2.2. Materials 929 2.3. Factors Influencing Charge Mobility 931 2.3.1. Molecular Packing 931 2.3.2. Disorder 932 2.3.3. Temperature 933 2.3.4. Electric Field 934 2.3.5. Impurities 934 2.3.6. Pressure 934 2.3.7. Charge-Carrier Density 934 2.3.8. Size/molecular Weight 935 3. The Charge-Transport Parameters 935 3.1. Electronic Coupling 936 3.1.1. The Energy-Splitting-in-Dimer Method 936 3.1.2. The Orthogonality Issue 937 3.1.3. Impact of the Site Energy 937 3.1.4. Electronic Coupling in Oligoacene Derivatives 938

Charge transport in organic semiconductors.

We demonstrate very high efficiency electrophosphorescence in organic light-emitting devices employing a phosphorescent molecule doped into a wide energy gap host. Using bis(2-phenylpyridine)iridium(III) acetylacetonate [(ppy)2Ir(acac)] doped into 3-phenyl-4(1′-naphthyl)-5-phenyl-1,2,4-triazole, a maximum external quantum efficiency of (19.0±1.0)% and luminous power efficiency of (60±5) lm/W are achieved. The calculated internal quantum efficiency of (87±7)% is supported by the observed absence of thermally activated nonradiative loss in the photoluminescent efficiency of (ppy)2Ir(acac). Thus, very high external quantum efficiencies are due to the nearly 100% internal phosphorescence efficiency of (ppy)2Ir(acac) coupled with balanced hole and electron injection, and triplet exciton confinement within the light-emitting layer.

Nearly 100% internal phosphorescence efficiency in an organic light emitting device

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.

Functionalized acenes and heteroacenes for organic electronics.

Organic–inorganic hybrid perovskite materials are attracting great interest for their applications in photovoltaics where they have demonstrated excellent efficiency. Here, Dou et al. demonstrate room temperature, solution-processed hybrid perovskite photodetectors with fast response and high detectivity.

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Solution-processed hybrid perovskite photodetectors with high detectivity

One of the keys to highly efficient phosphorescent emission in organic light-emitting devices is to confine triplet excitons generated within the emitting layer. We employ “starburst” perfluorinated phenylenes (C60F42) as a both hole- and exciton-block layer, and a hole-transport material 4,4′,4″-tri(N-carbazolyl) triphenylamine as a host for the phosphorescent dopant dye in the emitting layer. A maximum external quantum efficiency reaches to 19.2%, and keeps over 15% even at high current densities of 10–20 mA/cm2, providing several times the brightness of fluorescent tubes for lighting. The onset voltage of the electroluminescence is as low as 2.4 V and the peak power efficiency is 70–72 lm/W, promising for low-power display devices.

Highly efficient phosphorescence from organic light-emitting devices with an exciton-block layer

We report the synthesis and characterization of perfluoropentacene as an n-type semiconductor for organic field-effect transistors (OFETs). Perfluoropentacene is a planar and crystalline material that adopts a herringbone structure as observed for pentacene. OFETs with perfluoropentacene were constructed using top-contact geometry, and an electron mobility of 0.11 cm2 V-1 s-1 was observed. Bipolar OFETs with perfluoropentacene and pentacene function at both negative and positive gate voltages. The improved p−n junctions are probably due to the similar d-spacings of both acenes. Complementary inverter circuits were fabricated, and the transfer characteristics exhibit a sharp inversion of the output signal with a high-voltage gain.

Perfluoropentacene: high-performance p-n junctions and complementary circuits with pentacene.

[n]Cycloparaphenylenes (n = 8–13, CPPs) were synthesized, and their physical properties were systematically investigated. [8] and [12]CPPs were selectively prepared from the reaction of 4,4′-bis(trimethylstannyl)biphenyl and 4,4′′-bis(trimethylstannyl)terphenyl, respectively, with Pt(cod)Cl2 (cod = 1,5-cyclooctadiene) through square-shaped tetranuclear platinum intermediates. A mixture of [8]–[13]CPPs was prepared in good combined yields by mixing biphenyl and terphenyl precursors with platinum sources. Products were easily separated and purified by using gel permeation chromatography. In 1H NMR spectra, the proton of the CPPs shifts to a lower field as n increased due to an anisotropic effect from the nearby PP moieties. Although the UV–vis spectra were rather insensitive to the size of the CPPs, the fluorescence spectra changed significantly in relation to their size. A larger Stokes shift was observed for the smaller CPPs. Redox properties of the CPPs were measured for the first time by using cyclic vo...

Selective and Random Syntheses of [n]Cycloparaphenylenes (n = 8–13) and Size Dependence of Their Electronic Properties

Synthesis, Characterization, and Electron-Transport Property of Perfluorinated Phenylene Dendrimers

The charge-transport parameters of the perfluoropentacene and perfluorotetracene crystals are studied with a joint experimental and theoretical approach that combines gas-phase ultraviolet photoelectron spectroscopy and density functional theory. To gain a better understanding of the role of perfluorination, the results for perfluoropentacene and perfluorotetracene are compared to those for their parent oligoacenes, that is, pentacene and tetracene. Perfluorination is calculated to increase the ionization potentials and electron affinities by approximately 1 eV, which is expected to reduce significantly the injection barrier for electrons in organic electronics devices. Perfluorination also leads to significant changes in the crystalline packing, which greatly affects the electronic properties of the crystals and their charge-transport characteristics. The calculations predict large conduction and valence bandwidths and low hole and electron effective masses in the perfluoroacene crystals, with the largest mobilities expected along the pi-stacks. Perfluorination impacts as well both local and nonlocal vibrational couplings, whose strengths increase by a factor of about 2 with respect to the parent compounds.

Youichi Sakamoto

Papers

Highly efficient phosphorescence from organic light-emitting devices with an exciton-block layer

Perfluoropentacene: high-performance p-n junctions and complementary circuits with pentacene.

Selective and Random Syntheses of [n]Cycloparaphenylenes (n = 8–13) and Size Dependence of Their Electronic Properties

Synthesis, Characterization, and Electron-Transport Property of Perfluorinated Phenylene Dendrimers

Impact of Perfluorination on the Charge-Transport Parameters of Oligoacene Crystals