Simulation and investigation of factors affecting high aspect ratio UV embossing

UV embossing is a replication method whereby an UV-curable polymer is pressed against a patterned mold and cured with UV irradiation, resulting in a patterned polymeric substrate. High aspect ratio UV embossing will find diverse applications in tissue engineering, micro-optics, display technologies, and sensors. Demolding of an UV-embossed polymer pattern with aspect ratio of 5 from the mold has previously been demonstrated experimentally. In this paper, parameters that affect the demolding process have been identified and investigated. They include cross-linking shrinkage during curing by UV irradiation, modulus of cured polymer, interfacial fracture strength and toughness, and loading method during demolding. Shrinkage is an important parameter, and an optimum level of shrinkage to avoid breakage of the embossing during demolding was found to exist. This optimum level is that at which the maximum stress (sigma(1)max) experienced by the polymer during demolding is minimized. The micromechanics of demolding was found to be different for shrinkage values lower or larger than the optimum value.     

Light stamping lithography: microcontact printing without inks

We report a new patterning method, called light-stamping lithography (LSL), that uses UV-induced adhesion of poly(dimethylsiloxane) (PDMS). LSL is based on the direct transfer of the contact surface of the PDMS stamp to a substrate via a UV (254 nm)-induced surface bonding between the stamp and the substrate. This procedure can be adopted in automated printing machines that generate patterns with a wide range of feature sizes on diverse substrates. To demonstrate its usefulness, the LSL method was applied to prepare several PDMS patterns on a variety of substrates. The PDMS patterns were then used as templates for selective deposition of TiO2 thin film using atomic layer deposition as well as resists for selective wet etching.     

利用软模板和紫外光固化技术制备超疏水表面

研究了一种制备超疏水表面的新方法.该方法以复制了荷叶表面结构的聚二甲基硅氧烷(PDMS)弹性体为软模板.利用可紫外光交联预聚物在模板压印条件下固化成型,得到了具有微乳突结构的仿荷叶表面.制备的仿荷叶表面表现出了超疏水性能.通过对紫外光固化体系中的单体含量、交联剂含量、引发剂含量、以及紫外曝光时间等因素的研究,得到了使仿荷叶表面的疏水性优化的条件.     

Polybenzoxazine as a mold-release agent for nanoimprint lithography

One of the most important tasks remaining to be resolved in nanoimprint lithography is the elimination of the resist sticking to the mold during demolding. Previously, the main approach was to apply a thin layer of fluorinated alkyl silane mold-release agent on the surface on the mold; however, this involves complicated steps and high costs. The low surface free energy material polybenzoxazine provides an efficient mold-release agent for silicon molds that is easier to process, costs less, and has no side reactions.     

Hybrid organic–inorganic sol–gel materials for micro and nanofabrication

In this review hybrid organic–inorganic (HOI) resists as emerging materials alternative to organic polymers for micro and nanolithography are presented and discussed. In particular, results on sol–gel materials belonging to 3-glycidoxypropyltrimethoxysilane based HOI are presented and reviewed, highlighting as various lithographic techniques can be used to pattern their surface and showing examples of micro- and nano-patterned structures achieved with radiation assisted lithography (UV, X-rays and electron beam) or imprint techniques. It will be demonstrated the particular versatility shown by some of these materials, that in some case can be processed with all the lithographic methods herein considered, without any significant modification of their main composition and synthesis procedure. Moreover, results about the investigation of interaction between radiation and HOI materials and thermal treatment will be discussed, as well as possible synthesis strategies and composition modification developed in order to improve efficiency of curing, tailor HOI properties to specific needs (optical properties, resist composition, mechanical stability, etc.) and explore innovative and non conventional patterning techniques. The reported results highlight as these novel materials, thanks to their solution processability and higher performances respect to commercial polymeric resists, allow to use the above mentioned lithographic techniques in a direct patterning process, strongly simplifying conventional technique and reducing their processing time and costs.     

