Emergent Topological Hall Effect from Exchange Coupling in Ferromagnetic Cr2Te3/Noncoplanar Antiferromagnetic Cr2Se3 Bilayers.

The topological Hall effect has been observed in magnetic materials of complex spin structures or bilayers of trivial magnets and strong spin-orbit-coupled systems. In view of current attention on dissipationless topological electronics, the occurrence of the topological Hall effect in new systems or by an unexpected mechanism is fascinating. Here, we report a robust topological Hall effect generated in bilayers of a ferromagnet and a noncoplanar antiferromagnet, from the interfacial Dzyaloshinskii-Moriya interaction due to the exchange coupling of magnetic layers. Molecular beam epitaxy has been utilized to fabricate heterostructures of a ferromagnetic metal Cr2Te3 and a noncoplanar antiferromagnet Cr2Se3. A significant topological Hall effect at low temperature implies the development of nontrivial spin chirality, and density functional theory calculations explain the correlation of the Dzyaloshinskii-Moriya interaction increase and inversion symmetry breaking at the interface. The presence of noncoplanar ordering in the antiferromagnet plays a pivotal role in producing the topological Hall effect. Our results suggest that the exchange coupling in ferromagnet/noncoplanar antiferromagnet bilayers could be an alternative mechanism toward topologically protected magnetic structures.

Facile electrodeposition of V-doped CoP on vertical graphene for efficient alkaline water electrolysis.

In this work, we demonstrate a highly enhanced electrocatalytic activity of vanadium-doped CoP (V-CoP), directly grafted on a vertical graphene/carbon cloth electrode (VG/CC) by a facile electrochemical deposition method. Impressively, V-CoP/VG/CC exhibited a superior catalytic activity toward the hydrogen evolution reaction (HER) in alkaline solution. Compared to CoP/VG/CC, V-doping decreased the overpotential for HER at 10 mA cm-2 by more than half to 40 mV. The new catalyst even outperformed Pt/C beyond 150 mA cm-2. The overpotential for OER at 50 mA cm-2 was merely 314 mV, more than 100 mV lower than that of IrO2. Moreover, our novel catalyst worked as an excellent bifunctional catalyst with a low cell voltage of 1.69 V to achieve a current density of 50 mA cm-2. Detailed characterizations revealed that the V-doping in CoP resulted in improved electrical conductivity and increased active sites. Our findings highlight the significant advantage of V doping on the catalytic activities of CoP, already boosted by VG. Furthermore, concurrent doping with the electrodeposition of catalyst offers a new approach for practical water electrolysis.

Induced Superaerophobicity onto a Non-superaerophobic Catalytic Surface for Enhanced Hydrogen Evolution Reaction.

Despite tremendous progress in the development of novel electrocatalysts for hydrogen evolution reaction (HER), the accumulation of hydrogen gas bubbles produced on the catalyst surface has been rather poorly addressed. The bubbles block the surface of the electrode, thus resulting in poor performance even when excellent electrocatalysts are used. In this study, we show that vertically grown graphene nanohills (VGNHs) possess an excellent capability to quickly disengage the produced hydrogen gas bubbles from the electrode surface, and thus exhibit superaerophobic properties. To compensate for the poor electrolytic properties of graphene toward HER, the graphene surface was modified with WS2 nanoparticles to accelerate the water-splitting process by using this hybrid catalyst (VGNHs-WS2). For comparison purposes, WS2 nanoparticles were also deposited on the flat graphene (FG) surface. Because of its superior superaerophobic properties, VGNHs-WS2 outperformed FG-WS2 in terms of both catalytic activity toward the HER and superaerophobicity. Furthermore, VGNHs-WS2 exhibited a low onset potential (36 mV compared to 288 mV for FG-WS2) and long-term stability in the HER over an extended period of 20 h. This study provides an efficient way to utilize highly conductive and superaerophobic VGNHs as support materials for intrinsic semiconductors, such as WS2, to simultaneously achieve superaerophobicity and high catalytic activity.

Suppressed weak antilocalization in the topological insulator Bi2Se3 proximity coupled to antiferromagnetic NiO.

