Real-Time Ratiometric Optical Nanoscale Thermometry.

All-optical nanothermometry has become a powerful, remote tool for measuring nanoscale temperatures in applications ranging from medicine to nano-optics and solid-state nanodevices. The key features of any candidate nanothermometer are brightness, sensitivity, and (signal, spatial, and temporal) resolution. Here, we demonstrate a real-time, diamond-based nanothermometry technique with excellent sensitivity (1.8% K-1) and record-high resolution (5.8 × 104 K Hz-1/2 W cm-2) based on codoped nanodiamonds. The distinct performance of our approach stems from two factors: (i) temperature sensors─nanodiamonds cohosting two group IV color centers─engineered to emit spectrally separated Stokes and anti-Stokes fluorescence signals under excitation by a single laser source and (ii) a parallel detection scheme based on filtering optics and high-sensitivity photon counters for fast readout. We demonstrate the performance of our method by monitoring temporal changes in the local temperature of a microcircuit and a MoTe2 field-effect transistor. Our work advances a powerful, alternative strategy for time-resolved temperature monitoring and mapping of micro-/nanoscale devices such as microfluidic channels, nanophotonic circuits, and nanoelectronic devices, as well as complex biological environments such as tissues and cells.

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.

Room temperature coherent control of spin defects in hexagonal boron nitride.

Optically active spin defects are promising candidates for solid-state quantum information and sensing applications. To use these defects in quantum applications coherent manipulation of their spin state is required. Here, we realize coherent control of ensembles of boron vacancy centers in hexagonal boron nitride (hBN). Specifically, by applying pulsed spin resonance protocols, we measure a spin-lattice relaxation time of 18 microseconds and a spin coherence time of 2 microseconds at room temperature. The spin-lattice relaxation time increases by three orders of magnitude at cryogenic temperature. By applying a method to decouple the spin state from its inhomogeneous nuclear environment the optically detected magnetic resonance linewidth is substantially reduced to several tens of kilohertz. Our results are important for the employment of van der Waals materials for quantum technologies, specifically in the context of high resolution quantum sensing of two-dimensional heterostructures, nanoscale devices, and emerging atomically thin magnets.

Bottom-Up Synthesis of Hexagonal Boron Nitride Nanoparticles with Intensity-Stabilized Quantum Emitters.

Fluorescent nanoparticles are widely utilized in a large range of nanoscale imaging and sensing applications. While ultra-small nanoparticles (size ≤10 nm) are highly desirable, at this size range, their photostability can be compromised due to effects such as intensity fluctuation and spectral diffusion caused by interaction with surface states. In this article, a facile, bottom-up technique for the fabrication of sub-10-nm hexagonal boron nitride (hBN) nanoparticles hosting photostable bright emitters via a catalyst-free hydrothermal reaction between boric acid and melamine is demonstrated. A simple stabilization protocol that significantly reduces intensity fluctuation by ≈85% and narrows the emission linewidth by ≈14% by employing a common sol-gel silica coating process is also implemented. This study advances a promising strategy for the scalable, bottom-up synthesis of high-quality quantum emitters in hBN nanoparticles.

Quantum Energy and Charge Transfer at Two-Dimensional Interfaces.

Energy and charge transfer processes in interacting donor-acceptor systems are the bedrock of many fundamental studies and technological applications ranging from biosensing to energy storage and quantum optoelectronics. Central to the understanding and utilization of these transfer processes is having full control over the donor-acceptor distance. With their atomic thickness and ease of integrability, two-dimensional materials are naturally emerging as an ideal platform for the task. Here, we review how van der Waals semiconductors are shaping the field. We present a selection of some of the most significant demonstrations involving transfer processes in layered materials that deepen our understanding of transfer dynamics and are leading to intriguing practical realizations. Alongside current achievements, we discuss outstanding challenges and future opportunities.

Identifying carbon as the source of visible single-photon emission from hexagonal boron nitride.

