Surface modification of SU-8 for enhanced biofunctionality and nonfouling properties

SU-8 is a chemically amplified, epoxy-based negative photoresist typically used for producing ultrathick resist layers during device manufacturing in the semiconductor industry. As a simple resist, SU-8 has garnered attention as a possible material for a variety of biomedical applications, including tissue engineering, drug delivery, as well as cell-based screening and sensing. However, as a hydrophobic material, the use of SU-8 is limited due to a high degree of nonspecific adsorption of biomolecules, as well as limited cell attachment. In this work, surface chemistry is utilized to modify the SU-8 surface by covalently attaching poly(ethylene glycol) (PEG) to increase biofunctionality and improve its nonfouling properties. Different molecular weights and concentrations of PEG were used to form films of various grafting densities on SU-8 surfaces. X-ray photoelectron spectroscopy (XPS) was used to verify the presence of PEG moieties on the SU-8 surface. High-resolution C1s spectra show that, with an increase in concentration and immobilization time, the grafting density of PEG also increases. Further, a standard overlayer model was used to calculate the thickness of the PEG films formed. The effect of PEG-modified SU-8 was examined in terms of protein adsorption on the surface and fibroblast-surface interactions.     

The influence of the photoacid-generator structure on chemical amplification in a resist

The effect of structure of a photoacid generator (triarylsulfonium and diaryliodonium salts) on the trends of image formation in a chemically amplified resist based on a methyl methacrylate copolymer with methacrylic acid and ethoxyethyl methacrylate was studied. It was shown that the type and quality of image in the resist depend on the structure of the Brönsted acid produced upon UV irradiation, on postexposure bake temperature, and on exposure radiation energy.     

Thermal and acid-catalyzed reaction of bifunctional vinyl ether urethane in nonionic and ionic polymer matrices

A bifunctional vinyl ether urethane derivative (BVU) was synthesized and characterzed. Photoresist systems consisting of BVU and a photoacid generator (PAG) along with various matrix polymers were prepared and the photoresist characteristics were evaluated. In the presence of BVU and a PAG, poly(methylmethacrylate-co-acrylic acid) and poly(methylmethacrylate) exhibited positive and negative tone behavior, respectively, where as poly(p-hydroxystyrene) showed both positive and negative working properties depending on the prebake temperature of the system. The depandence of the photoresist behaviors on these matrix polymers was studied. The mechanism of the thermal and photochemical reactions was revealed.     

高聚物微流控芯片镍阳模的简易加工技术

提出了一种简便快速制作高聚物微流控芯片镍阳模的新方法。采用抛光镍片作为电铸基底,涂覆SU-8光胶层后,光刻得到SU-8微结构。以镍基片作为阳极,用16～30A/dm2的电流密度电解刻蚀5min,清除SU-8微结构间隙底部镍片表面的氧化物,并刻蚀得到10～20μm深的凹坑,有效地提高了随后电沉积镍结构和基底镍片间结合力。利用SU-8微结构作为电铸模板,以镍基片作为阴极,电铸5h后制得了微结构倾角为83°深宽比较大的镍阳模。实现了在普通化学实验室中长寿命镍阳模的制作。用热压法制得500多片聚甲基丙烯酸甲酯(PMMA)聚合物芯片,并成功用于DNA片段的分离。     

Simple and fast method for the fabrication of switchable bicomponent micropatterned polymer surfaces

We report on the fabrication of micropatterned polymer surfaces that allow the reversible inversion of surface topography, charge, and wettability. Micropatterned surfaces were prepared by grafting two oppositely charged polyelectrolytes (poly(acrylic acid) and poly(2-vinylpyridine)) using a combination of photolithography, "lift off", and "grafting to" techniques. The switchable surfaces are of interest in microprinting and for the design of microfluidic devices and programmed protein adsorption.     

Gas transport in surface‐modified low‐density polyethylene films with acrylic acid as a grafting agent

The modification of polyethylene by the grafting of poly(acrylic acid) onto the surface of one of the faces of low‐density polyethylene films with UV radiation is reported. The transport of oxygen, nitrogen, carbon monoxide, carbon dioxide, methane, ethane, ethylene, propane, and argon across surface‐modified films containing 3.7% poly(acrylic acid) has been investigated at several temperatures. The layer of poly(acrylic acid) grafted onto the surface of one of the faces of the films reduces the permeability coefficient of the gases by a factor of about 1/6. The sharp drop in the gas permeability as a result of the poly(acrylic acid) layer may arise either from the formation of ordered structures of the grafted chains or from the development of highly crosslinked structures. The values of the polymer–gas enthalpic interaction parameter for the modified film are higher than those for the unmodified one. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2828–2840, 2006     

