Study of the time evolution of the surface morphology of thin asymmetric diblock copolymer films under solvent vapor

The time development of the surface morphology of asymmetric polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) thin films ‘annealing’ in methanol vapor, a selective solvent for minority P4VP block, was investigated by atomic force microscopy(AFM). For PS-b-P4VP with cylindrical structure in bulk, as annealing time progressed, the surface morphology underwent structural transitions from featureless topography to hybrid morphology of cylindrical and spherical pits, to cylinders, to nanoscale depressions, back to cylinders again. The different film thickness made the number of the transitions observed, at any given annealing time, different. The thicker the film is the more transitions at a given annealing time can be observed. If the film was not thick enough, depressions appeared. For PS-b-P4VP with spherical structure in bulk, it displayed nanoscale depressions with the annealing time increasing. A possible mechanism of the transition of morphologies during solvent annealing was proposed.     

Solvent vapor induced dewetting in diblock copolymer thin films

The dewetting pattern development of thin film of poly(styrene)-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer has been studied after ‘annealing’ in the PMMA block selective solvent vapor. Initially, typical circular dewetted holes are observed. Further annealing, however, results in the formation of fractal-like holes. The heterogeneous stress induced by the residual solvent remaining in the film after spin-coating induces the anisotropy of the polymer mobility during the annealing process, which triggers the formation of the intriguing surface patterns.     

Water-induced morphology evolution of block copolymer micellar thin films

Morphology evolution of diblock copolymer polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) micellar thin film in the presence of water was investigated. Surface holes with nanoscale cavities in hexagonal order could be induced by water treatment for certain periods. The nanoscale surface cavities could be transformed into isolated nanospheres in a dry environment or back to protruding densely packed spheres by toluene (a selective solvent for PS coronae) treatment. The morphology evolution of micellar thin film strongly depended on the slow evaporation of toluene solvent, the swelling of P4VP cores in the humid environment, and the subsequent movement of PS chains induced by air and toluene. The incompatibility between solvent and block, and that between the unlike blocks also played an important role in the morphology evolution.     

Re-assembly behaviors of polystyrene-b-poly(acrylic acid) micelles

The re-assembly behaviors of spherical micelles of the polystyrene-b-poly(acrylic acid) (PS-b-PAA) diblock copolymer in different solvent mixtures were investigated using dynamic light scattering, transmission electron microscopy and atomic force microscopy. Depending on the nature of the solvent, PS-b-PAA micelles re-assembled from spheres to nanorings in toluene or to necklace-like aggregates in water induced by solvent evaporation. Systematic studies suggested that the re-assembly behaviors on a neutral surface are strongly correlated with the micellar surface components, the solvent polarity and the chain length of the micelle corona of the solvated blocks. We proposed that the formation of nanorings from PS-b-PAA micelles in toluene is mainly induced by the dewetting process of the solvent, while the necklace-like structure arises from the hydrogen bonding interactions among the partially dissociated PAA units.     

Structure and phase transition in thin films of block copolymer micelles complexed with inorganic precursors

Block copolymer micelle can be used as nano-reactor where separated domains serve as a compartment for the production of nanomaterials, ultimately creating nanocomposite materials. In this work, thin nanocomposite films generated from polystyrene-b-poly(acrylic acid) (PS-b-PAA) micellar solution in which small amount of inorganic precursor was added were investigated. The films were prepared by spin coating onto silicon substrate, and then solvent-annealed. As-spun films exhibit typical micellar structure with spherical shape along which inorganic nanoparticles are dispersed. Such morphology remains unchanged after solvent annealing for micellar films with small amount of inorganic precursor. However, further increase in the amount of inorganic precursors brings about the morphological changes, producing different organization of inorganic nanoparticles in composite films. This behavior was found to strongly depend on the types of precursors and solvents used for annealing. These results illustrate a simple yet useful route to generate the polymeric nanocomposites with diverse structure and composition.     

Fabrication of fibril like aggregates by self-assembly of block copolymer mixtures via interpolymer hydrogen bonding

This paper describes the formation of fibril like aggregates from the self-assembly of block copolymer mixture (polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) and polystyrene-b-poly(acrylic acid) (PS-b-PAA)) via interpolymer hydrogen bonding in nonselective solvent. The hydrogen bonding between P4VP and PAA in chloroform leads to the formation of complex. When all the pyridine units in P4VP were all hydrogen bonded to acrylic acid in PAA, the formed complex is insoluble, resulting in the formation of spherical micellar aggregates and nanorods. However, two kinds of supramolecules with insoluble or soluble complex are formed in the solution when PS-b-P4VP and PS-b-PAA are mixed with equal mole ratio. The fibril like aggregates can be formed from the self-assembly of supramolecule with soluble complex during spin-coating process. The effects of evaporation rate of solvent and solution concentrations on the formation of fibril like aggregates were investigated. The results prove that the kinetic factors play an important role in the formation of the fibril like aggregates.     