Characterization of the morphology and composition of commercial negative resists used for lithographic processes

We present a spectroscopic and microscopic characterization of the chemical composition, structure, and morphology of two commercial negative resists using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). For this purpose, films of a novolak-based resist (ma-N 2400) and hydrogen silsesquioxane (HSQ) are treated under different conditions (temperature, deep ultraviolet (DUV) exposure, CHF₃ plasma). Topographic AFM images show that both heating and DUV exposure strongly affect the surface morphology of as-prepared ma-N 2400 resist films. These different treatment conditions also lead to decreasing roughnesses, which indicates structural reorganization. Furthermore, the decrease of the photoactive compound (bisazide) in the ma-N 2400 resist films, observed in FTIR spectra, suggests cross-linking of the resist after CHF₃ plasma treatment, heating, or DUV exposure. XPS measurements on different CHF₃ plasma-treated surfaces reveal that a structurally homogeneous fluorine-containing polymer is generated that is responsible for an enhanced etch resistance. FTIR measurements of HSQ films show a correlation between the degree of HSQ cross-linking and baking time.     

Synthesis and characterization of bio-based epoxy blends from renewable resource based epoxidized soybean oil as reactive diluent

A novel bioresin, epoxidized soybean oil was synthesized by in situ method and was characterized employing FTIR and NMR. The bioresin was blended with epoxy(DGEBA) at different ratios as reactive diluents for improved processibility and toughened nature. The composition with 20 wt% bioresin exhibited improved impact strength to the tune of 60% as compared to virgin epoxy. Fracture toughness parameters critical stress intensity factor(KIC) and critical strain energy release rate(GIC) were evaluated using single edge notch bending test and demonstrated superior enhancement in toughness. Dynamic mechanical, thermal, thermo mechanical and fracture morphological analyses have been studied for bio-based epoxy blends. Curing kinetics has been evaluated through DSC analysis to investigate the effect of bioresin on cross-linking reaction of neat epoxy with triethylenetetramine as curing agent.     

橡胶增韧环氧树脂机理的研究

本文研究了固化剂种类、环氧基体平均网链长度和分散相与基体间键合情况对体系韧性等的影响.结果说明,基体平均网链长度是一个更为重要的影响因素.分散相与基体间的化学键合也是重要的.文中对橡胶增韧环氧树脂的机理提出了见解.在交联密度较低的材料中,在橡胶颗粒附近叠加的应力场诱发下发生纵深度较大的断裂过程.分散相与基体间的化学键合增大该应力场强度有利于加大断裂过程区.     

Chemical amplification resists: Inception,implementation in device manufacture,and new developments

The chemical amplification concept aimed at dramatically boosting the resist sensitivity was invented at IBM Research in San Jose, CA, in 1980. The sensitivity enhancement is achieved by generating acid by irradiation, which induces a cascade of chemical transformations in a resist film. A chemically amplified resist based on acid‐catalyzed deprotection was quickly employed in the mid‐80s in manufacture of 1 megabit (Mbit) dynamic random access memory (DRAM) devices by deep ultraviolet (UV) (～250 nm) lithography in IBM. The unexpectedly high‐resolution capability of chemical amplification resists promoted their acceptance in the resist community and the microelectronics industry. All the advanced lithographic technologies (current workhorse 248 nm, maturing 193 nm, and emerging 157 nm, extreme UV, and projection electron beam) depend on chemical amplification resists. This article describes the invention, implementation in device manufacturing, current status, and future perspective of chemical amplification resists. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3863–3870, 2003     

Properties of adhesive compositions based on thiirane

Comparative investigations of adhesive composite materials based on thiirane and its oxirane analog are carried out. It is shown that compositions based on thiirane provide for a high rate of adhesion and cohesion strength gain. It is established that the maximal values of the adhesion strength for thiirane are reached at essentially lower concentrations of a curing agent than in the case of oxirane derivatives.     

