Micellar Thin Films Research Articles

Stratification and film ripping induced by structural forces in granular micellar thin films

HypothesisInteractions across incredibly thin layers of fluids, known as thin films, underpin many important processes involving colloids, such as wetting-dewetting phenomena. Often in these systems, thin films are composed of complex fluids that contain dispersed components, such as spherical micelles, giving rise to oscillatory structural forces due to preferential layering under confinement. Modelling of thin film dynamics involving Derjaguin-Landau-Verwey-Overbeek (DLVO) type forces has been widely reported using the Stokes-Reynolds-Young-Laplace (SRYL) model, and we hypothesize that this theory can be extended to a concentrated micellar system by including an oscillatory structural force term in the disjoining pressure. ExperimentsWe study the drainage behaviour of thin films comprising sodium dodecyl sulfate (SDS) micelles across a range of concentrations and interaction conditions between an air bubble and a mica disk using a custom-built dual-wave interferometry apparatus. FindingsEarly-stage film behaviour is dominated by hydrodynamics, which can be well reproduced by the SRYL model. However, experimental profiles drain significantly faster than predicted, transitioning into a structural force dominated phase characterised by four types of film ripping instabilities that we term ‘waving’, ‘ridging’, ‘webbing’, and ‘hole-sheeting’. These instabilities were mapped according to SDS concentration and approach velocity, providing insight into the interplay between structural forces and hydrodynamic conditions.

Observation of ordered microphase separation of block copolymer micellar thin films under argon-plasma radiation

Block Copolymer (BCP) self-assembly has shown promise as a next generation nanolithography technology as their phase separation at a nanometre scale can overcome the limitations of conventional lithography. Here, we report on using an alternative method to conventional thermal and solvent annealing by exposing as-cast micellar polystyrene-b-poly(ethylene oxide) (PS-b-PEO) thin film to a mild argon plasma. Resulting films show controllable perpendicular and parallel (to the surface plane) orientations of a hexagonal phase forming PEO, depending on the morphology of the initial micelle shape. The ability to define orientation is a critical advantage because complex solvent or substrate control is usually needed. This method is a fast process, that could help to reduce thermo-solvent annealing time (hours) to few seconds, while allowing phase separation on large and industrial substrates. Further, etching is also realized during the plasma exposure. We discuss the balance between the energy input of the argon plasma leading to large-scale surface reorganisation, and the possible damage of the surface due to cross-linking and/or etching.

Tailoring block copolymer nanoporous thin films with acetic acid as a small guest molecule

AbstractBlock copolymers offer the fabrication of mesoporous thin films with distinct nanoscale structural features. In this contribution, we present the use of acetic acid (CH3COOH) as a low‐molecular‐weight guest molecule to tune the supramolecular assembly of poly[styrene‐block‐(4‐vinylpyridine)] (PS‐b‐P4VP), offering a versatile and straightforward method to obtain tailored nanostructured films with controlled topography and pore size. Spin‐coating toluene solutions of PS‐b‐P4VP, with a variable amount of CH3COOH, leads to micellar thin films, where the micelles contain the carboxylic acid as a guest molecule. The size can be conveniently modified in these films (from 48 to 75 nm) by varying the amount of organic acid in the starting solutions. Subsequent surface reconstruction of micellar films using ethanol leads to ring‐shaped copolymer nanoporous films with modulated diameter. Controlling the micelle reconstruction process, cylindrical porous films are also obtained. Interestingly, changing the type of aliphatic carboxylic acid leads to a modification of the observed film morphology from micelles to out‐of‐plane P4VP cylinders (or lamellae) in a PS matrix. © 2019 Society of Chemical Industry

