arXiv subjects

Dane R. McCamey

Publications and source records attributed to Dane R. McCamey.

16 recordsLinked to original sources

arXiv2026

Electrically detected magnetic resonance of $^{75}$As magnetic clock transitions in silicon

Magnetic clock transitions (CTs), defined by vanishing first-order sensitivity of the transition frequency to magnetic field fluctuations, provide a powerful route to suppress decoherence in donor spin systems. Here, we present the observation of magnetic field CTs from an ensemble of near-surface $^{75}$As ($I = 3/2$) spins in silicon using low-field ($< 10$~mT) continuous-wave electrically detected magnetic resonance (EDMR). As the CT condition is approached, pronounced linewidth broadening is observed, consistent with a donor Hamiltonian informed linewidth model. These results establish low-field EDMR as a sensitive probe of CTs in near-surface donor systems relevant to silicon-based quantum devices.

quant-ph↗

arXiv2026

Spatially-resolved coherence of organic molecular spins at room-temperature

Molecular spins are a versatile platform for quantum sensing. Not only are the spin-bearing molecules themselves widely tunable, they are also capable of being used as sensors as crystals, films and in solution. Using thin-films offers the advantages of high doping ratios and the ability to control the thickness with nanometre precision, however they also introduce disorder to the system. High proximity sensing can also be realised by using micro- and nano-crystals, however in many solid-state systems this leads to a reduction in coherence. In this paper we combine room-temperature optically detected coherent control of molecular spins and microscopy to image the coherence properties of both thin-films and micro-crystals of pentacene doped p-terphenyl. In thin-films we find large amounts of variation in both the contrast and coherence times, leading to a variability in the magnetic field sensitivity of approximately 7.6 %. Applying the technique to micro-crystals shows much lower sensitivity variability (1.3 %), and we find no evidence of coherence loss toward the edge of the crystal. Finally we perform optically-detected coherent control on a nano-crystal, showing minimal loss in coherence and contrast compared to the bulk crystal, with a coherence time of 1.09 μs and a contrast of 25 %.

cond-mat.mtrl-sci↗

arXiv2025

Mitigating Singlet Exciton Back-Transfer using 2D Spacer Layers for Perovskite-Sensitised Upconversion

Photon upconversion has potential applications in light-emitting diodes, photocatalysis, bio-imaging, microscopy, 3D printing, and photovoltaics. Bulk lead-halide perovskite films have emerged as promising sensitisers for solid-state photon upconversion via triplet-triplet annihilation due to their excellent optoelectronic properties. In this system, a perovskite sensitiser absorbs photons and subsequently generates triplet excitons in an adjacent emitter material, where triplet-triplet annihilation can occur allowing for the emission of higher energy photons. However, a major loss pathway in perovskite-sensitised upconversion is the back-transfer of singlet excitons from the emitter to the sensitiser via Förster Resonance Energy Transfer. In this investigation we introduce a 2D perovskite spacer layer between the bulk perovskite sensitiser and a rubrene emitter to mitigate back-transfer of singlet excitons from rubrene to the bulk perovskite sensitiser. This modification reveals the inherent balance between efficient triplet exciton transfer across the interface with a potential barrier versus the mitigation of near-field back-transfer by increasing the distance between the sensitiser and singlet excitons in the emitter. Notably, the introduction of this spacer layer enhances the relative upconversion efficiency at lower excitation power densities while also sustaining performance over extended timescales. This work represents significant progress toward the practical applications of perovskite-sensitised photon upconversion.

cond-mat.mtrl-sci↗

arXiv2025

Revealing localised dark-exciton populations in 2D perovskites via magneto-optical microscopy

The successful development of optoelectronic devices is contingent on a detailed understanding of interactions between light and excited energy states in photoactive materials. In 2D perovskites, excitons are the dominant photogenerated species and their energetic structure plays a pivotal role, governing photon absorption and emission processes. In these materials, dark exciton states can undergo photoluminescence due to the relaxation of selection rules and this process can be modulated by an external magnetic field, enabling unambiguous identification of the exciton fine structure. Previous reports of magneto-optical spectroscopy on 2D perovskites have been restricted to the macroscopic response, where key information is lost regarding the microscopic heterogeneity of the photoluminescence. Here, we use magneto-optical microscopy for the first time on perovskite materials to elucidate the spatial variation of exciton emission processes. In 2D perovskite thin films, we distinguish between regions of localised bright and dark exciton populations, correlated to the film morphology. In single crystals, we show that dark excitons become localised at the edges, where excitons can be trapped in two distinct types of sub-gap states. This work represents significant progress in understanding the properties of exciton emission in 2D perovskites, which is crucial for the development of optoelectronic technology.

