Thermal Diffusivities of Functionalized Pentacene Semiconductors

We have measured the interlayer and in-plane (needle axis) thermal diffusivities of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-Pn). The needle axis value is comparable to the phonon thermal conductivities of quasi-one dimensional organic metals with excellent pi-orbital overlap, and its value suggests that a significant fraction of heat is carried by optical phonons. Furthermore, the interlayer (c-axis) thermal diffusivity is at least an order of magnitude larger, and this unusual anisotropy implies very strong dispersion of optical modes in the interlayer direction, presumably due to interactions between the silyl-containing side groups. Similar values for both in-plane and interlayer diffusivities have been observed for several other functionalized pentacene semiconductors with related structures.Comment: 9 pages, including 4 figures; submitted to Applied Physics Letter

Silylethynylated Heteroacenes and Electronic Devices Made Therewith

Novel silylethynylated heteroacenes and electronic devices made with those compounds are disclosed

Enhanced Charge Photogeneration Promoted by Crystallinity in Small-Molecule Donor-Acceptor Bulk Heterojunctions

We examined sub-nanosecond time-scale charge carrier dynamics in crystalline films of a functionalized anthradithiophene (ADT) donor (D) with three different acceptor (A) molecules. A four-fold enhancement in ultrafast charge carrier separation efficiency was observed in D/A blends with a fullerene acceptor added at 7–10 wt. % concentrations, whereas a gradual decrease in peak photocurrent amplitude with acceptor concentration was observed with functionalized pentacene and indenofluorene acceptors. The results were directly correlated with the ADT-tri(ethylsilyl)ethynyl-F donor crystallinity. In the best-performing blends, the presence of crystalline acceptor domains was also established

Frequency-Dependent Photothermal Measurement of Transverse Thermal Diffusivity of Organic Semiconductors

We have used a photothermal technique, in which chopped light heats the front surface of a small ( ~ 1 mm2) sample and the chopping frequency dependence of thermal radiation from the back surface is measured with a liquid nitrogen cooled infrared detector. In our system, the sample is placed directly in front of the detector within its dewar. Because the detector is also sensitive to some of the incident light which leaks around or through the sample, measurements are made for the detector signal that is in quadrature with the chopped light. Results are presented for layered crystals of semiconducting 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-pn) and for papers of cellulose nanofibrils coated with semiconducting poly(3,4-ethylene-dioxythiophene):poly(styrene-sulfonate) (NFC-PEDOT). For NFC-PEDOT, we have found that the transverse diffusivity, smaller than the in-plane value, varies inversely with thickness, suggesting that texturing of the papers varies with thickness. For TIPS-pn, we have found that the interlayer diffusivity is an order of magnitude larger than the in-plane value, consistent with previous estimates, suggesting that low-frequency optical phonons, presumably associated with librations in the TIPS side-groups, carry most of the heat.Comment: 10 pages including 4 figures. To be published in J. Appl. Phy

Spray Printing of Organic Semiconducting Single Crystals

Single-crystal semiconductors have been at the forefront of scientific interest for more than 70 years, serving as the backbone of electronic devices. Inorganic single crystals are typically grown from a melt using time-consuming and energy-intensive processes. Organic semiconductor single crystals, however, can be grown using solution-based methods at room temperature in air, opening up the possibility of large-scale production of inexpensive electronics targeting applications ranging from field-effect transistors and light-emitting diodes to medical X-ray detectors. Here we demonstrate a low-cost, scalable spray-printing process to fabricate high-quality organic single crystals, based on various semiconducting small molecules on virtually any substrate by combining the advantages of antisolvent crystallization and solution shearing. The crystals’ size, shape and orientation are controlled by the sheer force generated by the spray droplets’ impact onto the antisolvent’s surface. This method demonstrates the feasibility of a spray-on single-crystal organic electronics

Low-Voltage Polymer/Small-Molecule Blend Organic Thin-Film Transistors and Circuits Fabricated via Spray Deposition

