The Elastic Properties and Plastic Behavior of Two‐Dimensional Polymer Structures Fabricated by Laser Interference Lithography

The elastic and plastic properties within a two‐dimensional polymer (SU8) structure with sixfold symmetry fabricated via interference lithography are presented. There is a nonuniform spatial distribution in the elastic modulus, with a higher elastic modulus obtained for nodes (brightest regions in the laser interference pattern) and a lower elastic modulus for beams (darkest regions in the laser interference pattern) of the photopatterned films. We suggest that such a nonuniformity and unusual plastic behavior are related to the variable material properties “imprinted” by the interference pattern.     

Drug Delivery: Bio‐inspired Heterostructured Bead‐on‐String Fibers That Respond to Environmental Wetting (Adv. Funct. Mater. 8/2011)

Inspired by the geometric structure of ecribellate spider capture silk and its spinning characteristics, we propose a one‐step electrohydrodynamic method to fabricate bead‐on‐string heterostructured fibers (BSHFs). By combining electrospinning and electrospraying strategies using a sprayable outer fluid with low viscosity and a spinnable inner fluid with high viscosity in a coaxial jetting process, hydrophilic poly(ethylene glycol) beads are successfully imprinted on a hydrophobic polystyrene string. It is demonstrated that the BSHFs are capable of intelligently responding to environmental change. With a change in relative humidity, the fibers show a segmented swelling and shrinking behavior in the “bead” parts whereas the “string” parts remain the same. The elastic BSHFs with alternating hydrophilic and hydrophobic surface characteristics represent a type of mesoscale analogues that block copolymers and may bring about new properties and applications. Moreover, the combined electrohydrodynamic approach developed herein should open new routes to multifunctional one‐dimensional heterostructured materials.     

Cover Picture: Photolithographic Route to the Fabrication of Micro/Nanowires of III–V Semiconductors (Adv. Funct. Mater. 1/2005)

The cover shows a patterned assembly of GaAs nanowires with their ends tethered to a bulk single‐crystal wafer as described on p. 30 by Rogers and co‐workers. These wires, which have triangular cross‐sections, were fabricated via a top–down process that combines photolithography and anisotropic chemical etching. Nano/microwires of semiconducting materials (e.g., GaAs and InP) with triangular cross‐sections can be fabricated by “top–down” approaches that combine lithography of high‐quality bulk wafers (using either traditional photolithography or phase‐shift optical lithography) with anisotropic chemical etching. This method gives good control over the lateral dimensions, lengths, and morphologies of free‐standing wires. The behaviors of many different resist layers and etching chemistries are presented. It is shown how wire arrays with highly ordered alignments can be transfer printed onto plastic substrates. This “top–down” approach provides a simple, effective, and versatile way of generating high‐quality single‐crystalline wires of various compound semiconductors. The resultant wires and wire arrays have potential applications in electronics, optics, optoelectronics, and sensing.     

Pattern‐Transfer Fidelity in Soft Lithography: The Role of Pattern Density and Aspect Ratio

Using high‐aspect‐ratio nanostructures fabricated via two‐photon laser‐scanning lithography, we examine the deformation of elastomeric stamps used in soft nanolithography and the fidelity of patterns and replicas made using these stamps. Two‐photon laser‐scanning lithography enables us to systematically regulate the aspect ratio and pattern density of the nanostructures by varying laser‐scanning parameters such as the intensity of the laser beam, the scanning speed, the focal depth inside the resist, and the scanning‐line spacing. Two commercially available stamp/mold materials with different moduli have been investigated. We find that the pattern‐transfer fidelity is strongly affected by the pattern density. In addition, we demonstrate that true three‐dimensional structures can be successfully replicated because of the flexible nature of elastomeric poly(dimethylsiloxane).     

