Temperature Dependence of Relativistic Valence Band Splitting Induced by an Altermagnetic Phase Transition.

Altermagnetic (AM) materials exhibit non-relativistic, momentum-dependent spin-split states, ushering in new opportunities for spin electronic devices. While the characteristics of spin-splitting are documented within the framework of the non-relativistic spin group symmetry, there is limited exploration of the inclusion of relativistic symmetry and its impact on the emergence of a novel spin-splitting in the band structure. This study delves into the intricate relativistic electronic structure of an AM material, α-MnTe. Employing temperature-dependent angle-resolved photoelectron spectroscopy across the AM phase transition, the emergence of a relativistic valence band splitting concurrent with the establishment of magnetic order is elucidated. This discovery is validated through disordered local moment calculations, modeling the influence of magnetic order on the electronic structure and confirming the magnetic origin of the observed splitting. The temperature-dependent splitting is ascribed to the advent of relativistic spin-splitting resulting from the strengthening of AM order in α-MnTe as the temperature decreases. This sheds light on a previously unexplored facet of this intriguing material.

Ultrafast Coherent THz Lattice Dynamics Coupled to Spins in the van der Waals Antiferromagnet FePS3.

Coherent THz optical lattice and hybridized phonon-magnon modes are triggered by femtosecond laser pulses in the antiferromagnetic van der Waals semiconductor FePS3 . The laser-driven lattice and spin dynamics are investigated in a bulk crystal as well as in a 380 nm-thick exfoliated flake as a function of the excitation photon energy, sample temperature and applied magnetic field. The pump-probe magneto-optical measurements reveal that the amplitude of a coherent phonon mode oscillating at 3.2 THz decreases as the sample is heated up to the Néel temperature. This signal eventually vanishes as the phase transition to the paramagnetic phase occurs, thus revealing its connection to the long-range magnetic order. In the presence of an external magnetic field, the optically triggered 3.2 THz phonon hybridizes with a magnon mode, which is utilized to excite the hybridized phonon-magnon mode optically. These findings open a pathway toward the optical control of coherent THz photo-magnonic dynamics in a van der Waals antiferromagnet, which can be scaled down to the 2D limit.

Enhancing Electron Correlation at a 3d Ferromagnetic Surface.

Spin-resolved momentum microscopy and theoretical calculations are combined beyond the one-electron approximation to unveil the spin-dependent electronic structure of the interface formed between iron (Fe) and an ordered oxygen (O) atomic layer, and an adsorbate-induced enhancement of electronic correlations is found. It is demonstrated that this enhancement is responsible for a drastic narrowing of the Fe d-bands close to the Fermi energy (EF ) and a reduction of the exchange splitting, which is not accounted for in the Stoner picture of ferromagnetism. In addition, correlation leads to a significant spin-dependent broadening of the electronic bands at higher binding energies and their merging with satellite features, which are manifestations of a pure many-electron behavior. Overall, adatom adsorption can be used to vary the material parameters of transition metal surfaces to access different intermediate electronic correlated regimes, which will otherwise not be accessible. The results show that the concepts developed to understand the physics and chemistry of adsorbate-metal interfaces, relevant for a variety of research areas, from spintronics to catalysis, need to be reconsidered with many-particle effects being of utmost importance. These may affect chemisorption energy, spin transport, magnetic order, and even play a key role in the emergence of ferromagnetism at interfaces between non-magnetic systems.

Disproportionation of Nitric Oxide at a Surface-Bound Nickel Porphyrinoid.

Uncommon metal oxidation states in porphyrinoid cofactors are responsible for the activity of many enzymes. The F430 and P450nor co-factors, with their reduced NiI - and FeIII -containing tetrapyrrolic cores, are prototypical examples of biological systems involved in methane formation and in the reduction of nitric oxide, respectively. Herein, using a comprehensive range of experimental and theoretical methods, we raise evidence that nickel tetraphenyl porphyrins deposited in vacuo on a copper surface are reactive towards nitric oxide disproportionation at room temperature. The interpretation of the measurements is far from being straightforward due to the high reactivity of the different nitrogen oxides species (eventually present in the residual gas background) and of the possible reaction intermediates. The picture is detailed in order to disentangle the challenging complexity of the system, where even a small fraction of contamination can change the scenario.

