Jeffrey M. Mativetsky

Guiding Crystallization around Bends and Sharp Corners

Control over the molecular orientation in organic thin films is demonstrated with precise in-plane spatial resolution over large areas. By exploiting the differential crystallization rates on substrates with different surface energies, the radial symmetry of spherulitic growth can be disrupted by preferentially selecting the molecular orientations that promote growth along the paths of the underlying patterns.

Quantifying resistances across nanoscale low- and high-angle interspherulite boundaries in solution-processed organic semiconductor thin films.

The nanoscale boundaries formed when neighboring spherulites impinge in polycrystalline, solution-processed organic semiconductor thin films act as bottlenecks to charge transport, significantly reducing organic thin-film transistor mobility in devices comprising spherulitic thin films as the active layers. These interspherulite boundaries (ISBs) are structurally complex, with varying angles of molecular orientation mismatch along their lengths. We have successfully engineered exclusively low- and exclusively high-angle ISBs to elucidate how the angle of molecular orientation mismatch at ISBs affects their resistivities in triethylsilylethynyl anthradithiophene thin films. Conductive AFM and four-probe measurements reveal that current flow is unaffected by the presence of low-angle ISBs, whereas current flow is significantly disrupted across high-angle ISBs. In the latter case, we estimate the resistivity to be 22 MΩμm(2)/width of the ISB, only less than a quarter of the resistivity measured across low-angle grain boundaries in thermally evaporated sexithiophene thin films. This discrepancy in resistivities across ISBs in solution-processed organic semiconductor thin films and grain boundaries in thermally evaporated organic semiconductor thin films likely arises from inherent differences in the nature of film formation in the respective systems.

Elucidating the nanoscale origins of organic electronic function by conductive atomic force microscopy

Electronic and optoelectronic devices comprising organic materials are highly promising for mechanically flexible and low-cost applications. In recent years, conductive atomic force microscopy (C-AFM) has played a significant part in deciphering the nanoscopic and mesoscopic origins of organic electronic function. C-AFM is uniquely capable of measuring local electrical properties with nanoscale resolution; moreover, in conjunction with complementary atomic force microscope modes, C-AFM enables simultaneous mapping of nanoscale structure and electrical function. This feature article highlights recent progress in applying C-AFM to characterize organic electronic systems including self-assembled monolayers, graphene and related materials, organic semiconductors, and organic photovoltaic heterojunctions.

Charge Transport Over Multiple Length Scales in Supramolecular Fiber Transistors: Single Fiber Versus Ensemble Performance

Self-assembled organic fibers combine facile solution processing with the performance benefits of single crystals. Here, the first evidence is shown of band-like transport in an n-type solution-processed small molecule system, a limited role of shallow traps, and a single fiber electron mobility that is several orders of magnitude higher than that measured in fiber ensembles or spin-cast films.

Supramolecular Approaches to Nanoscale Morphological Control in Organic Solar Cells

Having recently surpassed 10% efficiency, solar cells based on organic molecules are poised to become a viable low-cost clean energy source with the added advantages of mechanical flexibility and light weight. The best-performing organic solar cells rely on a nanostructured active layer morphology consisting of a complex organization of electron donating and electron accepting molecules. Although much progress has been made in designing new donor and acceptor molecules, rational control over active layer morphology remains a central challenge. Long-term device stability is another important consideration that needs to be addressed. This review highlights supramolecular strategies for generating highly stable nanostructured organic photovoltaic active materials by design.

Mapping the Competition between Exciton Dissociation and Charge Transport in Organic Solar Cells

The competition between exciton dissociation and charge transport in organic solar cells comprising poly(3-hexylthiophene) [P3HT] and phenyl-C61-butyric acid methyl ester [PCBM] is investigated by correlated scanning confocal photoluminescence and photocurrent microscopies. Contrary to the general expectation that higher photoluminescence quenching is indicative of higher photocurrent, microscale mapping of bulk-heterojunction solar-cell devices shows that photoluminescence quenching and photocurrent can be inversely proportional to one another. To understand this phenomenon, we construct a model system by selectively laminating a PCBM layer onto a P3HT film to form a PCBM/P3HT planar junction on half of the device and a P3HT single junction on the other half. Upon thermal annealing to allow for interdiffusion of PCBM into P3HT, an inverse relationship between photoluminescence quenching and photocurrent is observed at the boundary between the PCBM/P3HT junction and P3HT layer. Incorporation of PCBM in P3HT works to increase photoluminescence quenching, consistent with efficient charge separation, but conductive atomic force microscopy measurements reveal that PCBM acts to decrease P3HT hole mobility, limiting the efficiency of charge transport. This suggests that photoluminescence-quenching measurements should be used with caution in evaluating new organic materials for organic solar cells.

