• Energy Research

Conjugated polymer (CP)‐di‐ureasil composite materials displaying a tunable emission color from blue to yellow through white have been prepared using a simple sol–gel processing method. The tunability of the emission color arises from a combination of energy transfer between the di‐ureasil and the CP dopant and the excitation wavelength dependence of the di‐ureasil emission. Incorporation of the CP does not adversely affect the bulk or local structure of the di‐ureasil, enabling retention of the structural and mechanical properties of the host. Furthermore, CP‐di‐ureasils display superior thermal and photostability compared to the parent CPs. Thermogravimetric analysis shows that the onset of thermal decomposition can be increased by up to 130 °C for CP‐di‐ureasils, while photostability studies reveal a significant decrease in the extent of photodegradation. Steady‐state photoluminescence spectroscopy and picosecond time‐resolved emission studies indicate that the observed tunable emission arises as a consequence of incomplete energy transfer between the di‐ureasil and the CP dopant, resulting in emission from both species on direct excitation of the di‐ureasil matrix. The facile synthetic approach and tunable emission demonstrate that CP‐di‐ureasils are a highly promising route to white‐light‐emitters that simultaneously improve the stability and reduce the complexity of CP‐based multilayer device architectures.

AbstractThe authors investigated organic tandem solar cells with solution processed recombination contacts made from a TiO2 sol in combination with PEDOT:PSS. Tandem cells were prepared either with two P3HT:PCBM-based subcells or by combining PCDTBT:PC[70]BM and PCPDTBT:PC[70]BM. Optical modeling is used to predict experimental short circuit currents of the tandem solar cells as a function of layer thickness. Both types of tandem cells yield energy conversion efficiencies of ca. 3.3%. We propose that a significant improvement of the performance of the PCDTBT:PC[70]BM - PCPDTBT:PC[70]BM tandem is possible by optimization of the recombination contact and layer thicknesses of both subcells.

Abstract We report on the efficiency enhancement for bulk-heterojunction hybrid solar cells based on hexanoic acid treated trioctylphosphine/oleic acid-capped CdSe quantum dots (QDs) and low bandgap polymer poly[2,6-(4,4-bis-(2-ethylhexyl)-4 H -cyclopenta[2,1- b ;3,4- b ′]-dithiophene)- alt -4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) compared to devices based on poly(3-hexylthiophene) (P3HT). Photovoltaic devices with optimized polymer:QD weight ratio, photoactive film thickness, thermal annealing treatment, and cathode materials exhibited a power conversion efficiency of 2.7% after spectral mismatch correction, which is the highest reported value for spherical CdSe QD based photovoltaic devices. The efficiency enhancement is attributed to the surface treatment of the QDs together with the use of the low bandgap polymer PCPDTBT leading to an increased short-circuit current density due to additional light absorption between 650 and 850 nm. Our results suggest that the hexanoic acid treatment is generally applicable to various ligand-capped CdSe and confirm that low bandgap polymers with adequate HOMO and LUMO levels are promising to be incorporated into hybrid solar cells for further device performance improvement.

Low-bandgap near-infrared polymers are usually synthesized using the common donor-acceptor (D-A) approach. However, recently polymer chemists are introducing more complex chemical concepts for better fine tuning of their optoelectronic properties. Usually these studies are limited to one or two polymer examples in each case study so far, though. In this study, the dependence of optoelectronic and macroscopic (device performance) properties in a series of six new D-A1 -D-A2 low bandgap semiconducting polymers is reported for the first time. Correlation between the chemical structure of single-component polymer films and their optoelectronic properties has been achieved in terms of absorption maxima, optical bandgap, ionization potential, and electron affinity. Preliminary organic photovoltaic results based on blends of the D-A1 -D-A2 polymers as the electron donor mixed with the fullerene derivative [6,6]-phenyl-C71 -butyric acid methyl ester demonstrate power conversion efficiencies close to 4% with short-circuit current densities (J sc ) of around 11 mA cm-2 , high fill factors up to 0.70, and high open-circuit voltages (V oc s) of 0.70 V. All the devices are fabricated in an inverted architecture with the photoactive layer processed in air with doctor blade technique, showing the compatibility with roll-to-roll large-scale manufacturing processes.

