Thin Solid Films, Vol.537, 124-130, 2013
Formation of stoichiometric, sub-stoichiometric undoped and hydrogen doped tungsten oxide films, enabled by pulsed introduction of O-2 or H-2 during hot-wire vapor deposition
Tungsten oxide films with various stoichiometries, undoped and hydrogen doped were deposited by heating a W wire at 660 degrees C and at a base pressure of 13 Pa set by various gasses (O-2, N-2, H-2) or gas mixtures (N-2-O-2 10% in O-2, forming gas, FG) and pulsed injection of O-2 or H-2. Using this method and dependent on the deposition conditions four classes of hot-wire (hw) tungsten oxide films were synthesized: i) stoichiometric (hwWO(3)), ii) oxygen deficient (sub-stoichiometric, hwWO(x) with x < 3), iii) stoichiometric and hydrogen doped (hwWO(3):H), and iv) sub-stoichiometric and hydrogen doped (hwWO(x):H). Due to the pulsed injection of O-2 the W wire re-oxidizes during deposition thus creating WO3 vapors continuously, so films deposited by this method do not suffer by thickness limitations and, moreover, exhibit high porosity. The optical properties of these classes of films, studied with spectroscopic ellipsometry (SE) measurements, differ substantially between them indicating corresponding differences in their electronic structures. So, hwWO(3) films were semiconducting exhibiting a band gap near 3 eV. Sub-stoichiometric hwWO(x) deposited with up to 2 injections of O-2 were semi-metallic preserving some features of the electronic structure of the pure metal, while further injection of O-2 leads to stoichiometric films. Fourier transform infrared spectroscopy and SE measurements indicated that hwWO(x) films contain H bonded with the O ions while in hwWO(3):H and hwWO(x):H the H is incorporated in films by direct bonding with the W ions. (C) 2013 Elsevier B.V. All rights reserved.
Keywords:Tungsten oxide;Doped oxide;Hot-wire chemical vapor deposition;Pulsed injection;Optical properties