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The exciton dynamics of violanthrone-79 are investigated in solution and in the solidstate. In solution, the photo-prepared singlet is found to exhibit a strong ground-state bleachand stimulated emission feature, but when sensitized in its triplet state, exhibits only a narrowand weak ground-state bleach. As supported by density functional theory calculations,this is explained by the triplet state having absorptions in the same region, with a similaroscillator strength, as the ground state molecule. In solid films, the excited singlet isfound to survive only 100 ps, giving way to a long-lived transient absorption spectrum withcharacteristics reminiscent of the triplet in solution. This is interpreted in terms of singletfission in the solid film.

The operating temperature of PV modules affects the rate of degradation. We show the extent to which module operating temperature can be reduced by increasing the efficiency of the PV module via a tandem architecture or singlet Fission, the latter being of interest as a potentially endothermic process. PV modules that employ tetracene as a singlet fission material are found to be resilient against degradation since the degradation product is transparent to solar radiation.

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 solid-state 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 µT Hz−1/2 µm−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.

Modifying surfaces using free radical polymerization (FRP) offers a means to incorporate the diverse physicochemical properties of vinyl polymers onto new materials. Here, we harness the universal surface attachment of polydopamine (PDA) to "prime" a range of different surfaces for free radical polymer attachment, including glass, cotton, paper, sponge, and stainless steel. We show that the intrinsic free radical species present in PDA can serve as an anchor point for subsequent attachment of propagating vinyl polymer macroradicals through radical-radical coupling. Leveraging a straightforward, twofold soak-wash protocol, FRP over the PDA-functionalized surfaces results in covalent polymer attachment on both porous and nonporous substrates, imparting new properties to the functionalized materials, including enhanced hydrophobicity, fluorescence, or temperature responsiveness. Our strategy is then extended to covalently incorporate PDA nanoparticles into organo-/hydrogels via radical cross-linking, yielding tunable PDA-polymer composite networks. The propensity of PDA free radicals to quench FRP is studied using in situ

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 thermalization 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 categorize these attempts in order to assess the state of the field and identify the most promising avenues of future research and development.

Devices that exploit the quantum properties of materials are widespread, with quantum information processors and quantum sensors showing significant progress. Organic materials 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 moving 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 2D map of a hyperfine spin property-the Overhauser field-in traditional organic light-emitting diodes (OLEDs). Intra-device variabilities are found to exceed ≈30% while spatially correlated behavior is exhibited on lengths beyond 7 µm, similar in size to pixels in state-of-the-art active-matrix OLED arrays, which has implications for the reproducibility and integration of organic quantum devices.

Most of the reported 2D Ruddlesden-Popper (RP) lead halide perovskites with the general formula of A

Photon upconversion is a process that creates high-energy photons under low photon energy excitation. The effect of molecular geometry on the triplet fusion upconversion process has been investigat...

Molecular chirality can be exploited as a sensitive reporter of the nature of intra- and interchromophore interactions in π-conjugated systems. In this report, we designed an intramolecular singlet fission (iSF)-based pentacene dimer with an axially chiral binaphthyl bridge (2,2'-(2,2'-dimethoxy-[1,1'-binaphthalene]-3,3'-diyl) n-octyl-di-isopropyl silylethynyl dipentacene, BNBP) to utilize its chiroptical response as a marker of iSF chromophore-bridge-chromophore (SFC-β-SFC) interactions. The axial chirality of the bridge enforces significant one-handed excitonic coupling of the pentacene monomer units; as such, BNBP exhibits significant chiroptical response in the ground and excited states. We analyzed the chiroptical response of BNBP using the exciton coupling method and quadratic response density functional theory calculations to reveal that higher energy singlet transitions in BNBP involve significant delocalization of the electronic density on the bridging binaphthyl group. Our results highlight the promising application of chiroptical techniques to investigate the nature of SFC-β-SFC interactions that impact singlet fission dynamics.

