Silicon-Aluminum Phase-Transformation-Induced Superconducting Rings.

The development of devices that exhibit both superconducting and semiconducting properties is an important endeavor for emerging quantum technologies. We investigate superconducting nanowires fabricated on a silicon-on-insulator (SOI) platform. Aluminum from deposited contact electrodes is found to interdiffuse with Si along the entire length of the nanowire, over micrometer length scales and at temperatures well below the Al-Si eutectic. The phase-transformed material is conformal with the predefined device patterns. The superconducting properties of a transformed mesoscopic ring formed on a SOI platform are investigated. Low-temperature magnetoresistance oscillations, quantized in units of the fluxoid, h/2e, are observed.

Photochemical Upconversion in Solution: The Role of Oxygen and Magnetic Field Response.

Upconversion processes effectively convert two or more low energy photons into one higher energy photon, and they have diverse prospective applications in photovoltaics and biomedicine. We focus on two specific mechanisms for photochemical upconversion in solution: triplet-triplet annihilation (TTA) and singlet oxygen mediated energy transfer (SOMET). TTA is spin-selective, whereas SOMET is not, so the interplay between these two upconversion mechanisms can be examined via their different magnetic field responses. A kinetic model is developed and applied to explain the different photoluminescence profiles of oxygenated versus deoxygenated systems. From the magnetic field response, the triplet-triplet annihilation rate constant is estimated. The conditions required to maximize upconversion photoluminescence intensity in oxygenated solution are determined, providing a set of design principles to guide molecule choices for robust and air-stable upconversion systems in the future.

Two-dimensional spectroscopy beyond the perturbative limit: The influence of finite pulses and detection modes.

Ultra-fast and multi-dimensional spectroscopy gives a powerful looking glass into the dynamics of molecular systems. In particular, two-dimensional electronic spectroscopy (2DES) provides a probe of coherence and the flow of energy within quantum systems, which is not possible with more conventional techniques. While heterodyne-detected (HD) 2DES is increasingly common, more recently fluorescence-detected (FD) 2DES offers new opportunities, including single-molecule experiments. However, in both techniques, it can be difficult to unambiguously identify the pathways that dominate the signal. Therefore, the use of numerically modeling of 2DES is vitally important, which, in turn, requires approximating the pulsing scheme to some degree. Here, we employ non-perturbative time evolution to investigate the effects of finite pulse width and amplitude on 2DES signals. In doing so, we identify key differences in the response of HD and FD detection schemes, as well as the regions of parameter space where the signal is obscured by unwanted artifacts in either technique. Mapping out parameter space in this way provides a guide to choosing experimental conditions and also shows in which limits the usual theoretical approximations work well and in which limits more sophisticated approaches are required.

Bilirubin analogues as model compounds for exciton coupling.

A series of phycobilin analogues have been investigated in terms of coupled excitonic systems. These compounds consist of a monomer, a tetrapyrrole structurally similar to bilirubin (bR), and two conjugated bR analogues. Spectroscopic and computational methods have been used to investigate the degree of interchromophore coupling. We find the synthesised bR analogue shows stronger excitonic coupling than bR, owing to a different molecular geometry. The excitonic coupling in the conjugated molecules can be controlled by modifying the bridge side-group. New computed energy levels for bR using the DFT/MRCI method are also presented, which improve on published values and re-assign the character of excited singlet states.

Towards understanding two-level-systems in amorphous solids: insights from quantum circuits.

Amorphous solids show surprisingly universal behaviour at low temperatures. The prevailing wisdom is that this can be explained by the existence of two-state defects within the material. The so-called standard tunneling model has become the established framework to explain these results, yet it still leaves the central question essentially unanswered-what are these two-level defects (TLS)? This question has recently taken on a new urgency with the rise of superconducting circuits in quantum computing, circuit quantum electrodynamics, magnetometry, electrometry and metrology. Superconducting circuits made from aluminium or niobium are fundamentally limited by losses due to TLS within the amorphous oxide layers encasing them. On the other hand, these circuits also provide a novel and effective method for studying the very defects which limit their operation. We can now go beyond ensemble measurements and probe individual defects-observing the quantum nature of their dynamics and studying their formation, their behaviour as a function of applied field, strain, temperature and other properties. This article reviews the plethora of recent experimental results in this area and discusses the various theoretical models which have been used to describe the observations. In doing so, it summarises the current approaches to solving this fundamentally important problem in solid-state physics.

