Fabrication of large-scale periodic silicon nanopillar arrays for 2D nanomold using modified nanosphere lithography

We present a fabrication procedure that can form large-scale periodic silicon nanopillar arrays for 2D nanomold which determines the feature size of nanoimprint lithography, using modified nanosphere lithography. The size of silicon nanopillars can be easily controlled by an etching and oxidation process. The period and density of nanopillar arrays are determined by the initial diameter of polystyrene (PS) spheres. In our experiment, the smallest nanopillar has a full width half maximum (FWHM) of approximately 50 nm, and the density of silicon pillar is ∼10⁹/cm². Using this approach, it is possible to fabricate 2D nanoimprint lithography mask with 50 nm resolution.     

纳米压印多孔硅模板的研究

纳米压印模板通常采用极紫外光刻、聚焦离子束光刻和电子束光刻等传统光刻技术制备,成本较高.寻找一种简单、低成本的纳米压印模板制备方法以提升纳米压印光刻技术的应用成为研究的重点与难点.本文以多孔氧化铝为母模板,采用纳米压印光刻技术对纳米多孔硅模板的制备进行了研究.在硅基表面成功制备出纳米多孔阵列结构,孔间距为350—560 nm,孔径在170—480 nm,孔深为200 nm.在激发波长为514 nm时,拉曼光谱的测试结果表明,相对于单面抛光的硅片,纳米多孔结构的硅模板拉曼光强有了约12倍左右的提升,对提升硅基光电器件的应用具有重要的意义.最后,利用多孔硅模板作为纳米压印母模板,通过热压印技术,成功制备出了聚合物纳米柱软模板.     

Design and analysis of the single-step nanoimprinting lithography equipment for sub-100 nm linewidth

Nanoimprint lithography (NIL) is the cutting-edge technology to produce sub-100 nm scale features on substrates. The fundamental procedure of nanoimprint lithography is replicating the patterns defined in the stamp to any deformable materials such as photoresist spun on substrates by pressing and the physical shape of the resist is deformed during the imprinting process. In this study, for the single-step nanoimprinting process, the 4-in. imprinting head, the fabricated 4-in. mask, the alignment system for multi-layer processes, and the six-DOF compliant mechanism of a wafer stage for single-step nanoimprinting on a 4-in. wafer are proposed. Using the designed nanoimprinting equipment, the nanoscale patterns with 100 nm linewidth and 150 nm height were clearly patterned on the substrate. Finally, the nanoimprinting results show the validity of the developed equipment.     

Surface adhesion and demolding force dependence on resist composition in ultraviolet nanoimprint lithography

Demolding, the process to separate stamp from molded resist, is most critical to the success of ultraviolet nanoimprint lithography (UV-NIL). In the present study we investigated adhesion and demolding force in UV-NIL for different compositions of a model UV-curable resist system containing a base (either tripropyleneglycol diacrylate with shorter oligomer length or polypropyleneglycol diacrylate with longer oligomer length), a cross-linking agent (trimethylolpropane triacrylate) and a photoinitiator (Irgacure 651). The demolding force was measured using a tensile test machine with homemade fixtures after imprinting the UV resist on a silicon stamp. While decreasing the cross-linking agent content from 49 to 0 wt% has little effect on the resist surface energy, it reduces the resist's elastic modulus drastically. The decrease in elastic modulus results in a decreased adhesion force at the resist/stamp interface thereby facilitating the demolding. The decrease in elastic modulus and, therefore, demolding force by lowering the cross-linking agent content was markedly less pronounced in tripropyleneglycol diacrylate-based resists due to its shorter oligomer length. These general findings will be useful in designing new resists for UV-NIL process.     

Light Trapping and Down‐Shifting Effect of Periodically Nanopatterned Si‐Quantum‐Dot‐Based Structures for Enhanced Photovoltaic Properties

Periodically nanopatterned Si structures have been prepared by using a nanosphere lithography technique. The formed nanopatterned structures exhibit good anti‐reflection and enhanced optical absorption characteristics. The mean surface reflectance weighted by AM1.5 solar spectrum (300–1200 nm) is as low as 5%. By depositing Si quantum dot/SiO₂ multilayers (MLs) on the nanopatterned Si substrate, the optical absorption is higher than 90%, which is significantly improved compared with the same multilayers deposited on flat Si substrate. Furthermore, the prototype n‐Si/Si quantum dot/SiO₂ MLs/p‐Si heterojunction solar cells has been fabricated, and it is found that the external quantum efficiency is obviously enhanced for nanopatterned cell in a wide spectral range compared with the flat cell. The corresponding short‐circuit current density is increased from 25.5 mA cm^?2 for flat cell to 29.0 mA cm^?2 for nano‐patterned one. The improvement of cell performance can be attributed both to the reduced light loss and the down‐shifting effect of Si quantum dots/SiO₂ MLs by forming periodically nanopatterned structures.     

