An Oligonucleotide-Distortion-Responsive Organic Transistor for Platinum-Drug-Induced DNA-Damage Detection.

Organic transistor with DNA-damage evaluation ability can open up novel opportunities for bioelectronic devices. Even though trace amounts of drugs can cause cumulative gene damage in vivo, the extremely low occurrence proportion makes them hardly transduced into detectable electric signals. Here, an ultrasensitive DNA-damage sensor based on an oligonucleotide-distortion-responsive organic transistor (DROT) is reported by creating controllable conformation change of double-stranded DNA on the surface of organic semiconductors. In combination with interfacial charge redistribution and efficient signal amplification, the DROT provides an ultrasensitive single-site DNA-damage response with 20.5 s even upon 1 × 10-12 m cisplatin. The high generalizability of this DROT to three generations of classical platinum drugs and gene-relevant DNA damage is demonstrated. A biochip is further designed for intelligent damage analysis in complex environments, which holds the potential for high-throughput biotoxicity evaluation and drug screening in the future.

Designing Donor-Acceptor Copolymers for Stable and High-Performance Organic Electrochemical Transistors.

Organic electrochemical transistors (OECTs) are oft-used for bioelectronic applications, and a variety of OECT channel materials have been developed in recent years. However, the majority of these materials are still limited by long-term performance and stability challenges. To resolve these issues, we implemented a next-generation design of polymers for OECTs. Specifically, diketopyrrolopyrrole (DPP) building blocks were copolymerized with propylene dioxythiophene-based (Pro-based) monomers to create a donor-acceptor-type conjugated polymer (PProDOT-DPP). These PProDOT-DPP macromolecules were synthesized using a straightforward direct arylation polymerization synthetic route. The PProDOT-DPP polymer thin film exhibited excellent electrochemical response, low oxidation potential, and high crystallinity, as evidenced by spectroelectrochemical measurements and grazing incidence wide-angle X-ray scattering measurements. Thus, the resultant polymer thin films had high charge mobility and volumetric capacitance values (i.e., µC* as high as 310 F cm-1 V-1 s-1) when they were used as the active layer materials in OECT devices, which places PProDOT-DPP among the highest performing accumulation-mode OECT polymers reported to date. The performance of the PProDOT-DPP thin films was also retained for 100 cycles and over 2000 s of ON-OFF cycling, indicating the robust stability of the materials. Therefore, this effort provides a clear roadmap for the design of electrochemically active macromolecules for accumulation-mode OECTs, where crystalline acceptor cores are incorporated into an all-donor polymer. We anticipate that this will ultimately inspire future polymer designs to enable OECTs with both high electrical performance and operational stability.

Enhanced Thermoelectric Performance of n-Type Organic Semiconductor via Electric Field Modulated Photo-Thermoelectric Effect.

Modulating photophysical processes is a fundamental way for tuning performance of many organic devices. However, it has not been explored as an effective strategy to manipulate the thermoelectric (TE) conversion of organic semiconductors (OSCs) owing to their critical requirement to carrier concentration (>1018 cm-3 ) and the fact of low exciton separation efficiency in single element OSCs. Here, an electric field modulated photo-thermoelectric (P-TE) effect in an n-type OSC is demonstrated to realize a significant improvement of TE performance. The electrical and spectroscopy characterizations reveal that the electric field gating generates combined modulation of exciton separation, charge screening, and carrier recombination, which produces a more than ten times improvement of photoinduced carrier concentration. These coupled processes contribute to the unconventional Seebeck coefficient (S)-electrical conductivity (σ) trade-off relationship of the photoexcited films, therefore leading to a more than 500% enhancement in the power factor for n-type OTE semiconductors. This work opens a unique way toward state-of-the-art organic P-TE materials for energy harvesting applications.

Mimicking Sensory Adaptation with Dielectric Engineered Organic Transistors.

Mimicking sensory adaptation with transistors is essential for developing next-generation smart circuits. A key challenge is how to obtain controllable and reversible short-term signal decay while simultaneously maintaining long-term electrical stability. By introducing a buried dynamic-trapping interface within the dielectric layer, an organic adaptive transistor (OAT) with sensory adaptation functionality is developed. The device induces self-adaptive interfacial trapping to enable volatile shielding of the gating field, thereby leading to rapid and temporary carrier concentration decay in the conductive channel without diminishing the mobility upon a fixed voltage bias. More importantly, the device exhibits a fine-tuned decay constant ranging from 50 ms to 5 s, accurately matching the adaptation timescales in bio-systems. This not only suggests promising applications of OATs in flexible artificial intelligent elements, but also provides a strategy for engineering organic devices toward novel biomimetic functions.

Enabling Multifunctional Organic Transistors with Fine-Tuned Charge Transport.

