Influence of oxygen-rich and zinc-rich conditions on donor and acceptor states and conductivity mechanism of ZnO films grown by ALD—Experimental studies

Understanding the origin of the strong difference of electrical parameters between as grown and annealed undoped ZnO films prepared at a temperature range of 100–200 °C by thermal atomic layer deposition is essential for their future applications. In this paper, we show that the conductivity drop by up to 4 orders of magnitude as effect of post-growth annealing is accompanied by multiple simultaneous effects like a two orders of magnitude decrease of hydrogen impurity content, a strong width reduction of the luminescence peaks, and an increase of crystallite sizes influencing the carrier scattering. We show that a level of structural and optical improvement as well as the final electrical parameters of annealed films strongly depend on the previously employed growth temperature, which is related to transition from oxygen- to zinc-rich conditions influencing a type and concentration of native point defects. The growth temperature does not only influence the bandgap energy but also the binding energies of existing donors and the relative ratio between the number of donors and acceptors; hence, it determines the final electrical characteristics of the films. This means that electrical properties of undoped ZnO-atomic layer deposition films can be tuned by native defects engineering.