Spin is a quantum property fundamental to the charge-light conversion process in optoelectronic devices. Organic materials offer unique opportunities to exploit spin due to their long coherence and lifetimes. The hyperfine interaction, which dominates the spin-dependent recombination processes of these materials, can be chemically tuned on a molecular level while retaining the large-scale fabrication techniques of those materials. To date, this property has been treated monolithically, characterized by a single value across a device. We utilize optical microscopy to spatially resolve the magnetoluminescence effect of an OLED and show the intra-device variation of this spin property reaches nearly 30%. We explore how the variation of this property changes with the operating bias to probe the underlying spin physics and show that these molecular-scale interactions are spatially correlated microscopically over the device.

The exciton dynamics of violanthrone-79 are investigated in solution and in the solidstate. In solution, the photo-prepared singlet is found to exhibit a strong ground-state bleachand stimulated emission feature, but when sensitized in its triplet state, exhibits only a narrowand weak ground-state bleach. As supported by density functional theory calculations,this is explained by the triplet state having absorptions in the same region, with a similaroscillator strength, as the ground state molecule. In solid films, the excited singlet isfound to survive only 100 ps, giving way to a long-lived transient absorption spectrum withcharacteristics reminiscent of the triplet in solution. This is interpreted in terms of singletfission in the solid film.

Spins in the ``semiconductor vacuum'' of silicon-28 ($^{28}\mathrm{Si}$) are suitable qubit candidates due to their long coherence times. An isotopically purified substrate or epilayer of $^{28}\mathrm{Si}$ is required to limit the decoherence pathway caused by magnetic perturbations from surrounding $^{29}\mathrm{Si}$ nuclear spins ($I=1/2$), present in natural Si ($^{\text{nat}}\mathrm{Si}$) at an abundance of 4.67%. We isotopically enrich surface layers of $^{\text{nat}}\mathrm{Si}$ by sputtering using high fluence ${}^{28}{\text{Si}}^{\ensuremath{-}}$ implantation. Phosphorus (P) donors implanted into one such $^{28}\mathrm{Si}$ layer with $\ensuremath{\sim}3000$ ppm $^{29}\mathrm{Si}$, produced by implanting 30 keV ${}^{28}{\text{Si}}^{\ensuremath{-}}$ ions at a fluence of $4\ifmmode\times\else\texttimes\fi{}{10}^{18}\phantom{\rule{4pt}{0ex}}{\mathrm{cm}}^{\ensuremath{-}2}$, were measured with pulsed electron spin resonance, confirming successful donor activation upon annealing. The monoexponential decay of the Hahn echo signal indicates a depletion of $^{29}\mathrm{Si}$. A coherence time of ${T}_{2}=285\ifmmode\pm\else\textpm\fi{}14\phantom{\rule{4pt}{0ex}}\ensuremath{\mu}\mathrm{s}$ is extracted, which is longer than that obtained in ${}^{\text{nat}}\text{Si}$ for similar doping concentrations and can be increased by reducing the P concentration in the future. Guided by simulations, the isotopic enrichment was improved by employing one-for-one ion sputtering using 45 keV ${}^{28}{\text{Si}}^{\ensuremath{-}}$ implanted with a fluence of $2.63\ifmmode\times\else\texttimes\fi{}{10}^{18}\phantom{\rule{4pt}{0ex}}{\mathrm{cm}}^{\ensuremath{-}2}$ into ${}^{\text{nat}}\text{Si}$. This resulted in an isotopically enriched surface layer $\ensuremath{\sim}100$ nm thick, suitable for providing a sufficient volume of $^{28}\mathrm{Si}$ for donor qubits implanted into the near-surface region. We observe a depletion of $^{29}\mathrm{Si}$ to 250 ppm as measured by secondary ion mass spectrometry. The impurity content and the crystallization kinetics via solid phase epitaxy are discussed. The $^{28}\mathrm{Si}$ layer is confirmed to be a single crystal using transmission electron microscopy. This method of Si isotopic enrichment shows promise for incorporation into the fabrication process flow of Si spin-qubit devices.

