3D Out‐of‐Plane Rotational Etching with Pinned Catalysts in Metal‐Assisted Chemical Etching of Silicon

Pinned structures in conjunction with shaped catalysts are used in metal‐assisted chemical etching (MACE) of silicon to induce out‐of‐plane rotational etching. Sub‐micro‐ and nanostructures are fabricated in silicon, which include scooped‐out channels and curved subsurface horns, along with vertically oriented thin metal structures. Five different etching modes induced by catalyst and pinning geometry are identified: 1) fully pinned–no etching, 2) rotation via twist, 3) rotation via delamination, 4) in‐plane bending, and 5) swinging. The rotation angle is roughly controlled through catalyst geometry. The force and pressure experienced by the catalyst are calculated from the deformation of the catalyst and range between 0.5–3.5 μN and 0.5–3.9 MPa, respectively. This is a new, simple method to fabricate 3D, heterogeneous sub‐micro‐ and nanostructures in silicon with high feature fidelity on the order of tens of nanometers while providing a method to measure the forces responsible for catalyst motion during MACE.     

Patterning Colloidal Crystals and Nanostructure Arrays by Soft Lithography

As one of the most robust and versatile routes to fabricate ordered micro‐ and nanostructures, soft lithography has been extensively applied to pattern a variety of molecules, polymers, biomolecules, and nanomaterials. This paper provides an overview on recent developments employing soft lithography methods to pattern colloidal crystals and related nanostructure arrays. Lift‐up soft lithography and modified microcontact printing methods are applied to fabricate patterned and non‐close‐packed colloidal crystals with controllable lattice spacing and lattice structure. Combining selective etching, imprinting, and micromolding methods, these colloidal crystal arrays can be employed as templates for fabrication of nanostructure arrays. Realization of all these processes is favored by the solvent swelling, elasticity, thermodecomposition, and thermoplastic characteristics of polymer materials. Applications of these colloidal crystals and nanostructure arrays have also been explored, such as biomimetic antireflective surfaces, superhydrophobic coatings, surface‐enhanced Raman spectroscopy substrates, and so on.     

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.     

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.     

Large‐Area Nanoscale Patterning of Functional Materials by Nanomolding in Capillaries

Within the past years there has been much effort in developing and improving new techniques for the nanoscale patterning of functional materials used in promising applications like nano(opto)electronics. Here a high‐resolution soft lithography technique—nanomolding in capillaries (NAMIC)—is demonstrated. Composite PDMS stamps with sub‐100 nm features are fabricated by nanoimprint lithography to yield nanomolds for NAMIC. NAMIC is used to pattern different functional materials such as fluorescent dyes, proteins, nanoparticles, thermoplastic polymers, and conductive polymers at the nanometer scale over large areas. These results show that NAMIC is a simple, versatile, low‐cost, and high‐throughput nanopatterning tool.     

Rapid Fabrication of Micro‐ and Nanoscale Patterns by Replica Molding from Diatom Biosilica

Diatoms are single‐celled micro‐algae that possess an exoskeleton (called frustule) comprised of diverse and highly ordered 3D porous silica structures and that hold considerable promise for biological or biomimetic fabrication of nanostructured materials and devices. We have used, for the first time, a soft lithographic approach of replica molding to replicate porous diatom structures into polymers. Two centric diatom species, Coscinodiscus sp., Thalassiosira eccentrica cultured in our laboratory were used as masters for replication. In the first step, replica molding onto soft and elastic polymer using poly(dimethylsiloxane) PDMS produced a negative replica of the diatom frustule. These PDMS replicas were then used as a mold to fabricate the positive polymer replicas of diatoms using a mercaptol ester type UV curable polymer (NOA 60). Fabricated polymer replicas were characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM). In all cases, diatom micro‐ and nanoscale porous structures were successfully transferred with high precision into polymer replicas. Such an accomplishment effectively demonstrates the potential for using diatoms as blueprints for rapid and simple fabrication of polymer nanostructures. The prepared replicas were used as diffraction gratings and as nanowells to hold polymeric nanoparticles effectively demonstrating the functional properties of these biomimetic structures.     

