The aim of this study is motivated by the pursuit to investigate the performance of new and as yet untested precursors such as hydrazinium chloride (N2H5Cl) and triisobutylaluminum Al(C4H9)3 in the AlN atomic layer deposition (ALD) process as well as to study effects of successive annealing on the quality of the resulting layer. Both precursors are significantly cheaper than their conventional counterparts while also being widely available and can boast easy handling. Furthermore, Al(C4H9)3 being a rather large molecule might promote steric hindrance and prevent formation of undesired hydrogen bonds. Chemical analysis is provided by X-ray photoelectron spectroscopy (XPS) and secondary-ion mass spectrometry (SIMS) techniques; surface morphology was studied using atomic force microscopy (AFM). Chlorine containing precursors such as AlCl3 are usually avoided in ALD process due to the risk of chamber contamination. However, experimental data of this study demonstrated that the use of N2H5Cl does not result in chlorine contamination due to the fact that temperature needed for HCl molecules to become reactive cannot be reached within the AlN ALD window (200–350 °C). No amount of chlorine was detected even by the most sensitive techniques such as SIMS, meaning it is fully removed out of the chamber during purge stages. A part of the obtained samples was subjected to annealing (1350 °C) to study effects of high-temperature processing in nitrogen atmosphere, the comparisons with unprocessed samples are provided.