Conjugated conducting polymers constitute a subject of research lying at the interface between solid-state physics and molecular science. Electronic absorption and vibrational spectroscopies of doped conjugated polymers, whose ground states are nondegenerate, are reviewed from a viewpoint of molecular spectroscopy. Raman spectroscopy is a powerful tool for studying the structures of polarons and bipolarons, which are associated with electrical, magnetic, and optical properties of the polymers. Electronic absorption and Raman spectra of doped polymers have been analyzed on the basis of those of model compounds. These analyses have led us to the conclusion that polarons are the major species generated by doping in most nondegenerate conjugated polymers such as polythiophene, poly(p-phenylene), and poly(p-phenylenevinylene), in contrast with the previous view that bipolarons are the major species. The theoretical and experimental bases of these two contradictory views are discussed.

Electronic absorption and vibrational spectroscopies of conjugated conducting polymers

Raman spectra of neutral and electrochemically doped regioregular poly(3-decylthiophene) were studied using different excitation lines, namely, 457.9, 514.5, 676, and 1064 nm. Contrary to the case of nonregioregular poly(3-decylthiophene) obtained by polymerization with FeCl3, in regioregular polymer the position of the principal band (due to the CαCβ stretchings) is essentially independent of the excitation wavelength, proving its high structural homogeneity and extended conjugation. Raman spectroelectrochemical studies of oxidative doping of regioregular poly(3-decylthiophene) can be clearly correlated with cyclic voltammetry and UV−visible−near-IR spectroelectrochemistry provided that appropriate excitation wavelengths are selected. In particular, the use of the red (676.4 nm) and near-IR (1064 nm) excitation lines enables us to register the doping induced changes in the Raman spectra, whereas the green (514.5 nm) line always reveals the vibrations from the undoped segments of the polymer chain indepen...

Raman Spectroscopic Studies of Regioregular Poly(3-alkylthiophenes)

Spectroelectrochemical studies of poly(3,4-ethylenedioxythiophene) in aqueous medium

The relaxation dynamics of photoexcitations in cast films of the polydiacetylenes, poly[4,6-decadiyne-1,10-diol bis([(n-butoxycarbonyl)methyl]urethane)] (PDA-3BCMU) and poly[5,7-dodecadiyne-1,12-diol bis([n-butoxycarbonyl)methyl]urethane)] (PDA-4BCMU), and in electrochemically prepared films of poly(3-methylthiophene) (P3MT) were investigated by femtosecond absorption and picosecond luminescence spectroscopies. 1Bu free excitons, generated by 100-fsec pump pulses, relaxed to the self-trapped (ST) state with time constants of 150 ± 50 fsec in PDA-3BCMU and 70 ± 50 fsec in P3MT. The difference was explained in terms of the relative sizes of the side chains. PDA-3BCMU has bulky side chains that are linked by hydrogen bonds, while P3MT has a repeating unit that contains a ring structure with a small methyl group. The lifetimes of the ST excitons at 10 K (290 K) were 2.0 ± 0.1 (1.5 ± 0.1) psec in PDA-3BCMU, 3.0 ± 0.3 (2.1 ± 0.2) psec in PDA-4BCMU, and 800 ± 100 (800 ± 100) fsec in P3MT. The decay kinetics of the ST exciton were explained by potential crossing and tunneling between two potential curves of the ST exciton and the ground state. The weak temperature dependence indicates that the activation process over the potential barrier between the ST exciton and the ground state is not dominant in the radiationless relaxation of the ST exciton. The relaxation dynamics of fluorescence from the PDA-4BCMU film cannot be represented by a single exponential decay; however, it can be described in terms of a random walk in the fractal dimension. By applying the fractal-dimension model, the spectral dimension was determined to be between 0.50 and 0.85. The spectral changes that are due to several nonlinear-optical processes, i.e., hole burning, Raman gain, and the dynamic Stark effect, were also observed in femtosecond-resolved spectra. The third-order susceptibility was determined for these nonlinear processes, such as absorption saturation at the exciton transition, Raman gain, and the resonant Kerr effect from the observed spectral change. The third-order susceptibility that corresponds to absorption saturation in PDA-3BCMU and in P3MT was obtained as Im[χ1111(3)(−ω;ω,ω,−ω)] equal to −2.6 × 10−9 and −3.5 × 10−10 esu, respectively, for ħω = 1.97 eV. The third-order susceptibility that corresponds to the Raman gain in PDA-3BCMU and in P3MT was determined to be Im[χ1111(3)(−ω2;ω2,ω1,−ω1)] equal to 5.8 × 10−10 and −1.5 × 10−10 esu, respectively, for ħω1 = 1.97 eV and ħω2 = 1.79 eV. From the resonant Kerr experiment in the P3MT film, |Δχ(3)|≡|χ1111(3)(−ω2;ω2,ω1,−ω1)−χ1122(3)(−ω2;ω2,ω1,−ω1)|=3.9×10−11 esu was determined for ħω1 = 1.97 eV and ħω2 = 1.88 eV.

Relaxation dynamics of photoexcitations in polydiacetylenes and polythiophene

We studied the carriers generated in regioregular poly(3-hexylthiophene) (P3HT) upon FeCl3 vapor and solution doping using visible/near-infrared (VIS/NIR) absorption, infrared (IR), and Raman spectroscopy. Upon doping with an FeCl3 solution in air, the main carriers that were generated were positive polarons. Upon doping with FeCl3 vapor, positive polarons also formed initially, but at higher doping levels, positive bipolarons formed with the concomitant disappearance of the positive polarons. The Raman and IR spectra of the positive bipolarons and the positive polarons were obtained. Raman spectroscopy is very useful for characterizing positive polarons and bipolarons. The Raman results indicated that the positive bipolarons were converted to polarons upon heating to 85 °C, indicating that the positive bipolarons formed a metastable state. The temporal changes in the electrical conductivity of a P3HT film upon doping with FeCl3 vapor were measured. The conductivity reached a maximum and then decreased by...

H.E. Schaffer

Papers

Infrared activity of photoexcitations in polythiophene