Large area UV casting using diverse polyacrylates of microchannels separated by high aspect ratio microwalls

Large area molding of long and deep microchannels separated by high aspect ratio microwalls is important for high sensitivity and high throughput microfluidic devices. Ultraviolet (UV) casting is a feasible, economical and convenient method of replication of such microstructures in plastics. It is shown that a wide variety of polyacrylates with diverse properties such as those made from epoxy (EP), polyurethane (UR), polyester (ES), poly (ethylene glycol) (EG) and poly(propylene glycol) (PG) can be used for the high aspect ratio (7-9) UV casting of such linear microstructures over a 100 mm diameter, enlarging the range of applications of the replicated microstructures. Some challenges arise. With the EG formulation, wavy microstructures were observed; this can be overcome by stress relaxation. With non-polar PG formulation, poor adhesion between the polyester substrate and resin can lead to delamination of the casting from the substrate during demolding; this can be overcome by pre-coating a partially cured same resin on the polyester substrate. An optimum UV irradiation time was important for cure at the deepest end of the microstructure without excessive crosslinking leading to much increased demolding forces. The viscosity and wetting capability of the formulations were found to affect replication fidelity.     

Polymerization shrinkage of (meth)acrylate determined by reflective laser beam scanning

The real‐time study of the shrinkage during UV‐curing of (meth)acrylate monomers is limited due to the very fast curing rate, their thin sample geometry (<100 μm), and low viscosity. We report a reflective laser scanning system for direct measurement of UV‐curing shrinkage. A low‐power laser beam at a wavelength of 650 nm, different from the polymerization wavelength (395 nm), was used. This noncontact method of measurement makes it possible to analyze the thin liquid monomer with a very low shrinkage (measuring accuracy 0.02 μm), and very fast curing rate (fast sampling speed of 50 KHz). Eight different kinds of UV monomers were tested using 2–5 mg specimens, and the shrinkage process was examined. The results proved that this new method was accurate and precise, and could be applied to different kinds of (meth)acrylates. Furthermore, the shrinkage capability of acrylic double bonds was determined as 23.98 mL/mol using this novel method. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Enhanced self-cleaning, antibacterial and UV protection properties of nano TiO2 treated textile through enzymatic pretreatment

Textile materials can be treated with some enzymes to improve their functionality. The usual enzymatic treatment hydrolyzes the textile surfaces that leads to increase the functional groups. Here, the polyester/wool fabric as a blend of fibers fabric was selected and treated with the two different types of enzymes to increase the surface activity with a propose of higher nano-TiO(2) adsorption. The fabric was first treated with proteases and lipases to hydrolyze the wool and the polyester surfaces, respectively. It has been then dipped into an ultrasound bath containing nano TiO(2) and cross-linking agent followed by curing. The cross-linking agent, butane tetracarboxylic acid (BTCA), also assisted to enhance the nano-particles adsorption and stabilization on the fabric surface. The self-cleaning properties of the fabrics were examined through evaluating the color removal from the stained fabric with Acid Blue 113. The antibacterial properties were determined by reduction growth of a Gram-negative bacteria E. coli. and the UV protection was assessed by UV-reflectance spectrum. The SEM pictures and EDX spectrums of some samples were also reported.     

A method for improving the adhesion strength of UV-curable polymer compositions to metal

A method for improving the adhesion strength of UV-curable polymer compositions to metal is suggested that is based on the production of an adhesion layer at a metal surface, which is able to undergo polymerization with the components of the applied composition under the action of UV irradiation.     

Electron-beam and x-ray resists for microlithography

Firstly, general considerations about microlithography and resists were presented, leading to the conclusion that positive resists seemed to be more suitable than negative resists to provide high resolution in electron-beam lithography and in X-ray lithography. Therefore, parameters affecting the sensitivity of positive resists to such types of radiation were outlined. Among these positive resists, poly (fluoroalkyl methacrylates) were shown to be interesting candidates, due to their enhanced radiation absorption. Thus, poly(1-, 1- dimethyl 2, 2, 3, 3-tetrafluoropropyl methacrylate) (called FBP resist) was synthesized and physico-chemically characterized. The lithographic performances of such a resist were evaluated both upon electron-beam and X-ray exposures. Its dry-etch resistance was also studied. Furthermore, fabrication of Field-Effect Transistors using this resist was demonstrated.     