Manipulating and monitoring nanoparticles in micellar thin film superstructures

Understanding the dynamics of discrete self-assembled structures under influence of external triggers is of interest to harvest the potential of nano- and mesoscale materials. In particular, controlling the hierarchical organization of (macro)molecular and nanoparticle building blocks in monolayer superstructures is of paramount importance for tuning properties and characteristics. Here we show how the electron beam in cryo-transmission electron microscopy can be exploited to induce and follow local migration of building blocks and global migration of micellar aggregates inside micrometer-sized superstructures. We employ stroboscopic exposure to heat up and convert the vitrified superstructure into a liquid-like thin film under cryogenic conditions, resulting in controlled evaporation of water that finally leads to rupture of the micelle-containing superstructure. Micelle-embedded nanoparticles prove a powerful tool to study the complex hierarchically built-up superstructures, and to visualize both global movement of individual dendrimicelles and local migration of nanoparticles inside the micellar core during the exposure series.

Structured nanoporous surfaces from hybrid block copolymer micelle films with metal ions

We present a novel method for producing structured nanoporous thin films using block copolymer (BCP) micelles loaded with metallic ions. The BCP micellar thin films containing gold (Au) ions were prepared by spin-coating poly(styrene-block-4-vinylpyridine) (PS-b-P4VP) micelle solutions in which Au precursors (AuCl4−) were selectively loaded onto the P4VP core. When the micellar films were exposed to cetyltrimethylammonium bromide (CTAB) solutions, the Au precursors were selectively extracted from the P4VP domains due to their strong electrostatic interaction with CTAB, leading to the formation of pores in the micelles. Consequently, regularly patterned nanoporous surfaces were formed. By controlling the molecular weight (Mn) of PS-b-P4VP and the amount of Au precursors (λ) that were loaded in the P4VP domains, the pore size and depth could be tuned precisely. In particular, when a sufficient amount of Au precursors was loaded (λ ≥ 0.3), the porous surface nanostructure was well developed. In addition, the pore size and depth of the nanostructure increased as the λ value increased. For instance, when the λ value increased from 0.3 to 1.0, the pore size increased from 22.8 nm to 28.8 nm, and the pore depth increased from 2.1 nm to 3.2 nm. Interestingly, the transition from the nonporous structures to the porous structures in the micellar film could be reversibly controlled by adding and removing the Au precursors in the film. Moreover, our method for the preparation of nanoporous films can be extended to micellar film by incorporating other metal ions such as silver (Ag) and iron (Fe).

Crystal growth of gold nanoparticles through annealing induced phase transition of semifluorinated block copolymer micellar films

The preparation of gold nanoparticles incorporated in self-assembled and ordered semifluorinated poly(ethylene oxide)-b-poly(1H,1H-dihydroperfluorooctyl methacrylate) (PEO-b-PFOMA) thin films was explored through annealing induced phase transition. The micellar thin films containing gold nanoparticles whose average size was dependent on the block length of the copolymer were produced by spin casting the solution of PEO10k-b-PFOMA12k and PEO20k-b-PFOMA22k in chloroform with a gold precursor, LiAuCl4. Three annealing modes were attempted for the Au-loaded micellar films: solvent vapor annealing, supercritical CO2 at 70°C and thermal annealing at 100°C. The nanoparticles dispersed in PEO regions were forced to follow the morphological change of the PEO phase and grew into larger single particles in PEO domains. The solvent annealing produced higher ordering of Au nanoparticles than scCO2 or thermal annealing.

Nanodomain Development of Semifluorinated Diblock Copolymeric Thin Films via Solvent Vapor Annealing

The effect of solvent vapor annealing on the morphological change of poly(ethylene oxide)-b-poly(1H,1H dihydrofluorooctyl methacrylate) (PEO-b-PFOMA) micellar thin films has been studied. The time development of the nanodomain structure in PEO(5k)-b-PFOMA(10k) thin films was investigated with the vapor treatment of perfluoroalkanes. The block copolymeric thin film was initially cast from chloroform which is a good solvent for PEO. The as-cast film which has disordered morphology can be changed to ordered cylindrical morphology and at last to highly ordered morphology consisting of PEO spherical domains and PFOMA continuous phase by varying the annealing time.