cond-mat.mtrl-sci↗

arXiv2024

Electronic Structure at the Perovskite Rubrene Interface: The Effect of Surface Termination

Perovskite films have rapidly emerged as leading active materials in optoelectronic devices due to their strong optical absorption, high carrier mobility and ease of fabrication. Whilst proving to be promising materials for solar cells and light-emitting diodes, another application of perovskites which makes effective use of their unique properties is sensitisation for photon upconversion. Consisting of a bulk perovskite sensitiser alongside an adjacent organic semiconductor film, the upconverting system can absorb multiple low-energy photons to emit high-energy photons. In this work, density functional theory, in conjunction with GW theory, is utilised to investigate the electronic structure at the MAPbI$_3$/rubrene interface for different surface terminations of MAPbI$_3$. From this investigation, we reveal that the surface termination of the perovskite layer greatly affects the charge density at the interface and within the rubrene layer driven by the formation of interfacial dipole layers. The formation of a strong interfacial dipole for the lead-iodide terminated perovskite alters the band alignment of the heterojunction and is expected to facilitate more efficient hole transfer. For the perovskite surface terminated with the methylammonium iodide layer, the highest occupied molecular orbital of the adjacent rubrene layer lies deep within the perovskite band gap. This termination type is further characterized by a lower density of states near the band edges thereby acting as a spacer which is anticipated to decrease the probability of charge transfer across the interface. Thus based on our results, PbI$_2$-terminated perovskite surfaces are predicted to be favourable for applications where hole transfer to a rubrene layer is ideal, highlighting the significance of surface termination for all systems where the electronic environment at the interface is crucial to performance.

cond-mat.mtrl-sci↗

arXiv2024

A Room-Temperature Solid-State Maser Amplifier

Masers once represented the state-of-the-art in low noise microwave amplification technology, but eventually became obsolete due to their need for cryogenic cooling. Masers based on solid-state spin systems perform most effectively as amplifiers, since they provide a large density of spins and can therefore operate at relatively high powers. Whilst solid-state masers oscillators have been demonstrated at room temperature, continuous-wave amplification in these systems has only ever been realized at cryogenic temperatures. Here we report on a continuous-wave solid-state maser amplifier operating at room temperature. We achieve this feat using a practical setup that includes an ensemble of nitrogen-vacancy center spins in a diamond crystal, a strong permanent magnet and simple laser diode. We describe important amplifier characteristics including gain, bandwidth, compression power and noise temperature and discuss the prospects of realizing a room-temperature near-quantum-noise-limited amplifier with this system. Finally, we show that in a different mode of operation the spins can be used to cool the system noise in an external circuit to cryogenic levels, all without the requirement for physical cooling.

quant-ph↗

arXiv2024

Room-temperature optically detected coherent control of molecular spins

Benefiting from both molecular tunability and versatile methods for deployment, optically interfaced molecular spins are a promising platform for quantum technologies such as sensing and imaging. Room-temperature optically detected coherent spin control is a key enabler for many applications, combining sensitive readout, versatile spin manipulation, and ambient operation. Here we demonstrate such functionality in a molecular spin system. Using the photoexcited triplet state of organic chromophores (pentacene doped in a para-terphenyl host), we optically detect coherent spin manipulation with photoluminescence contrasts exceeding 10% and microsecond coherence times at room temperature. We further demonstrate how coherent control of multiple triplet sublevels can significantly enhance optical spin contrast, and extend optically detected coherent control to a thermally evaporated thin film, retaining high photoluminescence contrast and coherence times of order one microsecond. These results open opportunities for room-temperature quantum technologies that can be systematically tailored through synthetic chemistry.

quant-ph↗

arXiv2023

Singlet fission spin dynamics from molecular structure: a modular computational pipeline

