A comparative study of the polyaniline thin films produced by the cluster beam deposition and laser ablation methods

Polyaniline (PANI) thin films have been prepared by applying the novel neutral and ionized cluster beam deposition (NCBD and ICBD) methods and the pulsed laser deposition (PLD) technique to the PANI samples of half-oxidized emeraldine base (EB-PANI) and protoemeraldine base forms in a high-vacuum condition. Characterization of the oxidation states and structural changes of pristine and doped thin films has been performed by Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, and x-ray photoelectron spectroscopy. Spectroscopic measurements demonstrate that the dominant structure of NCBD and ICBD thin films corresponds to the reduced leucoemeraldine base state, whereas the chemical composition of PLD thin films depends critically on the laser fluence and the molecular weight of PANI target. The congruent deposition is only obtained for the PLD films deposited by the laser-induced decomposition of the low-molecular-weight targets in the low to intermediate fluence regime (below 100 mJ/cm² with a pulse duration of 7 ns). The surface morphology examined by atomic force microscopy measurements shows that the cluster and laser beams are effective in producing smooth, uniform polymeric thin films. After I₂ and HCl doping, the electrical conductivities of the NCBD, ICBD, and particularly PLD thin films are increased significantly. The higher conductivity of PLD films is ascribed to higher amounts of quinoid di-imine doping sites in the EB-PANI state, and the overall structure- conductivity characteristics are consistent with the spectroscopic observations.