have shown high sensitivity, excellent selectivity, and fast response in target analyte detection and specific cellular recognition. We anticipate that DPN-based technologies could offer great potential opportunities to fabricate multiplexed, programmable, and commercial array-based sensing biochips.

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 10nm 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.

Lithographic Processes for the Scalable Fabrication of Micro- and Nanostructures for Biochips and Biosensors.

Since the early 2000s, extensive research has been performed to address numerous challenges in biochip and biosensor fabrication in order to use them for various biomedical applications. These biochips and biosensor devices either integrate biological elements (e.g., DNA, proteins or cells) in the fabrication processes or experience post fabrication of biofunctionalization for different downstream applications, including sensing, diagnostics, drug screening, and therapy. Scalable lithographic techniques that are well established in the semiconductor industry are now being harnessed for large-scale production of such devices, with additional development to meet the demand of precise deposition of various biological elements on device substrates with retained biological activities and precisely specified topography. In this review, the lithographic methods that are capable of large-scale and mass fabrication of biochips and biosensors will be discussed. In particular, those allowing patterning of large areas from 10 cm2 to m2, maintaining cost effectiveness, high throughput (>100 cm2 h–1), high resolution (from micrometer down to nanometer scale), accuracy, and reproducibility. This review will compare various fabrication technologies and comment on their resolution limit and throughput, and how they can be related to the device performance, including sensitivity, detection limit, reproducibility, and robustness.

Large Area Patterning of Nanoparticles and Nanostructures: Current Status and Future Prospects.

Nanoparticles possess exceptional optical, magnetic, electrical, and chemical properties. Several applications, ranging from surfaces for optical displays and electronic devices, to energy conversion, require large-area patterns of nanoparticles. Often, it is crucial to maintain a defined arrangement and spacing between nanoparticles to obtain a consistent and uniform surface response. In the majority of the established patterning methods, the pattern is written and formed, which is slow and not scalable. Some parallel techniques, forming all points of the pattern simultaneously, have therefore emerged. These methods can be used to quickly assemble nanoparticles and nanostructures on large-area substrates into well-ordered patterns. Here, we review these parallel methods, the materials that have been processed by them, and the types of particles that can be used with each method. We also emphasize the maximal substrate areas that each method can pattern and the distances between particles. Finally, we point out the advantages and disadvantages of each method, as well as the challenges that still need to be addressed to enable facile, on-demand large-area nanopatterning.

The patterning toolbox FIB-o-mat: Exploiting the full potential of focused helium ions for nanofabrication.

Focused beams of helium ions are a powerful tool for high-fidelity machining with spatial precision below 5 nm. Achieving such a high patterning precision over large areas and for different materials in a reproducible manner, however, is not trivial. Here, we introduce the Python toolbox FIB-o-mat for automated pattern creation and optimization, providing full flexibility to accomplish demanding patterning tasks. FIB-o-mat offers high-level pattern creation, enabling high-fidelity large-area patterning and systematic variations in geometry and raster settings. It also offers low-level beam path creation, providing full control over the beam movement and including sophisticated optimization tools. Three applications showcasing the potential of He ion beam nanofabrication for two-dimensional material systems and devices using FIB-o-mat are presented.