Search

Photo-induced electron transfer between poly-(3-hexylthiophene) (P3HT) and small (2.4 nm) PbS quantum dots (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. Although 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. [ABSTRACT FROM AUTHOR]

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(3-hexylthiophene) (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 nongeminate recombination. [ABSTRACT FROM AUTHOR]

Different approaches of surface modification of the quantum dots (QDs), namely, solution-phase (octylamine, octanethiol) and post-deposition (acetic acid, 1,4-benzenedithiol) ligand exchange were used in the fabrication of hybrid bulk heterojunction solar cell containing poly (3-hexylthiophene) (P3HT) and small (2.4 nm) PbS QDs. We show that replacing oleic acid by shorter chain ligands improves the figures of merit of the solar cells. This can possibly be attributed to a combination of a reduced thickness of the barrier for electron transfer and an optimized phase separation. The best results were obtained for post-deposition ligand exchange by 1,4-benzenedithiol, which improves the power conversion efficiency of solar cells based on a bulk heterojunction of lead sulfide (PbS) QDs and P3HT up to two orders of magnitude over previously reported hybrid cells based on a bulk heterojunction of P3HT:PbS QDs, where the QDs are capped by acetic acid ligands. The optimal performance was obtained for solar cells with 69 wt.% PbS QDs. Besides the ligand effects, the improvement was attributed to the formation of an energetically favorable bulk heterojunction with P3HT, when small size (2.4 nm) PbS QDs were used. Dark current density-voltage (J-V) measurements carried out on the device provided insight into the working mechanism: the comparison between the dark J-V characteristics of the bench mark system P3HT:PCBM and the P3HT:PbS blends allows us to conclude that a larger leakage current and a more efficient recombination are the major factors responsible for the larger losses in the hybrid system. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Monolithically integrated hybrid tandem solar cells that effectively combine solution-processed colloidal quantum dot (CQD) and organic bulk heterojunction subcells to achieve tandem performance that surpasses the individual subcell efficiencies have not been demonstrated to date. In this work, we demonstrate hybrid tandem cells with a low bandgap PbS CQD subcell harvesting the visible and near-infrared photons and a polymer:fullerene—poly (diketopyrrolopyrrole-terthiophene) (PDPP3T):[6,6]-phenyl-C60-butyric acid methyl ester (PC61BM)—top cell absorbing effectively the red and near-infrared photons of the solar spectrum in a complementary fashion. The two subcells are connected in series via an interconnecting layer (ICL) composed of a metal oxide layer, a conjugated polyelectrolyte, and an ultrathin layer of Au. The ultrathin layer of Au forms nano-islands in the ICL, reducing the series resistance, increasing the shunt resistance, and enhancing the device fill-factor. The hybrid tandems reach a power conversion efficiency (PCE) of 7.9%, significantly higher than the PCE of the corresponding individual single cells, representing one of the highest efficiencies reported to date for hybrid tandem solar cells based on CQD and polymer subcells. [ABSTRACT FROM AUTHOR]

An entirely optical, dynamic thermometry technique based on the temperature dependence of a fluorescence spectrum is presented. Different from conventional intensity-based fluorescence thermometry, in this work, neural network recognition is employed to extract the sample temperature from the magnitude and shape of recorded fluorescence spectra. As a demonstration to determine the depth profile of dynamical temperature variations and of the thermal and optical properties of semitransparent samples, in-depth photothermally induced periodical temperature oscillations of a rhodamine B and copper chloride dyed glycerol sample were measured with an accuracy of 4.2 mK·Hz–1/2 and fitted well by a 1D thermal diffusion model. [ABSTRACT FROM AUTHOR]

