Since the discovery of highly conducting polyacetylene by Shirakawa, MacDiarmid, and Heeger in 1977, π-conjugated systems have attracted much attention as futuristic materials for the development and production of the next generation of electronics, that is, organic electronics. Conceptually, organic electronics are quite different from conventional inorganic solid state electronics because the structural versatility of organic semiconductors allows for the incorporation of functionality by molecular design. This versatility leads to a new era in the design of electronic devices. To date, the great number of π-conjugated semiconducting materials that have either been discovered or synthesized generate an exciting library of π-conjugated systems for use in organic electronics. 11 However, some key challenges for further advancement remain: the low mobility and stability of organic semiconductors, the lack of knowledge regarding structure property relationships for understanding the fundamental chemical aspects behind the structural design, and realization of desired properties. Organic field-effect transistors (OFETs) are a kind of device consisting of an organic semiconducting layer, a gate insulator layer, and three terminals (drain, source, and gate electrodes). OFETs are not only essential building blocks for the next generation of cheap and flexible organic circuits, but they also provide an important insight into the charge transport of πconjugated systems. Therefore, they act as strong tools for the exploration of the structure property relationships of πconjugated systems, such as parameters of field-effect mobility (μ, the drift velocity of carriers under unit electric field), current on/off ratio (the ratio of the maximum on-state current to the minimum off-state current), and threshold voltage (the minimum gate voltage that is required to turn on the transistor). 17 Since the discovery of OFETs in the 1980s, they have attracted much attention. Research onOFETs includes the discovery, design, and synthesis of π-conjugated systems for OFETs, device optimization, development of applications in radio frequency identification (RFID) tags, flexible displays, electronic papers, sensors, and so forth. It is beyond the scope of this review to cover all aspects of π-conjugated systems; hence, our focus will be on the performance analysis of π-conjugated systems in OFETs. This should make it possible to extract information regarding the fundamental merit of semiconducting π-conjugated materials and capture what is needed for newmaterials and what is the synthesis orientation of newπ-conjugated systems. In fact, for a new science with many practical applications, the field of organic electronics is progressing extremely rapidly. For example, using “organic field effect transistor” or “organic field effect transistors” as the query keywords to search the Web of Science citation database, it is possible to show the distribution of papers over recent years as shown in Figure 1A. It is very clear

Semiconducting π-conjugated systems in field-effect transistors: a material odyssey of organic electronics.

Organic semiconducting oligomers for use in thin film transistors.

The past couple of years have witnessed a remarkable burst in the development of organic field-effect transistors (OFETs), with a number of organic semiconductors surpassing the benchmark mobility of 10 cm2/(V s). In this perspective, we highlight some of the major milestones along the way to provide a historical view of OFET development, introduce the integrated molecular design concepts and process engineering approaches that lead to the current success, and identify the challenges ahead to make OFETs applicable in real applications.

Integrated materials design of organic semiconductors for field-effect transistors

