The thermal properties of five homoleptic bismuth amides of the general type ((RRN)-R-1-N-2)(3)Bi (R-1, R-2 = Me 1, R-1, R-2 = Et 2, R-1, R-2 = n-Pr 3, = Me, R-2 = Et 4, R-1 = n-Bu, R-2 = Et 5) and the cyclo-dibismadiazane [(Me3Si)(2)NBi-mu-NSiMe3](2) 6 were studied by DSC and TGA/DTA (1, 6) and their reactions with (Et3Si)(2)Te were investigated by in situ NMR spectroscopy. Based on these results, the potential application of 1, 4 and 6 to serve as ALD precursors for the deposition of Bi2Te3 films in reactions with (Et3Si)(2)Te were investigated. The resulting films were characterized by XRD, EDX, AFM and SEM and the crucial role of the substrate material and substrate temperature on the film growth rate and the morphology and chemical composition of the Bi2Te3 films was determined. (C) 2017 Elsevier B.V. All rights reserved.