Passive On-Chip Superconducting Circulator Using a Ring of Tunnel Junctions.

We present the design of a passive, on-chip microwave circulator based on a ring of superconducting tunnel junctions. We investigate two distinct physical realizations, based on Josephson junctions (JJs) or quantum phase slip elements (QPS), with microwave ports coupled either capacitively (JJ) or inductively (QPS) to the ring structure. A constant bias applied to the center of the ring provides an effective symmetry breaking field, and no microwave or rf bias is required. We show that this design offers high isolation, robustness against fabrication imperfections and bias fluctuations, and a bandwidth in excess of 500 MHz for realistic device parameters.

Signatures of spatially correlated noise and non-secular effects in two-dimensional electronic spectroscopy.

We investigate how correlated fluctuations affect oscillatory features in rephasing and non-rephasing two-dimensional (2D) electronic spectra of a model dimer system. Based on a beating map analysis, we show that non-secular environmental couplings induced by uncorrelated fluctuations lead to oscillations centered at both cross- and diagonal-peaks in rephasing spectra as well as in non-rephasing spectra. Using an analytical approach, we provide a quantitative description of the non-secular effects in terms of the Feynman diagrams and show that the environment-induced mixing of different inter-excitonic coherences leads to oscillations in the rephasing diagonal-peaks and non-rephasing cross-peaks. We demonstrate that as correlations in the noise increase, the lifetime of oscillatory 2D signals is enhanced at rephasing cross-peaks and non-rephasing diagonal-peaks, while the other non-secular oscillatory signals are suppressed. We discuss that the asymmetry of 2D lineshapes in the beating map provides information on the degree of correlations in environmental fluctuations. Finally we investigate how the oscillatory features in 2D spectra are affected by inhomogeneous broadening.

Bloch-Redfield equations for modeling light-harvesting complexes.

We challenge the misconception that Bloch-Redfield equations are a less powerful tool than phenomenological Lindblad equations for modeling exciton transport in photosynthetic complexes. This view predominantly originates from an indiscriminate use of the secular approximation. We provide a detailed description of how to model both coherent oscillations and several types of noise, giving explicit examples. All issues with non-positivity are overcome by a consistent straightforward physical noise model. Herein also lies the strength of the Bloch-Redfield approach because it facilitates the analysis of noise-effects by linking them back to physical parameters of the noise environment. This includes temporal and spatial correlations and the strength and type of interaction between the noise and the system of interest. Finally, we analyze a prototypical dimer system as well as a 7-site Fenna-Matthews-Olson complex in regards to spatial correlation length of the noise, noise strength, temperature, and their connection to the transfer time and transfer probability.

All-optical thermometry and thermal properties of the optically detected spin resonances of the NV(-) center in nanodiamond.

The negatively charged nitrogen-vacancy (NV(-)) center in diamond is at the frontier of quantum nanometrology and biosensing. Recent attention has focused on the application of high-sensitivity thermometry using the spin resonances of NV(-) centers in nanodiamond to subcellular biological and biomedical research. Here, we report a comprehensive investigation of the thermal properties of the center's spin resonances and demonstrate an alternate all-optical NV(-) thermometry technique that exploits the temperature dependence of the center's optical Debye-Waller factor.

A framework for multiexcitonic logic.

Exciton science sits at the intersection of chemical, optical and spin-based implementations of information processing, but using excitons to conduct logical operations remains relatively unexplored. Excitons encoding information could be read optically (photoexcitation-photoemission) or electrically (charge recombination-separation), travel through materials via exciton energy transfer, and interact with one another in stimuli-responsive molecular excitonic devices. Excitonic logic offers the potential to mediate electrical, optical and chemical information. Additionally, high-spin triplet and quintet (multi)excitons offer access to well defined spin states of relevance to magnetic field effects, classical spintronics and spin-based quantum information science. In this Roadmap, we propose a framework for developing excitonic computing based on singlet fission (SF) and triplet-triplet annihilation (TTA). Various molecular components capable of modulating SF/TTA for logical operations are suggested, including molecular photo-switching and multi-colour photoexcitation. We then outline a pathway for constructing excitonic logic devices, considering aspects of circuit assembly, logical operation synchronization, and exciton transport and amplification. Promising future directions and challenges are identified, and the potential for realizing excitonic computing in the near future is discussed.

