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Orientation-dependent reactivity and band-bending are evidenced upon Tideposition (1-10 \AA) on the polar ZnO(0001)-Zn and ZnO(000$\bar{1}$)-Osurfaces. At the onset of the Ti deposition, a downward band-bending wasobserved on ZnO(000$\bar{1}$)-O while no change occurred on ZnO(0001)-Zn.Combining this with the photoemission analysis of the Ti 2p core level and ZnL$_3$(L$_2$)M$_{45}$M$_{45}$ Auger transition, it is established that theTi/ZnO reaction is of the form Ti + 2 ZnO $\rightarrow$ TiO$_2$ + 2 Zn onZnO(0001)-Zn and Ti + y ZnO $\rightarrow$ TiZn$_x$O$_y$ + (y-x) Zn onZnO(000$\bar{1}$)-O. Consistently, upon annealing thicker Ti adlayers, themetallic zinc is removed to leave ZnO(0001)-Zn surfaces covered withTiO$_2$-like phase and ZnO(000$\bar{1}$)-O surfaces covered with a defined (Ti,Zn, O) compound. Finally, a difference in the activation temperature betweenthe O-terminated (500 K) and Zn-terminated (700 K) surfaces is observed, whichis tentatively explained by different electric fields in the space charge layerat ZnO surfaces.

Orientation-dependent chemistry and band-bending of Ti on polar ZnO surfaces