We demonstrate that Fe4 molecules can be deposited on gold by thermal sublimation in ultra-high vacuum with retention of single molecule magnet behavior. A magnetic hysteresis comparable to that found in bulk samples is indeed observed when a submonolayer film is studied by X-ray magnetic circular dichroism. Scanning tunneling microscopy evidences that Fe4 molecules are assembled in a two-dimensional lattice with short-range hexagonal order and coexist with a smaller contaminant. The presence of intact Fe4 molecules and the retention of their bistable magnetic behavior on the gold surface are supported by density functional theory calculations.
Metal halide perovskites have emerged as materials of high interest for solar energy-to-electricity conversion, and in particular, the use of mixed-ion structures has led to high power conversion efficiencies and improved stability. For this reason, it is important to develop means to obtain atomic level understanding of the photoinduced behavior of these materials including processes such as photoinduced phase separation and ion migration. In this paper, we implement a new methodology combining visible laser illumination of a mixed-ion perovskite ((FAPbI3)0.85(MAPbBr3)0.15) with the element specificity and chemical sensitivity of core-level photoelectron spectroscopy. By carrying out measurements at a synchrotron beamline optimized for low X-ray fluxes, we are able to avoid sample changes due to X-ray illumination and are therefore able to monitor what sample changes are induced by visible illumination only. We find that laser illumination causes partially reversible chemistry in the surface region, including enrichment of bromide at the surface, which could be related to a phase separation into bromide- and iodide-rich phases. We also observe a partially reversible formation of metallic lead in the perovskite structure. These processes occur on the time scale of minutes during illumination. The presented methodology has a large potential for understanding light-induced chemistry in photoactive materials and could specifically be extended to systematically study the impact of morphology and composition on the photostability of metal halide perovskites.
We have studied the growth of pentacene molecules on the unreconstructed and stoichiometric surface of TiO2(110). At variance with its characteristic homeotropic growth mode, pentacene is found to be physisorbed on this dielectric substrate with its long molecular axis oriented parallel to the surface and aligned along the [001] direction. Pentacene molecules couple side-by-side into long stripes running along the [11̅0] direction, where the overlayer preserves the substrate lattice periodicity (∼6.5 Å). In the opposite direction, head-to-head pentacene repulsion drives the ordering of the stripes, whose spacing simply depends on the surface coverage. By near-edge X-ray absorption, NEXAFS, we have determined the pentacene molecules to be tilted by ∼25° off the surface around their long axis. At the monolayer coverage, the pentacene orientation and spacing are very close to that of the (010) bulk planes (also called a−c planes) of pentacene crystals. We have observed that at least two additional layers can be grown on top of the monolayer following a planar configuration. Both the strong side-by-side intermolecular attraction and the full development of the bulklike electronic states, as probed by NEXAFS, suggest an optimal charge transport along the monolayer stripes of lying-down molecules.
Single-molecule magnets (SMMs) present a promising avenue to develop spintronic technologies. Addressing individual molecules with electrical leads in SMM-based spintronic devices remains a ubiquitous challenge: interactions with metallic electrodes can drastically modify the SMM's properties by charge transfer or through changes in the molecular structure. Here, we probe electrical transport through individual Fe4 SMMs using a scanning tunnelling microscope at 0.5 K. Correlation of topographic and spectroscopic information permits identification of the spin excitation fingerprint of intact Fe4 molecules. Building from this, we find that the exchange coupling strength within the molecule's magnetic core is significantly enhanced. First-principles calculations support the conclusion that this is the result of confinement of the molecule in the two-contact junction formed by the microscope tip and the sample surface.
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