Magnetic fields reveal signatures of triplet-pair multi-exciton photoluminescence in singlet fission.

The photophysical processes of singlet fission and triplet fusion have numerous emerging applications. They involve the separation of a photo-generated singlet exciton into two dark triplet excitons and the fusion of two dark triplet excitons into an emissive singlet exciton, respectively. The role of the excimer state and the nature of the triplet-pair state in these processes have been a matter of contention. Here we analyse the room temperature time-resolved emission of a neat liquid singlet fission chromophore and show that it exhibits three spectral components: two that correspond to the bright singlet and excimer states and a third component that becomes more prominent during triplet fusion. This spectrum is enhanced by magnetic fields, confirming its origins in the recombination of weakly coupled triplet pairs. It is thus attributed to a strongly coupled triplet pair state. These observations unite the view that there is an emissive intermediate in singlet fission and triplet fusion, distinct from the broad, unstructured excimer emission.

Delocalized oxygen as the origin of two-level defects in Josephson junctions.

One of the key problems facing superconducting qubits and other Josephson junction devices is the decohering effects of bistable material defects. Although a variety of phenomenological models exist, the true microscopic origin of these defects remains elusive. For the first time we show that these defects may arise from delocalization of the atomic position of the oxygen in the oxide forming the Josephson junction barrier. Using a microscopic model, we compute experimentally observable parameters for phase qubits. Such defects are charge neutral but have nonzero response to both applied electric field and strain. This may explain the observed long coherence time of two-level defects in the presence of charge noise, while still coupling to the junction electric field and substrate phonons.

Monitoring ion-channel function in real time through quantum decoherence.

In drug discovery, there is a clear and urgent need for detection of cell-membrane ion-channel operation with wide-field capability. Existing techniques are generally invasive or require specialized nanostructures. We show that quantum nanotechnology could provide a solution. The nitrogen-vacancy (NV) center in nanodiamond is of great interest as a single-atom quantum probe for nanoscale processes. However, until now nothing was known about the quantum behavior of a NV probe in a complex biological environment. We explore the quantum dynamics of a NV probe in proximity to the ion channel, lipid bilayer, and surrounding aqueous environment. Our theoretical results indicate that real-time detection of ion-channel operation at millisecond resolution is possible by directly monitoring the quantum decoherence of the NV probe. With the potential to scan and scale up to an array-based system, this conclusion may have wide-ranging implications for nanoscale biology and drug discovery.

Magnetic Field Effects in Triplet-Triplet Annihilation Upconversion: Revisiting Atkins and Evans' Theory.

In their seminal description of magnetic field effects on chemiluminescent fluid solutions, Atkins and Evans considered the spin-dependent interactions between two triplets, incorporating the effects of the diffusion of the molecules in the liquid phase. Their results, crucial for the advancement of photochemical upconversion, have received renewed attention due to the increasing interest in triplet-triplet annihilation for photovoltaic and optoelectronic applications. Here we revisit their approach, using a modern formulation of open quantum system dynamics and extend their results. We provide corrections to the theory of the magnetic field response of the fluorescent triplet pair state with singlet multiplicity. These corrections are timely, as improvements in the precision and range of available experimental methods are supported by the determination of quantitatively accurate rotational and interaction model parameters. We then extend Atkins and Evans' theory to obtain the magnetic field response of triplet pair states with triplet and quintet multiplicity. Although these states are not optically active, transitions between them are becoming imperative to study the working mechanism of spin-mediated upconversion and downconversion processes, thanks to advances in electron spin resonance and time-resolved transient absorption spectroscopy.

Tuning the Photoluminescence Anisotropy of Semiconductor Nanocrystals.

Semiconductor nanocrystals are promising optoelectronic materials. Understanding their anisotropic photoluminescence is fundamental for developing quantum-dot-based devices such as light-emitting diodes, solar cells, and polarized single-photon sources. In this study, we experimentally and theoretically investigate the photoluminescence anisotropy of CdSe semiconductor nanocrystals with various shapes, including plates, rods, and spheres, with either wurtzite or zincblende structures. We use defocused wide-field microscopy to visualize the emission dipole orientation and find that spheres, rods, and plates exhibit the optical properties of 2D, 1D, and 2D emission dipoles, respectively. We rationalize the seemingly counterintuitive observation that despite having similar aspect ratios (width/length), rods and long nanoplatelets exhibit different defocused emission patterns by considering valence band structures calculated using multiband effective mass theory and the dielectric effect. The principles are extended to provide general relationships that can be used to tune the emission dipole orientation for different materials, crystalline structures, and shapes.