Bio‐inspired Heterostructured Bead‐on‐String Fibers That Respond to Environmental Wetting

Inspired by the geometric structure of ecribellate spider capture silk and its spinning characteristics, we propose a one‐step electrohydrodynamic method to fabricate bead‐on‐string heterostructured fibers (BSHFs). By combining electrospinning and electrospraying strategies using a sprayable outer fluid with low viscosity and a spinnable inner fluid with high viscosity in a coaxial jetting process, hydrophilic poly(ethylene glycol) beads are successfully imprinted on a hydrophobic polystyrene string. It is demonstrated that the BSHFs are capable of intelligently responding to environmental change. With a change in relative humidity, the fibers show a segmented swelling and shrinking behavior in the “bead” parts whereas the “string” parts remain the same. The elastic BSHFs with alternating hydrophilic and hydrophobic surface characteristics represent a type of mesoscale analogues that block copolymers and may bring about new properties and applications. Moreover, the combined electrohydrodynamic approach developed herein should open new routes to multifunctional one‐dimensional heterostructured materials.     

Reversible Diffraction Efficiency of Photochromic Polymer Gratings Related to Photoinduced Dimensional Changes

In this Full Paper, the possibility of reversibly changing the diffraction efficiency of gratings, fabricated by soft molding lithography on polymer films, containing photochromic molecules, is demonstrated. In particular, alternating UV and visible laser irradiation of the gratings causes the doped photochromic molecules to undergo transformations, which induce reversible dimensional changes to the samples. As a result, reversible changes are monitored in the intensity of the beams of a diode laser, transmitted and diffracted from the gratings. These changes affect the diffraction efficiency, which is increased upon irradiation with UV and decreased after irradiation with visible laser light. Such gratings are promising candidates for the fabrication of modern optical components such as optical switching devices.     

Photolithographic Route to the Fabrication of Micro/Nanowires of III–V Semiconductors

Nano/microwires of semiconducting materials (e.g., GaAs and InP) with triangular cross‐sections can be fabricated by “top–down” approaches that combine lithography of high‐quality bulk wafers (using either traditional photolithography or phase‐shift optical lithography) with anisotropic chemical etching. This method gives good control over the lateral dimensions, lengths, and morphologies of free‐standing wires. The behaviors of many different resist layers and etching chemistries are presented. It is shown how wire arrays with highly ordered alignments can be transfer printed onto plastic substrates. This “top–down” approach provides a simple, effective, and versatile way of generating high‐quality single‐crystalline wires of various compound semiconductors. The resultant wires and wire arrays have potential applications in electronics, optics, optoelectronics, and sensing.     

3D Micro‐ and Nanostructures via Interference Lithography

Interference lithography (IL) holds the promise of fabricating large‐area, defect‐free 3D structures on the submicrometer scale both rapidly and cheaply. A stationary spatial variation of intensity is created by the interference of two or more beams of light. The pattern that emerges out of the intensity distribution is transferred to a light sensitive medium, such as a photoresist, and after development yields a 3D bicontinuous photoresist/air structure. Importantly, by a proper choice of beam parameters one can control the geometrical elements and volume fraction of the structures. This article provides an overview of the fabrication of 3D structures via IL (e.g., the formation of interference patterns, their dependence on beam parameters and several requirements for the photoresist) and highlights some of our recent efforts in the applications of these 3D structures in photonic crystals, phononic crystals and as microframes, and for the synthesis of highly non spherical polymer particles. Our discussion concludes with perspectives on the future directions in which this technique could be pursued.     

Cover Picture: An Epoxy Photoresist Modified by Luminescent Nanocrystals for the Fabrication of 3D High‐Aspect‐Ratio Microstructures (Adv. Funct. Mater. 13/2007)

