Dopant Distribution in Atomic Layer Deposited ZnO:Al Films Visualized by Transmission Electron Microscopy and Atom Probe Tomography

Chem Mater. 2018 Feb 27;30(4):1209-1217. doi: 10.1021/acs.chemmater.7b03501. Epub 2018 Feb 5.

Abstract

The maximum conductivity achievable in Al-doped ZnO thin films prepared by atomic layer deposition (ALD) is limited by the low doping efficiency of Al. To better understand the limiting factors for the doping efficiency, the three-dimensional distribution of Al atoms in the ZnO host material matrix has been examined on the atomic scale using a combination of high-resolution transmission electron microscopy (TEM) and atom probe tomography (APT). Although the Al distribution in ZnO films prepared by so-called "ALD supercycles" is often presented as atomically flat δ-doped layers, in reality a broadening of the Al-dopant layers is observed with a full-width-half-maximum of ∼2 nm. In addition, an enrichment of the Al at grain boundaries is observed. The low doping efficiency for local Al densities > ∼1 nm-3 can be ascribed to the Al solubility limit in ZnO and to the suppression of the ionization of Al dopants from adjacent Al donors.