纳米压印技术

传统光学光刻技术的高成本促使科学家去开发新的非光学方法,以取代集成电路工厂目前所用的工艺.另外,微机电系统(MEMS)的成功启发科学家借用MEMS中的相关技术,将其使用到纳米科技中去,这是得到纳米结构的一种有效途经.纳米压印在过去的几年里受到了高度重视,因为它成功地证明了它有成本低、分辨率高的潜力.纳米压印技术主要包括热压印、紫外压印(含步进-闪光压印)和微接触印刷等.本文详细讨论纳米压印材料的制备及常用的三种工艺的工艺步骤和它们各自的优缺点.并对这三种工艺进行了比较.最后列举了一些典型应用,如微镜、金属氧化物半导体场效应管、光栅等.     

纳米压印技术的研究进展

纳米压印技术由于具有操作简单、高分辨率、成本低、重复性高等优点,近年来受到国内外研究机构的高度重视.本文主要介绍了目前主流的几种纳米压印技术,并简要概述了纳米压印技术的研究现状和应用前景.     

纳米压印技术进展及应用

半导体加工几十年里一直采用光学光刻技术实现图形转移,最先进的浸润式光学光刻在45 nm节点已经形成产能,然而,由于光学光刻技术固有的限制,已难以满足半导体产业继续沿着摩尔定律快速发展.在下一代图形转移技术中,电子束直写、X射线曝光和纳米压印技术占有重要地位.其中纳米压印技术具有产量高、成本低和工艺简单的优点,是纳米尺寸电子器件的重要制作技术.介绍了传统纳米压印技术以及纳米压印技术的新进展,如热塑纳米压印技术、紫外固化纳米压印技术、微接触纳米压印技术、气压辅助纳米压印技术、激光辅助压印技术、静电辅助纳米压印技术、超声辅助纳米压印技术和滚轴式纳米压印技术等.     

纳米压印用压印胶的研究进展

纳米压印需采用压印胶进行图案转移,作为压印技术的关键材料,压印胶的性能直接影响到纳米压印的质量。根据压印技术的工艺特点对压印胶进行了分类,介绍了纳米压印用热压印胶和紫外压印胶的发展研究现状和性能优缺点,分析了目前压印胶存在的主要问题,并指出压印胶的研究主要是提高压印胶的脱模性能、固化速率以及简化工艺,主要列举了含氟硅类压印胶、双表面能压印胶的性能特点,并展望了未来的发展方向。     

电磁辅助纳米压印

纳米压印技术是最近十几年提出的新的图形转移技术,此技术有产量高、成本低和工艺简单的优点,因此得到了飞速的发展。传统的纳米技术有热塑纳米压印技术、紫外固化纳米压印技术和微接触纳米压印技术。近几年又出现了纳米压印技术的新方法,如金属薄膜直写技术、滚轴式纳米压印技术、气压辅助纳米压印技术和静电辅助纳米压印技术。主要介绍利用静电辅助压印技术和气压辅助纳米压印技术相结合的一种新型纳米压印方法,并利用仿真软件Ansys进行仿真,通过仿真实验和理论研究,证明此方法是可行的。     

基于光刻版的无留膜紫外纳米压印技术研究

针对纳米压印光刻技术中压印脱模后的留膜去除问题,提出了一种基于光刻版的无留膜紫外纳米压印技术.采用传统的光刻版作为紫外压印模版,由于模版上铬层的遮蔽作用.使得铬层下面的光刻胶不被曝光,从而可以轻易地被去除.实验结果表明,该技术综合了压印与光刻各自的优点,可以获得无留膜厚度的压印图形,省去了压印后的留膜刻蚀工艺.从而避免了由于留膜厚度不均匀所带来的过刻蚀或欠刻蚀的问题.     

热压印技术制作纳米光栅

通过分析脱模过程的摩擦力,讨论了模具表面处理工艺与压模质量的关系,给出了降低脱膜过程摩擦力的工艺方法.实验结果表明,用类聚四氟乙烯膜作为脱模剂能大大减小模具表面与聚合物表面的摩擦力.研究了压模、脱模工艺参数对实验结果的影响,基于HEX-02塑铸系统,真空条件下,在压模温度为195℃,模压压强为8 MPa的环境下,利用热压印技术在PMMA薄膜上复制出周期为120 nm的纳米光栅.     

