胶体刻蚀——纳米结构化表面的构筑与应用

综述了近年来胶体刻蚀领域的研究进展, 分别讨论了基于胶体微粒和胶体晶体为模板的可控沉积与可控刻蚀及在固体平面基质、曲面基质和气液界面等不同基质上构筑结构化表面的方法. 同时还探讨了利用胶体刻蚀方法形成的微纳结构在光、电、磁以及表面润湿和生物学等方面的应用.     

Fabrication of large-area ferromagnetic arrays using etched nanosphere lithography

Nanosphere lithography (NSL) is a simple, cost-effective, and powerful technique capable of producing large-area arrays of ferromagnetic nanostructures with dimensions below 100 nm. These properties make NSL an attractive process for the fabrication of arrays of magnetic elements with applications in magnetic data storage. The main disadvantage with conventional NSL is that the monolayer of spheres always contains imperfections that are transferred to the resulting nanostructures. This can significantly affect the structural and magnetic properties of the fabricated array. In this paper we present a novel adaptation of NSL that reduces the effect of such defects on the resulting nanostructures. The technique also offers excellent control over the diameter, aspect ratio, and pitch of the fabricated elements. These properties are demonstrated through the fabrication of arrays of Ni elements of 210 nm diameter and arrays of Co elements with diameters between 200 and 320 nm.     

Top-down approaches to the formation of silica nanoparticle patterns

This article reports a simple, versatile approach to the fabrication of lithographically defined mesoscopic colloidal silica nanoparticle patterns over large areas using spin-coating, interferometric lithography, and reactive-ion etching. One-dimensional nanoparticle films (bands) and 2D discs, diamonds, and holes with sub-micrometer periodicity, high quality, and excellent uniformity were successfully fabricated over large areas. The well-defined shape and period of the patterned nanoparticle film were controlled in the interferometric lithography step, while the thickness of nanoparticle film was easily tuned in the spin-coating step. This approach can extend to other deposition methods such as convective self-assembly, electrostatic self-assembly, and other materials such as metallic and ferromagnetic nanoparticles. We have also been able to generate sparse, random, isolated particle patterns, using a combination of interferometric lithography and layer-by-layer deposition as an extension of this approach to another deposition method, and to generate disc nanoparticle patterns using colloidal lithography as an extension of this approach to another lithography technique. These patterned films will find important applications in the fields of material growth, biosensors, and catalysis, as well as serving as building blocks for further fabrication.     

Electrochemical Characterization of Vertically Aligned Carbon Nanofiber Arrays Prepared by Hole‐mask Colloidal Lithography

Nanoelectrode arrays consisting of vertically aligned carbon nanofibers were prepared through plasma enhanced chemical vapor deposition and patterned using hole‐mask colloidal lithography (HCL), a simple fabrication method employed as a cost‐effective patterning alternative to the conventional electron beam lithography. The density of the carbon nanofibers was easily altered by changing the concentration of the polystyrene spheres employed in HCL. Cyclic voltammetry and chronoamperometry were used to electrochemically characterize the arrays of different density. Results indicate that the density of the carbon nanofibers leads to differences in the macro/micro electroactive surface areas.     

Fabrication of heterogeneous binary arrays of nanoparticles via colloidal lithography

Heterogeneous binary arrays of metallic nanoparticles have been constructed by consecutively depositing gold and silver into monolayers of hexagonally close-packed latex spheres at the incidence angles of 15 and -15 degrees, followed by removal of the colloidal masks. The present approach is independent of the chemical nature of both colloidal masks and deposition materials. The pattern feature of the resulting binary nanoparticle arrays is dependent on the colloidal mask registry.     

Facile Fabrication of Large Area Polystyrene Colloidal Crystal Monolayer via Surfactant-free Langmuir-Blodgett Technique

A facile and novel method for the production of a large area of well-ordered polystyrene(PS)colloidal crystal monolayer was established using the surfactant-free Langmuir-Blodgett(LB)technique.The hydrophobic property(film-forming ability)of PS spheres was improved by a thermo-rheology treatment before LB assembly,and a large film was obtained.In contrast to the traditional LB technique,no surfactant was needed in this method,which could eliminate the additional contamination of surfactants in the preparation process and provided the products with versatile applications in nanosphere lithography(NSL)for biosensor,surface plasmon resonance,and surface enhanced Raman spectroscopy.     

