Diblock Copolymer Thin Films Research Articles

Cyclic Water Storage Behavior of Doubly Thermoresponsive Poly(sulfobetaine)-Based Diblock Copolymer Thin Films

The cyclic swelling and collapse behavior of a doubly thermoresponsive diblock copolymer thin film, consisting of a zwitterionic poly(sulfobetaine), poly(N,N-dimethyl-N-(3-methacrylamidopropyl)-amm...

Kinetic Pathways of Block Copolymer Directed Self-Assembly: Insights from Efficient Continuum Modeling.

We introduce a computationally efficient continuum technique to simulate the complex kinetic pathways of block copolymer self-assembly. Subdiffusive chain dynamics is taken into account via nonlocal Onsager coefficients. An application to directed self-assembly of thin films of diblock copolymers on patterned substrates reveals the conditions under which experimentally observed metastable structures intervene in the desired thin-film morphology. The approach generalizes easily to multiblock copolymers and more complex guiding patterns on the substrate, and its efficiency allows for the systematic optimization of guiding patterns and process conditions.

Solvent Vapor Annealing of a Diblock Copolymer Thin Film with a Nonselective and a Selective Solvent: Importance of Pathway for the Morphological Changes.

Diblock copolymer thin films of polystyrene-block-poly(dimethyl siloxane) (PS-b-PDMS) featuring PDMS cylinders in a PS matrix are investigated during solvent vapor annealing with mixtures of n-heptane (which is strongly selective for PDMS) and toluene (which is close to nonselective for both blocks). Swelling in the vapor of one of the pure solvents and exchanging it stepwise by the vapor of the other solvent is compared to swelling in a given binary solvent vapor mixture for a prolonged time. The resulting structural changes, such as ordering of the cylinders on a hexagonal lattice and their transition into lamellae, are followed using in situ, real-time grazing-incidence small-angle X-ray scattering (GISAXS). In three runs, the sequence of solvent vapor swelling and vapor exchange is varied. Compiling the resulting morphologies in a diagram of states in dependence on the solvent content in the film and in the minority nanodomains allows insight into the role of the glass transition of the PS matrix for the ordering processes and their time scales. Based on these findings, a protocol is suggested to efficiently obtain an order-to-order transition from the cylindrical morphology with random domain orientation to the oriented lamellar state.

Phase Transition Kinetics of Doubly Thermoresponsive Poly(sulfobetaine)-Based Diblock Copolymer Thin Films

The swelling and phase transition behavior upon increasing temperature of a doubly thermoresponsive diblock copolymer thin film in steps above the characteristic cloud points (CPs) of the blocks is...

Directed Self-Assembly in Diblock Copolymer Thin Films for Uniform Hemisphere Pattern Formation

Directed self-assembly of block copolymers has shown to be an effective bottom-up approach to creating periodic nanoscale surface patterns. This work offers a computational study of sphere-forming ...

Self-Assembly in ultrahigh molecular weight sphere-forming diblock copolymer thin films under strong confinement

Ultrahigh molecular weight (UHMW) diblock copolymers (DBCs) have emerged as a promising template for fabricating large-sized nanostructures. Therefore, it is of high significance to systematically study the influence of film thickness and solvent vapor annealing (SVA) on the structure evolution of UHMW DBC thin films. In this work, spin coating of an asymmetric linear UHMW polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) DBC is used to fabricate thin films, which are spherically structured with an inter-domain distance larger than 150 nm. To enhance the polymer chain mobility and facilitate approaching equilibrium nanostructures, SVA is utilized as a post-treatment of the spin coated films. With increasing film thickness, a local hexagonal packing of PMMA half-spheres on the surface can be obtained, and the order is improved at larger thickness, as determined by grazing incidence small angle X-ray scattering (GISAXS). Additionally, the films with locally hexagonal packed half-spherical morphology show a poor order-order-poor order transition upon SVA, indicating the realization of ordered structure using suitable SVA parameters.

Defect Removal by Solvent Vapor Annealing in Thin Films of Lamellar Diblock Copolymers

Solvent vapor annealing (SVA) is known to be a simple, low-cost and highly efficient technique to produce defect-free diblock copolymer (BCP) thin films. Not only can the solvent weaken the BCP segmental interactions, but it can vary the characteristic spacing of the BCP microstructures. We carry out systematic theoretical studies on the effect of adding solvent into lamellar BCP thin films on the defect removal close to the BCP order-disorder transition. We find that the increase of the lamellar spacing, as is induced by addition of solvent, facilitates more efficient removal of defects. The stability of a particular defect in a lamellar BCP thin film is given in terms of two key controllable parameters: the amount of BCP swelling and solvent evaporation rate. Our results highlight the SVA mechanism for obtaining defect-free BCP thin films, as is highly desired in nanolithography and other industrial applications.

