YBa2Cu3Ox sputter deposited cold on MgO grows in O2 annealing epitaxially to a transparent, superconducting film with Tc 80K. The unscraped surfaces of these films are smooth showing XPS lines changing with photoelectron take-off angle. This enhanced data base allows to separate the different chemical compounds (hydroxide, peroxide, carbonate, carboxyle, cuprate, graphite ...) and to obtain their spatial distribution. This yields the compounds, their amount and distribution making up the cinder growing with O2-anneal at internal and external surfaces. The cinder stoichiometry gives insights in the chemistry going on in O2 annealing. Below the cinder the signature of cˆ-axis oriented YBa2Cu3Ox is identified, showing that a Ba-oxide layer forms the stable surface. This coats insulating CuO2 and Y-oxide layers yielding so an intrinsic dead layer.