Disproportionation of Nitric Oxide at a Surface-Bound Nickel Porphyrinoid.

Uncommon metal oxidation states in porphyrinoid cofactors are responsible for the activity of many enzymes. The F430 and P450nor co-factors, with their reduced NiI- and FeIII-containing tetrapyrrolic cores, are prototypical examples of biological systems involved in methane formation and in the reduction of nitric oxide, respectively. Herein, using a comprehensive range of experimental and theoretical methods, we raise evidence that nickel tetraphenyl porphyrins deposited in vacuo on a copper surface are reactive towards nitric oxide disproportionation at room temperature. The interpretation of the measurements is far from being straightforward due to the high reactivity of the different nitrogen oxides species (eventually present in the residual gas background) and of the possible reaction intermediates. The picture is detailed in order to disentangle the challenging complexity of the system, where even a small fraction of contamination can change the scenario.

Positive Magnetoresistance and Chiral Anomaly in Exfoliated Type-II Weyl Semimetal Td-WTe2.

Layered van der Waals semimetallic Td-WTe2, exhibiting intriguing properties which include non-saturating extreme positive magnetoresistance (MR) and tunable chiral anomaly, has emerged as a model topological type-II Weyl semimetal system. Here, ∼45 nm thick mechanically exfoliated flakes of Td-WTe2 are studied via atomic force microscopy, Raman spectroscopy, low-T/high-µ0H magnetotransport measurements and optical reflectivity. The contribution of anisotropy of the Fermi liquid state to the origin of the large positive transverse MR⊥ and the signature of chiral anomaly of the type-II Weyl Fermions are reported. The samples are found to be stable in air and no oxidation or degradation of the electronic properties is observed. A transverse MR⊥∼1200 % and an average carrier mobility of 5000 cm2V-1s-1 at T=5K for an applied perpendicular field µ0H⊥=7T are established. The system follows a Fermi liquid model for T≤50K and the anisotropy of the Fermi surface is concluded to be at the origin of the observed positive MR. Optical reflectivity measurements confirm the anisotropy of the electronic behaviour. The relative orientation of the crystal axes and of the applied electric and magnetic fields is proven to determine the observed chiral anomaly in the in-plane magnetotransport. The observed chiral anomaly in the WTe2 flakes is found to persist up to T=120K, a temperature at least four times higher than the ones reported to date.

Room-Temperature On-Spin-Switching and Tuning in a Porphyrin-Based Multifunctional Interface.

Molecular interfaces formed between metals and molecular compounds offer a great potential as building blocks for future opto-electronics and spintronics devices. Here, a combined theoretical and experimental spectro-microscopy approach is used to show that the charge transfer occurring at the interface between nickel tetraphenyl porphyrins and copper changes both spin and oxidation states of the Ni ion from [Ni(II), S = 0] to [Ni(I), S = 1/2]. The chemically active Ni(I), even in a buried multilayer system, can be functionalized with nitrogen dioxide, allowing a selective tuning of the electronic properties of the Ni center that is switched to a [Ni(II), S = 1] state. While Ni acts as a reversible spin switch, it is found that the electronic structure of the macrocycle backbone, where the frontier orbitals are mainly localized, remains unaffected. These findings pave the way for using the present porphyrin-based system as a platform for the realization of multifunctional devices where the magnetism and the optical/transport properties can be controlled simultaneously by independent stimuli.

Extremely low-energy ARPES of quantum well states in cubic-GaN/AlN and GaAs/AlGaAs heterostructures.

Quantum well (QW) heterostructures have been extensively used for the realization of a wide range of optical and electronic devices. Exploiting their potential for further improvement and development requires a fundamental understanding of their electronic structure. So far, the most commonly used experimental techniques for this purpose have been all-optical spectroscopy methods that, however, are generally averaging in momentum space. Additional information can be gained by angle-resolved photoelectron spectroscopy (ARPES), which measures the electronic structure with momentum resolution. Here we report on the use of extremely low-energy ARPES (photon energy ~ 7 eV) to increase depth sensitivity and access buried QW states, located at 3 nm and 6 nm below the surface of cubic-GaN/AlN and GaAs/AlGaAs heterostructures, respectively. We find that the QW states in cubic-GaN/AlN can indeed be observed, but not their energy dispersion, because of the high surface roughness. The GaAs/AlGaAs QW states, on the other hand, are buried too deep to be detected by extremely low-energy ARPES. Since the sample surface is much flatter, the ARPES spectra of the GaAs/AlGaAs show distinct features in momentum space, which can be reconducted to the band structure of the topmost surface layer of the QW structure. Our results provide important information about the samples' properties required to perform extremely low-energy ARPES experiments on electronic states buried in semiconductor heterostructures.

