Beam Pen Lithography Research Articles

Photopolymerized Features via Beam Pen Lithography as a Novel Tool for the Generation of Large Area Protein Micropatterns.

A cantilever-free scanning probe lithography (CF-SPL)-based method for the rapid polymerization of nanoscale features onasurfacevia crosslinking and thiol-acrylate photoreactions is described, whereinthenanoscale position, height, and diameter of each feature can be finely and independently tuned. With precise spatiotemporal control over the illumination pattern, beam pen lithography (BPL) allows for the photo-crosslinking of polymers into ultrahigh resolution features over centimeter-scale areas using massively parallel >160 000 pen arrays of individually addressable pens that guide and focus light onto the surface with sub-diffraction resolution. The photoinduced crosslinking reaction of the ink material, which is composed of photoinitiator, diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide, poly(ethylene glycol) diacrylate, and thiol-modified functional binding molecules (i.e., thiol-PEG-biotin or 16-mercaptohexanoic acid), proceeds to ≈80% conversion with UV exposure (72mWcm-2 ) for short time periods (0.5s). Such polymer patterns are further reacted with proteins (streptavidin and fibronectin) to yield protein arrays with feature arrangements at high resolution and densities controlled by local UV exposure. This platform, which combines polymer photochemistry and massive arrays of scanning probes, constitutes a new approach to making biomolecular microarrays in a high-throughput and high-yielding manner, opening new routes for biochip synthesis, bioscreening, and cell biology research.

Evolution of Dip-Pen Nanolithography (DPN): From Molecular Patterning to Materials Discovery.

Dip-pen nanolithography (DPN) is a nanofabrication technique that can be used to directly write molecular patterns on substrates with high resolution and registration. Over the past two decades, DPN has evolved in its ability to transport molecular and material "inks" (e.g., alkanethiols, biological molecules like DNA, viruses, and proteins, polymers, and nanoparticles) to many surfaces in a high-throughput fashion, enabling the synthesis and study of complex chemical and biological structures. In addition, DPN has laid the foundation for a series of related scanning probe methodologies, for example, polymer pen lithography (PPL), scanning probe block copolymer lithography (SPBCL), and beam-pen lithography (BPL), which do not rely on cantilever tips. Structures prepared with these methodologies have been used to understand the consequences of miniaturization and open a door to new capabilities in catalysis, optics, biomedicine, and chemical synthesis, where, in sum, a process originally intended to compete with tools used by the semiconductor industry for rapid prototyping has transcended that application to advanced materials discovery. This review outlines the major DPN advances, the subsequent methods based on the technique, and the opportunities for future fundamental and technological exploration. Most importantly, it commemorates the 20th anniversary of the discovery of DPN.

Massively Multiplexed Tip-Based Photochemical Lithography under Continuous Capillary Flow

Summary Multiplexed microarrays—where different biological probes are spatially encoded onto a surface into spots with micrometer-scale diameters—have facilitated the rapid advancement of "omics" research. Further miniaturization of feature diameters could increase the number of probes in a microarray, reduce the sample required for analysis, and decrease costs. Tip-based lithography (TBL) has gained popularity for patterning delicate, biologically active materials, but no versatile TBL-based multiplexing strategy has been devised. Here, we combine microfluidics, beam pen lithography, and photochemical surface reactions to create multiplexed arrays. For proof of concept, the thiol-ene reaction was optimized, and the reaction kinetics were analyzed. Subsequently, we created several patterns containing multiple fluorescent alkenes, where each pattern was designed to demonstrate a different capability of this instrument. This patterning strategy is a powerful approach to studying and optimizing organic reactions on surfaces and creating massively multiplexed arrays and, as such, could provide an entirely new approach for miniaturizing biochips or understanding interfacial reactivity.

Maskless beam pen lithography based on integrated microlens array and spatial-filter array

A beam pen lithography system is proposed for ultraviolet (UV) patterning of complicated patterns in a maskless manner. The system consists of a single UV light-emitting diode (LED), a double-sided microlens/spatial-filter array (MLSFA), and a motorized x-y stage. The double-sided MLSFA contains a pinhole array sandwiched by two microlens arrays. The microlens arrays are fabricated by an excimer laser micromachining system to achieve accurate and optimized lens profiles obtained from optical simulation. Techniques have been developed in the fabrication processes to guarantee good alignment between the pinhole array and the two microlens arrays. Finally, arrayed UV spots are formed with feature size around 4 to 5 μm. Through mechanical movement of stage and intensity control on the UV LED, a number of complicated patterns are experimentally demonstrated using this type of beam pen lithography. It offers a simple, inexpensive, and portable choice on maskless UV patterning with great potential for future applications.

