Copolymer Thin Films Research Articles

Surface Depth Analysis of Chemical Changes in Random Copolymer Thin Films Composed of Hydrophilic and Hydrophobic Silicon-Based Monomers Induced by Plasma Treatment as Studied by Hard X-ray Photoelectron Spectroscopy and Neutron Reflectivity Measurements.

In this study, a silicon-based copolymer, poly(tris(trimethylsiloxy)-3-methacryloxypropylsilane)-co-poly(N,N-dimethyl acrylamide), thin film was subjected to plasma surface treatment to make its surface hydrophilic (biocompatible). Neutron reflectivity (NR) measurement of the plasma-treated thin film showed a decrease in the film thickness (etching width: ∼20 nm) and an increase in the scattering length density (SLD) near the surface (∼15 nm). The region with a considerably high SLD adsorbed water (D2O) from its saturated vapor, indicating its superior surface hydrophilicity. Nevertheless of the hydrophilicity, the swelling of the thin film was suppressed. Hard X-ray photoelectron spectroscopy (HAXPES) performed at various takeoff angles revealed that the thin-film surface (∼20 nm depth) underwent extensive oxidation. NR and HAXPES analysis quantitatively yielded the depth profiling of elemental compositions in a few tens of nm scale. Si oxidation and hydrogen elimination (probably CH3 groups) in the vicinity of the surface region increased the SLD and decreased the hydrophobicity. A combination of Soft X-ray photoelectron spectroscopy and NR measurements revealed the surface chemical composition and mass density. It was considered that the surface near the film was chemically composed close to SiO2, forming a gel-like (three-dimensional network) structure that is hydrophilic and suppresses swelling due to moisture, indicating it can be expected to maintain stable hydrophilicity on the film surface.

Macroscopic Monograin Nano-Gyroid Thin Films in 4-inch Scale Through Shear-Rolling and Subsequent Solvent Annealing.

The gyroid structure from self-assembly is highly attractive for optical applications such as photonic crystals and metamaterials. However, due to the direction-dependent nature of these applications, achieving a monograin-level structure over a large area has remained challenging. In this study, the fabrication of unidirectionally oriented anisotropic nanocylinders of polystyrene-block-polydimethylsiloxane (PS-b-PDMS) is reported block copolymer thin films up to a 4-inch scale via a shear-rolling process, followed by solvent annealing to induce phase transition to nearly monograin gyroid structures. Grazing-incidence small-angle X-ray scattering (GISAXS) analysis and cross-sectional scanning electron microscope (SEM) images in the direction parallel to the shear-rolling direction reveal the preferential orientation with the (111) plane onto the YZ axis of the film, while only the (110) plane on the YZ axis of the film is observed in the perpendicular direction, with grain sizes approaching single-grain levels. For metamaterial applications, the PDMS domain is selectively removed, and gold is electroplated to produce monograin gold gyroid films.

Fabrication and Thermoresponsive Properties of Thin Copolymer Films of N-Isopropylacrylamide and Acrylamide

Fabrication and Thermoresponsive Properties of Thin Copolymer Films of N-Isopropylacrylamide and Acrylamide

Thin-film fabrication of polythiophene block copolymer via friction transfer

Abstract A thin film of thiophene block copolymer composed of 3-dodecylthiophene and 3-benzenesulfonato–thiophene was fabricated by using the friction-transfer method. The benzenesulfonato moiety was transformed by heating to the corresponding sulfonic acid, which induced self-doping. The obtained friction-transfer film showed different morphology from the related cast film. It was also revealed that the film indicated anisotropy parallel/perpendicular toward the drawing direction, which induced absorption dichroism and anisotropy of electric conductivity.

SYNTHESIS of P(N-ISOPROPYL ACRYLAMIDE - HYDROXYPROPYL METHACRYLATE) THERMO RESPONSIVE COPOLYMER FILMs BY INITIATED CHEMICAL VAPOR DEPOSITION METHOD

