Bis(beta-diketonato)- and allyl-(beta-diketonato)palladium(II) complexes: synthesis, characterization and MOCVD application

K. Assim, M. Melzer, M. Korb, T. Rueffer, A. Jakob, J. Noll, C. Georgi, S. E. Schulz, H. Lang

Research output: Contribution to journalArticle

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Abstract

The syntheses and characterization of the palladium complexes [Pd(accp)(2)] (7), [Pd(acch)(2)] (8), [Pd(eta(CH2CMeCH2)-C-3)(accp)] (11), [Pd(eta(3)-CH2CMeCH2)(acch)] (12), [Pd(eta(3)-CH(2)CtBuCH(2))(accp)] (13) and [Pd(eta(3)CH(2)CtBuCH(2))(acch)] (14) (accp = 2-acetylcyclopentanoate; acch = 2-acetylcyclohexanoate) are reported. These complexes are available by the reaction of Haccp (2-acetylcyclopentanone) and Hacch (2-acetylcyclohexanone) with Na-2[Pd2Cl6] forming 7 and 8 or with [(Pd(eta(3)-CH2CRCH2)(m-Cl))(2)] (9, R = Me; 10, R = Bu-t) forming 11-14. The molecular structures of 7, 8 and 14 are discussed. Complexes 7 and 8 consist of a square-planar coordinated Pd atom with two trans-positioned bidentate b-diketonate ligands. The asymmetric unit of 14 exhibits one molecule of the palladium complex and a half molecule of water. The thermal behavior of 7, 8 and 11-14 and their vapor pressure data were investigated to show, if the appropriate complexes are suited as CVD precursors for palladium layer formation. Thermogravimetric studies showed the evaporation of the complexes at atmospheric pressure upon heating. The vapor pressure of 7, 8 and 11-14 was measured by using thermogravimetric analysis, giving vapor pressure values ranging from 0.62 to 2.22 mbar at 80 degrees C. Chemical vapor deposition studies were carried out applying a vertical cold wall CVD reactor. Either oxygen or forming gas (N-2/H-2, ratio 90/10, v/v) was used as reactive gas. Substrate temperatures of 350 and 380 degrees C were utilized. With 11-14 dense and conformal as well as particulate palladium films were obtained, as directed by SEM studies, whereas 7 and 8 failed to give thin films, which is probably attributed to their high thermal stability in the gas phase. For all deposited layers, XPS measurements confirmed the partial oxidation of palladium to palladium(II) oxide at 380 degrees C, when oxygen was used as reactive gas. In contrast, thin layers of solely metallic palladium were obtained utilizing forming gas during the deposition experiments.

Original languageEnglish
Pages (from-to)102557-102569
Number of pages13
JournalRSC Advances
Volume6
Issue number104
DOIs
Publication statusPublished - 2016
Externally publishedYes

