Stephen G. Yeates

Organic field effect transistors from ambient solution processed low molar mass semiconductor–insulator blends

The morphology and organic field effect transistor (OFET) properties of two component blends of semi-crystalline 6,13-bis(triisopropylsilylethinyl)pentacene (TIPS-pentacene) with selected amorphous and semi-crystalline side chain aromatic low permittivity insulating binders deposited at room temperature under vacuum from a good solvent are reported. When blended with an amorphous binder there is evidence from X-ray photoelectron spectroscopy (XPS) of a strong interaction between TIPS-pentacene and the binder in the solidified film giving rise to twisted TIPS-pentacene crystals containing dislocations. Due to this strong interaction we see no evidence of segregation of TIPS-pentacene towards the active interface and hence we observe a rapid fall off in saturated hole mobility at an active concentration less than 50 wt%. When blended with a crystalline binder there is no evidence from XPS of any interaction between TIPS-pentacene and the binder in the solidified film. We propose that when a semi-crystalline binder is used, which crystallizes more slowly from solution than TIPS-pentacene, we observe stratification of the active material to both interfaces and as a result retention of saturated hole mobility even down to 10 wt%. The potential applications of the approach are in the formulation of low-cost organic semiconductors whose solution and solid state properties can be fine-tuned by careful binder selection.

Heterostructures Produced from Nanosheet-Based Inks

The new paradigm of heterostructures based on two-dimensional (2D) atomic crystals has already led to the observation of exciting physical phenomena and creation of novel devices. The possibility of combining layers of different 2D materials in one stack allows unprecedented control over the electronic and optical properties of the resulting material. Still, the current method of mechanical transfer of individual 2D crystals, though allowing exceptional control over the quality of such structures and interfaces, is not scalable. Here we show that such heterostructures can be assembled from chemically exfoliated 2D crystals, allowing for low-cost and scalable methods to be used in device fabrication.

High performance, acene-based organic thin film transistors

1,4,8,11-Methyl-substituted 6,13-triethylsilylethynylpentacene shows extended pi-pi overlap when deposited from solution, yielding organic thin film transistors with high and reproducible hole mobility with negligible hysteresis.

Inkjet printing of polymer solutions and the role of chain entanglement

The influence of polymer concentration, going from the dilute through the overlap into the concentrated regime, during drop on demand inkjet printing is investigated for a range of cellulose ester (CE) polymers from visual examination of ligament stretching as a function of applied wave form. The physical behaviour of the polymer fluids in drop formation is indicative of the dominance of viscoelastic effects within the timescale of the process, in preventing ligament break-up at the pinch point compared with a water–glycerol–isopropanol blend Newtonian fluid of similar viscosity. This has previously been described in terms of the polymer chain undergoing a coil–stretch transition at the strain rates experienced in the inkjet process. When formulated at the coil overlap concentration all polymers showed qualitatively similar behaviour with respect to time and length of ligament at rupture irrespective of polymer molecular weight. Beyond the overlap concentration the ligament rupture time continues to increase with increasing elasticity of the solution but the ligament rupture length decreases rapidly. In this regime chain entanglement becomes important, dramatically increasing the elastic nature of the ligament. Additionally it is proposed that in the case of weakly associating polymers such as cellulose esters, the effective relaxation time is further increased due to the possibility that on chain extension intramolecular H-bonds are broken and may reform as intermolecular associations whilst the polymer chains are extended. These intermolecular associations act as physical crosslinks, thereby creating a transient network structure. This network structure is capable of having a finite large viscosity. Once the strain is removed the network will decay as the chains return to the more thermodynamically stable coil state.

Inkjet printed paper based frequency selective surfaces and skin mounted RFID tags: the interrelation between silver nanoparticle ink, paper substrate and low temperature sintering technique

Inkjet printing of functional frequency selective surfaces (FSS) and radio frequency identification (RFID) tags on commercial paper substrates using silver nanoparticle inks sintered using low temperature thermal, plasma and photonic techniques is reported. Printed and sintered FSS devices demonstrate performances which achieve wireless communication requirements having a forward transmission scattering parameter, S21, depth greater than -20 dB at 13 GHz. Printed and plasma sintered RFID tags on transfer paper, which are capable of being mounted on skin, improved read distances compared to previously reported single layer transfer RFID tags fabricated by conventional thermal sintering. This journal is cop. The Royal Society of Chemistry 2015.

Reducing dynamic disorder in small-molecule organic semiconductors by suppressing large-amplitude thermal motions

Thermal vibrations and the dynamic disorder they create can detrimentally affect the transport properties of van der Waals bonded molecular semiconductors. The low-energy nature of these vibrations makes it difficult to access them experimentally, which is why we still lack clear molecular design rules to control and reduce dynamic disorder. In this study we discuss the promising organic semiconductors rubrene, 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothio-phene and 2,9-di-decyl-dinaphtho-[2,3-b:20,30-f]-thieno-[3,2-b]-thiophene in terms of an exceptionally low degree of dynamic disorder. In particular, we analyse diffuse scattering in transmission electron microscopy, to show that small molecules that have their side chains attached along the long axis of their conjugated core are better encapsulated in their crystal structure, which helps reduce large-amplitude thermal motions. Our work provides a general strategy for the design of new classes of very high mobility organic semiconductors with a low degree of dynamic disorder.

