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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.

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...

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 (

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.

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.

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.

Electrically detected spin-Rabi beat oscillation of pairs of paramagnetic near interface states at the phosphorous doped (${10}^{16}$ cm${}^{\ensuremath{-}3}$) Si(111)/SiO${}_{2}$ interface is reported. Due to the $g$-factor anisotropy of the P${}_{b}$ center (a silicon surface dangling bond), one can tune intrapair Larmor frequency differences (Larmor separations) by orientation of the crystal with regard to an external magnetic field. Since Larmor separation governs the number of beating spin pairs, crystal orientation can control the beat current. This is used to identify spin states that are paired by mutual electronic transitions. The experiments confirm the presence of the previously reported ${}^{31}$P-P${}_{b}$ transition and provide direct experimental evidence of the previously hypothesized P${}_{b}$-${E}^{\ensuremath{'}}$ center (a near interface SiO${}_{2}$ bulk state) transition.

The ability to probe the spin properties of solid state systems electrically underlies a wide variety of emerging technology. Here, we extend electrical readout of the nuclear spin states of phosphorus donors in silicon to the coherent regime with modified Hahn echo sequences. We find that, whilst the nuclear spins have electrically detected phase coherence times exceeding 2 ms, they are nonetheless limited by the artificially shortened lifetime of the probing donor electron., 10 pages, 3 figures

Pulsed electrically detected magnetic resonance offers a unique avenue to distinguish between polaron-pair (PP) and triplet-exciton polaron (TEP) spin-dependent recombination, which control the conductivity and magnetoresistivity of organic semiconductors. Which of these two fundamental processes dominates depends on carrier balance: by injecting surplus electrons we show that both processes simultaneously impact the device conductivity. The two mechanisms are distinguished by the presence of a half-field resonance, indicative of TEP interactions, and transient spin beating, the signature of PPs. Coherent spin Rabi flopping in the half-field (triplet) channel is observed, demonstrating that the triplet exciton has an ensemble phase coherence time of at least 60 ns, offering insight into the effect of carrier correlations on spin dephasing.

We present a theoretical investigation of the effect of spin manipulation of polaron pairs PPs on the conductivity of organic semiconductors. Control of the PP spin state is achieved using pulsed electron-spin resonance. We demonstrate that manipulation of PPs will result in changes in the free-polaron density in the material, with corresponding changes in the conductivity due to the contribution of PP dissociation to the free-carrier density. The time-dependent form of this conductivity change following spin resonant perturbation is determined, and the effect of a number of experimental variables investigated. We find that, under certain conditions, these time-dependent current measurements reveal the dynamics of PP intersystem crossing. We compare these predictions with previous experiments on organic light-emitting diodes made of poly2-methoxy-5-2-ethyl-hexyloxy-1,4-phenylene vinylene and conclude that PP intersystem crossing times isc in this material may exceed 10 s at low temperatures.

31 P =1 0 15 cm �3 and 31 P =1 0 16 cm �3 at about liquid- 4 He temperatures T =5–1 5 K. Using pulsed electrically detected magnetic resonance pEDMR, spin-dependent transitions between the 31 P donor state and two distinguishable interface states are observed, namely, i Pb centers, which can be identified by their characteristic anisotropy, and ii a more isotropic center which is attributed to E defects of the SiO2 bulk close to the interface. Correlation measurements of the dynamics of spin-dependent recombination confirm that previously proposed transitions between 31 P and the interface defects take place. The influence of these electronic near-interface transitions on the 31 P donor spin-coherence time T2 as well as the donor spin-lattice relaxation time T1 is then investigated by comparison of spin Hahn-echo decay measurements obtained from conventional bulk sensitive pulsed electron paramagnetic resonance and surface sensitive pEDMR, as well as surface sensitive electrically detected inversion recovery experiments. The measurements reveal that the T2 times of both interface states and 31 P donor electron spins in proximity to them are consistently shorter than the T1 times, and both T2 and T1 times of the near-interface donors are reduced by several orders of magnitude from those in the bulk, at T 13 K. The T2 times of the 31 P donor electrons are in agreement with the prediction by de Sousa that they are limited by interface-defect induced field noise.

A study of charge-carrier recombination in intrinsic hydrogenated amorphous silicon (a-Si:H) is presented using pulsed electrically and pulsed optically detected magnetic-resonance spectroscopies in order to measure the influence of spin-dependent recombination on photoluminescence (PL) and photoconductivity (PC). The experiments show band tail state recombination influencing the PL but not the PC which constitutes geminate recombination of correlated charge carriers that do not contribute to charge transport. In contrast, nongeminate recombination through silicon dangling bonds is observed influencing both PL and PC. The experiments presented constitute a direct and unambiguous observation of geminate and nongeminate recombination in a-Si:H.

An experimental study on the nature of spin-dependent excess charge-carrier transitions at the interface between (111)-oriented phosphorous-doped ([P]≈1015 cm−3) crystalline silicon and silicon dioxide at high magnetic field (B0≈8.5 T) is presented. Electrically detected magnetic-resonance (EDMR) spectra of the hyperfine split 31P donor-electron transitions and paramagnetic interface defects were conducted at temperatures in the range of 3 K≤T≤12 K. The results at these previously unattained (for EDMR) magnetic-field strengths reveal the dominance of spin-dependent processes that differ from the previously well investigated recombination between the 31P donor and the Pb state, which dominates at low magnetic fields. While magnetic resonant current responses due to 31P and Pb states are still present, they do not correlate and only the Pb contribution can be associated with an interface process due to spin-dependent tunneling between energetically and physically adjacent Pb states. This work provides an experimental demonstration of spin-dependent tunneling between physically adjacent and identical electronic states as proposed by Kane Nature (London) 393 133 (1998)] for readout of donor qubits.