Formation of Au nano-patterns on various substrates using simplified nano-transfer printing method

For future device applications, fabrication of the metal nano-patterns on various substrates, such as Si wafer, non-planar glass lens and flexible plastic films become important. Among various nano-patterning technologies, nano-transfer print method is one of the simplest techniques to fabricate metal nano-patterns. In nano-transfer printing process, thin Au layer is deposited on flexible PDMS mold, containing surface protrusion patterns, and the Au layer is transferred from PDMS mold to various substrates due to the difference of bonding strength of Au layer to PDMS mold and to the substrate. For effective transfer of Au layer, self-assembled monolayer, which has strong bonding to Au, is deposited on the substrate as a glue layer.In this study, complicated SAM layer coating process was replaced to simple UV/ozone treatment, which can activates the surface and form the -OH radicals. Using simple UV/ozone treatments on both Au and substrate, Au nano-pattern can be successfully transferred to as large as 6 in. diameter Si wafer, without SAM coating process. High fidelity transfer of Au nano-patterns to non-planar glass lens and flexible PET film was also demonstrated.     

Sol–gel concave micro-lens arrays fabricated by combining the replicated PDMS soft mold with UV-cured imprint process

Photosensitive TiO₂/organically modified silane organic–inorganic hybrid thin films were synthesized by combining a low-temperature sol–gel process with a spin-coating method. Optical transmittance properties and the photochemical activities of the planar hybrid films were characterized by UV–Visible spectroscopy and Fourier transform infrared spectroscopy. Advantages for fabrication of the concave micro-lens arrays (MLAs) based on the photosensitive hybrid films were demonstrated by using the replicated polydimethylsiloxane (PDMS) soft mold as the imprint mold and a UV soft imprint technique. Morphological and surface profile properties of the master, the PDMS soft molds and the as-fabricated sol–gel concave MLAs were observed by scanning electron microscopy and laser confocal scanning microscopy. Contact angles of water on the PDMS soft molds baked at different temperatures were studied. Optical imaging properties of the as-fabricated concave MLAs were confirmed by a self-made optical test system. Results indicate that the as-prepared photo-patternable hybrid materials have great applicability for the fabrication of photonic components, thus providing an effective method to fabricate concave MLAs based on the as-synthesized hybrid films by combining the UV-cured imprint technique with the replicated PDMS soft mold, which has advantages of simplicity, cost-effective and mass production and potential application in industry production.     

PDMS梯度光栅结构制备技术研究

由于传统方法制作的梯度光栅,工艺条件苛刻,制作过程复杂,难以控制,制作成本高,周期较长,提出了一种成本低、工艺简单、可大量制备梯度光栅的工艺方法,采用基于刚性薄膜/柔性衬底的自组装工艺和氧等离子体(Plasma)的方法制备了微米尺度的梯度光栅,利用Plasma时间的可控性和聚二甲基硅氧烷(PDMS)优异的弹性制得所需要尺寸的光栅。首先在聚乙烯对苯二酸脂(PET)薄膜上旋涂一层PDMS薄膜,待PDMS薄膜固化后将双层薄膜弯曲并用Plasma处理,在其表面生成一层刚性氧化层,借助柔性的PET对刚性层施加均匀应力,当应力超过临界值时,在PDMS基底上自组装形成光栅褶皱结构。由于弯曲时预应力的变化,所以在PDMS薄膜上会形成周期和高度呈阶梯状的的光栅褶皱,也就是梯度光栅。采用可见光作为梯度光栅的性能测试光源,选用一级衍射光作为检测对象,从图谱中可以看出以PDMS为基底制备的光栅具有很好的衍射效应,并可实现很好的分光效果。实验表明：梯度光栅具有明显的衍射现象,并且衍射角变化显著,可广泛用于应力测量。这种方法制备的柔性梯度光栅也可以作为微型应变装置来检测应力的变化,未来有望用于微型光谱仪、扫描仪、光通讯等领域中。     