Single-photon emitters (SPEs) in hexagonal boron nitride (hBN) have garnered increasing attention over the last few years due to their superior optical properties. However, despite the vast range of experimental results and theoretical calculations, the defect structure responsible for the observed emission has remained elusive. Here, by controlling the incorporation of impurities into hBN via various bottom-up synthesis methods and directly through ion implantation, we provide direct evidence that the visible SPEs are carbon related. Room-temperature optically detected magnetic resonance is demonstrated on ensembles of these defects. We perform ion-implantation experiments and confirm that only carbon implantation creates SPEs in the visible spectral range. Computational analysis of the simplest 12 carbon-containing defect species suggest the negatively charged [Formula: see text] defect as a viable candidate and predict that out-of-plane deformations make the defect environmentally sensitive. Our results resolve a long-standing debate about the origin of single emitters at the visible range in hBN and will be key to the deterministic engineering of these defects for quantum photonic devices.

Versatile direct-writing of dopants in a solid state host through recoil implantation.

Modifying material properties at the nanoscale is crucially important for devices in nano-electronics, nanophotonics and quantum information. Optically active defects in wide band gap materials, for instance, are critical constituents for the realisation of quantum technologies. Here, we demonstrate the use of recoil implantation, a method exploiting momentum transfer from accelerated ions, for versatile and mask-free material doping. As a proof of concept, we direct-write arrays of optically active defects into diamond via momentum transfer from a Xe+ focused ion beam (FIB) to thin films of the group IV dopants pre-deposited onto a diamond surface. We further demonstrate the flexibility of the technique, by implanting rare earth ions into the core of a single mode fibre. We conclusively show that the presented technique yields ultra-shallow dopant profiles localised to the top few nanometres of the target surface, and use it to achieve sub-50 nm positional accuracy. The method is applicable to non-planar substrates with complex geometries, and it is suitable for applications such as electronic and magnetic doping of atomically-thin materials and engineering of near-surface states of semiconductor devices.

Optical Thermometry with Quantum Emitters in Hexagonal Boron Nitride.

Nanoscale optical thermometry is a promising noncontact route for measuring local temperature with both high sensitivity and spatial resolution. In this work, we present a deterministic optical thermometry technique based on quantum emitters in nanoscale hexagonal boron nitride. We show that these nanothermometers show better performance than homologous, all-optical nanothermometers in both sensitivity and the range of working temperature. We demonstrate their effectiveness as nanothermometers by monitoring the local temperature at specific locations in a variety of custom-built microcircuits. This work opens new avenues for nanoscale temperature measurements and heat flow studies in miniaturized, integrated devices.

Initialization and read-out of intrinsic spin defects in a van der Waals crystal at room temperature.

Optically addressable spins in wide-bandgap semiconductors are a promising platform for exploring quantum phenomena. While colour centres in three-dimensional crystals such as diamond and silicon carbide were studied in detail, they were not observed experimentally in two-dimensional (2D) materials. Here, we report spin-dependent processes in the 2D material hexagonal boron nitride (hBN). We identify fluorescence lines associated with a particular defect, the negatively charged boron vacancy ([Formula: see text]), showing a triplet (S = 1) ground state and zero-field splitting of ~3.5 GHz. We establish that this centre exhibits optically detected magnetic resonance at room temperature and demonstrate its spin polarization under optical pumping, which leads to optically induced population inversion of the spin ground state-a prerequisite for coherent spin-manipulation schemes. Our results constitute a step forward in establishing 2D hBN as a prime platform for scalable quantum technologies, with potential for spin-based quantum information and sensing applications.

Author Correction: Quantum nanophotonics with group IV defects in diamond.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Quantum nanophotonics with group IV defects in diamond.

Diamond photonics is an ever-growing field of research driven by the prospects of harnessing diamond and its colour centres as suitable hardware for solid-state quantum applications. The last two decades have seen the field shaped by the nitrogen-vacancy (NV) centre with both breakthrough fundamental physics demonstrations and practical realizations. Recently however, an entire suite of other diamond defects has emerged-group IV colour centres-namely the Si-, Ge-, Sn- and Pb-vacancies. In this perspective, we highlight the leading techniques for engineering and characterizing these diamond defects, discuss the current state-of-the-art group IV-based devices and provide an outlook of the future directions the field is taking towards the realisation of solid-state quantum photonics with diamond.

Quantum emission from localized defects in zinc sulfide.

