We have studied the influence of electric field and humidity on
photoconductivity and fluorescence in particles
of highly photoconductive Y-form TiOPc dispersed in a
poly(vinylbutyral) polymer matrix. Both
integrated
and time-resolved fluorescence quenching by electric field were
measured. Integrated fluorescence quenching
showed a linear dependence at low applied fields and a linear
correlation with carrier generation efficiency.
Time-resolved fluorescence decays were analyzed by fitting the
data to a sum of two exponentials representing
fast and slow fluorescence components. Qualitative features of
fluorescence decay were the same for low
and high humidity levels. The amplitude and lifetime changes of
the two fluorescence components upon the
application of the electric field are in agreement with theory which
describes energy transfer between free
and trapped exciton states. These results indicate that carrier
generation in Y-TiOPc originates from both
relaxed and nonrelaxed intrinsic excited singlet states, while the
trapped excitons do not lead to significant
carrier production. The field dependence of integrated
fluorescence quenching supports the existence of a
carrier precursor state with charge-transfer character.
The effect of electric fields on the fluorescence decay of block-copolymers containing poly(pphenylenevinylene) (PPV) and polynorbornene (polyNBE) was measured. Electric fields of up to 200 V/µm do not perturb the fluorescence decay profiles when the average size of the PPV block is small (i.e., PPV 3 -block-polyNBE 200 or PPV 3 -block-polyNBE 25 ). It appears that for short isolated PPV segments the electric field accessible for these studies does not allow dissociation of photogenerated excitons into electron-hole pairs. For larger PPV segments, as in PPV 20 -block-polyNBE 200 , the electric field reduces considerably the fluorescence lifetime and quantum yield. In addition, irradiating the sample under an electric field changes permanently its fluorescence characteristics. Control experiments show that neither irradiation nor the field alone can degrade the polymer.
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