Air-stable N-type Semiconductor Research Articles

Carbonyl-Functionalized Cyclazines as Colorants and Air-Stable n-Type Semiconductors.

A series of π-extended cycl[3,3,2]azines (3) bearing additional carbonyl groups were synthesized via aldol condensations. Two strong electron acceptor molecules (4 and 5), with low-lying LUMO energy levels of -3.99 and -3.95 eV, respectively, were obtained. Organic thin-film transistors (TFTs) based on the cyanated cyclazine derivatives 5 were fabricated by vapor deposition, exhibiting extraordinarily stable n-type semiconductor character under ambient condition with the highest electron mobility of 0.06 cm2 V-1 s-1 consistently for more than 30 months.

Strategies for the synthesis of functional naphthalene diimides.

Naphthalene diimides, which have for a long time been in the shadow of their higher homologues the perylene diimides, currently belong to the most investigated classes of organic compounds. This is primarily due to the initial synthetic studies on core functionalization that were carried out at the beginning of the last decade, which facilitated diverse structural modifications of the naphthalene scaffold. Compounds with greatly modified optical and electronic properties that can be easily and effectively modulated by appropriate functionalization were made accessible through relatively little synthetic effort. This resulted in diverse interesting applications. The electron-deficient character of these compounds makes them highly valuable, particularly in the field of organic electronics as air-stable n-type semiconductors, while absorption bands over the whole visible spectral range through the introduction of core substituents enabled interesting photosystems and photovoltaic applications. This Review provides an overview on different approaches towards core functionalization as well as on synthetic strategies for the core expansion of naphthalene diimides that have been developed mainly in the last five years.

Arene Trifluoromethylation: An Effective Strategy to Obtain Air-Stable n-Type Organic Semiconductors with Tunable Optoelectronic and Electron Transfer Properties

Modulation of organic semiconductor band gap, electron affinities (EA), ionization potentials (IP), and reorganization energies (λ) associated with charge transfer is critical for its applications. We report here that trifluoromethylation not only increases both IP and EA significantly as expected but also narrows the HOMO-LUMO band gaps and increases considerably the air-stability of arene-based n-type organic semiconductors. The increased air-stability results from relatively high EA energies and a change in oxidation mechanism. Calculated EAs and IPs show that trifluoromethylated arenes are excellent candidates for n-type semiconductor materials; though a moderate increase of inner-sphere reorganization energy (λi) associated with charge transfer is the penalty for the improved performance of the trifluoromethylated compounds. However, since λi decreases as the π conjugation increases, a rational design to produce air-stable n-type semiconductor materials with reasonably small λi is simply to prepare trifluoromethylated arenes with extended π conjugation. Furthermore, we found that structural isomerization can fine-tune the optoelectronic and electronic transfer properties of the corresponding aromatics.

Stepwise Cyanation of Naphthalene Diimide for n-Channel Field-Effect Transistors

Stepwise cyanation of tetrabromonaphthalenediimide (NDI) 1 gave a series of cyanated NDIs 2-5 with the monocyanated NDI 2 and dicyanated NDI 3 isolated. The tri- and tetracyano- NDIs 4 and 5 show intrinsic instability toward moisture because of their extremely low-lying LUMO energy levels. The partially cyanated intermediates can be utilized as air-stable n-type semiconductors with OFET electron mobility up to 0.05 cm(2) V(-1) s(-1).

A thermally resistant and air-stable n-type organic semiconductor: Naphthalene diimide of 3,5-bis-trifluoromethyl aniline

We report a thermally resistant and air-stable n-type semiconductor based on our study of naphthalene diimide (NTCDI) derivatives ( N1, N2, and N3) with various numbers of electron-withdrawing CF 3 groups. The device using N3, which contains aromatic NTCDI, was found to exhibit an electron mobility ( μ e) of 0.15 (±0.04) cm 2/V s (the maximum μ e observed was 0.24 cm 2/V s) and an I on/I off (at V d = 80 V) of approximately 2 × 10 5. Moreover, the N3 device exhibits excellent air stability, even when exposed to the open air for 42 days, and significantly better thermal resistance than the previously reported benzylic imide derivative R1.

High-mobility bottom-contact n-channel organic transistors and their use in complementary ring oscillators

The electrical characteristics of bottom-contact organic field-effect transistors fabricated with the air-stable n-type semiconductor N,N′-bis(n-octyl)-dicyanoperylene-3,4:9,10-bis(dicarboximide) (PDI-8CN2) are described. The mobility, threshold voltage, subthreshold swing, and Ion∕Ioff ratio(VDS=40V, VG=0∼40V) are 0.14cm2∕Vs, 1.6V, 2.0V/decade, and 1.2×103, respectively. The effect of electrode/dielectric surface treatment on these devices is also examined, with a combination of 1-octadecanethiol and hexamethyldisilazane. Organic complementary five-stage ring oscillators were fabricated using pentacene and PDI-8CN2, and operated at an oscillation frequency of 34kHz and a propagation delay per stage of 3μs.