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.

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.

(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.

Vertical full-colour micro-LEDs via 2D materials-based layer transfer.

Micro-LEDs (µLEDs) have been explored for augmented and virtual reality display applications that require extremely high pixels per inch and luminance1,2. However, conventional manufacturing processes based on the lateral assembly of red, green and blue (RGB) µLEDs have limitations in enhancing pixel density3-6. Recent demonstrations of vertical µLED displays have attempted to address this issue by stacking freestanding RGB LED membranes and fabricating top-down7-14, but minimization of the lateral dimensions of stacked µLEDs has been difficult. Here we report full-colour, vertically stacked µLEDs that achieve, to our knowledge, the highest array density (5,100 pixels per inch) and the smallest size (4 µm) reported to date. This is enabled by a two-dimensional materials-based layer transfer technique15-18 that allows the growth of RGB LEDs of near-submicron thickness on two-dimensional material-coated substrates via remote or van der Waals epitaxy, mechanical release and stacking of LEDs, followed by top-down fabrication. The smallest-ever stack height of around 9 µm is the key enabler for record high µLED array density. We also demonstrate vertical integration of blue µLEDs with silicon membrane transistors for active matrix operation. These results establish routes to creating full-colour µLED displays for augmented and virtual reality, while also offering a generalizable platform for broader classes of three-dimensional integrated devices.

Biosensors for the Rapid Detection of Cardiovascular Biomarkers of Vital Interest: Needs, Analysis and Perspectives.

We have previously surveyed a panel of 508 physicians from around the world about which biomarkers would be relevant if obtained in a very short time frame, corresponding to emergency situations (life-threatening or not). The biomarkers that emerged from this study were markers of cardiovascular disease: troponin, D-dimers, and brain natriuretic peptide (BNP). Cardiovascular disease is a group of disorders affecting the heart and blood vessels. At the intersection of medicine, basic research and engineering, biosensors that address the need for rapid biological analysis could find a place of choice in the hospital or primary care ecosystem. Rapid, reliable, and inexpensive analysis with a multi-marker approach, including machine learning analysis for patient risk analysis, could meet the demand of medical teams. The objective of this opinion review, proposed by a multidisciplinary team of experts (physicians, biologists, market access experts, and engineers), is to present cases where a rapid biological response is indeed valuable, to provide a short overview of current biosensor technologies for cardiac biomarkers designed for a short result time, and to discuss existing market access issues.

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.

Relevant Biomarkers in Medical Practices: An Analysis of the Needs Addressed by an International Survey.

(1) Backround: Technological advances should foster gains in physicians' efficiency. For example, a reduction of the medical decision time can be enabled by faster biological tests. The main objective of this study was to collect responses from an international panel of physicians on their needs for biomarkers and also to convey the improvement in the outcome to be made possible by the potential development of fast diagnostic tests for these biomarkers. (2) Methods: we distributed a questionnaire on the Internet to physicians. (3) Results: 508 physicians participated in this survey. The mean age was 38 years. General practice and emergency medicine were heavily represented, with 95% CIs of 44% (39.78, 48.41) and 32% (27.84, 35.94)), respectively. The two most represented countries were France (95% CI: 74% (70.20, 77.83)) and the USA (95% CI: 11% (8.65, 14.18)). Ninety-eight percentages of the physicians thought that obtaining cited biomarkers more quickly would be beneficial to their practice and to patient's care. The main biomarkers of interest identified by our panel were troponin (95% CI: 51% (46.24, 54.94)), C-reactive protein (95% CI: 42% (38.03, 46.62)), D-dimer (95% CI: 29% (24.80, 32.68)), and brain natriuretic peptide (95% CI: 13% (10.25, 16.13)). (4) Conclusions: Our study highlights the real technological need for fast biomarker results, which could be provided by biosensors. The relevance of some answers such as troponin is questionable.

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.

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.

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.

Highly Ordered Boron Nitride/Epigraphene Epitaxial Films on Silicon Carbide by Lateral Epitaxial Deposition.

The realization of high-performance nanoelectronics requires control of materials at the nanoscale. Methods to produce high quality epitaxial graphene (EG) nanostructures on silicon carbide are known. The next step is to grow van der Waals semiconductors on top of EG nanostructures. Hexagonal boron nitride (h-BN) is a wide bandgap semiconductor with a honeycomb lattice structure that matches that of graphene, making it ideally suited for graphene-based nanoelectronics. Here, we describe the preparation and characterization of multilayer h-BN grown epitaxially on EG using a migration-enhanced metalorganic vapor phase epitaxy process. As a result of the lateral epitaxial deposition (LED) mechanism, the grown h-BN/EG heterostructures have highly ordered epitaxial interfaces, as desired in order to preserve the transport properties of pristine graphene. Atomic scale structural and energetic details of the observed row-by-row growth mechanism of the two-dimensional (2D) epitaxial h-BN film are analyzed through first-principles simulations, demonstrating one-dimensional nucleation-free-energy-barrierless growth. This industrially relevant LED process can be applied to a wide variety of van der Waals materials.

Controlled crack propagation for atomic precision handling of wafer-scale two-dimensional materials.

