Color centers in hexagonal boron nitride (hBN) are promising candidates as quantum light sources for future technologies. In this work, we utilize a scattering-type near-field optical microscope (s-SNOM) to study the photoluminescence (PL) emission characteristics of such quantum emitters in metalorganic vapor phase epitaxy grown hBN. On the one hand, we demonstrate direct near-field optical excitation and emission through interaction with the nanofocus of the tip resulting in a subdiffraction limited tip-enhanced PL hotspot. On the other hand, we show that indirect excitation and emission via scattering from the tip significantly increases the recorded PL intensity. This demonstrates that the tip-assisted PL (TAPL) process efficiently guides the generated light to the detector. We apply the TAPL method to map the in-plane dipole orientations of the hBN color centers on the nanoscale. This work promotes the widely available s-SNOM approach to applications in the quantum domain including characterization and optical control.

Single-photon emitters (SPEs) in 2D materials are highly promising candidates for quantum technologies. SPEs in hexagonal boron nitride (hBN) are widely investigated, but mostly in exfoliated or powder samples that require an activation process, making it difficult to compare studies and reproduce results. Here, this problem is addressed and a platform based on large-area metalorganic vapor phase epitaxy (MOVPE)-grown hBN is proposed, which combines reproducibility and scalability with the ability to readily host SPEs without activation. Through the creation of bubbles via electron-beam irradiation, additional functionalities are achieved, including an interference-mediated enhancement of emission by approximately 100-200%, dedicated structures that allow the relocation of individual emitters across different systems, and the opportunity to investigate strain-induced effects. Moreover, in contrast to other gas-filled bubbles that deflate at low temperatures, the bubbles remain stable under cryogenic conditions, allowing studies as a function of temperature. To improve the control over the shape and position of bubbles, a mask-based method is demonstrated that enables deterministic control over bubble formation. The presented hBN bubbles constitute a versatile platform for reproducible studies of hBN-based emitters, providing a reliable insight into their nature and properties.

Hexagonal boron nitride (hBN) is a promising material for next-generation semiconductor and optoelectronic devices due to its wide bandgap and remarkable optical properties. To apply this material in the semiconductor industry, it is necessary to grow large-area layers on the wafer-scale. For this purpose, chemical vapor deposition methods are highly preferable. However, in the case of epitaxial BN, its fragility and susceptibility to delamination and fold formation during wet processing, such as lithography, present significant challenges to its integration into device fabrication. In this work, we introduce a controlled delamination and redeposition method that effectively prevents the layer from degradation, allowing for multi-step lithographic processes. This approach is applicable to BN layers across a broad thickness range, from tens to hundreds of nanometers, and ensures compatibility with standard photolithographic techniques without compromising the material's intrinsic properties. By addressing key processing challenges, this method paves the way for integrating epitaxial BN into advanced semiconductor and optoelectronic technologies.

Raman spectroscopy is a powerful analytical method widely used in many fields of science and applications. However, one of the inherent issues of this method is a low signal-to-noise ratio for ultrathin and two-dimensional (2D) materials. To overcome this problem, techniques like surface-enhanced Raman spectroscopy (SERS) that rely on nanometer scale metallic particles are commonly employed. Here, we demonstrate a different approach that is based on a microcavity structure consisting of a hexagonal boron nitride (h-BN) membrane spanning over an air-filled trench in germanium. In this structure, the h-BN membrane is an integral part of the cavity and, at the same time, shows an about 10-fold, polarisation-dependent h-BN Raman signal enhancement. With h-BN being transparent, flat, and chemically robust, it provides an excellent interface between the cavity and adjacent materials. We show that the Raman enhancement is also present for graphene layers transferred on top of the h-BN membrane, which proves that our approach can be extended to van der Waals heterostructures. The observed polarisation and position-dependent enhancements are in very good agreement with numerical simulations of the electric field intensity of the cavity. These results, together with the presented facile h-BN membrane fabrication process, which does not require any lithographic methods, open up new possibilities for enhancing Raman signals of 2D crystals without the need for metal particles.

