Volatile Hexavalent Oxo-amidinate Complexes: Molybdenum and Tungsten Precursors for Atomic Layer Deposition
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- 作者：Aidan R. Mouat ; Anil U. Mane ; Jeffrey W. Elam ; Massimiliano Delferro ; Tobin J. Marks ; Peter C. Stair
- 刊名：Chemistry of Materials
- 出版年：2016
- 出版时间：March 22, 2016
- 年：2016
- 卷：28
- 期：6
- 页码：1907-1919
- 全文大小：766K
- ISSN：1520-5002
文摘
New complexes MoO2(tBuAMD)2 (1) and WO2(tBuAMD)2 (2) (AMD = acetamidinato) are synthesized and fully characterized as precursors for atomic layer deposition (ALD). They contain metal-oxo functionalities not previously utilized in ALD-type growth processes and are fully characterized by 1H and 13C NMR, X-ray diffraction (XRD), Fourier transform infrared, thermogravimetric analysis, single-crystal XRD, and elemental analysis. Guided by quartz-crystal microbalance studies, ALD growth methodologies for both complexes have been developed. Remarkably, these isostructural compounds exhibit dramatic differences in ALD properties. Using 1 and O3, amorphous, ultrathin molybdenum oxynitride (MoON) films are grown on Si(100) wafers. Using 2 and H2O yields amorphous WO3 films on Si(100) wafers that crystallize as WO3 nanowires upon annealing. Although 1/H2O and 2/O3 growth was attempted, effective ALD growth could only be obtained with 1/O3 and 2/H2O, underscoring reactivity differences in these precursors. Film thicknesses, compositions, and optical and electrical parameters are characterized by variable angle spectroscopic ellipsometry, X-ray reflectivity, grazing incidence X-ray diffraction, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and atomic force microscopy techniques. The hitherto unknown ALD chemistry of group VI metal-oxo compounds lays a foundation for their use in the ALD synthesis of heterogeneous catalysts.