Nonlinear Bicolor Holography Using Plasmonic Metasurfaces.

Nonlinear metasurface holography shows the great potential of metasurfaces to control the phase, amplitude, and polarization of light while simultaneously converting the frequency of the light. The possibility of tailoring the scattering properties of a coherent beam, as well as the scattering properties of nonlinear signals originating from the meta-atoms, facilitates a huge degree of freedom in beam shaping application. Recently, several approaches showed that virtual objects or any kind of optical information can be generated at a wavelength different from the laser input beam. Here, we demonstrate a single-layer nonlinear geometric-phase metasurface made of plasmonic nanostructures for a simultaneous second- and third-harmonic generation. Different from previous works, we demonstrate a two-color hologram with dissimilar types of nanostructures that generate the color information by different nonlinear optical processes. The amplitude ratio of both harmonic signals can be adapted depending on the nanostructures' resonance as well as the power and the wavelength of the incident laser beam. The two-color holographic image is reconstructed in the Fourier space at visible wavelengths with equal amplitudes using a single near-infrared wavelength. Nonlinear holography using multiple nonlinear processes simultaneously provides an alternative path to holographic color display applications, enhanced optical encryption schemes, and multiplexed optical data storage.

Ferrous to Ferric Transition in Fe-Phthalocyanine Driven by NO2 Exposure.

Due to its unique magnetic properties offered by the open-shell electronic structure of the central metal ion, and for being an effective catalyst in a wide variety of reactions, iron phthalocyanine has drawn significant interest from the scientific community. Nevertheless, upon surface deposition, the magnetic properties of the molecular layer can be significantly affected by the coupling occurring at the interface, and the more reactive the surface, the stronger is the impact on the spin state. Here, we show that on Cu(100), indeed, the strong hybridization between the Fe d-states of FePc and the sp-band of the copper substrate modifies the charge distribution in the molecule, significantly influencing the magnetic properties of the iron ion. The FeII ion is stabilized in the low singlet spin state (S=0), leading to the complete quenching of the molecule magnetic moment. By exploiting the FePc/Cu(100) interface, we demonstrate that NO2 dissociation can be used to gradually change the magnetic properties of the iron ion, by trimming the gas dosage. For lower doses, the FePc film is decoupled from the copper substrate, restoring the gas phase triplet spin state (S=1). A higher dose induces the transition from ferrous to ferric phthalocyanine, in its intermediate spin state, with enhanced magnetic moment due to the interaction with the atomic ligands. Remarkably, in this way, three different spin configurations have been observed within the same metalorganic/metal interface by exposing it to different doses of NO2 at room temperature.

Ultrafast Charge-Transfer Exciton Dynamics in C60 Thin Films.

The high flexibility of organic molecules offers great potential for designing the optical properties of optically active materials for the next generation of optoelectronic and photonic applications. However, despite successful implementations of molecular materials in today's display and photovoltaic technology, many fundamental aspects of the light-to-charge conversion in molecular materials have still to be uncovered. Here, we focus on the ultrafast dynamics of optically excited excitons in C60 thin films depending on the molecular coverage and the light polarization of the optical excitation. Using time- and momentum-resolved photoemission with femtosecond extreme ultraviolet (fs-XUV) radiation, we follow the exciton dynamics in the excited states while simultaneously monitoring the signatures of the excitonic charge character in the renormalization of the molecular valence band structure. Optical excitation with visible light results in the instantaneous formation of charge-transfer (CT) excitons, which transform stepwise into Frenkel-like excitons at lower energies. The number and energetic position of the CT and Frenkel-like excitons within this cascade process are independent of the molecular coverage and the light polarization of the optical excitation. In contrast, the depopulation times of the CT and Frenkel-like excitons depend on the molecular coverage, while the excitation efficiency of CT excitons is determined by the light polarization. Our comprehensive study reveals the crucial role of CT excitons for the excited-state dynamics of homomolecular fullerene materials and thin films.

