可蒸镀自旋交叉配合物的薄膜与器件

doi:10.6023/A22050212

化学学报 ›› 2022, Vol. 80 ›› Issue (9): 1351-1363.DOI: 10.6023/A22050212 上一篇下一篇

综述

可蒸镀自旋交叉配合物的薄膜与器件

张琪^a, 江梦云^a, 刘天一^a, 曾意迅^a, 石胜伟^a^,^b^,^*()

a 武汉工程大学材料科学与工程学院武汉 430205
b 中国科学院长春应用化学研究所高分子物理与化学国家重点实验室长春 130022

投稿日期:2022-05-06 发布日期:2022-07-01
通讯作者: 石胜伟

作者简介:

张琪, 男, 武汉工程大学材料学院在读硕士研究生, 主要研究方向为基于自旋交叉配合物的开关存储器件.

江梦云, 女, 武汉工程大学材料学院在读硕士研究生, 主要研究方向为室温以上自旋交叉配合物的分子设计与制备.

石胜伟, 男, 博士毕业于中国科学院长春应用化学研究所, 现为武汉工程大学特聘教授, 主要研究方向为有机半导体材料与器件、柔性电子、自旋交叉现象及其器件应用等.

基金资助:
国家自然科学基金(52173183); 湖北省自然科学基金(2021CFB598); 中国科学院高分子物理与化学国家重点实验室开放课题(2020-13)

Thin Films and Devices of Evaporable Spin Crossover Complexes

Qi Zhang^a, Mengyun Jiang^a, Tianyi Liu^a, Yixun Zeng^a, Shengwei Shi^a^,^b()

a School of Materials Science and Engineering, Wuhan Institute of Technology, Wuhan 430205
b State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022

Received:2022-05-06 Published:2022-07-01
Contact: Shengwei Shi
Supported by:
National Natural Science Foundation of China(52173183); Natural Science Foundation of Hubei Province(2021CFB598); Open Research Fund of State Key Laboratory of Polymer Physics and Chemistry, Chinese Academy of Sciences(2020-13)

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摘要/Abstract

自旋交叉配合物在温度、压力、光照和磁场等刺激下可以发生高低自旋态之间的可逆转变, 通常还伴随着颜色、体积和电导率变化以及热滞等效应, 因此这类材料在光热开关、传感器、显示和存储等领域具有潜在的应用. 由于可以获得高质量的超洁净薄膜, 高真空蒸镀工艺常用于分子电子学与分子磁学等的器件制备, 目前报道的可蒸镀自旋交叉配合物种类较少, 大大限制了自旋交叉配合物的器件应用. 针对可蒸镀自旋交叉配合物的薄膜与器件进行了系统的综述, 介绍了几种主要的适于高真空蒸镀的自旋交叉配合物, 结合不同的表征手段分析了衬底对分子薄膜自旋转变特性的影响, 并针对相关的概念性器件进行了讨论, 最后对自旋交叉配合物在器件应用中存在的难点和未来的发展趋势进行了展望和评述, 希望能够为自旋交叉领域的器件应用提供一些借鉴.

关键词: 自旋交叉配合物, 自旋转变, 蒸镀, 薄膜, 器件应用

Spin states of the spin crossover complexes can be switched reversibly between high spin and low spin under different stimulations such as temperature, pressure, irradiation and magnetic field. Generally, it is also accompanied by the change of color, volume and conductivity, and the thermo-induced magnetic hysteresis. Therefore, they show potential applications in optical/thermal switches, sensors, display, and memory devices. Additionally, high-vacuum evaporation is generally applied to fabricate devices in molecular electronics/spintronics with high-quality and ultra-clean films. However, there are very few evaporable spin crossover complexes which greatly limit their applications. In this paper, we systematically summarize the recent progress of evaporable spin crossover complexes in films and devices. Several reported evaporable spin crossover complexes are discussed, and the effect of the substrate on spin transition has been investigated with different techniques, furthermore, the related conceptual devices are discussed. At the end, the existed difficulties and future trends of spin crossover complexes in device applications are prospected and reviewed to provide useful guidance for the future device developments.

Key words: spin crossover complexes, spin transition, evaporation, thin film, device applications

引用此文

张琪, 江梦云, 刘天一, 曾意迅, 石胜伟. 可蒸镀自旋交叉配合物的薄膜与器件[J]. 化学学报, 2022, 80(9): 1351-1363.

Qi Zhang, Mengyun Jiang, Tianyi Liu, Yixun Zeng, Shengwei Shi. Thin Films and Devices of Evaporable Spin Crossover Complexes[J]. Acta Chimica Sinica, 2022, 80(9): 1351-1363.