Synthesis and Properties of Diblock Copolymers Containing Poly(3-Hexylthiophene) and Poly(Fluorooctyl Methacrylate)

This study reports the synthesis of regioregular poly(3-hexylthiophene)-b-poly(1H,1H-dihydro perfluorooctyl methacrylate) (P3HT-b-PFOMA) block copolymers by atom transfer radical polymerization of FOMA using P3HT macroinitiators. The P3HT macroinitiator was previously prepared by chemical modification of hydroxy terminated P3HT The block copolymers were characterized by 1H-NMR, 13C-NMR, GPC, DSC, TGA and TEM. The block copolymers are able to self-assemble into phase separated micellar thin film morphology from chloroform.

Fabrication of gold dot, ring, and corpuscle arrays from block copolymer templates via a simple modification of surface energy

We demonstrate a simple method for tuning the morphologies of as-spun micellar thin films by modifying the surface energy of silicon substrates. When a polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) copolymer dissolved in o-xylene was spin-coated onto a PS-modified surface, a dimple-type structure consisting of a thick PS shell and P2VP core was obtained. Subsequently, when the films were immersed in metal precursor solutions at certain periods of time and followed by plasma treatment, metal individual dots in a ring-shaped structure, metal nanoring, and metal corpuscle arrays were fabricated, depending on the loading amount of metal precursors. In contrast, when PS-b-P2VP films cast onto silicon substrates with a native oxide were used as templates, only metal dotted arrays were obtained. The combination of micellar thin film and surface energy modification offers an effective way to fabricate various nanostructured metal or metal oxide films.

Fabrication of Poly(FOMA-b-EO)/Silver Nanocomposite Hybrid Films

A facile synthesis of silver nanoparticles (with a diameter of 5 nm)/polymer hybrid films was studied through auto-reduction of silver nitrate (AgNO3) in poly(1H,1H-dihydroperfluorooctyl methacrylate-b-ethylene oxide) (poly(FOMA(10k)-b-EO(10k micellar thin films at ambient temperature. Silver nanoparticles well dispersed in the block copolymeric micellar films were prepared by rendering the silver precursor AgNO3 to interact favorably with PEO blocks. With annealing of the micellar film containing AgNO3 in supercritical CO2, the domains and continuous phase of the micellar film morphology were inverted and silver nanoparticles with a diameter of 10 nm were produced in PEO domains. The synthesis of silver nanoparticles in the copolymeric films was confirmed by transmission electron microscope and UV-visible spectrophotometric analysis.

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.

Dynamic spreading of droplets containing nanoparticles

Recent experiments and models for the spreading of liquids laden with nanoparticles have demonstrated particle layering at the three-phase contact line; this is associated with the structural component of the disjoining pressure. Effects driven by structural disjoining pressures occur on scales longer than the diameter of a particle, below which other disjoining pressure components such as van der Waals and electrostatic forces are dominant. Motivated by these experimental observations, we investigate the dynamic spreading of a droplet laden with nanoparticles in the presence of structural disjoining pressure effects. We use lubrication theory to derive evolution equations for the interfacial location and the concentration of particles. These equations account for the presence of the structural component of the disjoining pressure for film thicknesses exceeding the diameter of a nanoparticle; below such thicknesses, van der Waals forces are assumed to be operative. The resulting evolution equations, for the particle motion and free surface position, are solved allowing for the viscosity to vary as a function of nanoparticle concentration. The results of our numerical simulations demonstrate qualitative agreement with experimental observations of a "step" emerging from the contact line. The results are also relevant to a wide range of other phenomena involving layering, or terraced spreading of nanodroplets, or stepwise thinning of micellar thin films.