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.

Defects in two-dimensional boron nitride (BN) are candidates for a manifold of applications, for example, as single-photon emitters or optically addressable spin defects. However, the topic has proven to be complex and despite extensive research efforts, knowledge on midgap defects and their signature in photoluminescence (PL) remains fragmentary. Mass production of high-quality layered BN by Metal Organic Vapor Phase Epitaxy (MOVPE) is possible and effective, thus understanding the conditions of formation and identifying defects that arise in the material grown by this method is extremely important. Here, we present an analysis of the influence of the MOVPE growth conditions of layered BN on the occurrence of specific structural defects. PL spectra in the visible range were analysed involving the Huang-Rhys theory implemented in the fitting procedure for polycrystalline samples grown under various conditions. Such an approach allowed us to separate bands from individual entities. Two bands at 1.57 eV and 2.6 eV with phonon replicas were observed. The three additional bands are characterized by a broad emission centered at 1.38 eV, 1.9 eV and 2.24 eV. Further properties, including an analysis of the surface morphology, the impact of annealing and laser bleaching on the PL spectra and Positron Annihilation Spectroscopy (PAS) were considered to draw conclusions about the nature of the examined defects. The PAS analysis correlated with the PL of the BN layers allows us to classify the studied samples in terms of the concentrations of boron vacancies and their complexes. Based on the obtained results, we propose that the rich family of PL bands observed in various sp2-BN layers is associated with different defect complexes build of boron vacancies (VB), boron antisite defects (BN), substitutional carbon defects (CB, CN) and their donor-acceptor pairs. The main value of this paper is the transfer of knowledge gained about defects and the corresponding luminescent bands to characterize high-quality continuous epitaxial sp2-BN layers. The presented results constitute an important step toward the deterministic manipulation of defect concentrations in twodimensional boron nitride, which opens up new pathways for future optoelectronic device application.

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.

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.

Boron nitride exhibits various crystal structures. The subgroup of layered boron nitrides includes several polytypes such as hexagonal (hBN), Bernal (bBN), and rhombohedral (rBN) BN. The latter two are non-centrosymmetric, potentially leading to piezoelectric or ferroelectric properties. A key challenge related to the polytypism of sp2-bonded BN is distinguishing between these polytypes. We demonstrate that the optical response of the 4.1-eV defect can be used to differentiate hBN from rBN. Photoluminescence and cathodoluminescence measurements on samples grown by metalorganic vapor phase epitaxy (MOVPE) show a zero-phonon line at 4.096 eV for hBN and 4.143 eV for rBN. Our calculations confirm that the photoluminescence originates from a carbon dimer, CBCN (C2), which is sensitive to the local environments of different polytypes. We demonstrate that different polytypic compositions of hBN and rBN can be achieved by MOVPE, which could pave the way for future applications in large-area van der Waals heterostructures.

Defects play a very important role in semiconductors and only the control over the defect properties allows the implementation of materials in dedicated applications. We present an investigation of the UV luminescence of defects in hexagonal boron nitride (h-BN) grown by Metal Organic Vapor Phase Epitaxy (MOVPE). Such intentionally introduced defects are important for applications like deep UV emission and quantum information. In this work, we performed photoluminescence and cathodoluminescence experiments on a set of h-BN layers grown by MOVPE at different growth temperatures (tgr). The obtained defect-related spectra in the ultraviolet range include well-known lines at about 230 nm (X230, hν = 5.4 eV) and 300 nm (C300 - the brightest one, hν = 4.14 eV) as well as a rarely observed band with a zero-phonon line at 380 nm (C380, hν = 3.24 eV). The C300 and C380 bands have the characteristic of a color centre showing sharp lines (0.6 nm width) at 5 K. These lines are most probably an internal transition of carbon-related defects. We show that for samples grown at high temperatures (tgr > 1200 °C), the lines related to the color centres C are replaced by broad bands at 330 nm and 400 nm, which we marked as D330 and D400, respectively. The D bands have similar central energies to the C bands but extend over a large energy range, so we propose that the D emission is due to a shallow donor to deep acceptor recombination. Time-resolved photoluminescence analysis determined the lifetimes of the individual lines in the range from 0.9 ns (C300), 1.8 ns (C380) to 4 ns (D400). The C300 and C380 color centre bands are composed of a series of characteristic lines that are due to the interaction with phonons. The E1u (198 meV) and A2u (93 meV) phonon replicas have been identified.

