Surface passivation of semiconducting oxides by self-assembled nanoparticles.

Physiochemical interactions which occur at the surfaces of oxide materials can significantly impair their performance in many device applications. As a result, surface passivation of oxide materials has been attempted via several deposition methods and with a number of different inert materials. Here, we demonstrate a novel approach to passivate the surface of a versatile semiconducting oxide, zinc oxide (ZnO), evoking a self-assembly methodology. This is achieved via thermodynamic phase transformation, to passivate the surface of ZnO thin films with BeO nanoparticles. Our unique approach involves the use of Be(x)Zn(1-x)O (BZO) alloy as a starting material that ultimately yields the required coverage of secondary phase BeO nanoparticles, and prevents thermally-induced lattice dissociation and defect-mediated chemisorption, which are undesirable features observed at the surface of undoped ZnO. This approach to surface passivation will allow the use of semiconducting oxides in a variety of different electronic applications, while maintaining the inherent properties of the materials.

Recrystallization of highly-mismatched Be(x)Zn(1-x)O alloys: formation of a degenerate interface.

We investigate the effect of thermally induced phase transformations on a metastable oxide alloy film, a multiphase Be(x)Zn(1-x)O (BZO), grown on Al2O3(0001) substrate for annealing temperatures in the range of 600-950 °C. A pronounced structural transition is shown together with strain relaxation and atomic redistribution in the annealed films. Increasing annealing temperature initiates out-diffusion and segregation of Be and subsequent nucleation of nanoparticles at the surface, corresponding to a monotonic decrease in the lattice phonon energies and band gap energy of the films. Infrared reflectance simulations identify a highly conductive ZnO interface layer (thicknesses in the range of ≈ 10-29 nm for annealing temperatures ≥ 800 °C). The highly degenerate interface layers with temperature-independent carrier concentration and mobility significantly influence the electronic and optical properties of the BZO films. A parallel conduction model is employed to determine the carrier concentration and conductivity of the bulk and interface regions. The density-of-states-averaged effective mass of the conduction electrons for the interfaces is calculated to be in the range of 0.31 m0 and 0.67 m0. A conductivity as high as 1.4 × 10(3) S · cm(-1) is attained, corresponding to the carrier concentration n(Int) = 2.16 × 10(20) cm(-3) at the interface layers, and comparable to the highest conductivities achieved in highly doped ZnO. The origin of such a nanoscale degenerate interface layer is attributed to the counter-diffusion of Be and Zn, rendering a high accumulation of Zn interstitials and a giant reduction of charge-compensating defects. These observations provide a broad understanding of the thermodynamics and phase transformations in Be(x)Zn(1-x)O alloys for the application of highly conductive and transparent oxide-based devices and fabrication of their alloy nanostructures.