Neutral-layer-free directed self-assembly of block copolymer in trench using capillary force-induced meniscus.

We propose trench-directed self-assembly (TDSA) of a block copolymer (BCP) driven by a capillary force-induced meniscus as a facile scalable nanolithography method. Unlike conventional directed self-assembly methods, TDSA enables the achievement of neutral surface-free vertical orientations of the BCP nanopatterns irrespective of the polarizability of the substrate, which may be, for example, a ceramic (SiO2) on Semiconductor (Si). In our demonstration of the proposed method, we generated various morphologies of the BCP nanopatterns by varying the trench width, and molecular weight of the BCP. The proposed TDSA method is potentially advantageous for the design of a process/device layout required for the development of an effective manufacturing process.

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.

Bimodal phase separated block copolymer/homopolymer blends self-assembly for hierarchical porous metal nanomesh electrodes.

Transparent conducting electrodes (TCEs) are essential components in various optoelectronic devices. Nanostructured metallic thin film is one of the promising candidates to complement current metal oxide films, such as ITO, where high cost rare earth elements have been a longstanding issue. Herein, we present that multiscale porous metal nanomesh thin films prepared by bimodal self-assembly of block copolymer (BCP)/homopolymer blends may offer a new opportunity for TCE. This hierarchical concurrent self-assembly consists of macrophase separation between BCP and homopolymer as well as microphase separation of BCP, and thus provides a straightforward spontaneous production of a highly porous multiscale pattern over an arbitrary large area. Employing a conventional pattern transfer process, we successfully demonstrated a multiscale highly porous metallic thin film with reasonable optical transparency, electro-conductance, and large-area uniformity, taking advantage of low loss light penetration through microscale pores and significant suppression of light reflection at the nanoporous structures. This well-defined controllable bimodal self-assembly can offer valuable opportunities for many different applications, including optoelectronics, energy harvesting, and membranes.

Wafer-Scale Synthesis of Reliable High-Mobility Molybdenum Disulfide Thin Films via Inhibitor-Utilizing Atomic Layer Deposition.

A reliable and rapid manufacturing process of molybdenum disulfide (MoS2 ) with atomic-scale thicknesses remains a fundamental challenge toward its successful incorporation into high-performance nanoelectronics. It is imperative to achieve rapid and scalable production of MoS2 exhibiting high carrier mobility and excellent on/off current ratios simultaneously. Herein, inhibitor-utilizing atomic layer deposition (iALD) is presented as a novel method to meet these requirements at the wafer scale. The kinetics of the chemisorption of Mo precursors in iALD is governed by the reaction energy and the steric hindrance of inhibitor molecules. By optimizing the inhibition of Mo precursor absorption, the nucleation on the substrate in the initial stage can be spontaneously tailored to produce iALD-MoS2 thin films with a significantly increased grain size and surface coverage (>620%). Moreover, highly crystalline iALD-MoS2 thin films, with thicknesses of only a few layers, excellent room temperature mobility (13.9 cm2 V-1 s-1 ), and on/off ratios (>108 ), employed as the channel material in field effect transistors on 6″ wafers, are successfully prepared.

Flash Light Millisecond Self-Assembly of High χ Block Copolymers for Wafer-Scale Sub-10 nm Nanopatterning.

One of the fundamental challenges encountered in successful incorporation of directed self-assembly in sub-10 nm scale practical nanolithography is the process compatibility of block copolymers with a high Flory-Huggins interaction parameter (χ). Herein, reliable, fab-compatible, and ultrafast directed self-assembly of high-χ block copolymers is achieved with intense flash light. The instantaneous heating/quenching process over an extremely high temperature (over 600 °C) by flash light irradiation enables large grain growth of sub-10 nm scale self-assembled nanopatterns without thermal degradation or dewetting in a millisecond time scale. A rapid self-assembly mechanism for a highly ordered morphology is identified based on the kinetics and thermodynamics of the block copolymers with strong segregation. Furthermore, this novel self-assembly mechanism is combined with graphoepitaxy to demonstrate the feasibility of ultrafast directed self-assembly of sub-10 nm nanopatterns over a large area. A chemically modified graphene film is used as a flexible and conformal light-absorbing layer. Subsequently, transparent and mechanically flexible nanolithography with a millisecond photothermal process is achieved leading the way for roll-to-roll processability.