Controlling the Morphology of Carbon Nanotube Films by Varying the Areal Density of Catalyst Nanoclusters Using Block‐Copolymer Micellar Thin Films

In spite of much research progress in the science and synthesis of carbon nanotubes (CNTs), control over the location and orientation of CNTs on substrates remains a major challenge. A key breakthrough was the synthesis of vertically aligned CNT (VA-CNT) arrays using thermal chemical vapor deposition (CVD) and plasma-enhanced CVD, where the CNTs self-orient perpendicular to the substrate surface due to initial crowding and continue to grow upward in this direction. These CNT arrays have wide-ranging applications, including membranes, heat dissipation, electrical interconnects, and nanoelectronics. The catalysts for synthesis of VACNTs are commonly prepared by sputtering or evaporating a thin metal film onto a substrate, which dewets to form catalyst nanoparticles at an elevated temperature prior to growth. While these catalysts are easily prepared and patterned by shadow masking or lithography, these approaches are not easily able to create nanocluster catalysts that have monodisperse diameters and quantifiable areal densities. In thin metal films, both the nanocluster size and areal density are coupled to the film thickness, and the annealing procedure affects the size, density, and the chemical state of the nanoclusters. Recently, Huh et al. demonstrated a route for controlling the density of CNT growth using varying densities of colloidal cobalt nanoparticles; however, due to nanoparticle coalescence their route does not enable precise quantification of nanocluster areal density and leads to a broad distribution of CNT diameters. Zhang et al. also recently demonstrated the control of CNT growth by varying the density of Co–Mo nanoparticles, although their route is unable to independently vary the diameter and the areal density of nanoparticles. We employ a methodology for synthesizing iron oxide nanoclusters that utilizes micelles formed by the amphiphilic block copolymer, polystyrene-b-poly(acrylic acid) (PS-bPAA). This catalyst system has significant value because it enables the creation of nanocluster arrays of a chosen metal species, with independent control of the nanocluster diameter and areal density. In previous work, nanocluster diameters were varied between 5 and 16 nm and the areal density was varied from 6.0 × 10 to 1 × 10 cm, although variation outside of these ranges is easily accessible. At higher areal densities the nanoclusters are hexagonally ordered. Further, as we have presented separately, the nanocluster arrays can be patterned on the micrometer length scale using microcontact printing. Here, we utilize this system to create arrays of uniform-diameter iron oxide nanoclusters, with quantifiable areal densities that can be varied over more than an order of magnitude. We achieve vertical CNT growth from our catalyst system through appropriate selection of the substrate, catalyst preparation procedure, and reaction conditions. To the best of our knowledge, our work is the first example of vertical growth of CNTs from a block-copolymer-based catalyst. Because this catalyst system allows for precise quantification of the nanocluster areal density, we can estimate the percentage of nanoclusters that nucleate the growth of a CNT. By uniformly varying the areal density of iron oxide nanoclusters on the substrate surface, we manipulate the morphology of the CNT film from a tangled and sparse arrangement of individual CNTs, through a transition region with locally bunched and self-aligned CNTs, to rapid growth of thick vertical CNT films. The procedure for synthesizing the iron oxide nanocluster arrays utilized spherical micelles formed by PS-b-PAA in toluene, which were loaded with FeCl3, and then spin-cast onto a substrate (see Experimental Section). The polymer thin film was then treated in oxygen plasma to remove the organic components, leaving an iron oxide nanocluster array, as shown in Figure 1A. Previous studies have demonstrated that the iron oxide nanocluster structure is Fe2O3. [22,25] The molecular weight and metal-loading ratios of Figure 1A led to iron oxide nanocluster arrays with diameters of 16 ± 1.6 nm that were arranged in a quasihexagonal array with an areal density of 6.0 × 10 cm. The root-mean-square roughness of the nanocluster arrays was 2.2 nm, as determined from using atomic force microscopy (AFM). C O M M U N IC A TI O N S

Creating Patterned Carbon Nanotube Catalysts through the Microcontact Printing of Block Copolymer Micellar Thin Films

