Role of titanium and organic precursors in molecular layer deposition of “titanicone” hybrid materials
| dc.contributor.author | Muriqi, Arbresha | en |
| dc.contributor.author | Nolan, Michael | en |
| dc.contributor.funder | Science Foundation Ireland | |
| dc.contributor.funder | Horizon 2020 | |
| dc.contributor.funder | National Natural Science Foundation of China | |
| dc.date.accessioned | 2023-06-12T14:40:48Z | |
| dc.date.available | 2023-06-12T15:27:44Z | en |
| dc.date.available | 2023-06-12T14:40:48Z | |
| dc.date.issued | 2022-11-02 | |
| dc.date.updated | 2023-06-12T14:27:49Z | en |
| dc.description.abstract | 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. | |
| dc.description.status | Peer reviewed | en |
| dc.description.version | Published Version | |
| dc.format.mimetype | application/pdf | en |
| dc.identifier.citation | Muriqi, A. and Nolan, M. (2022) ‘Role of titanium and organic precursors in molecular layer deposition of “titanicone” hybrid materials’, Beilstein Journal of Nanotechnology, 13, pp. 1240–1255. https://doi.org/10.3762/bjnano.13.103. | |
| dc.identifier.doi | 10.3762/bjnano.13.103 | en |
| dc.identifier.eissn | 2190-4286 | |
| dc.identifier.issued | 1240 | |
| dc.identifier.journaltitle | Beilstein Journal of Nanotechnology | |
| dc.identifier.startpage | 1255 | |
| dc.identifier.uri | https://hdl.handle.net/10468/14557 | |
| dc.identifier.volume | 13 | |
| dc.language.iso | en | en |
| dc.publisher | Beilstein-Institut | |
| dc.relation.project | info:eu-repo/grantAgreement/EC/H2020::MSCA-ITN-ETN/765378/EU/A European Training Network for Functional Hybrid Coatings by Molecular Layer Deposition/HYCOAT | |
| dc.relation.project | info:eu-repo/grantAgreement/SFI/SFI-NSFC Partnership/17/NSFC/5279/IE/Process development and mechanistic investigation of barrier materials for advanced interconnect technology/ | |
| dc.rights | © 2022 Muriqi and Nolan; licensee Beilstein-Institut. This is an open access article licensed under the terms of the Beilstein-Institut Open Access License Agreement (https://www.beilstein-journals.org/bjnano/terms), which is identical to the Creative Commons Attribution 4.0 International License (https://creativecommons.org/licenses/by/4.0). The reuse of material under this license requires that the author(s), source and license are credited. Third-party material in this article could be subject to other licenses (typically indicated in the credit line), and in this case, users are required to obtain permission from the license holder to reuse the material. | |
| dc.rights.uri | https://creativecommons.org/licenses/by/4.0 | |
| dc.subject | Density functional theory (DFT) studies | |
| dc.subject | Double reactions | |
| dc.subject | Surface chemistry | |
| dc.subject | Titanicone | |
| dc.subject | Inorganic thin films | |
| dc.subject | Growth | |
| dc.subject | Electrode | |
| dc.subject | TICL4 | |
| dc.title | Role of titanium and organic precursors in molecular layer deposition of “titanicone” hybrid materials | |
| dc.type | Article (peer-reviewed) | en |
| dc.type | Article | en |