Ultrastable N-Type Semiconducting Fiber Organic Electrochemical Transistors for Highly Sensitive Biosensors.

Organic electrochemical transistors (OECTs) have attracted increasing attention due to their merits of high transconductance, low operating voltage, and good biocompatibility, ideal for biosensors. However, further advances in their practical applications face challenges of low n-type performance and poor stability. Here, it is demonstrated that wet-spinning the commercially available n-type conjugated polymer poly(benzimidazobenzophenanthroline) (BBL) into highly aligned and crystalline fibers enhances both OECT performance and stability. Although BBL is only soluble in high-boiling-point strong acids, it can be wet-spun into high-quality fibers with adjustable diameters. The BBL fiber OECTs exhibit a record-high area-normalized transconductance (gm,A) of 2.40 µS µm-2 and over 10 times higher figure-of-merit (µC*) than its thin-film counterparts. More importantly, these fiber OECTs exhibit remarkable stability with no noticeable performance attenuation after 1500 cycles over 4 h operation, outperforming all previously reported n-type OECTs. The superior performance and stability can be attributed to shorter π-π stacking distance and ordered molecular arrangement in the fibers, endowing the BBL fiber OECT-based biosensors with outstanding sensitivity while keeping a miniaturized form factor. This work demonstrates that, beyond new material development, developing new fabrication technology is also crucial for addressing the performance and stability issues in n-type OECTs.

Highly Ordered Small Molecule Organic Semiconductor Thin-Films Enabling Complex, High-Performance Multi-Junction Devices.

Organic semiconductors have opened up many new electronic applications, enabled by properties like flexibility, low-cost manufacturing, and biocompatibility, as well as improved ecological sustainability due to low energy use during manufacturing. Most current devices are made of highly disordered thin-films, leading to poor transport properties and, ultimately, reduced device performance as well. Here, we discuss techniques to prepare highly ordered thin-films of organic semiconductors to realize fast and highly efficient devices as well as novel device types. We discuss the various methods that can be implemented to achieve such highly ordered layers compatible with standard semiconductor manufacturing processes and suitable for complex devices. A special focus is put on approaches utilizing thermal treatment of amorphous layers of small molecules to create crystalline thin-films. This technique has first been demonstrated for rubrene─an organic semiconductor with excellent transport properties─and extended to some other molecular structures. We discuss recent experiments that show that these highly ordered layers show excellent lateral and vertical mobilities and can be electrically doped to achieve high n- and p-type conductivities. With these achievements, it is possible to integrate these highly ordered layers into specialized devices, such as high-frequency diodes or completely new device principles for organics, e.g., bipolar transistors.

Organic bipolar transistors.

Devices made using thin-film semiconductors have attracted much interest recently owing to new application possibilities. Among materials systems suitable for thin-film electronics, organic semiconductors are of particular interest; their low cost, biocompatible carbon-based materials and deposition by simple techniques such as evaporation or printing enable organic semiconductor devices to be used for ubiquitous electronics, such as those used on or in the human body or on clothing and packages1-3. The potential of organic electronics can be leveraged only if the performance of organic transistors is improved markedly. Here we present organic bipolar transistors with outstanding device performance: a previously undescribed vertical architecture and highly crystalline organic rubrene thin films yield devices with high differential amplification (more than 100) and superior high-frequency performance over conventional devices. These bipolar transistors also give insight into the minority carrier diffusion length-a key parameter in organic semiconductors. Our results open the door to new device concepts of high-performance organic electronics with ever faster switching speeds.

Highly efficient modulation doping: A path toward superior organic thermoelectric devices.

We investigate the charge and thermoelectric transport in modulation-doped large-area rubrene thin-film crystals with different crystal phases. We show that modulation doping allows achieving superior doping efficiencies even for high doping densities, when conventional bulk doping runs into the reserve regime. Modulation-doped orthorhombic rubrene achieves much improved thermoelectric power factors, exceeding 20 µW m-1 K-2 at 80°C. Theoretical studies give insight into the energy landscape of the heterostructures and its influence on qualitative trends of the Seebeck coefficient. Our results show that modulation doping together with high-mobility crystalline organic semiconductor films is a previosly unexplored strategy for achieving high-performance organic thermoelectrics.

Doped Highly Crystalline Organic Films: Toward High-Performance Organic Electronics.

