hBN Samples Research Articles

Optimisation of electron irradiation for creating spin ensembles in hexagonal boron nitride

Boron vacancy centre ( VB− ) ensembles in hexagonal boron nitride (hBN) have attracted recent interest for their potential as two-dimensional solid-state quantum sensors. Irradiation is necessary for VB− creation, however, to date only limited attention has been given to optimising the defect production process, especially in the case of bulk irradiation with high-energy particles, which offers scalability through the potential for creating ensembles in large volumes of material. Here we systematically investigate the effect of electron irradiation by varying the dose delivered to a range of hBN samples, which differ in their purity, and search for an optimum in measurement sensitivity. We find that moderate electron irradiation doses ( ≈5×1018 cm−2) appear to offer the best sensitivity, and also observe a dependence on the initial crystal purity. These results pave the way for the scalable and cost-effective production of hBN quantum sensors, and provide insight into the mechanisms limiting VB− spin properties.

Probing Defectivity Beneath the Hydrocarbon Blanket in 2D hBN Using TEM-EELS.

The controlled creation and manipulation of defects in 2D materials has become increasingly popular as a means to design and tune new material functionalities. However, defect characterization by direct atomic-scale imaging is often severely limited by surface contamination due to a blanket of hydrocarbons. Thus, analysis techniques that can characterize atomic-scale defects despite the contamination layer are advantageous. In this work, we take inspiration from X-ray absorption spectroscopy and use broad-beam electron energy loss spectroscopy (EELS) to characterize defect structures in 2D hexagonal boron nitride (hBN) based on averaged fine structure in the boron K-edge. Since EELS is performed in a transmission electron microscope (TEM), imaging can be performed in-situ to assess contamination levels and other factors such as tears in the fragile 2D sheets, which can affect the spectroscopic analysis. We demonstrate the TEM-EELS technique for 2D hBN samples irradiated with different ion types and doses, finding spectral signatures indicative of boron-oxygen bonding that can be used as a measure of sample defectiveness depending on the ion beam treatment. We propose that even in cases where surface contamination has been mitigated, the averaging-based TEM-EELS technique can be useful for efficient sample surveys to support atomically resolved EELS experiments.

Understanding the Intrinsic Water Wettability of Hexagonal Boron Nitride.

The water wettability of hexagonal boron nitride (hBN) has attracted a lot of research interest in the past 15 years. Experimentally, the static water contact angle (WCA) has been widely utilized to characterize the intrinsic water wettability of hBN. In the current study, we have investigated the effect of airborne hydrocarbons and defects on both static and dynamic WCAs of hBN. Our results showed that the static WCA is impacted by defects, which suggests that previously reported static WCAs do not characterize the intrinsic water wettability of hBN since the state-of-the-art hBN samples always have relatively high defect density. Instead, we found that the advancing WCA of freshly exfoliated hBN is not affected by the defects and airborne hydrocarbons. As a result, the advancing WCA on freshly exfoliated hBN, determined to be 79 ± 3°, best represents the intrinsic water wettability of hBN. A qualitative model has been proposed to describe the effect of airborne hydrocarbons and defects on the static and dynamic WCA of hBN, which is well supported by the experimental results. The finding here has important implications for the water wettability of 2D materials.

The investigation of synthesis and textured properties of in situ formed hBN with spark plasma sintering

Hexagonal boron nitride (hBN) exhibits high thermal conductivity within the in-plane direction and significantly lower thermal conductivity in the cross-plane direction because of its anisotropic nature. When the texture properties of bulk hBN are strong, it is a potentially promising application area for the insulating heat spreaders and heat sinks. In this study, hBN was synthesized in situ with the spark plasma sintering (SPS) technique and the effects of sintering temperature on the orientation of hBN grains were investigated. The precursor was prepared by chemically reacting urea and boric acid in heat treatment at 850 °C. The hBN was produced using the previous precursor in a SPS at 1500, 1700, and 1900 °C. The samples were characterized using XRD, FTIR, SEM and Raman spectroscopy. The properties of the samples were further determined through measurements of density, DSC and thermal diffusivity. The hBN samples obtained through the SPS process have nano and micron-size grains. The hBN was highly crystalline and homogeneous, as determined by the XRD pattern, Raman spectra and Raman maps. The orientation of hBN grains has been revealed in the c-axis of hBN crystallites and was preferably arranged within a plane parallel to the SPS pressing direction. The hBN orientation preference index (IOP) value of −19925.5 at 1700 °C indicates the highest quality texture orientation. Increasing the temperature to 1900 °C decreased the orientation in the direction parallel to the pressing direction. The highest thermal conductivity calculated according to the thermal diffusivity perpendicular to the sintering pressure direction was 8.86 W m−1K−1 at 1900 °C.

