Breath Figure Arrays: Unconventional Fabrications,Functionalizations, and Applications

A breath figure (BF) is the water droplet array that forms when moisture comes in contact with a cold substrate. This water droplet array has been widely utilized in the past two decades as a versatile soft template for the fabrication of polymeric porous films. Accordingly, the ordered pores on the polymer films formed with such a method are named a breath figure array (BFA).The BF templating technique is undergoing rapid development. Several unconventional BF processes have been established to prepare porous films with unique morphologies or primary materials, and various newly developed functionalization techniques have significantly improved the performance of polymeric films with BFA, leading to novel applications, including templates, biosensors, and separation membranes. These recent achievements will be described in this Minireview.     

Breath figures method to control the topography and the functionality of polymeric surfaces in porous films and microspheres

Polymeric films with porous structures and microsphere patterns were prepared by the method of breath figures, mixing poly(methyl methacrylate) (PMMA) and amphiphilic copolymers containing glucose moieties in their structure, glycopolymers. Statistical and block glycopolymers were used in a proportion of 10 wt %. The statistical glycopolymers were synthesized via conventional free radical copolymerization, whereas the block copolymer of methyl methacrylate and 2‐{[(D ‐glucosamin‐2‐Nyl) carbonyl]oxy}ethyl methacrylate, PMMA‐b‐PHEMAGl, was obtained by atom transfer radical polymerization. Glycopolymers were blended with a high molecular weight PMMA matrix and dissolved in a mixture of tetrahydrofuran and a small amount of water. Results showed that, depending on experimental conditions (water content, humidity, and type of copolymer), the observed final film morphology changes significantly. Thus, films with honeycomb pattern structures, spherical particles, or a mixture of both were obtained. In addition, polar glucose moieties were oriented principally either inside of the pores in the case of films and towards the surface in the case of particles. The specific surface bioactivity of these materials was examined using the specific lectin concanavalin A conjugated with fluorescein, Con A‐FITC. The successful binding of the Con A was demonstrated by fluorescence microscopy being more intense at the surface of the pores and of the particles. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Forming Lipid Bilayer Membrane Arrays on Micropatterned Polyelectrolyte Film Surfaces

A novel method of forming lipid bilayer membrane arrays on micropatterned polyelectrolyte film surfaces is introduced. Polyelectrolyte films were fabricated by the layer‐by‐layer technique on a silicon oxide surface modified with a 3‐aminopropyltriethoxysilane (APTES) monolayer. The surface pK_a value of the APTES monolayer was determined by cyclic voltammetry to be approximately 5.61, on the basis of which a pH value of 2.0 was chosen for layer‐by‐layer assembly. Micropatterned polyelectrolyte films were obtained by deep‐UV (254 nm) photolysis though a mask. Absorbed fluorescent latex beads were used to visualize the patterned surfaces. Lipid bilayer arrays were fabricated on the micropatterned surfaces by immersing the patterned substrates into a solution containing egg phosphatidylcholine vesicles. Fluorescence recovery after photobleaching studies yielded a lateral diffusion coefficient for probe molecules of 1.31±0.17 μm² s^?1 in the bilayer region, and migration of the lipid NBD PE in bilayer lipid membrane arrays was observed in an electric field.     

水滴模板法构筑蜂窝状有序多孔膜*

水滴模板法是利用凝结并自组织有序排列的水滴为模板构筑有序蜂窝状多孔薄膜的方法。这种方法具有方便、快速、廉价、作为模板的水滴可以自然蒸发而除去,且孔洞的尺寸可以通过改变相关的实验参数方便的进行调控的优点,因而近年来受到了人们的广泛关注。本文介绍了利用水滴模板法构筑有序多孔薄膜的实验方法,探讨了形成机理和相关实验条件对多孔薄膜结构的影响,并结合当前的研究热点针对多孔薄膜的进一步应用,着重综述了水滴模板法在不同性质的成膜材料体系的应用、多孔薄膜中亚有序结构的引入以及提高多孔薄膜稳定性的方法。最后,本文展望了利用水滴模板法构筑有序多孔薄膜这一研究领域的发展前景。     

Block copolymer films on patterned surfaces

We present results from a numerical study of a coarse-grained model of diblock copolymer (BCP) thin films cast on a chemically patterned surface. The patterned surface contains chemical inhomogeneities with a repeat spacing length scale comparable to the linear size of the BCP molecules. We find that the orientation of the lamellae in the thin film and the overlap of the film morphology with the preassigned surface pattern is strongly influenced by the commensurability between the bulk unconstrained lamellar size λ^*, and the linear size of the surface inhomogeneities w. PACS Numbers: 64.60.Cn, 61.41.+e, 64.60.My, 64.75.+g. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3127–3136, 1998     

Tunable nanopatterning by diblock copolymers in small confinements*

Here we study the effects of confinement on the self‐assembly of diblock copolymers. Specifically, we study the hexagonal cylindrical phase as it self‐assembles within a narrow confinement. We quantify the structural deformation of the cylindrical morphology that arises from the frustration that the narrow confinements exert on the system when the confinement width is incompatible with the lattice structure of the bulk mesophase. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3695–3700, 2004     

呼吸图法制备基于准聚轮烷的响应性薄膜

响应性薄膜能够响应外界的刺激来改变自身的结构或性能,是智能材料的重要组成部分.本工作以1,4-二乙氧基柱[5]芳烃(1,4-diethoxypillar[5]arene,DEP5A)和聚己内酯-b-聚乙二醇-b-聚己内酯(PCL-b-PEG-b-PCL)构建的准聚轮烷(polypseudorotaxane,PPR)为原...     