Independently controlling protein dot size and spacing in particle lithography

Particle lithography is a relatively simple, inexpensive technique used to pattern inorganics, metals, polymers, and biological molecules on the micro- and nanometer scales. Previously, we used particle lithography to create hexagonal patterns of protein dots in a protein resistant background of methoxy-poly(ethylene glycol)-silane (mPEG-sil). In this work, we describe a simple heating procedure to overcome a potential limitation of particle lithography: the simultaneous change in feature size and center-to-center spacing as the diameter of the spheres used in the lithographic mask is changed. Uniform heating was used to make single-diameter protein patterns with dot sizes of approximately 2-4 or 2-8 μm, depending on the diameter of the spheres used in the lithographic mask, while differential heating was used to make a continuous gradient of dot sizes of approximately 1-9 μm on a single surface. We demonstrate the applicability of these substrates by observing the differences in neutrophil spreading on patterned and unpatterned protein coated surfaces.     

Experimental design applied to spin coating of 2D colloidal crystal masks: a relevant method?

Monolayers of colloidal spheres are used as masks in nanosphere lithography (NSL) for the selective deposition of nanostructured layers. Several methods exist for the formation of self-organized particle monolayers, among which spin coating appears to be very promising. However, a spin coating process is defined by several parameters like several ramps, rotation speeds, and durations. All parameters influence the spreading and drying of the droplet containing the particles. Moreover, scientists are confronted with the formation of numerous defects in spin coated layers, limiting well-ordered areas to a few micrometers squared. So far, empiricism has mainly ruled the world of nanoparticle self-organization by spin coating, and much of the literature is experimentally based. Therefore, the development of experimental protocols to control the ordering of particles is a major goal for further progress in NSL. We applied experimental design to spin coating, to evaluate the efficiency of this method to extract and model the relationships between the experimental parameters and the degree of ordering in the particles monolayers. A set of experiments was generated by the MODDE software and applied to the spin coating of latex suspension (diameter 490 nm). We calculated the ordering by a homemade image analysis tool. The results of partial least squares (PLS) modeling show that the proposed mathematical model only fits data from strictly monolayers but is not predictive for new sets of parameters. We submitted the data to principal component analysis (PCA) that was able to explain 91% of the results when based on strictly monolayered samples. PCA shows that the ordering was positively correlated to the ramp time and negatively correlated to the first rotation speed. We obtain large defect-free domains with the best set of parameters tested in this study. This protocol leads to areas of 200 μm(2), which has never been reported so far.     

Metal patterning on silicon surface by site-selective electroless deposition through colloidal crystal templating

Site-selective Cu deposition on a Si substrate was achieved by a combination of colloidal crystal templating, hydrophobic treatment, and electroless plating. Uniformly sized nano/microstructures were produced on the substrate using a monolayer coating of colloidal spheres instead of a conventional resist. The Cu patterns obtained were of two different types: networklike honeycomb and isolated-island patterns with a minimum period of 200 nm. Each ordered pattern with the desired intervals was composed of clusters of Cu nanoparticles with a size range of 50-100 nm. By the present method, it is possible to control the periodicity of metal arrays by changing the diameter of the colloidal spheres used as an initial mask and to adjust the shape of the metal patterns by changing the mask structure for electroless plating.     

Fabrication of monodisperse asymmetric colloidal clusters by using contact area lithography (CAL)

We report a new fabrication method of asymmetric colloidal clusters by using contact area lithography with site-selective growth. Nanometric surface patterns (approximately 44, 60, and 81 nm in diameter) were prepared by coating surfaces with self-assembled monolayers (SAMs; octadecyltrichlorosilane (OTS) in this study) except the contact area either between colloidal particles or between colloids and substrate. Nanoscale site-specific heterogeneous nucleation and growth of oxide materials of titanium were studied using the patterns of OTS-SAMs onto the either flat or curved surfaces of SiO2. Experimental results suggest that a combination of the large difference in the surface energy between the growing and surrounding surfaces and the diffusion-controlled growth leads to complete nanoscale site specificity. We also fabricated superstructrures of silica spheres with hemispheres of titania (<20 nm in dimension) on their surfaces and discussed the optical properties of colloidal films consisting of the monodisperse asymmetric colloidal clusters in terms of photonic band gap.     