Troponin is the Ca2+ molecular switch that regulates striated muscle contraction. In the heart, troponin Ca2+ sensitivity is also modulated by the PKA-dependent phosphorylation of a unique 31-residue N-terminal extension region of the Troponin I subunit (NH2-TnI). However, the detailed mechanism for the propagation of the phosphorylation signal through Tn, which results in the enhancement of the myocardial relaxation rate, is difficult to examine within whole Tn. Several models exist for how phosphorylation modulates the troponin response in cardiac cells but these are mostly built from peptide-NMR studies and molecular dynamics simulations. Here we used a paramagnetic spin labeling approach to position and track the movement of the NH2-TnI region within whole Tn. Through paramagnetic relaxation enhancement (PRE)-NMR experiments, we show that the NH2-TnI region interacts with a broad surface area on the N-domain of the Troponin C subunit. This region includes the Ca2+ regulatory Site II and the TnI switch-binding site. Phosphorylation of the NH2-TnI both weakens and shifts this region to an adjacent site on TnC. Interspin EPR distances between NH2-TnI and TnC further reveal a phosphorylation induced re-orientation of the TnC N-domain under saturating Ca2+ conditions. We propose an allosteric model where phosphorylation triggered cooperative changes in both the interaction of the NH2-TnI region with TnC, and the re-orientation of the TnC interdomain orientation, together promote the release of the TnI switch-peptide. Enhancement of the myocardial relaxation rate then occurs. Knowledge of this unique role of phosphorylation in whole Tn is important for understanding pathological processes affecting the heart.

The absence of a crystal structure of the calcium free state of the cardiac isoform of the troponin complex has hindered our understanding of how the simple binding of Ca2+ triggers conformational changes in troponin which are then propagated to enable muscle contraction. Here we have used continuous wave (CW) and Double Electron-Electron Resonance (DEER) pulsed EPR spectroscopy to measure distances between TnI and TnC to track the movement of the functionally important regulatory 'switch' region of cardiac Tn. Spin labels were placed on the switch region of Troponin I and distances measured to Troponin C. Under conditions of high Ca2+, the interspin distances for one set (TnI151/TnC84) were 'short' (9-10A) with narrow distance distribution widths (3-8A) indicating the close interaction of the switch region with the N-lobe of TnC. Additional spin populations representative of longer interspin distances were detected by DEER. These longer distance populations, which were ∼16-19A longer than the short distance populations, possessed notably broader distance distribution widths (14-29A). Upon Ca2+ removal, the interspin population shifted toward the longer distances, indicating the release of the switch region from TnC and an overall increase in disorder for this region. Together, our results suggest that under conditions of low Ca2+, the close proximity of the TnI switch region to TnC in the cardiac isoform is necessary for promoting the interaction between the regulatory switch helix with the N-lobe of cardiac Troponin C, which, unlike the skeletal isoform, is largely in a closed conformation.

Nanodiamond is poised to become an attractive material for hyperpolarized $^{13}\mathrm{C}$ magnetic resonance imaging if large nuclear polarizations can be achieved without the accompanying rapid spin-relaxation driven by paramagnetic species. Here we report enhanced and long-lived $^{13}\mathrm{C}$ polarization in synthetic nanodiamonds tailored by acid-cleaning and air-oxidation protocols. Our results separate the contributions of different paramagnetic species on the polarization behavior, identifying the importance of substitutional nitrogen defect centers in the nanodiamond core. These results are likely of use in the development of nanodiamond-based imaging agents with size distributions of relevance for examining biological processes.

