Synthesis of volatile, reactive coinage metal 5,5-bicyclic amidinates with enhanced thermal stability for chemical vapor deposition

Tong, Liuchuan; Davis, Luke M.; Gong, Xian; Feng, Jun; Beh, Eugene S.; Gordon, Roy G.

doi:10.1039/c9dt01202h

Cited by 9 publications

(20 citation statements)

References 41 publications

(65 reference statements)

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“…The Ag triazenide 2 gave lower residual mass than the cyclic Ag amidinates (>10% for 10 mg samples). 5,22 As far as we know, the residual mass for 2 is the lowest reported for an exclusively Ag-N bonded compound. Compound 1 performed on par with cyclic Cu amidinates in stress tests, however, while more volatile, the Cu triazenide 1 appeared less thermally stable than the cyclic amidinates.…”

Section: Thermal Analysismentioning

confidence: 90%

“…A similar two-step process was postulated for the bicyclic Ag amidinate to explain why the volatilization kinetics resembled that of the dimeric bicyclic Cu amidinate. 22 Compound 3 showed two well defined mass loss events with onsets at ~175 °C and ~240 °C and a residual mass of 35%.…”

Section: Thermal Analysismentioning

confidence: 97%

“…5 Further constrained, bicyclic amidinates have been used to yield monovalent group 11 compounds with improved thermal stability over the iminopyrrolidinates (Figure 1c). 21,22 Using these compounds with H2 afforded Ag and Au films with ~6-7 at. % carbon by lowtemperature CVD.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Structure and Thermal Properties of Volatile Group 11 Triazenides as Potential Precursors for Vapor Deposition

Samii

Fransson

Zanders

et al. 2022

Preprint

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Group 11 thin films are desirable as interconnects in microelectronics. Although many M–N bonded Cu precursors have been explored for vapor deposition, there is currently a lack of suitable Ag and Au derivatives. Herein, we present monovalent Cu, Ag and Au 1,3-di-tert-butyltriazenides that have potential for use in vapor deposition. These compounds possess thermal stability and volatility that rival that of current state-of-the-art group 11 precursors with bidentate M–N bonded ligands. All compound sublime quantitatively between 120 and 130 °C at 0.5 mbar. Thermogravimetric analysis showed the Cu and Ag compounds both volatilized at ~200 °C with 0 and 2% residual mass, respectively. The Au triazenide showed two separated mass loss events at ~175 and 240 °C, and 35% residual mass. The crystal structure of the Cu compound showed a dimer, whilst the Ag and Au derivatives were tetrameric. Nuclear magnetic resonance spectroscopy showed dimers for the Cu and Au compounds and a dimer/tetramer equilibrium for the Ag compound. Electronic energies from density functional theory calculations confirmed dimeric preference for the Cu triazenide while Ag and Au preferred the tetrameric. However, all three compounds showed dimeric preference when accounting for entropy. Dimers are, therefore, expected to dominate in the gas phase for all three compounds during sublimation. Natural bond orbital analysis was used to identify orbital interactions important for the dimer/tetramer preference. Three factors were identified, in conjunction with strong metal-metal interactions, to increase the preference for rhombic tetramers.

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Section: Thermal Analysismentioning

confidence: 90%

Section: Thermal Analysismentioning

confidence: 97%

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Synthesis, Structure and Thermal Properties of Volatile Group 11 Triazenides as Potential Precursors for Vapor Deposition

Samii

Fransson

Zanders

et al. 2022

Preprint

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“…However, the ligand syntheses for 26 and 27 are time-consuming and only produce mediocre precursors for Au, although the Cu(I) analogue of 26 has superb thermal properties. 36 35,37,38 is a dimeric gold(I) guanidinate, 26 39,40 is an iminopyrrolidinate complex, and 27 41 is a bicyclic amidinate, 28, 42,43 29, 44 and 30 43 are trialkylphosphine and N-heterocyclic carbene complexes of gold(I) bis(trimethylsilyl)amide. a Calculated from Clausius-Clapeyron data, method unknown.…”

Section: Guanidinate Amidinate Amide and N-heterocyclic Carbene Complexes Of Gold(i)mentioning

confidence: 99%

“…Au(I) compounds previously used in CVD. Compound 2535,37,38 is a dimeric gold(I) guanidinate, 2639,40 is an iminopyrrolidinate complex, and 2741 is a bicyclic amidinate, 28,42,43 29,44 and 3043 are trialkylphosphine and N-heterocyclic carbene complexes of gold(I) bis(trimethylsilyl)amide.…”

mentioning

confidence: 99%

Thermal Ranges and Figures of Merit for Gold-Containing Precursors For ALD

Griffiths¹,

Dubrawski²,

Gordon³

et al. 2020

Preprint

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A Water‐Stable Terbium(III)–Organic Framework as a Chemosensor for Inorganic Ions, Nitro‐Containing Compounds and Antibiotics in Aqueous Solutions

Wei

Han

et al. 2019

Chemistry An Asian Journal

176

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Effective detectiono fo rganic/inorganic pollutants, such as antibiotics, nitro-compounds, excessive Fe 3 + and MnO 4 À ,i sc rucial for human health and environmental protection. Here, an ew terbium(III)-organic framework, namely [Tb(TATAB)(H 2 O)]·2H 2 O( Tb-MOF,H 3 TATAB = 4,4',4''-s-triazine-1,3,5-triyltri-m-aminobenzoic acid), was assembled and characterized.The Tb-MOF exhibits awater-stable 3D bnn framework. Due to the existence of competitive absorption, Tb-MOF has ahigh selectivity for detecting Fe 3 + ,MnO 4 À ,4-niro-phenola nd nitroimidazole( ronidazole, metronidazole, dimetridazole, ornidazole) in aqueous through luminescent quenching. The results suggest that Tb-MOF is as imple and reliable reagent with multiple sensor responses in practical applications. To the best of our knowledge, this work represents the first Tb III -based MOF as an efficient fluorescent sensorf or detecting metal ions, inorganic anions, nitro-compounds, and antibiotics simultaneously.[a] J.

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Synthesis of volatile, reactive coinage metal 5,5-bicyclic amidinates with enhanced thermal stability for chemical vapor deposition

Abstract: Coinage metal bicyclic amidinates for chemical vapor deposition.

Cited by 9 publications

References 41 publications

Synthesis, Structure and Thermal Properties of Volatile Group 11 Triazenides as Potential Precursors for Vapor Deposition

Synthesis, Structure and Thermal Properties of Volatile Group 11 Triazenides as Potential Precursors for Vapor Deposition

Thermal Ranges and Figures of Merit for Gold-Containing Precursors For ALD

A Water‐Stable Terbium(III)–Organic Framework as a Chemosensor for Inorganic Ions, Nitro‐Containing Compounds and Antibiotics in Aqueous Solutions

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