Tuning Rectification Properties of Molecular Electronic Devices by Mixed Monolayer

doi:10.6023/A19050192

Acta Chimica Sinica ›› 2019, Vol. 77 ›› Issue (10): 1031-1035.DOI: 10.6023/A19050192 Previous Articles Next Articles

Article

基于混合自组装单分子层的可控分子整流

王紫嫣^a, Khalid,Hira^a, 李柏力^a, 李瑶^b, 于曦^a^*(), 胡文平^a

^a 天津大学理学院天津市分子光电科学重点实验室天津 300072
^b 天津大学分子+研究院天津 300072

投稿日期:2019-05-24 发布日期:2019-08-13
通讯作者: 于曦 E-mail:xi.yu@tju.edu.cn
基金资助:
项目受国家自然科学基金(21773169);项目受国家自然科学基金(51633006);项目受国家自然科学基金(51733004)

Tuning Rectification Properties of Molecular Electronic Devices by Mixed Monolayer

Wang, Ziyan^a, Khalid, Hira^a, Li, Baili^a, Li, Yao^b, Yu, Xi^a^*(), Hu, Wenping^a

^a Tianjin Key Laboratory of Molecular Optoelectronic Sciences, School of Science, Tianjin University, Tianjin 300072, China
^b Institute of Molecular Plus, Tianjin University, Tianjin 300072, China

Received:2019-05-24 Published:2019-08-13
Contact: Yu, Xi E-mail:xi.yu@tju.edu.cn
Supported by:
Project supported by the National Natural Science Foundation of China(21773169);Project supported by the National Natural Science Foundation of China(51633006);Project supported by the National Natural Science Foundation of China(51733004)

1. Tuning Rectification Properties of Molecular Electronic Devices by Mixed Monolayer.PDF(1392KB)

Abstract

We demonstrate in this work that the performance of self-assembled monolayer (SAM) molecular devices can be modulated by the composition and supramolecular structure of the molecular layer using mixed self-assembled monolayer strategy. We prepared the mixed monolayer on gold surface (with ca. 1 nm roughness) by co-adsorption of 11-(ferrocenyl)- undecanethiol (FUT, rectifier) and 1-undecanethiol (C11-SH, diluent). Micrometer scale molecular junctions were formed by using indium gallium eutectic alloy (EGaIn) as the top electrode. Electrical characterization of the junction found that the ratio of FUT and C11-SH molecules can tune the rectifying performance of the monolayer device: the higher the proportion of ferrocene is, the better the rectifying performance is. To our surprise, mixed monolayer prepared by 20% C11-SH and 80% FUT mixed solution exhibited higher rectification ratio than pure FUT monolayer, due to reduced leaking current. Surface reflective IR spectroscopy and the monolayer thickness characterization by the ellipsometer revealed loosely packed molecules on the surface in the pure FUT monolayer due to the bulky head group of the FUT and the rough gold substrate. FUT that partially lied down on the surface, or buried in the layer therefore created defects, which in turn become the origin of the leakage current. Upon insertion of C11-SH molecules in between the ferrocene molecules, the molecules in the monolayer become more ordered with the support of the C11-SH, as evidenced by decreased wave number of the C—H stretching mode of methylene group by reflective IR spectroscopy. Meanwhile, an increase in thickness for 80% FUT monolayer relative to pure FUT monolayer implied a better orientation of the FUT molecule in mixed monolayer. The ordered structure and better orientation largely improved the stability and reproducibility of the molecular device, reduced the leaking current and afforded higher rectification ratio. Our approach therefore provides a facile and effective strategy for regulating the performance of monolayer devices by molecule aggregation state.

Key words: molecular electronics, self-assembled monolayer, dilution effect, rectification property, mixed monolayer

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Wang, Ziyan, Khalid, Hira, Li, Baili, Li, Yao, Yu, Xi, Hu, Wenping. Tuning Rectification Properties of Molecular Electronic Devices by Mixed Monolayer[J]. Acta Chimica Sinica, 2019, 77(10): 1031-1035.

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Fig. & Tab. 6

Figure 1. The surface of evaporated gold electrode by atomic force microscope. (a) cross section image, (b) 2D image

Figure 2. (a) The molecules that form SAMs. FUT is the organic rectifier. C11-HS is the diluent with no rectifier performance. (b) The thickness of mixed SAM

Figure 3. Infrared spectra of mixed SAMs (100% FUT, 80% FUT, 60% FUT, 40% FUT and 20% FUT)

Figure 4. (a) Cyclic voltammograms of mixed SAMs. The scan rate is 50 mV/s. As the curve goes from top to bottom, the ratios of FUT is 100%, 80%, 60%, 40% and 20% respectively. (b) Surface concentration of FUT in mixed SAMs

Figure 5. (a), (b), (c), (d), (e) is heat maps of semi-log10|I|-V curves of EGaIn/Ga2O3//SAM//Au molecular junctions. From (a) to (e) the ratios of FUT in solution is 100%, 80%, 60%, 40%, 20%. (f) The averaged I-V curves of all the molecular junctions

Figure 6. Schematic diagram of the structure of single-component FUT SAM (a) and mixed SAM (b)

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基于混合自组装单分子层的可控分子整流

Tuning Rectification Properties of Molecular Electronic Devices by Mixed Monolayer

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