Aligned nanowires and nanodots by directed block copolymer assembly

The directed self-assembly of block copolymers (BCPs) is a promising route to generate highly ordered arrays of sub-10 nm features. Ultradense arrays of a monolayer of spherical microdomains or cylindrical microdomains oriented parallel to the surface have been produced where the lateral ordering is guided by surface patterning and the lattice defined by the patterning can be commensurate or incommensurate with the natural period of the BCP. Commensurability between the two can be used to elegantly manipulate the lateral ordering and orientation of the BCP microdomains so as to form well-aligned arrays of 1D nanowires or 2D addressable nanodots. No modification of the substrate surface, aside from the patterning, was used, making the influence of lattice mismatch and pattern amplification on the size, shape and pitch of the BCP microdomains more transparent. A skew angle between incommensurate lattices, defining a stretching or compression of the BCP chains to compensate for the lattice mismatch, is presented.     

H-bonding driven assembly of colloidal Au nanoparticles on nanostructured poly(styrene-b-ethylene oxide) block copolymer templates

A facile, cost-effective, and general solution-based “bottom-up” method for nanopatterning dense arrays of colloidal Au nanoparticles (NPs) has been developed. The organization of the NPs has been successfully achieved onto a microphase-separated poly(styrene-block-ethylene oxide) (PS-b-PEO) block copolymer (BCP) thin film which acts as structural template. The NP assembly process occurs by incubating the BCP films in dispersions of the ex situ synthesized Au NPs, not requiring any chemical pre-treatment or activation step of the copolymer surface, and has demonstrated to be distinctively controlled by multiple, cooperative, and selective hydrogen bonding interactions between hydroxyl functionalities of the capping molecules coating the Au NP surface and the hydrophilic PEO block. The effect of incubation time and concentration of NPs on the selectivity of the assembly has been investigated by atomic force and scanning electron microscopy. The results show that the BCP pattern is preserved after decoration with the Au NPs. The fabricated nanopatterns are good candidates for nanostructure integration in sensing and optoelectronic applications, as well as in memory devices and photonic systems. Moreover, the proposed immobilization protocol represents a model system that can be extended to other NPs having different compositions and surface chemistries.     

Carbohydrate‐Based Block Copolymer Thin Films: Ultrafast Nano‐Organization with 7 nm Resolution Using Microwave Energy

Block copolymers (BCP) can self‐assemble into nanoscale patterns with a wide variety of applications in the semiconductor industry. The self‐assembly of BCPs is commonly accomplished by solvent vapor or thermal annealing, but generally these methods require long time (few hours) to obtain nanostructured thin films. In this contribution, a new and ultrafast method (using microwaves) is proposed—high temperature solvent vapor annealing (HTSVA), combining solvent vapor annealing with thermal annealing, to achieve fast and controllable self‐assembly of amphiphilic BCP thin films. A promising carbohydrate‐based BCP capable of forming cylindrical patterns with some of the smallest feature sizes is used for demonstrating how to obtain a highly ordered vertical cylindrical pattern with sub‐10 nm feature sizes in few seconds by HTSVA. HTSVA provides not only a simple way to achieve BCP fast self‐assembly in practical applications but also a tool to study the self‐assembly behavior of BCPs under extreme conditions.     

The effect of nanoparticle on microdomain alignment in block copolymer thin films under an electric field

Controlling microdomain structure of block copolymers (BCPs) under electric field has been one of the most challenging research tasks. In this study, we examined the effect of nanoparticles on the microdomain orientations in BCP/nanoparticle thin films under electric field using cross-sectional transmission electron microscopy experiments. Gold and cadmium selenide nanoparticles with a tailored surface property were incorporated to control microdomain orientations in BCP/nanoparticle thin films by varying dielectric constant of one constituting block. It was revealed that the microdomain orientation of BCP/nanoparticle thin films under electric field was suppressed by the introduction of gold nanoparticles. Thus, it can be inferred that gold nanoparticles can show a shielding effect under external electric field. The effect of complementary parameters such as NPs concentration, exposure time, and field strength were also demonstrated. In addition, it was also found that the suppression effect lessened with cadmium selenide nanoparticles having a dipole from the noncentrosymmetric structure. This work can provide fundamental data for understanding of microdomain alignment behavior of BCP/nanoparticle system under electric field.     

Charged molecular effect on the degree of ordering of mesostructured silica thin film templated by mixed ionic micelles

We have synthesized highly oriented mesostructured silica thin films templated with nonionic and cationic mixed surfactant micelles by a solvent evaporation-induced self-assembly process. The mesostructured silica thin films showed constant body-centered cubic lattice structures over a wide range of mixing mole ratios of the cationic surfactant in the nonionic surfactant-rich phase. The degree of ordering of the mixed micellar arrays in the mesostructured silica thin films was enhanced by tuning the mixing mole ratio of the cationic surfactants to nonionic surfactant.     

