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Above-room-temperature ferroelectricity in a single-component molecular crystal

机译：单组分分子晶体中高于室温的铁电

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摘要

铁电性化合物在实践应用中有一系列有用的特rn性，包括在电场中的极性反转、温度敏感性及将rn机械应力转换成电力的能力。人们一般假设，rn铁电现象是罕见的。在有机化合物中最差。但rnHoriuchi等人现在却报告了高于室温的铁电现rn象的发现，在有机晶体巴豆酸(黑色染料的一rn个成分)中有相对较高的极化。这些特性在这rn一简单分子的晶体形式中并不是一下子就能显rn现出来，但它们在施加一个较小的电场后便会rn出现，该电场能诱导一种分子一拓扑酮一烯醇rn转化。这一发现提出一个可能性：有机铁电体rn也许要比人们以前所想的丰富得多。%Ferroelectrics are electro-active materials that can store and switch their polarity (ferroelectricity), sense temperature changes (pyro-electricity), interchange electric and mechanical functions (piezoelectricity), and manipulate light (through optical nonlinearities and the electro-optic effect): all of these functions have practical applications. Topological switching of π-conjugation in organic molecules, such as the keto-enol transformation, has long been anticipated as a means of realizing these phenomena in molecular assemblies and crystals. Croconic acid, an ingredient of black dyes, was recently found to have a hydrogen-bonded polar structure in a crystalline state. Here we demonstrate that application of an electric field can coherently align the molecular polarities in crystalline croconic acid, as indicated by an increase of optical second harmonic generation, and produce a well-defined polarization hysteresis at room temperature. To make this simple pentagonal molecule ferroelectric, we switched the π-bond topology using synchronized proton transfer instead of rigid-body rotation. Of the organic ferroelectrics, this molecular crystal exhibits the highest spontaneous polarization (～20 μC cm~(-2)) in spite of its small molecular size, which is in accord with first-principles electronic-structure calculations. Such high polarization, which persists up to 400 K, may find application in active capacitor and nonlinear optics elements in future organic electronics.
机译：铁电性化合物在实践应用中有一系列有用的特rn性，包括在电场中的极性反转、温度敏感性及将rn机械应力转换成电力的能力。人们一般假设，rn铁电现象是罕见的。在有机化合物中最差。但rnHoriuchi等人现在却报告了高于室温的铁电现rn象的发现，在有机晶体巴豆酸(黑色染料的一rn个成分)中有相对较高的极化。这些特性在这rn一简单分子的晶体形式中并不是一下子就能显rn现出来，但它们在施加一个较小的电场后便会rn出现，该电场能诱导一种分子一拓扑酮一烯醇rn转化。这一发现提出一个可能性：有机铁电体rn也许要比人们以前所想的丰富得多。%Ferroelectrics are electro-active materials that can store and switch their polarity (ferroelectricity), sense temperature changes (pyro-electricity), interchange electric and mechanical functions (piezoelectricity), and manipulate light (through optical nonlinearities and the electro-optic effect): all of these functions have practical applications. Topological switching of π-conjugation in organic molecules, such as the keto-enol transformation, has long been anticipated as a means of realizing these phenomena in molecular assemblies and crystals. Croconic acid, an ingredient of black dyes, was recently found to have a hydrogen-bonded polar structure in a crystalline state. Here we demonstrate that application of an electric field can coherently align the molecular polarities in crystalline croconic acid, as indicated by an increase of optical second harmonic generation, and produce a well-defined polarization hysteresis at room temperature. To make this simple pentagonal molecule ferroelectric, we switched the π-bond topology using synchronized proton transfer instead of rigid-body rotation. Of the organic ferroelectrics, this molecular crystal exhibits the highest spontaneous polarization (～20 μC cm~(-2)) in spite of its small molecular size, which is in accord with first-principles electronic-structure calculations. Such high polarization, which persists up to 400 K, may find application in active capacitor and nonlinear optics elements in future organic electronics.

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  • 来源
    《Nature》 |2010年第7282期|789-792iii|共5页
  • 作者

    Sachio Horiuchi; Yusuke Tokunaga; Gianluca Giovannetti; Silvia Picozzi; Hirotake Itoh; Ryo Shimano; Reiji Kumai; Yoshinori Tokura;

  • 作者单位

    National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba 305-8562, Japan;

    Multiferroics Project, ERATO, Japan Science and Technology Agency (JST), Wako, Saitama 351-0198, Japan;

    Consiglio Nazionale delle Ricerche-1st. Naz. Fisica Materia (CNR-INFM), CASTI Regional Laboratory, 67100 L'Aquila, Italy lnstitut Lorenz for Theoretical Physics, Leiden University, The Netherlands;

    Consiglio Nazionale delle Ricerche-1st. Naz. Fisica Materia (CNR-INFM), CASTI Regional Laboratory, 67100 L'Aquila, Italy;

    Multiferroics Project, ERATO, Japan Science and Technology Agency (JST), Wako, Saitama 351-0198, Japan;

    Multiferroics Project, ERATO, Japan Science and Technology Agency (JST), Wako, Saitama 351-0198, Japan Department of Physics, The University of Tokyo, Tokyo 113-8656, Japan;

    National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba 305-8562, Japan;

    National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba 305-8562, Japan Multiferroics Project, ERATO, Japan Science and Technology Agency (JST), Wako, Saitama 351-0198, Japan Department of Applied Physics, The University of Tokyo, Tokyo 113-8656, Japan;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
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