Controlled Synthesis of Poly(pentafluorostyrene-ran-methyl methacrylate) Copolymers by Nitroxide Mediated Polymerization and Their Use as Dielectric Layers in Organic Thin-film Transistors.

A library of statistically random pentafluorostyrene (PFS) and methyl methacrylate (MMA) copolymers with narrow molecular weight distributions was produced, using nitroxide mediated polymerization (NMP) to study the effect of polymer composition on the performance of bottom-gate top-contact organic thin-film transistors, when utilized as the dielectric medium. Contact angle measurements confirmed the ability to tune the surface properties of copolymer thin films through variation of its PFS/MMA composition, while impedance spectroscopy determined the effect of this variation on dielectric properties. Bottom-gate, top-contact copper phthalocyanine (CuPc) based organic thin-film transistors were fabricated using the random copolymers as a dielectric layer. We found that increasing the PFS content led to increased field-effect mobility, until a point after which the CuPc no longer adhered to the polymer dielectric.

Developing and Comparing 2,6-Anthracene Derivatives: Optical, Electrochemical, Thermal, and Their Use in Organic Thin Film Transistors.

Anthracene-based semiconductors have attracted great interest due to their molecular planarity, ambient and thermal stability, tunable frontier molecular orbitals and strong intermolecular interactions that can lead to good device field-effect transistor performance. In this study, we report the synthesis of six anthracene derivatives which were di-substituted at the 2,6-positions, their optical, electrochemical and thermal properties, and their single crystal structures. It was found that 2,6-functionalization with various fluorinated phenyl derivatives led to negligible changes in the optical behaviour while influencing the electrochemical properties. Furthermore, the choice of fluorinated phenyl moiety had noticeable effects on melting point and thermal stability (ΔTm < 55 °C and ΔTd < 65 °C). Bottom-gate top-contact (BGTC) organic thin transistors (OTFTs) were fabricated and characterized using the 2,6-anthracene derivatives as the semiconducting layer. The addition of fluorine groups on the phenyl groups led to a transition from p-type behaviour to n-type behaviour in BGBC OTFTs.

Air and temperature sensitivity of n-type polymer materials to meet and exceed the standard of N2200.

N-type organic semiconductors are notoriously unstable in air, requiring the design of new materials that focuses on lowering their LUMO energy levels and enhancing their air stability in organic electronic devices such as organic thin-film transistors (OTFTs). Since the discovery of the notably air stable and high electron mobility polymer poly{[N,N'-bis (2-octyldodecyl)- naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,29-bisthiophene)} (N2200), it has become a popular n-type semiconductor, with numerous materials being designed to mimic its structure. Although N2200 itself is well-studied, many of these comparable materials have not been sufficiently characterized to compare their air stability to N2200. To further the development of air stable and high mobility n-type organic semiconductors, N2200 was studied in organic thin film transistors alongside three N2200-based analogues as well as a recently developed polymer based on a (3E,7E)-3,7-bis(2-oxoindolin-3-ylidene)benzo[1,2-b:4,5-b']difuran-2,6(3 H,7 H)-dione (IBDF) core. This IBDF polymer has demonstrated promising field-effect mobility and air stability in drop-cast OTFTs. While N2200 outperformed its analogues, the IBDF-based polymer displayed superior air and temperature stability compared to N2200. Overall, polymers with more heteroatoms displayed greater air stability. These findings will support the development of new air-stable materials, and further demonstrate the persistent need for the development of novel n-type semiconductors.

On-the-Spot Detection and Speciation of Cannabinoids Using Organic Thin-Film Transistors.