Responding Depth of Photocatalytic Activity of TiO2 Self-assembled Films

The electrostatically self-assembly method is getting strategically important to prepare multilayer thin films. With careful choice of component materials, this method should allow for the preparation of multilayer thin films with a variety of excellent technological properties. Ti02/PSS multilayer thin films with ordered structure were prepared by electrostatic self-assembly method. UV-Vis-NIR spectrophotometer, X-ray photoelectron spectroscopy (XPS), and atom force microscopy (AFM) were used to characterize the structure and performance of the multilayer films. Because electrostatically self-assembly method allows molecular-level control over the film composition and thickness, this paper studied the responding depth of photocatalytic activity of Ti02 self-assembled films in detail.     

Negative‐Tone Block Copolymer Lithography by In Situ Surface Chemical Modification

Negative‐tone block copolymer (BCP) lithography based on in situ surface chemical modification is introduced as a highly efficient, versatile self‐assembled nanopatterning. BCP blends films consisting of end‐functionalized low molecular weight poly(styrene‐ran‐methyl methacrylate) and polystyrene‐block‐Poly(methyl methacylate) can produce surface vertical BCP nanodomains on various substrates without prior surface chemical treatment. Simple oxygen plasma treatment is employed to activate surface functional group formation at various substrates, where the end‐functionalized polymers can be covalently bonded during the thermal annealing of BCP thin films. The covalently bonded brush layer mediates neutral interfacial condition for vertical BCP nanodomain alignment. This straightforward approach for high aspect ratio, vertical self‐assembled nanodomain formation facilitates single step, site‐specific BCP nanopatterning widely useful for various substrates. Moreover, this approach is compatible with directed self‐assembly approaches to produce device oriented laterally ordered nanopatterns.     

Palladium and gold nanoparticle array films formed by using self-assembly of block copolymer

The well-arrayed Pd and Au nanoparticle thin films were successfully prepared by making use of self-assembled PS-b-P4VP block copolymer (BCP) as a mask for the reduction of PdCl2 deposited on glass substrate. The films consisted of spherialcal nanoparticles with an average diameter of about 45 nm. For monitoring the size, shape and array formation of Pd nanopaticle films, this procedure was proved better to the conventional process in which PdCl2 impregnated in the channels of self assembled BCP film is reduced to form nanoparticle array. This observations of Pd nanoparticle array film formation is supported by the AFM and UV-VIS studies of Au nanoparticle array films formed by conventional method.     

Nanoparticle assemblies in thin films of supramolecular nanocomposites

We demonstrated a versatile approach to obtain layered nanoparticle sheets with in-plane hexagonal order and 3-D ordered arrays of single nanoparticle chains in thin films upon blending nanoparticles with block copolymer (BCP)-based supramolecules. Basic understanding on the thermodynamic and kinetic aspects of the assembly process paved a path to manipulate these assemblies to meet demands in nanoparticle-based device fabrication and understand structure-property correlations.     

Nanostructure engineering by templated self-assembly of block copolymers

Self-assembling materials are the building blocks for bottom-up nanofabrication processes, but many self-assembled nanostructures contain defects and lack sufficient long-range order for certain nanotechnology applications. Here we investigate the formation of defects in a self-assembled array of spherical block-copolymer microdomains, using topographical templates to control the local self-assembly. Perfect ordered sphere arrays can form in both constant-width templates and width-modulated templates. For modulated templates, transition between configurations having a constant number of rows and configurations of stable arrays with varying numbers of rows is shown to be analogous to dislocation formation in an epitaxial thin film system. Based on the configuration transition energy and fluctuation energy, designed templates with a high tolerance for lithographical imperfections can direct precisely modulated block-copolymer nanostructures. This study provides insights into the design of hybrid systems combining top-down and bottom-up fabrication.     

Vapor-phase synthesis of indium (III) oxide nanocrystals

A new way for chemical vapor deposition of indium (111) oxide is presented. It can be used to obtain both polycrystalline films and different arrays of nanocrystals. Used as a catalyst, In or Au thin films can afford selective deposition on an arbitrary spot of surface. The obtained materials were characterized electron microscopy, X-ray diffraction and cathodoluminescence methods.     

