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基于自组装单分子层的金属-绝缘体-金属结中的分子整流

Molecular rectification in a metal-insulator-metal junction based on self-assembled monolayers.

作者信息

Chabinyc Michael L, Chen Xiaoxi, Holmlin R Erik, Jacobs Heiko, Skulason Hjalti, Frisbie C Daniel, Mujica Vladimiro, Ratner Mark A, Rampi Maria Anita, Whitesides George M

机构信息

Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, MA 02138, USA.

出版信息

J Am Chem Soc. 2002 Oct 2;124(39):11730-6. doi: 10.1021/ja020506c.

Abstract

An electrical junction formed by mechanical contact between two self-assembled monolayers (SAMs)--a SAM formed from an dialkyl disulfide with a covalently linked tetracyanoquinodimethane group that is supported by silver (or gold) and a SAM formed from an alkanethiolate SAM that is supported by mercury-rectifies current. The precursor to the SAM on silver (or gold) was bis(20-(2-((2,5-cyclohexadiene-1,4-diylidene)dimalonitrile))decyl)) disulfide and that for the SAM on mercury was HS(CH(2))(n-1)CH(3) (n = 14, 16, 18). The electrical properties of the junctions were characterized by current-voltage measurements. The ratio of the conductivity of the junction in the forward bias (Hg cathodic) to that in the reverse bias (Hg anodic), at a potential of 1 V, was 9 +/- 2 when the SAM on mercury was derived from HS(CH(2))(15)CH(3). The ratio of the conductivity in the forward bias to that in the reverse bias increased with decreasing chain length of the alkanethiol used to form the SAM on mercury. These results demonstrate that a single redox center asymmetrically placed in a metal-insulator-metal junction can cause the rectification of current and indicate that a fixed dipole in the insulating region of a metal-insulator-metal junction is not required for rectification.

摘要

由两个自组装单分子层(SAMs)之间的机械接触形成的电结——一个由带有共价连接的四氰基对苯二醌二甲烷基团的二烷基二硫化物形成且由银(或金)支撑的SAM,以及一个由烷硫醇盐SAM形成且由汞支撑的SAM——能使电流整流。银(或金)上SAM的前体是双(20 -(2 -((2,5 - 环己二烯 - 1,4 - 二亚基)二丙二腈)癸基))二硫化物,汞上SAM的前体是HS(CH₂)(n - 1)CH₃(n = 14、16、18)。通过电流 - 电压测量对结的电学性质进行了表征。当汞上的SAM源自HS(CH₂)₁₅CH₃时,在1 V的电位下,正向偏置(汞阴极)时结的电导率与反向偏置(汞阳极)时结的电导率之比为9 ± 2。正向偏置时的电导率与反向偏置时的电导率之比随着用于在汞上形成SAM的烷硫醇链长的减小而增加。这些结果表明,不对称放置在金属 - 绝缘体 - 金属结中的单个氧化还原中心可导致电流整流,并表明金属 - 绝缘体 - 金属结的绝缘区域中不需要固定偶极来实现整流。

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