Quality control is imperative for Cannabis since the primary cannabinoids, Δ9-tetrahydrocannabinol (THC) and cannabidiol (CBD), elicit very different pharmacological effects. THC/CBD ratios are currently determined by techniques not readily accessible by consumers or dispensaries and which are impractical for use in the field by law-enforcement agencies. CuPc- and F16-CuPc-based organic thin-film transistors have been combined with a cannabinoid-sensitive chromophore for the detection and differentiation of THC and CBD. The combined use of these well-characterized and inexpensive p- and n-type materials afforded the determination of the CBD/THC ratio from rapid plant extracts, with results indistinguishable from high-pressure liquid chromatography. Analysis of the prepyrolyzed sample accurately predicted postpyrolysis THC/CBD, which ultimately influences the psychotropic and medicinal effects of the specific plant. The devices were also capable of vapor-phase sensing, producing a unique electrical output for THC and CBD relative to other potentially interfering vaporized organic products. The analysis of complex medicinal plant extracts and vapors, normally reserved for advanced analytical infrastructure, can be achieved with ease, at low cost, and on the spot, using organic thin-film transistors.

Developing 9,10-anthracene Derivatives: Optical, Electrochemical, Thermal, and Electrical Characterization.

Anthracene-based semiconductors are a class of molecules that have attracted interest due to their air stability, planarity, potential for strong intermolecular interactions, and favorable frontier molecular orbital energy levels. In this study seven novel 9,10-anthracene-based molecules were synthesized and their optical, electrochemical, and thermal properties were characterized, along with their single crystal arrangement. We found that functionalization of the 9,10-positions with different phenyl derivatives resulted in negligible variation in the optical properties with minor (±0.10 eV) changes in electrochemical behavior, while the choice of phenyl derivative greatly affected the thermal stability (Td > 258 °C). Preliminary organic thin film transistors (OTFTs) were fabricated and characterized using the 9,10-anthracene-based molecules as the semiconductor layer. These findings suggest that functionalization of the 9,10-position of anthracene leads to an effective handle for tuning of the thermal stability, while having little to no effect on the optical properties and the solid-state arrangement.

Old Molecule, New Chemistry: Exploring Silicon Phthalocyanines as Emerging N-Type Materials in Organic Electronics.

Efficient synthesis of silicon phthalocyanines (SiPc) eliminating the strenuous reaction conditions and hazardous reagents required by classical methods is described. Implementation into organic thin-film transistors (OTFTs) affords average electron field-effect mobility of 3.1 × 10-3 cm2 V-1 s-1 and threshold voltage of 25.6 V for all synthetic routes. These results demonstrate that our novel chemistry can lead to high performing SiPc-based n-type OTFTs.

P and N type copper phthalocyanines as effective semiconductors in organic thin-film transistor based DNA biosensors at elevated temperatures.

Many health-related diagnostics are expensive, time consuming and invasive. Organic thin film transistor (OTFT) based devices show promise to enable rapid, low cost diagnostics that are an important aspect to enabling increased access and availability to healthcare. Here, we describe OTFTs based upon two structurally similar P (copper phthalocyanine - CuPc) and N (hexdecafluoro copper phthalocyanine - F16-CuPc) type semiconductor materials, and demonstrate their potential for use as both temperature and DNA sensors. Bottom gate bottom contact (BGBC) OTFTs with either CuPc or F16-CuPc semiconducting layers were characterized within a temperature range of 25 °C to 90 °C in both air and under vacuum. CuPc devices showed small positive shifts in threshold voltage (V T) in air and significant linear increases in mobility with increasing temperature. F16-CuPc devices showed large negative shifts in V T in air and linear increases in mobility under the same conditions. Similar OTFTs were exposed to DNA in different hybridization states and both series of devices showed positive V T increases upon DNA exposure, with a larger response to single stranded DNA. The N-type F16-CuPc devices showed a much greater sensing response than the P-type CuPc. These findings illustrate the use of these materials, especially the N-type semiconductor, as both temperature and DNA sensors and further elucidate the mechanism of DNA sensing in OTFTs.

Metal phthalocyanine organic thin-film transistors: changes in electrical performance and stability in response to temperature and environment.