Although flakes of two-dimensional (2D) heterostructures at the micrometer scale can be formed with adhesive-tape exfoliation methods, isolation of 2D flakes into monolayers is extremely time consuming because it is a trial-and-error process. Controlling the number of 2D layers through direct growth also presents difficulty because of the high nucleation barrier on 2D materials. We demonstrate a layer-resolved 2D material splitting technique that permits high-throughput production of multiple monolayers of wafer-scale (5-centimeter diameter) 2D materials by splitting single stacks of thick 2D materials grown on a single wafer. Wafer-scale uniformity of hexagonal boron nitride, tungsten disulfide, tungsten diselenide, molybdenum disulfide, and molybdenum diselenide monolayers was verified by photoluminescence response and by substantial retention of electronic conductivity. We fabricated wafer-scale van der Waals heterostructures, including field-effect transistors, with single-atom thickness resolution.

Polarity governs atomic interaction through two-dimensional materials.

The transparency of two-dimensional (2D) materials to intermolecular interactions of crystalline materials has been an unresolved topic. Here we report that remote atomic interaction through 2D materials is governed by the binding nature, that is, the polarity of atomic bonds, both in the underlying substrates and in 2D material interlayers. Although the potential field from covalent-bonded materials is screened by a monolayer of graphene, that from ionic-bonded materials is strong enough to penetrate through a few layers of graphene. Such field penetration is substantially attenuated by 2D hexagonal boron nitride, which itself has polarization in its atomic bonds. Based on the control of transparency, modulated by the nature of materials as well as interlayer thickness, various types of single-crystalline materials across the periodic table can be epitaxially grown on 2D material-coated substrates. The epitaxial films can subsequently be released as free-standing membranes, which provides unique opportunities for the heterointegration of arbitrary single-crystalline thin films in functional applications.

Gas sensors boosted by two-dimensional h-BN enabled transfer on thin substrate foils: towards wearable and portable applications.

The transfer of GaN based gas sensors to foreign substrates provides a pathway to enhance sensor performance, lower the cost and extend the applications to wearable, mobile or disposable systems. The main keys to unlocking this pathway is to grow and fabricate the sensors on large h-BN surface and to transfer them to the flexible substrate without any degradation of the performances. In this work, we develop a new generation of AlGaN/GaN gas sensors with boosted performances on a low cost flexible substrate. We fabricate 2-inch wafer scale AlGaN/GaN gas sensors on sacrificial two-dimensional (2D) nano-layered h-BN without any delamination or cracks and subsequently transfer sensors to an acrylic surface on metallic foil. This technique results in a modification of relevant device properties, leading to a doubling of the sensitivity to NO2 gas and a response time that is more than 6 times faster than before transfer. This new approach for GaN-based sensor design opens new avenues for sensor improvement via transfer to more suitable substrates, and is promising for next-generation wearable and portable opto-electronic devices.

Flexible metal-semiconductor-metal device prototype on wafer-scale thick boron nitride layers grown by MOVPE.

Practical boron nitride (BN) detector applications will require uniform materials over large surface area and thick BN layers. To report important progress toward these technological requirements, 1~2.5 µm-thick BN layers were grown on 2-inch sapphire substrates by metal-organic vapor phase epitaxy (MOVPE). The structural and optical properties were carefully characterized and discussed. The thick layers exhibited strong band-edge absorption near 215 nm. A highly oriented two-dimensional h-BN structure was formed at the film/sapphire interface, which permitted an effective exfoliation of the thick BN film onto other adhesive supports. And this structure resulted in a metal-semiconductor-metal (MSM) device prototype fabricated on BN membrane delaminating from the substrate. MSM photodiode prototype showed low dark current of 2 nA under 100 V, and 100 ± 20% photoconductivity yield for deep UV light illumination. These wafer-scale MOVPE-grown thick BN layers present great potential for the development of deep UV photodetection applications, and even for flexible (opto-) electronics in the future.

Nanoselective area growth of defect-free thick indium-rich InGaN nanostructures on sacrificial ZnO templates.

Nanoselective area growth (NSAG) by metal organic vapor phase epitaxy of high-quality InGaN nanopyramids on GaN-coated ZnO/c-sapphire is reported. Nanopyramids grown on epitaxial low-temperature GaN-on-ZnO are uniform and appear to be single crystalline, as well as free of dislocations and V-pits. They are also indium-rich (with homogeneous 22% indium incorporation) and relatively thick (100 nm). These properties make them comparable to nanostructures grown on GaN and AlN/Si templates, in terms of crystallinity, quality, morphology, chemical composition and thickness. Moreover, the ability to selectively etch away the ZnO allows for the potential lift-off and transfer of the InGaN/GaN nanopyramids onto alternative substrates, e.g. cheaper and/or flexible. This technology offers an attractive alternative to NSAG on AlN/Si as a platform for the fabrication of high quality, thick and indium-rich InGaN monocrystals suitable for cheap, flexible and tunable light-emitting diodes.

Investigation of the Performance of HEMT-Based NO, NO2 and NH3 Exhaust Gas Sensors for Automotive Antipollution Systems.

We report improved sensitivity to NO, NO2 and NH3 gas with specially-designed AlGaN/GaN high electron mobility transistors (HEMT) that are suitable for operation in the harsh environment of diesel exhaust systems. The gate of the HEMT device is functionalized using a Pt catalyst for gas detection. We found that the performance of the sensors is enhanced at a temperature of 600 °C, and the measured sensitivity to 900 ppm-NO, 900 ppm-NO2 and 15 ppm-NH3 is 24%, 38.5% and 33%, respectively, at 600 °C. We also report dynamic response times as fast as 1 s for these three gases. Together, these results indicate that HEMT sensors could be used in a harsh environment with the ability to control an anti-pollution system in real time.