Rapid and mask-less laser-processing technique for the fabrication of microstructures in polydimethylsiloxane

We report a rapid laser-based method for structuring polydimethylsiloxane (PDMS) on the micron-scale. This mask-less method uses a digital multi-mirror device as a spatial light modulator to produce a given spatial intensity pattern to create arbitrarily shaped structures via either ablation or multi-photon photo-polymerisation in a master substrate, which is subsequently used to cast the complementary patterns in PDMS. This patterned PDMS mould was then used for micro-contact printing of ink and biological molecules

Low loss high index contrast nanoimprinted polysiloxane waveguides

Nanoimprint lithography is gaining rapid acceptance in fields as diverse as microelectronics and microfluidics due to its simplicity high resolution and low cost. These properties are critically important for the fabrication of photonic devices, where cost is often the major inhibiting deployment factor for high volume applications. We report here on the use of nanoimprint technology to fabricate low loss broadband high index contrast waveguides in a Polysiloxane polymer system for the first time

Micro/Nano Patterning on Polymers Using Soft Lithography Technique

Microfabrication is essential in the field of science and technology. The development and innovations in this field are already prominent in the society through microelectronics and optoelectronics. The lithography or transfer of pattern to the substrate/surface of a layer is an important process step in microfabrication and is usually carried out with photolithography. Though photolithography is a well-established technique, it suffers from drawbacks such as limited feature size due to optical diffraction, requirement of high-energy radiation for small features, and high-cost involvement for sophisticated instruments. Also, it cannot be applied to nonplanar surfaces. Soft lithography is complement to photolithography which overcomes the above-mentioned drawbacks. Soft lithography is a simple and inexpensive method, and also, it suits to wide range of materials and very large surface areas. High-quality micropatterns or nanopatterns can be made using a patterned elastomeric stamp. This article briefly describes the various soft lithography techniques to obtain high-resolution structures for nanofabrication

3D integration of micro- and nanostructures into bio-analytical devices

This study aims to develop a process which allows 3D integration of micro and nanostructures in microchannels. A fabrication process was established for the large area integration of hierarchical micro and nanostructures in microchannels. This novel process, which is called 3D molding, takes advantage of an intermediate thin flexible stamp such as PDMS from soft lithography and a hard mold such as brass from hot embossing process. However, the use of a thin intermediate polydimethylsiloxane (PDMS) stamp inevitably causes dimensional changes in the 3D molded channel, with respect to those in the brass mold protrusion and the intermediate PDMS stamp structures. We have investigated the deformation behavior of the 3D molded poly(methyl methacrylate) (PMMA) substrate and the intermediate PDMS stamp in 3D molding through both experimentation and numerical simulation. It was found that for high aspect ratio brass mold protrusion, the maximum strain of the intermediate layer occurs in the bottom center of the 3D channels. However, with decreasing the aspect ratio of brass mold protrusion the highest elongation occurs at the bottom corners of the channel causing less elongation of the intermediate PDMS stamp and imprinted structures on the bottom surface of the 3D channel. A modified 3D molding process which is called 3D nanomolding is developed which allows nanopatterning the surface of small microfeatures. Using 3D nanomolding process and solvent assisted bonding microdevices with no side, one side, three sides and four sides patterned were fabricated. To characterize 3D flow patterns induced by the surface structures on microdevices, confocal microscopy was used as dyed water and undyed water injected from separate inlets of micromixer were mixed along the microchannel at flow rates of 10 and 40 μL/min. The standard deviation of the normalized intensity measured in the confocal image of the cross section of the channel was used for quantifying the degree of mixing and evaluating the mixing performance of all four different microdevices. Experimental and simulation results show that by patterning the surface of the micromixer, flow patterns can be manipulated, which can improve mixing through stretching and folding of fluid elements and therefore increasing the interfacial area between fluids and cutting down the diffusion length. The effect of increasing velocity on increasing standard deviation (decreasing mixing) was also found to be less for the micromixers whose surfaces are patterned compared to the plain channel