Cite this

Assim, K. ; Melzer, M. ; Korb, M. ; Rueffer, T. ; Jakob, A. ; Noll, J. ; Georgi, C. ; Schulz, S. E. ; Lang, H. / Bis(beta-diketonato)- and allyl-(beta-diketonato)palladium(II) complexes : synthesis, characterization and MOCVD application. In: RSC Advances. 2016 ; Vol. 6, No. 104. pp. 102557-102569.
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abstract = "The syntheses and characterization of the palladium complexes [Pd(accp)(2)] (7), [Pd(acch)(2)] (8), [Pd(eta(CH2CMeCH2)-C-3)(accp)] (11), [Pd(eta(3)-CH2CMeCH2)(acch)] (12), [Pd(eta(3)-CH(2)CtBuCH(2))(accp)] (13) and [Pd(eta(3)CH(2)CtBuCH(2))(acch)] (14) (accp = 2-acetylcyclopentanoate; acch = 2-acetylcyclohexanoate) are reported. These complexes are available by the reaction of Haccp (2-acetylcyclopentanone) and Hacch (2-acetylcyclohexanone) with Na-2[Pd2Cl6] forming 7 and 8 or with [(Pd(eta(3)-CH2CRCH2)(m-Cl))(2)] (9, R = Me; 10, R = Bu-t) forming 11-14. The molecular structures of 7, 8 and 14 are discussed. Complexes 7 and 8 consist of a square-planar coordinated Pd atom with two trans-positioned bidentate b-diketonate ligands. The asymmetric unit of 14 exhibits one molecule of the palladium complex and a half molecule of water. The thermal behavior of 7, 8 and 11-14 and their vapor pressure data were investigated to show, if the appropriate complexes are suited as CVD precursors for palladium layer formation. Thermogravimetric studies showed the evaporation of the complexes at atmospheric pressure upon heating. The vapor pressure of 7, 8 and 11-14 was measured by using thermogravimetric analysis, giving vapor pressure values ranging from 0.62 to 2.22 mbar at 80 degrees C. Chemical vapor deposition studies were carried out applying a vertical cold wall CVD reactor. Either oxygen or forming gas (N-2/H-2, ratio 90/10, v/v) was used as reactive gas. Substrate temperatures of 350 and 380 degrees C were utilized. With 11-14 dense and conformal as well as particulate palladium films were obtained, as directed by SEM studies, whereas 7 and 8 failed to give thin films, which is probably attributed to their high thermal stability in the gas phase. For all deposited layers, XPS measurements confirmed the partial oxidation of palladium to palladium(II) oxide at 380 degrees C, when oxygen was used as reactive gas. In contrast, thin layers of solely metallic palladium were obtained utilizing forming gas during the deposition experiments.",
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author = "K. Assim and M. Melzer and M. Korb and T. Rueffer and A. Jakob and J. Noll and C. Georgi and Schulz, {S. E.} and H. Lang",
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Assim, K, Melzer, M, Korb, M, Rueffer, T, Jakob, A, Noll, J, Georgi, C, Schulz, SE & Lang, H 2016, 'Bis(beta-diketonato)- and allyl-(beta-diketonato)palladium(II) complexes: synthesis, characterization and MOCVD application' RSC Advances, vol. 6, no. 104, pp. 102557-102569. https://doi.org/10.1039/c6ra22887a

Bis(beta-diketonato)- and allyl-(beta-diketonato)palladium(II) complexes : synthesis, characterization and MOCVD application. / Assim, K.; Melzer, M.; Korb, M.; Rueffer, T.; Jakob, A.; Noll, J.; Georgi, C.; Schulz, S. E.; Lang, H.

In: RSC Advances, Vol. 6, No. 104, 2016, p. 102557-102569.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Bis(beta-diketonato)- and allyl-(beta-diketonato)palladium(II) complexes

T2 - synthesis, characterization and MOCVD application

AU - Assim, K.

AU - Melzer, M.

AU - Korb, M.

AU - Rueffer, T.

AU - Jakob, A.

AU - Noll, J.

AU - Georgi, C.

AU - Schulz, S. E.

AU - Lang, H.

PY - 2016

Y1 - 2016

N2 - The syntheses and characterization of the palladium complexes [Pd(accp)(2)] (7), [Pd(acch)(2)] (8), [Pd(eta(CH2CMeCH2)-C-3)(accp)] (11), [Pd(eta(3)-CH2CMeCH2)(acch)] (12), [Pd(eta(3)-CH(2)CtBuCH(2))(accp)] (13) and [Pd(eta(3)CH(2)CtBuCH(2))(acch)] (14) (accp = 2-acetylcyclopentanoate; acch = 2-acetylcyclohexanoate) are reported. These complexes are available by the reaction of Haccp (2-acetylcyclopentanone) and Hacch (2-acetylcyclohexanone) with Na-2[Pd2Cl6] forming 7 and 8 or with [(Pd(eta(3)-CH2CRCH2)(m-Cl))(2)] (9, R = Me; 10, R = Bu-t) forming 11-14. The molecular structures of 7, 8 and 14 are discussed. Complexes 7 and 8 consist of a square-planar coordinated Pd atom with two trans-positioned bidentate b-diketonate ligands. The asymmetric unit of 14 exhibits one molecule of the palladium complex and a half molecule of water. The thermal behavior of 7, 8 and 11-14 and their vapor pressure data were investigated to show, if the appropriate complexes are suited as CVD precursors for palladium layer formation. Thermogravimetric studies showed the evaporation of the complexes at atmospheric pressure upon heating. The vapor pressure of 7, 8 and 11-14 was measured by using thermogravimetric analysis, giving vapor pressure values ranging from 0.62 to 2.22 mbar at 80 degrees C. Chemical vapor deposition studies were carried out applying a vertical cold wall CVD reactor. Either oxygen or forming gas (N-2/H-2, ratio 90/10, v/v) was used as reactive gas. Substrate temperatures of 350 and 380 degrees C were utilized. With 11-14 dense and conformal as well as particulate palladium films were obtained, as directed by SEM studies, whereas 7 and 8 failed to give thin films, which is probably attributed to their high thermal stability in the gas phase. For all deposited layers, XPS measurements confirmed the partial oxidation of palladium to palladium(II) oxide at 380 degrees C, when oxygen was used as reactive gas. In contrast, thin layers of solely metallic palladium were obtained utilizing forming gas during the deposition experiments.

