High-resolution submicron patterning of self-assembled monolayers using a molecular fluorine laser at 157 nm

Using a molecular fluorine laser at 157 nm wavelength, submicron patterning of organosilane self-assembled monolayers (SAMs) is demonstrated utilizing mask-contact photolithography. An organosilane, namely, octadecyltrimethoxysilane [ODS, CH(3)(CH(2))(17)Si(OCH(3))(3)], SAM is chemisorbed onto Si substrates covered with a 2 nm thick oxide layer and subsequently patterned using the laser. The optical path of the laser beam and the photomask-sample space are evacuated and then backfilled and purged with nitrogen during laser firing. The resulting pattern is investigated using various measurement techniques. The scanning probe microscopy images show that patterns are transferred to the SAM-covered Si substrates and that 500 nm features are successfully photoprinted in this way.     

通过硅烷偶联剂在硅和铟锡氧化物(ITO)表面嫁接寡聚芴分子

通过硅烷偶联剂γ-氨丙基三乙氧基硅烷(3-aminopropyl-triethoxysilane,APTES)的“分子桥梁”作用,采用两种不同的方法,把修饰后的寡聚芴分子键联到硅表面和铟锡氧化物(ITO)表面上。X射线光电子能谱(XPS)、原子力显微镜(AFM)和循环伏安(CV)方法等的表征证实了通过硅烷偶联剂在硅表面和ITO表面嫁接寡聚芴分子可行性。     

Cell patterning using a template of microstructured organosilane layer fabricated by vacuum ultraviolet light lithography

Micropatterning techniques have become increasingly important in cellular biology. Cell patterning is achieved by various methods. Photolithography is one of the most popular methods, and several light sources (e.g., excimer lasers and mercury lamps) are used for that purpose. Vacuum ultraviolet (VUV) light that can be produced by an excimer lamp is advantageous for fabricating material patterns, since it can decompose organic materials directly and efficiently without photoresist or photosensitive materials. Despite the advantages, applications of VUV light to pattern biological materials are few. We have investigated cell patterning by using a template of a microstructured organosilane layer fabricated by VUV lithography. We first made a template of a microstructured organosilane layer by VUV lithography. Cell adhesive materials (poly(d-lysine) and polyethyleneimine) were chemically immobilized on the organosilane template, producing a cell adhesive material pattern. Primary rat cardiac and neuronal cells were successfully patterned by culturing them on the pattern substrate. Long-term culturing was attained for up to two weeks for cardiac cells and two months for cortex cells. We have discussed the reproducibility of cell patterning and made suggestions to improve it.     

Improved Process for Producing Well-Adhered/Abrasion-Resistant Optical Coatings on an Optical Plastic Substrate

Abstract

A well-adhered and abrasion-resistant coating on a typical optical substrate [polymethylmethacrylate (PMMA)] can be achieved by polymerizing organosilane in a low-temperature polymerization process. The substrate surface can be initially modified with hydrophilic functionalities in a radio-frequency plasma of argon/water vapor mixture in the pressure range 0.05-0.15 mbar to attach hydroxyl functionalities covalently to the substrate surface, which act as “anchorage sites” for polymerizing organosilane. This modified surface is then coated with polyvinyltrimethoxysilane at a power loading in the 20-60 W range and a flow rate of monomer in the 0.7-2.0 cm³-min^?1 range. The polymeric films deposited in this manner on PMMA substrates consistently passed adhesion and abrasive tests even after prolonged storage and thermal cycling in boiling water for at least 10 minutes as exposure to extreme differential thermal expansion conditions. The posttreatment of deposited films with plasmas of inert gases for stress relief had an insignificant effect on peel-off tests and, therefore, it was believed to be not as important as surface modification prior to coatings. The optical properties are essentially not affected by the organosilane coatings irrespective of film thickness, and the coated substrates are virtually transparent above 400 nm.     

Novel adamantane-based periodic mesoporous organosilica film with ultralow dielectric constant and high mechanical strength

Journal of Sol-Gel Science and Technology - In this work, a novel bridged organosilane precursor, adamantane-bridged organosilane (ADBO), was synthesized successfully which was employed to prepare...     