The bismuth (Bi) substitutional donor in silicon (Si) is an attractive qubit candidate for quantum computing proposals due to its large Hilbert space, clock transitions, and potential to couple to superconducting flux qubits. Single-qubit control, coupling, and readout by surface nanocircuitry requires a Bi depth of ∼20 nm in Si. This can be achieved using ion implantation of ∼25 keV Bi. This work explores the activation properties of Bi implanted at 26 keV with fluences of 1×1014 and 6×1012cm-2 into both crystalline and preamorphized Si. The Bi electrical activation yield was measured over a broad range of annealing conditions using resistivity and Hall effect measurements, enabling optimal annealing strategies to be proposed for the different implant parameters. For the high and low fluences, the maximum Bi activation yields achieved were 64% and 46%, respectively. Above a critical thermal budget, a substantial fraction of Bi forms electrically inactive complexes in the high fluence sample only. The substitutional fraction and diffusion of high fluence Bi was quantified, with diffusion coefficients D0=4.0±0.5 and 7.5±0.5cm2s-1 found for implantation into crystalline and preamorphized Si, respectively, using Rutherford backscattering spectrometry. To demonstrate the successful activation and quantum control of near-surface implanted Bi, the full hyperfine spectrum of these donors is obtained using continuous-wave electron spin resonance at 25 K, supporting the suitability for Bi donor qubits.

This paper reports on the execution and results of an interdisciplinary design project using advanced luminescent solar concentrator PV (LSC PV) technologies in new contexts of use such as the built environment, mobility and consumer products. In the past years LSC PV technologies have been rapidly maturing showing increasing efficiencies up to 10% with high expectations regarding further improvements at low costs. In this context in 2019 a summer school of one week took place aiming at optimally combining design features of LSC PV devices and further enhancements of their performance by scientific research. This design-driven project resulted in several interesting new LSC PV applications which are presented in this paper.

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., Comment: Supplemental Material available via email

Singlet fission, in which two triplet excitons are generated from a single absorbed photon, is a key third-generation solar cell concept. Conservation of angular momentum requires that singlet fission populates correlated multiexciton states, which can subsequently dissociate to generate free triplets. However, little is known about electronic and spin correlations in these systems since, due to its typically short lifetime, the multiexciton state is challenging to isolate and study. Here, we use bridged pentacene dimers, which undergo intramolecular singlet fission while isolated in solution and in solid matrices, as a unimolecular model system that can trap long-lived multiexciton states. We combine transient absorption and time-resolved electron spin resonance spectroscopies to show that spin correlations in the multiexciton state persist for hundreds of nanoseconds. Furthermore, we confirm long-standing predictions that singlet fission produces triplet pair states of quintet character. We compare two different pentacene–bridge–pentacene chromophores, systematically tuning the coupling between the pentacenes to understand how differences in molecular structure affect the population and dissociation of multiexciton quintet states. Experiments show how molecular structure affects the interaction and dynamics of the triplet exciton pairs produced when an excited singlet exciton decays via singlet fission — a process that could be harnessed for optoelectronic applications.

Singlet fission, an exciton multiplication process, can augment existing solar cell technologies. We explore the current challenges facing the research field and how optical and magnetic resonance spectroscopies can help identify promising materials.

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., Comment: 7 pages, 8 figures, typos corrected

Singlet fission—that is, the generation of two triplets from a lone singlet state—has recently resurfaced as a promising process for the generation of multiexcitons in organic systems. Although advances in this area have led to the discovery of modular classes of chromophores, controlling the fate of the multiexciton states has been a major challenge; for example, promoting fast multiexciton generation while maintaining long triplet lifetimes. Unravelling the dynamical evolution of the spin- and energy conversion processes from the transition of singlet excitons to correlated triplet pairs and individual triplet excitons is necessary to design materials that are optimized for translational technologies. Here, we engineer molecules featuring a discrete energy gradient that promotes the migration of strongly coupled triplet pairs to a spatially separated, weakly coupled state that readily dissociates into free triplets. This ’energy cleft’ concept allows us to combine the amplification and migration processes within a single molecule, with rapid dissociation of tightly bound triplet pairs into individual triplets that exhibit lifetimes of ~20 µs. Although they are synthetically tunable, organic molecules that undergo singlet fission (the generation of two excitons from one photon) have not demonstrated the excited-state properties necessary to improve optoelectronic devices. Now, a general ‘energy cleft’ molecular design scheme has been demonstrated that enables rapid generation and long lifetimes of multiple triplet excitons that are for device applications.

