Atomically Flat, 2D Edge-Directed Self-Assembly of Block Copolymers.

Nanoscale shape engineering is an essential requirement for the practical use of 2D materials, aiming at precisely customizing optimal structures and properties. In this work, sub-10-nm-scale block copolymer (BCP) self-assembled nanopatterns finely aligned along the atomic edge of 2D flakes, including graphene, MoS2 , and h-BN, are exploited for reliable nanopatterning of 2D materials. The underlying mechanism for the alignment of the self-assembled nanodomains is elucidated based on the wetting layer alternation of the BCP film in the presence of intermediate 2D flakes. The resultant highly aligned nanocylinder templates with remarkably low levels of line edge roughness (LER) and line-width roughness (LWR) yield a sub-10-nm-wide graphene nanoribbon (GNR) array with noticeable switching characteristics (on-to-off ratio up to ≈6 × 104 ).

Multilevel Self-Assembly of Block Copolymers and Polymer Colloids for a Transparent and Sensitive Gas Sensor Platform.

The recent emerging significance of the Internet of Things (IoT) demands sensor devices to be integrated with many different functional structures and devices while conserving their original functionalities. To this end, optical transparency and mechanical flexibility of sensor devices are critical requirements for optimal integration as well as high sensitivity. In this work, a transparent, flexible, and sensitive gas sensor building platform is introduced by using multilevel self-assembly of block copolymers (BCPs) and polystyrene (PS) colloids. For the demonstration of an H2 gas sensor, a hierarchically porous Pd metal mesh structure is obtained by overlaying the two different patterned template structures with synergistic, distinctive characteristic length scales. The hierarchical Pd mesh shows not only high transparency over 90% but also superior sensing performance in terms of response and recovery time owing to enhanced Pd-to-hydride ratio and short H2 diffusion lengths from the enlarged active surface areas. The hierarchical morphology also endows high mechanical flexibility while securing reliable sensing performance even under severe mechanical deformation cycles. Our scalable self-assembly based multiscale nanopatterning offers an intriguing generalized platform for many different multifunctional devices requiring hidden in situ monitoring of environmental signals.

A 2D Ultrathin Nanopatterned Interlayer to Suppress Lithium Dendrite Growth in High-Energy Lithium-Metal Anodes.

A novel strategy for robust and ultrathin (<1 µm) multilayered protective structures to address uncontrolled Lithium (Li) dendrite growth at Li-metal battery anodes is reported. Synergetic interaction among Ag nanoparticles (Ag NPs), reduced graphene oxide (rGO) films, and self-assembled block-copolymer (BCP) layers enables effective suppression of dendritic Li growth. While Ag NP layer confines the growth of Li metal underneath the rGO layer, BCP layer facilitates the fast and uniformly distributed flux of Li-ion transport and mechanically supports the rGO layer. Notably, highly aligned nanochannels with ≈15 nm diameter and ≈600 nm length scale interpenetrating within the BCP layer offer reversible well-defined pathways for Li-ion transport. Dramatic stress relaxation with the multilayered structure is confirmed via structural simulation considering the mechanical stress induced by filamentary-growth of Li metal. Li-metal anodes modified with the protective layer well-maintain stable reaction interfaces with limited solid-electrolyte interphase formation, yielding outstanding cycling stability and enhanced rate capability, as demonstrated by the full-cells paired with high-loading of LiFePO4 cathodes. The idealized design of multilayer protective layer provides significant insight for advanced Li-metal anodes.

Block Copolymer Nanopatterning for Nonsemiconductor Device Applications.

Block copolymer (BCP) nanopatterning has emerged as a versatile nanoscale fabrication tool for semiconductor devices and other applications, because of its ability to organize well-defined, periodic nanostructures with a critical dimension of 5-100 nm. While the most promising application field of BCP nanopatterning has been semiconductor devices, the versatility of BCPs has also led to enormous interest from a broad spectrum of other application areas. In particular, the intrinsically low cost and straightforward processing of BCP nanopatterning have been widely recognized for their large-area parallel formation of dense nanoscale features, which clearly contrasts that of sophisticated processing steps of the typical photolithographic process, including EUV lithography. In this Review, we highlight the recent progress in the field of BCP nanopatterning for various nonsemiconductor applications. Notable examples relying on BCP nanopatterning, including nanocatalysts, sensors, optics, energy devices, membranes, surface modifications and other emerging applications, are summarized. We further discuss the current limitations of BCP nanopatterning and suggest future research directions to open up new potential application fields.

Large-Area Uniform 1-nm-Level Amorphous Carbon Layers from 3D Conformal Polymer Brushes. A "Next-Generation" Cu Diffusion Barrier?

A reliable method for preparing a conformal amorphous carbon (a-C) layer with a thickness of 1-nm-level, is tested as a possible Cu diffusion barrier layer for next-generation ultrahigh-density semiconductor device miniaturization. A polystyrene brush of uniform thickness is grafted onto 4-inch SiO2 /Si wafer substrates with "self-limiting" chemistry favoring such a uniform layer. UV crosslinking and subsequent carbonization transforms this polymer film into an ultrathin a-C layer without pinholes or hillocks. The uniform coating of nonplanar regions or surfaces is also possible. The Cu diffusion "blocking ability" is evaluated by time-dependent dielectric breakdown (TDDB) tests using a metal-oxide-semiconductor (MOS) capacitor structure. A 0.82 nm-thick a-C barrier gives TDDB lifetimes 3.3× longer than that obtained using the conventional 1.0 nm-thick TaNx diffusion barrier. In addition, this exceptionally uniform ultrathin polymer and a-C film layers hold promise for selective ion permeable membranes, electrically and thermally insulating films in electronics, slits of angstrom-scale thickness, and, when appropriately functionalized, as a robust ultrathin coating with many other potential applications.

