Dean M. DeLongchamp

Microstructural Characterization and Charge Transport in Thin Films of Conjugated Polymers

The performance of semiconducting polymers has been steadily increasing in the last 20 years. Improved control over the microstructure of these materials and a deeper understanding of how the microstructure affects charge transport are partially responsible for such trend. The development and widespread use of techniques that allow to characterize the microstructure of semiconducting polymers is therefore instrumental for the advance of these materials. This article is a review of the characterization techniques that provide information used to enhance the understanding of structure/property relationships in semiconducting polymers. In particular, the applications of optical and X-ray spectroscopy, X-ray diffraction, and scanning probe techniques in this context are described.

Molecular Packing of High-Mobility Diketo Pyrrolo-Pyrrole Polymer Semiconductors with Branched Alkyl Side Chains

We describe a series of highly soluble diketo pyrrolo-pyrrole (DPP)-bithiophene copolymers exhibiting field effect hole mobilities up to 0.74 cm(2) V(-1) s(-1), with a common synthetic motif of bulky 2-octyldodecyl side groups on the conjugated backbone. Spectroscopy, diffraction, and microscopy measurements reveal a transition in molecular packing behavior from a preferentially edge-on orientation of the conjugated plane to a preferentially face-on orientation as the attachment density of the side chains increases. Thermal annealing generally reduces both the face-on population and the misoriented edge-on domains. The highest hole mobilities of this series were obtained from edge-on molecular packing and in-plane liquid-crystalline texture, but films with a bimodal orientation distribution and no discernible in-plane texture exhibited surprisingly comparable mobilities. The high hole mobility may therefore arise from the molecular packing feature common to the entire polymer series: backbones that are strictly oriented parallel to the substrate plane and coplanar with other backbones in the same layer.

Molecular origin of high field-effect mobility in an indacenodithiophene–benzothiadiazole copolymer

One of the most inspiring and puzzling developments in the organic electronics community in the last few years has been the emergence of solution-processable semiconducting polymers that lack significant long-range order but outperform the best, high-mobility, ordered semiconducting polymers to date. Here we provide new insights into the charge-transport mechanism in semiconducting polymers and offer new molecular design guidelines by examining a state-of-the-art indacenodithiophene-benzothiadiazole copolymer having field-effect mobility of up to 3.6 cm(2) V(-1) s(-1) with a combination of diffraction and polarizing spectroscopic techniques. Our results reveal that its conjugated planes exhibit a common, comprehensive orientation in both the non-crystalline regions and the ordered crystallites, which is likely to originate from its superior backbone rigidity. We argue that charge transport in high-mobility semiconducting polymers is quasi one-dimensional, that is, predominantly occurring along the backbone, and requires only occasional intermolecular hopping through short π-stacking bridges.

Substrate-dependent interface composition and charge transport in films for organic photovoltaics

The buried interface composition of polymer-fullerene blends is found by near-edge x-ray absorption fine structure spectroscopy to depend on the surface energy of the substrate upon which they are cast. The interface composition determines the type of charge transport measured with thin film transistors. These results have implications for organic photovoltaics device design and the use of transistors to evaluate bulk mobility in blends.

Connecting dopant bond type with electronic structure in n-doped graphene

Robust methods to tune the unique electronic properties of graphene by chemical modification are in great demand due to the potential of the two dimensional material to impact a range of device applications. Here we show that carbon and nitrogen core-level resonant X-ray spectroscopy is a sensitive probe of chemical bonding and electronic structure of chemical dopants introduced in single-sheet graphene films. In conjunction with density functional theory based calculations, we are able to obtain a detailed picture of bond types and electronic structure in graphene doped with nitrogen at the sub-percent level. We show that different N-bond types, including graphitic, pyridinic, and nitrilic, can exist in a single, dilutely N-doped graphene sheet. We show that these various bond types have profoundly different effects on the carrier concentration, indicating that control over the dopant bond type is a crucial requirement in advancing graphene electronics.

