Detlef-M. Smilgies

A Bicontinuous Double Gyroid Hybrid Solar Cell

We report the first successful application of an ordered bicontinuous gyroid semiconducting network in a hybrid bulk heterojunction solar cell. The freestanding gyroid network is fabricated by electrochemical deposition into the 10 nm wide voided channels of a self-assembled, selectively degradable block copolymer film. The highly ordered pore structure is ideal for uniform infiltration of an organic hole transporting material, and solid-state dye-sensitized solar cells only 400 nm thick exhibit up to 1.7% power conversion efficiency. This patterning technique can be readily extended to other promising heterojunction systems and is a major step toward realizing the full potential of self-assembly in the next generation of device technologies.

Scherrer grain-size analysis adapted to grazing-incidence scattering with area detectors

Ever since its formulation, the Scherrer formula has been the workhorse for quantifying finite size effects in X-ray scattering. Various aspects of Scherrer-type grain-size analysis are discussed with regard to the characterization of thin films with grazing-incidence scattering methods utilizing area detectors. After a brief review of the basic features of Scherrer analysis, a description of resolution-limiting factors in grazing-incidence scattering geometry is provided. As an application, the CHESS D1 beamline is characterized for typical scattering modes covering length scales from the molecular scale to the nanoscale.

High-Lamellar Ordering and Amorphous-Like π-Network in Short-Chain Thiazolothiazole−Thiophene Copolymers Lead to High Mobilities

Owing to their superior transport properties, poly(alkylthiophenes) and their derivatives emerged as one of the most widely studied semiconducting polymers with potential applications in organic electronics. It is now generally acknowledged that one of the particularly effective ways to increase the carrier mobility in these materials is by increasing the length of the conjugated backbones. Some recent reports suggest also that carrier mobilities can be further enhanced by highly crystalline arrangement (and interdigitation) of alkyl side chains possibly because it promotes the formation of extensive layered structures favorable for carrier transport. Results presented here demonstrate that, surprisingly, none of these factors are actually necessary for good electronic performance of polythiophene-like systems. Thiophene-based semiconducting polymers bearing thiazolothiazole unit (PTzQT) described here were shown to have very high carrier mobilities (approximately 0.3 cm(2)/Vs) despite their low molecular weight and uneven spacing of alkyl side chains, which suppressed high side chain crystallinity/interdigitation as revealed by thermal analysis and X-ray scattering. The highly disordered nature of these materials extended to the nanoscale level as evident from atomic force microscopy images, which have shown only the presence of small domains packed into isotropic amorphous-like superstructures with lateral correlation lengths increasing with the length of alkyl side chains. The observed concomitant increase of carrier mobilities points to the possible role of characteristic length of surface roughness as the key parameter controlling carrier transport in disordered, noninterdigitating systems.

Tetrathienoacene Copolymers As High Mobility, Soluble Organic Semiconductors

Increasing the rigidity of the thiophene monomer through the use of an alkyl-substituted core that consists of four fused thiophene rings is shown to be a promising route toward high-performance organic semiconductors. We report on a dialkylated tetrathienoacene copolymer that can be deposited from solution to yield ordered films with a short pi-pi distance of 3.76 A and with a field-effect hole mobility that exceeds 0.3 cm2/V.s. This polymer enables simple transistor fabrication at relatively low temperatures, which is particularly important for the realization of large-area, mechanically flexible electronics.

Reduction in the surface energy of liquid interfaces at short length scales

Liquid–vapour interfaces, particularly those involving water, are common in both natural and artificial environments. They were first described as regions of continuous variation of density, caused by density fluctuations within the bulk phases. In contrast, the more recent capillary-wave model assumes a step-like local density profile across the liquid–vapour interface, whose width is the result of the propagation of thermally excited capillary waves. The model has been validated for length scales of tenths of micrometres and larger, but the structure of liquid surfaces on submicrometre length scales—where the capillary theory is expected to break down—remains poorly understood. Here we report grazing-incidence X-ray scattering experiments that allow for a complete determination of the free surface structure and surface energy for water and a range of organic liquids. We observe a large decrease of up to 75% in the surface energy of submicrometre waves that cannot be explained by capillary theory, but is in accord with the effects arising from the non-locality of attractive intermolecule interactions as predicted by a recent density functional theory. Our data, and the results of comparable measurements on liquid solutions, metallic alloys, surfactants, lipids and wetting films should thus provide a stringent test for any new theories that attempt to describe the structure of liquid interfaces with nanometre-scale resolution.