We report the observation of singlet fission in aqueous suspensions of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-Pn) nanoparticles (NPs) synthesized using the reprecipitation method. By altering the synthesis conditions we are able to fabricate NPs which evolve from a system of poorly coupled to highly coupled chromophores. This morphological evolution can also be suppressed for a period of several months. Absorption spectra confirm that the particles evolve over time, displaying increased intermolecular interaction, if the initial reaction conditions seeded a polycrystalline sample. We correlate these differences in morphologies to different rates of singlet state decay, where higher intermolecular interaction drives a more rapid rate of decay. Ultrafast time-resolved photoluminescence spectroscopy confirms a short first excited singlet state lifetime (

Pulsed electrically and optically-detected magnetic resonance are extremely sensitive to changes in the permutation symmetry of weakly-coupled spin pairs, and are well-suited for investigating devices with a small number of spins. However, the change in observable from conventional electron spin resonance modifies the results of standard inductively-detected pulse sequences which are routinely used to obtain phase coherence and lifetimes. Whilst these effects have been discussed for single-pulse experiments, their role in multi-pulse sequences is less clear. Here, we investigate this effect in Hahn echo and inversion-recovery sequences, and show a second set of narrower echoes are produced that distort measurement outcomes. We demonstrate that phase cycling is able to deconvolve the additional echo signals, allowing spin relaxation times to be reliably extracted.

Photochemical upconversion via triplet-triplet annihilation is a promising technology for improving the efficiency of photovoltaic devices. Previous studies have shown that the efficiency of upconversion depends largely on two rate constants intrinsic to the emitting species. Here, we report that one of these rate constants can be altered by deuteration, leading to enhanced upconversion efficiency. For perylene, deuteration decreases the first order decay rate constant by 16 ± 9% at 298 K, which increases the linear upconversion response by 45 ± 21% in the low excitation regime.

Despite the promise of photochemical upconversion as a means to extend the light-harvesting capabilities of a range of photovoltaic solar energy conversion devices, it remains a challenge to create efficient, solid-state upconverting materials. Until now, a material has yet to be found which is as efficient as a liquid composition. Here, a gelated photochemical upconversion material is reported with a performance indistinguishable from an otherwise identical liquid composition. The sensitizer phosphorescence lifetime, Stern–Volmer quenching constants and upconversion performance (6% under one-sun illumination) were all found to be unchanged in a quasi-solid gelated sample when compared to the liquid sample. The result paves the way to a new family of efficient photochemical upconversion materials comprised of macroscopically solid, but microscopically liquid gel, for application in photovoltaics and photocatalytic water-splitting.

A method for investigating recombination dynamics of photo-induced charge carriers in thin film semiconductors, specifically in photovoltaic materials such as organo-lead halide perovskites is presented. The perovskite film thickness and absorption coefficient are initially characterized by profilometry and UV-VIS absorption spectroscopy. Calibration of both laser power and cavity sensitivity is described in detail. A protocol for performing Flash-photolysis Time Resolved Microwave Conductivity (TRMC) experiments, a non-contact method of determining the conductivity of a material, is presented. A process for identifying the real and imaginary components of the complex conductivity by performing TRMC as a function of microwave frequency is given. Charge carrier dynamics are determined under different excitation regimes (including both power and wavelength). Techniques for distinguishing between direct and trap-mediated decay processes are presented and discussed. Results are modelled and interpreted with reference to a general kinetic model of photoinduced charge carriers in a semiconductor. The techniques described are applicable to a wide range of optoelectronic materials, including organic and inorganic photovoltaic materials, nanoparticles, and conducting/semiconducting thin films.

