Vacuum production of OTFTs by vapour jet deposition of dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DNTT) on a lauryl acrylate functionalised dielectric surface

Roll-to-roll (R2R) production of organic transistors and circuits require patterned deposition of organic layers at high deposition rate. Here we demonstrate a vapour-jet process for the rapid deposition of the organic semiconductor dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT). The deposition rate achieved, equivalent to ~200 nm/s onto a stationary substrate, was several orders of magnitude faster than ordinary thermal evaporation. Nevertheless, transistor yield was 100% with an average mobility of 0.4 cm2/Vs in a single pass deposition onto a substrate moving at 0.15 m/min. We also demonstrate a vacuum, high rate R2R-compatible process for surfacefunctionalising a gate dielectric layer with lauryl acrylate which enabled an all-vacuum route to the fabrication of a five-stage ring oscillator

Stable organic static random access memory from a roll-to-roll compatible vacuum evaporation process

An organic Static Random Access Memory (SRAM) based on p-type, six-transistor cells is demonstrated. The bottom-gate top-contact thin film transistors composing the memory were fabricated on flexible polyethylene naphthalate substrates. All metallization layers and the p-type semiconductor dinaphtho[2,3-b:2',3'-f] thieno[3,2-b]thiophene were deposited by thermal evaporation. The gate dielectric was deposited in a vacuum roll-to-roll environment at a web speed of 25 m/min by flash-evaporation and subsequent plasma polymerisation of tripropyleneglycol diacrylate (TPGDA). Buffering the TPGDA with a polystyrene layer yields hysteresis-free transistor characteristics with turn-on voltage close to zero. The static transfer characteristic of diode-connected load inverters were also hysteresis-free with maximum gain >2 and noise margin ∼2.5 V. When incorporated into SRAM cells the time-constant for writing data into individual SRAM cells was less than 0.4 ms. Little change occurred in the magnitude of the stored voltages, when the SRAM was powered continuously from a −40 V rail for over 27 h testifying to the electrical stability of the threshold voltage of the individual transistors. Unencapsulated SRAM cells measured two months after fabrication showed no significant degradation after storage in a clear plastic container in normal laboratory ambient

Organic Digital Logic and Analog Circuits Fabricated in a Roll-to-Roll Compatible Vacuum-Evaporation Process

We report the fabrication of a range of organic circuits produced by a high-yielding, vacuum-based process compatible with roll-to-roll production. The circuits include inverters, NAND and NOR logic gates, a simple memory element (set-reset latch), and a modified Wilson current mirror circuit. The measured circuit responses are presented together with simulated responses based on a previously reported transistor model of organic transistors produced using our fabrication process. Circuit simulations replicated all the key features of the experimentally observed circuit performance. The logic gates were capable of operating at frequencies in excess of 1 kHz while the current mirror circuit produced currents up to 18 μA

Non-steady state operation of polymer/TiO2 photovoltaic devices

We present data on the initial period of operation of Gilch-route NMH-PPV/TiO2 composite solar cells (CSCs) which show that during this period the CSCs operate in a non-steady state regime. The behavior is complex and may include a gradual rise of the open circuit voltage (V-oc) and of the short-circuit current density (J(sc)) with time, a passage through a maximum of either or both parameters, and even a sign reversal. The mechanisms most probably contributing to the transient processes are: i) diffusion driven redistribution of charges resulting in the build up of a quasi steady state charge density profile across the device; ii) photo-doping resulting in a relatively slow increase of the average charge carrier concentration and consequently of the conductivity of the device. The latter is responsible for a strong decrease in V-oc, and is evidenced by the significant increase in dark current after device illumination

Nanocomposite titanium dioxide/polymer photovoltaic cells: effects of TiO2 microstructure, time and illumination power.

Nanocomposite titanium dioxide/polymer photovoltaic cells have been fabricated using poly[2-(2-ethylhexyloxy)-5-methoxy-1,4-phenylenevinylene] (MEHPPV). Two different types of titanium dioxide were used, one synthesized using a sol-gel method, the other was a commercial paste. The crystal structure, porosity and absorption spectra of the titanium dioxide layers were measured, and the titanium dioxide synthesized using the sol-gel method had a much lower level of anatase. The photovoltaic properties of the ITO/TiO2/MEHPPV/Au cells, which were similar for both types of TiO2, were measured as a function of illumination power and compared with equivalent circuit models. A simple equivalent circuit model incorporating a diode, two resistances and a light induced current was inconsistent with the illumination - dependent data and was improved by adding an illumination dependent shunt resistance. A very long lived, photo-induced increase in dark current was observed, which could not be explained by a polymer degradation mechanism or an increase in temperature under illumination, but was more likely to be due to trapped charge

A high-yield vacuum-evaporation-based R2R-compatible fabrication route for organic electronic circuits

