Regulating Optoelectronic and Thermoelectric Properties of Organic Semiconductors by Heavy Atom Effects.

Heavy atom effects can be used to enhance intermolecular interaction, regulate quinoidal resonance properties, increase bandwidths, and tune diradical characters, which have significant impacts on organic optoelectronic devices, such as organic field-effect transistors (OFETs), organic light-emitting diodes (OLEDs), organic photovoltaics (OPVs), etc. Meanwhile, the introduction of heavy atoms is shown to promote charge transfer, enhance air stability, and improve device performances in the field of organic thermoelectrics (OTEs). Thus, heavy atom effects are receiving more and more attention.

Thermoelectric Performance in Triplet-Ground-State Polymer Intrinsically Boosted by Enhanced Proquinoidal Characteristic.

Over the past decade, polymer thermoelectric materials featuring flexibility, lightness, and bio-friendliness have been paid increasing attention as promising candidates for waste heat recovery and energy generation. For a long time, the dominant approach to optimizing the thermoelectric performance of most organic materials is chemical doping, which, however, is not always ideal for practical applications due to its tendency to involve intricate processing procedure and trigger material and device instability. Currently, the pursuit of single-component neutral thermoelectric materials without exogenous doping presents a compelling alternative.

Efficient and air-stable n-type doping in organic semiconductors.

Chemical doping of organic semiconductors (OSCs) enables feasible tuning of carrier concentration, charge mobility, and energy levels, which is critical for the applications of OSCs in organic electronic devices. However, in comparison with p-type doping, n-type doping has lagged far behind. The achievement of efficient and air-stable n-type doping in OSCs would help to significantly improve electron transport and device performance, and endow new functionalities, which are, therefore, gaining increasing attention currently.

Unraveling two distinct polymorph transition mechanisms in one n-type single crystal for dynamic electronics.

Cooperativity is used by living systems to circumvent energetic and entropic barriers to yield highly efficient molecular processes. Cooperative structural transitions involve the concerted displacement of molecules in a crystalline material, as opposed to typical molecule-by-molecule nucleation and growth mechanisms which often break single crystallinity. Cooperative transitions have acquired much attention for low transition barriers, ultrafast kinetics, and structural reversibility.

New semi-ladder polymers for ambipolar organic light-emitting transistors.

Organic light-emitting transistors (OLETs) combine the light-emitting and gate-modulated electrical switching functions in a single device. Over the past two decades, progress has been made in developing new fluorescent semiconductors and device engineering to improve the properties of OLETs. In this paper, we give a brief review of the achievement and disadvantages of the present polymer-based OLETs, while highlighting the recent developments in semi-ladder polymers from our lab for new electroluminescent materials.

Foldable semi-ladder polymers: novel aggregation behavior and high-performance solution-processed organic light-emitting transistors.

A critical issue in developing high-performance organic light-emitting transistors (OLETs) is to balance the trade-off between charge transport and light emission in a semiconducting material. Although traditional materials for organic light-emitting diodes (OLEDs) or organic field-effect transistors (OFETs) have shown modest performance in OLET devices, design strategies towards high-performance OLET materials and the crucial structure-performance relationship remain unclear. Our research effort in developing cross-conjugated weak acceptor-weak donor copolymers for luminescent properties lead us to an unintentional discovery that these copolymers form coiled foldamers with intramolecular H-aggregation, leading to their exceptional OLET properties.

Synergy between Photoluminescence and Charge Transport Achieved by Finely Tuning Polymeric Backbones for Efficient Light-Emitting Transistor.

The lack of design principle for developing high-performance polymer materials displaying strong fluorescence and high ambipolar charge mobilities limited their performance in organic light-emitting transistors (OLETs), electrically pumped organic laser, and other advanced electronic devices. A series of semiladder polymers by copolymerization of weak acceptors (TPTQ or TPTI) and weak donors (fluorene (F) or carbazole (C)) have been developed for luminescent and charge transporting properties. It was found that enhanced planarity, high crystallinity, and a delicate balance in interchain aggregation obtained in the new copolymer, TPTQ-F, contributed to high ambipolar charge mobilities and photoluminescent quantum yield.

Finely Designed P3HT-Based Fully Conjugated Graft Polymer: Optical Measurements, Morphology, and the Faraday Effect.

In this work, our group synthesized and characterized a fully conjugated graft polymer comprising of a donor-acceptor molecular backbone and regioregular poly(3-hexylthiophene) (RRP3HT) side chains. Here, our macromonomer () was synthesized via Kumada catalyst transfer polycondensation reaction based on ditin-benzodithiophene (BDT) initiator. The tin content of was then investigated by inductively coupled plasma-mass spectrometry (ICP-MS), which allowed for accurate control of donor/acceptor monomer ratio of 1:1 for the following Stille coupling polymerization toward our graft polymer ().