Singlet fission, which has applications in areas ranging form solar energy to quantum information, relies critically on transitions within a multi-spin manifold. These transitions are driven by fluctuations in the spin-spin exchange interaction, which have been linked to changes in nuclear geometry or exciton migration. Whilst simple calculations have supported this mechanism, to date little effort has been made to model realistic fluctuations which are informed by the actual structure and properties of physical materials. In this paper, we develop a modular computational pipeline for calculating singlet fission spin dynamics by way of electronic structural calculations, molecular dynamics, and numerical models of spin dynamics. The outputs of this pipeline aid in the interpretation of measured spin dynamics and allow us to place constraints on geometric fluctuations which are consistent with these observations.

physics.chem-ph↗

arXiv2023

Influence of Organic Spacer Cation on Dark Excitons in 2D Perovskites

The organic spacer cation plays a crucial role in determining the exciton fine structure in two-dimensional (2D) perovskites. Here, we use low-temperature magneto-optical spectroscopy to gain insight into the influence of the organic spacer on dark excitons in Ruddlesden-Popper (RP) perovskites. We show that by using modest magnetic field strengths (<1.5 T), the spin-forbidden dark exciton state can be identified and its emission properties significantly modulated through the application of in-plane magnetic fields, up to temperatures of 15 K. At low temperatures, an increase in collected photoluminescence efficiency of >30% is demonstrated, signifying the critical role of the dark exciton state for light-emitting applications of 2D perovskites. The exciton fine structure and the degree of magnetic-field-induced mixing are impacted by the choice of organic spacer cation, with 4-methoxyphenethylammonium (MeO-PEA) showing the largest effect due to larger bright-dark exciton splitting. Our results suggest that dark excitons preferentially form biexcitons depending on the choice of spacer. We distinguish between interior (bulk) and surface dark-exciton emission, showing that bright-dark exciton splitting differs between the interior and surface. Our results emphasize the significance of the organic spacer cation in controlling the exciton fine structure in 2D perovskites and have important implications for the development of optoelectronic technology based on 2D perovskites.

cond-mat.mtrl-sci↗

arXiv2022

Sub-micron spin-based magnetic field imaging with an organic light emitting diode

Quantum sensing and imaging of magnetic fields has attracted broad interests due to its potential for high sensitivity and spatial resolution. Common systems used for quantum sensing require either optical excitation (e.g., nitrogen-vacancy centres in diamond, atomic vapor magnetometers), or cryogenic temperatures (e.g., SQUIDs, superconducting qubits), which pose challenges for chip-scale integration and commercial scalability. Here, we demonstrate an integrated organic light emitting diode (OLED) based quantum sensor for magnetic field imaging, which employs spatially resolved magnetic resonance to provide a robust mapping of magnetic fields. By considering the monolithic OLED as an array of individual virtual sensors, we achieve sub-micron magnetic field mapping with field sensitivity of ~160 $μ$T Hz$^{-1/2}$ um$^{-2}$. Our work demonstrates a chip-scale OLED-based laser free magnetic field sensor and an approach to magnetic field mapping built on a commercially relevant and manufacturable technology.

quant-ph↗

arXiv2022

Quintet formation and exchange fluctuations: The role of stochastic resonance in singlet fission

Singlet fission describes the spin-conserving production of two triplet excitons from one singlet exciton. The existence of a spin-2 (quintet) triplet-pair state as a product of singlet fission is well established in the literature, and control of quintet formation is an important step towards applying singlet fission in photovoltaics and quantum information. However, a definitive mechanism for quintet formation is yet to be established, which makes it difficult to design materials for optimal quintet formation. Here we outline a mechanism in which inter-triplet exchange coupling fluctuations drive fast and efficient quintet formation. In contrast with conventional wisdom, we show that quintet population can arise despite strong exchange coupling. We evaluate the performance of this quintet formation mechanism in two regimes of conformational freedom, and relate quintet dynamics to material properties of singlet fission molecules.

