Versatile multilevel soft lithography method with micrometer alignment using all-flexible rubber stamps and moiré fringe technique

Soft lithography has gathered wide interest for the fabrication of unconventional micrometer and nanometer-sized structures and devices. Nevertheless, accurate alignment is essential to achieve multilevel soft lithography. Because of the soft nature of the stamp materials, such as soft polydimethylsiloxane, they are susceptible to mechanical distortions, which lower the registration accuracy. To reduce the distortions we backed the stamp with a polymer foil and minimized the overall forces applied to the stamp. We furthermore employed an alignment method using additive type moiré fringe technique that is easy to implement and does not require extensive processing steps. The alignment results show less than 1 μm misalignment when the stamp is brought again onto a previously structured rigid template. When performing two consecutive lithography steps by transfer printing of thin gold films, we were able to obtain average registration accuracy of 1.3 μm over an area of 400 mm(2). This method is versatile and can be used for several soft lithography techniques. Better results can be obtained with smaller moiré gratings and the use of harder materials.     

Stamp collapse in soft lithography

We have studied the so-called roof collapse in soft lithography. Roof collapse is due to the adhesion between the PDMS stamp and substrate, and it may affect the quality of soft lithography. Our analysis accounts for the interactions of multiple punches and the effect of elastic mismatch between the PDMS stamp and substrate. A scaling law among the stamp modulus, punch height and spacing, and work of adhesion between the stamp and substrate is established. Such a scaling law leads to a simple criterion against the unwanted roof collapse. The present study agrees well with the experimental data.     

薄层软刻蚀法制备PMMA微图案结构

对现有的软刻蚀方法提出了改进,让其与压印技术及毛细力刻蚀技术相结合形成一种薄层软刻蚀技术,并以这种技术制备出PMMA薄膜微图案化结构.在30 mm/h的拉膜速度以及弹性印章表面图形深度确定不变的情况下,PMMA流体能够完全填充到弹性印章的微通道中,SEM和光学显微镜照片证明得到的PMMA微图案是相互分离的.因此,薄层软刻蚀技术可以克服普通微模塑方法制备分离图形困难和纳米压印技术中需要使用巨大机械压力的缺点.     

A Simple Method for Fabricating Patterned Curvilinear Microstructures in Poly(dimethylsiloxane) by Selective Wetting

The fabrication of patterned microstructures in poly(dimethylsiloxane) (PDMS) is a prerequisite for soft lithography. Herein, curvilinear surface relief microstructures in PDMS are fabricated through a simple three‐stage approach combining microcontact printing (μCP), selective surface wetting/dewetting and replica molding (REM). First, using an original PDMS stamp (first‐generation stamp) with linear relief features, a chemical pattern on gold substrate is generated by μCP using hexadecanethiol (HDT) as an ink. Then, by a dip‐coating process, an ordered polyethylene glycol (PEG) polymer‐dot array forms on the HDT‐patterned gold substrate. Finally, based on a REM process, the PEG‐dot array on gold substrate is used to fabricate a second‐generation PDMS stamp with microcavity array, and the second‐generation PDMS stamp is used to generate third‐generation PDMS stamp with microbump array. These fabricated new‐generation stamps are utilized in μCP and in micromolding in capillaries (MIMIC), allowing the generation of surface micropatterns which cannot be obtained using the original PDMS stamp. The method will be useful in producing new‐generation PDMS stamps, especially for those who want to use soft lithography in their studies but have no access to the microfabrication facilities.     

Control of self-organized contact instability and patterning in soft elastic films

The surface of a soft elastic film becomes unstable and forms a labyrinth pattern when a rigid flat plate is brought into adhesive contact, without application of any external pressure. These isotropic undulations have a characteristic wavelength, lambda approximately 3H, where H is the film thickness. We present here technique of ordering, aligning, and modulating these micro-labyrinth structures by using a patterned stamp, by varying the stamp-film inter-surface distance, by a lateral confinement of the instability and even by a simple shear motion of a flat stamp. Many complex structures, such as an array of femto-liter beakers and doubly periodic channels, are generated from a simple stamp consisting of parallel channels. The elastic nature of the patterns allows an in-situ tuning, manipulation, and reconfiguration of the microstructures. Regardless of their precise morphology, the structures continue to have the elastic length scale, lambda approximately 3H. The structures can also be made permanent as required by UV-ozone-induced oxidation of the structures. The underlying principles of the elastic contact instability presented here have the potential to develop into a new soft lithography technique-elastic contact lithography (ECL), allowing a simple, rapid and large area patterning of soft solids.     

