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Paramagnetic point defects in silicon provide qubits that could open up pathways towards silicon-technology based, low-cost, room-temperature (RT) quantum sensing. The silicon dangling bond (db) is a natural candidate, given its sub-nanometer localization and direct involvement in spin-dependent charge-carrier recombination, allowing for electrical spin readout. In crystalline silicon, however, rapid loss of db spin-coherence at RT due to free-electron trapping, strongly limits quantum applications. In this work, by combining density-functional theory and multifrequency (100 MHz-263 GHz) pulsed electrically detected magnetic resonance spectroscopy, we show that upon electron capture, dbs in a hydrogenated amorphous silicon matrix form metastable spin pairs in a well-defined quasi two-dimensional (2D) configuration. Although highly localized, these entangled spin pairs exhibit nearly vanishing intrinsic dipolar and exchange coupling. The formation of this magic-angle-like configuration involves a >0.3 eV energy relaxation of a trapped electron, stabilizing the pair. This extends RT spin coherence times into the microsecond range in silicon required for a future spin-based quantum sensing technology., Comment: Manuscript: 19 pages, 4 figures, Supporting Information: 22 pages, 5 figures, 1 table

We report the observation of a three-photon resonant transition of charge-carrier spins in an organic light-emitting diode using electrically detected magnetic resonance (EDMR) spectroscopy at room temperature. Under strong magnetic-resonant drive (drive field $B_1$ ~ static magnetic field $B_0$), a $B_0$-field swept EDMR line emerges when $B_0$ is approximately threefold the one-photon resonance field. Ratios of drive-induced shifts of this line to those of two- and one-photon shifts agree with analytical expressions derived from the Floquet Hamiltonian and confirm the nature of these three-photon transitions, enabling access of spin physics to a hitherto inaccessible domain of quantum mechanics., Comment: 32 pages, 18 figures

We present Floquet theory-based predictions and electrically detected magnetic resonance (EDMR) experiments scrutinizing the nature of two-photon magnetic resonance shifts of charge-carrier spin states in the perdeuterated $\pi$-conjugated polymer poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylene vinylene] (d-MEH-PPV) under strong magnetic resonant drive conditions (radiation amplitude $B_1$ ~ Zeeman field $B_0$). Numerical calculations show that the two-photon resonance shift with power is nearly drive-helicity independent. This is in contrast to the one-photon Bloch-Siegert shift that only occurs under non-circularly polarized strong drive conditions. We therefore treated the Floquet Hamiltonian analytically under arbitrary amplitudes of the co- and counter-rotating components of the radiation field to gain insight into the nature of the helicity dependence of multi-photon resonance shifts. In addition, we tested Floquet-theory predictions experimentally by comparing one-photon and two-photon charge-carrier spin resonance shifts observed through room-temperature EDMR experiments on d-MEH-PPV-based bipolar injection devices [i.e., organic light emitting diode structures (OLEDs)]. We found that under the experimental conditions of strong, linearly polarized drive, our observations consistently agree with theory, irrespective of the magnitude of $B_1$, and therefore underscore the robustness of Floquet theory in predicting nonlinear magnetic resonance behaviors., Comment: 22 pages, 5 figures

We report measurements of room-temperature spin-relaxation times $T_1$ and $T_2$ of charge-carrier spins in a $\pi$-conjugated polymer thin film under bipolar injection and low ($1\mbox{ mT}\lesssim B_0\lesssim 10\mbox{ mT}$) static magnetic fields, using electrically detected magnetic resonant Hahn-echo and inversion-recovery pulse sequences. The experiments confirm the correlation between the magnetic-field sensitive observables of radical-pair processes, which include both the spin-dependent recombination currents in organic semiconductors and the associated spin-relaxation times when random local hyperfine fields and external magnetic fields compete in magnitude. Whereas a striking field dependence of spin-lattice relaxation exists in the low-field regime, the apparent spin decoherence time remains field independent as the distinction between the two is lifted at low fields., Comment: Manuscript: 14 pages, 4 figures; Supplemental Material: 13 pages, 7 figures

We have experimentally tested the hypothesis of free charge carrier mediated spin-transport in the small molecule organic semiconductor Alq3 at room temperature. A spin current was pumped into this material by pulsed ferromagnetic resonance of an adjacent NiFe layer, while a charge current resulting from this spin current via the inverse spin-Hall effect (ISHE) was detected in a Pt layer adjacent on the other side of the Alq3 layer, confirming a pure spin current through the Alq3 layer. Charge carrier spin states in Alq3, were then randomized by simultaneous application of electron paramagnetic resonance (EPR). No influence of the EPR excitation on the ISHE current was found, implying that spin-transport is not mediated by free charge-carriers in Alq3., Comment: Manuscript: 11 pages, 3 figures; Supplemental Material: 5 pages, 3 figures

