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At least 343 records · Page 19

Exfoliation of Cu-Containing Poly(triazine imide): From Three-Dimensional to Two-Dimensional Particle Morphology

Controlling the morphological parameters of extended covalent organic frameworks remains challenging and represents an important yet often elusive metric of consideration. Typically, carbon nitride materials possess local ordering but remain largely amorphous in terms of their long-range order and orientation. This study probes the synthesis of a crystalline carbon nitride, poly(triazine imide) lithium bromide which possesses an atomically-precise extended structure, and demonstrates its exfoliation into a two-dimensional hexagonal sheet-like morphology. Furthermore, a previously unreported carbon nitride material, poly(triazine imide) copper bromide, or PTI-CuBr, was developed through an additional flux-assisted cation-exchange process and is shown to retain its internal Cu cations during solvothermal exfoliation. Characterization by dynamic light scattering and high-angle annular dark-field scanning electron microscopy reveals the morphological changes and captures the high aspect ratio of the thin carbon nitride sheets with <10 nm thickness while maintaining hundreds of nm in width. Additional characterization by energy-dispersive spectroscopy and X-ray photoelectron spectroscopy confirms that the Cu:Br:N molar ratio was maintained within the extended layers throughout the exfoliation process. This top-down synthesis approach differs from typical methods that isolate thin sheets for subsequent metal−cation coordination and illustrates the importance of maintaining oxygen-free conditions to minimize copper clustering. Thus, this new approach is demonstrated to provide a consistent and more homogeneous occupancy of the PTI pore spaces throughout the carbon nitride framework.

Exfoliation↗

Engineering Assembly Kinetics and Line Roughness in Solvent Vapor-Annealed Block Copolymer/Homopolymer Blends

Block copolymer (BCP) directed self-assembly (DSA) is a promising route to enhance lithography resolution by multiplying nanopattern density and reducing feature roughness. Eliminating kinetically trapped self-assembly defects requires fast self-assembly. However, acceleration strategies like solvent vapor annealing or homopolymer blending broaden domain interfaces, implying a trade-off in increased feature roughness. In this work, we experimentally investigate this apparent dilemma between self-assembly kinetics and line roughness for solvent vapor-annealed thin films of a lamellar poly(styrene-block-2-vinylpyridine) (PS-b-P2VP) BCP blended with PS and P2VP homopolymers. Binary blends with PS or P2VP homopolymers and ternary blends incorporating both in equal weight fractions were solvent vapor annealed using acetone, a near-neutral solvent for PS and P2VP, followed by P2VP-selective vapor-phase infiltration with alumina (AlOx) and polymer etching. Binary blends with P2VP exhibit a modest kinetic enhancement but also higher line-edge and -width roughness due to the increased frequency of P2VP protrusions and bridge defects in the alumina line patterns. In contrast, binary blends with PS self-assemble noticeably faster, while domain asymmetry from the added PS homopolymer reduces roughness by curbing the number of alumina protrusions and bridge defects. Ternary blends maintain DSA line patterns across a wider composition window and, at higher homopolymer loadings, reduce roughness at length scales near the lamellar period, consistent with a reduced impact of intradomain compositional fluctuations. These findings provide important insights for codesigning blend compositions and process flows to achieve high-resolution, defect free patterns with minimal roughness through BCP DSA.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cold Seeded Epitaxy and Flexomagnetism in GdAuGe Membranes Exfoliated From Graphene/Ge(111)

Remote and van der Waals epitaxy are promising approaches for synthesizing single crystalline membranes for flexible electronics and discovery of new properties via extreme strain; however, a fundamental challenge is that most materials do not wet the graphene surface. We develop a cold seed approach for synthesizing smooth intermetallic films on graphene that can be exfoliated to form few nanometer thick single crystalline membranes. Our seeded GdAuGe films have narrow X-ray rocking curve widths of 9–24 arc seconds, which is 2 orders of magnitude lower than their counterparts grown by typical high temperature methods, and have atomically sharp interfaces observed by transmission electron microscopy. Upon exfoliation and rippling, strain gradients in GdAuGe membranes induce an antiferromagnetic to ferri/ferromagnetic transition. Finally, our smooth, ultrathin membranes provide a clean platform for discovering new flexomagnetic effects in quantum materials.

