Excitons, polarons, and laser action in poly(p-phenylene vinylene) films

Abstract

We have used a multitude of linear and nonlinear cw optical spectroscopies to study the optical properties of water precursor poly(p-phenylene vinylene) (PPV) thin films. These spectroscopies include absorption, photoluminescence, photoinduced absorption and their respective optically detected magnetic resonance, and electroabsorption spectroscopy. We have studied singlet and triplet excitons, polarons, and laser action in PPV films. We found that the lowest-lying absorption band is excitonic in origin. It consists of two absorption components due to a bimodal distribution of the polymer chain conjugation lengths. Electroabsorption spectroscopy unambiguously shows the positions of the lowest-lying odd parity exciton 1Bu at 2.59 eV and two of the higher-lying even-parity excitons, namely, mAg at 3.4 eV and kAg at 3.7 eV. From these exciton energies we obtained a lower bound for the exciton binding energy in PPV, Eb(min)=E(mAg)−E(1Bu)=0.8 eV. The quantum efficiency spectrum for triplet exciton photogeneration consists of two contributions; the intersystem crossing and, at higher energies, singlet fission. From the onset of the singlet fission process at ESF=2ET, we could estimate the energy of the lowest-lying triplet exciton, 1 3Bu, at 1.55 eV, with a singlet–triplet splitting as large as 0.9 eV. From photoinduced absorption spectroscopy we measured the triplet–triplet transition, T→T*, to be 1.45 eV. The quantum efficiency spectrum for polaron photogeneration also consists of two contributions: one extrinsic and the other intrinsic. The latter shows a monotonically increasing function of energy with an energy onset at 3.3 eV. The intrinsic photogeneration process is analyzed with a model of free-electron–hole pair photogeneration, which separate more effectively at higher energy. The carrier generation quantum yield at 3.65 eV is estimated to be 0.5%. The quantum efficiency for photoluminescence, on the other hand, shows one single step-function process, with an onset at 2.4 eV. The photoluminescence spectrum is well structured, showing five phonon side bands with 190 meV separation. We have also studied laser action in PPV thin films and microcavities such as microrings and microdisks. The effective gain spectrum is calculated and the estimated threshold excitation intensity for laser action for the 0-1 transition is found to be in good agreement with the data, with an estimated exciton density of 2×1018 cm−3. Lasing from microring devices shows several narrow waveguide modes, with intermode spacing of 0.45 nm that corresponds to an effective mode refractive index, neff=1.45. The spectral width of the laser modes is resolution limited and gives a lower estimate of the cavity quality factor, Q. For microrings we found Q>5000, which is limited by self-absorption in the polymer film.