Block Copolymer Response to Photothermal Stress Fields

Block copolymer materials can be aligned using shear forces; in order to fully exploit this phenomenon for controlling nanoscale order, the coupling between applied forces and molecular properties must be elucidated. We use a photothermal method to generate extreme and controllable thermal and stress fields in thin films of cylinder-forming block copolymers. By studying morphological ordering as a function of time, shear rate, polymer material, molecular weight, and film thickness, we elucidate the critical parameters with respect to efficient ordering. We find that ordering efficiency depends weakly on the block copolymer interaction parameter and strongly on the difference in mechanical response of the two phases. Morphologies can be aligned only when the inverse shear rate is smaller than the material’s relaxation time. Overall, photothermal shear alignment provides an efficient means of ordering and aligning nanoscale morphologies over macroscopic areas, using a surprisingly short (subsecond) shear pulse

Millisecond Ordering of Block Copolymer Films <i>via</i> Photothermal Gradients

For the promise of self-assembly to be realized, processing techniques must be developed that simultaneously enable control of the nanoscale morphology, rapid assembly, and, ideally, the ability to pattern the nanostructure. Here, we demonstrate how photothermal gradients can be used to control the ordering of block copolymer thin films. Highly localized laser heating leads to intense thermal gradients, which induce a thermophoretic force on morphological defects. This increases the ordering kinetics by at least 3 orders of magnitude compared to conventional oven annealing. By simultaneously exploiting the thermal gradients to induce shear fields, we demonstrate uniaxial alignment of a block copolymer film in less than a second. Finally, we provide examples of how control of the incident light field can be used to generate prescribed configurations of block copolymer nanoscale patterns

Rapid Ordering in “Wet Brush” Block Copolymer/Homopolymer Ternary Blends

The ubiquitous presence of thermodynamically unfavored but kinetically trapped topological defects in nanopatterns formed <i>via</i> self-assembly of block copolymer thin films may prevent their use for many envisioned applications. Here, we demonstrate that lamellae patterns formed by symmetric polystyrene-<i>block</i>-poly­(methyl methacrylate) diblock copolymers self-assemble and order extremely rapidly when the diblock copolymers are blended with low molecular weight homopolymers of the constituent blocks. Being in the “wet brush” regime, the homopolymers uniformly distribute within their respective self-assembled microdomains, preventing increases in domain widths. An order-of-magnitude increase in topological grain size in blends over the neat (unblended) diblock copolymer is achieved within minutes of thermal annealing as a result of the significantly higher power law exponent for ordering kinetics in the blends. Moreover, the blends are demonstrated to be capable of rapid and robust domain alignment within micrometer-scale trenches, in contrast to the corresponding neat diblock copolymer. These results can be attributed to the lowering of energy barriers associated with domain boundaries by bringing the system closer to an order–disorder transition through low molecular weight homopolymer blending

Latent Alignment in Pathway-Dependent Ordering of Block Copolymer Thin Films

Block copolymers spontaneously form well-defined nanoscale morphologies during thermal annealing. Yet, the structures one obtains can be influenced by nonequilibrium effects, including processing history or pathway-dependent assembly. Here, we explore various pathways for ordering of block copolymer thin films, using oven-annealing, as well as newly disclosed methods for rapid photothermal annealing and photothermal shearing. We report the discovery of an efficient pathway for ordering self-assembled films: ultrarapid shearing of as-cast films induces “latent alignment” in the disordered morphology. Subsequent thermal processing can then develop this directly into a uniaxially aligned morphology with low defect density. This deeper understanding of pathway-dependence may have broad implications in self-assembly

Self-Assembled Phases of Block Copolymer Blend Thin Films

The patterns formed by self-assembled thin films of blended cylindrical and lamellar polystyrene-<i>b</i>-poly(methyl methacrylate) block copolymers can be either a spatially uniform, single type of nanostructure or separate, coexisting regions of cylinders and lamellae, depending on fractional composition and molecular weight ratio of the blend constituents. In blends of block copolymers with different molecular weights, the morphology of the smaller molecular weight component more strongly dictates the resulting pattern. Although molecular scale chain mixing distorts microdomain characteristic length scales from those of the pure components, even coexisting morphologies exhibit the same domain spacing. We quantitatively account for the phase behavior of thin-film blends of cylinders and lamellae using a physical, thermodynamic model balancing the energy of chain distortions with the entropy of mixing

Cooperative Ordering and Kinetics of Cellulose Nanocrystal Alignment in a Magnetic Field

Cellulose nanocrystals (CNCs) are emerging nanomaterials that form chiral nematic liquid crystals above a critical concentration (<i>C</i>*) and additionally orient within electromagnetic fields. The control over CNC alignment is significant for materials processing and end use; to date, magnetic alignment has been demonstrated using only strong fields over extended or arbitrary time scales. This work investigates the effects of comparatively weak magnetic fields (0–1.2 T) and CNC concentration (1.65–8.25 wt %) on the kinetics and degree of CNC ordering using small-angle X-ray scattering. Interparticle spacing, correlation length, and orientation order parameters (η and <i>S</i>) increased with time and field strength following a sigmoidal profile. In a 1.2 T magnetic field for CNC suspensions above <i>C</i>*, partial alignment occurred in under 2 min followed by slower cooperative ordering to achieve nearly perfect alignment in under 200 min (<i>S</i> = −0.499 where <i>S</i> = −0.5 indicates perfect antialignment). At 0.56 T, nearly perfect alignment was also achieved, yet the ordering was 36% slower. Outside of a magnetic field, the order parameter plateaued at 52% alignment (<i>S</i> = −0.26) after 5 h, showcasing the drastic effects of relatively weak magnetic fields on CNC alignment. For suspensions below <i>C</i>*, no magnetic alignment was detected