Correlating Nanostructure, Optical and Electronic Properties of Nanogranular Silver Layers during Polymer-Template-Assisted Sputter Deposition.

Tailoring the optical and electronic properties of nanostructured polymer-metal composites demonstrates great potential for efficient fabrication of modern organic optical and electronic devices such as flexible sensors, transistors, diodes, or photovoltaics. Self-assembled polymer-metal nanocomposites offer an excellent perspective for creating hierarchical nanostructures on macroscopic scales by simple bottom-up processes. We investigate the growth processes of nanogranular silver (Ag) layers on diblock copolymer thin film templates during sputter deposition. The Ag growth is strongly driven by self-assembly and selective wetting on the lamella structure of polystyrene-block-poly(methyl methacrylate). We correlate the emerging nanoscale morphologies with collective optical and electronic properties and quantify the difference in Ag growth on the corresponding homopolymer thin films. Thus, we are able to determine the influence of the respective polymer template and observe substrate effects on the Ag cluster percolation threshold, which affects the insulator-to-metal transition (IMT). Optical spectroscopy in the UV-vis regime reveals localized surface plasmon resonance for the metal-polymer composite. Their maximum absorption is observed around the IMT due to the subsequent long-range electron conduction in percolated nanogranular Ag layers. Using X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy, we identify the oxidation of Ag at the acrylate side chains as an essential influencing factor driving the selective wetting behavior in the early growth stages. The results of polymer-templated cluster growth are corroborated by atomic force microscopy and field emission scanning electron microscopy.

Shear-solvo defect annihilation of diblock copolymer thin films over a large area.

Achieving defect-free block copolymer (BCP) nanopatterns with a long-ranged orientation over a large area remains a persistent challenge, impeding the successful and widespread application of BCP self-assembly. Here, we demonstrate a new experimental strategy for defect annihilation while conserving structural order and enhancing uniformity of nanopatterns. Sequential shear alignment and solvent vapor annealing generate perfectly aligned nanopatterns with a low defect density over centimeter-scale areas, outperforming previous single or sequential combinations of annealing. The enhanced order quality and pattern uniformity were characterized in unprecedented detail via scattering analysis and incorporating new mathematical indices using elaborate image processing algorithms. In addition, using an advanced sampling method combined with a coarse-grained molecular simulation, we found that domain swelling is the driving force for enhanced defect annihilation. The superior quality of large-scale nanopatterns was further confirmed with diffraction and optical properties after metallized patterns, suggesting strong potential for application in optoelectrical devices.

Printed Thin Diblock Copolymer Films with Dense Magnetic Nanostructure

Thin hybrid films with dense magnetic structures for sensor applications are printed using diblock copolymer (DBC) templating magnetic nanoparticles (MNPs). To achieve a high-density magnetic structure, the printing ink is prepared by mixing polystyrene- block-poly(methyl methacrylate) (PS- b-PMMA) with a large PS volume fraction and PS selective MNPs. Solvent vapor annealing is applied to generate a parallel cylindrical film morphology (with respect to the substrate), in which the MNP-residing PS domains are well separated by the PMMA matrix, and thus, the formation of large MNP agglomerates is avoided. Moreover, the morphologies of the printed thin films are determined as a function of the MNP concentration with real and reciprocal space characterization techniques. The PS domains are found to be saturated with MNPs at 1 wt %, at which the structural order of the hybrid films reaches a maximum within the studied range of MNP concentration. As a beneficial aspect, the MNP loading improves the morphological order of the thin DBC films. The dense magnetic structure endows the thin films with a faster superparamagnetic responsive behavior, as compared to thick films where identical MNPs are used, but dispersed inside the minority domains of the DBC.

Self-Assembly Investigations of Sulfonated Poly(methyl methacrylate-block-styrene) Diblock Copolymer Thin Films

Poly(methyl methacrylate-block-styrene) block copolymers (BCs) of low dispersity were selectively sulfonated on the styrenic segment. Several combinations of degree of polymerization and volume fraction of each block were investigated to access different self-assembled morphologies. Thin films of the sulfonated block copolymers were prepared by spin-coating and exposed to solvent vapor (SVA) or thermal annealing (TA) to reach equilibrium morphologies. Atomic force microscopy (AFM) was employed for characterizing the films, which exhibited a variety of nanometric equilibrium and nonequilibrium morphologies. Highly sulfonated samples revealed the formation of a honeycomb-like morphology obtained in solution rather than by the self-assembly of the BC in the solid state. The described morphologies may be employed in applications such as templates for nanomanufacturing and as cover and binder of catalytic particles in fuel cells.

