L. J. Brillson

The structure and properties of metal-semiconductor interfaces

Abstract In this review, we examine the contributions of surface science research to the understanding of metal-semiconductor interfaces. In particular, we survey conventional concepts of Schottky barrier formation, indicate the wide range of ultrahigh vacuum techniques now available for probing metal-semiconductor interfaces on an atomic scale, and assess the current state of knowledge of the chemical, geometrical, and electronic structures of metal-semiconductor interfaces.

ZnO Schottky barriers and Ohmic contacts

ZnO has emerged as a promising candidate for optoelectronic and microelectronic applications, whose development requires greater understanding and control of their electronic contacts. The rapid pace of ZnO research over the past decade has yielded considerable new information on the nature of ZnO interfaces with metals. Work on ZnO contacts over the past decade has now been carried out on high quality material, nearly free from complicating factors such as impurities, morphological and native point defects. Based on the high quality bulk and thin film crystals now available, ZnO exhibits a range of systematic interface electronic structure that can be understood at the atomic scale. Here we provide a comprehensive review of Schottky barrier and ohmic contacts including work extending over the past half century. For Schottky barriers, these results span the nature of ZnO surface charge transfer, the roles of surface cleaning, crystal quality, chemical interactions, and defect formation. For ohmic contacts...

Role of Near-Surface States in Ohmic-Schottky Conversion of Au Contacts to ZnO

A conversion from ohmic to rectifying behavior is observed for Au contacts on atomically ordered polar ZnO surfaces following remote, room-temperature oxygen plasma treatment. This transition is accompanied by reduction of the “green” deep level cathodoluminescence emission, suppression of the hydrogen donor-bound exciton photoluminescence and a ∼0.75eV increase in n-type band bending observed via x-ray photoemission. These results demonstrate that the contact type conversion involves more than one mechanism, specifically, removal of the adsorbate-induced accumulation layer plus lowered tunneling due to reduction of near-surface donor density and defect-assisted hopping transport.

Observation of 4H–SiC to 3C–SiC polytypic transformation during oxidation

We have observed the formation of single and multiple stacking faults that sometimes give rise to 3C–SiC bands in a highly doped n-type 4H–SiC epilayer following dry thermal oxidation. Transmission electron microscopy following oxidation revealed single stacking faults and bands of 3C–SiC in a 4H–SiC matrix within the 4H–SiC epilayer. These bands, parallel to the (0001) basal plane, were not detected in unoxidized control samples. In addition to the 3.22 eV peak of 4H–SiC, Cathodoluminescence spectroscopy at 300 K after oxidation revealed a spectral peak at 2.5 eV photon energy that was not present in the sample prior to oxidation. The polytypic transformation is tentatively attributed to the motion of Shockley partial dislocations on parallel (0001) slip planes. The generation and motion of these partials may have been induced by stresses caused either by the heavy doping of the epilayer or nucleation from defect.

Characterization of electronic structure and defect states of thin epitaxial BiFeO3 films by UV-visible absorption and cathodoluminescence spectroscopies

UV-visible absorption and cathodoluminescence spectra of phase-pure epitaxial BiFeO3 thin films grown on SrTiO3(001) substrates by ultrahigh vacuum sputtering reveal a bandgap of 2.69–2.73eV for highly strained ∼70nm thick BiFeO3 films. This bandgap value agrees with theoretical calculations and recent experimental results of epitaxial BiFeO3 films, demonstrating only minimal bandgap change with lattice distortion. Both absorption and cathodoluminescence spectra show defect transitions at 2.20 and 2.45eV, of which the latter can be attributed to defect states due to oxygen vacancies.

Dominant Effect of Near-Interface Native Point Defects on ZnO Schottky Barriers

The authors used depth-resolved cathodoluminescence spectroscopy and current-voltage measurements to probe metal-ZnO diodes as a function of native defect concentration, oxygen plasma processing, and metallization. The results show that resident native defects in ZnO single crystals and native defects created by the metallization process dominate metal-ZnO Schottky barrier heights and ideality factors. Results for ZnO(0001¯) faces processed with room temperature remote oxygen plasmas to remove surface adsorbates and reduce subsurface native defects demonstrate the pivotal importance of crystal growth quality and metal-ZnO reactivity in forming near-interface states that control Schottky barrier properties.

Direct observation of copper depletion and potential changes at copper indium gallium diselenide grain boundaries

We have used micro-Auger electron spectroscopy, cathodoluminescence spectroscopy, and work function measurements in copper indium gallium diselenide polycrystalline solar cell films cleaved in ultrahigh vacuum. We establish that, relative to the grain interior, the grain boundary shows (1) a Cu composition decrease, as large as a factor of two, (2) a work function decrease of up to 480 meV, and (3) no additional radiative recombination centers despite a high concentration of grain boundary (GB) defects. These results confirm theoretical predictions that (i) polar GB interfaces are stabilized by massive (∼50%) removal of Cu atoms, leading to (ii) a valence band offset between GB and grain interiors that (iii) repels holes from the GB, thus likely reducing GB electron-hole recombination and improving photovoltaic (and other photonic) device operation.

Remote hydrogen plasma doping of single crystal ZnO

We demonstrate that remote plasma hydrogenation can increase electron concentrations in ZnO single crystals by more than an order of magnitude. We investigated the effects of this treatment on Hall concentration and mobility as well as on the bound exciton emission peak I4 for a variety of ZnO single crystals–bulk air annealed, Li doped, and epitaxially grown on sapphire. Hydrogen increases I4 intensity in conducting samples annealed at 500 and 600 °C and partially restores emission in the I4 range for Li-diffused ZnO. Hydrogenation increases carrier concentration significantly for the semi-insulating Li doped and epitaxial thin film samples. These results indicate a strong link between the incorporation of hydrogen, increased donor-bound exciton PL emission, and increased n-type conductivity.

Chemical reaction and charge redistribution at metal–semiconductor interfaces

Interface compound formation and metal‐induced surface states are observed at representative metal–semiconductor interfaces. These phenomena are associated with microscopic dipoles at the intimate contacts which account for the macroscopic Schottky barrier heights. The barrier heights exhibit a correlation with chemical reactivity and display a pronounced transition between reactive and unreactive interfaces. Thus, local charge redistribution rather than any intrinsic surface states of the semiconductor determine Schottky barrier formation at the metal–semiconductor interfaces.

Electron energy loss spectroscopy and the optical properties of polymethylmethacrylate from 1 to 300 eV

Energy loss spectra of 80 keV electrons transmitted through thin films polymethylmethacrylate (PMMA) were measured with a resolution of 0.1 eV for energy losses from 1 to 300 eV. From the loss spectra, the dielectric response function of PMMA was obtained from 1 to 100 eV and compared with recent synchrotron radiation results. The spectrum of valence excitations from 5 to 13 eV is shown to be characteristic of the pendant group and is compared to experimental gas phase spectra and molecular orbital (CNDO/S) calculations of model molecules. The spectrum of core electron excitations above 285 eV provides a measure of the distribution of empty molecular orbitals and, when the carbon 1s binding energies are taken into account, a qualitatively accurate description of the observed spectrum is made from the CNDO ground state calculation. The energy loss spectra of 20, 40, and 100 eV electrons reflected from the surface of PMMA exhibit a triplet excitation at 4.2 eV and indicate the extreme sensitivity of this ma...