This PDF file contains the front matter associated with SPIE Proceedings Volume 10365, including the Title Page, Copyright information, Table of Contents, Introduction (if any), and Conference Committee listing.

Thiophene-phenylene co-oligomers (TPCO) single crystals are promising materials for organic light-emitting devices, e.g., light-emitting transistors (OLETs), due to their ability to combine high luminescence and efficient charge transport. However, optical confinement in platy single crystals strongly decreases light emission from their top surface degrading the device performance. To avoid optical waveguiding, single crystals thinner than 100 nm would be beneficial. Herein, we report on solution-processed ultrathin single crystals of TPCO and study their charge transport properties. As materials we used 1,4-bis(5'-hexyl-2,2'-bithiophene-5-yl)benzene (DH-TTPTT) and 1,4-bis(5'-decyl-2,2'-bithiophene-5-yl)benzene (DD-TTPTT). The ultrathin single crystals were studied by optical polarization, atomic-force, and transmission electron microscopies, and as active layers in organic field effect transistors (OFET). The OFET hole mobility was increased tenfold for the oligomer with longer alkyl substituents (DD-TTPTT) reaching 0.2 cm²/Vs. Our studies of crystal growth indicate that if the substrate is wetted, it has no significant effect on the crystal growth. We conclude that solution-processed ultrathin TPCO single crystals are a promising platform for organic optoelectronic field-effect devices.

Over the past several decades, conventional electronic circuits have been used for both analytical and digital logic circuits. Printed electronics has the potential to reduce fabrication complexity of electronic circuits and using lower-cost and large area manufacturing techniques. The performance of film transistors (OTFTS) has also improved and these devices could be applied to circuit applications where the high performance, high speed, and high energy consumption offered by conventional electronics is not needed. Amongst many factors that govern circuit design, the scale factor (W/L) serves as a crucial variable for tuning a circuit performance. Here we present printing techniques developed in order to adjust aspect ratios of printed transistors using solution processed electronic materials on to flexible substrates. By combining high-speed doctor blade and surface energy patterning we can demonstrate arrays of OTFTs that are later integrated to form circuits. In the surface energy patterning process, a hydrophobic self-assembled monolayer is deposited on a plastic substrate, and plasma etching is used to create hydrophilic regions. The desirable ink is deposited on the hydrophilic regions using doctor blading and only hydrophilic regions are patterned with the ink. Device aspect ratios are increased and controlled by patterning intermitted SD electrodes and controlling the size of the semiconductor island. We utilize screen printing method to interconnect devices to demonstrate several circuit designs such as enhancement-load Inverter, NAND and NOR on the same printing batch. We will discuss how machine learning is used to train this circuits and applied to sensing applications.

Low-cost infrared photo-transistors with improved detectivity (i.e. higher signal-to-noise ratio) could find further use in spectral analysis, which is important for chemical identifications, as well as other applications from environmental monitoring to optical communications. Accordingly, the main goal of this research is to advance printed, flexible photo-transistors by using a family of novel donor-acceptor polymers with narrow bandgap that are responsive in the short wavelength infrared (SWIR) region. In particular, the transistors show optical response extending out to a wavelength of 1.8 micrometer. The external quantum efficiency and the rectification ratio are used to characterize the performance of devices with different polymer layer thickness, in order to optimize detectivity. The individual transistors could further be exploited for the fabrication of integrated arrays for bio-medical and/ or robotic applications. It paves the way to large-area, conformal designs that are currently not achievable with conventional inorganic SWIR materials.

