Application of Hexagonal Boron Nitride to a Heat-Transfer Medium of an InGaN/GaN Quantum-Well Green LED.

Group III-nitride light-emitting diodes (LEDs) fabricated on sapphire substrates typically suffer from insufficient heat dissipation, largely due to the low thermal conductivities (TCs) of their epitaxial layers and substrates. In the current work, we significantly improved the heat-dissipation characteristics of an InGaN/GaN quantum-well (QW) green LED by using hexagonal boron nitride (hBN) as a heat-transfer medium. Multiple-layer hBN with an average thickness of 11 nm was attached to the back of an InGaN/GaN-QW LED (hBN-LED). As a reference, an LED without the hBN (Ref-LED) was also prepared. After injecting current, heat-transfer characteristics inside each LED were analyzed by measuring temperature distribution throughout the LED as a function of time. For both LED chips, the maximum temperature was measured on the edge n-type electrode brightly shining fabricated on an n-type GaN cladding layer and the minimum temperature was measured at the relatively dark-contrast top surface between the p-type electrodes. The hBN-LED took 6 s to reach its maximum temperature (136.1 °C), whereas the Ref-LED took considerably longer, specifically 11 s. After being switched off, the hBN-LED took 35 s to cool down to 37.5 °C and the Ref-LED took much longer, specifically 265 s. These results confirmed the considerable contribution of the attached hBN to the transfer and dissipation of heat in the LED. The spatial heat-transfer and distribution characteristics along the vertical direction of each LED were theoretically analyzed by carrying out simulations based on the TCs, thicknesses, and thermal resistances of the materials used in the chips. The results of these simulations agreed well with the experimental results.

Wafer-Scale van der Waals Heterostructures with Ultraclean Interfaces via the Aid of Viscoelastic Polymer.

Two-dimensional (2D) van der Waals (vdW) heterostructures exhibit novel physical and chemical properties, allowing the development of unprecedented electronic, optical, and electrochemical devices. However, the construction of wafer-scale vdW heterostructures for practical applications is still limited due to the lack of well-established growth and transfer techniques. Herein, we report a method for the fabrication of wafer-scale 2D vdW heterostructures with an ultraclean interface between layers via the aid of a freestanding viscoelastic polymer support layer (VEPSL). The low glass transition temperature ( Tg) and viscoelastic nature of the VEPSL ensure absolute conformal contact between 2D layers, enabling the easy pick-up of layers and attaching to other 2D layers. This eventually leads to the construction of random sequence 2D vdW heterostructures such as molybdenum disulfide/tungsten disulfide/molybdenum diselenide/tungsten diselenide/hexagonal boron nitride. Furthermore, the VEPSL allows the conformal transfer of 2D vdW heterostructures onto arbitrary substrates, irrespective of surface roughness. To demonstrate the significance of the ultraclean interface, the fabricated molybdenum disulfide/graphene heterostructure employed as an electrocatalyst yielded excellent results of 73.1 mV·dec-1 for the Tafel slope and 0.12 kΩ of charge transfer resistance, which are almost twice as low as that of the impurity-trapped heterostructure.

Wafer-scale single-crystal hexagonal boron nitride film via self-collimated grain formation.

Although polycrystalline hexagonal boron nitride (PC-hBN) has been realized, defects and grain boundaries still cause charge scatterings and trap sites, impeding high-performance electronics. Here, we report a method of synthesizing wafer-scale single-crystalline hBN (SC-hBN) monolayer films by chemical vapor deposition. The limited solubility of boron (B) and nitrogen (N) atoms in liquid gold promotes high diffusion of adatoms on the surface of liquid at high temperature to provoke the circular hBN grains. These further evolve into closely packed unimodal grains by means of self-collimation of B and N edges inherited by electrostatic interaction between grains, eventually forming an SC-hBN film on a wafer scale. This SC-hBN film also allows for the synthesis of wafer-scale graphene/hBN heterostructure and single-crystalline tungsten disulfide.

Highly concentrated single-chain atomic crystal LiMo3Se3 solution using ion-exchange chromatography.

Ion-exchange chromatography can be used to effectively replace the lithium ion of LiMo3Se3 with a proton. The enlargement of the Stern layer distance caused by this ion exchange improves the dispersibility of (Mo3Se3-)∞ chains and also prevents the re-bundling and aggregation of nanowires in aqueous solutions, even at high concentrations (1 mg mL-1).

Synthesis of Large-Area Tungsten Disulfide Films on Pre-Reduced Tungsten Suboxide Substrates.

We report a facile method for the synthesis of large-area tungsten disulfide (WS2) films by means of chemical vapor deposition (CVD). To promote WS2 film growth, the precursor solution, which includes pre-reduced tungsten suboxides, is prepared by using hydrazine as the strong reducing agent and spin-coated onto the growth substrate. Growth is then carried out in a CVD chamber vaporized with dimethyl disulfide as the sulfur precursor. Although only WS2 flakes are grown with unreduced tungsten precursors under a hydrogen atmosphere, WS2 films are readily attained on pre-reduced tungsten suboxide substrates without the need for further reduction by hydrogen, which is noted to induce discontinuity of the grown film. The result presents the coverage of WS2 to be proportional to the amount of reduced tungsten suboxides, which is revealed by X-ray photoelectron spectroscopy. Furthermore, it is found that the multilayer WS2 flakes grow along the grain boundary, which allows the analysis of the grain size of WS2 films by optical microscopy images only. WS2 field effect transistors are fabricated by conventional photolithography and show an average electron mobility of 0.4 cm2 V-1 s-1 and a high on/off ratio of 106 at room temperature.

