Room-temperature spin injection across a chiral perovskite/III-V interface.

Spin accumulation in semiconductor structures at room temperature and without magnetic fields is key to enable a broader range of optoelectronic functionality1. Current efforts are limited owing to inherent inefficiencies associated with spin injection across semiconductor interfaces2. Here we demonstrate spin injection across chiral halide perovskite/III-V interfaces achieving spin accumulation in a standard semiconductor III-V (AlxGa1-x)0.5In0.5P multiple quantum well light-emitting diode. The spin accumulation in the multiple quantum well is detected through emission of circularly polarized light with a degree of polarization of up to 15 ± 4%. The chiral perovskite/III-V interface was characterized with X-ray photoelectron spectroscopy, cross-sectional scanning Kelvin probe force microscopy and cross-sectional transmission electron microscopy imaging, showing a clean semiconductor/semiconductor interface at which the Fermi level can equilibrate. These findings demonstrate that chiral perovskite semiconductors can transform well-developed semiconductor platforms into ones that can also control spin.

Printing Air-Stable High-Tc Molecular Magnet with Tunable Magnetic Interaction.

High-Tc molecular magnets have amassed much promise; however, the long-standing obstacle for its practical applications is the inaccessibility of high-temperature molecular magnets showing dynamic and nonvolatile magnetization control. In addition, its functional durability is prone to degradation in oxygen and heat. Here, we introduce a rapid prototyping and stabilizing strategy for high Tc (360 K) molecular magnets with precise spatial control in geometry. The printed molecular magnets are thermally stable up to 400 K and air-stable for over 300 days, a significant improvement in its lifetime and durability. X-ray magnetic circular dichroism and computational modeling reveal the water ligands controlling magnetic exchange interaction of molecular magnets. The molecular magnets also show dynamical and reversible tunability of magnetic exchange interactions, enabling a colossal working temperature window of 86 K (from 258 to 344 K). This study provides a pathway to flexible, lightweight, and durable molecular magnetic devices through additive manufacturing.

Separation of Spin and Charge Transport in Pristine π-Conjugated Polymers.

We have experimentally tested whether spin-transport and charge-transport in pristine π-conjugated polymer films at room temperature occur via the same electronic processes. We have obtained the spin diffusion coefficient of several π-conjugated polymer films from the spin diffusion length measured by the technique of inverse spin Hall effect and the spin relaxation time measured by pulsed electrically detected magnetic resonance spectroscopy. The charge diffusion coefficient was obtained from the time-of-flight mobility measurements on the same films. We found that the spin diffusion coefficient is larger than the charge diffusion coefficient by about 1-2 orders of magnitude and conclude that spin and charge transports in disordered polymer films occur through different electronic processes.

Magneto-electroluminescence response in 2D and 3D hybrid organic-inorganic perovskite light emitting diodes.

We have studied the magneto-electroluminescence (MEL) response in light emitting diodes based on 2D-(PEA)2PbI4 and 3D-MAPbI3 hybrid organic-inorganic perovskites at cryogenic temperatures. We found that the MEL is negative, i.e., the EL decreases with the applied field strength, B. In addition, the MEL(B) response has a Lorentzian line shape whose width depends on the perovskite used. We interpret the MEL(B) response using the "Δg mechanism" in which the spin of the injected electron-hole (e-h) pairs oscillates between singlet and triplet configurations due to different precession frequencies of the electron and hole constituents that originate from the difference, Δg, in the electron and hole gyromagnetic constants, g. In this model, the MEL(B) linewidth is inversely proportional to the spin lifetime and Δg. The model used is validated by directly measuring the spin lifetime of photogenerated e-h pairs using the circularly polarized pump-probe transmission technique with 100 fs resolution.

Control of Whispering Gallery Modes and PT-Symmetry Breaking in Colloidal Quantum Dot Microdisk Lasers with Engineered Notches.

