Akitsugu Niwa

Temperature dependence of photoluminescence properties in a thermally activated delayed fluorescence emitter

Using steady-state and time-resolved photoluminescence (PL) spectroscopy, we have investigated the temperature dependence of PL properties of 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyano-benzene (4CzIPN), which have a small energy gap between its singlet and triplet excited states and thus exhibits efficient thermally activated delayed fluorescence [H. Uoyama et al., Nature 492, 235 (2012)]. Below around 100 K, PL quantum efficiency of 4CzIPN thin films is largely suppressed and strong photoexcitation intensity dependence appears. These features can be explained by using rate equations for the densities of singlet and triplet excited states considering a triplet-triplet annihilation process.

Emission properties of thermally activated delayed fluorescence emitters: Analysis based on a four-level model considering a higher triplet excited state

Abstract. A four-level model consisting of a higher triplet excited state (T2), the lowest singlet and triplet excited states (S1 and T1), and the ground state was previously used to understand emission properties of a thermally activated delayed fluorescence (TADF) emitter, 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN). In this report, we discuss the four-level model in more detail and apply to the other two TADF emitters, i.e., 1,2,4,5-tetrakis(carbazol-9-yl)-3,6-dicyanobenzene (4CzTPN) and 1,2-bis(carbazol-9-yl)-4,5-dicyanobenzene (2CzPN), in order to determine their excited-state structures. It is suggested that in all the emitters T2 lies between S1 and T1 and play an essential role in the emitting process. In 4CzTPN, phosphorescence from T2 is clearly observed around 100 K as in 4CzIPN. Compared to the other two emitters, 2CzPN has a wider energy gap between S1 and T1 so that delayed fluorescence at room temperature is thought to be mixed with phosphorescence. Because of this mixing, the spectrum characteristic of phosphorescence from T2 in 2CzPN cannot be identified.

Triplet-triplet annihilation in a thermally activated delayed fluorescence emitter lightly doped in a host

Triplet-triplet annihilation (TTA) will change the ratio between fluorescence and phosphorescence in the photoluminescence spectrum of a thermally activated delayed fluorescence emitter at very low temperature. Using the resultant spectral blueshift, this study investigated the nature of TTA in 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) doped in a host material. The spectral blueshift is not caused by singlet-triplet annihilation and the emitter saturation effect and is less influenced by the emitter aggregates, particularly for the case of a lower doping concentration. Using these features, it is possible to focus on TTA. For 4CzIPN, the spectral blueshift due to TTA is recognized even in samples with the doping concentration as low as 1 wt. %.

Photoluminescence Properties of Polymorphic Modifications of Low Molecular Weight Poly(3-hexylthiophene)

The structural and photoluminescence (PL) properties of thin films of poly(3-hexylthophene) (P3HT) with molecular weights (MWs) of 3000 and 13,300 have been investigated. Although high MW P3HT always self-organizes into one packing structure (form I), low MW P3HT forms two different packing structures (forms I and II) depending on the fabrication conditions. In this work, several fabrication techniques have been examined to obtain form II samples with little inclusion of a form I component. It is found that drop-cast thin films of low MW P3HT (form II) exhibit a PL spectrum that is different from that of form I and does not contain the form I component. The PL spectrum can thus be attributed to form II. The differences in PL properties between forms I and II can be understood in terms of weakened interchain interactions due to the longer interchain distance in form II.