Time-reversal symmetry (TRS) breaking of the topological insulators (TIs) is a prerequisite to observe the quantum anomalous Hall effect (QAHE) and topological magnetoelectric effect (TME). Although antiferromagnetism as well as ferromagnetism could break the TRS and generate massive Dirac surface states in the TIs, no attention has been paid to the antiferromagnet-TI heterostructures. Herein, we report the magnetotransport measurements of Bi2Se3 proximately coupled to antiferromagnetic NiO. Thin films of Bi2Se3 were successfully grown on the NiO (001) single crystalline substrates by molecular beam epitaxy. Unexpectedly, we observed a strong suppression of the weak antilocalization effect, which is similar to the case of TIs coupled to the ferromagnetic materials. For the 5 nm-thick Bi2Se3 sample on NiO, we even observed a crossover to weak localization at 2 K. These behaviors are attributed to the strong magnetic exchange field from the Ni 3d electrons. Our results show the effectiveness of the antiferromagnetic materials in breaking the TRS of TIs by the proximity effect and their possible applications for QAHE and TME observations.

Hydrophobic Surface Treatment and Interrupted Atomic Layer Deposition for Highly Resistive Al2O3 Films on Graphene.

The deposition of thin and uniform dielectric film on graphene is an important step for electronic applications. Here, we tackled this problem by combining a simple chemical treatment of graphene surface and a modification of standard atomic layer deposition (ALD). Instead of common approaches trying to convert hydrophobic graphene surface into hydrophilic one, we took the opposite way by applying a self-assembled-monolayer, hexamethyldisilazane (HMDS) to make defect-independent, more hydrophobic surface condition. In addition, Al2O3 ALD using trimethylaluminum (TMA) and water (H2O) was interrupted several times and the surface was air-exposed during the interruption to seed the following ALD processes. This combination greatly improved the uniformity of dielectric film and accomplished a successful deposition of 10 nm-thick Al2O3 on graphene with subnanometer roughness except for the locations of wrinkles and poly(methyl methacrylate) (PMMA) residues. Electrochemical impedance measurements revealed a 300-fold increase in the charge-transfer resistance by employing this modified ALD process. No change in the Raman spectra was observed after the dielectric film growth, demonstrating that the method proposed here is nondetrimental to the graphene quality.

Direct growth of patterned graphene on SiO2 substrates without the use of catalysts or lithography.

We demonstrate a one-step fabrication of patterned graphene on SiO2 substrates through a process free from catalysts, transfer, and lithography. By simply placing a shadow mask during the plasma enhanced chemical vapor deposition (PECVD) of graphene, an arbitrary shape of graphene can be obtained on SiO2 substrate. The formation of graphene underneath the shadow mask was effectively prevented by the low-temperature, catalyst-free process. Growth conditions were optimized to form polycrystalline graphene on SiO2 substrates and the crystalline structure was characterized by Raman spectroscopy and transmission electron microscopy (TEM). Patterned graphene on SiO2 functions as a field-effect device by itself. Our method is compatible with present device processing techniques, and should be highly desirable for the proliferation of graphene applications.

Direct integration of polycrystalline graphene into light emitting diodes by plasma-assisted metal-catalyst-free synthesis.

The integration of graphene into devices is a challenging task because the preparation of a graphene-based device usually includes graphene growth on a metal surface at elevated temperatures (∼1000 °C) and a complicated postgrowth transfer process of graphene from the metal catalyst. Here we report a direct integration approach for incorporating polycrystalline graphene into light emitting diodes (LEDs) at low temperature by plasma-assisted metal-catalyst-free synthesis. Thermal degradation of the active layer in LEDs is negligible at our growth temperature, and LEDs could be fabricated without a transfer process. Moreover, in situ ohmic contact formation is observed between DG and p-GaN resulting from carbon diffusion into the p-GaN surface during the growth process. As a result, the contact resistance is reduced and the electrical properties of directly integrated LEDs outperform those of LEDs with transferred graphene electrodes. This relatively simple method of graphene integration will be easily adoptable in the industrialization of graphene-based devices.

Ordered growth of topological insulator Bi2Se3 thin films on dielectric amorphous SiO2 by MBE.

