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Register a new userThe general electronic principle driving size-dependent surface chemical activities of nanomaterials
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Size can widely affect the surface chemical activities (SCAs) of nanomaterials in chemisorption, catalysis, surface effects, etc., but the underlying electronic nature has long remained mysterious. We report a general electronic principle that drives the origin of size-dependent SCAs by combining experimental probing and theoretical modeling. Using the chemisorption of H2O2 on TiO2 as a model reaction, we experimentally reveal that the central electronic process of surface chemical interactions lies in the competitive redistribution of surface atomic orbitals from energy band states into surface coordination bonds. By defining orbital potential, a site-dependent intrinsic electronic property that determines surface activities, we further establish a mathematical model to uncover the physical nature of how structural factors correlate to SCAs, particularly the roles of size. We discover that the electronic nature of size effect lies in its inverse correlation to orbital potential and amplification effect on other structural factors like defects and coordination numbers.
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A detailed investigation of electronic-transport properties of Nd0.5Sr0.5CoO3 has been carried out as a function of grain size ranging from micrometer order down to an average size of 28 nm. Interestingly, we observe a size induced metal-insulator transition in the lowest grain size sample while the bulk-like sample is metallic in the whole measured temperature regime. An analysis of the temperature dependent resistivity in the metallic regime reveals that the electron-electron interaction is the dominating mechanism while other processes like electron-magnon and electron-phonon scatterings are also likely to be present. The fascinating observation of enhanced low temperature upturn and minimum in resistivity on reduction of grain size is found due to electron-electron interaction (quantum interference effect). This effect is attributed to enhanced disorder on reduction of grain size. Interestingly, we observed a cross over from positive to negative magnetoresistance in the low temperature regime as the grain size is reduced. This observed sign reversal is attributed to enhanced phase separation on decreasing the grain size of the cobaltite.
We analyze the electronic structure of the Os(0001) surface by means of first-principle calculations based on Fully Relativistic (FR) Density Functional Theory (DFT) and a Projector Augmented-Wave (PAW) approach. We investigate surface states and resonances analyzing their spin-orbit induced energy splitting and their spin polarization. The results are compared with previously studied surfaces Ir(111), Pt(111), and Au(111). We do not find any surface state in the gap similar to the L-gap of the (111) fcc surfaces, but find Rashba split resonances that cross the Fermi level and, as in the recently studied Ir(111) surface, have a characteristic downward dispersion. Moreover, for some selected surface states we study the spin polarization with respect to ${bf k}_{parallel}$, the wave-vector parallel to the surface. In some cases, such as the Rashba split resonances, the spin polarization shows a smooth behavior with slow rotations, in others the rotation is faster, due to mixing and anti-crossing of the states.
Palladium diselenide (PdSe$_2$), a new type of two-dimensional noble metal dihalides (NMDCs), has received widespread attention for its excellent electrical and optoelectronic properties. Herein, high-quality continuous centimeter-scale PdSe$_2$ films with layers in the range of 3L-15L were grown using Chemical Vapor Deposition (CVD) method. The absorption spectra and DFT calculations revealed that the bandgap of the PdSe$_2$ films decreased with increasing number of layers, which is due to PdSe$_2$ enhancement of orbital hybridization. Spectroscopic ellipsometry (SE) analysis shows that PdSe2 has significant layer-dependent optical and dielectric properties. This is mainly due to the unique strong exciton effect of the thin PdSe$_2$ film in the UV band. In particular, the effect of temperature on the optical properties of PdSe$_2$ films was also observed, and the thermo-optical coefficients of PdSe$_2$ films with different number of layers were calculated. This study provides fundamental guidance for the fabrication and optimization of PdSe$_2$-based optoelectronic devices.
The electronic structure in the new transition metal carbide Ti4SiC3 has been investigated by bulk-sensitive soft x-ray emission spectroscopy and compared to the well-studied Ti3SiC2 and TiC systems. The measured high-resolution Ti L, C K and Si L x-ray emission spectra are discussed with ab initio calculations based on density-functional theory including core-to-valence dipole matrix elements. The detailed investigations of the Ti-C and Ti-Si chemical bonds provide increased understanding of the physical properties of these nanolaminates. A strongly modified spectral shape is detected for the buried Si monolayers due to Si 3p hybridization with the Ti 3d orbitals. As a result of relaxation of the crystal structure and the charge-transfer from Ti (and Si) to C, the strength of the Ti-C covalent bond is increased. The differences between the electronic and crystal structures of Ti4SiC3 and Ti3SiC2 are discussed in relation to the number of Si layers per Ti layer in the two systems and the corresponding change of materials properties.
Modifying the optoelectronic properties of nanostructured materials through introduction of dopant atoms has attracted intense interest. Nevertheless, the approaches employed are often trial and error, preventing rational design. We demonstrate the power of large-scale electronic structure calculations with density functional theory (DFT) to build an atlas of preferential dopant sites for a range of M(II) and M(III) dopants in the representative III-V InP magic sized cluster (MSC). We quantify the thermodynamic favorability of dopants, which we identify to be both specific to the sites within the MSC (i.e., interior vs surface) and to the nature of the dopant atom (i.e., smaller Ga(III) vs larger Y(III) or Sc(III)). These observations motivate development of maps of the most and least favorable doping sites, which are consistent with some known experimental expectations but also yield unexpected observations. For isovalent doping (i.e., Y(III)/Sc(III) or Ga(III), we observed stronger sensitivity of the predicted energetics to the type of ligand orientation on the surface than to the dopant type, but divergent behavior is observed for whether interior doping is favorable. For charge balancing with M(II) (i.e., Zn or Cd) dopants, we show that the type of ligand removed during the doping reaction is critical. We show that limited cooperativity with dopants up to moderate concentrations occurs, indicating rapid single-dopant estimations of favorability from DFT can efficiently guide rational design. Our work emphasizes the strong importance of ligand chemistry and surface heterogeneity in determining paths to favorable doping in quantum dots, an observation that will be general to other III-V and II-VI quantum dot systems generally synthesized with carboxylate ligands.
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