Organic electronic materials are desirable due to facile and low-cost manufacturing through solution deposition. However, the inherit difficulties of reproducibility and solvent compatibility, as well as the hazards associated with the solvents, have stifled the progress of realizing practical solution-deposition methods. As a result, organic thin-films used in industry are typically produced by thermal evaporation techniques, which largely negate the benefits due to the higher cost and complexity of vacuum and evaporation equipment. Here we report the use of a conventional office laser printer to electrophotographically deposit the organic semiconductor layer in thin-film transistors. We have successfully used this solvent-free, low-cost method to produce the first laser-printed organic semiconductor layer in thin-film transistors. We printed on flexible and transparent polyethylene terephthalate (PET) substrates. We used the highly hydrophobic fluoropolymer Cytop as the dielectric in a bottom-gate, bottom-contact configuration, a feat that is not possible with traditional solution-deposition. The organic semiconductor layer consisted of a toner powder based on triisopropylsilylethynyl pentacene (TIPS Pn). Grazing incidence wide-angle X-ray scattering (GIWAXS) images indicated both edge- and face-on orientations of the semiconductor for these devices while electrical measurements revealed field-effect mobilities up to 10-3 cm2V¬-1s-1 and on/off current ratio of 103. Our method has the combined advantages of low temperature and ambient pressure deposition while eliminating the drawbacks of solvents or the high cost of evaporation equipment. Further, as a digital printing method, the laser-printed layer is easily patternable as designed by any convenient graphics software. Since the powder is transferred in a dry state, surface dewetting is no longer an issue, which opens the door to even more substrate/dielectric materials that would otherwise reject solutions from adhering.

In the future, a large variety of electronic devices will be wearable and operate in close contact with the skin. To accommodate deformations such as twisting and elongation, these devices should ideally be stretchable. One viable approach toward stretchable electronics is the development of intrinsically stretchable electronic materials, devices and circuits. Recently, the first intrinsically stretchable transistors have been demonstrated [1-7]. However, for the realization of stretchable circuits, stretchable interconnects are equally important. For the deployment of highly stretchable materials as interconnects and electrodes, patterning is crucial. Therefore, we developed a process for inkjet printing of intrinsically stretchable PEDOT:PSS-based interconnects and conductors. Ionic additives act as dopants and plasticisers in this approach [8]. A customized ink was printed on stretchable polymeric substrates (SEBS, styrene-ethylene-butadiene-styrene) and optimized to achieve a smooth morphology of the printed features by adjusting the surface tension and suppressing the coffee stain effect. The printed interconnects have a conductivity of 700 S/cm, sustain strains above 100% and show good stability in 1000-cycle stretching experiments. In addition to morphology, electrical properties and stretchability, we also investigated bias-stress stability, long-term stability in ambient air and cycling stability.

Organic semiconductor/insulator polymer blends have been widely used in the manufacturing process of field-effect transistors (FETs) to overcome the disadvantages of FETs based on organic semiconductor. In this study, phase-separation characteristics and structural developments of 6,13-bis(triisopropylsilylethynyl)-pentacene (TIPS-pentacene)/insulating polymers were examined to enhance electrical properties of their blends for uses in active layers of FETs. Especially, phase-separation characteristics of TIPS-pentacene/insulating polymer blends were greatly affected by the processing condition such as spin coating time. Although TIPS-pentacene-top/insulating polymer-bottom vertically phase separated structures were formed onto the substrate regardless of spin-time, spin coating time governed growth mode of phase-separated TIPS-pentacene onto phase-separated insulating polymer. Excess residual solvent in short spin-coating time induces convective flow in a drying droplet, thereby resulted in one-dimensional (1D) growth of TIPS-pentacene crystals. On the other hand, optimum residual solvent in moderate spin coating time led to two-dimensional (2D) growth of TIPS-pentacene crystals. These 2D spherulites onto insulating polymer was quite advantageous for increasing field-effect mobility of FETs because of higher perfectness and coverage of TIPS-pentacene crystals compared to those of 1D crystals. In addition, when TIPS-pentacene was blended with various types of insulating polymers, critical spin-coating time was changed due to the different surface energy of the insulating polymers. Insulating polymer with lower surface energy was advantageous for increasing film formation time, thereby increasing time for phase-separation and crystallization.