Dynamic Thermal Field-Induced Gradient Soft-Shear for Highly Oriented Block Copolymer Thin Films

As demand for smaller, more powerful, and energy-efficient devices continues, conventional patterning technologies are pushing up against fundamental limits. Block copolymers (BCPs) are considered prime candidates for a potential solution <i>via</i> directed self-assembly of nanostructures. We introduce here a facile directed self-assembly method to rapidly fabricate unidirectionally aligned BCP nanopatterns at large scale, on rigid or flexible template-free substrates <i>via</i> a thermally induced dynamic gradient soft-shear field. A localized differential thermal expansion at the interface between a BCP film and a confining polydimethylsiloxane (PDMS) layer due to a dynamic thermal field imposes the gradient soft-shear field. PDMS undergoes directional expansion (along the annealing direction) in the heating zone and contracts back in the cooling zone, thus setting up a single cycle of oscillatory shear (maximum lateral shear stress ∼12 × 10⁴ Pa) in the system. We successfully apply this process to create unidirectional alignment of BCP thin films over a wide range of thicknesses (nm to μm) and processing speeds (μm/s to mm/s) using both a flat and patterned PDMS layer. Grazing incidence small-angle X-ray scattering measurements show absolutely no sign of isotropic population and reveal ≥99% aligned orientational order with an angular spread Δθ_fwhm ≤ 5° (full width at half-maximum). This method may pave the way to practical industrial use of hierarchically patterned BCP nanostructures

Linear Mesostructures in DNA–Nanorod Self-Assembly

The assembly of molecules and nanoscale objects into one-dimensional (1D) structures, such as fibers, tubules, and ribbons, typically results from anisotropic interactions of the constituents. Conversely, we found that a 1D structure can emerge <i>via</i> a very different mechanism, viz, the spontaneous symmetry breaking of underlying interparticle interactions during structure formation. For systems containing DNA-decorated nanoscale rods, this mechanism, driven by flexible DNA chains, results in the formation of 1D ladderlike mesoscale ribbons with a side-by-side rod arrangement. Detailed structural studies using electron microscopy and <i>in situ</i> small-angle X-ray scattering (SAXS), as well as analysis of assembly kinetics, reveal the role of collective DNA interactions in the formation of the linear structures. Moreover, the reversibility of DNA binding facilitates the development of hierarchical assemblies with time. We also observed similar linear structures of alternating rods and spheres, which implies that the discovered mechanism is generic for nanoscale objects interacting <i>via</i> flexible multiple linkers

Injectable Anisotropic Nanocomposite Hydrogels Direct in Situ Growth and Alignment of Myotubes

While injectable in situ cross-linking hydrogels have attracted increasing attention as minimally invasive tissue scaffolds and controlled delivery systems, their inherently disorganized and isotropic network structure limits their utility in engineering oriented biological tissues. Traditional methods to prepare anisotropic hydrogels are not easily translatable to injectable systems given the need for external equipment to direct anisotropic gel fabrication and/or the required use of temperatures or solvents incompatible with biological systems. Herein, we report a new class of injectable nanocomposite hydrogels based on hydrazone cross-linked poly­(oligoethylene glycol methacrylate) and magnetically aligned cellulose nanocrystals (CNCs) capable of encapsulating skeletal muscle myoblasts and promoting their differentiation into highly oriented myotubes in situ. CNC alignment occurs on the same time scale as network gelation and remains fixed after the removal of the magnetic field, enabling concurrent CNC orientation and hydrogel injection. The aligned hydrogels show mechanical and swelling profiles that can be rationally modulated by the degree of CNC alignment and can direct myotube alignment both in two- and three-dimensions following coinjection of the myoblasts with the gel precursor components. As such, these hydrogels represent a critical advancement in anisotropic biomimetic scaffolds that can be generated noninvasively <i>in vivo</i> following simple injection

Nanostructured Surfaces Frustrate Polymer Semiconductor Molecular Orientation

Nanostructured grating surfaces with groove widths less than 200 nm impose boundary conditions that frustrate the natural molecular orientational ordering within thin films of blended polymer semiconductor poly(3-hexlythiophene) and phenyl-C₆₁-butyric acid methyl ester, as revealed by grazing incidence X-ray scattering measurements. Polymer interactions with the grating sidewall strongly inhibit the polymer lamellar alignment parallel to the substrate typically found in planar films, in favor of alignment perpendicular to this orientation, resulting in a preferred equilibrium molecular configuration difficult to achieve by other means. Grating surfaces reduce the relative population of the parallel orientation from 30% to less than 5% in a 400 nm thick film. Analysis of in-plane X-ray scattering with respect to grating orientation shows polymer backbones highly oriented to within 10 degrees of parallel to the groove direction