Defects In hBN Research Articles

Quantum Emitters in Hexagonal Boron Nitride.

Hexagonal boron nitride (hBN) has emerged as a fascinating platform to explore quantum emitters and their applications. Beyond being a wide-bandgap material, it is also a van der Waals crystal, enabling direct exfoliation of atomically thin layers─a combination which offers unique advantages over bulk, 3D crystals. In this Mini Review we discuss the unique properties of hBN quantum emitters and highlight progress toward their future implementation in practical devices. We focus on engineering and integration of the emitters with scalable photonic resonators. We also highlight recently discovered spin defects in hBN and discuss their potential utility for quantum sensing. All in all, hBN has become a front runner in explorations of solid-state quantum science with promising future prospects.

High Sensitivity Spin Defects in hBN Created by High‐Energy He Beam Irradiation

AbstractRecently the negatively charged boron vacancies () in hexagonal boron nitride (hBN) have been shown as spin defects that have great potential in quantum sensing. However, so far the sensitivity is limited by either photoluminescence (PL) intensity or the optically detected magnetic resonance (ODMR) contrast, and linewidth. In this work, the generation of these spin defects is demonstrated using high‐energy helium ion beams, and ODMR measurements with different laser and microwave powers are performed. The spin defects generated by high‐energy helium ions exhibit a high PL intensity and ODMR contrast while keeping a small linewidth, hence a good sensitivity. By comparing different fluences of helium irradiations, an optimal fluence is determined which is sufficient in creating spin defects without damaging the overall crystal lattice structure. With this optimal fluence, a high signal‐to‐noise ratio ODMR spectrum can be obtained with an accurate measurement of zero‐field splitting frequency, and a best sensitivity as . Moreover, with a focused beam, such spin defects can be created deterministically with nanometer precision.

Wide field imaging of van der Waals ferromagnet Fe3GeTe2 by spin defects in hexagonal boron nitride

Emergent color centers with accessible spins hosted by van der Waals materials have attracted substantial interest in recent years due to their significant potential for implementing transformative quantum sensing technologies. Hexagonal boron nitride (hBN) is naturally relevant in this context due to its remarkable ease of integration into devices consisting of low-dimensional materials. Taking advantage of boron vacancy spin defects in hBN, we report nanoscale quantum imaging of low-dimensional ferromagnetism sustained in Fe3GeTe2/hBN van der Waals heterostructures. Exploiting spin relaxometry methods, we have further observed spatially varying magnetic fluctuations in the exfoliated Fe3GeTe2 flake, whose magnitude reaches a peak value around the Curie temperature. Our results demonstrate the capability of spin defects in hBN of investigating local magnetic properties of layered materials in an accessible and precise way, which can be extended readily to a broad range of miniaturized van der Waals heterostructure systems.

Front Cover: Free‐Space Quantum Key Distribution with Single Photons from Defects in Hexagonal Boron Nitride (Adv. Quantum Technol. 9/2022)

Quantum key distribution (QKD) is one of the most mature applications of single photon sources. The cover image shows on demand generation of single photons and their subsequent polarization encoding to prepare flying qubits in QKD. In article number 2200059, Çağlar Samaner and colleagues implement an isolated defect in hexagonal boron nitride (hBN) as the efficient single photon source and control their polarization by an electro-optic modulator to demonstrate free-space B92 based QKD. These results suggest that optically active defects in hBN have a great potential for applications within quantum information technologies including practical QKD systems.

Free‐Space Quantum Key Distribution with Single Photons from Defects in Hexagonal Boron Nitride

AbstractEfficient single photon generation is an important requirement for several practical applications in quantum technologies, including quantum cryptography. A proof‐of‐concept demonstration of free‐space quantum key distribution (QKD) is presented with single photons generated from an isolated defect in hexagonal boron nitride (hBN). The bright source operating at room temperature is integrated into a QKD system based on B92 protocol and a sifted key rate of 238 bps with a quantum bit error rate of 8.95% are achieved at 1 MHz clock rate. The effect of temporal filtering of detected photons on the performance of QKD parameters is also studied. It is believed that these results will stimulate the research on optically active defects in hBN as well as other 2D‐based quantum emitters and their applications within quantum information technologies including practical QKD systems.

