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.

Structural, Optical, and Electrical Properties of Hafnium-Aluminum-Zinc-Oxide Films Grown by Atomic Layer Deposition for TCO Applications.

ZnO is a widely studied material that exhibits versatile doping possibilities. Most research presents singly doped ZnO, leaving the potential of codoping unexplored. Within this study, hafnium-aluminum codoped zinc oxide (HAZO) thin films were grown on a glass substrate using the atomic layer deposition technique at 200 °C. A comprehensive analysis of the surface morphology and electrical and optical properties of the samples was conducted for varying the Al/Hf doping ratio. X-ray diffraction studies showed that the obtained films are polycrystalline, exhibiting a preferential growth direction along the (1 0 0) plane without any detectable precipitates. Moreover, the electrical measurements of HAZO films revealed that they exhibit lower resistivity (∼9.5 × 10-4 Ωcm) than the commonly used aluminum zinc oxide films (AZO). This improvement can be primarily attributed to the promotion of the n-type carrier concentration to 4.45 × 1020 cm-3 while maintaining a mobility value equal to 14.7 cm2/Vs. The doping also influences the optical properties of the material by widening the band gap and changing the refractive index, as observed by spectroscopy and ellipsometry studies. These findings highlight the potential of proposed HAZO thin films for future applications in electronic devices utilizing transparent conducting oxides.

Poly(Vinylidene Fluoride-co-Hexafluoropropylene) Films Filled in Iron Nanoparticles for Infrared Shielding Applications.

In order to use the infrared (IR) radiation shielding materials, they should take a form of thin film coatings deposited on glass/polymer substrates or be used as fillers of glass/polymer. The first approach usually suffers from several technological problems. Therefore, the second strategy gains more and more attention. Taking into account this trend, this work presents the usage of iron nanoparticles (Fe NPs) embedded into the poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) films as the shielding material in near-infrared (NIR) and mid-infrared (MIR) region. The performed investigations show that the transmittance of copolymer films decreases with increasing content of the Fe NPs inside them. It is found that the average fade of IR transmittance for 1, 2.5, 5, 10, and 50 mg of Fe NPs is about 13%, 24%, 31%, 77%, and 98%, respectively. Moreover, it is observed that the PVDF-HFP films filled in the Fe NPs almost does not reflect the NIR and MIR radiation. Hence, the IR shielding properties of the PVDF-HFP films can be effectively tuned by the addition of proper amount of the Fe NPs. This, in turn, shows that the PVDF-HFP films filled in the Fe NPs constitute a great option for IR antireflective and shielding applications.

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.

Enhanced Performance of Camphorsulfonic Acid-Doped Perovskite Solar Cells.

High-quality perovskite film with large grains and therefore reduced grain boundaries plays a significant role in improving the power conversion efficiency (PCE) and ensuring good long-term stability of the perovskite solar cells. In this work, we found that adding camphorsulfonic acid (CSA), a Lewis base, to the perovskite solution results in the crystallization of larger perovskite grains. By varying the concentration of CSA, we found that the optimal concentration of the additive is 1 mg/mL, which leads to an 20% increase in PCE of the cells compared to the reference CSA-free cell. Interestingly, we observed that the PCE of cells with an excess of CSA was initially poor, but may increase significantly over time, possibly due to CSA migration to the hole-transporting layer, leading to an improvement in its conductivity.

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.

Evolution of Structural and Magnetic Properties of Fe-Co Wire-like Nanochains Caused by Annealing Atmosphere.

Thermal treatment is a post-synthesis treatment that aims to improve the crystallinity and interrelated physical properties of as-prepared materials. This process may also cause some unwanted changes in materials like their oxidation or contamination. In this work, we present the post-synthesis annealing treatments of the amorphous Fe1-xCox (x = 0.25; 0.50; 0.75) Wire-like nanochains performed at 400 °C in two different atmospheres, i.e., a mixture of 80% nitrogen and 20% hydrogen and argon. These processes caused significantly different changes of structural and magnetic properties of the initially-formed Fe-Co nanostructures. All of them crystallized and their cores were composed of body-centered cubic Fe-Co phase, whereas their oxide shells comprised of a mixture of CoFe2O4 and Fe3O4 phases. However, the annealing carried out in hydrogen-containing atmosphere caused a decomposition of the initial oxide shell layer, whereas a similar process in argon led to its slight thickening. Moreover, it was found that the cores of thermally-treated Fe0.25Co0.75 nanochains contained the hexagonal closest packed (hcp) Co phase and were covered by the nanosheet-like shell layer in the case of annealing performed in argon. Considering the evolution of magnetic properties induced by structural changes, it was observed that the coercivities of annealed Fe-Co nanochains increased in comparison with their non-annealed counterparts. The saturation magnetization (MS) of the Fe0.25Co0.75 nanomaterial annealed in both atmospheres was higher than that for the non-annealed sample. In turn, the MS of the Fe0.75Co0.25 and Fe0.50Co0.50 nanochains annealed in argon were lower than those recorded for non-annealed samples due to their partial oxidation during thermal processing.

Growth of highly oriented MoS2via an intercalation process in the graphene/SiC(0001) system.

A method of growing highly oriented MoS2 is presented. First, a Mo film is deposited on a graphene/SiC(0001) substrate and the subsequent annealing of it at 750 °C leads to intercalation of Mo underneath the graphene layer, which is confirmed by secondary ion mass spectrometry (SIMS) measurements. Formation of highly oriented MoS2 layers is then achieved by sulfurization of the graphene/Mo/SiC system using H2S gas. X-ray diffraction reveals that the MoS2 layers are highly oriented and parallel to the underlying SiC substrate surface. Further SIMS experiments reveal that the intercalation process occurs via the atomic step edges of SiC and Mo and S atoms gradually diffuse along SiC atomic terraces leading to the creation of the MoS2 layer. This observation can be explained by a mechanism of highly oriented growth of MoS2: nucleation of the crystalline MoS2 phase occurs underneath the graphene planes covering the flat parts of SiC steps and Mo and S atoms create crystallization fronts moving along terraces.

Hydrostatic-pressure-induced changes of magnetic anisotropy in (Ga, Mn)As thin films.

The impact of hydrostatic pressure on magnetic anisotropy energies in (Ga, Mn)As thin films with in-plane and out-of-plane magnetic easy axes predefined by epitaxial strain was investigated. In both types of sample we observed a clear increase in both in-plane and out-of-plane anisotropy parameters with pressure. The out-of-plane anisotropy constant is well reproduced by the mean-field p-d Zener model; however, the changes in uniaxial anisotropy are much larger than expected in the Mn-Mn dimer scenario.