New routes to poly(4,4-dialkylcyclopentadithiophene-2,6-diyls)

Two new polymerisation routes to poly(4,4-dioctylcyclopentadithiophene-2,6-diyl) are reported. The polymer prepared by Kumada type cross-coupling showed significantly reduced molecular weight over that prepared by direct oxidative polymerisation using iron(III) chloride. The higher molecular weight polymer was shown to have extended conjugation by UV-visible spectroscopy.

Towards inkjet-printed low cost passive UHF RFID skin mounted tattoo paper tags based on silver nanoparticle inks

The present work describes the inkjet printing and low temperature sintering of silver nanoparticle inks onto transfer tattoo paper. Our approach results in silver features of excellent resolution and conductivity and, subsequently the first passive UHF RFID transfer tattoo tags functional mounted on human skin of improved performance when compared to screen printed passive UHF RFID transfer tattoo paper tags. Moreover, inkjet printed passive UHF RFID transfer tattoo tags show similar performance to copper etched passive UHF RFID tags on plastic substrates. This study compares the image quality (resolution) and electrical performance of two commercial silver nanoparticle inks inkjet printed on transfer tattoo paper. The optimal printing and sintering parameters to obtain high resolution features of resistivities 20 to 57 times the resistivity of bulk silver (1.59 × 10−6 ohm cm) are described. We demonstrate how, by selectively depositing ink in specific areas of the antenna, read distance of passive UHF RFID tags can be increased from 54 to 68 cm whilst decreasing the amount of ink used by 33%. Furthermore, this approach results in inkjet printed passive UHF RFID tattoo tags with larger read distance than silver screen printed passive UHF RFID tattoo tags, 45 cm, and similar to copper etched passive UHF RFID plastic tags, 75 cm. Moreover, inkjet printed passive UHF RFID tattoo tags in this work are considerably thinner (1–5 μm) than screen and etched passive UHF RFID tags (tens of micrometers) hence, making the former more appealing to the end user. In addition to this, inkjet printing is compatible with large area manufacturing techniques and has the potential to evolve as one of the most promising RFID mass-production techniques. Therefore, this work represents a step towards the commercialization of on-body transfer tattoo paper passive UHF RFID tags.

Poly(styrene oxide)-poly(ethylene oxide) block copolymers: From "classical" chemotherapeutic nanocarriers to active cell-response inducers.

Two poly(styrene oxide)-poly(ethylene oxide) (PSO-PEO) triblock copolymers with different chain lengths were analyzed as potential chemotherapeutic nanocarriers, and their ability to inhibit the P-glycoprotein (P-gp) efflux pump in a multidrug resistant (MDR) cell line were measured in order to establish possible cell-responses induced by the presence of the copolymer molecules. Thus, EO33SO14EO33 and EO38SO10EO38 polymeric micelles were tested regarding doxorubicin (DOXO) entrapment efficiency (solubilization test), physical stability (DLS), cytocompatibility (fibroblasts), release profiles at various pHs (in vitro tests), as well as P-gp inhibition and evasion and cytotoxicity of the DOXO-loaded micelles in an ovarian MDR NCI-ADR/RES cell line and in DOXO-sensitive MCF-7 cells. EO33SO14EO33 and EO38SO10EO38 formed spherical micelles (~13nm) at lower concentration than other copolymers under clinical evaluation (e.g. Pluronic®), exhibited 0.2% to 1.8% loading capacity, enhancing more than 60 times drug apparent solubility, and retained the cargo for long time. The copolymer unimers inhibited P-gp ATPase activity in a similar way as Pluronic P85, favoring DOXO accumulation in the resistant cell line, but not in the sensitive cell line. DOXO loaded in the micelles accumulated more slowly inside the cells, but caused greater cytotoxicity than free drug solutions in the NCI-ADR-RES cell line, which overexpressed P-gp. Hence, PSO-PEO block copolymers offer interesting features as new biological response modifiers to be used in the design of efficient nanocarriers for cancer chemotherapy.

Solubilisation capacity of Brij surfactants

The aim of this study was to investigate the potential of selected Brij non-ionic surfactants for enhancing the solubility of poorly water-soluble drugs. Griseofulvin was selected as a model drug candidate enabling comparisons to be made with the solubilisation capacities of other poly(ethylene oxide)-based copolymers. UV/Vis and (1)H NMR spectroscopies were used to quantify the enhancement of solubility of griseofulvin in 1 wt% aqueous micellar solutions of Brij 78 (C(18)H(37)E(20)), Brij 98 (C(18)H(35)E(20)) and Brij 700 (C(18)H(37)E(100)) (where E represents the OCH(2)CH(2) unit of the poly(ethylene oxide) chain) at 25, 37 and 40 °C. Solubilisation capacities (S(cp) expressed as mg griseofulvin per g Brij) were similar for Brij 78 and 98 (range 6-11 mg g(-1)) but lower for Brij 700 (3-4 mg g(-1)) as would be expected for the surfactant with the higher ethylene oxide content. The drug loading capacity of micelles of Brij 78 was higher than many di- and triblock copolymers with hydrophilic E-blocks specifically designed for enhancement of drug solubility.