Dense ensembles of nitrogen-vacancy (NV) centers in diamond are of interest for various applications, including magnetometry, masers, hyperpolarization, and quantum memory. All of the applications above may benefit from a nonlinear response of the ensemble, and hence multiphoton processes are important. An enhancement of the multiphoton response is demonstrated by coupling the NV ensemble to a superconducting cavity. Moreover, the measured multiphoton response of the NV ensemble exhibits a regular pattern, which suggests that a dipolar coupling to nitrogen-14 substitutional defects (P1) plays a role in this process. As an example of an application, increased responsivity to magnetic field is demonstrated.
Dense ensembles of nitrogen-vacancy (NV) centers in diamond are of interest for various applications, including magnetometry, masers, hyperpolarization, and quantum memory. All of the applications above may benefit from a nonlinear response of the ensemble, and hence multiphoton processes are important. An enhancement of the multiphoton response is demonstrated by coupling the NV ensemble to a superconducting cavity. Moreover, the measured multiphoton response of the NV ensemble exhibits a regular pattern, which suggests that a dipolar coupling to nitrogen-14 substitutional defects (P1) plays a role in this process. As an example of an application, increased responsivity to magnetic field is demonstrated.
Nitrogen-vacancy (NV) defect centers in diamond have generated much interest for their uses in quantum information and sensing. Despite the ongoing improvements in sensitivity and the range of new applications, much about the NV basic physics remains unresolved, which is important to understand in order to fully exploit potential uses. In this work I describe a series of experiments on NV basic properties, applications, and projects in between. First, I describe an NV singlet absorption spectroscopy experiment, which searched for additional NV electronic states and studied the 1A1 phonon modes. Next, I discuss an NV microwave saturation spectroscopy experiment, which is useful for NV thermometry, removes inhomogeneous broadening, and can yield information about diamond magnetic spin bath dynamics. I then describe an NV relaxation experiment that senses GHz-frequency magnetic noise, which we demonstrated using paramagnetic substitutional nitrogen (P1) centers. Finally, I describe open questions on the NV singlet states, saturation spectroscopy, and relaxation (and how to address them), and report on my ongoing work on using NVs for nuclear polarization and rotation sensing.
Nitrogen Vacancy (NV) centers are point defects in diamond that allow magnetic field sensing based on Optically Detected Magnetic Resonance (ODMR). They are processed in ultrapure single-domain CVD grown diamond crystals and can be operated at room temperature. This results in solid-state sensors with a wide variety of applications. Ensemble of NV centers can be used to perform wide-field magnetic imaging with sensitivity in the nT range. Single NV centers can also be processed, which allows sensing at the atomic scale. This possibility, combined with its unique coherence properties, make NV center an ideal candidate for quantum sensing.
High-density nitrogen-vacancy (NV) centers exceeding 1016/cm3 inside a diamond can be achieved by femtosecond laser irradiation. The number of pulses and pulse energy were adjusted considering the increasing trend of the NV concentration and damage generation. The NV concentration first grew as the number of laser pulses was increased, and then the concentration was temporarily saturated or decreased. By increasing the number of laser pulses more than 2.5–5 × 107, the concentration increased again. The Hahn-echo measurement revealed that electron spins of the substitutional nitrogen center (P1) were dominant source for decoherence and the number of paramagnetic defects induced by the laser irradiation was not significant for degradation of spin coherence of the laser-induced NV centers even without a post-annealing process. Such high-dense ensemble NV centers are crucial for a high-sensitive quantum sensor.
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.
The coupling between defects in diamond and a superconducting microwave resonator is studied in the nonlinear regime. Both negatively charged nitrogen-vacancy and P1 defects are explored. The measured cavity mode response exhibits strong nonlinearity near a spin resonance. Data is compared with theoretical predictions and a good agreement is obtained. The nonlinear effect under study in the current paper is expected to play a role in any cavity-based magnetic resonance imaging technique and to impose a fundamental limit upon its sensitivity.
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.