hBN Flakes Research Articles

Plasmonic Nanocavity to Boost Single Photon Emission From Defects in Thin Hexagonal Boron Nitride

AbstractEfficient and compact single photon emission platforms operating at room temperature with ultrafast speed and high brightness will be fundamental components of the emerging quantum communications and computing fields. However, so far, it is very challenging to design practical deterministic single photon emitters based on nanoscale solid‐state materials that meet the fast emission rate and strong brightness demands. Here, a solution is provided to this longstanding problem by using metallic nanocavities integrated with hexagonal boron nitride (hBN) flakes with defects acting as nanoscale single photon emitters (SPEs) at room temperature. The presented hybrid nanophotonic structure creates a rapid speedup and large enhancement in single photon emission at room temperature. Hence, the nonclassical light emission performance is substantially improved compared to plain hBN flakes and hBN on gold‐layered structures without nanocavity. Extensive theoretical calculations are also performed to accurately model the new hybrid nanophotonic system and prove that the incorporation of plasmonic nanocavity is key to efficient SPE performance. The proposed quantum nanocavity single photon source is expected to be an element of paramount importance to the envisioned room‐temperature integrated quantum photonic networks.

Engineering Boron Vacancy Defects in Boron Nitride Nanotubes.

Spin defects in hexagonal boron nitride (hBN) are emerging as promising platforms for quantum sensing applications. In particular, the negatively charged boron vacancy (VB-) centers have been engineered in bulk hBN and few-layer hBN flakes, and employed for sensing. Here, we investigate the engineering of VB- spin defects in boron nitride nanotubes (BNNTs). The generated spin defects are distributed along and around the BNNTs. Moreover, in contrast to hBN flakes, the spins in BNNTs exhibit a directional response relative to the direction of a surrounding magnetic field, which is consistent with the tubular geometry. The unique geometry of BNNTs allows for a more controlled and predictable placement of spin defects compared to bulk hBN, paving the way for innovative sensing applications with high spatial resolution and optomechanical studies of spin defects in hBN.

Enhanced optical properties of MoSe2 grown by molecular beam epitaxy on hexagonal boron nitride

Transition metal dichalcogenides (TMDs) like MoSe2 exhibit remarkable optical properties such as intense photoluminescence (PL) in the monolayer form. To date, narrow-linewidth PL is only achieved in micrometer-sized exfoliated TMD flakes encapsulated in hexagonal boron nitride (hBN). In this work, we develop a growth strategy to prepare monolayer MoSe2 on hBN flakes by molecular beam epitaxy in the van der Waals regime. It constitutes the first step toward the development of large area single crystalline TMDs encapsulated in hBN for potential integration in electronic or optoelectronic devices. For this purpose, we define a two-step growth strategy to achieve monolayer-thick MoSe2 grains on hBN flakes. The high quality of MoSe2 allows us to detect very narrow PL linewidth down to 5.5 meV at 13 K, comparable to the one of encapsulated exfoliated MoSe2 flakes. Moreover, sizeable PL can be detected at room temperature as well as clear reflectivity signatures of A, B, and charged excitons.

Electron Beam Restructuring of Quantum Emitters in Hexagonal Boron Nitride

AbstractHexagonal boron nitride (hBN) holds promise as a solid state, van der Waals host of single photon emitters for on‐chip quantum photonics. The B‐center defect emitting at 436 nm is particularly compelling as it can be generated by electron beam irradiation. However, the emitter generation mechanism is unknown, the robustness of the method is variable, and it has only been applied successfully to thick flakes of hBN (≫ 10 nm). Here, it is used in situ time‐resolved cathodoluminescence (CL) spectroscopy to investigate the kinetics of B‐center generation. It is shown that the generation of B‐centers is accompanied by quenching of a carbon‐related emission at ≈305 nm and that both processes are rate‐limited by electromigration of defects in the hBN lattice. It identifies problems that limit the efficacy and reproducibility of the emitter generation method and solve them using a combination of optimized electron beam parameters and hBN pre‐and postprocessing treatments. It is achieved B‐center quantum emitters in hBN flakes as thin as 8 nm, elucidate the mechanisms responsible for electron beam restructuring of quantum emitters in hBN, and gain insights toward the identification of the atomic structure of the B‐center quantum emitter.