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.

The substrate is one of the key components that determines the quality of the epitaxial layers. However, the implications of growing two-dimensional layers on three-dimensional bulk substrates have not yet been fully understood, and these implications need to be studied for different combinations of materials and substrates. Here, we present a study that addresses the influence of the sapphire substrate off-cut angle on the final growth of two-dimensional layers of hexagonal boron nitride (h-BN) by metal-organic vapor phase epitaxy (MOVPE). A two-step wafer-scale process was used in one epitaxial MOVPE procedure. The main process starts with a self-limiting continuous growth of a BN buffer followed by flow-modulated epitaxy in the second step, and is used to study substrates with different off-cuts angles, pre-growth nitridation steps, and post-growth annealing. An initial nitridation step at the growth temperature allowed for the growth of an AlN sublayer. This layer is shown to smooth out the underlying sapphire and establishes an ‘effective’ sapphire/AlN substrate. This step is also responsible for enforcing a specific growth of the BN layer in a crystallographic orientation, which is shown to strongly deviate from the substrate for off-cut angles larger than 0.3°. A substrate with off-cut angle of 1° clearly yields the highest quality of h-BN layers as evidenced by the lowest amount of debris on the surface, most intense x-ray diffraction signal, minimal Raman phonon line width and thinnest amorphous BN (a-BN) at the interface with the effective substrate. Our study shows that the off-cut angles of sapphire substrates strongly influence the final epitaxial h-BN, clearly indicating the importance of optimal substrate preparation for the growth of two-dimensional BN layers. Post-growth annealing in N 2 atmosphere at 800 °C improves the top surface morphology of the final stack, as well as suppresses further the presence of a-BN.

The versatile range of applications for two-dimensional (2D) materials has encouraged scientists to further engineer the properties of these materials. This is often accomplished by stacking layered materials into more complex van der Waals heterostructures. A much less popular but technologically promising approach is the alloying of 2D materials with different element compositions. In this work, we demonstrate a first step in manipulating the hBN bandgap in terms of its width and indirect/direct character of the optical transitions. We present a set of aluminum alloyed hexagonal boron nitride (hBAlN) samples that were grown by metal organic vapor phase epitaxy (MOVPE) on 2-inch sapphire substrates with different aluminum concentration. Importantly, the obtained samples revealed a sp$^2$-bonded crystal structure. Optical absorption experiments disclosed two strong peaks in the excitonic spectral range with absorption coefficient $\alpha \sim 10^6$ cm$^{-1}$. Their energies correspond very well with the energies of indirect and direct bandgap transitions in hBN. However, they are slightly redshifted. This observation is in agreement with predictions that alloying with Al leads to a decrease of the bandgap energy. The observation of two absorption peaks can be explained in terms of mixing electronic states in the K and M conduction band valleys, which leads to a significant enhancement of the absorption coefficient for indirect transitions.

We explore the proximity effect between hexagonal boron nitride and two-dimensional magnets. A strong correlation between the optical emission from hBN and a magnetic phase transition in CrBr 3 is found. Our approach demonstrates a novel method to locally apply magnetic fields and address selected defects.

