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二硫化钼场效应晶体管沟道上硝基螺吡喃和部花青分子的光异构化及热复位化学过程

Chemistry of the photoisomerization and thermal reset of nitro-spiropyran and merocyanine molecules on the channel of the MoS field effect transistor.

作者信息

Mamun Muhammad Shamim Al, Sainoo Yasuyuki, Takaoka Tsuyoshi, Waizumi Hiroki, Wang Zhipeng, Alam Md Iftekharul, Ando Atsushi, Arafune Ryuichi, Komeda Tadahiro

机构信息

Department of Chemistry, Graduate School of Science, Tohoku University, Aramaki-Aza-Aoba, Aoba-Ku, Sendai 9808578, Japan.

Institute of Multidisciplinary Research for Advanced Materials (IMRAM, Tagen), Tohoku University, 2-1-1, Katahira, Aoba-Ku, Sendai 9800877, Japan.

出版信息

Phys Chem Chem Phys. 2021 Dec 15;23(48):27273-27281. doi: 10.1039/d1cp04283a.

Abstract

We have explored the chemical reaction of the photoisomerization and thermal reaction of the photochromic spiropyran (SP) 1',3'-Dihydro-1',3',3' trimethyl-6-nitrospiro[2H-1 benzopyran-2,2'-(2H)-indole] molecule deposited on the atomic thin channel of a MoS field-effect transistor (FET) through the analysis of the FET property. With four monolayers of SP molecules on the channel, we observed a clear shift of the threshold voltage in the drain-current vs gate-voltage plot with UV-light injection on the molecule, which was due to the change of the SP molecule to merocyanine (MC). A complete reset from MC to SP molecule was achieved by thermal annealing, while the injection of green light could revert the FET property to the original condition. In the process of change from MC to SP, two types of decay rates were confirmed. The quick- and slow-decay components corresponded to the molecules attached directly to the substrate and those in the upper layer, respectively. The activation energies for the conversion of MC to SP molecules were estimated as 71 kJ/mol and 90 kJ/mol for the former and latter, respectively. Combined with DFT calculations, we concluded that the - shift with photoisomerization from SP to MC is due to the upper layer molecules and the dipole moment in the surface normal direction. Based on the estimated activation energy of 90 kJ/mol for the reset process, we calculated the conversion rate in a controllable temperature range. From these values, we consider that the chemical state of MC can be maintained and switched in a designated time period, which demonstrates the possibility of this system in logical operation applications.

摘要

我们通过对场效应晶体管(FET)特性的分析,研究了沉积在二硫化钼(MoS)场效应晶体管原子级薄沟道上的光致变色螺吡喃(SP)1',3'-二氢-1',3',3'-三甲基-6-硝基螺[2H-1-苯并吡喃-2,2'-(2H)-吲哚]分子的光异构化化学反应和热反应。在沟道上有四层SP分子时,我们观察到在对分子注入紫外光后,漏极电流与栅极电压关系图中的阈值电压出现明显偏移,这是由于SP分子转变为部花青(MC)所致。通过热退火实现了从MC到SP分子的完全复位,而注入绿光可使FET特性恢复到原始状态。在从MC转变为SP的过程中,确认了两种衰减速率。快速衰减和缓慢衰减成分分别对应直接附着在衬底上的分子和上层的分子。前者和后者从MC转变为SP分子的活化能估计分别为71 kJ/mol和90 kJ/mol。结合密度泛函理论(DFT)计算,我们得出结论,从SP到MC的光异构化引起的 - 偏移是由于上层分子和表面法线方向的偶极矩。基于复位过程估计的90 kJ/mol活化能,我们计算了可控温度范围内的转化率。从这些值来看,我们认为MC的化学状态可以在指定时间段内保持和切换,这证明了该系统在逻辑运算应用中的可能性。

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