Organic field-effect transistors (OFETs) are promising candidates for many electronic applications not only because of the intrinsic features of organic semiconductors in mechanical flexibility and solution processability but also owing to their multifunctionalities promised by combined signal switching and transduction properties. In contrast to rapid developments of high performance devices, the construction of multifunctional OFETs remains challenging. A key issue is fine-tuning the charge transport by modulating electric fields that are coupled with various external stimuli. Given that the charge transport is determined by complicated factors involving material and device engineering, the development of effective strategies to manipulate charge transport is highly desired toward state-of-the-art multifunctional OFETs. In this Account, we present our recent progress on device-engineered OFETs for sensing applications and thermoelectric studies of organic semiconductors. The interactions between organic semiconductors and the target analyte determine the performance of chemical sensors based on OFETs. We introduced gas receptors and in situ tailored molecular antenna on the surface of ultrathin active layers. The engineered interfaces enable direct and specific semiconductor-analyte interactions, as demonstrated in developed chemical sensors and biosensors with prominent sensitivity and good selectivity. In comparison with chemical stimuli, many physical stimuli such as pressure typically possess a limit effect on the charge transport properties of organic semiconductors. By utilizing the suspended-gate geometry, the carrier concentration in a conductive channel can be controlled quantitatively by the pressure dominated changes in the capacitance of an air dielectric layer, allowing for ultrasensitive pressure detection in a unique manner. More importantly, the transduced current can be further processed by a synaptic OFET, in which the proton/electron coupling interfaces contribute to the dynamic modulation of carrier concentration, thus mimicking biological synapses. The integrated pressure sensor and synaptic OFETs, namely, the dual-organic-transistor-based tactile-perception element, has exhibited promising applications in artificial intelligence elements. Aiming at revealing thermoelectric (TE) properties of organic semiconductors, we also investigated field-modulated TE performance of several high-mobility semiconductors by varying the driving electric field to the temperature gradient. This has been confirmed to offer a strategy to accelerate the search for promising TE materials from well-developed organic semiconductors. By tuning the charge transport process in the device, the functional modulation of OFETs has experienced significant progress in the preceding years. The exploration of new ways to create OFETs with more fascinating functionalities is still full of opportunities to obtain greater benefit from organic transistors.

Exploring Peltier effect in organic thermoelectric films.

Organic materials are emerging thermoelectric candidates for flexible power generation and solid-cooling applications. Although the Peltier effect is a fundamental thermoelectric effect that enables site-specific and on-demand cooling applications, the Peltier effect in organic thermoelectric films have not been investigated. Here we experimentally observed and quasi-quantitatively evaluated the Peltier effect in a poly(Ni-ett) film through the fabrication of thermally suspended devices combined with an infrared imaging technique. The experimental and simulation results confirm effective extraction of the Peltier effect and verify the Thomson relations in organic materials. More importantly, the working device based on poly(Ni-ett) film yields maximum temperature differences as large as 41 K at the two contacts and a cooling of 0.2 K even under heat-insulated condition. This exploration of the Peltier effect in organic thermoelectric films predicts that organic materials hold the ultimate potential to enable flexible solid-cooling applications.

Rolling up transition metal dichalcogenide nanoscrolls via one drop of ethanol.

Two-dimensional transition metal dichalcogenides (TMDs) have attracted lots of interest because of their potential for electronic and optoelectronic applications. Atomically thin TMD flakes were believed capable to scroll into nanoscrolls (NSs) with distinct properties. However, limited by mechanical strength and chemical stability, production of high-quality TMD NSs remains challenging. Here, we scroll chemical vapor deposition-grown monolayer TMD flakes into high-quality NSs in situ in 5 s with a nearly 100% yield by only one droplet of ethanol solution. An obvious photoluminescence is demonstrated in NSs and the self-encapsulated structure makes NSs more insensitive to external factors in optical and electrical properties. Furthermore, based on the internal open topology, NSs hybridized with a variety of functional materials have been fabricated, which is expected to confer TMD NSs with additional properties and functions attractive for potential application.

Trichalcogenasumanene ortho-Quinones: Synthesis, Properties, and Transformation into Various Heteropolycycles.

The regioselective transformation of heterobuckybowl trichalcogenasumanenes 1 a,b at peripheral butoxy groups afforded trichalcogenasumanene ortho-quinones 2 a,b. Compounds 2 a,b are distinct from 1 a,b in terms of their molecular geometry and electronic state; that is, they have a shallower bowl depth and show absorbance in the NIR region. The reaction of 2 a,b with diamines resulted in a variety of heteropolycycles, including molecular spoon 3 a-6 a, planar π-systems 3 b-6 b, and highly twisted [7-6-6]-fused systems 7 a,b. These new heteropolycycles had different optical/electrical properties: 4 a,b showed hole mobility of approximately 0.002 cm2 V-1 s-1 , 6 a displayed red emission in both solution and the solid state, and 7 a,b formed tight stacks of the curved π-surface.