Influence of neutron irradiation on X-ray diffraction, Raman spectrum and photoluminescence from pyrolytic and hot-pressed hexagonal boron nitride

Hexagonal boron nitride (hBN) is considered as an ideal semiconductor material for solid-state neutron detector, owing to its large neutron scattering section because of the low atomic number of B and excellent physical properties. Here we study the influence of neutron irradiation on crystal structure and on intermediate energy state (IMES) levels induced by the presence of impurities and defects in hBN. Large-size and thick pyrolytic and hot-pressed hBN (PBN and HBN) samples, which can be directly applied for neutron detector devices, are prepared and bombarded by neutrons with different irradiation fluences. The SEM and TEM are used to observe the sample difference of PBN and HBN. X-ray diffraction and Raman spectroscopy are applied to examine the influence of neutron irradiation on lattice structures along different crystal directions of PBN and HBN samples. Photoluminescence (PL) is employed to study the effect of neutron irradiation on IMESs in these samples. We find that the neutron irradiation does not alter the in-plane lattice structures of both PBN and HBN samples, but it can release the inter-layer tensions induced by sample growth of the PBN samples. Interestingly and surprisingly, the neutron irradiation does not affect the IMES levels responsible for PL generation, where PL is attributed mainly from phonon-assisted radiative electron-hole coupling for both PBN and HBN samples. Furthermore, the results indicate that the neutron irradiation can weaken the effective carrier-phonon coupling and exciton transitions in PBN and HBN samples. Overall, both PBN and HBN samples show some degree of the resistance to neutron irradiation in terms of these basic physical properties. The interesting and important findings from this work can help us to gain an in-depth understanding of the influence of neutron irradiation on basic physical properties of hBN materials. These effects can be taken into account when designing and applying the hBN materials for neutron detectors.

Coherent dynamics of strongly interacting electronic spin defects in hexagonal boron nitride

Optically active spin defects in van der Waals materials are promising platforms for modern quantum technologies. Here we investigate the coherent dynamics of strongly interacting ensembles of negatively charged boron-vacancy ({{{{{{{{rm{V}}}}}}}}}_{{{{{{{{rm{B}}}}}}}}}^{-}) centers in hexagonal boron nitride (hBN) with varying defect density. By employing advanced dynamical decoupling sequences to selectively isolate different dephasing sources, we observe more than 5-fold improvement in the measured coherence times across all hBN samples. Crucially, we identify that the many-body interaction within the {{{{{{{{rm{V}}}}}}}}}_{{{{{{{{rm{B}}}}}}}}}^{-} ensemble plays a substantial role in the coherent dynamics, which is then used to directly estimate the concentration of {{{{{{{{rm{V}}}}}}}}}_{{{{{{{{rm{B}}}}}}}}}^{-}. We find that at high ion implantation dosage, only a small portion of the created boron vacancy defects are in the desired negatively charged state. Finally, we investigate the spin response of {{{{{{{{rm{V}}}}}}}}}_{{{{{{{{rm{B}}}}}}}}}^{-} to the local charged defects induced electric field signals, and estimate its ground state transverse electric field susceptibility. Our results provide new insights on the spin and charge properties of {{{{{{{{rm{V}}}}}}}}}_{{{{{{{{rm{B}}}}}}}}}^{-}, which are important for future use of defects in hBN as quantum sensors and simulators.

An Evaluation of Item Harmonization Strategies Between Assessment Tools of Psychopathology in Children and Adolescents.