AB - The syntheses and characterization of the palladium complexes [Pd(accp)(2)] (7), [Pd(acch)(2)] (8), [Pd(eta(CH2CMeCH2)-C-3)(accp)] (11), [Pd(eta(3)-CH2CMeCH2)(acch)] (12), [Pd(eta(3)-CH(2)CtBuCH(2))(accp)] (13) and [Pd(eta(3)CH(2)CtBuCH(2))(acch)] (14) (accp = 2-acetylcyclopentanoate; acch = 2-acetylcyclohexanoate) are reported. These complexes are available by the reaction of Haccp (2-acetylcyclopentanone) and Hacch (2-acetylcyclohexanone) with Na-2[Pd2Cl6] forming 7 and 8 or with [(Pd(eta(3)-CH2CRCH2)(m-Cl))(2)] (9, R = Me; 10, R = Bu-t) forming 11-14. The molecular structures of 7, 8 and 14 are discussed. Complexes 7 and 8 consist of a square-planar coordinated Pd atom with two trans-positioned bidentate b-diketonate ligands. The asymmetric unit of 14 exhibits one molecule of the palladium complex and a half molecule of water. The thermal behavior of 7, 8 and 11-14 and their vapor pressure data were investigated to show, if the appropriate complexes are suited as CVD precursors for palladium layer formation. Thermogravimetric studies showed the evaporation of the complexes at atmospheric pressure upon heating. The vapor pressure of 7, 8 and 11-14 was measured by using thermogravimetric analysis, giving vapor pressure values ranging from 0.62 to 2.22 mbar at 80 degrees C. Chemical vapor deposition studies were carried out applying a vertical cold wall CVD reactor. Either oxygen or forming gas (N-2/H-2, ratio 90/10, v/v) was used as reactive gas. Substrate temperatures of 350 and 380 degrees C were utilized. With 11-14 dense and conformal as well as particulate palladium films were obtained, as directed by SEM studies, whereas 7 and 8 failed to give thin films, which is probably attributed to their high thermal stability in the gas phase. For all deposited layers, XPS measurements confirmed the partial oxidation of palladium to palladium(II) oxide at 380 degrees C, when oxygen was used as reactive gas. In contrast, thin layers of solely metallic palladium were obtained utilizing forming gas during the deposition experiments.

KW - CHEMICAL-VAPOR-DEPOSITION

KW - ALLYL(BETA-DIKETONATO)PALLADIUM(II) COMPLEXES

KW - CATALYTIC MATERIALS

KW - CRYSTAL-STRUCTURE

KW - PALLADIUM FILMS

KW - THIN-FILMS

KW - PRECURSORS

KW - PLATINUM

KW - TEMPERATURE

KW - TRANSISTORS

U2 - 10.1039/c6ra22887a

DO - 10.1039/c6ra22887a

M3 - Article

VL - 6

SP - 102557

EP - 102569

JO - RSC Advances

JF - RSC Advances

SN - 2046-2069

IS - 104

ER -