The Use of External Fields (Magnetic, Electric, and Strain) in Molecular Beam Epitaxy-The Method and Application Examples.

Molecular beam epitaxy (MBE) is a powerful tool in modern technologies, including electronic, optoelectronic, spintronic, and sensoric applications. The primary factor determining epitaxial heterostructure properties is the growth mode and the resulting atomic structure and microstructure. In this paper, we present a novel method for growing epitaxial layers and nanostructures with specific and optimized structural and magnetic properties by assisting the MBE process using electromagnetic and mechanical external stimuli: an electric field (EF), a magnetic field (MF), and a strain field (SF). The transmission of the external fields to the sample is realized using a system of specialized sample holders, advanced transfers, and dedicated manipulators. Examples of applications include the influence of MFs on the growth and anisotropy of epitaxial magnetite and iron films, the use of EFs for in situ resistivity measurements, the realization of in situ magneto-optic measurements, and the application of SFs to the structural modification of metal films on mica.

Magnetic-Field-Assisted Molecular Beam Epitaxy: Engineering of Fe3O4 Ultrathin Films on MgO(111).

Molecular beam epitaxy is widely used for engineering low-dimensional materials. Here, we present a novel extension of the capabilities of this method by assisting epitaxial growth with the presence of an external magnetic field (MF). MF-assisted epitaxial growth was implemented under ultra-high vacuum conditions thanks to specialized sample holders for generating in-plane or out-of-plane MF and dedicated manipulator stations with heating and cooling options. The significant impact of MF on the magnetic properties was shown for ultra-thin epitaxial magnetite films grown on MgO(111). Using in situ and ex situ characterization methods, scanning tunneling microscopy, conversion electron Mössbauer spectroscopy, and the magneto-optic Kerr effect, we showed that the in-plane MF applied during the reactive deposition of 10 nm Fe3O4(111)/MgO(111) heterostructures influenced the growth morphology of the magnetite films, which affects both in-plane and out-of-plane characteristics of the magnetization process. The observed changes are explained in terms of modification of the effective magnetic anisotropy.

Modulation of ODH Propane Selectivity by Zeolite Support Desilication: Vanadium Species Anchored to Al-Rich Shell as Crucial Active Sites.

The commercially available zeolite HY and its desilicated analogue were subjected to a classical wet impregnation procedure with NH4VO3 to produce catalysts differentiated in acidic and redox properties. Various spectroscopic techniques (in situ probe molecules adsorption and time-resolved propane transformation FT-IR studies, XAS, 51V MAS NMR, and 2D COS UV-vis) were employed to study speciation, local coordination, and reducibility of the vanadium species introduced into the hierarchical faujasite zeolite. The acid-based redox properties of V centres were linked to catalytic activity in the oxidative dehydrogenation of propane. The modification of zeolite via caustic treatment is an effective method of adjusting its basicity-a parameter that plays an important role in the ODH process. The developed mesopore surface ensured the attachment of vanadium species to silanol groups and formation of isolated (SiO)2(HO)V=O and (SiO)3V=O sites or polymeric, highly dispersed forms located in the zeolite micropores. The higher basicity of HYdeSi, due to the presence of the Al-rich shell, aided the activation of the C-H bond leading to a higher selectivity to propene. Its polymerisation and coke formation were inhibited by the lower acid strength of the protonic sites in desilicated zeolite. The Al-rich shell was also beneficial for anchoring V species and thus their reducibility. The operando UV-vis experiments revealed higher reactivity of the bridging oxygens V-O-V over the oxo-group V=O. The (SiO)3V=O species were found to be ineffective in propane oxidation when temperature does not exceed 400 °C.

Reduction and Oxidation of Cu Species in Cu-Faujasites Studied by IR Spectroscopy.

The process of reduction (by hydrogen and ethanol) and oxidation (by oxygen and NO) of Cu sites in dealuminated faujasite-type zeolites (of Si/Al = 31) was studied by infrared (IR) spectroscopy with CO (for Cu+) and NO (for Cu2+) as probe molecules. Two zeolites were studied: one of them contained mostly Cu+exch., whereas another one contained mostly Cu2+ and Cu+ox. The susceptibility of various forms of Cu for reduction were investigated. IR experiments of CO sorption evidenced that Cu+ox. was more prone for the reduction than Cu+exch. According to NO sorption studies, Cu2+exch. was reduced in the first order before Cu2+ox. Ethanol reduced mostly Cu2+ and, also, some amounts of Cu+. The treatment with oxygen caused the oxidation of Cu+ (both Cu+exch. and Cu+ox.) to Cu2+. The adsorption of NO at 190K produced Cu+(NO)2 dinitrosyls, but heating to room temperature transformed dinitrosyls to mononitrosyls and increased the Cu2+ content.

Au nanoparticles on Fe-modified rutile TiO2(110): Dispersion, thermal stability, and CO adsorption.

Gold clusters on an iron-modified rutile TiO2(110) surface have been characterized via scanning tunneling microscopy and x-ray photoelectron spectroscopy. This study is focused on the impact of submonolayer preadsorbed Fe on the morphologies, surface compositions, and thermal stabilities of bimetallic Au-Fe systems by comparing them to elemental Au and Fe adsorbates. We found that a submonolayer gold adsorbate followed the nucleation mode of the iron precursor, which considerably enhanced the dispersion of nano-gold while improving its thermal stability. Finally, the temperature-programmed CO desorption spectra of Au and Au-Fe nanoparticles on TiO2(110) were compared.