Quantum computers hold the promise of massive performance enhancements across a range of applications, from cryptography and databases to revolutionary scientific simulation tools. Such computers would make use of the same quantum mechanical phenomena that pose limitations on the continued shrinking of conventional information processing devices. Many of the key requirements for quantum computing differ markedly from those of conventional computers. However, silicon, which plays a central part in conventional information processing, has many properties that make it a superb platform around which to build a quantum computer.

Elucidating the decay mechanisms of photoexcited charge carriers is key to improving the efficiency of solar cells based on organo-lead halide perovskites. Here we investigate the spectral dependence (via above-, inter- and sub-bandgap optical excitations) of direct and trap-mediated decay processes in CH3NH3PbI3 using time resolved microwave conductivity (TRMC). We find that the total end-of-pulse mobility is excitation wavelength dependent - the mobility is maximized (172 cm(2) V(-1) s(-1)) when charge carriers are excited by near bandgap light (780 nm) in the low charge carrier density regime (10(9) photons per cm(2)), and is lower for above- and sub-bandgap excitations. Direct recombination is found to occur on the 100-400 ns timescale across excitation wavelengths near and above the bandgap, whereas indirect recombination processes displayed distinct behaviour following above- and sub-bandgap excitations, suggesting the influence of different trap distributions on recombination dynamics.

Spin Control Controlling and manipulating the spin of an electron is a central requirement for applications in spintronics. Some of the challenges researchers are facing include efficient creation of spin currents, minimization of Joule heating, and extending the lifetime of electronic spins, which is especially important for quantum information applications. Costache and Valenzuela (p. 1645 ) address the first challenge by designing and fabricating an efficient and simple superconducting-based single-electron transistor that can produce spin current with controlled flow. Key to the design is asymmetric tunneling, which leads to a ratchet effect (or diode-like behavior), allowing the separation of up and down spins. Jonietz et al. (p. 1648 ) use electric currents five orders of magnitude smaller than those used previously in nanostructures to manipulate magnetization in a bulk material, MnSi, pointing the way toward decreased Joule heating in spintronic devices. This so-called spin-torque effect causes the rotation of the skyrmion lattice of spins, characteristic of MnSi, which is detected by neutron scattering. Finally, McCamey et al. (p. 1652 ) extend the short lifetime of an electronic spin of a phosphorous dopant by mapping it onto the much longer lived nuclear spin of the atom. Mapping the nuclear spin back onto the electronic spin allows production of a spin memory with a storage time exceeding 100s, which should prove useful for future practical applications.

Carbon-based materials have an intrinsically weak spin-orbit coupling which imposes spin selection rules on many electronic transitions. The spin degree of freedom of electrons and nuclei can therefore play a crucial role in the electronic and optical properties of these materials. Spin-selection rules can be studied via magnetic resonance techniques such as electron-spin resonance and optically detected magnetic resonance as well as electrically detected magnetic resonance (EDMR). The latter has progressed in recent years to a degree where the observation of coherent spin motion via current detection has become possible, providing experimental access to many new insights into the role that paramagnetic centers play for conductivity and photoconductivity. While mostly applied to inorganic semiconductor materials such as silicon, this new, often called pulsed-(p) EDMR spectroscopy, has much potential for organic (carbon-based) semiconductors. In this study, progress on the development of pEDMR spectroscopy on carbon-based materials is reviewed. Insights into materials properties that can be gained from pEDMR experiments are explained and limitations are discussed. Experimental data on radiative polaron-pair recombination in poly[2-methoxy-5-(20-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) organic light emitting diodes (OLEDs) are shown, revealing that under operating conditions the driving current of the device can be modulated by spin-Rabi nutation of the polaron spin within the charge carrier pairs. From this experimental data it becomes clear that for polaron pairs, the precursor states during exciton formation, exchange interaction is not the predominant influence on the observed pEDMR spectra.

