| 高分子 Vol.73 No.2 |
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特集 共役高分子の光電子機能
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| 展望 COVER STORY: Highlight Reviews |
| 高分子太陽電池の最近の進歩 Recent Progress in Polymer Solar Cells |
大北 英生 Hideo OHKITA |
| ＜要旨＞ 高分子太陽電池は1990年代の開発当初は変換効率1％未満であったがその後の材料開発により着実に効率が向上し、2023年には20％を超える論文が報告されるようになった。本稿では、効率向上の経緯を振り返るとともに、さらなる高効率化に求められる課題を電流、電圧、曲線因子の観点から概説し、今後の展望について述べる。 Keywords: Polymer Solar Cell / Conjugated Polymer / Fullerene / Nonfullerene Acceptor / Ternary Blend / Short-Circuit Current Density / Open-Circuit Voltage / Fill Factor |
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| 常温液状共役高分子のエレクトレット応用 Room-Temperature Liquid Conjugated Polymer Electrets |
中西 尚志 Takashi NAKANISHI |
| ＜要旨＞ 剛直なπ共役高分子の主鎖骨格に柔軟で嵩高く、絶縁性の分岐型アルキル鎖を導入する分子設計戦略では、常温液状の共役高分子を創成できる。ここでは、液状化された共役高分子の粘弾性、相分離制御、および光電子機能、とくに帯電処理により注入される静電荷イオン種を安定に保持したエレクトレットとしての応用開発事例を中心に概説する。 Keywords: Conjugated Polymers / Room-Temperature Liquids / Viscoelastic Polymers / Electrets / Mechanoelectric Generators / Mechanochromic Fluorescence / Compatibility Control |
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| 有機薄膜太陽電池における半導体高分子の分子配向制御 Orientation Control of Semiconducting Polymers in Organic Solar Cells |
但馬 敬介 Keisuke TAJIMA |
| ＜要旨＞ 有機薄膜を用いた電子デバイスを高性能化する上で、有機半導体分子の配向制御は避けては通れない課題である。分子の構造に加えて、薄膜の作成プロセスや分子間および薄膜界面との相互作用などが関係する複雑な問題となっている。本稿ではおもに有機薄膜太陽電池における薄膜中の分子配向制御を中心に現状を俯瞰する。 Keywords: Organic Thin-Films / Molecular Orientation / Organic Electronics / Organic Solar Cells / Semiconducting Polymers |
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| トピックス COVER STORY: Topics and Products |
| 近赤外光・短波赤外光検出用有機光ダイオード材料の開発 Organic Photodiode Materials for Near-Infrared and Short-Wave Infrared Light Detection |
中山 英典 Hidenori NAKAYAMA |
| ＜要旨＞ We report on new materials for solution-processable organic photodiodes (OPDs) for near-infrared (NIR) and short-wave infrared (SWIR) detection compatible with CMOS image sensors. We selected a conventional structure (p-i-n) with a polymeric hole transport layer (HTL) that we originally made for organic light-emitting diodes. The HTL is free from acids and dopants, contributing to excellent device stability. The average roughness of the HTL on a 8-inch SiO2/Si wafer is less than 3 nm. For infrared sensing materials in the active layer, we developed novel non-fullerene acceptors (NFAs). An OPD targeting 940 nm achieved an external quantum yield (EQE) of 80% at the wavelength with a dark current in the order of 1×10－6 mA/cm－2 at －5 V. Another OPD targeting SWIR achieved EQE of 45％ at 1,100 nm with a dark current of 4×10－5 mA/cm－2 at －5 V. Novel NFAs targeting even longer wavelengths are under development. Keywords: Conjugated Polymer / Non-Fullerene Acceptor / Photodiode / Bulk Heterojunction / Organic Electronics / Image Sensor |
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| 水素結合を用いた伸縮性半導体高分子 Stretchable Polymer Semiconductors Utilizing Hydrogen Bonding Interactions |
芦沢 実 Minoru ASHIZAWA |
| ＜要旨＞ Conjugation breakers (CBs) with different H-bonding chemistries and linker flexibilities are designed and incorporated into a diketopyrrolopyrrole (DPP)-based conjugated polymer backbone. The impact of bonding interactions on polymer semiconductor morphology, mechanical properties, and electrical performance are systematically investigated. We observe that CBs with an H-bonding self-association constant ＞0.7 or a denser packing tendency are able to induce higher polymer chain aggregation and crystallinity in as-casted thin films, resulting in a higher modulus and crack on-set strain. In addition, we evaluate their electrical performances under mechanical strain in fully stretchable field-effect transistors. The polymer with the highest crack on-set strain has the least degradation in mobility as a function of strain. Overall, these observations suggest that we can finely tune the mechanical properties of a polymer semiconductor by modulating intermolecular interactions, such as H-bonding chemistry and linker flexibility. Such understanding provides molecular design guidelines for future stretchable semiconductors. Keywords: Organic Electronics / Stretchable Polymer Semiconductor / Hydrogen Bonding / Conjugation Breaker / Field Effect Transistor / Stretchable Transistor |
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| 共役高分子ナノ粒子のサイズ・表面制御とバイオ分野への応用 Size- and Surface-Controlled Synthesis of Conjugated Polymer Nanoparticles and its Applications for Biomedical Field |