Multiphoton Lithography of Unconstrained Three‐Dimensional Protein Microstructures

Multiphoton lithography (MPL) is a highly versatile strategy for creating 3D microscale objects with complex geometrical arrangements, including nested boxes, interlocking blocks, and braided threads. Of the various chemistries used to produce solid forms in MPL, protein photocrosslinking has been of particular value in biological applications, yielding materials with high porosity, tunable elasticity, and a diverse set of chemical and biochemical properties. Unfortunately, the potential for object drift, and consequent distortion, during this direct‐write process has required that microforms be constructed in integral contact with an immobile surface, precluding fabrication of protein‐based objects that retain rotational and translational degrees of freedom. Here, the development of a high‐viscosity protein‐based reagent that can be used to fabricate complex 3D microstructures that are not adhered to a surface, including chains of Möbius strips, paddlewheels, and unconstrained (free‐floating) probes for bacterial motility, is reported.     

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.     

2D Material Enabled Offset‐Patterning with Atomic Resolution

Atomic‐precision patterning at large scale is a central requirement for nanotechnology and future electronics that is hindered by the limitations of lithographical techniques. Historically, imperfections of the fabrication tools have been compensated by multi‐patterning using sequential lithography processes. The realization of nanometer‐scale features from much larger patterns through offset stacking of atomically thin masks is demonstrated. A unique mutual stabilization effect between two graphene layers produces atomically abrupt transitions that selectively expose single‐layer covered regions. Bilayer regions, on the other hand, protect the underlying substrate from removal for several hours permitting transfer of atomic thickness variations into lateral features in various semiconductors. Nanoscopic offsets between two 2D materials layers could be introduced through bottom‐up and top‐down approaches, opening up new routes for high‐resolution patterning. A self‐aligned templating approach yields nanometer‐wide bilayer graphene nanoribbons with macroscopic length that produces high‐aspect‐ratio silicon nanowalls. Moreover, offset‐transfer of lithographically patterned graphene layers enables multipatterning of large arrays of semiconductor features whose resolution is not limited by the employed lithography and could reach <10 nm feature size. The results open up a new route to combining design flexibility with unprecedented resolution at large scale.     

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.     

Marker Pen Lithography for Flexible and Curvilinear On‐Chip Energy Storage

On‐chip energy storage using microsupercapacitors can serve the dual role of supplementing batteries for pulse power delivery, and replacement of bulky electrolytic capacitors in ac‐line filtering applications. Despite complexity and processing costs, microfabrication techniques are being employed in fabricating a great variety of microsupercapacitor devices. Here, a simple, cost‐effective, and versatile strategy is proposed to fabricate flexible and curvilinear microsupercapacitors (MSCs). The protocol involves writing sacrificial ink patterns using commercial marker pens on rigid, flexible, and curvilinear substrates. It is shown that this process can be used in both lift‐off and etching modes, and the possibility of multistack design of active materials using simple pen lithography is demonstrated. As a prototype, this method is used to produce conducting polymer MSCs involving both poly(3,4‐ethylenedioxythiophene), polyaniline, and metal oxide (MnO₂) electrode materials. Typical values of energy density in the range of 5–11 mWh cm^?3 at power densities of 1–6 W cm^?3 are achieved, which is comparable to thin film batteries and superior to the carbon and metal oxide based microsupercapacitors reported in the literature. The simplicity and broad scope of this innovative strategy can open up new avenues for easy and scalable fabrication of a wide variety of on‐chip energy storage devices.     

Patterning Si at the 1 nm Length Scale with Aberration‐Corrected Electron‐Beam Lithography: Tuning of Plasmonic Properties by Design

Patterning of materials at single nanometer resolution allows engineering of quantum confinement effects, as these effects are significant at these length scales, and yields direct control over electro‐optical properties. Silicon is by far the most important material in electronics, and the ability to fabricate Si‐based devices of the smallest dimensions for novel device engineering is highly desirable. The work presented here uses aberration‐corrected electron‐beam lithography combined with dry reactive ion etching to achieve both: patterning of 1 nm features and surface and volume plasmon engineering in Si. The nanofabrication technique employed here produces nanowires with a line edge roughness (LER) of 1 nm (3σ). In addition, this work demonstrates tuning of the Si volume plasmon energy by 1.2 eV from the bulk value, which is one order of magnitude higher than previous attempts of volume plasmon engineering using lithographic methods.     