Gas transport in surface grafted polypropylene films with poly(acrylic acid) chains

This work describes the grafting reaction of poly(acrylic acid) (PA) onto the surface of polypropylene (PP) films carried out with ultraviolet radiation, using benzophenone as photoinitiator and water as solvent. By increasing the reaction time, graft percentages of 3.5, 6.5, 12.9, 19.8, 29.4, and 36.0% were obtained. Micrographs of the modified films show that grafting exclusively occurs on the PP films surface. The values of the permeability coefficient of oxygen, nitrogen, carbon dioxide, carbon monoxide, argon, methane, ethane, ethylene, and propane across the grafted films undergo a sharp drop. The interpretation of the permeation results suggest that radicals created in the tertiary carbons of the grafted chains by effect of UV light or by chain transfer reactions may highly crosslink the PA grafted layer. A rigid layer involving both strong hydrogen bonding and chains crosslinking is formed at grafting percentages of 3.5% that strongly hinders gas permeation across that layer. Destruction of hydrogen bonding by partially replacing protons of acrylic acid residues by sodium/silver cations increases the permeability of the surface grafted films. Finally, the films permselectivity is hardly affected by the grafted layer. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2421–2431, 2007     

Retrospective of work at Bell Laboratories on the effect of fluorine substitution on the properties of photoacid generators

An overview is given on the work done at Bell Laboratories in which fluorine substitution was employed to tune the structure property relationships of chemically amplified resists. In particular, this paper will detail how structural changes in 2-nitrobenzyl photoacid generator (PAG) affect molecular properties such as quantum yield, thermal stability, and in turn also influence the lithographic characteristics of photoresist formulations such as sensitivity and post-exposure bake (PEB) and post-exposure delay (PED) latitude.     

High intensity light emitting diode array as an alternative exposure source for the fabrication of electrophoretic microfluidic devices

A commercially available array of light emitting diodes (LEDs), namely a UV Shark series LED high flux array, was evaluated as a light source for photolithographic patterning of SU-8 photoresist for the fabrication of templates suitable to make poly(dimethylsiloxane) (PDMS) microchips for electrophoresis. At a distance of 15 cm from the substrate, a relatively even intensity of 0.76+/-0.05 mW/cm(2) was obtained over an area sufficient for patterning a 10 cm (4 in.) silicon wafer. The exposure source was evaluated using a spiral mask design covering a 10 cm wafer. PDMS replicates of this template made in a 25 microm thick layer of SU-8 3025 showed little variation in width over the surface of the substrate, with a variation of 3.2% RSD (n=36) and a maximum range in widths of 7.8% of the mean channel width. The use of the optional metal reflector available with the LED array provided partial collimation of the light allowing near vertical structures to be produced across the entire wafer, something which was not possible without the reflector. SU-8 masters prepared using the LED array were compared to masters made using an alternative cheap lithographic source, namely a gel crosslinker. The SU-8 features were much narrower with the LED array than the crosslinker due to the multiple light sources in the crosslinker. A PDMS microchip made using a SU-8 template created using the Shark UV LED array was used for the electrophoretic separation of three anionic fluorescent dyes, with efficiencies up to 32,000 plates. Given that the LED array can be purchased and assembled for less than US$ 500, the Shark UV LED array is a promising alternative to more expensive lithographic light sources and will have significant appeal to many researchers wishing to undertake research in microfluidics around the world.     

Thermo- and pH-responsive polypropylene microporous membrane prepared by the photoinduced RAFT-mediated graft copolymerization

Thermo- and pH-responsive polypropylene microporous membrane prepared by photoinduced reversible addition–fragmentation chain transfer (RAFT) graft copolymerization of acrylic acid and N-isopropyl acrylamide by using dibenzyltrithiocarbonate as a RAFT agent. Attenuated total reflection-Fourier transform infrared spectroscopy (ATR/FT-IR), X-ray photoelectron spectroscopy (XPS) and field emission scanning electron microscopy (FE-SEM) were used to characterize the structural and morphological changes on the membrane surface. Results of ATR/FT-IR and XPS clearly indicated that poly(acrylic acid) (PAAc) and poly(N-isopropyl acrylamide) (PNIPAAm) were successfully grafted onto the membrane surface. The grafting chain length of PAAc on the membrane surface increased with the increase of UV irradiation time, and decreased with the increase of the concentration of chain transfer agent. The PAAc grafted membranes containing macro-chain transfer agents, or the living membrane surfaces were further functionalized via surface-initiated block copolymerization with N-isopropyl acrylamide in the presence of free radical initiator, 2,2′-azobisisobutyronitrile. It was found that PNIPAAm can be grafted onto the PAAc grafted membrane surface. The results demonstrated that polymerization of AAc and NIPAAm by the RAFT method could be accomplished under UV irradiation and the process possessing the living character. The PPMMs with PAAc and PNIPAAm grafting chains exhibited both pH- and temperature-dependent permeability to aqueous media.     

