Obadiah G. Reid

Polymer Nanowire/Fullerene Bulk Heterojunction Solar Cells: How Nanostructure Determines Photovoltaic Properties

We report studies of bulk heterojunction solar cells composed of self-assembled poly(3-butylthiophene) nanowires (P3BT-nw) as the donor component with a fullerene acceptor. We show that the nanostructure of these devices is the single most important variable determining their performance, and we use a combination of solvent and thermal annealing to control it. A combination of conductive and photoconductive atomic force microscopy provides direct connections between local nanostructure and overall device performance. Films with a dense random web of nanowires cause the fullerene to aggregate in the interstices, giving a quasi-ordered interpenetrating heterojunction with high short-circuit current density (10.58 mA/cm(2)), but relatively low open circuit voltage (520 mV). Films with a low density of nanowires result in a random bulk heterojunction composed of small crystalline PCBM and P3BT phases. Fewer nanowires result in higher open circuit voltage (650 mV) but lower current density (6.02 mA/cm(2)). An average power conversion efficiency of 3.35% was achieved in a structure which balances these factors, with intermediate nanowire density. The best photovoltaic performance would be realized in a material structure which maintains the interpenetrating network of nanowires and fullerene phases (high current density), but avoids the device bridging we observe, and the recombination and shunt losses associated with it (high open-circuit voltage).

Space Charge Limited Current Measurements on Conjugated Polymer Films using Conductive Atomic Force Microscopy

We describe local (~150 nm resolution), quantitative measurements of charge carrier mobility in conjugated polymer films that are commonly used in thin-film transistors and nanostructured solar cells. We measure space charge limited currents (SCLC) through these films using conductive atomic force microscopy (c-AFM) and in macroscopic diodes. The current densities we measure with c-AFM are substantially higher than those observed in planar devices at the same bias. This leads to an overestimation of carrier mobility by up to 3 orders of magnitude when using the standard Mott-Gurney law to fit the c-AFM data. We reconcile this apparent discrepancy between c-AFM and planar device measurements by accounting for the proper tip-sample geometry using finite element simulations of tip-sample currents. We show that a semiempirical scaling factor based on the ratio of the tip contact area diameter to the sample thickness can be used to correct c-AFM current-voltage curves and thus extract mobilities that are in good agreement with values measured in the conventional planar device geometry.

Imaging the Evolution of Nanoscale Photocurrent Collection and Transport Networks during Annealing of Polythiophene/Fullerene Solar Cells

We use photoconductive atomic force microscopy to image nanoscale spatial variations in photocurrent across the surfaces of photovoltaic cells made from blends of the conjugated polymer regioregular poly(3-hexylthiopene) (P3HT) with phenyl-C(61)-butyric acid methyl ester (PCBM). We study how the spatial variations in photocurrent evolve with thermal annealing, and we correlate these changes with the evolution of macroscopic film and device properties such as external quantum efficiency and carrier mobility. We use conductive atomic force microscopy to examine the development of injection and transport networks for both electrons and holes as a function of annealing. We find that the hole transport, electron transport, and photocurrent collection networks become increasingly heterogeneous with thermal annealing and remain heterogeneous on the 10-100 nm length scale even in the most efficient P3HT/PCBM devices. After annealing, the regions of the greatest dark hole currents, greatest dark electron currents, and greatest photocurrents are each associated with different regions of the nanostructured films. These results suggest spatial heterogeneity can contribute to the imperfect internal quantum efficiency even in relatively efficient organic photovoltaics and that fully 3D modeling is needed to describe the devices physics of polymer blend solar cells.

Submicrosecond time resolution atomic force microscopy for probing nanoscale dynamics.

We propose, simulate, and experimentally validate a new mechanical detection method to analyze atomic force microscopy (AFM) cantilever motion that enables noncontact discrimination of transient events with ~100 ns temporal resolution without the need for custom AFM probes, specialized instrumentation, or expensive add-on hardware. As an example application, we use the method to screen thermally annealed poly(3-hexylthiophene):phenyl-C(61)-butyric acid methyl ester photovoltaic devices under realistic testing conditions over a technologically relevant performance window. We show that variations in device efficiency and nanoscale transient charging behavior are correlated, thereby linking local dynamics with device behavior. We anticipate that this method will find application in scanning probe experiments of dynamic local mechanical, electronic, magnetic, and biophysical phenomena.

Efficient charge extraction and slow recombination in organic–inorganic perovskites capped with semiconducting single-walled carbon nanotubes

Metal-halide based perovskite solar cells have rapidly emerged as a promising alternative to traditional inorganic and thin-film photovoltaics. Although charge transport layers are used on either side of perovskite absorber layers to extract photogenerated electrons and holes, the time scales for charge extraction and recombination are poorly understood. Ideal charge transport layers should facilitate large discrepancies between charge extraction and recombination rates. Here, we demonstrate that highly enriched semiconducting single-walled carbon nanotube (SWCNT) films enable rapid (sub-picosecond) hole extraction from a prototypical perovskite absorber layer and extremely slow back-transfer and recombination (hundreds of microseconds). The energetically narrow and distinct spectroscopic signatures for charges within these SWCNT thin films enables the unambiguous temporal tracking of each charge carrier with time-resolved spectroscopies covering many decades of time. The efficient hole extraction by the SWCNT layer also improves electron extraction by the compact titanium dioxide electron transport layer, which should reduce charge accumulation at each critical interface. Finally, we demonstrate that the use of thin interface layers of semiconducting single-walled carbon nanotubes between the perovskite absorber layer and a prototypical hole transport layer improves device efficiency and stability, and reduces hysteresis.