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.

Electrochemistry at the Edge of a van der Waals Heterostructure.

Artificial van der Waals heterostructures, obtained by stacking two-dimensional (2D) materials, represent a novel platform for investigating physicochemical phenomena and applications. Here, the electrochemistry at the one-dimensional (1D) edge of a graphene sheet, sandwiched between two hexagonal boron nitride (hBN) flakes, is reported. When such an hBN/graphene/hBN heterostructure is immersed in a solution, the basal plane of graphene is encapsulated by hBN, and the graphene edge is exclusively available in the solution. This forms an electrochemical nanoelectrode, enabling the investigation of electron transfer using several redox probes, e.g., ferrocene(di)methanol, hexaammineruthenium, methylene blue, dopamine and ferrocyanide. The low capacitance of the van der Waals edge electrode facilitates cyclic voltammetry at very high scan rates (up to 1000Vs-1), allowing voltammetric detection of redox species down to micromolar concentrations with sub-second time resolution. The nanoband nature of the edge electrode allows operation in water without added electrolyte. Finally, two adjacent edge electrodes are realized in a redox-cycling format. All the above-mentioned phenomena can be investigated at the edge, demonstrating that nanoscale electrochemistry is a new application avenue for van der Waals heterostructures. Such an edge electrode will be useful for studying electron transfer mechanisms and the detection of analyte species in ultralow sample volumes.

Sharp zero-phonon lines of single organic molecules on a hexagonal boron-nitride surface

Single fluorescent molecules embedded in the bulk of host crystals have proven to be sensitive probes of the dynamics in their nano environment, thanks to their narrow (about 30–50 MHz or 0.1–0.2 μeV) optical linewidth of the 0-0 zero-phonon line (0-0 ZPL) at cryogenic temperatures. However, the optical linewidths of the 0-0 ZPL have been found to increase dramatically as the single molecules are located closer to a surface or interface, while no 0-0 ZPL has been detected for single molecules on any surface. Here we study single terrylene molecules adsorbed on the surface of hexagonal boron-nitride (hBN) substrates. Our low-temperature results show that it is possible to observe the 0-0 ZPL of fluorescent molecules on a surface. We compare our results for molecules deposited on the surfaces of annealed and non-annealed hBN flakes and we see a marked improvement in the spectral stability of the emitters after annealing.

Creation of Boron Vacancies in Hexagonal Boron Nitride Exfoliated from Bulk Crystals for Quantum Sensing.

Boron vacancies (VB-) in hexagonal boron -nitride (hBN) have sparked great interest in recent years due to their optical and spin properties. Since hBN can be readily integrated into devices where it interfaces a huge variety of other 2D materials, boron vacancies may serve as a precise sensor which can be deployed at very close proximity to many important materials systems. Boron vacancy defects may be produced by a number of existing methods, the use of which may depend on the final application. Any method should reproducibly generate defects with controlled density and desired pattern. To date, however, detailed studies of such methods are missing. In this paper, we study various techniques for the preparation of hBN flakes from bulk crystals and relevant postprocessing treatments, namely, focused ion beam (FIB) implantation, for creation of VB-s as a function of flake thickness and defect concentrations. We find that flake thickness plays an important role when optimizing implantation parameters, while careful sample cleaning proved important to achieve consistent results.

Internal oriented strategy of the hBN composite resin with enhanced in-plane or through-plane thermal conductivity via 3D printing

In this work, we report a facile preparation of the composite resin with significantly enhanced high in-plane or through-plane thermal conductivity via controlling the layer thickness of digital light processing (DLP) 3D printing less than the lateral size of hBN. The thermal conductivity of the composite resin reaches up to 7.962 W∙m−1∙K−1 along the oriented direction at the content of 30 wt% hBN flakes with a lateral size of 25 μm under the 3D printing layer thickness of 15 μm, which is about 44 times greater than that of the pure resin. It is found that a lower thickness of the printing layer leads to a higher degree of the hBN flake orientation and higher thermal conductivity of the composite resin. Inspired by this method, the thermal conductivity prediction model based on the process parameters is established and has a higher accuracy than the traditional model. In addition, the 3D printed composite resin exhibits excellent thermostability, low water absorption and volume shrinkage, favorable mechanical properties, and great dielectric properties. This approach provides a new vision for the application of 3D printing in thermal management.

