Control of crystal polarity in a wurtzite crystal: ZnO films grown by plasma-assisted molecular-beam epitaxy on GaN

Abstract

ZnO/GaN heterointerfaces are engineered to control the polarity of ZnO films grown by plasma-assisted molecular beam epitaxy on Ga-polar GaN templates. The polarity of ZnO films is determined both by coaxial impact collision ion scattering spectroscopy (CAICISS) and by convergent beam electron diffraction (CBED). Polarity inversion can be achieved by inserting an interface layer with a center of symmetry, because the polarity comes from a lack of the center of symmetry. An O-polar (anion-polar) ZnO film can be grown on Ga-polar (cation-polar) GaN by inserting a ${\mathrm{Ga}}_{2}{\mathrm{O}}_{3}$ layer at the interface, while Zn-polar ZnO is grown on GaN without forming an interface layer. A single-crystalline monoclinic ${\mathrm{Ga}}_{2}{\mathrm{O}}_{3}$ layer, which has a center of symmetry, is formed by O-plasma preexposure on the Ga-polar GaN surface prior to ZnO growth, while the ZnO/GaN interface without any extra layer is formed by Zn preexposure. The orientation relationship between ZnO, ${\mathrm{Ga}}_{2}{\mathrm{O}}_{3},$ and GaN is determined as $[2\ensuremath{-}1\ensuremath{-}10{]}_{\mathrm{ZnO}}\ensuremath{\parallel}[010{]}_{{\mathrm{Ga}}_{2}{\mathrm{O}}_{3}}\ensuremath{\parallel}[2\ensuremath{-}1\ensuremath{-}10{]}_{\mathrm{GaN}}$ and ${(0001)}_{\mathrm{ZnO}}\ensuremath{\parallel}{(001)}_{{\mathrm{Ga}}_{2}{\mathrm{O}}_{3}}\ensuremath{\parallel}{(0001)}_{\mathrm{GaN}}.$ The CAICISS results reveal the growth of an O-polar ZnO film on O-plasma-preexposed GaN, while a Zn-polar ZnO film on Zn-preexposed GaN. The origin of the observed features in polar-angle-dependent CAICISS spectra can be analyzed by considering the shadow cones of Zn and O atoms formed by incident ions and shadowing and focusing effects of scattered ions. Azimuthal-angle-dependent CAICISS spectra reveal the surfaces of both Zn- and O-polar ZnO films as mixture of c and $c/2$ planes with a ratio of about 50:50. The ZnO film with a ${\mathrm{Ga}}_{2}{\mathrm{O}}_{3}$ interface layer shows a degradation in the crystal quality as evidenced by a broadening of the x-ray rocking curves. The CBED results for the O-plasma-preexposed samples reveal Ga-polar GaN and O-polar ZnO for the O-plasma-preexposed samples, which directly confirms polarity inversion from cation to anion polar. On the other hand, Zn-polar ZnO CBED patterns are obtained from ZnO films grown on Zn-preexposed Ga-polar GaN, which indicates the same cation polarity for a ZnO/GaN interface without the formation of an interface layer. It is noted that no planar or faceted inversion domain boundaries are formed to invert the polarity (from Ga polar to O polar). This indicates that we can control the polarity by engineering interfaces.