有机硅溶胶-凝胶防腐蚀涂层研究进展

有机硅溶胶-凝胶涂层是指以烷基烷氧基硅烷为前驱体通过溶胶-凝胶技术制备的涂层。有机硅是分子水平上的有机-无机杂化分子,因此有机硅溶胶-凝胶涂层兼具了有机材料和无机材料的性能,并且能通过合理的调控有机和无机成分来获得所需的性能。其热稳定、耐刮擦性与无机材料的结合性能明显高于普通的有机材料,柔韧性与有机材料的结合性能明显高于一般的无机涂层。近年来,这种新型的、具有特殊性能的涂层被广泛研究用来保护金属材料(如铝、铁、镁、铜基材料)。介绍了有机硅溶胶-凝胶涂层涉及的基本反应、硅烷在金属表面上的成键机理以及在不同金属上的应用等方面的研究进展,并展望了有机硅溶胶-凝胶涂层应用前景及未来的研究方向。     

High-resolution electron beam lithography and DNA nano-patterning for molecular QCA

Electron beam lithography (EBL) patterning of poly(methylmethacrylate) (PMMA) is a versatile tool for defining molecular structures on the sub-10-nm scale. We demonstrate lithographic resolution to about 5 nm using a cold-development technique. Liftoff of sub-10-nm Au nanoparticles and metal lines proves that cold development completely clears the PMMA residue on the exposed areas. Molecular liftoff is performed to pattern DNA rafts with high fidelity at linewidths of about 100 nm. High-resolution EBL and molecular liftoff can be applied to pattern Creutz-Taube molecules on the scale of a few nanometers for quantum-dot cellular automata.     

EBL- and AFM-based techniques for nanowires fabrication on Si/SiGe

Two approaches for sub-100 nm patterning are applied to Si/SiGe samples.The first one combines electron beam lithography (EBL) and anisotropic wet etching to fabricate wires with triangular section whose top width is narrower than the beam size. Widths as small as 20 nm on silicon and 60 nm on Si/SiGe heterostructures are obtained.The second lithographic approach is based on the local anodization of an aluminum film induced by an atomic force scanning probe. Using atomic force microscopy (AFM) anodization and selective wet etching, aluminum and aluminum oxide nanostructures are obtained and used as masks for reactive ion etching (RIE). Sub-100 nm wide wires are fabricated on Si/SiGe substrates.     

Fabrication and Characterization of Graphitic Carbon Nanostructures with Controllable Size,Shape, and Position

The incorporation of carbon materials in micro‐ and nanoscale devices is being widely investigated due to the promise of enhanced functionality. Challenges in the positioning and addressability of carbon nanotubes provide the motivation for the development of new processes to produce nanoscale carbon materials. Here, the fabrication of conducting, nanometer‐sized carbon structures using a combination of electron beam lithography (EBL) and carbonisation is reported. EBL is used to directly write predefined nanometer‐sized patterns in a thin layer of negative resist in controllable locations. Careful heat treatment results in carbon nanostructures with the size, shape, and location originally defined by EBL. The pyrolysis process results in significant shrinkage of the structures in the vertical direction and minimal loss in the horizontal direction. Characterization of the carbonized material indicates a structure consisting of both amorphous and graphitized carbon with low levels of oxygen. The resistivity of the material is similar to other disordered carbon materials and the resistivity is maintained from the bulk to the nanoscale. This is demonstrated by fabricating a nanoscale structure with predictable resistance. The ability to fabricate these conductive structures with known dimensions and in predefined locations can be exploited for a number of applications. Their use as nanoband electrodes is also demonstrated.     

Chemical tailoring of hybrid sol-gel thick coatings as hosting matrix for functional patterned microstructures

A phenyl-based hybrid organic - inorganic coating has been synthesized and processed by hard X-ray lithography. The overall lithography process is performed in a two-step process only (X-rays exposure and chemical etching). The patterns present high aspect ratio, sharp edges, and high homogeneity. The coating has been doped with a variety of polycyclic aromatic hydrocarbon functional molecules, such as anthracene, pentacene, and fullerene. For the first time, hard X-rays have been combined with thick hybrid functional coatings, using the sol-gel thick film directly as resist. A new technique based on a new material combined with hard X-rays is now available to fabricate optical devices. The effect due to the high-energy photon exposure has been investigated using FT-IR and Raman spectroscopy, laser scanner, optical profilometer, and confocal and electron microscope. High-quality thick hybrid fullerene-doped microstructures have been fabricated.     

Nanoimprint Lithography: Methods and Material Requirements

Nanoimprint lithography (NIL) is a nonconventional lithographic technique for high‐throughput patterning of polymer nanostructures at great precision and at low costs. Unlike traditional lithographic approaches, which achieve pattern definition through the use of photons or electrons to modify the chemical and physical properties of the resist, NIL relies on direct mechanical deformation of the resist material and can therefore achieve resolutions beyond the limitations set by light diffraction or beam scattering that are encountered in conventional techniques. This Review covers the basic principles of nanoimprinting, with an emphasis on the requirements on materials for the imprinting mold, surface properties, and resist materials for successful and reliable nanostructure replication.     

