Christine K. Luscombe

All-inkjet-printed flexible electronics fabrication on a polymer substrate by low-temperature high-resolution selective laser sintering of metal nanoparticles

All-printed electronics is the key technology to ultra-low-cost, large-area electronics. As a critical step in this direction, we demonstrate that laser sintering of inkjet-printed metal nanoparticles enables low-temperature metal deposition as well as high-resolution patterning to overcome the resolution limitation of the current inkjet direct writing processes. To demonstrate this process combined with the implementation of air-stable carboxylate-functionalized polythiophenes, high-resolution organic transistors were fabricated in ambient pressure and room temperature without utilizing any photolithographic steps or requiring a vacuum deposition process. Local thermal control of the laser sintering process could minimize the heat-affected zone and the thermal damage to the substrate and further enhance the resolution of the process. This local nanoparticle deposition and energy coupling enable an environmentally friendly and cost-effective process as well as a low-temperature manufacturing sequence to realize large-area, flexible electronics on polymer substrates.

Externally initiated regioregular P3HT with controlled molecular weight and narrow polydispersity.

The ability of chemists to design and synthesize pi-conjugated organic polymers with precise control remains the key to technological breakthroughs for using polymer materials in electronic and photonic devices. In this communication, the controlled chain-growth polymerization of regioregular poly(3-hexylthiophene) (P3HT) from an external initiator using 1,3-bis(diphenylphosphino)propane (dppp) as a catalyst ligand is reported. The complexes cis-chloro(phenyl)(dppp)nickel(II) and cis-chloro(o-tolyl)(dppp)nickel(II) were synthesized and characterized by (31)P NMR spectroscopy. These complexes served as initiators in the polymerization of 2-bromo-5-chloromagnesio-3-hexylthiophene in THF at room temperature, affording fully regioregular P3HT with controlled molecular weights and narrow molecular weight distributions, as demonstrated by gel-permeation chromatography and (1)H NMR spectroscopy. MALDI-TOF mass spectrometry revealed that the polymers had almost complete incorporation of the initiating aryl group, and when the aryl group was o-tolyl, only Tol/H end groups were observed. Although external initiators have been used previously with a PPh(3) ligand, that methodology led to polymers with broad molecular weight distributions. This is the first example in which complete control over the externally initiated P3HT polymerization has been achieved.

Air stable high resolution organic transistors by selective laser sintering of ink-jet printed metal nanoparticles

A high resolution organic field effect transistor (OFET) fabrication process has been developed based on the selective laser sintering of ink-jet printed nanoparticle inks and the recent development of an air stable carboxylate-functionalized polythiophene semiconducting polymer. The entire fabrication and device characterization are performed at room temperature, ambient pressure, and air environment without using complex lithographic methods. This low temperature OFET fabrication process based on nanoparticle laser sintering has great potential for realizing inexpensive, large area flexible electronics on heat sensitive polymer substrates.

The Role of Mesoscopic PCBM Crystallites in Solvent Vapor Annealed Copolymer Solar Cells

Solution processable methanofullerene-based solar cells are the most widely studied class of organic photovoltaics (OPVs). The evolution of the electronic properties with solvent vapor annealing (SVA) in polyfluorene-copolymer and [6,6]phenyl-C61-butyric acid methyl ester (PCBM) blended OPVs is studied using various scanning probe techniques: light beam induced current spectroscopy (LBIC), conductive atomic force microscopy (c-AFM), and photoconductive AFM (pc-AFM). We demonstrate that SVA improves the power conversion efficiency by 40% while forming mesoscopic PCBM crystallites and a approximately 3 nm copolymer-rich overlayer at the cathode interface. We find that the large crystallites created during annealing do not directly improve the local performance of the device, but instead attribute the performance improvement to the ripened blend morphology and an increase in the hole mobility of the copolymer in comparison to the unannealed blend. The PCBM-rich aggregates act as a sink for excess PCBM, although excess PCBM is initially required to form the appropriate structural features prior to the annealing process.

Printable polythiophene gas sensor array for low-cost electronic noses

A route for generating arrays of printable polythiophene-based gas sensor materials suitable for low-cost manufacturing is demonstrated. Materials with complementary sensor responses are synthesized by incorporating functional groups into the molecule, either along the polymer backbone or as end-capping groups. Using these materials as printable sensor inks, a functional, integrated gas sensor array chip is fabricated using additive deposition techniques. The sensor array shows sensitivity to a range of volatile organic compounds down to concentrations of 10ppm. A three-terminal thin film transistor structure is used, allowing the extraction of multiple parameters that help to elucidate the mechanisms responsible for sensor response and the role of the functional groups in this response.

