Enhancing Photovoltaic Performance Using an All‐Conjugated Random Copolymer to Tailor Bulk and Interfacial Morphology of the P3HT:ICBA Active Layer

Bulk heterojunction (BHJ) solar cells are fabricated using active material blends of poly(3‐hexylthiophene) (P3HT) donor, indene‐C₆₀ bisadduct (ICBA) acceptor, and an all‐conjugated random copolymer (RCP) additive. By optimizing RCP loading, power conversion efficiencies (PCEs) up to 20% higher than those of a binary P3HT:ICBA mixture are achieved. The improved device characteristics are rationalized in terms of the differences between the photoactive thin film morphologies. Energy‐filtered transmission electron micro­scopy reveals that incorporation of the RCP improves the degree of structural order of the BHJ fibrillar network and increases the extent of microphase separation between P3HT and ICBA. Additionally, a combination of atomic force microscopy and X‐ray photoelectron spectroscopy analysis indicates segregation of the RCP at the free interface, leading to a shift in the surface potentials measured by Kelvin probe force microscopy. These changes, both in the bulk morphology and in the interfacial composition/energetics, are correlated to improved carrier collection efficiency due to a reduction of non‐geminate recombination, which is measured by charge extraction of photo­generated carriers by linearly increasing voltage.     

Ortho‐ vs Bay‐Functionalization: A Comparative Study on Tetracyano‐Terrylenediimides

In this paper n‐type semiconductors synthesized via selective fourfold cyanation of the ortho‐ and bay‐positions (2,5,10,13‐ and 1,6,9,14‐positions respectively) of teyrrylenediimides are reported. A detailed study about the impact of the diverse functionalization topologies on the optoelectronic properties, self‐organization from solution, solid‐state packing, and charge carrier transport in field‐effect transistors is presented. The ortho‐substitution preserves the planarity of the core and favors high order in solution processed films. However, the strong intermolecular interactions lead to a microstructure with large aggregates and pronounced grain boundaries which lower the charge carrier transport in transistors. In contrast, the well‐soluble bay‐functionalized terrylenediimide forms only disordered films which surprisingly result in n‐type average mobilities of 0.17 cm²/Vs after drop‐casting with similar values in air. Processing by solvent vapor diffusion enhances the transport to 0.65 cm²/Vs by slight improvement of the order and surface arrangement of the molecules. This mobility is comparable to highest n‐type conductivities measured for solution processed PDI derivatives demonstrating the high potential of TDI‐based semiconductors.     

Effects of PCBM concentration on the electrical properties of the Au/P3HT:PCBM/n-Si (MPS) Schottky barrier diodes

In this study, the gold/poly(3-hexylthiophene):[6,6]-phenyl C61 butyric acid methyl ester/n-type silicon (Au/P3HT:PCBM/n-Si) metal–polymer–semiconductor (MPS) Schottky barrier diodes (SBDs) were investigated in terms of the effects of PCBM concentration on the electrical parameters. The forward and reverse bias current–voltage (I–V) characteristics of the Au/P3HT:PCBM/n-Si MPS SBDs fabricated by using the different P3HT:PCBM mass ratios were studied in the dark, at room temperature. The main electrical parameters, such as ideality factor (n), barrier height (Φ_B0), series resistance (R_s), shunt resistance (R_sh), and density of interface states (N_ss) were determined from I–V characteristics for the different P3HT:PCBM mass ratios (2:1, 6:1 and 10:1) used diodes. The values of n, R_s, Φ_B0, and N_ss were reduced, while the carrier mobility and current were increased, by increasing the PCBM concentration in the P3HT:PCBM organic blend layer. The ideal values of electrical parameters were obtained for 2:1 P3HT:PCBM mass ratio used diode. This shows that the electrical properties of MPS diodes strongly depend on the PCBM concentration of the P3HT:PCBM organic layer. Moreover, increasing the PCBM concentration in P3HT:PCBM organic blend layer improves the quality of the Au/P3HT:PCBM/n-Si (MPS) SBDs which enables the fabrication of high-quality electronic and optoelectronic devices.     