And There Was Light: Prospects for the Creation of Micro- and Nanostructures through Maskless Photolithography.

In photolithographic processes, the light inducing the photochemical reactions is confined to a small volume, which enables direct writing of micro- and nanoscale features onto solid surfaces without the need of a predefined photomask. The direct writing process can be used to generate topographic patterns through photopolymerization or photo-cross-linking or can be employed to use light to generate chemical patterns on the surface with high spatial control, which would make such processes attractive for bioapplications. The prospects of maskless photolithography technologies with a focus on two-photon lithography and scanning-probe-based photochemical processes based on scanning near-field optical microscopy or beam pen lithography are discussed.

Solution-Phase Photochemical Nanopatterning Enabled by High-Refractive-Index Beam Pen Arrays.

A high-throughput, solution-based, scanning-probe photochemical nanopatterning approach, which does not require the use of probes with subwavelength apertures, is reported. Specifically, pyramid arrays made from high-refractive-index polymeric materials were constructed and studied as patterning tools in a conventional liquid-phase beam pen lithography experiment. Two versions of the arrays were explored with either metal-coated or metal-free tips. Importantly, light can be channeled through both types of tips and the appropriate solution phase (e.g., H2O or CH3OH) and focused on subwavelength regions of a substrate to effect a photoreaction in solution that results in localized patterning of a self-assembled monolayer (SAM)-coated Au thin film substrate. Arrays with as many as 4500 pyramid-shaped probes were used to simultaneously initiate thousands of localized free-radical photoreactions (decomposition of a lithium acylphosphinate photoinitiator in an aqueous solution) that result in oxidative removal of the SAM. The technique is attractive since it allows one to rapidly generate features less than 200 nm in diameter, and the metal-free tips afford more than 10-fold higher intensity than the tips with nanoapertures over a micrometer propagation length. In principle, this mask-free method can be utilized as a versatile tool for performing a wide variety of photochemistries across multiple scales that may be important in high-throughput combinatorial screening applications related to chemistry, biology, and materials science.

High Throughput Synthesis of Multifunctional Oxide Nanostructures within Nanoreactors Defined by Beam Pen Lithography.

Reliably obtaining nanostructures of complex oxides over large area with nanoscale resolution and well-controlled shape, spacing, and pattern symmetry remains a major challenge. In this article, millions of nanowells have been routinely generated by beam pen lithography. Each attoliter volume nanowell functions as a "nanoreactor", inside which oxide nanostructures are synthesized from their sol-gel precursors. Importantly, these nanometer scale entities are in single crystalline or textured forms and epitaxial to the underlying substrates, which promises functionalities including ferroelectricity, ferromagnetism, and multiferroicity. This method provides a general solution which allows one to rapidly screen structural parameters of oxide nanostructures comprising of three or more elements for prominent properties.

Deastigmatism, circularization, and focusing of a laser diode beam using a single biconvex microlens

A single biconvex microlens is proposed to correct the astigmatism and ellipticity of a laser diode (LD) beam and focus it to a smallest circular spot. The microlens has three different profiles in which one cylindrical input surface is to collimate the beam in the fast-axis (y-axis) direction. Output surface, on the other hand, holds two different parabolic profiles in fast- and slow-axis (x-axis) directions to correct the astigmatism and focus the beam into a smallest circular spot. A simulation software is used to design and optimize those lens profiles. Theoretically, the smallest focused spot size is around 4.24 μm in diameter. The three profiles are then transferred to photo-masks to fabricate the microlens on polycarbonate material using an excimer laser dragging method with alignment accuracy of 1 μm. The machined microlens is assembled with the LD using double-sided optically clear adhesive tape. The experimental focused spot is found to be 16.75 μm in diameter. Circularity of the focused spot is demonstrated by a single-shot exposure test on thin photoresist layer that shows a circular-dot diameter of 7.32 μm. The proposed technique has great potential in applications such as beam pen lithography, fiber coupling, and optical read-write head.

Liquid-Phase Beam Pen Lithography.

Beam pen lithography (BPL) in the liquid phase is evaluated. The effect of tip-substrate gap and aperture size on patterning performance is systematically investigated. As a proof-of-concept experiment, nanoarrays of nucleotides are synthesized using BPL in an organic medium, pointing toward the potential of using liquid phase BPL to perform localized photochemical reactions that require a liquid medium.

Beam pen lithography based on focused laser diode beam with single microlens fabricated by excimer laser.