Detachment Lithography of Photosensitive Polymers: A Route to Fabricating Three‐Dimensional Structures

A technique to create arrays of micrometer‐sized patterns of photosensitive polymers on the surface of elastomeric stamps and to transfer these patterns to planar and nonplanar substrates is presented. The photosensitive polymers are initially patterned through detachment lithography (DL), which utilizes the difference in adhesion forces to induce the mechanical failure in the film along the edges of the protruded parts of the mold. A polydimethylsiloxane (PDMS) stamp with a kinetically and thermally adjustable adhesion and conformal contact can transfer the detached patterns to etched or curved substrates, as well as planar ones. These printed patterns remain photochemically active for further modification via photolithography, and/or can serve as resists for subsequent etching or deposition, such that photolithography can be used on highly nonconformal and nonplanar surfaces. Various 3D structures fabricated using the process have potential applications in MEMS (micro‐electromechanical systems) sensors/actuators, optical devices, and microfluidics.     

Merging Top‐Down and Bottom‐Up Approaches to Fabricate Artificial Photonic Nanomaterials with a Deterministic Electric and Magnetic Response

Artificial photonic nanomaterials made from densely packed scatterers are frequently realized either by top‐down or bottom‐up techniques. While top‐down techniques offer unprecedented control over achievable geometries for the scatterers, by trend they suffer from being limited to planar and periodic structures. In contrast, materials fabricated with bottom‐up techniques do not suffer from such disadvantages but, unfortunately, they offer only little control on achievable geometries for the scatterers. To overcome these limitations, a nanofabrication strategy is introduced that merges both approaches. A large number of scatterers are fabricated with a tailored optical response by fast character projection electron‐beam lithography and are embedded into a membrane. By peeling‐off this membrane from the substrate, scrambling, and densifying it, a bulk material comprising densely packed and randomly arranged scatterers is obtained. The fabrication of an isotropic material from these scatterers with a strong electric and magnetic response is demonstrated. The approach of this study unlocks novel opportunities to fabricate nanomaterials with a complex optical response in the bulk but also on top of arbitrarily shaped surfaces.     

Direct Patterning of Metal Chalcogenide Semiconductor Materials

Lithography is one of the most widely used methods for cutting‐edge research and industrial applications, mainly owing to its ability to draw patterns in the micro and even nanoscale. However, the fabrication of semiconductor micro/nanostructures via conventional electron or optical lithography technologies often requires a time‐consuming multistep process and the use of expensive facilities. Herein, a low‐cost, high‐resolution, facile, and versatile direct patterning method based on metal–organic molecular precursors is reported. The ink‐based metal–organic precursors are found to operate as negative resists, with the material exposed by different methods (electron‐beam/laser/heat/ultraviolet (UV)) to render them insoluble in the development process. This technical process can deliver metal chalcogenide semiconductors with arbitrary 2D/3D patterns with sub‐50 nm resolution. Electron beam lithography, two‐photon absorption lithography, thermal scanning probe lithography, and UV photolithography are demonstrated for the direct patterning process. Different metal chalcogenide semiconductor nanodevices, such as photoconductive selenium‐doped Sb₂S₃ nanoribbons, p‐type PbS single‐nanowire field‐effect transistors, and p‐n junction CdS/Cu₂S nanowire solar cells, are fabricated by this method. This direct patterning technique is a versatile and simple micro/nanolithography technology with considerable potential for “lab‐on‐a‐chip” preparation of semiconductor devices.     

