Recent Progress in Organic Phototransistors: Semiconductor Materials, Device Structures and Optoelectronic Applications

In this study, we report an effective approach to tune the crystallization, microstructure and charge transport of solution-processed organic semiconductors by blending with a conjugated polymer additive poly(3-hexylthiophene) (P3HT). When 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS pentacene) was used as a model semiconductor material to mix with different amount of P3HT, their intermolecular interactions led to distinctive TIPS pentacene film morphologies, including randomly-oriented crystal ribbons, elongated needles with enhanced long-range order, and grass-like curved microwires with interlinkages. Each type of morphology was found to further correlate to considerably different charge transport and device performance. As compared to pristine TIPS pentacene devices, bottom-gate, top-contact OTFTs with 2% in weight P3HT additive showed a 2-fold and 5-fold improvement of average field-effect mobility and performance consistency (defined as the ratio of average mobility to the standard deviation), respectively. The improvement in transistor electrical performance can be attributed to the combined effect of enhanced crystal orientation and uniformity, as well as increased areal coverage. This work can be applied beyond the particular example demonstrated in this study and to tune the charge transport of other small-molecule organic semiconductors in general.

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Conjugated Polymer Controlled Morphology and Charge Transport of Small-Molecule Organic Semiconductors.

Although much research progress has recently been achieved in solution-soluble, small-molecule, organic semiconductors, their randomly oriented crystals still remain as an issue that leads to nonuniform charge transport and severely degrades performance consistency of organic thin film transistors (OTFTs). In the paper, we reviewed the various small-molecule additives that have been reported to blend with these semiconductors in order to reduce their crystal misorientation and mobility variations of OTFTs. By mainly studying the examples of a representative small-molecule organic semiconductor 6,13-bis(triisopropylsilylethynyl) pentacene, we intend to disclose the important effects of the various additives on controlling the semiconductor crystallization, film morphology, and charge transport. This work can be facilely employed to align the crystal orientation and tweak the electrical performance of newly discovered small-molecule organic semiconductors, and will provide an in-depth understanding of the important application in high-performance, solution-based, large-area organic electronics devices.

Small-molecule additives for organic thin film transistors

The electrical performance of solution-processed, small-molecule organic semiconductors is largely restricted by their severe charge carrier mobility variations. In this work, we demonstrate an effective method to reduce such variations of the semiconductor mobilities and improve the performance consistency of organic thin film transistors (OTFTs) by adding poly(α-methylstyrene) (PαMS) as a polymer additive. By using 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS pentacene) as an example, we found that while pristine TIPS pentacene film exhibited random crystal orientation and large film gaps, the addition of PαMS polymer promoted the growth of semiconductor crystals, which formed uniformly aligned needles with significantly improved orientation and coverage within the channel regions. An ultra-low misorientation angle of 2.2° ± 1° was obtained from TIPS pentacene/PαMS blend film, which is a 20-fold reduction as compared to pristine TIPS pentacene. Bottom-gate, top-contact OTFTs with TIPS pentacene crystals aligned perpendicularly from source to drain contact electrodes demonstrated a hole mobility of up to 0.26 cm2/V s, as well a 6-fold enhancement of average mobility as compared to the pristine TIPS pentacene based counterparts. Notably, the addition of PαMS led to a performance consistency factor of 3.35, as defined by the ratio of the average mobility to standard deviation, implying a great reduction of charge carrier mobility variations. The improvement of electrical performance of OTFTs can be attributed to the combined outcome of crystal rigid alignment, extended long-range order, and almost full coverage of charge transport channel.

Poly(α-methylstyrene) polymer and small-molecule semiconductor blend with reduced crystal misorientation for organic thin film transistors

Bilayer p-n heterojunctions are promising structures to construct ambipolar organic field-effect transistors (aOFETs) for organic integrated circuits. However, due to the lack of effective strategies for high-quality p-n heterojunctions with clear interfaces, the performance of aOFETs is commonly and substantially lower than that of their unipolar counterparts, which hinders the development of aOFETs toward practical applications. Herein, a one-step solution crystallization strategy was proposed for the preparation of high-quality bilayer p-n heterojunctions. A mixed solution of a p- and an n-type organic semiconductor was dropped on a liquid substrate, and vertical phase separation occurred spontaneously during crystallization to produce bilayer p-n heterojunctions composed of molecularly thin two-dimensional molecular crystals. Due to the clear interface of the bilayer p-n heterojunctions, the maximum mobility (average mobility) reached 1.96 cm2 V−1 s−1 (1.12 cm2 V−1 s−1) for holes and 1.27 cm2 V−1 s−1 (0.61 cm2 V−1 s−1) for electrons in ambient air. So far as we know, these values were the highest among double-channel aOFETs measured in ambient air. This work provides a simple yet efficient strategy to construct high-quality bilayer p-n heterojunctions, which lays a foundation for their application in high-performance optoelectronic devices.

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Youngmoo Eun

Papers

Interdigitated Ambipolar Active Layer for Organic Phototransistor with Balanced Charge Transport