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.

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.

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. These results show that the RISC process is not governed by the hyperfine interaction as thought previously, but proceeds through spin-mixing in the triplet exciplex. The observations are corroborated by electrically detected transient spin nutation experiments that show relatively long dephasing time at ambient temperature, and interpreted in the context of a model that involves exchange and hyperfine interactions in the spin triplet exciplex. These findings deepen the understanding of the RISC process in TADF materials.

Spin Wave Excitation, Detection, and Utilization in the Organic-Based Magnet, V(TCNE)x (TCNE = Tetracyanoethylene).

Spin waves, quantized as magnons, have low energy loss and magnetic damping, which are critical for devices based on spin-wave propagation needed for information processing devices. The organic-based magnet [V(TCNE)x ; TCNE = tetracyanoethylene; x ≈ 2] has shown an extremely low magnetic damping comparable to, for example, yttrium iron garnet (YIG). The excitation, detection, and utilization of coherent and non-coherent spin waves on various modes in V(TCNE)x is demonstrated and show that the angular momentum carried by microwave-excited coherent spin waves in a V(TCNE)x film can be transferred into an adjacent Pt layer via spin pumping and detected using the inverse spin Hall effect. The spin pumping efficiency can be tuned by choosing different excited spin wave modes in the V(TCNE)x film. In addition, it is shown that non-coherent spin waves in a V(TCNE)x film, excited thermally via the spin Seebeck effect, can also be used as spin pumping source that generates an electrical signal in Pt with a sign change in accordance with the magnetization switching of the V(TCNE)x . Combining coherent and non-coherent spin wave detection, the spin pumping efficiency can be thermally controlled, and new insight is gained for the spintronic applications of spin wave modes in organic-based magnets.

Perdeuterated Conjugated Polymers for Ultralow-Frequency Magnetic Resonance of OLEDs.

The formation of excitons in OLEDs is spin dependent and can be controlled by electron-paramagnetic resonance, affecting device resistance and electroluminescence yield. We explore electrically detected magnetic resonance in the regime of very low magnetic fields (<1 mT). A pronounced feature emerges at zero field in addition to the conventional spin- 1 / 2 Zeeman resonance for which the Larmor frequency matches that of the incident radiation. By comparing a conventional π-conjugated polymer as the active material to a perdeuterated analogue, we demonstrate the interplay between the zero-field feature and local hyperfine fields. The zero-field peak results from a quasistatic magnetic-field effect of the RF radiation for periods comparable to the carrier-pair lifetime. Zeeman resonances are resolved down to 3.2 MHz, approximately twice the Larmor frequency of an electron in Earth's field. However, since reducing hyperfine fields sharpens the Zeeman peak at the cost of an increased zero-field peak, we suggest that this result may constitute a fundamental low-field limit of magnetic resonance in carrier-pair-based systems. OLEDs offer an alternative solid-state platform to investigate the radical-pair mechanism of magnetic-field effects in photochemical reactions, allowing models of biological magnetoreception to be tested by measuring spin decoherence directly in the time domain by pulsed experiments.

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.

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.

OLEDs as models for bird magnetoception: detecting electron spin resonance in geomagnetic fields.

Certain species of living creatures are known to orientate themselves in the geomagnetic field. Given the small magnitude of approximately 48 µT, the underlying quantum mechanical phenomena are expected to exhibit coherence times in the microsecond regime. In this contribution, we show the sensitivity of organic light-emitting diodes (OLEDs) to magnetic fields far below Earth's magnetic field, suggesting that coherence times of the spins of charge-carrier pairs in these devices can be similarly long. By electron paramagnetic resonance (EPR) experiments, a lower bound for the coherence time can be assessed directly. Moreover, this technique offers the possibility to determine the distribution of hyperfine fields within the organic semiconductor layer. We extend this technique to a material system exhibiting both fluorescence and phosphorescence, demonstrating stable anticorrelation between optically detected magnetic resonance (ODMR) spectra in the singlet (fluorescence) and triplet (phosphorescence) channels. The experiments demonstrate the extreme sensitivity of OLEDs to both static as well as dynamic magnetic fields and suggest that coherent spin precession processes of coulombically bound electron-spin pairs may play a crucial role in the magnetoreceptive ability of living creatures.

Sign reversal of magnetoresistance and inverse spin Hall effect in doped conducting polymers.

