Polarizability,Susceptibility, and Dielectric Constant of Nanometer‐Scale Molecular Films: A Microscopic View

The size‐dependence of the polarizability, susceptibility, and dielectric constant of nanometer‐scale molecular layers is explored theoretically. First‐principles calculations based on density functional theory are compared to phenomenological modeling based on polarizable dipolar arrays for a model system of organized monolayers composed of oligophenyl chains. Size trends for all three quantities are primarily governed by a competition between out‐of‐plane polarization enhancement and in‐plane polarization suppression. Molecular packing density is the single most important factor controlling this competition and it strongly affects the bulk limit of the dielectric constant as well as the rate at which it is approached. Finally, the polarization does not reach its “bulk” limit, as determined from the Clausius–Mossotti model, but the susceptibility and dielectric constant do converge to the correct bulk limit. However, whereas the Clausius–Mossotti model describes the dielectric constant well at low lateral densities, finite size effects of the monomer units cause it to be increasingly inaccurate at high lateral densities.     

Electronic characterization of heterojunctions by surface potential monitoring

An original approach for studying the formation of semiconductor heterojunctions and their electronic properties is discussed and illustrated. Monitoring the changes in the surface potential during the heterojunction formation lends itself to direct measurement of the band discontinuities, Debye length, and the width of the space-charge region at heterojunction interfaces. The contribution of an interface dipole is considered. The technique is demonstrated by a technologically significant experimental example.     

Radiation damage to alkyl chain monolayers on semiconductor substrates investigated by electron spectroscopy

Monolayers of alkyl chains, attached through direct Si-C bonds to Si(111), via phosphonates to GaAs(100) surfaces, or deposited as alkyl-silane monolayers on SiO2, are investigated by ultraviolet and inverse photoemission spectroscopy and X-ray absorption spectroscopy. Exposure to ultraviolet radiation from a He discharge lamp, or to a beam of energetic electrons, leads to significant damage, presumably associated with radiation- or electron-induced H-abstraction leading to carbon-carbon double-bond formation in the alkyl monolayer. The damage results in an overall distortion of the valence spectrum, in the appearance of (occupied) states above the highest occupied molecular orbital of the alkyl molecule, and in a characteristic (unoccupied state) pi resonance at the edge of the carbon absorption peak. These distortions present a serious challenge for the interpretation of the electronic structure of the monolayer system. We show that extrapolation to zero damage at short exposure times eliminates extrinsic features and allows a meaningful extraction of the density of state of the pristine monolayer from spectroscopy measurements.     

Photoemission spectra of deuterated silicon clusters: experiment and theory

We compare experimentally measured and ab initio computed photoelectron spectra of negatively charged deuterated silicon clusters ( , 4m10, 0n2) produced in a plasma environment. Based on this comparison, we discuss the kinetics and thermodynamics of the cluster formation and the effect of deuterium on the geometrical and electronic structure of the clusters.     

Size-dependent spintronic properties of dilute magnetic semiconductor nanocrystals

The electronic structure and magnetic properties of Mn-doped Ge, GaAs, and ZnSe nanocrystals are investigated using real space ab initio pseudopotentials constructed within the local spin-density approximation. The ferromagnetic and half-metallicity trends found in the bulk are preserved in the nanocrystals. However, the Mn-related impurity states become much deeper in energy with decreasing nanocrystalline size, causing the ferromagnetic stabilization to be dominated by double exchange via localized holes rather than by a Zener-like mechanism.     

Hybrids of organic molecules and flat, oxide-free silicon: high-density monolayers, electronic properties, and functionalization

Since the first report of Si-C bound organic monolayers on oxide-free Si almost two decades ago, a substantial amount of research has focused on studying the fundamental mechanical and electronic properties of these Si/molecule surfaces and interfaces. This feature article covers three closely related topics, including recent advances in achieving high-density organic monolayers (i.e., atomic coverage >55%) on oxide-free Si(111) substrates, an overview of progress in the fundamental understanding of the energetics and electronic properties of hybrid Si/molecule systems, and a brief summary of recent examples of subsequent functionalization on these high-density monolayers, which can significantly expand the range of applicability. Taken together, these topics provide an overview of the present status of this active area of research.     

Density functional theory of transition metal phthalocyanines,II: electronic structure of MnPc and FePc—symmetry and symmetry breaking

We present a two-part systematic density functional theory (DFT) study of the electronic structure of selected transition metal phthalocyanines. We use a semi-local generalized gradient approximation (GGA) functional, as well as several hybrid exchange-correlation functionals, and compare the results to experimental photoemission data. Here, we study the intermediate spin systems MnPc and FePc. We show that DFT calculations of these systems are extremely sensitive to the choice of functional and basis set with respect to the obtained electronic configuration and to symmetry breaking. Interestingly, all simulated spectra are in good agreement with experiment despite the differences in the underlying electronic configurations.