Thiophene polymer semiconductors for organic thin-film transistors

Printed organic thin-film transistors (OTFTs) have received great interests as potentially low-cost alternative to silicon technology for application in large-area, flexible, and ultra-low-cost electronics. One of the critical materials for TFTs is semiconductor, which has a dominant impact on the transistor properties. We review here the structural studies and design of thiophene-based polymer semiconductors with respect to solution processability, ambient stability, molecular self-organization, and field-effect transistor properties for OTFT applications. We show that through judicial monomer design, delicately controlled pi-conjugation, and strategically positioned pendant side-chain distribution, novel solution-processable thiophene polymer semiconductors with excellent self-organization ability to form extended lamellar pi-stacking orders can be developed. OTFTs using semiconductors of this nature processed in ambient conditions have provided excellent field-effect transistor properties.     

Organic semiconductors for solution-processable field-effect transistors (OFETs)

The cost-effective production of flexible electronic components will profit considerably from the development of solution-processable, organic semiconductor materials. Particular attention is focused on soluble semiconductors for organic field-effect transistors (OFETs). The hitherto differentiation between "small molecules" and polymeric materials no longer plays a role, rather more the ability to process materials from solution to homogeneous semiconducting films with optimal electronic properties (high charge-carrier mobility, low threshold voltage, high on/off ratio) is pivotal. Key classes of materials for this purpose are soluble oligoacenes, soluble oligo- and polythiophenes and their respective copolymers, and oligo- and polytriarylamines. In this context, micro- or nanocrystalline materials have the general advantage of somewhat higher charge-carrier mobilities, which, however, could be offset in the case of amorphous, glassy materials by simpler and more reproducible processing.     

Cyanation: providing a three-in-one advantage for the design of n-type organic field-effect transistors

The theoretical work presented here demonstrates that, when substitution takes place at appropriate positions, cyanation could be a useful tool for reducing the internal reorganization energy of molecules. A molecular-orbital-based explanation is given for this fundamentally important phenomenon. Some of the cyanated pentacene derivatives (nCN-PENT-n) not only have internal reorganization energies for electron transfer (lambda(-)) smaller than that of pentacene, but the lambda(-) values are even of the same magnitude as the internal reorganization energy for hole transfer (lambda(+)) of pentacene, a small value that few organic compounds have surpassed. In addition, cyanation raises the electron affinity of the parent compound and may afford good electronic couplings between neighboring molecules, because of its ability in promoting pi-stacking. For the design of high performance n-Type Organic field-effect transistors, high electron affinities, large intermolecular electronic couplings, and small reorganization energies are necessary. Cyanation may help in all three aspects. Two cyanated trialkylsilylethynyl pentacene derivatives with known pi-stacking structures are predicted to provide reasonably small internal reorganization energies, large electronic couplings, and high electron affinities. They have the potential to outperform N-fluoroalkylated dicyanoperylene-3,4:9,10-bis(dicarboximides) (PDI-FCN(2)) in terms of electron mobility.     

Air-stable n-type organic field-effect transistors based on solution-processable, electronegative oligomers containing dicyanomethylene-substituted cyclopenta[b]thiophene

Solution-processable, electronegative, π-conjugated systems containing dicyanomethylene-substituted cyclopenta[b]thiophene were synthesized as potential active materials for air-stable n-type organic field-effect transistors (OFETs). Electrochemical measurements revealed that these compounds exhibited electrochemical stability and that the lowest unoccupied molecular orbital (LUMO) had an energy level less than -4.0 eV. Flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements were performed, and the value of intradomain electron mobility was determined to be as high as 0.1 cm(2) V(-1) s(-1) . The OFETs were fabricated by spin-coating thin films of the compounds as an active layer. The electron mobility of the OFETs was 3.5×10(-3) cm(2) V(-1) s(-1) in vacuum. Furthermore, electron mobility of the same order of magnitude and stable characteristics were obtained under air-exposed conditions. X-ray diffraction measurements of the spin-coated thin films revealed the difference of molecular arrangements depending on the inner conjugated units. Atomic force microscopy measurements of crystalline-structured films exhibited the formation of grains. The accomplishment of air-stability was attributed to the combined effect of the low-lying LUMO energy level and the molecular arrangements in the solid state, avoiding both the quenching of electron carriers and the intrusion of oxygen and/or moisture.     

Molecular design of n-type organic semiconductors for high-performance thin film transistors

This digest aims to provide organic chemists with an overview of recent progress on n-type organic semiconductors for application in organic thin film transistors (OTFTs) with an emphasis on molecular design. Herein, we survey n-type organic semiconductors with field effect mobility of 1 cm²/Vs or higher in OTFTs after a brief introduction to the structure and operation of OTFTs and discussion of two key factors (frontier molecular orbitals and molecular packing) of organic semiconductors. On the basis of this survey, we finally reach conclusions on the current status of n-type organic semiconductors for OTFTs and provide an outlook for molecular design.     

