Ultrathin MgO Films Research Articles

In situ study of catalytic CO oxidation on ultrathin MgO film supported Pd nanoparticles by sum frequency generation: size and site effects.

Controlling the reactive sites of nanoparticles (NPs) is crucial to improve catalyst efficiency. In this work, sum-frequency generation is used to probe CO vibrational spectra on MgO(100) ultrathin film/Ag(100) supported Pd nanoparticles ranging from 3 to 6 nm in diameter and compared to those of coalesced Pd NPs and Pd(100) single crystals. We aim to demonstrate in situ the role played by active adsorption sites in the catalytic CO oxidation reactivity trends varying with the NP size. From ultrahigh vacuum to the mbar range and temperatures from 293 K to 340 K, our observations suggest that bridge sites are the main active sites for CO adsorption and catalytic oxidation. On Pd(100) single crystals at 293 K, CO oxidation predominates over CO poisoning at a pressure ratio of O2/CO greater than 300; on Pd NPs, both the site coordination due to NP geometry and MgO-induced Pd-Pd interatomic distance change impact the reactivity trend varying with size in different ways. Edge sites with low coordination are more reactive than facet sites, while facet sites with a smaller Pd-Pd atomic length are more reactive than that with a larger length. The interplay of both site and size effects gives rise to a non-monotonic reactivity trend of CO on the MgO(100) ultrathin film supported Pd NPs: the reactivity of Pd NPs increases for the smaller NP size side due to a higher edge/facet ratio and meanwhile increases for the larger NP size side due to the terrace facet with a smaller Pd-Pd atomic length at the NP surface and a lower diffusion barrier.

Photocathode performance characterisation of ultra-thin MgO films on polycrystalline copper

The performance expected from the next generation of electron accelerators is driving research into photocathode technology as this fundamentally limits the achievable beam quality. The performance characteristics of a photocathode are most notably: normalised emittance, brightness and energy spread. Ultra–thin oxide films on metal substrates have been shown to lower the work function (WF) of the surface, enhancing commonly utilised metal photocathodes, potentially improving lifetime and performance characteristics.We present the characterisation of two MgO/Cu photocathodes grown at Daresbury. The surface properties such as: surface roughness, elemental composition and WF, have been studied using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). The photoemissive properties have been characterised with quantum efficiency (QE) measurements at 266 nm. Additionally, we measure the Transverse Energy Distribution Curves (TEDC) for these photocathodes under illumination at various wavelengths using ASTeC’s Transverse Energy Spread Spectrometer (TESS) and extract the Mean Transverse Energy (MTE).

Enhanced performance of an Ag(100) photocathode by an ultra-thin MgO film

Metal photocathodes are widely utilized as electron sources for particle accelerators for their ease of use, high durability, and fast response time. However, the high work function (WF) and low quantum efficiency (QE) typically observed in metals necessitate the use of high power deep UV lasers. Metal oxide ultra-thin films on metals offer a route to photocathodes with a lower WF and improved QE while maintaining photocathode durability and response time. We show how the photocathode performance of an Ag(100) single crystal is enhanced by the addition of an ultra-thin MgO film. The film growth and WF reduction of 1 eV are characterized, and the QE and mean transverse energy (MTE) are measured as a function of illumination wavelength. An eightfold increase of QE is achieved at 266 nm without adding to MTE through additional surface roughness, and the resistance of the photocathode to O2 gas is greatly improved.

Charge and adsorption height dependence of the self-metalation of porphyrins on ultrathin MgO(001) films.

We have experimentally determined the adsorption structure, charge state, and metalation state of porphin, the fundamental building block of porphyrins, on ultrathin Ag(001)-supported MgO(001) films by scanning tunneling microscopy and photoemission spectroscopy, supported by calculations based on density functional theory. By tuning the substrate work function to values below and above the critical work function for charging, we succeeded in the preparation of 2H-P monolayers which contain negatively charged and uncharged molecules. It is shown that the porphin molecules self-metalate at room temperature, forming the corresponding Mg-porphin, irrespective of their charge state. This is in contrast to self-metalation of tetraphenyl porphyrin (TPP), which occurs on planar MgO(001) only if the molecules are negatively charged. The different reactivity is explained by the reduced molecule-substrate distance of the planar porphin molecule compared to the bulkier TPP. The results of this study shed light on the mechanism of porphyrin self-metalation on oxides and highlight the role of the adsorption geometry on the chemical reactivity.

