Hydrogen Confinement in Hexagonal Boron Nitride Bubbles Using UV Laser Illumination.

Hexagonal boron nitride (h-BN) bubbles are of significant interest to micro-scale hydrogen storage thanks to their ability to confine hydrogen gas molecules. Previous reports of h-BN bubble creation from grown h-BN films require electron beams under vacuum, making integrating with other experimental setups for hydrogen production impractical. Therefore, in this study, the formation of h-BN bubbles is demonstrated in a 20 nm h-BN film grown on a sapphire substrate with a 213 nm UV laser beam. Using atomic force microscopy, it is shown that longer illumination time induces larger h-BN bubbles up to 20 µm with higher density. It is also demonstrated that h-BN bubbles do not collapse for more than 6 months after their creation. The internal pressure and gravimetric storage capacity of h-BN bubbles are reported. A maximum internal pressure of 41 MPa and a gravimetric storage capacity of 6% are obtained. These findings show that h-BN bubbles can be a promising system for long-term hydrogen storage.

Monolithic 3D integration of 2D materials-based electronics towards ultimate edge computing solutions.

Three-dimensional (3D) hetero-integration technology is poised to revolutionize the field of electronics by stacking functional layers vertically, thereby creating novel 3D circuity architectures with high integration density and unparalleled multifunctionality. However, the conventional 3D integration technique involves complex wafer processing and intricate interlayer wiring. Here we demonstrate monolithic 3D integration of two-dimensional, material-based artificial intelligence (AI)-processing hardware with ultimate integrability and multifunctionality. A total of six layers of transistor and memristor arrays were vertically integrated into a 3D nanosystem to perform AI tasks, by peeling and stacking of AI processing layers made from bottom-up synthesized two-dimensional materials. This fully monolithic-3D-integrated AI system substantially reduces processing time, voltage drops, latency and footprint due to its densely packed AI processing layers with dense interlayer connectivity. The successful demonstration of this monolithic-3D-integrated AI system will not only provide a material-level solution for hetero-integration of electronics, but also pave the way for unprecedented multifunctional computing hardware with ultimate parallelism.

High energy density in artificial heterostructures through relaxation time modulation.

Electrostatic capacitors are foundational components of advanced electronics and high-power electrical systems owing to their ultrafast charging-discharging capability. Ferroelectric materials offer high maximum polarization, but high remnant polarization has hindered their effective deployment in energy storage applications. Previous methodologies have encountered problems because of the deteriorated crystallinity of the ferroelectric materials. We introduce an approach to control the relaxation time using two-dimensional (2D) materials while minimizing energy loss by using 2D/3D/2D heterostructures and preserving the crystallinity of ferroelectric 3D materials. Using this approach, we were able to achieve an energy density of 191.7 joules per cubic centimeter with an efficiency greater than 90%. This precise control over relaxation time holds promise for a wide array of applications and has the potential to accelerate the development of highly efficient energy storage systems.

(Al, Ga)N-Based Quantum Dots Heterostructures on h-BN for UV-C Emission.

Aluminium Gallium Nitride (AlyGa1-yN) quantum dots (QDs) with thin sub-µm AlxGa1-xN layers (with x > y) were grown by molecular beam epitaxy on 3 nm and 6 nm thick hexagonal boron nitride (h-BN) initially deposited on c-sapphire substrates. An AlN layer was grown on h-BN and the surface roughness was investigated by atomic force microscopy for different deposited thicknesses. It was shown that for thicker AlN layers (i.e., 200 nm), the surface roughness can be reduced and hence a better surface morphology is obtained. Next, AlyGa1-yN QDs embedded in Al0.7Ga0.3N cladding layers were grown on the AlN and investigated by atomic force microscopy. Furthermore, X-ray diffraction measurements were conducted to assess the crystalline quality of the AlGaN/AlN layers and examine the impact of h-BN on the subsequent layers. Next, the QDs emission properties were studied by photoluminescence and an emission in the deep ultra-violet, i.e., in the 275-280 nm range was obtained at room temperature. Finally, temperature-dependent photoluminescence was performed. A limited decrease in the emission intensity of the QDs with increasing temperatures was observed as a result of the three-dimensional confinement of carriers in the QDs.

Crystalline Quality and Surface Morphology Improvement of Face-to-Face Annealed MBE-Grown AlN on h-BN.

In this study, AlN epilayers were grown by ammonia-assisted molecular beam epitaxy on 3 nm h-BN grown on c-sapphire substrates. Their structural properties were investigated by comparing as-grown and postgrowth annealed layers. The role of annealing on the crystalline quality and surface morphology was studied as a function of AlN thickness and the annealing duration and temperature. Optimum annealing conditions were identified. The results of X-ray diffraction showed that optimization of the annealing recipe led to a significant reduction in the symmetric (0 0 0 2) and skew symmetric (1 0 -1 1) reflections, which was associated with a reduction in edge and mixed threading dislocation densities (TDDs). Furthermore, the impact on the crystalline structure of AlN and its surface was studied, and the results showed a transition from a surface with high roughness to a smoother surface morphology with a significant reduction in roughness. In addition, the annealing duration was increased at 1650 °C to further understand the impact on both AlN and h-BN, and the results showed a diffusion interplay between AlN and h-BN. Finally, an AlN layer was regrown on the top of an annealed template, which led to large terraces with atomic steps and low roughness.

