Energy-Level Alignment and Orbital-Selective Femtosecond Charge Transfer Dynamics of Redox-Active Molecules on Au, Ag, and Pt Metal Surfaces

doi:10.1021/acs.jpcc.1c04655

HFCAS OpenIR

	Energy-Level Alignment and Orbital-Selective Femtosecond Charge Transfer Dynamics of Redox-Active Molecules on Au, Ag, and Pt Metal Surfaces
	Zhang, Ziyu 1; Cao, Liang 2; Chen, Xue 2; Thompson, Damien 3; Qi, Dongchen 4; 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	被引频次：2[WOS] [WOS记录] [WOS相关记录]
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).