36 MATERIALS SCIENCE↗

Imaging Ferroelastic Domain Walls in Hybrid Improper Ferroelectric Sr 3 Sn 2 O 7

For this work, we combined synchrotron-based near field infrared spectroscopy and atomic force microscopy to image the properties of ferroelastic domain walls in Sr 3 Sn 2 O 7 . Although frequency shifts at the walls are near the limit of our sensitivity, we can confirm semiconducting rather than metallic character and widths between 20 and 60 nm. The latter is significantly narrower than in other hybrid improper ferroelectrics like Ca 3 Ti 2 O 7 . We attribute this trend to the softer lattice in Sr 3 Sn 2 O 7 , which may enable the octahedral tilt and rotation order parameters to evolve more quickly across the wall without significantly increased strain. These findings are crucial for the understanding of phononic properties at interfaces and the development of domain wall-based devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Purcell-Enhanced Emissions from Diamond Color Centers in Slow Light Photonic Crystal Waveguides

Diamond color centers are promising candidates for optically addressable quantum memories, which motivates the development of efficient photonic interfaces, often using nanophotonic cavities with narrow spectral line widths and small mode volumes. However, they require perfect spectral and spatial overlap between the cavity mode and quantum emitter, which is challenging. This is especially true for solid-state quantum emitters that are often randomly positioned and suffer from inhomogeneous broadening. Another approach to enhance light-matter interaction across large optical bandwidths and areas is using slow light waveguides. Here, in this study, we demonstrate diamond slow light photonic crystal (PhC) waveguides optically coupled to embedded silicon-vacancy (SiV) color centers. We use the recently developed thin-film diamond approach to fabricate fully suspended two-dimensional PhC waveguides. We demonstrate waveguide modes with high group indices up to 70 and observe Purcell-enhanced emissions of the SiVs. Our approach represents a practical diamond platform for robust spin-photon interfaces with color centers.

2D photonic crystal waveguide↗

Anatomy of Local Structural Disorder of Ni(II) Species in MgCl 2 –KCl Molten Salts

Understanding the speciation of metal ions dissolved in molten salts (MS) is critical for enabling a broad range of high-temperature energy applications, including MS nuclear reactors and concentrated solar power plants. However, due to the inherent dynamicity of metal species in the MS environment and the strong temperature dependencies of their multiple coexisting forms, they are difficult to resolve structurally. Herein, we show that combining in situ X-ray absorption spectroscopy (XAS) with ab initio molecular dynamics (AIMD) simulations is necessary to uncover and quantify the coexisting coordination states of Ni(II) in molten MgCl 2 –KCl mixtures and explain how the temperature and salt composition control their relative populations. Furthermore, from the interionic angle and distance distributions of nickel in different coordination states obtained from AIMD simulations, it is evident that for each coordination state, the width and skewness of their bonding distributions increase with increasing coordination number. In conclusion, the combination of XAS with first-principles modeling to resolve metastable metal species in MS is critical for understanding their behavior over a wide range of temperatures and chemical environments in nuclear and solar applications.

36 MATERIALS SCIENCE↗

Optically Addressable Light Valve Based on a GaN:Mn Photoconductor

Semi-insulating manganese-doped gallium nitride (GaN:Mn) layers epitaxially grown on unintentionally doped GaN substrates were used as photoconductors in optically addressable light valves (OALVs) to withstand higher operational laser fluences compared to current state-of-the-art OALVs where bismuth silicon oxide (BSO; Bi 12 SiO 20 ) layers are used as photoconductors. GaN:Mn promises to be an exciting material for optoelectronic operations due to its large laser fluence handling capability and photoresponsivity near the band edge. The laser damage thresholds for the semi-insulating epitaxial GaN:Mn layer and the n-type substrate layer were measured to be 2.4 and 4.2 J/cm 2 , respectively. These are 6–10 times higher than that of BSO (0.4 J/cm 2 ). These measurements were performed by exposing ~200 sites on the samples to increasing fluence levels from a Gaussian pulsed Nd:YAG laser system (1064 nm) operating at a 5 Hz repetition rate with a 3 ns pulse width. Photoresponsivity of the GaN:Mn material was investigated at discrete wavelengths of 447, 405, and 380 nm. Further, the peak photoresponsivity was observed under an illumination wavelength of 380 nm and is attributed to stronger absorption. The OALV was fabricated by attaching a 110-μm-thick GaN:Mn layer grown on a 280-μm-thick n-GaN layer to a 3-mm-thick BK7 optical window. A twisted nematic E7 liquid crystal was introduced to the 5 μm gap between the two components. Transmission levels of >90% were achieved for the fabricated OALVs for a peak voltage of 40 V, constrained by transmission “bleed-through”.