Advances are described in a vacuum-evaporation-based approach for the roll-to-roll (R2R) production of organic thin film transistors (TFTs) and circuits. Results from 90-transistor arrays formed directly onto a plasma-polymerised diacrylate gate dielectric are compared with those formed on polystyrene-buffered diacrylate. The latter approach resulted in stable, reproducible transistors with yields in excess of 90%. The resulting TFTs had low turn-on voltage, on-off ratios ∼106 and mobility ∼1 cm2/V s in the linear regime, as expected for dinaphtho[2,3-b: 2′,3′-f] thieno[3,2-b]thiophene the air stable small molecule used as the active semiconductor. We show that when device design is constrained by the generally poor registration ability of R2R processes, parasitic source-drain currents can lead to a >50% increase in the mobility extracted from the resulting TFTs, the increases being especially marked in low channel width devices. Batches of 27 saturated-load inverters were fabricated with 100% yield and their behaviour successfully reproduced using TFT parameters extracted with Silvaco's UOTFT Model. 5- and 7-stage ring oscillator (RO) outputs ranged from ∼120 Hz to >2 kHz with rail voltages, VDD, increasing from -15 V to -90 V. From simulations an order of magnitude increase in frequency could be expected by reducing parasitic gate capacitances. During 8 h of continuous operation at VDD = -60 V, the frequency of a 7-stage RO remained almost constant at ∼1.4 kHz albeit that the output signal amplitude decreased from ∼22 V to ∼10 V. Over the next 30 days of intermittent operation further degradation in performance occurred although an unused RO showed no deterioration over the same period. © 2014 The Authors. Published by Elsevier B.V

Nanoscale depth-resolved polymer dynamics probed by the implantation of low energy muons

The low energy muon (LEM) technique has been used to probe local changes in the dynamical spectrum of thin film polymer samples taking place as a function of the temperature and the implantation depth below the free surface. The studies have been made on samples of polydimethylsiloxane (PDMS) and polybutadiene (PB) using the transverse magnetic field (TF) configuration and diamagnetic probe muons. In PDMS evidence is found for suppression of the glass transition temperature near the surface, along with significantly modified dynamics in the near-surface region as well as at depths significantly below the surface. For PB the LEM technique reveals well-defined layers of dynamical and spatial inhomogeneity at depths of order 0.1–0.2 μm below the free surface. These inhomogeneous regions may be assigned to nanopores produced by solvent streaming during preparation of spin-cast films. A thermal annealing procedure is shown to significantly reduce the thickness of these inhomogeneous layers. These results demonstrate that using LEM in the TF configuration provides a promising new method for studying surface-modified local dynamics of polymers that is also able to reveal nanostructured buried layers in polymer films

Twofold efficiency increase in nanocrystalline-TiO2/polymer photovoltaic devices by interfacial modification with a lithium salt

Modification of the interface of titanium dioxide/poly[2-(2-ethylhexyloxy)-5-methoxy-1,4,-phenylenevinylene] (TiO2/MEH-PPV) nanocomposite photovoltaic devices with a lithium salt, Li[CF3SO2](2)N, is shown to result in a twofold increase in device efficiency. The devices are of the type ITO/TiO2/MEH-PPV/Au. The TiO2 layer is deposited by doctor blading a colloidal anatase paste, and the polymer is then spin-coated on top followed by thermal evaporation of gold contacts. Careful control of manufacturing conditions and use of a 35 nm polymer layer leads to a device efficiency of 0.48% for un-modified devices. The increased efficiency following Li treatment is the result of a 40% increase in both the short-circuit current and fill factor, while the open-circuit voltage remains unchanged. A maximum efficiency of 1.05% has been achieved under 80% sun illumination. This represents a record efficiency for this type of cell. Photoconductivity experiments show a substantial increase in conductivity of the TiO2 layer following Li modification. Interfacial modification is done via a simple soaking procedure, and the effect of varying the concentration of Li[CF3SO2](2)N is discussed. We report investigations into optimization and the mechanism of such improvement, for example by varying processing parameters of the modification procedure or the ionic species themselves

Aluminium oxide barrier films on polymeric web and their conversion for packaging applications

In recent years, inorganic transparent barrier layers such as aluminium oxide or silicon oxide deposited onto polymer films have emerged as an attractive alternative to polymer based transparent barrier layers for flexible food packaging materials. For this application, barrier properties against water vapour and oxygen are critical. Aluminium oxide coatings can provide good barrier levels at thicknesses in the nanometre range, compared to several micrometres for polymer-based barrier layers. These ceramic barrier coatings are now being produced on a large scale using industrial high speed vacuum deposition techniques, here, reactive evaporation on a 'boat-type' roll-to-roll metalliser. For the thin barrier layer to be useful in its final packaging application, it needs to be protected. This can be either via lamination or via an additional topcoat. This study reports on acrylate topcoats, but also undercoats, on aluminium oxide coated biaxially oriented polypropylene films. The effect of the acrylate layer on barrier levels and surface topography and roughness was investigated. The acrylate was found to smooth the substrate surface and improve barrier properties. Furthermore, the activation energy for water vapour and oxygen permeation was determined in order to investigate barrier mechanisms. The oxide coated film was, additionally, converted via adhesive lamination, which also provided improvement in barrier levels. © 2013 Elsevier B.V. All rights reserved