Sub-50 nm UV-curing nanoimprint based on fluoropolymer,CYTOP, mold

In addition to the advantages of conventional fluoropolymers (i.e., chemical resistance, optical transparency, especially low surface energy), CYTOP, a commercially available cyclic fluoropolymer, can be dissolved in a special fluorinated solvent, thus it can be coated on the substrate by a spin-coating or solution casting method. In this paper, we introduced CYTOP as a rapid prototyping mold material for UV-curing nanoimprint lithography. The CYTOP mold is fabricated by a thermal nanoimprint technique on a quartz substrate or a direct solution casting on a master mold. Nanostructures with different geometries and down to sub-50 nm feature size are faithfully duplicated by CYTOP molds through a UV-curing imprint process. The CYTOP mold preserves its lower surface energy property after 20 repeated imprint cycles and there is no peeling off problem or contamination and damage on CYTOP mold observed. However, it is found that the high aspect ratio nanostructures on the CYTOP mold are tilted or deformed after separation with the master mold.     

Replication of mold for UV-nanoimprint lithography using AAO membrane

A simple and highly effective method to the replication of soft mold based on the anodic aluminum oxide (AAO) membrane was developed. The soft mold with nanopillar arrays was composed of the toluene diluted PDMS layer supported by the soft PDMS. A water contact angle as high as 114° was achieved. The hexagonally well-order arrays of holes of nanometer dimensions, ∼100 nm pore diameter and 125 nm center-to-center pore, could be gained over large areas by UV-nanoimprint lithography (UV-NIL) with the replicated soft PDMS mold. It is expected that the developed soft mold would find applications in light emitting diodes devices.     

Sub-microns period grating couplers fabricated by silicon mold

This paper describes a novel simple process suitable for fabrication of micro-periodic structure in optical waveguide. The mold was fabricated using electron beam lithography and fast atom beam etching. Sub-micron-scale patterns were transferred from silicon mold to polymer layer. Grating coupler was fabricated by the mold and normal optical mask. In the proposed method, no press which is needed for imprint lithography is required and the mold structure can be duplicated with high aspect ratio. Experimental coupling efficiency is about 25%. This technique can also be used to fabricate other nanometer-scale structures.     

Flexible subwavelength gratings fabricated by reversal soft UV nanoimprint

We present a replication process, named reversal soft ultraviolet (UV) nanoimprint, to fabricate a high- aspect-ratio flexible subwavelength grating (SWG) on a polyurethane acrylate (PUA). This nanopatterning technique consists of casting, reversal UV imprint, and dry release. The UV curing process of PUA to avoid pattern collapse is investigated. Revalpha film acts as the supporting and sacrificial layer during the whole process due to its special surface energy property. The free-standing PUA structures with a period of 200 nm and a depth of 350 nm can be automatically released from the Revalpha film by heating. The PUA resist is well suited to replicate fine patterns of the mold with high aspect ratio and large area precisely and uniformly for low surface energy and low viscosity. The measured transmittance is compared with the calculation results based on rigorous coupled-wave analysis in the wavelength region ranging from 500 to 800 nm. The experimental results agree well with the theoretical calculations.     

Mechanics of plasma exposed spin-on-glass (SOG) and polydimethyl siloxane (PDMS) surfaces and their impact on bond strength

Silicone polymer (PDMS), widely used for micro-fluidic and biosensor applications, possesses an extremely dynamic surface after it is subjected to an oxygen plasma treatment process. The surface becomes extremely hydrophilic immediately after oxygen plasma exposure by developing silanol bond (SiOH), which promotes its adhesion to some other surfaces like, silicon, silicon dioxide, glass, etc. Such a surface, if left in ambient dry air, shows a gradual recovery of hydrophobicity. We have found an identical behavior to occur to surfaces coated with a thin continuous film of SOG (methyl silsesquioxane). The chemistry induced by oxygen plasma treatment of a spin-on-glass (SOG) coated surface provides a much higher density of surface silanol groups in comparison to precleaned glass, silicon or silicon dioxide substrates thus providing a higher bond strength with polydimethyl siloxane (PDMS). The bonding protocol developed by using the spin coated and cured SOG intermediate layer provides an universal regime of multi level wafer bonding of PDMS to a variety of substrates. The paper describes a contact angle based estimation of bond strength for SOG and PDMS surfaces exposed to various combinations of plasma parameters. We have found that the highest bond strength condition is achieved if the contact angle on the SOG surface is less than 10°.     

