This paper discusses the formation of nanosized hexagonal tungsten oxide (h-WO 3 ) during the annealing of hexagonal ammonium tungsten bronze (HATB), (NH 4 ) 0.33-x WO 3-y . This process was investigated by TG/DTA-MS, XRD, SEM, Raman, XPS, and 1 H-MAS NMR analyses. Through adjusting the temperature and atmosphere of annealing HATB, the composition (W oxidation state, residual NH 4 + and NH 3 content) of h-WO 3 could be controlled. The effect of composition on the conductivity and gas sensitivity of h-WO 3 was studied. New structural information was obtained about both HATB and h-WO 3 . It was found that NH 4+ and NH 3 could be situated at three different positions in HATB. Residual NH 4 + and NH 3 in the hexagonal channels seemed to be vital for stabilizing h-WO 3 : when they were completely released, the hexagonal framework collapsed. We propose that the structure of h-WO 3 cannot be maintained without some stabilizing ions or molecules in the hexagonal channels.
Transparent and conductive patterns of carboxyl functionalized single-walled carbon nanotubes (SWCNT-COOHs) and the composites of those with poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) were deposited on various substrates by inkjet printing. For low print repetitions, the PEDOT-PSS/SWCNT-COOH composite patterns show enhanced conductance as compared to the corresponding PEDOT-PSS conductors. The results suggest a decreased percolation threshold for the printed composite since the nanotubes establish electrical interconnections between the separate PEDOT-PSS (conductive phase) islands being dispersed in the insulating PSS-phase. However, the interaction between PEDOT-PSS and SWCNTs becomes insignificant and the conductivity is not enhanced by the nanotubes, when the amount of PEDOT-PSS is sufficient to form a continuous conducting phase. Up to now, patterns having sheet resistivities as low as ~1 kΩ/ᮀ could be achieved. Though there is a trade-off between transparency and conductivity -we achieved highly transparent patterns (~90%) with a reasonably low resistivity of ~10 kΩ/ᮀ. The ink and printing method proposed here offer new alternatives of conventional transparent conductive materials based on either polymers or indium oxides; and pose scaleable production of cost-effective transparent electronics.
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