Chemically synthesized colloidal quantum dots can easily be incorporated into conjugated polymer host systems allowing for novel organic/inorganic hybrid materials combining the natural advantages from both organic as well as inorganic components into one system. In order to obtain tailored optoelectronic properties, a profound knowledge of the fundamental electronic energy transfer processes between the inorganic and organic parts is necessary. Previous studies have attributed the observed efficient energy transfer to a dipole-dipole coupling with Förster radii of about 50-70 A. Here, we report on resonant energy transfer of nonequilibrium excitons in an amorphous polyfluorene donor CdSe/ZnS core-shell nanocrystal acceptor system. By time-resolved photoluminescence (PL) spectroscopy, we have investigated the PL decay behavior of the primarily excited polyfluorene as a function of temperature. We show that the transfer efficiency drops from about 30% at room temperature to around 5% at low temperature. These results shed light on the importance of temperature-activated exciton diffusion in the energy transfer process. As a consequence the exciton has to migrate very close to the surface of the quantum dot in order to couple to the quantum dot. Hence, the coupling strength is much weaker than that anticipated in previous work and requires treatment beyond Förster theory.

Abstract We report on improved power conversion efficiencies (PCEs) approaching 3.5% for bulk-heterojunction (BHJ) hybrid solar cells based on CdSe nanorods and the low band gap polymer poly[2,6-(4,4-bis-(2-ethylhexyl)- 4H -cyclopenta[2,1- b ;3,4- b ′]-dithiophene)- alt -4,7-(2,1,3-benzothiadiazole)] (PCPDTBT). Different post-synthetic surface treatments of CdSe nanorods are applied and the performances of the resulting hybrid solar cells are compared. The improved PCE values are attributed to the advanced post-synthetic surface treatment of the CdSe nanorods, leading to an effective reduction of synthesis ligands from the nanorod surfaces prior to ligand exchange with pyridine. The sequential decrease of the ligands is confirmed by a combination of thermogravimetric analysis-mass spectrometry (TGA-MS).

AbstractThe high efficiencies reported for organic solar cells and an almost negligible thermal activation measured for the photogeneration of charge carriers have called into question whether photoinduced interfacial charge transfer states are bound by a significant coulomb attraction, and how this can be reconciled with very low activation energies. Here, this question is addressed in a combined experimental and theoretical approach. The interfacial binding energy of a charge‐transfer state in a blend of MeLPPP:PCBM is determined by using energy resolved electrochemical impedance spectroscopy and is found to be about 0.5 eV. Temperature‐dependent photocurrent measurements on the same films, however, give an activation energy that is about one order of magnitude lower. Using analytical calculations and Monte Carlo simulation the authors illustrate how i) interfacial energetics and ii) transport topology reduce the activation energy required to separate the interfacial electron–hole pair, with about equal contributions from both effects. The activation energy, however, is not reduced by entropy, although entropy increases the overall photodissociation yield.

AbstractThe efficient synthesis of a new solution‐processable n‐type conjugated polymer network (PNT1) is reported through palladium‐catalyzed Stille cross‐coupling reaction conditions following the A3 + B2 synthetic approach. A benzo[1,2‐b:3,4‐b′:5,6‐b″]trithiophene derivative is used as the A3 knot and an alkyl functionalized naphthalenediimide is utilized as the B2 linker. The thermal, optical, and electrochemical properties are examined in detail, showing high thermal stability, absorbance in the visible part of the solar spectrum, and reversible reduction characteristics similar to those of the fullerene derivative [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM). PNT1 is employed as the electron acceptor in solution‐processed bulk heterojunction organic solar cells, demonstrating the potential of this new type of materials for optoelectronic applications.