This PDF file contains the front matter associated with SPIE Proceedings Volume 9943, including the Title Page, Copyright information, Table of Contents, Introduction (if any), and Conference Committee listing.

Electrolyte gated transistors (EGTs) are a sub-class of thin film transistors that are extremely promising for biological sensing applications. These devices employ a solid electrolyte as the gate insulator; the very large capacitance of the electrolyte results in low voltage operation and high transconductance or gain. This talk will describe the fabrication of floating gate EGTs and their use as ricin sensors. The critical performance metrics for EGTs compared with other types of TFTs will also be reviewed.

We have recently focused our attention on the application of perovskite materials to a semiconducting layer in field-effect transistors. Because perovskite materials are expected to promise the processability and flexibility inherent to organic semiconductors as well as the superior carrier transport inherent to inorganic semiconductors, we believe that organic semiconductor-like cost-effective, flexible transistors with inorganic semiconductor-like high carrier mobility can be realized using perovskite semiconductors in future. In this study, we have prepared the tin iodide-based perovskite as a semiconducting layer on silicon dioxide layers treated with a self-assembled monolayer containing ammonium iodide terminal groups by spin coating and, then, source-drain electrodes on the perovskite layer by vacuum deposition for the fabrication of a top-contact perovskite transistor. Because of a well-developed perovskite layer formed on the treated substrate and reduced contact resistance resulting from the top-contact structure, we have obtained a new record hole mobility of up to 12 cm2 V–1 s–1 in our perovskite transistors, which is about five times higher than a previous record hole mobility and is considered to be a very good value when compared with widely investigated organic transistors. Along with the high hole mobility, we have demonstrated that this surface treatment leads to smaller hysteresis in output and transfer characteristics and better stress stability under constant gate voltage application. These findings open the way for huge advances in solution-processable high-mobility transistors.

In electronic systems, components often require different supply voltage for operation. In order to meet this requirement and to optimize power consumption for flexible electronics, we demonstrate a pulsed voltage multiplier that boosts the voltage at specific circuit nodes above the supply voltage. A five-stage pulsed voltage multiplier is shown to provide an output voltage up to 18 V from a supply voltage of 10 V, with minimum 10 ms pulse rise time for a 70 pF load. A key requirement for the pulsed voltage multiplier circuit is low device leakage to boost the output voltage level. To minimize leakage, the composition of the organic semiconducting layer is modified by blending an insulating polymer with the small molecule semiconductor. This modification allows control over the transistor turn-on voltage, which enables low leakage current required for operation of the circuits. The printed multiplier allows a single power source to deliver multiple voltage levels and enables integration of lower voltage logic with components that require higher operating voltage, for example, in the case of recording data into memory cells in sensor tags.

Organic field effect transistors (OFET) operated in aqueous environments are emerging as ultra-sensitive biosensors and transducers of electrical and electrochemical signals from a biological environment. Their applications range from detection of biomarkers in bodily fluids to implants for bidirectional communication with the central nervous system. They can be used in diagnostics, advanced treatments and theranostics. Several OFET layouts have been demonstrated to be effective in aqueous operations, which are distinguished either by their architecture or by the respective mechanism of doping by the ions in the electrolyte solution. In this work we discuss the unification of the seemingly different architectures, such as electrolyte-gated OFET (EGOFET), organic electrochemical transistor (OECT) and dual-gate ion-sensing FET. We first demonstrate that these architectures give rise to the frequency-dependent response of a synapstor (synapse-like transistor), with enhanced or depressed modulation of the output current depending on the frequency of the time-dependent gate voltage. This behavior that was reported for OFETs with embedded metal nanoparticles shows the existence of a capacitive coupling through an equivalent network of RC elements. Upon the systematic change of ions in the electrolyte and the morphology of the charge transport layer, we show how the time scale of the synapstor is changed. We finally show how the substrate plays effectively the role of a second bottom gate, whose potential is actually fixed by the pH/composition of the electrolyte and the gate voltage applied.