Decoherence of V{}_{{{{{{{{rm{B}}}}}}}}}^{-} spin defects in monoisotopic hexagonal boron nitride

Spin defects in hexagonal boron nitride (hBN) are promising quantum systems for the design of flexible two-dimensional quantum sensing platforms. Here we rely on hBN crystals isotopically enriched with either 10B or 11B to investigate the isotope-dependent properties of a spin defect featuring a broadband photoluminescence signal in the near infrared. By analyzing the hyperfine structure of the spin defect while changing the boron isotope, we first confirm that it corresponds to the negatively charged boron-vacancy center ({{{{{{{{rm{V}}}}}}}}}_{{{{{{{{rm{B}}}}}}}}}^{-}). We then show that its spin coherence properties are slightly improved in 10B-enriched samples. This is supported by numerical simulations employing cluster correlation expansion methods, which reveal the importance of the hyperfine Fermi contact term for calculating the coherence time of point defects in hBN. Using cross-relaxation spectroscopy, we finally identify dark electron spin impurities as an additional source of decoherence. This work provides new insights into the properties of {{{{{{{{rm{V}}}}}}}}}_{{{{{{{{rm{B}}}}}}}}}^{-} spin defects, which are valuable for the future development of hBN-based quantum sensing foils.

Electron-Nuclear Coherent Coupling and Nuclear Spin Readout through Optically Polarized VB- Spin States in hBN.

Coherent coupling of defect spins with surrounding nuclei along with the endowment to read out the latter are basic requirements for an application in quantum technologies. We show that negatively charged boron vacancies (VB-) in hexagonal boron nitride (hBN) meet these prerequisites. We demonstrate Hahn-echo coherence of the VB- spin with a characteristic decay time Tcoh = 15 μs, close to the theoretically predicted limit of 18 μs for defects in hBN. Elongation of the coherence time up to 36 μs is demonstrated by means of the Carr-Purcell-Meiboom-Gill decoupling technique. Modulation of the Hahn-echo decay is shown to be induced by coherent coupling of the VB- spin with the three nearest 14N nuclei via a nuclear quadrupole interaction of 2.11 MHz. DFT calculation confirms that the electron-nuclear coupling is confined to the defective layer and stays almost unchanged with a transition from the bulk to the single layer.

Engineering Optically Active Defects in Hexagonal Boron Nitride Using Focused Ion Beam and Water

Hexagonal boron nitride (hBN) has emerged as a promising material platform for nanophotonics and quantum sensing, hosting optically active defects with exceptional properties such as high brightness and large spectral tuning. However, precise control over deterministic spatial positioning of emitters in hBN remained elusive for a long time, limiting their proper correlative characterization and applications in hybrid devices. Recently, focused ion beam (FIB) systems proved to be useful to engineer several types of spatially defined emitters with various structural and photophysical properties. Here we systematically explore the physical processes leading to the creation of optically active defects in hBN using FIB and find that beam–substrate interaction plays a key role in the formation of defects. These findings are confirmed using transmission electron microscopy, which reveals local mechanical deterioration of the hBN layers and local amorphization of ion beam irradiated hBN. Additionally, we show that, upon exposure to water, amorphized hBN undergoes a structural and optical transition between two defect types with distinctive emission properties. Moreover, using super-resolution optical microscopy combined with atomic force microscopy, we pinpoint the exact location of emitters within the defect sites, confirming the role of defected edges as primary sources of fluorescent emission. This lays the foundation for FIB-assisted engineering of optically active defects in hBN with high spatial and spectral control for applications ranging from integrated photonics, to nanoscale sensing, and to nanofluidics.

Generation of Spin Defects by Ion Implantation in Hexagonal Boron Nitride.

