Trisha L. Andrew

Confining Light to Deep Subwavelength Dimensions to Enable Optical Nanopatterning

Subwavelength Patterning Microscopists have recently achieved fluorescence imaging at subwavelength resolution by focusing one beam of light in a halo around another beam, thereby quenching the glow of fluorescent dyes in all but the very center of the illuminated spot. Three studies have now adapted this approach to photolithography (see the Perspective by Perry). Andrew et al. (p. 917, published online 9 April) coated a photo-resist with molecules that, upon absorbing the ultraviolet etching beam, isomerized to a transparent layer but returned to the initially opaque form upon absorption of visible light. Applying an interference pattern with ultraviolet peaks superimposed on visible nodes restricted etching to narrow regions in the center of these nodes, yielding lines of subwavelength width. Scott et al. (p. 913, published online 9 April) used a central beam to activate polymerization initiators, while using a halo-shaped surrounding beam to trigger inhibitors that would halt polymerization. Li et al. (p. 910, published online 9 April) found that use of a different initiator molecule allowed both beams to share the same wavelength (800 nanometers), with a relatively weak quenching beam lagging a highly intense initiating beam slightly in time. Both the latter techniques produced three-dimensional features honed to subwavelength dimensions. Molecules that photoisomerize and change in transparency are used to define narrow features on photoresists. In the past, the formation of microscale patterns in the far field by light has been diffractively limited in resolution to roughly half the wavelength of the radiation used. Here, we demonstrate lines with an average width of 36 nanometers (nm), about one-tenth the illuminating wavelength λ1 = 325 nm, made by applying a film of thermally stable photochromic molecules above the photoresist. Simultaneous irradiation of a second wavelength, λ2 = 633 nm, renders the film opaque to the writing beam except at nodal sites, which let through a spatially constrained segment of incident λ1 light, allowing subdiffractional patterning. The same experiment also demonstrates a patterning of periodic lines whose widths are about one-tenth their period, which is far smaller than what has been thought to be lithographically possible.

Effect of synthetic accessibility on the commercial viability of organic photovoltaics

For organic photovoltaics (OPVs) to become a viable source of renewable energy, the synthesis of organic active-layer materials will need to be scaled to thousands of kilograms. Additionally, the ultimate cost of these materials will need to be low enough to constitute only a small fraction of the cost of the solar cell module. In this study, we present a quantitative analysis, based on published small-scale synthetic procedures, to estimate the materials costs for several promising OPV materials when produced in large quantities. The cost in dollars-per-gram (

Improving the performance of P3HT-fullerene solar cells with side-chain-functionalized poly(thiophene) additives: a new paradigm for polymer design.

per g) is found to increase linearly with the number of synthetic steps required to produce each organic photoactive compound. We estimate the cost-per-Watt (

Color-Pure Violet-Light-Emitting Diodes Based on Layered Lead Halide Perovskite Nanoplates

per Wp) as a function of power conversion efficiency (PCE) for an archetypal OPV structure and find that a relatively simple molecule requiring only 3 synthetic steps will contribute a cost of 0.001 to 0.01

Development of Lead Iodide Perovskite Solar Cells Using Three-Dimensional Titanium Dioxide Nanowire Architectures

per Wp, given a solar module PCE of 10%. In contrast, a relatively complicated molecule requiring 14 synthetic steps will contribute costs in the range of 0.075 to 0.48

Bias-Stress Effect in 1,2-Ethanedithiol-Treated PbS Quantum Dot Field-Effect Transistors

per Wp. Our findings suggest that the commercial viability of an OPV technology may depend on the synthetic accessibility of its constituent active layer materials. Additionally, this work stresses the importance of optimizing synthetic routes to minimize solvent and reagent usage as well as to minimize the number of required workup procedures in the scaled production of OPV materials.

An Air-Stable Low-Bandgap n-Type Organic Polymer Semiconductor Exhibiting Selective Solubility in Perfluorinated Solvents†

The motivation of this study is to determine if small amounts of designer additives placed at the polymer-fullerene interface in bulk heterojunction (BHJ) solar cells can influence their performance. A series of AB-alternating side-chain-functionalized poly(thiophene) analogues, P1-6, are designed to selectively localize at the interface between regioregular poly(3-hexylthiophene) (rr-P3HT) and PC(n)BM (n = 61, 71). The side chains of every other repeat unit in P1-6 contain various terminal aromatic moieties. BHJ solar cells containing ternary mixtures of rr-P3HT, PC(n)BM, and varying weight ratios of additives P1-6 are fabricated and studied. At low loadings, the presence of P1-6 consistently increases the short circuit current and decreases the series resistance of the corresponding devices, leading to an increase in power conversion efficiency (PCE) compared to reference P3HT/PC(61)BM cells. Higher additive loadings (>5 wt %) lead to detrimental nanoscale phase separation within the active layer blend and produce solar cells with high series resistances and low overall PCEs. Small-perturbation transient open circuit voltage decay measurements reveal that, at 0.25 wt % incorporation, additives P1-6 increase charge carrier lifetimes in P3HT/PC(61)BM solar cells. Pentafluorophenoxy-containing polymer P6 is the most effective side-chain-functionalized additive and yields a 28% increase in PCE when incorporated into a 75 nm thick rr-P3HT/PC(61)BM BHJ at a 0.25 wt % loading. Moreover, devices with 220 nm thick BHJs containing 0.25 wt % P6 display PCE values of up to 5.3% (30% PCE increase over a control device lacking P6). We propose that additives P1-6 selectively localize at the interface between rr-P3HT and PC(n)BM phases and that aromatic moieties at side-chain termini introduce a dipole at the polymer-fullerene interface, which decreases the rate of bimolecular recombination and, therefore, improves charge collection across the active layer.

