Isotope Effect in the Magneto-Optoelectronic Response of Organic Light-Emitting Diodes Based on Donor-Acceptor Exciplexes.

The isotope effect is studied in the magneto-electroluminescence (MEL) and pulsed electrically detected magnetic resonance of organic light-emitting diodes based on thermally activated delayed fluorescence (TADF) from donor-acceptor exciplexes that are either protonated (H) or deuterated (D). It is found that at ambient temperature, the exchange of H to D has no effect on the spin-dependent current and MEL responses in the devices. However, at cryogenic temperatures, where the reverse intersystem crossing (RISC) from triplet to singlet exciplex diminishes, a pronounced isotope effect is observed.

Effects of fast back-fusion of charge transfer excimers on magneto-photocurrent in organic light emitting diodes.

We report the magnetic field dependence of the magneto-photocurrent (MPC) in organic light emitting diodes made of homo-polymer organic layers and compare it to the measured magneto-conductance (MC) in the same diodes. We find that the response MPC(B) is very different from MC(B) in at least two respects. (a) The low field (B < 50 mT) response of MPC(B) is narrower by a factor of ∼5 from that of MC(B).

Transient Magnetic Field Effect of Photoexcitations in Donor-Acceptor Organic Semiconductors.

We report transient photoinduced absorption (t-PA) and magnetic field ( B)-dependent t-PA (t-MPA( B)) in a pristine low band gap π-conjugated copolymer composed of donor and acceptor moieties, namely, the poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thi-eno[3,4- b]thiophenediyl]]) (or PTB7) used in photovoltaic applications. Unlike traditional π-conjugated polymers in which the primary photoexcitations are singlet excitons (SE), in pristine PTB7 we find at short times coexistence of two primary photoexcitation species, namely, SE and triplet-triplet (TT) pair. Both species are photogenerated directly from the ground state and are spin-correlated.

Giant Rashba splitting in 2D organic-inorganic halide perovskites measured by transient spectroscopies.

Two-dimensional (2D) layered hybrid organic-inorganic halide perovskite semiconductors form natural "multiple quantum wells" that have strong spin-orbit coupling due to the heavy elements in their building blocks. This may lead to "Rashba splitting" close to the extrema in the electron bands. We have used a plethora of ultrafast transient, nonlinear optical spectroscopies and theoretical calculations to study the primary (excitons) and long-lived (free carriers) photoexcitations in thin films of 2D perovskite, namely, (CHCHNH)PbI.

Transient Magnetophotoinduced Absorption Studies of Photoexcitations in π-Conjugated Donor-Acceptor Copolymers.

We have utilized a plethora of transient and steady state optical and magneto-optical spectroscopies in a broad spectral range (0.25-2.5 eV) for elucidating the primary and long-lived photoexcitations in a low band-gap π-conjugated donor-acceptor (DA) copolymer used for efficient photovoltaic solar cells.

Doping-Induced Absorption Bands in P3HT: Polarons and Bipolarons.

In this work, we focus on the formation of different kinds of charge carriers such as polarons and bipolarons upon p-type doping (oxidation) of the organic semiconductor poly(3- hexylthiophene-2,5-diyl) (P3HT). We elucidate the cyclic voltammogram during oxidation of this polymer and present spectroscopic changes upon doping in the UV/Vis/near-IR range as well as in the mid-IR range. In the low-oxidation regime, two absorption bands related to sub-gap transitions appear, one in the UV/Vis range and another one in the mid-IR range.

Short-lived charge-transfer excitons in organic photovoltaic cells studied by high-field magneto-photocurrent.

The main route of charge photogeneration in efficient organic photovoltaic cells based on bulk hetero-junction donor-acceptor blends involves short-lived charge-transfer excitons at the donor-acceptor interfaces. The cell efficiency is critically affected by the charge-transfer exciton recombination and dissociation processes. By measuring the magneto-photocurrent under ambient conditions at room temperature, we show here that magnetic field-induced spin-mixing among the charge-transfer exciton spin sublevels occurs in fields up to at least 8.

The first decade of organic spintronics research.

The first decade of organic spintronics research has benefitted from the analogy and previous experience of the inorganic spintronics field, coupled with the unlimited versatility of organic materials synthesis. At the same time, the field of organic spintronics has developed into an attractive and promising field of its own, with rich physics and promising unique potential applications. We review here a set of significant milestones achieved in organic spintronic devices such as organic spin valves, bipolar spin-valves, and hybrid organic/inorganic light emitting diodes in comparison with representative inorganic spintronic devices.