Thermocapillary approaches to the deliberate patterning of polymers

The phenomenon of thermocapillarity, the response of fluids to thermal gradients due to thermal alteration of their surface tension, was first reported over a century ago. Since then, research has focused generally on either the fundamentals or mitigation of this effect during the processing of materials. Only in the past two decades has the deliberate use of thermocapillary forces for the patterning of polymers been actively pursued, either for the ordering of internal structure or the introduction of topographic features. This review seeks to highlight this work and to identify directions for further investigation. In particular, while thermocapillary forces are often inextricably bound to other mechanisms, there are emerging directions in the deliberate coupling of forces to improve the capabilities of each mechanism. Further, the applications of thermocapillary patterning to polymer-nanoparticle composites has recently provided another promising route to active architectures. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1649–1668     

Synthesis and morphology investigations of a novel alkyne‐functionalized diblock copolymer

We reported the synthesis and morphology of a novel alkyne‐functionalized diblock copolymer (di‐BCP) poly(methyl methacrylate‐random‐propargyl methacrylate)‐block‐poly(4‐bromostyrene). The di‐BCPs were synthesized by atom transfer radical polymerization and postpolymerization deprotection, with good control over molecular weight and polydispersity index. Microphase separation in bulk di‐BCPs was confirmed by thermal analysis, small‐angle X‐ray scattering, and transmission electron microscopy. Microphase‐separated morphologies were also observed in thin films, and the orientation of the microdomains can be conveniently controlled by annealing under different solvents. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Phase separation in thin films of end‐grafted block copolymers

An atomic force microscopy investigation was carried out on various thick (30–120 nm) polymethyl methacrylate‐b‐polystyrene and poly(2‐(dimethyl amino)ethyl methacrylate)‐b‐polystyrene films prepared via a grafting‐from method. The structure of the films was examined with both topographic and phase imaging. Several different morphologies were observed including a perforated lamellar phase with irregular perforations. In addition, complementary small‐angle X‐ray scattering and reflectometry results measurements on a non‐grafted polymer are presented. Copyright © 2009 John Wiley & Sons, Ltd.     

基于静态呼吸图技术的图案化方法

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.     

Formation of long‐range stripe patterns with sub‐10‐nm half‐pitch from directed self‐assembly of block copolymer

We have demonstrated directed self‐assembly of poly(styrene‐b‐dimethylsiloxiane) (PS‐b‐PDMS) down to sub‐10‐nm half‐pitch by using grating Si substrate coated with PDMS. The strong segregation between PS and PDMS enables us to direct the self‐assembly in wide grooves of the grating substrate up to 500 nm in width. This process can be applied to form various type of sub‐10‐nm stripe pattern along variety of grating shape. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Highly ordered nanoporous thin films by blending of PSt‐b‐PMMA block copolymers and PEO additives as structure directing agents

Herein, we present a simple method for producing nanoporous templates with a high degree of lateral ordering by self‐assembly of block copolymers. A key feature of this approach is control of the orientation of polymeric microdomains through the use of hydrophilic additives as structure directing agents. Incorporation of hydrophilic poly(ethylene oxide) (PEO) moieties into poly(styrene‐b‐methyl methacrylate) (PSt‐b‐PMMA) diblock copolymers gives vertical alignment of PMMA cylinders on the substrate after solvent annealing. Because of the miscibility between PEO and PMMA, PEO additives were selectively positioned within PMMA microdomains and by controlling the processing conditions, it was found that ordering of PSt‐b‐PMMA diblock copolymers could be achieved. The perpendicular orientation of PMMA cylinders was achieved by increasing the molecular size of the PEO additives leading to an increased hydrophilicity of the PMMA domains and consequently to control the orientation of microdomains in PSt‐b‐PMMA block copolymer thin films. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8041–8048, 2008     

Multiscale Dewetting of Low‐Molecular‐Weight Block Copolymer Ultrathin Films

Ultrathin films of a low‐molecular‐weight block copolymer spontaneously dewet after several days at ambient temperature. Film rupture produces macroscopic holes and a residual pancake brush layer ≈ 2 nm thick with intermittent mounds measuring up to 25 nm in thickness. Multiscale dewetting likewise occurs when the films are heated and returned to ambient temperature. Regardless of the surface pattern that forms during heating, submicron mounds develop on the dewetted copolymer film, and fine holes emerge along the substrate surface, after cooling.     