Detection of Explosives via Photolytic Cleavage of Nitroesters and Nitramines

Violet electroluminescence is rare in both inorganic and organic light-emitting diodes (LEDs). Low-cost and room-temperature solution-processed lead halide perovskites with high-efficiency and color-tunable photoluminescence are promising for LEDs. Here, we report room-temperature color-pure violet LEDs based on a two-dimensional lead halide perovskite material, namely, 2-phenylethylammonium (C6H5CH2CH2NH3(+), PEA) lead bromide [(PEA)2PbBr4]. The natural quantum confinement of two-dimensional layered perovskite (PEA)2PbBr4 allows for photoluminescence of shorter wavelength (410 nm) than its three-dimensional counterpart. By converting as-deposited polycrystalline thin films to micrometer-sized (PEA)2PbBr4 nanoplates using solvent vapor annealing, we successfully integrated this layered perovskite material into LEDs and achieved efficient room-temperature violet electroluminescence at 410 nm with a narrow bandwidth. This conversion to nanoplates significantly enhanced the crystallinity and photophysical properties of the (PEA)2PbBr4 samples and the external quantum efficiency of the violet LED. The solvent vapor annealing method reported herein can be generally applied to other perovskite materials to increase their grain size and, ultimately, improve the performance of optoelectronic devices based on perovskite materials.

Synthesis, Reactivity, and Electronic Properties of 6,6-Dicyanofulvenes

Three-dimensional (3D) nanowire (NW) architectures are considered as superior electrode design for photovoltaic devices compared to NWs or nanoparticle systems in terms of improved large surface area and charge transport properties. In this paper, we report development of lead iodide perovskite solar cells based on a novel 3D TiO2 NW architectures. The 3D TiO2 nanostructure was synthesized via surface-reaction-limited pulsed chemical vapor deposition (SPCVD) technique that also implemented the Kirkendall effect for complete ZnO NW template conversion. It was found that the film thickness of 3D TiO2 can significantly influence the photovoltaic performance. Short-circuit current increased with the TiO2 length, while open-circuit voltage and fill factor decreased with the length. The highest power conversion efficiency (PCE) of 9.0% was achieved with ∼ 600 nm long 3D TiO2 NW structures. Compared to other 1D nanostructure arrays (TiO2 nanotubes, TiO2-coated ZnO NWs and ZnO NWs), 3D TiO2 NW architecture was able to achieve larger amounts of perovskite loading, enhanced light harvesting efficiency, and increased electron-transport property. Therefore, its PCE is 1.5, 2.3, and 2.8 times higher than those of TiO2 nanotubes, TiO2-coated ZnO NWs, and ZnO NWs, respectively. The unique morphological advantages, together with the largely suppressed hysteresis effect, make 3D hierarchical TiO2 a promising electrode selection in designing high-performance perovskite solar cells.

Bulk heterojuction solar cells containing 6,6-dicyanofulvenes as n-type additives.

We investigate the bias-stress effect in field-effect transistors (FETs) consisting of 1,2-ethanedithiol-treated PbS quantum dot (QD) films as charge transport layers in a top-gated configuration. The FETs exhibit ambipolar operation with typical mobilities on the order of μ(e) = 8 × 10(-3) cm(2) V(-1) s(-1) in n-channel operation and μ(h) = 1 × 10(-3) cm(2) V(-1) s(-1) in p-channel operation. When the FET is turned on in n-channel or p-channel mode, the established drain-source current rapidly decreases from its initial magnitude in a stretched exponential decay, manifesting the bias-stress effect. The choice of dielectric is found to have little effect on the characteristics of this bias-stress effect, leading us to conclude that the associated charge-trapping process originates within the QD film itself. Measurements of bias-stress-induced time-dependent decays in the drain-source current (I(DS)) are well fit to stretched exponential functions, and the time constants of these decays in n-channel and p-channel operation are found to follow thermally activated (Arrhenius) behavior. Measurements as a function of QD size reveal that the stressing process in n-channel operation is faster for QDs of a smaller diameter while stress in p-channel operation is found to be relatively invariant to QD size. Our results are consistent with a mechanism in which field-induced nanoscale morphological changes within the QD film result in screening of the applied gate field. This phenomenon is entirely recoverable, which allows us to repeatedly observe bias stress and recovery characteristics on the same device. This work elucidates aspects of charge transport in chemically treated lead chalcogenide QD films and is of relevance to ongoing investigations toward employing these films in optoelectronic devices.