Magnetic nature and hyperfine interactions of transition metal atoms adsorbed on ultrathin insulating films: a challenge for DFT.

The magnetic ground state and the hyperfine coupling parameters of some first-row transition metal (TM) atoms (Ti, Cr, Mn, Fe, Co, and Ni) adsorbed on ultrathin insulating oxide films are studied by means of DFT calculations. The results obtained using GGA, screened hybrid, and GGA+U functionals are compared for TMs adsorbed on free-standing MgO(100). Then, the case of adsorption on MgO mono- and bilayers supported on Ag(100) is studied using GGA+U. Along with the problematic aspects inherent to the calculation of hyperfine coupling constants, a critical dependence on the magnetic state and electron configuration of the TM is reported, which implies a real challenge for the state-of-the-art DFT methods. In the cases where all functionals considered provide a coherent magnetic and electron configuration, however, the calculated hyperfine parameters do not depend significantly on the choice of the functional. In this respect, the role of the metal support in the hyperfine coupling constants is highly system-dependent and becomes crucial in all cases where the support modifies the oxidation state of the adatom, induces a change in the bonding site or simply induces a rearrangement of the orbital energy diagram. This has important implications for the modelling of single TM atoms deposited on insulating ultrathin films supported on metals for application in quantum technologies or as memory devices.

Growth-mode and interface structure of epitaxial ultrathin MgO/Ag(001) films

MgO ultrathin films are of great technological importance as electron tunneling barrier in electronics and spintronics, and as template for metallic clusters in catalysis and for molecular networks for 2D electronics. The wide band-gap of MgO allows for a very effective decoupling from the substrate. The films morphology and the detailed structure of the interface are crucial for applications, controlling the electronic transfer. Using surface x-ray diffraction, we studied the growth-mode and the structure of MgO/Ag(001) ultrathin films elaborated by reactive molecular beam epitaxy as function of the substrate temperature. We observed that deposition of about 1 monolayer results in an MgO(001) film in coherent epitaxy, with the oxygen atoms on top of silver as predicted by DFT calculations, and an interlayer distance at the interface of about 270 pm. Under well-defined conditions, a sharp MgO bilayer is formed covering a fraction of the substrate surface.

Charge-Promoted Self-Metalation of Porphyrins on an Oxide Surface.

Metalation and self‐metalation reactions of porphyrins on oxide surfaces have recently gained interest. The mechanism of porphyrin self‐metalation on oxides is, however, far from being understood. Herein, we show by a combination of results obtained with scanning tunneling microscopy, photoemission spectroscopy, and DFT computations, that the self‐metalation of 2H‐tetraphenylporphyrin on the surface of ultrathin MgO(001) films is promoted by charge transfer. By tuning the work function of the MgO(001)/Ag(001) substrate, we are able to control the charge and the metalation state of the porphyrin molecules on the surface.

Magnetic Relaxation Mechanisms in Ho Single Atom Magnets

Surface-supported single atoms with long magnetic lifetime, also called single atom magnets, represent the ultimate limit of downscaling of a magnetic bit. Due to the possibility to write, store and read information in their magnetic states, these atoms are model systems for future ultra-high-density magnetic storage devices. In this review, the properties of the most investigated single atom magnet, namely a Ho atom adsorbed on an ultrathin MgO film, will be presented together with the techniques used to address its quantum level structure and magnetic stability. The temperature and field dependent relaxation mechanisms of this unconventional magnetic system will be discussed based on recent findings. Finally, an overview of the open issues and possible future directions of the research will be provided.