M. Lucia Curri and co‐workers report on p. 2009 an epoxy‐based negative tone photoresist that can be functionalized with red emitting CdSe@ZnS core/shell type nanocrystals and patterned by UV lithography. The 3D high aspect ratio of the microfabricated structures proves that lithographic properties of the functional nanocomposite are retained and the nanocrystals properties conveyed into the resist. The emitting nanocomposite represents a convenient model for material functionalization expandable to nanocrystals with different properties. An epoxy‐based negative‐tone photoresist, which is known as a suitable material for high‐aspect‐ratio surface micromachining, is functionalized with red‐light‐emitting CdSe@ZnS nanocrystals (NCs). The proper selection of a common solvent for the NCs and the resist is found to be critical for the efficient incorporation of the NCs in the epoxy matrix. The NC‐modified resist can be patterned by standard UV lithography down to micrometer‐scale resolution, and high‐aspect‐ratio structures have been successfully fabricated on a 100 mm scaled wafer. The “as‐fabricated”, 3D, epoxy‐based surface microstructures show the characteristic luminescent properties of the embedded NCs, as verified by fluorescence microscopy. This issue demonstrates that the NC emission properties can be conveniently conveyed into the polymer matrix without deteriorating the lithographic performance of the latter. The dimensions, the resolution, and the surface morphology of the NC‐modified‐epoxy microstructures exhibit only minor deviations with respect to that of the unmodified reference material, as examined by means of microscopic and metrologic investigations. The proposed approach of the incorporation of emitting and non‐bleachable NCs into a photoresist opens novel routes for surface patterning of integrated microsystems with inherent photonic functionality at the micro‐ and nanometer‐scale for light sensing and emitting applications.     

Hydrothermal Growth: Polymer‐Templated Hydrothermal Growth of Vertically Aligned Single‐Crystal ZnO Nanorods and Morphological Transformations Using Structural Polarity (Adv. Funct. Mater. 18/2010)

Position‐configurable, vertical, single‐crystalline ZnO nanorod arrays are fabricated via a polymer‐templated hydrothermal growth method at a low temperature of 93 °C. A sol‐gel processed dense c‐oriented ZnO seed layer film is employed to grow nanorods along the c‐axis direction [0001] regardless of any substrate crystal mismatches. Here, one‐beam laser‐interference lithography is utilized to fabricate nanoscale holes over an entire 2‐in. wafer during the preparation of the polymer template. As such, vertically aligned ZnO nanorods can be grown from the seed layer exposed at the bottom of each hole. Furthermore, morphological transformations of the ZnO nanorods into pencil‐like, needle‐like, tubular, tree‐like, and spherical shapes are obtained by controlling the growth conditions and utilizing the structural polarity of the ZnO nanorods.     

Rapid and Large‐Scale Fabrication of Full Color Woodpile Photonic Crystals via Interference from a Conformal Multilevel Phase Mask

The practical use of photonic crystals with structural colors requires technology capable of rapidly producing large‐area, three‐dimensional (3D) periodic nanostructures. Until now, the fabrication of 3D photonic crystals has relied mainly on additive manufacturing and colloidal self‐assembly. These technologies have provided a useful academic platform based on precisely controlled 3D periodicity but have not evolved into mass production technology. Here, optical lithography for the rapid fabrication of large‐area 3D photonic crystals with structural colors is introduced. The key strategy is to incorporate two orthogonal line gratings (periodicity: 300 nm) made of an elastomer to create a conformal multilevel phase mask. When the mask is irradiated with a 355 nm laser, the five beam interference is established in the proximity region. The interlayer thickness between the two orthogonal line gratings controls the phase difference, which is closely related to the symmetry of the resulting 3D interference pattern. The interlayer thickness is designed to produce a woodpile structure with a planar periodicity of 300 nm and a vertical periodicity of 716 nm. The pattern area of the woodpile photonic crystal is expanded to 1 in². Red, green, and blue colors are experimentally realized by controlling the vertical shrinkage of the photoresist.     