Metal phthalocyanines (MPcs) are a widely studied class of materials that are frequently used in organic thin-film transistors (OTFTs), organic photovoltaics (OPVs) and organic light emitting diodes (OLEDs). The stability of these devices and the materials used in their fabrication is important to realize their widespread adoption. Seven P-type MPcs: zinc (ZnPc), magnesium (MgPc), aluminum (AlClPc), iron (FePc), cobalt (CoPc), and titanium (TiOPc) were investigated as the semiconductors in OTFTs under varying temperatures (25 °C to 150 °C) and environmental conditions (air and vacuum, P < 0.1 Pa). Devices using the divalent MPcs (except MgPc) showed significant shifts in threshold voltage and field-effect mobility with rising temperature in both air and vacuum. AlClPc and TiOPc, on the other hand, had more stable electrical properties, making them useful for applications requiring consistent performance. Distinct variations in film morphology as determined by atomic force microscopy may explain the different thermal response between the two groups of MPcs, while thermal gravimetric analysis in air and nitrogen (N2) provides additional insight into their susceptibility to oxidation at elevated temperature. To demonstrate proof-of-concept thermal sensing under realistic operating conditions, current changes were monitored in response to temperature stimuli using two more sensitive divalent MPcs. This comparative study of the effect of central atom inclusion in MPcs, the resulting material stability and thin-film characteristics will facilitate design of future sensors and other OTFT applications.

Organic Thin Film Transistors Incorporating Solution Processable Thieno[3,2-b]thiophene Thienoacenes.

Bottom-gate bottom-contact organic thin film transistors (OTFTs) were prepared with four novel star-shaped conjugated molecules containing a fused thieno[3,2-b]thiophene moiety incorporated either in the core and/or at the periphery of the molecular framework. The molecules were soluble in CS2, allowing for solution-processing techniques to be employed. OTFTs with different channel geometries were characterized in both air and vacuum in order to compare environmental effects on performance. Blending the small molecules with poly(styrene), an insulating polymer, facilitated the formation of an even semiconducting film, resulting in an order of magnitude increase in device mobility. The highest field-effect mobilities were in air and on the order of 10-3 cm²/Vs for three of the four molecules, with a maximum mobility of 9.2 × 10-3 cm²/Vs achieved for the most conjugated small molecule. This study explores the relationship between processing conditions and OTFT devices performance for four different molecules within this new family of materials, resulting in a deeper insight into their potential as solution-processable semiconductors.

Orthogonally Processable Carbazole-Based Polymer Thin Films by Nitroxide-Mediated Polymerization.

Cross-linking of hole-transporting polymer thin films in organic light emitting diodes (OLEDs) has been shown to increase device efficacy when subsequent layers are deposited from solution. This improvement, due to resistance of the films to dissolution, could also be achieved by covalently grafting the polymer film to the substrate. Using nitroxide-mediated polymerization (NMP), we synthesized a novel poly(9-(4-vinylbenzyl)-9H-carbazole) (poly(VBK)) copolymer which can be cross-linked and also developed two simple methods for the grafting-to or grafting-from, also known as surface-initiated polymerization, of poly(VBK) to indium tin oxide (ITO) substrates. All three of these methods produced thin films that could be orthogonally processed; that is, they resisted dissolution when the spin-coating of a subsequent layer was simulated. Similar electrochemical behavior for the poly(VBK) films was observed regardless of the technique used, suggesting that all three techniques could be used in the engineering of organic electronic devices. We expect that all three methods would be worth investigating in the solution-based assembly of OLEDs and other organic electronic devices.

Phthalocyanine-Based Organic Thin-Film Transistors: A Review of Recent Advances.

Metal phthalocyanines (MPcs) are versatile conjugated macrocycles that have attracted a great deal of interest as active components in modern organic electronic devices. In particular, the charge transport properties of MPcs, their chemical stability, and their synthetic versatility make them ideal candidate materials for use in organic thin-film transistors (OTFTs). This article reviews recent progress in both the material design and device engineering of MPc-based OTFTs, including the introduction of solubilizing groups on the MPcs and the surface modification of substrates to induce favorable MPc self-assembly. Finally, a discussion on emerging niche applications based on MPc OTFTs will be explored, in addition to a perspective and outlook on these promising materials in OTFTs. The scope of this review is focused primarily on the advances made in the field of MPc-based OTFTs since 2008.