Quentin M. Ramasse

Visualizing the Stoichiometry of Industrial-Style Co-Mo-S Catalysts with Single-Atom Sensitivity†

The functional properties of transition metal dichalcogenides (TMDs) may be promoted by the inclusion of other elements. Here, we studied the local stoichiometry of single cobalt promoter atoms in an industrial-style MoS2-based hydrotreating catalyst. Aberration-corrected scanning transmission electron microscopy and electron energy loss spectroscopy show that the Co atoms occupy sites at the (-100) S edge terminations of the graphite-supported MoS2 nanocrystals in the catalyst. Specifically, each Co atom has four neighboring S atoms that are arranged in a reconstructed geometry, which reflects an equilibrium state. The structure agrees with complementary studies of catalysts that were prepared under vastly different conditions and on other supports. In contrast, a small amount of residual Fe in the graphite is found to compete for the S edge sites, so that promotion by Co is strongly sensitive to the purity of the raw materials. The present single-atom-sensitive analytical method therefore offers a guide for advancing preparative methods for promoted TMD nanomaterials.

Fluid-induced organic synthesis in the solar nebula recorded in extraterrestrial dust from meteorites

Significance Organic matter from the parent molecular cloud of our solar system can be located in primitive extraterrestrial samples like meteorites and cometary grains. This pristine matter contains among the most primitive organic molecules that were delivered to the early Earth 4.5 billion years ago. We have analyzed these organics by a high-resolution electron microscope that is exceptionally suited to study these beam-sensitive materials. Different carbon and nitrogen functional groups were identified on a submicron scale and can be attributed to early cometary and meteoritic organic reservoirs. Our results demonstrate for the first time to our knowledge that certain highly aromatic and nitrogen-containing ubiquitous organics were transformed from an oxygen-rich organic reservoir by parent body fluid synthesis in the early solar system. Isotopically anomalous carbonaceous grains in extraterrestrial samples represent the most pristine organics that were delivered to the early Earth. Here we report on gentle aberration-corrected scanning transmission electron microscopy investigations of eight 15N-rich or D-rich organic grains within two carbonaceous Renazzo-type (CR) chondrites and two interplanetary dust particles (IDPs) originating from comets. Organic matter in the IDP samples is less aromatic than that in the CR chondrites, and its functional group chemistry is mainly characterized by C–O bonding and aliphatic C. Organic grains in CR chondrites are associated with carbonates and elemental Ca, which originate either from aqueous fluids or possibly an indigenous organic source. One distinct grain from the CR chondrite NWA 852 exhibits a rim structure only visible in chemical maps. The outer part is nanoglobular in shape, highly aromatic, and enriched in anomalous nitrogen. Functional group chemistry of the inner part is similar to spectra from IDP organic grains and less aromatic with nitrogen below the detection limit. The boundary between these two areas is very sharp. The direct association of both IDP-like organic matter with dominant C–O bonding environments and nanoglobular organics with dominant aromatic and C–N functionality within one unique grain provides for the first time to our knowledge strong evidence for organic synthesis in the early solar system activated by an anomalous nitrogen-containing parent body fluid.

The role of chemical structure on the magnetic and electronic properties of Co2FeAl0.5Si0.5/Si(111) interface

We show that Co2FeAl0.5Si0.5film deposited on Si(111) has a single crystal structure and twin related epitaxial relationship with the substrate. Sub-nanometer electron energy loss spectroscopy shows that in a narrow interface region there is a mutual inter-diffusion dominated by Si and Co. Atomic resolution aberration-corrected scanning transmission electron microscopy reveals that the film has B2 ordering. The film lattice structure is unaltered even at the interface due to the substitutional nature of the intermixing. First-principles calculations performed using structural models based on the aberration corrected electron microscopy show that the increased Si incorporation in the film leads to a gradual decrease of the magnetic moment as well as significant spin-polarization reduction. These effects can have significant detrimental role on the spin injection from the Co2FeAl0.5Si0.5 film into the Si substrate, besides the structural integrity of this junction.

