Ferroelectric Polymer Nanofibers Reminiscent of Morphotropic Phase Boundary Behavior for Improved Piezoelectric Energy Harvesting.

Ferroelectric and piezoelectric polymers have attracted great attention from many research and engineering fields due to its mechanical robustness and flexibility as well as cost-effectiveness and easy processibility. Nevertheless, the electrical performance of piezoelectric polymers is very hard to reach that of piezoelectric ceramics basically and physically, even in the case of the representative ferroelectric polymer, poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)). Very recently, the concept for the morphotropic phase boundary (MPB), which has been exclusive in the field of high-performance piezoelectric ceramics, has been surprisingly confirmed in P(VDF-TrFE) piezoelectric copolymers by the groups. This study demonstrates the exceptional behaviors reminiscent of MPB and relaxor ferroelectrics in the feature of widely utilized electrospun P(VDF-TrFE) nanofibers. Consequently, an energy harvesting device that exceeds the performance limitation of the existing P(VDF-TrFE) materials is developed. Even the unpoled MPB-based P(VDF-TrFE) nanofibers show higher output than the electrically poled normal P(VDF-TrFE) nanofibers. This study is the first step toward the manufacture of a new generation of piezoelectric polymers with practical applications.

Harnessing Colloidal Crack Formation by Flow-Enabled Self-Assembly.

Self-assembly of nanomaterials to yield a wide diversity of high-order structures, materials, and devices promises new opportunities for various technological applications. Herein, we report that crack formation can be effectively harnessed by elaborately restricting the drying of colloidal suspension using a flow-enabled self-assembly (FESA) strategy to yield large-area periodic cracks (i.e., microchannels) with tunable spacing. These uniform microchannels can be utilized as a template to guide the assembly of Au nanoparticles, forming intriguing nanoparticle threads. This strategy is simple and convenient. As such, it opens the possibility for large-scale manufacturing of crack-based or crack-derived assemblies and materials for use in optics, electronics, optoelectronics, photonics, magnetic device, nanotechnology, and biotechnology.

A Nonconventional Approach to Patterned Nanoarrays of DNA Strands for Template-Assisted Assembly of Polyfluorene Nanowires.

DNA molecules have been widely recognized as promising building blocks for constructing functional nanostructures with two main features, that is, self-assembly and rich chemical functionality. The intrinsic feature size of DNA makes it attractive for creating versatile nanostructures. Moreover, the ease of access to tune the surface of DNA by chemical functionalization offers numerous opportunities for many applications. Herein, a simple yet robust strategy is developed to yield the self-assembly of DNA by exploiting controlled evaporative assembly of DNA solution in a unique confined geometry. Intriguingly, depending on the concentration of DNA solution, highly aligned nanostructured fibrillar-like arrays and well-positioned concentric ring-like superstructures composed of DNAs are formed. Subsequently, the ring-like negatively charged DNA superstructures are employed as template to produce conductive organic nanowires on a silicon substrate by complexing with a positively charged conjugated polyelectrolyte poly[9,9-bis(6'-N,N,N-trimethylammoniumhexyl)fluorene dibromide] (PF2) through the strong electrostatic interaction. Finally, a monolithic integration of aligned arrays of DNA-templated PF2 nanowires to yield two DNA/PF2-based devices is demonstrated. It is envisioned that this strategy can be readily extended to pattern other biomolecules and may render a broad range of potential applications from the nucleotide sequence and hybridization as recognition events to transducing elements in chemical sensors.

Topographically-designed triboelectric nanogenerator via block copolymer self-assembly.

Herein, we report a facile and robust route to nanoscale tunable triboelectric energy harvesters realized by the formation of highly functional and controllable nanostructures via block copolymer (BCP) self-assembly. Our strategy is based on the incorporation of various silica nanostructures derived from the self-assembly of BCPs to enhance the characteristics of triboelectric nanogenerators (TENGs) by modulating the contact-surface area and the frictional force. Our simulation data also confirm that the nanoarchitectured morphologies are effective for triboelectric generation.

An unconventional route to high-efficiency dye-sensitized solar cells via embedding graphitic thin films into TiO2 nanoparticle photoanode.

