Controlled laser-induced dehydrogenation of free-standing graphane probed by pump–probe X-ray photoemission

The effects of optical excitation on fully hydrogenated free-standing nanoporous graphene have been characterized by pump–probe X-ray photoemission spectroscopy. Hydrogenated graphene, known as graphane, is characterized by a sp3 hybridization, which induces a sp3 component in the C 1s core level whose intensity can be used to monitor the hydrogen content. Under optical excitation we observe a partial dehydrogenation of graphane, which we attribute to local laser-induced heating; such result allows us to estimate the thermal conductivity of the material, for which we found an upper limit of 0.2 W/(m K), four orders of magnitude smaller than that of graphene. Such stark difference, combined with the possibility of dehydrogenating the graphane substrate via laser exposure, may be exploited to engineer nanostructured heat conduction channels in organic and hybrid organic–inorganic devices. We then explored the sub-nanosecond dynamics of the C 1s core level, which displays a kinetic energy shift and a peak broadening with two different decay constants, 210 ps and 130 ps, respectively. We assign the former to surface photovoltage, and the latter to transient lattice heating

Ultrafast Ge-Te bond dynamics in a phase-change superlattice

A long-standing question for avant-garde data storage technology concerns the nature of the ultrafast photoinduced phase transformations in the wide class of chalcogenide phase-change materials (PCMs). Overall, a comprehensive understanding of the microstructural evolution and the relevant kinetics mechanisms accompanying the out-of-equilibrium phases is still missing. Here, after overheating a phase-change chalcogenide superlattice by an ultrafast laser pulse, we indirectly track the lattice relaxation by time resolved x-ray absorption spectroscopy (tr-XAS) with a sub-ns time resolution. The approach to the tr-XAS experimental results reported in this work provides an atomistic insight of the mechanism that takes place during the cooling process; meanwhile a first-principles model mimicking the microscopic distortions accounts for a straightforward representation of the observed dynamics. Finally, we envisage that our approach can be applied in future studies addressing the role of dynamical structural strain in PCMs.M.M. acknowledges the support of the BACH beamline staff during the synchrotron experiments and Roberta Ciprian for insightful discussions. This work was supported by EU within FP7 project PASTRY [GA 317764]

Relating Energy Level Alignment and Amine-Linked Single Molecule Junction Conductance

Using photoemission spectroscopy, we determine the relationship between electronic energy level alignment at a metal-molecule interface and single-molecule junction transport data. We measure the position of the highest occupied molecular orbital (HOMO) relative to the Au metal Fermi level for three 1,4-benzenediamine derivatives on Au(111) and Au(110) with ultraviolet and resonant x-ray photoemission spectroscopy. We compare these results to scanning tunnelling microscope based break-junction measurements of single molecule conductance and to first-principles calculations. We find that the energy difference between the HOMO and Fermi level for the three molecules adsorbed on Au(111) correlate well with changes in conductance, and agree well with quasiparticle energies computed from first-principles calculations incorporating self-energy corrections. On the Au(110) which present Au atoms with lower-coordination, critical in break-junction conductance measurements, we see that the HOMO level shifts further from the Fermi level. These results provide the first direct comparison of spectroscopic energy level alignment measurements with single molecule junction transport data

Phase separation in the non-equilibrium Verwey transition in magnetite

We present equilibrium and out-of-equilibrium studies of the Verwey transition in magnetite. In the equilibrium optical conductivity, we find a step-like change at the phase transition for photon energies below about 2 eV. The possibility of triggering a non-equilibrium transient metallic state in insulating magnetite by photo excitation was recently demonstrated by an x-ray study. Here we report a full characterization of the optical properties in the visible frequency range across the non-equilibrium phase transition. Our analysis of the spectral features is based on a detailed description of the equilibrium properties. The out-of-equilibrium optical data bear the initial electronic response associated to localized photo-excitation, the occurrence of phase separation, and the transition to a transient metallic phase for excitation density larger than a critical value. This allows us to identify the electronic nature of the transient state, to unveil the phase transition dynamics, and to study the consequences of phase separation on the reflectivity, suggesting a spectroscopic feature that may be generally linked to out-of-equilibrium phase separation

Vacuum space charge effects in sub-picosecond soft X-ray photoemission on a molecular adsorbate layer

Vacuum space charge induced kinetic energy shifts of O 1s and Ru 3d core levels in femtosecond soft X-ray photoemission spectra (PES) have been studied at a free electron laser (FEL) for an oxygen layer on Ru(0001). We fully reproduced the measurements by simulating the in-vacuum expansion of the photoelectrons and demonstrate the space charge contribution of the high-order harmonics in the FEL beam. Employing the same analysis for 400 nm pump-X-ray probe PES, we can disentangle the delay dependent Ru 3d energy shifts into effects induced by space charge and by lattice heating from the femtosecond pump pulse

Implantation of a Sutureless Valve Into a Surgically Enlarged Aortic Root: A Bailout Option

Sutureless bioprostheses such as the Sorin Perceval Valve (SPV; Sorin Group, Srl, Saluggia, Italy) have been proposed for replacing stenotic native valves within small aortic roots of geriatric patients with significant comorbidity. Their use seems as safe as that of stented bioprostheses and enables significantly reduced length of surgery. Low transprosthetic pressure gradients have been measured. Because of the radial force of its self-expandable nitinol stent, aortic annulus interruption could be a relative contraindication to SPV use. Off-label implantation of the SPV into a surgically enlarged ascending aorta was first reported in this study, as a bailout option in the presence of a tiny aortic root

Pump-Probe X-ray Photoemission Reveals Light-Induced Carrier Accumulation in Organic Heterojunctions

The energy level alignment in the heterojunction formed by tetracene and copper phthalocyanine grown on the Ag(111) substrate has been studied for two different sequences of layer stacking. Filled and empty molecular levels as well as charge transfer states have been characterized by combining ultraviolet and two-photon photoemission spectroscopies. It is shown that the layer in contact with the substrate determines the molecular arrangements of the whole system, thus inducing different interface dipoles at the heterojunction, depending on the stacking sequence. Such dipoles strongly influence the exciton dynamics and charge separation at the interface. The accumulation of the charge carriers in the heterojunction has been observed by measuring the transient shift of core level photoemission lines, which arises after the resonant excitation of either of the two molecular constituents

Photo-induced lattice distortion in 2H-MoTe2 probed by time-resolved core level photoemission

The technological interest in MoTe2 as a phase engineered material is related to the possibility of triggering the 2H-1T ' phase transition by optical excitation, potentially allowing for an accurate patterning of metallic areas into a semiconducting canvas via laser irradiation. In this paper, we investigate the photo-induced modifications of a bulk 2H-MoTe2 crystal by means of time-resolved X-ray photoemission spectroscopy. We observe that in the microsecond timescale, the core levels shift to higher kinetic energies due to surface photovoltage fields, while in the sub-nanosecond range, the photoemission peaks shift in the opposite direction. With the support of DFT calculations, we ascribe the latter effect to the deformation of the lattice in the out-of-plane direction, which is along the pathway for the 2H-1T ' phase transition. Our data indicate an intermediate lattice excitation state with a measured lifetime in the order of 600 ps, in which the displacement of Mo and Te atoms causes the Te 4d electrons to shift towards higher binding energies