Whispering gallery mode resonators have been demonstrated to be a great way to achieve superior optical cavities with high quality factor and small mode volume. However, due to the high sensitivity of these modes to the properties of the resonator boundary, they are susceptible to parasitic splitting of clockwise and counterclockwise modes. In this work, we investigate the effect of implantation of an engineered notch into the boundary of a circular microdisk resonator fabricated from colloidal quantum dots, which are particularly sensitive to boundary defects. We observed a strong reduction of parasitic mode splitting with introduction of a large engineered notch, as well as enhanced directionality of laser emission. We further investigate the performance of these resonators in evanescently coupled pairs, where the modal interaction allows modulation of laser behavior through variation of the gain and loss induced by the optical pump. We show that two distinct cases of modal interaction can be achieved by adjusting the size of the engineered notch, providing a bridge between intra- and interdisk modal interactions for laser spectral control.

Organic-based magnon spintronics.

Magnonics concepts utilize spin-wave quanta (magnons) for information transmission, processing and storage. To convert information carried by magnons into an electric signal promises compatibility of magnonic devices with conventional electronic devices, that is, magnon spintronics 1 . Magnons in inorganic materials have been studied widely with respect to their generation2,3, transport4,5 and detection 6 . In contrast, resonant spin waves in the room-temperature organic-based ferrimagnet vanadium tetracyanoethylene (V(TCNE) x (x ≈ 2)), were detected only recently 7 . Herein we report room-temperature coherent magnon generation, transport and detection in films and devices based on V(TCNE) x using three different techniques, which include broadband ferromagnetic resonance (FMR), Brillouin light scattering (BLS) and spin pumping into a Pt adjacent layer. V(TCNE) x can be grown as neat films on a large variety of substrates, and it exhibits extremely low Gilbert damping comparable to that in yttrium iron garnet. Our studies establish an alternative use for organic-based magnets, which, because of their synthetic versatility, may substantially enrich the field of magnon spintronics.

Surface-enhanced spin current to charge current conversion efficiency in CH3NH3PbBr3-based devices.

Hybrid organic-inorganic perovskites have shown great promise for spintronic applications due to their large spin-orbit coupling induced by the Pb and halogen atoms. Particularly, the large observed surface-induced Rashba splitting in CH3NH3PbBr3 indicates efficient spin-current-to-charge-current (StC) conversion, which, however, has not been demonstrated yet. In this work, the StC conversion efficiency in ferromagnet/CH3NH3PbBr3-based devices is studied using the pulsed spin-pumping technique measured by the inverse spin Hall effect. We found that the StC conversion efficiency is anomalous in that it increases at small perovskite layer thickness. This indicates the existence of a surface-dominated StC mechanism such as the inverse Rashba-Edelstein effect. By inserting a thin LiF layer between the ferromagnet and the perovskite film, the StC conversion efficiency is greatly suppressed, validating the existence of a Rashba surface in the CH3NH3PbBr3 film.

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. We show that both singlet excitons (SE) and intrachain triplet-triplet (TT) pairs are photogenerated in the DA-copolymer chains. From the picosecond transient magnetic field response of these species we conclude that the SE and TT spin states are coupled. The TT decomposition into two intrachain geminate triplet excitons maintains spin coherence and thus their spin entanglement lasts into the microsecond time domain.

Exciton versus free carrier photogeneration in organometal trihalide perovskites probed by broadband ultrafast polarization memory dynamics.

We studied the ultrafast transient response of photoexcitations in two hybrid organic-inorganic perovskite films used for high efficiency photovoltaic cells, namely, CH(3)NH(3)PbI(3) and CH(3)NH(3)PbI(1.1)Br(1.9) using polarized broadband pump-probe spectroscopy in the spectral range of 0.3-2.7 eV with 300 fs time resolution. For CH(3)NH(3)PbI(3) with above-gap excitation we found both photogenerated carriers and excitons, but only carriers are photogenerated with below-gap excitation. In contrast, mainly excitons are photogenerated in CH(3)NH(3)PbI(1.1)Br(1.9). Surprisingly, we also discovered in CH(3)NH(3)PbI(3), but not in CH(3)NH(3)PbI(1.1)Br(1.9), transient photoinduced polarization memory for both excitons and photocarriers, which is also reflected in the steady state photoluminescence. From the polarization memory dynamics we obtained the excitons diffusion constant in CH(3)NH(3)PbI(3), D≈0.01 cm(2) s(-1).