AFM method for investigation of irradiated polymers

Tracks of swift heavy ions (Xe and Bi) at the surface of polymer (PET) were studied using AFM and surface defects—cavities (for Xe) and hillocks with cavities on its top (for Bi) were found. Thermal behavior of these Bi-irradiated samples (during annealing from 70°C to 180°C) was investigated. It was found that low-temperature annealing does not change the shape of surface defects, while high-temperature annealing leads to slow disappearance of these defects.

Irradiation of a stack of ultra-thin PET films by fission fragments was carried out and some sheets were then investigated separately. Two types of defects, corresponding to two main types of incident fragments (according to average energy distribution) were found. The deep structure of a track was studied and the ranges for two types of fragments were estimated. The increase of area of destruction was found at the depth 10–12 μm, which may be associated with changing of mechanism of interaction of passing particle with polymer and the dominant role of nuclear interaction. The obtained results are supported by a model calculation.     

Issues on nanoimprint lithography with a single-layer resist structure

We summarize our key developments in nanoimprint lithography (NIL) that employs a single layer resist lift-off process: lowering of the imprint temperature (for thermal imprint) and pressure, achieving uniform resist thickness and low residual resist layer thickness in the trenches, and eliminating metal ‘rabbit ears’ for the single-layer lift-off. In thermal NIL, our requirements for lower operating temperature and pressure motivated us to develop an alternative resist that is a viscous fluid at room temperature and cures at a lower temperature of 70 °C than the operating temperature of the conventional thermal NIL (≈200 °C). For UV NIL, we devised a method to dispense the resist onto a hydrophobic mold and use the hydrophilic substrate surface to spread the resist via surface wetting to engineer a continuous and uniform film. We also explored the use of Si(110) substrates as molds to produce features with perfectly vertical side walls, and the use of aqua regia to directly etch away rabbit ears. PACS 86.65.+h; 81.16.Nd; 81.16.Rf     

基于近红外光谱的柔性基底紫外臭氧改性效果表征研究

近年来,随着纳米科技、聚合物材料和先进制造技术的发展,以柔性传感器为代表的新兴柔性电子器件在可穿戴、健康医疗、物联网终端等领域发挥着越来越重要的作用。作为柔性电子器件的载体,柔性基底对传感器的机械可靠性和电学传感性能等方面有着重要的意义。但由于其表面非极性键造成的高疏水性限制了功能性材料在其表面的沉积,常常造成柔性基底层与电极层/敏感层之间不稳定的界面结合。因此,利用紫外臭氧处理对柔性基底表面改性受到了广泛的关注。利用近红外光谱技术对柔性基底的紫外臭氧处理效果进行快速精准评估,旨在从基团分子层面探究其改性效果,在实际应用中是对传统依靠接触角测量评估方法的有效补充。具体而言,对四种常见的柔性基底材料聚二甲基硅氧烷(PDMS)、聚萘二甲酸乙二醇酯（PEN）、聚对苯二甲酸乙二醇酯（PET）和聚酰亚胺（PI）进行了1/2/5/10 min不同时长的紫外臭氧（UVO）改性处理,并利用近红外光谱对其改性效果进行表征研究,最后利用接触角测量方法对上述的表征结果进行了验证分析。近红外光谱分析表明：对于柔性PDMS基底,紫外光能量不足以切断其中的甲基（—CH₃）官能团和（—C—Si—）等化学键,无法引入羟基、羧基等亲水性基团。对于柔性PEN和PET基底而言,紫外臭氧处理的效果要优于柔性PDMS基底,且对柔性PET基底的处理效果要优于柔性PEN基底,其原因可能是PEN基底材料中萘环的双环结构具有很强的紫外光吸收能力,阻隔了380 nm以下的大部分紫外线能量。对于柔性PI基底,紫外臭氧处理可以有效引入羟基（—OH）和羧基（—COOH）等活性基团,且这些官能团的强度和数量随着处理时间的增加而增加,从而在短时间内使得PI基底表面能增大、接触角减小、湿润性提高。接触角测试结果验证：紫外臭氧处理对于柔性PDMS基底处理效果不明显（接触角下降幅度为8.4%）;对柔性PET基底处理的效果（接触角下降幅度为39.6%）要优于柔性PEN基底的处理效果（接触角下降幅度为9.4%）;紫外臭氧处理的效果对柔性PI基底处理效果最佳,接触角下降幅度达到了62.7%。     