Design and Fabrication of a Four-Arm-Structure MEMS Gripper

This paper is focused on the design and fabrication of a four-arm-structure microelectromechanical systems gripper integrated with sidewall piezoresistive force sensors. Surface and bulk micromachining technologies are employed to fabricate the microgripper from a single-crystal silicon wafer (i.e., no silicon-on-insulator wafer is used). A vertical sidewall surface piezoresistor etching technique is used to form the side direction force sensors. The end effector of this gripper is a four-arm structure: two fixed cantilever arms integrated with piezoresistive sensors are designed to sense the gripping force. The resolution of the force sensor is in the micronewton range and, therefore, provides feedback of the forces that dominate the micromanipulation processes. An electrostatically driven microactuator is designed to provide the force to operate the other two movable arms. In this way, it creates a deflection of 25 mum at the arm tip, and the range of the operation is 30-130 mum. Experimental results show that it can successfully provide force sensing and play a main role in preventing the damage of microparts in micromanipulation and microassembly tasks.     

Cross‐Linked Gold Nanoparticle Composite Membranes as Highly Sensitive Pressure Sensors

In this article, highly sensitive differential pressure sensors based on free‐standing membranes of cross‐linked gold nanoparticles are demonstrated. The nanoparticle membranes are employed as both diaphragms and resistive transducers. The elasticity and the pronounced resistive strain sensitivity of these nanometer‐thin composites enable the fabrication of sensors achieving high sensitivities exceeding 10^?3 mbar^?1 while maintaining an overall small membrane area. Furthermore, by combining micro‐bulge tests with atomic force microscopy and in situ resistance measurements the membranes’ electromechanical responses are studied through precise observation of the concomitant changes of the membranes’ topography. The study demonstrates the high potential of free‐standing nanoparticle composites for the fabrication of highly sensitive force and pressure sensors and introduces a unique and powerful method for the electromechanical investigation of these materials.     

Fabrication of Biofunctionalized Quasi‐Three‐Dimensional Microstructures of a Nonfouling Comb Polymer Using Soft Lithography

This paper describes a simple set of patterning methods that are applicable to diverse substrates and allow the routine and rapid fabrication of protein patterns embedded within a background that consists of quasi‐three‐dimensional microstructures of a cell‐resistant polymer. The ensemble of methods reported here utilizes three components to create topographically nonfouling polymeric structures that present cell‐adhesive protein patterns in the regions between the microstructures: the first component is an amphiphilic comb polymer that is comprised of a methyl methacrylate backbone and pendant oligo(ethylene glycol) moieties along the side chain, physically deposited films of which are protein‐ and cell‐resistant. The second component of the fabrication methodology involves the use of different variants of soft lithography, such as microcontact printing to create nonfouling topographical features of the comb polymer that demarcate cell‐adhesive regions of the third component: a cell‐adhesive extracellular protein or peptide. The ensemble of methods reported in this paper was used to fabricate quasi‐three‐dimensional patterns that present topographical and biochemical cues on a variety of substrates, and was shown to successfully maintain cellular patterns for up to two months in serum‐containing medium. We believe that this, and other such methods under development that allow independent and systematic control of chemistry, topography and substrate compliance will provide versatile “test‐beds” for fundamental studies in cell biology as well as allow the discovery of rational design principles for the development of biomaterials and tissue‐engineering scaffolds.     

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。     

Triangular Elastomeric Stamps for Optical Applications: Near‐Field Phase Shift Photolithography, 3D Proximity Field Patterning,Embossed Antireflective Coatings,and SERS Sensing

The use of a decal transfer lithography technique to fabricate elastomeric stamps with triangular cross‐sections, specifically triangular prisms and cones, is described. These stamps are used in demonstrations for several prototypical optical applications, including the fabrication of multiheight 3D photoresist patterns with near zero‐width features using near‐field phase shift lithography, fabrication of periodic porous polymer structures by maskless proximity field nanopatterning, embossing thin‐film antireflection coatings for improved device performance, and efficient fabrication of substrates for surface‐enhanced Raman spectroscopic sensing. The applications illustrate the utility of the triangular poly(dimethylsiloxane) decals for a wide variety of optics‐centric applications, particularly those that exploit the ability of the designed geometries and materials combinations to manipulate light–matter interactions in a predictable and controllable manner.