A method is proposed to minimize the focused spot size of an elliptically-diverging laser diode beam by means of a circular aperture and a single plano-convex aspherical microlens. The proposed microlens is fabricated using an excimer laser dragging method and has two different profiles in the x- and y-axis directions. The focused spot size of the beam is examined both numerically and experimentally. The feasibility of the proposed approach for beam pen lithography applications is demonstrated by patterning dotted, straight-line and spiral features on a photo resist layer followed by thin gold layer deposition and metal lift-off. The minimum feature size for dotted pattern is around 2.57 μm, while the minimum line-widths for straight-line and spiral pattern are 3.05 μm and 4.35 μm, respectively. Thus, the technique can be applied to write any arbitrary pattern for high-resolution lithography.

Patterning via optical saturable transitions--fabrication and characterization.

This protocol describes the fabrication and characterization of nanostructures using a novel nanolithographic technique called Patterning via Optical Saturable Transitions (POST). In this technique the chemical properties of organic photochromic molecules that undergo single-photon reactions are exploited, enabling rapid top-down nanopatterning over large areas at low light intensities, thereby, allowing for the circumvention of the far-field diffraction barrier.(4) Simple, cost-effective, high throughput and resolution alternatives to nanopatterning are being explored, such as, two-photon polymerization(5,6), beam pen lithography (BPL)(7), scanning electron beam lithography (SEBL), and focused ion beam (FIB) patterning. However, multi-photon approaches require high light intensities, which limit their potential for high throughput and offer low image contrast. Although, electron and ion beam lithographic processes offer increased resolution, the serial nature of the process is limited to slow writing speeds, which also prevents patterning of features over large areas. Beam-pen lithography is an approach towards parallel near-field optical lithography. However, the gap between the source of the beam and the surface of the photoresist needs to be controlled extremely precisely for good pattern uniformity and this is very challenging to accomplish for large arrays of beams. Patterning via Optical Saturable Transitions (POST) is an alternative optical nanopatterning technique for patterning sub-wavelength features(1-3). Since this technique uses single photons instead of electrons, it is extremely fast and does not require high light intensities(1-3), opening the door to massive parallelization.

Apertureless beam pen lithography based on fully metal-coated polyurethane-acrylate (PUA) pyramidal microstructure array.

This work demonstrates a form of arrayed transmitting apertureless near-field photolithography, called apertureless beam pen lithography. An array of fully chromium-coated polyurethane acrylate (PUA) pyramidal microstructures was illuminated by a traditional Ultraviolet (UV) lamp to generate an array of massive UV beam pens for realizing apertureless beam pen lithography. Experimental results reveal that significant UV energy can pass through the apex of a fully metal-coated PUA pyramid even though the thickness of the metallic coating exceeded the penetration depth. The patterned photoresist profiles were 117 nm deep and the full-width-at-half-magnitude (FWHM) was 180 nm when the exposure dosage was 54 mJ/cm(2) and the wavelength was 365 nm. Both depth and FWHM increased with exposure dosage, implying that the profiles depended on exposure dosage rather than on physical imprinting. With the adjustment of the thickness of the photoresist layer and the exposure parameters, the lift-off process yields arrayed metal dots with a diameter of 300 nm. Finite-element simulation of the intensity distribution near the apex of the pyramid and within the photoresist layer was carried out to reveal that the energy concentration within the pyramids is increased by approximately an order of magnitude, significantly enhancing the UV energy that passes through the fully metal-coated apex. The contrast curve model of the photoresist was used to calculate the patterned photoresist profiles for various energies. Experimental results, theoretical analysis and potential improvements of the method are presented.

Fabrication of a seamless roller mold with wavy microstructures using mask-less curved surface beam pen lithography

Roller imprinting is one of the most commonly used methods for the fabrication of continuous functional structures over large areas. However, the fabrication of roller molds with seamless and complex patterns poses a significant challenge. This paper presents an innovative technique for fabricating a seamless roller mold with wavy microstructures using a novel mask-less curved surface beam pen lithography technique. The major steps in the proposed technique include spray coating a thin photo-resist (PR) layer on the roller, exposing the PR layer though a translating micro-lens array (MLA), etching the patterned PR layer, and electro-polishing the etched microstructures. The proposed method is used to pattern roller molds with different wavy microstructures by varying the rotation speed of the roller, the translation speed of the MLA holder, and the translation distance of the MLA holder. The patterned metal roller molds are then used to replicate wavy microstructures on a thin polyethylene terephthalate substrate by means of continuous UV-type roller imprinting methods. The line-width and height of the wavy microstructure are 84.5 µm and 25.5 µm, respectively.