Controlled polymerizations for the synthesis of semiconducting conjugated polymers

Conjugated polymers have been under active development since the 1970s as the active material in organic field-effect transistors (OFETs), photovoltaic devices and the emissive layer in light-emitting diodes (LEDs). Extensive work has been performed to investigate the physics and chemistry of these materials, and a variety of semiconducting polymers have been synthesized using a range of polymerization techniques. One of the most important key technologies is to obtain a well-controlled polymerization, which provides polymers with narrow polydispersities and defined molecular weights. In this paper, we describe the recent progress on the synthesis of semiconducting polymers as classified as polyphenylenes, polyphenylenevinylenes, polythiophenes, polyfluorene and their block copolymers by the use of controlled polymerizations.

Controlling Vertical Morphology within the Active Layer of Organic Photovoltaics Using Poly(3-hexylthiophene) Nanowires and Phenyl-C61-butyric Acid Methyl Ester

In this study, we demonstrate how the vertical morphology of bulk heterojunction solar cells, with an active layer consisting of self-assembled poly(3-hexylthiophene) (P3HT) nanowires and phenyl-C(61)-butyric acid methyl ester (PCBM), can be beneficially influenced. Most device fabrication routes using similar materials employ an annealing step to influence active layer morphology, but this process can create an unfavorable phase migration where P3HT is driven toward the top of the active layer. In contrast, we demonstrate devices that exhibit an increase in relative fullerene concentration at the top of the active layer by introducing the donor phase as a solid nanowire in the active layer solution and altering the pre-spin drying time. X-ray photoelectron spectroscopy and conductive and photoconductive atomic force microscopy provide detailed images of how the surface of the active layer can be influenced; this is done by tracking the concentration and alignment of P3HT and PCBM domains. Using this new procedure, devices are made with power conversion efficiencies surpassing 2%. Additionally, we show that nanowires grown in the presence of the fullerene perform differently than those that are grown and mixed separately; exposure to the nanowire during self-assembly may allow the fullerene to coat nanowire surfaces and influence the photocurrent within the device.

Surface-Initiated Synthesis of Poly(3-methylthiophene) from Indium Tin Oxide and its Electrochemical Properties

Poly(3-methylthiophene) (P3MT) was synthesized directly from indium tin oxide (ITO) electrodes modified with a phosphonic acid initiator, using Kumada catalyst transfer polymerization (KCTP). This work represents the first time that polymer thickness has been controlled in a surface initiated KCTP reaction, highlighting the utility of KCTP in achieving controlled polymerizations. Polymer film thicknesses were regulated by the variation of the solution monomer concentration and ranged from 30 to 265 nm. Electrochemical oxidative doping of these films was used to manipulate their near surface composition and effective work function. Doped states of the P3MT film are maintained even after the sample is removed from solution and potential control confirming the robustness of the films. Such materials with controllable thicknesses and electronic properties have the potential to be useful as interlayer materials for organic electronic applications.

Oligoselenophene Derivatives Functionalized with a Diketopyrrolopyrrole Core for Molecular Bulk Heterojunction Solar Cells

Solution-processable oligoselenophenes functionalized with diketopyrrolopyrrole cores have been synthesized for use as the donor material in bulk heterojunction solar cells. The optical absorption of these materials extends to the edge of the visible spectrum. Power conversion efficiencies of 1.53 ± 0.04% for DPPS and 0.84 ± 0.04% for DPPDS were obtained under simulated 100 mW/cm(2) AM 1.5G irradiation for devices when PC(61)BM was used as an acceptor. DPPS showed hole mobilities of 4 × 10(-5) cm(2)/(V s) and a peak external quantum efficiency (EQE) of 25%, while DPPDS showed hole mobilities of 2 × 10(-5) cm(2)/(V s) and a peak EQE of 19%. To the best of our knowledge, these are the first oligoselenophenes that have been reported in molecular bulk heterojunction solar cells and this study could serve as a springboard for the design and optimization of high-performance selenophene-containing photovoltaics.

Thiophene based hyperbranched polymers with tunable branching using direct arylation methods

An efficient one-pot synthesis of branched poly(3-alkylthiophene)s (b-P3ATs) is achieved via a dehydrohalogenative polycondensation reaction. The structures of the b-P3ATs are assigned based on 1H NMR spectra by comparing them to a model dendritic polymer and oligo(3-hexylthiophene-2,4-diyl). The palladium-catalyzed dehydrohalogenative polycondensation of 2-bromo-3-alkylthiophenes was found to provide P3AT with tunable degree of branching (DB = 0–0.42) and high molecular weights. Viscosity measurements of the different b-P3ATs indicate that they display a more globular morphology compared to regiorandom P3AT and regioregular P3AT in solution, thereby confirming the branched structure.