Natural Boron and 10B-Enriched Hexagonal Boron Nitride for High-Sensitivity Self-Biased Metal-Semiconductor-Metal Neutron Detectors.

Metal-semiconductor-metal (MSM) detectors based on Ti/Au and Ni/Au interdigitated structures were fabricated using 2.5 micrometer thick hexagonal boron nitride (h-BN) layer with both natural and 10B-enriched boron. Current-voltage (I-V) and current-time (I-t) curves of the fabricated detectors were recorded with (I N) and without (I d) neutron irradiation, allowing the determination of their sensitivity (S = (I N - I d)/I d = ΔI/I d). Natural and 10B-enriched h-BN detectors exhibited high neutron sensitivities of 233 and 367% at 0 V bias under a flux of 3 × 104 n/cm2/s, respectively. An imbalance in the distribution of filled traps between the two electric contacts could explain the self-biased operation of the MSM detectors. Neutron sensitivity is further enhanced with electrical biasing, reaching 316 and 1192% at 200 V and a flux of 3 × 104 n/cm2/s for natural and 10B-enriched h-BN detectors, respectively, with dark current as low as 2.5 pA at 200 V. The increased performance under bias has been attributed to a gain mechanism based on neutron-induced charge carrier trapping at the semiconductor/metal interface. The response of the MSM detectors under thermal neutron flux and bias voltages was linear. These results clearly indicate that the thin-film monocrystal BN MSM neutron detectors can be optimized to operate sensitively with the absence of external bias and generate stronger signal detection using 10B-enriched boron.

Towards P-Type Conduction in Hexagonal Boron Nitride: Doping Study and Electrical Measurements Analysis of hBN/AlGaN Heterojunctions.

Reliable p-doped hexagonal boron nitride (h-BN) could enable wide bandgap optoelectronic devices such as deep ultra-violet light emitting diodes (UV LEDs), solar blind photodiodes and neutron detectors. We report the study of Mg in h-BN layers as well as Mg h-BN/AlGaN heterostructures. Mg incorporation in h-BN was studied under different biscyclopentadienyl-magnesium (Cp2Mg) molar flow rates. 2θ-ω x-ray diffraction scans clearly evidence a single peak, corresponding to the (002) reflection plane of h-BN with a full-width half maximum increasing with Mg incorporation in h-BN. For a large range of Cp2Mg molar flow rates, the surface of Mg doped h-BN layers exhibited characteristic pleats, confirming that Mg doped h-BN remains layered. Secondary ion mass spectrometry analysis showed Mg incorporation, up to 4 × 1018 /cm3 in h-BN. Electrical conductivity of Mg h-BN increased with increased Mg-doping. Heterostructures of Mg h-BN grown on n-type Al rich AlGaN (58% Al content) were made with the intent of forming a p-n heterojunction. The I-V characteristics revealed rectifying behavior for temperatures from 123 to 423 K. Under ultraviolet illumination, photocurrent was generated, as is typical for p-n diodes. C-V measurements evidence a built-in potential of 3.89 V. These encouraging results can indicate p-type behavior, opening a pathway for a new class of wide bandgap p-type layers.

Control of the Mechanical Adhesion of III-V Materials Grown on Layered h-BN.

Hexagonal boron nitride (h-BN) can be used as a p-doped material in wide-bandgap optoelectronic heterostructures or as a release layer to allow lift-off of grown three-dimensional (3D) GaN-based devices. To date, there have been no studies of factors that lead to or prevent lift-off and/or spontaneous delamination of layers. Here, we report a unique approach of controlling the adhesion of this layered material, which can result in both desired lift-off layered h-BN and mechanically inseparable robust h-BN layers. This is accomplished by controlling the diffusion of Al atoms into h-BN from AlN buffers grown on h-BN/sapphire. We present evidence of Al diffusion into h-BN for AlN buffers grown at high temperatures compared to conventional-temperature AlN buffers. Further evidence that the Al content in BN controls lift-off is provided by comparison of two alloys, Al0.03B0.97N/sapphire and Al0.17B0.83N/sapphire. Moreover, we tested that management of Al diffusion controls the mechanical adhesion of high-electron-mobility transistor (HEMT) devices grown on AlN/h-BN/sapphire. The results extend the control of two-dimensional (2D)/3D hetero-epitaxy and bring h-BN closer to industrial application in optoelectronics.

Effectiveness of selective area growth using van der Waals h-BN layer for crack-free transfer of large-size III-N devices onto arbitrary substrates.

Selective Area van der Waals Epitaxy (SAVWE) of III-Nitride device has been proposed recently by our group as an enabling solution for h-BN-based device transfer. By using a patterned dielectric mask with openings slightly larger than device sizes, pick-and-place of discrete LEDs onto flexible substrates was achieved. A more detailed study is needed to understand the effect of this selective area growth on material quality, device performance and device transfer. Here we present a study performed on two types of LEDs (those grown on h-BN on patterned and unpatterned sapphire) from the epitaxial growth to device performance and thermal dissipation measurements before and after transfer. Millimeter-size LEDs were transferred to aluminum tape and to silicon substrates by van der Waals liquid capillary bonding. It is shown that patterned samples lead to a better material quality as well as improved electrical and optical device performances. In addition, patterned structures allowed for a much better transfer yield to silicon substrates than unpatterned structures. We demonstrate that SAVWE, combined with either transfer processes to soft or rigid substrates, offers an efficient, robust and low-cost heterogenous integration capability of large-size devices to silicon for photonic and electronic applications.