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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Performance Enhancement of Electronic and Energy Devices via Block Copolymer Self-Assembly.

The use of self-assembled block copolymers (BCPs) for the fabrication of electronic and energy devices has received a tremendous amount of attention as a non-traditional approach to patterning integrated circuit elements at nanometer dimensions and densities inaccessible to traditional lithography techniques. The exquisite control over the dimensional features of the self-assembled nanostructures (i.e., shape, size, and periodicity) is one of the most attractive properties of BCP self-assembly. Harmonic spatial arrangement of the self-assembled nanoelements at desired positions on the chip may offer a new strategy for the fabrication of electronic and energy devices. Several recent reports show the great promise in using BCP self-assembly for practical applications of electronic and energy devices, leading to substantial enhancements of the device performance. Recent progress is summarized here, with regard to the performance enhancements of non-volatile memory, electrical sensor, and energy devices enabled by directed BCP self-assembly.

Self-Structured Conductive Filament Nanoheater for Chalcogenide Phase Transition.

Ge2Sb2Te5-based phase-change memories (PCMs), which undergo fast and reversible switching between amorphous and crystalline structural transformation, are being utilized for nonvolatile data storage. However, a critical obstacle is the high programming current of the PCM cell, resulting from the limited pattern size of the optical lithography-based heater. Here, we suggest a facile and scalable strategy of utilizing self-structured conductive filament (CF) nanoheaters for Joule heating of chalcogenide materials. This CF nanoheater can replace the lithographical-patterned conventional resistor-type heater. The sub-10 nm contact area between the CF and the phase-change material achieves significant reduction of the reset current. In particular, the PCM cell with a single Ni filament nanoheater can be operated at an ultralow writing current of 20 µA. Finally, phase-transition behaviors through filament-type nanoheaters were directly observed by using transmission electron microscopy.

Flexible one diode-one phase change memory array enabled by block copolymer self-assembly.

Flexible memory is the fundamental component for data processing, storage, and radio frequency communication in flexible electronic systems. Among several emerging memory technologies, phase-change random-access memory (PRAM) is one of the strongest candidate for next-generation nonvolatile memories due to its remarkable merits of large cycling endurance, high speed, and excellent scalability. Although there are a few approaches for flexible phase-change memory (PCM), high reset current is the biggest obstacle for the practical operation of flexible PCM devices. In this paper, we report a flexible PCM realized by incorporating nanoinsulators derived from a Si-containing block copolymer (BCP) to significantly lower the operating current of the flexible memory formed on plastic substrate. The reduction of thermal stress by BCP nanostructures enables the reliable operation of flexible PCM devices integrated with ultrathin flexible diodes during more than 100 switching cycles and 1000 bending cycles.

Flexible piezoelectric thin-film energy harvesters and nanosensors for biomedical applications.

The use of inorganic-based flexible piezoelectric thin films for biomedical applications has been actively reported due to their advantages of highly piezoelectric, pliable, slim, lightweight, and biocompatible properties. The piezoelectric thin films on plastic substrates can convert ambient mechanical energy into electric signals, even responding to tiny movements on corrugated surfaces of internal organs and nanoscale biomechanical vibrations caused by acoustic waves. These inherent properties of flexible piezoelectric thin films enable to develop not only self-powered energy harvesters for eliminating batteries of bio-implantable medical devices but also sensitive nanosensors for in vivo diagnosis/therapy systems. This paper provides recent progresses of flexible piezoelectric thin-film harvesters and nanosensors for use in biomedical fields. First, developments of flexible piezoelectric energy-harvesting devices by using high-quality perovskite thin film and innovative flexible fabrication processes are addressed. Second, their biomedical applications are investigated, including self-powered cardiac pacemaker, acoustic nanosensor for biomimetic artificial hair cells, in vivo energy harvester driven by organ movements, and mechanical sensor for detecting nanoscale cellular deflections. At the end, future perspective of a self-powered flexible biomedical system is also briefly discussed with relation to the latest advancements of flexible electronics.

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.

Flexible crossbar-structured resistive memory arrays on plastic substrates via inorganic-based laser lift-off.

Crossbar-structured memory comprising 32 × 32 arrays with one selector-one resistor (1S-1R) components are initially fabricated on a rigid substrate. They are transferred without mechanical damage via an inorganic-based laser lift-off (ILLO) process as a result of laser-material interaction. Addressing tests of the transferred memory arrays are successfully performed to verify mitigation of cross-talk on a plastic substrate.

Laser-induced solid-phase doped graphene.

There have been numerous efforts to improve the performance of graphene-based electronic devices by chemical doping. Most studies have focused on gas-phase doping with chemical vapor deposition. However, that requires a complicated transfer process that causes undesired doping and defects by residual polymers. Here, we report a solid-phase synthesis of doped graphene by means of silicon carbide (SiC) substrate including a dopant source driven by pulsed laser irradiation. This method provides in situ direct growth of doped graphene on an insulating SiC substrate without a transfer step. A numerical simulation on the temperature history of the SiC surface during laser irradiation reveals that the surface temperature of SiC can be accurately controlled to grow nitrogen-doped graphene from the thermal decomposition of nitrogen-doped SiC. Laser-induced solid-phase doped graphene is highly promising for the realization of graphene-based nanoelectronics with desired functionalities.