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Energy-Level Alignment and Orbital-Selective Femtosecond Charge Transfer Dynamics of Redox-Active Molecules on Au, Ag, and Pt Metal Surfaces | |
Zhang, Ziyu1; Cao, Liang2; Chen, Xue2; Thompson, Damien3; Qi, Dongchen4; Nijhuis, Christian A.1,5,6,7 | |
2021-08-26 | |
发表期刊 | JOURNAL OF PHYSICAL CHEMISTRY C |
ISSN | 1932-7447 |
通讯作者 | Thompson, Damien(Damien.Thompson@ui.ie) ; Qi, Dongchen(dongchen.qi@qut.edu.au) ; Nijhuis, Christian A.(c.a.nijhuis@utwente.nl) |
摘要 | Charge transfer (CT) dynamics across metal-molecule interfaces has important implications for performance and function of molecular electronic devices. CT times, on the order of femtoseconds, can be precisely measured using synchrotron-based core-hole clock (CHC) spectroscopy, but little is known about the impact on CT times of the metal work function and the bond dipole created by metals and the anchoring group. To address this, here we measure CT dynamics across self-assembled monolayers bound by thiolate anchoring groups to Ag, Au, and Pt. The molecules have a terminal ferrocene (Fc) group connected by varying numbers of methylene units to a diphenylacetylene (DPA) wire. CT times measured using CHC with resonant photoemission spectroscopy (RPES) show that conjugated DPA wires conduct electricity faster than aliphatic carbon wires of a similar length. Shorter methylene connectors exhibit increased conjugation between Fc and DPA, facilitating CT by providing greater orbital mixing. We find nearly 10-fold increase in the CT time on Pt compared to Ag due to a larger bond dipole generated by partial electron transfer from the metal-sulfur bond to the carbon-sulfur bond, which creates an electrostatic field that impedes CT from the molecules. By fitting the RPES signal, we distinguish electrons coming from the Fe center and from cyclopentadienyl (Cp) rings. The latter shows faster CT rates because of the delocalized Cp orbitals. Our study demonstrates the fine tuning of CT rates across junctions by careful engineering of several parts of the molecule and the molecule-metal interface. |
DOI | 10.1021/acs.jpcc.1c04655 |
关键词[WOS] | SELF-ASSEMBLED MONOLAYERS ; GALLIUM-INDIUM EGAIN ; ELECTRONIC-STRUCTURE ; WORK FUNCTION ; LIQUID-METAL ; JUNCTIONS ; TRANSPORT ; ORGANIC/METAL ; CURRENTS |
收录类别 | SCI |
语种 | 英语 |
资助项目 | Ministry of Education[MOE2018-T2-1-088] ; Prime Minister's Office, Singapore under its Medium Sized Centre program ; Australian Research Council[FT160100207] ; Science Foundation Ireland (SFI)[15/CDA/3491] ; Science Foundation Ireland (SFI)[12/RC/2275_P2] ; National Natural Science Foundation of China[12074385] |
项目资助者 | Ministry of Education ; Prime Minister's Office, Singapore under its Medium Sized Centre program ; Australian Research Council ; Science Foundation Ireland (SFI) ; National Natural Science Foundation of China |
WOS研究方向 | Chemistry ; Science & Technology - Other Topics ; Materials Science |
WOS类目 | Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary |
WOS记录号 | WOS:000692021300042 |
出版者 | AMER CHEMICAL SOC |
引用统计 | |
文献类型 | 期刊论文 |
条目标识符 | http://ir.hfcas.ac.cn:8080/handle/334002/125260 |
专题 | 中国科学院合肥物质科学研究院 |
通讯作者 | Thompson, Damien; Qi, Dongchen; Nijhuis, Christian A. |
作者单位 | 1.Natl Univ Singapore, Dept Chem, Singapore 117543, Singapore 2.Chinese Acad Sci, Anhui Prov Key Lab Condensed Matter Phys Extreme, High Magnet Field Lab, Hefei 230031, Anhui, Peoples R China 3.Univ Limerick, Bernal Inst, Dept Phys, Limerick V94 T9PX, Ireland 4.Queensland Univ Technol, Ctr Mat Sci, Sch Chem & Phys, Brisbane, Qld 4001, Australia 5.Natl Univ Singapore, Ctr Adv 2D Mat, Singapore 117546, Singapore 6.Univ Twente, Fac Sci & Technol, Hybrid Mat Optoelect Grp, Dept Mol & Mat,MESA Inst Nanotechnol, NL-7500 AE Enschede, Netherlands 7.Univ Twente, Fac Sci & Technol, Ctr Brain Inspired Nano Syst, NL-7500 AE Enschede, Netherlands |
推荐引用方式 GB/T 7714 | Zhang, Ziyu,Cao, Liang,Chen, Xue,et al. Energy-Level Alignment and Orbital-Selective Femtosecond Charge Transfer Dynamics of Redox-Active Molecules on Au, Ag, and Pt Metal Surfaces[J]. JOURNAL OF PHYSICAL CHEMISTRY C,2021,125. |
APA | Zhang, Ziyu,Cao, Liang,Chen, Xue,Thompson, Damien,Qi, Dongchen,&Nijhuis, Christian A..(2021).Energy-Level Alignment and Orbital-Selective Femtosecond Charge Transfer Dynamics of Redox-Active Molecules on Au, Ag, and Pt Metal Surfaces.JOURNAL OF PHYSICAL CHEMISTRY C,125. |
MLA | Zhang, Ziyu,et al."Energy-Level Alignment and Orbital-Selective Femtosecond Charge Transfer Dynamics of Redox-Active Molecules on Au, Ag, and Pt Metal Surfaces".JOURNAL OF PHYSICAL CHEMISTRY C 125(2021). |
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