The fabrication of 3-D nanostructures by a low- voltage EBL

Three-dimensional (3-D) structures are used in many applications, including the fabrication of opto-electronic and bio-MEMS devices. Among the various fabrication techniques available for 3-D structures, nano imprint lithography (NIL) is preferred for producing nanoscale 3-D patterns because of its simplicity, relatively short processing time, and high manufacturing precision. For efficient replication in NIL, a precise 3-D stamp must be used as an imprinting tool. Hence, we attempted the fabrication of original 3-D master molds by low-voltage electron beam lithography (EBL). We then fabricated polydimethylsiloxane (PDMS) stamps from the original 3-D mold via replica molding with ultrasonic vibration.First, we experimentally analyzed the characteristics of low-voltage EBL in terms of various parameters such as resist thickness, acceleration voltage, aperture size, and baking temperature. From these e-beam exposure experiments, we found that the exposure depth and width were almost saturated at 3 kV or lesser, even when the electron dosage was increased. This allowed for the fabrication of various stepped 3-D nanostructures at a low voltage. In addition, by using line-dose EBL, V-groove patterns could be fabricated on a cured electron resist (ER) at a low voltage and low baking temperature. Finally, the depth variation could be controlled to within 10 nm through superposition exposure at 1 kV. From these results, we determined the optimum electron beam exposure conditions for the fabrication of various 3-D structures on ERs by low-voltage EBL. We then fabricated PDMS stamps via the replica molding process.     

Spin-cast planarization of liquid-crystal-on-silicon microdisplays

A simplified method for planarizing liquid-crystal-on-silicon (LCOS) backplanes is presented. The method relies on the planarizing capability of spin-cast benzocyclobutene (BCB) polymeric resin. BCB planarization shows a sixfold reduction in step height on the surface of a typical LCOS backplane. Contact with the underlying pixel circuitry is made by dry etching through openings in the BCB layer. Reflective metal (87% reflectivity) is deposited over the planarized surface and patterned to form high-aperture-ratio pixel mirrors (84%). An average resistance of 0.75 Omega per via was achieved with 3.6-microm-diameter vias in 2-microm-thick BCB. The method and the results of this LCOS backplane planarization and postprocessing are described.     

Hydrophobic recovery of UV/ozone treated poly(dimethylsiloxane): adhesion studies by contact mechanics and mechanism of surface modification

