BJNANO - Role of titanium and organic precursors in molecular layer deposition of “titanicone” hybrid materials

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Role of titanium and organic precursors in molecular layer deposition of “titanicone” hybrid materials

Arbresha Muriqi and Michael Nolan

Beilstein J. Nanotechnol. 2022, 13, 1240–1255. https://doi.org/10.3762/bjnano.13.103

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Muriqi, A.; Nolan, M. Beilstein J. Nanotechnol. 2022, 13, 1240–1255. doi:10.3762/bjnano.13.103

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TY  - JOUR
A1  - Muriqi, Arbresha
A1  - Nolan, Michael
T1  - Role of titanium and organic precursors in molecular layer deposition of “titanicone” hybrid materials
JF  - Beilstein Journal of Nanotechnology
PY  - 2022///
VL  - 13
SP  - 1240
EP  - 1255
SN  - 2190-4286
DO  - 10.3762/bjnano.13.103
PB  - Beilstein-Institut
JA  - Beilstein J. Nanotechnol.
UR  - https://doi.org/10.3762/bjnano.13.103
KW  - density functional theory (DFT) studies
KW  - double reactions
KW  - surface chemistry
KW  - titanicone
N2  - The development of hybrid inorganic–organic films with well-controlled properties is important for many applications. Molecular layer deposition (MLD) allows the deposition of these hybrid films using sequential, self-limiting reactions, similar to atomic layer deposition (ALD). In this paper, we use first principles density functional theory (DFT) to investigate the growth mechanism of titanium-containing hybrid organic–inorganic MLD films, known as “titanicones”. We investigate in detail the chemistry between the most common Ti precursors, namely titanium tetrachloride (TiCl4) and tetrakis(dimethylamido)titanium (Ti(DMA)4), and ethylene glycol (EG) and glycerol (GL) as the organic precursors. 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. Calculated energetics show that while TiCl4 is reactive towards the anatase and rutile TiO2 surfaces, it is not reactive towards the Al2O3 surface. Ti(DMA)4 is reactive towards all surfaces. This is attributed to the stronger Ti–Cl bonds in TiCl4 compared to Ti–N bonds in Ti(DMA)4. Ti(DMA)4 also shows high reactivity to the organics compared to TiCl4. Double reactions of EG and GL with the TiCl3 species from TiCl4 and TiDMA species from Ti(DMA)4 are also explored to better understand the origin of the different thicknesses of EG–titanicone and GL–titanicone films observed in experimental work. We find that EG and GL coupled with TiCl4 can orient in a flat lying configuration on anatase while on rutile, the preferred orientation is upright. When combined with Ti(DMA)4, EG and GL prefer the flat lying configuration on all surfaces. This work shows that the choice of the surface and the metallic precursor has a major impact on the behaviour of organic species. DFT findings provide motivation to develop a low temperature rutile TiO2/titanicone film suggesting that the desired film growth could be achieved.
ER  -

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Mäkinen, M.; Laasonen, K. Modelling of growth reaction pathways of zincone ALD/MLD hybrid thin films: a DFT study of precursor screening and the diethyl zinc pulse. RSC advances 2025, 15, 16299.
Mäkinen, M.; Laasonen, K. Modelling of growth reaction pathways of zincone ALD/MLD hybrid thin films: a DFT study of precursor screening and the diethyl zinc pulse. RSC Advances 2025, 15, 16299–16311. doi:10.1039/d5ra00686d
Kim, M.; Oh, H.; Shong, B. Reaction mechanisms of α,ω-bifunctional molecules toward atomic layer deposition versus molecular layer deposition. Materials Chemistry and Physics 2024, 318, 129273. doi:10.1016/j.matchemphys.2024.129273
Wambua, C.; Sefadi, J. S.; Mwema, F.; Tanui, J.; Jen, T.-C. Density functional theory study of adsorption pathways of TiCl<sub>4</sub> on Polyether Ether Ketone. In 2023 2nd International Conference on Multidisciplinary Engineering and Applied Science (ICMEAS), IEEE, 2023; pp 1–5. doi:10.1109/icmeas58693.2023.10379323

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