Conducting polymers, where pristine polymers are doped by active dopants, have been used in a variety of flexible optoelectronic device applications due to their tunable conductivity values. Charge transport in these materials has been intensively studied for over three decades. However, spin transport properties in these compounds have remained elusive. Here, we studied two polaron-dominated and trap-dominated spin transport processes in two types of PEDOT:PSS polymers that are lightly and heavily doped, respectively. Using pulsed spin-pumping and spin-injection techniques, we found the sign of inverse spin Hall effect and magnetoresistance obtained from the lightly doped PEDOT:PSS film can reverse its polarity as a function of temperature and applied bias, in contrast to that in the heavily doped PEDOT:PSS film. Our work provides an alternative approach for studying the spin transport in conducting polymer films.

Freestanding Organic Charge-Transfer Conformal Electronics.

Wearable conformal electronics are essential components for next-generation humanlike sensing devices that can accurately respond to external stimuli in nonplanar and dynamic surfaces. However, to explore this potential, it is indispensable to achieve the desired level of deformability and charge-transport mobility in strain-accommodating soft semiconductors. Here, we show pseudo-two-dimensional freestanding conjugated polymer heterojunction nanosheets integrated into substrate-free conformal electronics owing to their exceptional crystalline controlled charge transport and high level of mechanical strength. These freestanding and mechanical robust polymer nanosheets can be adapted into a variety of artificial structured surfaces such as fibers, squares, circles, etc., which produce large-area stretchable conformal charge-transfer sensors for real-time static and dynamic monitoring.

Isotropic Effective Spin-Orbit Coupling in a Conjugated Polymer.

Conjugated polymers are anisotropic in shape and with regard to electronic properties. Little is known as to how electronic anisotropy impacts the underlying characteristics of the electron spin, such as the coupling to orbital magnetic moments. Using multifrequency electrically detected magnetic resonance spectroscopy extending over 12 octaves in frequency, we explore the effect of spin-orbit coupling by examining the pronounced broadening of resonance spectra with increasing magnetic field. Whereas in three commonly used materials, the high-field spectra show asymmetric broadening, as would be expected from anisotropic g-strain effects associated with the molecular structure, in the conducting polymer poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) the spectra broaden isotropically, providing a direct measure of the microscopic distribution in g-factors. This observation implies that effective charge-carrier g-tensors are isotropic, which likely originates from motional narrowing in this high-mobility material.

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.

Monolithic OLED-Microwire Devices for Ultrastrong Magnetic Resonant Excitation.

Organic light-emitting diodes (OLEDs) make highly sensitive probes to test magnetic resonance phenomena under unconventional conditions since spin precession controls singlet-triplet transitions of electron-hole pairs, which in turn give rise to distinct recombination currents in conductivity. Electron paramagnetic resonance can therefore be detected in the absence of spin polarization. We exploit this characteristic to explore the exotic regime of ultrastrong light-matter coupling, where the Rabi frequency of a charge carrier spin is of the order of the transition frequency of the two-level system. To reach this domain, we have to lower the Zeeman splitting of the spin states, defined by the static magnetic field B0, and raise the strength of the oscillatory driving field of the resonance, B1. This is achieved by shrinking the OLED and bringing the source of resonant radio frequency (RF) radiation as close as possible to the organic semiconductor in a monolithic device structure, which incorporates an OLED fabricated directly on top of an RF microwire within one monolithic thin-film device structure. With an RF driving power in the milliwatt range applied to the microwire, the regime of bleaching and inversion of the magnetic resonance signal is reached due to the onset of the spin-Dicke effect. In this example of ultrastrong light-matter coupling, the individual resonant spin transitions of electron-hole pairs become indistinguishable with respect to the driving field, and superradiance of the magnetic dipole transitions sets in.

Hexacyanobutadienide-Based Frustrated and Weak Ferrimagnets: M(HCBD)2·zCH2Cl2 (M = V, Fe).

Hexacyanobutadiene (HCBD) and M(CO)x (M = V, x = 6; Fe, x = 5) react in CH2Cl2 to form new organic-based magnets of M[HCBD]2·z(CH2Cl2) composition. Analysis of the IR spectrum [M = V: ν(CN) 2193 and 2116 cm(-1) (fwhh ∼400 cm(-1)); Fe: 2196 and 2145 (fwhh ∼150 cm(-1))] suggests that HCBD is reduced to the radical anion, [HCBD](•-), and the broadness suggests multiple and variable nitriles sites are coordinated to the V(II), leading to a complex mixture of magnetic couplings and behaviors that deviate from paramagnetic behavior below ∼150 K, and a frustrated magnet with Tc ≈ 9 K is observed for V[HCBD]2, the first cyanocarbon-based frustrated magnet. Fe[HCBD]2 behaves as a weak ferromagnet (canted antiferromagnet) with some spin glass behavior with a 10 K Tc.

