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International audience; Heavily carbon-doped Mn$_5$Ge$_3$ is a unique compound for spintronics applications as it meets all the requirements for spin injection and detection in group-IV semiconductors. Despite the great improvement of the magnetic properties induced by C incorporation into Mn$_5$Ge$_3$ compounds, very little information is available on its structural properties and the genuine role played by C atoms. In this paper, we have used a combination of advanced techniques to extensively characterize the structural and magnetic properties of Mn$_5$Ge$_3$C$_x$ films grown on Ge(111) by solid phase epitaxy as a function of C concentration. The increase of the Curie temperature induced by C doping up to 435 K is accompanied by a decrease of the out-of-plane c-lattice parameter. The Mn and C chemical environments and positions in the Mn$_5$Ge$_3$ lattice have been thoroughly investigated using x-ray absorption spectroscopy techniques (x-ray absorption near-edge structures and extended x-ray absorption fine structures) and scanning transmission electronic microscopy (STEM) combined to electron energy loss spectroscopy for the chemical analysis. The results have been systematically compared to a variety of structures that were identified as favorable in terms of formation energy by ab initio calculations. For $x \le$ 0.5, the C atoms are mainly located in the octahedral voids formed by Mn atoms, which is confirmed by simulations and seen for the first time in real space by STEM. However, the latter reveals an inhomogeneous C incorporation, which is qualitatively correlated to the broad magnetic transition temperature. A higher C concentration leads to theformation of manganese carbide clusters that we identified as Mn$_{23}$C$_6$. Interestingly, other types of defects, such as interstitial Ge atoms, vacancies of Mn, and their association into line defects have been detected. They take part in the strain relaxation process and are likely to be intimately related to the growth process. This paper provides a complete picture of the structure of Mn$_5$Ge$_3$C$_x$ in thin films grown by solid phase epitaxy, which is essential for optimizing their magnetic properties.

Heavily carbon-doped Mn5Ge3 is a unique compound for spintronics applications as it meets all the requirements for spin injection and detection in group-IV semiconductors. Despite the great improvement of the magnetic properties induced by C incorporation into Mn5Ge3 compounds, very little information is available on its structural properties and the genuine role played by C atoms. In this paper, we have used a combination of advanced techniques to extensively characterize the structural and magnetic properties of Mn5Ge3Cx films grown on Ge(111) by solid phase epitaxy as a function of C concentration. The increase of the Curie temperature induced by C doping up to 435 K is accompanied by a decrease of the out-of-plane c-lattice parameter. The Mn and C chemical environments and positions in the Mn5Ge3 lattice have been thoroughly investigated using x-ray absorption spectroscopy techniques (x-ray absorption near-edge structures and extended x-ray absorption fine structures) and scanning transmission electronic microscopy (STEM) combined to electron energy loss spectroscopy for the chemical analysis. The results have been systematically compared to a variety of structures that were identified as favorable in terms of formation energy by ab initio calculations. For x≤0.5, the C atoms are mainly located in the octahedral voids formed by Mn atoms, which is confirmed by simulations and seen for the first time in real space by STEM. However, the latter reveals an inhomogeneous C incorporation, which is qualitatively correlated to the broad magnetic transition temperature. A higher C concentration leads to the formation of manganese carbide clusters that we identified as Mn23C6. Interestingly, other types of defects, such as interstitial Ge atoms, vacancies of Mn, and their association into line defects have been detected. They take part in the strain relaxation process and are likely to be intimately related to the growth process. This paper provides a complete picture of the structure of Mn5Ge3Cx in thin films grown by solid phase epitaxy, which is essential for optimizing their magnetic properties.

Thin film nanocomposite (TFN) membranes of polymer of intrinsic microporosity PIM-1 incorporating graphene oxide (GO) nanosheets of different sizes and chemistries are presented. These membranes show an improved separation performance for the recovery of n-butanol from aqueous solutions through pervaporation; an improvement of ca. a third of the value achieved for pristine PIM-1 thin films is obtained for TFN membranes filled with nanometer-sized reduced octyl-functionalized GO. In addition, these nanometer-sized fillers lead to a maximum increase in total flux of approximately 40%. The thickness of the supported films is in the range 1–1.5 µm, and fillers used are micrometer- and nanometer-sized alkyl-functionalized GO nanosheets and their chemically reduced counterparts. As evidenced by a superior overall membrane performance, the interfacial interaction between the filler and the polymer matrix is enhanced for those whose lateral size is in the nanometer range. Moreover, an enhancement in the separation performance and productivity of such membranes is observed for higher operating temperatures and higher contents of n-butanol in the feed.

We report the controlled alloying, oxidation, and subsequent reduction of individual AgAu nanoparticles in the scanning transmission electron microscope (STEM). Through sequential application of electron beam induced oxidation and in situ heating and quenching, we demonstrate the transformation of Ag–Au core–shell nanoparticles into: AgAu alloyed, Au–Ag core–shell, hollow Au–Ag2O core–shell, and Au–Ag2O yolk-shell nanoparticles. We are able to directly image these morphological transformations in real-time at atomic resolution and perform energy dispersive X-ray (EDX) spectrum imaging to map changing elemental distributions with sub-nanometre resolution. By combining aberration corrected STEM imaging and high efficiency EDX spectroscopy we are able to quantify not only the growth and coalescence of Kirkendall voids during oxidation but also the compositional changes occurring during this reaction. This is the first time that it has been possible to track the changing distribution of elements in an individual nanoparticle undergoing oxidation driven shell growth and hollowing.

We have characterized a film of Ge_0.9Mn_0.1 forming self-organized nanocolumns perpendicular to the Ge substrate with high resolution scanning transmission electron microscopy combined with electron energy loss spectroscopy, and bulk magnetization and positive muon spin rotation and relaxation (muSR) measurements. The Mn-rich nanocolumns form a triangular lattice with no detectable Mn atoms in the matrix. They consist of cores surrounded by shells. The combined analysis of bulk magnetization and muSR data enables us to characterize the electronic and magnetic properties of both the cores and shells. The discovered phase separation of the columns between a core and a shell is probably relevant for other transition-metal doped semiconductors., 5 pages, 5 figures, and supplemental material