Organic spin-valves: from unipolar to bipolar devices.

We review the recent advances in both unipolar and bipolar organic spin valves. We discuss mechanisms that dominate the spin relaxation of injected spin aligned carriers and limit their spin diffusion length. A space charge limited current model with ferromagnetic electrodes is used to describe the bipolar organic spin valve operation.

Spin-polarized light-emitting diode based on an organic bipolar spin valve.

The spin-polarized organic light-emitting diode (spin-OLED) has been a long-sought device within the field of organic spintronics. We designed, fabricated, and studied a spin-OLED with ferromagnetic electrodes that acts as a bipolar organic spin valve (OSV), based on a deuterated derivative of poly(phenylene-vinylene) with small hyperfine interaction. In the double-injection limit, the device shows ~1% spin valve magneto-electroluminescence (MEL) response, which follows the ferromagnetic electrode coercive fields and originates from the bipolar spin-polarized space charge-limited current.

Magnetoconductance response in unipolar and bipolar organic diodes at ultrasmall fields.

We measured magnetoconductance (MC) response in a number of unipolar and bipolar organic diodes based on π-conjugated polymers and small molecules at fields |B|<100  mT and various bias voltages and temperatures. Similar to magneto-electroluminescence, the MC(B) response in bipolar diodes shows a sign reversal at ultrasmall |B|<1-2  mT due to interplay of hyperfine and Zeeman interactions in opposite-charge polaron pairs. Surprisingly, similar MC(B) response was also measured in unipolar devices, indicating the existence of like-charge polaron pairs, however, with a clear difference between the hyperfine interaction constants of electron polaron and hole polaron.

Isotope effect in spin response of pi-conjugated polymer films and devices.

Recent advances in organic spin response include long polaron spin-coherence times measured by optically detected magnetic resonance (ODMR), substantive room-temperature magnetoelectroluminescence and magnetoconductance obtained in organic light-emitting diodes (OLEDs) and spin-polarized carrier injection from ferromagnetic electrodes in organic spin valves (OSVs). Although the hyperfine interaction (HFI) has been foreseen to have an important role in organic spin response, no clear experimental evidence has been reported so far. Using the chemical versatility advantage of the organics, we studied and compared spin responses in films, OLED and OSV devices based on pi-conjugated polymers made of protonated, H-, and deuterated, D-hydrogen having a weaker HFI strength.

Polaron spin-lattice relaxation time in pi-conjugated polymers from optically detected magnetic resonance.

We describe a method for obtaining the polaron spin-lattice relaxation time T{SL} in pi-conjugated polymers by measuring the optically detected magnetic resonance (ODMR) dynamics as a function of microwave power and laser intensity. The peculiar ODMR dynamics is well described by a spin dependent recombination model where both recombination and spin relaxation rates determine together the response dynamics. We apply this method to the spin 1/2 ODMR in films of pristine 2-methoxy-5-(2{'}-ethylhexyloxy) phenylene vinylene [MEH-PPV] polymer, as well as MEH-PPV doped with various concentrations of radical impurities.

Linear and nonlinear photoexcitation dynamics in pi-conjugated polymers.

Linear and nonlinear recombination kinetics with various lifetime distributions were identified for long-lived photoexcitations in a series of pi-conjugated polymer films using modulation frequency and excitation intensity dependencies of the photoinduced absorption. This includes monomolecular, bimolecular, and defect-limited recombination processes that lead to saturation. Using generalized kinetics parameters, we found characteristic plots for all recombination processes.

Semiconductor quantum dot: a quantum light source of multicolor photons with tunable statistics.

We investigate the intensity correlation properties of single photons emitted from an optically excited single semiconductor quantum dot. The second order temporal coherence function of the photons emitted at various wavelengths is measured as a function of the excitation power. We show experimentally and theoretically that a quantum dot is not only a source of nonclassically correlated monochromatic photons but is also a source of multicolor photons with tunable correlation properties.

Silver-halide optical fiber for infrared absorption spectroscopy: optically pumped intersubband transitions in quantum-well structures.

A silver-halide infrared optical fiber is used in a double-beam spectrometer, demonstrating the ability to guide small infrared signals efficiently. We show that a fractional transmission change of less than 1% is easily measured. Use of the fiber may obviate the necessity for the unfriendly optics currently used in spectrometry systems to probe remote sample zones.