Symmetry‐Breaking Response of Azo Molecular Glass Microspheres to Interfering Circularly Polarized Light: From Shape Manipulation to 3D Patterning

This work investigates symmetry‐breaking deformation of azo molecular glass microspheres induced by interfering circularly polarized light, and related particle shape manipulation as well as 3D patterning. The isolated microspheres and microsphere monolayers are obtained from an azo molecular glass (IA‐Chol) by the solution dispersion method and soft‐lithography, respectively. Unique symmetry‐breaking deformation is observed for the microspheres upon exposure to the spatially modulated light field, which is produced by interference of two orthogonally polarized laser beams with the right‐circular polarization (RCP) and left‐circular polarization (LCP). Two distinct deformation modes are developed upon the irradiation with the interfering beams in RCP:LCP and LCP:RCP superposition manners, respectively. The unique morphologies with the symmetry‐breaking characteristics are caused by mass transfer induced by the light irradiation. For the microsphere monolayers, the deformations of the microspheres not only capture and record the polarization states of the light field, but also create various surface patterns combining the symmetry‐breaking deformations and periodic surface modulation. A variety of unique surface patterns are obtained by irradiation with the interfering circularly polarized waves with the orthogonal and also the same‐handed polarizations. The material and methodology developed in this study are promising for applications in sensing, optics, responsive surfaces, and others.     

Direct polymer-transfer lithography for high-throughput fabrication of Cu line patterns

A novel direct polymer-transfer lithography (DPTL) technique is proposed for fabricating fine patterns having feature sizes ranging from ten to several tens of micrometers with extremely high throughput. By means of this technique, a homemade fluorine-containing polymer “ink”, which has good water repellency, was imprinted directly onto a Cu/polyimide sheet by using an elastomeric polydimethylsiloxane (PDMS) stamp; imprinting was followed by wet etching of the Cu layer, with the transferred polymer patterns serving as an etch mask. Under the optimized imprinting conditions, Cu lead patterns with a minimum line width of approximately 10 μm were successfully fabricated with high accuracy and good reproducibility. The DPTL technique will be very useful for manufacturing flexible printed circuit boards (FPCs).     

Replication of high ordered nano-sphere array by nanoimprint lithography

High ordered nano-sphere array patterns on Si substrate were fabricated using nanoimprint lithography. First, using hot embossing method, poly vinyl chloride (PVC) based polymer replica template was duplicated from original high ordered nano-sphere array patterns, which was fabricated by evaporation method. The monolayer transferring condition can be achieved by varying hot embossing pressure. Then, through UV nanoimprint lithography with the replicated polymer template, imprinted patterns, which has high ordered nano-sphere array patterns, was successfully fabricated on Si and flexible PET substrate.     

Magnetic Molecularly Imprinted Polymer Nanocomposites via Surface‐Initiated RAFT Polymerization

A general protocol to synthesize superparamagnetic molecularly imprinted polymer particles, using a RAFT‐mediated approach, is described. S‐ propranolol‐imprinted composites were obtained by functionalizing commercially available amino‐modified Fe₃O₄ nanoparticles with a trithiocarbonate agent and subsequently by polymerizing thin molecularly imprinted layers. Different parameters were optimized and their effect on both nanomorphology and imprinting behaviour was studied. Optimum conditions allowed the synthesis of 40 nm composite particles with a 7 nm MIP shell, exhibiting superparamagnetic properties and specific molecular recognition of S‐ propranolol. The possibility of fine‐tuning the surface properties of the particles is demonstrated by using the “living” nature of active RAFT fragments present on the surface of the composites to further functionalize the particles with ethylene glycol methacrylate phosphate polymer brushes.     

Simple Holographic Patterning for High‐Aspect‐Ratio Three‐Dimensional Nanostructures with Large Coverage Area

Using the vertical standing wave phenomena commonly regarded as a deterrent in holographic lithography, multifaceted three‐dimensional (3D) nanostructures are fabricated on polymeric photoresist materials using a simple two‐beam interferometer. Large‐area 3D nanostructures with high aspect ratios (greater than 10) are readily produced using this methodology, including grating, pillar and pore patterns. Furthermore, manipulation of the lithography process conditions results in unique sidewall profiles of the nanostructures. Such 3D holographic control even produces highly porous polymer membranes composed of 3D interconnected pore networks, which resembles the 3D photonic crystal compound nanostructures that were previously attainable only with limited pattern coverage area using complex multibeam holographic lithography processes. Such well‐tailored high‐aspect‐ratio 3D nanostructures with large pattern coverage area further enable the fabrication of novel nanostructures for functionalized materials via various additive and subtractive pattern transfer techniques such as etching, deposition, and molding. In particular, direct molding followed by thermal decomposition process leads to the synthesis of hierarchical titanium oxide nanostructures of tunable 3D geometry, which would be of great significance in applications of photonic crystals, photovoltaic solar cells, and photocatalyst in water decontamination.     