We report a route for synthesizing patterned carbon nanotube (CNT) catalysts through the microcontact printing of iron-loaded poly(styrene-block-acrylic acid) (PS-b-PAA) micellar solutions onto silicon wafers coated with thin aluminum oxide (Al(2)O(3)) layers. The amphiphilic block copolymer, PS-b-PAA, forms spherical micelles in toluene that can form quasi-hexagonal arrays of spherical PAA domains within a PS matrix when deposited onto a substrate. In this report, we dip a poly(dimethylsiloxane) (PDMS) molded stamp into an iron-loaded micellar solution to create a thin film on the PDMS features. The PDMS stamp is then put in contact with a substrate, and uniaxial compressive stress is applied to transfer the micellar thin film from the PDMS stamp onto the substrate in a defined pattern. The polymer is then removed by oxygen plasma etching to leave a patterned iron oxide nanocluster array on the substrate. Using these catalysts, we achieve patterned vertical growth of multiwalled CNTs, where the CNTs maintain the fidelity of the patterned catalyst, forming high-aspect-ratio standing structures.

One-Step Route to the Fabrication of Highly Porous Polyaniline Nanofiber Films by Using PS-b-PVP Diblock Copolymers as Templates

We report a new method to control both the nucleation and growth of highly porous polyaniline (PANI) nanofiber films using porous poly(styrene-block-2-vinylpyridine) diblock copolymer (PS-b-P2VP) films as templates. A micellar thin film composed of P2VP spheres within a PS matrix is prepared by spin coating a PS-b-P2VP micellar solution onto substrates. The P2VP domains are swollen in a selective solvent of acetic acid, which results in the formation of pores in the block copolymer film. PANI is then deposited onto the substrates modified with such a porous film using electrochemical methods. During the deposition, the nucleation and growth of PANI occur only at the pores of the block copolymer film. After the continued growth of PANI by the electrochemical deposition, a porous PANI nanofiber film is obtained.

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.

Using Block Copolymer Micellar Thin Films as Templates for the Production of Catalysts for Carbon Nanotube Growth

We report a novel approach that uses block copolymer micelles as a means to create large area arrays of iron-containing nanoclusters capable of catalyzing the growth of carbon nanotubes (CNTs). The amphiphilic block copolymer poly(styrene-block-acrylic acid) (PS-b-PAA) forms micelles in solution which are capable of self-organizing into ordered structures on surfaces. By spin-coating these solutions onto a variety of substrates, we can create quasi-hexagonal arrays of PAA spheres within a PS matrix. The carboxylic acids groups in the PAA domains can be utilized in an ion-exchange protocol to selectively sequester iron ions, which results in iron-containing nanoclusters that are nearly monodisperse in size (diameter ∼8 nm) and patterned at a density of approximately 1011 particles per cm2. In principle, this route for synthesizing iron-containing nanoclusters offers the capability of controlling the cluster size and spacing by altering the molecular weight of the block copolymer. In this report, we demonst...

Cavitated Block Copolymer Micellar Thin Films: Lateral Arrays of Open Nanoreactors

We report the formation of novel self-assembled ultrathin (ca. 20 nm) films comprising in-plane arrays of nanoscale surface cavities. The original micellar thin films, formed by casting kinetically stable reverse micelles from a solution of a styrene (PS)−acrylic acid (PAA) diblock copolymer in toluene onto silicon nitride substrates, consist of lateral hexagonal arrays of spherical PAA microdomains in PS matrix. Upon aqueous treatment to load metal ions into the PAA domains, cavitation of the individual PAA micelle cores occurs, leading to the formation of cavities in the center of the micelles and exposing the PAA domains to the film's surface. Experimental evidence reveals that cavitation takes place as a result of hydration and swelling of the PAA micelle cores during sample treatment in an alkaline solution. The use of these cavitated, metal-loaded PAA domains as arrays of open nanoreactors for inorganic nanocluster synthesis is demonstrated.