Michael F. Toney

Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts

Electrocatalysis will play a key role in future energy conversion and storage technologies, such as water electrolysers, fuel cells and metal-air batteries. Molecular interactions between chemical reactants and the catalytic surface control the activity and efficiency, and hence need to be optimized; however, generalized experimental strategies to do so are scarce. Here we show how lattice strain can be used experimentally to tune the catalytic activity of dealloyed bimetallic nanoparticles for the oxygen-reduction reaction, a key barrier to the application of fuel cells and metal-air batteries. We demonstrate the core-shell structure of the catalyst and clarify the mechanistic origin of its activity. The platinum-rich shell exhibits compressive strain, which results in a shift of the electronic band structure of platinum and weakening chemisorption of oxygenated species. We combine synthesis, measurements and an understanding of strain from theory to generate a reactivity-strain relationship that provides guidelines for tuning electrocatalytic activity.

High K/sub u/ materials approach to 100 Gbits/in/sup 2/

High K/sub u/, uniaxial magnetocrystalline anisotropy, materials are generally attractive for ultrahigh density magnetic recording applications as they allow smaller, thermally stable media grains. Prominent candidates are rare-earth transition metals (Co/sub 5/Sm,...), and tetragonal intermetallic compounds (L1/sub 0/ phases FePt, CoPtY,...), which have 20-40 times higher K/sub u/ than todays hexagonal Co-alloy based media. This allows for about 3 times smaller grain diameters, D, and a potential 10-fold areal density increase (/spl prop/1/D/sup 2/), well beyond the currently projected 40-100 Gbits/in/sup 2/ mark, Realization of such densities will depend on a large number of factors, not all related to solving media microstructure problems, In particular it is at present not known how to record into such media, which may require write fields in the order of 10-100 kOe. Despite this unsolved problem, there is considerable interest in high Ku alternative media, both for longitudinal and perpendicular recording. Activities in this area will be reviewed and data on sputtered and evaporated thin FePt films, with coercivities exceeding 10000 Oe will be presented.

A general relationship between disorder, aggregation and charge transport in conjugated polymers

Conjugated polymer chains have many degrees of conformational freedom and interact weakly with each other, resulting in complex microstructures in the solid state. Understanding charge transport in such systems, which have amorphous and ordered phases exhibiting varying degrees of order, has proved difficult owing to the contribution of electronic processes at various length scales. The growing technological appeal of these semiconductors makes such fundamental knowledge extremely important for materials and process design. We propose a unified model of how charge carriers travel in conjugated polymer films. We show that in high-molecular-weight semiconducting polymers the limiting charge transport step is trapping caused by lattice disorder, and that short-range intermolecular aggregation is sufficient for efficient long-range charge transport. This generalization explains the seemingly contradicting high performance of recently reported, poorly ordered polymers and suggests molecular design strategies to further improve the performance of future generations of organic electronic materials.

Tuning charge transport in solution-sheared organic semiconductors using lattice strain

Circuits based on organic semiconductors are being actively explored for flexible, transparent and low-cost electronic applications. But to realize such applications, the charge carrier mobilities of solution-processed organic semiconductors must be improved. For inorganic semiconductors, a general method of increasing charge carrier mobility is to introduce strain within the crystal lattice. Here we describe a solution-processing technique for organic semiconductors in which lattice strain is used to increase charge carrier mobilities by introducing greater electron orbital overlap between the component molecules. For organic semiconductors, the spacing between cofacially stacked, conjugated backbones (the π–π stacking distance) greatly influences electron orbital overlap and therefore mobility. Using our method to incrementally introduce lattice strain, we alter the π–π stacking distance of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-pentacene) from 3.33 Å to 3.08 Å. We believe that 3.08 Å is the shortest π–π stacking distance that has been achieved in an organic semiconductor crystal lattice (although a π–π distance of 3.04 Å has been achieved through intramolecular bonding). The positive charge carrier (hole) mobility in TIPS-pentacene transistors increased from 0.8 cm2 V−1 s−1 for unstrained films to a high mobility of 4.6 cm2 V−1 s−1 for a strained film. Using solution processing to modify molecular packing through lattice strain should aid the development of high-performance, low-cost organic semiconducting devices.

Ultra-high mobility transparent organic thin film transistors grown by an off-centre spin-coating method

Organic semiconductors with higher carrier mobility and better transparency have been actively pursued for numerous applications, such as flat-panel display backplane and sensor arrays. The carrier mobility is an important figure of merit and is sensitively influenced by the crystallinity and the molecular arrangement in a crystal lattice. Here we describe the growth of a highly aligned meta-stable structure of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) from a blended solution of C8-BTBT and polystyrene by using a novel off-centre spin-coating method. Combined with a vertical phase separation of the blend, the highly aligned, meta-stable C8-BTBT films provide a significantly increased thin film transistor hole mobility up to 43 cm(2) Vs(-1) (25 cm(2) Vs(-1) on average), which is the highest value reported to date for all organic molecules. The resulting transistors show high transparency of >90% over the visible spectrum, indicating their potential for transparent, high-performance organic electronics.