小型微纳米图形电子束曝光制作系统(英文)

为了满足科学实验过程中对制作半导体器件和微纳米结构的需要,同时避免受到昂贵的工业级电子束曝光(electron beam lithography,EBL)机的条件制约,构建了一种基于普通扫描电子显微镜(scanning electron microsco-py,SEM)的桌面级小型电子束曝光系统.建立了以浮点DSP为控制核心的高速图形发生器硬件系统.利用线性计算方法实现了电子束曝光场的增益、旋转和位移的校正算法.在本曝光系统中应用了新型压电陶瓷电机驱动的精密位移台来实现纳米级定位.利用此位移台所具有的纳米定位能力,采用标记追逐法实现了电子束曝光场尺寸和形状的校准.电子束曝光实验结果表明,场拼接及套刻精度误差小于100 nm.为了测试曝光分辨率,在PMMA抗蚀剂上完成了宽度为30 nm的密集线条曝光实验.利用此系统,在负胶SU8和双层PMMA胶表面进行了曝光实验;并通过电子束拼接和套刻工艺实现了氮化物相变存储器微电极的电子束曝光工艺.     

New laser plasma source for extreme-ultraviolet lithography

As the demands of lithographic fabrication of computer chips push toward ever-decreasing feature sizes, projection extreme-ultraviolet (EUV) lithography becomes an increasingly attractive technology. The radiation source of choice for this approach is a laser plasma with a high repetition rate. We report an investigation of a new candidate laser plasma source for EUV lithography that is based on line emission from ice-water targets. This radiation source has the potential to meet all the strict requirements of EUV conversion, debris elimination, operation, and cost for a demonstration lithographic system.     

Directed Self‐Assembly of Liquid‐Crystalline Molecular Building Blocks for Sub‐5 nm Nanopatterning

The thin‐film directed self‐assembly of molecular building blocks into oriented nanostructure arrays enables next‐generation lithography at the sub‐5 nm scale. Currently, the fabrication of inorganic arrays from molecular building blocks is restricted by the limited long‐range order and orientation of the materials, as well as suitable methodologies for creating lithographic templates at sub‐5 nm dimensions. In recent years, higher‐order liquid crystals have emerged as functional thin films for organic electronics, nanoporous membranes, and templated synthesis, which provide opportunities for their use as lithographic templates. By choosing examples from these fields, recent progress toward the design of molecular building blocks is highlighted, with an emphasis on liquid crystals, to access sub‐5 nm features, their directed self‐assembly into oriented thin films, and, importantly, the fabrication of inorganic arrays. Finally, future challenges regarding sub‐5 nm patterning with liquid crystals are discussed.     

Compatibility enhancement of polyimide-silica hybrid sol-gel materials without incorporation of silane-coupling agent

A facile route has been developed to enhance compatibility between organic polyimide matrix and dispersed phase of inorganic silica particles without addition of conventional silane-coupling agent. The as-prepared hybrid sol-gel materials having reduced size of SiO2 particle dispersed in polyimide matrix were successfully synthesized through pre-catalyzed sol-gel route using an organic diamine base. The PI-silica hybrid materials through conventional polyamic acid-catalyzed sol-gel route with/without silane-coupling agent were also prepared for comparative control studies. Morphological feature of as-prepared sol-gel materials prepared from three different approaches was also compared based on the studies of transmission electron microscopy. Effects of the material composition, in three different catalyzed routes, were investigated by thermal stability, mechanical strength, optical clarity, gas barrier and water absorption measurements of polyimide and a series of polyimide-silica hybrid sol-gel materials, respectively.     

Infrared spectroscopic and electron microscopic characterization of gold nanogap structure fabricated by focused ion beam

Using infrared spectroscopy of plasmonic resonances and mapping of elemental composition and structure, we investigated the correlation between optical and structural properties of nanometre-scale gaps in gold nanorod dimers fabricated by electron beam lithography (EBL) and focused ion beam (FIB) milling. In spite of their very similar scanning electron microscopy (SEM) images, a fully cut nanogap and a shallower cut with slight imperfection near the gap region were clearly distinguished by their strongly different infrared plasmonic resonance behaviour. The differences in the infrared spectra are related to different structural and chemical results from elaborated cross-sectional transmission electron micrographs and energy dispersive x-ray spectrometry (EDX) mapping of the gap region.     

应用于纳米制造的新型电子束抗蚀剂Calixarene的工艺研究

为了满足电子束光刻（EBL）对高分辨率、性能优秀抗蚀剂的需求,研究了将Calixarene衍生物作为电子束抗蚀剂在胶液配制、电子束曝光及显影等工艺过程中的相关技术.其中电子束曝光实验在JEOL JBX-5000LS系统上进行.实验结果表明,在入射电子能量50 keV、束流50 pA的条件下,Calixarene可以方便地形成50 nm的单线、50nm等线宽与间距的图形结构.通过与常用电子束抗蚀剂的对比,总结了Calixarene在电子束光刻性能上的优缺点,并分析了其成因.作为一种新型的高分辨率电子束光刻抗蚀剂,Calixarene有望应用在纳米结构制造、纳米尺寸器件及电路的研制等领域.     