Towards Active Monitoring of The Micro Transfer Printing Process

Current microelectronics and micro-electromechanical systems (MEMS) fabrication techniques are optimized for the production of very large volume of parts on a limited range of substrates. These processes have been designed to produce excellent results but still consume large amounts of time and resources and require expensive machinery and facilities. Over the past few years many low cost, fast printing processes have begun to emerge capable of economically producing electronics and MEMS on a variety of substrates. Examples of printed electronic devices include sensors, organic photovoltaic, intelligent packaging, radio frequency identification devices and flexible displays. One such process currently under development at the University of Illinois is micro transfer printing. Micro transfer printing is a process by which micro devices and circuit elements fabricated using standard micro fabrication techniques are picked up and printed onto a destination substrate using a patterned flexible elastomeric stamp. The advantages of the process are low cost, high flexible, high through put, novel target substrates and the devices maintain performance of the host semiconductor. Commercialization of this process depends on the development of innovative technologies for the application of the process to fast and flexible process paradigms realizing innovative products and the ability to integrate the process into existing fabrication processes. This thesis describes the theoretical and practical design of a suite of technologies designed to increase the ease of usage, flexibility, robustness and printing capabilities of the transfer printing tool. We present the design and construction of an instrumented stamp for contact sensing at the device level to close the loop around the pickup and printing process and iv provide a means of feedback. This method has provided an alternative to detect process events and has also been shown to provide means of diagnosing the process as it is running. Along with the instrumented stamps a remote center of compliance tip tilt stage used to perform alignment with minimal loss of registration was also designed and developed for the transfer printer

Hot punching of high-aspect-ratio 3D polymeric microstructures for drug delivery

Hot punching: a highly versatile method of fabricating high-aspect-ratio 3D microstructures for drug delivery with good replication fidelity and yield.</p

MEMS micro-contact printing engines

This thesis investigates micro-contact printing (µCP) engines using micro-electro-mechanical systems (MEMS). Such engines are self-contained and do not require further optical alignment and precision manipulation equipment. Hence they provide a low-cost and accessible method of multilevel surface patterning with sub-micron resolution. Applications include the field of biotechnology where the placement of biological ligands at well controlled locations on substrates is often required for biological assays, cell studies and manipulation, or for the fabrication of biosensors. A miniaturised silicon µCP engine is designed and fabricated using a wafer-scale MEMS fabrication process and single level and bi-level µCP are successfully demonstrated. The performance of the engine is fully characterised and two actuation modes, mechanical and electrostatic, are investigated. In addition, a novel method of integrating the stamp material into the MEMS process flow by spray coating is reported. A second µCP engine formed by wafer-scale replica moulding of a polymer is developed to further drive down cost and complexity. This system carries six complementary patterns and allows six-level µCP with a layer-to-layer accuracy of 10 µm over a 5 mm x 5 mm area without the use of external aligning equipment. This is the first such report of aligned multilevel µCP. Lastly, the integration of the replica moulded engine with a hydraulic drive for controlled actuation is investigated. This approach is promising and proof of concept has been provided for single-level patterning

Polymer Pen Printing: A Tool for Studying 2D Enzymatic Lithography and Printing 3D Carbon Features

