Discrimination Between Spin-Dependent Charge Transport and Spin-Dependent Recombination in Π-Conjugated Polymers by Correlated Current and Electroluminescence-Detected Magnetic Resonance

Spin-dependent processes play a crucial role in organic electronic devices. Spin coherence can give rise to spin mixing due to a number of processes such as hyperfine coupling, and leads to a range of magnetic field effects. However, it is not straightforward to differentiate between pure single-carrier spin-dependent transport processes which control the current and therefore the electroluminescence, and spin-dependent electron-hole recombination which determines the electroluminescence yield and in turn modulates the current. We therefore investigate the correlation between the dynamics of spin-dependent electric current and spin-dependent electroluminescence in two derivatives of the conjugated polymer poly(phenylene-vinylene) using simultaneously measured pulsed electrically detected (pEDMR) and optically detected (pODMR) magnetic resonance spectroscopy. This experimental approach requires careful analysis of the transient response functions under optical and electrical detection. At room temperature and under bipolar charge-carrier injection conditions, a correlation of the pEDMR and the pODMR signals is observed, consistent with the hypothesis that the recombination currents involve spin-dependent electronic transitions. This observation is inconsistent with the hypothesis that these signals are caused by spin-dependent charge-carrier transport. These results therefore provide no evidence that supports earlier claims that spin-dependent transport plays a role for room-temperature magnetoresistance effects. At low temperatures, however, the correlation between pEDMR and pODMR is weakened, demonstrating that more than one spin-dependent process influences the optoelectronic materials’ properties. This conclusion is consistent with prior studies of half-field resonances that were attributed to spin-dependent triplet exciton recombination, which becomes significant at low temperatures when the triplet lifetime increases

Temperature and current dependence of the magnetoresistive behavior of poly(styrene-sulfonate)-doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS)

We investigate the magnetic field effects in thin-film diodes made of the conducting polymer poly(styrene-sulfonate)-doped poly(3,4-ethylenedioxythiophene) as a function of temperature and electrical current. Magnetoresistance of these devices can be measured to high precision on two distinct magnetic field scales: <3 mT, where a pronounced nonmonotonic magnetoresistance response can be resolved, owing to weak hyperfine coupling, and at intermediate magnetic fields, ranging between 3 and 10 mT, where strong monotonic magnetoresistance is seen. The detailed examination of the magnetoresistance effects in both regimes allows one to scrutinize the accuracy of the underlying models for the behavior of these kinds of materials. (C) The Authors. Published by SPIE under a Creative Commons Attribution 3.0 Unported License

Separating hyperfine from spin-orbit interactions in organic semiconductors by multi-octave magnetic resonance using coplanar waveguide microresonators

Separating the influence of hyperfine from spin-orbit interactions in spin-dependent carrier recombination and dissociation processes necessitates magnetic resonance spectroscopy over a wide range of frequencies. We have designed compact and versatile coplanar waveguide resonators for continuous-wave electrically detected magnetic resonance, and tested these on organic light-emitting diodes. By exploiting both the fundamental and higher-harmonic modes of the resonators we cover almost five octaves in resonance frequency within a single setup. The measurements with a common pi-conjugated polymer as the active material reveal small but non-negligible effects of spin-orbit interactions, which give rise to a broadening of the magnetic resonance spectrum with increasing frequency

g-Factor Tuning and Manipulation of Spins by an Electric Current

We investigate the Zeeman splitting of two-dimensional electrons in an asymmetric silicon quantum well, by electron-spin-resonance (ESR) experiments. Applying a small dc current we observe a shift in the resonance field due to the additional current-induced Bychkov-Rashba (BR) type of spin-orbit (SO) field. This finding demonstrates SO coupling in the most straightforward way: in the presence of a transverse electric field the drift velocity of the carriers imposes an effective SO magnetic field. This effect allows selective tuning of the g-factor by an applied dc current. In addition, we show that an ac current may be used to induce spin resonance very efficiently.Comment: 4 pages, 4 figure

Nanoscopic Current Effects on Photovoltaics

Silicon heterojunction (SHJ) solar cells represent a promising technological approach toward higher photovoltaic efficiencies and lower fabrication cost. While the device physics of SHJ solar cells has 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 are 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 at room temperature, revealing the profound complexity of electronic SHJ interface processes. Using conduction atomic force microscopy, it is shown that the macroscopic current–voltage characteristics of SHJ solar cells are 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 local photovoltages (VOCloc) as high as 1.2 V (eVOCloc > EgapSi). This is not in violation of photovoltaic device physics but a consequence of the nature of nanometer-scale charge percolation pathways that originate from trap-assisted tunneling causing dark leakage current. We show that the broad distribution of nanoscopic 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

Floquet spin states in OLEDs

Electron and hole spins in organic light-emitting diodes constitute prototypical two-level systems for the exploration of the ultrastrong-drive regime of light-matter interactions. Floquet solutions to the time-dependent Hamiltonian of pairs of electron and hole spins reveal that, under non-perturbative resonant drive, when spin-Rabi frequencies become comparable to the Larmor frequencies, hybrid light-matter states emerge that enable dipole-forbidden multi-quantum transitions at integer and fractional g-factors. To probe these phenomena experimentally, we develop an electrically detected magnetic-resonance experiment supporting oscillating driving fields comparable in amplitude to the static field defining the Zeeman splitting; and an organic semiconductor characterized by minimal local hyperfine fields allowing the non-perturbative light-matter interactions to be resolved. The experimental confirmation of the predicted Floquet states under strong-drive conditions demonstrates the presence of hybrid light-matter spin excitations at room temperature. These dressed states are insensitive to power broadening, display Bloch-Siegert-like shifts, and are suggestive of long spin coherence times, implying potential applicability for quantum sensing

Perdeuteration of poly[2-methoxy-5-(2'- ethylhexyloxy)-1,4-phenylenevinylene] (d-MEH-PPV): control of microscopic charge-carrier spin–spin coupling and of magnetic-field effects in optoelectronic devices

Control of the effective local hyperfine fields in a conjugated polymer, poly[2-methoxy-5-(2 '-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), by isotopic engineering is reported. These fields, evident as a frequency-independent line broadening mechanism in electrically detected magnetic resonance (EDMR) spectroscopy, originate from the unresolved hyperfine coupling between the electronic spin of charge carrier pairs and the nuclear spins of surrounding hydrogen isotopes. The room temperature study of effects caused by complete deuteration of this polymer through magnetoresistance, magnetoelectroluminescence, coherent pulsed and multi-frequency EDMR, as well as inverse spin-Hall effect measurements, confirm the weak hyperfine broadening of charge-carrier magnetic resonance lines. As a consequence, we can resolve coherent charge-carrier spin-beating, allowing for direct measurements of the magnitude of electronic spin-spin interactions. In addition, the weak hyperfine coupling allows us to resolve substantial spin-orbit coupling effects in the EDMR spectra, even at low magnetic field strengths. These results illustrate the dramatic influence of hyperfine fields on the spin physics of organic light-emitting diode (OLED) materials at room temperature, and point to routes to reaching exotic ultra-strong resonant-drive regimes in the study of light-matter interactions