This work demonstrates efficient Forster resonance energy transfer (FRET) between ensembles of shallow nitrogen-vacancy (NV) centers located 7 nm and 9 nm below a single-crystal diamond surface and a naturally occurring fluorophore, namely a mixture of chlorophyll a and b molecules extracted from Arabidopsis thaliana. The broad fluorescence band of NV centers spectrally overlaps with the absorption of chlorophyll molecules, enabling FRET. As a result, depositing a chlorophyll layer on the diamond surface reduces the NV fluorescence lifetime from approximately 14 ns to below 4 ns, indicating efficient energy transfer. Laser-induced photobleaching of chlorophyll restores the unquenched NV lifetime. In contrast, NV centers located deeper within the diamond at depths of 40 nm and 72 nm remain unaffected, confirming that the observed quenching originates from a short-range FRET mechanism. The NV ensembles retain their optically detected magnetic resonance contrast while FRET is observed, demonstrating preservation of their spin properties. These proof-of-principle experiments establish the feasibility of combining FRET-based distance measurements with magnetic sensing using optically readable spins.
This work demonstrates efficient Forster resonance energy transfer (FRET) between ensembles of shallow nitrogen-vacancy (NV) centers located 7 nm and 9 nm below a single-crystal diamond surface and a naturally occurring fluorophore, namely a mixture of chlorophyll a and b molecules extracted from Arabidopsis thaliana. The broad fluorescence band of NV centers spectrally overlaps with the absorption of chlorophyll molecules, enabling FRET. As a result, depositing a chlorophyll layer on the diamond surface reduces the NV fluorescence lifetime from approximately 14 ns to below 4 ns, indicating efficient energy transfer. Laser-induced photobleaching of chlorophyll restores the unquenched NV lifetime. In contrast, NV centers located deeper within the diamond at depths of 40 nm and 72 nm remain unaffected, confirming that the observed quenching originates from a short-range FRET mechanism. The NV ensembles retain their optically detected magnetic resonance contrast while FRET is observed, demonstrating preservation of their spin properties. These proof-of-principle experiments establish the feasibility of combining FRET-based distance measurements with magnetic sensing using optically readable spins.
ABSTRACT This work demonstrates efficient Förster resonance energy transfer (FRET) between ensembles of shallow nitrogen‐vacancy (NV) centers located and below a single‐crystal diamond surface and a naturally occurring fluorophore, here a mixture of chlorophyll a and b molecules extracted from Arabidopsis thaliana . The broad fluorescence band of NV centers spectrally overlaps with the chlorophyll molecule's absorption, enabling FRET. Consequently, depositing a chlorophyll layer on the diamond surface reduces the NV fluorescence lifetime from approximately to below , indicating efficient FRET. Laser‐induced photobleaching of chlorophyll restores the unquenched NV lifetime. NV centers located deeper within the diamond ( and ) remain unaffected, confirming that the observed quenching originates from a short range FRET mechanism. The NV ensembles retain their optically detected magnetic resonance (ODMR) contrast while observing FRET, demonstrating preservation of their spin properties. Consequently, these proof‐of‐principle experiments demonstrate the feasibility of combining FRET‐based distance measurements with magnetic sensing using optically readable spins.
Sensing nano-scale magnetic field sources is at the heart of many applications in nano-science and biology. Given its very small size and high magnetic sensitivity, the nitrogen vacancy (NV) colour centre in diamond is one of the leading candidates for such applications. However, issues regarding the stability and performance of the NV centre near the diamond's surface are the major obstacle in the practical realization of theses sensors. So far, conventional implantation and growth techniques did not produce practical and/or repeatable solutions to this problem. In this report, we show first results of shallow layers of NVs created using plasma immersion ion implantation (PIII). We show, using Forster Resonance Energy Transfer (FRET), that most NVs are within 3.6 nm from the diamond's surface. Despite the relatively low quality of the diamond substrates used and the simplicity of our PIII system, we have an estimated magnetic sensitivity of around 2.29 μT/[Formula: see text].