Ge quantum dot molecules and crystals: Preparation and properties

Templated self-organization has been used to prepare two-dimensional arrays as well as three-dimensional quantum dot crystals (QDC) containing Ge dots in a Si host crystal. Si(1 0 0) substrates have been patterned with two-dimensional hole gratings using extreme ultra-violet interference lithography (EUV-IL) and reactive ion etching. The EUV-IL was realized by multiple beam diffraction using Cr gratings on SiN_x membranes fabricated by e-beam lithography. Si/Ge overgrowth was performed by molecular beam epitaxy. The impact of the microscopic shape and size of the prepattern using the mask design and the EUV-IL exposure dose as parameters on the Ge dot nucleation has been studied with atomic force microscopy, transmission electron microscopy and photoluminescence measurements. Adjusting the growth parameters in multiple layer deposition the initial two-dimensional configuration was transferred into three-dimensional QDC.     

Nanofabricated periodic arrays of silver elliptical discs as SERS substrates

Signal enhancement observed in surface‐enhanced Raman spectroscopy (SERS) is attributable to the presence of noble‐metal nanostructures on substrate surfaces. The rational development of SERS‐active substrates depends critically on the homogeneity and intensity of surface plasmon resonances, properties that are strongly dependent on both the morphology and dielectric properties of the metals and composite materials making up the SERS substrates. Enhancement can be controlled by the shape, size, and spacing of metallic nanoparticles. Previous studies in our group have shown that arrays of elliptical nanodiscs have promising geometries for this purpose. Using electron beam lithography (EBL), we fabricate close‐packed arrays of these discs with lateral dimensions ranging from 300:50 to 300:300 nm (long axis : short axis). The arrays are composed of a negative photoresist that, once the lithography process is complete, are coated with a noble metal through physical vapor deposition (PVD). In this work, optimum thickness and deposition rate of noble metal are determined for these substrates. The lithographically produced nanopatterns are studied by Raman spectroscopy to examine the effect of altering the elliptical aspect ratio on SERS activity, while scanning electron microscopy (SEM) is used to examine pattern surfaces post lithographic development and post noble‐metal deposition. Atomic force microscopy (AFM) is used to inspect the roughness of substrate surfaces. Reproducibility between different arrays of the same pattern ranges from 12 to 28%. Homogeneity of our uniform‐morphology EBL/PVD‐fabricated substrates is examined and compared to our random‐morphology polymer nanocomposite substrates. Using rhodamine 6G as an analyte, an increase in SERS signal is noted as the aspect ratio of ellipses goes from 6:1 to 6:6. Our experimental data, in terms of trends in SERS activity, correlate with trends in field enhancements calculated using a simple electrostatic model and with the magnitude of the broad red‐shifted spectral continuum observed for the substrates. Copyright © 2008 John Wiley & Sons, Ltd.     

Focused ion beam/scanning electron microscopy characterization of cell behavior on polymer micro-/nanopatterned substrates: a study of cell-substrate interactions

Topographic micro and nanostructures can play an interesting role in cell behaviour when cells are cultured on these kinds of patterned substrates. It is especially relevant to investigate the influence of the nanometric dimensions topographic features on cell morphology, proliferation, migration and differentiation. To this end, some of the most recent fabrication technologies, developed for the microelectronics industry, can be used to produce well-defined micro and nanopatterns on biocompatible polymer substrates. In this work, osteoblast-like cells are grown on poly(methyl methacrylate) substrates patterned by nanoimprint lithography techniques. Examination of the cell-substrate interface can reveal important details about the cell morphology and the distribution of the focal contacts on the substrate surface. For this purpose, a combination of focused ion beam milling and scanning electron microscopy techniques has been used to image the cell-substrate interface. This technique, if applied to samples prepared by freeze-drying methods, allows high-resolution imaging of cross-sections through the cell and the substrate, where the interactions between the nanopatterned substrate, the cell and the extracellular matrix, which are normally hidden by the bulk of the cell, can be studied.     

Pulsed laser deposition of uniform semiconductor nanodot arrays

Uniform arrays of silicon (Si), gallium arsenide (GaAs) and zinc oxide (ZnO) nanodots have been deposited using Pulsed Laser Deposition (PLD) technique combined with a contact mask consisting of nano-holes fabricated by E-beam lithography (EBL). These nanocrystalline semiconductor nanodots have been deposited by PLD on Si and GaAs substrates at room temperature. Characterization of the nanodots has been carried out using different techniques including X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), Auger Electron Spectroscopy (AES), and Raman spectroscopy. This work demonstrates a novel technique for deposition of uniform array of semiconductor nanostructures using a contact mask at room temperature for photonic applications.     