Ultrathin MgO coating on fabricated O3–NaNi0.45Mn0.3Ti0.2Zr0.05O2 composite cathode via magnetron sputtering for enhanced kinetic and durable sodium-ion batteries

An innovative and convenient method has been performed to stabilize the surface of O3-type NaNi0.45Mn0.3Ti0.2Zr0.05O2 composited electrode by ultrathin MgO film. There are few reports on the modification on the fabricated electrode instead of the active material powder, especially by radio frequency magnetron sputtering. Besides, the surface stability and capacity retention of MgO coated cathode are superior compared to the bare one under the high rate. The protective effect could physically enhance electrochemical performance because the MgO coating has been identified strictly. Three main reasons are discovered by investigating the mechanisms. Firstly, the MgO layer suppresses the dissolution of the active material into electrolyte; this might be the origin for more stable electrode structure. Secondly, the MgO layer boosts sodium-ion and electron transport owing to its location of the deposition. Finally, the appropriate thickness of MgO can minimize transmission resistance and SEI formation. Particularly, the half-cell constructed with NaNi0.45Mn0.3Ti0.2Zr0.05O2–MgO cathode delivers a good rate performance (80.3 and 70.3 mA h g−1 at 1200 and 1920 mA g−1) and a long cycle life (71.6 mA h g−1 at 240 mA g−1 for 300 cycles) when sputtering time is 10 s; meanwhile, the reversible discharge capacity (140.7 mA h g−1 at 12 mA g−1) with a cut-off voltage of 2–4 V is also a considerable achievement. The work provides a broad idea to apply MgO as a protective coating.

Controlling the electronic and physical coupling on dielectric thin films.

Ultrathin dielectric/insulating films on metals are often used as decoupling layers to allow for the study of the electronic properties of adsorbed molecules without electronic interference from the underlying metal substrate. However, the presence of such decoupling layers may effectively change the electron donating properties of the substrate, for example, by lowering its work function and thus enhancing the charging of the molecular adsorbate layer through electron tunneling. Here, an experimental study of the charging of para-sexiphenyl (6P) on ultrathin MgO(100) films supported on Ag(100) is reported. By deliberately changing the work function of the MgO(100)/Ag(100) system, it is shown that the charge transfer (electronic coupling) into the 6P molecules can be controlled, and 6P monolayers with uncharged molecules (Schottky–Mott regime) and charged and uncharged molecules (Fermi level pinning regime) can be obtained. Furthermore, it was found that charge transfer and temperature strongly influence the orientation, conformation, and wetting behavior (physical coupling) of the 6P layers on the MgO(100) thin films.

Controlling the Charge Transfer across Thin Dielectric Interlayers

AbstractWhether intentional or unintentional, thin dielectric interlayers can be found in technologies ranging from catalysis to organic electronics. While originally considered as passive decoupling layers, recently it has been shown that they can actively promote charge transfer from the underlying metal to adsorbates. This charging can have profound effects on the surface chemistry of atoms, atomic clusters, and molecules, their magnetic moments, and charge injection at the contacts of organic devices. Yet, controlled studies required to understand the charge transfer process in depth are still lacking. Here, a comprehensive analysis of the phenomenon of charge transfer using the atomically controlled system of pentacene on ultrathin MgO(100) films on Ag(100) is presented. It is shown that the charge transfer process is governed by the charged and uncharged molecular species with distinct energy levels in the first monolayer. The experimental approach applied in this work allows to observe and control their ratio through direct tuning of either the work function or the thickness of the dielectric interlayer.

