A-site doped SrTiO3 is considered as a promising substitute for traditional anodic metals in solid oxide fuel cells (SOFCs). In this study, we present the reactivity of La0.2Sr0.25Ca0.45TiO3 (LCSTO), La0.2Sr0.7TiO3 (LSTO), and SrTiO3 (STO) toward H2 by operando ambient pressure NEXAFS spectroscopy and theoretical spectra simulation with FDMNES code. The samples were synthesized by MBE (molecular beam epitaxy), hydrothermal, and modified-Pechini routes. We found that the reducibility of the samples depends not only on their stoichiometry but also on the morphology, which is determined by the synthetic method. The results of these experiments give insight into the reducibility of Ti4+ in perovskites as well as the opportunity to further optimize the synthesis of these materials to obtain the best performance for SOFC applications.
Methane is a valuable resource and its valorization is an important challenge in heterogeneous catalysis. Here it is shown that CeO2/CuO composite prepared by ball milling activates methane at a temperature as low as 250 °C. In contrast to conventionally prepared catalysts, the formation of partial oxidation products such as methanol and formaldehyde is also observed. Through an in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) and operando Near Edge X-Ray Absorption Fine Structure Spectroscopy (NEXAFS) approach, it can be established that this unusual reactivity can be attributed to the presence of Ce4+/Cu+ interfaces generated through a redox exchange between Ce3+ and Cu2+ atoms facilitated by the mechanical energy supplied during milling. DFT modeling of the electronic properties confirms the existence of a charge transfer mechanism. These results demonstrate the effectiveness and distinctiveness of the mechanical approach in creating unique and resilient interfaces thereby enabling the optimization and refining of CeO2/CuO catalysts in methane activation reactions.
In the field of hydrogen production, MoS2 demonstrates good catalytic properties for the hydrogen evolution reaction (HER) which improve when doped with metal cations. However, while the role of sulfur atoms as active sites in the HER is largely reported, the role of metal atoms (i.e. molybdenum or the dopant cations) has yet to be studied in depth. To understand the role of the metal dopant, we study MoS2 thin films doped with Co and Mn ions. We identify the contribution of the electronic bands of the Mn and Co dopants to the integral valence band of the material using in situ resonant photoemission measurements. We demonstrate that Mn and Co dopants act differently: Mn doping favors the shift of the S–Mo hybridized band towards the Fermi level, while in the case of Co doping it is the less hybridized Co band that shifts closer to the Fermi level. Doping with Mn increases the effectiveness of S as the active site, thus improving the HER, while doping with Co introduces the metallic site of Co as the active site, which is less effective in improving HER properties. We therefore clarify the role of the dopant cation in the electronic structure determining the active site for hydrogen adsorption/desorption. Our results pave the way for the design of efficient materials for hydrogen production via the doping route, which can be extended to different catalytic reactions in the field of energy applications.
In the search of low cost and more efficient electronic devices, here the properties of SrVO3 transparent conductor oxide (TCO) thin film are investigated, both visible-range optically transparent and highly conductive, it stands as a promising candidate to substitute the standard indium-tin-oxide (ITO) in applications. Its surface stability under water (both liquid and vapor) and other gaseous atmospheres is especially addressed. Through the use of spectroscopy characterizations, X-ray photoemission and operando X-ray absorption measurements, the formation of a thin Sr-rich V5+ layer located at the surface of the polycrystalline SrVO3 film with aging is observed, and for the first time how it can be removed from the surface by solvating in water atmosphere. The surface recovery is associated to an etching process, here spectroscopically characterized in operando conditions, allowing to follow the stoichiometric modification under reaction. Once exposed in oxygen atmosphere, the Sr-rich V5+ layer forms again. The findings improve the understanding of aging effects in perovskite oxides, allowing for the development of functionalized films in which it is possible to control or to avoid an insulating surface layer. This constitutes an important step towards the large-scale use of V-based TCOs, with possible implementations in oxide-based electronics.
Hydrogen production from methanol decomposition to syngas (H2 + CO) is a promising alternative route for clean energy transition. One major challenge is related to the quest for stable, cost-effective, and selective catalysts operating below 400 °C. We illustrate an investigation of the surface reactivity of a Ni3Sn4 catalyst working at 250 °C, by combining density functional theory, operando X-ray absorption spectroscopy, and high-resolution transmission electron microscopy. We discovered that the catalytic reaction is driven by surface tin-oxide phases, which protects the underlying Ni atoms from irreversible chemical modifications, increasing the catalyst durability. Moreover, we found that Sn content plays a key role in enhancing the H2 selectivity, with respect to secondary products such as CO2. These findings open new perspectives for the engineering of scalable and low-cost catalysts for hydrogen production.
Phase transitions are key in determining and controlling the quantum properties of correlated materials. Here, by using the combination of material synthesis and photoelectron spectroscopy, we demonstrate a genuine Mott transition undressed of any symmetry breaking side effects in the thin films of V2O3. In particular and in contrast with the bulk V2O3, we unveil the purely electronic dynamics approaching the metal–insulator transition, disentangled from the structural transformation that is prevented by the residual substrate-induced strain. On approaching the transition, the spectral signal evolves slowly over a wide temperature range, the Fermi wave-vector does not change, and the critical temperature is lower than the one reported for the bulk. Our findings are fundamental in demonstrating the universal benchmarks of a genuine nonsymmetry breaking Mott transition, extendable to a large array of correlated quantum systems, and hold promise of exploiting the metal–insulator transition by implementing V2O3 thin films in devices.