有机硅橡胶/蒙脱土纳米复合弹性印章的制备

聚二甲基硅氧烷硅橡胶(PDMS)是用于制作软刻蚀技术[1,2]中弹性印章的最常用材料, 但使用单一的硅橡胶制作的印章存在易变形、易溶胀等缺点. 本文用有机蒙脱土(MMT)和硅橡胶进行插层纳米复合改性, 用树脂固化仪对复合体系进行固化行为分析和固化配方优化, 并对复合材料的耐溶胀性能及其弹性印章的表面形貌进行观察比较.     

Biocatalytic microcontact printing

Immobilized biocatalytic lithography is presented as an application of soft lithography. In traditional microcontact printing, diffusion limits resolution of pattern transfer. By using an immobilized catalyst, the lateral resolution of microcontact printing would depend only on the length and flexibility of the tether (<2 nm) as opposed to diffusion (>100 nm). In the work, exonuclease reversibly immobilized on a relief-patterned stamp is used to ablate ssDNA monolayers Percent of ablation was determined via confocal fluorescence microscopy to be approximately 70%.     

Replication of vertical features smaller than 2 nm by soft lithography

This communication demonstrates a simple, soft lithographic approach to the replication and metrology of nanoscale vertical displacements. We patterned test structures with regular patterns that minimize artifacts in measurements by atomic force microscopy. A composite stamp of poly(dimethylsiloxane) (PDMS) molded against the original test structure served as a template to generate polyurethane replicas. We replicated vertical displacements down to approximately 1.5 nm. This replication demonstrates the capability of soft lithography to reproduce features with dimensions similar to those of large molecules.     

Emergent Soft Lithographic Tools for the Fabrication of Functional Polymeric Microstructures

Polymeric microstructures (PMs) are useful to a broad range of technologies applicable to, for example, sensing, energy storage, and soft robotics. Due to the diverse application space of PMs, many techniques (e. g., photolithography, 3D printing, micromilling, etc.) have been developed to fabricate these structures. Stemming from their generality and unique capabilities, the tools encompassed by soft lithography (e. g., replica molding, microcontact printing, etc.), which use soft elastomeric materials as masters in the fabrication of PMs, are particularly relevant. By taking advantage of the characteristics of elastomeric masters, particularly their mechanical and chemical properties, soft lithography has enabled the use of non-planar substrates and relatively inexpensive equipment in the generation of many types of PMs, redefining existing communities and creating new ones. Traditionally, these elastomeric masters have been produced from relief patterns fabricated using photolithography; however, recent efforts have led to the emergence of new methods that make use of masters that are self-forming, dynamic in their geometric and chemical properties, 3D in architecture, and/or sacrificial (i. e., easily removed/released using phase changes). These “next generation” soft lithographic masters include self-assembled liquid droplets, microscale balloons, templates derived from natural materials, and hierarchically microstructured surfaces. The new methods of fabrication supported by these unique masters enable access to numerous varieties of PMs (e. g., those with hierarchical microstructures, overhanging features, and 3D architectures) that would not be possible following established methods of soft lithography. This review explores these emergent soft lithographic methods, addressing their operational principles and the application space they can impact.     

All-silica nanofluidic devices for DNA-analysis fabricated by imprint of sol-gel silica with silicon stamp

We present a simple and cheap method for fabrication of silica nanofluidic devices for single-molecule studies. By imprinting sol-gel materials with a multi-level stamp comprising micro- and nanofeatures, channels of different depth are produced in a single process step. Calcination of the imprinted hybrid sol-gel material produces purely inorganic silica, which has very low autofluorescence and can be fusion bonded to a glass lid. Compared to top-down processing of fused silica or silicon substrates, imprint of sol-gel silica enables fabrication of high-quality nanofluidic devices without expensive high-vacuum lithography and etching techniques. The applicability of the fabricated device for single-molecule studies is demonstrated by measuring the extension of DNA molecules of different lengths confined in the nanochannels.     

