Jason Locklin

Organic Field-Effect Transistors

The remarkable development of organic thin film transistors (OTFTs) has led to their emerging use in active matrix flat-panel displays, radio frequency identification cards, and sensors. Exploring one class of OTFTs, Organic Field-Effect Transistors provides a comprehensive, multidisciplinary survey of the present theory, charge transport studies, synthetic methodology, materials characterization, and current applications of organic field-effect transistors (OFETs). Covering various aspects of OFETs, the book begins with a theoretical description of charge transport in organic semiconductors at the molecular level. It then discusses the current understanding of charge transport in single-crystal devices, small molecules and oligomers, conjugated polymer devices, and charge injection issues in organic transistors. After describing the design rationales and synthetic methodologies used for organic semiconductors and dielectric materials, the book provides an overview of a variety of characterization techniques used to probe interfacial ordering, microstructure, molecular packing, and orientation crucial to device performance. It also describes the different processing techniques for molecules deposited by vacuum and solution, followed by current technological examples that employ OTFTs in their operation. Featuring respected contributors from around the world, this thorough, up-to-date volume presents both the theory behind OFETs and the latest applications of this promising technology.

Crystalline Ultrasmooth Self-Assembled Monolayers of Alkylsilanes for Organic Field-Effect Transistors

Crystalline self-assembled monolayers (SAMs) of organosilane compounds such as octadecyltrimethoxysilane (OTMS) and octadecyltrichlorosilane (OTCS) were deposited by a simple, spin-casting technique onto Si/SiO(2) substrates. Fabrication of the OTMS SAMs and characterization using ellipsometry, contact angle, atomic force microscopy (AFM), grazing angle attenuated total reflectance Fourier transform infrared (GATR-FTIR) spectroscopy and grazing incidence X-ray diffraction (GIXD) are described. The characterization confirms that these monolayers exhibit a well-packed crystalline phase and a remarkably high degree of smoothness. Semiconductors deposited by vapor deposition onto the crystalline OTS SAM grow in a favorable two-dimensional layered growth manner which is generally preferred morphologically for high charge carrier transport. On the OTMS SAM treated dielectric, pentacene OFETs showed hole mobilities as high as 3.0 cm(2)/V x s, while electron mobilities as high as 5.3 cm(2)/V x s were demonstrated for C(60).

Water-stable organic transistors and their application in chemical and biological sensors.

The development of low-cost, reliable sensors will rely on devices capable of converting an analyte binding event to an easily read electrical signal. Organic thin-film transistors (OTFTs) are ideal for inexpensive, single-use chemical or biological sensors because of their compatibility with flexible, large-area substrates, simple processing, and highly tunable active layer materials. We have fabricated low-operating voltage OTFTs with a cross-linked polymer gate dielectric, which display stable operation under aqueous conditions over >104 electrical cycles using the p-channel semiconductor 5,5′-bis-(7-dodecyl-9H-fluoren-2-yl)-2,2′-bithiophene (DDFTTF). OTFT sensors were demonstrated in aqueous solutions with concentrations as low as parts per billion for trinitrobenzene, methylphosphonic acid, cysteine, and glucose. This work demonstrates of reliable OTFT operation in aqueous media, hence opening new possibilities of chemical and biological sensing with OTFTs.

High Density Orthogonal Surface Immobilization via Photoactivated Copper-Free Click Chemistry

Surfaces containing reactive ester polymer brushes were functionalized with cyclopropenone-masked dibenzocyclooctynes for the light activated immobilization of azides using catalyst-free click chemistry. The photodecarbonylation reaction in the amorphous brush layer is first order for the first 45 s with a rate constant of 0.022 s(-1). The catalyst-free cycloaddition of surface bound dibeznocyclooctynes proceeds rapidly in the presence of azides under ambient conditions. Photolithography using a shadow mask was used to demonstrate patterning with multiple azide containing molecules. This surface immobilization strategy provides a general and facile platform for the generation of multicomponent surfaces with spatially resolved chemical functionality.

Formation of photochromic spiropyran polymer brushes via surface-initiated, ring-opening metathesis polymerization: reversible photocontrol of wetting behavior and solvent dependent morphology changes.

