Investigating magneto-chemical interactions at molecule-substrate interfaces by X-ray photo-emission electron microscopy

The magneto-chemical interaction of spin-bearing molecules with substrates is interesting from a coordination chemistry point of view and relevant for spintronics. Unprecedented insight is provided by X-ray photo-emission electron microscopy combined with X-ray magnetic circular dichroism spectroscopy. Here the coupling of a Mn-porphyrin ad-layer to the ferromagnetic Co substrate through suitably modified interfaces is analyzed with this technique

Plasmon-enhanced optical control of magnetism at the nanoscale via the inverse Faraday effect

The relationship between magnetization and light has been the subject of intensive research for the past century, focusing on the impact of magnetic moments on light polarization. Conversely, the manipulation of magnetism through polarized light is being investigated to achieve all-optical control of magnetism in spintronics. While remarkable discoveries such as single pulse all-optical switching of the magnetization in thin films and sub-micrometer structures have been reported, the demonstration of local optical control of magnetism at the nanoscale has remained elusive. Here, we show that exciting gold nanodiscs with circularly polarized femtosecond laser pulses leads to the generation of sizeable local magnetic fields that enable ultrafast local control of the magnetization of an adjacent magnetic film. In addition, we find that the highest magnetic fields are generated when exciting the sample at a wavelength larger than that of the actual plasmonic resonance of the gold nanodiscs, so avoiding undesired heating effects due to absorption. Our study paves the way for light-driven control in nanoscale spintronic devices and provides important insights into the generation of magnetic fields in plasmonic nanostructures

Magnetic exchange coupling of a synthetic Co(II)-complex to a ferromagnetic Ni substrate

On-surface assembly of a spin-bearing and non-aromatic porphyrin-related synthetic Co(II)-complex on a ferromagnetic Ni thin film substrate and subsequent magnetic exchange interaction across the interface were studied by scanning tunnelling microscopy (STM), X-ray absorption spectroscopy (XAS), X-ray magnetic circular dichroism (XMCD) and density functional theory +U (DFT + U) calculations

Antiferromagnetic coupling of Cr-porphyrin to a bare Co substrate

We report the discovery of an antiferromagnetic coupling of the magnetic moment of chromium(II) tetraphenyl-porphyrin (CrTPP) molecules to the magnetization of the clean ferromagnetic Co(001) substrate. We assign this unusual molecule-substrate exchange coupling to the less than half-filled chromium 3d orbitals interacting with Co valence band electrons via porphyrin-ligand molecular orbitals. X-ray magnetic circular dichroism, x-ray photoelectron spectroscopy, and scanning tunneling microscopy are combined with DFT+U calculations and provide evidence for a surprising type of antiferromagnetic 90∘ indirect magnetic exchange coupling

Direct observation of enhanced magnetism in individual size- and shape-selected 3d transition metal nanoparticles

Magnetic nanoparticles are critical building blocks for future technologies ranging from nanomedicine to spintronics. Many related applications require nanoparticles with tailored magnetic properties. However, despite significant efforts undertaken towards this goal, a broad and poorly understood dispersion of magnetic properties is reported, even within monodisperse samples of the canonical ferromagnetic 3d transition metals. We address this issue by investigating the magnetism of a large number of size- and shape-selected, individual nanoparticles of Fe, Co, and Ni using a unique set of complementary characterization techniques. At room temperature, only superparamagnetic behavior is observed in our experiments for all Ni nanoparticles within the investigated sizes, which range from 8 to 20 nm. However, Fe and Co nanoparticles can exist in two distinct magnetic states at any size in this range: (i) a superparamagnetic state, as expected from the bulk and surface anisotropies known for the respective materials and as observed for Ni, and (ii) a state with unexpected stable magnetization at room temperature. This striking state is assigned to significant modifications of the magnetic properties arising from metastable lattice defects in the core of the nanoparticles, as concluded by calculations and atomic structural characterization. Also related with the structural defects, we find that the magnetic state of Fe and Co nanoparticles can be tuned by thermal treatment enabling one to tailor their magnetic properties for applications. This paper demonstrates the importance of complementary single particle investigations for a better understanding of nanoparticle magnetism and for full exploration of their potential for applications

A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface

Oxidation of bromide in aqueous environments initiates the formation of molecular halogen compounds, which is important for the global tropospheric ozone budget. In the aqueous bulk, oxidation of bromide by ozone involves a [Br•OOO−] complex as intermediate. Here we report liquid jet X-ray photoelectron spectroscopy measurements that provide direct experimental evidence for the ozonide and establish its propensity for the solution-vapor interface. Theoretical calculations support these findings, showing that water stabilizes the ozonide and lowers the energy of the transition state at neutral pH. Kinetic experiments confirm the dominance of the heterogeneous oxidation route established by this precursor at low, atmospherically relevant ozone concentrations. Taken together, our results provide a strong case of different reaction kinetics and mechanisms of reactions occurring at the aqueous phase-vapor interface compared with the bulk aqueous phase

Single shot time-resolved magnetic x-ray absorption at a Free Electron Laser

Ultrafast dynamics are generally investigated using stroboscopic pump-probe measurements, which characterize the sample properties for a single, specific time delay. These measurements are then repeated for a series of discrete time delays to reconstruct the overall time trace of the process. As a consequence, this approach is limited to the investigation of fully reversible phenomena. We recently introduced an off-axis zone plate based X-ray streaking technique, which overcomes this limitation by sampling the relaxation dynamics with a single femtosecond X-ray pulse streaked over a picosecond long time window. In this article we show that the X-ray absorption cross section can be employed as the contrast mechanism in this novel technique. We show that changes of the absorption cross section on the percent level can be resolved with this method. To this end we measure the ultrafast magnetization dynamics in CoDy alloy films. Investigating different chemical compositions and infrared pump fluences, we demonstrate the routine applicability of this technique. Probing in transmission the average magnetization dynamics of the entire film, our experimental findings indicate that the demagnetization time is independent of the specific infrared laser pump fluence. These results pave the way for the investigation of irreversible phenomena in a wide variety of scientific areas.Comment: 9 pages, 5 figure