Excited conjugated polymers

Fig. 9.27 Schematic representation of the decay of photo-excited conjugated polymers. Reproduced with permission of the Institute of Physics from Gadermeier and Lanzani (2002).

Scheme 13.3 Energy transfer from an electronically excited conjugated polymer to fluorescein.

For spin-1/2 excitations such as electrons and holes in normal semiconductors or polarons in conjugated polymers, a single resonance is found centered at the Field... 

The enormous progress in the field of electroluminescent conjugated polymers has led to performances of oiganic light-emitting devices (LEDs) that are comparable and in some aspects superior to their inorganic counterparts 11). Quantum efficiencies in excess of 5% have been demonstrated [2] and show that a high fraction of the injected carriers in a polymeric electroluminescence (EL) device form electronic excitations which recombine radiatively. 

Generally, photooxidation has an even stronger negative effect on lasing and stimulated emission in conjugated polymers than it has on the EL-performance. It not only reduces the number of excited 5j states but additionally creates charged absorbing species that partly compensate the stimulated emission due to the neutral excited states. 

Figure 10-12. Lcfi hand side Slruclure of a PPV microcavily. A thin film of ihe conjugated polymer is deposited on top of a highly reflective distributed Bragg refieclor (DBR). The second mirror is then fabricated by evaporation of a silver layer. Right hand side Emission spectra of the microcavily at excitation cnetgics or 0.0S pJ (dashed line) and l. l pJ (solid line), respectively. Laser pulses ol duration 200-300 ps and a wavelength of 355 nm were used for optical excitation (according to Ref. [39]).

Excitation conditions and threshold vulues for lasing in different conjugated polymers. Different resonator structures are used to achieve real lasing. Note that it is in some cases difficult to compare the values due to the different laser pulse duration used in the experiments. indicates the wavelength for excitation, r(,u< is the pulse duration of the exciting laser pulse atu A the urea of the spot on the sample. 

Conjugated polymers are centrosymmetric systems where excited states have definite parity of even (A,) or odd (B ) and electric dipole transitions are allowed only between states of opposite parity. The ground state of conjugated polymers is an even parity singlet state, written as the 1A... PM spectroscopy is a linear technique probing dipole allowed one-photon transitions. Non linear spectroscopies complement these measurements as they can couple to dipole-forbidden trail-... 

Optically detected magnetic resonance (ODMR) has yielded valuable information about dynamics of long-lived pholoexcitations of conjugated polymers. The technique relies upon the paramagnetic interaction of excitations with an applied magnetic field. For a particle with non-zero spin, placed in a magnetic field, the Hamiltonian is ... 

The role of disorder in the photophysics of conjugated polymers has been extensively described by the work carried out in Marburg by H. Bassler and coworkers. Based on ultrafast photoluminescence (PL) (15], field-induced luminescence quenching [16J and site-selective PL excitation [17], a model for excited state thermalizalion was proposed, which considers interchain exciton migration within the inhomogenously broadened density of states. We will base part of the interpretation of our results in m-LPPP on this model, which will be discussed in some detail in Sections 8.4 and 8.6. 

The proposed scenario is mainly based on the molecular approach, which considers conjugated polymer films as an ensemble of short (molecular) segments. The main point in the model is that the nature of the electronic state is molecular, i.e. described by localized wavefunctions and discrete energy levels. In spite of the success of this model, in which disorder plays a fundamental role, the description of the basic intrachain properties remains unsatisfactory. The nature of the lowest excited state in m-LPPP is still elusive. Extrinsic dissociation mechanisms (such as charge transfer at accepting impurities) are not clearly distinguished from intrinsic ones, and the question of intrachain versus interchain charge separation is not yet answered. 

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