Enhancing domain wall velocity through interface intermixing in W-CoFeB-MgO films with perpendicular anisotropy

We study the influence of He+ irradiation induced interface intermixing on magnetic domain wall (DW) dynamics in W-CoFeB (0.6 nm)-MgO ultrathin films, which exhibit high perpendicular magnetic anisotropy and large Dzyaloshinskii-Moriya interaction (DMI) values. Whereas the pristine films exhibit strong DW pinning, we observe a large increase in the DW velocity in the creep regime upon He+ irradiation, which is attributed to the reduction of pinning centers induced by interface intermixing. Asymmetric in-plane field-driven domain expansion experiments show that the DMI value is slightly reduced upon irradiation, and a direct relationship between DMI and interface anisotropy is demonstrated. Our findings provide insights into the material design and interface control for DW dynamics, as well as for DMI, enabling the development of high-performance spintronic devices based on ultrathin magnetic layers.

Spin Excitations in a 4f-3d Heterodimer on MgO.

We report on the magnetic properties of HoCo dimers as a model system for the smallest intermetallic compound of a lanthanide and a transition metal atom. The dimers are adsorbed on ultrathin MgO(100) films grown on Ag(100). New for 4f elements, we detect inelastic excitations with scanning tunneling spectroscopy and prove their magnetic origin by applying an external magnetic field. In combination with density functional theory and spin Hamiltonian analysis, we determine the magnetic level distribution, as well as sign and magnitude of the exchange interaction between the two atoms. In contrast to typical 4f-3d bulk compounds, we find ferromagnetic coupling in the dimer.

CH3Br adsorption on MgO/Mo ultrathin films: A DFT study

The adsorption of methyl bromide on MgO ultrathin films supported on Mo(100) was studied by means of density functional theory calculations, in comparison to the MgO(100) and Mo(100) surfaces. The adsorption energy and geometry were shown to depend on the thickness of the supported oxide film. MgO films as thick as 2ML (or more) display adsorptive properties similar to MgO(100), i.e. the adsorption of CH3Br is mostly due to dispersion and the molecule lies in a tilted geometry almost parallel to the surface. The CH3Br HOMO-LUMO gap is almost unaltered with respect to the gas phase. On metallic Mo(100) surfaces the bonding is completely different with the CH3Br molecule strongly bound and the C–Br bond axis almost vertical with respect to the metal surface. The MgO monolayer supported on Mo exhibits somehow intermediate properties: the tilt angle is larger and the bonding is stronger than on MgO(100), due to the effect of the supporting metal. In this case, a small reduction of the HOMO-LUMO gap of the adsorbed molecule is reported. The results help to rationalize the observed behavior in photodissociation of CH3Br supported on different substrates.

MgO monolayer epitaxy on Ni (100)

The growth of two-dimensional oxide films with accurate control of their structural and electronic properties is considered challenging for engineering nanotechnological applications. We address here the particular case of MgO ultrathin films grown on Ni (100), a system for which neither crystallization nor extended surface ordering has been established previously in the monolayer range. Using Scanning Tunneling Microscopy and Auger Electron Spectroscopy, we report on experiments showing MgO monolayer (ML) epitaxy on a ferromagnetic nickel surface, down to the limit of atomic thickness. Alternate steps of Mg ML deposition, O2 gas exposure, and ultrahigh vacuum thermal treatment enable the production of a textured film of ordered MgO nano-domains. This study could open interesting prospects for controlled epitaxy of ultrathin oxide films with a high magneto-resistance ratio on ferromagnetic substrates, enabling improvement in high-efficiency spintronics and magnetic tunnel junction devices.

Tuning the ultrafast photodissociation dynamics of CH3Br on ultrathin MgO films by reducing the layer thickness to the 2D limit

The femtosecond-laser induced photodissociation of CH3Br adsorbed at sub-monolayer coverage on a solid surface was investigated by time-resolved pump-probe mass spectrometry. To tune the interaction of the CH3Br molecules with the substrate, an Mo(100) surface was covered with ultrathin insulating MgO layers of variable thickness. By gradually decreasing the magnesia layer thickness to the 2D limit the photodissociation dynamics observed by detection of the methyl fragment indicates an energetic lowering of the relevant methyl bromide excited states due to the increasing spatial proximity of the metallic support. Potential orientational effects of the methyl bromide adsorption geometry are also considered.

