Scanning Tunneling Microscopy Studies of the Initial Stages of Thin Film Growth: the Role of the Surface Dangling Bonds

We present STM and photoemission studies of the reactions of Si(100)-(2×1) and Si(111)–(7×7) with NH3. STM allows us to image the occupied and unoccupied states of the reacting systems and to obtain electronic spectra with atomic lateral resolution. Thus, for the first time, a surface chemical reaction can be probed at the atomic level. We find that both surfaces are reactive even at 100K. However, both the extent of the reaction and the reaction products at 300K are different on the two surfaces. STM also shows that while surface dangling bonds are essential for low-temperature reactivity, not all triplycoordinated Si sites are chemically equivalent. On the 7×7 surface the rest-atoms are more reactive than center-adatoms which, in turn, are more reactive than corner-adatoms.