The structural, electronic, and magnetic properties of Sr-hole-doped epitaxial La1–xSrxMnO3 (0.15 ≤ x ≤ 0.45) thin films deposited using the molecular beam epitaxy technique on 4° vicinal STO (001) substrates are probed by the combination of X-ray diffraction and various synchrotron-based spectroscopy techniques. The structural characterizations evidence a significant shift in the LSMO (002) peak to the higher diffraction angles owing to the increase in Sr doping concentrations in thin films. The nature of the LSMO Mn mixed-valence state was estimated from X-ray photoemission spectroscopy together with the relative changes in the Mn L2,3 edges observed in X-ray absorption spectroscopy (XAS), both strongly affected by doping. CTM4XAS simulations at the XAS Mn L2,3 edges reveal the combination of epitaxial strain, and different MnO6 crystal field splitting give rise to a peak at ∼641 eV. The observed changes in the occupancy of the eg and the t2g orbitals as well as their binding energy positions toward the Fermi level with hole doping are discussed. The room-temperature magnetic properties were probed at the end by circular dichroism.
We unravel the interplay of topological properties and the layered (anti)ferromagnetic ordering in EuSn2P2, using spin and chemical selective electron and X-ray spectroscopies supported by first-principle calculations. We reveal the presence of in-plane long-range ferromagnetic order triggering topological invariants and resulting in the multiple protection of topological Dirac states. We provide clear evidence that layer-dependent spin-momentum locking coexists with ferromagnetism in this material, a cohabitation that promotes EuSn2P2 as a prime candidate axion insulator for topological antiferromagnetic spintronics applications.
The emergence of Dirac semimetals has stimulated growing attention, owing to the considerable technological potential arising from their peculiar exotic quantum transport related to their nontrivial topological states. Especially, materials showing type-II Dirac fermions afford novel device functionalities enabled by anisotropic optical and magnetotransport properties. Nevertheless, real technological implementation has remained elusive so far. Definitely, in most Dirac semimetals, the Dirac point lies deep below the Fermi level, limiting technological exploitation. Here, it is shown that kitkaite (NiTeSe) represents an ideal platform for type-II Dirac fermiology based on spin-resolved angle-resolved photoemission spectroscopy and density functional theory. Precisely, the existence of type-II bulk Dirac fermions is discovered in NiTeSe around the Fermi level and the presence of topological surface states with strong (≈50%) spin polarization. By means of surface-science experiments in near-ambient pressure conditions, chemical inertness towards ambient gases (oxygen and water) is also demonstrated. Correspondingly, NiTeSe-based devices without encapsulation afford long-term efficiency, as demonstrated by the direct implementation of a NiTeSe-based microwave receiver with a room-temperature photocurrent of 2.8 µA at 28 GHz and more than two orders of magnitude linear dynamic range. The findings are essential to bringing to fruition type-II Dirac fermions in photonics, spintronics, and optoelectronics.
In this work, we apply for the first time ambient pressure operando soft X-ray absorption spectroscopy (XAS) to investigate the location, structural properties, and reactivity of the defective sites present in the prototypical metal–organic framework HKUST-1. We obtained direct evidence that Cu+ defective sites form upon temperature treatment of the powdered form of HKUST-1 at 160 °C and that they are largely distributed on the material surface. Further, a thorough structural characterization of the Cu+/Cu2+ dimeric complexes arising from the temperature-induced dehydration/decarboxylation of the pristine Cu2+/Cu2+ paddlewheel units is reported. In addition to characterizing the surface defects, we demonstrate that CO2 may be reversibly adsorbed and desorbed from the surface defective Cu+/Cu2+ sites. These findings show that ambient pressure soft-XAS, combined with state-of-the-art theoretical calculations, allowed us to shed light on the mechanism involving the decarboxylation of the paddlewheel units on the surface to yield Cu+/Cu2+ complexes and their reversible restoration upon exposure to gaseous CO2.
Due to their peculiar quasiparticle excitations, topological metals have high potential for applications in the fields of spintronics, catalysis, and superconductivity. Here, by combining spin- and angle-resolved photoemission spectroscopy, scanning tunneling microscopy/spectroscopy, and density functional theory, we discover surface-termination-dependent topological electronic states in the recently discovered mitrofanovite Pt3Te4. Mitrofanovite crystal is formed by alternating, van der Waals bound layers of Pt2Te2 and PtTe2. Our results demonstrate that mitrofanovite is a topological metal with termination-dependent (i) electronic band structure and (ii) spin texture. Despite their distinct electronic character, both surface terminations are characterized by electronic states exhibiting strong spin polarization with a node at the Γ point and sign reversal across the Γ point, indicating their topological nature and the possibility of realizing two distinct electronic configurations (both of them with topological features) on the surface of the same material.
