Formation and Structure of Highly Ordered Self-Assembled Monolayers by Adsorption of Acetyl-Protected Conjugated Thiols on Au(111) in Tetrabutylammonium Cyanide Solution
Formation and Structure of Highly Ordered Self-Assembled Monolayers by Adsorption of Acetyl-Protected Conjugated Thiols on Au(111) in Tetrabutylammonium Cyanide Solution
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四丁基氰化铵溶液中乙酰基保护的共轭硫醇吸附在 Au(111) 上形成高度有序自组装单分子层并形成结构
DOI：
10.1021/acs.jpcc.9b00521
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Jaegeun
中科院分区：
文献类型：
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作者：
Park;Taesung Kang;Hungu Seong;Sicheon Han;Seulki Son;Young Ji Ito;Eisuke Hayashi;Tomohiro Hara;Masahiko Noh;Jaegeun
用扫描隧道显微镜（STM）和X射线光电子能谱（XPS）研究了以1-乙酰硫基-4-[（苯基）乙炔基]苯（OPE 2-SAc）为模板的Au（111）表面自组装单分子膜（SAMs）的表面结构和结合状态。扫描隧道显微镜（STM）观察表明，室温下OPE 2-SAc在1 mM甲醇溶液中直接吸附24 h后，在Au（111）表面形成的OPE 2-S自组装膜由短程有序相和无序相组成。相反，OPE 2-SAc自组装膜在Au（111）上在50 °C的较高溶液温度下吸附24 h导致形成完全有序的相，其畴尺寸略有增加。当使用TBACN时，在Au（111）上的OPE 2-S自组装膜的结构质量显著提高。室温下，OPE 2-S自组装膜具有良好的（103 × 107）R30°结构，畴尺寸大于80 nm。在50 °C下沉积的自组装膜包含非常均匀和高度有序的畴，其尺寸超过100 nm，可以归属于（2 × 3 π 3）矩形结构。XPS测量表明，OPE 2-S自组装膜主要是通过硫与Au（111）表面之间的化学相互作用形成的，与使用TBACN脱保护剂无关。在这项研究中，我们报告了第一个分子尺度上的特征的OPE 2-S自组装膜的Au（111）与高度有序的结构域衍生自OPE 2-SAc，并清楚地表明，TBACN可以作为一种有效的脱保护剂，用于形成均匀和良好有序的OPE 2-S自组装膜的长程结构域衍生自硫代乙酰基保护的OPE 2-S分子的Au（111）。
The surface structure and binding conditions of self-assembled monolayers (SAMs) on Au(111) derived from 1-acetylthio-4-[(phenyl)ethynyl]benzene (OPE2-SAc) without and with tetrabutylammonium cyanide (TBACN) as a deprotection reagent were examined using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). STM observation revealed that OPE2-S SAMs on Au(111) formed from direct adsorption of OPE2-SAc in 1 mM methanol solution at room temperature (RT) for 24 h were composed of short-range, ordered phase separated by a disordered phase. In contrast, adsorption of OPE2-SAc SAMs on Au(111) at a higher solution temperature of 50 °C for 24 h led to formation of a fully ordered phase with slightly increased domain size. The structural quality of OPE2-S SAMs on Au(111) was remarkably enhanced when TBACN was used. OPE2-S SAMs at RT had a well-ordered (√3 × √7)R30° structure with a domain size larger than 80 nm. The SAMs deposited at 50 °C contained very uniform and highly ordered domains with a size exceeding 100 nm, which can be assigned to a (2 × 3√3)rect structure. XPS measurements showed that OPE2-S SAMs were mainly formed via chemical interactions between sulfur and the Au(111) surface regardless of the use of a TBACN deprotection reagent. In this study, we reported the first molecular-scale features of OPE2-S SAMs on Au(111) with highly ordered domains derived from OPE2-SAc and clearly demonstrated that TBACN can be used as an effective deprotection reagent for formation of uniform and well-ordered OPE2-S SAMs with long-range domains derived from thioacetyl-protected OPE2-S molecules on Au(111).