Edge spreading lithography and its application to the fabrication of mesoscopic gold and silver rings

A new form of edge lithography, edge spreading lithography (ESL), has been demonstrated and applied to the formation of coinage metal rings. In this process, alkanethiols are delivered from a flat PDMS stamp to the surface of a metal film through a two-dimensional array of spherical silica colloids. The thiols further spread on the metal surface, forming highly ordered SAMs in the form of a ring pattern. Following lift-off of beads, the pattern in the SAMs can be transferred into the metal film through wet chemical etching, with SAMs serving as the resist. The dimensions of the rings can be readily controlled by several parameters such as the beads diameter, the concentration of the thiol solution, and the contact time between the stamp and the silica beads.     

Molecular scale modeling of polymer imprint nanolithography

We present the results of large-scale molecular dynamics simulations of two different nanolithographic processes, step-flash imprint lithography (SFIL), and hot embossing. We insert rigid stamps into an entangled bead-spring polymer melt above the glass transition temperature. After equilibration, the polymer is then hardened in one of two ways, depending on the specific process to be modeled. For SFIL, we cross-link the polymer chains by introducing bonds between neighboring beads. To model hot embossing, we instead cool the melt to below the glass transition temperature. We then study the ability of these methods to retain features by removing the stamps, both with a zero-stress removal process in which stamp atoms are instantaneously deleted from the system as well as a more physical process in which the stamp is pulled from the hardened polymer at fixed velocity. We find that it is necessary to coat the stamp with an antifriction coating to achieve clean removal of the stamp. We further find that a high density of cross-links is necessary for good feature retention in the SFIL process. The hot embossing process results in good feature retention at all length scales studied as long as coated, low surface energy stamps are used.     

Soft colloidal lithography by strong physical contact using swollen magnetic microspheres and magnetic force

Herein we report on pattern formation of a self-assembled monolayer (SAM) using soft colloidal lithography, based on strong physical contact between microspheres and substrate. In typical colloidal lithography, weak contact of microspheres with the substrate does not block the formation of a SAM. To establish conformal contact between microspheres and substrate to block the formation of a SAM, magnetic force was exerted on softened paramagnetic microspheres that had been swollen by a solvent. The soft colloidal lithography with controlled buoyance enables pattern formation through simple wet chemistry.     

硅表面有机单层膜 :微印章、微加工与微阵列

总结了作者的实验室在将有机物结合到硅表面方面的研究进展.发现并发展了将有机单层膜组装到硅、氧化硅和相关材料表面的新方法.这些方法简单、可重复，并可得到物理、化学性能良好的致密单层膜.这些单层膜在许多方面有令人鼓舞的应用，包括（a）应用于软印刷术，特别是微接触印章法; （b）用作硅的微加工（微机电系统，MEMS）的单层膜润滑剂; （c）用作DNA和蛋白质微阵列功能分子固定的基底.     

Patterning adjacent supported lipid bilayers of desired composition to investigate receptor-ligand binding under shear flow

To achieve efficient targeting, carriers containing either drugs or imaging agents must have surface properties that promote binding to targets yet at the same time block rapid immune system clearance. Here we describe a versatile technique that allows simultaneous comparison of the effects of carrier surface composition on binding properties under identical flow conditions. Parallel lanes of supported lipid bilayers that mimic the surface of liposomal delivery vehicles are formed using the vesicle fusion method in microfluidic channels created via standard soft lithography techniques. Vesicle stock solutions are premixed and injected into lanes formed by a poly(dimethylsiloxane) (PDMS) stamp reversibly sealed to a glass slide to create adjacent lanes of distinct composition. After removing the stamp, an adsorbed layer of bovine serum albumin (BSA) is used to prevent bilayer spreading before assembling the patterned substrate into a flow chamber for binding studies. Advantages of this method include easy and rapid preparation of bilayers with desired compositions from an unlimited number of lipid types, choice of feature size, time-stable features, and low nonspecific binding. Feature sizes on the order of tens of microns allow multiple compositions to be analyzed in one field of view, thereby reducing the number of experiments, ensuring identical flow conditions, and enabling simultaneous incorporation of controls. We show that the presence of a long poly(ethylene glycol) (PEG) tether (MW 2000) between the lipid and ligand results in higher detachment resistances as compared to a short six-carbon spacer.     