Single-photon sources in solid-state systems are widely explored as fundamental constituents of numerous quantum-based technologies. We report the observation of single-photon emitters in zinc sulfide and present their photophysical properties via established spectroscopy techniques. The emitter behaves like a three-level system with an intermediate metastable state. It emits at ∼640 nm, and its emission is linearly polarized, with a lifetime of (2.2±0.8) ns. The existence of single-photon sources in zinc sulfide is appealing due to the well-established manufacturing techniques of the material, its versatile technological uses, as well as the availability of many zinc isotopes with potential for designing ad hoc emitter-host pairs with tailored properties.

Anti-Stokes excitation of solid-state quantum emitters for nanoscale thermometry.

Color centers in solids are the fundamental constituents of a plethora of applications such as lasers, light-emitting diodes, and sensors, as well as the foundation of advanced quantum information and communication technologies. Their photoluminescence properties are usually studied under Stokes excitation, in which the emitted photons are at a lower energy than the excitation ones. In this work, we explore the opposite anti-Stokes process, where excitation is performed with lower-energy photons. We report that the process is sufficiently efficient to excite even a single quantum system-namely, the germanium-vacancy center in diamond. Consequently, we leverage the temperature-dependent, phonon-assisted mechanism to realize an all-optical nanoscale thermometry scheme that outperforms any homologous optical method used to date. Our results frame a promising approach for exploring fundamental light-matter interactions in isolated quantum systems and harness it toward the realization of practical nanoscale thermometry and sensing.

Engineering and Tuning of Quantum Emitters in Few-Layer Hexagonal Boron Nitride.

Quantum technologies require robust and photostable single photon emitters (SPEs). Hexagonal boron nitride (hBN) has recently emerged as a promising candidate to host bright and optically stable SPEs operating at room temperature. However, the emission wavelength of the fluorescent defects in hBN has, to date, been shown to be uncontrolled, with a widespread of zero phonon line (ZPL) energies spanning a broad spectral range (hundreds of nanometers), which hinders the potential development of hBN-based devices and applications. Here we demonstrate chemical vapor deposition growth of large-area, few-layer hBN films that host large quantities of SPEs: ∼100-200 per 10 × 10 µm2. More than 85% of the emitters have a ZPL at (580 ± 10) nm, a distribution that is an order of magnitude narrower than reported previously. Furthermore, we demonstrate tuning of the ZPL wavelength using ionic liquid devices over a spectral range of up to 15 nm-the largest obtained to date from any solid-state SPE. The fabricated devices illustrate the potential of hBN for the development of hybrid quantum nanophotonic and optoelectronic devices based on two-dimensional materials.

All-optical control and super-resolution imaging of quantum emitters in layered materials.

Layered van der Waals materials are emerging as compelling two-dimensional platforms for nanophotonics, polaritonics, valleytronics and spintronics, and have the potential to transform applications in sensing, imaging and quantum information processing. Among these, hexagonal boron nitride (hBN) is known to host ultra-bright, room-temperature quantum emitters, whose nature is yet to be fully understood. Here we present a set of measurements that give unique insight into the photophysical properties and level structure of hBN quantum emitters. Specifically, we report the existence of a class of hBN quantum emitters with a fast-decaying intermediate and a long-lived metastable state accessible from the first excited electronic state. Furthermore, by means of a two-laser repumping scheme, we show an enhanced photoluminescence and emission intensity, which can be utilized to realize a new modality of far-field super-resolution imaging. Our findings expand current understanding of quantum emitters in hBN and show new potential ways of harnessing their nonlinear optical properties in sub-diffraction nanoscopy.

Room-temperature spontaneous superradiance from single diamond nanocrystals.

Superradiance (SR) is a cooperative phenomenon which occurs when an ensemble of quantum emitters couples collectively to a mode of the electromagnetic field as a single, massive dipole that radiates photons at an enhanced rate. Previous studies on solid-state systems either reported SR from sizeable crystals with at least one spatial dimension much larger than the wavelength of the light and/or only close to liquid-helium temperatures. Here, we report the observation of room-temperature superradiance from single, highly luminescent diamond nanocrystals with spatial dimensions much smaller than the wavelength of light, and each containing a large number (~ 103) of embedded nitrogen-vacancy (NV) centres. The results pave the way towards a systematic study of SR in a well-controlled, solid-state quantum system at room temperature.

