John D. Roehling

Packing Dependent Electronic Coupling in Single Poly(3-hexylthiophene) H- and J-Aggregate Nanofibers

Nanofibers (NFs) of the prototype conjugated polymer, poly(3-hexylthiophene) (P3HT), displaying H- and J-aggregate character are studied using temperature- and pressure-dependent photoluminescence (PL) spectroscopy. Single J-aggregate NF spectra show a decrease of the 0-0/0-1 vibronic intensity ratio from ~2.0 at 300 K to ~1.3 at 4 K. Temperature-dependent PL line shape parameters (i.e., 0-0 energies and 0-0/0-1 intensity ratios) undergo an abrupt change in the range of ~110-130 K suggesting a change in NF chain packing. Pressure-dependent PL lifetimes also show increased contributions from an instrument-limited decay component which is attributed to greater torsional disorder of the P3HT backbone upon decreasing NF volume. It is proposed that the P3HT alkyl side groups change their packing arrangement from a type I to type II configuration causing a decrease in J-aggregate character (lower intrachain order) in both temperature- and pressure-dependent PL spectra. Chain packing dependent exciton and polaron relaxation and recombination dynamics in NF aggregates are next studied using transient absorption spectroscopy (TAS). TAS data reveal faster polaron recombination dynamics in H-type P3HT NFs indicative of interchain delocalization whereas J-type NFs exhibit delayed recombination suggesting that polarons (in addition to excitons) are more delocalized along individual chains. Both time-resolved and steady-state spectra confirm that excitons and polarons in J-type NFs are predominantly intrachain in nature that can acquire interchain character with small structural (chain packing) perturbations.

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.

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.

Direct-Write Optical Patterning of P3HT Films Beyond the Diffraction Limit

Doping-induced solubility control is a patterning technique for semiconducting polymers, which utilizes the reduction in polymer solubility upon p-type doping to provide direct, optical control of film topography and doping level. In situ direct-write patterning and imaging are demonstrated, revealing sub-diffraction-limited topographic features. Photoinduced force microscopy shows that doping level can be optically modulated with similar resolution.

Nanoscale Morphology of PTB7 Based Organic Photovoltaics as a Function of Fullerene Size

High efficiency polymer:fullerene photovoltaic device layers self-assemble with hierarchical features from ångströms to 100’s of nanometers. The feature size, shape, composition, orientation, and order all contribute to device efficiency and are simultaneously difficult to study due to poor contrast between carbon based materials. This study seeks to increase device efficiency and simplify morphology measurements by replacing the typical fullerene acceptor with endohedral fullerene Lu3N@PC80BEH. The metal atoms give excellent scattering contrast for electron beam and x-ray experiments. Additionally, Lu3N@PC80BEH has a lower electron affinity than standard fullerenes, which can raise the open circuit voltage of photovoltaic devices. Electron microscopy techniques are used to produce a detailed account of morphology evolution in mixtures of Lu3N@PC80BEH with the record breaking donor polymer, PTB7 and coated using solvent mixtures. We demonstrate that common solvent additives like 1,8-diiodooctane or chloronapthalene do not improve the morphology of endohedral fullerene devices as expected. The poor device performance is attributed to the lack of mutual miscibility between this particular polymer:fullerene combination and to co-crystallization of Lu3N@PC80BEH with 1,8-diiodooctane. This negative result explains why solvent additives mixtures are not necessarily a morphology cure-all.

Genesis of Delaminated-Zeolite Morphology: 3-D Characterization of Changes by STEM Tomography

Zeolite delamination increases the external surface area available for catalyzing the conversion of bulky molecules, but a fundamental understanding of the delamination process remains unknown. Here we report morphological changes accompanying delamination on the length scale of individual zeolite clusters determined by 3-D imaging in scanning transmission electron microscopy. The results are tomograms that demonstrate delamination as it proceeds on the nanoscale through two distinct key steps: a chemical treatment that leads to a swelled material and a subsequent calcination that leads to curling and peeling off of delaminated zeolite sheets over hundreds of nanometers. These results characterize the direct, local, 3-D morphological changes accompanying delaminated materials synthesis and, with corroboration by mercury porosimetry, provide unique insight into the morphology of these materials, which is difficult to obtain with any other technique.