Design and fabrication of structural color by local surface plasmonic meta-molecules

In this paper, we propose a new form of nanostructures with Al film deposited on a patterned dielectric material for generating structural color, which is induced by local surface plasmonic resonant(LSPR) absorption in sub-wavelengthindented hole/ring arrays. Unlike other reported results obtained by using focus ion beam(FIB) to create metallic nanostructures, the nano-sized hole/ring arrays in Al film in this work are replicated by high resolution electron beam lithography(EBL) combined with self-aligned metallization. Clear structural color is observed and systematically studied by numerical simulations as well as optical characterizations. The central color is strongly related to the geometric size, which provides us with good opportunities to dye the colorless Al surface by controlling the hole/ring dimensions(both diameter and radius), and to open up broad applications in display, jewelry decoration, green production of packing papers, security code,and counterfeits prevention.     

Lithography potentials of UV-nanoimprint

In the past decade nanoimprint has been developed to a serious alternative for next generation lithography (NGL). In this work, the most recent developments of UV-nanoimprint Lithography (UV-NIL) with special emphasis to the work accomplished at AMO and the IHT-RWTH Aachen are reviewed and functional applications demonstrated. Further the potentials of various UV-NIL concepts are evaluated and possible interests in certain application areas are discussed.     

Ultrahigh-density storage media prepared by artificially assisted self-assembling methods

Two types of recording media possessing nanodot structures were investigated. The media were prepared by an artificially assisted self-assembling (AASA) method, which includes simple nanopatterning using a nanoimprint and fine nanopatterning using self-assembling organic molecules. One type of recording media is circumferential magnetic patterned media prepared on a 2.5-in.-diam glass plate. A Ni master disk possessing spiral patterns with 60-250 nm width lands and a 400 nm width groove was pressed to a resist film on a CoCrPt film to transfer the spiral patterns. A diblock copolymer solution was cast into the obtained grooves, and then annealed to prepare self-assembling dot structures aligned along the grooves. According to the dot patterns, the lower magnetic films were patterned by ion milling to yield patterned media with 40 nm diameter. We have also prepared FePt dot media with high magnetic anisotropy for near-field and magnetic-field hybrid recording aiming at more than 1 Tbin.2 density. A Ni stamp disk with aligned dot structures was also prepared by the AASA method to produce patterned media at the lowest cost. The other type of media was organic patterned media for X-Y type near-field optical storage. Bulky dye molecules were evaporated in vacuum to produce self-assembling amorphous nanodots. The dots were arranged by the AASA method, i.e., according to the polymethylmethacrylate film hole arrays or chemically patterned surface.     

Carbon nanodot arrays grown as replicas of specially widened anodic aluminum oxide pore arrays

Via a specially widened anodic aluminum oxide (AAO) pore arrays, carbon nanodot arrays with uniform size and high density were obtained through filtered cathodic arc plasma (FCAP) technique. The AAO template was prepared in oxalic acid by multi-steps to get a specially enlarged opening which plays an important role in the deposition of nanodots. The morphology of the nanodots was studied by a field emission scanning electron microscopy (FESEM). The diameter of the as-prepared nanodot demonstrated here is about 100 nm at the bottom and less than 40 nm at the top, and the density was estimated to 10¹⁰ cm⁻². Field emission properties of the nanodot arrays were investigated and a low threshold field of 5.1 V/μm at 10 mA/cm² was obtained. In this paper, the carbon nanodot arrays grown as replicas of the specially widened AAO template may support a strategy to realize the fabrication of nanodot arrays with various materials.     

Superhydrophobic,antireflective, flexible hard coatings with mechanically ultra-resilient moth-eye structure for foldable displays

Biomimetic inspiration from the moth-eye structure has led to many studies combining nanoimprint lithography (NIL) to realize low cost and large area anti-reflection (AR) coatings. However, the scope of application is severely limited by poor mechanical performance due to the intrinsic properties of the coating materials and the nanosized patterns. In this work, we demonstrate a moth-eye structured epoxy-siloxane molecular hybrid (ME-ESMH) fabricated using single UV-based NIL (UV-NIL) on a colorless polyimide (CPI), to be utilized as a flexible cover window (FCW) for foldable displays. Low reflection, a superhydrophobicity and good inward foldability were achieved, together with excellent thermal and chemical resistance. Furthermore, in situ uniaxial compression tests revealed that the fabricated structure can be elastically deformed and nearly restored to its original shape even after a large degree of compression. Our findings provide an easy-to-integrate solution for flexible hard coatings with superhydrophobic and AR properties, applicable to foldable optoelectronics.     