We investigated the relationship between ferromagnetism and metallicity in strained La0.67Ca0.33MnO3 films grown on lattice-mismatched NdGaO3 (001) by means of spectroscopic techniques directly sensitive to the ferromagnetic state, to the band structure, and to the chemical state of the atoms. In this system, the ferromagnetic metallic (FMM) phase spatially coexists with an insulating one in most of the phase diagram. First, the observation of an almost 100% spin polarization of the photoelectrons at the Fermi level in the fundamental state provides direct evidence of the half-metallicity of the FMM phase, a result that has been previously observed through direct probing of the valence band only on unstrained, phase-homogeneous La0.67Sr0.33MnO3. Second, the spin polarization results to be correlated with the occupancy at the Fermi level for all the investigated temperature regimes. These outcomes show that the half-metallic behavior predicted by a double-exchange model persists even in phase-separated manganites. Moreover, the correlation between metallicity and ferromagnetic alignment is confirmed by X-ray magnetic circular dichroism, a more bulk-sensitive technique, allowing one to explain transport properties in terms of the conduction through aligned FMM domains.
Quantum materials are central for the development of novel functional systems that are often based on interface specific phenomena. Fabricating controlled interfaces between quantum materials requires adopting a flexible growth technique capable to synthesize different materials within a single-run deposition process with high control of structure, stoichiometry, and termination. Among the various available thin film growth technologies, pulsed laser deposition (PLD) allows controlling the growth of diverse materials at the level of single atomic layers. In PLD the atomic species are supplied through an ablation process of a stoichiometric target either in form of polycrystalline powders or of a single crystal. No carrier gases are needed in the deposition process. The ablation process is compatible with a wide range of background pressure. We present results of thin-film growth by PLD obtained by using an Nd:YAG infrared pulsed laser source operating at its first harmonics. With respect to the traditional PLD systems—based on excimer KrF UV-lasers—optimal conditions for the growth of thin films and heterostructures are reached at large target-to-substrate distance. Merits and limitations of this approach for growing oxide and non-oxide thin films are discussed. The merits of an Nd:YAG laser to grow very high-quality thin films suggest the possibility of implementing compact in-situ setups e.g. integrated with analytical instrumentation under ultra-high vacuum conditions.
Research on ultrathin quantum materials requires full control of the growth and surface quality of the specimens in order to perform experiments on their atomic structure and electron states leading to ultimate analysis of their intrinsic properties. We report results on epitaxial FeSe thin films grown by pulsed laser deposition (PLD) on CaF2 (001) substrates as obtained by exploiting the advantages of an all-in-situ ultra-high vacuum (UHV) laboratory allowing for direct high-resolution surface analysis by scanning tunnelling microscopy (STM), synchrotron radiation X-ray photoelectron spectroscopy (XPS) and angle-resolved photoemission spectroscopy (ARPES) on fresh surfaces. FeSe PLD growth protocols were fine-tuned by optimizing target-to-substrate distance d and ablation frequency, atomically flat terraces with unit-cell step heights are obtained, overcoming the spiral morphology often observed by others. In-situ ARPES with linearly polarized horizontal and vertical radiation shows hole-like and electron-like pockets at the Γ and M points of the Fermi surface, consistent with previous observations on cleaved single crystal surfaces. The control achieved in growing quantum materials with volatile elements such as Se by in-situ PLD makes it possible to address the fine analysis of the surfaces by in-situ ARPES and XPS. The study opens wide avenues for the PLD based heterostructures as work-bench for the understanding of proximity-driven effects and for the development of prospective devices based on combinations of quantum materials.
Here, we present an integrated ultra-high vacuum apparatus—named MBE-Cluster —dedicated to the growth and in situ structural, spectroscopic, and magnetic characterization of complex materials. Molecular Beam Epitaxy (MBE) growth of metal oxides, e.g., manganites, and deposition of the patterned metallic layers can be fabricated and in situ characterized by reflection high-energy electron diffraction, low-energy electron diffraction, Auger electron spectroscopy, x-ray photoemission spectroscopy, and azimuthal longitudinal magneto-optic Kerr effect. The temperature can be controlled in the range from 5 K to 580 K, with the possibility of application of magnetic fields H up to ±7 kOe and electric fields E for voltages up to ±500 V. The MBE-Cluster operates for in-house research as well as user facility in combination with the APE beamlines at Sincrotrone-Trieste and the high harmonic generator facility for time-resolved spectroscopy.
The redox process of pretreated Co3O4 thin film coatings has been studied by ambient pressure soft X-ray absorption spectroscopy. The Co3O4 coatings were composed of nanoparticles of about 10 nm in size as prepared by pulsed laser deposition. The thin film coatings were pretreated in He or in H2 up to 150 °C prior to exposure to the reactive gases. The reactivity toward carbon monoxide and oxygen was monitored by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy during gas exposures. The results indicate that the samples pretreated in He show reactivity only at high temperature, while the samples pretreated in H2 are reactive also at room temperature. X-ray photoemission spectroscopy measurements in ultra-high vacuum and NEXAFS simulations with the CTM4XAS code further specify the results.