Building Tunable Degradation into High-Performance Poly(acrylate) Pressure-Sensitive Adhesives.

Pressure-sensitive adhesives (PSAs) based on poly(acrylate) chemistry are common in a wide variety of applications, but the absence of backbone degradability causes issues with recycling and sustainability. Here, we report a strategy to create degradable poly(acrylate) PSAs using simple, scalable, and functional 1,2-dithiolanes as drop-in replacements for traditional acrylate comonomers. Our key building block is α-lipoic acid, a natural, biocompatible, and commercially available antioxidant found in various consumer supplements. α-Lipoic acid and its derivative ethyl lipoate efficiently copolymerize with n-butyl acrylate under conventional free-radical conditions leading to high-molecular-weight copolymers (Mn > 100 kg mol-1) containing a tunable concentration of degradable disulfide bonds along the backbone. The thermal and viscoelastic properties of these materials are practically indistinguishable from nondegradable poly(acrylate) analogues, but a significant reduction in molecular weight is realized upon exposure to reducing agents such as tris (2-carboxyethyl) phosphine (e.g., Mn = 198 kg mol-1 → 2.6 kg mol-1). By virtue of the thiol chain ends produced after disulfide cleavage, degraded oligomers can be further cycled between high and low molecular weights through oxidative repolymerization and reductive degradation. Transforming otherwise persistent poly(acrylates) into recyclable materials using simple and versatile chemistry could play a pivotal role in improving the sustainability of contemporary adhesives.

Facile synthesis of porous transition metal hydroxides from a poly(4-vinyl pyridine) film by controlling pH.

Non-noble transition metal hydroxides have been widely used in electrochemical devices because of low cost and multiple redox states. In particular, self-supported porous transition metal hydroxides are used to improve the electrical conductivity, as well as achieving fast electron and mass transfer and a large effective surface area. Herein, we introduce facile synthesis of self-supported porous transition metal hydroxides using a poly(4-vinyl pyridine) (P4VP) film. We used metal cyanide as a transition metal precursor capable of forming metal hydroxide anions in aqueous solution, which is the seed for transition metal hydroxides. To increase the coordination between P4VP and the transition metal cyanide precursors, we dissolved the precursors in buffer solutions with various pH. When the P4VP film was immersed in the precursor solution with lower pH, the metal cyanide precursors were sufficiently coordinated with the protonated nitrogen in P4VP. When reactive ion etching was performed on the precursor-containing P4VP film, the P4VP region without coordination was etched out and became pores. Then, the coordinated precursors were aggregated as metal hydroxide seeds and became the metal hydroxide backbone, resulting in the formation of porous transition metal hydroxide structures. We successfully fabricated various self-supported porous transition metal hydroxides (Ni(OH)2, Co(OH)2, and FeOOH). Finally, we prepared a pseudo-capacitor based on self-supported porous Ni(OH)2, which showed a good specific capacitance (780 F g-1 at 5 A g-1).

Soft Template-Assisted Fabrication of Mesoporous Graphenes for High-Performance Energy Storage Systems.

Graphene is a promising active material for electric double layer supercapacitors (EDLCs) due to its high electric conductivity and lightweight nature. However, for practical uses as a power source of electronic devices, a porous structure is advantageous to maximize specific energy density. Here, we propose a facile fabrication approach of mesoporous graphene (m-G), in which self-assembled mesoporous structures of poly(styrene)-block-poly(2-vinylpyridine) copolymer (PS-b-P2VP) are exploited as both mesostructured catalytic template and a carbon source. Notably, the mesostructured catalytic template is sufficient to act as a rigid support without structural collapse, while PS-b-P2VP converts to graphene, generating m-G with a pore diameter of ca. 3.5 nm and high specific surface area of 186 m2/g. When the EDLCs were prepared using the obtained m-G and ionic liquids, excellent electrochemical behaviors were achieved even at high operation voltages (0 ∼ 3.5 V), including a large specific capacitance (130.2 F/g at 0.2 A/g), high-energy density of 55.4 W h/kg at power density of 350 W/kg, and excellent cycle stability (>10,000 cycles). This study demonstrates that m-G is a promising material for high-performance energy storage devices.

Triboelectric Nanogenerators: Enhancing Performance by Increasing the Charge-Generating Layer Compressibility.

Triboelectric nanogenerators (TENGs) have received significant attention for next-generation wearable electronics due to their simple device structure and low cost. Although the performance of TENGs is intimately tied to compressibility effects in the charge-generating layer, achieving high compressibility with conventional elastomers is challenging because molecular entanglements place a lower bound on the softness of cross-linked networks. Here, we demonstrate that bottlebrush elastomers are efficient charge-generating layers that improve the output performance of TENGs, including voltage, current, and surface potential, by minimizing entanglements and decreasing the compressive modulus (E). For example, a cross-linked bottlebrush with poly(dimethylsiloxane) side chains yielded TENGs with an output voltage (120 V) more than two times larger than a linear PDMS network (55 V). In conclusion, this study highlights the advantage of designing new charge-generating layers with improved compressibility to enhance TENG performance.