Colloidal crystals formed by aqueous suspensions of monodispersed silica, polystyrene, and poly(methyl methacrylate) colloidal spheres

Colloidal crystals consisted of silica, polystyrene, and poly(methyl methacrylate) monodispersed suspensions; deionized sufficiently in water at the same condition; were formed; and their properties were compared changing sphere diameter and volume fraction systematically. The size of these colloidal crystals was maximized at their critical sphere concentration irrespective of their sphere size. The Bragg peak wavelengths of these colloidal crystals were uniquely determined only by the sphere diameter and volume fraction for all kinds of colloidal spheres used in this work. The larger the sphere volume fraction, the larger the crystal growth rates, and there were no significant differences among the colloidal spheres. The rigidity of colloidal crystals increased in proportion to the number density of spheres. Consequently, the crystallization mechanism and properties of colloidal crystals formed by these spheres are not dependent on the kind of spheres, but they are dependent only on the sphere diameter and number density.     

Size dependent catalysis with CTAB-stabilized gold nanoparticles

CTAB-stabilized gold nanoparticles were synthesized by applying the seeding-growth approach in order to gain information about the size dependence of the catalytic reduction of p-nitrophenol to p-aminophenol with sodium borohydride. Five different colloidal solutions of stabilized gold nanoparticles have been characterized by TEM, AFM, UV-Vis, SAXS, and DLS for their particle size distributions. Gold nanoparticles (mean sizes: 3.5, 10, 13, 28, 56 nm diameter) were tested for their catalytic efficiency. Kinetic data were acquired by UV-Vis spectroscopy at different temperatures between 25 and 45 °C. By studying the p-nitrophenol to p-aminophenol reaction kinetics we determined the nanoparticle size which is needed to gain the fastest conversion under ambient conditions in the liquid phase. Unexpectedly, CTAB-stabilized gold nanoparticles with a diameter of 13 nm are most efficient.     

PET/PC共混体系的酯交换反应对其高压结晶行为的影响

利用转矩流变仪、DSC、SEM及WAXD等表征手段研究了PET/PC共混体系的酯交换反应对其高压结晶行为的影响.SEM观察表明,PET和PC熔混时的酯交换反应有利于PET/PC体系在高压结晶时生成厚度较大的伸直链晶体,且可以促进其高压下酯交换反应的发生.楔形伸直链晶体和弯曲伸直链晶体的存在证明链滑移扩散和酯交换反应两种机制对体系中聚酯伸直链晶体的增厚有贡献.拟合分峰法和War-ren-Averbach傅里叶分析法的计算结果表明,随PET/PC体系熔混时酯交换反应程度的增加,高压结晶共混物的结晶度降低,PET的平均微晶尺寸增大,点阵畸变平均值则减小,而微晶尺寸分布变宽.提出了在共聚物组分都具备结晶能力时,结晶诱导化学反应和化学反应诱导结晶两种过程在一定条件下可同时发生的观点.     

Chemically Organizable Nanosized Materials Preparation and Applications

We are interested in fabricating well-organized assemblies of nanosized materials with wet chemical approaches for the purpose of investigating various interfacial and mesoscopic phenomena. The paper describes how to use self-assembling techniques to prepare assemblies of colloidal nanoparticles and single walled carbon nanotubes on solid surfaces. Gold nanocolloids are taken as the model system, including preparation of functionalized nanoparticles, assembling on tailored substrates, surface reorganization, and 1D, 0D controlled assembling with the aid of scanning probe lithography. The typical work we have been doing using these elaborated nanoparticle assemblies includes, the quantitative investigations of die electromagnetic coupling of particle-particle and particle-substrate in surface enhanced Raman scattering (SERS), the single electron tunneling in nanoparticle assemblies measured with scanning probe microscopy (SPM) technique, the atomic force microscopy (AFM) lithography using the surface-confined gold nanoparticles as mask.     

胶体颗粒在聚电解质多层膜表面的可控组装

利用原子力显微镜和扫描电子显微镜研究了磺化聚苯乙烯胶体颗粒在由聚二甲基二烯丙基氯化铵和聚苯乙烯磺酸钠层状自组装而成的多层膜表面的组装.该组装受表面性质影响,通过对多层膜的最外层的组装条件或利用盐溶液对多层膜进行后处理可以控制胶体颗粒在膜表面的组装密度.     

