Matteo Monti

Magnetism in nanometer-thick magnetite

The oldest known magnetic material, magnetite, is of current interest for use in spintronics as a thin film. An open question is how thin can magnetite films be and still retain the robust ferrimagnetism required for many applications. We have grown 1-nm-thick magnetite crystals and characterized them in situ by electron and photoelectron microscopies including selected-area x-ray circular dichroism. Well-defined magnetic patterns are observed in individual nanocrystals up to at least 520 K, establishing the retention of ferrimagnetism in magnetite two unit cells thick.

Insight into Magnetite’s Redox Catalysis from Observing Surface Morphology during Oxidation

We study how the (100) surface of magnetite undergoes oxidation by monitoring its morphology during exposure to oxygen at ~650 °C. Low-energy electron microscopy reveals that magnetites surface steps advance continuously. This growth of Fe3O4 crystal occurs by the formation of bulk Fe vacancies. Using Raman spectroscopy, we identify the sinks for these vacancies, inclusions of α-Fe2O3 (hematite). Since the surface remains magnetite during oxidation, it continues to dissociate oxygen readily. At steady state, over one-quarter of impinging oxygen molecules undergo dissociative adsorption and eventual incorporation into magnetite. From the independence of growth rate on local step density, we deduce that the first step of oxidation, dissociative oxygen adsorption, occurs uniformly over magnetites terraces, not preferentially at its surface steps. Since we directly observe new magnetite forming when it incorporates oxygen, we suggest that catalytic redox cycles on magnetite involve growing and etching crystal.

Room temperature in-plane ⟨100⟩ magnetic easy axis for Fe3O4/SrTiO3(001):Nb grown by infrared pulsed laser deposition

We examine the magnetic easy-axis directions of stoichiometric magnetite films grown on SrTiO{sub 3}:Nb by infrared pulsed-laser deposition. Spin-polarized low-energy electron microscopy reveals that the individual magnetic domains are magnetized along the in-plane 〈100〉 film directions. Magneto-optical Kerr effect measurements show that the maxima of the remanence and coercivity are also along in-plane 〈100〉 film directions. This easy-axis orientation differs from bulk magnetite and films prepared by other techniques, establishing that the magnetic anisotropy can be tuned by film growth.We examine the magnetic easy-axis directions of stoichiometric magnetite films grown on SrTiO3:Nb by infrared pulsed-laser deposition. Spin-polarized low-energy electron microscopy reveals that the individual magnetic domains are magnetized along the in-plane film directions. Magneto-optical Kerr effect measurements show that the maxima of the remanence and coercivity are also along in-plane film directions. This easy-axis orientation differs from bulk magnetite and films prepared by other techniques, establishing that the magnetic anisotropy can be tuned by film growth.

Formation and emission of large furans and oxygenated hydrocarbons from flames

Significance Furans and related large oxygenated organic carbon species (OC) are highly toxic pollutants. Their integration into soot particles may greatly enhance soot’s hygroscopicity, leading to regional and global climate change. We show that furans are the primary oxygenated functional group on soot formed in hydrocarbon combustion and report a reaction scheme that elucidates the interplay between nonoxygenated and oxygenated hydrocarbons. We expect this reaction pathway to be important in many hydrocarbon oxidation systems spanning geosciences, astrophysics, and energy research. We discovered ∼100 oxygenated species previously unaccounted for in hydrocarbon models. This study advances the understanding of the oxidation chemistry of OC, which is critical to many processes, from controlling emissions of toxic combustion by-products to reducing anthropogenic climate change. Many oxygenated hydrocarbon species formed during combustion, such as furans, are highly toxic and detrimental to human health and the environment. These species may also increase the hygroscopicity of soot and strongly influence the effects of soot on regional and global climate. However, large furans and associated oxygenated species have not previously been observed in flames, and their formation mechanism and interplay with polycyclic aromatic hydrocarbons (PAHs) are poorly understood. We report on a synergistic computational and experimental effort that elucidates the formation of oxygen-embedded compounds, such as furans and other oxygenated hydrocarbons, during the combustion of hydrocarbon fuels. We used ab initio and probabilistic computational techniques to identify low-barrier reaction mechanisms for the formation of large furans and other oxygenated hydrocarbons. We used vacuum-UV photoionization aerosol mass spectrometry and X-ray photoelectron spectroscopy to confirm these predictions. We show that furans are produced in the high-temperature regions of hydrocarbon flames, where they remarkably survive and become the main functional group of oxygenates that incorporate into incipient soot. In controlled flame studies, we discovered ∼100 oxygenated species previously unaccounted for. We found that large alcohols and enols act as precursors to furans, leading to incorporation of oxygen into the carbon skeletons of PAHs. Our results depart dramatically from the crude chemistry of carbon- and oxygen-containing molecules previously considered in hydrocarbon formation and oxidation models and spearhead the emerging understanding of the oxidation chemistry that is critical, for example, to control emissions of toxic and carcinogenic combustion by-products, which also greatly affect global warming.