Topological insulators (TIs) are exotic materials which have topologically protected states on the surface due to strong spin-orbit coupling. However, a lack of ordered growth of TI thin films on amorphous dielectrics and/or insulators presents a challenge for applications of TI-junctions. We report the growth of topological insulator Bi2Se3 thin films on amorphous SiO2 by molecular beam epitaxy (MBE). To achieve the ordered growth of Bi2Se3 on an amorphous surface, the formation of other phases at the interface is suppressed by Se passivation. Structural characterizations reveal that Bi2Se3 films are grown along the [001] direction with a good periodicity by the van der Waals epitaxy mechanism. A weak anti-localization effect of Bi2Se3 films grown on amorphous SiO2 shows a modulated electrical property by the gating response. Our approach for ordered growth of Bi2Se3 on an amorphous dielectric surface presents considerable advantages for TI-junctions with amorphous insulator or dielectric thin films.

Graphitic carbon grown on fluorides by molecular beam epitaxy.

We study the growth mechanism of carbon molecules supplied by molecular beam epitaxy on fluoride substrates (MgF2, CaF2, and BaF2). All the carbon layers form graphitic carbon with different crystallinities depending on the cation. Especially, the growth on MgF2 results in the formation of nanocrystalline graphite (NCG). Such dependence on the cation is a new observation and calls for further systematic studies with other series of substrates. At the same growth temperature, the NCG on MgF2 has larger clusters than those on oxides. This is contrary to the general expectation because the bond strength of the carbon-fluorine bond is larger than that of the carbon-oxygen bond. Our results show that the growth of graphitic carbon does not simply depend on the chemical bonding between the carbon and the anion in the substrate.

Methane as an effective hydrogen source for single-layer graphene synthesis on Cu foil by plasma enhanced chemical vapor deposition.

A single-layer graphene is synthesized on Cu foil in the absence of H(2) flow by plasma enhanced chemical vapor deposition (PECVD). In lieu of an explicit H(2) flow, hydrogen species are produced during the methane decomposition process into their active species (CH(x<4)), assisted with the plasma. Notably, the early stage of growth depends strongly on the plasma power. The resulting grain size (the nucleation density) has a maximum (minimum) at 50 W and saturates when the plasma power is higher than 120 W because hydrogen partial pressures are effectively tuned by a simple control of the plasma power. Raman spectroscopy and transport measurements show that decomposed methane alone can provide a sufficient amount of hydrogen species for high-quality graphene synthesis by PECVD.

Reduction of graphene damages during the fabrication of InGaN/GaN light emitting diodes with graphene electrodes.

Although graphene looks attractive to replace indium tin oxide (ITO) in optoelectronic devices, the luminous efficiency of light emitting diodes (LEDs) with graphene transparent conducting electrodes has been limited by degradation in graphene taking place during device fabrication. In this study, it was found that the quality of graphene after the device fabrication was a critical factor affecting the performance of GaN-based LEDs. In this paper, the qualities of graphene after two different device fabrication processes were evaluated by Raman spectroscopy and atomic force microscopy. It was found that graphene was severely damaged and split into submicrometer-scale islands bounded by less conducting boundaries when graphene was transferred onto LED structures prior to the GaN etching process for p-contact formation. On the other hand, when graphene was transferred after the GaN etch and p-contact metallization, graphene remained intact and the resulting InGaN/GaN LEDs showed electrical and optical properties that were very close to those of LEDs with 200 nm thick ITO films. The forward-voltages and light output powers of LEDs were 3.03 V and 9.36 mW at an injection current of 20 mA, respectively.

Graphitic carbon growth on crystalline and amorphous oxide substrates using molecular beam epitaxy.

We report graphitic carbon growth on crystalline and amorphous oxide substrates by using carbon molecular beam epitaxy. The films are characterized by Raman spectroscopy and X-ray photoelectron spectroscopy. The formations of nanocrystalline graphite are observed on silicon dioxide and glass, while mainly sp2 amorphous carbons are formed on strontium titanate and yttria-stabilized zirconia. Interestingly, flat carbon layers with high degree of graphitization are formed even on amorphous oxides. Our results provide a progress toward direct graphene growth on oxide materials.PACS: 81.05.uf; 81.15.Hi; 78.30.Ly.