Abstract
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.
Original language | English (US) |
---|---|
Pages (from-to) | 1907-1919 |
Number of pages | 13 |
Journal | Chemistry of Materials |
Volume | 28 |
Issue number | 6 |
DOIs | |
State | Published - Mar 22 2016 |
ASJC Scopus subject areas
- Chemistry(all)
- Chemical Engineering(all)
- Materials Chemistry
Fingerprint
Dive into the research topics of 'Volatile Hexavalent Oxo-amidinate Complexes: Molybdenum and Tungsten Precursors for Atomic Layer Deposition'. Together they form a unique fingerprint.Datasets
-
CCDC 1473008: Experimental Crystal Structure Determination
Mouat, A. R. (Creator), Mane, A. U. (Creator), Elam, J. W. (Creator), Delferro, M. (Creator), Marks, T. J. (Creator) & Stair, P. (Creator), Cambridge Crystallographic Data Centre, 2016
DOI: 10.5517/ccdc.csd.cc1lfsd6, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lfsd6&sid=DataCite
Dataset
-
CCDC 1473009: Experimental Crystal Structure Determination
Mouat, A. R. (Creator), Mane, A. U. (Creator), Elam, J. W. (Creator), Delferro, M. (Creator), Marks, T. J. (Creator) & Stair, P. (Creator), Cambridge Crystallographic Data Centre, 2016
DOI: 10.5517/ccdc.csd.cc1lfsf7, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lfsf7&sid=DataCite
Dataset
-
CCDC 1473007: Experimental Crystal Structure Determination
Mouat, A. R. (Creator), Mane, A. U. (Creator), Elam, J. W. (Creator), Delferro, M. (Creator), Marks, T. J. (Creator) & Stair, P. (Creator), Cambridge Crystallographic Data Centre, 2016
DOI: 10.5517/ccdc.csd.cc1lfsc5, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lfsc5&sid=DataCite
Dataset