Translation of chirality and asymmetry across structural motifs and length scales plays a fundamental role in nature, enabling unique functionalities in contexts ranging from biological systems to ...synthetic materials. Here, we introduce a structural chirality transfer across the organic-inorganic interface in two-dimensional hybrid perovskites using appropriate chiral organic cations. The preferred molecular configuration of the chiral spacer cations, R-(+)- or S-(-)-1-(1-naphthyl)ethylammonium and their asymmetric hydrogen-bonding interactions with lead bromide-based layers cause symmetry-breaking helical distortions in the inorganic layers, otherwise absent when employing a racemic mixture of organic spacers. First-principles modeling predicts a substantial bulk Rashba-Dresselhaus spin-splitting in the inorganic-derived conduction band with opposite spin textures between R- and S-hybrids due to the broken inversion symmetry and strong spin-orbit coupling. The ability to break symmetry using chirality transfer from one structural unit to another provides a synthetic design paradigm for emergent properties, including Rashba-Dresselhaus spin-polarization for hybrid perovskite spintronics and related applications.
Recently the hybrid organic-inorganic trihalide perovskites have shown remarkable performance as active layers in photovoltaic and other optoelectronic devices. However, their spin characteristic ...properties have not been fully studied, although due to the relatively large spin-orbit coupling these materials may show great promise for spintronic applications. Here we demonstrate spin-polarized carrier injection into methylammonium lead bromide films from metallic ferromagnetic electrodes in two spintronic-based devices: a 'spin light emitting diode' that results in circularly polarized electroluminescence emission; and a 'vertical spin valve' that shows giant magnetoresistance. In addition, we also apply a magnetic field perpendicular to the injected spins orientation for measuring the 'Hanle effect', from which we obtain a relatively long spin lifetime for the electrically injected carriers. Our measurements initiate the field of hybrid perovskites spin-related optoelectronic applications.
The Rashba splitting in hybrid organic-inorganic lead-halide perovskites (HOIP) is particularly promising and yet controversial, due to questions surrounding the presence or absence of inversion ...symmetry. Here we utilize two-photon absorption spectroscopy to study inversion symmetry breaking in different phases of these materials. This is an all-optical technique to observe and quantify the Rashba effect as it probes the bulk of the materials. In particular, we measure two-photon excitation spectra of the photoluminescence in 2D, 3D, and anionic mixed HOIP crystals, and show that an additional band above, but close to the optical gap is the signature of new two-photon transition channels that originate from the Rashba splitting. The inversion symmetry breaking is believed to arise from ionic impurities that induce local electric fields. The observation of the Rashba splitting in the bulk of HOIP has significant implications for the understanding of their spintronic and optoelectronic device properties.
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. In stark contrast to the response properties of homopolar OSV devices, the MEL response in the double-injection device is practically independent of bias voltage, and its temperature dependence follows that of the ferromagnetic electrode magnetization. Our findings provide a pathway for organic displays controlled by external magnetic fields.
Resonantly enhanced light transmission through periodic subwavelength aperture arrays perforated in metallic films has generated significant interest because of potential applications in near-field ...microscopy, photolithography, displays, and thermal emission. The enhanced transmission was originally explained by a mechanism where surface plasmon polaritons (collective electronic excitations in the metal surface) mediate light transmission through the grating. In this picture, structural periodicity is perceived to be crucial in forming the transmission resonances. Here we demonstrate experimentally that, in contrast to the conventional view, sharp transmission resonances can be obtained from aperiodic aperture arrays. Terahertz transmission resonances are observed from several arrays in metallic films that exhibit unusual local n-fold rotational symmetries, where n = 10, 12, 18, 40 and 120. This is accomplished by using quasicrystals with long-range order, as well as a new type of 'quasicrystal approximates' in which the long-range order is somewhat relaxed. We find that strong transmission resonances also form in these aperiodic structures, at frequencies that closely match the discrete Fourier transform vectors in the aperture array structure factor. The shape of these resonances arises from Fano interference of the discrete resonances and the non-resonant transmission band continuum related to the individual holes. Our approach expands potential design parameters for aperture arrays that are aperiodic but contain discrete Fourier transform vectors, and opens new avenues for optoelectronic devices.
Exploration of spin currents in organic semiconductors (OSECs) induced by resonant microwave absorption in ferromagnetic substrates is appealing for potential spintronics applications. Owing to the ...inherently weak spin-orbit coupling (SOC) of OSECs, their inverse spin Hall effect (ISHE) response is very subtle; limited by the microwave power applicable under continuous-wave (cw) excitation. Here we introduce a novel approach for generating significant ISHE signals in OSECs using pulsed ferromagnetic resonance, where the ISHE is two to three orders of magnitude larger compared to cw excitation. This strong ISHE enables us to investigate a variety of OSECs ranging from π-conjugated polymers with strong SOC that contain intrachain platinum atoms, to weak SOC polymers, to C60 films, where the SOC is predominantly caused by the curvature of the molecule's surface. The pulsed-ISHE technique offers a robust route for efficient injection and detection schemes of spin currents at room temperature, and paves the way for spin orbitronics in plastic materials.
Two-dimensional hybrid organic–inorganic perovskites (2D-HOIPs) that form natural multiple quantum wells have attracted increased research interest due to their interesting physics and potential ...applications in optoelectronic devices. Recent studies have shown that spintronics applications can also be introduced to 2D-HOIPs upon integrating chiral organic ligands into the organic layers. Here we report spin-dependent photovoltaic and photogalvanic responses of optoelectronic devices based on chiral 2D-HOIPs, namely, (R-MBA)2PbI4 and (S-MBA)2PbI4. The out-of-plane photocurrent response in vertical photovoltaic devices exhibits ∼10% difference upon right and left circularly polarized light (CPL) excitation, which originates from selective spin transport through the chiral multilayers. In contrast, the in-plane photocurrent response generated by CPL excitation of planar photoconductive devices shows a typical response of chirality-induced circular photogalvanic effect that originates from the Rashba splitting in the electronic bands of these compounds. Our studies may lead to potential applications of chiral 2D-HOIPs in optoelectronic devices that are sensitive to the light helicity.
Utilizing the spin degree of freedom of photoexcitations in hybrid organic inorganic perovskites for quantum information science applications has been recently proposed and explored. However, it is ...still unclear whether the stable photoexcitations in these compounds correspond to excitons, free/trapped electron-hole pairs, or charged exciton complexes such as trions. Here we investigate quantum beating oscillations in the picosecond time-resolved circularly polarized photoinduced reflection of single crystal methyl-ammonium tri-iodine perovskite (MAPbI
) measured at cryogenic temperatures. We observe two quantum beating oscillations (fast and slow) whose frequencies increase linearly with B with slopes that depend on the crystal orientation with respect to the applied magnetic field. We assign the quantum beatings to positive and negative trions whose Landé g-factors are determined by those of the electron and hole, respectively, or by the carriers left behind after trion recombination. These are Formula: see text = 2.52 and Formula: see text= 2.63 for electrons, whereas Formula: see text= 0.28 and Formula: see text= 0.57 for holes. The obtained g-values are in excellent agreement with an 8-band K.P calculation for orthorhombic MAPbI
. Using the technique of resonant spin amplification of the quantum beatings we measure a relatively long spin coherence time of ~ 11 (6) nanoseconds for electrons (holes) at 4 K.
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. π-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.
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