Mechanism for rapid growth of organic–inorganic halide perovskite crystals

Optoelectronic devices based on hybrid halide perovskites have shown remarkable progress to high performance. However, despite their apparent success, there remain many open questions about their intrinsic properties. Single crystals are often seen as the ideal platform for understanding the limits of crystalline materials, and recent reports of rapid, high-temperature crystallization of single crystals should enable a variety of studies. Here we explore the mechanism of this crystallization and find that it is due to reversible changes in the solution where breaking up of colloids, and a change in the solvent strength, leads to supersaturation and subsequent crystallization. We use this knowledge to demonstrate a broader range of processing parameters and show that these can lead to improved crystal quality. Our findings are therefore of central importance to enable the continued advancement of perovskite optoelectronics and to the improved reproducibility through a better understanding of factors influencing and controlling crystallization.

Additive-assisted supramolecular manipulation of polymer:fullerene blend phase morphologies and its influence on photophysical processes

It is well known that even small variations in the solid-state microstructure of polymer:fullerene bulk heterojunctions can drastically change their organic solar cell device performance. We employ pBTTT:PC61BM as a model system and manipulate co-crystal formation of 1 : 1 (by weight) blends with the assistance of fatty acid methyl esters as additives. This allows us to evaluate the role of the intermixed phase in such binary blends through manipulation of their phase morphology—from fully intercalated to partially and predominantly non-intercalated systems—and its effect on the exciton- and carrier- dynamics and the efficiency of charge collection, with relevance for future device design and manufacturing.

Tuning the driving force for exciton dissociation in single-walled carbon nanotube heterojunctions

Understanding the kinetics and energetics of interfacial electron transfer in molecular systems is crucial for the development of a broad array of technologies, including photovoltaics, solar fuel systems and energy storage. The Marcus formulation for electron transfer relates the thermodynamic driving force and reorganization energy for charge transfer between a given donor/acceptor pair to the kinetics and yield of electron transfer. Here we investigated the influence of the thermodynamic driving force for photoinduced electron transfer (PET) between single-walled carbon nanotubes (SWCNTs) and fullerene derivatives by employing time-resolved microwave conductivity as a sensitive probe of interfacial exciton dissociation. For the first time, we observed the Marcus inverted region (in which driving force exceeds reorganization energy) and quantified the reorganization energy for PET for a model SWCNT/acceptor system. The small reorganization energies (about 130 meV, most of which probably arises from the fullerene acceptors) are beneficial in minimizing energy loss in photoconversion schemes.

Photoinduced spontaneous free-carrier generation in semiconducting single-walled carbon nanotubes

Strong quantum confinement and low dielectric screening impart single-walled carbon nanotubes with exciton-binding energies substantially exceeding kBT at room temperature. Despite these large binding energies, reported photoluminescence quantum yields are typically low and some studies suggest that photoexcitation of carbon nanotube excitonic transitions can produce free charge carriers. Here we report the direct measurement of long-lived free-carrier generation in chirality-pure, single-walled carbon nanotubes in a low dielectric solvent. Time-resolved microwave conductivity enables contactless and quantitative measurement of the real and imaginary photoconductance of individually suspended nanotubes. The conditions of the microwave conductivity measurement allow us to avoid the complications of most previous measurements of nanotube free-carrier generation, including tube–tube/tube–electrode contact, dielectric screening by nearby excitons and many-body interactions. Even at low photon fluence (approximately 0.05 excitons per μm length of tubes), we directly observe free carriers on excitation of the first and second carbon nanotube exciton transitions.

Nanostructure determines the intensity-dependence of open-circuit voltage in plastic solar cells

We use photoconductive atomic force microscopy to make local measurements of the open-circuit voltage (VOC) as a function of light intensity in several polymer/fullerene bulk heterojunction blend solar cells. We find significant local variations in the slope of the open-circuit voltage plotted versus the log of the light intensity. By studying a model alkoxy-poly(p)-pheneylene-vinylene/phenyl-C61-butyric acid methyl ester system with known vertical structure, and by comparing our results with a simple numerical model, we associate these local differences in VOC versus light intensity with lateral variations in vertical morphology/composition. These results not only provide a qualitative method of mapping lateral variations in vertical structure/composition by making local measurements of VOC as a function of light intensity but suggest that the unusual light-intensity dependence of VOC (diode ideality factors in the light) of many organic photovoltaics can be linked with morphological heterogeneity.