Novel non-chemically amplified resist utilizing interaction between hexafluoroisopropylalcohol-containing styrene and photochemical acid generator

It is very important in the design of positive-type resists to consider the dissolution inhibition effect to form high-resolution patterns. Previously, the phenomenon of the inhibition of hexafluoroisopropylalcohol-containing polystyrene's dissolution into alkaline developers by sulfonium salt photochemical acid generator (PAG) was studied. In the present study, patterning was conducted to examine whether the above platform can be applied to positive-type resists. As a result, the platform was found to be useful for the formation of resist patterns and be a novel non-chemically amplified resist. On the other hand, a decrease in sensitivity was observed with an increase in the amount of PAG to enhance the dissolution inhibition effect, and an increase in the amounts of residues derived from decomposition products of PAG occurred by making the resist films thinner to improve the sensitivity. It was suggested that enhancement of the interaction and light transmittance by changing polymer compositions and structures of PAG and improvement of miscibility of PAG with alkaline developers might be effective. This resist system is expected to be one of the platforms as a solution when resist materials with nearly critical dimensions for which chemically amplified type cannot be applied are required in the future.     

Characterization by Raman microspectrometry of residual compressive stresses induced by resin curing in single filament composite samples

The present work concerns monofilament composite samples used in the pull-out test to quantify the effect of different fibre surface treatments on the adhesion of a high modulus polyethylene in a polyester resin. Optical observations revealed local deformations induced by a compressive stress generated in the fibre by the resin shrinkage during the curing. The sensitivity of the polyethylene Raman peak at 1130 cm⁻¹ to elastic strain has been used to characterize the local compression state still present in the fibre after the curing. The results show residual stresses varying along the fibre embedded length up to a level depending on the applied surface treatment i.e. on the degree of adhesion between the fibre and the resin. This is consistent with the localization and the morphologies of shear bands observed in the samples. More the Raman microspectrometry has been used to determine the tensile stress profile along the embedded part of the fibre when its free part is stretched. Corrected of the initial compression state this profile represents the stress transfer effectively realized from the fibre to the resin for different adhesion conditions. Its knowledge is very useful to clarify the interface damage and pull-out mechanisms.     

Modification of Chemically Amplified Resists by Radical Copolymerization

Modification of a phenolic resist has been carried out by copolymerization with methacrylic monomers. Influence of irradiation source and its intensity has been studied by analyzing sensitive curves of a various resist composition. Inversion of imaging type at varying post exposure bake temperature has been investigated for resists based on copolymers containing methacrylic acid units, which has been related with crosslinking of macromolecules.     

Competing fracture in kinetically controlled transfer printing

Transfer printing by kinetically switchable adhesion to an elastomeric stamp shows promise as a powerful micromanufacturing method to pickup microstructures and microdevices from the donor substrate and to print them to the receiving substrate. This can be viewed as the competing fracture of two interfaces. This paper examines the mechanics of competing fracture in a model transfer printing system composed of three laminates: an elastic substrate, an elastic thin film, and a viscoelastic member (stamp). As the system is peeled apart, either the interface between the substrate and thin film fails or the interface between the thin film and the stamp fails. The speed-dependent nature of the film/stamp interface leads to the prediction of a critical separation velocity above which separation occurs between the film and the substrate (i.e., pickup) and below which separation occurs between the film and the stamp (i.e., printing). Experiments verify this prediction using films of gold adhered to glass, and the theoretical treatment extends to consider the competing fracture as it applies to discrete micro-objects. Temperature plays an important role in kinetically controlled transfer printing with its influences, making it advantageous to pickup printable objects at the reduced temperatures and to print them at the elevated ones.     

New Developments in Photoinitiators

New developments of photoinitiators are the base for the further extension of the radiation curing technology. Three different approaches are presented: The optimized combination of a bisacylphosphine oxide photoinitiator with a suitable stabilizer package allows the UV curing of clear coatings with an excellent performance in outdoor use. The design of new oxime ester derivatives allowed the introduction of a new tailor-made photoinitiator for color filter resists applications that considerably improves the color quality of the color filter. A novel photoinitiator class capable of releasing strong amine bases opens new opportunities for expanding radiation curing into resins types that crosslink by base-catalyzed processes.