Interfacial charge transfer and Schottky barriers at c-Si/a-In heterojunctions

Metal-Semiconductor (M/S) heterojunctions, better known as Schottky junctions play a crucial role in modern electronics. At present, the mechanisms behind the M/S junctions are still a subject of discussion. In this work, we investigate the interfaces between semiconducting crystalline Si and amorphous metallic indium, Si{0 0 1}/a-In and Si{1 1 1}/a-In using both ab initio molecular dynamics simulations and a Schottky-Mott approach. The simulations reveal the formation of a distinct border between the Si substrates and amorphous In at the interfaces. The In atoms adjacent to the interfaces exhibit atomic ordering. Charge transfer occurs from In to Si, forming c-Si−q/a-In+q charge barriers at the interfaces. This indicates that a crystalline p-Si/a-In heterojunction will have rectifying properties, which agrees with an analysis using the Schottky-Mott model which predicts a Schottky barrier height of 1.3 eV for crystalline p-Si/a-In using the calculated work function for a-In (3.82 eV). We further discuss the interfacial charge transfer, related hole-depletion regions in Si adjacent to the interfaces and the Schottky-Mott approximations.Electronic InstrumentationEKL Processin

Energy, metastability, and optical properties of anion-disordered R Ox H3-2x (R= Y, La) oxyhydrides: A computational study

In this paper, we investigate by ab initio DFT how the O:H ratio influences the formation and lattice energy, metastability, and optical properties of Y and La anion-disordered ROxH3-2x oxyhydrides. To achieve this, a set of special quasirandom structures (SQS) is introduced to model anion-disorder along the whole RH3-R2O3 composition line. A comparison with an extensive set of anion-ordered polymorphs of the same composition shows the comparable energy of the anion-disordered phase, which, in particular, in the H-rich composition interval showed the lowest relative energy. In turn, the metastability of the anion-disordered phase depends on the cation size (Y versus La), which determines the maximum H content above which the CaF2-type structure itself becomes unstable. To overcome the accuracy limitations of classical DFT, the modified Becke-Johnson (mBJ) scheme is employed in the study of the electronic properties. We show that major differences occur between H-rich and O-rich R oxyhydrides, as the octahedral H- present for x<1 form electronic states at the top of the valence band, which reduce the energy band gap and dominate the electronic transitions at lower energies, thus increasing the refractive index of the material in the VIS-nIR spectral range. Comparing the DFT results to experimental data on photochromic Y oxyhydride films reinforces the hypothesis of anion-disorder in the H-rich films (x<1), while it hints towards some degree of anion ordering in the O-rich ones (x>1). Our paper exemplifies a strategy to calculate ab initio the electronic/optical properties of a wide range of materials with occupational disorder.ChemE/Materials for Energy Conversion & StorageFluid MechanicsRST/Fundamental Aspects of Materials and EnergyChemE/Chemical Engineerin

Exploring Multi-Anion Chemistry in Yttrium Oxyhydrides: Solid-State NMR Studies and DFT Calculations

Rare earth oxyhydrides REOxH(3-2x), with RE = Y, Sc, or Gd and a cationic FCC lattice, are reversibly photochromic in nature. It is known that structural details and anion (O2-:H-) composition dictate the efficiency of the photochromic behavior. The mechanism behind the photochromism is, however, not yet understood. In this study, we use 1H, 2H, 17O, and 89Y solid-state NMR spectroscopy and density functional theory (DFT) calculations to study the various yttrium, hydrogen, and oxygen local environments, anion oxidation states, and hydride ion dynamics. DFT models of YOxH(3-2x) with both anion-ordered and anion-disordered sublattices are constructed for a range of compositions and show a good correlation with the experimental NMR parameters. Two-dimensional 17O-1H and 89Y-1H NMR correlation experiments reveal heterogeneities in the samples, which appear to consist of hydride-rich (x ≈ 0.25) and hydride-poor domains (x ≈ 1) rather than a single composition with homogeneous anion mixing. The compositional variation (as indicated by the different x values in YOxH(3-2x)) is determined by comparing static 1H NMR line widths with calculated 1H-1H dipolar couplings of yttrium oxyhydride models. The 1D 17O MAS spectrum demonstrates the presence of a small percentage of hydroxide (OH-) ions. DFT modeling indicates a reaction between the protons of hydroxides and hydrides to form molecular hydrogen (H+ + H- → H2). 1H MAS NMR indicates the presence of a mobile component that, based on this finding, is attributed to trapped molecular H2 in the lattice.ChemE/Materials for Energy Conversion and StorageRST/Fundamental Aspects of Materials and EnergyChemE/Chemical Engineerin