Hexagonally ordered arrays of metallic nanodots from thin films of functional block copolymers

We demonstrate a new and simple route to fabricate highly dense arrays of hexagonally close packed inorganic nanodots using functional diblock copolymer (PS-b-P4VP) thin films. The deposition of pre-synthesized inorganic nanoparticles selectively into the P4VP domains of PS-b-P4VP thin films, followed by removal of the polymer, led to highly ordered metallic patterns identical to the order of the starting thin film. Examples of Au, Pt and Pd nanodot arrays are presented. The affinity of the different metal nanoparticles towards P4VP chains is also understood by extending this approach to PS-b-P4VP micellar thin films. The procedure used here is simple, eco-friendly, and compatible with the existing silicon-based technology. Also the method could be applied to various other block copolymer morphologies for generating 1-dimensional (1D) and 2-dimensional (2D) structures.     

A new approach in the study of tethered diblock copolymer surface morphology and its tethering density dependence

A poly(l-lactic acid)-block-polystyrene-block-poly(methyl methacrylate) (PLLA-b-PS-b-PMMA) triblock copolymer was synthesized with a crystalline PLLA end block. Single crystals of this triblock copolymer grown in dilute solution could generate uniformly tethered diblock copolymer brushes, PS-b-PMMA, on the PLLA single crystal substrate. The diblock copolymer brushes exhibited responsive, characteristic surface structures after solvent treatment depending upon the quality of the solvent in relation to each block. The chemical compositions of these surface structures were detected via the surface enhanced Raman scattering technique. Using atomic force microscopy, the physical morphologies of these surface structures were identified as micelles in cyclohexane and “onion”-like morphologies in 2-methoxyethanol, especially when the PS-b-PMMA tethered chains were at low tethering density.     

Effects of substrate roughness on the orientation of cylindrical domains in thin films of a polystyrene-poly(methylmethacrylate) diblock copolymer studied using atomic force microscopy and cyclic voltammetry

This paper describes the orientation of cylindrical domains in thin films of a polystyrene-poly(methylmethacrylate) diblock copolymer (PS-b-PMMA; 0.3 as the PMMA volume fraction) on gold and oxide-coated Si substrates having different surface roughness. Atomic force microscopy images of PS-b-PMMA films having thickness similar to the domain periodicity permitted us to study the effects of substrate roughness and block affinity on domain orientation. PS-b-PMMA films on gold substrates showed metastable vertical domain orientation that was attained more slowly on rougher substrates. In contrast, the domains were horizontally oriented on oxide-coated Si regardless of surface roughness and the annealing conditions examined. In addition, cyclic voltammetry data for PS-b-PMMA films on gold substrates whose PMMA domains were etched suggested that the metastable vertically oriented domains reached the underlying substrates. These results indicate that PS-b-PMMA films containing vertically oriented cylindrical domains can be obtained by using rough gold substrates upon annealing under controlled conditions.     

Tuned phase behavior of weakly interacting polystyrene-block-poly(n-pentyl methacrylate) by selective solvent

We investigated, via small angle X-ray scattering, depolarized light scattering, rheometry, and transmission electron microscopy, the phase behavior of the mixture of a symmetric polystyrene-block-poly(n-pentyl methacrylate) copolymer (PS-b-PnPMA) showing the closed-loop phase behavior and excellent baroplasticity, and dodecanol, a PnPMA-selective solvent. We found that the addition of a selective solvent is simple, but very effective to obtain various microdomains including hexagonally packed cylinders and gyroids. Also, with increasing temperature, the mixtures showed multiple ordered-to-ordered transitions (OOTs) in addition to upper ordered-to-disordered transition (UODT). The first observation of gyroid microdomains in PS-b-PnPMA is very important, although they have been widely reported in many block copolymers, for instance, PS-block-polyisoprene copolymer (PS-b-PI) and PS-block-poly(d,l-lactide) copolymer (PS-b-PLA). Since the gyroid microdomains of PS-b-PnPMA show excellent baroplasticity, external pressure instead of temperature could easily change the microdomains.     

Vesicle formation of polystyrene-block-poly (ethylene oxide) block copolymers induced by supercritical CO2 treatment

A novel route for a preparation of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) block copolymer vesicles induced by supercritical carbon dioxide (scCO₂) is demonstrated. When PS-b-PEO block copolymer solutions in tetrahydrofuran (THF) are treated with scCO₂ at 70 °C for different times, PS-b-PEO copolymers first assemble into aggregated spheres; then aggregated spheres change into large compound micelles and finally evolve into vesicles. The possible formation mechanism of the vesicles is discussed.     

