Ab Initio Study of Hot Carriers in the First Picosecond after Sunlight Absorption in Silicon

Hot carrier thermalization is a major source of efficiency loss in solar cells. Because of the subpicosecond time scale and complex physics involved, a microscopic characterization of hot carriers is challenging even for the simplest materials. We develop and apply an ab initio approach based on density functional theory and many-body perturbation theory to investigate hot carriers in semiconductors. Our calculations include electron-electron and electron-phonon interactions, and require no experimental input other than the structure of the material. We apply our approach to study the relaxation time and mean free path of hot carriers in Si, and map the band and k dependence of these quantities. We demonstrate that a hot carrier distribution characteristic of Si under solar illumination thermalizes within 350 fs, in excellent agreement with pump-probe experiments. Our work sheds light on the subpicosecond time scale after sunlight absorption in Si, and constitutes a first step towards ab initio quantification of hot carrier dynamics in materials

Lead-supported germanium nanowire growth

The Pb-assisted growth of Ge nanowires (NWs) has been investigated under high and low pressure conditions via thermal decomposition of diphenylgermane. Highly crystalline Ge NWs were obtained and Pb was established as a viable growth promoter with the Pb particle being in the solid and liquid state

Laboratory Measurements of Gravel Thermal Conductivity: An Update Methodological Approach

Abstract Direct measurements of gravel thermal properties are usually quite challenging to be performed in laboratory, due to the very coarse sediments size. As a consequence, the reference thermal values provided by literature for gravels are quite limited and dispersed. A guarded hot plate Taurus Instruments TLP 800, usually used for measuring the thermal conductivity of buildings materials, was slightly modified in order to measure the thermal conductivity of some gravel samples. The tests were performed both in dry and wet conditions. The paper presents the first obtained results

Surface composition changes of CuNi-ZrO2 during methane decomposition: An operando NAP-XPS and density functional study

AbstractBimetallic CuNi nanoparticles of various nominal compositions (1:3, 1:1, 3:1) supported on ZrO2 were employed for operando spectroscopy and theoretical studies of stable surface compositions under reaction conditions of catalytic methane decomposition up to 500°C. The addition of Cu was intended to increase the coke resistance of the catalyst. After synthesis and (in situ) reduction the CuNi nanoparticles were characterized by HR-TEM/EDX, XRD, FTIR (using CO as probe molecule) and NAP-XPS, all indicating a Cu rich surface, even when the overall nanoparticle composition was rich in Ni. Density functional (DF) theory modelling, applying a recently developed computational protocol based on the construction of topological energy expressions, confirmed that in any studied composition Cu segregation on surface positions is an energetically favourable process, with Cu preferentially occupying corner and edge sites. Ni is present on terraces only when not enough Cu atoms are available to occupy all surface sites.When the catalysts were applied for methane decomposition they were inactive at low temperature but became active above 425°C. Synchrotron-based operando NAP-XPS indicated segregation of Ni on the nanoparticle surface when reactivity set in for CuNi-ZrO2. Under these conditions C 1s core level spectra revealed the presence of various carbonaceous species at the surface. DF calculations indicated that both the increase in temperature and especially the adsorption of CHx groups (x=0-3) induce the segregation of Ni atoms on the surface, with CH3 providing the lowest and C the highest driving force.Combined operando and theoretical studies clearly indicate that, independent of the initial surface composition after synthesis and reduction, the CuNi-ZrO2 catalyst adopts a specific Ni rich surface under reaction conditions. Based on these findings we provide an explanation why Cu rich bimetallic systems show improved coke resistance

Surface-structure libraries: multifrequential oscillations in catalytic hydrogen oxidation on rhodium

Multifrequential oscillating spatiotemporal patterns in the catalytic hydrogen oxidation on rhodium have been observed in situ in the 10 -6 mbar pressure range using photoemission electron microscopy. The effect is manifested by periodic chemical waves, which travel over the polycrystalline Rh surface and change their oscillation frequency while crossing boundaries between different Rh(hkl) domains. Each crystallographically specific μm-sized Rh(hkl) domain exhibits an individual wave pattern and oscillation frequency, despite the global diffusional coupling of the surface reaction, altogether creating a structure library. This unique reaction behavior is attributed to the ability of stepped surfaces of high-Miller-index domains to facilitate the formation of subsurface oxygen, serving as a feedback mechanism of kinetic oscillations. Formation of a network of subsurface oxygen as a result of colliding reaction fronts was observed in situ. Microkinetic model analysis was used to rationalize the observed effects and to reveal the relation between the barriers for surface oxidation and oscillation frequency. Structural limits of the oscillations, the existence range of oscillations, as well as the effect of varying hydrogen pressure are demonstrated

