Large-Area Growth of High-Optical-Quality MoSe2/hBN Heterostructures with Tunable Charge Carrier Concentration.

Van der Waals heterostructures open up vast possibilities for applications in optoelectronics, especially since it was recognized that the optical properties of transition-metal dichalcogenides (TMDC) can be enhanced by adjacent hBN layers. However, although many micrometer-sized structures have been fabricated, the bottleneck for applications remains the lack of large-area structures with electrically tunable photoluminescence emission. In this study, we demonstrate the electrical charge carrier tuning for large-area epitaxial MoSe2 grown directly on epitaxial hBN. The structure is produced in a multistep procedure involving Metalorganic Vapor Phase Epitaxy (MOVPE) growth of large-area hBN, a wet transfer of hBN onto a SiO2/Si substrate, and the subsequent Molecular Beam Epitaxy (MBE) growth of monolayer MoSe2. The electrically induced change of the carrier concentration is deduced from the evolution of well-resolved charged and neutral exciton intensities. Our findings show that it is feasible to grow large-area, electrically addressable, high-optical-quality van der Waals heterostructures.

Homoepitaxy of Boron Nitride on Exfoliated Hexagonal Boron Nitride Flakes.

Although large efforts have been made to improve the growth of hexagonal boron nitride (hBN) by heteroepitaxy, the non-native substrates remain a fundamental factor that limits the quality. This problem can be solved by homoepitaxy, which is the growth of hBN on hBN substrates. In this report, we demonstrate the homoepitaxial growth of triangular BN grains on exfoliated hBN flakes by Metal-Organic Vapor Phase Epitaxy and show by atomic force microscopy and photoluminescence that the stacking of these triangular islands can deviate from the AA' stacking of hBN. We show that the stacking order is enforced by the crystallographic direction of the edge of the exfoliated hBN flakes, with armchair edges allowing for centrosymmetric stacking, whereas zigzag edges lead to the growth of noncentrosymmetric BN polytypes. Our results indicate pathways to grow homoepitaxial BN with tunable layer stacking, which is required to induce piezoelectricity or ferroelectricity.

Strain modulation of epitaxial h-BN on sapphire: the role of wrinkle formation for large-area two-dimensional materials.

Strain built-in electronic and optoelectronic devices can influence their properties and lifetime. This effect is particularly significant at the interface between two-dimensional materials and substrates. One such material is epitaxial hexagonal boron nitride (h-BN), which is grown at temperatures often exceeding 1000 °C. Due to the high growth temperature, h-BN based devices operating at room temperature can be strongly affected by strain generated during cooling due to the differences in lattice thermal expansion of h-BN and the substrate. Here, we present results of temperature-dependent Raman studies of the in-plane E2ghighphonon mode in the temperature range of 300-1100 K measured for h-BN grown by metalorganic vapor phase epitaxy. We observe a change, by an order of magnitude, in the rate of the temperature-induced frequency shift for temperatures below 900 K, indicating a strong reduction of the effective h-BN/substrate interaction. We attribute this behavior to the creation of h-BN wrinkles which results in strain relaxation. This interpretation is supported by the observation that no change of layer/substrate interaction and no wrinkles are observed for delaminated h-BN films transferred onto silicon. Our findings demonstrate that wrinkle formation is an inherent process for two-dimensional materials on foreign substrates that has to be understood to allow for the successful engineering of devices based on epitaxially grown van der Waals heterostructures.

All-BN distributed Bragg reflectors fabricated in a single MOCVD process.

Distributed Bragg Reflectors (DBR) are well-established photonic structures that are used in many photonic applications. However, most of the DBRs are based on different materials or require post-process etching which can hinder integration with other components in the final photonic structure. Here, we demonstrate the fabrication of DBR structures consisting only of undoped boron nitride (BN) layers with high refractive index contrast by using metal-organic chemical vapor deposition (MOCVD). This has been achieved in a single process, without the need for any post-process etching. The difference in the refractive index of the component BN layers stems from different degrees of porosity of the individual BN layers, which is a direct result of a different growth temperature. The fabricated DBR structures consist of 15.5 pairs of BN layers and exhibit a reflectance of 87 ± 1% at the maximum. The wavelength of maximum reflectance can be tuned from 500 nm up to the infrared region (IR), by simply adjusting the growth periods of subsequent BN layers. We also demonstrate that the fabricated structures can be used to create an optical microcavity. The fabricated DBRs are very promising candidates for future applications, for example in combination with single-photon emitters in h-BN, which could allow the building of a cavity-based all-BN single-photon source.

Epitaxial Hexagonal Boron Nitride for Hydrogen Generation by Radiolysis of Interfacial Water.

