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.

Dithienoindophenines: p-Type Semiconductors Designed by Quinoid Stabilization for Solar-Cell Applications.

Compared with the dominant aromatic conjugated materials, photovoltaic applications of their quinoidal counterparts featuring rigid and planar molecular structures have long been unexplored despite their narrow optical bandgaps, large absorption coefficients, and excellent charge-transport properties. The design and synthesis of dithienoindophenine derivatives (DTIPs) by stabilizing the quinoidal resonance of the parent indophenine framework is reported here. Compared with the ambipolar indophenine derivatives, DTIPs with the fixed molecular configuration are found to be p-type semiconductors exhibiting excellent unipolar hole mobilities up to 0.22 cm2 V-1 s-1 , which is one order of magnitude higher than that of the parent IP-O and is even comparable to that of QQT(CN)4-based single-crystal field-effect transistors (FET). DTIPs exhibit better photovoltaic performance than their aromatic bithieno[3,4-b]thiophene (BTT) counterparts with an optimal power-conversion efficiency (PCE) of 4.07 %.

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.

Photothermoelectric Response of Ti3C2Tx MXene Confined Ion Channels.

With recent growing interest in biomimetic smart nanochannels, a biological sensory transduction in response to external stimuli has been of particular interest in the development of biomimetic nanofluidic systems. Here we demonstrate the MXene-based subnanometer ion channels that convert external temperature changes to electric signals via preferential diffusion of cations under a thermal gradient. In particular, coupled with a photothermal conversion feature of MXenes, an array of the nanoconfined Ti3C2Tx ion channels can capture trans-nanochannel diffusion potentials under a light-driven axial temperature gradient. The nonisothermal open-circuit potential across channels is enhanced with increasing cationic permselectivity of confined channels, associated with the ionic concentration or pH of permeant fluids. The photothermoelectric ionic response (evaluated from the ionic Seebeck coefficient) reached up to 1 mV·K-1, which is comparable to biological thermosensory channels, and demonstrated stability and reproducibility in the absence and presence of an ionic concentration gradient. With advantages of physicochemical tunability and easy fabrication process, the lamellar ion conductors may be an important nanofluidic thermosensation platform possibly for biomimetic sensory systems.

A thermally activated and highly miscible dopant for n-type organic thermoelectrics.

N-doping plays an irreplaceable role in controlling the electron concentration of organic semiconductors thus to improve performance of organic semiconductor devices. However, compared with many mature p-doping methods, n-doping of organic semiconductor is still of challenges. In particular, dopant stability/processability, counterion-semiconductor immiscibility and doping induced microstructure non-uniformity have restricted the application of n-doping in high-performance devices. Here, we report a computer-assisted screening approach to rationally design of a triaminomethane-type dopant, which exhibit extremely high stability and strong hydride donating property due to its thermally activated doping mechanism. This triaminomethane derivative shows excellent counterion-semiconductor miscibility (counter cations stay with the polymer side chains), high doping efficiency and uniformity. By using triaminomethane, we realize a record n-type conductivity of up to 21 S cm-1 and power factors as high as 51 µW m-1 K-2 even in films with thicknesses over 10 µm, and we demonstrate the first reported all-polymer thermoelectric generator.

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.

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.

Efficient Solution-Processed n-Type Small-Molecule Thermoelectric Materials Achieved by Precisely Regulating Energy Level of Organic Dopants.

To achieve efficient n-type doping, three dopants, 2-Cyc-DMBI-H, (2-Cyc-DMBI)2, and (2-Cyc-DMBI-Me)2, with precisely regulated electron-donating ability were designed and synthesized. By doping with a small-molecule 2DQTT-o-OD with high electron mobility, an unexpectedly high power factor of 33.3 µW m-1 K-2 was obtained with the new dopant (2-Cyc-DMBI-Me)2. Notably, with the intrinsically low lateral thermal conductivity of 0.28 W m-1 K-1, the figure of merit was determined to be 0.02 at room temperature. Thus, we have demonstrated that small molecules with high electron mobility and low-lying LUMO energy levels can achieve high doping efficiency and excellent thermoelectric properties by doping with n-type dopants featuring highly matched energy levels and excellent miscibility.

Device Engineered Organic Transistors for Flexible Sensing Applications.

Organic thin-film transistors (OFETs) represent a promising candidate for next-generation sensing applications because of the intrinsic advantages of organic semiconductors. The development of flexible sensing devices has received particular interest in the past few years. The recent efforts of developing OFETs for sensitive and specific flexible sensors are summarized from the standpoint of device engineering. The tuning of signal transduction and signal amplification are highlighted based on an overview of active-layer thickness modulation, functional receptor implantation and device geometry optimization.