Data aggregation in mental health is complicated by using different questionnaires, and little is known about the impact of item harmonization strategies on measurement precision. Therefore, we aimed to assess the impact of various item harmonization strategies for a target and proxy questionnaire using correlated and bifactor models. Data were obtained from the Brazilian High-Risk Study for Mental Conditions (BHRCS) and the Healthy Brain Network (HBN; N = 6,140, ages 5-22 years, 39.6% females). We tested six item-wise harmonization strategies and compared them based on several indices. The one-by-one (1:1) expert-based semantic item harmonization presented the best strategy as it was the only that resulted in scalar-invariant models for both samples and factor models. The between-questionnaires factor correlation, reliability, and factor score difference in using a proxy instead of a target measure improved little when all other harmonization strategies were compared with a completely at-random strategy. However, for bifactor models, between-questionnaire specific factor correlation increased from 0.05-0.19 (random item harmonization) to 0.43-0.60 (expert-based 1:1 semantic harmonization) in BHRCS and HBN samples, respectively. Therefore, item harmonization strategies are relevant for specific factors from bifactor models and had little impact on p-factors and first-order correlated factors when the child behavior checklist (CBCL) and strengths and difficulties questionnaire (SDQ) were harmonized.

Hexagonal boron nitride: optical properties in the deep ultraviolet

We review the recent advance in the understanding of the optoelectronic properties of hexagonal boron nitride (hBN) in the deep ultraviolet. The comparison between bulk hBN and monolayer hBN highlights some of their major differences such the bandgap nature, the excitonic binding energy and the phonon-assisted broadening of the excitonic lines. Perspectives point out the relevance of addressing the regime of hBN samples made of a very few number of monolayers, including twisted hBN monolayers in the context of twistronics.

Position-controlled quantum emitters with reproducible emission wavelength in hexagonal boron nitride

Single photon emitters (SPEs) in low-dimensional layered materials have recently gained a large interest owing to the auspicious perspectives of integration and extreme miniaturization offered by this class of materials. However, accurate control of both the spatial location and the emission wavelength of the quantum emitters is essentially lacking to date, thus hindering further technological steps towards scalable quantum photonic devices. Here, we evidence SPEs in high purity synthetic hexagonal boron nitride (hBN) that can be activated by an electron beam at chosen locations. SPE ensembles are generated with a spatial accuracy better than the cubed emission wavelength, thus opening the way to integration in optical microstructures. Stable and bright single photon emission is subsequently observed in the visible range up to room temperature upon non-resonant laser excitation. Moreover, the low-temperature emission wavelength is reproducible, with an ensemble distribution of width 3 meV, a statistical dispersion that is more than one order of magnitude lower than the narrowest wavelength spreads obtained in epitaxial hBN samples. Our findings constitute an essential step towards the realization of top-down integrated devices based on identical quantum emitters in 2D materials.

Effect of borates on the synthesis of nanoscale hexagonal boron nitride by a solid-state method.

This study delves deeply into the effect of different borates (lithium tetraborate, sodium tetraborate, calcium metaborate, ammonium pentaborate) on the production and fundamental characteristic features of nanoscale hexagonal boron nitride (hBN) structure with the assistant of standard characteristic measurement methods, namely, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM). The hBN samples are synthesized by reaction of powder urea, boron oxide, and different kinds of borates via the modified O'Connor method (performed at a relatively lower main heat treatment temperature of 1,100°C). All the results obtained show that the usage of borates affects positively the formation of nanoscale hBN structure. In more detail, the FTIR experiment results reveal that the presence of two strong c peaks appeared at ~1,380 and ~780 cm-1 in the spectra points out the conventional BN in-plane and out-of-plane vibrations, respectively. The XRD patterns also confirm the production of high-ordered hBN as the existence of the main peaks of the corresponding hexagonal system. As for the SEM examination, it is found that all the hBN materials exhibit totally different crystallinity quality and microstructural characteristics. The hBN compound prepared by the sodium tetraborate content shows the most uniform surface appearance with the smoothest/densest crystal structure, best grain orientations, and finest grain interactions. Hence, the material with strong stretching of interatomic bonds shows the highest material (fracture) strength. Moreover, the TEM images illustrate that all the products are composed of uniform multi-walled nanotubes and nanorods with an average length of ~250 nm.