Advanced 3-D Reconstruction Algorithms for Electron Tomography

htmlabstractElectron tomography in the physical sciences has become a powerful tool for nanomaterial analysis. Recently, electron tomography is finding applications in more beam sensitive materials such as catalysts. For beam sensitive materials, the goal is to acquire the smallest number of images as possible but still maintain an accurate and high resolution 3-D reconstruction. Standard methods of 3D reconstruction, such as weighted back projection (WBP) and simultaneous iterative reconstruction technique (SIRT), are not equipped to handle this lack of information, and create significant blurring. This gives rise to a search for new methods of reconstruction. Two of the recent successful algorithms are the discrete algebraic reconstruction technique (DART) and total variation (TV) minimization within compressed sensing (CS). The DART algorithm uses ART and pairs it with the prior knowledge that there are only a small number (two or three) of different materials in the sample, each corresponding to a different gray value in the reconstruction. An initial reconstruction is computed and rounded to the chosen fixed gray values based on some threshold, and iteratively refined using ART. The method of TV minimization stems from the mathematical theory of compressed sensing and only recently became available due to new algorithms for solving the TV minimization problem. The method considers the characterization of real images and encourages the reconstruction to take larger jumps in gray values to create clear boundaries, hence creating a similar effect to that of DART. The advantage of DART is that an accurate selection of the gray values and the rounding procedure for the reconstruction gives extremely valuable information otherwise not available in any other reconstruction technique. The TV minimization procedure has fewer parameter selections, giving a stable method for reconstruction. Moreover, the introduction of the TV norm has the potential for creating boundaries alternate to what a DART reconstruction would find. Both methods are extremely valuable. In this presentation we discuss the pros and cons of each method, and show examples to illustrate when to use one method over the other. One comparison is shown in Figures 1-2 to demonstrate the differences for a layered zeolite material. This research was funded in part by the DOE BES DE-SC0005822 and the LDRD and Chemical Imaging Initiative programs at PNNL. The Pacific Northwest National Laboratory is operated by Battelle under contract DE-AC05-76RL01830.

Hierarchical spidroin micellar nanoparticles as the fundamental precursors of spider silks

Significance The true physical form of the proteins within the silk glands of spiders that permits storage at very high concentrations rather than as precipitated material prior to being transformed into solid silk fibers remains one of the fundamental mysteries that has limited our ability to produce artificial silks of the quality of natural silks. Here we determine that spider silk proteins are stored as complex micellar nanoparticles composed of assembled subdomains. When extruded during the silk spinning process, these subdomains undergo fibrillization while remaining assembled in micelles. Knowledge of the nanostructured protein assemblies in the dope is critical to the basic understanding of the spinning process and to our ability to mimic the natural material properties in synthetic analogues. Many natural silks produced by spiders and insects are unique materials in their exceptional toughness and tensile strength, while being lightweight and biodegradable–properties that are currently unparalleled in synthetic materials. Myriad approaches have been attempted to prepare artificial silks from recombinant spider silk spidroins but have each failed to achieve the advantageous properties of the natural material. This is because of an incomplete understanding of the in vivo spidroin-to-fiber spinning process and, particularly, because of a lack of knowledge of the true morphological nature of spidroin nanostructures in the precursor dope solution and the mechanisms by which these nanostructures transform into micrometer-scale silk fibers. Herein we determine the physical form of the natural spidroin precursor nanostructures stored within spider glands that seed the formation of their silks and reveal the fundamental structural transformations that occur during the initial stages of extrusion en route to fiber formation. Using a combination of solution phase diffusion NMR and cryogenic transmission electron microscopy (cryo-TEM), we reveal direct evidence that the concentrated spidroin proteins are stored in the silk glands of black widow spiders as complex, hierarchical nanoassemblies (∼300 nm diameter) that are composed of micellar subdomains, substructures that themselves are engaged in the initial nanoscale transformations that occur in response to shear. We find that the established micelle theory of silk fiber precursor storage is incomplete and that the first steps toward liquid crystalline organization during silk spinning involve the fibrillization of nanoscale hierarchical micelle subdomains.

Imaging the Rapid Solidification of Metallic Alloys in the TEM

The macroscopic properties of a metal solidified from a liquid melt are strongly dependent on the final microstructure, which in turn is the result of the solidification conditions. With the growing popularity of laser-based additive manufacturing (AM), there is an increasing need to understand the microstructures that result from rapid solidification processes. Rapidly solidified alloy microstructures are typically far from equilibrium and therefore traditional thermodynamic approaches used to predict structure and composition (i.e., phase diagrams) must be extended to describe these deviations from equilibrium and ensuing metastable states. This work highlights progress toward corroborating predictive (phase-field) modeling capabilities [1] with in situ experimental observations [2] in order to better understand the non-equilibrium structures produced during rapid solidification following laser melting.

Imaging Irreversible Transformations with Movie-Mode Dynamic Transmission Electron Microscopy

In situ transmission electron microscopy (TEM) has been utilized for decades to image materials processes at high spatial resolution. Yet the relevant dynamics of many of these processes often remain elusive, as they unfold too rapidly to discern at small spatial scales using conventional TEM imaging conditions. For example, consider a transformation front moving with a relatively low velocity of 0.1 mm/s. In situ TEM imaging conducted with conventional acquisition rates of 30 frames/s corresponds to a temporal resolution of ~33 ms and, limited by motion blur, provides a spatial resolution of only ~3 μm. Given the rapid microstructural evolution of many types of irreversible transformation fronts—on the order of mm/s to m/s—nanosecond temporal resolutions are required to capture these processes.