Structural and electronic criteria for ambient stability in n-type organic materials for organic field-effect transistors (OFETs) are investigated by systematically varying LUMO energetics and molecular substituents of arylene diimide-based materials Six OFETs on n+-Si/SiO2 substrates exhibit OFET response parameters as follows: N,N'-bis(n-octyl)perylene-3,4:9,10-bis(dicarboximide) (PDI-8): mu = 032 cm2 V(-1) s(-1), Vth = 55 V, I(on)/I(off) = 10(5); N,N'-bis(n-octyl)-1,7- and N,N'-bis(n-octyl)-1,6-dibromoperylene-3,4:9,10-bis(dicarboximide) (PDI-8Br2): mu = 3 x 10(-5) cm2 V(-1) s(-1), Vth = 62 V, I(on)/I(off) = 10(3); N,N'-bis(n-octyl)-1,6,7,12-tetrachloroperylene-3,4:9,10-bis(dicarboximide) (PDI-8Cl4): mu = 4 x 10(-3) cm2 V(-1) (s-1), Vth = 37 V, I(on)/I(off) = 10(4); N,N'-bis(n-octyl)-2-cyanonaphthalene-1,4,5,8-bis(dicarboximide) (NDI-8CN): mu = 47 x 10(-3) cm2 V(-1) s(-1), Vth = 28, I(on)/I(off) = 10(5); N,N'-bis(n-octyl)-1,7- and N,N'-bis(n-octyl)-1,6-dicyanoperylene-3,4:9,10-bis(dicarboximide) (PDI-8CN2): mu = 013 cm2 V(-1) s(-1), Vth = -14 V, I(on)/I(off) = 10(3); and N,N'-bis(n-octyl)-2,6-dicyanonaphthalene-1,4,5,8-bis(dicarboximide) (NDI-8CN2): mu = 015 cm2 V(-1) s(-1), Vth = -37 V, I(on)/I(off) = 10(2) Analysis of the molecular geometries and energetics in these materials reveals a correlation between electron mobility and substituent-induced arylene core distortion, while Vth and I(off) are generally affected by LUMO energetics Our findings also indicate that resistance to ambient charge carrier trapping observed in films of N-(n-octyl)arylene diimides occurs at a molecular reduction potential more positive than approximately -01 V (vs SCE) OFET threshold voltage shifts between vacuum and ambient atmosphere operation suggest that, at E(red1) -01 V, the trap density increase is negligible OFETs fabricated with the present n-type materials having E(red1) > -01 V operate at conventional gate biases with minimal hysteresis in air This reduction potential corresponds to an overpotential for the reaction of the charge carriers with O2 of approximately 06 V N,N'-1H,1H-Perfluorobutyl derivatives of the perylene-based semiconductors were also synthesized and used to fabricate OFETs, resulting in air-stable devices for all fluorocarbon-substituted materials, despite generally having E(red1) < -01 V This behavior is consistent with a fluorocarbon-based O2 barrier mechanism OFET cycling measurements in air for dicyanated vs fluorinated materials demonstrate that energetic stabilization of the charge carriers results in greater device longevity in comparison to the OFET degradation observed in air-stable semiconductors with fluorocarbon barriers

Tuning orbital energetics in arylene diimide semiconductors. materials design for ambient stability of n-type charge transport.

This study describes a general approach for probing semiconductor−dielectric interfacial chemistry effects on organic field-effect transistor performance parameters using bilayer gate dielectrics. Organic semiconductors exhibiting p-/n-type or ambipolar majority charge transport are grown on six different bilayer dielectric structures consisting of various spin-coated polymers/HMDS on 300 nm SiO2/p+-Si, and are characterized by AFM, SEM, and WAXRD, followed by transistor electrical characterization. In the case of air-sensitive (generally high LUMO energy) n-type semiconductors, dielectric surface modifications induce large variations in the corresponding OTFT performance parameters although the film morphologies and microstructures remain similar. In marked contrast, the device performance of air-stable n-type and p-type semiconductors is not significantly affected by the same dielectric surface modifications. Among the bilayer dielectric structures examined, nonpolar polystyrene coatings on SiO2 having ...

Gate Dielectric Chemical Structure−Organic Field-Effect Transistor Performance Correlations for Electron, Hole, and Ambipolar Organic Semiconductors

Various cyclohexyl end-capped oligomeric semiconductors based on oligothiophene, oligothiophene-fluorene, and perylene diimide have been synthesized using Stille and Suzuki coupling. These materials exhibit increased solubility over their unsubstituted and hexyl-substituted counterparts and have been successfully employed as the active component in organic field-effect transistors. The morphology of vacuum-deposited films made with these oligomers has been investigated using atomic force microscopy (AFM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). Field effect mobility as high as 0.17 cm2/V·s was observed in fluorene-thiophene oligomers deposited at elevated substrate temperatures. With the series of materials, a correlation between the size of the endgroup with respect to the size of the inner semiconducting core of the molecule is found to be an important factor in orienting the molecules with their long axis perpendicular to the substrate surface in the thin film phase, and di...

Rigoberto Advincula, ,† and

Papers

Organic Thin Film Transistors Based on Cyclohexyl-Substituted Organic Semiconductors