Abstract Quantum sensors based on nitrogen vacancy (NV) defects in diamond have a demonstrated capability to detect nuclear magnetic resonance (NMR) spectra from proximate molecular nuclei, thereby promising an alternative with higher sensitivity to conventional NMR spectrometers for micro-scale samples. Fluorescence-based readout of these sensors is limited by higher shot noise due to the small number of emitters and photoionisation induced instabilities, meaning there is still significant scope to maximise their sensitivity and temporal resolution. In this work, we demonstrate a new readout protocol based on parameter fitting to a precise model of the NV photo-physics, thereby demonstrating an improvement of 36% in sensitivity and 85% gain in measurement speed. Whereas typical approaches to improvement involve expensive diamond material, and optical and microwave engineering, our method can be readily implemented into existing NV quantum sensing protocols.
Abstract Quantum sensors based on nitrogen vacancy (NV) defects in diamond have a demonstrated capability to detect nuclear magnetic resonance (NMR) spectra from proximate molecular nuclei, thereby promising an alternative with higher sensitivity to conventional NMR spectrometers for micro-scale samples. Fluorescence-based readout of these sensors is limited by higher shot noise due to the small number of emitters and photoionisation induced instabilities, meaning there is still significant scope to maximise their sensitivity and temporal resolution. In this work, we demonstrate a new readout protocol based on parameter fitting to a precise model of the NV photo-physics, thereby demonstrating an improvement of 36% in sensitivity and 85% gain in measurement speed. Whereas typical approaches to improvement involve expensive diamond material, and optical and microwave engineering, our method can be readily implemented into existing NV quantum sensing protocols.
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.
For quantum sensing, it is vital to develop an efficient technique for determining the quantum state of the sensor. We optimize the weighting of the photoluminescence intensity for readout of the spin state of the nitrogen-vacancy (NV) center in diamond. We find that adopting a physical model that considers the optical transitions and relaxations of the NV center allows for an efficient readout. Our method improves the signal-to-noise ratio of the readout by 5.4% in a short time of 3 s, while the existing methods typically require 1 min of integration time. We also show that our technique enhances the readout of the nuclear spin memory. The demonstrated way is helpful for a wide range of measurements, from a few minutes to several days.
In modern-day quantum metrology, quantum sensors are widely employed to detect weak magnetic fields or nanoscale signals. Quantum devices, exploiting quantum coherence, are inevitably connected to physical constants and can achieve accuracy, repeatability, and precision approaching fundamental limits. As a result, these sensors have shown utility in a wide range of research domains spanning both science and technology. A rapidly emerging quantum sensing platform employs atomic-scale defects in crystals. In particular, magnetometry using nitrogen-vacancy (NV) color centers in diamond has garnered increasing interest. NV systems possess a combination of remarkable properties, optical addressability, long coherence times, and biocompatibility. Sensors based on NV centers excel in spatial resolution and magnetic sensitivity. These diamond-based sensors promise comparable combination of high spatial resolution and magnetic sensitivity without cryogenic operation. The above properties of NV magnetometers promise increasingly integrated quantum measurement technology, as a result, they have been extensively developed with various protocols and find use in numerous applications spanning materials characterization, nuclear magnetic resonance (NMR), condensed matter physics, paleomagnetism, neuroscience and living systems biology, and industrial vector magnetometry. In this chapter, NV centers are explored for magnetic sensing in a number of contexts. In general, we introduce novel regimes for magnetic-field probes with NV ensembles. Specifically, NV centers are developed for sensitive magnetometers for applications where microwaves (MWs) are prohibitively invasive and operations need to be carried out under zero ambient magnetic field. The primary goal of our discussion is to improve the utility of these NV center-based magnetometers.