We report the experimental study of hole transport in poly(vinylcarbazole) (PVK) films doped with colloidal CdSe/ZnS core-shell quantum dots (QDs) determined using the Time-of-Flight (TOF) method. The miscibility between PVK and the QDs is improved by capping the QDs with a novel 11-(N-carbazolyl) undecanoic acid (C11) ligand instead of commonly used organic ligands, such as oleic acid. The study of the hole mobility of the pristine and doped PVK films with a doping concentration of the C11 capped QDs ranging from 1.61 × 1017 to 7.10 × 1018 dots/cm3 was performed as a function of electric field and temperature in the range of 105-106 V/cm and 298-338 K, respectively. Upon increasing the QD concentration, a decrease of hole mobility was observed by up to nearly 2 orders in magnitude at a doping concentration of 3.87 × 1018 dots/cm3 at T = 298 K. This suggests that the QDs induce shallow hole traps. The field and temperature dependence of the hole mobility was characterized using the Bässler disorder model and showed an increase of the energetic disorder (σ) from 124 to 204 meV as well as of the spatial disorder (Σ) from 0.95 to 5 when the concentration of the QDs was increased to 3.87 × 1018 dots/cm3. At higher concentration of the QDs (7.10 × 1018 dots/cm3), an increase of the hole mobility was observed suggesting hopping of the holes through the QD clusters. In addition, we also found that for this high doping concentration, the field dependence of the hole mobility was no longer in agreement with the Bässler disorder model. One should consider that at this doping concentration, the volume occupied by the inorganic (CdSe + ZnS) and organic (C11) components of the QDs in the doped film was estimated to be 14.6 and 15.8 volume %, respectively. This implies that the volume fraction of the inorganic material is very close to the percolation threshold, which amounts to 17 volume % for small spherical particles embedded in a three dimensional matrix. Furthermore, the conductivity data suggest a qualitative change in film properties between the samples with 3.87 × 1018 and 7.10 × 1018 dots/cm3. The study of film morphology by atomic force microscopy (AFM) experiment shows that while for the film with 3.87 × 1018 dots/cm3 the surface of the film has still the same features as that of a pristine PVK film, this is no longer the case for the film with 7.10 × 1018 dots/cm3, where shallow holes with a diameter of 100 to 200 nm become visible. These holes with the size much larger than the diameter of an individual QD likely correspond to clusters of the QDs. Upon further increasing the QD concentration to 9.68 × 1018 dots/cm3, the density of these holes is also increased. A correlation between the conductivity data and the film morphologies indicates that the presence of these QD clusters in the sample with 7.10 × 1018 dots/cm3 does not only change the homogeneity and roughness of the film but also leads to a significant change in the shape of the density of states of the energy sites for hopping holes resulting in a field and temperature dependence of the hole mobility that is no longer compatible with the Gaussian disorder model for this sample. Furthermore, the presence of these 'hole' structures observed with AFM might imply a formation of large QD clusters in the polymer film, which form continuous pathways for charge carrier hopping between the opposite electrodes. [ABSTRACT FROM AUTHOR]

Monolithically integrated hybrid tandem solar cells that effectively combine solution-processed colloidal quantum dot (CQD) and organic bulk heterojunction subcells to achieve tandem performance that surpasses the individual subcell efficiencies have not been demonstrated to date. In this work, we demonstrate hybrid tandem cells with a low bandgap PbS CQD subcell harvesting the visible and near-infrared photons and a polymer:fullerene-poly (diketopyrrolopyrrole-terthiophene) (PDPP3T):[6,6]-phenyl-C 60 -butyric acid methyl ester (PC 61 BM)-top cell absorbing effectively the red and near-infrared photons of the solar spectrum in a complementary fashion. The two subcells are connected in series via an interconnecting layer (ICL) composed of a metal oxide layer, a conjugated polyelectrolyte, and an ultrathin layer of Au. The ultrathin layer of Au forms nano-islands in the ICL, reducing the series resistance, increasing the shunt resistance, and enhancing the device fill-factor. The hybrid tandems reach a power conversion efficiency (PCE) of 7.9%, significantly higher than the PCE of the corresponding individual single cells, representing one of the highest efficiencies reported to date for hybrid tandem solar cells based on CQD and polymer subcells.