A Combined TEM/STEM and Micromagnetic Study of the Anisotropic Nature of Grain Boundaries and Coercivity in Nd-Fe-B Magnets

The nanoanalytical high resolution TEM/STEM investigation of the intergranular grain boundary phase of anisotropic sintered and rapidly quenched heavy rare earth-free Nd-Fe-B magnet materials revealed a difference in composition for grain boundaries parallel (large Fe-content) and perpendicular (low Fe content) to the alignment direction. This behaviour vanishes in magnets with a high degree of misorientation. The numerical finite element micromagnetic simulations are based on the anisotropic compositional behaviour of GBs and show a decrease of the coercive field with an increasing thickness of the grain boundary layer. The magnetization reversal and expansion of reversed magnetic domains primarily start as Bloch domain wall at grain boundaries parallel to the c-axis and secondly as Néel domain wall perpendicular to the c-axis into the adjacent hard magnetic grains. The increasing misalignment of grains leads to the loss of the anisotropic compositional behaviour and therefore to an averaged value of the grain boundary composition. In this case the simulations show an increase of the coercive field compared to the anisotropic magnet. The calculated coercive field values of the investigated magnet samples are in the order of μ0HcJ=1.8 T–2.1 T for a mean grain boundary thickness of 4 nm, which agrees perfectly with the experimental data

Se Nanopowder Conversion into Lubricious 2D Selenide Layers by Tribochemical Reactions

: Transition metal dichalcogenide (TMD) coatings have attracted enormous scientific and industrial interest due to their outstanding tribological behavior. The paradigmatic example is MoS2 , even though selenides and tellurides have demonstrated superior tribological properties. Here, an innovative in operando conversion of Se nanopowders into lubricious 2D selenides, by sprinkling them onto sliding metallic surfaces coated with Mo and W thin films, is described. Advanced material characterization confirms the tribochemical formation of a thin tribofilm containing selenides, reducing the coefficient of friction down to below 0.1 in ambient air, levels typically reached using fully formulated oils. Ab initio molecular dynamics simulations under tribological conditions reveal the atomistic mechanisms that result in the shear-induced synthesis of selenide monolayers from nanopowders. The use of Se nanopowder provides thermal stability and prevents outgassing in vacuum environments. Additionally, the high reactivity of the Se nanopowder with the transition metal coating in the conditions prevailing in the contact interface yields highly reproducible results, making it particularly suitable for the replenishment of sliding components with solid lubricants, avoiding the long-lasting problem of TMD-lubricity degradation caused by environmental molecules. The suggested straightforward approach demonstrates an unconventional and smart way to synthesize TMDs in operando and exploit their friction- and wear-reducing impact

New tools to support the designing of efficient and reliable ground source heat exchangers: the Cheap-GSHPs databases and maps

Abstract. The final aim of the EU funded Cheap-GSHPs project is to reduce the total installation cost of closed-loop shallow geothermal systems. As part of the project a Decision Support System (DSS) has been developed and released on the web, in order to support the design of new closed-loop geo-exchange systems. The Cheap-GSHP project addresses all the aspects involved in planning and dimensioning a new borefield and therefore, the DSS is composed of several databases and tools that collect and elaborate the preliminary data and information that are necessary during the sizing phase, such as the geological and drilling aspects as well as the heating and cooling building demand. This paper briefly introduces the content of the databases and the mapping methodology developed for the Cheap-GSHPs DSS. All these researches are further deepen in the EU project GEO4CIVHIC, with a special attention to the application of shallow geothermal systems for building conditioning to historical buildings.</p

An updated ground thermal properties database for GSHP applications

Abstract When a new ground source heat exchanger field is planned, underground thermal properties input data are necessary for the correct sizing of the geo-exchange system. To support the design, the EU founded Cheap-GSHPs project developed a Decision Support System, that comprises a new database of thermal properties for both rocks and unconsolidated sediments. The thermal properties database has been developed by integrating and comparing data (1) provided by the most important international guidelines, (2) acquired from a wide literature review and (3) obtained from more than 400 direct measurements. The data are mainly thermal conductivity data, hence the convective contribution provided by groundwater flow to heat transfer is not included. This paper presents and analyses the collected database

EU project "Cheap-GSHPs": the geoexchange field laboratory

Abstract The Molinella test site is the open-air laboratory of the EU project entitled "Cheap-GSHPs: Cheap and Efficient Application of Reliable Ground Source Heat Exchangers and Pumps". Here, innovative helical heat baskets and steel coaxial probes are installed next to the traditional double-U. The tests involve the probes design as well as materials and drilling techniques and machines, therefore the newly developed GSHEs can be directly compared with the traditional ones with respect to technical issues and energetic performances. The Molinella test site therefore represents a very extraordinary possibility to improve the knowledge of heat transfer processes in shallow geo-exchange systems