Covalent immobilization of chitosan on surfaces with anchoring layers of poly(glycidyl methacrylate) and maleic anhydride copolymers

The method for producing chitosan coatings on solid surfaces with anchoring layers of poly(glycidyl methacrylate) and maleic anhydride copolymers has been proposed. It is shown that, owing to a high reactivity of epoxy and anhydride groups, the efficiency of immobilization and the stability of the coatings are considerably higher than those prepared by the conventional method of chitosan grafting onto the surface modified by poly(acrylic acid). The properties of chitosan coatings are examined via atomic force microscopy, X-ray photoelectron spectroscopy, ellipsometry, and electrokinetic measurements. Depending on the anchoring layer used, the total thickness of the coatings is 6–16 nm with an rms roughness less than 1.2 nm, while the isoelectric points of the surfaces modified with chitosan are located in the pH range 5–6.     

Decomposition of poly(propylene carbonate) with UV sensitive iodonium salts

The decomposition characteristics of poly(propylene carbonate) containing a photoacid generator have been studied. The influence of casting solvent, photoacid concentration and type, UV exposure dose, substrate surface, and ambient gas were included in this study. Dynamic thermogravimetric analysis was used to analyze the decomposition characteristics. Kinetic parameters were extracted using the Kissinger method and the Coats-Redfern method. Fourier Transform Infrared Spectroscopy was used to analyze effects of casting solvent. The highest thermal stability was found to occur in high molecular weight, high-purity poly(propylene carbonate) samples. Cyclohexanone and trichloroethylene solvents were found to increase the thermal stability. Photoacid generators based on diphenyliodonium salts lowered the onset decomposition temperature and activation energy.     

Ultrathin binary grafted polymer layers with switchable morphology

Polymer surface layers comprised of mixed chains grafted to a functionalized silicon surface with a total layer thickness of only 1-3 nm are shown to exhibit reversible switching of their structure. Carboxylic acid-terminated polystyrene (PS) and poly (butyl acrylate) (PBA) were chemically attached to a silicon surface that was modified with an epoxysilane self-assembled monolayer by a "grafting to" routine. While one-step grafting resulted in large, submicron microstructures, a refined, two-step sequential grafting procedure allowed for extremely small spatial dimensions of PS and PBA domains. By adjusting the grafting parameters, such as concentration of each phase and molecular weight, very finely structured surfaces resulted with roughly 10-nm phase domains and less than 0.5-nm roughness. Combining the glassy PS and the rubbery PBA, we implemented a design approach to fabricate a mixed brush from two immiscible polymers so that switching of the surface nanomechanical properties is possible. Post-grafting hydrolysis converted PBA to poly(acrylic acid) to amplify this switching in surface wettability. Preliminary tribological studies showed a difference in wear behavior of glassy and rubbery surface layers. Such switchable coatings have practical applications as surface modifications of complex nanoscale electronic devices and sensors, which is why we restricted total thickness for potential nanoscale gaps.     

SU-8 flow field plates for a micro PEMFC

A SU-8 photoresist microfabrication process was developed for micro proton exchange membrane fuel cell flow structures for both anode and cathode flow field plates with a cross section of 5 cm² (22.5 mm×22.5 mm) and thickness (for a single cell) of about 750 µm. The new design for flow field plates would have SU-8 used as not only a photoresist but also as a microstructure material. A thickness of 30 nm Pt sputter loading deposited onto a Nafion 117 for membrane electrode assembly was made, with both scanning electron microscopy and atomic force microscopy characterization. Air flows were completed in hydrogen fuel cells with air breathing and forced air flows of low input pressure as well as low velocity. Performance tests of polarization curves and power density distribution as well as impendence measurements were conducted and discussed to examine the effects of orientation of the cathode surface with five hydrogen feeding rates as well as different airflow feeding modes.     