Generally, the differences in crystal polymorph exhibit different narrow band structures, electron-phonon coupling, optoelectronic characteristics and charge transport properties, thus leading to different device performances of organic semiconductors for application in organic field-effect transistors (OFETs). Nowadays it still remains a big challenge to control organic crystal polymorph because the slight non-directional intermolecular interactions lead to the very small differences instructure and energy of cystal phases with several alternative packing arrangements. Therefore, the control of the crystal polymorphism towards high device performance has become a crucial issue in the field of organic semiconductors. Thienoacenes have been intensively investigated as very promising organic semiconductors with high stability and superior mobility for OFETs in the last decade. However, scare studies focused on the crystal polymorph of thienoacenes. Herein, we report the controllable growth of different crystal phases of dihexyl-substituted dibenzo[d,d′]thieno[3,2-b;4,5-b′]dithiophene (C6-DBTDT), which was synthesized in a new, facile and efficient method. Furthermore, OFETs based on microribbon-shaped β phase crystals showed the hole mobility up to 18.9 cm2 V-1 s-1, which is one of the highest value for p-type organic semiconductors measured under ambient conditions, while platelet-shaped α phase crystals displayed the lower hole mobility of 8.5 cm2 V-1 s-1. We clearly demonstrated that the selective growth of different crystal polymorph for C6-DBTDT can be achieved by using different substrate and solvents. The simple drop-cast fabrication with controllable crystal phase and air operation stability would open the possibility of thienoacene derivatives in the construction of micro- and nanoelectronics.

Organic field-effect transistors (OFETs) have the potential to lead to low-cost flexible displays, wearable electronics, and sensors. While recent efforts have focused greatly on improving the maximum charge mobility that can be achieved in such devices, studies about the stability and reliability of such high performance devices are relatively scarce. In this talk, we will discuss the results of recent studies aimed at improving the stability of OFETs under operation and their shelf lifetime. In particular, we will focus on device architectures where the gate dielectric is engineered to act simultaneously as an environmental barrier layer. In the past, our group had demonstrated solution-processed top-gate OFETs using TIPS-pentacene and PTAA blends as a semiconductor layer with a bilayer gate dielectric layer of CYTOP/Al2O3, where the oxide layer was fabricated by atomic layer deposition, ALD. Such devices displayed high operational stability with little degradation after 20,000 on/off scan cycles or continuous operation (24 h), and high environmental stability when kept in air for more than 2 years, with unchanged carrier mobility. Using this stable device geometry, simple circuits and sensors operating in aqueous conditions were demonstrated. However, the Al2O3 layer was found to degrade due to corrosion under prolonged exposure in aqueous solutions. In this talk, we will report on the use of a nanolaminate (NL) composed of Al2O3 and HfO2 by ALD to replace the Al2O3 single layer in the bilayer gate dielectric use in top-gate OFETs. Such OFETs were found to operate under harsh condition such as immersion in water at 95 °C. This work was funded by the Department of Energy (DOE) through the Bay Area Photovoltaics Consortium (BAPVC) under Award Number DE-EE0004946.

The high performance air stable organic semiconductor small molecule dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT) was chosen as active layer for field effect transistors built to realize flexible amplifier circuits. Initial device on rigid Si/SiO₂ substrate showed appreciable performance with hysteresis-free characteristics. A number of approaches were applied to simplify the process, improve device performance and decrease the operating voltage: they include an oxide interfacial layer to decrease contact resistance; a polymer passivation layer to optimize semiconductor/dielectric interface and an anodized high-k oxide as dielectric layer for low voltage operation. The devices fabricated on plastic substrate yielded excellent electrical characteristics, showing mobility of 1.6 cm²/Vs, lack of hysteresis, operation below 5 V and on/off current ratio above 10⁵. An OFET model based on variable ranging hopping theory was used to extract the relevant parameters from the transfer and output characteristics, which enabled us to simulate our devices achieving reasonable agreement with the measurements