纳米压印光刻技术--下一代批量生产的光刻技术

纳米压印光刻技术已被证实是纳米尺寸大面积结构复制的最有前途的下一代技术之一。这种速度快、成本低的方法成为生物化学、μ级流化学、μ-TAS和通信器件制造以及纳米尺寸范围内广泛应用的一种日渐重要的方法,如生物医学、纳米流体学、纳米光学应用、数据存储等领域。由于标准光刻系统的波长限制、巨大的开发工作量、以及高昂的工艺和设备成本,纳米压印光刻技术可能成为主流IC产业中一种真正富有竞争性方法。对细小到亚10nm范围内的极小复制结构,纳米压印技术没有物理极限。从几种纳米压印光刻技术中选择两种前景广阔的方法——热压印光刻(HEL)和紫外压印光刻(UV-NIL)技术给予介绍。两种技术对各种各样的材料以及全部作图的衬底大批量生产提供了快速印制。重点介绍了HEL和UV-NIL两种技术的结果。全片压印尺寸达200mm直径,图形分辨力高,拓展到纳米尺寸范围。     

纳米压印光刻技术

为了避免纳米压印光刻技术与光刻技术混淆，纳米压印光刻技术严谨的专业术语定义是：不使用光线或者辐射使光刻胶感光成形，而是直接在硅衬底或者其他衬底上利用物理学机理构造纳米级别的图形。这种纳米成像技术真正地实现了纳米级别的图形印制。     

纳米压印技术专利分析

在信息存储、生物传感器、亚波长光学器件等领域,纳米压印技术已成为价格相对较低、性能可靠、具有量产能力的制备技术。通过对纳米压印技术专利文献的定量和定性分析,从技术层面和竞争层面上把握纳米压印的技术发展脉络和竞争格局,研究了纳米压印技术领域的发展概况、技术群聚和各国的技术情况,试图显示出世界纳米压印技术的现状、特点和发展趋势。     

纳米压印光刻胶

光刻胶是纳米压印的关键材料,其性能将影响压印图形复制精度、图形缺陷率和图形向底材转移时刻蚀选择性。提出了成膜性能、硬度黏度、固化速度、界面性质和抗刻蚀能力等压印光刻胶的性能指标。并根据工艺特点和材料成分对光刻胶分类,介绍了热压印光刻胶、紫外压印光刻胶、步进压印式光刻胶和滚动压印式光刻胶的特点以及碳氧类纯有机材料、有机氟材料、有机硅材料做压印光刻胶的优缺点。列举了热压印、紫外压印、步进压印工艺中具有代表性的光刻胶实例,详细分析了其配方中各组分的比例和作用。介绍了可降解光刻胶的原理。展望了压印光刻胶的发展趋势。     

A Universal Scheme for Patterning of Oxides via Thermal Nanoimprint Lithography

Direct patterning of oxides using thermal nanoimprint lithography is performed using either the sol‐gel or methacrylate route. The sol‐gel method results in resists with long shelf‐life, but with high surface energy and a considerable amount of solvent that affects the quality of imprinting. The methacrylate route, which is limited to certain oxides, produces polymerizable resists, leading to low surface energy, but suffers from the shorter shelf‐life of precursors. By combining the benignant elements from both these routes, a universal method of direct thermal nanoimprinting of oxides is demonstrated using precursors produced by reacting an alkoxide with a polymerizable chelating agent such as 2‐(methacryloyloxy)ethyl acetoacetate (MAEAA). MAEAA possesses β‐ketoester, which results in the formation of environmentally stable, chelated alkoxide with long shelf‐life, and methacrylate groups, which provide a reactive monomer pendant for in situ copolymerization with a cross‐linker during imprinting. Polymerization leads to trapping of cations, lowering of surface energy, strengthening of imprints, which enables easy and clean demolding over 1 cm × 2 cm patterned area with ≈100% yield. Heat‐treatment of imprints gives amorphous/crystalline oxide patterns. This alliance between two routes enables the successful imprinting of numerous oxides including Al₂O₃, Ga₂O₃, In₂O₃, Y₂O₃, B₂O₃, TiO₂, SnO₂, ZrO₂, GeO₂, HfO₂, Nb₂O₅, Ta₂O₅, V₂O₅, and WO₃.     