Silicone elastomers (Sylgard 184 and 170), based on poly(dimethylsiloxane) (PDMS), were surface treated by a combined exposure to UV and ozone. The effects of the treatments were analyzed as a function of time elapsed after stopping the treatments using different standard surface characterization techniques, such as water contact angle measurements, XPS and atomic force microscopy (AFM). However, the primary focus of this study was to apply the Johnson–Kendall–Roberts (JKR) contact mechanics approach to investigate PDMS samples prior to and following UV/ozone surface treatment. A gradual formation of a hydrophilic, silica-like surface layer with increasing modulus was observed with increasing UV/ozone exposure. A subsequent hydrophobic recovery after UV/ozone exposure was observed, as indicated by increasing contact angles. This supports the hypothesis that the hydrophobic recovery is mainly caused by the gradual coverage of a permanent silica-like structure with free siloxanes and/or reorientation of polar groups. PDMS containing a homogenously dispersed filler (Sylgard 184), exhibited a decreasing surface roughness (by AFM) when the oxidized surface region “collapsed” into a smooth SiO_x layer (final surface roughness <2 nm). PDMS containing heterogeneously distributed, aggregated filler particles (Sylgard 170), exhibited an increasing surface roughness with treatment dose, which was attributed to the “collapse” of the oxidized surface region thus exposing the contours of the underlying filler aggregates (final surface roughness ∼140 nm). A dedicated device was designed and built to study the contact mechanics behavior of PDMS prior to, and following surface treatment. The value of the combined elastic modulus obtained for PDMS lens and semi-infinite flat surface system showed an increase in full agreement with the formation of a silica-like layer exhibiting a high elastic modulus (compared with untreated PDMS). The work of adhesion observed in JKR experiments exhibited an increasing trend as a function of treatment done in agreement with contact angle data. JKR experiments showed hydrophobic recovery behavior as anticipated from contact angle measurements. Single pull-off force measurements by JKR and numerical analysis of full-approach JKR curves were in quantitative agreement regarding practical work of adhesion values.     

Ultra smooth NiO thin films on flexible plastic (PET) substrate at room temperature by RF magnetron sputtering and effect of oxygen partial pressure on their properties

Transparent p-type nickel oxide thin films were grown on polyethylene terephthalate (PET) and glass substrates by RF magnetron sputtering technique in argon + oxygen atmosphere with different oxygen partial pressures at room temperature. The morphology of the NiO thin films grown on PET and glass substrates was studied by atomic force microscope. The rms surface roughnesses of the films were in the range 0.63-0.65 nm. These ultra smooth nanocrystalline NiO thin films are useful for many applications. High resolution transmission electron microscopic studies revealed that the grains of NiO films on the highly flexible PET substrate were purely crystalline and spherical in shape with diameters 8-10 nm. XRD analysis also supported these results. NiO films grown on the PET substrates were found to have better crystalline quality with fewer defects than those on the glass substrates. The sheet resistances of the NiO films deposited on PET and glass substrates were not much different; having values 5.1 and 5.3 kΩ/□ and decreased to 3.05, 3.1 kΩ/□ respectively with increasing oxygen partial pressure. The thicknesses of the films on both substrates were ∼700 nm. It was also noted that further increase in oxygen partial pressure caused increase in resistivity due to formation of defects in NiO.     

等温等效替代热压印法成型 超薄导光板的工艺分析

针对超薄导光板微结构模具难加工的问题,结合等温热压印法,提出了一种新型的"等效替代"压印工艺,即通过控制成型工艺参数来降低微结构复制高度,实现了在基片上成型出小于模具微结构尺寸的等效结构,突破了热压印过程中模具微结构完全等大复制的思想禁锢,降低了微结构模具加工难度,从而革新了高质量超薄导光板的成型工艺。以聚甲基丙烯酸甲酯(PMMA)为基片,设计具体实验,加工0.25 mm厚的导光板,验证这一方法的可行性。实验结果表明,这种新型的"等效替代"压印工艺不仅可以降低模具的制造难度和加工成本,而且可以大大改善超薄导光板的性能,与等温热压印工艺相比均匀度提高了23%,整个成型时间缩短到了20 s。     

Immobilization of immunoglobulin G in a highly oriented manner on a protein-A terminated multilayer system

