arXiv subjects

J. M. Lupton

Publications and source records attributed to J. M. Lupton.

13 recordsLinked to original sources

arXiv2023

Three-photon electron spin resonances

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.

quant-ph↗

arXiv2023

Non-Bloch-Siegert-type power-induced shift of two-photon electron paramagnetic resonances of charge-carrier spin states in an OLED

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 $π$-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.

cond-mat.mes-hall↗

arXiv2023

Crossover from non-thermal to thermal photoluminescence from metals excited by ultrashort light pulses

Photoluminescence from metal nanostructures following intense ultrashort illumination is a fundamental aspect of light-matter interactions. Surprisingly, many of its basic characteristics are under ongoing debate. Here, we resolve many of these debates by providing a comprehensive theoretical framework that describes this phenomenon, and support it by experimental confirmation. Specifically, we identify aspects of the emission that are characteristic to either non-thermal or thermal emission, in particular, differences in the spectral and electric field-dependence of these two contributions to the emission. Overall, non-thermal emission is characteristic of the early stages of light emission, while the later stages show thermal characteristics. The former dominate only for moderately high illumination intensities for which the electron temperature reached after thermalization remains close to room temperature. The theory is complemented by experimental evidence that demonstrates the novel aspects of our considerations.

physics.optics↗

arXiv2022

Spin relaxation dynamics of radical-pair processes at low magnetic fields

We report measurements of room-temperature spin-relaxation times $T_1$ and $T_2$ of charge-carrier spins in a $π$-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.

cond-mat.mes-hall↗

arXiv2020

Floquet spin states in OLEDs

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.

cond-mat.mes-hall↗

arXiv2019

Two-photon absorption in a two-level system enabled by noise

We address the textbook problem of dynamics of a spin placed in a dc magnetic field and subjected to an ac drive. If the drive is polarized in the plane perpendicular to the dc field, the drive photons are resonantly absorbed when the spacing between the Zeeman levels is close to the photon energy. This is the only resonance when the drive is circularly polarized. For linearly polarized drive, additional resonances corresponding to absorption of three, five, and multiple odd numbers of photons is possible. Interaction with the environment causes the broadening of the absorption lines. We demonstrate that the interaction with environment enables the forbidden two-photon absorption. We adopt a model of the environment in the form of random telegraph noise produced by a single fluctuator. As a result of the synchronous time fluctuations of different components of the random field, the shape of the two-photon absorption line is non-Lorentzian and depends dramatically on the drive amplitude. This shape is a monotonic curve at strong drive, while, at weak drive, it develops a two-peak structure reminiscent of an induced transparency on resonance.

quant-ph↗

arXiv2018

Electric-field quenching of optically detected magnetic resonance in a $π$-conjugated polymer

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.

cond-mat.mes-hall↗

arXiv2018

High-Field Magnetoresistance of Organic Semiconductors

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 Landé 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 Δg mechanism, which originates from differences in the charge-carrier g-factors induced by spin-orbit coupling.

cond-mat.mes-hall↗

arXiv2018

Tuning effective hyperfine fields in PEDOT:PSS thin films by doping

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.

cond-mat.mes-hall↗

arXiv2018

Revealing weak spin-orbit coupling effects on charge carriers in a $π$-conjugated polymer

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.

cond-mat.mes-hall↗

arXiv2016

Molecular polygons probe the role of intramolecular strain in the photophysics of pi-conjugated chromophores

Pi-conjugated segments - chromophores - constitute the electronically active units of polymer materials used in organic electronics. To elucidate the effect of bending of these linear moieties on elementary electronic properties such as luminescence colour and radiative rate we introduce a series of molecular polygons. The pi-system in these molecules becomes so distorted in bichromophores (digons) that these absorb and emit light of arbitrary polarisation: any part of the chain absorbs and emits radiation with equal probability. Bending leads to a cancellation of transition dipole moment (TDM), increasing excited-state lifetime. Simultaneously, fluorescence shifts to the red as radiative transitions require mixing of the excited state with vibrational modes. However, strain can become so large that excited-state localisation on shorter units of the chain occurs, compensating TDM cancellation. Since these effects counteract, underlying correlations between shape and photophysics can only be resolved in single molecules.

physics.chem-ph↗

arXiv2016

Interactions between pi-conjugated chromophores in a giant molecular spoked wheel

We discuss the intriguing photophysics of a giant molecular spoked wheel of pi-conjugated arylenealkynylene chromophores on the single-molecule level. This "molecular mesoscopic" tructure, C1878H2682, shows fast switching between the 12 identical chromophores since the fluorescence is unpolarised but only one chromophore emits at a time.

physics.chem-ph↗

arXiv2016

Morphology effects on spin-dependent transport and recombination in polyfluorene thin films

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.

cond-mat.mtrl-sci↗