Self-Assembly of Hierarchical High-χ Fluorinated Block Copolymers with an Orthogonal Smectic-within-Lamellae 3 nm Sublattice and Vertical Surface Orientation.

Hierarchical structure-within-structure assemblies offer a route toward increasingly complex and multifunctional materials while pushing the limits of block copolymer self-assembly. We present a detailed study of the self-assembly of a series of fluorinated high-χ block copolymers (BCPs) prepared via postmodification of a single poly(styrene)-block-poly(glycidyl methacrylate) (S-b-G) parent polymer with the fluorinated alkylthiol pendent groups containing 1, 6, or 8 fluorinated carbons (termed trifluoro-ethanethiol (TFET), perfluoro-octylthiol (PFOT), and perfluoro-decylthiol (PFDT), respectively). Bulk X-ray scattering of thermally annealed samples demonstrates hierarchical molecular assembly with phase separation between the two blocks and within the fluorinated block. The degree of ordering within the fluorinated block is highly sensitive to synthetic variation; a lamellar sublattice was formed for S-b-GPFOT and S-b-GPFDT. Thermal analyses of S-b-GPFOT reveal that the fluorinated block exhibits liquid crystal-like ordering. The complex thin-film self-assembly behavior of an S-b-GPFOT polymer was investigated using real-space (atomic force microscopy and scanning electron microscopy) and reciprocal-space (resonant soft X-ray scattering (RSoXS), grazing incidence small- and wide-angle scattering) measurements. After thermal annealing in nitrogen or vacuum, films thicker than 1.5 times the primary lattice spacing exhibit a 90-degree grain boundary, exposing a thin layer of vertical lamellae at the free interface, while exhibiting horizontal lamellae on the preferential (polystyrene brush) substrate. RSoXS measurements reveal the near-perfect orthogonality between the primary and sublattice orientations, demonstrating hierarchical patterning at the nanoscale.

Direct-ink-write cross-linkable bottlebrush block copolymers for on-the-fly control of structural color.

Additive manufacturing capable of controlling and dynamically modulating structures down to the nanoscopic scale remains challenging. By marrying additive manufacturing with self-assembly, we develop a UV (ultra-violet)-assisted direct ink write approach for on-the-fly modulation of structural color by programming the assembly kinetics through photo-cross-linking. We design a photo-cross-linkable bottlebrush block copolymer solution as a printing ink that exhibits vibrant structural color (i.e., photonic properties) due to the nanoscopic lamellar structures formed post extrusion. By dynamically modulating UV-light irradiance during printing, we can program the color of the printed material to access a broad spectrum of visible light with a single ink while also creating color gradients not previously possible. We unveil the mechanism of this approach using a combination of coarse-grained simulations, rheological measurements, and structural characterizations. Central to the assembly mechanism is the matching of the cross-linking timescale with the assembly timescale, which leads to kinetic trapping of the assembly process that evolves structural color from blue to red driven by solvent evaporation. This strategy of integrating cross-linking chemistry and out-of-equilibrium processing opens an avenue for spatiotemporal control of self-assembled nanostructures during additive manufacturing.

Concentration-Driven Self-Assembly of PS-b-PLA Bottlebrush Diblock Copolymers in Solution.

Bottlebrush polymers are a class of semiflexible, hierarchical macromolecules with unique potential for shape-, architecture-, and composition-based structure-property design. It is now well-established that in dilute to semidilute solution, bottlebrush homopolymers adopt a wormlike conformation, which decreases in extension (persistence length) as the concentration and molecular overlap increase. By comparison, the solution phase self-assembly of bottlebrush diblock copolymers (BBCP) in a good solvent remains poorly understood, despite critical relevance for solution processing of ordered phases and photonic crystals. In this work, we combine small-angle X-ray scattering, coarse-grained simulation, and polymer synthesis to map the equilibrium phase behavior and conformation of a set of large, nearly symmetric PS-b-PLA bottlebrush diblock copolymers in toluene. Three BBCP are synthesized, with side chains of number-averaged molecular weights of 4500 (PS) and 4200 g/mol (PLA) and total backbone degrees of polymerization of 100, 255, and 400 repeat units. The grafting density is one side chain per backbone repeat unit. With increasing concentration in solution, all three polymers progress through a similar structural transition: from dispersed, wormlike chains with concentration-dependent (decreasing) extension, through the onset of disordered PS/PLA compositional fluctuations, to the formation of a long-range ordered lamellar phase. With increasing concentration in the microphase-separated regimes, the domain spacing increases as individual chains partially re-extend due to block immiscibility. Increases in the backbone degree of polymerization lead to changes in the scattering profiles which are consistent with the increased segregation strength. Coarse-grained simulations using an implicit side-chain model are performed, and concentration-dependent self-assembly behavior is qualitatively matched to experiments. Finally, using the polymer with the largest backbone length, we demonstrate that lamellar phases develop a well-defined photonic band gap in solution, which can be tuned across the visible spectrum by varying polymer concentration.

