P3HT-Based Solar Cells: Structural Properties and Photovoltaic Performance

Each year we are bombarded with B.Sc. and Ph.D. applications from students that want to improve the world. They have learned that their future depends on changing the type of fuel we use and that solar energy is our future. The hope and energy of these young people will transform future energy technologies, but it will not happen quickly. Organic photovoltaic devices are easy to sketch, but the materials, processing steps, and ways of measuring the properties of the materials are very complicated. It is not trivial to make a systematic measurement that will change the way other research groups think or practice. In approaching this chapter, we thought about what a new researcher would need to know about organic photovoltaic devices and materials in order to have a good start in the subject. Then, we simplified that to focus on what a new researcher would need to know about poly-3-hexylthiophene:phenyl-C61-butyric acid methyl ester blends (P3HT: PCBM) to make research progress with these materials. This chapter is by no means authoritative or a compendium of all things on P3HT:PCBM. We have selected to explain how the sample fabrication techniques lead to control of morphology and structural features and how these morphological features have specific optical and electronic consequences for organic photovoltaic device applications

Quantifying organic solar cell morphology: A computational study of three-dimensional maps

Establishing how fabrication conditions quantitatively affect the morphology of organic blends opens the possibility of rationally designing higher efficiency materials; yet such a relationship remains elusive. One of the major challenges stems from incomplete three-dimensional representations of morphology, which is due to the difficulties of performing accurate morphological measurements. Recently, three-dimensional measurements of mixed organic layers using electron tomography with high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) provided maps of morphology with high resolution and detail. Using a simple, yet powerful, computational tool kit, these complex 3D datasets are converted into a set of physically meaningful morphology descriptors. These descriptors provide means for converting these large, complicated datasets (∼5 × 107 voxels) into simple, descriptive parameters, enabling a quantitative comparison among morphologies fabricated under different conditions. A set of P3HT:endohedral fullerene bulk-heterojunctions, fabricated under conditions specifically chosen to yield a wide range of morphologies, are examined. The effects of processing conditions and electrode presence on interfacial area, domain size distribution, connectivity, and tortuosity of charge transport paths are herein determined directly from real-space data for the first time. Through this characterization, quantitative insights into the role of processing in morphology are provided, as well as a more complete picture of the consequences of a three-phase morphology. The analysis demonstrates a methodology which can enable a deeper understanding into morphology control. © The Royal Society of Chemistry 2013

Reducing residual stress by selective large-area diode surface heating during laser powder bed fusion additive manufacturing

High residual stresses are typical in additively manufactured metals and can reach levels as high as the yield strength, leading to distortions and even cracks. Here, an in situ method for controlling residual stress during laser powder bed fusion additive manufacturing was demonstrated. By illuminating the surface of a build with homogeneously intense, shaped light from a set of laser diodes, the thermal history was controlled thereby reducing the residual stress in as-built parts. 316L stainless steel bridge-shaped parts were built to characterize the effect of in situ annealing on the residual stress. A reduction in the overall residual stress value of up to 90% was realized without altering the as-built grain structure (no grain growth). Some annealing effects on the cellular-dendritic solidification structure (patterns of higher solute content)occurred in areas that experienced prolonged exposure to elevated temperature. A comparison of the in situ process to conventional post-build annealing demonstrated equivalent stress reduction compared to rule-of-thumb thermal treatments. Use of this method could reduce or remove the need for post processing to remove residual stresses

The effect of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane charge transfer dopants on the conformation and aggregation of poly(3-hexylthiophene)

The effect of the strong electron acceptor, 2,3,5,6-tetrafluoro-7,7,8,8- tetracyanoquinodimethane (F4-TCNQ), on poly(3-hexylthiophene) (P3HT) aggregates is studied. F4-TCNQ is commonly used as a dopant for P3HT, however, relatively little is currently known about its effect on polymer conformation and packing in the presence of fullerenes. Resonance Raman and optical spectra of pristine P3HT or blends with [6,6]-phenyl-C 61-butyric acid methyl ester (PCBM) doped with F4-TCNQ up to ∼10% w/w show a loss of pristine-type P3HT aggregates with increasing dopant concentration. Complexed P3HT chains possess greater backbone planarity due to hole injection which is corroborated from density functional theory (DFT) calculations of oligothiophene surrogates and F4-TCNQ. Morphologies of doped P3HT/PCBM systems are characterized using scanning transmission electron microscopy (STEM) with electron energy loss spectroscopy (EELS) detection and images reveal mixed clusters of P3HT/F4-TCNQ fibril-like domains that increase in size with dopant loading. The apparent preference of F4-TCNQ for P3HT aggregates is attributed to efficient charge separation stemming owing to the more polarizable nature of chains comprising the aggregate π-stack. © 2013 The Royal Society of Chemistry

The effect of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane charge transfer dopants on the conformation and aggregation of poly(3-hexylthiophene)