Control over the surface plasmon band of block copolymer/Ag/Au nanoparticles composites by the addition of single walled carbon nanotubes

In this study, we demonstrate control over the localized surface plasmon band (SPB) of a micellar poly(styrene-block-4vinylpyridine) (PS-b-P4VP) copolymer thin film composite that includes Ag and Au nanoparticles (NPs) in the presence of single walled carbon nanotubes (SWCNTs). Ag and Au NPs are preferentially located in the P4VP core and the PS corona of ordered spherical PS-b-P4VP copolymer micelles, respectively. This structure gave rise to a single SPB due to the coupling of Ag and Au SPBs. The non-covalent addition of SWCNTs in the block copolymer micelles shifts the coupled SPB to a lower wavelength. The maximum shift in the coupled SPB of approximately 30 nm was achieved in the PS-b-P4VP/Ag/Au NPs composite. The carbon nanotube induced modulation of the coupled SPB stems from the charge accumulation effect of the SWCNTs placed between the two types of nanoparticles.     

Reversible morphology control of three-dimensional block copolymer nanostructures by the solvent-annealing-induced wetting in anodic aluminum oxide templates

In this work, the authors study the fabrication of three-dimensional block copolymer nanostructures in which the morphologies can be reversibly controlled. Polystyrene-block-polydimethylsiloxane (PS-b-PDMS), a promising candidate for nanolithography, is introduced into cylindrical nanopores of anodic aluminum oxide (AAO) templates using a solvent annealing–induced nanowetting in templates (SAINT) method. Not only the morphologies of the infiltrated PS-b-PDMS nanostructures can be tuned by the annealing solvents, but also the solvent-vapor-controlled morphologies can be altered reversibly by annealing the samples repeatedly between different solvent vapors.     

Preparation of nanoporous films from self-assembled poly(vinyl chloride-g-methyl methacrylate) graft copolymer

We report on the preparation of nanoporous films based on an amphiphilic graft copolymer of poly(vinyl chloride-graft-methyl methacrylate), i.e., PVC-g-PMMA. The PVC-g-PMMA graft copolymer was synthesized via atom transfer radical polymerization (ATRP), as confirmed by nuclear magnetic resonance spectroscopy (¹H NMR), Fourier transform-infrared (FT-IR) spectroscopy, and gel permeation chromatography (GPC) analysis. The PVC-g-PMMA graft copolymer molecularly self-assembled into nanophase domains of PVC main chains and PMMA side chains, as revealed by wide angle X-ray scattering (WAXS) and transmission electron microscopy (TEM). The graft copolymer film prepared from tetrahydrofuran (THF), a good solvent for both chains, had a random microphase-separated morphology. However, when prepared from dimethyl sulfoxide (DMSO), a solvent selectively good for PVC, the film exhibited a micellar morphology consisting of a PMMA core and a PVC corona. Nanoporous films with different pore sizes and shapes were prepared through the selective etching of PMMA chains using a combined process of UV irradiation and acetic acid treatment.     

Surface morphology evolution of poly(styrene-block-4-vinylpyridine) (PS-b-P4VP)(H) and poly(methyl methacrylate)-dibenzo-18-crown-6-poly(methyl methacrylate) (PMCMA) supramolecular film

Well-ordered nanostructured polymeric supramolecular thin films were fabricated from the supramolecular assembly of poly(styrene-block-4-vinylpyridine) (PS-b-P4VP)(H⁺) and poly(methyl methacrylate)-dibenzo-18-crown-6-poly(methyl methacrylate) (PMCMA). A depression of cylindrical nanodomains was formed by the block of P4VP(H⁺) and PMCMA associates surrounded by PS. The repulsive force aroused from the incompatibility between the block of P4VP(H⁺) and PMCMA was varied through changing the molecule weight (M_w) of PMCMA, the volume fraction of the block of P4VP(H⁺), and annealing the film at high temperature. Increasing the repulsive force led to a change of overall morphology from ordered nanoporous to featureless structures. The effects of solvent nature and evaporation rate on the film morphology were also investigated. Further evolution of surface morphologies from nanoporous to featureless to nanoporous structures was observed upon exposure to carbon bisulfide vapors for different treatment periods. The wettability of the film surface was changed from hydrophilicity to hydrophobicity due to the changes of the film surface microscopic composition.     