Strong modification of the transport level alignment in organic materials after optical excitation.

Organic photovoltaic devices operate by absorbing light and generating current. These two processes are governed by the optical and transport properties of the organic semiconductor. Despite their common microscopic origin-the electronic structure-disclosing their dynamical interplay is far from trivial. Here we address this issue by time-resolved photoemission to directly investigate the correlation between the optical and transport response in organic materials. We reveal that optical generation of non-interacting excitons in a fullerene film results in a substantial redistribution of all transport levels (within 0.4 eV) of the non-excited molecules. As all observed dynamics evolve on identical timescales, we conclude that optical and transport properties are completely interlinked. This finding paves the way for developing novel concepts for transport level engineering on ultrafast time scales that could lead to novel functional optoelectronic devices.

Enhancing Light Emission in Interface Engineered Spin-OLEDs through Spin-Polarized Injection at High Voltages.

The quest for a spin-polarized organic light-emitting diode (spin-OLED) is a common goal in the emerging fields of molecular electronics and spintronics. In this device, two ferromagnetic (FM) electrodes are used to enhance the electroluminescence intensity of the OLED through a magnetic control of the spin polarization of the injected carriers. The major difficulty is that the driving voltage of an OLED device exceeds a few volts, while spin injection in organic materials is only efficient at low voltages. The fabrication of a spin-OLED that uses a conjugated polymer as bipolar spin collector layer and ferromagnetic electrodes is reported here. Through a careful engineering of the organic/inorganic interfaces, it is succeeded in obtaining a light-emitting device showing spin-valve effects at high voltages (up to 14 V). This allows the detection of a magneto-electroluminescence (MEL) enhancement on the order of a 2.4% at 9 V for the antiparallel (AP) configuration of the magnetic electrodes. This observation provides evidence for the long-standing fundamental issue of injecting spins from magnetic electrodes into the frontier levels of a molecular semiconductor. The finding opens the way for the design of multifunctional devices coupling the light and the spin degrees of freedom.

Modification of Pb quantum well states by the adsorption of organic molecules.

The successful implementation of nanoscale materials in next generation optoelectronic devices crucially depends on our ability to functionalize and design low dimensional materials according to the desired field of application. Recently, organic adsorbates have revealed an enormous potential to alter the occupied surface band structure of tunable materials by the formation of tailored molecule-surface bonds. Here, we extend this concept of adsorption-induced surface band structure engineering to the unoccupied part of the surface band structure. This is achieved by our comprehensive investigation of the unoccupied band structure of a lead (Pb) monolayer film on the Ag(1 1 1) surface prior and after the adsorption of one monolayer of the aromatic molecule 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA). Using two-photon momentum microscopy, we show that the unoccupied states of the Pb/Ag(1 1 1) bilayer system are dominated by a parabolic quantum well state (QWS) in the center of the surface Brillouin zone with Pb p[Formula: see text] orbital character and a side band with almost linear dispersion showing Pb p[Formula: see text] orbital character. After the adsorption of PTCDA, the Pb side band remains completely unaffected while the signal of the Pb QWS is fully suppressed. This adsorption induced change in the unoccupied Pb band structure coincides with an interfacial charge transfer from the Pb layer into the PTCDA molecule. We propose that this charge transfer and the correspondingly vertical (partially chemical) interaction across the PTCDA/Pb interface suppresses the existence of the QWS in the Pb layer. Our results hence unveil a new possibility to orbital selectively tune and control the entire surface band structure of low dimensional systems by the adsorption of organic molecules.

Activating the molecular spinterface.

The miniaturization trend in the semiconductor industry has led to the understanding that interfacial properties are crucial for device behaviour. Spintronics has not been alien to this trend, and phenomena such as preferential spin tunnelling, the spin-to-charge conversion due to the Rashba-Edelstein effect and the spin-momentum locking at the surface of topological insulators have arisen mainly from emergent interfacial properties, rather than the bulk of the constituent materials. In this Perspective we explore inorganic/molecular interfaces by looking closely at both sides of the interface. We describe recent developments and discuss the interface as an ideal platform for creating new spin effects. Finally, we outline possible technologies that can be generated thanks to the unique active tunability of molecular spinterfaces.

