We investigated the surface chemistry and valence band (VB) structure of as-grown thin InN(0001)-2 Â 2 films as well as their change upon the exposure to oxygen and water. The InN films were grown by plasma-assisted molecular beam epitaxy (PAMBE) and in situ characterized by reflection high electron energy diffraction (RHEED) and photoelectron spectroscopy (UPS, XPS). The oxygen and water exposure was directly performed on the as-grown, contamination-free InN surfaces at room temperature and leads to changes in the chemical surface states as well as the electronic properties. For 2 Â 2 reconstructed InN surfaces one observes directly after growth a surface state at the Fermi-edge which decreases continuously with oxygen and water exposure. Furthermore, two oxygen related electronic states develop in the VB at binding energies at around 5 and 10 eV. For water exposure a third weak state around 8 eV is additionally observed. The impact of oxygen and water on the work function F as well as the variation of surface band bending was investigated. In both cases for initially 2 Â 2 reconstructed surfaces a reduction in the downward band bending is found, while F increases in the case of oxygen exposure but in the case of interaction with water a reduced work function is observed. The oxygen uptake rates reveal a higher reactivity of water with InN surfaces compared to oxygen. Furthermore, during oxidation and water exposure different chemical oxygen bonds are formed, but a direct assignment to In-O or N-O bonds is difficult due to changes in the In3d and N1s XPS core level peak shape.

The influence of selected donor- and acceptor-type adsorbates on the electronic properties of InN(0001) surfaces is investigated implementing in-situ photoelectron spectroscopy. The changes in work function, surface band alignment, and chemical bond configurations are characterized during deposition of potassium and exposure to oxygen. Although an expected opponent charge transfer characteristic is observed with potassium donating its free electron to InN, while dissociated oxygen species extract partial charge from the substrate, a reduction of the surface electron accumulation occurs in both cases. This observation can be explained by adsorbate-induced saturation of free dangling bonds at the InN resulting in the disappearance of surface states, which initially pin the Fermi level and induce downward band bending.

The interaction of n-type GaN(0001) surfaces with potassium and water is investigated using photoelectron spectroscopy, with special focus on adsorbate–substrate charge-transfer processes and water dissociation. Potassium atoms adsorb at the surface, forming a distinct surface dipole layer. For very low K coverage, the attached ionized K adsorbates result in a drop of the work function and the released electrons induce a reduction of the initial upward band bending. After stabilization of both quantities in the sub-monolayer regime, a reverse effect is observed for higher K coverage up to one monolayer (ML), exceeding the upward band bending of the clean surface. If the K-covered surface is exposed to water, hydroxyl groups are formed, whereas during long K and H2O coadsorption, a potassium hydroxide film grows. In both cases, a further reduction of the work function and an abrupt change in the surface depletion layer is recorded. For the coadsorption, initially an electron accumulation layer forms at the surface, approaching flat band conditions for higher KOH thickness. Overall, the surface band bending can be drastically modified in the range between +0.5 and −0.6 eV. These observations clearly show that the electron density at the GaN(0001) surface can be reversibly tuned by alkali-based adsorbates. Different reactions are observed, which are directly linked to the charge-transfer processes and chemical reactions induced by the K 4s electrons.

In this work we investigate the interaction of potassium and water with 2×2 reconstructed InN(0001) surfaces prepared by plasma‐assisted molecular beam epitaxy. The influence of adsorbate‐substrate‐interaction on surface properties is characterized in‐situ by photoelectron spectroscopy. Potassium exposure leads to a strong reduction in the work function Φ to 1.6 eV revealing a charge transfer from the adsorbate to the InN surface. In parallel, a reduction of the surface downward band bending by 0.2 eV and hence a reduced electron accumulation density is observed. While interaction of water with clean InN(0001)‐2×2 surfaces induces only minor changes in the surface band bending, water adsorption at potassium covered InN(0001) leads to a reversal of the K‐induced reduction in surface band bending and a slight increase of Φ to 2.4 eV. These results show that surrounding water modifies the interaction of potassium with InN(0001) surfaces. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

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