Research On Lewis-base Stabilized Silver(Ι) Precursors And The Preparation Of Interconnect Material

With the continuous development of micro fabrication technology in the production ofcomponents and wiring, the components on the integrated circuits continues to increase and the largescale integration is becoming the Ultra Large Scale Integration （ULSI）. Metal interconnect material inthe traditional integrated circuit manufacturing process has been restricted. However, the use of lowerresistivity interconnect material could reduce the width and thickness of the line, low-K material asthe dielectric layer could reduce the distributed capacitance, it plays an important role in reducingtime delay of interconnect and increasing the density of integrated circuits. Silver is a promisinginterconnect material in microelectronics due to the lowest resistivity and the highest thermalconductivity. Metal Organic Chemical Vapor Deposition （MOCVD） is a very effective technique forthe contacts in ultra large-scale integration （ULSI） devices, because of its high deposition rates withgood step coverage and high aspect ratio in the multilevel metallization structure.In this dissertation, one series of Lewis-Base stabilized silver（I） complexes （precursors） havebeen synthesized. The complexes obtained have been characterized by IR spectroscopy,¹H NMR,¹³C{H} NMR,³¹P{H} NMR, elemental analysis and X-ray single crystal analysis, respectively. Then,the thermal analysis of the complexes was studied by ThemoGravimetry （TG） and DifferentialScanning Calorimetric （DSC）. Finally, several screened silver（I） complexes have been tested asprecursors for the deposition of silver by means of MOCVD techniques. The specific contents of thisdissertation are presented as follows:（1） Research on organophosphine/phosphate stabilized silver（Ι） alkyl sulphonates precursors and thepreparation of interconnect material.Using methanedisulphonic acid or methanesulfonic acid as primary ligand andorganophosphine/phosphate as ancillary ligands, disilver（I） methanedisulphonates complexes[CH₂（SO₃）₂Ag₂Ln]（L=PPh₃; n=2,1a; n=3,1b; n=4,1c; n=5,1d; n=6,1e; L=P（OEt）₃; n=2,1f; n=4,1g; n=6,1h; L=P（OMe）₃; n=2,1i; n=4,1j; n=6,1k） and silver（I） methanesulfonatescomplexes [CH₃SO₃Ag L’n]（L’=P（OMe）₃; n=1,1l; n=2,1m） were prepared. The influence ofprimary ligand and the ancillary ligands on decomposition mechanism, thermal stability and the filmperformance were studied and discussed.（2） Research on Lewis-Base stabilized N-silver（Ι） succinimide precursors and the preparation ofinterconnect material. Using succinimide as primary ligand and Lewis-Base as ancillary ligands, N-silver（Ι）succinimide complexes [Ln Rm AgNC₄H₄O₂]（L=P（OMe）₃; m=0, n=1,2a; L=P（OMe）₃; m=0, n=2,2b; L=P（OEt）₃; m=0, n=1,2c; L=TEMEDA; m=0, n=1,2d; L=TEMEDA, R=P（OMe）₃;m=1, n=1,2e） were prepared. The influence of the ancillary ligands on decomposition mechanism,thermal stability and the film performance were studied and discussed as well.（3） Research on organophosphine/phosphate stabilized N-silver（I） acetylbenzamide precursors and thepreparation of interconnect material.Using acetylbenzamide as primary ligand and organophosphine/phosphate as ancillary ligands,N-silver（I） acetylbenzamide complexes [Ln AgNC₉H₈O₂]（L=PPh3; n=1,3a; n=2,3b; n=3,3c; L=P（OEt）₃; n=1,3d; n=2,3e; n=3,3f） were prepared. The influence of the ancillary ligands ondecomposition mechanism, thermal stability and the film performance were studied and discussed.（4） Research on organophosphine/phosphate stabilized silver（Ι） N-hydroxysuccinimide precursors andthe preparation of interconnect material.Using N-hydroxysuccinimide as primary ligand and organophosphine/phosphate as ancillaryligands, silver（Ι） N-hydroxysuccinimide complexes [Ln AgO₃C₄H₄N]（L=PPh₃; n=1,4a; n=2,4b;L=P（OEt）₃; n=1,4c; n=2,4d; L=P（OMe）₃; n=1,4e; n=2,4f） were prepared. A preliminarystudy of the formation of substituted methane shows dichloromethane can react withtriphenylphosphine stabilized silver（I） N-hydroxysuccinimide complexes under mild conditions.