Hot-pressing and characterization of TiB2–SiC composites with different amounts of BN additive

This research aimed to study the influence of different amounts of hBN additive on the mechanical properties and microstructure of TiB2-15 vol% SiC samples. All ceramics, containing 0, 3.5, and 7 vol% hBN, were sintered at 2000 °C using a hot-pressing route and reached their near full densities. Thanks to two different chemical reactions among the SiC reinforcement and the TiB2 surface oxides (B2O3 and TiO2), the in-situ phases of SiO2 and TiC were generated over the sintering process. The intergranular mode was identified as the predominant fracture type in all three composite samples. The hBN additive could contribute to grain refining of composites so that the sample containing 7 vol% hBN reached the finest microstructure. Finally, the highest Vickers hardness of 25.4 HV0.5 kg and flexural strength of 776 MPa were attained for the TiB2–SiC and TiB2–SiC-7 vol% hBN samples, respectively.

Large few-layer hexagonal boron nitride flakes for nonlinear optics.

Hexagonal boron nitride (hBN) is a layered dielectric material with a wide range of applications in optics and photonics. In this work, we demonstrate a fabrication method for few-layer hBN flakes with areas up to 5000µm2. We show that hBN in this form can be integrated with photonic microstructures: as an example, we use a circular Bragg grating (CBG). The layer quality of the exfoliated hBN flake on and off a CBG is confirmed by Raman spectroscopy and second-harmonic generation (SHG) microscopy. We show that the SHG signal is uniform across the hBN sample outside the CBG and is amplified in the center of the CBG.

Effects of SiC on densification, microstructure and nano-indentation properties of ZrB2–BN composites

Introducing the SiC additive resulted in a noticeable enhancement in the sintering behavior of the ZrB2–hBN composite, profiting from the SiC involvement in the surface oxide removal. This research intended to compare two ceramics of ZrB2–hBN and ZrB2–SiC–hBN in terms of sinterability, microstructure, and mechanical features. Both samples were spark plasma sintered at 2000 °C for 5 min under 30 MPa. The SiC-free specimen reached a relative density of lower than 95%, while incorporating SiC improved this value up to 99.3%, resulting in near fully dense material. The role of SiC on oxide removal was found to be the chief cause in enhancing the sinterability of the ZrB2–SiC–hBN sample compared to ZrB2–hBN. According to the field emission scanning electron microscopy (FESEM), field emission-electron probe microanalyzer (FE-EPMA), X-ray diffractometry (XRD), and X-ray photoelectron spectroscopy (XPS) studies, both systems were unreactive, and no major in-situ phase could be produced over the sintering process. The ZrB2–SiC–hBN composite reached an elastic modulus of 374 GPa and a Vickers hardness of 19 GPa.

Estimated Prevalence of Nonverbal Learning Disability Among North American Children and Adolescents

Nonverbal learning disability (NVLD) is a neurodevelopmental disorder characterized by deficits in visual-spatial processing but not in reading or verbal ability; in addition, problems in math calculation, visual executive functioning, fine-motor skills, and social skills are often present. To our knowledge, there are no population-based estimates of the prevalence of NVLD in community samples. To estimate the prevalence of the NVLD cognitive profile in 3 independent samples of children and adolescents from studies centered around brain imaging in the US and Canada. This cross-sectional study used data from 2 samples recruited from the community and overselected for children with psychiatric disorders (Healthy Brain Network [HBN], January 1, 2015, to December 31, 2019, and Nathan Kline Institute-Rockland Sample [NKI], January 1, 2011, to December 31, 2018) and 1 community-ascertained population sample (Saguenay Youth Study [SYS], January 1, 2003, to December 31, 2012) overselected for active maternal smoking during pregnancy. Prevalence of NVLD. Criteria for NVLD were based on clinical records of deficits in visual-spatial reasoning and impairment in 2 of 4 domains of function (fine-motor skills, math calculation, visual executive functioning, and social skills). Sample weighting procedures adjusted for demographic differences in sample frequencies compared with underlying target populations. Inflation factor weights accounted for overrepresentation of psychiatric disorders (HBN and NKI samples). Across 3 independent samples, the prevalence of NVLD was estimated among 2596 children and adolescents aged 6 to 19 years (mean [SD] age, 12.5 [3.4] years; 1449 male [55.8%]). After sample and inflation weights were applied, the prevalence of NVLD was 2.78% (95% CI, 2.03%-3.52%) in the HBN sample and 3.9% (95% CI, 1.96%-5.78%) in the NKI sample. In the SYS sample, the prevalence of NVLD was 3.10% (95% CI, 1.93%-4.27%) after applying the sample weight. Across samples and estimation strategies, the population prevalence of NVLD was estimated to range from 3% to 4%. When applied to the US population younger than 18 years, 2.2 million to 2.9 million children and adolescents were estimated to have NVLD. The findings suggest that the prevalence of NVLD in children and adolescents may be 3% to 4%. Given that few youths are diagnosed with NVLD and receive treatment, increased awareness, identification of the underlying neurobiological mechanisms, and development and testing interventions for the disorder are needed.