Power Dependence of the Magnetic Field Effect on Triplet Fusion: A Quantitative Model.

Two strategies for improving solar energy efficiencies, triplet fusion and singlet fission, rely on the details of triplet-triplet interactions. In triplet fusion, there are several steps, each of which is a possible loss mechanism. In solution, the parameters describing triplet fusion collisions are difficult to inspect. Here we show that these parameters can be determined by examining the magnetic field dependence of triplet fusion upconversion. We show that there is a reduction of the magnetic field effect for perylene triplet fusion as the system moves from the quadratic to linear annihilation regimes with an increase in laser power. Our data are modeled with a small set of parameters that characterize the triplet fusion dynamics. These parameters are cross-validated with molecular dynamics simulations. This approach can be applied to both solution and solid state materials, providing a tool for screening potential annihilators for photon upconversion.

Top-down patterning of topological surface and edge states using a focused ion beam.

The conducting boundary states of topological insulators appear at an interface where the characteristic invariant ℤ2 switches from 1 to 0. These states offer prospects for quantum electronics; however, a method is needed to spatially-control ℤ2 to pattern conducting channels. It is shown that modifying Sb2Te3 single-crystal surfaces with an ion beam switches the topological insulator into an amorphous state exhibiting negligible bulk and surface conductivity. This is attributed to a transition from ℤ2 = 1 → ℤ2 = 0 at a threshold disorder strength. This observation is supported by density functional theory and model Hamiltonian calculations. Here we show that this ion-beam treatment allows for inverse lithography to pattern arrays of topological surfaces, edges and corners which are the building blocks of topological electronics.

The Hong-Ou-Mandel effect in the context of few-photon scattering.

The Hong-Ou-Mandel effect is studied in the context of two-photon transport in a one-dimensional waveguide with a single scatterer. We numerically investigate the scattering problem within a time-dependent, wave-function-based framework. Depending on the realization of the scatterer and its properties, we calculate the joint probability of finding both photons on either side of the waveguide after scattering. We specifically point out how Hong-Ou-Mandel interferometry techniques could be exploited to identify effective photon-photon interactions which are mediated by the scatterer. The Hong-Ou-Mandel dip is discussed in detail for the case of a single two-level atom embedded in the waveguide, and dissipation and dephasing are taken into account by means of a quantum jump approach.

Spin guides and spin splitters: waveguide analogies in one-dimensional spin chains.

Here we show a mapping between waveguide theory and spin-chain transport, opening an alternative approach to solid-state quantum information transport. By applying temporally varying control profiles to a spin chain, we design a virtual waveguide or "spin guide" to conduct spin excitations along defined space-time trajectories of the chain. We show that the concepts of confinement, adiabatic bend loss, and beam splitting can be mapped from optical waveguide theory to spin guides, and hence to "spin splitters." Importantly, the spatial scale of applied control pulses is required to be large compared to the interspin spacing, thereby allowing the design of scalable control architectures.

Influence of Device Geometry and Imperfections on the Interpretation of Transverse Magnetic Focusing Experiments.

Spatially separating electrons of different spins and efficiently generating spin currents are crucial steps towards building practical spintronics devices. Transverse magnetic focusing is a potential technique to accomplish both those tasks. In a material where there is significant Rashba spin-orbit interaction, electrons of different spins will traverse different paths in the presence of an external magnetic field. Experiments have demonstrated the viability of this technique by measuring conductance spectra that indicate the separation of spin-up and spin-down electrons. However the effect that the geometry of the leads has on these measurements is not well understood. By simulating an InGaAs-based transverse magnetic focusing device, we show that the resolution of features in the conductance spectra is affected by the shape, separation and width of the leads. Furthermore, the number of subbands occupied by the electrons in the leads affects the ratio between the amplitudes of the spin-split peaks in the spectra. We simulated devices with random onsite potentials and observed that transverse magnetic focusing devices are sensitive to disorder. Ultimately we show that careful choice and characterisation of device geometry are crucial for correctly interpreting the results of transverse magnetic focusing experiments.