A Novel and Facile Route to Synthesize Atomic-Layered MoS2 Film for Large-Area Electronics.

High-quality and large-area molybdenum disulfide (MoS2 ) thin film is highly desirable for applications in large-area electronics. However, there remains a challenge in attaining MoS2 film of reasonable crystallinity due to the absence of appropriate choice and control of precursors, as well as choice of suitable growth substrates. Herein, a novel and facile route is reported for synthesizing few-layered MoS2 film with new precursors via chemical vapor deposition. Prior to growth, an aqueous solution of sodium molybdate as the molybdenum precursor is spun onto the growth substrate and dimethyl disulfide as the liquid sulfur precursor is supplied with a bubbling system during growth. To supplement the limiting effect of Mo (sodium molybdate), a supplementary Mo is supplied by dissolving molybdenum hexacarbonyl (Mo(CO)6 ) in the liquid sulfur precursor delivered by the bubbler. By precisely controlling the amounts of precursors and hydrogen flow, full coverage of MoS2 film is readily achievable in 20 min. Large-area MoS2 field effect transistors (FETs) fabricated with a conventional photolithography have a carrier mobility as high as 18.9 cm2 V-1 s-1 , which is the highest reported for bottom-gated MoS2 -FETs fabricated via photolithography with an on/off ratio of ≈105 at room temperature.

Water-Assisted Synthesis of Molybdenum Disulfide Film with Single Organic Liquid Precursor.

We report on the synthesis of large-area molybdenum disulfide (MoS2) film on an insulating substrate by means of chemical vapor deposition. A single mixture of molybdenum hexacarbonyl (Mo(CO)6) and dimethyl disulfide (C2H6S2) was utilized as an organic liquid precursor for the synthesis of MoS2 film. Carbon impurities stemming from the dissociation of the organic precursor are effectively removed by water oxidation, and hydrogen gas, which is a by-product of the oxidation of carbon impurities, inhibits the formation of molybdenum oxides. The use of a liquid precursor assisted with water oxidation ensures high reproducibility and full-coverage of MoS2 film for large area, which is not typically achieved with solid precursors such as molybdenum oxide and sulfur powder. We believe that our approach will advance the synthesis of transition metal dichalcogenides.

Effective characterization of polymer residues on two-dimensional materials by Raman spectroscopy.

Large-area two-dimensional (2D) materials grown by chemical vapor deposition need to be transferred onto a target substrate for real applications. Poly(methyl methacrylate) as a supporting layer is widely used during the transfer process and removed after finishing it. However, it is a challenge to diminish the polymer layer completely. It is necessary to readily characterize the polymer residues on 2D materials to facilitate the removal process. Here, we report a method that characterizes the polymer residues on 2D materials by tracking the presence of G-band of amorphous carbons (a-Cs) in the Raman spectrum after forming carbonized a-Cs through thermal annealing. The (13)C-graphene is employed to separate the Raman signal G-band between (12)C-a-Cs and (13)C-graphene in the Raman spectrum. The residence of the polymer residues is clearly confirmed by the different Raman signals of two different isotopes ((12)C and (13)C) due to differences in mass. Our effective method recognizes that while the polymer residue is not easily removed on graphene, those on hexagonal boron nitride and molybdenum disulfide are almost diminished under optimum thermal annealing conditions. Our method will not only contribute to the development of a new transfer process, but also help to achieve a clean surface of 2D materials.

Synthesis of large-area multilayer hexagonal boron nitride for high material performance.

Although hexagonal boron nitride (h-BN) is a good candidate for gate-insulating materials by minimizing interaction from substrate, further applications to electronic devices with available two-dimensional semiconductors continue to be limited by flake size. While monolayer h-BN has been synthesized on Pt and Cu foil using chemical vapour deposition (CVD), multilayer h-BN is still absent. Here we use Fe foil and synthesize large-area multilayer h-BN film by CVD with a borazine precursor. These films reveal strong cathodoluminescence and high mechanical strength (Young's modulus: 1.16 ± 0.1 TPa), reminiscent of formation of high-quality h-BN. The CVD-grown graphene on multilayer h-BN film yields a high carrier mobility of ∼ 24,000 cm(2) V(-1) s(-1) at room temperature, higher than that (∼ 13,000 (2) V(-1) s(-1)) with exfoliated h-BN. By placing additional h-BN on a SiO2/Si substrate for a MoS2 (WSe2) field-effect transistor, the doping effect from gate oxide is minimized and furthermore the mobility is improved by four (150) times.

Synthesis of centimeter-scale monolayer tungsten disulfide film on gold foils.

We report the synthesis of centimeter-scale monolayer WS2 on gold foil by chemical vapor deposition. The limited tungsten and sulfur solubility in gold foil allows monolayer WS2 film growth on gold surface. To ensure the coverage uniformity of monolayer WS2 film, the tungsten source-coated substrate was placed in parallel with Au foil under hydrogen sulfide atmosphere. The high growth temperature near 935 °C helps to increase a domain size up to 420 µm. Gold foil is reused for the repeatable growth after bubbling transfer. The WS2-based field effect transistor reveals an electron mobility of 20 cm(2) V(-1) s(-1) with high on-off ratio of ∼10(8) at room temperature, which is the highest reported value from previous reports of CVD-grown WS2 samples. The on-off ratio of integrated multiple FETs on the large area WS2 film on SiO2 (300 nm)/Si substrate shows within the same order, implying reasonable uniformity of WS2 FET device characteristics over a large area of 3 × 1.5 cm(2).