Impact of F and S doping on (Mn,Fe)₂(P,Si) giant magnetocaloric materials

The quarternary (Mn,Fe)2(P,Si)-based materials with a giant magnetocaloric effect (GMCE) at the ferromagnetic transition TC are promising bulk materials for solid-state magnetic refrigeration. In the present study we demonstrate that doping with the light elements fluorine and sulfur can be used to adjust TC near room temperature and tune the magnetocaloric properties. For F doping the first-order magnetic transition (FOMT) of Mn0.60Fe1.30P0.64Si0.36Fx (x = 0.00, 0.01, 0.02, 0.03) is enhanced, which is explained by an enhanced magnetoelastic coupling. The magnetic entropy change |ΔSm| at a field change (Δμ0H) of 2 T markedly improved by 30% from 14.2 Jkg−1K−1 (x = 0.00) at 335 K to 20.2 Jkg−1K−1 (x = 0.03) at 297 K. For the F doped material the value of |ΔSm| for Δμ0H = 1 T reaches 11.6 Jkg−1K−1 at 294 K, which is consistent with the calorimetric data (12.4 Jkg−1K−1). Neutron diffraction experiments reveal enhanced magnetic moments by F doping in agreement with the prediction of DFT calculation. For S doping in Mn0.60Fe1.25P0.66-ySi0.34Sy (y = 0.00, 0.01, 0.02, 0.03, 0.04) three impurity phases have been found from microstructural analysis, which reduce the stability of the FOMT in the main phase and decrease TC, e.g. the |ΔSm| reduces from 7.9(12.6) Jkg-1K-1 (332 K) for the undoped sample to 3.4(6.2) Jkg-1K-1 (313 K) for the maximum doped sample for Δμ0H = 1(2) T. Neutron diffraction experiments combined with first-principles theoretical calculation, distinguish the occupation of F/S dopants and the tuning mechanism for light element doping, corresponding to subtle structural changes and a strengthening of the covalent bonding between metal and metalloid atoms. It is found that the light elements F and S can effectively regulate the magnetocaloric properties and provide fundamental understanding of (Mn,Fe)2(P,Si)-based intermetallic compounds.RST/Fundamental Aspects of Materials and Energ

Aliovalent Calcium Doping of Yttrium Oxyhydride Thin Films and Implications for Photochromism

To develop an understanding of the photochromic effect in rare-earth metal oxyhydride thin films (REH3-2xOx, here RE = Y), we explore the aliovalent doping of the RE cation. We prepared Ca-doped yttrium oxyhydride thin films ((CazY1-z)HxOy) by reactive magnetron cosputtering with Ca doping concentrations between 0 and 36 at. %. All of the films are semiconductors with a constant optical band gap for Ca content below 15%, while the band gap expands for compositions above 15%. Ca doping affects the photochromic properties, resulting in (1) a lower photochromic contrast, likely due to a lower H- concentration, and (2) a faster bleaching speed, caused by a higher pre-exponential factor. Overall, these results point to the importance of the H- concentration for the formation of a "darkened"phase and the local rearrangement of these H- for the kinetics of the process. ChemE/Materials for Energy Conversion & StorageQN/Kavli Nanolab DelftChemE/O&O groepRST/Fundamental Aspects of Materials and EnergyInstrumenten groepRST/Storage of Electrochemical EnergyChemE/Chemical Engineerin

Erratum to: Aliovalent Calcium Doping of Yttrium Oxyhydride Thin Films and Implications for Photochromism (The Journal of Physical Chemistry C (2022) 126:34 (14742−14749) DOI:10.1021/acs.jpcc.2c04456)

The energy axes of the RBS and ERD data (contained in Figures 2a,b,d,e, and S4) were originally underestimated, and the corrected figures appear below and in the Supporting Information. The change is in the conversion from raw data to the energy scale, which was initially converted incorrectly. The rescaled x-axis does not change the data conclusions since the assignment of peaks to atoms remains the same and the intensity of the peaks is unaffected. Hence, it has no influence on the calculations and conclusions in the original text. (Figure presented).Erratum DOI 10.1021/acs.jpcc.2c04456ChemE/Materials for Energy Conversion and StorageQN/Kavli Nanolab DelftChemE/O&O groepRST/Fundamental Aspects of Materials and EnergyRID/TS/Instrumenten groepChemE/Chemical Engineerin