High-resolution charge carrier mobility mapping of heterogeneous organic semiconductors

Organic electronic device performance is contingent on charge transport across a heterogeneous landscape of structural features. Methods are therefore needed to unravel the effects of local structure on overall electrical performance. Using conductive atomic force microscopy, we construct high-resolution out-of-plane hole mobility maps from arrays of 5000 to 16 000 current-voltage curves. To demonstrate the efficacy of this non-invasive approach for quantifying and mapping local differences in electrical performance due to structural heterogeneities, we investigate two thin film test systems, one bearing a heterogeneous crystal structure [solvent vapor annealed 5,11-Bis(triethylsilylethynyl)anthradithiophene (TES-ADT)—a small molecule organic semiconductor] and one bearing a heterogeneous chemical composition [p-DTS(FBTTh2)2:PC71BM—a high-performance organic photovoltaic active layer]. TES-ADT shows nearly an order of magnitude difference in hole mobility between semicrystalline and crystalline areas, alo...

Targeted deposition of organic semiconductor stripes onto rigid, flexible, and three-dimensional substrates

Efficient solution-based growth of electronic materials is needed to enable low-cost wearable electronics, medical sensors, soft robotics, and energy harvesting technologies. In this study, a wetting-mediated two-phase dip coating method is developed to deposit high-performance organic semiconductor stripes at pre-specified locations on rigid, flexible, and three-dimensional substrates. This approach produces highly-oriented 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) crystallites, leading to hole mobilities up to 0.83 cm2 V−1 s−1 along the crystallite axis. The deposition method requires minimal amounts of starting material (4 μL per centimeter of substrate length) and can easily be scaled for deposition onto large (meter-scale) substrates. Wetting-mediated two-phase dip coating also enables the targeted deposition of organic semiconductors onto folded and complex three-dimensional substrates creating new opportunities for unconventional electronic applications.

Effective charge collection area during conductive and photoconductive atomic force microscopy

Conductive atomic force microscopy (C-AFM) has been widely used to map the nanoscale electrical properties of conducting polymers, nanomaterials, and organic electronic devices. While these measurements provide valuable insight into the spatial dependence of electrical performance, reported current densities and electrical conductivities measured by C-AFM are consistently much higher than those measured at the macroscopic scale. Here, we demonstrate that these anomalously high current densities and conductivities arise from ignoring current spreading and hence underestimating the current-carrying area. We present a simple experimental means of estimating the effective charge collection area during C-AFM measurements. Using semiconducting polymer poly(3-hexylthiophene) films as a test case, we find that the effective charge collection area can be as much as three orders of magnitude larger than the mechanical contact area between the probe and the film. Calibrated conductivity maps are obtained, with a quantitative correspondence with accepted values, and C-AFM photocurrent measurements of a nanostructured hybrid organic-inorganic solar cell active layer yield short-circuit current densities that match those reported for macroscopic devices. Finally, we address the observation that current spreading increases the effective charge collection area beyond the size of the probe-sample contact but does not preclude an imaging resolution below 10 nm.Conductive atomic force microscopy (C-AFM) has been widely used to map the nanoscale electrical properties of conducting polymers, nanomaterials, and organic electronic devices. While these measurements provide valuable insight into the spatial dependence of electrical performance, reported current densities and electrical conductivities measured by C-AFM are consistently much higher than those measured at the macroscopic scale. Here, we demonstrate that these anomalously high current densities and conductivities arise from ignoring current spreading and hence underestimating the current-carrying area. We present a simple experimental means of estimating the effective charge collection area during C-AFM measurements. Using semiconducting polymer poly(3-hexylthiophene) films as a test case, we find that the effective charge collection area can be as much as three orders of magnitude larger than the mechanical contact area between the probe and the film. Calibrated conductivity maps are obtained, with a qua...

An air gap moderates the performance of nanowire array transistors

Solution-processed nanowires are promising for low-cost and flexible electronics. When depositing nanowires from solution, due to stacking of the nanowires, an air gap exists between the substrate and much of the active material. Here, using confocal Raman spectroscopy, we quantify the thickness of the air gap in transistors comprising organic semiconductor nanowires. The average air gap thickness is found to be unexpectedly large, being at least three times larger than the nanowire diameter, leading to a significant impact on transistor performance. The air gap acts as an additional dielectric layer that reduces the accumulation of charge carriers due to a gate voltage. Conventional determination of the charge carrier mobility ignores the presence of an air gap, resulting in an overestimate of charge carrier accumulation and an underestimate of charge carrier mobility. It is shown that the larger the air gap, the larger the mobility correction (which can be greater than an order of magnitude) and the larger the degradation in on-off current ratio. These results demonstrate the importance of minimizing the air gap and of taking the air gap into consideration when analyzing the electrical performance of transistors consisting of stacked nanowires. This finding is applicable to all types of stacked one-dimensional materials including organic and inorganic nanowires, and carbon nanotubes.