The structural, optical, and electrical properties of ZnO are intimately intertwined. In the present work, the structural and transport properties of 100 nm thick polycrystalline ZnO films obtained by atomic layer deposition (ALD) at a growth temperature (T_g) of 100–300 °C were investigated. The electrical properties of the films showed a dependence on the substrate (a-Al₂O₃ or Si (100)) and a high sensitivity to T_g, related to the deviation of the film stoichiometry as demonstrated by the RT-Hall effect. The average crystallite size increased from 20–30 nm for as grown samples to 80–100 nm after rapid thermal annealing, which affects carrier scattering. The ZnO layers deposited on silicon showed lower strain and dislocation density than on sapphire at the same T_g. The calculated half crystallite size (D/2) was higher than the Debye length (L_D) for all as grown and annealed ZnO films, except for annealed ZnO/Si films grown within the ALD window (100–200 °C), indicating different homogeneity of charge carrier distribution for annealed ZnO/Si and ZnO/a-Al₂O₃ layers. For as grown films the hydrogen impurity concentration detected via secondary ion mass spectrometry (SIMS) was 10²¹ cm⁻³ and was decreased by two orders of magnitude after annealing, accompanied by a decrease in Urbach energy in the ZnO/a-Al₂O₃ layers.

In this work, the properties of ZnO films of 100 nm thickness, grown using atomic layer deposition (ALD) on a–(100) and c–(001) oriented Al₂O₃ substrate are reported. The films were grown in the same growth conditions and parameters at six different growth temperatures (T_g) ranging from 100 °C to 300 °C. All as-grown and annealed films were found to be polycrystalline, highly (001) oriented for the c–Al₂O₃ and highly (101) oriented for the a–Al₂O₃ substrate. The manifestation of semi-polar-(101) and polar (001)–oriented ZnO films on the same substrate provided the opportunity for a comparative study in terms of the influence of polarization on the electrical and structural properties of ZnO films. It was found that the concentration of hydrogen, carbon, and nitrogen impurities in polar (001)–oriented films was considerably higher than in semi-polar (101)–oriented ZnO films. The study showed that when transparent conductive oxide applications were considered, the ZnO layers could be deposited at a temperature of about 160 °C, because, at this growth temperature, the high electrical conductivity was accompanied by surface smoothness in the nanometer scale. On the contrary, semi-polar (101)–oriented films might offer a perspective for obtaining p-type ZnO films, because the concentration of carbon and hydrogen impurities is considerably lower than in polar films.

A Scanning Photoelectron Microscopy (SPEM) experiment has been applied to ZnO:N films deposited by Atomic Layer Deposition (ALD) under O-rich conditions and post-growth annealed in oxygen at 800 °C. State-of-the-Art spatial resolution (130 nm) allows for probing the electronic structure of single column of growth. The samples were cleaved under ultra-high vacuum (UHV) conditions to open atomically clean cross-sectional areas for SPEM experiment. It has been shown that different columns reveal considerably different shape of the valence band (VB) photoemission spectra and that some of them are shifted towards the bandgap. The shift of the VB maximum, which is associated with hybridization with acceptor states, was found to be correlated with carbon content measured as a relative intensity of the $C1s$ and $Zn3d$ core levels. Generalized Gradient Approximation (GGA) supplemented by +U correction was applied to both $Zn3d$ and $O2p$ orbitals for calculation of the $V_{\mathrm{Zn}}$ migration properties by the Nudged Elastic Band (NEB) method. The results suggest that interstitial -${\mathrm{CH}}_x$ groups facilitate the formation of acceptor complexes due to additional lattice perturbation.