Singlet fission of hot excitons in π-conjugated polymers.

We used steady-state photoinduced absorption (PA), excitation dependence (EXPA(ω)) spectrum of the triplet exciton PA band, and its magneto-PA (MPA(B)) response to investigate singlet fission (SF) of hot excitons into two separated triplet excitons, in two luminescent and non-luminescent π-conjugated polymers. From the high energy step in the triplet EXPA(ω) spectrum of the luminescent polymer poly(dioctyloxy)phenylenevinylene (DOO-PPV) films, we identified a hot-exciton SF (HE-SF) process having threshold energy at E≈2E(T) (=2.8 eV, where ET is the energy of the lowest lying triplet exciton), which is about 0.8 eV above the lowest singlet exciton energy. The HE-SF process was confirmed by the triplet MPA(B) response for excitation at E>2E(T), which shows typical SF response. This process is missing in DOO-PPV solution, showing that it is predominantly interchain in nature. By contrast, the triplet EXPA(ω) spectrum in the non-luminescent polymer polydiacetylene (PDA) is flat with an onset at E=E(g) (≈2.25 eV). From this, we infer that intrachain SF that involves a triplet-triplet pair state, also known as the 'dark' 2A(g) exciton, dominates the triplet photogeneration in PDA polymer as E(g)>2E(T). The intrachain SF process was also identified from the MPA(B) response of the triplet PA band in PDA. Our work shows that the SF process in π-conjugated polymers is a much more general process than thought previously.

Electric Field Effects in Hybrid Perovskites Studied via Picosecond Kerr Microscopy.

We present time-resolved Kerr rotation (TRKR) spectra in thin films of CH3NH3PbI3 (MAPI) hybrid perovskite using a unique picosecond microscopy technique at 4 K having a spatial resolution of 2 µm and temporal resolution of 1 ps, subjected to both an in-plane applied magnetic field up to 700 mT and an electric field up to 104 V/cm. We demonstrate that the obtained TRKR dynamics and spectra are substantially inhomogeneous across the MAPI films with prominent resonances at the exciton energy and interband transition of this compound. From the obtained quantum beating response as a function of magnetic field in the Voigt configuration, we also extract the inhomogeneity of the electron and hole Lande g-values and spin coherence time, T2*. We also report the TRKR dependence on both the applied magnetic field and electric field. From the change in the quantum beating dynamics, we found that T2* substantially decreases upon the application of an electric field. At the same time, from the induced spatial TRKR changes, we show that the electric field induced effects are caused by ion migration in the MAPI films.

Concentration of broadband terahertz radiation using a periodic array of conically tapered apertures.

We describe the optical concentration properties of periodic arrays of conically tapered metallic apertures measured using terahertz (THz) time-domain spectroscopy. As a first step in this process, we optimize the geometrical properties of individual apertures, keeping the output aperture diameter fixed, and find that the optimal taper angle is 30°. A consequence of increasing the taper angle is that the effective cutoff frequency red shifts, which can be readily explained using conventional waveguide theory. We then fabricate and measure the transmission properties of a periodic (hexagonal) array of optimized tapered apertures. In contrast to periodic arrays of subwavelength apertures in thin metal films, which are characterized by narrowband transmission resonances associated with the periodic spacing, here we observe broadband enhanced transmission above the effective cutoff frequency. Further enhancement in the concentration capabilities of the array can be achieved by tilting the apertures towards the array center, although the optical throughput of individual tapered apertures is reduced with increasing tilt angle. Finally, we discuss possible future directions that utilize cascaded structures, as a means for obtaining further enhancement in the amplitude of the transmitted THz radiation.

Transmission resonances through aperiodic arrays of subwavelength apertures.

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.

Liquid metal-based plasmonics.