This study illustrates the deposition of thermo responsive p(N-isopropyl acrylamide-hydroxypropyl methacrylate) p(NIPAAm-HPMA) copolymer thin films by initiated chemical vapor deposition (iCVD) method using tert-butyl peroxide (TBPO) as the initiator. Copolymers were deposited at three different HPMA flow rates and the effects of NIPAAm/HPMA flow rate ratio on the deposition rate, structure and responsive properties of the as-deposited films were investigated. The highest deposition rate of 50 nm/min was observed for the copolymer deposited using lowest NIPAAm/HPMA monomer ratio studied. The deposition rate showed a significant increase with decreasing NIPAAm/HPMA flow ratio. Results of FTIR and XPS spectroscopy analyses revealed a significant preservation of structural retention in iCVD p(NIPAAm-HPMA) thermo-responsive films. Lower critical solution temperatures (LCST) of p(NIPAAm-HPMA) films were determined by carrying out a temperature-dependent contact angle analysis. Accordingly, it was shown that LCST was varied between 19 and 23 oC, which was observed to be dependent on the NIPAAm/HPMA monomer ratio. That LCST range is considerably below the literature- reported values for pNIPAAM, which makes the as-deposited copolymer suitable for applications that require thermos-responsive properties at lower temperatures.

SYNTHESIS AND ELECTROCHEMICAL PROPERTIES OF 2-[4-(2-METHACRYLOYL)-PIPERAZINE-1-YLMETHYL]-9Н-THIOXANTHEN-9-ONE-S,S-DIOXIDE AND ITS COPOLYMER WITH METHYL METHACRYLATE

2-[4-(2-Methacryloyl)-piperazine-1-ylmethyl]-9H-thioxanthen-9-one-S,S-dioxide 1, an electrochemically active monomer, has been synthesised from 2-(piperazine-1-ylmethyl)-9Н-thioxanthen-9-one-S,S-dioxide and methacryloyl chloride. Subsequent radical copolymerisation of the synthesised compound with methyl methacrylate leads to an electroactive copolymer (PMMA-co-ThxSO2) with the ratio of methyl methacrylate fragments in the chain to the pendant (side) groups of the 9Н-thioxanthen-9-one S,S-dioxide structure equal to 95 : 5, respectively. It has been shown by cyclic voltammetry that the electrochemical reduction (ECR) of 1 in acetonitrile (MeCN) is a two-electron and two-stage process, with the formation of long-living radical anion at the first one-electron stage and unstable dianion at the second stage. Electrochemical reduction of PMMA-co-ThxSO2 is due to the reductive electrochemical activity of the pendant groups, and its mechanism is similar to the ECR of monomer 1. This compound is a polymer with pendant groups that play the role of efficient electron traps during charge transport inside the thin copolymer film, and it can be used in the resistive memory technologies (ReRAM - Resistive Random Access Memory) as the active working layer of memristors.

Synthesis and characterization of stretchable isoprene-acrylic acid copolymer thin films

Copolymer thin films of isoprene with acrylic acid were synthesized using PECVD. In that way, the stretchable functionality of polyisoprene (PI) was combined with the hydrophilic functionality of poly(acrylic acid) (PAA) to obtain stretchable thin films with adjustable wettabilities. Deposition rates were found to change between 9 and 5.5 nm/min depending on the monomer flowrates. The analysis of water contact angle (WCA) values indicated that films having more AA units in their structures were more wettable. The stretchability of the films was assessed on laboratory gloves through stretch-release test and on PET sheet through bend-release test. No significant changes in the WCA values with no observable cracks and failures after successive tests were indication of stretchability of the copolymer films.

Role of Annealing with Electric Field Toward Improvement of Ferroelectric and Electroactive Properties of PVDF Copolymer and Terpolymer Thin Films.

The present study elucidates the role of annealing with electric field on lamellar crystalline structure and molecular orientation of polymer chains in ferroelectric copolymer (P(VDF-TrFE)) and ferroelectric terpolymer (P(VDF-TrFE-CFE)) spin-coated thin films. The ferroelectric polymer thin films annealed under an electric field support the growth of nanostructure with an "edge-on" lamellar crystalline structure having in-plane molecular chain orientation. The poled P(VDF-TrFE) thin films have higher remnant polarization (Pr) ≈6.2µCcm-2 and saturation polarization (Ps) ≈8.2µCcm-2 at an applied electric field of 250 MV/m compared to unpoled thin films having Pr ≈4.7 and Ps ≈6.2µCcm-2. Also, poled P(VDF-TrFE) thin films show lower coercive field (Ec) ≈94 MV/m compared to an unpoled thin film having Ec ≈105 MV/m. Similarly, poled PVDF-TrFE-CFE thin film shows better ferroelectric properties having Pr ≈0.4 and Ps ≈5.7µCcm-2 at an applied electric field of 200 MVm-1 compared to unpoled thin films having Pr ≈0.4 and Ps ≈4.1µCcm-2. The storage energy efficiency of unpoled and poled P(VDF-TrFE-CFE) thin films is measured to be ≈75% and 80%. Annealing of ferroelectric P(VDF-TrFE) polymer thin films under an electric field demonstrates improved ferroelectric and electroactive properties.