Patterned polymer brushes

This critical review summarizes recent developments in the fabrication of patterned polymer brushes. As top-down lithography reaches the length scale of a single macromolecule, the combination with the bottom-up synthesis of polymer brushes by surface-initiated polymerization becomes one main avenue to design new materials for nanotechnology. Recent developments in surface-initiated polymerizations are highlighted along with diverse strategies to create patterned polymer brushes on all length scales based on irradiation (photo- and interference lithography, electron-beam lithography), mechanical contact (scanning probe lithography, soft lithography, nanoimprinting lithography) and on surface forces (capillary force lithography, colloidal lithography, Langmuir-Blodgett lithography) (116 references).     

Components for integrated poly(dimethylsiloxane) microfluidic systems

This review describes the design and fabrication of microfluidic systems in poly(dimethylsiloxane) (PDMS). PDMS is a soft polymer with attractive physical and chemical properties: elasticity, optical transparency, flexible surface chemistry, low permeability to water, and low electrical conductivity. Soft lithography makes fabrication of microfluidic systems in PDMS particularly easy. Integration of components, and interfacing of devices with the user, is also convenient and simpler in PDMS than in systems made in hard materials. Fabrication of both single and multilayer microfluidic systems is straightforward in PDMS. Several components are described in detail: a passive chaotic mixer, pneumatically actuated switches and valves, a magnetic filter, functional membranes, and optical components.     

Force-controlled inorganic crystallization lithography

Lithography plays a key role in integrated circuits, optics, information technology, biomedical applications, catalysis, and separation technologies. However, inorganic lithography techniques remain of limited utility for applications outside of the typical foci of integrated circuit manufacturing. In this communication, we have developed a novel stamping method that applies pressure on the upper surface of the stamp to regulate the dewetting process of the inorganic buffer and the evaporation rate of the solvent in this buffer between the substrate and the surface of the stamp. We focused on generating inorganic microstructures with specific locations and also on enabling the ability to pattern gradients during the crystallization of the inorganic salts. This approach utilized a combination of lithography with bottom-up growth and assembly of inorganic crystals. This work has potential applications in a variety of fields, including studying inorganic material patterning and small-scale fabrication technology.     

Micro/nanopatterning of proteins via contact printing using high aspect ratio PMMA stamps and nanoimprint apparatus

Micro- and nanoscale protein patterns have been produced via a new contact printing method using a nanoimprint lithography apparatus. The main novelty of the technique is the use of poly(methyl methacrylate) (PMMA) instead of the commonly used poly(dimethylsiloxane) (PDMS) stamps. This avoids printing problems due to roof collapse, which limits the usable aspect ratio in microcontact printing to 10:1. The rigidity of the PMMA allows protein patterning using stamps with very high aspect ratios, up to 300 in this case. Conformal contact between the stamp and the substrate is achieved because of the homogeneous pressure applied via the nanoimprint lithography instrument, and it has allowed us to print lines of protein approximately 150 nm wide, at a 400 nm period. This technique, therefore, provides an excellent method for the direct printing of high-density sub-micrometer scale patterns, or, alternatively, micro-/nanopatterns spaced at large distances. The controlled production of these protein patterns is a key factor in biomedical applications such as cell-surface interaction experiments and tissue engineering.     

Microscale features and surface chemical functionality patterned by electron beam lithography: a novel route to poly(dimethylsiloxane) (PDMS) stamp fabrication

Poly(dimethylsiloxane) (PDMS) has become a ubiquitous material for microcontact printing, yet there are few methods available to pattern a completed PDMS stamp in a single step. It is shown here that electron beam lithography (EBL) is effective in writing patterns directly onto cured PDMS stamps, thus overcoming the need for multiple patterning steps. Not only does this method allow the modification of an existing lithographic pattern, but new 3D features such as cones, pits, and channels can also be fabricated. EBL can also be used to fabricate PDMS masks for photolithography whereby 1:1 pattern transfer into a photoresist is achieved. Additionally, direct EBL writing of surface chemical features has been achieved using a PDMS stamp coated with a self-assembled monolayer. An electrostatic mechanism appears to be operative in the EBL patterning process, as supported by calculations, thermogravimetric analysis, time-of-flight secondary ion mass spectroscopy, optical and atomic force microscopy, and chemical functionalization assays.