光束路径排布对称性与光功率分布均匀性

报道了６０路激光束的入射窗在球形靶室上的经度和纬度的计算方法。以靶丸表面激光功率分布的几何均匀性为判据,分析结果表明：靶区光路排布“凸３２ 面体模型”中的不等边六边形的邻边边长比例因子为１．１４～１．２５ 时,入射光束空间排布的几何对称性达到最佳状态,直接驱动的辐照均匀性亦随之得到改善。     

Polymer‐Templated Hydrothermal Growth of Vertically Aligned Single‐Crystal ZnO Nanorods and Morphological Transformations Using Structural Polarity

Position‐configurable, vertical, single‐crystalline ZnO nanorod arrays are fabricated via a polymer‐templated hydrothermal growth method at a low temperature of 93 °C. A sol‐gel processed dense c‐oriented ZnO seed layer film is employed to grow nanorods along the c‐axis direction [0001] regardless of any substrate crystal mismatches. Here, one‐beam laser‐interference lithography is utilized to fabricate nanoscale holes over an entire 2‐in. wafer during the preparation of the polymer template. As such, vertically aligned ZnO nanorods can be grown from the seed layer exposed at the bottom of each hole. Furthermore, morphological transformations of the ZnO nanorods into pencil‐like, needle‐like, tubular, tree‐like, and spherical shapes are obtained by controlling the growth conditions and utilizing the structural polarity of the ZnO nanorods.     

An Epoxy Photoresist Modified by Luminescent Nanocrystals for the Fabrication of 3D High‐Aspect‐Ratio Microstructures

An epoxy‐based negative‐tone photoresist, which is known as a suitable material for high‐aspect‐ratio surface micromachining, is functionalized with red‐light‐emitting CdSe@ZnS nanocrystals (NCs). The proper selection of a common solvent for the NCs and the resist is found to be critical for the efficient incorporation of the NCs in the epoxy matrix. The NC‐modified resist can be patterned by standard UV lithography down to micrometer‐scale resolution, and high‐aspect‐ratio structures have been successfully fabricated on a 100 mm scaled wafer. The “as‐fabricated”, 3D, epoxy‐based surface microstructures show the characteristic luminescent properties of the embedded NCs, as verified by fluorescence microscopy. This issue demonstrates that the NC emission properties can be conveniently conveyed into the polymer matrix without deteriorating the lithographic performance of the latter. The dimensions, the resolution, and the surface morphology of the NC‐modified‐epoxy microstructures exhibit only minor deviations with respect to that of the unmodified reference material, as examined by means of microscopic and metrologic investigations. The proposed approach of the incorporation of emitting and non‐bleachable NCs into a photoresist opens novel routes for surface patterning of integrated microsystems with inherent photonic functionality at the micro‐ and nanometer‐scale for light sensing and emitting applications.     

激光显示中散斑的抑制

文章首先概述了散斑的形成机理,接着简述了在近场条件下通过降低激光的时间或空 间相干性来抑制散斑的许多方法,并具体分析了仅通过降低激光的相干性来减弱激光显示中散斑的缺陷。提出一种在远场条件下减弱散斑的两维扫描复面转镜,且详细说明了该转镜的工作原理,当合成的激光束通过旋转的复面镜时,移动的干涉条纹在屏幕上产生“沸腾”的散斑图样。最后以红光为例,说明了合成光束通过转镜时显示屏幕上散斑对比度的降低,显示了二维转镜有效地抑制了激光显示中的散斑现象。