Orientation and Morphology Control of the Liquid Crystalline Block Copolymer Thin Film by Liquid Crystalline Solvent.

The critical challenge to engineer the morphological structures in the strongly phase-segregated block copolymer thin film is to overcome the preferential wetting of the blocks at the interface and direct the self-assembly process. Herein, we utilize surface activity and selective solvation of a nematic (N) liquid crystalline (LC) solvent, 5CB, to facilely alter the LC anchoring and the orientation of the nanophase separated structures of the smectic-nematic (S-N) LC block copolymer thin film. For the neat S-N diblock copolymer thin film, the nanostructures are parallel aligned. In contrast, with continuous introduction of 5CB into the system, the orientations of the characteristic nanostructures and the morphologies of the LC thin film can be consequently changed, yielding the perpendicularly oriented lamellar or cylindrical structures with the feature size below 10 nm. The homeotropic alignment of the 5CB nematics near the air interface plays a critical role to induce this unique behavior in the S-N/5CB systems, which offers an opportunity to fine-tune the interfacial structures and the morphological patterning in the block copolymer thin film.

Enhanced Corrugation and Chemical Contrast of Diblock Copolymer Films by Sequential Solvent Exposures

Planar cylinder polystyrene–block-poly(2-vinylpyridine) (PS–P2VP) diblock copolymer thin films, with no corrugation and a uniform PS surface, undergo major restructuring upon sequential solvent swelling, yielding 10 nm P2VP ridges separated by PS troughs. Oven-annealed thin films were exposed to P2VP selective solvents, with or without an intermediate tetrahydrofuran vapor treatment, and the resulting surface morphologies were characterized. Experiments indicate that tetrahydrofuran enhances the permeability of the PS matrix to the P2VP selective solvents, with the ultimate swelling topography dictated by the hydrocarbon chain length and pKa of the selective solvent. We show that the film swelling occurs in stages, with P2VP punching to the surface as puckered pillars that eventually link into ridges separated by PS troughs. The chemical duality of the surfaces allows the selective deposition of negatively charged gold nanoparticles on the P2VP ridges.

Nanoscale Resolution of Electric-field Induced Motion in Ionic Diblock Copolymer Thin Films.

Understanding the responses of ionic block copolymers to applied electric fields is crucial when targeting applications in areas such as energy storage, microelectronics, and transducers. This work shows that the identity of counterions in ionic diblock copolymers substantially affects their responses to electric fields, demonstrating the importance of ionic species for materials design. In situ neutron reflectometry measurements revealed that thin films containing imidazolium based cationic diblock copolymers, tetrafluoroborate counteranions led to film contraction under applied electric fields, while bromide counteranions drove expansion under similar field strengths. Coarse-grained molecular dynamics simulations were used to develop a fundamental understanding of these responses, uncovering a nonmonotonic trend in thickness change as a function of field strength. This behavior was attributed to elastic responses of microphase separated diblock copolymer chains resulting from variations in interfacial tension of polymer-polymer interfaces due to the redistribution of counteranions in the presence of electric fields.

Pattern formation mechanisms in sphere-forming diblock copolymer thin films

The order-disorder transition of a sphere-forming block copolymer thin film was numerically studied through a Cahn-Hilliard model. Simulations show that the fundamental mechanisms of pattern formation are spinodal decomposition and nucleation and growth. The range of validity of each relaxation process is controlled by the spinodal and order-disorder temperatures. The initial stages of spinodal decomposition are well approximated by a linear analysis of the evolution equation of the system. In the metastable region, the critical size for nucleation diverges upon approaching the order--disorder transition, and reduces to the size of a single domain as the spinodal is approached. Grain boundaries and topological defects inhibit the formation of superheated phases above the order--disorder temperature. The numerical results are in good qualitative agreement with experimental data on sphere-forming diblock copolymer thin films.
 Received: 22 August 2017, Accepted: 12 December 2017; Edited by: R. Dickman; Reviewed by: A. Peters, Dept. Chemical Engineering, Louisiana Tech Univ., Ruston, USA; DOI: http://dx.doi.org/10.4279/PIP.100001
 Cite as: L R Gómez, N A García, R A Register, D A Vega, Papers in Physics 10, 100001 (2018)
 This paper, by L R Gómez, N A García, R A Register, D A Vega, is licensed under the Creative Commons Attribution License 4.0.

Shear-induced parallel and transverse alignments of cylinders in thin films of diblock copolymers.