Control of ZnO nanowire arrays by nanosphere lithography (NSL) on laser-produced ZnO substrates

Nanosphere lithography (NSL) is a successful technique for fabricating highly ordered arrays of ZnO nanowires typically on sapphire and GaN substrates. In this work, we investigate the use of thin ZnO films deposited on Si by pulsed laser deposition (PLD) as the substrate. This has a number of advantages over the alternatives above, including cost and potential scalability of production and it removes any issue of inadvertent n-type doping of nanowires by diffusion from the substrate. We demonstrate ordered arrays of ZnO nanowires, on ZnO-coated substrates by PLD, using a conventional NSL technique with gold as the catalyst. The nanowires were produced by vapor phase transport (VPT) growth in a tube furnace system and grew only on the areas pre-patterned by Au. We have also investigated the growth of ZnO nanowires using ZnO catalyst points deposited by PLD through an NSL mask on a bare silicon substrate.     

FIB快速加工纳米孔点阵的新方法

纳米尺度的点阵在纳米器件和基础科学研究方面都具有非常重要的应用.目前普遍采用的聚焦离子束和电子束曝光技术可以很方便的在衬底上加工纳米量级的微细结构，但大面积的图形加工过程需要花费太多的机时.介绍一种利用设计图形BMP文件的像素点阵和实际加工区域之间的匹配关系，通过聚焦离子束加工获得所需要的纳米孔点阵的新方法.采用这种方法可以在短时间内获得大面积的纳米点阵结构. 关键词： 聚焦离子束 电子束曝光 纳米孔点阵     

UV-curable nanoimprint resin with enhanced anti-sticking property

This paper reports on a newly developed anti-sticking resin obtained by mixing a fluorine-containing monomer (F-monomer) for UV nanoimprinting lithography (UV-NIL) to reduce the contact adhesion force during the demolding process. The new resin system shows an enhanced reliability and resolution of pattern transfer with no treatment on the surface of the quartz stamp. We fabricated various nanopatterns with F-monomer resins of various concentrations in the low pressure UV-NIL. The number of process steps of a release layer treatment for UV-NIL was reduced by using F-monomer with anti-sticking property.     

Room-temperature deposition of crystalline patterned ZnO films by confined dewetting lithography

In this work patterned ZnO films were prepared at room-temperature by deposition of ∼5 nm size ZnO nanoparticles using confined dewetting lithography, a process which induces their assembly, by drying a drop of ZnO colloidal dispersion between a floating template and the substrate. Crystalline ZnO nanoparticles exhibit a strong visible (525 nm) light emission upon UV excitation (λ = 350 nm). The resulting films were characterized by scanning electron microscopy (SEM) and atomic force microscope (AFM). The method described herein presents a simple and low cost method to prepare crystalline ZnO films with geometric patterns without additional annealing. Such transparent conducting films are attractive for applications like light emitting diodes (LEDs). As the process is carried out at room temperature, the patterned crystalline ZnO films can even be deposited on flexible substrates.     

Electrochemically fabricated nanovolcano arrays for SERS applications

Nanovolcano arrays were fabricated by electrodepositing Ni/Cu alloys into a monolayer of self‐assembled nanospheres and then electrochemically etching the deposited alloy film. The fabricated nanovolcano arrays feature highly ordered hexagonally arranged concave nanobowls decorated with triangular nanopores at their interstices. After coated with Ag, the nanovolcano arrays serve as high‐performance substrates for surface enhancement Raman spectroscopy (SERS) measurements. The experimental study shows that the structural features of the nanovolcano arrays, including concave nanobowls, nanopores, and their long‐range orders, all contribute to the observed strong SERS enhancement in a synergetic manner, which is further confirmed by the simulation results obtained using the finite‐difference time‐domain method. Copyright © 2012 John Wiley & Sons, Ltd.     

Large-scale fabrication of polymer/Ag core–shell nanorod array as flexible SERS substrate by combining direct nanoimprint and electroless deposition

We demonstrate a highly sensitive surface-enhanced Raman scattering (SERS) substrate, which consists of Ag nanoparticles (NPs) assembled on the surface of a nanopatterned polymer film. The fabrication route of a polymer/Ag core–shell nanorod (PACSN) array employed a direct nanoimprint technique to create a high-resolution polymer nanorod array. The obtained nanopatterned polymer film was subjected to electroless deposition to form a sea-cucumber-like Ag shell over the surface of the polymer nanorod. The morphology and structures of PACSNs were analyzed by using scanning electron microscopy and X-ray diffraction. The as-synthesized PACSNs exhibited a remarkable SERS activity and Raman signal reproducibility to rhodamine 6G, and a concentration down to 10^?12 M can be identified. The effect of electroless deposition time of Ag NPs onto the polymer nanorod surface was investigated. It was found that the electroless deposition time played an important role in SERS activity. Our results revealed that the combination of direct nanoimprint and electroless deposition provided a convenient and cost-effective way for large-scale fabrication of reliable SERS substrates without the requirement of expensive instruments.