基于纳米压印的超材料近红外吸收器的制备研究

超材料吸收器的高吸收率源于表面金属颗粒与介质层之间产生的局域等离激元共振以及由金属颗粒--介质层--金属反射层构成的微腔所导致的共振吸收。其吸收特性与金属颗粒的尺寸、形貌和介质层的材料和厚度密切相关。设计优化了一个在近红外波段1.2 μm处具有近完美吸收的超材料吸收器。以该设计为蓝图,利用纳米压印技术制备了一系列具有不同介质层厚度的器件,并利用红外反射谱定量研究了这些器件的吸收特性。实验结果证实,用纳米压印技术制备的超材料器件具有工艺可靠性好、加工精度高等优点。实验测得的吸收率变化趋势与理论预期相符,吸收率较高。     

Nanoimprint Lithography and the Role of Viscoelasticity in the Generation of Residual Stress in Model Polystyrene Patterns

Understanding polymer deformation during the nanoimprinting process is key to achieving robust polymer nanostructures. Information regarding this process can be extracted from monitoring the decay of the imprinted polymer patterns during thermal annealing. In the present work, the effect of both the molar mass and the imprinting temperature on the pattern decay behavior during thermal annealing is investigated. Previously, it was found that the decay rate is fastest for a highly entangled polymer due to the elastic recovery caused by the residual stress created during the imprinting process. The present paper demonstrates that this residual stress level can be modified through control of the imprinting temperature. These results are contrasted with those for an unentangled polymer over a similar range of imprinting temperatures, where it is found that the pattern decay is controlled by simple Newtonian flow. In particular, the pattern decay is well described by surface‐tension‐driven viscous flow, and no imprinting‐temperature effect is observed during thermal annealing. It is shown that the stability of the film against pattern decay can be optimized for moderately entangled polymer films. This effect is attributed to the competition between the effect of increased viscosity with increasing molar mass and increased residual stresses with entanglements. These observations provide guidance for the optimization of imprinting process in terms of selection of molar mass and processing temperatures.     

Nanoimprint Lithography Facilitated Plasmonic-Photonic Coupling for Enhanced Photoconductivity and Photocatalysis

Imprint lithography has emerged as a reliable, reproducible, and rapid method for patterning colloidal nanostructures. As a promising alternative to top-down lithographic approaches, the fabrication of nanodevices has thus become effective and straightforward. In this study, a fusion of interference lithography (IL) and nanosphere imprint lithography on various target substrates ranging from carbon film on transmission electron microscope grid to inorganic and dopable polymer semiconductor is reported. 1D plasmonic photonic crystals are printed with 75% yield on the centimeter scale using colloidal ink and an IL-produced polydimethylsiloxane stamp. Atomically smooth facet, single-crystalline, and monodisperse colloidal building blocks of gold (Au) nanoparticles are used to print 1D plasmonic grating on top of a titanium dioxide (TiO₂) slab waveguide, producing waveguide-plasmon polariton modes with superior 10 nm spectral line-width. Plasmon-induced hot electrons are confirmed via two-terminal current measurements with increased photoresponsivity under guiding conditions. The fabricated hybrid structure with Au/TiO₂ heterojunction enhances photocatalytic processes like degradation of methyl orange (MO) dye molecules using the generated hot electrons. This simple colloidal printing technique demonstrated on silicon, glass, Au film, and naphthalenediimide polymer thus marks an important milestone for large-scale implementation in optoelectronic devices.     