Negative‐working photoresist of methacrylate polymers based on the transesterification of the 2‐hydroxyethyl group in the presence of an acid

This article reports a novel crosslinking functionality of the 2‐hydroxyethyl methacrylate unit (HEMA) in the presence of an acid. The polymeric compositions, consisting of a polymer containing the HEMA unit and a photoacid generator, were insolubilized in an aqueous base developer on exposure to UV light and a successive baking process to provide a negative‐working photoresist. A series of poly(benzyl methacrylate‐co‐methacrylic acid‐co‐2‐hydroxyethyl methacrylate) terpolymers with various contents of HEMA were prepared to elucidate the photopolymeric characteristics. The polymer behavior in films was examined by a comparison of the photosensitivity and IR spectroscopic method. Experiments with a model compound were also carried out. On the basis of the results, we found that the resist was insolubilized by crosslinking through the transesterification of HEMA segments due to acid generated from the photoacid generator and subsequent heating. The advantage of using the 2‐hydroxyethyl group is that in the terpolymer, the HEMA unit is transparent at a short‐wavelength region and is a promising crosslinking unit for ArF lithographic photoresists. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1858–1867, 2002     

Negative‐working photoresist based on a first‐generation dendrimer consisting of 4,4‐diphenylpentyloxy units

A first‐generation dendrimer ( 2 ), containing phenol groups in the exterior for solubilization in aqueous alkaline solutions, was evaluated as a new negative‐working, alkaline‐developable photoresist material. A negative‐working photoresist based on 2 , 4,4′‐methylenebis[2,6‐bis(hydroxymethyl)phenol] as a crosslinker, and diphenyliodonium 9,10‐dimethoxyanthracene‐2‐sulfonate as a photoacid generator was demonstrated. This resist gave a clear negative pattern through postbaking at 90 °C after exposure to UV light, which was followed by development with a 2.38% aqueous tetramethyl ammonium hydroxide solution at room temperature. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1210–1215, 2005     

二步法聚丙烯/丙烯酸表面接枝聚合研究

研究了二步法聚丙烯膜表面的丙烯酸接枝反应 .实验发现 ,以醋酐为溶剂的反应体系所得接枝率明显好于以水为溶剂的体系 ;接枝率随光敏剂浓度、单体浓度增大而增加 ;提高反应温度 ,可使接枝率明显增大 ;接枝后的聚丙烯膜表面亲水性可明显改善 .并用红外光谱证实了丙烯酸在聚丙烯膜表面的接枝 .     

一种新型深紫外正型光致抗蚀剂材料的研究

通过松香酸和丙烯酸的Diels-Alder反应得到了一种二酸——丙烯海松酸.丙烯海松酸有大的脂环结构和良好的成膜性,在固体膜层中,它可以和二乙烯基醚,如1,3-二乙烯氧基乙氧基苯,在加热条件下(80℃以上)发生反应,产物在稀碱水中难溶.这样形成的产物在光产酸剂产生的强酸催化下,在温度高于100℃时,可以迅速分解,从而变成稀碱水易溶.因此,用此二酸、二乙烯基醚和产酸剂可组成一种正型的光致抗蚀剂,当用254 nm的低压汞灯曝光时,其感度在30 mJ/cm²以下.     

Graft copolymerization kinetics of acrylic acid onto the poly(ethylene terephthalate) surface by atmospheric pressure plasma inducement

After one atmospheric pressure plasma treatment of poly(ethylene terephthalate) (PET) film, acrylic acid (AAc) in aqueous solution was successfully graft‐copolymerized onto PET films. The effects of reaction time, AAc monomer concentration and reaction temperature on grafting behavior of AAc were systematically studied. Possible reaction kinetics of plasma‐induced graft copolymerization, starting from initial hydroperoxide decomposition, were proposed. Through the Arrhenius analysis about graft copolymerization kinetics of AAc monomers on PET surface, it was revealed that the activation energies of decomposition, propagation and termination were 98.4, 63.5, and 17.5 kJ/mol, respectively. The temperature around 80 °C was favorable not only for the formation of oxide radicals through the thermal decomposition of hydroperoxide on PET surface but also for the extension of graft copolymer chain through direct polymer grafting. Poly(acrylic acid) (PAAc) grains grafted onto PET surfaces possessed relatively uniform size and both PAAc grain size and surface roughness increased with increasing the grafting degree of AAc. The increase of grain size with increasing grafting degree results from the possibility of forming long chain graft copolymers and their shielding of reactive sites. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1594–1601, 2008     

石墨烯/SU-8复合导电光刻胶的制备及传感应用

将导电导热性石墨烯(GR)引入光刻胶SU-8中, 制备了具有导电性的复合光刻胶. 采用超景深显微镜和万用表表征了石墨烯在复合光刻胶中的分散性及复合光刻胶的导电性. 通过光刻法将设计的图案转移到氧化铟锡(ITO)玻璃表面制备了一种新型的GR/SU-8图案化电极元件. 进一步在GR/SU-8/ITO表面电化学原位还原CuNPs, 制备了一种新型无酶传感器. 实验结果表明, 该传感器具有优异的电子转移性能, 在110 mmol/L浓度范围内对过氧化氢具有良好的响应(R²=0.999), 同时稳定性优异, 15 d后电流响应仍可保持90%以上, 表明该导电光刻胶可用于电化学传感领域.