在导电陶瓷基体中加入hBN薄片来创制材料性能的各向异性

在导电陶瓷基体中加入hBN薄片来创制材料性能的各向异性

Optically Active Spin Defects in Few-Layer Thick Hexagonal Boron Nitride.

Optically active spin defects in hexagonal boron nitride (hBN) are promising quantum systems for the design of two-dimensional quantum sensing units offering optimal proximity to the sample being probed. In this Letter, we first demonstrate that the electron spin resonance frequencies of boron vacancy centers (V_{B}^{-}) can be detected optically in the limit of few-atomic-layer thick hBN flakes despite the nanoscale proximity of the crystal surface that often leads to a degradation of the stability of solid-state spin defects. We then analyze the variations of the electronic spin properties of V_{B}^{-} centers with the hBN thickness with a focus on (i)the zero-field splitting parameters, (ii)the optically induced spin polarization rate and (iii)the longitudinal spin relaxation time. This Letter provides important insights into the properties of V_{B}^{-} centers embedded in ultrathin hBN flakes, which are valuable for future developments of foil-based quantum sensing technologies.

Chemically detaching hBN crystals grown at atmospheric pressure and high temperature for high-performance graphene devices

In this work, we report on the growth of hexagonal boron nitride (hBN) crystals from an iron flux at atmospheric pressure and high temperature and demonstrate that (i) the entire sheet of hBN crystals can be detached from the metal in a single step using hydrochloric acid and that (ii) these hBN crystals allow to fabricate high carrier mobility graphene-hBN devices. By combining spatially-resolved confocal Raman spectroscopy and electrical transport measurements, we confirm the excellent quality of these crystals for high-performance hBN-graphene-based van der Waals heterostructures. The full width at half maximum of the graphene Raman 2D peak is as low as 16 cm−1, and the room temperature charge carrier mobilitiy is around 80 000 cm2/(Vs) at a carrier density 1 × 1012 cm−12. This is fully comparable with devices of similar dimensions fabricated using crystalline hBN synthesized by the high pressure and high temperature method. Finally, we show that for exfoliated high-quality hBN flakes with a thickness between 20 and 40 nm the line width of the hBN Raman peak, in contrast to the graphene 2D line width, is not useful for benchmarking hBN in high mobility graphene devices.

Thickness-Controlled Synthesis of Uniform Hexagonal Boron Nitride Films on Metal Alloys by Chemical Vapor Deposition

Two-dimensional (2D) multilayer hexagonal boron nitride (hBN) is a superior substrate for other 2D materials due to its insulating property, atomic-scale smoothness, and absence of dangling bonds, enhancing electrical or optical properties in high-performance 2D material-based devices. In most fabrication processes for 2D heterostructure devices, thick hBN flakes exfoliated from bulk have been used because of their high quality and simplicity in the process. However, exfoliated hBN flakes are limited in size and thickness control, impeding scale-up production for industrialization. Therefore, new synthesis strategies are required to overcome the drawback of the exfoliation method. In this work, we investigated the synthesis of large-area, multilayer hBN via atmospheric pressure chemical vapor deposition using single crystalline metal and single crystal alloy substrates. The synthesized results are characterized by optical microscopy, scanning electron microscopy, Raman spectroscopy, atomic force microscopy, etc. These studies provide a more comprehensive understanding of the growth mechanism of hexagonal boron nitride.

Novel Mixed-Dimensional hBN-Passivated Silicon Nanowire Reconfigurable Field Effect Transistors: Fabrication and Characterization.