In this study, we have fabricated a multilayer system consisting of 3-glycidoxypropyldimethylmethoxysilane (GPDS), poly(dimethylsiloxane) bis 3-aminopropyl terminated (PDMS) and protein-A on a silicon wafer surface for oriented immobilization of immunoglobilin G (IgG). The multilayer system with a different component in each layer was characterized by ellipsometry, contact-angle goniometer, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) and fluorescence microscopy. The epoxy-terminated monolayer was formed by the chemisorption of GPDS molecules on the hydroxylated silicon surface. The PDMS film about 4.5 nm thick was produced on the GPDS-monolayer by the chemical reaction between the amine groups at the end of PDMS chain and the epoxy groups of GPDS molecules. By introducing the PDMS chains, the hydrophilic character of GPDS-monolayer decreased. Study of the time dependence of polymer grafting showed that the chemisorption of GPDS is fast, whereas at least 16 h is needed to generate the homogeneous PDMS layer. For immobilization of IgG molecules in a highly oriented manner, protein-A molecules were first chemically bound to an ultrathin (∼4.5 nm) PDMS reactive polymer layer and later used to capture IgG. It was shown that the existence of protein-A in the multilayer system has a strong influence on the binding properties of IgG not only in the efficiency of binding, but also in its specificity. In conclusion, the multilayer system with protein-A has the potential to be further developed into an efficient immunoassay protein chip.     

Casting mold patterning for lateral capillary force migration on PDMS microchannel

The casting molds including various shapes within axial and lateral resolution (110 μm and 5 μm) could be precisely fabricated and were suitable for the fabrication of PDMS microchannel possessing the larger inner volume for the purpose of the rapid capillary force migration. The tight bonding between PDMS mold and SiO₂/Si surface not only was governed by the flexibility and the degree of tilted angle (TA) of PDMS microchannel which shows the minimum value at the 0.2 weight ratio (W_r) of curing agent but also efficiently generates the capillary migration.     

Self-organizing magnetic beads for biomedical applications

In the field of biomedicine magnetic beads are used for drug delivery and to treat hyperthermia. Here we propose to use self-organized bead structures to isolate circulating tumor cells using lab-on-chip technologies. Typically blood flows past microposts functionalized with antibodies for circulating tumor cells. Creating these microposts with interacting magnetic beads makes it possible to tune the geometry in size, position and shape. We developed a simulation tool that combines micromagnetics and discrete particle dynamics, in order to design micropost arrays made of interacting beads. The simulation takes into account the viscous drag of the blood flow, magnetostatic interactions between the magnetic beads and gradient forces from external aligned magnets. We developed a particle-particle particle-mesh method for effective computation of the magnetic force and torque acting on the particles.     

Transformation of medical grade silicone rubber under Nd:YAG and excimer laser irradiation: First step towards a new miniaturized nerve electrode fabrication process

Medical grade silicone rubber, poly-dimethylsiloxane (PDMS) is a widely used biomaterial. Like for many polymers, its surface can be modified in order to change one or several of its properties which further allow this surface to be functionalized. Laser-induced surface modification of PDMS under ambient conditions is an easy and powerful method for the surface modification of PDMS without altering its bulk properties. In particular, we profit from both UV laser inducing surface modification and of UV laser micromachining to develop a first part of a new process aiming at increasing the number of contacts and tracks within the same electrode surface to improve the nerve selectivity of implantable self sizing spiral cuff electrodes. The second and last part of the process is to further immerse the engraved electrode in an autocatalytic Pt bath leading in a selective Pt metallization of the laser irradiated tracks and contacts and thus to a functionalized PDMS surface. In the present work, we describe the different physical and chemical transformations of a medical grade PDMS as a function of the UV laser and of the irradiation conditions used. We show that the ablation depths, chemical composition, structure and morphology vary with (i) the laser wavelength (using an excimer laser at 248 nm and a frequency-quadrupled Nd:YAG laser at 266 nm), (ii) the conditions of irradiation and (iii) the pulse duration. These different modified properties are expected to have a strong influence on the nucleation and growth rates of platinum which govern the adhesion and the thickness of the Pt layer on the electrodes and thus the DC resistance of tracks.