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.
Two-dimensional (2D) metallic states induced by oxygen vacancies (VOs) at oxide surfaces and interfaces provide opportunities for the development of advanced applications, but the ability to control the behavior of these states is still limited. We used angle resolved photoelectron spectroscopy combined with density-functional theory (DFT) to study the reactivity of VO-induced states at the (001) surface of anatase TiO2, where both 2D metallic and deeper lying in-gap states (IGs) are observed. The 2D and IG states exhibit remarkably different evolutions when the surface is exposed to molecular O2: while IGs are almost completely quenched, the metallic states are only weakly affected. DFT calculations indeed show that the IGs originate from surface VOs and remain localized at the surface, where they can promptly react with O2. In contrast, the metallic states originate from subsurface vacancies whose migration to the surface for recombination with O2 is kinetically hindered on anatase TiO2 (001), thus making them much less sensitive to oxygen dosing.
Here, we report on a novel narrowband High Harmonic Generation (HHG) light source designed for ultrafast photoelectron spectroscopy (PES) on solids. Notably, at 16.9 eV photon energy, the harmonics bandwidth equals 19 meV. This result has been obtained by seeding the HHG process with 230 fs pulses at 515 nm. The ultimate energy resolution achieved on a polycrystalline Au sample at 40 K is ∼22 meV at 16.9 eV. These parameters set a new benchmark for narrowband HHG sources and have been obtained by varying the repetition rate up to 200 kHz and, consequently, mitigating the space charge, operating with ≈3×107 electrons/s and ≈5×108 photons/s. By comparing the harmonics bandwidth and the ultimate energy resolution with a pulse duration of ∼105 fs (as retrieved from time-resolved experiments on bismuth selenide), we demonstrate a new route for ultrafast space-charge-free PES experiments on solids close to transform-limit conditions.
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.
We combine time-resolved pump-probe magneto-optical Kerr effect and photoelectron spectroscopy experiments supported by theoretical analysis to determine the relaxation dynamics of delocalized electrons in half-metallic ferromagnetic manganite La1−xSrxMnO3. We observe that the half-metallic character of La1−xSrxMnO3 determines the timescale of both the electronic phase transition and the quenching of magnetization, revealing a quantum isolation of the spin system in double-exchange ferromagnets extending up to hundreds of picoseconds. We demonstrate the use of time-resolved hard x-ray photoelectron spectroscopy as a unique tool to single out the evolution of strongly correlated electronic states across a second-order phase transition in a complex material.
In the rapidly growing field of spintronics, simultaneous control of electronic and magnetic properties is essential, and the perspective of building novel phases is directly linked to the control of tuning parameters, for example, thickness and doping. Looking at the relevant effects in interface-driven spintronics, the reduced symmetry at a surface and interface corresponds to a severe modification of the overlap of electron orbitals, that is, to a change of electron hybridization. Here we report a chemically and magnetically sensitive depth-dependent analysis of two paradigmatic systems, namely La1−xSrxMnO3 and (Ga,Mn)As. Supported by cluster calculations, we find a crossover between surface and bulk in the electron hybridization/correlation and we identify a spectroscopic fingerprint of bulk metallic character and ferromagnetism versus depth. The critical thickness and the gradient of hybridization are measured, setting an intrinsic limit of 3 and 10 unit cells from the surface, respectively, for (Ga,Mn)As and La1−xSrxMnO3, for fully restoring bulk properties.
This thesis completes my work as doctoral student of the Scuola di Dottorato in Fisica, Astrofisica e Fisica Applicata at the Università degli Studi di Milano that has been carried out, starting in November 4236, mostly at the Laboratorio TASC of IOM-CNR3 in the premises of the Elettra - Sincrotrone Trieste and FERMI@Elettra infrastructures4, in the framework of the NFFA and APE-beamline facilites5, as well as by accessing international large scale infrastructures and laboratories. The activity has addressed the development of experimental methodologies and novel instrumentation oriented to the study of the dynamical properties of highly correlated materials after high energy excitation. The science programme has been carried out by exploiting ultrafast femtosecond probes from the optical regime (Ti-Sa lasers, fibre laser oscillators) to the extreme UV-soft X rays at FERMI, to the picosecond hard X-rays from the SPring-: and Diamond synchrotron radiation source. The sample synthesis of correlated oxides and its characterization has been performed within the NFFA facility and APE-group collaboration in Trieste as well as the design and construction of the all new laser High Harmonic Generation beam line NFFA-SPRINT and its end station for time resolved vectorial electron spin polarimetry.
In this work the experimental uncertainties concerning electron spin polarization (SP) under various realistic measurement conditions are theoretically derived. The accuracy of the evaluation of the SP of the photoelectron current is analysed as a function of the detector parameters and specifications, as well as of the characteristics of the photoexcitation sources. In particular, the different behaviour of single counter or twin counter detectors when the intensity fluctuations of the source are considered have been addressed, leading to a new definition of the SP detector performance. The widely used parameter called the figure of merit is shown to be inadequate for describing the efficiency of SP polarimeters, especially when they are operated with time-structured excitation sources such as free-electron lasers. Numerical simulations have been performed and yield strong implications in the choice of the detecting instruments in spin-polarization experiments, that are constrained in a limited measurement time. Our results are therefore applied to the characteristics of a wide set of state-of-the-art spectroscopy facilities all over the world, and an efficiency diagram for SP experiments is derived. These results also define new mathematical instruments for handling the correct statistics of SP measurements in the presence of source intensity fluctuations.
ULTRASPIN is an apparatus devoted to the measurement of the spin polarization (SP) of electrons ejected from solid surfaces in a UHV environment. It is designed to exploit ultrafast light sources (free electron laser or laser high harmonic generation) and to perform (photo)electron spin analysis by an arrangement of Mott scattering polarimeters that measure the full SP vector. The system consists of two interconnected UHV vessels: one for surface science sample cleaning treatments, e-beam deposition of ultrathin films, and low energy electron diffraction/AES characterization. The sample environment in the polarimeter allows for cryogenic cooling and in-operando application of electric and magnetic fields. The photoelectrons are collected by an electrostatic accelerator and transport lens that form a periaxial beam that is subsequently directed by a Y-shaped electrostatic deflector to either one of the two orthogonal Mott polarimeters. The apparatus has been designed to operate in the extreme conditions of ultraintense single-X-ray pulses as originated by free electron lasers (up to 1 kHz), but it allows also for the single electron counting mode suitable when using statistical sources such as synchrotron radiation, cw-laser, or e-gun beams (up to 150 kcps).
This thesis reports on the construction and commissioning tests of the novel experimental set-up needed for a long term research project, named ULTRASPIN, aiming at establishing time resolved spin-resolved photoemission measurements with ultra-short (10−14 s) photon pulses from Free Electron Laser beamlines or from table-top UV/Soft-X beamlines.
The ULTRASPIN project started in the summer 2013, building on competences and instrumentation in part available from the APE-beamline group of IOM-CNR at Elettra, and with the partial support of an European contract (EXSTASY-EXperimental STation for the Analysis of the Spin Dynamics, Grant agreement N.PIIF-GA-2012-326641) and related fellowship of a world-expert of Mott scattering.
I have been involved from the beginning in the final design, in the construction and commissioning of a novel stray-field free UHV apparatus for preparing and hosting atomically clean surfaces and for measuring the spin-polarization of the photo-emitted electrons with “single pulse” sensitivity down to the 10−14 s time scale, as well as in the standard high frequency spectroscopy mode. In the commissioning phase I have participated to test experiments on ULTRASPIN as well as to relevant experiments conducted in other apparatuses.