Quantitative determination of organic semiconductor microstructure from the molecular to device scale

The authors would like to thank M. Chabinyc, H. Ade, B. Collins, R. Noriega, K. Vandewal, and D. Duong for fruitful discussions in the preparation of this review. Stanford Synchrotron Radiation Lightsource (SSRL) is a national user facility operated by Stanford University on behalf of the U.S. Department of Energy, Office of Basic Energy Sciences. This publication was partially supported by the Center for Advanced Molecular Photovoltaics (Award No. KUS-C1-015-21), made by King Abdullah University of Science and Technology (KAUST).

Siloxane-Terminated Solubilizing Side Chains: Bringing Conjugated Polymer Backbones Closer and Boosting Hole Mobilities in Thin-Film Transistors

We introduce a novel siloxane-terminated solubilizing group and demonstrate its effectiveness as a side chain in an isoindigo-based conjugated polymer. An average hole mobility of 2.00 cm(2) V(-1) s(-1) (with a maximum mobility of 2.48 cm(2) V(-1) s(-1)), was obtained from solution-processed thin-film transistors, one of the highest mobilities reported to date. In contrast, the reference polymer with a branched alkyl side chain gave an average hole mobility of 0.30 cm(2) V(-1) s(-1) and a maximum mobility of 0.57 cm(2) V(-1) s(-1). This is largely explained by the polymer packing: our new polymer exhibited a π-π stacking distance of 3.58 Å, while the reference polymer showed a distance of 3.76 Å.

Side-Chain Tunability of Furan-Containing Low-Band-Gap Polymers Provides Control of Structural Order in Efficient Solar Cells

The solution-processability of conjugated polymers in organic solvents has classically been achieved by modulating the size and branching of alkyl substituents appended to the backbone. However, these substituents impact structural order and charge transport properties in thin-film devices. As a result, a trade-off must be found between material solubility and insulating alkyl content. It was recently shown that the substitution of furan for thiophene in the backbone of the polymer PDPP2FT significantly improves polymer solubility, allowing for the use of shorter branched side chains while maintaining high device efficiency. In this report, we use PDPP2FT to demonstrate that linear alkyl side chains can be used to promote thin-film nanostructural order. In particular, linear side chains are shown to shorten π-π stacking distances between backbones and increase the correlation lengths of both π-π stacking and lamellar spacing, leading to a substantial increase in the efficiency of bulk heterojunction solar cells.

Crystalline Ultrasmooth Self-Assembled Monolayers of Alkylsilanes for Organic Field-Effect Transistors

Crystalline self-assembled monolayers (SAMs) of organosilane compounds such as octadecyltrimethoxysilane (OTMS) and octadecyltrichlorosilane (OTCS) were deposited by a simple, spin-casting technique onto Si/SiO(2) substrates. Fabrication of the OTMS SAMs and characterization using ellipsometry, contact angle, atomic force microscopy (AFM), grazing angle attenuated total reflectance Fourier transform infrared (GATR-FTIR) spectroscopy and grazing incidence X-ray diffraction (GIXD) are described. The characterization confirms that these monolayers exhibit a well-packed crystalline phase and a remarkably high degree of smoothness. Semiconductors deposited by vapor deposition onto the crystalline OTS SAM grow in a favorable two-dimensional layered growth manner which is generally preferred morphologically for high charge carrier transport. On the OTMS SAM treated dielectric, pentacene OFETs showed hole mobilities as high as 3.0 cm(2)/V x s, while electron mobilities as high as 5.3 cm(2)/V x s were demonstrated for C(60).

The Influence of Poly(3-Hexylthiophene) Regioregularity on Fullerene-Composite Solar Cell Performance

A comparison of three samples of poly(3-hexylthiophene) having regioregularities of 86, 90, and 96% is used to elucidate the effect of regioregularity on polymer-fullerene-composite solar cell performance. It is observed that polymer samples with lower regioregularity are capable of generating fullerene composites that exhibit superior thermal stability. The enhanced thermal stability of the composites is attributed to a lower driving force for polymer crystallization in the less regioregular polymer samples, which is supported with two-dimensional grazing incidence X-ray scattering and differential scanning calorimetry measurements. Furthermore, it is demonstrated that all three polymer samples are capable of generating solar cells with equivalent peak efficiencies of approximately 4% in blends with [6,6]-phenyl-C61-butyric acid methyl ester. While it may be non-intuitive that polymers with lower regioregularity can exhibit higher efficiencies, it is observed that the charge-carrier mobility of the three polymers is on the same order of magnitude (10(-4) cm2 V(-1) s(-1)) when measured from the space-charge-limited current, suggesting that highly regioregular and crystalline polythiophenes are not required in order to effectively transport charges in polymer solar cells. Overall, these results suggest a design principle for semicrystalline conjugated polymers in fullerene-composite solar cells in which crystallization-driven phase separation can be dramatically suppressed via the introduction of a controlled amount of disorder into the polymer backbone.