Raj René Janssen

Poly(diketopyrrolopyrrole-terthiophene) for ambipolar logic and photovoltaics.

A new semiconducting polymer, PDPP3T, with alternating diketopyrrolopyrrole and terthiophene units is presented. PDPP3T has a small band gap of 1.3 eV and exhibits nearly balanced hole and electron mobilities of 0.04 and 0.01 cm(2) V(-1) s(-1), respectively, in field-effect transistors (FETs). By the combination of two identical ambipolar transistors, an inverter was constructed that exhibits a gain of approximately 30. When PDPP3T was combined with [60]PCBM or [70]PCBM in a 1:2 weight ratio, photovoltaic cells were made that provide a photoresponse up to 900 nm and an AM1.5 power conversion efficiency of 3.8 or 4.7%, respectively. In contrast to the almost constant FET mobility, the efficiency of the photovoltaic cells was found to be strongly dependent on the molecular weight of PDPP3T and the use of diiodooctane as a processing agent.

Efficient tandem and triple-junction polymer solar cells.

We demonstrate tandem and triple-junction polymer solar cells with power conversion efficiencies of 8.9% and 9.6% that use a newly designed, high molecular weight, small band gap semiconducting polymer and a matching wide band gap polymer.

Efficient Solar Cells Based on an Easily Accessible Diketopyrrolopyrrole Polymer

A new easily accessible, high molecular weight, alternating dithieno-diketopyrrolopyrrolophenylene copolymer provides high electron and hole mobilities exceeding 0.02 cm2 V-1 s-1 in FETs and AM1.5 power conversion efficiencies of 4.6% and 5.5% in solar cells when combined with [60]PCBM and [70]PCBM. The performance of the solar cells strongly depends on the use of a processing agent.

The use of ZnO as optical spacer in polymer solar cells : theoretical and experimental study

For organic solar cells, insertion of an optical spacer between the active layer and the reflective electrode results in a redistribution of the optical electric field. In this paper, theoretical calculations using optical modeling are compared with experimental results for devices with ZnO as optical spacer. An excellent agreement was found for blends composed of poly(3-hexylthiophene) and a fullerene derivative [6,6]-phenyl C61 butyric acid methyl ester.

Synthesis and Characterization of a Low Bandgap Conjugated Polymer for Bulk Heterojunction Photovoltaic Cells

Low optical bandgap conjugated polymers may improve the efficiency of organic photovoltaic devices by increasing the absorption in the visible and near infrared region of the solar spectrum. Here we demonstrate that condensation polymerization of 2,5-bis(5-trimethylstannyl-2-thienyl)-N-dodecylpyrrole and 4,7-dibromo-2,1,3-benzothiadiazole in the presence of Pd(PPh3)2Cl2 as a catalyst affords a novel conjugated oligomeric material (PTPTB), which exhibits a low optical bandgap as a result of the alternation of electron-rich and electron-deficient units along the chain. By varying the molar ratio of the monomers in the reaction and fractionation of the reaction product, two different molecular weight fractions (PTPTB-I and PTPTB-II, see Experimental section) were isolated, containing 5–17 and 13–33 aromatic units respectively, as inferred from matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Thin films of PTPTB-I and PTPTB-II exhibit an optical bandgap of 1.60 and 1.46 eV, respectively. Photoinduced absorption (PIA) and photoluminescence spectroscopy of blends of PTPTB-I and a methanofullerene (1-(3-methoxycarbonyl)-propyl-1-phenyl-[6,6]C61, PCBM) gave direct spectral evidence of the photoinduced electron-transfer reaction from PTPTB-I as a donor to the fullerene derivative as an acceptor. Thin PTPTB-I:PCBM composite films were sandwiched between indium tin oxide/poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonic acid) (ITO/PEDOT:PSS) and Al electrodes to prepare working photovoltaic devices, which show an open circuit voltage of 0.67 V under white-light illumination. The spectral dependence of the device shows an onset of the photocurrent at 1.65 eV (750 nm).

Efficient Small Bandgap Polymer Solar Cells with High Fill Factors for 300 nm Thick Films

A high-molecular-weight conjugated polymer based on alternating electron-rich and electron-deficient fused ring systems provides efficient polymer solar cells when blended with C60 and C70 fullerene derivatives. The morphology of the new polymer/fullerene blend reduces bimolecular recombination and allows reaching high fill factors and power conversion efficiencies for films up to 300 nm thickness.

