Jakob, Alexander ; Shen, Yingzhong ; Wächtler, Thomas ; Schulz, Stefan E. ; Gessner, Thomas ; Riedel, Ralf ; Fasel, Claudia ; 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, 634 (12-13)
doi: 10.1002/zaac.200800189
Artikel, Bibliographie
Kurzbeschreibung (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.
| Typ des Eintrags: | Artikel |
|---|---|
| Erschienen: | 2008 |
| Autor(en): | Jakob, Alexander ; Shen, Yingzhong ; Wächtler, Thomas ; Schulz, Stefan E. ; Gessner, Thomas ; Riedel, Ralf ; Fasel, Claudia ; Lang, Heinrich |
| Art des Eintrags: | Bibliographie |
| Titel: | Copper(I) Carboxylates of Type [(nBu3P)mCuO2CR] (m = 1, 2, 3) - Synthesis, Properties, and their Use as CVD Precursors |
| Sprache: | Englisch |
| Publikationsjahr: | Oktober 2008 |
| Verlag: | Wiley |
| Titel der Zeitschrift, Zeitung oder Schriftenreihe: | Zeitschrift für anorganische und allgemeine Chemie |
| Jahrgang/Volume einer Zeitschrift: | 634 |
| (Heft-)Nummer: | 12-13 |
| DOI: | 10.1002/zaac.200800189 |
| Kurzbeschreibung (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. |
| Freie Schlagworte: | Copper, Carboxylates, Tri-n-butylphosphane, Electrolysis, CVD, TG, DSC, SEM, EDX |
| Fachbereich(e)/-gebiet(e): | 11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft > Fachgebiet Disperse Feststoffe 11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft 11 Fachbereich Material- und Geowissenschaften |
| Hinterlegungsdatum: | 16 Apr 2012 08:38 |
| Letzte Änderung: | 05 Mär 2013 10:00 |
| PPN: | |
| Sponsoren: | 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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