This thesis focuses on the spin physics of nitrogen-vacancy (NV) centres in nanodiamonds (NDs) via their coupling to external fields. In the first part, we theoretically investigate the feasibility of coupling a ND with a high density of NV centres to a gap-tunable flux qubit. We calculate the optimum position including the tolerance for maximizing the coupling and calculate its dependence on the orientation of the ND. We demonstrate that the coherent coupling of a 150-nm ND containing many (10³) NV centres and a flux qubit with dephasing time of ~1 μs is feasible. In the second part, we investigate the spin-coherence properties of NV centres in NDs and discuss them in the context of the NVs-to-flux qubit coupling. In particular, we manipulate the NV spins via an external microwave field using two distinct methods. The first, more conventional method employs a thin wire in direct contact with the sample as the microwave antenna. The second method has been developed by our group. It uses a cavity to produce the microwave field at the position of the NV spins with the advantage over the wire architecture of addressing the NV centre spins, without sample heating and over macroscopic spatial distances (milli-meters versus micro-meters).
This thesis focuses on the spin physics of nitrogen-vacancy (NV) centres in nanodiamonds (NDs) via their coupling to external fields. In the first part, we theoretically investigate the feasibility of coupling a ND with a high density of NV centres to a gap-tunable flux qubit. We calculate the optimum position including the tolerance for maximizing the coupling and calculate its dependence on the orientation of the ND. We demonstrate that the coherent coupling of a 150-nm ND containing many (10³) NV centres and a flux qubit with dephasing time of ~1 μs is feasible. In the second part, we investigate the spin-coherence properties of NV centres in NDs and discuss them in the context of the NVs-to-flux qubit coupling. In particular, we manipulate the NV spins via an external microwave field using two distinct methods. The first, more conventional method employs a thin wire in direct contact with the sample as the microwave antenna. The second method has been developed by our group. It uses a cavity to produce the microwave field at the position of the NV spins with the advantage over the wire architecture of addressing the NV centre spins, without sample heating and over macroscopic spatial distances (milli-meters versus micro-meters).
This thesis represents several steps in the development of Nitrogen-Vacancy Nanodiamond as an effective optical label for biological measurements and as a tool for nanometry and quantum information techniques. In this thesis I cover concrete progress in many areas of nanodiamond research, demonstrating that optical interactions alone can be used to control NV spin polarisation and measure NV temperature. I develop a method for high-contrast imaging of NV centres using magnetic modulation, and also show a method for measuring the Raman scattering of water to an unprecedented level of accuracy. This thesis also contains the outlines of two more experiments: one aimed at measuring NV concentration in aqueous nanodiamond suspensions, and another whose aim is to use multiple NV centres in a single nanodiamond to measure the orientation and strength of an external magnetic field.
The Nitrogen-Vacancy (NV) centre in diamond possesses an optical read out of its spin state and shows great promise for applications in solid state quantum technologies. Its broad phonon assisted emission spectrum, with only 4% of emission from the zero-phonon line, is a major drawback to this. The optical microcavity will be essential in efficiently interfacing these centres with photonic networks. Here we present investigations into the coupling of NV centres in nanodiamond to tunable open-microcavities, both at room temperature and at cryogenic temperatures. These structures will be shown to achieve good photon confinement, with mode volumes down to 5λ3. Room temperature studies on ensembles of NVs will illustrate the tunable spectral and spatial overlap between the emitter and the cavity mode. It will be shown that small enhancements are possible in this regime. After the preparation and characterisation of single emitters, low temperature coupling to the narrowed zero-phonon line will be the central theme of this thesis. Single photon emission into the cavity mode is verified. We observe the enhancement of the light-matter interaction in this regime, by a 39% increase in the emission rate when cavity-coupled, with the dependence on mode volume also demonstrated. These results are important for the realisation of a spin-photon interface in scalable quantum networks.
The Nitrogen-Vacancy (NV) centre in diamond possesses an optical read out of its spin state and shows great promise for applications in solid state quantum technologies. Its broad phonon assisted emission spectrum, with only 4p of emission from the zero-phonon line, is a major drawback to this. The optical microcavity will be essential in efficiently interfacing these centres with photonic networks. Here we present investigations into the coupling of NV centres in nanodiamond to tunable open-microcavities, both at room temperature and at cryogenic temperatures. These structures will be shown to achieve good photon confinement, with mode volumes down to 5λ3. Room temperature studies on ensembles of NVs will illustrate the tunable spectral and spatial overlap between the emitter and the cavity mode. It will be shown that small enhancements are possible in this regime. After the preparation and characterisation of single emitters, low temperature coupling to the narrowed zero-phonon line will be the central theme of this thesis. Single photon emission into the cavity mode is verified. We observe the enhancement of the light-matter interaction in this regime, by a 39p increase in the emission rate when cavity-coupled, with the dependence on mode volume also demonstrated. These results are important for the realisation of a spin-photon interface in scalable quantum networks.
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.
Diamond is unique. Whether mechanical, thermal, electrical or optical, its properties are within the most extreme compared to those of any other material. This, together with the fact that in the last fifty years the synthesis of artificial diamond has become a reality, makes it very attractive for engineering and technological purposes. The range of diamond-based applications is very diverse and, among the others, includes its use in mechanical machining, high-power high-frequency electronics and high transmissivity optics. -- Diamond is also host to a wide variety of crystallographic defects. Appropriately controlled, they can be used to tune the characteristics of the material, but even more interestingly they often possess attractive optical properties on their own. In particular, nitrogen-vacancy (NV) centres in diamond have been the subject of extensive study in the last few years. They possess unique room-temperature optical and spin properties which make them promising systems for solid-state qubits in quantum information technologies and for emerging applications in biotechnology, nanomedicine and high resolution magnetometry, such as drug delivery, fluorescent biomarking and spin imaging. -- This thesis is focused on NV centres in diamond. I first present an extensive review on diamond as a material, describing in detail its physical properties, the methods that have been developed to synthesise it and some of its possible applications. I then move the attention specifically to NV centres in nanodiamonds (NDs), i.e. diamond crystals in the nanometre size range (0-100 nm). They are a potential candidate for emerging technologies including high-resolution magnetometry and biomedical imaging. For these applications, specific material requirements, such as the small size of the diamond nanocrystals and the optical stability of the hosted NV centres, are crucial. The NV stability with respect to the nanodiamond size and surface is the central theme of this thesis. I analyse the optical behaviour of NV centres in nanodiamond while varying a number of key parameters such as size, surface termination and diamond origin. Based on the measurements, I conclude whether the nanodiamond size and the NV surface proximity are factors that must be taken into consideration in order to control the material and realise nanotechnologies based on NV centres in nanodiamonds.
Color centers in diamond, and in particular the nitrogen-vacancy center (NV center), have proven promising for the emerging field of quantum technologies. In this thesis, new concepts for the manipulation of the NV center dynamics will be addressed, along with the proposal of novel fields of application. It comprises: (i) A study of the NV coupling to intrinsic acoustical phonons in nanocrystals, and concepts to exploit that mechanism for conditional quantum operations. (ii) The proposal for the bottom-up creation of NV arrangements on the nanoscale by the ordered arrangement of nanodiamonds directed by biological scaffold structures. A framework is developed for coherently addressing and manipulating NV centers in such structures along with studies of noise and imperfections. (iii) The interferometry with nanodiamonds in search of signatures of quantum gravity. (iv) The creation of an illustrative (filter-based) framework for the analysis and design of hybrid NV-nuclear spin couplings.