Today's organic electronic devices, such as the highly successful OLED displays, are based on disordered films, with carrier mobilities orders of magnitude below those of inorganic semiconductors like silicon or GaAs. For organic devices such as diodes and transistors, higher charge carrier mobilities are paramount to achieve high performance. Organic single crystals have been shown to offer these required high mobilities. However, manufacturing and processing of these crystals are complex, rendering their use outside of laboratory-scale applications negligible. Furthermore, doping cannot be easily integrated into these systems, which is particularly problematic for devices mandating high mobility materials. Here, it is demonstrated for the model system rubrene that highly ordered, doped thin films can be prepared, allowing high-performance organic devices on almost any substrate. Specifically, triclinic rubrene crystals are created by abrupt heating of amorphous layers and can be electrically doped during the epitaxial growth process to achieve hole or electron conduction. Analysis of the space charge limited current in these films reveals record vertical mobilities of 10.3(49) cm2 V-1 s-1. To demonstrate the performance of this materials system, monolithic pin-diodes aimed for rectification are built. The f 3 d b of these diodes is over 1 GHz and thus higher than any other organic semiconductor-based device shown so far. It is believed that this work will pave the way for future high-performance organic devices based on highly crystalline thin films.

Efficient and low-voltage vertical organic permeable base light-emitting transistors.

Organic light-emitting transistors, three-terminal devices combining a thin-film transistor with a light-emitting diode, have generated increasing interest in organic electronics. However, increasing their efficiency while keeping the operating voltage low still remains a key challenge. Here, we demonstrate organic permeable base light-emitting transistors; these three-terminal vertical optoelectronic devices operate at driving voltages below 5.0 V; emit in the red, green and blue ranges; and reach, respectively, peak external quantum efficiencies of 19.6%, 24.6% and 11.8%, current efficiencies of 20.6 cd A-1, 90.1 cd A-1 and 27.1 cd A-1 and maximum luminance values of 9,833 cd m-2, 12,513 cd m-2 and 4,753 cd m-2. Our simulations demonstrate that the nano-pore permeable base electrode located at the centre of the device, which forms a distinctive optical microcavity and regulates charge carrier injection and transport, is the key to the good performance obtained. Our work paves the way towards efficient and low-voltage organic light-emitting transistors, useful for power-efficient active matrix displays and solid-state lighting.

Modulation Doping for Threshold Voltage Control in Organic Field-Effect Transistors.

Organic electronics is the technology enabling truly flexible electronic devices. However, despite continuous improvements in the charge-carrier mobility, devices used for digital circuits based on organic field-effect transistors (OFETs) have still not achieved a commercial breakthrough. A substantial hurdle to the realization of effective digital circuitry is the proper control of the threshold voltage Vth. Previous approaches include doping or self-assembled monolayers to provide the threshold voltage control. However, while self-assembled monolayers-modified OFETs often do not show the level of reproducibility which is required in digital circuit engineering, direct doping of the channel material results in a poor on/off ratio leading to unfavorable power dissipation. Furthermore, direct doping of the channel material in organic semiconductors could cause the formation of trap states impeding the charge-carrier transport. Employing the concept of modulation-doped field-effect transistors (MODFETs), which is well established in inorganic electronics, the semiconductor-dopant interaction is significantly reduced, thereby solving the above-described problems. Here, we present the concept of an organic semiconductor MODFET which is composed of an organic-organic heterostructure between a highly doped wide-energy-gap material and an undoped narrow-energy-gap material. The effectiveness of charge transfer across the interface is controlled by the doping concentration and thickness of an undoped buffer layer. A complete picture of the energy landscape of this heterostructure is drawn using impedance spectroscopy and ultraviolet photoelectron spectroscopy. Furthermore, we analyze the effect of the dopant density on the charge-carrier transport properties. The incorporation of these heterostructures into OFETs enables a precise adjustment of the threshold voltage by using the modulation doping concept.

Vertical organic permeable dual-base transistors for logic circuits.

The main advantage of organic transistors with dual gates/bases is that the threshold voltages can be set as a function of the applied second gate/base bias, which is crucial for the application in logic gates and integrated circuits. However, incorporating a dual gate/base structure into an ultra-short channel vertical architecture represents a substantial challenge. Here, we realize a device concept of vertical organic permeable dual-base transistors, where the dual base electrodes can be used to tune the threshold voltages and change the on-currents. The detailed operation mechanisms are investigated by calibrated TCAD simulations. Finally, power-efficient logic circuits, e.g. inverter, NAND/AND computation functions are demonstrated with one single device operating at supply voltages of <2.0 V. We believe that this work offers a compact and technologically simple hardware platform with excellent application potential for vertical-channel organic transistors in complex logic circuits.

Piriformospora indica symbiosis improves water stress tolerance of rice through regulating stomata behavior and ROS scavenging systems.