Harnessing “Click”‐Type Chemistry for the Preparation of Novel Electronic Materials

Sequence‐independent or “click”‐type chemistry is applied for the preparation of novel π‐conjugated oligomers. A variety of bi‐functional monomers for Wittig–Horner olefination are developed and applied in a sequential protection–deprotection process for the preparation of structurally similar π‐conjugated oligomers. Selected oligomers are incorporated as the organic semiconductors in light‐emitting diodes and a field‐effect transistor, demonstrating the potential of the approach.     

Photovoltaic Devices: High‐Performance Organic Solar Cells with Spray Coated Hole‐Transport and Active Layers (Adv. Funct. Mater. 1/2011)

In this study, we report high performance organic solar cells with spray coated hole‐transport and active layers. With optimized ink formulations we are able to deposit films with controlled thickness and very low surface roughness (<10 nm). Specifically we deposit smooth and uniform 40 nm thick films of poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as well as films composed of a mixture of poly(3‐hexyl thiophene) (P3HT) and the C₆₀‐derivative (6,6)‐phenyl C61‐butyric acid methyl ester (PCBM) with thicknesses in the range 200–250 nm. To control film morphology, formation and thickness, the optimized inks incorporate two solvent systems in order to take advantage of surface tension gradients to create Marangoni flows that enhance the coverage of the substrate and reduce the roughness of the film. Notably, we achieve fill factors above 70% and attribute the improvement to an enhanced P3HT crystallization, which upon optimized post‐drying thermal annealing results in a favorable morphology. As a result, we could extend the thickness of the layer to several hundreds of nanometers without noticing a substantial decrease of the transport properties of the layer. By proper understanding of the spreading and drying dynamics of the inks we achieve spray coated devices with power conversion efficiency of 3.75%, with fill factor, short circuit current and open circuit voltage of 70%, 9.8 mA cm^?2 and 550 mV, respectively.     

Inverted Organic Solar Cells with Sol–Gel Processed High Work‐Function Vanadium Oxide Hole‐Extraction Layers

For large‐scale and high‐throughput production of organic solar cells (OSCs), liquid processing of the functional layers is desired. We demonstrate inverted bulk‐heterojunction organic solar cells (OSCs) with a sol–gel derived V₂O₅ hole‐extraction‐layer on top of the active organic layer. The V₂O₅ layers are prepared in ambient air using Vanadium(V)‐oxitriisopropoxide as precursor. Without any post‐annealing or plasma treatment, a high work function of the V₂O₅ layers is confirmed by both Kelvin probe analysis and ultraviolet photoelectron spectroscopy (UPS). Using UPS and inverse photoelectron spectroscopy (IPES), we show that the electronic structure of the solution processed V₂O₅ layers is similar to that of thermally evaporated V₂O₅ layers which have been exposed to ambient air. Optimization of the sol gel process leads to inverted OSCs with solution based V₂O₅ layers that show power conversion efficiencies similar to that of control devices with V₂O₅ layers prepared in high‐vacuum.     

Photovoltaic Devices: Highly Conductive PEDOT:PSS Electrode with Optimized Solvent and Thermal Post‐Treatment for ITO‐Free Organic Solar Cells (Adv. Funct. Mater. 6/2011)

Highly conductive poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) films as stand‐alone electrodes for organic solar cells have been optimized using a solvent post‐treatment method. The treated PEDOT:PSS films show enhanced conductivities up to 1418 S cm^?1, accompanied by structural and chemical changes. The effect of the solvent treatment on PEDOT:PSS has been investigated in detail and is shown to cause a reduction of insulating PSS in the conductive polymer layer. Using these optimized electrodes, ITO‐free, small molecule organic solar cells with a zinc phthalocyanine (ZnPc):fullerene C₆₀ bulk heterojunction have been produced on glass and PET substrates. The system was further improved by pre‐heating the PEDOT:PSS electrodes, which enhanced the power conversion efficiency to the values obtained for solar cells on ITO electrodes. The results show that optimized PEDOT:PSS with solvent and thermal post‐treatment can be a very promising electrode material for highly efficient flexible ITO‐free organic solar cells.