Fabrication of 3D metal dot arrays by geometrically structured dynamic shadowing lithography

Sphere lithography (SL), sometimes erroneously generalized as nanosphere lithography (NSL), stands out as a versatile technique capable of producing 2D periodic micro- and nanostructures with general materials applicability, flexible size and shape control, high throughput, and elegance of simplicity. Many of the fundamental aspects of the features produced by SL have been investigated in a systematic manner, including the optical, magnetic, electronic, and catalytic behaviors with emphasis toward applications in biosensing, ultrasensitive spectroscopy, and nanodevice fabrication. Previous work has primarily focused on two-dimensional patterning, however, with little attention paid to vertical growth of the SL features. In this work, the 3D structural evolution of metal dot arrays at two different length scales was demonstrated by SL-based geometrically structured dynamic shadowing lithography (GSDSL). An empirically derived model of structural growth is also developed to predict the shape and size of the features in this system.     

Plasmonic films based on colloidal lithography

This paper reviews recent advances in the field of plasmonic films fabricated by colloidal lithography. Compared with conventional lithography techniques such as electron beam lithography and focused ion beam lithography, the unconventional colloidal lithography technique with advantages of low-cost and high-throughput has made the fabrication process more efficient, and moreover brought out novel films that show remarkable surface plasmon features. These plasmonic films include those with nanohole arrays, nanovoid arrays and nanoshell arrays with precisely controlled shapes, sizes, and spacing. Based on these novel nanostructures, optical and sensing performances can be greatly enhanced. The introduction of colloidal lithography provides not only efficient fabrication processes but also plasmonic films with unique nanostructures, which are difficult to be fabricated by conventional lithography techniques.     

Fabrication of spherical colloidal crystals using electrospray

We demonstrated the use of electrohydrodynamic atomization to prepare uniform-sized emulsion droplets in which equal spheres of silica or polystyrene were dispersed. The size of the emulsion droplets was easily controlled by the electric field strength and the flow rate, independently of the diameter of the nozzles. During the evaporation of solvent in the droplets, spherical colloidal crystals were formed by self-assembly of the monodisperse colloidal spheres. The diameter of the spherical colloidal crystals was in the range of 10-40 microm. Depending on the stability of colloidal particles, the morphology of the self-assembled structure was varied. In particular, silica spheres in ethanol droplets were self-assembled into compactly packed silica colloidal crystals in spherical shapes, whereas polystyrene latex spheres in toluene droplets self-assembled into spherical colloidal crystal shells with hollow cores. The silica colloidal assemblies reflected diffraction colors according to the three-dimensionally ordered arrangement of silica spheres.     

General bottom-up construction of spherical particles by pulsed laser irradiation of colloidal nanoparticles: a case study on CuO

The development of a general method to fabricate spherical semiconductor and metal particles advances their promising electrical, optical, magnetic, plasmonic, thermoelectric, and optoelectric applications. Herein, by using CuO as an example, we systematically demonstrate a general bottom-up laser processing technique for the synthesis of submicrometer semiconductor and metal colloidal spheres, in which the unique selective pulsed heating assures the formation of spherical particles. Importantly, we can easily control the size and phase of resultant colloidal spheres by simply tuning the input laser fluence. The heating-melting-fusion mechanism is proposed to be responsible for the size evolution of the spherical particles. We have systematically investigated the influence of experimental parameters, including laser fluence, laser wavelength, laser irradiation time, dispersing liquid, and starting material concentration on the formation of colloidal spheres. We believe that this facile laser irradiation approach represents a major step not only for the fabrication of colloidal spheres but also in the practical application of laser processing for micro- and nanomaterial synthesis.     

Effects of liquid bridge between colloidal spheres and evaporation temperature on fabrication of colloidal multilayers

For the application of colloidal crystal films as "photonic band gap" materials, their domain size and thickness are significant. The substrate withdrawing speed, the colloidal suspension volume fraction, and the colloidal suspension temperature have been studied for the domain size and thickness controls of colloidal crystals in this study. Stable dispersions of monodispersed polystyrene spheres with a diameter of 245 nm were synthesized according to a general emulsion polymerization for colloidal crystal films. By experimental results and the theoretical relationship between the number of layers and other parameters, we could know that the water bridge between colloidal spheres (which is formed by capillary force) influences the number of colloidal crystal layers significantly.