This work demonstrates the novel concept of a mixed-dimensional reconfigurable field effect transistor (RFET) by combining a one-dimensional (1D) channel material such as a silicon (Si) nanowire with a two-dimensional (2D) material as a gate dielectric. An RFET is an innovative device that can be dynamically programmed to perform as either an n- or p-FET by applying appropriate gate potentials. In this work, an insulating 2D material, hexagonal boron nitride (hBN), is introduced as a gate dielectric and encapsulation layer around the nanowire in place of a thermally grown or atomic-layer-deposited oxide. hBN flake was mechanically exfoliated and transferred onto a silicon nanowire-based RFET device using the dry viscoelastic stamping transfer technique. The thickness of the hBN flakes was investigated by atomic force microscopy and transmission electron microscopy. The ambipolar transfer characteristics of the Si-hBN RFETs with different gating architectures showed a significant improvement in the device's electrical parameters due to the encapsulation and passivation of the nanowire with the hBN flake. Both n- and p-type characteristics measured through the top gate exhibited a reduction of hysteresis by 10-20 V and an increase in the on-off ratio (ION/IOFF) by 1 order of magnitude (up to 108) compared to the values measured for unpassivated nanowire. Specifically, the hBN encapsulation provided improved electrostatic top gate coupling, which is reflected in the enhanced subthreshold swing values of the devices. For a single nanowire, an improvement up to 0.97 and 0.5 V/dec in the n- and p-conduction, respectively, is observed. Due to their dynamic switching and polarity control, RFETs boast great potential in reducing the device count, lowering power consumption, and playing a crucial role in advanced electronic circuitry. The concept of mixed-dimensional RFET could further strengthen its functionality, opening up new pathways for future electronics.

Enhanced intensity of Raman signals from hexagonal boron nitride films

Optical spectroscopy is commonly used to study the properties of 2D materials. In order to obtain the best signal-to-noise ratio, it is important to optimize the incoupling of the excitation laser and, at the same time, reduce spurious light reflection. We performed Raman spectroscopy on exfoliated hexagonal boron nitride (hBN) flakes of different thicknesses, placed on a 300 nm SiO2 on Si substrate. By changing the hBN layer thickness, we found a specific thickness, where the Raman signals from the substrate and the hBN showed maximum intensity, whereas the backscattered laser light was suppressed. To explain the increased emission, we calculated the reflectivity and transmissivity of the full layer system (air, hBN, SiO2, and Si) as a function of hBN layer thicknesses for different excitation wavelengths (457, 532, and 633 nm), using the transfer-matrix algorithm. To compare theory with the experiment, we performed Raman measurements with these three different excitation wavelengths on different flakes and determined their thicknesses with AFM measurements. The experimental results are in good agreement with the calculations, which shows the importance of thin film interference to obtain optimum spectroscopic conditions. Since interference colors are easily visible in an optical microscope, this facilitates the choice of optimum flakes for a wide range of optical characterization techniques, including Raman, photoluminescence, and single defect spectroscopy.

Extremely High Intrinsic Carrier Mobility and Quantum Hall Effect Of Single Crystalline Graphene Grown on Ge(110)

AbstractThe successful synthesis of wafer‐scale single crystalline graphene on semiconducting Ge substrate has been considered a significant breakthrough toward the manufacturing of graphene‐based electronic and photonic devices; however, the assumed extremely high electrical mobility has not been found yet due to the lack of an adequate characterization method. Herein, state‐of‐the‐art transfer methods are developed to encapsulate the single crystalline graphene, which is grown on semiconducting Ge(110), in two hexagonal boron nitride (hBN) flakes, then acquire its inherent electrical mobility precisely via edge‐contact technique. It is found that single crystalline graphene grown on Ge(110) possesses a maximum carrier mobility of over 100 000 cm2 V−1 s−1 at low temperatures (2.3 K), which is superior to that obtained from graphene grown on other nonmetal substrates. Due to the extremely high mobility, well‐defined quantum Hall effect and Shubnikov‐de Haas oscillations can be observed at low temperatures as well. The study suggests that the excellent carrier mobility of graphene grown on Ge(110) may open an avenue to develop the practical graphene‐based nanodevices with high performance.

Creation and repair of luminescence defects in hexagonal boron nitride by irradiation and annealing for optical neutron detection

Hexagonal boron nitride (hBN) is promising for applications in neutron detection and quantum sensing. Here we created spin-dependent luminescence defects in hBN using 50 keV helium ion beam. The irradiated hBN flakes with a dose around 2 × 1014–1 × 1015/cm2 have the maximum photoluminescence (PL) intensity. The PL spectra are in the range of 700–1000 nm with a peak around 818 nm at 297 K after irradiation with a dose of less than 2 × 1014/cm2, which can be eliminated by high temperature annealing at 1097 K due to defects repair according to Raman spectra. However, the PL peaks exhibit a redshift from 818 nm to 830 nm when the irradiation dose is no less than 1 × 1015/cm2. Combining with constrained density functional theory calculations, it is found that high dose irradiation can cause local lattice swelling and further induce the redshift of PL spectra by 12 nm/0.33% strain. Furthermore, we proposal a novel optical neutron detection method by recording the intensity and position of PL signal of luminescence defects induced by neutron-10B nuclear reaction daughter particles. This work would be helpful to create luminescence defects in hBN for quantum sensing, and develop a novel neutron detector.

