We present here the systematic synthesis and comparative physicochemical characterization of a series of regiochemically varied and core size extension-modulated arene(perfluoroarene)-thiophene oligomers. The molecules investigated are: 5,5''-diphenyl-2,2':5',2'':5'',2'''-quaterthiophene (1), 5,5'-bis[1-[4-(thien-2-yl)phenyl]]-2,2'-dithiophene (2), 4,4'-bis[5-(2,2'-dithiophenyl)]-biphenyl (3), 5,5''-diperfluorophenyl-2,2':5',2'':5'',2'''-quaterthiophene (4), 5,5'-bis[1-[4-(thien-2-yl)perfluorophenyl]]-2,2'-dithiophene (5), 4,4'-bis[5-(2,2'-dithiophenyl)]-perfluorobiphenyl (6), 5,5''-diperfluorophenyl-2,2':5',2''-tertthiophene (7), 5,5'-diperfluorophenyl-2,2'-dihiophene (8), and 5,5-diperfluorophenylthiophene (9). Trends in optical absorption and emission parameters, molecular structures as defined by single-crystal X-ray diffraction, as well as electrochemical redox processes are described. The morphologies and microstructures of the vapor-deposited films grown over a range of growth temperatures have also been characterized. Field-effect transistor (FET) measurements demonstrate that all of these materials are FET-active and, depending on the molecular architecture, exhibit comparably good p- or n-type mobility when optimum film microstructural order is achieved. A very large n-channel mobility of approximately 0.5 cm2/Vs with I(on)/I(off) ratios > 10(8) is achieved for films of 4.

Fluorocarbon-modified organic semiconductors: molecular architecture, electronic, and crystal structure tuning of arene- versus fluoroarene-thiophene oligomer thin-film properties

A high-performance ambipolar light-emitting transistor (LET) that has high hole and electron mobilities and excellent luminescence characteristics is described. By using this device, a conspicuous light-confined edge emission and current-density-dependent spectral evolution are observed. These findings will result in broader utilization of device potential and they provide a promising route for realizing electrically driven organic lasers.

High Mobility and Luminescent Efficiency in Organic Single-Crystal Light-Emitting Transistors

Lasing applications have spread over various aspects of human life. To meet the developing trends of the laser industry towards being miniature, portable, and highly integrated, new laser technologies are in urgent demand. Organic semiconductors are promising gain medium candidates for novel laser devices, due to their convenient processing techniques, ease of spectral and chemical tuning, low refractive indexes, mechanical flexibilities, and low thresholds, etc. organic solid-state lasers (OSSLs) open up a new horizon of simple, low-cost, time-saving, versatile and environmental-friendly manufacturing technologies for new and desirable laser structures (micro-, asymmetric, flexible, etc.) to unleash the full potential of semiconductor lasers for future electronics. Besides the development of optical feedback structures, the design and synthesis of robust organic gain media is critical as a vigorous aspect of OSSLs. Herein, we provide a comprehensive review of recent advances in organic gain materials, mainly focused on organic semiconductors for OSSLs. The significant breakthroughs toward electrical pumping of OSSLs are emphasized. Opportunities, challenges and future research directions for the design of organic gain media are also discussed.

Organic solid-state lasers: a materials view and future development.

Synthesis and properties of molecular rods. 2. Zig-zag rods

A series of thiophene-containing oligomers that are less electron rich than alpha-6T were synthesized, and the thin film morphologies and field-effect transistor characteristics of the oligomers were evaluated. Phenyl and thiazole rings were included in many of the oligomers, and a new synthesis of perfluoroalkylmethyl-terminated oligomers was developed. Desirably low off currents were associated with calculated highest occupied molecular orbital energies above ca. 5.0 eV relative to vacuum. Some of the oligomers displayed mobilities above 0.01 cm2 (Vs)-1, but there was no correlation of mobility with calculated orbital energies and some compounds with seemingly continuous morphologies had low mobilities nonetheless. One compound, 1,4-bis(5‘-hexyl-2,2‘-bithiophen-5-yl)benzene, showed promising behavior as a solution-deposited semiconductor, with mobility up to 0.02 cm2 (Vs)-1 and an on/off ratio up to 20 000.

T. Tamaki

Papers

Synthesis of thiophene/phenylene co-oligomers. I. Phenyl-capped oligothiophenes