Weakly spin-orbit coupled electron and hole spins in organic light-emitting diodes (OLEDs) constitute near-perfect two-level systems to explore the interaction of light and matter in the ultrastrong-drive regime. Under such highly non-perturbative conditions, the frequency at which the spin oscillates between states, the Rabi frequency, becomes comparable to its natural resonance frequency, the Larmor frequency. For such conditions, we develop an intuitive understanding of the emergence of hybrid light-matter states, illustrating how dipole-forbidden multiple-quantum transitions at integer and fractional g-factors arise. A rigorous theoretical treatment of the phenomena comes from a Floquet-style solution to the time-dependent Hamiltonian of the electron-hole spin pair under resonant drive. To probe these phenomena experimentally requires both the development of a magnetic-resonance setup capable of supporting oscillating driving fields comparable in magnitude to the static field defining the Zeeman splitting; and an organic semiconductor which is characterized by minimal inhomogeneous broadening so as to allow the non-linear light-matter interactions to be resolved. The predicted exotic resonance features associated with the Floquet states are indeed found experimentally in measurements of spin-dependent steady-state OLED current under resonant drive, demonstrating that complex hybrid light-matter spin excitations can be formed and probed at room temperature. The spin-Dicke state arising under strong drive is insensitive to power broadening so that the Bloch-Siegert shift of the resonance becomes apparent, implying long coherence times of the dressed spin state with potential applicability for quantum sensing., Comment: Manuscript: 26 pages, 3 figures; supplementary information: 28 pages, 7 figures

Silicon heterojunction (SHJ) solar cells represent a promising technological approach towards higher photovoltaics efficiencies and lower fabrication cost. While the device physics of SHJ solar cells have been studied extensively in the past, the ways in which nanoscopic electronic processes such as charge-carrier generation, recombination, trapping, and percolation affect SHJ device properties macroscopically have yet to be fully understood. We report the study of atomic scale current percolation at state-of-the-art a-Si:H/c-Si heterojunction solar cells under ambient operating conditions, revealing the profound complexity of electronic SHJ interface processes. Using conduction atomic force microscopy (cAFM), it is shown that the macroscopic current-voltage characteristics of SHJ solar cells is governed by the average of local nanometer-sized percolation pathways associated with bandtail states of the doped a-Si:H selective contact leading to above bandgap open circuit voltages ($V_{\mbox{OC}}$) as high as 1.2 V ($V_{\mbox{OC}}>e E_{\mbox{gap}}^{\mbox{Si}}$). This is not in violation of photovoltaic device physics but a consequence of the nature of nanometer-scale charge percolation pathways which originate from trap-assisted tunneling causing dark leakage current. We show that the broad distribution of local photovoltage is a direct consequence of randomly trapped charges at a-Si:H dangling bond defects which lead to strong local potential fluctuations and induce random telegraph noise of the dark current., Comment: Manuscript: 27 pages, 3 figures; Supplementary Information: 19 pages, 9 figures

We have studied the nature and dynamics of spin-dependent charge carrier recombination in Tris(8-hydroxyquinolinato) aluminum (Alq$_3$) films in light emitting diodes at room temperature using continuous wave and pulsed electrically detected magnetic resonance (EDMR) spectroscopy. We found that the EDMR signal is dominated by an electron-hole recombination process, and another, weaker EDMR signal whose fundamental nature was investigated. From the pulsed EDMR measurements we obtained a carrier spin relaxation time, $T_2 = 45\pm 25$ ns which is much shorter than $T_2$ in conjugated polymers, but relatively long for a molecule containing elements with high atomic number. Using multi-frequency continuous wave EDMR spectroscopy, we obtained the local hyperfine field distributions for electrons and holes, as well as their respective spin-orbit coupling induced g-factor and g-strain values., Comment: 18 pages, 5 figures

Electric fields are central to the operation of optoelectronic devices based on conjugated polymers since they drive the recombination of electrons and holes to excitons in organic light-emitting diodes but are also responsible for the dissociation of excitons in solar cells. One way to track the microscopic effect of electric fields on charge carriers formed under illumination of a polymer film is to exploit the fluorescence arising from delayed recombination of carrier pairs, a process which is fundamentally spin dependent. Such spin-dependent recombination can be probed directly in fluorescence, by optically detected magnetic resonance (ODMR). Depending on the relative orientation, an electric field may either dissociate or stabilize an electron-hole carrier pair. We find that the ODMR signal in a polymer film is quenched in an electric field, but that, at fields exceeding 1 MV/cm, this quenching saturates. This finding contrasts the complete ODMR suppression that was previously observed in polymeric photodiodes, indicating that exciton-charge interactions---analogous to Auger recombination in crystalline semiconductors---may constitute the dominant carrier-pair dissociation process in organic electronics., Comment: 25 pages, 3 figures