We demonstrate that liquid metals support surface plasmon-polaritons (SPPs) at terahertz (THz) frequencies, and can thus serve as an attractive material system for a wide variety of plasmonic and metamaterial applications. We use eutectic gallium indium (EGaIn) as the liquid metal injected into a polydimethylsiloxane (PDMS) mold fabricated by soft lithography techniques. Using this approach, we observe enhanced THz transmission through a periodic array of subwavelength apertures. Despite of the fact that the DC conductivity of EGaIn is an order of magnitude smaller than many conventional metals, we clearly observe well-defined transmission resonances. This represents a first step in developing reconfigurable and tunable plasmonic devices that build upon well-developed microfluidic capabilities.

Measurement of surface plasmon correlation length differences using Fibonacci deterministic hole arrays.

Using terahertz (THz) transmission measurements through two-dimensional Fibonacci deterministic subwavelength hole arrays fabricated in metal foils, we find that the surface plasmon-polariton (SPP) correlation lengths for aperiodic resonances are smaller than those associated with the underlying grid. The enhanced transmission spectra associated with these arrays contain two groups of Fano-type resonances: those related to the two-dimensional Fibonacci structure and those related to the underlying hole grid array upon which the aperiodic Fibonacci array is built. For both groups the destructive interference frequencies at which transmission minima occur closely match prominent reciprocal vectors in the hole array (HA) structure-factor in reciprocal space. However the Fibonacci-related transmission resonances are much weaker than both their calculated Fourier intensity in k space and the grid-related resonances. These differences may arise from the complex, multi-fractal dispersion relations and scattering from the underlying grid arrays. We also systematically studied and compared the transmission resonance strength of Fibonacci HA and periodic HA lattices as a function of the number of holes in the array structure. We found that the Fibonacci-related resonance strengths are an order of magnitude weaker than that of the periodic HA, consistent with the smaller SPP correlation length for the aperiodic structure.

Rashba splitting in organic-inorganic lead-halide perovskites revealed through two-photon absorption spectroscopy.

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.

Transient quantum beatings of trions in hybrid organic tri-iodine perovskite single crystal.

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 (MAPbI3) 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 MAPbI3. 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.

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. 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.

Engineering the properties of terahertz filters using multilayer aperture arrays.

We experimentally demonstrate the ability to create additional transmission resonances in a double-layer aperture array by varying the interlayer gap spacing. In the case of periodic aperture arrays, these additional resonances are sharply peaked, while for random aperture arrays the resonances are broad. Surprisingly, these additional resonances only occur when the interlayer gap spacing is greater than half the aperture spacing on a single array. Since there is no corresponding periodicity in the random arrays, these resonances occur regardless of how small the gap spacing is made. This phenomenon can be accurately modeled only if the correct frequency-dependent complex dielectric function of a metal film perforated with subwavelength apertures is used. Using THz time-domain spectroscopy, we are able to directly obtain the complex dielectric response function from the THz experimental transmission measurements. We conclude by demonstrating several passive free-space THz filters using multilayer aperture arrays. Importantly, we show that the magnitude of the lowest order resonance can be approximately maintained, while the background transmission can be significantly suppressed leading to a significant improvement in the optical filter fidelity.

Proton switching molecular magnetoelectricity.

The convergence of proton conduction and multiferroics is generating a compelling opportunity to achieve strong magnetoelectric coupling and magneto-ionics, offering a versatile platform to realize molecular magnetoelectrics. Here we describe machine learning coupled with additive manufacturing to accelerate the design strategy for hydrogen-bonded multiferroic macromolecules accompanied by strong proton dependence of magnetic properties. The proton switching magnetoelectricity occurs in three-dimensional molecular heterogeneous solids. It consists of a molecular magnet network as proton reservoir to modulate ferroelectric polarization, while molecular ferroelectrics charging proton transfer to reversibly manipulate magnetism. The magnetoelectric coupling induces a reversible 29% magnetization control at ferroelectric phase transition with a broad thermal hysteresis width of 160 K (192 K to 352 K), while a room-temperature reversible magnetic modulation is realized at a low electric field stimulus of 1 kV cm-1. The findings of electrostatic proton transfer provide a pathway of proton mediated magnetization control in hierarchical molecular multiferroics.