三正丁基膦稳定的铜(Ⅰ)β-二酮配合物的合成、表征以及作为前驱物用化学汽相沉积法生长铜膜(英文)

Synthesis of Tri-n-butylphosphine Copper(Ⅰ) a-Diketonates and Their Use in Chemical Vapour Deposition of Copper

合成了一系列三正丁基膦辅助配体稳定的铜髣β鄄二酮配合物,对合成的配合物用元素分析、红外、核磁共振以及热重和差热等手段进行了表征。筛选出性能优良的配合物为前驱物用化学汽相沉积(CVD)的方法生长出金属铜膜,用SEM和EDX等手段对生长的铜膜进行了表征。

A series of copper(Ⅰ) a-diketonate complexes of type [(nBu3P)mCuL] [m=1 or 2. m=1: L=acac (4), acac=acetylacetonate; L=dbac (5), dbac=1,3-di-tert-butylacetonate; L=hfac (6), hfac=1, 1, 1, 5, 5, 5-hexafluoroacetylacetonate; m=2: L=acac (7); L=dbac (8); L=hfac (9)] with nBu3P as ancillary Lewis-base ligand is accessible by the reaction of [(nBu3P)mCuCl] (1: m=1, 2: m=2) with the sodium-a-diketonate salts NaL (3a: L=acac; 3b: L=dbac; 3c: L=hfac) in a 1∶1 molar ratio. Complexes 7~9 can also be prepared by treatment of 4~6 with one equivalent of nBu3P (10). Spectroscopic data (IR, 1H-, 13C{1H}-NMR) of 4~9 reveal that the respective a-diketonates are chelate-bound to copper(Ⅰ), thus resulting in a tri-(4~6) or tetra-coordination (7~9) at the transition metal ion. The thermal properties of 4~9 were studied by ThermoGravimetric analysis (TG) and Differential Scanning Calorometry (DSC). Hot-wall Chemical Vapour Deposition experiments (CVD) were carried-out by using, for example, complexes 4 and 7 as precursors for the deposition of copper onto TiN-coated SiO2 wafers. SEM and EDX studies were applied to characterize the obtained copper films.