36 MATERIALS SCIENCE↗

Integrated Strategies for Overcoming Resolution Limits in Electron Beam Lithography of Chemically Amplified Resists

Electron beam lithography (EBL) of chemically amplified resists (CARs) faces fundamental challenges, including stochastic electron scattering and acid diffusion, that limit resolution and reproducibility. Using SU-8 as a model CAR, this study systematically investigated complementary strategies to address these challenges, combining multipass exposure, proximity effect correction (PEC) with midrange correction factors, base quencher incorporation, and post-exposure bake (PEB) suppression. Monte Carlo simulations and calibrated PEC modeling revealed that extending the point spread function to include a midrange scattering component significantly improved critical dimension (CD) control across varying pattern densities, correcting deviations that conventional two-term PEC failed to capture. Multipass exposure, particularly 4-pass writing with a 25% offset, redistributed the dose to average stochastic beam and scattering fluctuations, reducing line-width roughness by more than 50% and yielding more uniform nanoscale features. Photoacid confinement was investigated by adding urea as a base quencher, which successfully reduced acid diffusion but introduced substantial sensitivity penalties without improving ultimate resolution or Z-factor performance, underscoring the trade-offs of chemical versus physical confinement. Suppressing PEB most directly minimized acid diffusion, resulting in improved Z-factors and reproducible 30 nm half-pitch dense line/space patterns. Overall, these results demonstrated that PEC with midrange correction, multipass strategies, quencher additives, and PEB-free processing addresses different aspects of the EBL process window and that their integration provides a comprehensive framework for managing stochastic scattering, diffusion, and chemical amplification effects. This framework advances dense nanoscale patterning in CARs and establishes guiding principles for optimizing resist design and process strategies in high-resolution EBL and potentially other advanced lithographies, such as extreme ultraviolet (EUV) lithography.

36 MATERIALS SCIENCE↗

Heterovalent Substitution of K 2 SrP 2 O 7 :Cr 3+ to Achieve Anti-Thermal-Quenching Broadband Near-Infrared Luminescence

Broadband near-infrared (NIR) light sources based on phosphor-converted light-emitting diodes are highly desirable for biochemical analysis and medical diagnosis applications. However, thermal quenching remains a demanding challenge for developing efficient NIR phosphors. Herein, we report the enhancement of both quantum efficiency and thermal stability in Cr 3+ -activated K 2 SrP 2 O 7 phosphors through a heterovalent substitution strategy by replacing Sr 2+ with Al 3+ in K 2 Sr 1–x Al x P 2 O 7 (0.05 ≤ x ≤ 0.2) to obtain optimized broadband NIR emission. Structural modulation via Al 3+ substitution leads to the optimized composition, K 2 Sr 0.88 Al 0.1 P 2 O 7 :0.02Cr 3+ , which emits across a broad NIR range of 650–1100 nm peaking at 807 nm with a full width at half-maximum of ∼130 nm under 448 nm excitation. Remarkably, its emission intensity at 150 °C remains 120% of the initial value at room temperature, demonstrating a rare antithermal-quenching behavior. Temperature-dependent XRD studies further reveal that Al 3+ substitution effectively suppresses lattice expansion at elevated temperatures, indicating enhanced lattice stability under thermal excitation. Detailed structural and spectral analyses show that the substitution enhances local site symmetry, reduces electron–phonon coupling, increases thermally induced absorption probability, and fortifies energetic barriers against nonradiative transitions. These synergistic effects collectively endow this NIR phosphor with a superior thermal stability. Furthermore, NIR light-emitting diodes fabricated with this phosphor exhibit strong potential for applications in information identification, nondestructive detection, and night vision technologies. This study demonstrates a local structure engineering strategy for designing thermally robust Cr 3+ -activated NIR phosphors, offering valuable insights into material discovery and NIR spectroscopy device development.

