A spin valve is a layered structure of magnetic and non-magnetic (spacer) materials whose electrical resistance depends on the spin state of electrons passing through the device and so can be controlled by an external magnetic field. The discoveries of giant magnetoresistance and tunnelling magnetoresistance in metallic spin valves have revolutionized applications such as magnetic recording and memory, and launched the new field of spin electronics--'spintronics'. Intense research efforts are now devoted to extending these spin-dependent effects to semiconductor materials. But while there have been noteworthy advances in spin injection and detection using inorganic semiconductors, spin-valve devices with semiconducting spacers have not yet been demonstrated. pi-conjugated organic semiconductors may offer a promising alternative approach to semiconductor spintronics, by virtue of their relatively strong electron-phonon coupling and large spin coherence. Here we report the injection, transport and detection of spin-polarized carriers using an organic semiconductor as the spacer layer in a spin-valve structure, yielding low-temperature giant magnetoresistance effects as large as 40 per cent.

Several spectroscopic methods were applied to study the characteristic properties of the electronic excitations in thin films of regioregular and regiorandom polythiophene polymers. In the regioregular polymers, which form two-dimensional lamellar structures, increased interchain coupling strongly influences the traditional one-dimensional electronic properties of the polymer chains. The photogenerated charge excitations (polarons) show two-dimensional delocalization that results in a relatively small polaronic energy, multiple absorption bands in the gap where the lowest energy band becomes dominant, and associated infrared active vibrations with reverse absorption bands caused by electron-vibration interferences. The relatively weak absorption bands of the delocalized polaron in the visible and near-infrared spectral ranges may help to achieve laser action in nanocrystalline polymer devices using current injection.

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. We demonstrate that the HFI does indeed have a crucial role in all three spin responses. OLED films based on the D-polymers show substantially narrower magneto-electroluminescence and ODMR responses, and as a result of the longer spin diffusion obtained, OSV devices based on D-polymers show a substantially larger magnetoresistance.

Chiral-induced spin selectivity (CISS) occurs when the chirality of the transporting medium selects one of the two spin ½ states to transport through the media while blocking the other. Monolayers of chiral organic molecules demonstrate CISS but are limited in their efficiency and utility by the requirement of a monolayer to preserve the spin selectivity. We demonstrate CISS in a system that integrates an inorganic framework with a chiral organic sublattice inducing chirality to the hybrid system. Using magnetic conductive-probe atomic force microscopy, we find that oriented chiral 2D-layered Pb-iodide organic/inorganic hybrid perovskite systems exhibit CISS. Electron transport through the perovskite films depends on the magnetization of the probe tip and the handedness of the chiral molecule. The films achieve a highest spin-polarization transport of up to 86%. Magnetoresistance studies in modified spin-valve devices having only one ferromagnet electrode confirm the occurrence of spin-dependent charge transport through the organic/inorganic layers.

In traditional optoelectronic approaches, control over spin, charge, and light requires the use of both electrical and magnetic fields. In a spin-polarized light-emitting diode (spin-LED), charges are injected, and circularly polarized light is emitted from spin-polarized carrier pairs. Typically, the injection of carriers occurs with the application of an electric field, whereas spin polarization can be achieved using an applied magnetic field or polarized ferromagnetic contacts. We used chiral-induced spin selectivity (CISS) to produce spin-polarized carriers and demonstrate a spin-LED that operates at room temperature without magnetic fields or ferromagnetic contacts. The CISS layer consists of oriented, self-assembled small chiral molecules within a layered organic-inorganic metal-halide hybrid semiconductor framework. The spin-LED achieves ±2.6% circularly polarized electroluminescence at room temperature.

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Transient and CW spectroscopies unravel giant Rashba splitting in 2D hybrid perovskite multilayers.

Electroluminescence in organic light-emitting diodes arises from a charge-transfer reaction between the injected positive and negative charges by which they combine to form singlet excitons that subsequently decay radiatively. The quantum yield of this process (the number of photons generated per electron or hole injected) is often thought to have a statistical upper limit of 25 per cent. This is based on the assumption that the formation cross-section of singlet excitons, sigmaS, is approximately the same as that of any one of the three equivalent non-radiative triplet exciton states, sigmaT; that is, sigmaS/sigmaT approximately 1. However, recent experimental and theoretical work suggests that sigmaS/sigmaT may be greater than 1. Here we report direct measurements of sigmaS/sigmaT for a large number of pi-conjugated polymers and oligomers. We have found that there exists a strong systematic, but not monotonic, dependence of sigmaS/sigmaT on the optical gap of the organic materials. We present a detailed physical picture of the charge-transfer reaction for correlated pi-electrons, and quantify this process using exact valence bond calculations. The calculated sigmaS/sigmaT reproduces the experimentally observed trend. The calculations also show that the strong dependence of sigmaS/sigmaT on the optical gap is a signature of the discrete excitonic energy spectrum, in which higher energy excitonic levels participate in the charge recombination process.