In this article, we described a method for the formation of photochromic polymer brushes grafted from oxide surfaces using surface-initiated ring-opening metathesis polymerization of spiropyran-based monomers in the presence of second generation Grubbs catalyst. The growth of the polymer film, as monitored by ellipsometry and atomic force microscopy (AFM), is strongly influenced by the initial concentrations of the catalyst and monomer, as well as reaction time. These densely packed and highly smooth polymer films were successfully used as surfaces with switchable color and wettability using light as the external stimulus. The relatively nonpolar spiropyran can be switched to a polar, zwitterionic merocyanine isomer (with a larger dipole moment) using light of the appropriate wavelength. This process is reversible and can be switched back using visible light. The spiropyran-merocyanine photoinduced isomerization gives a reversible contact angle change up to 15 degrees for smooth Si/SiO 2 substrate under sequential irradiation cycles with UV and visible light. This contact angle change can be amplified by complexing the merocyanine form with metal ions through the phenolate oxygen, which enhances the switching of wettability with these polymer brushes. Irradiation in the presence of cobalt(II) ions gives rise to a contact angle variation as high as 35 degrees . This is the largest change in photoinduced surface wettability observed for a flat substrate. Photoisomerization in spiropyrans also yields a change in the refractive index of the film, which we have investigated using ellipsometric imaging. Lastly, morphological changes accompanying photochromism were investigated using atomic force microscopy. Significant morphological changes can only be induced in the films by irradiating in polar solvents that help to stabilize the merocyanine ring open form.

Surface-initiated polymerization of conjugated polymers

In this feature article, we highlight the recent developments in the chain growth polymerization mechanism of conjugated polymers. With a particular emphasis on Kumada catalyst-transfer polycondensation, this article focuses on the surface-initiated polymerization of conjugated polymers, along with the opportunities and challenges associated with this technique.

Spectroscopic Analysis of Metal Ion Binding in Spiropyran Containing Copolymer Thin Films

In this article, we describe the synthesis and characterization of a series of spiropyran containing copolymers that were used as colorimetric sensors for a series of divalent metal ions. The composition of spiropyran contained in the polymer backbone was varied from 10-100 mol % to investigate the influence of free volume and sterics on the photochromic response. Fourier transform-infrared (FT-IR) spectroscopy was used to characterize the photoinduced conversion, as well as the merocyanine-metal ion (MC-M(2+)) interaction. FT-IR spectra were analyzed using chemometric methods to elucidate the chemical binding environment between MC and M(2+) and to selectively identify different metal ions bound to MC. By means of UV-vis absorption spectroscopy, we also demonstrate that each metal ion gives rise to a unique colorimetric response that is dependent on the amount of spiropyran comonomer contained in the polymer backbone and that by increasing the concentration of chromophore in the copolymer, the selectivity between different metal ions decreases. With the use of chemometric methods, UV-vis spectra can be analyzed to quantitatively identify metal ions in a concentration range from 1 microM to 100 mM.

Thiol–isocyanate “click” reactions: rapid development of functional polymeric surfaces

Functional, micropatterned and multicomponent polymer brush surfaces can be rapidly fabricated via base-catalyzed thiol–isocyanate “click” reactions.

Photoreactive polymer brushes for high-density patterned surface derivatization using a Diels-Alder photoclick reaction.

Reactive polymer brushes grown on silicon oxide surfaces were derivatized with photoreactive 3-(hydroxymethyl)naphthalene-2-ol (NQMP) moieties. Upon 300 or 350 nm irradiation, NQMP efficiently produces o-naphthoquinone methide (oNQM), which in turn undergoes very rapid Diels-Alder addition to vinyl ether groups attached to a substrate, resulting in the covalent immobilization of the latter. Any unreacted oNQM groups rapidly add water to regenerate NQMP. High-resolution surface patterning is achieved by irradiating NQMP-derivatized surfaces using photolithographic methods. The Diels-Alder photoclick reaction is orthogonal to azide-alkyne click chemistry, enabling sequential photoclick/azide-click derivatizations to generate complex surface functionalities.

One-Step Photochemical Synthesis of Permanent, Nonleaching, Ultrathin Antimicrobial Coatings for Textiles and Plastics

Antimicrobial copolymers of hydrophobic N-alkyl and benzophenone containing polyethylenimines were synthesized from commercially available linear poly(2-ethyl-2-oxazoline), and covalently attached to surfaces of synthetic polymers, cotton, and modified silicon oxide using mild photo-cross-linking. Specifically, these polymers were applied to polypropylene, poly(vinyl chloride), polyethylene, cotton, and alkyl-coated oxide surfaces using solution casting or spray coating and then covalently cross-linked rendering permanent, nonleaching antimicrobial surfaces. The photochemical grafting of pendant benzophenones allows immobilization to any surface that contains a C-H bond. Incubating the modified materials with either Staphylococcus aureus or Escherichia coli demonstrated that the modified surfaces had substantial antimicrobial capacity against both Gram-positive and Gram-negative bacteria (>98% microbial death).