Fabrication of Au/SiO2 Nanocomposite Films by Self-Assembly Multilayer Method

Gold colloid was prepared by chemical reduction of hydrogen tetrachloroaurate, polyelectrolyte/gold nanoparticle/silica nanoparticie composite films were fabricated via an electrostatic self-assembly multilayer method, and composite films of gold nanoparticle dispersed in silica matrix were formed by heat-treating the polyelectrolyte/gold nanoparticle/silica nanoparticle composite films to eliminate the polyelectrolyte. The obtained composite films were investigated with UV-vis, TEM, AFM and XRD. The results show that the self-assembly multilayer method is a promising process to produce composite films of gold nanoparticle-dispersed in organic and/or inorganic matrixes.     

Directed Self‐Assembly of Star‐Block Copolymers by Topographic Nanopatterns through Nucleation and Growth Mechanism

Exploring the ordering mechanism and dynamics of self‐assembled block copolymer (BCP) thin films under confined conditions are highly essential in the application of BCP lithography. In this study, it is aimed to examine the self‐assembling mechanism and kinetics of silicon‐containing 3‐arm star‐block copolymer composed of polystyrene (PS) and poly(dimethylsiloxane) blocks as nanostructured thin films with perpendicular cylinders and controlled lateral ordering by directed self‐assembly using topographically patterned substrates. The ordering process of the star‐block copolymer within fabricated topographic patterns with PS‐functionalized sidewall can be carried out through the type of secondary (i.e., heterogeneous) nucleation for microphase separation initiated from the edge and/or corner of the topographic patterns, and directed to grow as well‐ordered hexagonally packed perpendicular cylinders. The growth rate for the confined microphase separation is highly dependent upon the dimension and also the geometric texture of the preformed pattern. Fast self‐assembly for ordering of BCP thin film can be achieved by lowering the confinement dimension and also increasing the concern number of the preformed pattern, providing a new strategy for the design of BCP lithography from the integration of top‐down and bottom‐up approaches.     

Simple orientational control over cylindrical organic-inorganic block copolymer domains for etch mask applications

Bottom-up patterning methodologies, predicated on chemical self-assembly, have the potential to transcend limitations associated with more traditional lithographies. By controlling the domain orientation of a cylinder-forming organic-inorganic block copolymer, poly(styrene-block-ferrocenyldimethylsilane), it is possible to straightforwardly fabricate massive arrays of either nanoscale dots or wires out of a film composed of a wide variety of materials. In the work reported here, orientational control is achieved by manipulating the polymer film thickness in concert with the annealing treatment. For films much thinner than the equilibrium periodicity of the microdomains, the cylinders spontaneously orient themselves perpendicular to the substrate. Films with thickness close to the equilibrium periodicity exhibit the more common in-plane orientation following thermal annealing. Solvent annealing leads to an in-plane orientation for the full range of film thicknesses studied. As a demonstration of the effectiveness of this method, semiconductor substrates were patterned with arrays of posts and wires, respectively, using the same starting polymeric material as the etch mask. Compatibility of this polymer with various substrate materials is also demonstrated.     

Large-scale, reliable and robust SERS-active nanowire substrates prepared using porous alumina templates

nanowire arrays for surface-enhanced Raman scattering applications. These nanowire films were synthesized via electrodeposition using porous alumina templates of varying order, thickness and pore diameters. Mechanical polishing has been shown to be a very effective method to prepare nanowire arrays with monodisperse length over comprehensively large dimensions. On the other hand, a convenient synthesis route has been suggested that allows the formation of nanoparticle rrays using very thin and/or large area porous alumina films. It is reckoned that even films with the smallest obtainable pore sizes can be utilized to prepare large area, fine nanoparticle arrays. Such arrays may also find use in other areas, such as solar cells and electrochemistry. Preliminary Raman experiments indicated that the nanowire/nanoparticle arrays are indeed surface-enhanced Raman scattering-active. Finally, the potentials offered by the reported processing methods for fabricating substrates with predictable and high Raman amplifications are discussed.     

ZnO纳米棒阵列和薄膜的同步外延生长及其光电化学性能

使用化学气相沉积法在a面蓝宝石衬底上同步外延生长氧化锌(ZnO)竖直纳米棒阵列和薄膜,研究了阵列和薄膜的光电化学性能。结果表明,纳米结构中的竖直单晶纳米棒有六棱柱形和圆柱形,其底部ZnO薄膜使竖直纳米棒互相联通。与ZnO纳米薄膜的比较表明,这种纳米结构具有优异的光电化学性能,其入射光电流效率是ZnO纳米薄膜的2.4倍;光能转化效率是ZnO纳米薄膜的5倍。这种纳米结构优异的光电化学性能,可归因于其高表面积-体积比以及其底部薄膜提供的载流子传输通道。本文分析了这种纳米结构的生长过程,提出了协同生长机理：Au液化吸收气氛中的Zn原子生成合金,合金液滴过饱和后ZnO开始成核,随后在衬底表面生成了ZnO薄膜。同时,还发生了Zn自催化的气-固(VS)生长和Au催化的气-液-固(VLS)生长,分别生成六棱柱纳米棒和圆柱形纳米棒,制备出底部由薄膜连接的竖直纳米棒阵列。     

