Upon exchanging long chain alkylamine ligands with a carbazole terminated fatty acid as 6-(N-carbazolyl)-hexanoic acid (C6) and 11-(N-carbazolyl) undecanoic acid (C11), efficient photoluminescence (PL) of CdSe/ZnS colloidal quantum dots (QDs) was observed upon excitation in the absorption band of the carbazole moiety at 330 nm. This effect, which occurred both in solution and in a poly(N-vinylcarbazole) (PVK) matrix doped with the QDs, is attributed to sensitization of the QDs by PVK and the ligands. More efficient energy transfer was observed in solution for the shorter ligand (C6) capped QDs, due to a shorter average distance between the donor (carbazole) and the acceptor (QD). The binding of C6 and C11 to the QDs was confirmed by 1H solution nuclear magnetic resonance, which showed line broadening of the carbazole signal due to a decrease of the mobility of the carbazoles upon binding to the QDs compared with the sharp lines observed for the free molecules in solution. In doped PVK films, the significant enhancement of the energy transfer to the QD core could also be related to a better miscibility between the QDs and the PVK as confirmed by optical transmission and confocal microscopy images. In contrast to the experiment in solution, the overall energy transfer in the doped films was found more efficient for QDs capped with C11. To study in more detail the energy transfer between the carbazole moieties and the QDs, time-resolved fluorescence measurements were performed for solutions of C6 and C11, capped QDs and PVK films doped with the QDs. In contrast to the large enhancement of the QD emission indicated by steady-state PL spectra, the latter experiments suggested only a relatively low efficiency (19.6% and 10.8%) for singlet transfer from the carbazole ligands to the QDs. This suggests that the enhancement of the QD emission must be largely due to triplet transfer.

The charge carrier transport in thin film hybrid solar cells is analyzed and correlated with device performance and the mechanisms responsible for recombination loss. The hybrid bulk heterojunction consisted of a blend of poly(3hexylthiophene) (P3HT) and small size (2.4 nm) PbS quantum dots (QDs). The charge transport in the P3HT:PbS blends was determined by measuring the space-charge limited current in hole-only and electron-only devices. When the loading of PbS QDs exceeds the percolation threshold a significant increase of the electron mobility is observed in the blend with PbS QDs.The hole mobility, on the other hand, only slightly decreased upon increasing the loading of PbS QDs. We also showed that the photocurrent is limited by the low shunt resistance rather than by space-charge effects. The significant reduction of the fill factor at high light intensity suggests that under these conditions the non-geminate recombination dominates. However, at open-circuit conditions, the trap-assisted recombination dominates over non-geminate recombination.

Photo-induced electron transfer between P3HT and small (2.4 nm) PbS QDs, capped by different ligands, was studied by picosecond and femtosecond time-resolved fluorescence and by photo-induced absorption (PIA) measurements. In line with previous experiments, we observed that the efficiency of the quenching of P3HT by PbS QDs increased upon decreasing the average thickness of the ligand shell. This trend was also observed in the PIA spectra and in prior work on the performance of photovoltaic devices where the active layer was a blend of P3HT with PbS QDs capped by different ligands.Combining the pico-and femtosecond fluorescence decays showed that the quenching in blend films of P3HT and PbS QDs treated with 1,4-benzenedithiol occurred over a broad time scale ranging from tens of femtoseconds to hundreds of picoseconds. This complex kinetics was attributed to exciton hopping followed by electron transfer to the conduction band of the QDs. We also compared the wavelength dependence of the internal quantum efficiency (IQE) in the hybrid photovoltaic devices to those devices where the photoactive layer consists of PbS QDs only. While excitation in the first excitonic transition of the PbS QDs yielded a similar IQE in both devices, the IQE of the hybrid devices tripled at wavelengths where also P3HT started to absorb. This suggests that upon excitation of P3HT in the latter devices charge generation occurs by photo-induced electron transfer from P3HT to the QDs rather than by energy transfer to the QDs followed by exciton dissociation in the QDs.

A novel π-conjugated triad and a polymer incorporating indolo[3,2-b]-carbazole (ICZ) and 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) were synthesized via a Sonogashira coupling. Compared to the parent BODIPY the absorption and fluorescence spectrum were for both compounds broader and redshifted. The redshift of the fluorescence and the decrease of the fluorescence quantum yield and decay time upon increasing solvent polarity were attributed to the formation of a partial charge-transfer state. Upon excitation in the ICZ absorption band the ICZ fluorescence was quenched in both compounds mainly due to energy transfer to the BODIPY moiety. In a similar ICZ-π-DPP polymer (where DPP is diketopyrrolopyrrole), a smaller redshift of the absorption and fluorescence spectra compared to the parent DPP was observed. A less efficient quenching of the ICZ fluorescence in the ICZ-π-DPP polymer could be related to the unfavorable orientation of the transition dipoles of ICZ and DPP. The rate constant for energy transfer was for all compounds an order of magnitude smaller than predicted by Förster theory. While in a solid film of the triad a further redshift of the absorption maximum of nearly 100 nm was observed, no such shift was observed for the ICZ-π-BODIPY polymer.

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