Shallow, negatively charged nitrogen-vacancy centers (NV -) in diamond have been proposed for high-sensitivity magnetometry and spin-polarization transfer applications.However, surface effects tend to favor and stabilize the less useful neutral form, the NV 0 centers.Here, we report the effects of green laser irradiation on ensembles of nanometer-shallow NV centers in flat and nanostructured diamond surfaces as a function of laser power in a range not previously explored (up to 150 mW/μm 2 ).Fluorescence spectroscopy, optically detected magnetic resonance (ODMR), and charge-photoconversion detection are applied to characterize the properties and dynamics of NV -and NV 0 centers.We demonstrate that high laser power strongly promotes photoconversion of NV 0 to NV -centers.Surprisingly, the excess NV -population is stable over a timescale of 100 ms after switching off the laser, resulting in long-lived enrichment of shallow NV -.The beneficial effect of photoconversion is less marked in nanostructured samples.Our results are important to inform the design of samples and experimental procedures for applications relying on ensembles of shallow NV -centers in diamond.
The fluorescence of the nitrogen-vacancy (NV) centre in artificial diamond has been widely studied for applications such as quantum communication protocols, quantum computation, fluorescence-based biolabelling, and optical sensing. Optical sensing by itself encompasses a wide range of possible applications: from magnetic and electric field sensing to temperature sensing and enabling, for example, the detection of paramagnetic ions and the identification of molecules by nuclear magnetic resonance. Compared to many other systems capable of optical sensing, the NV centre works at room temperature, and its spin-dependent fluorescence emission is the key property to achieve a high sensitivity to the surrounding environment. Additionally, the NV centre emission is highly photostable, has a relatively short lifetime (~ 12ns) and spans a broad wavelength range, from the red to the near-infrared region of the electromagnetic spectrum (600 - 800nm). While the common denominator of all mentioned applications is the NV centre, the properties of the artificial diamond surrounding the NV centre have a significant impact on its sensing performance. At present, the processing of artificial diamond has not been fully optimised, and research and development towards the realisation of the `best¿ diamond sample for optical sensing is far from over. Specifically, the role of other defects in diamond and their effects on the photo-physical properties of the NV centres are not entirely understood. In this thesis, I will discuss the potential benefits of a novel processing technique to create ensembles of NV centres, and the importance that surrounding nitrogen defects has on the achievable magnetic field sensitivity. Additionally, I will show both theoretical and experimental investigations of the NV centres photo-physical processes, with focus on magnetic field sensing. I will initially explore a protocol for microwave-free magnetometry. This protocol predicts a theoretical magnetic field sensitivity <10µT/√Hz in the range 0.3 - 30mT and I will demonstrate it experimentally with a maximum sensitivity of 3.6mT/Hz. Following, I will focus on exploring techniques to increase the magnetic field sensitivity by improving the material properties of the diamond samples. I will demonstrate that the simultaneous electron irradiation and annealing improves the creation efficiency of an ensemble of NV centres by up to 117%. Finally, I will investigate how substitutional nitrogen defects in the surrounding lattice affects the charge state of the NV centre, its emission intensity, its lifetime and its magnetic field sensitivity. I will study a sample characterised by multiple regions across its volume, with nitrogen concentration changing between 10ppm and 100ppm in each region. There si an optimal region with ~ 40ppm of substitutional nitrogen which demonstrates the highest fluorescence emission, mainly from the negatively-charged NV centre, and the highest magnetic field sensitivity of 1.6 ± 0.2µT/√Hz. However, both the regions with lower and higher substitutional nitrogen concentration than the optimal region show lower emission intensity and worse magnetic field sensitivity. Following is a summary of the content in each chapter: Chapter 1 will present an introduction to the diamond material and the classification of artificial diamond samples. It will introduce the NV centre, its fluorescence properties and the process to create NV centres in diamond. The chapter will also introduce the concepts around optical magnetometry and the working principle that allows the NV centre to sense magnetic fields as well as other external quantities, such as temperature or pressure. Finally, it will include a brief overview of the defects that are found in artificial diamond or are created during the sample processing. Chapter 2 will describe the working principle of the instruments utilised in this work. I will list