Organic thin-film electronics have long been considered an enticing candidate in achieving high-throughput manufacturing of low-power ubiquitous electronics. However, to achieve this goal, more work is required to reduce operating voltages and develop suitable mass-manufacture techniques. Here, we demonstrate low-voltage spray-cast organic thin-film transistors based on a semiconductor blend of 2,8-difluoro- 5,11-bis (triethylsilylethynyl) anthradithiophene and poly(triarylamine). Both semiconductor and dielectric films are deposited via successive spray deposition in ambient conditions (air with 40%–60% relative humidity) without any special precautions. Despite the simplicity of the deposition method, p-channel transistors with hole mobilities of \u3e1 cm2/Vs are realized at −4 V operation, and unipolar inverters operating at −6 V are demonstrated

Grain Boundary Induced Bias Instability in Soluble Acene-Based Thin-Film Transistors

Since the grain boundaries (GBs) within the semiconductor layer of organic field-effect transistors (OFETs) have a strong influence on device performance, a substantial number of studies have been devoted to controlling the crystallization characteristics of organic semiconductors. We studied the intrinsic effects of GBs within 5,11-bis(triethylsilylethynyl) anthradithiophene (TES-ADT) thin films on the electrical properties of OFETs. The GB density was easily changed by controlling nulceation event in TES-ADT thin films. When the mixing time was increased, the number of aggregates in as-spun TES-ADT thin films were increased and subsequent exposure of the films to 1,2-dichloroethane vapor led to a significant increase in the number of nuleation sites, thereby increasing the GB density of TES-ADT spherulites. The density of GBs strongly influences the angular spread and crystallographic orientation of TES-ADT spherulites. Accordingly, the FETs with higher GB densities showed much poorer electrical characteristics than devices with lower GB density. Especially, GBs provide charge trapping sites which are responsible for bias-stress driven electrical instability. Dielectric surface treatment with a polystyrene brush layer clarified the GB-induced charge trapping by reducing charge trapping at the semiconductor-dielectric interface. Our study provides an understanding on GB induced bias instability for the development of high performance OFETs

Topography-Guided Spreading and Drying of 6,13-bis(triisopropylsilylethynyl)-pentacene Solution on a Polymer Insulator for the Field-Effect Mobility Enhancement

We report on the enhancement of the field-effect mobility of solution-processed 6,13-bis(triisopropylsilylethynyl)-pentacene (TIPS-pentacene) by unidirectional topography (UT) of an inkjet-printed polymer insulator. The UT leads to anisotropic spreading and drying of the TIPS-pentacene droplet and enables to spontaneously develop the ordered structures during the solvent evaporation. The mobility of the UT-dictated TIPS-pentacene film (0.202 ± 0.012 cm2/Vs) is found to increase by more than a factor of two compared to that of the isotropic case (0.090 ± 0.032 cm2/Vs). The structural arrangement of the TIPS-pentacene molecules in relation to the mobility enhancement is described within an anisotropic wetting formalism. Our UT-based approach to the mobility enhancement is easily applicable to different classes of soluble organic field-effect transistors by adjusting the geometrical parameters such as the height, the width, and the periodicity of the UT of an inkjet-printed insulator

Low-Temperature Phase Transitions in a Soluble Oligoacene and Their Effect on Device Performance and Stability

The use of organic semiconductors in high-performance organic field-effect transistors requires a thorough understanding of the effects that processing conditions, thermal, and bias-stress history have on device operation. Here, we evaluate the temperature dependence of the electrical properties of transistors fabricated with 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene, a material that has attracted much attention recently due to its exceptional electrical properties. We have discovered a phase transition at T = 205 K and discuss its implications on device performance and stability. We examined the impact of this low-temperature phase transition on the thermodynamic, electrical, and structural properties of both single crystals and thin films of this material. Our results show that while the changes to the crystal structure are reversible, the induced thermal stress yields irreversible degradation of the devices