ABSTRACTState-of-the-art first-principles calculations allow detailed studies of the mechanisms by which hydrogen and fluorine interact with silicon. The results for hydrogen are presented in the form of an energy diagram which includes many different configurations. The theoretical values allow a discussion of issues such as hydrogen solubility, and desorption from a Si surface. For fluorine, we investigate the behavior as an interstitial impurity in the bulk, as well as Si-F interactions at or near the surface. A study of the insertion of F atoms into Si-Si bonds elucidates the microscopic mechanisms of etching, and the dependence of etch rate on doping. Thermodynamic aspects of HF etching are briefly discussed.