Hydrogen is an important building block in global strategies toward a future green energy system. To make this transition possible, intense scientific efforts are needed, also in the field of materials science. Two-dimensional crystals, such as hexagonal boron nitride (hBN), are very promising in this regard, as it has been demonstrated that micrometer-sized flakes are excellent barriers to molecular hydrogen. However, it remains an open question whether large-area layers fabricated by industrially relevant methods preserve such promising properties. In this work, we show that electron-beam-induced splitting of water creates hBN bubbles that effectively store molecular hydrogen for weeks and under extreme mechanical deformation. We demonstrate that epitaxial hBN allows direct visualization and monitoring of the process of hydrogen generation by radiolysis of interfacial water. Our findings show that hBN is not only a potential candidate for hydrogen storage but also holds promise for the development of unconventional hydrogen production schemes.

Raman Optical Activity of 1T-TaS2.

Measurements of optical activity can be readily performed in transparent matter by means of a rotation of transmitted light polarization. In the case of opaque bulk materials, such measurements cannot be performed, making it difficult to assess possible chiral properties. In this work, we present full angular polarization dependencies of the Raman modes of bulk 1T-TaS2, which has recently been suggested to have chiral properties after pulsed laser excitation. We found that a mechanical rotation of the sample does not alter polarization-resolved Raman spectra, which can only be explained by introducing an antisymmetric Raman tensor, frequently used to describe Raman optical activity (ROA). Raman spectra obtained under circularly polarized excitation demonstrate that 1T-TaS2 indeed shows ROA, providing strong evidence that 1T-TaS2 is chiral under the used conditions of laser excitation. Our results suggest that ROA may be used as a universal tool to study chiral properties of quantum materials.

Heteroepitaxial Growth of High Optical Quality, Wafer-Scale van der Waals Heterostrucutres.

Transition metal dichalcogenides (TMDs) are materials that can exhibit intriguing optical properties like a change of the bandgap from indirect to direct when being thinned down to a monolayer. Well-resolved narrow excitonic resonances can be observed for such monolayers although only for materials of sufficient crystalline quality and so far mostly available in the form of micrometer-sized flakes. A further significant improvement of optical and electrical properties can be achieved by transferring the TMD on hexagonal boron nitride (hBN). To exploit the full potential of TMDs in future applications, epitaxial techniques have to be developed that not only allow the growth of large-scale, high-quality TMD monolayers but also allow the growth to be performed directly on large-scale epitaxial hBN. In this work, we address this problem and demonstrate that MoSe2 of high optical quality can be directly grown on epitaxial hBN on an entire 2 in. wafer. We developed a combined growth theme for which hBN is first synthesized at high temperature by metal organic vapor phase epitaxy (MOVPE) and as a second step MoSe2 is deposited on top by molecular beam epitaxy (MBE) at much lower temperatures. We show that this structure exhibits excellent optical properties, manifested by narrow excitonic lines in the photoluminescence spectra. Moreover, the material is homogeneous on the area of the whole 2 in. wafer with only ±0.14 meV deviation of excitonic energy. Our mixed growth technique may guide the way for future large-scale production of high quality TMD/hBN heterostructures.

Properties of graphene deposited on GaN nanowires: influence of nanowire roughness, self-induced nanogating and defects.

We present detailed Raman studies of graphene deposited on gallium nitride nanowires with different variations in height. Our results indicate that different density and height of nanowires impact graphene properties such as roughness, strain, and carrier concentration as well as density and type of induced defects. Tracing the manifestation of those interactions is important for the application of novel heterostructures. A detailed analysis of Raman spectra of graphene deposited on different nanowire substrates shows that bigger differences in nanowires height increase graphene strain, while a higher number of nanowires in contact with graphene locally reduces the strain. Moreover, the value of graphene carrier concentration is found to be correlated with the density of nanowires in contact with graphene. The lowest concentration of defects is observed for graphene deposited on nanowires with the lowest density. The contact between graphene and densely arranged nanowires leads to a large density of vacancies. On the other hand, grain boundaries are the main type of defects in graphene on rarely distributed nanowires. Our results also show modification of graphene carrier concentration and strain by different types of defects present in graphene. Therefore, the nanowire substrate is promising not only for strain and carrier concentration engineering but also for defect engineering.

Tuning Light-Driven Water Oxidation Efficiency of Molybdenum-Doped BiVO4 by Means of Multicomposite Catalysts Containing Nickel, Iron, and Chromium Oxides.

Mo-doped BiVO4 has emerged as a promising material for photoelectrodes for photoelectrochemical water splitting, however, still shows a limited efficiency for light-driven water oxidation. We present the influence of an oxygen-evolution catalyst composed of Ni, Fe, and Cr oxides on the activity of Mo:BiVO4 photoanodes. The photoanodes are prepared by spray-coating, enabling compositional and thickness gradients of the incorporated catalyst. Two different configurations are evaluated, namely with the catalyst embedded into the Mo:BiVO4 film or deposited on top of it. Both configurations provide a significantly different impact on the photoelectrocatalytic efficiency. Structural characterisation of the materials by means of SEM, TEM and XRD as well as the photoelectrocatalytic activity investigated by means of an optical scanning droplet cell and in situ detection of oxygen using scanning photoelectrochemical microscopy are presented.