Size-Dependent Isovalent Impurity Doping for Ambipolar Control in Cu₃N

Substitutional doping, involving the replacement of a host with an aliovalent impurity ion, is widely used to attain ambipolar controllability in semiconductors, which is crucial for device application. However, its effectiveness for p-type doping is limited in monovalent cation compounds due to the lack of suitable aliovalent (i.e., zerovalent) impurities. We propose an alternative approach for p- and n-type doping, mediated by the sizes of isovalent alkali metal impurities in Cu(I)-based semiconductors, such as copper nitride with an electron concentration of ∼10¹⁵ cm^–3. Doping of isovalent Li with a smaller size to interstitial positions improves n-type conductivity, and electron concentration is controllable in the range of 10¹⁵ to 10¹⁸ cm^–3. In contrast, larger isovalent Cs and Rb impurities facilitate p-type conversion, resulting in a hole concentration controllability of 10¹⁴ to 10¹⁷ cm^–3. First-principles calculations indicate that Li is placed as an interstitial impurity acting as a shallow donor in conjunction with the formation of a neutral impurity on Cu defects. As the impurity size increases beyond the capacity of the vacant space, the formation of multiple acceptor-type Cu vacancies is enhanced owing to the repulsion between host Cu⁺ and Cs⁺/Rb⁺ impurities. Consequently, the Cs or Rb impurity is located at the sites of the N accompanied by six neighboring Cu vacancies, forming acceptor defect complexes. This size-dependent isovalent impurity doping scheme opens up an alternative avenue for advancement in optoelectronic devices using monovalent cation-based semiconductors.