Different Nucleation Mechanisms during Atomic Layer Deposition of HfS2 on Cobalt Oxide Surfaces
Abstract The atomic layer deposition (ALD) of HfS2 is investigated on atomically defined CoO(100) and CoO(111) surfaces under ultrahigh‐vacuum (UHV) conditions. The ALD process is performed by sequential dosing of the precursors tetrakis(dimethylamido)hafnium (TDMAH) and deuterium sulfide (D2S) sepa...
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Wiley-VCH
2025-01-01
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| Series: | Advanced Materials Interfaces |
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| Online Access: | https://doi.org/10.1002/admi.202400371 |
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| author | Georg Fickenscher Nikolai Sidorenko Kira Mikulinskaya Jörg Libuda |
| author_facet | Georg Fickenscher Nikolai Sidorenko Kira Mikulinskaya Jörg Libuda |
| author_sort | Georg Fickenscher |
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| description | Abstract The atomic layer deposition (ALD) of HfS2 is investigated on atomically defined CoO(100) and CoO(111) surfaces under ultrahigh‐vacuum (UHV) conditions. The ALD process is performed by sequential dosing of the precursors tetrakis(dimethylamido)hafnium (TDMAH) and deuterium sulfide (D2S) separated by purging periods. The growth and nucleation reactions are monitored by in situ infrared reflection absorption spectroscopy (IRAS). HfS2 films nucleate and grow on both cobalt oxide surfaces, despite the fact that CoO(100) lacks acidic protons and CoO(111) exposes only very few OH groups at defects. On these OH‐free or OH‐lean surfaces, the nucleation step involves a Lewis acid‐base reaction instead. The stoichiometry of the ─Hf(NMe2)x nuclei changes during the first ALD half cycle. On CoO(100), the split‐off ligands bind as ─NMe2 to surface cobalt ions. The nucleation on CoO(111) is more complex and the split‐off ligands undergo dehydrogenation to form various surface species with C═N double and C≡N triple bonds and surface OH. These findings reveal a new nucleation mechanism for ALD in the absence of acidic protons and show that other factors such as Lewis acidity, surface structure, and surface reactivity must also be considered in the nucleation event. |
| format | Article |
| id | doaj-art-3ef5442b53df4b2d93d79d4ed45419ed |
| institution | Kabale University |
| issn | 2196-7350 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Wiley-VCH |
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| series | Advanced Materials Interfaces |
| spelling | doaj-art-3ef5442b53df4b2d93d79d4ed45419ed2025-01-03T08:39:29ZengWiley-VCHAdvanced Materials Interfaces2196-73502025-01-01121n/an/a10.1002/admi.202400371Different Nucleation Mechanisms during Atomic Layer Deposition of HfS2 on Cobalt Oxide SurfacesGeorg Fickenscher0Nikolai Sidorenko1Kira Mikulinskaya2Jörg Libuda3Interface Research and Catalysis ECRC Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Egerlandstraße 3 91058 Erlangen GermanyInterface Research and Catalysis ECRC Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Egerlandstraße 3 91058 Erlangen GermanyInterface Research and Catalysis ECRC Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Egerlandstraße 3 91058 Erlangen GermanyInterface Research and Catalysis ECRC Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Egerlandstraße 3 91058 Erlangen GermanyAbstract The atomic layer deposition (ALD) of HfS2 is investigated on atomically defined CoO(100) and CoO(111) surfaces under ultrahigh‐vacuum (UHV) conditions. The ALD process is performed by sequential dosing of the precursors tetrakis(dimethylamido)hafnium (TDMAH) and deuterium sulfide (D2S) separated by purging periods. The growth and nucleation reactions are monitored by in situ infrared reflection absorption spectroscopy (IRAS). HfS2 films nucleate and grow on both cobalt oxide surfaces, despite the fact that CoO(100) lacks acidic protons and CoO(111) exposes only very few OH groups at defects. On these OH‐free or OH‐lean surfaces, the nucleation step involves a Lewis acid‐base reaction instead. The stoichiometry of the ─Hf(NMe2)x nuclei changes during the first ALD half cycle. On CoO(100), the split‐off ligands bind as ─NMe2 to surface cobalt ions. The nucleation on CoO(111) is more complex and the split‐off ligands undergo dehydrogenation to form various surface species with C═N double and C≡N triple bonds and surface OH. These findings reveal a new nucleation mechanism for ALD in the absence of acidic protons and show that other factors such as Lewis acidity, surface structure, and surface reactivity must also be considered in the nucleation event.https://doi.org/10.1002/admi.202400371atomic layer depositioncobalt oxideHfS2infrared reflection absorption spectroscopyLewis acid–base reaction |
| spellingShingle | Georg Fickenscher Nikolai Sidorenko Kira Mikulinskaya Jörg Libuda Different Nucleation Mechanisms during Atomic Layer Deposition of HfS2 on Cobalt Oxide Surfaces Advanced Materials Interfaces atomic layer deposition cobalt oxide HfS2 infrared reflection absorption spectroscopy Lewis acid–base reaction |
| title | Different Nucleation Mechanisms during Atomic Layer Deposition of HfS2 on Cobalt Oxide Surfaces |
| title_full | Different Nucleation Mechanisms during Atomic Layer Deposition of HfS2 on Cobalt Oxide Surfaces |
| title_fullStr | Different Nucleation Mechanisms during Atomic Layer Deposition of HfS2 on Cobalt Oxide Surfaces |
| title_full_unstemmed | Different Nucleation Mechanisms during Atomic Layer Deposition of HfS2 on Cobalt Oxide Surfaces |
| title_short | Different Nucleation Mechanisms during Atomic Layer Deposition of HfS2 on Cobalt Oxide Surfaces |
| title_sort | different nucleation mechanisms during atomic layer deposition of hfs2 on cobalt oxide surfaces |
| topic | atomic layer deposition cobalt oxide HfS2 infrared reflection absorption spectroscopy Lewis acid–base reaction |
| url | https://doi.org/10.1002/admi.202400371 |
| work_keys_str_mv | AT georgfickenscher differentnucleationmechanismsduringatomiclayerdepositionofhfs2oncobaltoxidesurfaces AT nikolaisidorenko differentnucleationmechanismsduringatomiclayerdepositionofhfs2oncobaltoxidesurfaces AT kiramikulinskaya differentnucleationmechanismsduringatomiclayerdepositionofhfs2oncobaltoxidesurfaces AT jorglibuda differentnucleationmechanismsduringatomiclayerdepositionofhfs2oncobaltoxidesurfaces |