Optically addressable spin defects in wide-band-gap semiconductors as promising systems for quantum information and sensing applications have recently attracted increased attention. Spin defects in two-dimensional materials are expected to show superiority in quantum sensing due to their atomic thickness. Here, we demonstrate that an ensemble of negatively charged boron vacancies (VB–) with good spin properties in hexagonal boron nitride (hBN) can be generated by ion implantation. We carry out optically detected magnetic resonance measurements at room temperature to characterize the spin properties of ensembles of VB– defects, showing a zero-field splitting frequency of ∼3.47 GHz. We compare the photoluminescence intensity and spin properties of VB– defects generated using different implantation parameters, such as fluence, energy, and ion species. With the use of the proper parameters, we can successfully create VB– defects with a high probability. Our results provide a simple and practicable method to create spin defects in hBN, which is of great significance for realizing integrated hBN-based devices.

Spin defects in hexagonal boron nitride for strain sensing on nanopillar arrays.

Two-dimensional hexagonal boron nitride (hBN) has attracted much attention as a platform for studies of light-matter interactions at the nanoscale, especially in quantum nanophotonics. Recent efforts have focused on spin defects, specifically negatively charged boron vacancy (VB-) centers. Here, we demonstrate a scalable method to enhance the VB- emission using an array of SiO2 nanopillars. We achieve a 4-fold increase in photoluminescence (PL) intensity, and a corresponding 4-fold enhancement in optically detected magnetic resonance (ODMR) contrast. Furthermore, the VB- ensembles provide useful information about the strain fields associated with the strained hBN at the nanopillar sites. Our results provide an accessible way to increase the emission intensity as well as the ODMR contrast of the VB- defects, while simultaneously form a basis for miniaturized quantum sensors in layered heterostructures.

Modulation of optical and electrical properties in hexagonal boron nitride by defects induced via oxygen plasma treatment

Defects in hexagonal boron nitride (hBN) have attracted much attention since they are effectively used for nanoelectronics, such as single-photon emitters or memristors. The method for generating and controlling hBN defects is important because the defects are critical factors determining the optical and electrical properties of hBN. Here, we demonstrate the modulation of optical and electrical properties of hBN by defects generated via mild oxygen plasma treatment. The photoluminescence peaks related to defects were observed at a broad range (∼3.8 eV), and the current of plasma-treated hBN flow at the lower threshold voltage compared to the as-exfoliated hBN due to the formation of defect paths inside the hBN structure. We also demonstrate that the bandgap structure of hBN can be tuned by the oxygen plasma treatment. Our findings are useful for the stable and reliable fabrication of two-dimensional electronic devices using hBN in the future.

Synthesis of hexagonal boron nitrides by chemical vapor deposition and their use as single photon emitters

Two-dimensional (2D) hexagonal boron nitride (hBN), due to its extraordinary thermal, chemical, and optical properties, has arisen as an enticing material for the research community to explore for various applications, including the use of site defects in hBN as single photon emitters (SPEs). In this review, we systematically summarize recent advanced strategies towards the controllable synthesis of 2D hBN using chemical vapor deposition, towards a full control of the domain size, orientation, morphology, layer number, and stacking order, etc . Moreover, we review the underlying mechanisms for single photon emission (SPE) in hBN and methods to selectively generate and tune the SPEs. Defects ( e.g ., carbon substituted defects) are discussed for the potential use as emission sites. We finally give an outlook of future challenges and opportunities on desirable hBN synthesis and further investigation of SPEs in hBN, targeting to utilize hBN as single photon emitters in an industrial scale.

Spin defects in hBN as promising temperature, pressure and magnetic field quantum sensors

Spin defects in solid-state materials are strong candidate systems for quantum information technology and sensing applications. Here we explore in details the recently discovered negatively charged boron vacancies (VB−) in hexagonal boron nitride (hBN) and demonstrate their use as atomic scale sensors for temperature, magnetic fields and externally applied pressure. These applications are possible due to the high-spin triplet ground state and bright spin-dependent photoluminescence of the VB−. Specifically, we find that the frequency shift in optically detected magnetic resonance measurements is not only sensitive to static magnetic fields, but also to temperature and pressure changes which we relate to crystal lattice parameters. We show that spin-rich hBN films are potentially applicable as intrinsic sensors in heterostructures made of functionalized 2D materials.

