Patterning is of paramount importance in many areas of modern science and technology. As a valuable part in miniaturized devices, large-scale aligned CNTs with serial port configuration is highly desirable. Here, we reported that the synthesis of a pair of patterned carbon nanotubes with the shape of serial port by CVD starting from different breath figure templates, cross-linked polymer matrix and ferrous inorganic micropatterns. The growth mechanism of the isolated CNT bundles is attributed to the selectively interfacial aggregation of the ferrocene to the walls of the cavities, a so-called Pickering-emulsion effect, whereas the honeycomblike skeleton of the dense CNT arrays develop from the catalytically functionalized hexagonal edges. This synthesis strategy exemplifies a new possibility for making use of CNTs to fabricate functional carbons with unique geometry or specific properties in a controllable way. We expect that the methodology can be also applied onto the fabrication of patterned graphene.

对呼吸图技术制备二维有序多孔结构的研究进展进行了综合评述, 并重点介绍了本课题组发展的静态呼吸图技术。利用静态呼吸图法, 可制备高度有序的聚合物、聚合物/无机物微孔膜。这些有序的结构可以直接应用于光掩膜。进一步, 多孔聚合物膜可以被紫外光交联和改性。表面改性的多孔聚合物膜可以用于细胞支架。而交联的聚合物/无机物前驱体微孔膜可以用来制备无机纳米材料阵列。结果表明, 静态呼吸图技术是一种简单、高效的对聚合物、聚合物/无机物薄膜进行图案化的通用方法, 并展示了图案化薄膜广阔的功能化前景.

We describe a facile method to micropattern solid substrates: breath figure lithography (BFL). A honeycomb structured gold mask was prepared by sputter-coating a micro-porous polymer film with BF arrays, and then inductively coupled plasma reactive ion etching (ICP–RIE) transferred the patterns onto silicon wafer. The large etching rate selectivity between golden mask and substrate plays an important role in the effective transfer of the patterns. The versatility of the method was demonstrated by forming micropatterns on various solid substrates with adjustable sizes. Furthermore, the micropatterns on solid substrate could be replicated by PDMS stamp.

在含亲二氧化碳链段聚二甲基硅氧烷（PDMS）的嵌段聚合物中, 用超临界二氧化碳选择溶胀的方法得到了闭合的纳米孔。采用反应离子刻蚀,可以将聚合物膜内部的多孔结构暴露出来, 然后用原子力显微镜和扫描电镜表征。结果表明, 纳米孔的形成不是简单的PDMS 纳米微区溶胀,而是由相邻纳米微区在超临界流体处理过程中合并以后形成的。纳米孔的密度和孔径分别为7.0×1010/cm2和20nm。

Highly ordered honeycomb films are prepared by breath-figure method using an amphiphilic diblock copolymer of polystyrene-block-polyacrylic acid (PS-b-PAA). By simply cross-linking PS matrix via deep ultraviolet (UV) irradiation, both the solvent and thermal stability of the porous films was significantly improved while retaining the three-dimensional (3D) structures. The film surface wettability was changed from hydrophobicity to hydrophilicity by the formed polar groups during the photochemical process. After 6 h UV cross-linking, the honeycomb structures could be preserved up to 320 ◦C, an increase of more than 200 K as compared to the non-cross-linked films.

Topical microbicides offer women the opportunity to protect themselves from sexual HIV transmission under their own control. A series of poly[styrene-alt-(maleic anhydride)] derivatives were prepared by amidation or hydrolysis of the anhydride moiety. The derivatives were shown to be of low cell toxicity and effectively inhibited HIV-1 infections in an in vitro cellular model. Poly[styrene-alt-(maleic acid, sodium salt)] was the most potent inhibitor, being 100-fold more potent than dextran sulfate suggesting its potential application as a new class of polyanionic microbicides.

Recently, the carbon dioxide (CO2) process with sphere forming block copolymer (bcp) templates successfully introduced nanometer cells into polymeric materials. CO2 selectively swells CO2-philic domains of fluorinated blocks and introduces nanometer voids in the CO2-philic domains. We extended the same methodology to bcp templates with nonspherical domains. Depending on the initial morphologies controlled by selectivity of casting solvents, vertically or horizontally aligned polymer nanosheets spontaneously appeared after the CO2 process and were confirmed by scanning electron microscopy and grazing incident small-angle X-ray scattering. Selective swelling of minority domains with CO2 induces transition to lamellar morphology during the process and results in stacking sheet structure after depressurization of CO2.

Analysis of nanostructures is of increasing importance with advances of nanotechnology. Embedded nanostructures in thin films in particular are of recent interest. Grazing incident small angle x-ray scattering (GISAXS) has been recognized to be a powerful method to probe such embedded nanostructures; however, quantitative analysis of scattering pattern is not always trivial due to complex refraction and reflection at surface and interfaces. We prepared nanocellular thin films using block copolymer template with carbon dioxide (CO2); CO2 "bubbles" were formed in the CO2-philic block domains. Such nanocellular structures were analyzed by GISAXS and simulated using distorted wave Born approximation DWBA. Unlike traditional transmission x-ray scattering, GISAXS requires a careful choice of incident angle to analyze the form factor of scatters embedded in a thin film. Nevertheless, the GISAXS measurements under optimized geometry with quantitative calculations using DWBA revealed that the nanocells are spherical and aligned in a single layer of hexagonal lattice and are surrounded by CO2-philic block domains.

A fabricating method of nanocellular structures in single-layer polymeric thin films was developed using supercritical carbon dioxide and fluorinated copolymer templates as reported in our previous communication [Li, L.; Yok oyama, H.; Nemoto, T.; Sugiyama, K. AdV. Mater. 2004, 16, 1226-1229]. This paper presents thedetails of the fabrication of nanocellular thin films. The morphology in the as-cast films depends on the solvent casting process and plays an important role for the final structures after the following the scCO2 process. However, the nanocellular structures are not simply templated from the nanodomains; reconstruction of the structures during the CO2 processes is not negligible. The number density of nanocells is significantly smaller than that of PFMA nanodomains before the CO2 process. Starting from spherical domains followed by an scCO2 process at a pressure from 8 to 20 MPa, nanocells appear with an average diameter ranging from 15 to 30nm. SEM cross-sectional views in addition to in-plane views of the nanocellular thin films prove that not open porous but closed cellular structures are formed in films irrespective of thickness. Such nanocellular formation is primarily due to swelling of PFMA domains followed by gentle removal of CO2 at reduced temperature, but expansion on depressurization still influences the size and its distribution. The size distribution of cells is effectively reduced either by lowering depressurization temperature or by adding a low molecular weight homopolymer.

Textures of liquid crystalline polymers with two-dimensional mesogens have been investigated by using polarizing optical microscopy. Disclinations, strength lSl up to 3/2 and 5/2, were found easily in each sample. Occasionally, even high strength disclination pair can be found. These high strength disclinations are very sable in high temperature although they are energy unfavorable according to the theory of Nehring and Saupe. The rare textures may be ascribed to the unique shape of the molecular mesogenic units. The stability of the high strength disclination is attributed to the energy dispersion and high viscosity in polymer melt.