Fabrication of an inorganic nano structure for a large area via electrohydrodynamic lithography (EHL)

Electrohydrodynamic lithography (EHL) is one of several unusual lithographic techniques for fabricating sub-micrometer structures over a large area. EHL uses the electrohydrodynamic (EHD) film instability induced by a laterally modulated electric field, which allows it to fabricate not only general organic structures but also structures of various components, such as diblock copolymers and inorganic materials, without contact between the resist and the stamp. Furthermore, EHL is a very special lithographic technique in that diverse structures are fabricated from one stamp via electric field modulation. The electric field is controlled by the replication time, air layer thickness, etc. A replicated inorganic structure was demonstrated from a hexagonal hole and line arrays. The heat treatment of the replicated pattern was carried out to obtain the crystalline phase, after which the samples were characterized via Raman spectroscopy. These values were ascertained using field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). The results will be useful in providing a facile route for patterning functional metal oxides over a large area. Such a technique can be used to produce photovoltaic cells, memory devices, display devices, etc.     

Proton microbeam irradiation effects on PtBA polymer

Proton beam lithography has made it possible to make various types of 3D-structures in polymers. Usually PMMA, SU-8, PS polymers have been used as resist materials for lithographic purpose. Microbeam irradiation effects on poly-tert-butyl-acrylate (PtBA) polymer using 20 MeV proton microbeam are reported. Preliminary results on pattern formation on PtBA are carried out as a function of fluence. After writing the pattern, a thin layer of Ge is deposited. Distribution of Ge in pristine and ion beam patterned surface of PtBA polymer is studied using the optical and secondary electron microscopic experimental methods.     

Advanced patterning techniques for nanodevice fabrication

The key elements in the fabrication of future devices are lithography and pattern transfer. The continuous advances in miniaturization and increasing integration densities are a direct result of improved lithographic resolution and overlay accuracy. Electron beam direct write and e-beam projection lithography are potential candidates for the mass production of microelectronic devices with critical dimensions below 100 nm. To realize these nanometer patterns by this technology, the performance of exposure tools and resist materials should be increased. In this paper, the method of direct write e-beam lithography is demonstrated and critical issues are discussed.     

聚己内酯/ 环氧树脂/ SiO2杂化材料的制备及性能

采用端硅氧烷基聚己内酯( PCL-TESi) 作为无机前躯物, 通过环氧树脂/ KB-2 的固化反应和PCL-TESi的溶胶2凝胶过程, 制备了聚己内酯/ 环氧树脂/ SiO₂ ( PCL/ EP/ SiO₂ ) 有机-无机杂化材料。利用红外光谱、透射电镜( TEM) 、热失重分析( TGA) 及在甲苯溶液中的溶胀试验对不同SiO₂ 含量的杂化材料进行分析。研究发现, 随着PCL-TESi 含量增大杂化体系交联密度降低; 此杂化体系中存在环氧和Si —O —Si 两种交联网络, 微观上形成纳米两相结构; Si —O —Si 交联网络的形成显著提高了材料的耐热性能, 使失重5 %时的热分解温度从120.5 ℃(纯环氧树脂/ KB-2 体系) 提高到277.6 ℃(SiO₂质量分数为3. 84 %的杂化体系) 。      

A chemically amplified fullerene-derivative molecular electron-beam resist

Current lithographic resists depend on large polymeric materials, which are starting to limit further improvements in line-width roughness and feature size. Fullerene molecular resists use much smaller molecules to avoid this problem. However, such resists have poor radiation sensitivity. Chemical amplification of a fullerene derivative using an epoxy crosslinker and a photoacid generator is demonstrated. The sensitivity of the material is increased by two orders of magnitude, and 20-nm line widths are patterned.     

Fire resistant melamine based organic-geopolymer hybrid composites

Hybrid composite materials based on geopolymer and epoxy melamine resins have been designed to produce a novel material showing high compatibility between the organic and inorganic phases. This has been realized through a synthetic method based on the co-reticulation in mild condition of the two phases. These materials show good interpenetration of the resin into the inorganic matrix up to nanometric level and significantly improved mechanical properties in respect to un-modified geopolymer without compromising the good thermal stability and fire resistance typical of unmodified geopolymers. These properties make the novel materials very attractive for the realization of thermo-resistant and thermo-insulating panels.     

Facile scheme for fabricating solid-state nanostructures using e-beam lithography and solution precursors

We demonstrate a facile approach for site-specific fabrication of organic, inorganic, and hybrid solid-state nanostructures through a novel combination of electron-beam lithography (eBL) and spin coating of liquid and sol-gel precursors, termed soft eBL. By using eBL patterned resists as masks in combination with a low cost process such as spin coating, directed growth of nanostructures with controlled dimensions is achieved without the need for the costly and difficult process step of etching ceramics. The highly versatile nature of the scheme is highlighted through the fabrication of nanostructures of a variety of materials such as ferroelectric, optoelectronic, and conducting polymeric materials at different length scales and spatial densities on a multitude of substrates.