Identification of the monolayer thickness difference in a mechanically exfoliated thick flake of hexagonal boron nitride and graphite for van der Waals heterostructures

Exfoliated flakes of layered materials, such as hexagonal boron nitride (hBN) and graphite with a thickness of several tens of nanometers, are used to construct van der Waals heterostructures. A flake with a desirable thickness, size, and shape is often selected from many exfoliated flakes placed randomly on a substrate using an optical microscope. This study examined the visualization of thick hBN and graphite flakes on SiO2/Si substrates through calculations and experiments. In particular, the study analyzed areas with different atomic layer thicknesses in a flake. For visualization, the SiO2 thickness was optimized based on the calculation. As an experimental result, the area with different thicknesses in a hBN flake showed different brightness in the image obtained using an optical microscope with a narrow band-pass filter. The maximum contrast was 12% with respect to the difference of monolayer thickness. In addition, hBN and graphite flakes were observed by differential interference contrast (DIC) microscopy. In the observation, the area with different thicknesses exhibited different brightnesses and colors. Adjusting the DIC bias had a similar effect to selecting a wavelength using a narrow band-pass filter.

Plasmon Enhanced Quantum Properties of Single Photon Emitters with Hybrid Hexagonal Boron Nitride Silver Nanocube Systems

AbstractHexagonal boron nitride (hBN) has emerged as a promising ultrathin host of single photon emitters (SPEs) with favorable quantum properties at room temperature, making it a highly desirable element for integrated quantum photonic networks. One major challenge of using these SPEs in such applications is their low quantum efficiency. Recent studies have reported an improvement in quantum efficiency by up to two orders of magnitude when integrating an ensemble of emitters such as boron vacancy defects in multilayered hBN flakes embedded within metallic nanocavities. However, these experiments have not been extended to SPEs and are mainly focused on multiphoton effects. Here, the quantum single‐photon properties of hybrid nanophotonic structures composed of SPEs created in ultrathin hBN flakes coupled with plasmonic silver nanocubes (SNCs) are studied. The authors demonstrate 200% plasmonic enhancement of the SPE properties, manifested by a strong increase in the SPE fluorescence. Such enhancement is explained by rigorous numerical simulations where the hBN flake is in direct contact with the SNCs that cause the plasmonic effects. The presented strong and fast single photon emission obtained at room temperature with a compact hybrid nanophotonic platform can be very useful to various emerging applications in quantum optical communications and computing.

Spatially Controlled Single Photon Emitters in hBN‐Capped WS2 Domes

AbstractMonolayers (MLs) of transition‐metal dichalcogenides host efficient single‐photon emitters (SPEs) usually associated to the presence of nanoscale mechanical deformations or strain. Large‐scale spatial control of strain would enhance the scalability of such SPEs and allow for their incorporation into photonic structures. Here, the formation of regular arrays of strained hydrogen‐filled one‐layer‐thick micro‐domes obtained by H‐ion irradiation and lithography‐based approaches is reported. Typically, the H2 liquefaction for temperatures T<32 K causes the disappearance of the domes preventing their use as potential SPEs. Here, it is shown that the dome deflation can be overcome by hBN heterostructuring, that is by depositing thin hBN flakes on the domes. This leads to the preservation of the dome structure at all temperatures, as found by micro‐Raman and micro‐photoluminescence (µ‐PL) studies. Eventually, spatially controlled hBN‐capped WS2 domes show the appearance, at 5 K, of intense emission lines originating from localized excitons, which are shown to behave as quantum emitters here. The electronic properties of the emitters are addressed by time‐resolved µ‐PL yielding time decays of 1–10 ns, and by magneto‐µ‐PL measurements. The latter provide an exciton magnetic moment a factor of two larger than the value observed in planar strain‐free MLs.