the details of each instrument and describe the methods used for the analysis of the data. Chapter 3 will introduce the background of modelling the fluorescence emission from NV centres. I will discuss the implementation of a computational model based on the Lindblad master equation to simulate the photo-physical dynamics of the NV centre. I will demonstrate the successful simulation of the saturation emission, fluorescence lifetime and optically detected magnetic resonance using the theoretical model. Finally, I will explore the theoretically predicted sensitivity of microwave-free magnetometry, based on the NV centre emission intensity change under an external magnetic field. Chapter 4 will demonstrate experimentally the microwave-free magnetometry technique. In relation to the study of microwave-free magnetometry, this chapter will explore an unexpected increase in emission intensity at high magnetic fields > 100mT. Combining the experimental observations and the theoretical simulation developed in the previous chapter, I will identify and discuss a phenomenological decrease in the NV centre transition rate from the triplet state to the singlet state. The chapter will conclude comparing the experimental and theoretical sensitivities associated with the microwave-free magnetometry technique. Chapter 5 will show the characterisation of a diamond sample at each step of the process to create NV centres. I will study the electron irradiation followed by separate annealing on a high-pressure high-temperature diamond sample. I will then characterise the sample employing visible and infrared absorption spectroscopy, as well as measure the fluorescence spectra and lifetime of the defects identified at each step. Chapter 6 will examine an alternative method to create NV centres in diamond. I will compare diamond samples irradiated and annealed separately with samples simultaneously irradiated and annealed (referred to as 'annealing in situ'). To compare the two processes, I will estimate the concentration of nitrogen defects and NV centres and calculate their N-to-NV conversion efficiency. Chapter 7 will discuss the effects of substitutional nitrogen on the properties of the NV centres in diamond. For this discussion, I will use a single-crystal diamond that shows the presence of 4 growth sectors. Each growth sector is characterised by a different nitrogen concentration, as I will demonstrate at the beginning of the chapter. I will focus on 4 main properties affected by the concentration of nitrogen in the different sectors: the balance between the charge states of the NV centre, the overall fluorescence intensity from each sector, the fluorescence lifetime and its relation to non-radiative processes, and the magnetic field sensitivity obtained with the optically detected magnetic resonance technique. Chapter 8 will gather the results and conclusions of the entire body of work. It will also discuss future avenues of research in the topic of diamond processing and characterisations, to improve the existing optical sensing applications.
High spatial resolution quantum sensing of near-surface nitrogen vacancy (NV) centers in diamond has enabled detection of magnetic, electrical, and thermal signals at the nanoscale. At depths of just a few nanometers, NV centers serve as localized quantum probes for external spins or low-dimensional materials, but their proximity to the surface also enhances decoherence caused by fluctuating nuclear spins. While advances in surface engineering have stabilized the charge state of NV centers at depths of tens of nanometers, achieving both ultra-shallow implantation (0.5-2 nm) and long-term spin coherence remains a central challenge. In this work, we show using first-principles modeling that, by exploiting the interaction of surface-induced strain and weak dc magnetic fields, the spin coherence times of 1-nm-deep NV centers can be greatly improved near the spin-phonon-confined regime at room temperature in 12C-rich diamonds. We also demonstrate that this protocol benefits ~ 10-nm-deep NV centers in natural diamond, enabling vector magnetometry at the nanoscale. Shallow NV centers in diamond are advantageous for quantum sensing but suffer from surface magnetic noise. Using first-principles simulations supported by experiments, the authors show that a combination of small magnetic fields and surface strain can significantly enhance spin coherence of 1 nm-deep NV centers.
Laser-induced fluorescence quenching in nitrogen-vacancy (NV) centers in diamond is studied simultaneously with in situ measurements of the heating-induced shift of the electron spin resonance of NV centers in the presence of a microwave field. These experiments reveal a strong correlation between fluorescence suppression in NV centers and the rise of the local temperature inside the diamond crystal. This finding sheds light on quantum pathways behind stimulated fluorescence quenching in NV centers of diamond and may imply significant limitations on the applications of this effect as a method of superresolving imaging in biological systems.