Self-Assembly of Complex Multimetal Nanostructures from Perforated Lamellar Block Copolymer Thin Films.

We introduce a facile and effective fabrication of complex multimetallic nanostructures through block copolymer self-assembly. Two- and three-dimensional complex nanostructures, such as "nanomesh," "double-layered nanomeshes," and "surface parallel cylinders on nanomesh," can be fabricated using the self-assembly of perforated lamellar morphology in block copolymer thin films. Simultaneous integration of various metallic elements, including Pt, Au, and Co, into the self-assembled morphologies generates multimetal complex nanostructures with highly interconnected morphology and a large surface. The resultant metal nanostructures with a large surface area, robust electrical connectivity, and well-defined alloy composition demonstrate a high-performance electrochemical catalysis for hydrogen evolution reaction (current density: 6.27 mA/cm2@0.1 V and Tafel slope: 43 mV/dec).

Evenly transferred single-layered graphene membrane assisted by strong substrate adhesion.

We explored the transfer of a single-layered graphene membrane assisted by substrate adhesion. A relatively larger adhesion force was measured on the SiO2 substrate compared with its van der Waals contribution, which is expected to result from the additional contribution of the chemical bonding force. Density functional theory calculations verified that the strong adhesion force was indeed accompanied by chemical bonding. The transfer of single-layered graphene and subsequent deposition of the dielectric layer were best performed on the SiO2 substrate exhibiting a larger adhesion force. This study suggests the selection and/or modification of the underlying substrate for proper transfer of graphene as well as other 2D materials similar to graphene.

Self-Aligned Multichannel Graphene Nanoribbon Transistor Arrays Fabricated at Wafer Scale.

We present a novel method for fabricating large-area field-effect transistors (FETs) based on densely packed multichannel graphene nanoribbon (GNR) arrays using advanced direct self-assembly (DSA) nanolithography. The design of our strategy focused on the efficient integration of the FET channel and using fab-compatible processes such as thermal annealing and chemical vapor deposition. We achieved linearly stacked DSA nanopattern arrays with sub-10 nm half-pitch critical dimensions (CD) by controlling the thickness of topographic Au confinement patterns. Excellent roughness values (∼10% of CD) were obtained, demonstrating the feasibility of integrating sub-10 nm GNRs into commercial semiconductor processes. Based on this facile process, FETs with such densely packed multichannel GNR arrays were successfully fabricated on 6 in. silicon wafers. With these high-quality GNR arrays, we achieved FETs showing the highest performance reported to date (an on-to-off ratio larger than 10(2)) for similar devices produced using conventional photolithography and block-copolymer lithography.

Complex High-Aspect-Ratio Metal Nanostructures by Secondary Sputtering Combined with Block Copolymer Self-Assembly.

High-resolution (10 nm), high-areal density, high-aspect ratio (>5), and morphologically complex nanopatterns are fabricated from a single conventional block copolymer (BCP) structure with a 70 nm scale resolution and an aspect ratio of 1, through the secondary-sputtering phenomenon during the Ar-ion-bombardment process. This approach provides a foundation for the design of new routes to BCP lithography.

Mesostructured HfxAlyO2 Thin Films as Reliable and Robust Gate Dielectrics with Tunable Dielectric Constants for High-Performance Graphene-Based Transistors.