Realisation of magnetically and atomically abrupt half-metal/semiconductor interface : Co2FeSi0.5Al0.5/Ge(111)

Halfmetal-semiconductor interfaces are crucial for hybrid spintronic devices. Atomically sharp interfaces with high spin polarisation are required for efficient spin injection. In this work we show that thin film of half-metallic full Heusler alloy Co2FeSi0.5Al0.5 with uniform thickness and B2 ordering can form structurally abrupt interface with Ge(111). Atomic resolution energy dispersive X-ray spectroscopy reveals that there is a small outdiffusion of Ge into specific atomic planes of the Co2FeSi0.5Al0.5 film, limited to a very narrow 1 nm interface region. First-principles calculations show that this selective outdiffusion along the Fe-Si/Al atomic planes does not change the magnetic moment of the film up to the very interface. Polarized neutron reflectivity, x-ray reflectivity and aberration-corrected electron microscopy confirm that this interface is both magnetically and structurally abrupt. Finally, using first-principles calculations we show that this experimentally realised interface structure, terminated by Co-Ge bonds, preserves the high spin polarization at the Co2FeSi0.5Al0.5/Ge interface, hence can be used as a model to study spin injection from half-metals into semiconductors.

Controlling the half-metallicity of Heusler/Si(1 1 1) interfaces by a monolayer of Si-Co-Si

By using first-principles calculations we show that the spin-polarization reverses its sign at atomically abrupt interfaces between the half-metallic Co2(Fe,Mn)(Al,Si) and Si(1 1 1). This unfavourable spin-electronic configuration at the Fermi-level can be completely removed by introducing a Si-Co-Si monolayer at the interface. In addition, this interfacial monolayer shifts the Fermi-level from the valence band edge close to the conduction band edge of Si. We show that such a layer is energetically favourable to exist at the interface. This was further confirmed by direct observations of CoSi2 nano-islands at the interface, by employing atomic resolution scanning transmission electron microscopy.

Experimental and density functional study of Mn doped Bi2Te3 topological insulator

We present a nanoscale structural and density functional study of the Mn doped 3D topological insulator Bi2Te3. X-ray absorption near edge structure shows that Mn has valency of nominally 2+. Extended x-ray absorption fine structure spectroscopy in combination with electron energy loss spectroscopy (EELS) shows that Mn is a substitutional dopant of Bi and Te and also resides in the van der Waals gap between the quintuple layers of Bi2Te3. Combination of aberration-corrected scanning transmission electron microscopy and EELS shows that Mn substitution of Te occurs in film regions with increased Mn concentration. First-principles calculations show that the Mn dopants favor octahedral sites and are ferromagnetically coupled.

Robust theoretical modelling of core ionisation edges for quantitative electron energy loss spectroscopy of B- and N-doped graphene

Electron energy loss spectroscopy (EELS) is a powerful tool for understanding the chemical structure of materials down to the atomic level, but challenges remain in accurately and quantitatively modelling the response. We compare comprehensive theoretical density functional theory (DFT) calculations of 1s core-level EEL K-edge spectra of pure, B-doped and N-doped graphene with and without a core-hole to previously published atomic-resolution experimental electron microscopy data. The ground state approximation is found in this specific system to perform consistently better than the frozen core-hole approximation. The impact of including or excluding a core-hole on the resultant theoretical band structures, densities of states, electron densities and EEL spectra were all thoroughly examined and compared. It is concluded that the frozen core-hole approximation exaggerates the effects of the core-hole in graphene and should be discarded in favour of the ground state approximation. These results are interpreted as an indicator of the overriding need for theorists to embrace many-body effects in the pursuit of accuracy in theoretical spectroscopy instead of a system-tailored approach whose approximations are selected empirically.

Polar Spinel-Perovskite Interfaces: an atomistic study of Fe3O4(111)/SrTiO3(111) structure and functionality

Atomic resolution scanning transmission electron microscopy and electron energy loss spectroscopy combined with ab initio electronic calculations are used to determine the structure and properties of the Fe3O4(111)/SrTiO3(111) polar interface. The interfacial structure and chemical composition are shown to be atomically sharp and of an octahedral Fe/SrO3 nature. Band alignment across the interface pins the Fermi level in the vicinity of the conduction band of SrTiO3. Density functional theory calculations demonstrate very high spin-polarization of Fe3O4 in the interface vicinity which suggests that this system may be an excellent candidate for spintronic applications.

Atomic and electronic structure study of a Co 2 FeAl 0.5 Si 0.5 half-metal thin film on Si(111)

Halfmetal/semiconductor interfaces are the key element for integration of semiconductors and magnetic materials for hybrid spintronics devices aiming at the realization of a revolutionary and energy-efficient information technology [1]. One of the biggest challenges is to directly deposit/grow halfmetal on Si, the most widely used semi-conductor substrate for these applications, due to extensive interdiffusion of the electrode elements and Si across the growth interface [2].