The ferroelectric nature of polymer ferroelectrics such as poly(vinylidene fluoride) (PVDF) has been known for over 45 years. However, its role in interfacial transport in organic/polymeric field-effect transistors (FETs) is not that well understood. Dielectrics based on PVDF and its copolymers are a perfect test-bed for conducting transport studies where a systematic tuning of the dielectric constant with temperature may be achieved. The charge transport mechanism in an organic semiconductor often occurs at the intersection of band-like coherent motion and incoherent hopping through localized states. By choosing two small molecule organic semiconductors - pentacene and 6,13 bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) – along with a copolymer of PVDF (PVDF-TrFe) as the dielectric layer, the transistor characteristics are monitored as a function of temperature. A negative coefficient of carrier mobility is observed in TIPS-pentacene upwards of 200 K with the ferroelectric dielectric. In contrast, TIPS-pentacene FETs show an activated transport with non-ferroelectric dielectrics. Pentacene FETs, on the other hand, show a weak temperature dependence of the charge carrier mobility in the ferroelectric phase of PVDF-TrFE, which is attributed to polarization fluctuation driven transport resulting from a coupling of the charge carriers to the surface phonons of the dielectric layer. Further, we show that there is a strong correlation between the nature of traps in the organic semiconductor and interfacial transport in organic FETs, especially in the presence of a ferroelectric dielectric.

Organic electrochemical transistors (OECTs) have gained considerable interest for applications in bioelectronics, neuromorphic computing, and logic circuitry. Their defining characteristic is the bulk-modulation of channel conductance owing to the facile penetration of ions into the (semi)conducting polymeric channel. In the realm of bioelectronics, OECTs have shown promise as amplifying transducers due to their stability in aqueous conditions and high transconductance. These devices can be fabricated in conformable form factors for in vivo stimulation/recording, and for cutaneous EEG and ECG recordings in human subjects. The performance of these devices, their operating conditions, and suitability for certain applications is linked intimately with their form factor and the transport properties of the active materials. In this work we show how thickness can be used to design optimal devices for a range of electrophysiological recording applications. Scaling of device performance with geometry reveals the importance of the active material’s mobility and charge storage capacity (per unit volume) in benchmarking new materials. Such findings have led to the development of a new class of polymers which outperform prototypical conducting polymers (i.e. PEDOT:PSS), and can potentially open new paths for the utility of OECTs in a number of application areas.

We present the synthesis and characterization of four conjugated polymers containing a novel chromophore for organic electronics based on an indigoid structure. These polymers exhibit extremely small band gaps of ∼1.2 eV, impressive crystallinity, and extremely high n-type mobility exceeding 3 cm2 V s–1. The n-type charge carrier mobility can be correlated with the remarkably high crystallinity along the polymer backbone having a correlation length in excess of 20 nm. Theoretical analysis reveals that the novel polymers have highly rigid nonplanar geometries demonstrating that backbone planarity is not a prerequisite for either narrow band gap materials or ultrahigh mobilities. Furthermore, the variation in backbone crystallinity is dependent on the choice of comonomer. We find that electron mobility can be correlated to the degree of order along the conjugated polymer backbone. Finally, we use this novel system to begin to understand the complicated effect of alkyl chain variation on the solid state packing in all 3 dimensions.

The interface between organic molecules and metallic surfaces is integral to the performance of organic optoelectronic devices. Considerable efforts have been focused on the synthesis and processing of novel donor and acceptor materials for high performance devices. Despite this, there is little understanding of the fundamental behaviour of these molecules at relevant metallic surfaces. The truxenone family of small molecule semiconductors exhibit three-fold symmetry, have stabilised lowest unoccupied molecular orbital (LUMO) energy levels, independently conjugated branches from the core and have been shown to exhibit promising properties as electron acceptors in organic solar cells. Our recent work has demonstrated that Truxenones self-assemble to form epitaxial open-pored structures on Cu (111), a highly unusual observation in semiconducting organic molecules. This assembly is affected by the choice of metal substrate and data from analogous Ag (111) and Au (111) interfaces will be compared and contrasted. In addition the use of a commensurate epitaxial truxenone template to direct the growth of commensurate epitaxial C60 layers will be shown. This strategy imparts the structural symmetry and in-plane structural order of the substrate into the molecular template and subsequent C60 layers and has implications for the growth of single-crystalline organic interfaces and devices.

