The NV defect center in diamond forms a pseudo-atomic quantum system with discreet optically excitable transitions between ground and excited states in the gap between valence and conduction bands, making the NV center a deep-level defect center in diamond. For the negatively charged NV center (NV-), both the ground and excited states are spin triplets (S=1) and coupling between optical and spin states provides unique opportunities for optical detection of magnetic resonance (ODMR) and quantum metrology under ambient conditions. As an atomically sized point defect that is stable in single nanodiamonds as small as a few nanometers, the NV center enables spin based imaging of temperature, electric fields, magnetic fields and mechanical strain with nanoscale spatial resolution. Made of carbon, nanodiamonds are also ideal nanoparticles for use in biological systems, exhibiting extremely low cytotoxicity, no photo bleaching and exceptional contrast in transmission electron and light microscopy. With the ability to act as both a passive, non perturbing sensor (e.g. a diamagnetic material used for sensing magnetic fields) and a connection point for two way, direct coupling of far field optics to NV$^-$ spins and indirectly to the highly localized neighborhood of atoms, electronic states and phonon modes in the local vicinity, NV diamond provides a route to nanoscale field sensing and spin based optical microscopy. These sensors are also stable in nanodiamonds. For nanoparticles, the reduction in particle diameter dramatically enhances the proportion of the material that is surface exposed, enhancing any surface related properties. Nitrogen Vacancy centers in nanodiamonds provide another example of material properties that vary with particle size. In chapter 5, evidence that modulation of nanodiamonds fluorescent emissions by electrical perturbations in their surrouding environment allows transduction of local electrodynamics into a far field optical signal capable of mapping action potentials in cardiomyocytes in presented. The unifying theme for all of the work presented in this dissertation is to enable the use of magnetic resonance signals and interactions for imaging and sensing in previously inaccessible regimes. The specific focus is on methods and techniques to enable nanoscale physical sensing and functional imaging in live tissues, with the ultimate aim to lay the predicate for the combination of both without compromise.
The NV defect center in diamond forms a pseudo-atomic quantum system with discreet optically excitable transitions between ground and excited states in the gap between valence and conduction bands, making the NV center a deep-level defect center in diamond. For the negatively charged NV center (NV-), both the ground and excited states are spin triplets (S=1) and coupling between optical and spin states provides unique opportunities for optical detection of magnetic resonance (ODMR) and quantum metrology under ambient conditions. As an atomically sized point defect that is stable in single nanodiamonds as small as a few nanometers, the NV center enables spin based imaging of temperature, electric fields, magnetic fields and mechanical strain with nanoscale spatial resolution. Made of carbon, nanodiamonds are also ideal nanoparticles for use in biological systems, exhibiting extremely low cytotoxicity, no photo bleaching and exceptional contrast in transmission electron and light microscopy. With the ability to act as both a passive, non perturbing sensor (e.g. a diamagnetic material used for sensing magnetic fields) and a connection point for two way, direct coupling of far field optics to NV− spins and indirectly to the highly localized neighborhood of atoms, electronic states and phonon modes in the local vicinity, NV diamond provides a route to nanoscale field sensing and spin based optical microscopy. These sensors are also stable in nanodiamonds. For nanoparticles, the reduction in particle diameter dramatically enhances the proportion of the material that is surface exposed, enhancing any surface related properties. Nitrogen Vacancy centers in nanodiamonds provide another example of material properties that vary with particle size. In chapter 5, evidence that modulation of nanodiamonds fluorescent emissions by electrical perturbations in their surrouding environment allows transduction of local electrodynamics into a far field optical signal capable of mapping action potentials in cardiomyocytes in presented. The unifying theme for all of the work presented in this dissertation is to enable the use of magnetic resonance signals and interactions for imaging and sensing in previously inaccessible regimes. The specific focus is on methods and techniques to enable nanoscale physical sensing and functional imaging in live tissues, with the ultimate aim to lay the predicate for the combination of both without compromise.
Abstract Powered by the mutual developments in instrumentation, materials and theoretical descriptions, sensing and imaging capabilities of quantum emitters in solids have significantly increased in the past two decades. Quantum emitters in solids, whose properties resemble those of atoms and ions, provide alternative ways to probing natural and artificial nanoscopic systems with minimum disturbance and ultimate spatial resolution. Among those emerging quantum emitters, the nitrogen vacancy (NV) color center in diamond is an outstanding example due to its intrinsic properties at room temperature (highly-luminescent, photo-stable, biocompatible, highly-coherent spin states). This review article summarizes recent advances and achievements in using NV centers within nano- and single crystal diamonds in sensing and imaging. We also highlight prevalent challenges and material aspects for different types of diamond and outline the main parameters to consider when using color centers as sensors. As a novel sensing resource, we highlight the properties of NV centers as light emitting electrical dipoles and their coupling to other nanoscale dipoles e.g. graphene.