Nanostructures of functionalized gold nanoparticles prepared by particle lithography with organosilanes

Periodic arrays of organosilane nanostructures were prepared with particle lithography to define sites for selective adsorption of functionalized gold nanoparticles. Essentially, the approach for nanoparticle lithography consists of procedures with two masks. First, latex mesospheres were used as a surface mask for deposition of an organosilane vapor, to produce an array of holes within a covalently bonded, organic thin film. The latex particles were readily removed with solvent rinses to expose discrete patterns of nanosized holes of uncovered substrate. The nanostructured film of organosilanes was then used as a surface mask for a second patterning step, with immersion in a solution of functionalized nanoparticles. Patterned substrates were fully submerged in a solution of surface-active gold nanoparticles coated with 3-mercaptopropyltrimethoxysilane. Regularly shaped, nanoscopic areas of bare substrate produced by removal of the latex mask provided sites to bind silanol-terminated gold nanoparticles, and the methyl-terminated areas of the organosilane film served as an effective resist, preventing nonspecific adsorption on masked areas. Characterizations with atomic force microscopy demonstrate the steps for lithography with organosilanes and functionalized nanoparticles. Patterning was accomplished for both silicon and glass substrates, to generate nanostructures with periodicities of 200-300 nm that match the diameters of the latex mesospheres of the surface masks. Nanoparticles were shown to bind selectively to uncovered, exposed areas of the substrate and did not attach to the methyl-terminal groups of the organosilane mask. Billions of well-defined nanostructures of nanoparticles can be generated using this high-throughput approach of particle lithography, with exquisite control of surface density and periodicity at the nanoscale.     

Sorting of brownian rods by the use of an asymmetric potential

We present here a method for sorting nanometer scale brownian rods by using a switching asymmetric periodic potential. A two stage sorting process is used to isolate particles with specific dimensions, with acceptable sorting times as well as realizable potential barrier lengths. The method was tested using computer simulations. The ability to sort the nanometer scale anisotropic particles, such as gold nanorods, portends important applications in large scale data recording, photothermal surgery, and bioimaging.     

Self-assembled monolayers and preorganization of organosilanes prior to surface grafting onto silica: a quantum mechanical study

Quantum chemical calculations have been carried out on the grafting of chain organosilane compounds on SiO(2)-hydroxylated solid surfaces. It is shown that a single molecule interacting with the surface lies flat to it, inhibiting further homogeneous film growth. This adsorption exhibits two molecule/surface interactions: a covalent bond on one side of the molecule and a hydrogen bond on the other side. We then investigate the possible preorganization of the molecules before grafting due to the presence of water molecules either in the gas/liquid phase or near the surface. This gives rise to the formation of dimerized chains. We then demonstrate that this preorganization process prevents subsequent lying flat of the molecules to the substrate after grafting. Energetics and associated configurations of the overall deposition process are discussed in detail and provide new insights on the understanding of the formation of self-assembled homogeneous organic films on microelectronics-type substrates.     

Vapor-phase self-assembled monolayer for improved mold release in nanoimprint lithography

Resist adhesion to the mold is one of the challenges for nanoimprint lithography. The main approach to overcoming it is to apply a self-assembled monolayer of an organosilane release agent to the mold surface, either in the solution phase or vapor phase. We compared the atomic force microscopy, ellipsometry, reflection-absorption infrared spectroscopy, and contact angle results collected from substrates treated by two different application processes and found that the vapor-phase process was superior. The vapor-treated substrates had fewer aggregates of the silane molecules on the surface, because the lower density of the agent in the vapor phase was not conducive to aggregation formation, and received a superior coating of the releasing agent, because the vapor was more effective than the solution in penetrating into the nanoscale gaps of the mold. A pattern transfer of 20 parallel nanowires with a line width of 40 nm at 100 nm pitch-size was performed faithfully with the vapor-treated mold without any resist adhesion.     