Ensembles of nitrogen-vacancy (NV) centers in diamond are versatile quantum sensors with broad applications in the physical and life sciences. The concentration of neutral substitutional nitrogen ( [ N s 0 ]) strongly influences NV electronic spin coherence times, sensitivity, and optimal sensing strategies. Diamonds with [ N s 0 ] ∼ 1–10 ppm are a focus of recent material engineering efforts, with higher concentrations being favorable for continuous-wave optically detected magnetic resonance (CW-ODMR) and lower concentrations expected to benefit pulsed magnetometry techniques through extended NV spin coherence times and improved sensing duty cycles. In this work, we synthesize and characterize low- [ N s 0 ] ( ∼ 0.8 ppm), NV-enriched diamond material, engineered through low-strain chemical vapor deposition (CVD) growth on high-quality substrates, 12 C isotopic purification, and controlled electron irradiation and annealing. Our results demonstrate good strain homogeneity in diamonds grown on CVD substrates and spin-bath-limited NV dephasing times. By measuring NV spin and charge properties across a wide range of optical NV excitation intensity, we provide direct comparisons of photon-shot-noise-limited magnetic field sensitivity between the current low- [ N s 0 ] and previously studied higher- [ N s 0 ] ( ∼ 14 ppm) NV-diamond sensors. We show that low- [ N s 0 ] diamond can outperform higher- [ N s 0 ] diamond at moderate and low optical NV excitation intensity. Our results provide practical benchmarks and guidance for selecting NV-diamond sensors tailored to specific experimental constraints and sensing requirements.
Nitrogen vacancy centers in diamond are among the leading solid state quantum platforms, offering exceptional spatial resolution and sensitivity for applications such as magnetic field sensing, thermometry, and bioimaging. However, in high background environments,such as those encountered in in vitro diagnostics, the performance of NV based sensors can be compromised by strong background fluorescence, particularly from substrates such as nitrocellulose. In this work, we analytically and experimentally investigate the use of pulsed laser excitation combined with time gating techniques to suppress background fluorescence and enhance the signal to noise ratio in NV based quantum sensing, with an emphasis on spin enhanced biosensing. Through experimental studies using mixed ensembles of silicon vacancy and NV centers in bulk diamond, as well as fluorescent nanodiamonds on NC substrates, we demonstrate significant improvements in NV spin resonance visibility, demonstrated by an increase of the SNR by up to 4x, and a resulting measurement time reduction by 16x. The presented technique and results here can help significantly increase the readout efficiency and speed in future applications of NV centers in high background environments, such as in IVD, where the NV centers are used as a fluorescent label for biomolecules.
Quantum technologies are expected to significantly change our world in the next decades and the possible applications are diverse – ranging from quantum computation and encryption to metrology with unprecedented sensitivity. This thesis focuses on quantum sensing and imaging based on single nitrogen-vacancy (NV) centres in diamond to measure magnetic fields. Its electronic spin qualifies this point defect as a highly sensitive quantum sensor and its atomic size offers nanoscale spatial resolution. The simple optical initialisation and readout, together with the relatively long coherence time at ambient conditions, make NV centres promising candidates for biological applications and in particular for nuclear magnetic resonance (NMR) on the nanoscale. Recording the spectral information on the nanoscale allows to determine the structure of single or just a few molecules. However, the current main problems and challenges include insufficient spectral resolution, artificial signals and overall poor performance. In this thesis new spectroscopic techniques which tackle these issues are presented. First, it is shown that by randomisation of control pulse phases spurious harmonic signals can be suppressed, which otherwise complicate spectrum interpretation and can lead to false signal identification. At the same time the effects of pulse imperfections are mitigated. Furthermore, a protocol allowing to measure with a coherence independent spectral resolution is presented. It is demonstrated that linewidths below 1mHz are possible, which is an improvement of more than seven orders of magnitude compared to traditional methods. Due to its simple implementation, the protocol is relevant for many applications. Initially developed to measure signals oscillating up to several megahertz, it is further shown that modifications allow to extend the frequency range into the gigahertz domain. Finally, quantum frequency discrimination with the task to differentiate between two frequency distributions using a quantum sensor is analysed. An optimised protocol is introduced and the influences of different readout strategies are discussed with respect to the probability to make an incorrect decision. These findings are useful for diagnostic tests in NMR.