Sonocatalytic activity of a heterostructured β-Bi2O3/Bi2O2CO3 nanoplate in degradation of bisphenol A

Novel heterostructured β-Bi2O3/Bi2O2CO3 nanoplates (hBN) were synthesized to observe the sonocatalytic degradation of bisphenol A (BPA) (widely used as a model pollutant) under ultrasonic (US) irradiation. Prior to obtaining the hBN, the Bi2O2CO3 micropowder precursor was prepared under hydrothermal conditions and then converted to hBN by increasing the calcination temperature to 300 °C. The synthesized hBN samples were characterized by field emission scanning electron microscope with energy dispersive X-ray analysis (FESEM/EDX), transmission electron microscopy (TEM), X-ray diffraction (XRD), ultraviolet–visible spectrophotometer diffuse reflection spectroscopy (UV–vis DRS), and X-ray photoelectron spectroscopy (XPS). The hBN/US system exhibited greater sonocatalytic activity for the degradation of BPA than the US treatment with the single element bismuth oxide, β-Bi2O3 prepared by annealing the Bi2O2CO3 precursor at 400 °C for 1 h. The US frequency and US power intensity in the hBN/US system were the key operating parameters, which were responsible for the complete degradation of BPA during 6 h of reactions. The degradation efficiency of BPA under the US irradiation was positively correlated with the dose of hBN. Our findings indicate that heterostructured hBN can be used as an efficient sonocatalyst for the catalytic degradation of BPA in water and wastewater treatment.

Influence of point defects on the near edge structure of hexagonal boron nitride

Hexagonal boron nitride (hBN) is a wide-band-gap semiconductor with applications including gate insulation layers in graphene transistors, far-ultraviolet light emitting devices and as hydrogen storage media. Due to its complex microstructure, defects in hBN are challenging to identify. Here, we combine x-ray absorption near edge structure (XANES) spectroscopy with ab initio theoretical modeling to identify energetically favorable defects. Following annealing of hBN samples in vacuum and oxygen, the B and N $K$ edges exhibited angular-dependent peak modifications consistent with in-plane defects. Theoretical calculations showed that the energetically favorable defects all produce signature features in XANES. Comparing these calculations with experiments, the principle defects were attributed to substitutional oxygen at the nitrogen site, substitutional carbon at the boron site, and hydrogen passivated boron vacancies. Hydrogen passivation of defects was found to significantly affect the formation energies, electronic states, and XANES. In the B $K$ edge, multiple peaks above the major $1s$ to ${\ensuremath{\pi}}^{*}$ peak occur as a result of these defects and the hydrogen passivated boron vacancy produces the frequently observed doublet in the $1s$ to ${\ensuremath{\sigma}}^{*}$ transition. While the N $K$ edge is less sensitive to defects, features attributable to substitutional C at the B site were observed. This defect was also calculated to have mid-gap states in its band structure that may be responsible for the 4.1-eV ultraviolet emission frequently observed from this material.