Global water shortage seriously threatens rice growth especially in irrigated production areas. Association of plants with beneficial soil microbes is one strategy for plant adaption to environmental stresses. In this study, rice (Oryza sativa L.) plants were colonized by the beneficial root-colonizing endophytic fungus Piriformospora indica (P. indica). We demonstrate that grain yield were higher in P. indica-colonized rice plants compared to the uncolonized plants grown in soil. Moreover, P. indica effect on improving water stress tolerance in rice and its physiological mechanism were investigated in a hydroponic culture system. Polyethylene glycol (PEG) was applied to the culture solution to conduct the water stress condition. Water stress-induced leaf wilting and impairments in photosynthetic efficiency were diminished in P. indica-colonized plants. Furthermore, P. indica colonization promotes stomata closure and increases the leaf surface temperature under water stress. The malondialdehyde level (as an indicator for oxidative stress) was lower and the reduced to oxidized glutathione ratio was higher in P. indica-colonized and PEG-exposed rice plants compared to the uncolonized plants. Furthermore, the activities of the antioxidant enzymes catalase and glutathione reductase were up-regulated in inoculated rice seedlings under water stress. In conclusion, P. indica promotes rice performance under water stress by stomata closure and lower oxidative stress.

Light-mediated modulation of helix angle and rate of seminal root tip movement determines root morphology of young rice seedlings.

Seminal root growth is one of the factors to determine rice seedling establishment. Our previous reports showed light can induce Z-type wavy root and coiling root morphology in several rice (Oryza sativa L.) varieties, and the regulated Z-type and unregulated coil seminal roots were resulted by different circumnutational trajectories. Moreover, the light-induced seminal root waving was conducted by an NO-dependent signaling pathway. In order to further reveal the difference of root tip movement between straight and wavy seminal roots; here, the root tip movement trajectories of Tainung 67 variety (TNG67; presented straight root in light conditions) and Taichung Native 1 (TCN1; presented Z-type wavy root in light) were recorded and analyzed in both white light and dark (dim far-red light was applied in dark for taking time-lapse photography) conditions. The results showed the root tip movement of both rice varieties in low intensity of dim far-red light conditions were followed the circumnutation path. However, the stimuli of high intensity of white light would increase the root helix angle in TCN1 seedlings but not in TNG67. In addition, slowing down the rate of root helix was induced by white light treatment in TCN1 but not in TNG67 seedlings. In conclusion, changes of TCN1 rice seminal root morphology from straight to wavy type stimulated by light was resulted by both helix angle increasing and circumnutation rate slowing of root tip movement.

Light-modulated seminal wavy roots in rice mediated by nitric oxide-dependent signaling.

Rice (Oryza sativa L.) seminal roots from germinated seeds help establish seedlings, but the seminal root growth and morphology are sensitive to environmental factors. Our previous research showed that several indica-type rice varieties such as Taichung native 1 (TCN1) showed light-induced wavy roots. Also, auxin and oxylipins are two signaling factors regulating the wavy root photomorphology. To investigate the signaling pathway, here, we found that nitric oxide (NO) was a second messenger triggering the signal transduction of light stimuli to induce the wavy morphology of seminal roots in rice. Moreover, interactions between oxylipins and phytohormones such as ethylene and auxin participating in the NO-dependent regulatory pathway of light-induced wavy roots were examined. The order of action of signaling components in the pathway was NO, oxylipins, ethylene, and auxin.

Effect of the interaction between light and touch stimuli on inducing curling seminal roots in rice seedlings.

Root development is sensitive to environmental stimuli. We have recently reported that the light signal could promote the helical growth of seminal roots and drive the wavy root morphology in rice (Oryza sativa L.) young seedlings. The light-stimulated wavy roots were mostly performed in indica-type rice varieties (e.g. Taichung Native 1; TCN1) but not in japonica rice (e.g. Tainung 67; TNG67). Here, we demonstrated that the light-driven circumutation trajectory of TCN1 seminal roots could be changed if the seedling roots were grown in the medium containing high concentration of Phytagel. The data showed the root morphology would be modulated from wavy to curling when the Phytagel concentration was increased to 2%. However, the touch-stimulated curling root phenotype could not be performed in dark. In addition, the touch-induced curling roots were not appeared in the TNG67 rice cultivar. Although touch stimuli could not induce wavy/curling root phenotype in dark, it could modify the light-promoted helical growth to conduct curling roots in TCN1 rice seedlings. Thus, it was suggested that there is a crosstalk mechanism between touching-induced root curling and light-stimulated root waving.

Rice develop wavy seminal roots in response to light stimulus.