The recent decade has witnessed exciting developments in quantum science and technology. Quantum sensing is a rapidly growing branch, which exploits the fragility of quantum systems to detect small external signals. The extreme control at the single-atom level and the remarkably long coherence time of engineered quantum systems enable unprecedented sensitivity and precision, beating the performance of classical techniques. The nitrogen-vacancy (NV) center in diamond is one of the most promising quantum sensors. Its unique advantages have attracted considerable attention, including a long spin coherence time throughout a broad temperature range, nanoscale resolution limited by the sensor-sample distance, convenient optical control of its spin states and remarkably versatile sensing capabilities. Its properties are well studied under a bias magnetic field oriented along its quantization axis. However, its sensing capabilities in the presence of an off-axis magnetic field are much less explored. My research aims to unlock the full potential of NV quantum sensor by developing new sensing modalities under a magnetic field acting perpendicular to the NV axis, and furthermore, integrating them into a scanning probe microscope. In this dissertation, I will report our progress toward building a scanning NV multimodal quantum imaging platform, which will open up exciting opportunities in measuring nanoscale phenomena. The first chapter provides an introduction to the background of quantum sensing with NV centers, followed by a discussion on its basic properties and established sensing techniques. The second and third chapters are dedicated to two experiments performed under a perpendicular magnetic field where traditional NV magnetometry based on the Zeeman effect fails. In the second chapter, I will introduce a new sensing strategy that uses the entanglement between the electron and nuclear spins to restore the magnetic field sensitivity under this unfavored condition. This allows us to sense small changes in the magnetic field angle relative to the NV axis, and to detect anisotropic magnetic noise in the local environment. In the third chapter, I will present our latest development of scanning NV electrometry, where a single NV at the apex of a diamond scanning probe images external alternating (AC) and direct (DC) electric fields with sub-100 nm resolution. In the last chapter, I will discuss our efforts on four experiments that were left unfinished. I will present the results we have achieved, analyze the challenges that we faced and propose potential solutions to overcome them.
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.
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.
Quantum sensing using nitrogen-vacancy (NV) centers in diamond has emerged as a powerful platform for detecting ultra-low magnetic fields under ambient conditions. Owing to their long spin coherence times, optical addressability, and compatibility with aqueous environments, it has found widespread applications in biosensing and bio-imaging. This review presents the fundamental principles and recent advances in NV-based quantum magnetometry for biosensing applications, with a particular focus on measurements in aqueous medium and at cellular and molecular length scales. We discuss the underlying spin physics of NV centers and highlight two primary detection modalities: optically detected magnetic resonance (ODMR) and T1 relaxometry-based sensing and how these approaches aids in the detection of both static magnetic fields and dynamic magnetic noise arising from biological processes. The review explores key application areas, including nanoscale nuclear magnetic resonance (NMR), monitoring of neural activity, detection of abnormal or rogue cells using NV-based platforms etc. In addition, strategies for enhancing sensitivity, such as surface functionalization of nanodiamonds, femtosecond (fs) laser-written photonic structures, and integration with microfluidic and lab-on-chip systems have also been discussed in depth. We also address the critical challenges, including surface-induced decoherence, charge-state instability, and signal-to-noise limitations in biofluids associated with NV-based biosensing applications. Finally, we outline future prospects, highlighting how NV-based magnetic biosensing provides a promising pathway for translating quantum sensing technologies into practical biomedical applications.
Powered by the mutual developments in instrumentation, materials andtheoretical descriptions, sensing and imaging capabilities of quantum emitters insolids have significantly increased in the past two decades. Quantum emitters insolids, whose properties resemble those of atoms and ions, provide alternative waysto probing natural and artificial nanoscopic systems with minimum disturbance andultimate spatial resolution. Among those emerging quantum emitters, the nitrogen-vacancy (NV) color center in diamond is an outstanding example due to its intrinsicproperties at room temperature (highly-luminescent, photo-stable, biocompatible,highly-coherent spin states). This review article summarizes recent advances andachievements in using NV centers within nano- and single crystal diamonds in sensingand imaging. We also highlight prevalent challenges and material aspects for differenttypes of diamond and outline the main parameters to consider when using color centersas sensors. As a novel sensing resource, we highlight the properties of NV centersas light emitting electrical dipoles and their coupling to other nanoscale dipoles e.g.graphene.