Organic field-effect transistors (OFET) are important elements in thin-film electronics, being considered for flat-panel or flexible displays, radio frequency identification systems, and sensor arrays. To optimize the devices for high-frequency operation, the channel length, defined as the horizontal distance between the source and the drain contact, can be scaled down. Here, an architecture with a vertical current flow, in particular the Organic Permeable-Base Transistors (OPBT), opens up new opportunities, because the effective transit length in vertical direction is precisely tunable in the nanometer range by the thickness of the semiconductor layer. We present an advanced OPBT, competing with best OFETs while a low-cost, OLED-like fabrication with low-resolution shadow masks is used (Klinger et al., Adv. Mater. 27, 2015). Its design consists of a stack of three parallel electrodes separated by two semiconductor layers of C60 . The vertical current flow is controlled by the middle base electrode with nano-sized openings passivated by an native oxide. Using insulated layers to structure the active area, devices show an on/off ratio of 10⁶ , drive 11 A/cm² at an operation voltage of 1 V, and have a low subthreshold slope of 102 mV/decade. These OPBTs show a unity current-gain transit frequency of 2.2 MHz and off-state break-down fields above 1 MV/cm. Thus, our optimized setup does not only set a benchmark for vertical organic transistors, but also outperforms best lateral OFETs using similar low-cost structuring techniques in terms of power efficiency at high frequencies.

Due to their ease of processing, organic semiconductors are promising candidates for applications in high performance flexible displays and fast organic electronic circuitry. Recently, a lot of advances have been made on organic semiconductors exhibiting surprisingly high performance and carrier mobilities exceeding those of amorphous silicon. However, there remain significant concerns about their operational and environmental stability, particularly in the context of applications that require a very high level of threshold voltage stability, such as active-matrix addressing of organic light-emitting diode (OLED) displays. Here, we report a novel technique for dramatically improving the operational stress stability, performance and uniformity of high mobility polymer field-effect transistors by the addition of specific small molecule additives to the polymer semiconductor film. We demonstrate for the first time polymer FETs that exhibit stable threshold voltages with threshold voltage shifts of less than 1V when subjected to a constant current operational stress for 1 day under conditions that are representative for applications in OLED active matrix displays. The approach constitutes in our view a technological breakthrough; it also makes the device characteristics independent of the atmosphere in which it is operated, causes a significant reduction in contact resistance and significantly improves device uniformity. We will discuss in detail the microscopic mechanism by which the molecular additives lead to this significant improvement in device performance and stability.

The organic electrochemical transistor (OECT), capable of amplifying small electrical signals in an aqueous environment, is an ideal device to utilize in organic bioelectronic applications involving for example neural interfacing and diagnostics. Currently, most OECTs are fabricated with commercially available conducting poly(3,4-ethylenedioxythiophene)-based suspensions such as PEDOT:PSS and are therefore operated in depletion mode giving rise to devices that are permanently on with non-optimal operational voltage. With the aim to develop and utilize efficient accumulation mode OECT devices, we discuss here our recent results regarding the design, synthesis and performance of novel intrinsic semiconducting polymers. Covering key aspects such as ion and charge transport in the bulk semiconductor and operational voltage and stability of the materials and devices, we have elucidated important structure-property relationships. We illustrate the improvements this approach has afforded in the development of high performance accumulation mode OECT materials.

Highly ordered organic semiconductors in solid state with optimal molecular packing are critical to their electrical performance. Single crystals with long-range molecular orders and nearly perfect molecular packing are the best candidates, which already have been verified to exhibit the highest performance whether based on inorganic or small organic materials. However, in comparison, preparing high quality polymer crystals remains a big challenge in polymer science because of the easy entanglements of the long and flexible polymer chains during self-assembly process, which also significantly limits the development of their crystalline polymeric electronic devices. Here we have carried out systematical investigations to prepare high quality semiconducting polymers and high performance semiconducting polymer crystal optoelectronic devices have been successfully fabricated. The semiconducting polymeric devices demonstrate significantly enhanced charge carreir transport compared to their thin films, and the highest carreir mobiltiy could be approcahing 30 cm2 V-1s-1, one of the highest mobiltiy values for polymer semiconductors.

