Theoretical prediction of isotope effects on charge transport in organic semiconductors

We suggest that the nuclear tunneling effect is important in organic semiconductors, which we showed is absent in both the widely employed Marcus theory and the band-like transport as described by the deformation potential theory. Because the quantum nuclear tunneling tends to favor electron transfer while heavier nuclei decrease the quantum effect, there should occur an isotope effect for carrier mobility. For N,N′-n-bis(n-hexyl)-naphthalene diimide, electron mobility of all-deuteration on alkyls and all ¹³C- substitution on the backbone decrease ∼18 and 7%, respectively. Similar isotope effects are found in the N,N′-n-bis(n-octyl)-perylene diimide. However, there is nearly no isotope effect for all-deuterated rubrene or tetracene. We have found that the isotopic effect only occurs when the substituted nuclei contribute actively to vibrations with appreciable charge reorganization energy and coupling with carrier motion. Thus, this prediction can shed light on the current dispute over the hopping versus band-like mechanisms in organic semiconductors.