The nature and impact of ZnO buffer layers on the initial stages of the hydride vapor phase epitaxy (HVPE) of GaN have been studied by x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), x-ray diffraction (XRD) and photoluminescence (PL). During pre-growth heating, the surface ZnO layer was found to both desorb from ZnO-coated sapphire and react with the underlying sapphire surface forming a thin ZnAl2O4 alloy layer between ZnO and sapphire surface. This ZnO-derived surface promotes the initial nucleation of the GaN and markedly improves material surface morphology, quality and growth reproducibility.

The development of new chemically based growth techniques has opened the range of possible GaN applications. This paper reviews some of the challenges in the chemically based growth of GaN and related materials. Ammonothermal-based growth, hydride vapor phase epitaxy and metal organic vapor phase epitaxy (MOVPE) are chemically complex systems wherein the underlying mechanisms of growth are not well understood at present. All these systems require substantial experimental and theoretical efforts to determine the nature and kinetics of GaN growth. In the case of metal organic vapor phase epitaxy, the application of computational techniques based on density functional theory have augmented the more conventional experimental approaches to determining the growth chemistry. These chemical reaction schemes, when combined with computational thermal-fluid models of the reactor environment, provide the opportunity to predict growth rates, uniformity and eve ntually materials properties.

A comparative study of two different MOVPE reactors used for GaN growth is presented. Computational fluid dynamics (CFD) was used to determine common gas phase and fluid flow behaviors within these reactors. This paper focuses on the common thermal fluid features of these two MOVPE reactors with different geometries and operating pressures that can grow device-quality GaN-based materials. Our study clearly shows that several growth conditions must be achieved in order to grow high quality GaN materials. The high-temperature gas flow zone must be limited to a very thin flow sheet above the susceptor, while the bulk gas phase temperature must be very low to prevent extensive pre-deposition reactions. These conditions lead to higher growth rates and improved material quality. A certain range of gas flow velocity inside the high-temperature gas flow zone is also required in order to minimize the residence time and improve the growth uniformity. These conditions can be achieved by the use of either a novel reactor structure such as a two-flow approach or by specific flow conditions. The quantitative ranges of flow velocities, gas phase temperature, and residence time required in these reactors to achieve high quality material and uniform growth are given.

An ammonia-based, in situ passivation of GaAs surfaces conducted within a metalorganic vapor phase epitaxy reactor is present. The shift of the GaAs surface Fermi level, and hence the surface charge density, resulting from this in situ passivation, has been studied using photoreflectance (PR) spectroscopy. Samples consisting of an undoped GaAs layer on highly doped n-GaAs (UN+) and p-GaAs (UP+) structures allow for the exact determination of the surface Fermi level position using PR These structures were grown by MOVPE and in situ thermal nitridation was performed after growth within the MOVPE system without exposure to the air. After nitridation, the surface Fermi level can be shifted by ∼ 0.23 eV towards the conduction band edge for UN+ structures and by ∼ 0.11 eV towards the valence band edge for UP+ structures from the normally mid-gap ‘pinned’ positions.

A novel Near-field Scanning Optical Microscopy (NSOM) technique is used to obtain simultaneous topology, photoluminescence and photoreflectance (PR) spectra. PR spectra from GaAs surfaces were obtained and the local electric fields were calculated. Sub-wavelength resolution is expected for this technique and achieved for PL and topology measurements. Photovoltages, resulting from the high intensity of light at the NSOM tip, can limit the spatial resolution of the electric field determination.

Selenium disulfide has been demonstrated to be an effective passivant for GaAs (001) surfaces. This chemical treatment can be more robust and effective in reducing surface-states-based Fermi level pinning than other analogous chemical treatments. We have studied SeS2-passivated surfaces, formed by treatment of GaAs in SeS2:CS2 solution, with synchrotron radiation photoemission spectroscopy. The SeS2-treated surface consists of a chemically stratified structure of several atomic layers thickness. The As-based sulfides and selenides appear to reside on the outermost surface with the Ga-based compounds adjacent to the bulk GaAs substrate. The motion of the Fermi level within the band gap was monitored during controlled annealing conditions allowing for the specific chemical moieties responsible for the reduction in surface charge to be identified. As-based species are removed at low annealing conditions with little motion of the Fermi level. GaSe-based species, formed on the surface, are clearly shown to be associated with the unpinning of the Fermi level.