The recent progress in the growth of large-area boron nitride epilayers opens up new possibilities for future applications. However, it remains largely unclear how weakly attached two-dimensional BN layers interact with their substrate and how their properties are influenced by defects. In this work, we investigate hBN layers grown by Metal Organic Vapor Phase Epitaxy (MOVPE) using Fourier-transform Infrared (FTIR) spectroscopy in the temperature range of 160-540 K. Our measurements reveal strong differences in the character of layer-substrate interaction for as-grown and delaminated epitaxial layers. A much weaker interaction of as-grown layers is explained by wrinkles formation that reduces strain at the layer-substrate interface, which for layers transferred to other substrates occurs only in a limited temperature range. The most striking result is the observation of a giant increase in the $E_{1u}$ phonon energy of up to $\sim6$ cm$^{-1}$ in a narrow temperature range. We show that the amplitude and temperature range of the anomaly is strongly modified by UV light illumination. The observed giant effect is explained in terms of strain generation resulting from charge redistribution between shallow traps and different defects, which can be interpreted as a result of strong electron-phonon coupling in hBN. The observed narrow temperature range of the anomaly indicates that the effect may be further enhanced for example by electrostrictive effects, expected for sp$^2$ boron nitride.

In recent years, inorganic 2D materials have been recognized as promising candidates for membrane filtration. In particular, theoretical studies predict the excellent desalination performance of nanoporous hexagonal boron nitride . However, studies showing the experimental realization of such systems are to this date missing. In this work, we demonstrate the desalinating properties of sp 2 -bonded boron nitride . Secondary Ion Mass Spectrometry experiments have shown the clear separation of NaCl and water by the boron nitride film: Na and Cl ions have been retained and trapped in the near-surface region, while water permeated through its whole depth. Analysis based on the diffusion equation revealed that the diffusion coefficient of water is over 3 orders of magnitude higher than the diffusion coefficient of NaCl in the temperature range of 25-65°C, manifesting that boron nitride is a material of high potential for use as a selective layer for membrane filtration.

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.

Van der Waals heterostructures based on hexagonal boron nitride (h-BN) and other 2D materials may pave the way for future electronic applications. Wafer-scale uniform h-BN substrates are a must in this respect. In this work, we demonstrate a new growth regime which allows for scalable, uniform synthesis of high quality h-BN layers on 2' sapphire substrates. We propose a new approach to metal organic vapour phase epitaxy of h-BN layers on sapphire substrates. The growth scheme involves an intermediary BN buffer layer grown under self-limiting conditions (continuous flow) followed by the final growth of h-BN with flow modulated epitaxy in one growth run. This scheme can be regarded as homoepitaxial growth of h-BN on a self-limiting buffer. Our studies show that the buffer layer allows to control the nucleation at the crucial early stages of BN layer growth, suppressing unwanted out-of-plane growth. It can also be used to control the density of point-like defects responsible for unwanted luminescence from the h-BN layer. Moreover, our results show that the buffer effectively suppresses the creation of amorphous BN at the sapphire/h-BN interface.

The possibility to fabricate van der Waals heterostructures on the wafer-scale would open up a wide range of potential applications. Hexagonal boron nitride (hBN) is one of the most important components in many structures of this kind. Obtaining high quality hBN and the ability to transfer large areas to arbitrary surfaces is a must for future applications of many less durable and less stable van der Waals materials. In this work, we point out key factors that allow us to delaminate large areas of hBN layers grown by metal-organic vapor phase epitaxy on two-inch sapphire substrates. Using scanning electron microscopy and X-ray diffraction, we also compare hBN layers before and after the delamination process.

We demonstrate quantum emission capabilities from boron nitride structures which are relevant for practical applications and can be seamlessly integrated into a variety of heterostructures and devices. First, the optical properties of polycrystalline BN films grown by metalorganic vapour-phase epitaxy are inspected. We observe that these specimens display an antibunching in the second-order correlation functions, if the broadband background luminescence is properly controlled. Furthermore, the feasibility to use flexible and transparent substrates to support hBN crystals that host quantum emitters is explored. We characterise hBN powders deposited onto polydimethylsiloxane films, which display quantum emission characteristics in ambient environmental conditions.