Effect of Li2CO3 on formation temperature of hBN by modified O'Connor model

This study is interested in the effect of lithium carbonate on the formation of hexagonal boron nitride (hBN) by means of the available experimental methods including TGA, XRD, FTIR, SEM and HR‐TEM. hBN samples were synthesized at the 1450 °C with different molar ratios of lithium carbonate by modified O'Connor routine. The crystalline hBN formation tended to improve with the increment of the Li2CO3 concentration level (especially after more 20 %). The dopant quantity decreased the residual stresses due to the presence of possible relaxation mechanisms along with the nanocrystal structure, even favored by XRD experimental findings regarding the enhancement of crystal plane alignments, crystallite sizes and lattice parameters. As for the FTIR surveys, the Li2CO3 foreign impurities strengthened more and more the covalent bonds between boron and nitrogen atoms. At the same time, the samples with 40 % lithium carbonate were annealed at the varied temperatures of 1000, 1150, 1300 and 1450 °C to determine the optimum annealing temperature. The XRD+FTIR investigations indicated that the degree of hexagonality improved with the increased annealing temperature. Similarly, the surface morphology confirmed not only the formation of regularity and flaky hexagonal BN structures, but also the strengthening of covalent bonds between the atoms.

Shear-induced phase transition of nanocrystalline hexagonal boron nitride to wurtzitic structure at room temperature and lower pressure

Disordered structures of boron nitride (BN), graphite, boron carbide (BC), and boron carbon nitride (BCN) systems are considered important precursor materials for synthesis of superhard phases in these systems. However, phase transformation of such materials can be achieved only at extreme pressure-temperature conditions, which is irrelevant to industrial applications. Here, the phase transition from disordered nanocrystalline hexagonal (h)BN to superhard wurtzitic (w)BN was found at room temperature under a pressure of 6.7 GPa after applying large plastic shear in a rotational diamond anvil cell (RDAC) monitored by in situ synchrotron X-ray diffraction (XRD) measurements. However, under hydrostatic compression to 52.8 GPa, the same hBN sample did not transform to wBN but probably underwent a reversible transformation to a high-pressure disordered phase with closed-packed buckled layers. The current phase-transition pressure is the lowest among all reported direct-phase transitions from hBN to wBN at room temperature. Usually, large plastic straining leads to disordering and amorphization; here, in contrast, highly disordered hBN transformed to crystalline wBN. The mechanisms of strain-induced phase transformation and the reasons for such a low transformation pressure are discussed. Our results demonstrate a potential of low pressure-room temperature synthesis of superhard materials under plastic shear from disordered or amorphous precursors. They also open a pathway of phase transformation of nanocrystalline materials and materials with disordered and amorphous structures under extensive shear.

Influence of Air, Oxygen, Nitrogen and Argon on 400 nm Luminescence in Hexagonal Boron Nitride

Influence of Air, Oxygen, Nitrogen and Argon on 400 nm Luminescence in Hexagonal Boron NitrideThe investigation is devoted to the influence of different surrounding gases on the defect-related luminescence in hexagonal boron nitride (hBN). The photoluminescence spectra of hBN powder were measured for an hBN sample placed in different surroundings formed by ambient air, vacuum, as well as oxygen, nitrogen and argon gases. It was found that the 400 nm luminescence caused by native defects in hBN is sensitive to the oxygen gas and ambient air. Presence of oxygen gas around hBN considerably reduces the intensity of this luminescence. The results evidence that hBN powder can successfully be applied as the material for oxygen sensors.

Disordered state in first-order phase transitions: Hexagonal-to-cubic and cubic-to-hexagonal transitions in boron nitride

The microscopic mechanism of diffusion-type solid-solid first-order transitions was studied in boron nitride. This substance exhibits an extreme case of transitions between very different lattices, hexagonal (graphite-like) and cubic (diamond-like) phases, accompanied by a large change in the volume. A boundary between the hexagonal and cubic phases was produced by local heating of either a cBN or hBN sample in a diamond-anvil cell under hydrostatic pressure with the aid of a laser so that the sample was partially transformed to another phase. The boundary was studied with the aid of micro-Raman and high-resolution electron microscopy. In the transient region between the two phases a mixture of highly fragmented disordered nanocrystallites and the amorphous state of BN was found. BN nanotubes growing from the amorphous state were also discovered in this region.