Triplet-triplet annihilation allows two low-energy photons to be upconverted into a single high-energy photon. By essentially engineering the solar spectrum, this allows solar cells to be made more efficient and even exceed the Shockley-Quiesser limit. Unfortunately, optimizing the reaction pathway is difficult, especially with limited access to the microscopic time scales and states involved in the process. Optical measurements can provide detailed information: triplet-triplet annihilation is intrinsically spin dependent and exhibits substantial magnetoluminescence in the presence of a static magnetic field. Pulsed optically detected magnetic resonance is especially suitable, since it combines high spin sensitivity with coherent manipulation. In this paper, we develop a time-domain theory of triplet-triplet annihilation for complexes with arbitrary spin-spin coupling. We identify unique ``Rabi fingerprints'' for each coupling regime and show that this can be used to characterize the microscopic Hamiltonian.

Molecular materials afford abundant flexibility in the tunability of physical and electronic properties. As such, they are ideally suited to engineering low-cost, flexible, light-harvesting materials that break away from the single-threshold paradigm. Single-threshold solar cells are capable of harvesting a maximum of 33.7% of incident sunlight, whereas two-threshold cells are capable of energy harvesting efficiencies exceeding 45%. In this Perspective, we provide the theoretical background with which upper efficiency limits for various multiple-threshold solar cell architectures may be calculated and review and discuss various reports that employ processes such as triplet–triplet annihilation and singlet fission in multiple-threshold devices comprised of molecular materials.

Quantifying the spin-spin interactions which influence electronic transitions in organic semiconductors is crucial for understanding their magneto-optoelectronic properties. By combining a theoretical model for three spin interactions in the coherent regime with pulsed electrically detected magnetic resonance experiments on $\ensuremath{\pi}$-conjugated polymer diodes (poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene]), we quantify the spin coupling within complexes comprising three spin-1/2 particles. We determine that these particles form triplet-exciton/polaron pairs, where the polaron-exciton exchange is over five orders of magnitude weaker ($l170$ MHz) than that within the exciton. This approach provides a direct spectroscopic approach for distinguishing between coupling regimes, and to test hypotheses relating microscopic properties to bulk characteristics of organic electronic devices.

Several microscopic pathways have been proposed to explain the large magnetic effects observed in organic semiconductors; however, it is difficult to identify and characterize the microscopic process which actually influences the overall magnetic field response in a particular instance. Pulsed electrically detected magnetic resonance provides an ideal platform for this task as it intrinsically monitors the charge carriers of interest and provides dynamical information which is inaccessible through conventional magnetoconductance measurements. Here we develop a general time-domain theory to describe the spin-dependent recombination of exciton-polaron complexes following the coherent manipulation of paramagnetic centers through electron paramagnetic resonance. A general Hamiltonian is treated, and it is shown that the transition frequencies and resonance positions of the exciton-polaron complex can be used to estimate interspecies coupling. This work also provides a general formalism for analyzing multipulse experiments which can be used to extract relaxation and transport rates.

Using silicon MOSFETs with thin (5nm) thermally grown SiO2 gate dielectrics, we characterize the density of electrically active traps at low-temperature after 16keV phosphorus ion-implantation through the oxide. We find that, after rapid thermal annealing at 1000oC for 5 seconds, each implanted P ion contributes an additional 0.08 plus/minus 0.03 electrically active traps, whilst no increase in the number of traps is seen for comparable silicon implants. This result shows that the additional traps are ionized P donors, and not damage due to the implantation process. We also find, using the room temperature threshold voltage shift, that the electrical activation of donors at an implant density of 2x10^12 cm^-2 is ~100%.

