Structure and stability of N–H complexes in single-crystal ZnO

Abstract

Zinc oxide (ZnO) is semiconductor with a wide band gap of 3.4 eV. It continues to gain more attention not only for its versatile use in industry but also its potential for further application in electronics, optics, spintronics, and transparent circuits. Many of these applications require p-type ZnO. Nitrogen substituting for oxygen is a possible acceptor for such applications. In this paper, we report a study of nitrogen-hydrogen (N–H) complexes grown into single-crystal ZnO, using seeded chemical vapor transport in an ammonia ambient. An infrared (IR) absorption peak arising from N–H complexes was observed at 3150.6 cm−1 at liquid-helium temperatures. The assignment of this peak was confirmed by nitrogen and hydrogen isotope substitution. Polarized IR spectroscopy shows that the N–H dipole is oriented at an angle ∼114° to the c axis, in agreement with previous first-principles calculations. To probe the stability of the N–H complexes, samples were annealed in air, oxygen, and argon. Samples annealed in oxygen at 725 °C showed a significant increase in resistivity, due to outdiffusion of hydrogen and compensation by nitrogen acceptors.