Coupling Spin Defects in Hexagonal Boron Nitride to Monolithic Bullseye Cavities.

Color centers in hexagonal boron nitride (hBN) are becoming an increasingly important building block for quantum photonic applications. Herein, we demonstrate the efficient coupling of recently discovered spin defects in hBN to purposely designed bullseye cavities. We show that boron vacancy spin defects couple to the monolithic hBN cavity system and exhibit a 6.5-fold enhancement. In addition, by comparative finite-difference time-domain modeling, we shed light on the emission dipole orientation, which has not been experimentally demonstrated at this point. Beyond that, the coupled spin system exhibits an enhanced contrast in optically detected magnetic resonance readout and improved signal-to-noise ratio. Thus, our experimental results, supported by simulations, constitute a first step toward integration of hBN spin defects with photonic resonators for a scalable spin-photon interface.

Femtosecond Laser Writing of Spin Defects in Hexagonal Boron Nitride

Optically active spin defects in wide-bandgap materials have many potential applications in quantum information and quantum sensing. Spin defects in two-dimensional layered van der Waals materials are just emerging to be investigated. Here we demonstrate that optically-addressable spin ensembles in hexagonal boron nitride (hBN) can be generated by femtosecond laser irradiation. We observe optically detected magnetic resonance (ODMR) of hBN spin defects created by laser irradiation. We show that the creation of spin defects in hBN is strongly affected by the pulse energy of the femtosecond laser. When the laser pulse number is less than a few thousand, the pulse number only affects the density of defects but not the type of defects. With proper laser parameters, spin defects can be generated with a high probability of success. Our work provides a convenient way to create spin defects in hBN by femtosecond laser writing, which shows promising prospects for quantum technologies.

Direct Visualization and Effects of Atomic‐Scale Defects on the Optoelectronic Properties of Hexagonal Boron Nitride

AbstractHexagonal boron nitride (hBN) has attracted a lot of attention in the past years, thanks to its many remarkable properties. These include the presence of single‐photon emitters with superior optical properties, which make it an ideal candidate for a plethora of photonic technologies. However, despite the large number of experimental results and theoretical calculations, the structure of the defects responsible for the observed emission is still under debate. In this work, individual atomic‐scale defects in hBN with atomic force microscopy under ambient conditions are visualized and multiple narrow emission lines from optically stable emitters are observed. This direct observation of the structure of the defects combined with density functional theory calculations of their band structures and electronic properties allows associating the existence of several single‐photon transitions to the observed defects. The work sheds light on the origin of single‐photon emission in hBN that is important for the understanding and tunability of high‐quality emitters in optoelectronics and quantum technologies.

Single‐Atom Quantum‐Point Contact Switch Using Atomically Thin Hexagonal Boron Nitride

The first report of a quantized conductance atomic threshold switch (QCATS) using an atomically-thin hexagonal boron nitride (hBN) layer is provided. This QCATS has applications in memory and logic devices. The QCATS device shows a stable and reproducible conductance quantization state at 1·G0 by forming single-atom point contact through a monoatomic boron defect in an hBN layer. An atomistic switching mechanism in hBN-QCATS is confirmed by in situ visualization of mono-atomic conductive filaments. Atomic defects in hBN are the key factor that affects the switching characteristic. The hBN-QCATS has excellent switching characteristics such as low operation voltage of 0.3V, low "off" current of 1 pA, fast switching of 50 ns, and high endurance> 107 cycles. The variability of switching characteristics, which are the major problems of switching device, can be solved by reducing the area and thickness of the switching region to form single-atom point contact. The switching layer thickness is scaled down to the single-atom (≈0.33nm) h-BN layer, and the switching area is limited to single-atom defects. By implementing excellent switching characteristics using single-layer hBN, the possibility of implementing stable and uniform atomic-switching devices for future memory and logic applications is confirmed.