太田 誠一 Seiichi OHTA |
| ＜要旨＞ Conjugated polymer nanoparticles (called Pdots) have attracted attention as a new class of fluorescent material for bioimaging and biosensing. Thanks to the spread of the conjugated π electron system, they exhibit strong fluorescence with tunable color. In this article, we introduce the control method for the size and surface of Pdots and their applications for the biomedical field. Pdots were synthesized by the nanoprecipitation method, in which conjugated polymer and poly(styrene-co-maleic anhydride) dissolved in THF were dropped into water under sonication. By adjusting pH and salt concentration in the aqueous phase, we achieved size control of the synthesized Pdots in the range from 20 to 200 nm. Furthermore, since carboxylic groups are exposed on the surface of the synthesized Pdots, various functional molecules can be modified to the Pdot surface via simple carbodiimide chemistry. We demonstrated that by using DNA linker-mediated assembly of single strand DNA-modified Pdots, sensitive detection of cell surface markers can be achieved. Keywords: Conjugated Polymer / Nanoparticles / Bioimaging / Size Control / Surface Modification |
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| 高分子トランジスタを活用した化学センサ Polymer Transistors for Chemical Sensing |
佐々木 由比・南 豪 Yui SASAKI, Tsuyoshi MINAMI |
| ＜要旨＞ The attention to the development of chemical sensors has increased owing to their beneficial abilities to visualize invisible chemical species related to diagnosis, environmental assessments, food analysis, etc. However, chemical sensors for real-sample analysis have not been fully established, in contrast to physical sensors. Hence, this topic summarizes methodologies using polymer materials for both receptor and transducer units in chemical sensor devices. Among sensor platforms, polymer field-effect transistors made of solution-processable π-conjugated semiconductive materials have been employed as transducers, because of their amplification abilities allowing highly sensitive detection in real-sample analysis. Moreover, molecularly imprinted polymers (MIPs) as molecular recognition materials provide three-dimensional recognition networks against specific analytes, which contributes to selective detection even in the presence of interferents. Indeed, a MIP-integrated polymer transistor has shown favorable sensor responses to salivary cortisol from the perspective of sensitivity, selectivity, and applicability to real-sample analysis. The demonstration revealed the potential of polymer materials as crucial components of chemical sensor devices. Keywords: Chemical Sensor / Polymer Transistor / Molecular Recognition / Real-Sample Analysis / Cortisol / Molecularly Imprinted Polymer |
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| グローイングポリマー Polymer Science and I: A Personal Account |
| 化学で社会に貢献する Contribution to Society with Chemistry |
徐 于懿 Yu-I HSU |
| ＜要旨＞ In this article, I describe why I chose chemistry, and the research what I did and what I am doing. Recently, I have been developing “salt-responsive” polymeric materials that are stable in freshwater but destabilize and degrade in seawater. These materials are expected to be next-generation marine biodegradable plastics. |
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| 高分子科学最近の進歩 Front-Line Polymer Science |
| 電子線による高分子結晶の構造解析 Structural Analysis of Polymer Crystals by Electron Microscopy |
狩野見 秀輔・陣内 浩司 Shusuke KANOMI, Hiroshi JINNAI |
| ＜要旨＞ The typical morphology of polymer crystals is plate-like crystals (lamellar crystals) with a thickness of about 10 nm. However, their original structure and structure formation mechanism still need to be fully understood. Since Keller revealed the structure of polyethylene single crystals, it was suggested that the folding polymer chains tilt with respect to the normal of the lamellar crystal surface （chain tilt）. The chain tilt inside the lamellar crystals has remained ambiguous due to the lack of proper analytical techniques. Nanodiffraction imaging （NDI）, a state-of-the-art electron microscopy technique, makes it possible to image the polymer chains tilting inside the lamellae. Such knowledge advances a deeper understanding of the thermodynamics of polymer chains in lamellar crystals. Keywords: Semicrystalline Polymer / Lamellar Crystal / Crystal Structure / Transmission Electron Microscopy / Electron Diffraction / Nanodiffraction Imaging |
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