This paper presents a detailed spectroscopic investigation of luminescence properties of 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP) and N,N,N′,N′-tetraphenylbenzidine (TAD) in solutions and neat films. These compounds are compared to their derivatives CDBP and TDAD that contain methyl groups in the 2 and 2′ position of the biphenyl core. We find that whereas steric twisting in CDBP and TDAD leads to a high triplet energy of about 3.0 and 3.1 eV, respectively, these compounds also tend to form triplet excimers in a neat film, in contrast to CBP and TAD. By comparison with N-phenylcarbazole (NPC) and triphenylamine (TPA), on which these compounds are based, as well as with the rigid spiro analogues to CBP and TAD we show that the reduced excimer formation in CBP and TAD can be attributed to a localization of the excitation onto the central biphenyl part of the molecule.
Using optical spectroscopy in solution and thin film, and supported by quantum chemical calculations, we investigated the aggregation process of the donor-acceptor type molecule p-DTS(FBTTH 2 ) 2 . We demonstrate that cooling a solution induces a disorder-order phase transition that proceeds in three stages analogous to the steps observed in semi-rigid conjugated polymers. By analyzing the spectra we are able to identify the spectral signature of monomer and aggregate in absorption and emission. From this we find that in films the fraction of aggregates is near 100 % which is in contrast to films made from semi-rigid conjugated polymers.3
Here, we report the synthesis, optical properties, and solid-state packing of monodisperse oligomers of diketopyrrolopyrrole (DPP) up to five repeating units. The optical properties of DPP oligomers in solution and the solid state were investigated by a combination of steady-state and transient spectroscopy. Transient absorption spectroscopy and time-correlated single photon counting (TCSPC) measurements show that the fluorescence lifetime decreases with an increase in the oligomer size from monomer to trimer, thereby reaching saturation for pentameric DPP oligomers. The solid-state packing and crystallinity were probed by using advanced techniques, which included grazing incidence small-angle X-ray scattering (GISAXS) and X-ray diffraction (XRD) to elucidate the structure-property trend. Collectively, our chain-length dependent studies establish the fundamental correlation between the structure and property and provide a comprehensive understanding of the solid-state properties in DPP-DPP based conjugated systems.
Novel S,N-heteroheptacenes SN7a–d with a variable thiophene–pyrrole ratio and a heteroring fusion sequence were synthesized and the electronic properties were characterized.
Efficient triplet exciton hopping (diffusion) in amorphous solid films is essential for triplet−triplet annihilation (TTA) and TTA-mediated photon upconversion (UC) at low excitation power densities. However, enhanced triplet diffusion, particularly in high-emitter-content UC films, also facilitates their trapping and quenching at nonradiative decay sites, thus deteriorating UC efficiency. In this work, triplet exciton diffusion and quenching are studied in matrix-free solid UC films based on two novel bisfluoreneanthracene (BFA) emitters, i.e., one with methyl substitution (BFA-Me) and the other with a phenyl substitution (BFA-Ph), and a standard platinum octaethylporphyrin (PtOEP) sensitizer. By analyzing temperature-dependent TTA-UC dynamics and accounting for various singlet exciton-related processes, we are able to discern triplet exciton quenching occurring explicitly in the emitter and show that it is one of the dominating mechanisms impeding the UC performance of BFA/PtOEP films, particularly at elevated temperatures. Regardless of the lower density of quenchers present in the BFA-Ph film, twice as large triplet diffusivity estimated in this film (D = (2.13 ± 0.64) × 10 −9 cm 2 •s −1 ) at room temperature as compared to that in the BFA-Me film caused more rapid triplet quenching. This resulted in the shifting of the optimal UC performance of BFA-Ph to lower temperatures (T = 160 K) with respect to that of BFA-Me (T = 220 K). To obtain a high UC quantum yield, which for these materials can be estimated to reach >5% at room temperature and above, the excessive diffusion to the remaining quenching sites needs to be suppressed, e.g., by increasing the intermolecular distance through side groups.
Since the key role of charge transfers (CT) states has been identified for organic solar cells (OSCs), research into their properties is a timely topic. Conventionally, their absorption and emission spectra are described in terms of Marcus’ electron transfer theory. This is a single site approach with the essential parameter being the reorganization energy. Thus, it ignores ensemble effects, notably the role of static disorder that is inevitably present in a spin‐coated OSC film. Here time dependent photoluminescence spectroscopy is applied on blends of the polymeric donor MeLPPP with either the non‐fullerene acceptor SF‐PDI2 or with PC61BM within a temperature range from 295 to 5 K. The authors monitor how initially excited singlet states are converted to emissive CT states. Concomitantly, emission from residual singlets on the acceptor is observed rather than hybrid CT‐states. The role of spectral diffusion in this process is discussed. From the temperature and time dependent linewidths of absorption, fluorescence, and CT emission, the static and dynamic contributions to the total disorder are inferred. In both blends, at 295 K, the contribution of static disorder is comparable to the dynamic disorder.
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