Cr3+↗

Increasing Branching and Functionalization Decreases Crystallinity and Crystallization Rate in Linear EVOH

Here, we report the crystallization behavior of a linear poly(ethylene-co-vinyl alcohol) (LEVOH) under isothermal crystallization as a function of both OH incorporation and undercooling, and compare the results to conventional branched EVOH. This LEVOH is synthesized by post-polymerization functionalization of polycyclooctene, and it exhibits a half-crystallization time and primary crystallization rate nearly an order of magnitude faster than branched EVOH at ~ 6 mol% OH incorporation. While the LEVOH obtains approximately twice the extent of crystallization compared to the branched equivalent, as OH incorporation increases, the crystallization kinetics and crystallinity of LEVOH decrease. The crystal structure of LEVOH is orthorhombic at low functionalization (≤ 11 mol% OH), a mixture of orthorhombic and hexagonal at moderate functionalization (17 - 21 mol%), and hexagonal at high functionalization (23 %). The LEVOH crystallizes into plates, with crystallite widths ~ 20 - 60 times the crystallite thickness. Ultimately, we show LEVOH crystallizes faster and to a greater extent than commercial branched EVOH, a potential advantage of post-polymerization functionalization as part of polymer-to-polymer upcycling.

36 MATERIALS SCIENCE↗

Eutectic Processing of Semiconductor Colloidal Nanocrystals for Energy Applications

Colloidal semiconductor nanocrystals (NCs) offer a costeffective platform for light-energy conversion in X-ray scintillators, photovoltaics, lasers, and display technologies. Yet, device-relevant NCs often require complex heterostructured compositions, where lattice imperfections compromise the efficiency and stability of photoconversion processes. Here, we show that a simple synthetic detour through a eutectic state of II−VI semiconductor NCs (e.g., CdSe, ZnSe) with halide salts (e.g., CdCl 2 , ZnCl 2 ) overcomes this limitation by melting and reconstructing NC lattices into defect-free alloyed and core/shell architectures. Applied to ternary CdSeTe NCs, this process produces downconverters with record brightness and minimal line widths, delivering a 3-fold increase in film-side external quantum efficiency of commercial CdTe photovoltaic modules (First Solar Inc.). Meanwhile, eutectic processing of CdSe-based core/shell emitters yields an 8-fold enhancement in their photoluminescence stability under backlight operation, addressing the reliability bottleneck for display technologies. Together, these findings establish eutectic NC processing as a scalable route to efficient, durable photoconversion materials for energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

ATLAS-MAP: An Automated Test Station for Gated Electronic Transport Measurements

The diversification of electronic materials in devices provides a strong incentive for methods to rapidly correlate device performance with fabrication decisions. In this work, we present a low-cost automated test station for gated electronic transport measurements of field-effect transistors. Utilizing open-source PyMeasure libraries for transparent instrument control, the “ATLAS-MAP” system serves as a customizable interface between sourcemeters and samples under test and is programmed to conduct transfer curve and van der Pauw methods with static and sweeping gate voltages. Zinc oxide transistors of variable thickness (5, 10, and 20 nm) and channel size (50 μm to 3 mm, of equal length and width) were fabricated to validate the design. Standardization of testing procedures and raw data formatting enabled automated data analysis. A detailed list of parts and code files for the system are provided.