Order-Order Transition in Statistical Copolymer Thin Film Induced by LCST-Type Behavior.

In this paper, we describe the formation of an ordered structure in a copolymer thin film through hydration, which subsequently transitions to a different ordered structure upon dehydration. A statistical copolymer of poly(N-octadecyl acrylamide-stat-hydroxymethyl acrylamide) with a comonomer content ratio of 1:1, denoted as p(ODA50/HEAm50), was synthesized via free radical copolymerization. We prepared a thin film of this copolymer on a solid substrate and annealed it at 60 °C under humid conditions. This treatment formed a side-chain segregated lamellar (SCSegL) structure, in which the ODA and HEAm units are oriented perpendicularly to the polymer backbone and opposite each other. Increasing the annealing temperature to 90 °C led to a transition to a side-chain mixed lamellar (SCMixL) structure, where the ODA and HEAm units are also oriented perpendicularly to the polymer backbone but in both directions. The quartz crystal microbalance (QCM) data indicate that p(ODA50/HEAm50) exhibits LCST-like behavior with a transition temperature of approximately 50 °C. We conclude that the formation of the SCSegL structure at 60 °C is due to pronounced segregation between the water-adsorbed HEAm groups and the hydrophobic ODA. Conversely, dehydration at 90 °C reduces the segregation forces, forming the SCMixL structure, which exhibits lower strain. These results demonstrate that the p(ODA50/HEAm50) film undergoes an order-to-order transition driven by the hydration-dehydration process. Additionally, we found that changes in the lamellar structure significantly alter the swelling properties of the film.

Ionic liquid mediated one-step perpendicular assembly in block copolymer thin films for ultrafiltration membrane applications

The rapid rise of oil and gas, petrochemical, food processing, and pharmaceutical industries has added a complex mixture of contaminants like oil, particulates, metals, and other organic compounds to wastewater. Multipurpose membranes with precise pore structure can offer a solution to this problem and block copolymers (BCP) can be used to achieve such structures. Achieving vertical assembly of BCP domains provides a perfect template for developing uniform through film channels for separation and transport of material, besides being useful for the rectification of defects in photolithography patterns. Producing such morphologies may require extensive film/substrate processing and is not always feasible for scale-up. With this article, we demonstrate a facile solution casting method to induce vertical domain assembly in as-cast diblock copolymer thin films in the presence of an ionic liquid (IL) additive that preferentially segregates to one block and neutralizes interfacial interactions. We also show the tunability of domain sizes by controlling the additive concentration. These vertically aligned morphologies are important for the development of next-generation lithographic techniques and form excellent templates for ultrafiltration membranes with uniform pore sizes. This article demonstrates how IL additives can be used to obtain stable non-equilibrium morphologies in as-cast BCP films and the effect of BCP molecular mass, block volume fractions, and IL content on self-assembly.

Ultrathin Ionic Diodes with Electrostatically Heterogeneous Hybrid Interfaces of Nanoporous SiO2 Nanofilms and Polymer Layer-by-Layer Multilayers.

Nanofluidic ionic diodes have attracted much attention due to their unique functions as unidirectional ion transportation ability and promising applications from molecular sensing, and energy harvesting to emerging neuromorphic devices. However, it remains a challenge to fabricate diode-like nanofluidic systems with ultrathin film thickness <100nm. Herein the formation of ultrathin ionic diodes from hybrid nanoassemblies of nanoporous (NP) SiO2 nanofilms and polyelectrolyte layer-by-layer (LbL) multilayers is described. Ultrathin ionic diodes are prepared by integrating polyelectrolyte multilayers onto photo-oxidized NP SiO2 nanofilms obtained from silsesquioxane-containing block copolymer thin films as a template. The obtained ultrathin ionic diodes exhibit ion current rectification (ICR) properties with high ICR factor = ≈20 under low ionic strength and asymmetric pH conditions. It is concluded that this ICR behavior arises from effective ion accumulation and depletion at the interface of NP SiO2 nanofilms and LbL multilayers attributed to high ion selectivity by combining the experimental data and theoretical calculations using finite element methods. These results demonstrate that the hybrid nano assemblies of NP SiO2 nanofilms and polyelectrolyte LbL multilayers have potential applications for (bio)sensing materials and integrated ionic circuits for seamless connection of human-machine interfaces.

