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Role of Anionic Backbone in NHC-Stabilized Coinage Metal Complexes: New Precursors for Atomic Layer Deposition.

ABSTRACT: Cu and Ag precursors that are volatile, reactive, and thermally stable are currently of high interest for their application in atomic-layer deposition (ALD) of thin metal films. In pursuit of new precursors for coinage metals, namely Cu and Ag, a series of new N-heterocyclic carbene (NHC)-based Cu^I and Ag^I complexes were synthesized. Modifications in the substitution pattern of diketonate-based anionic backbones led to five monomeric Cu complexes and four closely related Ag complexes with the general formula [M(^tBu NHC)(R)] (M=Cu, Ag; ^tBu NHC=1,3-di-tert-butyl-imidazolin-2-ylidene; R=diketonate). Thermal analysis indicated that most of the Cu complexes are thermally stable and volatile compared to the more fragile Ag analogs. One of the promising Cu precursors was evaluated for the ALD of nanoparticulate Cu metal deposits by using hydroquinone as the reducing agent at appreciably low deposition temperatures (145-160 °C). This study highlights the considerable impact of the employed ligand sphere on the structural and thermal properties of metal complexes that are relevant for vapor-phase processing of thin films.

SUBMITTER: Boysen N

PROVIDER: S-EPMC9303662 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature

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Role of Anionic Backbone in NHC-Stabilized Coinage Metal Complexes: New Precursors for Atomic Layer Deposition.

Boysen Nils N Philip Anish A Rogalla Detlef D Karppinen Maarit M Devi Anjana A

Chemistry (Weinheim an der Bergstrasse, Germany) 20220215 16

Cu and Ag precursors that are volatile, reactive, and thermally stable are currently of high interest for their application in atomic-layer deposition (ALD) of thin metal films. In pursuit of new precursors for coinage metals, namely Cu and Ag, a series of new N-heterocyclic carbene (NHC)-based Cu<sup>I</sup> and Ag<sup>I</sup> complexes were synthesized. Modifications in the substitution pattern of diketonate-based anionic backbones led to five monomeric Cu complexes and four closely related Ag ...[more]

PMID: 35044704

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Project description:Owing to the limited availability of suitable precursors for vapor phase deposition of rare-earth containing thin-film materials, new or improved precursors are sought after. In this study, we explored new precursors for atomic layer deposition (ALD) of cerium (Ce) and ytterbium (Yb) containing thin films. A series of homoleptic tris-guanidinate and tris-amidinate complexes of cerium (Ce) and ytterbium (Yb) were synthesized and thoroughly characterized. The C-substituents on the N-C-N backbone (Me, NMe2 , NEt2 , where Me=methyl, Et=ethyl) and the N-substituents from symmetrical iso-propyl (iPr) to asymmetrical tertiary-butyl (tBu) and Et were systematically varied to study the influence of the substituents on the physicochemical properties of the resulting compounds. Single crystal structures of [Ce(dpdmg)3 ] 1 and [Yb(dpdmg)3 ] 6 (dpdmg=N,N'-diisopropyl-2-dimethylamido-guanidinate) highlight a monomeric nature in the solid-state with a distorted trigonal prismatic geometry. The thermogravimetric analysis shows that the complexes are volatile and emphasize that increasing asymmetry in the complexes lowers their melting points while reducing their thermal stability. Density functional theory (DFT) was used to study the reactivity of amidinates and guanidinates of Ce and Yb complexes towards oxygen (O2 ) and water (H2 O). Signified by the DFT calculations, the guanidinates show an increased reactivity toward water compared to the amidinate complexes. Furthermore, the Ce complexes are more reactive compared to the Yb complexes, indicating even a reactivity towards oxygen potentially exploitable for ALD purposes. As a representative precursor, the highly reactive [Ce(dpdmg)3 ] 1 was used for proof-of-principle ALD depositions of CeO2 thin films using water as co-reactant. The self-limited ALD growth process could be confirmed at 160 °C with polycrystalline cubic CeO2 films formed on Si(100) substrates. This study confirms that moving towards nitrogen-coordinated rare-earth complexes bearing the guanidinate and amidinate ligands can indeed be very appealing in terms of new precursors for ALD of rare earth based materials.

Dataset Information

Role of Anionic Backbone in NHC-Stabilized Coinage Metal Complexes: New Precursors for Atomic Layer Deposition.

Publications

Role of Anionic Backbone in NHC-Stabilized Coinage Metal Complexes: New Precursors for Atomic Layer Deposition.

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