Bradley A. MacLeod

Electron accumulation on metal nanoparticles in plasmon-enhanced organic solar cells.

Plasmonic metal nanoparticles have been used to enhance the performance of thin-film devices such as organic photovoltaics based on polymer/fullerene blends. We show that silver nanoprisms accumulate long-lived negative charges when they are in contact with a photoexcited bulk heterojunction blend composed of poly(3-hexylthiophene)/phenyl-C61-butyric acid methyl ester (P3HT/PCBM). We report both the charge modulation and electroabsorption spectra of silver nanoprisms in solid-state devices and compare these spectra with the photoinduced absorption spectra of P3HT/PCBM blends containing silver nanoprisms. We assign a previously unidentified peak in the photoinduced absorption spectra to the presence of photoinduced electrons on the silver nanoprisms. We show that coating the nanoprisms with a 2.5 nm thick insulating layer can completely inhibit this charging. These results may inform methods for limiting metal-mediated losses in plasmonic solar cells.

Stability of inverted organic solar cells with ZnO contact layers deposited from precursor solutions

We report on investigations of the stability of inverted organic solar cells with ZnO electron collecting interlayer that are solution-processed from zinc acetate (ZnAc) or diethylzinc (deZn) precursors. Characterization of the respective solar cells suggests that the two materials initially function similarly in devices, however, we find that devices with ZnO from the deZn precursor are more stable under long-term illumination and load than devices with ZnO from the ZnAc precursor. A dipolar phosphonic acid that reduces the ZnO work function also improved device performance and stability when compared with unmodified ZnAc-based ZnO, but was problematic for deZn-based ZnO. The long-term device degradation analyses shows that the improved devices had increased and significantly more stable open-circuit voltage and fill factor characteristics. Chemical analyses suggests that defects in the ZnO films, most likely interstitial zinc, may be responsible for the observed disparities in stability within organic solar cells.

Spatially Modulating Interfacial Properties of Transparent Conductive Oxides: Patterning Work Function with Phosphonic Acid Self‐Assembled Monolayers

The interface between an organic semiconductor and a transparent conducting oxide is crucial to the performance of organic optoelectronics. We use microcontact printing to pattern pentafluorobenzyl phosphonic acid self-assembled monolayers (SAMs) on indium tin oxide (ITO). We obtain high-fidelity patterns with sharply defined edges and with large work function contrast (comparable to that obtained from phosphonic acid SAMs deposited from solution).

Built-In Potential in Conjugated Polymer Diodes with Changing Anode Work Function: Interfacial States and Deviation from the Schottky-Mott Limit.

We use electroabsorption spectroscopy to measure the change in built-in potential (VBI) across the polymer photoactive layer in diodes where indium tin oxide electrodes are systematically modified using dipolar phosphonic acid self-assembled monolayers (SAMs) with various dipole moments. We find that VBI scales linearly with the work function (Φ) of the SAM-modified electrode over a wide range when using a solution-coated poly(p-phenylenevinylene) derivative as the active layer. However, we measure an interfacial parameter of S = eΔVBI/ΔΦ < 1, suggesting that these ITO/SAM/polymer interfaces deviate from the Schottky-Mott limit, in contrast to what has previously been reported for a number of ambient-processed organic-on-electrode systems. Our results suggest that the energetics at these ITO/SAM/polymer interfaces behave more like metal/organic interfaces previously studied in UHV despite being processed from solution.

Efficient Modification of Metal Oxide Surfaces with Phosphonic Acids by Spray Coating

We report a rapid method of depositing phosphonic acid molecular groups onto conductive metal oxide surfaces. Solutions of pentafluorobenzyl phosphonic acid (PFBPA) were deposited on indium tin oxide, indium zinc oxide, nickel oxide, and zinc oxide by spray coating substrates heated to temperatures between 25 and 150 °C using a 60 s exposure time. Comparisons of coverage and changes in work function were made to the more conventional dip-coating method utilizing a 1 h exposure time. The data show that the work function shifts and surface coverage by the phosphonic acid were similar to or greater than those obtained by the dip-coating method. When the deposition temperature was increased, the magnitude of the surface coverage and work function shift was also found to increase. The rapid exposure of the spray coating was found to result in less etching of zinc-containing oxides than the dip-coating method. Bulk heterojunction solar cells made of polyhexylthiophene (P3HT) and bis-indene-C60 (ICBA) were tested with PFBPA dip and spray-modified ITO substrates as well as poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS)-modified ITO. The spray-modified ITO solar cells showed a similar open circuit voltage (VOC) and fill factor (FF) and a less than 5% lower short circuit current density (JSC) and power conversion efficiency (PCE) than the dip- and PEDOT:PSS-modified ITO. These results demonstrate a potential path to a scalable method to deposit phosphonic acid surface modifiers on metal oxides while overcoming the limitations of other techniques that require long exposure and post-processing times.