Dispersion of pristine single-walled carbon nanotubes in water by a thiolated organosilane: application in supramolecular nanoassemblies

We report a novel technique to disperse pristine single-walled carbon nanotubes in water by ultrasonication in the presence of a thiolated organosilane and subsequent ultracentrifugation. As revealed by the sharp features in the visible range of the absorption spectrum and by transmission electron microscopy, the collected supernatant fraction was composed of small bundles of nanotubes coated by a thin layer of organosilane molecules. We hypothesized and demonstrated that the organosilane adsorbed onto the nanotubes through the thiol group leaving the silane group extruding out. The pristine properties of the nanotubes and the versatile chemistry available for sol-gel materials make the reported dispersed nanotubes an excellent scaffold for the realization of supramolecular nanoassemblies suitable for different applications. As examples, we decorated them with silica nanobeads, by using a water-in-oil nanoemulsion system, and with gold nanoparticles, by a previous derivatization with a second layer of thiolated organosilane providing exposed thiol groups.     

Interfacial chemistries for nanoscale transfer printing

We describe a patterning technique that uses self-assembled monolayers and other surface chemistries for guiding the transfer of material from relief features on a stamp to a substrate. This purely additive contact printing technique is capable of nanometer resolution. Pattern transfer is fast and it occurs at ambient conditions. We illustrate the versatility of this method by printing single-layer metal patterns with feature sizes from a few tens of microns to a few tens of nanometers. We also demonstrate its use for patterning, in a single step, metal/dielectric/metal multilayers for functional thin film capacitors on plastic substrates.     

Substrate-induced modulation of the Raman scattering signals from self-assembled organic nanometric films

Raman scattering signals recorded by microscopy from organic self-assembled monolayers (thin nanometric films of calibrated thickness) on silica substrates were found to be much stronger than those obtained from identical films assembled on bulk silicon substrates. This effect, observed in the backscattering geometry, is shown to result from interferences between the direct and reflected beams (including both the excitation and scattered radiation) in front of a smooth reflecting surface. Strong dependence of the effect on the distance between the sampled monolayer and the bulk silicon substrate allows enhancement of the Raman signals of organic monolayer films on silicon by factors up to approximately 70 by using appropriate silica spacers. The dependence of the Raman signal intensity on film thickness was also studied for thicker nanometric films comprising a series of self-assembled organosilane multilayers on bulk silicon and fused silica substrates, and the predicted deviation from linearity in the case of the silicon substrate is experimentally confirmed.     

Fabrication of superhydrophobic surface from a supramolecular organosilane with quadruple hydrogen bonding

A supramolecular organosilane, 2-(3-(triethoxysilyl)propylaminocarbonylamino)-6-methyl-4[1H]pyrimidinone comprising quadruple hydrogen bonds has been synthesized in one step from commercially available starting materials. The synthesized supramolecular organosilane can be stabilized and phase-separated by dimerization via the linear array of quadruple hydrogen bonds in solution. This property of the supramolecular organosilane has been exploited to fabricate structuring materials having a superhydrophobic surface property. We have successfully generated the interconnected granular structure with adequate roughness for superhydrophobicity via sol-gel process.     

Long-range self-assembly of a polyunsaturated linear organosilane at the n-tetradecane/Au(111) interface studied by STM

We report on the formation of self-assembled monolayers of 13-(trimethylsilyl)-1-tridecene-6,12-diyne [C13H17-Si(CH3)3], an organosilane derivative with a linear polyunsaturated chain, on Au(111) substrates. Molecular resolution STM images recorded at the liquid-solid interface between gold and tetradecane reveal a long-range and densely packed hexagonal lattice with a ( radical3 x radical3)R30 degrees -like structure commensurate against gold adlattice.     

Nanoscale patterning of organosilane molecular thin films from the gas phase and its applications: fabrication of multifunctional surfaces and large area molecular templates for site-selective material deposition

A simple methodology to fabricate micrometer- and nanometer-scale patterned surfaces with multiple chemical functionalities is presented. Patterns with lateral dimensions down to 110 nm were made. The fabrication process involves multistep gas-phase patterning of amine, thiol, alkyl, and fluorinated alkyl-functional organosilane molecules using PDMS molds as shadow masks. Also, a combination process of channel diffused plasma etching of organosilane molecular thin films in combination with masked gas-phase deposition to fabricate multilength scale, multifunctional surfaces is demonstrated.     

