arXiv subjects

Mirko Cinchetti

Publications and source records attributed to Mirko Cinchetti.

31 records · Page 2Linked to original sources

arXiv2020

Molecular anchoring stabilizes low valence Ni(I)TPP on copper against thermally induced chemical changes

Many applications of molecular layers deposited on metal surfaces, ranging from single-atom catalysis to on-surface magnetochemistry and biosensing, rely on the use of thermal cycles to regenerate the pristine properties of the system. Thus, understanding the microscopic origin behind the thermal stability of organic/metal interfaces is fundamental for engineering reliable organic-based devices. Here, we study nickel porphyrin molecules on a copper surface as an archetypal system containing a metal center whose oxidation state can be controlled through the interaction with the metal substrate. We demonstrate that the strong molecule-surface interaction, followed by charge transfer at the interface, plays a fundamental role in the thermal stability of the layer by rigidly anchoring the porphyrin to the substrate. Upon thermal treatment, the molecules undergo an irreversible transition at 420 K, which is associated with an increase of the charge transfer from the substrate, mostly localized on the phenyl substituents, and a downward tilting of the latters without any chemical modification

cond-mat.mtrl-sci↗

arXiv2020

Signatures of an Atomic Crystal in the Band Structure of a Molecular Thin Film

Transport phenomena in molecular materials are intrinsically linked to the orbital character and the degree of localization of the valence states. Here, we combine angle-resolved photoemission with photoemission tomography to determine the spatial distribution of all molecular states of the valence band structure of a C$_{60}$ thin film. While the two most frontier valence states exhibit a strong band dispersion, the states at larger binding energies are characterized by distinct emission patterns in energy and momentum space. Our findings demonstrate the formation of an atomic crystal-like band structure in a molecular solid with delocalized $π$-like valence states and strongly localized $σ$-states at larger binding energies.

cond-mat.mes-hall↗

arXiv2020

Modification of the charge and magnetic order of a low dimensional ferromagnet by molecule-surface bonding

The ability to design and control the spin and charge order of low dimensional materials on the molecular scale offers an intriguing pathway towards the miniaturization of spintronic technology towards the nanometer scale. In this work, we focus on the adsorption induced modifications of the magnetic and electronic properties of a low dimensional ferromagnetic surface alloy after the adsorption of the prototypical organic molecule perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA). For this metal-organic interface, we observe the formation of a localized $σ$-like bond between the functional molecular groups and the surface alloy atoms. This strong chemical bonding coincides with a lifting of the characteristic surface alloy band structure and a reduction of the magnitude of the local magnetic moments of the Dy atoms by 18%. We attribute both findings to a mixing of spin-degenerate molecular states with spin-split states of the Dy-Ag surface alloy via the sigma-like bonds between PTCDA and the Dy surface alloy atoms. Our findings clearly demonstrate the potential of tailored molecule-surface sigma-bonds to control not only the electronic but also the magnetic order of low dimensional materials.

cond-mat.mes-hall↗

arXiv2020

Ultrafast charge carrier separation in Potassium-intercalated endohedral metallofullerene Sc$_3$N@C$_{80}$ thin films

Molecular materials have emerged as highly tunable materials for photovoltaic and light-harvesting applications. The most severe challenge of this class of materials is the trapping of charge carriers in bound electron-hole pairs, which severely limits the free charge carrier generation. Here, we demonstrate a significant modification of the exciton dynamics of thin films of endohedral metallofullerene complexes upon alkali metal intercalation. For the exemplary case of Sc$_3$N@C$_{80}$ thin films, we show that potassium intercalation results in an additional relaxation channel for the optically excited charge-transfer excitons that prevents the trapping of excitons in a long-lived Frenkel exciton-like state. Instead, K intercalation leads to an ultrafast exciton dissociation coinciding most likely with the generation of free charge carriers. In this way, we propose alkali metal doping of molecular films as a novel approach to enhance the light to-charge carrier conversion efficiency in photovoltaic materials.

