| 1. |
- Samii, Rouzbeh, et al.
(author)
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Synthesis and Thermal Study of Hexacoordinated Aluminum(III) Triazenides for Use in Atomic Layer Deposition
- 2021
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In: Inorganic Chemistry. - : American Chemical Society. - 0020-1669 .- 1520-510X. ; 60:7, s. 4578-4587
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Journal article (peer-reviewed)abstract
- Amidinate and guanidinate ligands have been used extensively to produce volatile and thermally stable precursors for atomic layer deposition. The triazenide ligand is relatively unexplored as an alternative ligand system. Herein, we present six new Al(III) complexes bearing three sets of a 1,3-dialkyltriazenide ligand. These complexes volatilize quantitatively in a single step with onset volatilization temperatures of similar to 150 degrees C and 1 Torr vapor pressures of similar to 134 degrees C. Differential scanning calorimetry revealed that these Al(III) complexes exhibited exothermic events that overlapped with the temperatures of their mass loss events in thermogravimetric analysis. Using quantum chemical density functional theory computations, we found a decomposition pathway that transforms the relatively large hexacoordinated Al(III) precursor into a smaller dicoordinated complex. The pathway relies on previously unexplored interligand proton migrations. These new Al(III) triazenides provide a series of alternative precursors with unique thermal properties that could be highly advantageous for vapor deposition processes of Al containing materials.
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| 2. |
- Samii, Rouzbeh, et al.
(author)
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Synthesis, characterisation and reactivity of a zinc triazenide for potential use in vapour deposition
- 2024
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In: Dalton Transactions. - : ROYAL SOC CHEMISTRY. - 1477-9226 .- 1477-9234. ; 53:13, s. 5911-5916
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Journal article (peer-reviewed)abstract
- In this study, we synthesised and characterised a new zinc(ii) triazenide for potential use in vapour deposition of zinc sulphide thin films. The compound is volatile and quantitatively sublimes at 80 degrees C under vacuum (0.5 mbar). Thermogravimetric analysis showed a one-step volatilisation with an onset temperature at similar to 125 degrees C and 5% residual mass. The compound also reacted with 2 or 4 molar equivalents of triphenylsilanethiol to give dimeric and monomeric zinc thiolates, respectively. The high volatility, thermal stability, and reactivity with sterically hindered thiols makes this compound a potential candidate for use in vapour deposition of zinc containing thin films. Herein, we synthesise and characterise a new volatile and thermally stable Zn(ii) triazenide. We also react it with a bulky thiol to give two different Zn(ii) thiolates. This new triazenide shows high promise as a precursor for vapour deposition of ZnS thin films.
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| 3. |
- Samii, Rouzbeh, et al.
(author)
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Synthesis, Characterization, and Thermal Study of Divalent Germanium, Tin, and Lead Triazenides as Potential Vapor Deposition Precursors
- 2021
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In: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 60:17, s. 12759-12765
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Journal article (peer-reviewed)abstract
- Only a few M-N bonded divalent group 14 precursors are available for vapor deposition, in particular for Ge and Pb. A majority of the reported precursors are dicoordinated with the Sn(II) amidinates, the only tetracoordinated examples. No Ge(II) and Pb(II) amidinates suitable for vapor deposition have been demonstrated. Herein, we present tetracoordinated Ge(II), Sn(II), and Pb(II) complexes bearing two sets of chelating 1,3-di-tert-butyltriazenide ligands. These compounds are thermally stable, sublime quantitatively between 60 and 75 degrees C (at 0.5 mbar), and show ideal single-step volatilization by thermogravimetric analysis.
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