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图/表 10

图1. Fe(II)自旋交叉配合物的自旋转变示意图

Figure 1. Schematic diagram of spin transition in Fe(II) complexes

图2. 可蒸镀的自旋交叉配合物分子结构

Figure 2. Structures of evaporable spin crossover complexes

图3. [FeII(phen)2(NCS)2]薄膜. (a) N 1s XPS光谱; (b) Fe 2p XPS光谱; (c) SQUID; (d) 室温下异质结的电流-电压特性[34]

Figure 3. XPS of [FeII(phen)2(NCS)2] films at (a) N 1s and (b) Fe 2p, (c) SQUID and (d) current-voltage characteristics for heterojunction device at room temperature[34]

图4. [FeII(phen)2(NCS)2]的Fe L2,3 XAS光谱. (a)粉末; (b) Cu(100)表面生长的超薄膜(200 K)[62]

Figure 4. XAS spectra of Fe L2,3 edges in [FeII(phen)2(NCS)2] for (a) powder, and (b) ultra-thin film on Cu(100) at 200 K[62]

图5. (a) [FeII(phen)2(NCS)2]/CuN/Cu(100)单分子器件的电流电压特性曲线. (b)不同极性电压脉冲诱导下的HS和LS之间的可逆开关效应. (c)两个连续相同极性电压脉冲对HS到LS的自旋转变的影响[63]

Figure 5. (a) I-V curves of [FeII(phen)2(NCS)2]/CuN/Cu(100). (b) The reversible switching between HS and LS induced by voltage pulses with different polarity. (c) The effect of two consecutive voltage pulses with the same polarity on spin transition from HS to LS[63]

图6. (a) 0.4个单分子层的[FeII(H2B(pz)2)2phen]在HOPG衬底的Fe L2,3 XAS的温度依赖关系, 在T=6 K绿光照射前后的光谱分别以蓝和绿色表示. (b)在6 K时, HS的分数与绿光照射量的关系[68]

Figure 6. (a) Temperature-dependent Fe L2,3 XAS of 0.4 ML [FeII(H2B- (pz)2)2phen] on HOPG. Spectra before and after illuminating with green light at T=6 K are shown in blue and green, respectively. (b) Fraction of HS molecules as a function of exposure time to green light at T=6 K[68]

图7. 微机电器件及相关磁驱动-压阻探测方法的示意图[70]

Figure 7. Scheme of the MEMS device and the associated magnetic actuation-piezoresistive detection method[70]

图8. (a) FeII[HB(3,5-(Me)2pz)3]2薄膜热处理前后高自旋态含量与温度的依赖性. (b) 130 nm薄膜在降温过程中的吸收光谱, 插图为热处理前后的吸收光谱比较[75]

Figure 8. (a) The dependence of HS fraction on temperature for FeII[HB(3,5-(Me)2pz)3]2 films before and after annealing. (b) Absorption spectra for 130-nm film, inserted is the comparison of spectra before and after annealing[75]

图9. (a)交叉结器件结构示意图; (b)温度依赖的紫外吸收光谱(317 nm); (c)不同温度下100 nm厚度交叉结的电流电压特性(电压扫描速率: 100 mV/s); (d) 12 V偏压下100 nm厚度交叉结的电流-温度关系曲线(温度变化速率: 5 K/min), 虚线给出了自旋转变温度(TSCO)[79]

Figure 9. (a) Scheme of the crossbar junctions; (b) temperature dependence of the UV absorbance of the films at 317 nm; (c) I-V curves of 100 nm thick junctions at different temperatures with a scan rate of 100 mV/s; (d) logI vs. 1/T curves of 100 nm thick junctions recorded with an applied bias of 12 V at a scan rate of 5 K/min. The dashed line shows the spin transition temperature (TSCO)[79]

图10. (a) [Fe(HB(tz)3)2]蒸镀薄膜表面的AFM形貌; (b) ITO/[Fe(HB(tz)3)2]的横截面AFM形貌; (c)带有封装的器件结构; (d) ITO/[Fe(HB(tz)3)2] (100 nm)/Al器件在不同温度下的电流电压曲线, 其中启动电压(Von)在低自旋态(20 ℃)和高自旋态(100 ℃)之间有明显的偏移[80]

Figure 10. AFM topography image of [Fe(HB(tz)3)2] thin film (a) and the cross-section of ITO/[Fe(HB(tz)3)2] (b), device structure with the encapsulation (c), and logI-V curves of ITO/[Fe(HB(tz)3)2] (100 nm)/Al at different temperatures evidencing a shift of the turn-on voltage (Von) between the LS (20 ℃) and HS (100 ℃) (d)[80]

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可蒸镀自旋交叉配合物的薄膜与器件

Thin Films and Devices of Evaporable Spin Crossover Complexes

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