Band structure evolution during the ultrafast ferromagnetic-paramagnetic phase transition in cobalt.

The evolution of the electronic band structure of the simple ferromagnets Fe, Co, and Ni during their well-known ferromagnetic-paramagnetic phase transition has been under debate for decades, with no clear and even contradicting experimental observations so far. Using time- and spin-resolved photoelectron spectroscopy, we can make a movie on how the electronic properties change in real time after excitation with an ultrashort laser pulse. This allows us to monitor large transient changes in the spin-resolved electronic band structure of cobalt for the first time. We show that the loss of magnetization is not only found around the Fermi level, where the states are affected by the laser excitation, but also reaches much deeper into the electronic bands. We find that the ferromagnetic-paramagnetic phase transition cannot be explained by a loss of the exchange splitting of the spin-polarized bands but instead shows rapid band mirroring after the excitation, which is a clear signature of extremely efficient ultrafast magnon generation. Our result helps to understand band structure formation in these seemingly simple ferromagnetic systems and gives first clear evidence of the transient processes relevant to femtosecond demagnetization.

Controlled manipulation of the Co-Alq3 interface by rational design of Alq3 derivatives.

Recently, research has revealed that molecules can be used to steer the local spin properties of ferromagnetic surfaces. One possibility to manipulate ferromagnetic-metal-molecule interfaces in a controlled way is to synthesize specific, non-magnetic molecules to obtain a desired interaction with the ferromagnetic substrate. Here, we have synthesized derivatives of the well-known semiconductor Alq3 (with q = 8-hydroxyquinolinate), in which the 8-hydroxyquinolinate ligands are partially or completely replaced by similar ligands bearing O- or N-donor sets. The goal of this study was to investigate how the presence of (i) different donor atom sets and (ii) aromaticity in different conjugated π-systems influences the spin properties of the metal-molecule interface formed with a Co(100) surface. The spin-dependent metal-molecule-interface properties have been measured by spin-resolved photoemission spectroscopy, backed up by DFT calculations. Overall, our results show that, in the case of the Co-molecule interface, chemical synthesis of organic ligands leads to specific electronic properties of the interface, such as exciton formation or highly spin-polarized interface states. We find that these properties are even additive, i.e. they can be engineered into one single molecular system that incorporates all the relevant ligands.

Modifying the Surface of a Rashba-Split Pb-Ag Alloy Using Tailored Metal-Organic Bonds.

Hybridization-related modifications of the first metal layer of a metal-organic interface are difficult to access experimentally and have been largely neglected so far. Here, we study the influence of specific chemical bonds (as formed by the organic molecules CuPc and PTCDA) on a Pb-Ag surface alloy. We find that delocalized van der Waals or weak chemical π-type bonds are not strong enough to alter the alloy, while localized σ-type bonds lead to a vertical displacement of the Pb surface atoms and to changes in the alloy's surface band structure. Our results provide an exciting platform for tuning the Rashba-type spin texture of surface alloys using organic molecules.

Dynamic spin filtering at the Co/Alq3 interface mediated by weakly coupled second layer molecules.

Spin filtering at organic-metal interfaces is often determined by the details of the interaction between the organic molecules and the inorganic magnets used as electrodes. Here we demonstrate a spin-filtering mechanism based on the dynamical spin relaxation of the long-living interface states formed by the magnet and weakly physisorbed molecules. We investigate the case of Alq3 on Co and, by combining two-photon photoemission experiments with electronic structure theory, show that the observed long-time spin-dependent electron dynamics is driven by molecules in the second organic layer. The interface states formed by physisorbed molecules are not spin-split, but acquire a spin-dependent lifetime, that is the result of dynamical spin-relaxation driven by the interaction with the Co substrate. Such spin-filtering mechanism has an important role in the injection of spin-polarized carriers across the interface and their successive hopping diffusion into successive molecular layers of molecular spintronics devices.