First Principles Modelling of Growth of Hybrid Organic-Inorganic Films
Authors: Muriqi Arbresha , Nolan Michael 
Published: February 2024

Hybrid organic-inorganic materials fabricated with molecular layer deposition (MLD) are a special class of materials that are attracting great interest in many economically and socially relevant technological applications due to their diphasic and tunable organic-inorganic structure. Despite the growing interest in these hybrid materials, knowledge around relevant precursor chemistries and reaction mechanisms, as well as details of many determined experimental results are unknown. Density functional theory (DFT) has proven to be a powerful tool to investigate and understand the atomic level details of the precursor chemistry and address aspects of the MLD experiments.
In our work, we use first principles DFT calculations to examine key steps in the mechanism of hybrid film deposition through MLD by modelling precursor-surface and precursor-precursor reactions. We explore the growth mechanism of aluminium and titanium containing hybrid films, namely alucones and titanicones. Both materials are of high interest for passivation layers in batteries. For alucones we investigate in detail the chemistry of the MLD process between the post-trimethylaluminium (TMA) pulse methyl-terminated Al2O3 surface with aromatic compounds with hydroxy and/or amino groups as reactive groups: hydroquinone (HQ), 4-aminophenol (AP) and p-phenylenediamine (PD). Double reactions of HQ, AP and PDA with the Al2O3 surface are explored in detail to assist the interpretation of the experimental findings regarding the differences found for hybrid films grown with aromatic and aliphatic organic precursors. DFT calculations show that in contrast to aliphatic organics, an upright configuration will be present for HQ, AP and PD so that the molecules are self-assembled in an upright configuration, which leads to thicker hybrid films. We predict that aromatic molecules are the best choice for stable hybrid films and their chemistry can be manipulated without degrading stability. [1]
We also investigate in detail the chemistry between the most common titanium precursors, namely titanium tetrachloride (TiCl4) and tetrakis(dimethylamido)titanium (Ti(DMA)4), and ethylene glycol (EG) and glycerol (GL) as the organic precursors for the fabrication of titanicone films. We analyse the impact of the substrate on the initial MLD reactions in titanicone film growth using three different surface models: anatase TiO2, rutile TiO2 and Al2O3. This work highlights the role of the phase of TiO2 and Ti-containing precursors in production of titanicone films and provides motivation to develop a new rutile TiO2 based hybrid film suggesting that the desired film growth, flexibility and stability can be achieved. [2]
[1] A. Muriqi, M. Karppinen and M. Nolan, Role of terminal groups in aromatic molecules on the growth of Al2O3-based hybrid materials, Dalton Transactions, 2021, 50, 17583-17593. doi.org/10.1039/D1DT03195C.
[2] Arbresha Muriqi and Michael Nolan, “Role of Titanium and Organic Precursors in Molecular Layer Deposition of “Titanicone” Hybrid Materials”, Beilstein Journal of Nanotechnology, 2022, 13, 1240–1255. doi.org/10.3762/bjnano.13.103.