The effect of the strong electron acceptor, 2,3,5,6-tetrafluoro-7,7,8,8- tetracyanoquinodimethane (F4-TCNQ), on poly(3-hexylthiophene) (P3HT) aggregates is studied. F4-TCNQ is commonly used as a dopant for P3HT, however, relatively little is currently known about its effect on polymer conformation and packing in the presence of fullerenes. Resonance Raman and optical spectra of pristine P3HT or blends with [6,6]-phenyl-C 61-butyric acid methyl ester (PCBM) doped with F4-TCNQ up to ∼10% w/w show a loss of pristine-type P3HT aggregates with increasing dopant concentration. Complexed P3HT chains possess greater backbone planarity due to hole injection which is corroborated from density functional theory (DFT) calculations of oligothiophene surrogates and F4-TCNQ. Morphologies of doped P3HT/PCBM systems are characterized using scanning transmission electron microscopy (STEM) with electron energy loss spectroscopy (EELS) detection and images reveal mixed clusters of P3HT/F4-TCNQ fibril-like domains that increase in size with dopant loading. The apparent preference of F4-TCNQ for P3HT aggregates is attributed to efficient charge separation stemming owing to the more polarizable nature of chains comprising the aggregate π-stack. © 2013 The Royal Society of Chemistry

P3HT:PCBM bulk-heterojunctions: Observing interfacial and charge transfer states with surface photovoltage spectroscopy

Surface photovoltage (SPV) spectra are reported for separate films of (6,6)-phenyl-C61-butyric acid methyl ester (PCBM) and for regioregular and regiorandom poly(3-hexylthiophene) (P3HT):PCBM bulk heterojunctions, as a function of wavelength, film thickness, thermal annealing, and substrate. In PCBM films, two photovoltage features are observed at 1.1-1.4 eV (F1) and 1.4-2.3 eV (F2), which are assigned to excitation of charge transfer states at the interface (F1) and in the bulk (F2) of the film. In BHJ films, five different photovoltage features are observed at 0.75-0.9 eV (F1), 0.9-1.3 eV (F2), 1.3-1.8 eV (F3), 1.8-2.0 eV (F4), and 2.0-2.4 eV (F5). This data can be analyzed on the basis of optical absorbance and fluorescence spectra of the films, and using SPV spectra for PCBM and P3HT only films, and for a BHJ film containing P3HT nanofibers for comparison. SPV features are assigned to states at the polymer-substrate interface (F1 and F2), the P3HT:PCBM charge transfer state (F3), the self-ionized (CT) state of P3HT (F4), and the band gap transition of P3HT (F5). This interpretation is also consistent with molecular orbital energy diagrams and electron microscopy-derived topological maps of the films. Photovoltage sign and substrate dependence can be understood with the depleted semiconductor model. Features F1-4 are caused by polarization of electrostatically bound charge pairs by the built-in electric field at the substrate-BHJ interface, whereas F5 is due to transport of free charge carriers through the film and through the substrate film interface. This work will promote the understanding of photochemical charge generation and transport in organic photovoltaic films. © 2014 American Chemical Society

Material profile influences in bulk-heterojunctions

The morphology in mixed bulk-heterojunction films are compared using three different quantitative measurement techniques. We compare the vertical composition changes using high-angle annular dark-field scanning transmission electron microscopy with electron tomography and neutron and x-ray reflectometry. The three measurement techniques yield qualitatively comparable vertical concentration measurements. The presence of a metal cathode during thermal annealing is observed to alter the fullerene concentration throughout the thickness of the film for all measurements. However, the absolute vertical concentration of fullerene is quantitatively different for the three measurements. The origin of the quantitative measurement differences is discussed. © 2014 Wiley Periodicals, Inc

Comparison of solution-mixed and sequentially processed P3HT:F4TCNQ films: Effect of doping-induced aggregation on film morphology

Doping polymeric semiconductors often drastically reduces the solubility of the polymer, leading to difficulties in processing doped films. Here, we compare optical, electrical, and morphological properties of P3HT films doped with F4TCNQ, both from mixed solutions and using sequential solution processing with orthogonal solvents. We demonstrate that sequential doping occurs rapidly (<1 s), and that the film doping level can be precisely controlled by varying the concentration of the doping solution. Furthermore, the choice of sequential doping solvent controls whether dopant anions are included or excluded from polymer crystallites. Atomic force microscopy (AFM) reveals that sequential doping produces significantly more uniform films on the nanoscale than the mixed-solution method. In addition, we show that mixed-solution doping induces the formation of aggregates even at low doping levels, resulting in drastic changes to film morphology. Sequentially coated films show 3-15 times higher conductivities at a given doping level than solution-doped films, with sequentially doped films processed to exclude dopant anions from polymer crystallites showing the highest conductivities. We propose a mechanism for doping induced aggregation in which the shift of the polymer HOMO level upon aggregation couples ionization and solvation energies. To show that the methodology is widely applicable, we demonstrate that several different polymer:dopant systems can be prepared by sequential doping