Polymer Pen Lithography (PPL) is a promising molecular printing approach which combines the advantages of both microcontact printing (low cost, high-throughput) and the dip pen lithography (DPN) (arbitrary writing, high-resolution) into one cohesive lithography method to create 2 dimensional (2-D) patterns with micro/nano-features on different substrates. The goal of this dissertation is to design and develop a new tool based upon PPL, which is not limited to forming 2D parallel patterns, but can also create 3D complex microstructures, finding applications in both biotechnology and Micro-Electro-Mechanical systems (MEMS) technology. This novel approach is named Polymer Pen Printing. Different from PPL using traditional dry-ink printing methods, an inking step is added to each printing repetition in the polymer pen printing process. Thus a wide range of ink materials with diverse viscosities can be transferred to substrates to create functional 2D and 3D microstructures. The polymer pen printing apparatus used in this thesis has been accomplished and introduced in Chapter 2. As a preliminary attempt, the single polymer pen printing approach was developed by simply attaching a solid polydimethylsiloxane (PDMS) pen tip to a multi-axis robot for small microarray fabrication. Compared to the single pen printing method, multi-pen printing can create large arrays of features. Therefore, an improved apparatus for polymer pen printing with high-throughput was discussed and built. Silicon molds, which consist of hundreds of uniform pyramidal openings, were photolithographically defined and etched using hydrofluoric acid (HF) followed by potassium hydroxide solution; after surface-modification with fluorosilane, these silicon molds were used to cast arrays of PDMS pyramidal pen tip. The cast PDMS pen array was mounted to a hollow holder with a 45° mirror inside. Therefore, each PDMS pen can be observed and monitored from the microscope on the side. To achieve prints less than 1 micron across, a Z axis stage with nanometer resolution was incorporated; and to control the compression of PDMS pen tips, a force gauge was also incorporated to detect 1 mg of applied force from the tips. The printing process for the multi-pen system is almost the same as single pen system. PDMS pens are coated with ink solution before each printing cycle by dipping into an inkwell and then brought into contact with the substrate surface. Thus multiple patterns, one from each tip, are created in parallel simultaneously. Furthermore, with control of the printing force, feature sizes could be controlled over the range submicron to tens of microns. Three ink candidates have been printed by polymer pen printing approach to fabricate 2D&3D microstructures. The first ink material is Barium Strontium Titanate (BST) nanocrystallites dispersed in a furfuryl alcohol (FA), which was printed by the single PDMS pen with 100 μm tip diameter (Chapter 3). After printing, samples were heated to crosslink FA monomers, forming a stable polymeric matrix with embedded BST nanocrystallites. Without shear-thinning properties, BST/FA ink cannot be used to build 3D posts, but it has the capability to create circular patterns with different thickness by the single or multi-tier deposition method. It was found that the thickness of film increased linearly with the number of deposits without changing the diameter significantly. This encouraging result could enable the formation of microcapacitors with multi-tiered structure. Moreover, the study of printing parameters, including printing height and ink pick-up position, shows that changes to the pen positions in the ink reservoir or substrate have essentially no impact on deposit thickness or diameter. Beyond that, the effect of surface chemistry of PDMS pen and silicon wafer have also been studied. The plasma treated hydrophilic PDMS pen can pen transfer more BST/FA than untreated one; and the larger diameters with smaller thickness were obtained on a hydrophilic silicon wafer. The second ink candidate is a dilute aqueous solution of enzyme Candia antartica lipase B (CALB), which is known to catalyze the decomposition of poly (ε-caprolactone) (PCL) films. By bringing enzymes into contact with pre-defined regions of a surface, a polymer film can be selectively degraded to form patterned features that are requited for applications in biotechnology and electronics. This so-called enzymatic lithography is an environmentally friendly process as it does not require any actinic radiation or synthetic chemicals to develop required features. But the need to restrict the mobility of the enzyme in order to maintain control of feature sizes poses a significant challenge. In Chapter 4, after writing 2D enzyme patterns onto a spin-cast PCL film by single pen printing, samples with CALB were incubated at 37 ℃ and 95% relative humidity (RH) for up to 7 days to develop features. The CALB selectively degraded the PCL film during incubation, forming openings through the film. The size of these features (10 to 50 μm diameter) is well suited for use as biocompatible micro-reactors. Previous study of patterning CALB by single polymer pen printing technique resulted in slow etch rates, low throughput and poor image quality. In Chapter 5, I present an improved enzymatic lithography approach, still based on enzyme CALB and PCL system, which can resolve fine-scale features (\u3c 1 μm across) in thick (0.1 - 2.0 μm) polymer films after 5 minutes to 2 hours of incubation at 37 ℃ and 87% RH. Immobilization of the enzyme on the polymer surface was monitored using fluorescence microscopy by labeling CALB with FITC. The crystallite size in the PCL films was systematically varied; small crystallites resulted in significantly faster etch rates (20 nm/min) and the ability to resolve smaller features (as fine as 1 μm). The effect of printing conditions and RH during incubation is also presented. Patterns formed in the PCL film were transferred to an underlying copper foil demonstrating a Green approach to the fabrication of printed circuit boards. In parallel, the third ink material is a mixture of 25 wt% graphite dispersed in a high viscosity phenolic resin n-methyl-2-pyrrolidone (NMP) solution, which can be converted into carbon/carbon composites after a pyrolysis process. The 3D polymeric posts were created by depositing multilayers of thixotropic phenolic ink on a silicon substrate by single polymer pen printing method with a 10 μm radius PDMS pen tip (Chapter 6). After pyrolysis at 1000 ℃ in a nitrogen (N2) atmosphere, the polymeric features were converted to the glassy carbon/graphite features with a high aspect ratio (\u3e2). These features may be used as microelectrodes. Last, arrays of needle-shaped glassy carbon have been developed by a drawing approach using multi-pen printing technique followed by simple pyrolysis process (Chapter 7). To build polymeric needles with ultra-high aspect ratio, the polymeric ink was prepared by dissolving phenolic resin in the high boiling point (204 ℃) solvent NMP without fillers to achieve good printability and suitable viscosity. By slowly lifting up the print head from substrate, liquid needle structures were formed and then solidified on silicon substrates or gold electrodes due to the solvent evaporation. In addition, suspended resin fibers connected to two electrodes have also been fabricated by precisely controlling the movement of the PDMS pen. After pyrolysis, these resin features were converted to glassy carbon and the 3D structures remained. The electrical characterization results showed that glassy carbon made by this method had relatively low resistivity (2.5 x 10-5 Ωm). Therefore the glassy carbon based microneedles are well-suited to be electrodes for electrochemical sensors for biological applications

