Adsorption of potassium on Cr₂O₃(0001) at ionic and metallic coverages and uv-laser-induced desorption

Translational energy distributions of neutral potassium atoms are reported as a function of potassium coverage after uv-laser-induced desorption from well-characterized adsorption sites on an epitaxial film of Cr₂O₃(0001)/Cr(110). Measurements using x-ray photoelectron spectroscopy, low-energy electron diffraction, and work-function measurements revealed that potassium adsorbs in a nonmetallic phase for deposition temperatures around 280–300 K allowing only a maximal saturation coverage to be grown for moderate growth rates. Aggregates are observed after deposition at 90 K; at this temperature any layer thickness is obtainable. The uv-laser-induced desorption for these two different phases was studied using excitation energies of 3.5 eV, 5.0 eV, and 6.4 eV and (1+1)-resonantly enhanced multiphonon ionization via the 6p²P state for detection. Desorption of potassium atoms from the nonmetallic phase proves to be ten times [σ(6.4eV)=(2±1)×10^-19cm²] more efficient than desorption from metallic potassium aggregates. The mechanism of desorption from the nonmetallic phase appears to be the inverse harpooning process starting with an ion pair followed by a transfer of hot electrons from the substrate to unoccupied potassium states to neutralize the initially positively charged potassium. The maximum of the translational energy distribution (starting at 0.65 eV for low coverages) decreases with increasing potassium coverage and is by a factor of approximately 4 smaller for desorption from large potassium aggregates (0.16 eV). The decrease of the translational energy with increasing coverages for isolated atoms is ascribed to an increasing lateral interaction between the adsorbates and a concomittant smooth change of the ionicity of the atoms from partially ionic to neutral.