Solvent Selectivity Governs the Emergence of Temperature Responsiveness in Block Copolymer Self-Assembly.
Ontology highlight
ABSTRACT:
SUBMITTER: Ianiro A
PROVIDER: S-EPMC8042846 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:The self-assembly of ultra-high molecular weight (UHMW) block copolymers (BCPs) remains a complex and time-consuming endeavor owing to the high kinetic penalties associated with long polymer chain entanglement. In this work, we report a unique strategy of overcoming these kinetic barriers through precision solvent annealing of an UHMW polystyrene-block-poly(2-vinylpyridine) BCP system (M w: ∼800 kg/mol) by fast swelling to very high levels of solvent concentration (ϕs). Phase separation on timescales of ∼10 min is demonstrated once a thickness-dependent threshold ϕs value of ∼0.80-0.86 is achieved, resulting in lamellar feature spacings of over 190 nm. The threshold ϕs value was found to be greater for films with higher dry thickness (D 0) values. Tunability of the domain morphology is achieved through controlled variation of both D 0 and ϕs, with the kinetically unstable hexagonal perforated lamellar (HPL) phase observed at ϕs values of ∼0.67 and D 0 values of 59-110 nm. This HPL phase can be controllably induced into an order-order transition to a lamellar morphology upon further increase of ϕs to 0.80 or above. As confirmed by grazing-incidence small-angle X-ray scattering, the lateral ordering of the lamellar domains is shown to improve with increasing ϕs up to a maximum value at which the films transition to a disordered state. Thicker films are shown to possess a higher maximum ϕs value before transitioning to a disordered state. The swelling rate is shown to moderately influence the lateral ordering of the phase-separated structures, while the amount of hold time at a particular value of ϕs does not notably enhance the phase separation process. These large period self-assembled lamellar domains are then employed to facilitate pattern transfer using a liquid-phase infiltration method, followed by plasma etching, generating ordered, high aspect ratio Si nanowall structures with spacings of ∼190 nm and heights of up to ∼500 nm. This work underpins the feasibility of a room-temperature, solvent-based annealing approach for the reliable and scalable fabrication of sub-wavelength nanostructures via BCP lithography.
| S-EPMC8280752 | biostudies-literature
Project description:Solvent vapor annealing is as an effective and versatile alternative to thermal annealing to equilibrate and control the assembly of polymer chains in thin films. Here, we present scientific and practical aspects of the solvent vapor annealing method, including the discussion of such factors as non-equilibrium conformational states and chain dynamics in thin films in the presence of solvent. Homopolymer and block copolymer films have been used in model studies to evaluate the robustness and the reproducibility of the solvent vapor processing, as well as to assess polymer-solvent interactions under confinement. Advantages of utilizing a well-controlled solvent vapor environment, including practically interesting regimes of weakly saturated vapor leading to poorly swollen states, are discussed. Special focus is given to dual temperature control over the set-up instrumentation and to the potential of solvo-thermal annealing. The evaluated insights into annealing dynamics derived from the studies on block copolymer films can be applied to improve the processing of thin films of crystalline and conjugated polymers as well as polymer composite in confined geometries.
| S-EPMC6722758 | biostudies-literature
Project description:Charged block copolymers are of great interest due to their unique self-assembly and physicochemical properties. Understanding of the phase behavior of charged block copolymers, however, is still at a primitive stage. Here we report the discovery of an intriguing superlattice morphology from compositionally symmetric charged block copolymers, poly[(oligo(ethylene glycol) methyl ether methacrylate-co-oligo(ethylene glycol) propyl sodium sulfonate methacrylate)]-b-polystyrene (POEGMA-PS), achieved by systematic variation of the molecular structure in general, and the charge content in particular. POEGMA-PS self-assembles into a superlattice lamellar morphology, a previously unknown class of diblock nanostructures, but strikingly similar to oxygen-deficient perovskite derivatives, when the fraction of charged groups in the POEGMA block is about 5-25%. The charge fraction and the tethering of the ionic groups both play critical roles in driving the superlattice formation. This study highlights the accessibility of superlattice morphologies by introducing charges in a controlled manner.