Electrically detected magnetic resonance is a sensitive technique for studying electron spins bound to phosphorus atoms in silicon. Using a high magnetic field of 8.6 T increases this sensitivity by accessing a mechanism for spin-to-charge conversion which is different to that in the more commonly used magnetic field of ∼0.33 T. The higher-field regime benefits from a long spin coherence time of over 100 µs because the phosphorus spins that are detected are not coupled to dangling-bonds. Additionally, the high field permits the spin qubits to reach an equilibrium polarization of over 95% at a temperature of 2.8 K. We demonstrate electrically detected Rabi oscillations of these electron spins in the high-field regime. The Rabi frequency is proportional to the square root of the excitation power as expected.

An appealing avenue for organic spintronics lies in direct coherent control of the spin population by means of pulsed electron spin resonance techniques. Whereas previous work has focused on the electrical detection of coherent spin dynamics, we demonstrate here the equivalence of an all-optical approach, allowing us to explore the influence of materials chemistry on the spin dynamics. We show that deuteration of the conjugated polymer side groups weakens the local hyperfine fields experienced by electron-hole pairs, thereby lowering the threshold for the resonant radiation intensity at which coherent coupling and spin beating occur. The technique is exquisitively sensitive to previously obscured material properties and offers a route to quantifying and tuning hyperfine fields in organic semiconductors.

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 parameters, such as modulation frequency, microwave power, and temperature; (3) radiative and nonradiative recombination cannot be distinguished due to the observed signs of cwODMR and cwEDMR experiments.

Magnetic field sensors based on organic thin-film materials have attracted considerable interest in recent years as they can be manufactured at very low cost and on flexible substrates. However, the technological relevance of such magnetoresistive sensors is limited owing to their narrow magnetic field ranges (∼30 mT) and the continuous calibration required to compensate temperature fluctuations and material degradation. Conversely, magnetic resonance (MR)-based sensors, which utilize fundamental physical relationships for extremely precise measurements of fields, are usually large and expensive. Here we demonstrate an organic magnetic resonance-based magnetometer, employing spin-dependent electronic transitions in an organic diode, which combines the low-cost thin-film fabrication and integration properties of organic electronics with the precision of a MR-based sensor. We show that the device never requires calibration, operates over large temperature and magnetic field ranges, is robust against materials degradation and allows for absolute sensitivities of, Magnetometers based on organic magnetoresistance are limited by narrow sensitivity ranges, degradation and temperature fluctuations. Baker et al. demonstrate a magnetic resonance-based organic thin film magnetometer, which overcomes these drawbacks by exploiting the metrological nature of magnetic resonance.

Vascular dysfunction that accompanies obesity and insulin resistance may be mediated by lipid metabolites. We sought to determine if vascular ceramide leads to arterial dysfunction and to elucidate the underlying mechanisms. Pharmacological inhibition of de novo ceramide synthesis, using the Ser palmitoyl transferase inhibitor myriocin, and heterozygous deletion of dihydroceramide desaturase prevented vascular dysfunction and hypertension in mice after high-fat feeding. These findings were recapitulated in isolated arteries in vitro, confirming that ceramide impairs endothelium-dependent vasorelaxation in a tissue-autonomous manner. Studies in endothelial cells reveal that de novo ceramide biosynthesis induced protein phosphatase 2A (PP2A) association directly with the endothelial nitric oxide synthase (eNOS)/Akt/Hsp90 complex that was concurrent with decreased basal and agonist-stimulated eNOS phosphorylation. PP2A attenuates eNOS phosphorylation by preventing phosphorylation of the pool of Akt that colocalizes with eNOS and by dephosphorylating eNOS. Ceramide decreased the association between PP2A and the predominantly cytosolic inhibitor 2 of PP2A. We conclude that ceramide mediates obesity-related vascular dysfunction by a mechanism that involves PP2A-mediated disruption of the eNOS/Akt/Hsp90 signaling complex. These results provide important insight into a pathway that represents a novel target for reversing obesity-related vascular dysfunction.