Electronic Structures and Optical Absorption of N-Type Conducting Polymers at Different Doping Levels

被引:29
作者
Ghosh, Sarbani [1 ]
Gueskine, Viktor [1 ]
Berggren, Magnus [1 ]
Zozoulenko, Igor V. [1 ]
机构
[1] Linkoping Univ, Dept Sci & Technol, SE-60174 Norrkoping, Sweden
基金
瑞典研究理事会;
关键词
FIELD-EFFECT TRANSISTOR; THIN-FILM TRANSISTORS; LADDER POLYMERS; ELECTRICAL-CONDUCTIVITY; ORGANIC POLYMERS; BIPOLARONS; POLARONS; BBL; POLY(3,4-ETHYLENEDIOXYTHIOPHENE); STABILITY;
D O I
10.1021/acs.jpcc.9b04634
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Theoretical understanding of the electronic structure and optical transitions in n-doped conducting polymers is still controversial for polaronic and bipolaronic states and is completely missing for the case of a high doping level. In the present paper, the electronic structure and optical properties of the archetypical n-doped conducting polymer, double-stranded benzimidazo-benzophenanthroline ladder (BBL), are studied using the density functional theory (DFT) and the time dependent DFT method. We find that a polaronic state in the BBL chain is a spin-resolved doublet where the spin degeneracy is lifted. The ground state of two electrons corresponds to a triplet polaron pair, which is in stark contrast to a commonly accepted picture where two electrons are postulated to form a spinless bipolaron. The total spin gradually increases until the reduction level reaches c(red) = 100% (i.e., one electron per monomer unit). With further increase of the reduction level, the total spin decreases until it becomes 0 for the reduction level c(red) = 200%. The calculated results reproduce the experimentally observed spin signal without any phenomenological parameters. A detailed analysis of the evolution of the electronic structure of BBL and its absorption spectra with increase in reduction level is presented. The calculated UV-vis-NIR spectra are compared with the available experimental results. The electronic structure and optical absorption for different reduction levels presented here are generic to a wide class of conducting polymers, which is illustrated by the corresponding calculations for another archetypical conducting polymer, poly(3,4-ethylenedioxythiophene) (best known as PEDOT).
引用
收藏
页码:15467 / 15476
页数:10
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