Functionalization of particles and selective functionalization of surfaces for the electroless metal plating process

Electroless plating is a metal deposition technique widely used in the coating industry. It is the method of choice to plate substrates with complex geometries and nonconductive surfaces, such as polymers and ceramics, since it is based on a chemical reduction in solution rather than on an external electrical energy source like the electroplating method. Among others, examples of well-established applications are the electroless deposition of decorative metal coatings such as gold and silver, wear and corrosion resistant nickel coatings, particularly to coat drive shafts, rotors, and bathroom fixtures, as well as the electroless deposition of copper in electronic devices as diffusion barriers and conductive circuit elements. In the academic research, electroless plating is extensively used thanks to its low cost, simple equipment and versatility that allow rapid prototyping. Two common applications are the coating of small particles and the selective plating of flat surfaces. Metal coated ceramic particles are of enormous interest in many scientific fields, e.g. fluorescent diagnostics in biochemistry, catalysis, and fabrication of photonic crystals. Metal coated ceramic nanoparticles and microparticles are also gaining attention as potential candidates in the fabrication of higher quality metal matrix Composites, which is one of the applications addressed by this work. Metal coated ceramic particles are easier to integrate in metal matrix composites, avoiding aggregation caused by the low wettability of the particles by the matrix metal, and are potentially shielded from oxidation and undesired chemical reactions that take place at the interface between the particles and the metal Matrix. Electroless plating is an autocatalytic process, meaning that the deposited metal atoms catalyze the deposition of further metal. In order to achieve the first stable metal seeds on a surface, the latter has to be functionalized. Without this functionalization the metal ions in the electroless plating bath are not reduced or are simply reduced to metal nanoparticles in solution. The traditional activation step for nonconductive surfaces is performed by immersion of the substrate in palladium based solutions, which is very time-consuming and extremely expensive. In particular for nanoparticles, previous work showed that at least 1015 Pd atoms/cm2 are required for a uniform activation of a surface, meaning that in the case of nanoparticles with a surface area of about 100 m2/g are necessary 6.4 g of palladium for each gram of substrate. Assuming a price of about 150 €/g (laboratory scale) for palladium nanoparticles and palladium precursors used for surface activation, it results that the activation of 1 g of nanoparticles costs around 1000 €. Such costs are suboptimal considering the typical production scale, and therefore alternative functionalization methods are desired. In this work, new organic-based functionalization methods based on (3-mercaptopropyl)triethoxysilane to functionalize oxide particles, 3-aminopropylphosphonic acid to activate carbide particles and a substrate-independent method based on the bioinspired polydopamine are developed and investigated in detail, together with the respective electroless plating baths, which often have to be specifically tailored regarding the different reactivity of the different molecules and substrates. Furthermore, in the fabrication of metallic patterns on substrates by electroless plating, new, simple, and cost-effective activation and metal deposition processes are desired. In this work, two new methods are presented, one based on the printing of (3-mercaptopropyl)triethoxysilane by microcontact printing, the other based on the capillary force lithography of polymethylmethacrylate