Band conjugated polymers

In real tran -polyacetylene, the structure is dimerized with two carbon atoms in the repeat unit. Thus the tt band is divided into occupied tt and unoccupied n bands. The bond-alternated structure of polyacetylene is characterishc of conjugated polymers. Consequently, since there are no partially filled bands, conjugated polymers are expected to be semiconductors, as pointed out earlier. However, for conducting polymers the interconnection of chemical and electronic structure is much more complex because of the relevance of non-linear excitations such as solitons (Heeger, 2001). 

Recently, photovoltaic cells that use a narrow band conjugated polymer PDDTT 196 as the electron donor and fullerene derivative 197 as the electron acceptor were developed. These cells show a short circuit density (J c) of 0.83mAcm , an open current voltage (Fqc) of 0.35 V, a fill factor (FF) of 38.6% under AM.5 simulator (lOOmWcm ) and unprecedented photocurrent response wavelengths up to llOOnm <2006APY081106>. 

Table 1. Optical Band Gaps For Conjugated Polymers...

Polyacetylene is considered to be the prototypical low band-gap polymer, but its potential uses in device applications have been hampered by its sensitivity to both oxygen and moisture in its pristine and doped states. Poly(thienylene vinylene) 2 has been extensively studied because it shares many of the useful attributes of polyacetylene but shows considerably improved environmental stability. The low band gap of PTV and its derivatives lends itself to potential applications in both its pristine and highly conductive doped state. Furthermore, the vinylene spacers between thiophene units allow substitution on the thiophene ring without disrupting the conjugation along the polymer backbone. 

Primary Photoexcitations in Conjugated Polymers Molecular Exciton versus Semiconductor Band Model (Ed. N.S. Sariciftci) World Scientific, Singapore 1997. 

We have studied the temporal dynamics of CPG in m-LPPP by performing field-assisted pump-probe experiments on LED structures, as described in Section 8.3.2. The narrow line-width PA assigned to polarons (see Section 8.5.2) is a fingerprint of charge generation in m-LPPP. Monitoring the dynamics of these PA band enables us, for the first time, to directly observe the CPG dynamics in a conjugated polymer with sub-picosecond time resolution [40],... 

Figure 15-10. Schematic band diagrams for single-layer conjugated polymer devices at various values of forward bias. Forward bias is defined with respect lo ITO.

Conjugated polymers are generally poor conductors unless they have been doped (oxidized or reduced) to generate mobile charge carriers. This can be explained by the schematic band diagrams shown in Fig. I.23 Polymerization causes the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the monomer to split into n and n bands. In solid-state terminology these are the valence and conduction bands, respectively. In the neutral forms shown in Structures 1-4, the valence band is filled, the conduction band is empty, and the band gap (Eg) is typically 2-3 eV.24 There is therefore little intrinsic conductivity. 

Our results fit also with a previous investigation (9) on polyenes based on a version of the 2h-lp Cl scheme restricted to the virtual one-electron states generated by a minimal basis. In our case, however, the fragmentation of lines into satellites is much more pronounced. The reason lies in the size-consistency of the ADC[3] approach (as contrasted with the size-inconsistency of any truncated form of Cl (27d), in the full handling of the virtual space, and (10) in the inclusion of correlation corrections to the reference ground state, leading to (37) a net reduction of the quasi-particle band gap of conjugated polymers. 

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