The magneto-electronic field effects in organic semiconductors at high magnetic fields are described by field-dependent mixing between singlet and triplet states of weakly bound charge carrier pairs due to small differences in their Land\'e g-factors that arise from the weak spin-orbit coupling in the material. In this work, we corroborate theoretical models for the high-field magnetoresistance of organic semiconductors, in particular of diodes made of the conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS) at low temperatures, by conducting magnetoresistance measurements along with multi-frequency continuous-wave electrically detected magnetic resonance experiments. The measurements were performed on identical devices under similar conditions in order to independently assess the magnetic field-dependent spin-mixing mechanism, the so-called {\Delta}g mechanism, which originates from differences in the charge-carrier g-factors induced by spin-orbit coupling., Comment: 12 pages, 3 figures

Using electrically detected magnetic resonance spectroscopy, we demonstrate that doping the conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS) with ethylene glycol allows for the control of effective local charge carrier hyperfine fields through motional narrowing. These results suggest that doping of organic semiconductors could enable the tuning of macroscopic material properties dependent on hyperfine fields such as magnetoresistance, the magneto-optical responses and spin-diffusion., Comment: 5 pages, 4 figures, supplemental material

We measure electrically detected magnetic resonance (EDMR) on organic light-emitting diodes (OLEDs) made of the polymer poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) at room temperature and high magnetic fields, where spectral broadening of the resonance due to spin-orbit coupling (SOC) exceeds that due to the local hyperfine fields. Density-functional-theory calculations on an open-shell model of the material reveal g-tensors of charge-carrier spins in the lowest unoccupied (electron) and highest occupied (hole) molecular orbitals. These tensors are used for simulations of magnetic resonance line-shapes. Besides providing the first quantification and direct observation of SOC effects on charge-carrier states in these weakly SO-coupled hydrocarbons, this procedure demonstrates that spin-related phenomena in these materials are fundamentally monomolecular in nature., Comment: 6 pages, 4 figures

We have studied the role of spin-dependent processes on conductivity in polyfluorene (PFO) thin films by conducting continuous wave (c.w.) electrically detected magnetic resonance (EDMR) spectroscopy at temperatures between 10 K and 293 K using microwave frequencies between about 100 MHz and 20 GHz as well as pulsed EDMR at X-band. Variable frequency EDMR allows us to establish the role of spin-orbit coupling in spin-dependent processes, pulsed EDMR probes coherent spin motion effects. We used PFO for this study in order to allow for the investigation of the effects of microscopic morphological ordering since this material can adopt two distinct intrachain morphologies: an amorphous (glassy) phase, and an ordered (beta) phase. In thin films of organic light-emitting diodes (OLEDs) the appearance of a particular phase can be controlled by deposition parameters, and is verified by electroluminescence spectroscopy. We conducted multi-frequency c.w. EDMR, electrically detected Rabi spinbeat experiments, Hahn-echo and inversion-recovery measurements. Coherent echo spectroscopy reveals electrically detected electron spin-echo envelope modulation (ESEEM) due to the precession of the carrier spins around the protons. Our results demonstrate that while conformational disorder can influence the observed EDMR signals, including the sign of the current changes on resonance as well as the magnitudes of local hyperfine fields and charge carrier spin-orbit interactions, it does not qualitatively affect the nature of spin-dependent transitions in this material. At 293 K and 10 K, polaron-pair recombination through weakly spin-spin coupled intermediate charge carrier pair states is dominant, while at low temperatures, additional signatures of spin-dependent charge transport through the interaction of polarons with triplet excitons are seen in the half-field resonance of a triplet spin-1 species., Comment: 27 pages, 2 tables, 11 figures, full abstract in article

The ESR response from highly metal-semiconductor(M-SC) separated SWCNTs for temperatures T between 0.39 and 200 K is characteristically different for the two systems. The signal originates from defect spins but interaction with free electrons leads to a larger line width for M tubes. The latter decreases with increasing T whereas it increases with T for SC tubes. The spins undergo a ferromagnetic phase transition below around 10 K. Indirect exchange is suggested to be responsible for the spin-spin interaction, supported by RKKY interaction in the case of M tubes. For SC tubes spin-lattice relaxation via an Orbach process is suggested to determine the line width.

We discuss the design and implementation of thin film superconducting coplanar waveguide micro- resonators for pulsed ESR experiments. The performance of the resonators with P doped Si epilayer samples is compared to waveguide resonators under equivalent conditions. The high achievable filling factor even for small sized samples and the relatively high Q-factor result in a sensitivity that is superior to that of conventional waveguide resonators, in particular to spins close to the sample surface. The peak microwave power is on the order of a few microwatts, which is compatible with measurements at ultra low temperatures. We also discuss the effect of the nonuniform microwave magnetic field on the Hahn echo power dependence.