36 MATERIALS SCIENCE↗

Automated Redox Titrations via Interdigitated Electrode Arrays: Application to the Mediated Electron Transfer Interrogation of Charge and Rate on Electrodeposited Polymers

Mediated electron transfer (MET) plays a crucial role in energy storage and conversion technologies such as redox targeting flow batteries (RTFBs), yet its experimental investigation often requires labor-intensive and low-throughput setups. To address this, we developed a microfabricated interdigitated electrode array (IDA) platform that enables automated, high-throughput electrochemical redox titration measurement to be performed to study the MET process. Our redox titration method enables simultaneous measurement of the charge capacity and rate of MET processes on a material or surface. Automated redox titration (ART) facilitates systematic investigation of the MET process across a broad parameter space, exemplified through the study of polypyrrole (PPy) and a pyrene-4,5,9,10-tetrone azo group-based polymer (PTAP), both redox-active polymers relevant to various energy storage applications. Using PPy as a model material, 500 redox titration measurements were conducted within 50 h, varying the electrode gap widths, polymer charging potentials, voltammetric scan rates, and electrolyte concentrations. Finite-element simulations confirmed the electrochemical responses and elucidated the kinetics of the MET reactions. Our automated methodology was further tested with PTAP, revealing a surprising charging potential dependence on the rate of MET. The automation, flexibility, and scalability of our redox titration platform pave the way not only for advanced studies of MET processes relevant to RTFBs, but also with implications in the understanding of next-generation energy storage materials, molecular electrocatalysis, and biosensing.

electrochemical analysis↗

Effect of Surface Oxidation and Crystal Thickness on the Magnetic Properties and Magnetic Domain Structures of Cr 2 Ge 2 Te 6

van der Waals (vdW) magnetic materials, such as Cr 2 Ge 2 Te 6 (CGT), show promise for memory and logic applications. This is due to their broadly tunable magnetic properties and the presence of topological magnetic features such as skyrmionic bubbles. A systematic study of thickness and oxidation effects on magnetic domain structures is important for designing devices and vdW heterostructures for practical applications. Here, we investigate thickness effects on magnetic properties, magnetic domains, and bubbles in oxidation-controlled CGT crystals. We find that CGT exposed to ambient conditions for 5 days forms an oxide layer approximately 5 nm thick. This oxidation leads to a significant increase in the oxidation state of the Cr ions, indicating a change in local magnetic properties. This is supported by real-space magnetic texture imaging through Lorentz transmission electron microscopy. By comparing the thickness-dependent saturation field of oxidized and pristine crystals, we find that oxidation leads to a nonmagnetic surface layer that is thicker than the oxide layer alone. We also find that the stripe domain width and skyrmionic bubble size are strongly affected by the crystal thickness in pristine crystals. Finally, these findings underscore the impact of thickness and surface oxidation on the properties of CGT, such as saturation field and domain/skyrmionic bubble size, and suggest a pathway for manipulating magnetic properties through a controlled oxidation process.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Amplified Spontaneous Emission from Electron–Hole Quantum Droplets in Colloidal CdSe Nanoplatelets

Two-dimensional cadmium selenide nanoplatelets (NPLs) exhibit large absorption cross sections and homogeneously broadened band-edge transitions that offer utility in wide-ranging optoelectronic applications. Here, we examine the temperature-dependence of amplified spontaneous emission (ASE) in 4- and 5-monolayer thick NPLs and show that the threshold for close-packed (neat) films decreases with decreasing temperature by a factor of 2-10 relative to ambient temperature owing to extrinsic (trapping) and intrinsic (phonon-derived line width) factors. Interestingly, for pump intensities that exceed the ASE threshold, we find development of intense emission to lower energy in particular provided that the film temperature is <= 200 K. For NPLs diluted in an inert polymer, both biexcitonic ASE and low-energy emission are suppressed, suggesting that described neat-film observables rely upon high chromophore density and rapid, collective processes. Transient emission spectra reveal ultrafast red-shifting with the time of the lower energy emission. Taken together, these findings indicate a previously unreported process of amplified stimulated emission from polyexciton states that is consistent with quantum droplets and constitutes a form of exciton condensate. For studied samples, quantum droplets form provided that roughly 17 meV or less of thermal energy is available, which we hypothesize relates to polyexciton binding energy. Polyexciton ASE can produce pump-fluence-tunable red-shifted ASE even 120 meV lower in energy than biexciton ASE. Finally, our findings convey the importance of biexciton and polyexciton populations in nanoplatelets and show that quantum droplets can exhibit light amplification at significantly lower photon energies than biexcitonic ASE.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coupling of Nondegenerate Topological Modes in Nitrogen Core-Doped Graphene Nanoribbons