Not All Aggregates Are Made the Same: Distinct Structures of Solution Aggregates Drastically Modulate Assembly Pathways, Morphology, and Electronic Properties of Conjugated Polymers.

Tuning structures of solution-state aggregation and aggregation-mediated assembly pathways of conjugated polymers is crucial for optimizing their solid-state morphology and charge-transport property. However, it remains challenging to unravel and control the exact structures of solution aggregates, let alone to modulate assembly pathways in a controlled fashion. Herein, aggregate structures of an isoindigo-bithiophene-based polymer (PII-2T) are modulated by tuning selectivity of the solvent toward the side chain versus the backbone, which leads to three distinct assembly pathways: direct crystallization from side-chain-associated amorphous aggregates, chiral liquid crystal (LC)-mediated assembly from semicrystalline aggregates with side-chain and backbone stacking, and random agglomeration from backbone-stacked semicrystalline aggregates. Importantly, it is demonstrated that the amorphous solution aggregates, compared with semicrystalline ones, lead to significantly improved alignment and reduced paracrystalline disorder in the solid state due to direct crystallization during the meniscus-guided coating process. Alignment quantified by the dichroic ratio is enhanced by up to 14-fold, and the charge-carrier mobility increases by a maximum of 20-fold in films printed from amorphous aggregates compared to those from semicrystalline aggregates. This work shows that by tuning the precise structure of solution aggregates, the assembly pathways and the resulting thin-film morphology and device properties can be drastically tuned.

Chiral emergence in multistep hierarchical assembly of achiral conjugated polymers.

Intimately connected to the rule of life, chirality remains a long-time fascination in biology, chemistry, physics and materials science. Chiral structures, e.g., nucleic acid and cholesteric phase developed from chiral molecules are common in nature and synthetic soft materials. While it was recently discovered that achiral but bent-core mesogens can also form chiral helices, the assembly of chiral microstructures from achiral polymers has rarely been explored. Here, we reveal chiral emergence from achiral conjugated polymers, in which hierarchical helical structures are developed through a multistep assembly pathway. Upon increasing concentration beyond a threshold volume fraction, dispersed polymer nanofibers form lyotropic liquid crystalline (LC) mesophases with complex, chiral morphologies. Combining imaging, X-ray and spectroscopy techniques with molecular simulations, we demonstrate that this structural evolution arises from torsional polymer molecules which induce multiscale helical assembly, progressing from nano- to micron scale helical structures as the solution concentration increases. This study unveils a previously unknown complex state of matter for conjugated polymers that can pave way to a field of chiral (opto)electronics. We anticipate that hierarchical chiral helical structures can profoundly impact how conjugated polymers interact with light, transport charges, and transduce signals from biomolecular interactions and even give rise to properties unimagined before.

Rapid, interface-driven domain orientation in bottlebrush diblock copolymer films during thermal annealing.

Favorable polymer-substrate interactions induce surface orientation fields in block copolymer (BCP) melts. In linear BCP processed near equilibrium, alignment of domains generally persists for a small number of periods (∼4-6 D0) before randomization of domain orientation. Bottlebrush BCP are an emerging class of materials with distinct chain dynamics stemming from substantial molecular rigidity, enabling rapid assembly at ultrahigh (>100 nm) domain periodicities with strong photonic properties (structural color). This work assesses interface-induced ordering in PS-b-PLA bottlebrush diblock copolymer films during thermal annealing between planar surfaces. To clearly observe the decay in orientational order from surface to bulk, we choose to study micron-scale films spanning greater than 200 lamellar periods. In situ optical microscopy and transmission UV-Vis spectroscopy are used to monitor photonic properties during annealing and paired with ex situ UV-Vis reflection measurement, cross-sectional scanning electron microscopy (SEM), and small-angle X-ray scattering (SAXS) to probe the evolution of domain microstructure. Photonic properties were observed to saturate within minutes of annealing at 150 °C, with distinct variation in transmission response as a function of film thickness. The depth of the highly aligned surface region was found to vary stochastically in the range of 30-100 lamellar periods, with the sharpness of the orientation gradient decreasing substantially with increasing film thickness. This observation suggests a competition between growth of aligned, heterogeneously nucleated, grains at the surface and orientationally isotropic, homogeneously nucleated, grains throughout the bulk. This work demonstrates the high potential of bottlebrush block copolymers in rapid fabrication workflows and provides a point of comparison for future application of directed self-assembly to BBCP ordering.