| S-EPMC6506472 | biostudies-literature
Project description:Continued scaling-down of lithographic-pattern feature sizes has brought templated self-assembly of block copolymers (BCPs) into the forefront of nanofabrication research. Technologies now exist that facilitate significant control over otherwise unorganized assembly of BCP microdomains to form both long-range and locally complex monolayer patterns. In contrast, the extension of this control into multilayers or 3D structures of BCP microdomains remains limited, despite the possible technological applications in next-generation devices. Here, we develop and analyse an orthogonal self-assembly method in which multiple layers of distinct-molecular-weight BCPs naturally produce nanomesh structures of cylindrical microdomains without requiring layer-by-layer alignment or high-resolution lithographic templating. The mechanisms for orthogonal self-assembly are investigated with both experiment and simulation, and we determine that the control over height and chemical preference of templates are critical process parameters. The method is employed to produce nanomeshes with the shapes of circles and Y-intersections, and is extended to produce three layers of orthogonally oriented cylinders.
| S-EPMC4736107 | biostudies-literature
Project description:Ultrafine, uniform nanostructures with excellent functionalities can be formed by self-assembly of block copolymer (BCP) thin films. However, extension of their geometric variability is not straightforward due to their limited thin film morphologies. Here, we report that unusual and spontaneous positioning between host and guest BCP microdomains, even in the absence of H-bond linkages, can create hybridized morphologies that cannot be formed from a neat BCP. Our self-consistent field theory (SCFT) simulation results theoretically support that the precise registration of a spherical BCP microdomain (guest, B-b-C) at the center of a perforated lamellar BCP nanostructure (host, A-b-B) can energetically stabilize the blended morphology. As an exemplary application of the hybrid nanotemplate, a nanoring-type Ge2Sb2Te5 (GST) phase-change memory device with an extremely low switching current is demonstrated. These results suggest the possibility of a new pathway to construct more diverse and complex nanostructures using controlled blending of various BCPs.
| S-EPMC3824169 | biostudies-literature
Project description:In this paper, the concept of the functional mechanism of copolymer membrane formation is explained and analyzed from the theoretical and experimental points of view. To understand the phase inversion process and control the final membrane morphology, styrene-acrylonitrile copolymer (SAN) membrane morphology through the self-assembly phenomena is investigated. Since the analysis of the membrane morphology requires the study of both thermodynamic and kinetic parameters, the effect of different membrane formation conditions is investigated experimentally; In order to perceive the formation mechanism of the extraordinary structure membrane, a thermodynamic hypothesis is also developed based on the hydrophilic coil migration to the membrane surface. This hypothesis is analyzed according to Hansen Solubility Parameters and proved using EDX, SAXS, and contact angle analysis of SAN25. Moreover, the SAN30 membrane is fabricated under different operating conditions to evaluate the possibility of morphological prediction based on the developed hypothesis.
| S-EPMC8760277 | biostudies-literature
Project description:Block copolymer (BCP) self-assembly has tremendous potential applications in next-generation nanolithography. It offers significant advantages, including high resolution and cost-effectiveness, effectively overcoming the limitations associated with conventional optical lithography. In this work, we demonstrate a focused solar annealing (FSA) technique that is facile, eco-friendly, and energy-efficient for fast self-assembly of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) thin films. The FSA principle involves utilizing a common biconvex lens to converge incident solar radiation into a high-temperature spot, which is directly used to drive the microphase separation of PS-b-PMMA thin films. As a result, PS-b-PMMA undergoes self-assembly, forming ordered nanostructures in a vertical orientation at seconds timescales on silicon substrates with a neutral layer. In addition, the FSA technique can be employed for grafting neutral polymer brushes onto the silicon substrate. Furthermore, the FSA's compatibility with graphoepitaxy-directed self-assembly (DSA) of BCP is also demonstrated in the patterning of contact holes. The results of contact hole shrinking show that contact hole prepatterns of ∼60.4 nm could be uniformly shrunk to ∼20.5 nm DSA hole patterns with a hole open yield (HOY) of 100 %. For contact hole multiplication, doublet DSA holes were successfully generated on elliptical templates, revealing an average DSA hole size of ∼21.3 nm. Most importantly, due to the direct use of solar energy, the FSA technique provides many significant advantages such as simplicity, environmental friendliness, solvent-free, low cost, and net-zero carbon emissions, and will open up a new direction for BCP lithography that is sustainable, pollution-free, and carbon-neutral.
