Surface modifications of InAs: effect of chemical processing on electronic structure and photoluminescent properties

• Main Author: Eassa, Nahswa Abo Alhassan Eassa
• Format: Others
• Language: English
• Published: Nelson Mandela Metropolitan University 2012
• Subjects: Indium arsenide; Chemical processes; Photoluminescence
• Online Access: http://hdl.handle.net/10948/8714

In this thesis, the effects of various chemical treatments on the surface modification of bulk InAs are investigated. The study focuses on the chemical processes that occur upon the exposure of the surface to sulphur-, chlorine- and bromine-containing solutions and oxygen, and the resulting changes to the electronic structure of the surface, as deduced from photoluminescence (PL) measurements, X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), Raman scattering and scanning electron microscopy (SEM). Three processing treatments were evaluated: i) treatment with sulphur-based solutions (Na2S:9H2O, (NH4)2S + S, [(NH4)2S / (NH4)2SO4] + S); ii) etching in halogen-based solutions (bromine-methanol and HCl: H2O); and iii) thermal oxidation. A significant overall enhancement in PL response was observed after chemical treatment or thermal oxidation, which is associated with a reduction in surface band bending. These changes correlate with the removal of the native oxide, in addition to the formation of well-ordered layers of In-S (or In-As)O as a passivating layer, indicating that electronic passivation occurs at the surface. The passivating effect on sulphide treated surfaces is unstable, however, with an increase in band bending, due to reoxidation, observed over periods of a few days. The lowest re-oxidation rate was observed for ([(NH4)2S / (NH4)2SO4] + S). Etching in HCl:H2O and Br-methanol solutions of appropriate concentrations and for moderate times (1 min) resulted in smooth and defect-free InAs surfaces. Etching completely removed the native oxides from the surface and enhanced the PL response. The adsorption of bromine and chlorine onto the InAs surface led to the formation of As-Brx , In-Brx, As-Clx and In-Clxcompounds (x = 1, 2, 3), as inferred from changes in the In 3d3/2; 5/2 and As 3d core level binding energies. The etch rate was found to decrease because of strong anisotropic effects. The improvements in surface properties were reversed, however, if the concentrations of the etchants increased or the etch time was too long. In the worst cases, pit formation and inverted pyramids with {111} side facets were observed. Surface treatments or thermal oxidisation significantly enhanced the PL intensity relative to that of the as-received samples. This was due to a reduction in the surface state density upon de-oxidation, or in some cases, to the formation of a well ordered oxide layer on the surface. The overall increase in PL intensity after treatment is ascribed to a reduction in band bending near the surface. This allows several welldefined peaks not observed or reported previously for bulk InAs (with a carrier concentration n~2x1016 cm-3), to be studied. A combination of PL and XPS measurements before and after the various treatments was used to identify the chemical nature of the impurities giving rise to bound exciton recombination in InAs (111).