Synthesis of mesoporous titania thin films by a simple route at low-temperature via plasma treatment

A new combination of techniques named evaporation-induced self-assembly–plasma etching (EISA–PE) method for mesoporous titania thin films preparation has been developed. The main advantage of this method is that the organic templates can be removed by plasma etching method thus the inorganic frameworks shrinkage or collapse induced by calcination can be avoided. Titania films prepared by this method have been characterized by Fourier transform infrared spectroscopy, thermogravimetric analyses, small and wide-angle X-ray diffraction, and field emission scanning electron microscope. The results show that titania thin film with well-resolved mesostructure can be created by EISA–PE method. The results also prove that plasma parameters have a great influence on the mesoporous property of the film and it is a good kind of catalyst support for methanol catalytic combustion.     

An emerging pore-making strategy: confined swelling-induced pore generation in block copolymer materials

Block copolymers (BCPs) composed of two or more thermodynamically incompatible homopolymers self-assemble into periodic microdomains. Exposing self-assembled BCPs with solvents selective to one block causes a swelling of the domains composed of this block. Strong swelling in the confinement imposed by the matrix of the other glassy block leads to well-defined porous structures via morphology reconstruction. This confined swelling-induced pore-making process has emerged recently as a new strategy to produce porous materials due to synergic advantages that include extreme simplicity, high pore regularity, involvement of no chemical reactions, no weight loss, reversibility of the pore forming process, etc. The mechanism, kinetics, morphology, and governing parameters of the confined swelling-induced pore-making process in BCP thin films are discussed, and the main applications of nanoporous thin films in the fields of template synthesis, surface patterning, and guidance for the areal arrangements of nanomaterials and biomolecules are summarized. Recent, promising results of extending this mechanism to produce BCP nanofibers or nanotubes and bulk materials with well-defined porosity, which makes this strategy also attractive to researchers outside the nanocommunity, are also presented.     

Investigation of thermally responsive block copolymer thin film morphologies using gradients

We report the use of a gradient library approach to characterize the structure and behavior of thin films of a thermally responsive block copolymer (BCP), poly(styrene-b-tert-butyl acrylate) (PS-b-PtBA), which exhibits chemical deprotection and morphological changes above a thermal threshold. Continuous gradients in temperature and film thickness, as well as discrete substrate chemistry conditions, were used to examine trends in deprotection, nanoscale morphology, and chemical structure. Thermal gradient annealing permitted the extraction of transformation rate constants (k(t)) for the completion of thermal deprotection and rearrangement of the film morphology from a single BCP library on hydroxyl and alkyl surfaces, respectively. The transformation rate constants ranged from 1.45 × 10(-4) s(-1) to 5.02 × 10(-5) s(-1) for temperatures between 185 and 140 °C for hydroxyl surfaces. For the same temperature range, the alkyl surfaces yielded k(t) values ranging from 4.76 × 10(-5) s(-1) to 5.73 × 10(-6) s(-1), an order of magnitude slower compared to hydroxyl surfaces. Activation energies of the thermal deprotection and film transformation on these surfaces were also extrapolated from linear fits to Arrhenius behavior. Moreover, we noted a morphology shift and orientation transformation from parallel lamellae to perpendicular cylinders at the free surface because of changes in volume fraction and surface energetics of the initially symmetric BCP. Using gradient techniques, we are able to correlate morphological and chemical structure changes in a rapid fashion, determine kinetics of transitions, and demonstrate the effect of surface chemistry on the deprotection reaction in thermally responsive BCP thin films.     

A Simple Top‐Down/Bottom‐Up Approach to Sectored,Ordered Arrays of Nanoscopic Elements Using Block Copolymers

A top‐down/bottom‐up approach is demonstrated by combining electron‐beam (e‐beam) lithography and a solvent annealing process. Micellar arrays of polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) with a high degree of lateral order can be produced on a surface where sectoring is defined by e‐beam patterning. The e‐beam is used to crosslink the block copolymer (BCP) film immediately after spin‐coating when the BCP is disordered or in a highly ordered solvent‐annealed film. Any patterns can be written into the BCP by crosslinking. Upon exposure to a preferential solvent for the minor component block followed by drying, cylindrical nanopores are generated within the nonexposed areas by a surface reconstruction process, while, in the exposed areas, the films remain unchanged. Nickel nanodot arrays can be placed over selected areas on a surface by thermal evaporation and lift‐off process.