Design of High-Performance Organic Light-Emitting Transistors.

Organic light-emitting transistors (OLETs) integrate the light-emitting and gate-modulated electrical switching functions in a single device. Over the past decades, progress has been made in developing new fluorescent semiconductors and device engineering that pushed efficiencies of OLET devices to 8%. However, this efficiency of transistors is still too low to be competitive with organic light-emitting diodes (OLEDs).

Air-Stable n-Type Thermoelectric Materials Enabled by Organic Diradicaloids.

Air-stable n-type thermoelectric materials are recognized as an important and challenging topic in organic thermoelectrics (OTEs) because conventional n-type OTE materials prepared by chemical doping are highly volatile upon exposure to air. Besides, doping efficiency and microstructure are hard to control with the incorporation of external dopants. We report herein the design and synthesis of unconventional n-type OTE materials based on the diradicaloids 2DQQT-S and 2DQQT-Se, which are proved to be neutral single-component organic conductors that exhibit an unprecedented air stability.

2,2'-Diamino-6,6'-diboryl-1,1'-binaphthyl: A Versatile Building Block for Temperature-Dependent Dual Fluorescence and Switchable Circularly Polarized Luminescence.

Temperature-dependent dual fluorescence and switchable circularly polarized luminescence (CPL) are two highly pursued but challenging properties for small organic molecules (SOMs). We herein disclose a triarylborane π-system based on a 2,2'-diamino-6,6'-diboryl-1,1'-binaphthyl scaffold that can serve as a versatile building block for achieving these two properties by simply choosing different amino groups. BNMe -BNaph with less bulky dimethylamino groups displays temperature-dependent dual fluorescence, and can thus be used as a highly sensitive ratiometric fluorescence thermometer.

Design of a Quinoidal Thieno[3,4-b]thiophene-Diketopyrrolopyrrole-Based Small Molecule as n-Type Semiconductor.

A quinoidal small-molecule semiconductor QDPPBTT was synthesized. Organic thin-film transistor (OTFT) devices based on QDPPBTT showed an electron mobility as high as 0.13 cm  V  s and I /I ratio of 10 under ambient conditions.

Quinoid-Resonant Conducting Polymers Achieve High Electrical Conductivity over 4000 S cm for Thermoelectrics.

New conducting polymers polythieno[3,4-]thiophene-Tosylate (PTT-Tos) are prepared by solution casting polymerization. Through tuning the alkyl group of TT, the electrical conductivity can be effectively enhanced from 0.0001 to 450 S cm.

Thieno[3,4-c]pyrrole-4,6-dione Oligothiophenes Have Two Crossed Paths for Electron Delocalization.

A new series of electron-deficient oligothiophenes, thieno[3,4-c]pyrrole-4,6-dione oligothiophenes (OTPD ), from the monomer to hexamer, is reported. The optical and structural properties in the neutral states have been analyzed by absorption and emission spectroscopy together with vibrational Raman spectroscopy. In their reduced forms, these molecules could stabilize both anions and dianions in similar ways.

Ullmann-Type Intramolecular C-O Reaction Toward Thieno[3,2-b]furan Derivatives with up to Six Fused Rings.

A new strategy for the efficient synthesis of thieno[3,2-b]benzofuran derivatives (15 examples) was achieved on the basis of successive regioselective intermolecular Suzuki and newly developed intramolecular Ullmann C-O reactions in up to a 70% overall yield. The fast intramolecular C-O reaction can be realized by an efficient catalytic combination of CuI/1,10-phenanthroline in up to a 97% yield. This method is suitable for the construction of highly fused thieno[3,2-b]furan-containing heterocycles including DTBDF and TTDBF.

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), and (2-Cyc-DMBI-Me), 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 K was obtained with the new dopant (2-Cyc-DMBI-Me).

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.

Diaceno[a,e]pentalenes from homoannulations of o-alkynylaryliodides utilizing a unique Pd(OAc)2/n-Bu4NOAc catalytic combination.

A heterogeneous catalytic system, Pd(OAc)2/n-Bu4NOAc, for the efficient synthesis of diaceno[a,e]pentalenes via a tandem Pd catalytic cycle is reported. The catalytic partner n-Bu4NOAc played indispensable and versatile roles, acting as both the media for recovering active Pd(0) species and their stabilizer. A series of new diaceno[a,e]pentalenes were obtained in moderate to high yields, among which the octacyclic dianthracenopentalene was found to be highly emissive.