The behavior of electrons in the conduction band of TiO2 and other transition-metal oxides is key to the many applications of these materials. Experiments seem to produce conflicting results: optical and spin-resonance techniques reveal strongly localized small polarons, while electrical measurements show high mobilities that can only be explained by delocalized free electrons. By means of hybrid functional calculations we resolve this apparent contradiction and show that small polarons can actually coexist with delocalized electrons in the conduction band of TiO2, the former being energetically only slightly more favorable. We also find that small polarons can form complexes with oxygen vacancies and ionized shallow-donor impurities, explaining the rich spectrum of Ti3+ species observed in electron spin resonance experiments.
Janotti A, Franchini C, Varley JB, Kresse G, Van de Walle CG (2013). Dual behavior of excess electrons in rutile TiO2. PHYSICA STATUS SOLIDI. RAPID RESEARCH LETTERS, 7(3), 199-203 [10.1002/pssr.201206464].
Dual behavior of excess electrons in rutile TiO2
Franchini CWriting – Review & Editing
;
2013
Abstract
The behavior of electrons in the conduction band of TiO2 and other transition-metal oxides is key to the many applications of these materials. Experiments seem to produce conflicting results: optical and spin-resonance techniques reveal strongly localized small polarons, while electrical measurements show high mobilities that can only be explained by delocalized free electrons. By means of hybrid functional calculations we resolve this apparent contradiction and show that small polarons can actually coexist with delocalized electrons in the conduction band of TiO2, the former being energetically only slightly more favorable. We also find that small polarons can form complexes with oxygen vacancies and ionized shallow-donor impurities, explaining the rich spectrum of Ti3+ species observed in electron spin resonance experiments.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.