Coarse-grained Langevin dynamics simulations were performed to investigate the alignment behavior of monolayer films of cylinder-forming diblock copolymers under steady shear, a structure of significant importance for many technical applications such as nanopatterning. The influences of shear conditions, the interactions involved in the films, and the initial morphology of the cylinder-forming phase were examined. Our results showed that above a critical shear rate, the cylinders can align either along the shearing direction or transverse (log-rolling) to the shearing direction depending on the relative strength between the interchain attraction in the cylinders (εAA) and the surface attraction of the confining walls with the film (εBW). To understand the underlying mechanism, the microscopic properties of the films under shear were systematically investigated. It was found that at low εAA/εBW, the majority blocks of the diblock polymer that are adsorbed on the confining walls prefer to move synchronously with the walls, inducing the cylinder-forming blocks to align along the flow direction. When εAA/εBW is above a threshold value, a strong attraction between the cylinder-forming blocks restrains their movement during shear, leading to the log-rolling motions of the cylinders. To predict the threshold εAA/εBW, we developed an approach based on equilibrium thermodynamics data and found good agreement with our shear simulations.

Field-Theoretic Simulations of the Distribution of Nanorods in Diblock Copolymer Thin Films.

Using block copolymer microphases to guide the self-assembly of nanorods in thin films can give rise to polymeric materials with unique optical, thermal, and mechanical properties beyond those found in neat block copolymers. Often the design and manufacture of these materials require exquisite control of the nanorod distribution, which is experimentally challenging due to the large parameter space spanned by this class of materials. Simulation approaches, on the other hand, can access the thermodynamics that contribute to the nanorod distribution and hence offer valuable guidance toward the design and manufacture of the materials. In this work, we employ complex Langevin field-theoretic simulations to examine the thermodynamic forces that govern the assembly of nanorods in thin films of block copolymers with a particular focus on vertically oriented cylindrical and lamellar domains. Our simulations show that the nanorod geometry, the substrate selectivity for the distinct blocks of the copolymer, and the film thickness all play important roles in engineering both the nanorod orientation and spatial distribution in diblock copolymer thin films. In addition, we employ thermodynamic integration to examine how the nanorods alter the stability of vertical and horizontal domains in thin films, where we find that the tendency of the nanorods to stabilize a vertical orientation depends on both the film thickness and the nanorod concentration.

Vertical Orientation of Nanocylinders in Liquid-Crystalline Block Copolymers Directed by Light.

The microphase-separated nanostructures of block copolymers are ideal nanotemplates for advanced fabrication, but they are greatly limited by the rapid and precise manipulation especially at room temperature. Here we report one method of light-directed regulation of nanostructures in thin films of liquid-crystalline diblock copolymers containing azobenzene units as photoresponsive mesogens. The in-plane orientated nanocylinders in thin film can be light-directed into out-of-plane on a time scale of seconds at room temperature. This fast regulation is beneficial from the fast process of photoinduced phase transition of the mesogenic block from liquid crystal to disordered isotropic phase. Several influence factors like the molecular weight of polymer, film thickness, light intensity, and relative humidity were studied in the light-directed processes. In addition, the photoregulated nanostructures demonstrate their capability of being photopatterned and further used as nanotemplates for fabrication of nanoparticles. The light-directed method shows noncontact, precise, and reversible features, enabling it to find further applications in fast control of nanostructures for nanofabrication and nanoengineering.

Self-Assembly in Block Copolymer Thin Films upon Solvent Evaporation: A Simulation Study

The self-assembly in cylinder-forming diblock copolymer thin films upon solvent evaporation is studied by lattice Monte Carlo simulations under the assumption that the solvent evaporation starts from the free surface and gradually propagates toward the substrate. The effects of solvent selectivity, surface preference, and solvent evaporation rate on the morphology evolution during solvent evaporation are systematically investigated. It is found that the perpendicular cylinder morphology tends to form under weak surface preference, whereas under strong surface preference this morphology is promoted by the fast solvent evaporation rate and the strong solvent selectivity. The surface preference window for forming perpendicular cylinders with solvent evaporation is found to be wider than with thermal annealing, and especially much wider when the solvent evaporation starts from random (disordered) initial states. A new mechanism of perpendicular cylinder formation is proposed and elucidated. Hexagonally packed...

Nanoscale spirals by directed self-assembly

Archimedean spiral patterns are formed by the directed self-assembly of diblock copolymer thin films within a circular template. The presence of a notch in the template promotes the formation of a spiral compared to concentric rings, and the notch shape determines the chirality of the spiral. Double spirals occur when the notch width is increased or when there are two notches. The spiral followed an Archimedean form with exponent ≈0.9. Self-consistent field theory reproduces the experimentally observed morphologies and demonstrates the templating of spirals in cylindrical-morphology block copolymer films.