Conjugated-Backbone Effect of Organic Small Molecules for n-Type Thermoelectric Materials with ZT over 0.2.

Conjugated backbones play a fundamental role in determining the electronic properties of organic semiconductors. On the basis of two solution-processable dihydropyrrolo[3,4-c]pyrrole-1,4-diylidenebis(thieno[3,2-b]thiophene) derivatives with aromatic and quinoid structures, we have carried out a systematic study of the relationship between the conjugated-backbone structure and the thermoelectric properties. In particular, a combination of UV-vis-NIR spectra, photoemission spectroscopy, and doping optimization are utilized to probe the interplay between energy levels, chemical doping, and thermoelectric performance. We found that a moderate change in the conjugated backbone leads to varied doping mechanisms and contributes to dramatic changes in the thermoelectric performance. Notably, the chemically doped A-DCV-DPPTT, a small molecule with aromatic structure, exhibits an electrical conductivity of 5.3 S cm-1 and a high power factor (PF373 K) up to 236 µW m-1 K-2, which is 50 times higher than that of Q-DCM-DPPTT with a quinoid structure. More importantly, the low thermal conductivity enables A-DCV-DPPTT to possess a figure of merit (ZT) of 0.23 ± 0.03, which is the highest value reported to date for thermoelectric materials based on organic small molecules. These results demonstrate that the modulation of the conjugated backbone represents a powerful strategy for tuning the electronic structure and mobility of organic semiconductors toward a maximum thermoelectric performance.

A Dual-Organic-Transistor-Based Tactile-Perception System with Signal-Processing Functionality.

Organic-device-based tactile-perception systems can open up new opportunities for the next generation of intelligent products. To meet the critical requirements of artificial perception systems, the efficient construction of organic smart elements with integrated sensing and signal processing functionalities is highly desired, but remains a challenge. This study presents a dual-organic-transistor-based tactile-perception element (DOT-TPE) with biomimetic functionality by the construction of organic synaptic transistors with integrated sensing transistors. The unique geometry of the DOT-TPE permits instantaneous sensing of pressure stimuli and synapse-like processing of an electric signal in a single element. More importantly, these organic-transistor-based tactile-perception elements can be built into arrays to serve as bionic tactile-perception systems. The combined biomimetic functionality of tactile-perception systems, together with their promising features of flexibility and large-area fabrication, makes this work represent a step forward toward novel e-skin devices for artificial intelligence.

Bismuth Interfacial Doping of Organic Small Molecules for High Performance n-type Thermoelectric Materials.

Development of chemically doped high performance n-type organic thermoelectric (TE) materials is of vital importance for flexible power generating applications. For the first time, bismuth (Bi) n-type chemical doping of organic semiconductors is described, enabling high performance TE materials. The Bi interfacial doping of thiophene-diketopyrrolopyrrole-based quinoidal (TDPPQ) molecules endows the film with a balanced electrical conductivity of 3.3 S cm(-1) and a Seebeck coefficient of 585 µV K(-1) . The newly developed TE material possesses a maximum power factor of 113 µW m(-1) K(-2) , which is at the forefront for organic small molecule-based n-type TE materials. These studies reveal that fine-tuning of the heavy metal doping of organic semiconductors opens up a new strategy for exploring high performance organic TE materials.

D-A1-D-A2 Copolymer Based on Pyridine-Capped Diketopyrrolopyrrole with Fluorinated Benzothiadiazole for High-Performance Ambipolar Organic Thin-Film Transistors.

A novel donor-acceptor-donor-acceptor (D-A1-D-A2) π-conjugated copolymer (PDBPyDT2FBT) has been prepared by Stille coupling reaction. It is found that PDBPyDT2FBT exhibits low LUMO energy level mainly because of multiple electron-deficient units and donor-acceptor interaction, which is favorable to obtain more efficient electron injection and transport in organic thin-film transistors (OTFTs). Moreover, introducing two electron-deficient moieties into the thiophene-containing copolymer increases the length of conjugated main chain and enhances the coplanarity of the backbone, which may be beneficial for promoting the molecular crystallinity and improving molecular ordering capability at low temperatures. High electron and hole mobilities up to 0.65 and 0.24 cm(2) V(-1) s(-1) were obtained at relatively low annealing temperatures of 100 and 80 °C, respectively, implying that PDBPyDT2FBT is a promising ambipolar polymer semiconductor applied in low-cost and large-area manufacturing of OTFTs.