Graphitic thin films embedded with highly dispersed titanium dioxide (TiO(2)) nanoparticles were incorporated for the first time into the conventional dye-sensitized solar cells (DSSCs), resulting in a remarkably improved cell efficiency due to its superior electron conductivity. Massively ordered arrays of TiO(2) dots embedded in carbon matrix were fabricated via UV-stabilization of polystyrene-block-poly(4-vinylpyridine) films containing TiO(2) precursors followed by direct carbonization. For dye-sensitized TiO(2) based solar cells containing carbon/TiO(2) thin layers at both sides of pristine TiO(2) layer, an increase of 62.3% [corrected] in overall power conversion efficiency was achieved compared with neat TiO(2)-based DSSCs. Such a remarkably improved cell efficiency was ascribed to the superior electron conductivity and extended electron lifetime elucidated by cyclic voltammetry and impedance spectroscopy.

Large-scale hierarchically structured conjugated polymer assemblies with enhanced electrical conductivity.

Stripes on a plane: A set of highly ordered microscopic stripes (purple; see scheme) were produced over a large area by using controlled evaporative self-assembly in a cylinder-on-Si geometry of conjugated homopolymers or all-conjugated diblock copolymer (P3BHT). The crystallinity of the as-prepared assemblies of P3BHT was greatly improved following chloroform vapor annealing, resulting in a fourfold increase in electrical conductivity.

The Stack Optimization of Magnetic Heterojunction Structures for Next-Generation Spintronic Logic Applications.

Magnetic heterojunction structures with a suppressed interfacial Dzyaloshinskii-Moriya interaction and a sustainable long-range interlayer exchange coupling are achieved with an ultrathin platinum insertion layer. The systematic inelastic light scattering spectroscopy measurements indicate that the insertion layer restores the symmetry of the system and, then, the interfacial Dzyaloshinskii-Moriya interaction, which can prevent the identical magnetic domain wall motions, is obviously minimized. Nevertheless, the strong interlayer exchange coupling of the system is maintained. Consequently, synthetic ferromagnetic and antiferromagnetic exchange couplings as a function of the ruthenium layer thickness are observed as well. Therefore, these optimized magnetic multilayer stacks can avoid crucial issues, such as domain wall tilting and position problems, for next-generation spintronic logic applications. Moreover, the synthetic antiferromagnetic coupling can open a new path to develop a radically different NOT gate via current-induced magnetic domain wall motions and inversions.

A simple route to hierarchically assembled micelles and inorganic nanoparticles.

Earning their stripes: A hierarchical assembly of micelles composed of an amphiphilic diblock copolymer, poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP), were made by combining controlled evaporative self-assembly of the confined PS-b-P4VP toluene solution in a cylinder-on-Si geometry with spontaneous self-assembly of micelles. This method gave microscopic stripes of nanometer-sized PS-b-P4VP micelles within the stripes (see pictures).

Micro-to-Nanometer Scale Patterning of Perovskite Inks via Controlled Self-Assemblies.

In the past decade, perovskite materials have gained intensive interest due to their remarkable material properties in optoelectronics and photodetectors. This review highlights recent advances in micro-to-nanometer scale patterning of perovskite inks, placing an undue emphasis on recently developed approaches to harness spatially ordered and crystallographically oriented structures with unprecedented regularity via controlled self-assemblies, including blade coating, inkjet printing, and nanoimprinting. Patterning of the perovskite elements at the micro- or nanometer scale might be a key parameter for their integration in a real system. Nowadays, unconventional approaches based on irreversible solution evaporation hold an important position in the structuring and integration of perovskite materials. Herein, easier type patterning techniques based on evaporations of polymer solutions and the coffee ring effect are systematically reviewed. The recent progress in the potential applications of the patterned perovskite inks is also introduced.

Facile Synthesis of Mesoporous Silica at Room Temperature for CO2 Adsorption.

Although mesoporous silica materials have been widely investigated for many applications, most silica materials are made by calcination processes. We successfully developed a convenient method to synthesize mesoporous materials at room temperature. Although the silica materials made by the two different methods, which are the calcination process and the room-temperature process, have similar specific surface areas, the silica materials produced with the room-temperature process have a significantly larger pore volume. This larger pore volume has the potential to attach to functional groups that can be applied to various industrial fields such as CO2 adsorption. This mesoporous silica with a larger pore volume was analyzed by TEM, FT-IR, low angle X-ray diffraction, N2-adsorption analysis, and CO2 adsorption experiments in comparison with the mesoporous silica synthesized with the traditional calcination method.