Vacuum-driven orientation of Nanostructured polystyrene-block-Poly(L-lactide) block copolymer thin films for Nanopatterning

Herein, we demonstrate a simple approach to control the orientation of cylinder-forming nanostructures in polystyrene-block-poly(L-lactide) (PS-b-PLLA) BCP thin films through thermal annealing under a high-vacuum environment. Surface tension discrepancy between the constituent blocks is critical in controlling the aimed orientation of self-assembled nanostructures in block copolymer (BCP) thin films. For BCP self-assembly, temperature has been widely utilized as a thermodynamic state variable under ambient pressure conditions, whereas the use of high vacuum (low pressure) for thermal annealing is limited. It has been observed that temperature can alter the surface tension only marginally with increasing temperature for polymeric materials; as a result, the pressure dependence of surface tension for PS and PLLA was investigated. By increasing the vacuum degree during thermal annealing, the surface tension discrepancy between the PS and PLLA blocks can be reduced significantly. Accordingly, during thermal annealing under high vacuum degree, a neutral air polymer interface can be generated for the BCP thin films, resulting in the formation of perpendicular cylinders from the neutral surface of the thin film through BCP microphase separation.

Annealing temperature-dependent induced supramolecular chiroptical response of copolymer thin films studied by pump-modulated transient circular dichroism spectroscopy

Copolymer thin films showing induced supramolecular chirality are of considerable interest for optoelectronic applications such as organic light-emitting diodes. Here, we introduce a new helicene-like chiral additive with two octyloxy substituents which displays excellent chiral induction properties in an achiral polyfluorene copolymer, leading to a circular dichroism (CD) response of up to 10,000 mdeg. This chiral inducer also displays very good thermal stability, which enables us to perform an extended study on the induced chiroptical properties of the cholesteric copolymer thin films annealed at different temperatures in the range 140–260 °C. Starting from about 180 °C, a distinct change in the morphology of the CD-active film is observed by CD microscopy, from micrometre-size granular to extended CD-active regions, where the latter ones display skewed distributions of the dissymmetry parameter gabs. Broadband Müller matrix spectroscopy finds a pronounced CD and circular birefringence (CB) response and only weak linear dichroism (LD, LD’) and linear birefringence (LB, LB’). Ultrafast transient CD spectroscopy with randomly polarised excitation reveals a clean mirror-image-type transient response, which shows a second-order decay of the S1 population due to singlet–singlet annihilation processes.

Impact of polyglycidol block architecture in polystyrene-b-polyglycidol copolymers on the properties of thin films and protein adsorption

The effect of the architecture of amphiphilic polystyrene-b-polyglycidol and polystyrene-b-(polyglycidol-g-polyglycidol) copolymers on their behavior in thin films and interaction with the protein has been studied. The properties of the copolymer films surface were investigated before and after incubation in water and aqueous solution of PBS buffer. Surface sensitive techniques: time-of-flight secondary ion mass spectrometry, atomic force microscopy, and contact angle measurements show the differences in film surfaces behavior depending on the copolymer architecture. It was found that exposure of the coil-brush copolymer to an aqueous solution reoriented the PGL segments, changing the properties of the surface layer. Greater exposure of antifouling PGL chains at the surface of the copolymer film modified the interaction with bovine serum albumin, significantly reducing its adsorption. In contrast, no changes in the orientation of the PGL chains were observed after incubation of the copolymer films in an aqueous solution of protein in PBS buffer. This suggests that protein adsorption to the thin copolymer film blocks the conformational changes of the copolymer chains and reduces their mobility under the protein molecules.

Bayesian model calibration for block copolymer self-assembly: Likelihood-free inference and expected information gain computation via measure transport

We consider the Bayesian calibration of models describing the phenomenon of block copolymer (BCP) self-assembly, which is to infer model parameters and their uncertainty from noisy image data produced by microscopy or X-ray scattering characterization of BCP structures. To account for the long-range disorder in BCP structures, we introduce auxiliary variables in the model to represent this aleatory uncertainty. These variables, however, result in an integrated likelihood function for high-dimensional image data that is generally intractable to evaluate. We tackle this Bayesian inference problem using a likelihood-free inference (LFI) approach based on measure transport together with the construction of summary statistics for the image data. We show that expected information gains (EIG) from observed data about the model parameters can be computed with no significant additional cost. Lastly, we present a numerical case study using the Ohta–Kawasaki model for diblock copolymer thin film self-assembly and top-down microscopy characterization. We introduce several domain-specific energy and Fourier-based summary statistics for calibration and quantify their informativeness using EIG. The effect of various data corruptions, summary statistics, and experimental designs on the calibration results are studied using the proposed LFI method.