cond-mat.mes-hall↗

arXiv2022

Singlet Fission Photovoltaics: Progress and Promising Pathways

Singlet fission is a form of multiple exciton generation which occurs in organic chromophores when a high energy singlet exciton separates into two lower energy triplet excitons, each with approximately half the singlet energy. Since this process is spin-allowed it can proceed on an ultrafast timescale of less than several picoseconds, outcompeting most other loss mechanisms and reaching quantitative yields approaching 200%. Due to this high quantum efficiency, the singlet fission process shows promise as a means of reducing thermalisation losses in photovoltaic cells. This would potentially allow for efficiency improvements beyond the thermodynamic limit in a single junction cell. Efforts to incorporate this process into solar photovoltaic cells have spanned a wide range of device structures over the past decade. In this review we compare and categorise these attempts in order to assess the state of the field and identify the most promising avenues of future research and development.

physics.app-ph↗

arXiv2021

Spatial Variation and Correlation of Spin Properties in Organic Light-Emitting Diodes

Devices which exploit the quantum properties of materials are widespread, with quantum information processors and quantum sensors showing significant progress. Organic devices offer interesting opportunities for quantum technologies owing to their engineerable spin properties, with spintronic operation and spin resonance magnetic-field sensing demonstrated in research grade devices, as well as proven compatibility with large scale fabrication techniques. Yet several important challenges remain as we move toward scaling these proof-of-principle quantum devices to larger integrated logic systems or spatially smaller sensing elements, particularly those associated with the variation of quantum properties both within and between devices. Here, spatially resolved magnetoluminescence is used to provide the first two-dimensional map of a spin property - the Overhauser field - in an organic light-emitting diode. We find intra-device variabilities exceeding 20% while spatially correlated behaviour is exhibited on lengths beyond $7 \, \mathsfμm$, similar in size to pixels in state-of-the-art AMOLED arrays, which has implications for the reproducibility and integration of organic quantum devices.

cond-mat.mes-hall↗

arXiv2019

Fluctuating exchange interactions enable quintet multiexciton formation in singlet fission

Several recent electron spin resonance studies have observed a quintet multiexciton state during the singlet fission process. Here we provide a general theoretical explanation for the generation of this state by invoking a time-varying exchange coupling between pairs of triplet excitons, and subsequently solving the relevant time-varying spin Hamiltonian for a range of transition times. We simulate experimental ESR spectra and draw qualitative conclusions about the adiabatic/diabatic transition between triplet pair spin states.

cond-mat.mtrl-sci↗

arXiv2017

Phase-Encoded Hyperpolarized Nanodiamond for Magnetic Resonance Imaging

Surface-functionalized nanomaterials can act as theranostic agents that detect disease and track biological processes using hyperpolarized magnetic resonance imaging (MRI). Candidate materials are sparse however, requiring spinful nuclei with long spin-lattice relaxation (T1) and spin-dephasing times (T2), together with a reservoir of electrons to impart hyperpolarization. Here, we demonstrate the versatility of the nanodiamond material system for hyperpolarized 13C MRI, making use of its intrinsic paramagnetic defect centers, hours-long nuclear T1 times, and T2 times suitable for spatially resolving millimeter-scale structures. Combining these properties, we enable a new imaging modality that exploits the phase-contrast between spins encoded with a hyperpolarization that is aligned, or anti-aligned with the external magnetic field. The use of phase-encoded hyperpolarization allows nanodiamonds to be tagged and distinguished in an MRI based on their spin-orientation alone, and could permit the action of specific bio-functionalized complexes to be directly compared and imaged.

physics.med-ph↗

arXiv2012

Modulation frequency dependence of continuous-wave optically/electrically detected magnetic resonance

Continuous wave optically and electrically detected magnetic resonance spectroscopy (cwODMR/cwEDMR) allow the investigation of paramagnetic states involved in spin-dependent transitions, like recombination and transport. Although experimentally similar to conventional electron spin resonance (ESR), there exist limitations when applying models originally developed for ESR to observables (luminescence and electric current) of cwODMR and cwEDMR. Here we present closed-form solutions for the modulation frequency dependence of cwODMR and cwEDMR based on an intermediate pair recombination model and discuss ambiguities which arise when attempting to distinguish the dominant spin-dependent processes underlying experimental data. These include: 1) a large number of quantitatively different models cannot be differentiated, 2) signs of signals are determined not only by recombination, but also by other processes like dissociation, intersystem-crossing, pair generation, and even experimental parameter such as, modulation frequency, microwave power, and temperature, 3) radiative and non-radiative recombination cannot be distinguished due to the observed signs of cwODMR and cwEDMR experiments.

cond-mat.mtrl-sci↗