cond-mat.mes-hall↗

arXiv2020

Ultrafast charge-transfer exciton dynamics in C$_{60}$ thin films

The high flexibility of organic molecules offers great potential for designing the optical properties of light-active materials for the next generation of optoelectronic and photonic applications. However, despite successful implementations of molecular materials in todays' display and photovoltaic technology, many fundamental aspects of the light-to-charge conversion have still to be uncovered. Here, we focus on the ultrafast dynamics of optically excited excitons in C$_{60}$ thin films depending on the molecular coverage and the light-polarization of the optical excitons. Using time- and momentum-resolved photoemission with fs-XUV radiation, we follow the depopulation dynamics in the excited states while simultaneously monitoring the signatures of the excitonic charge character in the molecular valence states. Optical excitation with visible light results in the instantaneous formation of charge-transfer (CT) excitons, which transform stepwise into energetically lower Frenkel-like excitons. While the number and energetic position of energy levels within this cascade process are independent of the molecular coverage and the light polarization of the optical excitation, we find quantitative differences in the depopulation times and the optical excitation efficiency. Our comprehensive study reveals the crucial role of CT excitons for the excited state dynamics of homo-molecular fullerene materials and thin films.

cond-mat.mes-hall↗

arXiv2020

Vertical bonding distances and interfacial band structure of PTCDA on a Sn-Ag surface alloy

Molecular materials enable a vast variety of functionalities for novel electronic and spintronic devices. The unique possibility to alter or substitute organic molecules or metallic substrates offers the opportunity to modify and optimize interfacial properties for almost any desired field of application. For this reason, we extend the successful approach to control molecular interfaces by surface alloying. We present a comprehensive characterization of the structural and electronic properties of the interface formed between the prototypical molecule PTCDA and a Sn-Ag surface alloy grown on an Ag(111) single crystal surface. We monitor the changes of adsorption height of the surface alloy atoms and electronic valence band structure upon adsorption of one layer of PTCDA using the normal incidence x-ray standing wave technique in combination with momentum-resolved photoelectron spectroscopy. We find that the vertical buckling and the surface band structure of the SnAg$_2$ surface alloy is not altered by the adsorption of one layer of PTCDA, in contrast to our recent study of PTCDA on a PbAg$_2$ surface alloy [Phys. Rev. Lett. 117, 096805 (2016)] . In addition, the vertical adsorption geometry of PTCDA and the interfacial energy level alignment indicate the absence of any chemical interaction between the molecule and the surface alloy. We attribute the different interactions at these PTCDA/surface alloy interfaces to the presence or absence of local $σ$-bonds between the PTCDA oxygen atoms and the surface atoms. Combining our findings with results from literature, we are able to propose an empiric rule for engineering the surface band structure of alloys by adsorption of organic molecules.

cond-mat.mes-hall↗

arXiv2015

Topological States on the Gold Surface

Gold surfaces host special electronic states that have been understood as a prototype of Shockley surface states (SSs). These SSs are commonly employed to benchmark the capability of angle-resolved photoemission spectroscopy (ARPES) and scanning tunneling spectroscopy. We find that these Shockley SSs can be reinterpreted as topologically derived surface states (TDSSs) of a topological insulator (TI), a recently discovered quantum state. Based on band structure calculations, the Z2 topological invariant can be well defined to characterize the nontrivial features of gold that we detect by ARPES. The same TDSSs are also recognized on surfaces of other well-known noble metals (e.g., silver, copper, platinum, and palladium). Besides providing a new understanding of noble metal SSs, finding topological states on late transition metals provokes interesting questions on the role of topological effects in surface-related processes, such as adsorption and catalysis.

cond-mat.mtrl-sci↗

arXiv2012

Structural, chemical and electronic properties of the Co2MnSi(001)/MgO interface

The performance of advanced magnetic tunnel junctions build of ferromagnetic (FM) electrodes and MgO as insulating barrier depends decisively on the properties of the FM/insulator interface. Here, we investigate interface formation between the half-metallic compound Co2MnSi (CMS) and MgO by means of Auger electron spectroscopy, low energy electron diffraction and low energy photoemission. The studies are performed for different annealing temperatures TA and MgO layer coverages (4, 6, 10, 20 and 50 ML). Thin MgO top layers (t_MgO<=10 ML) show distinct surface crystalline distortions, which can only be partly healed out by annealing and furthermore lead to distinct adsorption of carbon species after the MgO surface is exposed to air. For t_MgO> 10 ML the MgO layer surface exhibits clearly improved crystalline structure and hence only marginal amounts of adsorbates. We attribute these findings to MgO misfit dislocations occurring at the interface, inducing further defects throughout the MgO layer for up to at least 10 ML. Furthermore, spin-polarized photoemission spectra of the CMS/MgO interface are obtained for MgO coverages up to 20 ML, showing a clear positive spin polarization near the Fermi energy in all cases.

