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Comments 4: The binding energy shift for Zn2+, even if it is real (see point one of this report), it is accompanied by a similar shift in the O 1s peak assigned to ZnO. This simultaneous shift could also be due to the confinement of the ZnO dots. In fact, BE=-E(orbital) only in the absence of relaxations. In solids, mainly in oxides, relaxation effects may be so strong that, for may oxides, the binding energy for the metal ion in an oxide MO (M2+) may be higher than for a M2O3 (M3+). It should not be surprising if the confinement of the ZnO into a quantum dot resulted into a very different relaxation effect for the hole left behind by the ejected photoelectron and it is a very well known effect for the BE of metals in nanoparticles: it raises when the nanoparticle size decreases. Moreover, if the occurrence of Zn-O-Si bonds occurred at the surface, yet in the core of the quantum dot, a few bonds Zn-O-Zn should also exist. And given the dimensions of the quantum dots, the corresponding signal should not suffer considerable attenuation. Why should the Zn 2p3/2 present a single component? |
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