An extraordinarily large degree of tunability in geometry and dimension is demonstrated in films of a self-assembled block copolymer. A poly(2-vinylpyridine-b-dimethylsiloxane) block copolymer with highly incompatible blocks was spun-cast on patterned substrates and treated with various solvent vapors. The degree of selective swelling in the poly(2-vinylpyridine) matrix block could be controlled over an extensive range, leading to the formation of various microdomain morphologies such as spheres, cylinders, hexagonally perforated lamellae, and lamellae from the same block copolymer. The systematic control of swelling ratio and the choice of solvent vapors offer the unusual ability to control the width of very well-ordered linear features within a range between 6 and 31 nm. This methodology is particularly useful for nanolithography based on directed self-assembly in that a single block copolymer film can form microdomains with a broad range of geometries and sizes without the need to change molecular weight or volume fraction.
Graphene dots precisely controlled in size are interesting in nanoelectronics due to their quantum optical and electrical properties. However, most graphene quantum dot (GQD) research so far has been performed based on flaketype graphene reduced from graphene oxides. Consequently, it is extremely difficult to isolate the size effect of GQDs from the measured optical properties. Here, we report the sizecontrolled fabrication of uniform GQDs using self-assembled block copolymer (BCP) as an etch mask on graphene films grown by chemical vapor deposition (CVD). Electron microscope images show that as-prepared GQDs are composed of mono-or bilayer graphene with diameters of 10 and 20 nm, corresponding to the size of BCP nanospheres. In the measured photoluminescence (PL) spectra, the emission peak of the GQDs on the SiO 2 substrate is shown to be at ∼395 nm. The fabrication of GQDs was supported by the analysis of the Raman spectra and the observation of PL spectra after each fabrication step. Additionally, oxygen content in the GQDs is rationally controlled by additional air plasma treatment, which reveals the effect of oxygen content to the PL property.
The synergetic combination of low‐temperature thermal assistance with solvent annealing for the self‐assembly of block copolymers with a large Flory‐Huggins interaction parameter simultaneously achieves sub‐10 nm resolution and sub‐1 minute annealing time. It is shown that this method is applicable to different geometries of patterns such as nanoscale dots, lines, and holes.
Resistive random access memory (ReRAM) is a promising candidate for future nonvolatile memories. Resistive switching in a metal-insulator-metal structure is generally assumed to be caused by the formation/rupture of nanoscale conductive filaments (CFs) under an applied electric field. The critical issue of ReRAM for practical memory applications, however, is insufficient repeatability of the operating voltage and resistance ratio. Here, we present an innovative approach to reliably and reproducibly control the CF growth in unipolar NiO resistive memory by exploiting uniform formation of insulating SiOx nanostructures from the self-assembly of a Si-containing block copolymer. In this way, the standard deviation (SD) of set and reset voltages was markedly reduced by 76.9% and 59.4%, respectively. The SD of high resistance state also decreased significantly, from 6.3 × 10(7) Ω to 5.4 × 10(4) Ω. Moreover, we report direct observations of localized metallic Ni CF formation and their controllable growth using electron microscopy and discuss electrothermal simulation results based on the finite element method supporting our analysis results.
An extraordinarily facile sub-10 nm fabrication method using the synergic combination of nanotransfer printing and the directed self-assembly of block copolymers is introduced. The approach is realized by achieving the uniform self-assembly of polydimethylsiloxane (PDMS)-containing block copolymers on a PDMS mold through the stabilization of the block copolymer thin films. This simple printing method can be applied on oxides, metals, polymers, and non-planar substrates without pretreatments. The fabrication of well-aligned metallic and polymeric functional nanostructures and crossed wire structures is also presented.
While the uses of block copolymers (BCPs) with a high Flory-Huggins interaction parameter (χ) are advantageous for the improvement of resolution and line edge fluctuations of self-assembled nanoscale patterns, their slow chain diffusion results in a prolonged assembly time. Although solvent vapor annealing has shown great effectiveness in promoting the self-assembly of such BCPs, a practical methodology to achieve a uniform swelling level in wafer-scale BCP thin films has not been reported. Here, we show that a solvent-swollen polymer gel pad can be used as a highly controllable vapor source for the rapid, large-area (>200 mm in diameter) formation of sub-10-nm patterns from a high-χ BCP. The proximal injection of solvent vapors to BCP films and the systematic control of the swelling levels and temperatures can significantly boost the self-assembly kinetics, realizing the formation of well-aligned sub-10-nm half-pitch patterns within 1 min of self-assembly. Moreover, we show that the gel pad can be used for the shear-induced alignment of BCP microdomains in an extremely short time of ~5 s as well as for the generation of three-dimensional crossed-wire nanostructures with controlled alignment angles.
The directed self-assembly (DSA) of block copolymers (BCPs) is expected to complement conventional optical lithography due to its excellent pattern resolution and cost-effectiveness. Recent studies have shown that BCPs with a large Flory-Huggins interaction parameter (χ) are critical for a reduction of the thermodynamic defect density as well as an increase in pattern density. However, due to their slower self-assembly kinetics, high-χ BCPs typically necessitate solvent vapor annealing, which requires complex facilities and procedures compared to simple thermal annealing. Here, we introduce an immersion-triggered directed self-assembly (iDSA) process and demonstrate the combined advantages of excellent simplicity, productivity, large-area capability, and tunability. We show that the vapor-free, simple immersion of high-χ BCPs in a composition-optimized mixture of nonswelling and swelling solvents can induce the ultrafast (≤ 5 min) formation of nanoscale patterns with a pattern size ranging from 8-18 nm. Moreover, iDSA enables the reversible formation of seven different nanostructures from one sphere-forming BCP, demonstrating the outstanding controllability of this self-assembly route.
Phase change memory (PCM), which exploits the phase change behavior of chalcogenide materials, affords tremendous advantages over conventional solid-state memory due to its nonvolatility, high speed, and scalability. However, high power consumption of PCM poses a critical challenge and has been the most significant obstacle to its widespread commercialization. Here, we present a novel approach based on the self-assembly of a block copolymer (BCP) to form a thin nanostructured SiOx layer that locally blocks the contact between a heater electrode and a phase change material. The writing current is decreased 5-fold (corresponding to a power reduction by 1/20) as the occupying area fraction of SiOx nanostructures is increased from a fill factor of 9.1% to 63.6%. Simulation results theoretically explain the current reduction mechanism by localized switching of BCP-blocked phase change materials.
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