紫外纳米压印用PMMA转移层膜的制备及性能

以苯甲醚为溶剂,采用旋涂法制备PMMA(聚甲基丙烯酸甲酯)转移层膜。当PMMA的质量分数为5%、旋涂速度为2000～6000r/min时,转移层膜的厚度为90～150nm,粗糙度为0.3nm,可满足纳米压印要求。采用接触角测量仪测试计算出PMMA、PS转移层膜的表面能,并通过转移层膜与压印胶之间的粘附功和界面张力的计算,评价了PMMA、PS和Si片对压印胶的润湿和粘附性能。结果表明,PMMA膜可改善压印胶在基片上的润湿铺展性能和粘附性能,而PS膜虽能改善基片的润湿铺展性能,却不利于压印胶的粘附。     

纳米压印技术的最新进展

总结了纳米压印技术的最新进展,其中包括压印工艺、图形赋形方法以及纳米压印技术应用三方面最新的研究成果。在压印工艺的发展方面,大面积滚轴压印的发明最具有产业化意义,它不仅解决了常规平板压印很难大面积压印成型的困难,而且整个过程是一种柔性压印过程,降低了成本,提高了压印效率,但是最小特征尺寸还有待提高;在图形赋形方法的改进中,聚合物探针阵列技术集微米和纳米成型技术于一身,压印效率高,应用前景广阔;在压印技术应用的发展中,光伏电池、电子存储设备以及传感器等为纳米压印技术的应用提供了新的领域。     

Patterned Self‐Assembled Monolayers on Silicon Oxide Prepared by Nanoimprint Lithography and Their Applications in Nanofabrication

Nanoimprint lithography (NIL) is used as a tool to pattern self‐assembled monolayers (SAMs) on silicon substrates because of its ability to pattern in the micrometer and nanometer ranges. The polymer template behaves as a physical barrier preventing the formation of a SAM in the covered areas of the substrate. After polymer removal, SAM patterns are obtained. The versatility of the method is shown in various nanofabrication schemes. Substrates are functionalized with a second type of silane adsorbate. Pattern enhancement via selective electrostatic attachment of carboxylate‐functionalized particles is achieved. Further applications of the NIL‐patterned substrates include template‐directed adsorption of particles, as well as the fabrication of electrodes on top of a SAM.     

A Nanoimprint Lithography Hybrid Photoresist Based on the Thiol–Ene System

A novel hybrid resist for UV nanoimprint lithography (UV‐NIL) based on the thiol–ene photopolymerization is presented. Our system comprises mercaptopropyl polyhedral oligomeric silsesquioxane and benzyl methacrylate, with trimethylolpropane trimethacrylate as the crosslinker. The obtained hybrid resists possess a variety of characteristics desirable for UV‐NIL, such as low viscosity (6.1–25 cP), low bulk‐volumetric shrinkage (5.3%), high Young's modulus (0.9–5.2 GPa), high thermal stability, and excellent dry‐etch resistance. Based on these performances, the optimized components are evaluated as UV‐NIL resists. The result is a high‐resolution pattern with feature sizes in the range of 100 nm to several microns. The double‐layer resist approach is used for pattern transfer into silicon substrates. The excellent oxygen‐etch resistance of the barrier material enables a final transfer pattern that is about three times higher than that of the original NIL mold.     

Nanoimprint lithography fabrication of waveguide-integrated optical gratings with inexpensive stamps

We demonstrate that a replica grating can be effectively used as an inexpensive stamp for nanoimprint lithography to pattern diffractive optical couplers integrated with planar optical waveguides. Imprinted grating patterns were integrated with silicon oxynitride waveguide films to be used as an evanescent wave sensor in the input grating-coupler configuration. An anti-adhesion layer using an inexpensive, two-step chemical functionalization was developed for the stamps. The stamps were able to withstand imprint temperatures ranging from 140 to 190 °C and high fidelity imprints were obtained. The groove pattern was integrated in waveguide films by etch transfer and light-coupling properties of gratings with 1.2 μm pitch were tested using a λ = 1.55 μm laser. Compared to etched silicon masters, replica optical gratings provide uniform pattern density over their entire surface with no unstructured regions, are inexpensive, and readily available for R&D use.