Phosphite copper(I) trifluoroacetates [((RO)3P)mCuO2CCF3] (m = 1, 2, 3): synthesis, solid state structures and their potential use as CVD precursors

Robert Mothes; Tobias Rüffer; Yingzhong Shen; Alexander Jakob; Bernhard Walfort; Holm Petzold; Stefan E. Schulz; Ramona Ecke; Thomas Gessner; Heinrich Lang

doi:10.1039/C0DT00347F

Phosphite copper(i) trifluoroacetates [((RO)₃P)_mCuO₂CCF₃] (m = 1, 2, 3): synthesis, solid state structures and their potential use as CVD precursors†‡

Robert Mothes,^a Tobias Rüffer,^a Yingzhong Shen,^a Alexander Jakob,^a Bernhard Walfort,^a Holm Petzold,^a Stefan E. Schulz,^bc Ramona Ecke,^c Thomas Gessner^bc and Heinrich Lang*^a

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^a Faculty of Natural Sciences, Institute of Chemistry, Department of Inorganic Chemistry, Chemnitz University of Technology, Straße der Nationen 62, Chemnitz, Germany
E-mail: heinrich.lang@chemie.tu-chemnitz.de.
Fax: +49-(0)371-531-21219
Tel: +49-(0)371-531-21210

^b Faculty of Electrical Engineering and Information Technology, Center for Microtechnologies, Chemnitz University of Technology, Reichenhainer Straße 70, Chemnitz, Germany

^c Fraunhofer Research Institution for Electronic Nano Systems (ENAS), Reichenhainer Straße 88, Chemnitz, Germany

Abstract

Metal-organics [((RO)₃P)_mCuO₂CCF₃] (R = CH₃: 11a, m = 1; 11b, m = 2; 11c, m = 3. R = CH₂CH₃: 12a, m = 1; 12b, m = 2; 12c, m = 3. R = CH₂CF₃: 13a, m = 1; 13b, m = 2; 13c, m = 3) are either accessible by the reaction of [((RO)₃P)_mCuCl] (R = CH₃: 5a, m = 1; 5b, m = 2; 5c, m = 3. R = CH₂CH₃: 6a, m = 1; 6b, m = 2; 6c, m = 3) with [KO₂CCF₃] (7), or treatment of [Cu₂O] (8) with HO₂CCF₃ (9) and P(OR)₃ (2, R = CH₃; 3, R = CH₂CH₃; 4, R = CH₂CF₃). ³¹P{¹H} NMR spectra [((CH₃O)₃P)_mCuO₂CCF₃] (m = 1, 1.5, 2, 2.5, 3, 3.5, and 4) have been studied at 25 and −80 °C showing phosphite ligand exchange in solution. The molecular structures of 11a and 13a–13c in the solid state are reported. Complexes 11a and 13a are tetramers featuring μ-η²(1κO:2κO′)- and μ³-η²(1κO:2κO′:3κO′)-(11a) or μ³-η²(1κO:2κO′:3κO′)-bonded O₂CCF₃ ligands (13a) with the Cu(I) ions being part of CuPO₂ and CuPO₃ units (11a), while in 13a solely a CuPO₃ moiety is present. Skeletal isomerism of 11avs.13a is discussed. Compound 13b is dimeric ({CuP₂O₂}₂) with pseudo-tetrahedral Cu environments and μ-η²(1κO:2κO′)O₂CCF₃ functionalities. In monomeric 13c the O₂CCF₃ ligand is η¹(κO)-bonded to a tetra-coordinated Cu(I) ion. The thermal solid state properties of 11, 12 and 13 were studied by Thermo Gravimetry (TG). These complexes decompose by phosphite elimination, decarboxylation and dealkylation. Hot-wall Chemical Vapour Deposition (CVD) experiments were carried out at 380 °C using 11c as precursor for the deposition of copper onto pieces of TiN-coated oxidized silicon substrates. Copper layers of high purity were obtained with grain sizes between 200–1200 nm.

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Phosphite copper(i) trifluoroacetates [((RO)₃P)_mCuO₂CCF₃] (m = 1, 2, 3): synthesis, solid state structures and their potential use as CVD precursors†‡

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Phosphite copper(I) trifluoroacetates [((RO)₃P)_mCuO₂CCF₃] (m = 1, 2, 3): synthesis, solid state structures and their potential use as CVD precursors

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