The shallow-to-deep instability of hydrogen and muonium in II-VI and III-V semiconductors

The structure and electrical activity of monatomic hydrogen defect centres are inferred from the spectroscopy and charge-state transitions of muonium, the light pseudo-isotope of hydrogen. Introductions are given to all these topics. Special attention is paid to the shallow-donor behaviour recently established in a number of II-VI compounds and one III nitride. This contrasts with trapped-atom states suggestive of an acceptor function in other members of the II-VI family as well as with the deep-level amphoteric behaviour which has long been known in the elemental group-IV semiconductors and certain II-IV compounds. The systematics of this remarkable shallow-to-deep instability are examined in terms of simple chemical considerations, as well as current theoretical and computational models. The muonium data appear to confirm predictions that the switch from shallow to deep behaviour is governed primarily by the depth of the conduction-band minimum below the vacuum continuum. The threshold electron affinity is around 3.5 ey, which compares favourably with computational estimates of a so-called pinning level for hydrogen (+/-) charge-state transitions of between -3. and -4.5 eV. A purely ionic model gives some intuitive understanding of this behaviour as well as the invariance of the threshold. Another current description applies equally to covalent materials and, relates the threshold to the origin of the electrochemical scale. At the present level of approximation, zero-point energy corrections to the transition levels are small, so that muonium data should provide a reliable guide to the behaviour of hydrogen. Muonium spectroscopy proves to be more sensitive to the (0/+) donor level than to the (+/-) pinning level but, as a tool which does not rely on favourable hydrogen solubility, it looks set to test further predictions of these models in a large number of other materials, notably oxides. Certain candidate thin-film insulators and high-permittivity gate dielectrics appear to be uncomfortably close to conditions in which hydrogen impurity may cause electronic conduction. This review is dedicated to the memory of T L Estle (1931-2002).