Characterization of Tetracyanopyridine (TCNPy)-Based Magnets: V[TCNPy]2 ⋠z (CH2 Cl2 ) (Tc =111†K) and V[TCNPy]3 ⋠z (CH2 Cl2 ) (Tc =90†K).

The reaction of 2,3,5,6-tetracyanopyridine (TCNPy) with V(CO)6 in CH2 Cl2 forms new organic-based magnets of V[TCNPy]x ⋅z (CH2 Cl2 ) (x=2, 3) composition. Analysis of the IR spectra suggests that the TCNPy is reduced and coordinated to V(II) sites through the nitriles. V[TCNPy]x order as ferrimagnets with 111 and 90 K Tc values for V[TCNPy]2 and V[TCNPy]3 , respectively. Their respective remanent magnetizations and coercive fields are 1260 and 250 emuOe mol(-1) and 9 and 6 Oe at 5 K, and they exhibit some spin-glass behavior.

The Tetracyanopyridinide Dimer Dianion, σ-[TCNPy]2 (2.).

The reaction of 2,3,5,6-tetracyanopyridine (TCNPy) and Cr(C6 H6 )2 forms diamagnetic σ-[TCNPy]2 (2-) possessing a 1.572(3) Šintrafragment sp(3) -sp(3) bond. This is in contrast to the structurally related 1,2,4,5-tetracyanobenzene and 1,2,4,5-tetracyanopyrazine that form π-dimer dianions possessing long, multicenter bonds.

Inverse spin Hall effect from pulsed spin current in organic semiconductors with tunable spin-orbit coupling.

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.

Probing long-range carrier-pair spin-spin interactions in a conjugated polymer by detuning of electrically detected spin beating.

Weakly coupled electron spin pairs that experience weak spin-orbit interaction can control electronic transitions in molecular and solid-state systems. Known to determine radical pair reactions, they have been invoked to explain phenomena ranging from avian magnetoreception to spin-dependent charge-carrier recombination and transport. Spin pairs exhibit persistent spin coherence, allowing minute magnetic fields to perturb spin precession and thus recombination rates and photoreaction yields, giving rise to a range of magneto-optoelectronic effects in devices. Little is known, however, about interparticle magnetic interactions within such pairs. Here we present pulsed electrically detected electron spin resonance experiments on poly(styrene-sulfonate)-doped poly(3,4-ethylenedioxythiophene) ( PEDOT: PSS) devices, which show how interparticle spin-spin interactions (magnetic-dipolar and spin-exchange) between charge-carrier spin pairs can be probed through the detuning of spin-Rabi oscillations. The deviation from uncoupled precession frequencies quantifies both the exchange (<30 neV) and dipolar (23.5±1.5 neV) interaction energies responsible for the pair's zero-field splitting, implying quantum mechanical entanglement of charge-carrier spins over distances of 2.1±0.1 nm.

Coherent magnetic resonance of nanocrystal quantum-dot luminescence as a window to blinking mechanisms.

Blinking of colloidal nanocrystal quantum dots, random intermittency in the stream of photons emitted by single particles, has long commanded the curiosity of researchers. Why does the particle suddenly shut off, and what are the pathways to quench emission? Single-particle microscopy is not the only way to approach these fundamental questions on the interaction of light and matter: time-domain sub-ensemble spectroscopies can also yield relevant information on microscopic electronic processes. We illustrate recent advances in pulsed optically detected magnetic resonance and highlight the conceptual relevance to unravelling mechanisms controlling intermittency on the single-particle level. Magnetic resonance reveals two distinct luminescence quenching channels, which appear to be related to those previously surmised from single-particle studies: a trapped charge-separated state in which the exciton is quenched by dissociation and the particle remains neutral; and a charged state of the particle in which spin-dependent Auger recombination quenches luminescence.

Weak ferromagnetic ordering of the Li(+)[TCNE](•-) (TCNE = tetracyanoethylene) organic magnet with an interpenetrating diamondoid structure.

Li[TCNE] (TCNE = tetracyanoethylene) magnetically orders as a weak ferromagnet (canted antiferromagnet) below 21.0 ± 0.1 K, as observed from the bifurcation of the field-cooled and zero-field-cooled magnetizations, as well as remnant magnetization. The structure, determined ab initio from synchrotron X-ray powder diffraction data, consists of a planar µ4-[TCNE](•-) bound to four tetrahedral Li(+) ions. The structure consists of two interpenetrating diamondoid sublattices, with closest interlattice distances of 3.43 and 3.48 Å. At 5 K this magnetic state is characterized by a coercivity of ~30 Oe, a remnant magnetization of 10 emu·Oe/mol, and a canting angle of 0.5°.