Spectroscopic studies of photoexcitations in regioregular and regiorandom polythiophene films

Using a variety of optical probe techniques we studied the steady state and transient dynamics of charged and neutral photoexcitations in thin films of poly-3-alkyl thiophene with regioregular order, which forms self-assembled lamellae structures with increased interchain interaction, as well as regiorandom order that keeps a chain-like morphology. In regiorandom polythiophene films we found that intrachain excitons with correlated photoinduced absorption and stimulated emission bands are the primary photoexcitations; they give rise to a moderately strong photoluminescence band, and long-lived triplet excitons and intrachain charged polarons. In regioregular polythiophene films, on the contrary we found that the primary photoexcitations are excitons with much larger interchain component; this results in lack of stimulated emission, vanishing intersystem crossing, and a very weak photoluminescence band. The long-lived photoexcitations in regioregular polythiophene films are interchain excitons and delocalized polarons (DP) within the lamellae, with very small relaxation energy. The characteristic properties of the DP species are thoroughly investigated as a function of the alkyl side group of the polymer backbone, film deposition conditions and solvents used, as well as at high hydrostatic pressure. The quantum interference between the low energy absorption band of the DP species and a series of photoinduced infrared active vibrations, which give rise to antiresonances that are superimposed on the electronic absorption band is studied and explained by a Fano-type interference mechanism, using the amplitude mode model.

High Quantum Efficiencies in Polymer Solar Cells at Energy Losses below 0.6 eV

Diketopyrrolopyrrole-based conjugated polymers bridged with thiazole units and different donors have been designed for polymer solar cells. Quantum efficiencies above 50% have been achieved with energy loss between optical band gap and open-circuit voltage below 0.6 eV.

Optimizing polymer tandem solar cells

Optimized tandem solar cells based on wide-and small-bandgap polymer semiconductor cells reach an efficiency of 4.9%. In this tandem cell the short-circuit current exceeds that of the current-limiting subcell. The recombination layer that connects the two subcells does not impose important losses.

Diketopyrrolopyrrole polymers for organic solar cells

Conjugated polymers have been extensively studied for application in organic solar cells. In designing new polymers, particular attention has been given to tuning the absorption spectrum, molecular energy levels, crystallinity, and charge carrier mobility to enhance performance. As a result, the power conversion efficiencies (PCEs) of solar cells based on conjugated polymers as electron donor and fullerene derivatives as electron acceptor have exceeded 10% in single-junction and 11% in multijunction devices. Despite these efforts, it is notoriously difficult to establish thorough structure-property relationships that will be required to further optimize existing high-performance polymers to their intrinsic limits. In this Account, we highlight progress on the development and our understanding of diketopyrrolopyrrole (DPP) based conjugated polymers for polymer solar cells. The DPP moiety is strongly electron withdrawing and its polar nature enhances the tendency of DPP-based polymers to crystallize. As a result, DPP-based conjugated polymers often exhibit an advantageously broad and tunable optical absorption, up to 1000 nm, and high mobilities for holes and electrons, which can result in high photocurrents and good fill factors in solar cells. Here we focus on the structural modifications applied to DPP polymers and rationalize and explain the relationships between chemical structure and organic photovoltaic performance. The DPP polymers can be tuned via their aromatic substituents, their alkyl side chains, and the nature of the π-conjugated segment linking the units along the polymer chain. We show that these building blocks work together in determining the molecular conformation, the optical properties, the charge carrier mobility, and the solubility of the polymer. We identify the latter as a decisive parameter for DPP-based organic solar cells because it regulates the diameter of the semicrystalline DPP polymer fibers that form in the photovoltaic blends with fullerenes via solution processing. The width of these fibers and the photon energy loss, defined as the energy difference between optical band gap and open-circuit voltage, together govern to a large extent the quantum efficiency for charge generation in these blends and thereby the power conversion efficiency of the photovoltaic devices. Lowering the photon energy loss and maintaining a high quantum yield for charge generation is identified as a major pathway to enhance the performance of organic solar cells. This can be achieved by controlling the structural purity of the materials and further control over morphology formation. We hope that this Account contributes to improved design strategies of DPP polymers that are required to realize new breakthroughs in organic solar cell performance in the future.