Multiple-patterning colloidal lithography-implemented scalable manufacturing of heat-tolerant titanium nitride broadband absorbers in the visible to near-infrared.

Broadband perfect absorbers have been intensively researched for decades because of their near-perfect absorption optical property that can be applied to diverse applications. Unfortunately, achieving large-scale and heat-tolerant absorbers has been remained challenging work because of costly and time-consuming lithography methods and thermolability of materials, respectively. Here, we demonstrate a thermally robust titanium nitride broadband absorber with >95% absorption efficiency in the visible and near-infrared region (400-900 nm). A relatively large-scale (2.5 cm × 2.5 cm) absorber device is fabricated by using a fabrication technique of multiple-patterning colloidal lithography. The optical properties of the absorber are still maintained even after heating at the temperatures >600 ∘C. Such a large-scale, heat-tolerant, and broadband near-perfect absorber will provide further useful applications in solar thermophotovoltaics, stealth, and absorption controlling in high-temperature conditions.

Graphoepitaxy of Symmetric Six-Arm Star-Shaped Poly(methyl methacrylate)-block-Polystyrene Copolymer Thin Film.

The authors perform directed self-assembly based on graphoepitaxy of symmetric six-arm star-shaped poly(methyl methacrylate)-block-polystyrene copolymer [(PMMA-b-PS)6 ] thin film. The affinity between each block and the trench wall is adjusted by using polymer brushes or selective gold (Au) deposition. When the surface of the trench is strongly selective for the PMMA block, (n+0.75)L0 thick (n is the number of the lamellae, L0 is lamellar domain spacing) lamellae parallel to the trench wall are formed at each side, while nanotubes are formed away from the trench wall. However, for a trench grafted with PS brushes, nanotubes are formed beside (n+0.25)L0 thick lamellar layers. By adjusting the trench width (W) and the affinity between the block and the wall, various dual nanopatterns consisting of lines and nanotubes are fabricated. Moreover, when the trench wall is selectively deposited by Au, asymmetric dual nanopattern is formed, where different numbers of lines exist on each side wall, while nanotubes are formed in the middle of the trench. The observed morphologies depending on the commensurability condition between W and L0 are consistent with predictions by self-consistent field theory.

Light-Mediated Synthesis and Reprocessing of Dynamic Bottlebrush Elastomers under Ambient Conditions.

We introduce a novel grafting-through polymerization strategy to synthesize dynamic bottlebrush polymers and elastomers in one step using light to construct a disulfide-containing backbone. The key starting material-α-lipoic acid (LA)-is commercially available, inexpensive, and biocompatible. When installed on the chain end(s) of poly(dimethylsiloxane) (PDMS), the cyclic disulfide unit derived from LA polymerizes under ultraviolet (UV) light in ambient conditions. Significantly, no additives such as initiator, solvent, or catalyst are required for efficient gelation. Formulations that include bis-LA-functionalized cross-linker yield bottlebrush elastomers with high gel fractions (83-98%) and tunable, supersoft shear moduli in the ∼20-200 kPa range. An added advantage of these materials is the dynamic disulfide bonds along each bottlebrush backbone, which allow for light-mediated self-healing and on-demand chemical degradation. These results highlight the potential of simple and scalable synthetic routes to generate unique bottlebrush polymers and elastomers based on PDMS.

Multidomain Helical Nanostructure by A1BA2C Tetrablock Terpolymer Self-Assembly.

Among many possible nanostructures in block copolymer self-assembly, helical nanostructures are particularly important because of potential applications for heterogeneous catalysts and plasmonic materials. In this work, we investigated, via small-angle X-ray scattering and transmission electron microscopy, the morphology of a polystyrene-block-polyisoprene-block-polystyrene-block-poly(2-vinylpyridine) (S1IS2V) tetrablock terpolymer. Very interestingly, when the volume fraction of each block was 0.685, 0.125, 0.060, and 0.130, respectively, a multidomain double-stranded helical nanostructure (MH2) was formed: P2VP chains became a core helix, and PI chains formed double-stranded helices surrounding the core helix. Core and double-stranded helices are connected by short PS2 chains, and PS1 chains become the matrix. The experimentally observed morphology is in good agreement with the prediction by self-consistent field theory. We believe that this multidomain helical structure will be pave the way to the creation of multifunctional helical structures for various applications such as metamaterials.