We introduce a reliable and robust gate dielectric material with tunable dielectric constants based on a mesostructured HfxAlyO2 film. The ultrathin mesostructured HfxAlyO2 film is deposited on graphene via a physisorbed-precursor-assisted atomic layer deposition process and consists of an intermediate state with small crystallized parts in an amorphous matrix. Crystal phase engineering using Al dopant is employed to achieve HfO2 phase transitions, which produce the crystallized part of the mesostructured HfxAlyO2 film. The effects of various Al doping concentrations are examined, and an enhanced dielectric constant of ∼25 is obtained. Further, the leakage current is suppressed (∼10(-8) A/cm(2)) and the dielectric breakdown properties are enhanced (breakdown field: ∼7 MV/cm) by the partially remaining amorphous matrix. We believe that this contribution is theoretically and practically relevant because excellent gate dielectric performance is obtained. In addition, an array of top-gated metal-insulator-graphene field-effect transistors is fabricated on a 6 in. wafer, yielding a capacitance equivalent oxide thickness of less than 1 nm (0.78 nm). This low capacitance equivalent oxide thickness has important implications for the incorporation of graphene into high-performance silicon-based nanoelectronics.

MoS2-InGaZnO Heterojunction Phototransistors with Broad Spectral Responsivity.

We introduce an amorphous indium-gallium-zinc-oxide (a-IGZO) heterostructure phototransistor consisting of solution-based synthetic molybdenum disulfide (few-layered MoS2, with a band gap of ∼1.7 eV) and sputter-deposited a-IGZO (with a band gap of ∼3.0 eV) films as a novel sensing element with a broad spectral responsivity. The MoS2 and a-IGZO films serve as a visible light-absorbing layer and a high mobility channel layer, respectively. Spectroscopic measurements reveal that appropriate band alignment at the heterojunction provides effective transfer of the visible light-induced electrons generated in the few-layered MoS2 film to the underlying a-IGZO channel layer with a high carrier mobility. The photoresponse characteristics of the a-IGZO transistor are extended to cover most of the visible range by forming a heterojunction phototransistor that harnesses a visible light responding MoS2 film with a small band gap prepared through a large-area synthetic route. The MoS2-IGZO heterojunction phototransistors exhibit a photoresponsivity of approximately 1.7 A/W at a wavelength of 520 nm (an optical power of 1 µW) with excellent time-dependent photoresponse dynamics.

Thickness scaling of atomic-layer-deposited HfO2 films and their application to wafer-scale graphene tunnelling transistors.

The downscaling of the capacitance equivalent oxide thickness (CET) of a gate dielectric film with a high dielectric constant, such as atomic layer deposited (ALD) HfO2, is a fundamental challenge in achieving high-performance graphene-based transistors with a low gate leakage current. Here, we assess the application of various surface modification methods on monolayer graphene sheets grown by chemical vapour deposition to obtain a uniform and pinhole-free ALD HfO2 film with a substantially small CET at a wafer scale. The effects of various surface modifications, such as N-methyl-2-pyrrolidone treatment and introduction of sputtered ZnO and e-beam-evaporated Hf seed layers on monolayer graphene, and the subsequent HfO2 film formation under identical ALD process parameters were systematically evaluated. The nucleation layer provided by the Hf seed layer (which transforms to the HfO2 layer during ALD) resulted in the uniform and conformal deposition of the HfO2 film without damaging the graphene, which is suitable for downscaling the CET. After verifying the feasibility of scaling down the HfO2 thickness to achieve a CET of ~1.5 nm from an array of top-gated metal-oxide-graphene field-effect transistors, we fabricated graphene heterojunction tunnelling transistors with a record-low subthreshold swing value of <60 mV/dec on an 8" glass wafer.

3D Tailored Crumpling of Block-Copolymer Lithography on Chemically Modified Graphene.

Novel 3D self-assembled nanopatterning is presented via tailored crumpling of chemically modified graphene. Block-copolymer self-assembly formed on a layer of chemically modified graphene provides highly dense and uniform 2D nanopatterns, and the controlled crumpling of the chemically modified graphene by mechanical instabilities realizes the controlled 3D transformation of the self-assembled nanopatterns.