Combinatorial Mapping of Surface Energy Effects on Diblock Copolymer Thin Film Ordering

Combinatorial gradient techniques are used to map the morphology dependence of thin symmetric diblock copolymer films on film thickness and substrate surface energy. An inversion from symmetric to anti‐symmetric lamellar morphology occurs with a progressive change in surface energy. An intermediate neutral region is found between these limiting types of ordering. The width ω of this transitional energy range scales as a power of copolymer mass M, ω ∝ M^1.9.

Optical photograph of a combinatorial map of the thin‐film block‐copolymer morphology on a film thickness and surface energy gradient. Island and holes on the surface scatter light causing the film to appear cloudy (lighter in color) in the areas where they exist. The darker areas do not have surface features and do not scatter light.     

Surface and bulk ordering in thin films of a symmetrical diblock copolymer

Amphiphilic diblock copolymers have the ability to adapt their surface's molecular composition to the hydrophilicity of their environment. In the case of about equal volume fractions of the two polymer blocks, the bulk of these polymers is known to develop a laminar ordering. We report here our investigation of the relationship between bulk ordering and surface morphology/chemical composition in thin films of such an amphiphilic diblock copolymer. Upon annealing in vacuum, the expected lamella ordering in the bulk of the film is observed and we find the morphology of the film surface to be defined by the thickness of the as‐deposited film: If the as‐deposited thickness matches the height of a lamella stack, then the film exhibits a smooth surface. Otherwise, an incomplete lamella forms at the film surface. We show that the coverage of this incomplete layer can be quantified by X‐ray reflectivity. To establish the lamella ordering in the bulk, the film needs to be annealed above the glass temperature of the two blocks. Molecular segregation at the film surface, however, is already occurring at temperatures well below the glass temperature of the two blocks. This indicates that below the glass temperature of the blocks the bulk of the thin film is “frozen,” whereas the polymer chains composing the surface lamella have an increased mobility. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys., 2013 , 51, 1282–1287     

Anisotropic Lithium Ion Conductivity in Single‐Ion Diblock Copolymer Electrolyte Thin Films

Well‐defined single‐ion diblock copolymers consisting of a Li‐ion conductive poly(styrenesulfonyllithium(trifluoromethylsulfonyl)imide) (PSLiTFSI) block associated with a glassy polystyrene (PS) block have been synthesized via reversible addition fragmentation chain transfer polymerization. Conductivity anisotropy ratio up to 1000 has been achieved from PS‐b‐PSLiTFSI thin films by comparing Li‐ion conductivities of out‐of‐plane (aligned) and in‐plane (antialigned) cylinder morphologies at 40 °C. Blending of PS‐b‐PSLiTFSI thin films with poly(ethylene oxide) homopolymer (hPEO) enables a substantial improvement of Li‐ion transport within aligned cylindrical domains, since hPEO, preferentially located in PSLiTFSI domains, is an excellent lithium‐solvating material. Results are also compared with unblended and blended PSLiTFSI homopolymer (hPSLiTFSI) homologues, which reveals that ionic conductivity is improved when thin films are nanostructured.

     

Focused laser-induced marangoni dewetting for patterning polymer thin films

Highly-localized focused laser spike (FLaSk) heating of polymer thin films is a resist- and developer-free alternative to two-dimensional (2D) laser direct write for creating patterns on the single micron or, by exploiting overlap effects, submicron scale. The massive temporal and spatial thermal gradients and resulting thermal Marangoni stresses generated by FLaSk are an effective means for the directed dewetting and patterning of such films. Here, the general applicability of this technique to glassy amorphous polymer thin film systems is investigated through systematic investigation of film thickness, glass transition temperature, and polymer mobility. The results reveal that the important parameters are the film thickness (coupled to the optical heating effects through anti-reflection coating effects) and the high-temperature polymer melt mobility, allowing for generation of single features with linewidths of down to ∼1 μm. Further, the introduction of spatial mobility variations by using polymer brushes, bilayers, and microphase separated block copolymers leads to additional profile manipulation effects (i.e. spontaneous 2D pattern generation and flattened top profiles). © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 225–236     

Poly(ferrocenylsilane)‐block‐Polylactide Block Copolymers

A PFS/PLA block copolymer was studied to probe the effect of strong surface interactions on pattern formation in PFS block copolymer thin films. Successful synthesis of PFS‐b‐PLA was demonstrated. Thin films of these polymers show phase separation to form PFS microdomains in a PLA matrix, and ultrathin films (<5 nm) formed SINPATs on silicon and mica. The SINPATs consisted of strongly surface‐adsorbed PLA blocks on top of which the PFS blocks dewetted into sphere‐like features. The lateral spacing between these features was regular, and was typically much larger than the length scale associated with regular block copolymer phase separation.