Highly Aligned Carbon Nanowire Array by E-Field Directed Assembly of PAN-Containing Block Copolymers.

Nanoscale engineering of carbon materials is immensely demanded in various scientific areas. We present highly ordered nitrogen-doped carbon nanowire arrays via block copolymer (BCP) self-assembly under an electric field. Large dielectric constant difference between distinct polymer blocks offers rapid alignment of PMMA-b-PAN self-assembled nanodomains under an electric field. Lithographic patterning of the graphene electrode as well as straightforward thermal carbonization of the PAN block creates well-aligned carbon nanowire device structures. Diverse carbon nanopatterns including radial and curved arrays can be readily assembled by the modification of electrode shapes. Our carbon nanopatterns bear a nitrogen content over 26%, highly desirable for NO2 sensing, as the nitrogen element acts as adsorption sites for NO2 molecules. Aligned carbon nanowire arrays exhibits a 6-fold enhancement of NO2 sensitivity from a randomly aligned counterpart. Taking advantage of well-established benefits from device-oriented BCP nanopatterning, our approach proposes a viable route to highly ordered carbon nanostructures compatible to next-generation device architectures.

Large-Area Alignment of Supramolecular Columns by Photothermal Laser Writing.

Controlling the orientation of highly periodic supramolecular structures of small feature size (<5 nm) is the first step for potential applications in optoelectronics, membranes, and template synthesis. A new method, namely, laser photothermal writing, is introduced to direct the orientation of supramolecular columns over a large area. Supramolecular columns consisting of taper-shaped molecules with long aliphatic tail groups are aligned by a thermal gradient, which is induced by exposing a near-infrared laser beam to a graphene photothermal conversion layer. Intriguingly, the orientation of the supramolecular columns can be controlled in a facile manner by varying the laser scanning velocity and power. In contrast to previous methodologies for aligning supramolecular structures, this laser photothermal mechanism allows the directional and continuous alignment of supramolecular structures over an arbitrary large area with the easy control of laser irradiation. Besides, the laser process also enables area-selective orientation of the supramolecular structures for device-oriented nanopatterning.

Conformal 3D Nanopatterning by Block Copolymer Lithography with Vapor-Phase Deposited Neutral Adlayer.

Block copolymer (BCP) lithography is an effective nanopatterning methodology exploiting nanoscale self-assembled periodic patterns in BCP thin films. This approach has a critical limitation for nonplanar substrate geometry arising from the reflow and modification of BCP films upon the thermal or solvent annealing process, which is inevitable to induce the mobility of BCP chains for the self-assembly process. Herein, reflow-free, 3D BCP nanopatterning is demonstrated by introducing a conformally grown adlayer by the initiated chemical vapor deposition (iCVD) process. A highly cross-linked poly(divinylbenzene) layer was deposited directly onto the BCP thin film surface by iCVD, which effectively prevented the reflow of BCP thin film during an annealing process. BCP nanopatterns could be stabilized on various substrate geometry, including a nonplanar deformed polymer substrate, a pyramid shape substrate, and a graphene fiber surface. A fiber-type hydrogen evolution reaction (HER) catalyst is suggested by stabilizing lamellar Pt nanopatterns on severely rough graphene fiber surfaces.

Nanopatterns with a Square Symmetry from an Orthogonal Lamellar Assembly of Block Copolymers.

A nanosquare array is an indispensable element for the integrated circuit design of electronic devices. Block copolymer (BCP) lithography, a promising bottom-up approach for sub-10 nm patterning, has revealed a generic difficulty in the production of square symmetry because of the thermodynamically favored hexagonal packing of self-assembled sphere or cylinder arrays in thin-film geometry. Here, we demonstrate a simple route to square arrays via the orthogonal self-assembly of two lamellar layers on topographically patterned substrates. While bottom lamellar layers within a topographic trench are aligned parallel to the sidewalls, top layers above the trench are perpendicularly oriented to relieve the interfacial energy between grain boundaries. The size and period of the square symmetry are readily controllable with the molecular weight of BCPs. Moreover, such an orthogonal self-assembly can be applied to the formation of complex nanopatterns for advanced applications, including metal nanodot square arrays.

Ultralarge Area Sub-10 nm Plasmonic Nanogap Array by Block Copolymer Self-Assembly for Reliable High-Sensitivity SERS.

Effective surface enhancement of Raman scattering (SERS) requires strong near-field enhancement as well as effective light collection of plasmonic structures. To this end, plasmonic nanoparticle (NP) arrays with narrow gaps or sharp tips have been suggested as desirable structures. We present a highly dense and uniform Au nanoscale gap array enabled by the customized design of NP shape and arrangement employing block copolymer self-assembly. Block copolymer self-assembly in thin films offers uniform hexagonally packed nanopost template arrays over the entire surface of a 2 in. wafer. Conventional evaporative metal deposition over the nanotemplate surface allows precise geometric control and positional arrangement of metal NPs, constituting tunable, strong plasmonic near-field enhancement particularly at the "hot spots" near interparticular nanoscale gaps. Underlying field distribution has been investigated by a finite-difference time-domain simulation. In the detection of thiophenol, our Au nanogap array shows a remarkable enhancement of Raman intensity greater than ∼104, a standard deviation as small as 12.3% compared to that of the planar Au thin film. In addition, adenine biomolecules can be detected with a detection limit as low as 100 nM. Our approach proposes highly sensitive and reliable SERS on the basis of a scalable, low-cost bottom-up strategy.