Ac. Fou et Mf. Rubner, MOLECULAR-LEVEL PROCESSING OF CONJUGATED POLYMERS .2. LAYER-BY-LAYER MANIPULATION OF IN-SITU POLYMERIZED P-TYPE DOPED CONDUCTING POLYMERS, Macromolecules, 28(21), 1995, pp. 7115-7120
A novel thin-film processing technique has been developed for the fabr
ication of ultrathin films of conducting polymers with angstrom-level
control over thickness and multilayer architecture. As part 2 of this
series, we present here the molecular self-assembly of p-doped conduct
ing polymers (e.g., polypyrrole and polyaniline), a layer-by-layer pro
cess in which a substrate is alternately dipped into a chemically acti
ve aqueous solution of an in-situ polymerized conjugated polymer and a
solution of a palyanion. In-situ oxidative polymerization produces co
ntinuously the highly conductive, underivatized form of the conjugated
polymer, which is deposited in single layers of precisely controlled
thickness as it is formed. The thickness of each layer, ranging from 2
0 to 60 Angstrom, can be fine-tuned by adjusting the dipping time and
the solution chemistry. The surface chemistry of the substrate (hydrop
hobic, charged, etc.) is key in determining the deposition characteris
tics and uniformity of the film. Widely different deposition character
istics onto different surfaces make it possible to selectively deposit
conducting polymers onto certain, well-defined regions of a substrate
by patterning the surface with different chemistries. Typical multila
yer films exhibit conductivities in the range of 20-80 S/cm; however,
ultrathin films with conductivities over 300 S/cm can be made with sui
table adjustments to the solution chemistry.