The partially fluorinated oxo-alkoxide tungsten(VI) complexes WO(OR)4 [4; R = C(CH3)2CF3, 5; R = C(CH3)(CF3)2] have been synthesized as precursors for chemical vapour deposition (CVD) of WOx nanocrystalline material. Complexes 4 and 5 were prepared by salt metathesis between sodium salts of the fluoroalkoxides and WOCl4. Crystallographic structure analysis allows comparison of the bonding in 4 and 5 as the fluorine content of the fluoroalkoxide ligands is varied. Screening of as a CVD precursor by mass spectrometry and thermogravimetric analysis was followed by deposition of WOx nanorods.

Aerosol-assisted chemical vapor deposition (AACVD) of WOx was demonstrated using the oxo tungsten(VI) fluoroalkoxide single-source precursors, WO[OCCH3(CF3)2]4 and WO[OC(CH3)2CF3]4. Substoichiometric amorphous tungsten oxide thin films were grown on indium tin oxide (ITO) substrates in nitrogen at low deposition temperature (100-250 °C). At growth temperatures above 300 °C, the W18O49 monoclinic crystalline phase was observed. The surface morphology and roughness, visible light transmittance, electrical conductivity, and work function of the tungsten oxide materials are reported. The solvent and carrier gas minimally affected surface morphology and composition at low deposition temperature; however, material crystallinity varied with solvent choice at higher temperatures. The work function of the tungsten oxide thin films grown between 150 and 250 °C was determined to be in the range 5.0 to 5.7 eV, according to ultraviolet photoelectron spectroscopy (UPS).

Reactions of [WO(OR)4]x (x = 1, 2) complexes with bidentate ligands (LH = acacH, tbacH, dpmH, tbpaH) afforded complexes : [WO(OCH3)3(acac) (); WO(OCH2CH3)3(acac) (); WO(OCH(CH3)2)3(acac) (); WO(OCH3)3(tbac) (); WO(OCH2CH3)3(tbac) (); WO(OCH(CH3)2)3(tbac) (); WO(OCH2CH3)3(dpm) (); WO(OCH(CH3)2)3(dpm) (); WO(OCH2C(CH3)3)3(acac) (); WO(OCH2C(CH3)3)3(tbac) (); WO(OCH2C(CH3)3)3(dpm) (); WO(OCH2C(CH3)3)3(tbpa) (); WO(OC(CH3)3)3(tbac) ()]. The synthesis is facilitated by the lability of the bridging ligands of the [WO(OR)4]2 complexes in solution, which provides a pathway for exchange of L with an alkoxide ligand. Thermogravimetric analysis and the conditions for sublimation or distillation of demonstrate that they have sufficient vapor pressure and thermal stability for volatilization in a conventional Chemical Vapor Deposition (CVD) reactor. High solubility in hydrocarbon and ether solvents establishes that the complexes are also potential candidates for Aerosol-Assisted Chemical Vapor Deposition (AACVD). AACVD from on ITO or bare glass resulted in growth of continuous, dense and amorphous thin films of substoichiometric WOx between 250-350 °C and nanorods of W18O49 above 350 °C.

The soluble bis(fluoroalkoxide) dioxo tungsten(VI) complexes WO2(OR)2(DME) [1, R = C(CF3)2CH3; 2, R = C(CF3)3] have been synthesized by alkoxide-chloride metathesis and evaluated as precursors for aerosol-assisted chemical vapor deposition (AACVD) of WOx. The (1)H NMR and (19)F NMR spectra of 1 and 2 are consistent with an equilibrium between the dimethoxyethane (DME) complexes 1 and 2 and the solvato complexes WO2(OR)2(CD3CN)2 [1b, R = C(CF3)2CH3; 2b, R = C(CF3)3] in acetonitrile-d3 solution. Studies of the fragmentation of 1 and 2 by mass spectrometry and thermolysis resulted in observation of DME and the corresponding alcohols, with hexafluoroisobutylene also generated from 1. DFT calculations on possible decomposition mechanisms for 1 located pathways for hydrogen abstraction by a terminal oxo to form hexafluoroisobutylene, followed by dimerization of the resulting terminal hydroxide complex and dissociation of the alcohol. AACVD using 1 occurred between 100 and 550 °C and produced both substoichiometric amorphous WOx and a polycrystalline W18O49 monoclinic phase, which exhibits 1-D preferred growth in the [010] direction. The work function (4.9-5.6 eV), mean optical transmittance (39.1-91.1%), conductivity (0.4-2.3 S/cm), and surface roughness (3.4-7.9 nm) of the WOx films are suitable for charge injection layers in organic electronics.

Deposition of continuous, dense WOx films and nanorods was accomplished by aerosol-assisted chemical vapor deposition (AACVD) using the recently synthesized precursors WO(OCH3)3(acac) (1), WO(OCH2C(CH3)3)3(tbac) (2), WO(OCH2C(CH3)3)3(dpm) (3), WO(OC(CH3)3)3(tbac) (4), and WO(OCH2C(CH3)3)3(tbpa) (5). This works seeks to define the deposition conditions and precursors that yield C-free tungsten oxide and the potential to control the stoichiometry and phase of deposited WOx. In addition, the systematic variation of the ligand chemistry provides insight into precursor design. Variation of the precursor and growth temperature during deposition revealed a window where C-free WOx was deposited using 3, 4, and 5. The surface morphology of the WOx varied from amorphous thin film to crystalline nanorods to dendrites as temperature was increased. Films grown between 150 and 350°C in pure N2 atmosphere are sub-stoichiometric, amorphous and contaminated with carbide species (3–9 at.%). As the deposition temperature increased (400–550°C), the tungsten became more oxidized, the sub-stoichiometric crystalline W18O49 monoclinic phase formed, and increased surface bound C was detected. Material was also deposited under oxidizing conditions (1–2% O2 in N2) as well as annealing in air at the deposition temperature. The material grown in N2/O2 carrier gas at low temperatures (200 and 300°C) is amorphous WOx, similar to that grown in N2. At higher temperature (350 and 550°C), however, GIXRD results reveal WOx corresponding to a sub-stoichiometric tetragonal phase transitioning to the monoclinic WO3 phase for samples grown at 550°C. This demonstrates that crystalline structure of WOx is affected by the growth temperature and introducing O2 in the carrier gas. Air annealing samples grown in pure N2 also produced structural and compositional changes, but not identical to those grown in a N2/O2 carrier gas. Notably, annealing samples grown at 250 and 350°C at the same temperature, produced C-free material with unchanged amorphous morphology. The measured stoichiometry and crystallinity showed a dependence on the precursor structure. The growth rate of deposited material was measured as a function of temperature and activation energies were estimated for growth of amorphous and nanostructured material. The systematic variation in activation energies is consistent with initial dissociation of the alkoxide C-O bonds and modifications of the steric bulk of the β-diketonate ligand.

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