Beam pen lithography based on arrayed polydimethylsiloxane (PDMS) micro-pyramids spin-coated with carbon black photo-resist

This paper presents a new method for preparing a polydimethylsiloxane (PDMS) mold which can be used in beam pen lithography for patterning a photo-resist (PR) layer in a maskless and direct-write manner. The PDMS mold contains an array of micro-pyramids on its surface and is spin-coated with a layer of carbon black PR which is an opaque material. Because of the arrayed pyramidal surface profile, the spin-coated carbon black PR layer is either thinner at the pyramid tips or does not cover the tips at all, which allows ultraviolet (UV) light to pass through the PDMS mold and forms an array of UV beams. The aperture size of the UV beams can be controlled at a sub-micrometer scale and hence can be used for micro/nano-patterning. Applying this carbon black-PR-coated PDMS mold in beam pen lithography along with a metal lift-off process, various metal dot patterns with a dot-size around 400 to 500 nm are successfully obtained. Both experimental results and theoretical analysis are given along with possible improvements and applications in the future.

Beam pen lithography as a new tool for spatially controlled photochemistry, and its utilization in the synthesis of multivalent glycan arrays.

Herein, we describe how cantilever-free scanning probes can be used to deposit precursor material and subsequently irradiate the precursor to initiate polymerization, resulting in a 3D lithographic method wherein the position, height and diameter of each feature can be tuned independently. Specifically, acrylate and methacrylate monomers were patterned onto thiol terminated glass and subsequently exposed to UV light produced brush polymers by a photoinduced radical acrylate polymerization reaction. Here, we report the first examples of glycan arrays, comprised of methacrylate brush polymers that are side-chain functionalized with α-glucose, by this new lithographic approach. Their binding with fluorophore labeled concanavalin A (ConA) was assayed by fluorescence microscopy. The fluorescence of these brush polymers was compared to glycan arrays composed of monolayers of α-mannosides and α-glucosides prepared by combining polymer pen lithography (PPL) with the thiol-ene photochemical reaction or the copper-catalyzed azide-alkyne cycloaddition. At high ConA concentration, the fluorescence signal of the brush polymer was nearly 20 times greater than that of the glycan monolayers, and the brush polymer arrays had a detection limit nearly two orders of magnitude better than their monolayer counterparts. Because of the ability of this method to control precisely the polymer length, the relationship between limit of detection and multivalency could be explored, and it was found that the longer polymers (136 nm) are an order of magnitude more sensitive towards ConA binding than the shorter polymers (8 nm) and that binding affinity decreased systematically with length. These glycan arrays are a new tool to study the role of multivalency on carbohydrate recognition, and the photopolymerization route towards forming multivalent glycan scaffolds described herein, is a promising route to create multiplexed glycan arrays with nanoscale feature dimensions.

Desktop nanofabrication with massively multiplexed beam pen lithography

The development of a lithographic method that can rapidly define nanoscale features across centimeter-scale surfaces has been a long standing goal of the nanotechnology community. If such a ‘desktop nanofab’ could be implemented in a low-cost format, it would bring the possibility of point-of-use nanofabrication for rapidly prototyping diverse functional structures. Here we report the development of a new tool that is capable of writing arbitrary patterns composed of diffraction-unlimited features over square centimeter areas that are in registry with existing patterns and nanostructures. Importantly, this instrument is based on components that are inexpensive compared to the combination of state-of-the-art nanofabrication tools that approach its capabilities. This tool can be used to prototype functional electronic devices in a mask-free fashion in addition to providing a unique platform for performing high throughput nano- to macroscale photochemistry with relevance to biology and medicine.

Beam pen lithography

Lithography techniques are currently being developed to fabricate nanoscale components for integrated circuits, medical diagnostics and optoelectronics. In conventional far-field optical lithography, lateral feature resolution is diffraction-limited. Approaches that overcome the diffraction limit have been developed, but these are difficult to implement or they preclude arbitrary pattern formation. Techniques based on near-field scanning optical microscopy can overcome the diffraction limit, but they suffer from inherently low throughput and restricted scan areas. Highly parallel two-dimensional, silicon-based, near-field scanning optical microscopy aperture arrays have been fabricated, but aligning a non-deformable aperture array to a large-area substrate with near-field proximity remains challenging. However, recent advances in lithographies based on scanning probe microscopy have made use of transparent two-dimensional arrays of pyramid-shaped elastomeric tips (or 'pens') for large-area, high-throughput patterning of ink molecules. Here, we report a massively parallel scanning probe microscopy-based approach that can generate arbitrary patterns by passing 400-nm light through nanoscopic apertures at each tip in the array. The technique, termed beam pen lithography, can toggle between near- and far-field distances, allowing both sub-diffraction limit (100 nm) and larger features to be generated.