Ag(111)表面Ag配位结构的分等级组装

1. 1 北京大学电子学系, 纳米器件物理与化学教育部重点实验室, 碳基电子学中心, 北京 100871
2 天津第五中心医院, 天津市早产儿器官发育表观遗传学重点实验室中心实验室, 天津 300450
3 北京大学(天津滨海)新一代信息技术研究院, 天津 300450
4 法国国家科学研究中心, 材料与结构研究所, 表界面纳米研究组, 图卢兹 31055, 法国
5 北京量子信息科学研究院, 北京 100193
• 收稿日期:2020-11-23 录用日期:2020-12-01 发布日期:2020-12-14
• 通讯作者: 侯士敏,王永锋 E-mail:smhou@pku.edu.cn;yongfengwang@pku.edu.cn
• 基金资助:
中国科学技术部(2018YFA0306003);中国科学技术部(2017YFA0205003);国家自然科学基金(21972002);国家自然科学基金(21902003);国家自然科学基金(22002109)

Hierarchical Self-Assembly of Ag-Coordinated Motifs on Ag(111)

Ruoning Li1, Xue Zhang1, Na Xue2, Jie Li3, Tianhao Wu1, Zhen Xu1, Yifan Wang1, Na Li1, Hao Tang4, Shimin Hou1,3,*(), Yongfeng Wang1,5,*()

1. 1 Key laboratory for the Physics and Chemistry of Nanodevices and Center for Carbon-based Electronics, Department of Electronics, Peking University, Beijing 100871, China
2 Central Laboratory, Tianjin Key Laboratory of Epigenetics for Organ Development in Preterm Infants, the Fifth Central Hospital of Tianjin, Tianjin 300450, China
3 Peking University Information Technology Institute (Tianjin Binhai), Tianjin 300450, China
4 SINANO Group, CEMES/CNRS, Toulouse 31055, France
5 Beijing Academy of Quantum Information Sciences, Beijing 100193, China
• Received:2020-11-23 Accepted:2020-12-01 Published:2020-12-14
• Contact: Shimin Hou,Yongfeng Wang E-mail:smhou@pku.edu.cn;yongfengwang@pku.edu.cn
• About author:Email: yongfengwang@pku.edu.cn. Tel.: +86-10-62762722 (Y.W.)
Email: smhou@pku.edu.cn (S.H.)
• Supported by:
the Ministry of Science and Technology of China(2018YFA0306003);the Ministry of Science and Technology of China(2017YFA0205003);the National Natural Science Foundation of China(21972002);the National Natural Science Foundation of China(21902003);the National Natural Science Foundation of China(22002109)

Abstract:

Metal-organic nanostructures on surfaces have attracted considerable attention owing to their structural stability and potential applications. In metal-organic nanostructures, metal atoms are derived from the externally deposited metals or native surface atoms. Externally deposited metals are of rich diversity and depend on the targeted nanostructures. However, native surface atoms are restricted to single-crystalline metal surfaces of gold, silver, and copper, which are usually used in surface science. Metal-organic nanostructures mostly consist of Au- or Cu-coordinated motifs, while only a few consist of surface Ag atoms. Further investigation into the molecule-metal interactions is beneficial for the accurately controlled fabrication of the desired nanostructure. As for the building blocks, organic molecules coordinate with native surface atoms by M―C, M―N, and M―O bonds. The reactions of terminal alkynes or Ullmann couplings could realize the formation of C―M―C linkages. Cu and Au atoms could coordinate with molecules with terminal cyano or pyridyl groups to form N―M―N bonds. In addition, surface Ag adatoms could coordinate with phthalocyanine through Ag―N bonds. However, a comprehensive study of M―O coordination bonds is still lacking. Thus, we used hydroxyl-terminated molecules to coordinate with Ag adatoms to form metal-organic coordination nanostructures and study the O―Ag linkages. In this case, we successfully built and investigated a series of ordered structures by depositing 4, 4'-dihydroxy-1, 1': 3', 1''-terphenyl (H3PH) molecules on the Ag(111) surface by scanning tunneling microscopy. At room temperature, a close-packed ordered structure was formed by H3PH molecules through cyclic hydrogen bonds, and the repeat unit of such nanostructures contained eight H3PH molecules. Upon increasing the annealing temperature, the formation of O―Ag bond led to a change in the self-assembly pattern. When the annealing temperature was increased to 330 K, a new ordered nanostructure occurred due to the combination of O―Ag coordination and hydrogen bonds. Upon further increasing the annealing temperature to 420 K, a honeycomb structure and coexisting two-fold coordination chains appeared, which only consisted of O―Ag―O linkages. Density functional theory calculations were carried out to analyze the metal-molecule reaction pathways and energy barriers of the O―Ag―O bonds. The energy barrier of the O―Ag bond is 1.41 eV, which is less than that of the O―Ag―O linkage calculated to be 1.85 eV. The low energy barrier of the O―Ag bond and large coordination energy of the O―Ag―O linkage can be attributed to the formation of the hierarchical metal-organic nanostructure. The results obtained herein provide an effective approach for designing and building two-dimensional hierarchical structures with organic small molecules and metal adatoms on single-crystalline metal surfaces.

MSC2000:

• O649