Tunable structural color of bottlebrush block copolymers through direct-write 3D printing from solution.

Additive manufacturing of functional materials is limited by control of microstructure and assembly at the nanoscale. In this work, we integrate nonequilibrium self-assembly with direct-write three-dimensional (3D) printing to prepare bottlebrush block copolymer (BBCP) photonic crystals (PCs) with tunable structure color. After varying deposition conditions during printing of a single ink solution, peak reflected wavelength for BBCP PCs span a range of 403 to 626 nm (blue to red), corresponding to an estimated change in d-spacing of >70 nm (Bragg- Snell equation). Physical characterization confirms that these vivid optical effects are underpinned by tuning of lamellar domain spacing, which we attribute to modulation of polymer conformation. Using in situ optical microscopy and solvent-vapor annealing, we identify kinetic trapping of metastable microstructures during printing as the mechanism for domain size control. More generally, we present a robust processing scheme with potential for on-the-fly property tuning of a variety of functional materials.

Spin-coated fluorinated PbS QD superlattice thin film with high hole mobility.

Motivated by the oleophobic and electron-withdrawing nature of perfluorocarbons, we explore the effect of a trifluoromethyl coating on lead sulfide quantum dots (PbS QDs) in thin film transistor (TFT) geometry. The low surface energy conferred by the oleophobic perfluorocarbons creates QDs packed in a primitive cubic lattice with long range order, as confirmed by grazing incidence small angle X-ray scattering (GISAXS) and transmission electron microscopy (TEM). Hole mobilities as high as 0.085 cm2 V-1 s-1 were measured in the TFTs. No electron transport was observed. This suggests that the electron-withdrawing nature of the trifluoromethyl ligand is eclipsed by the excess holes present in the PbS QDs that likely stem from cation vacancies induced by the thiol group.

Super- and Ferroelastic Organic Semiconductors for Ultraflexible Single-Crystal Electronics.

Like silicon, single crystals of organic semiconductors are pursued to attain intrinsic charge transport properties. However, they are intolerant to mechanical deformation, impeding their application in flexible electronic devices. Such contradictory properties, namely exceptional molecular ordering and mechanical flexibility, are unified in this work. We found that bis(triisopropylsilylethynyl)pentacene (TIPS-P) crystals can undergo mechanically induced structural transitions to exhibit superelasticity and ferroelasticity. These properties arise from cooperative and correlated molecular displacements and rotations in response to mechanical stress. By utilizing a bending-induced ferroelastic transition of TIPS-P, flexible single-crystal electronic devices were obtained that can tolerate strains (ϵ) of more than 13 % while maintaining the charge carrier mobility of unstrained crystals (µ>0.7 µ0 ). Our work will pave the way for high-performance ultraflexible single-crystal organic electronics for sensors, memories, and robotic applications.

Multiscale assembly of solution-processed organic electronics: the critical roles of confinement, fluid flow, and interfaces.

Organic semiconducting small molecules and polymers provide a rich phase space for investigating the fundamentals of molecular and hierarchical assembly. Stemming from weak intermolecular interactions, their assembly sensitively depends on processing conditions, which in turn drastically modulate their electronic properties. Much work has gone into molecular design strategies that maximize intermolecular interactions and encourage close packing. Less understood, however, is the non-equilibrium assembly that occurs during the fabrication process (especially solution coating and printing) which is critical to determining thin film morphology across length scales. This encompasses polymorphism and molecular packing at molecular scale, assembly of π-bonding aggregates at the tens of nanometers scale, and the formation of domains at the micron-millimeter device scale. Here, we discuss three phenomena ubiquitous in solution processing of organic electronic thin films: the confinement effect, fluid flows, and interfacial assembly and the role they play in directing assembly. This review focuses on the mechanistic understanding of how assembly outcomes couple closely to the solution processing environment, supported by salient examples from the recent literature.