First-principle calculation study of (C<sub>N</sub>)<sub>3</sub>V<sub>B</sub> defect in hexagonal boron nitride monolayer

The point defect of two-dimensional hexagonal boron nitride (hBN) has recently been discovered to achieve single photon emission at room temperature, and it has become a research hotspot. Despite its important fundamental and applied research significance, the origin of the atomic structure of luminescence defects in hBN is still controversial. In this paper, first-principle calculations based on density functional theory are used to study a defect (C<sub>N</sub>)<sub>3</sub>V<sub>B</sub> in the hexagonal boron nitride monolayer (hBN) where three N atoms near the B vacancy are replaced by C atoms. At the B vacancy of hBN, the three N atoms each carry an in-plane dangling bond and the corresponding unpaired electron, and the unpaired electron can be eliminated by C substitution. We systematically study the geometric structure, electronic structure and optical properties of (C<sub>N</sub>)<sub>3</sub>V<sub>B</sub> defects, analyze the thermodynamic stability of defects through the calculation of the atomic structure, formation energy, and charge state of the defect, and analyze the position in the band gap and its atomic orbital contribution of defect state through energy band structure and wave function. We also analyze its optical properties through dielectric function and absorption coefficient, and predict its luminous photon energy. The results show that the defect can change from a symmetric metastable state to an asymmetric ground state structure with three C atoms connected together through atomic structure relaxation. The formation energy of asymmetric (C<sub>N</sub>)<sub>3</sub>V<sub>B</sub> is 7.94 eV, which is 3.72 eV lower than that of symmetric one. The formation of defects introduces some local defect states contributed by defect dangling σ bonds and reconstructed π bonds in hBN. The defects have valence states between –2 and +2, and the thermodynamic transition energy level of asymmetric (C<sub>N</sub>)<sub>3</sub>V<sub>B</sub> is higher than that of symmetric (C<sub>N</sub>)<sub>3</sub>V<sub>B</sub>. In the transition from the metastable state to the ground state, these defect states can redshift the light absorption boundary of hBN, enhance the absorption intensity of visible light by hBN, and cause internal optical transitions. Among them, there is a visible light transition with an energy threshold around 2.58 eV in the asymmetry (C<sub>N</sub>)<sub>3</sub>V<sub>B</sub> defect. Single boron atom vacancy defect and (C<sub>N</sub>)<sub>3</sub>V<sub>B</sub> have optical transitions near infrared and ultraviolet energy, respectively. The present work will help to further understand the composition and optical properties of point defects in hBN, and provide a theoretical basis for experimentally exploring the origin and properties of the atomic structure of light-emitting point defects.

Evidence of photochromism in a hexagonal boron nitride single-photon emitter

Solid-state single-photon emitters (SPEs) such as the bright, stable, room-temperature defects within hexagonal boron nitride (hBN) are of increasing interest for quantum information science. To date, the atomic and electronic origins of SPEs within hBN have not been well understood, and no studies have reported photochromism or explored cross correlations between hBN SPEs. Here, we combine irradiation time-dependent microphotoluminescence spectroscopy with two-color Hanbury Brown–Twiss interferometry in an investigation of the electronic structure of hBN defects. We identify evidence of photochromism in an hBN SPE that exhibits single-photon cross correlations and correlated changes in the intensity of its two zero-phonon lines.

Optical Repumping of Resonantly Excited Quantum Emitters in Hexagonal Boron Nitride

Resonant excitation of solid-state quantum emitters enables coherent control of quantum states and generation of coherent single photons, which are required for scalable quantum photonics applications. However, these systems can often decay to one or more intermediate dark states or spectrally jump, resulting in the lack of photons on resonance. Here, we present an optical co-excitation scheme which uses a weak non-resonant laser to reduce transitions to a dark state and amplify the photoluminescence from quantum emitters in hexagonal boron nitride (hBN). Utilizing a two-laser repumping scheme, we achieve optically stable resonance fluorescence of hBN emitters and an overall increase of ON time by an order of magnitude compared to only resonant excitation. Our results are important for the deployment of atom-like defects in hBN as reliable building blocks for quantum photonic applications.