Surface Characterization of Polythiophene:Fullerene Blends on Different Electrodes Using Near Edge X-Ray Absorption Fine Structure

We study the top surface composition of blends of the conjugated polymer regioregular poly-3-hexylthiophene (P3HT) with the fullerene (6,6)-phenyl-C(61)-butyric acid methyl ester (PCBM), an important model system for organic photovoltaics (OPVs), using near-edge X-ray absorption fine structure spectroscopy (NEXAFS). We compare the ratio of P3HT to PCBM near the air/film interface that results from preparing blend films on two sets of substrates: (1) poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) coated indium tin oxide (ITO) as is commonly used in conventional OPV structures and (2) ZnO substrates that are either unmodified or modified with a C(60)-like self-assembled monolayer, similar to those that have been recently reported in inverted OPV structures. We find that the top surface (the film/air interface) is enriched in P3HT compared to the bulk, regardless of substrate or annealing conditions, indicating that changes in device performance due to substrate modification treatments should be attributed to the buried substrate/film interface and the bulk of the film rather than the exposed film/air interface.

Phosphonic Acid Modification of GaInP2 Photocathodes Toward Unbiased Photoelectrochemical Water Splitting

The p-type semiconductor GaInP2 has a nearly ideal bandgap (∼1.83 eV) for hydrogen fuel generation by photoelectrochemical water splitting but is unable to drive this reaction because of misalignment of the semiconductor band edges with the water redox half reactions. Here, we show that attachment of an appropriate conjugated phosphonic acid to the GaInP2 electrode surface improves the band edge alignment, closer to the desired overlap with the water redox potentials. We demonstrate that this surface modification approach is able to adjust the energetic position of the band edges by as much as 0.8 eV, showing that it may be possible to engineer the energetics at the semiconductor/electrolyte interface to allow for unbiased water splitting with a single photoelectrode having a bandgap of less than 2 eV.

Formation of interfacial traps upon surface protonation in small molecule solution processed bulk heterojunctions probed by photoelectron spectroscopy

This work expands on the recently reported protonation of the donor molecule 7,7′-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b′]dithiophene-2,6-diyl)bis(4-(5′-hexyl-[2,2′-bithiophen]-5-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine) (d-DTS(PTTh2)2) by the poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) interlayer to include an electrostatic picture of interfacial energetic states. Ultraviolet photoemission spectroscopy results initially suggested favorable band level alignment for hole extraction between d-DTS(PTTh2)2 and PEDOT:PSS. However photovoltaic device performance yields a low fill factor and photovoltage, indicative of poor hole-extraction at the hole-collecting interface, relative to the nickel oxide device. Further investigation into the interfacial composition via theory and X-ray photoelectron studies of both the interface and a control system of d-DTS(PTTh2)2 reacted with p-toluenesulfonic acid verify the presence of a chemically unique species at the interface arising from protonation reaction with the residual acidic protons present in PEDOT:PSS that was masked in the UPS experiment. From these results, the energy band diagram is re-interpreted to account for the interfacial chemical reaction and modified interfacial density of states. Additionally, the detrimental protonation reaction is avoided when the pyridyl[1,2,5]thiadiazole acceptor unit was replaced with a 5-fluorobenzo[c][1,2,5]thiadiazole acceptor unit, which shows no such reaction with the PEDOT:PSS substrate. These results indicate the necessity of using a large analytical toolkit to elucidate the energetics and mechanisms of buried interfaces that will impact dynamics of hole collection.

Large n- and p-type thermoelectric power factors from doped semiconducting single-walled carbon nanotube thin films

Lightweight, robust, and flexible single-walled carbon nanotube (SWCNT) materials can be processed inexpensively using solution-based techniques, similar to other organic semiconductors. In contrast to many semiconducting polymers, semiconducting SWCNTs (s-SWCNTs) represent unique one-dimensional organic semiconductors with chemical and physical properties that facilitate equivalent transport of electrons and holes. These factors have driven increasing attention to employing s-SWCNTs for electronic and energy harvesting applications, including thermoelectric (TE) generators. Here we demonstrate a combination of ink chemistry, solid-state polymer removal, and charge-transfer doping strategies that enable unprecedented n-type and p-type TE power factors, in the range of 700 μW m−1 K−2 at 298 K for the same solution-processed highly enriched thin films containing 100% s-SWCNTs. We also demonstrate that the thermal conductivity appears to decrease with decreasing s-SWCNT diameter, leading to a peak material zT ≈ 0.12 for s-SWCNTs with diameters in the range of 1.0 nm. Our results indicate that the TE performance of s-SWCNT-only material systems is approaching that of traditional inorganic semiconductors, paving the way for these materials to be used as the primary components for efficient, all-organic TE generators.