Nitrogen core-doping of graphene nanoribbons (GNRs) allows trigonal planar carbon atoms along the backbone of GNRs to be substituted by higher-valency nitrogen atoms. The excess valence electrons are injected into the π-orbital system of the GNR, thereby changing not only its electronic occupation but also its topological properties. We have observed this topological change by synthesizing dilute nitrogen core-doped armchair GNRs with a width of five atoms (N 2 -5-AGNRs). The incorporation of pairs of trigonal planar nitrogen atoms results in the emergence of topological boundary states at the interface between doped and undoped segments of the GNR. These topological boundary states are offset in energy by approximately ΔE = 300 meV relative to the topological end states at the termini of finite 5-AGNRs. Scanning tunneling microscopy (STM) and spectroscopy (STS) reveal that for finite GNRs the two types of topological states can interact through a linear combination of orbitals, resulting in a pair of asymmetric hybridized states. This behavior is captured by an effective Hamiltonian of nondegenerate diatomic molecules, where the analogous interatomic hybridization interaction strength is tuned by the distance between GNR topological modes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tunable Spin Qubit Pairs in Quantum Dot–Molecule Conjugates

Organic molecules and quantum dots (QDs) have both shown promise as materials that can host quantum bits (qubits). This is in part because of their synthetic tunability. The current work employs a combination of both materials to demonstrate a series of tunable quantum dot–organic molecule conjugates that can both host photogenerated spin-based qubit pairs (SQPs) and sensitize molecular triplet states. The photogenerated qubit pairs, composed of a spin-correlated radical pair (SCRP), are particularly intriguing since they can be initialized in well-defined, nonthermally populated, quantum states. Additionally, the radical pair enables charge recombination to a polarized molecular triplet state, also in a well-defined quantum state. The materials underlying this system are an organic molecular chromophore and electron donor, 9,10-bis(phenylethynyl)anthracene, and a quantum dot acceptor composed of ZnO. We prepare a series of quantum dot–molecule conjugates that possess variable quantum dot size and two different linker lengths connecting the two moieties. Optical spectroscopy revealed that the QD–molecule conjugates undergo photoexcited charge separation to generate long-lived charge-separated radical pairs. The resulting spin states are probed using light-induced time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy, revealing the presence of singlet-generated SCRPs and molecular triplet states. Notably, the EPR spectra of the radical pairs are dependent on the geometry of this highly tunable system. The g value of the ZnO QD anion is size tunable, and the line widths are influenced by radical pair separation. Overall, this work demonstrates the power of synthetic tunability in adjusting the spin specific addressability, satisfying a key requirement of functional qubit systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Performance Near-Infrared Quantum Emission from Color Centers in hBN

Color centers hosted in hexagonal boron nitride (hBN) have emerged as a highly promising platform for single-photon emission and spin-photon technologies relevant to quantum communication and quantum networking. As a wide bandgap van der Waals material, hBN can host optically active quantum defects across a broad spectral range. Here, we demonstrate a simple and scalable oxygen-plasma process that reproducibly creates single quantum emitters in hBN with blinking-free zero-phonon lines (ZPLs) spanning near-infrared (NIR) from 700 up to 971 nm. These emitters combine MHz-level brightness, single-photon purity up to 99.9%, and ultranarrow cryogenic line widths down to 2.7 GHz under quasi-resonant excitation, placing them in a particularly attractive regime for quantum photonics. Photostability measurements further reveal resistance to photobleaching, subnanometer spectral stability over long time scales, and near-shot-noise-limited intensity fluctuations. Analysis of the phonon sidebands shows weak vibronic coupling and ZPL-dominated emission, with Debye–Waller factors approaching 50%. Control experiments together with elemental mapping support oxygen incorporation as a necessary ingredient in activating the NIR emitter population, while first-principles calculations identify O N V N and O N V N H as the leading defect candidates. These results establish a high-performance NIR quantum-emitter platform in hBN for free-space quantum networking and future integrated quantum-photonic architectures.

2D materials↗