Wide-field time-gated photoluminescence microscopy for fast ultrahigh-sensitivity imaging of photoluminescent probes.

Fluorescence microscopy is a fundamental technique for the life sciences, where biocompatible and photostable photoluminescence probes in combination with fast and sensitive imaging systems are continually transforming this field. A wide-field time-gated photoluminescence microscopy system customised for ultrasensitive imaging of unique nanoruby probes with long photoluminescence lifetime is described. The detection sensitivity derived from the long photoluminescence lifetime of the nanoruby makes it possible to discriminate signals from unwanted autofluorescence background and laser backscatter by employing a time-gated image acquisition mode. This mode enabled several-fold improvement of the photoluminescence imaging contrast of discrete nanorubies dispersed on a coverslip. It enabled recovery of the photoluminescence signal emanating from discrete nanorubies when covered by a layer of an organic fluorescent dye, which were otherwise invisible without the use of spectral filtering approaches. Time-gated imaging also facilitated high sensitivity detection of nanorubies in a biological environment of cultured cells. Finally, we monitor the binding kinetics of nanorubies to a functionalised substrate, which exemplified a real-time assay in biological fluids. 3D-pseudo colour images of nanorubies immersed in a highly fluorescent dye solution. Nanoruby photoluminescence is subdued by that of the dye in continuous excitation/imaging (left), however it can be recovered by time-gated imaging (right). At the bottom is schematic diagram of nanoruby assay in a biological fluid.

Nano-assembly of nanodiamonds by conjugation to actin filaments.

Fluorescent nanodiamonds (NDs) are remarkable objects. They possess unique mechanical and optical properties combined with high surface areas and controllable surface reactivity. They are non-toxic and hence suited for use in biological environments. NDs are also readily available and commercially inexpensive. Here, the exceptional capability of controlling and tailoring their surface chemistry is demonstrated. Small, bright diamond nanocrystals (size ˜30 nm) are conjugated to protein filaments of actin (length ˜3-7 µm). The conjugation to actin filaments is extremely selective and highly target-specific. These unique features, together with the relative simplicity of the conjugation-targeting method, make functionalised nanodiamonds a powerful and versatile platform in biomedicine and quantum nanotechnologies. Applications ranging from using NDs as superior biological markers to, potentially, developing novel bottom-up approaches for the fabrication of hybrid quantum devices that would bridge across the bio/solid-state interface are presented and discussed.

Emission and nonradiative decay of nanodiamond NV centers in a low refractive index environment.

The nitrogen vacancy (NV) center is the most widely studied single optical defect in diamond with great potential for applications in quantum technologies. Development of practical single-photon devices requires an understanding of the emission under a range of conditions and environments. In this work, we study the properties of a single NV center in nanodiamonds embedded in an air-like silica aerogel environment which provides a new domain for probing the emission behavior of NV centers in nanoscale environments. In this arrangement, the emission rate is governed primarily by the diamond crystal lattice with negligible contribution from the surrounding environment. This is in contrast to the conventional approach of studying nanodiamonds on a glass coverslip. We observe an increase in the mean lifetime due to the absence of a dielectric interface near the emitting dipoles and a distribution arising from the irregularities in the nanodiamond geometry. Our approach results in the estimation of the mean quantum efficiency (~0.7) of the nanodiamond NV emitters.

Effect of the nanodiamond host on a nitrogen-vacancy color-centre emission state.

Control over the quantum states of individual luminescent nitrogen-vacancy (NV) centres in nanodiamonds (NDs) is demonstrated by careful design of the crystal host: its size, surface functional groups, and interfacing substrate. By progressive etching of the ND host, the NV centres are induced to switch from latent, through continuous, to intermittent or "blinking" emission states. The blinking mechanism of the NV centre in NDs is elucidated and a qualitative model proposed to explain this phenomenon in terms of the centre electron(s) tunnelling to acceptor site(s). These measurements suggest that the substrate material and its proximity to the NV are responsible for the fluorescence intermittency.