Negative-tone block copolymer lithography by in situ surface chemical modification.

Negative-tone block copolymer (BCP) lithography based on in situ surface chemical modification is introduced as a highly efficient, versatile self-assembled nanopatterning. BCP blends films consisting of end-functionalized low molecular weight poly(styrene-ran-methyl methacrylate) and polystyrene-block-Poly(methyl methacylate) can produce surface vertical BCP nanodomains on various substrates without prior surface chemical treatment. Simple oxygen plasma treatment is employed to activate surface functional group formation at various substrates, where the end-functionalized polymers can be covalently bonded during the thermal annealing of BCP thin films. The covalently bonded brush layer mediates neutral interfacial condition for vertical BCP nanodomain alignment. This straightforward approach for high aspect ratio, vertical self-assembled nanodomain formation facilitates single step, site-specific BCP nanopatterning widely useful for various substrates. Moreover, this approach is compatible with directed self-assembly approaches to produce device oriented laterally ordered nanopatterns.

Direct 3-D nanoparticle assemblies in thin films via topographically patterned surfaces.

Simple yet versatile routes to generate macroscopically aligned 3-D NP arrays with tunable structures in supramolecular nanocomposite thin films are presented using faceted and lithographically patterned surfaces. These studies provide a powerful platform for the investigation of emerging structure-property relationships in functional nanocomposites, paving the way for the realization of next-generation devices.

Improved oxygen diffusion barrier properties of ruthenium-titanium nitride thin films prepared by plasma-enhanced atomic layer deposition.

Ru-TiN thin films were prepared from bis(ethylcyclopentadienyl)ruthenium and tetrakis(dimethylamino)titanium using plasma-enhanced atomic layer deposition (PEALD). The Ru and TiN were deposited sequentially to intermix TiN with Ru. The composition of Ru-TiN films was controlled precisely by changing the number of deposition cycles allocated to Ru, while fixing the number of deposition cycles allocated to TiN. Although both Ru and TiN thin films have a polycrystalline structure, the microstructure of the Ru-TiN films changed from a TiN-like polycrystalline structure to a nanocrystalline on increasing the Ru intermixing ratio. Moreover, the electrical resistivity of the Ru0.67-TiN0.33 thin films is sufficiently low at 190 microomega x cm and was maintained even after O2 annealing at 750 degrees C. Therefore, Ru-TiN thin films can be utilized as a oxygen diffusion barrier material for future dynamic (DRAM) and ferroelectric (FeRAM) random access memory capacitors.

A universal approach for template-directed assembly of ultrahigh density magnetic nanodot arrays.

L1(0) ordered alloys, such as FePt, CoPt and FePd alloys with high magnetocrystalline anisotropy, have attracted much attention due to their potential applications in ultrahigh density data storage. The assembly or organization of nanoparticle arrays is necessary for device application. A facile and general method to fabricate highly ordered ferromagnetic nanostructure arrays was demonstrated. It is found that simple oxygen plasma can make a hydrophilic polymer template, which would easily integrate with the widely used spin-coating process. With simple block copolymer lithography and spin-coating process, uniform ferromagnetic nanoparticle arrays can be easily fabricated over a large area. It is also significant that a very high coercivity up to 10 kOe was obtained in CoPt nanodot arrays. This method can find attractive applications in ultrahigh density storage media.

Surface energy modification by spin-cast, large-area graphene film for block copolymer lithography.

We demonstrate a surface energy modification method exploiting graphene film. Spin-cast, atomic layer thick, large-area reduced graphene film successfully played the role of surface energy modifier for arbitrary surfaces. The degree of reduction enabled the tuning of the surface energy. Sufficiently reduced graphene served as a neutral surface modifier to induce surface perpendicular lamellae or cylinders in a block copolymer nanotemplate. Our approach integrating large-area graphene film preparation with block copolymer lithography is potentially advantageous in creating semiconducting graphene nanoribbons and nanoporous graphene.