Molecular Characterization of Organic Electronic Films

Organic electronics have emerged as a viable competitor to amorphous silicon for the active layer in low-cost electronics. The critical performance of organic electronic materials is closely related to their morphology and molecular packing. Unlike their inorganic counterparts, polymers combine complex repeat unit structure and crystalline disorder. This combination prevents any single technique from being able to uniquely solve the packing arrangement of the molecules. Here, a general methodology for combining multiple, complementary techniques that provide accurate unit cell dimensions and molecular orientation is described. The combination of measurements results in a nearly complete picture of the organic film morphology.

Significant dependence of morphology and charge carrier mobility on substrate surface chemistry in high performance polythiophene semiconductor films

The authors report a significant dependence of the morphology and charge carrier mobility of poly(2,5-bis(3-dodecylthiophene-2-yl)thieno[3,2-b]thiophene) (pBTTT) films on the substrate surface chemistry upon heating into its liquid crystal phase. In contrast with films on bare silicon oxide surfaces, pBTTT films on oxide functionalized with octyltrichlorosilane exhibit substantial increases in the lateral dimensions of molecular terraces from nanometers to micrometers, increased orientational order, and higher charge carrier mobility. The large-scale crystallinity of this polymer plays an important role in the high carrier mobility observed in devices, but renders it more sensitive to substrate surface chemistry than other conjugated polymers.

Correlations between Mechanical and Electrical Properties of Polythiophenes

The elastic moduli of polythiophenes, regioregular poly(3-hexylthiophene) (P3HT) and poly-(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene) (pBTTT), are compared to their field effect mobility showing a proportional trend. The elastic moduli of the films are measured using a buckling-based metrology, and the mobility is determined from the electrical characteristics of bottom contact thin film transistors. Moreover, the crack onset strain of pBTTT films is shown to be less than 2.5%, whereas that of P3HT is greater than 150%. These results show that increased long-range order in polythiophene semiconductors, which is generally thought to be essential for improved charge mobility, can also stiffen and enbrittle the film. This work highlights the critical role of quantitative mechanical property measurements in guiding the development of flexible organic semiconductors.

Structural control of mixed ionic and electronic transport in conducting polymers.

Poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate), PEDOT:PSS, has been utilized for over two decades as a stable, solution-processable hole conductor. While its hole transport properties have been the subject of intense investigation, recent work has turned to PEDOT:PSS as a mixed ionic/electronic conductor in applications including bioelectronics, energy storage and management, and soft robotics. Conducting polymers can efficiently transport both holes and ions when sufficiently hydrated, however, little is known about the role of morphology on mixed conduction. Here, we show that bulk ionic and electronic mobilities are simultaneously affected by processing-induced changes in nano- and meso-scale structure in PEDOT:PSS films. We quantify domain composition, and find that domain purification on addition of dispersion co-solvents limits ion mobility, even while electronic conductivity improves. We show that an optimal morphology allows for the balanced ionic and electronic transport that is critical for prototypical mixed conductor devices. These findings may pave the way for the rational design of polymeric materials and processing routes to enhance devices reliant on mixed conduction.

Nanoscale structure measurements for polymer-fullerene photovoltaics

This review covers methods to measure key aspects of nanoscale structure in organic photovoltaic devices based on polymer-fullerene bulk heterojunctions. The importance of nanoscale structure to the power conversion efficiency and stability of these devices has been recognized, but robust correlations have yet to emerge despite a significant community-wide research investment. Our perspective is that more uniform selection, execution, and interpretation of nanoscale structure measurements will accelerate this endeavor. We will discuss organic bulk heterojunction structural measurements of contemporary interest and importance including vertical stratification, molecular orientation and order, and nanoscale morphology. Specific recommendations are made regarding the technical implementation of some popular techniques, with an eye toward the elimination of artifacts, ambiguous data, and misinterpretation. When possible, topics are highlighted where there is a community consensus on the results of nanoscale structure measurements and how they may relate to organic photovoltaic device performance.