Small molecular organic semiconductor crystals form interesting electronic systems of periodically arranged “charge clouds” whose mutual electronic coupling determines whether or not electronic states can be coherent over fluctuating molecules. This presentation focuses on two methods to reduce molecular fluctuation, which strongly restricts mobility of highly mobile charge in single-crystal organic transistors. The first example is to apply external hydrostatic pressure. Using Hall-effect measurement for pentacene FETs, which tells us the extent of the electronic coherence, we found a crossover from hopping-like transport of nearly localized charge to band transport of delocalized charge with full coherence. As the result of temperature dependence measurement, it turned out that reduced molecular fluctuation is mainly responsible for the crossover. The second is to apply uniaxial strain to single-crystal organic FETs. We applied stain by bending thin films of newly synthesized decyldinaphthobenzodithiophene (C10-DNBDT) on plastic substrate so that 3% strain is uniaxially applied. As the result, the room-temperature mobility increased by the factor of 1.7. In-depth analysis using X-ray diffraction (XRD) measurements and density functional theory (DFT) calculations reveal the origin to be the suppression of the thermal fluctuation of the individual molecules, which is confirmed by temperature dependent measurements. Our findings show that compressing the crystal structure directly restricts the vibration of the molecules, thus suppressing dynamic disorder, a unique mechanism in organic semiconductors. Since strain can easily be induced during the fabrication process, these findings can directly be exploited to build high performance organic devices.

In this contribution, we examine the main factors that define charge transport in organic semiconductors. We consider both crystals based on a single molecule building block, such as oligoacenes, and two-component donor-acceptor crystals in which one component acts as an electron donor and the other as an acceptor. We will first discuss the state-of-the-art methodologies used in the derivation of the microscopic parameters (electron-vibration couplings, transfer integrals, band gaps, bandwidths, and effective masses) describing charge transport. In particular, we will discuss the impact that the amount of nonlocal Hartree-Fock exchange included in a hybrid density functional has on these parameters. In order to understand the role of disorder we use a combination of electronic-structure calculations and molecular mechanics/molecular dynamics simulations complemented by ensemble and time average approaches to separate the static and dynamic disorder components. The temperature dependence of the charge carrier mobility is studied by treating the electron-phonon interaction as a perturbation (Boltzmann theory), in the static approximation (Kubo formalism) and in the framework of mixed quantum/classical dynamics. Finally, based on the results of the kinetic Monte Carlo simulations we will compare the merits of a hopping model and a mobility edge model in the description of the effect of charge-carrier concentration on the electrical conductivity, carrier mobility, and Fermi energy of organic semiconductors.

A new computational model to predict the hole mobility of poly-crystalline organic semiconductors in thin film was developed (refer to Phys. Chem. Chem. Phys., 2016, DOI: 10.1039/C6CP02993K). Site energy differences and transfer integrals in crystalline morphologies of organic molecules were obtained from quantum chemical calculation, in which the periodic boundary condition was efficiently applied to capture the interactions with the surrounding molecules in the crystalline organic layer. Then the parameters were employed in kinetic Monte Carlo (kMC) simulations to estimate the carrier mobility. Carrier transport in multiple directions has been considered in the kMC simulation to mimic polycrystalline characteristic in thin-film condition. Furthermore, the calculated mobility was corrected with a calibration equation based on the microscopic images of thin films to take the effect of grain boundary into account. As a result, good agreement was observed between the predicted and measured hole mobility values for 21 molecular species: the coefficient of determination (R²) was estimated to be 0.83 and the mean absolute error was 1.32 cm² V⁻¹ s⁻¹. This numerical approach can be applied to any molecules for which crystal structures are available and will provide a rapid and precise way of predicting the device performance.