UV laser-processed microstructure for building biohybrid actuators with anisotropic movement

Fabrication of a biohybrid actuator requires muscle cells anisotropically aligned in a line, curve, or combination of lines and curves (similar to the microstructure of living muscle tissue) to replicate lifelike movements, in addition to considering the arrangement of skeletal structure or muscular structure with anisotropic straight patterns. Here, we report a UV laser-processed microstructure for freely directing cellular alignment to engineer a biohybrid actuator composed of poly(styrene-block-butadiene-block-styrene triblock copolymer) (SBS) thin film with tailor-made microgrooves (MGs) and skeletal myotubes aligned along these MGs. Specifically, straight, circular, or curved MGs were transferred to SBS thin films from a UV laser-processed template, allowing for the successful alignment of myotubes along MGs. The biohybrid actuator, composed of anisotropically aligned myotubes on a curved microgrooved SBS thin film, was contracted by electrical stimulation. Contraction of biohybrid actuators with curved aligned myotubes permits twisted-like behavior, unlike straight microgrooved films. Therefore, the UV laser-ablation system is a unique maskless and rapid microfabrication technique that provides intriguing opportunities for omni-directional microgrooved structures to achieve the complex motion of living organisms.

Self-brushing for nanopatterning: achieving perpendicular domain orientation in block copolymer thin films.

The self-assembly of thin films of block copolymers (BCPs) with perpendicular domain orientation offers a promising approach for nanopatterning on a variety of substrates, which is required by advanced applications such as ultrasmall transistors in integrated circuits, nanopatterned materials for tissue engineering, and electrocatalysts for fuel cell applications. In this study, we created BCPs with an A-b-(B-r-C) architecture that have blocks with equal surface energy (γair) and that can bind to the substrate, effectively creating a non-preferential substrate coating via self-brushing that enables the formation of through-film perpendicular domains in thin films of BCPs. We employed a thiol-epoxy click reaction to functionalize polystyrene-block-poly(glycidyl methacrylate) with a pair of thiols to generate an A-b-(B-r-C) BCP and tune γair of the B-r-C block. The secondary hydroxyl and thiol ether functionality generated by the click reaction was utilized to bind the BCP to the substrates. Scanning electron microscopy revealed that perpendicular orientation was achieved by simply annealing a thin film of the BCP on the bare substrate without the usual extra step of coating a random copolymer brush on the substrate. The self-brushing capability of the BCP was also examined on gold, platinum, titanium, aluminum nitride, and silicon nitride surfaces. These results demonstrate that self-brushing is a promising approach for achieving perpendicular domain orientation in thin films of BCP for nanopatterning on a variety of useful surfaces.

Effects of alumina priming on the electrical properties of ZnO nanostructures derived from vapor-phase infiltration into self-assembled block copolymer thin films

Alumina priming, typically used for vapor-phase infiltration (VPI) of weakly reactive precursors, increases both ZnO VPI fidelity and its electrical conductivity, as demonstrated in the ZnO nanostructures derived from self-assembled block copolymers.

Diversifying self-assembled phases in block copolymer thin films via blending

Diversifying self-assembled phases in block copolymer thin films via blending

Effect of In‐Plane Electric Field on the Microphase Separation in Thin Films of a Symmetric ABA Triblock Copolymer

AbstractThe structure of a thin film of symmetric ABA triblock copolymer melts in an external in‐plane DC or AC electric field is studied theoretically. The situation is considered when the triblock copolymer forms a hexagonal morphology of standing cylinders in bulk in the absence of an external field. Self‐consistent field theory calculations are carried out to determine the most thermodynamically favorable thin film structure among the cylindrical phases perpendicular and parallel to the substrate and the lamellar phase perpendicular to the substrate. The results are presented as phase diagrams with the film thickness and electric field energy on the axes and as distributions of the local composition, which serve as an order parameter in the system. It is confirmed that electric fields only weakly affect the spinodal curves of block copolymers but they can reorient or markedly modify microphase‐separated morphologies in those systems. Such restructuring is consistent with a considerable modulation of the free surface of a copolymer film and it can lead to the coexistence of different phases that appear in the film areas with different local thicknesses.