Adsorption sites of individual metal atoms on ultrathin MgO(100) films

We use Ca doping during growth of one and two monolayer thick MgO films on Ag(100) to identify the adsorption sites of individual adatoms with scanning tunneling microscopy. For this we combine atomic resolution images of the bare MgO layer with images of the adsorbates and the substitutional Ca atoms taken at larger tip-sample distance. For Ho atoms, the adsorption sites depend on MgO thickness. On the monolayer, they are distributed on the O and bridge sites according to the abundance of those sites, 1/3 and 2/3 respectively. On the MgO bilayer, Ho atoms populate almost exclusively the O site. A third species adsorbed on Mg is predicted by density functional theory and can be created by atomic manipulation. Au atoms adsorb on the bridge sites for both MgO thicknesses, while Co and Fe atoms prefer the O sites, again for both thickness.

Probing specific oxides as potential supports for metal/oxide model catalysts: MgO(111) polar film

The growth of thermally evaporated magnesium oxide thin film on Mo(110) substrate in ultra-high vacuum was studied by means of Auger electron spectroscopy (AES), low-energy electron diffraction (LEED) and work function (WF) measurements. It is shown that at a growth rate of c.a. 0.1 monolayer per minute and the substrate temperature of 600K the film acquires the MgO(111) structure. This structure begins to form at two monolayers and holds up to six monolayers. At higher thickness the film disorders due to weakening of the ordering effect of the isosymmetric Mo(110) support. Adsorption of CO and H2 on the formed MgO(111) film cooled down to 90K was studied by means of ultraviolet photoelectron spectroscopy (UPS) and reflection absorption infrared spectroscopy (RAIRS) and compared with in-situ obtained results for CO on Pt(111). Comparison of UPS data of CO on MgO(111) and Pt(111) in combination with RAIRS results reveals quite different bonding mechanisms on the metal and the oxide supports. The main feature of CO on MgO(111) is quite high intensity of CO stretch vibration, considerably exceeding that on amorphous MgO, and comparable to that of CO on Pt(111). This is presumably due to the electrostatic effect of the uncompensated microscopic dipole moment of ultrathin MgO(111) film on the enhancing of CO dynamical dipole moment. Adsorption of H2 dramatically reduces the CO stretch intensity as a possible result of removing of dipole moment of MgO(111) surface by hydrogen and (CO+H2) interaction.

CO Chemisorption on Ultrathin MgO-Supported Palladium Nanoparticles

The adsorption of CO on Pd nanoparticles (NP) supported on MgO ultrathin films is studied by sum frequency generation (SFG) vibrational spectroscopy at room temperature as a function of CO coverage for NP lateral sizes ranging from 3 to 6 nm. While the spectroscopic signature of CO on (100) top facets dominates the spectra, other new bands are attributed to (111) facets, edges, and defects. CO remains strongly bonded for all sizes, but spectroscopic and kinetic parameters evolve as NP size decreases. It is only for the smallest NPs ∼3 nm in diameter that the deviation from Pd(100) single crystal is important. Modeling of adsorption kinetics, dipolar coupling and DFT calculations allow rationalizing the observations: the size dependent Pd–Pd bond extension by the substrate is the main parameter that controls CO frequency in the low coverage limit. SFG sensitivity is found to increase up to 10–4 ML as NP size decreases. This makes SFG particularly well suited to probe molecular adsorption in the submonolaye...

Band Bending in Mg-Colored and O2-Activated Ultrathin MgO(001) Films

Ultrathin MgO films grown on Ag(001) have been investigated using X-ray and ultraviolet photoemission spectroscopies for oxide films successively exposed to Mg and O2 flux. Studying work functions and layer-resolved Auger shifts allows us to keep track of band profiles from the oxide surface to the interface and reveal the charge-transfer mechanisms underlying the controlled creation of Mg-induced surface color centers and the catalytic enhancement of O2 activation. Our results demonstrate that one can intimately probe the catalytic properties of metal-supported ultrathin oxide films by studying the electronic band alignment at interfaces.