Flexible n-Type High-Performance Thermoelectric Thin Films of Poly(nickel-ethylenetetrathiolate) Prepared by an Electrochemical Method.

Flexible thin films of poly(nickel-ethylenetetrathiolate) prepared by an electrochemical method display promising n-type thermoelectric properties with the highest ZT value up to 0.3 at room temperature. Coexistence of high electrical conductivity and high Seebeck coefficient in this coordination polymer is attributed to its degenerate narrow-bandgap semiconductor behavior.

Flexible and self-powered temperature-pressure dual-parameter sensors using microstructure-frame-supported organic thermoelectric materials.

Skin-like temperature- and pressure-sensing capabilities are essential features for the next generation of artificial intelligent products. Previous studies of e-skin and smart elements have focused on flexible pressure sensors, whereas the simultaneous and sensitive detection of temperature and pressure with a single device remains a challenge. Here we report developing flexible dual-parameter temperature-pressure sensors based on microstructure-frame-supported organic thermoelectric (MFSOTE) materials. The effective transduction of temperature and pressure stimuli into two independent electrical signals permits the instantaneous sensing of temperature and pressure with an accurate temperature resolution of <0.1 K and a high-pressure-sensing sensitivity of up to 28.9 kPa(-1). More importantly, these dual-parameter sensors can be self-powered with outstanding sensing performance. The excellent sensing properties of MFSOTE-based devices, together with their unique advantages of low cost and large-area fabrication, make MFSOTE materials possess promising applications in e-skin and health-monitoring elements.

Sensitive Flexible Magnetic Sensors using Organic Transistors with Magnetic-Functionalized Suspended Gate Electrodes.

Utilizing a magnetic-functionalized suspended gate with combined features of outstanding conductivity, flexibility, and magnetic properties, flexible magnetic sensor based on an organic field-effect transistor (OFET), with a high sensitivity of 115.2% mT(-1) is demonstrated. Gate engineering enables the sensing devices to possess promising applications for flexible touchless switches and spatiallyresolved magnetic-imaging elements.

Flexible suspended gate organic thin-film transistors for ultra-sensitive pressure detection.

The utilization of organic devices as pressure-sensing elements in artificial intelligence and healthcare applications represents a fascinating opportunity for the next-generation electronic products. To satisfy the critical requirements of these promising applications, the low-cost construction of large-area ultra-sensitive organic pressure devices with outstanding flexibility is highly desired. Here we present flexible suspended gate organic thin-film transistors (SGOTFTs) as a model platform that enables ultra-sensitive pressure detection. More importantly, the unique device geometry of SGOTFTs allows the fine-tuning of their sensitivity by the suspended gate. An unprecedented sensitivity of 192 kPa(-1), a low limit-of-detection pressure of <0.5 Pa and a short response time of 10 ms were successfully realized, allowing the real-time detection of acoustic waves. These excellent sensing properties of SGOTFTs, together with their advantages of facile large-area fabrication and versatility in detecting various pressure signals, make SGOTFTs a powerful strategy for spatial pressure mapping in practical applications.

Interface-Located Photothermoelectric Effect of Organic Thermoelectric Materials in Enabling NIR Detection.

Organic photothermoelectric (PTE) materials are promising candidates for various photodetection applications. Herein, we report on poly[Cux(Cu-ett)]:PVDF, which is an excellent polymeric thermoelectric composite, possesses unprecedented PTE properties. The NIR light irradiation on the poly[Cu(x)(Cu-ett)]:PVDF film could induce obvious enhancement in Seebeck coefficient from 52 ± 1.5 to 79 ± 5.0 µV/K. By taking advantage of prominent photothermoelectric effect of poly[Cu(x)(Cu-ett)]:PVDF, an unprecedented voltage of 12 mV was obtained. This excellent performance enables its promising applications in electricity generation from solar energy and NIR detection to a wide range of light intensities ranging from 1.7 mW/cm(2) to 17 W/cm(2).

Specific and reproducible gas sensors utilizing gas-phase chemical reaction on organic transistors.

Utilizing a textbook reaction on the surface of an organic active channel, achieves sensitive detection of HCl, NH3 and NO2, with good selectivity, excellent reproducibility, and satisfactory stability. These results reveal gas-phase reaction assisted detection as a unique and promising approach to construct practical applicable gas sensors with typical organic transistors.