RESUMEN
Quantum technologic and spintronic applications require reliable material platforms that enable significant and long-living spin polarization of excitations, the ability to manipulate it optically in external fields, and the possibility to implement quantum correlations between spins, i.e., entanglement. Here it is demonstrated that these conditions are met in bulk crystals of lead halide perovskites. A giant optical orientation of 85% of excitons, approaching the ultimate limit of unity, in FA0.9Cs0.1PbI2.8Br0.2 crystals is reported. The exciton spin orientation is maintained during the exciton lifetime of 55 ps resulting in high circular polarization of the exciton emission. The optical orientation is robust to detuning of the excitation energy up to 0.3 eV above the exciton resonance and remains larger than 20% up to detunings of 0.9 eV. It evidences pure chiral selection rules and suppressed spin relaxation of electrons and holes, even with large kinetic energies. The exciton and electron-hole recombinations are distinguished by means of the spin dynamics detected via coherent spin quantum beats in magnetic field. Further, electron-hole spin correlations are demonstrated through linear polarization beats after circularly polarized excitation. These findings are supported by atomistic calculations. All-in-all, the results establish lead halide perovskite semiconductors as suitable platform for quantum technologies.
RESUMEN
Coherent spin dynamics of electrons and holes are studied in hybrid organic-inorganic lead halide perovskite FAPbBr3 bulk single crystals using the time-resolved Kerr ellipticity technique at cryogenic temperatures. The Larmor spin precession of the carrier spins in a magnetic field is monitored to measure the Landé g-factors of electrons (+2.44) and holes (+0.41). These g-factors are highly isotropic. The measured spin dephasing times amount to a few nanoseconds, and the longitudinal hole spin relaxation time is 470 ns. The important role of the strong hyperfine interaction between carrier spins and nuclear spins is demonstrated via dynamic nuclear polarization. At low temperatures, electron and hole spin relaxation predominantly occurs via the hyperfine interaction, whose importance significantly decreases at temperatures above 12 K. We overview the spin dynamics in various lead halide perovskite crystals and polycrystalline films and conclude on their common features provided by charge carrier localization at cryogenic temperatures.
RESUMEN
Molecular engineering is a unique methodology to take advantage of the electrochemical characteristics of materials that are used in energy-harvesting devices. Particularly in triboelectric nanogenerator (TENG) studies, molecular grafting on dielectric metal oxide surfaces can be regarded as a feasible way to alter the surface charge density that directly affects the charge potential of triboelectric layers. Herein, we develop a feasible methodology to synthesize organic-inorganic hybrid structures with tunable triboelectric features. Different types of self-assembled monolayers (SAMs) with electron-donating and withdrawing groups have been used to modify metal oxide (MO) surfaces and to modify their charge density on the surface. All the synthetic routes for hybrid material production have been clearly shown and the formation of covalent bonds on the MO's surface has been confirmed by XPS. The obtained hybrid structures were applied as dopants to distinct polymer matrices with various ratios and fiberization processes were carried out to the prepare opposite triboelectric layers. The formation of the fibers was analyzed by SEM, while their surface morphology and physicochemical features have been measured by AFM and a drop shape analyzer. The triboelectric charge potential of each layer after doping and their contribution to the TENG device's parameters have been investigated. For each triboelectric layer, the best-performing tribopositive and tribonegative material combination was separately determined and then these opposite layers were used to fabricate TENG with the highest efficiency. A comparison of the device parameters with the reference indicated that the best tribopositive material gave rise to a 40% increase in the output voltage and produced 231 V, whereas the best tribonegative one led to a 33.3% rise in voltage and generated 220 V. In addition, the best device collected ~83% more charge than the reference device and came up with 250 V that corresponds to 51.5% performance enhancement. This approach paved the way by addressing the issue of how molecular engineering can be used to manipulate the triboelectric features of the same materials.