| S-EPMC10825308 | biostudies-literature
Project description:Protein-polymer bioconjugate self-assembly has attracted a great deal of attention as a method to fabricate protein nanomaterials in solution and the solid state. To identify protein properties that affect phase behavior in protein-polymer block copolymers, a library of 15 unique protein-b-poly(N-isopropylacrylamide) (PNIPAM) copolymers comprising 11 different proteins was compiled and analyzed. Many attributes of phase behavior are found to be similar among all studied bioconjugates regardless of protein properties, such as formation of micellar phases at high temperature and low concentration, lamellar ordering with increasing temperature, and disordering at high concentration, but several key protein-dependent trends are also observed. In particular, hexagonal phases are only observed for proteins within the molar mass range 20-36 kDa, where ordering quality is also significantly enhanced. While ordering is generally found to improve with increasing molecular weight outside of this range, most large bioconjugates exhibited weaker than predicted assembly, which is attributed to chain entanglement with increasing polymer molecular weight. Additionally, order-disorder transition boundaries are found to be largely uncorrelated to protein size and quality of ordering. However, the primary finding is that bioconjugate ordering can be accurately predicted using only protein molecular weight and percentage of residues contained within ? sheets. This model provides a basis for designing protein-PNIPAM bioconjugates that exhibit well-defined self-assembly and a modeling framework that can generalize to other bioconjugate chemistries.
| S-EPMC6794641 | biostudies-literature
Project description:The existence of ferroelectricity and ferromagnetism in multiferroic materials and their coupling enables the manipulation of the electric polarization with applied magnetic field and vice versa, opening many doors for the practical applications. However, the preparation of polymeric multiferroic nanocomposites is often accompanied with aggregation of magnetic particles inside the ferroelectric polymeric matrix. To overcome this issue, we developed a simple and straightforward method to obtain multiferroic nanocomposites with an exceptional and selective dispersion of magnetic nanoparticles, using self-assembly of poly(vinylidene fluoride) (PVDF)-based block copolymers. Magnetic cobalt ferrite nanoparticles modified with gallic acid are selectively incorporated within poly(2-vinylpyridine) (P2VP) domains of the lamellar block copolymer due to strong hydrogen bond formation between the ligand and the P2VP block. Using this approach, phase separation between the blocks is improved, which leads to an increase in the degree of crystallinity, whereas the selective dispersion of nanoparticles inside amorphous domains prevents changes in the crystalline phase of the ferroelectric block. The obtained nanocomposites demonstrate both ferroelectric and magnetic properties without large conductive losses at high electric field, making them good candidates for improved multiferroic devices.
| S-EPMC8613863 | biostudies-literature
Project description:In this work, ladder-shaped block copolymer structures consisting of parallel bars, bends, and T-junctions are formed inside square confinement. We define binary states by the two degenerate alignment orientations, and study properties of the two-state system. We control the binary states by creating openings around the confinement, changing the confinement geometry, or placing lithographic guiding patterns inside the confinement. Self-consistent field theory simulations show templating effect from the wall openings and reproduce the experimental results. We demonstrate scaling of a single binary state into a larger binary state array with individual binary state control.
| S-EPMC6158142 | biostudies-literature