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Copper(I) Carboxylates of Type [(nBu3P)mCuO2CR] (m = 1, 2, 3) - Synthesis, Properties, and their Use as CVD Precursors

Jakob, Alexander and Shen, Yingzhong and Wächtler, Thomas and Schulz, Stefan E. and Gessner, Thomas and Riedel, Ralf and Fasel, Claudia and Lang, Heinrich (2008):
Copper(I) Carboxylates of Type [(nBu3P)mCuO2CR] (m = 1, 2, 3) - Synthesis, Properties, and their Use as CVD Precursors.
In: Zeitschrift für anorganische und allgemeine Chemie, Wiley, pp. 2226-2234, 634, (12-13), ISSN 00442313,
[Online-Edition: http://dx.doi.org/10.1002/zaac.200800189],
[Article]

Abstract

Copper(I) carboxylates of type [(nBu3P)mCuO2CR] (m = 1: 3a, R = Me; 3b, R = CF3; 3c, R = Ph; 3d, R = CH=CHPh. m = 2: 4a, R = Me; 4b, R = CF3; 4c, R = Ph; 4d, R = CH=CHPh. m = 3: 8a, R = Me; 8b, R = CF3; 8c, R = CH2Ph; 8d, R = (CH2OCH2)3H; 8e, R = cC4H7O) are accessible by following synthesis methodologies: the reaction of [CuO2CR] (1a, R = Me; 1b, R = CF3; 1c, R = Ph; 1d, R = CH=CHPh) with m equivalents of nBu3P (2) (m = 1, 2, 3), or treatment of [(nBu3P)mCuCl] (5a, m = 1; 5b, m = 2) with [KO2CCF3] (6). A more straightforward synthesis method for 8a – 8e is the electrolysis of copper in presence of HO2CR (7a, R = Me; 7b, R = CF3; 7c, R = CH2Ph; 7d, R = (CH2OCH2)3H; 7e, R = cC4H7O) and 2, respectively. This method allows to prepare the appropriate copper(I) carboxylate complexes in virtually quantitative yield, analytically pure form, and on an industrial scale.

IR spectroscopic studies reveal that the carboxylic units in 4, 5, and 8 bind in a unidentate, chelating or μ-bridging fashion to copper(I) depending on m and R.

The thermal properties of 4, 6, and 8 were determined by TG and DSC studies. Based on TG-MS experiments a conceivable mechanism for the thermally induced decomposition of these species is presented.

Hot-wall Chemical Vapor Deposition experiments (CVD) with precursor 4b showed that copper could be deposited at 480 °C onto a TiN-coated oxidized silicon substrate. The copper films were characterized by SEM and EDX studies. Pure layers were obtained with copper particles of size 200 – 780 nm.

Item Type: Article
Erschienen: 2008
Creators: Jakob, Alexander and Shen, Yingzhong and Wächtler, Thomas and Schulz, Stefan E. and Gessner, Thomas and Riedel, Ralf and Fasel, Claudia and Lang, Heinrich
Title: Copper(I) Carboxylates of Type [(nBu3P)mCuO2CR] (m = 1, 2, 3) - Synthesis, Properties, and their Use as CVD Precursors
Language: English
Abstract:

Copper(I) carboxylates of type [(nBu3P)mCuO2CR] (m = 1: 3a, R = Me; 3b, R = CF3; 3c, R = Ph; 3d, R = CH=CHPh. m = 2: 4a, R = Me; 4b, R = CF3; 4c, R = Ph; 4d, R = CH=CHPh. m = 3: 8a, R = Me; 8b, R = CF3; 8c, R = CH2Ph; 8d, R = (CH2OCH2)3H; 8e, R = cC4H7O) are accessible by following synthesis methodologies: the reaction of [CuO2CR] (1a, R = Me; 1b, R = CF3; 1c, R = Ph; 1d, R = CH=CHPh) with m equivalents of nBu3P (2) (m = 1, 2, 3), or treatment of [(nBu3P)mCuCl] (5a, m = 1; 5b, m = 2) with [KO2CCF3] (6). A more straightforward synthesis method for 8a – 8e is the electrolysis of copper in presence of HO2CR (7a, R = Me; 7b, R = CF3; 7c, R = CH2Ph; 7d, R = (CH2OCH2)3H; 7e, R = cC4H7O) and 2, respectively. This method allows to prepare the appropriate copper(I) carboxylate complexes in virtually quantitative yield, analytically pure form, and on an industrial scale.

IR spectroscopic studies reveal that the carboxylic units in 4, 5, and 8 bind in a unidentate, chelating or μ-bridging fashion to copper(I) depending on m and R.

The thermal properties of 4, 6, and 8 were determined by TG and DSC studies. Based on TG-MS experiments a conceivable mechanism for the thermally induced decomposition of these species is presented.

Hot-wall Chemical Vapor Deposition experiments (CVD) with precursor 4b showed that copper could be deposited at 480 °C onto a TiN-coated oxidized silicon substrate. The copper films were characterized by SEM and EDX studies. Pure layers were obtained with copper particles of size 200 – 780 nm.

Journal or Publication Title: Zeitschrift für anorganische und allgemeine Chemie
Volume: 634
Number: 12-13
Publisher: Wiley
Uncontrolled Keywords: Copper, Carboxylates, Tri-n-butylphosphane, Electrolysis, CVD, TG, DSC, SEM, EDX
Divisions: 11 Department of Materials and Earth Sciences > Material Science > Dispersive Solids
11 Department of Materials and Earth Sciences > Material Science
11 Department of Materials and Earth Sciences
Date Deposited: 16 Apr 2012 08:38
Official URL: http://dx.doi.org/10.1002/zaac.200800189
Identification Number: doi:10.1002/zaac.200800189
Funders: Financial support from the Deutsche Forschungsgemeinschaft (International Research Training Group GRK 1215, “Materials and Concepts for Advanced Interconnects“),, Financial support from the Fonds der Chemischen Industrie, and the BASF AG, Ludwigshafen is gratefully acknowledged.
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