PLASMA POLYMERIZED ORGANOSILANES AS A PROTECTIVE COATING ON METAL

Polymer-metal oxane bonds (M-O-Si) can be created in the form of tight networks bysilane plasma polymerization directly on the metal (e.g. copper) substrates. In this paperthe structure and properties of the plasma-deposited organosilane polymers, the corrosionperformance of such coating system on copper substrates were investigated.     

The oscillatory adsorption of self‐assembled organosilane films on aluminium oxide surfaces

The time‐dependent oscillatory growth mechanism of organosilane film self‐assembly on aluminium oxide has been investigated using X‐ray photoelectron spectroscopy. While this unusual oscillatory process has been reported for the trifunctional silane, propyltrimethoxysilane, we report here, for the first time, that this oscillatory behaviour is also present during the self‐assembly of the difunctional silane propylmethyldimethoxysilane. The presence of multiple oscillations in this growth mechanism is also first reported for propyltrimethoxysilane and propylmethyldimethoxysilane as a function of exposure time. Multiple oscillations indicate that the 3‐component model that is used to describe and fit a single coverage oscillation must be reconsidered and contain additional components to account for the multiple oscillations seen experimentally. The absence of such oscillatory behaviour in the growth of the monofunctional organosilane propyldimethylmethoxysilane, which in fact follows a Langmuir‐type growth mechanism, indicates that this measurable oscillatory behaviour is because of the ability of multifunctional silanes to oligomerise both on the substrate and in solution.     

Fabrication of submicron scale patterned plastic thin film fluidic devices with controllable thickness

We present a soft-lithography based method to fabricate plastic thin film fluidic devices on glass and plastic substrates. Principles of soft-lithography and spin casting were used to generate the films. The thickness of these films is controllable and the patterns we have generated have submicron scale dimensions. By using commercially available compact disc (CD) components as molds, we have been able to generate parallel line and cross patterns on these thin films. These patterned films could be lifted from the substrates and further folded into rolls.     

TiO2纳米薄膜的溶胶-凝胶工艺制备和表征

通过ｓｏｌ－ｇｅｌ工艺在普通钠钙玻璃表面制备了均匀透明的锐钛矿型ＴｉＯ２纳米薄膜,ＴｉＯ２薄膜的Ｘ射线衍射分析表明,当薄膜的厚度小于０．４６μ时,薄中未出现锐钛矿的衍射峰,随着镀膜次数或薄膜厚度的增加,薄膜中ＴｉＯ２纳米微晶的平均晶粒大小逐渐增大,ＴｉＯ２薄膜的透光率略有减小,其吸收阈值发生了明显的红移,ＸＰＳ实验结果表明：薄膜中除含有Ｔｉ、Ｏ元素外,还有一定量来自有机前驱物中未完全燃烧的碳和少量     

Guided self-assembly of diblock copolymer thin films on chemically patterned substrates

We study the guided self-assembly of symmetric/asymmetric diblock copolymer (BCP) films on heterogeneous substrates with chemically patterned surface by using a coarse-grained phase-separation model. During the procedure, the free energy employed for the BCP films was modeled by the Ginzburg-Landau free energy with nonlocal interaction, and the flat, chemically patterned surface was considered as a heterogeneous surface with short-range interaction with the BCP molecules. The resulting Cahn-Hilliard equation was solved by means of an efficient semi-implicit Fourier-spectral algorithm. Effects of pattern scale, surface chemical potential, and BCP asymmetry on the self-assembly process were explored in detail and compared with those without chemically patterned substrate surfaces. It was found that the morphology of both symmetric and asymmetric BCP films is strongly influenced by the commensurability between the unconstrained natural period lambda* of the bulk BCP and the artificial pattern period. Simulation shows that patterned surface with period close to lambda* leads to highly ordered morphology after self-assembly for both symmetric and asymmetric BCP films, and it also dramatically accelerates the guided self-assembly process. The present simulation is in a very good agreement with the recent experimental observation in BCP nanolithography. Finally, the present study also expects an innovative nanomanufacturing method to produce highly ordered nanodots based on the guided self-assembly of asymmetric BCP films on chemically patterned substrates.