Time-resolved site-selective spectroscopy of poly(p-phenylene vinylene) -: art. no. 115206

被引:30
作者
Kennedy, SP [1 ]
Garro, N [1 ]
Phillips, RT [1 ]
机构
[1] Univ Cambridge, Cavendish Lab, Cambridge CB3 0HE, England
来源
PHYSICAL REVIEW B | 2001年 / 64卷 / 11期
关键词
D O I
10.1103/PhysRevB.64.115206
中图分类号
T [工业技术];
学科分类号
08 ;
摘要
We report the dynamics of emission from the conjugated polymer poly(p-phenylene vinylene) after ultrafast optical excitation with a range of photon energies. Subpicosecond temporal resolution of the emission allows us to distinguish between photoluminescence and intense resonant scattering that decays within a few pico-seconds but dominates the time-integrated spectra. As the excitation energy is decreased the redshift of the photoluminescence over time is reduced, indicating a decreasing mobility of the excitons. The ratio between the intensities of the two highest-energy peaks in the spectrum increases for lower excitation energies and with increasing times after excitation. We deduce that the configurational energy change between ground and excited electronic states increases for excitons located on chain segments with shorter conjugation lengths. A Stokes shift of 20 meV between the excitation energy and the highest peak in emission is observed even when predominantly immobile excitons are generated. We attribute this shift to the preferential excitation into the higher levels of low-energy vibrational modes of states with electronic energy such that they are not in resonance with the excitation. This is supported by calculations that reproduce the experimental results only if these low-energy modes are considered. We show that when the low-energy phonon modes are important. site-selective spectroscopy excites a distribution of states that is broader than the spectral width of the excitation source.
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页数:7
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