Hierarchically organized structures engineered from controlled evaporative self-assembly.

By constraining an asymmetric comb block copolymer (CBCP) toluene solution to evaporate in a wedge-on-Si geometry composed of a wedge lens situated on a Si substrate, gradient concentric stripelike surface patterns of CBCP at the microscopic scale were yielded as a direct consequence of controlled evaporative self-assembly of CBCP. The formation of either straight stripes or jagged stripes was dictated by the height of the wedge. Upon subsequent solvent vapor annealing, hierarchically organized structures of CBCP were produced, resulting from the interplay of solvent vapor assisted, unfavorable interfacial interaction driven destabilization of CBCP from the Si substrate at the microscopic scale and the solvent vapor promoted reconstruction of CBCP nanodomains within the stripes at the nanometer scale. This facile approach of combining controlled evaporative self-assembly with subsequent solvent vapor annealing offers a new platform to rationally design and engineer self-assembling building blocks into functional materials and devices in a simple, cost-effective manner.

Controlled self-assembly of block copolymers in printed sub-20 nm cross-bar structures.

Directed self-assembly (DSA) of block copolymers (BCPs) has garnered much attention due to its excellent pattern resolution, simple process, and good compatibility with many other lithography methods for useful nanodevice applications. Here, we present a BCP-based multiple nanopatterning process to achieve three-dimensional (3D) pattern formation of metal/oxide hybrid nanostructures. We employed a self-assembled sub-20 nm SiO x line pattern as a master mold for nanotransfer printing (nTP) to generate a cross-bar array. By using the transfer-printed cross-bar structures as BCP-guiding templates, we can obtain well-ordered BCP microdomains in the distinct spaces of the nanotemplates through a confined BCP self-assembly process. We also demonstrate the morphological evolution of a cylinder-forming BCP by controlling the BCP film thickness, showing a clear morphological transition from cylinders to spheres in the designated nanospaces. Furthermore, we demonstrate how to control the number of BCP spheres within the cross-bar 3D pattern by adjusting the printing angle of the multiple nTP process to provide a suitable area for spontaneous BCP accommodation. This multiple-patterning-based approach is applicable to useful 3D nanofabrication of various devices with complex hybrid nanostructures.

Lithography-Free Route to Hierarchical Structuring of High-χ Block Copolymers on a Gradient Patterned Surface.

A chemically defined patterned surface was created via a combined process of controlled evaporative self-assembly of concentric polymer stripes and the selective surface modification of polymer brush. The former process involved physical adsorption of poly (methyl methacrylate) (PMMA) segments into silicon oxide surface, thus forming ultrathin PMMA stripes, whereas the latter process was based on the brush treatment of silicon native oxide surface using a hydroxyl-terminated polystyrene (PS-OH). The resulting alternating PMMA- and PS-rich stripes provided energetically favorable regions for self-assembly of high χ polystyrene-block-polydimethylsiloxane (PS-b-PDMS) in a simple and facile manner, dispensing the need for conventional lithography techniques. Subsequently, deep reactive ion etching and oxygen plasma treatment enabled the transition of the PDMS blocks into oxidized groove-shaped nanostructures.

Thermally assisted nanotransfer printing with sub-20-nm resolution and 8-inch wafer scalability.

Nanotransfer printing (nTP) has attracted considerable attention due to its good pattern resolution, process simplicity, and cost-effectiveness. However, the development of a large-area nTP process has been hampered by critical reliability issues related to the uniform replication and regular transfer printing of functional nanomaterials. Here, we present a very practical thermally assisted nanotransfer printing (T-nTP) process that can easily produce well-ordered nanostructures on an 8-inch wafer via the use of a heat-rolling press system that provides both uniform pressure and heat. We also demonstrate various complex pattern geometries, such as wave, square, nut, zigzag, and elliptical nanostructures, on diverse substrates via T-nTP. Furthermore, we demonstrate how to obtain a high-density crossbar metal-insulator-metal memristive array using a combined method of T-nTP and directed self-assembly. We expect that the state-of-the-art T-nTP process presented here combined with other emerging patterning techniques will be especially useful for the large-area nanofabrication of various devices.

