Ultraviolet-Visible-Near Infrared and Raman spectroelectrochemistry of poly(3,4-ethylenedioxythiophene) complexes with sulfonated polyelectrolytes. The role of inter- and intra-molecular interactions in polyelectrolyteстатья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 26 декабря 2017 г.
Аннотация:Poly(3,4-ethylenedioxythiophene) (PEDOT)
films were electrodeposited in galvanostatic mode in the
presence of salt or acid forms of sulfonated polyelectrolytes distinguished by different rigidity of the
polymer main chain and presence of amid fragments in their stricture. The
films obtained were
characterized by cyclic voltammetry, as well as Ultraviolet-Visible-Near Infrared and Raman
spectroelectrochemistry at
fixed potentials in non-aqueous and aqueous media, respectively. It was
found that bipolaronic fragments of PEDOT are hardly to be formed at high anodic potentials in the
films
prepared in the presence of acid forms of the rigid-chain amid-containing polyelectrolytes as distinct
from all other polyelectrolytes regardless of amide-groups content. In situ Raman studies during PEDOT
electrodeposition in the presence of the acid forms of the rigid-chain amid-containing polyelectrolytes
showed domination and retarded delocalization of radical cations being the moving force of the
electropolymerization. The results are discussed in terms of possibility/impossibility of proton-transfer
inter- and intra-molecular interactions between sulfonic and amid groups in the polyelectrolytes. These
result in the appearance of positive charges (confirmed by z-potential measurements) on the
polyelectrolyte chain, which create barriers for radical cations delocalization, their recombination into
bipolarons, as well as prevents growth of long PEDOT chains. The prepared materials were studied as a
hole-transport (buffer) layer in organic photovoltaic cells. The influence of polyelectrolyte structure on
the cells performance is discussed.