Equilibrium oxygen storage capacity of ultrathin CeO2-δ depends non-monotonically on large biaxial strain

Elastic strain is being increasingly employed to enhance the catalytic properties of mixed ion–electron conducting oxides. However, its effect on oxygen storage capacity is not well established. Here, we fabricate ultrathin, coherently strained films of CeO2-δ between 5.6% biaxial compression and 2.1% tension. In situ ambient pressure X-ray photoelectron spectroscopy reveals up to a fourfold enhancement in equilibrium oxygen storage capacity under both compression and tension. This non-monotonic variation with strain departs from the conventional wisdom based on a chemical expansion dominated behaviour. Through depth profiling, film thickness variations and a coupled photoemission–thermodynamic analysis of space-charge effects, we show that the enhanced reducibility is not dominated by interfacial effects. On the basis of ab initio calculations of oxygen vacancy formation incorporating defect interactions and vibrational contributions, we suggest that the non-monotonicity arises from the tetragonal distortion under large biaxial strain. These results may guide the rational engineering of multilayer and core–shell oxide nanomaterials.

Room temperature in-plane 〈100〉 magnetic easy axis for Fe{sub 3}O{sub 4}/SrTiO{sub 3}(001):Nb grown by infrared pulsed laser deposition

We examine the magnetic easy-axis directions of stoichiometric magnetite films grown on SrTiO{sub 3}:Nb by infrared pulsed-laser deposition. Spin-polarized low-energy electron microscopy reveals that the individual magnetic domains are magnetized along the in-plane 〈100〉 film directions. Magneto-optical Kerr effect measurements show that the maxima of the remanence and coercivity are also along in-plane 〈100〉 film directions. This easy-axis orientation differs from bulk magnetite and films prepared by other techniques, establishing that the magnetic anisotropy can be tuned by film growth.We examine the magnetic easy-axis directions of stoichiometric magnetite films grown on SrTiO3:Nb by infrared pulsed-laser deposition. Spin-polarized low-energy electron microscopy reveals that the individual magnetic domains are magnetized along the in-plane film directions. Magneto-optical Kerr effect measurements show that the maxima of the remanence and coercivity are also along in-plane film directions. This easy-axis orientation differs from bulk magnetite and films prepared by other techniques, establishing that the magnetic anisotropy can be tuned by film growth.

Room Temperature In-plane ?100? Magnetic Easy Axis for Fe3O4/SrTiO3(001):Nb Grown by Infrared PLD.

We examine the magnetic easy-axis directions of stoichiometric magnetite films grown on SrTiO{sub 3}:Nb by infrared pulsed-laser deposition. Spin-polarized low-energy electron microscopy reveals that the individual magnetic domains are magnetized along the in-plane 〈100〉 film directions. Magneto-optical Kerr effect measurements show that the maxima of the remanence and coercivity are also along in-plane 〈100〉 film directions. This easy-axis orientation differs from bulk magnetite and films prepared by other techniques, establishing that the magnetic anisotropy can be tuned by film growth.We examine the magnetic easy-axis directions of stoichiometric magnetite films grown on SrTiO3:Nb by infrared pulsed-laser deposition. Spin-polarized low-energy electron microscopy reveals that the individual magnetic domains are magnetized along the in-plane film directions. Magneto-optical Kerr effect measurements show that the maxima of the remanence and coercivity are also along in-plane film directions. This easy-axis orientation differs from bulk magnetite and films prepared by other techniques, establishing that the magnetic anisotropy can be tuned by film growth.