Deposition of silver nanoparticles on single wall carbon nanotubes via a self assembled block copolymer micelles

We demonstrate a facile route to decorate the surface of networked single walled carbon nanotubes (SWNTs) with silver nanoparticles (Ag NPs). The method is based on utilization of either spherical poly(styrene-b-4vinylpyridine) (PS-b-P4VP) or cylindrical poly(styrene-b-acrylic acid) (PS-b-PAA) copolymer micelles capable of stabilizing nanotubes in solution and subsequently forming a thin and uniform block copolymer/SWNTs composite film upon spin coating. The selective doping of silver acetate into either P4VP or PAA domains in a thin composite film, followed by thermal treatment, results in the formation of Ag NPs in the cores of micelles. Further heat treatment at 500 °C sufficiently high for degrading both block copolymers allows us to fabricate a thin SWNTs network in which Ag NPs are efficiently deposited on the surface of nanotubes. A sharp surface plasmon absorption band around 400 nm of the networked SWNTs with Ag NPs confirms the presence of Ag NPs with narrow distribution in their size.     

Fabrication of versatile nanoporous templates with high aspect ratios by incorporation of Si-containing block copolymer into the lithographic bilayer system

We report a new approach to fabricate versatile nanoporous templates with high aspect ratios by incorporating silicon-containing block copolymers into the lithographic bilayer system. This approach used a top thin film of self-assembled asymmetric polystyrene-block-poly(4-(tert-butyldimethylsilyl)oxystyrene) (PS-b-PSSi) as a hard etch mask and an underlying thick film of a negative-tone photoresist (SU-8) for pattern transfer. The assembly of PS-b-PSSi was well-controlled by solvent annealing on the SU-8 and deep nanopores were formed in the underlying layer by oxygen reactive ion etching due to high etch contrast. As a result, highly dense and uniform nanoporous templates with high aspect ratios were obtained over a large area. These templates have versatilities to easily control the sizes of nanopores and to make on the diverse functional substrates. Moreover, the dry-etch process during removal of nanotemplates prevented collapse and aggregation of nanostructures. As a demonstration, we fabricated vertically ordered freestanding gold nanorod arrays by using these templates.     

TEM characterization of diblock copolymer templated iron oxide nanoparticles: Bulk solution and thin film surface doping approach

The morphology of a novel diblock copolymer, poly(norbornene methanol)-b-poly(norbornene dicarboxylic acid), was investigated before and after metal oxide doping by transmission electron microscopy (TEM) using a novel iodine vapor staining method to image the undoped polymer. A lamellar morphology was observed by TEM after staining the undoped diblock copolymer with iodine vapor. Thin film surface doping resulted in a confinement of the iron oxide nanoparticles within the lamellar domains. Spherical nanoparticle aggregates were observed through a bulk solution doping method. It was observed that the particles were templated by the underlying lamellar structure of the copolymer when the thin film surface doping method was used.     

Morphology of poly(styrene‐block‐dimethylsiloxane) copolymer films

The morphologies of poly(styrene‐block‐di‐methylsiloxane) (PS‐b‐PDMS) copolymer thin films were analyzed via atomic force microscopy and transition electron microscopy (TEM). The asymmetric copolymer thin films spin‐cast from toluene onto mica presented meshlike structures, which were different from the spherical structures from TEM measurements. The annealing temperature affected the surface morphology of the PS‐b‐PDMS copolymer thin films; the polydimethylsiloxane (PDMS) phases at the surface were increased when the annealing temperature was higher than the PDMS glass‐transition temperature. The morphologies of the PS‐b‐PDMS copolymer thin films were different from solvent to solvent; for thin films spin‐cast from toluene, the polystyrene (PS) phase appeared as pits in the PDMS matrix, whereas the thin films spin‐cast from cyclohexane solutions exhibited an islandlike structure and small, separated PS phases as protrusions over the macroscopically flat surface. The microphase structure of the PS‐b‐PDMS copolymer thin films was also strongly influenced by the different substrates; for an asymmetric block copolymer thin film, the PDMS and PS phases on a silicon substrate presented a lamellar structure parallel to the surface at intervals. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1010–1018, 2007     

Solvent annealing thin films of poly(isoprene-b-lactide)

The use of solvent annealing to control the microdomain orientation and long-range ordering in poly(isoprene-b-d,l-lactide) thin films was investigated using scanning force microscopy and grazing incidence small angle X-ray scattering (GISAXS). Benzene and chloroform were used as annealing solvents. Both were found to improve the long-range order in the films. Additionally, at high concentrations of chloroform in the film, a perpendicular orientation of cylinders was observed where the solvent was able to mediate interfacial interactions sufficiently to prevent a preferential segregation of one of the blocks to the surface. In situ GISAXS measurements made during solvent swelling and evaporation allowed an examination of the film morphology over a wide range of solvent concentrations providing a efficient route to optimize conditions for morphology control by solvent annealing.