Transport in organic semiconductors has traditionally been investigated using measurements of the temperature and gate voltage dependent mobility of charge carriers within the channel of organic field-effect transistors (OFETs). In such measurements, the behavior of charge carrier mobility with temperature and gate voltage, studied together with carrier activation energies, provide a metric to quantify the extent of disorder within these van der Waals bonded materials. In addition to the mobility and activation energy, another potent but often-overlooked transport coefficient useful in understanding disorder is the Seebeck coefficient (also known as thermoelectric power). Fundamentally, the Seebeck coefficient represents the entropy per charge carrier in the solid state, and thus proves powerful in distinguishing materials in which charge carriers move freely from those where a high degree of disorder causes the induced carriers to remain trapped. This paper briefly covers the recent highlights in the field of organic thermoelectrics, showing how significant strides have been made both from an applied standpoint as well as from a viewpoint of fundamental thermoelectric transport physics. It shall be illustrated how thermoelectric transport parameters in organic semiconductors can be tuned over a significant range, and how this tunability facilitates an enhanced performance for heat-to-electricity conversion as well as quantifies energetic disorder and the nature of the density of states (DOS). The work of the authors shall be spotlighted in this context, illustrating how Seebeck coefficient measurements in the polymer indacenodithiophene-co-benzothiadiazole (IDTBT) known for its ultra-low degree of torsion within the polymer backbone, has a trend consistent with low disorder. ¹ Finally, using examples of the small molecules C8-BTBT and C10-DNTT, it shall be discussed how the Seebeck coefficient can aid the estimation of the density and distribution of trap states within these materials. ^{2, 3}

N-type semiconductor is a necessary component for high speed and low power dissipation complementary circuits. However, n-type organic field-effect transistors (OFETs) with both high electron mobility and good ambient stability are rare. In this contribution, we develop a strong electron-deficient small molecule, tetrafluorine benzodifurandione-based oligo(p-phenylenevinylene) (4F-BDOPV), for n-type OFETs. 4F-BDOPV has a low LUMO level down to −4.44 eV and a cofacial packing structure in single crystal. These fea-tures provide 4F-BDOPV with good ambient stability and large charge transfer integrals leading to a high electron mobility of up to 12.6 cm2 V−1 s−1 in air, which is among the highest values for n-type OFETs. This work demonstrates a new molecule system for high-performance air-stable n-type OFETs, which is highly promising for single crystal based electronics.

We present a novel SAM-forming molecule bisjulolidyldisulfide that reduces the WF of metal surfaces by ~1.2 eV and can lower the barrier for electron injection to organic semiconductors. Applied to Au and Ag surfaces, including inkjet-printed Ag on PET, we characterized bisjulolidyldisulfide monolayers by means of photoelectron spectroscopy (PES) and sessile drop technique, as well as their influence on the performance of n-type OFETs. Next a strong reduction of the contact resistance by two orders of magnitude, we found that this SAM treatment extends the shelf lifetime of ambient-stored OFET devices. Also, it improves the wettability and thereby facilitates solution processing of a subsequent layer with respect to the untreated surface. The full electrical functionality of bisjulolidyldisulfide SAMs was found to become manifest with only one minute of immersion in ethanol solution. PES measurements suggests that the surface coverage is thorough on Au, but only fractional on Ag, especially on printed Ag. However, the quality of SAM-treated bottom contacts in n-type OFETs is very similar for all three investigated metal surfaces (Au and Ag evaporated and printed Ag). This is especially important for printed Ag-electrodes, as their surface was found to be significantly worse for device performance in comparison to their evaporated Ag counterpart. Using this surface treatment we realized integrated unipolar n-type ring oscillators with inkjet printed Ag electrodes.

Organic thin film transistors (OTFTs) based on single crystalline thin films of organic semiconductors have seen considerable development in the recent years. The most successful method for the fabrication of single crystalline films are solution-based meniscus guided coating techniques such as dip-coating, solution shearing or zone casting. These upscalable methods enable rapid and efficient film formation without additional processing steps. The single-crystalline film quality is strongly dependent on solvent choice, substrate temperature and coating speed. So far, however, process optimization has been conducted by trial and error methods, involving, for example, the variation of coating speeds over several orders of magnitude. Through a systematic study of solvent phase change dynamics in the meniscus region, we develop a theoretical framework that links the optimal coating speed to the solvent choice and the substrate temperature. In this way, we can accurately predict an optimal processing window, enabling fast process optimization. Our approach is verified through systematic OTFT fabrication based on films grown with different semiconductors, solvents and substrate temperatures. The use of best predicted coating speeds delivers state of the art devices. In the case of C₈BTBT, OTFTs show well-behaved characteristics with mobilities up to 7 cm²/Vs and onset voltages close to 0 V. Our approach also explains well optimal recipes published in the literature. This route considerably accelerates parameter screening for all meniscus guided coating techniques and unveils the physics of single crystalline film formation.