Rice (Oryza sativa L.) seminal roots are the primary roots to emerge from germinated seeds. Here, we demonstrate that the photomorphology of the seminal roots was diverse among rice varieties, and the light-induced wavy roots were found mostly in indica-type rice varieties. The light-induced wavy morphology in rice seminal roots has been different with curling or coiling roots in some other specific conditions, such as high air humidity or high nitrogen nutrient. The efficiency of light-induced root waving was developmental stage dependent. The wavy root phenotype was caused by asymmetric cell growth around the stele. Using the inhibitors to block auxin polar transport and fatty acid oxygenation, the role of auxin and oxylipins in the morphogenesis of light-induced wavy roots was investigated. Expressions of genes encoded in the enzymes involved in fatty acid oxygenation in light-exposed roots were monitored by reverse transcriptase-polymerase chain reaction. Our results suggested that auxin polar transport was essential for inducing wavy seminal roots by light stimulus. In addition, the ketol oxylipins derived from allene oxide synthase (EC 4.2.1.92)-mediated fatty acid oxygenation function as intracellular signals for triggering the light-induced wavy root phenotype.

Simultaneous detection of eight genetically modified maize lines using a combination of event- and construct-specific multiplex-PCR technique.

To fulfill labeling and traceability requirement of genetically modified (GM) maize for trade and regulation, it is essential to develop an event-specific detection method for monitoring the presence of transgenes. In pursuit of this purpose, we systematically optimized and established a combined event- and construct-specific multiplex polymerase chain reaction (mPCR) technique for simultaneous detection of 8 GM maize lines. Altogether 9 sets of primers were designed, including six that were event-specific for Event176, Bt11, TC1507, NK603, MON863, and Mon810; two that were construct-specific for T25 and GA21, and one for an endogenous zein gene. The transgene in each GM maize line and the endogenous zein gene could be clearly detected and distinguished according to the different sizes of PCR amplicons. The limit of detection (LOD) was approximately 0.25% (v/v), although the detection can be as sensitive as 0.1% as demonstrated by the International Seed Testing Association (ISTA) proficiency test. This study further improves the current PCR-based detection method for GM maize. The method can be used in an easy, sensitive, and cost and time effective way for the identification and quality screening of a specific GM maize line.

New gene construction strategy in T-DNA vector to enhance expression level of sweet potato sporamin and insect resistance in transgenic Brassica oleracea.

Sporamin, an abundant storage protein in tuberous roots of sweet potato, possesses strong inhibitory activity against trypsin and pest-resistance. To promote consistent high-level expression of sporamin and insect resistance in transgenic Brassica plants, a wound-responsive sporamin promoter (Pspoa) alone or combined with matrix-attached-region-like DNA segment (spoMAR) were constructed for driving sporamin cDNA. The results showed the transgenic plants containing Pspoa-drived sporamin and spoMAR displayed the highest level and low inter-transformant variability of sporamin expression, and the ability of insect resistance of transformants positively correlated with sporamin activity. Furthermore, expressions of Pspoa-drived sporamin especially combined with the spoaMAR retains high and steady levels in the T(1) and T(2) generations, in marked contrast to the variable expression patterns observed in CaMV35S promoter-driven transformants. This study evidently indicates that the Pspoa and spoaMAR would be very efficient for high transgene expression in plants and obtaining inherently stable transformants in consecutive progenies.

Wound-response regulation of the sweet potato sporamin gene promoter region.

Sporamin, a tuberous storage protein of sweet potato, was systemically expressed in leaves and stems by wound stimulation. In an effort to demonstrate the regulatory mechanism of wound response on the sporamin gene, a 1.25 kb sporamin promoter was isolated for studying the wound-induced signal transduction. Two wound response-like elements, a G box-like element and a GCC core-like sequence were found in this promoter. A construct containing the sporamin promoter fused to a beta-glucuronidase (GUS) gene was transferred into tobacco plants by Agrobacterium-mediated transformation. The wound-induced high level of GUS activity was observed in stems and leaves of transgenic tobacco, but not in roots. This expression pattern was similar to that of the sporamin gene in sweet potatoes. Exogenous application of methyl jasmonate (MeJA) activated the sporamin promoter in leaves and stems of sweet potato and transgenic tobacco plants. A competitive inhibitor of ethylene (2,5-norbornadiene; NBD) down-regulated the effect of MeJA on sporamin gene expression. In contrast, salicylic acid (SA), an inhibitor of the octadecanoid pathway, strongly suppressed the sporamin promoter function that was stimulated by wound and MeJA treatments. In conclusion, wound-response expression of the sporamin gene in aerial parts of plants is regulated by the octadecanoid signal pathway.