Synthesis of novel organosilicon derivatives of [1]benzothieno[3,2-b][1]-benzothiophene (BTBT) linked though flexible aliphatic spacers to a disiloxane anchor group is reported. They were successfully used in monolayer OFETs with the charge carrier mobilities up to 0.02 cm² /Vs, threshold voltage close to 0 V and On/Off ratio up to 10,000. Influence of the chemical structure of the molecules synthesized on the morphology, molecular 2D ordering in the monolayers and their semiconducting properties is considered. The effect of different methods of the ultrathin semiconducting layer preparation, such as Langmuir-Blodgett, Langmuir-Schaefer, spin coating or doctor blade, on the OFET performance is discussed.

Low temperature transport measurements of classical semiconductors are a well-defined method to determine the physics of transport behavior. These measurements are also used to evaluate organic semiconductors, though physical interpretation is not yet fully developed. The similar energy ranges of the various processes involved in charge transport in organic semiconductors, including excitonic coupling, charge-phonon coupling, and trap distributions, result in ambiguity in the interpretation of temperature dependent electrical measurements. The wide variety of organic semiconductors, ranging from well-ordered small molecule crystals to disordered polymers, manifest varying degrees of “ideal” device behavior and require intensive studies in order to capture the full range of physical mechanisms involved in electronic transport in this class of materials. In addition, the physics at electrical contacts and dielectric material interfaces strongly affect device characteristics and results in temperature dependent behavior that is unrelated to the semiconductor itself. In light of these complications, our group is working toward understanding the origins of temperature dependent transport in single crystal, small molecule organic semiconductors with ordered packing. In order to disentangle competing physical effects on device characterization at low temperature, we use TEM and Raman spectroscopy to track changes in the structure and thermal molecular motion, correlated with density functional theory calculations. We perform electrical characterization, including DC current-voltage, AC impedance, and displacement current measurements, on transistors built with a variety of contact and dielectric materials in order to fully understand the origin of the transport behavior. Results of tetracene on silicon dioxide and Cytop dielectrics will be discussed.

The low processing temperature of polymeric materials and their wide range of applications make polar polymer based ferroelectric memory very promising and attractive. The typical configuration of the ferroelectric memory cell is the FeFET (Ferroelectric field-effect-transistor) with the polar polymer incorporated in the gate dielectric stack. The memory effect in these devices originates from the polarization of the ferroelectric polymer film and results in a hysteresis of the Id-Vg characteristics. In this study, we fabricated FeFETs based on ultrathin poly-Si channel and CP1- polymer (glass-transition temperature (Tg ~260 C) as the gate dielectric. We investigated the hysteresis of the Id-Vg curves over a wide range of temperatures and frequencies. We observed the effects of thermocycling on the device, such as the change of the hysteresis loop direction at temperatures close to Tg (associated with the change of the dominant hysteresis mechanism), and the simultaneous significant decrease in gate leakage current (which may indicate significant reduction of active defects in the polymer layer). The reversibility of the observed phenomena was also investigated through consecutive thermocycles. Soaking the chip in warm water (60 C) for 3 hours changes the magnitude of the hysteresis loop without changing the direction. The gate leakage current also remains very low. Thus, humidity may play some role in the hysteresis magnitude but not the loop direction, nor does it play any role in the leakage current. In this paper, we will discuss possible explanations of these observations.