Massively ordered microstructures composed of magnetic nanoparticles.

Magnetic γ-Fe(2)O(3) nanoparticle toluene solution was placed in a restricted, axially symmetric geometry composed of a spherical lens on a Si substrate (i.e., sphere-on-Si geometry), forming a capillary-held solution. The solvent evaporation led to the self-assembly of γ- Fe(2)O(3) nanoparticles into hundreds of spatially well-ordered, gradient concentric 'coffee rings'. The rings were two nanoparticle layers high with a monolayer of nanoparticle thin film formed in between. The ring width ranged from submicron to a few microns. The center-to-center distance between adjacent rings was on the order of a few microns. The size and packing of γ- Fe(2)O(3) nanoparticles, both within individual microscopic rings and in between, were dependent upon the preparation of the γ-Fe(2)O(3) nanoparticle toluene solution.

Pattern formation of metal-oxide hybrid nanostructures via the self-assembly of di-block copolymer blends.

The templated self-assembly of block copolymers (BCPs) with a high Flory-Huggins interaction parameter (χ) can effectively create ultrafine, well-ordered nanostructures in the range of 5-30 nm. However, the self-assembled BCP patterns remain limited to possible morphological geometries and materials. Here, we introduce a novel and useful self-assembly method of di-BCP blends capable of generating diverse hybrid nanostructures consisting of oxide and metal materials through the rapid microphase separation of A-B/B-C BCP blends. We successfully obtained various hybridized BCP morphologies which cannot be acquired from a single di-BCP, such as hexagonally arranged hybrid dot and dot-in-hole patterns by controlling the mixing ratios of the solvents with a binary solvent annealing process. Furthermore, we demonstrate how the binary solvent vapor annealing process can provide a wide range of pattern geometries to di-BCP blends, showing a well-defined spontaneous one-to-one accommodation in dot-in-hole nanostructures. Specifically, we show clearly how the self-assembled BCPs can be functionalized via selective reduction and/or an oxidation process, resulting in the excellent positioning of confined silica nanodots into each nanospace of a Pt mesh. These results suggest a new method to achieve the pattern formation of more diverse and complex hybrid nanostructures using various blended BCPs.

Convenient and Robust Route to Photoswitchable Hierarchical Liquid Crystal Polymer Stripes via Flow-Enabled Self-Assembly.

Hierarchically arranged stripes of photoswitchable liquid crystal polymers (LCPs) containing azobenzene moieties were conveniently crafted via a flow-enabled self-assembly (FESA). Interestingly, by subjecting a drop of LCP solution to dry in a restricted geometry comprising two nearly parallel plates with a stationary upper plate and a movable lower plate that programmably traveled in a "stop-and-move" manner during the FESA process, photoswitchable LCP stripes were yielded, displaying two modes of deposition, namely, periodic primary stripes of large dimensions and regularly spaced secondary stripes of small dimensions situated between adjacent primary stripes (i.e., forming hierarchical LCP stripes). Notably, these hierarchical azobenzene moieties-containing stripes demonstrated sequential photoinduced reversible phase transition (i.e., photoswitching) due to the thickness difference between primary and secondary stripes. A UV light-induced expansion effect was observed on the LCP stripes. Clearly, such rapid creation of hierarchical stripes by FESA represents a robust means of organizing polymers, nanoparticles, colloids, DNA, etc. into complex yet ordered patterns over a large area in a simple and controllable manner for potential use in surface relief grating, photoactuators, photoswitchable devices, antifake labels, etc.

Laser-induced phase separation of silicon carbide.

Understanding the phase separation mechanism of solid-state binary compounds induced by laser-material interaction is a challenge because of the complexity of the compound materials and short processing times. Here we present xenon chloride excimer laser-induced melt-mediated phase separation and surface reconstruction of single-crystal silicon carbide and study this process by high-resolution transmission electron microscopy and a time-resolved reflectance method. A single-pulse laser irradiation triggers melting of the silicon carbide surface, resulting in a phase separation into a disordered carbon layer with partially graphitic domains (∼2.5 nm) and polycrystalline silicon (∼5 nm). Additional pulse irradiations cause sublimation of only the separated silicon element and subsequent transformation of the disordered carbon layer into multilayer graphene. The results demonstrate viability of synthesizing ultra-thin nanomaterials by the decomposition of a binary system.