Three-Dimensional Nanoporous Metal Structures from Poly(2-vinylpyridine)-block-Poly(4-vinylpyridine) Copolymer Thin Film.

We fabricated 3D nanoporous metal structures from poly(2-vinylpyridine)-block-poly(4-vinylpyridine) copolymer (P24VP) thin film with vertically oriented lamellar nanodomains by coordinating corresponding metal precursors followed by reduction to metals. Although metal precursors are coordinated with both P2VP and P4VP blocks, the metal coordination power toward P4VP block is much greater than that toward P2VP block. Thus, most of the metal precursors are located in the P4VP block, while a few exist in the P2VP block. After the metal precursors were reduced to corresponding metals by reactive ion etching, metals located in P4VP regions became continuous main frames. However, metals in P2VP regions could not be continuous because of smaller amounts, resulting in nanoporous structures. Using these 3D nanoporous structures, we measured the electrocatalytic activity for hydrogen evolution reaction. 3D nanoporous platinum (Pt) showed enhanced catalytic activity compared with Pt flat film due to the large surface area. Moreover, 3D nanoporous Pt/cobalt bimetallic structures showed better catalytic activity than 3D nanoporous Pt structures.

Dual Nanopatterns Consisting of Both Nanodots and Nanoholes on a Single Substrate.

Block copolymers (BCPs) with various nanostructures such as spheres, cylinders, gyroid, and lamellae, have received great attention for their application in nanolithography through nanopattern transfer to substrates. However, the fabrication of diverse geometries, shapes and sizes of nanostructure on a single substrate at the desired position could not be achieved because the nanostructure based on BCPs is mainly determined by the volume fraction of one block. Here, we synthesize polystyrene-hv-poly(methyl methacrylate) copolymer (PS-hv-PMMA), which contains a photocleavable linker at the junction point between PS and PMMA blocks. After vertically oriented PMMA cylindrical nanodomains in a thin film on a substrate were obtained, dual nanopatterns composed of high-density array of nanodots and nanoholes were successfully fabricated at the desired area on a single substrate using selective irradiation with a mask. The dual nanopatterns could be used to prepare metal (or metal oxide) nanostructure arrays consisting of both nanodots and nanoholes, which are utilized for smart sensors capable of simultaneously detecting two independent molecules on nanodots and nanoholes.

Simultaneous fabrication of line and dot dual nanopatterns using miktoarm block copolymer with photocleavable linker.

Block copolymers with various nanodomains, such as spheres, cylinders, and lamellae, have received attention for their applicability to nanolithography. However, those microdomains are determined by the volume fraction of one block. Meanwhile, nanopatterns with multiple shapes are required for the next-generation nanolithography. Although various methods have been reported to achieve dual nanopatterns, all the methods need sophisticated processes using E-beam. Here, we synthesized a miktoarm block copolymer capable of cleavage of one block by ultraviolet. Original cylindrical nanodomains of synthesized block copolymer were successfully transformed to lamellar nanodomains due to the change of molecular architecture by ultraviolet. We fabricated dual nanopatterns consisting of dots and lines at desired regions on a single substrate. We also prepared dual nanopatterns utilizing another phase transformation from spheres to cylinders in a block copolymer with higher interaction parameter. Since our concept has versatility to any block copolymer, it could be employed as next-generation nanolithography.

Self-Positioned Nanosized Mask for Transparent and Flexible Ferroelectric Polymer Nanodiodes Array.

High density arrays of ferroelectric polymer nanodiodes have gained strong attention for next-generation transparent and flexible nonvolatile resistive memory. Here, we introduce a facile and innovative method to fabricate ferroelectric polymer nanodiode array on an ITO-coated poly(ethylene terephthalate) (PET) substrate by using block copolymer self-assembly and oxygen plasma etching. First, polystyrene-block-poly(2-vinylpyridine) copolymer (PS-b-P2VP) micelles were spin-coated on poly(vinylidene fluoride-ran-trifluoroethylene) copolymer (P(VDF-TrFE)) film/ITO-coated PET substrate. After the sample was immersed in a gold precursor (HAuCl4) containing solution, which strongly coordinates with nitrogen group in P2VP, oxygen plasma etching was performed. During the plasma etching, coordinated gold precursors became gold nanoparticles (GNPs), which successfully acted as self-positioned etching mask to fabricate a high density array of P(VDF-TrFE)) nanoislands with GNP at the top. Each nanoisland shows clearly individual diode property, as confirmed by current-voltage (I-V) curve. Furthermore, due to the transparent and flexible nature of P(VDF-TrFE)) nanoisland as well as the substrate, the P(VDF-TrFE) nanodiode array was highly tranparent, and the diode property was maintained even after a large number of bendings (for instance, 1000 times). The array could be used as the next-generation tranparent and flexible nonvolatile memory device.