On the nature of point defect and its effect on electronic structure of rocksalt hafnium nitride films

Abstract Although point defects are found to exist commonly in non-stoichiometric group-IVB transition metal nitrides, the identification of primary point defects still causes some disagreement. The formation mechanism and influence of primary point defects on electronic structures are not yet well explored. This study finds that the types and formation mechanism of primary point defects in rocksalt hafnium nitride (δ-HfN x ) films can be identified by a combination of first-principles calculations and grazing incidence X-ray diffraction, Raman and high-resolution transmission electron microscopy experiments. It is shown that the primary point defects in sub- and over-stoichiometric δ-HfN x films are N and Hf vacancies, respectively, which arise preferentially because they are thermodynamically more stable than other types of point defects, such as interstitials and antisites, because they have much lower formation energy and equilibrium formation enthalpy. Furthermore, it is found that the formation of N and Hf vacancies have an important role in changing electronic structures. N vacancies act as donor-like defects and can add extra free electrons to the conduction band at a rate of an electron per N vacancy, while Hf vacancies serve as acceptor-like defects and efficiently reduce free electrons at a rate of two electrons per Hf vacancy. Additionally, the formation of N vacancies can induce two new interband absorption bands centered at ∼0.81 and ∼2.27 eV, while the incorporation of Hf vacancies create an additional interband absorption band at ∼3.75 eV. These new insights are demonstrated by good agreement between calculations and experiments.