cond-mat.mtrl-sci↗

arXiv2012

Revealing the spin and symmetry properties of the buried Co2MnSi/MgO interface by low energy spin-resolved photoemission

We present a novel approach to study the spin and symmetry electronic properties of buried interfaces using low-energy spin-resolved photoemission spectroscopy. We show that this method is sensitive to interfaces buried below more than 20ML (~4nm) MgO, providing a powerful tool for the non-destructive characterization of spintronics interfaces. As a demonstration, we apply this technique to characterize the Co2MnSi/MgO interface, a fundamental building block of state-of-the-art magnetic tunnel junctions based on Heusler compounds. We find that a surface state with Δ1 symmetry and minority spin character dominating the electronic structure of the bare Co2MnSi(100) surface is quenched at the Co2MnSi(100)/MgO interface. As a result, the interface spin-dependent electronic structure resembles the theoretically expected Co2MnSi bulk band structure, with majority spin electronic states of both Δ1 and Δ5 symmetry. Furthermore we find an additional thermally-induced contribution in the minority channel, mirroring the Δ1/Δ5 asymmetry of the majority channel.

cond-mat.mtrl-sci↗

arXiv2012

Light-induced magnetization reversal of high-anisotropy TbCo alloy films

Magnetization reversal using circularly polarized light provides a new way to control magnetization without any external magnetic field and has the potential to revolutionize magnetic data storage. However, in order to reach ultra-high density data storage, high anisotropy media providing thermal stability are needed. Here, we evidence all-optical magnetization switching for different TbxCo1-x ferrimagnetic alloy composition and demonstrate all-optical switching for films with anisotropy fields reaching 6 T corresponding to anisotropy constants of 3x106 ergs/cm3. Optical magnetization switching is observed only for alloys which compensation temperature can be reached through sample heating.

cond-mat.mtrl-sci↗

arXiv2011

Surface spin polarization of the non-stoichiometric Heusler compound Co2Mn(alpha)Si

Using a combined approach of spin-resolved photoemission spectroscopy, band structure and photoemission calculations we investigate the influence of bulk defects and surface states on the spin polarization of Co2Mn(alpha)Si thin films with bulk L21 order. We find that for Mn-poor alloys the spin polarization at EF is negative due to the presence of Co_Mn antisite and minority surface state contributions. In Mn-rich alloys, the suppression of Co(Mn) antisites leads to a positive spin polarization at the Fermi energy, and the influence of minority surface states on the photoelectron spin polarization is reduced.

cond-mat.mtrl-sci↗

arXiv2009

Direct determination of the surface termination in full Heusler alloys by means of low energy electron diffraction

The performance of Heusler based magnetoresistive multilayer devices depends crucially on the spin polarization and thus on the structural details of the involved surfaces. Using low energy electron diffraction (LEED), one can non-destructively distinguish between important surface terminations of Co2XY full-Heusler alloys. We present an analysis of the LEED patterns of the Y-Z ,the vacancy-Z, the Co and the disordered B2 and A2 terminations. As an example, we show that the surface geometries of bulk L21 ordered Co2MnSi and bulk B2 disordered Co2Cr0.6Fe0.4Al can be determined by comparing the experimental LEED patterns with the presented reference patterns.

cond-mat.mtrl-sci↗

arXiv2009

Ultrafast demagnetization of ferromagnetic transition metals: The role of the Coulomb interaction

The Elliott-Yafet mechanism is arguably the most promising candidate to explain the ultrafast demagnetization dynamics in ferromagnetic transition metals on timescales on the order of 100 femtoseconds. So far, only electron-phonon scattering has been analyzed as the scattering process needed to account for the demagnetization due to the Elliott-Yafet mechanism. We show for the first time that the electron-electron scattering contribution to the Elliott-Yafet mechanism has the potential to explain time-resolved magneto-optical Kerr effect measurements on thin magnetic cobalt and nickel films, without reference to a phononic "spin bath."

cond-mat.mtrl-sci↗