Crystallization Kinetics of Organic–Inorganic Trihalide Perovskites and the Role of the Lead Anion in Crystal Growth

Methylammonium lead halide perovskite solar cells continue to excite the research community due to their rapidly increasing performance which, in large part, is due to improvements in film morphology. The next step in this progression is control of the crystal morphology which requires a better fundamental understanding of the crystal growth. In this study we use in situ X-ray scattering data to study isothermal transformations of perovskite films derived from chloride, iodide, nitrate, and acetate lead salts. Using established models we determine the activation energy for crystallization and find that it changes as a function of the lead salt. Further analysis enabled determination of the precursor composition and showed that the primary step in perovskite formation is removal of excess organic salt from the precursor. This understanding suggests that careful choice of the lead salt will aid in controlling crystal growth, leading to superior films and better performing solar cells.

Controlling Nanocrystal Superlattice Symmetry and Shape-Anisotropic Interactions through Variable Ligand Surface Coverage

The assembly of colloidal nanocrystals (NCs) into superstructures with long-range translational and orientational order is sensitive to the molecular interactions between ligands bound to the NC surface. We illustrate how ligand coverage on colloidal PbS NCs can be exploited as a tunable parameter to direct the self-assembly of superlattices with predefined symmetry. We show that PbS NCs with dense ligand coverage assemble into face-centered cubic (fcc) superlattices whereas NCs with sparse ligand coverage assemble into body-centered cubic (bcc) superlattices which also exhibit orientational ordering of NCs in their lattice sites. Surface chemistry characterization combined with density functional theory calculations suggest that the loss of ligands occurs preferentially on {100} than on reconstructed {111} NC facets. The resulting anisotropic ligand distribution amplifies the role of NC shape in the assembly and leads to the formation of superlattices with translational and orientational order.

Order Parameters and Areas in Fluid-Phase Oriented Lipid Membranes Using Wide Angle X-Ray Scattering

We used wide angle x-ray scattering (WAXS) from stacks of oriented lipid bilayers to measure chain orientational order parameters and lipid areas in model membranes consisting of mixtures of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC)/cholesterol and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC)/cholesterol in fluid phases. The addition of 40% cholesterol to either DOPC or DPPC changes the WAXS pattern due to an increase in acyl chain orientational order, which is one of the main properties distinguishing the cholesterol-rich liquid-ordered (Lo) phase from the liquid-disordered (Ld) phase. In contrast, powder x-ray data from multilamellar vesicles does not yield information about orientational order, and the scattering from the Lo and Ld phases looks similar. An analytical model to describe the relationship between the chain orientational distribution and WAXS data was used to obtain an average orientational order parameter, S(x-ray). When 40% cholesterol is added to either DOPC or DPPC, S(x-ray) more than doubles, consistent with previous NMR order parameter measurements. By combining information about the average chain orientation with the chain-chain correlation spacing, we extended a commonly used method for calculating areas for gel-phase lipids to fluid-phase lipids and obtained agreement to within 5% of literature values.

Solvent Additive Effects on Small Molecule Crystallization in Bulk Heterojunction Solar Cells Probed During Spin Casting

Solvent additive processing can lead to drastic improvements in the power conversion efficiency (PCE) in solution processable small molecule (SPSM) bulk heterojunction solar cells. In situ grazing incidence wide-angle X-ray scattering is used to investigate the kinetics of crystallite formation during and shortly after spin casting. The additive is shown to have a complex effect on structural evolution invoking polymorphism and enhanced crystalline quality of the donor SPSM.

Alkylsubstituted Thienothiophene Semiconducting Materials: Structure−Property Relationships

A family of conjugated polymers with fused structures consisting of three to five thiophene rings and with the same alkyl side chains has been synthesized as a means to understand structure-property relationships. All three polymers showed well-extended conjugation through the polymer backbone. Ionization potentials (IP) ranged from 5.15 to 5.21 eV; these large values are indicative of their excellent oxidative stability. X-ray diffraction and AFM studies suggest that the polymer with the even number of fused thiophene rings forms a tight crystalline structure due to its tilted side chain arrangement. On the other hand, the polymers with the odd number of fused thiophene rings packed more loosely. Characterization in a field-effect transistor configuration showed that the mobility of the polymer with the even number of rings is 1 order of magnitude higher than its odd-numbered counterparts. Through this structure-property study, we demonstrate that proper design of the molecules and properly arranged side chain positions on the polymer backbone can greatly enhance polymer electronic properties.