Synthesis,Structures, and Properties of Fused Thiophenes for Organic Field‐Effect Transistors

A series of fused thiophenes composed of fused α‐oligothiophene units as building blocks, end‐capped with either styrene or 1‐pentyl‐4‐vinylbenzene groups, has been synthesized through Stille coupling reactions. The compounds have been fully characterized by means of ¹H NMR spectrometry, high‐resolution mass spectrometry, and elemental analysis. The molecules present a trans–trans configuration between their double bonds, which has been verified and confirmed by Fourier‐transform infrared spectroscopy and single‐crystal X‐ray diffraction analysis. The X‐ray crystal structures showed π–π overlap and sulfur–sulfur interactions between the adjacent molecules. The decomposition temperatures were all found to be above 300 °C, indicating that compounds of this series possess excellent thermal stability. The fact that no phase transition occurs at low temperature indicates that they should be well‐suited for application in devices. Moreover, they possess low HOMO energy levels, based on cyclic voltammetry measurements, and suitable energy gaps, as determined from their thin‐film UV/Vis spectra. Thin‐film X‐ray diffraction analysis and atomic force microscopy revealed high crystallinity on supporting substrates. In addition, as the substrate temperature has a significant influence on the morphology and the degree of crystallinity, the device performance could be optimized by varying the substrate temperature. These materials were found to exhibit optimal field‐effect performance, with a mobility of 0.17 cm² V^?1 s^?1 and an on/off ratio of 10⁵, at a substrate temperature of 70 °C.     

Progresses in organic field-effect transistors and molecular electronics

In the past years, organic semiconductors have been extensively investigated as electronic materials for organic field-effect transistors (OFETs). In this review, we briefly summarize the current status of organic field-effect transistors including materials design, device physics, molecular electronics and the applications of carbon nanotubes in molecular electronics. Future prospects and investigations required to improve the OFET performance are also involved. __________ Translated from Huaxue Tongbao (Chemistry), 2006, 69(6) (in Chinese)     

Toward the rational design of functionalized pentacenes: reduction of the impact of functionalization on the reorganization energy.

For the widely studied high-carrier-mobility species, pentacene, it is found that perfluorination turned it into an n-type organic field-effect transistor (OFET), but doubled the internal reorganization energy (lambda) of the electron/hole hopping. Here, Cl- and N-functionalized pentacenes are designed to test two strategies that may reduce the impact of functionalization on lambda. Calculation results show that the strategies are feasible. Moreover, combined with crystal-structure data of Cl- and N-functionalized aromatic compounds, it is concluded that compared to fluorination, the presence of Cl and N atoms in pentacene not only reduces the influence of functionalization on lambda and affords a larger window for tuning HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) energies, but also provides the opportunity to promote pi-stacked structures through ClCl and C--HN interactions.     

高迁移率有机薄膜晶体管材料进展

对近几年来高迁移率有机薄膜晶体管材料研究的主要发展作了简要介绍和评述,讨论了高迁移率有机半导体材料存在的问题和发展方向．     

Synthesis and Properties of Semiconducting Bispyrrolothiophenes for Organic Field‐Effect Transistors

A series of new highly soluble bispyrrolothiophenes were synthesized from vinyl azides by using transition‐metal‐catalyzed C?H‐bond functionalization. In addition to modifying the substituents present on the end‐pyrrolothiophene moieties, the arene linker in between the two units was also varied. The solution‐state properties and field‐effect‐transistor (FET) electrical behavior of these bispyrrolothiophenes was compared. Our investigations identified that the optical properties and oxidation potential of our compounds were dominated by the pyrrolothiophene unit with a λ_max value of approximately 400 nm and oxidation at approximately 1 V. FET devices constructed with thin films of these bispyrrolothiophenes were also fabricated by means of thin‐film solution processing. One of these compounds, a bispyrrolothiophene linked with benzothiodiazole, exhibits a mobility of approximately 0.3 cm² V^?1 s^?1 and the I_on/I_off value is greater than 10⁶.     

Small molecule organic semiconductors on the move: promises for future solar energy technology

This article is written from an organic chemist's point of view and provides an up-to-date review about organic solar cells based on small molecules or oligomers as absorbers and in detail deals with devices that incorporate planar-heterojunctions (PHJ) and bulk heterojunctions (BHJ) between a donor (p-type semiconductor) and an acceptor (n-type semiconductor) material. The article pays particular attention to the design and development of molecular materials and their performance in corresponding devices. In recent years, a substantial amount of both, academic and industrial research, has been directed towards organic solar cells, in an effort to develop new materials and to improve their tunability, processability, power conversion efficiency, and stability. On the eve of commercialization of organic solar cells, this review provides an overview over efficiencies attained with small molecules/oligomers in OSCs and reflects materials and device concepts developed over the last decade. Approaches to enhancing the efficiency of organic solar cells are analyzed.     

Rational Design of Ambipolar Organic Semiconductors: Is Core Planarity Central to Ambipolarity in Thiophene–Naphthalene Semiconductors?

Herein, we report a new family of naphthaleneamidinemonoimide-fused oligothiophene semiconductors designed for facile charge transport in organic field-effect transistors (OFETs). These molecules have planar skeletons that induce high degrees of crystallinity and hence good charge-transport properties. By modulating the length of the oligothiophene fragment, the majority carrier charge transport can be switched from n-type to ambipolar behavior. The highest FET performance is achieved for solution-processed films of 10-[(2,2'-bithiophen)-5-yl]-2-octylbenzo[lmn]thieno[3',4':4,5]imidazo[2,1-b][3,8]phenanthroline-1,3,6(2H)-trione (NDI-3 Tp), with optimized film mobilities of 2×10(-2) and 0.7×10(-2) cm(2) V(-1) s(-1) for electrons and holes, respectively. Finally, these planar semiconductors are compared with their twisted-skeleton counterparts, which exhibit only n-type mobility, in order to understand the origin of the ambipolarity in this new series of molecular semiconductors.