WO2024082366A1 - Hydrogen bond organic framework nanocomposite material, and preparation method therefor and use thereof - Google Patents

Hydrogen bond organic framework nanocomposite material, and preparation method therefor and use thereof Download PDF

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WO2024082366A1
WO2024082366A1 PCT/CN2022/132126 CN2022132126W WO2024082366A1 WO 2024082366 A1 WO2024082366 A1 WO 2024082366A1 CN 2022132126 W CN2022132126 W CN 2022132126W WO 2024082366 A1 WO2024082366 A1 WO 2024082366A1
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organic framework
preparation
hydrogen
nanocomposite material
bonded organic
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张程
李阳
马春兰
程新利
陈默涵
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苏州科技大学
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    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • G06N3/00—Computing arrangements based on biological models
    • G06N3/004—Artificial life, i.e. computing arrangements simulating life
    • G06N3/008—Artificial life, i.e. computing arrangements simulating life based on physical entities controlled by simulated intelligence so as to replicate intelligent life forms, e.g. based on robots replicating pets or humans in their appearance or behaviour
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    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/20—Multistable switching devices, e.g. memristors

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  • the invention belongs to the field of bionic artificial synaptic devices, and specifically relates to a hydrogen-bond organic framework nanocomposite material and a preparation method and application thereof.
  • the use of chip size miniaturization strategies to improve its data storage and computing capabilities has reached a theoretical limit.
  • the development of brain-like neural network computing and the establishment of physical models of artificial synapses have attracted widespread attention from scientists.
  • the neural synapses in the human brain can realize computing and storage tasks in parallel, have the ability to store and compute in one, high-frequency information transmission and processing rate, ultra-high density information storage capacity and low device power consumption.
  • memristor materials are still inorganic transition metal oxide materials, but their performance is limited by the tunability and flexibility of the materials themselves and cannot be applied to the current popular flexible smart and wearable electronic products. Therefore, it is of great research significance to explore memristor materials that have both mechanical flexibility and synaptic properties.
  • Two-dimensional hydrogen-bonded organic conjugated framework materials (2D-HOFs) have the advantages of low production cost, good deformation tolerance, biocompatibility, layered self-assembly structure, periodic molecular arrangement, excellent crystallinity, etc., and have become a research hotspot in the field of two-dimensional materials, and have shined in the fields of biology, energy and environment.
  • 2D-HOFs Two-dimensional hydrogen-bonded organic conjugated framework materials
  • nano-heterojunctions of 2D-HOFs and metal materials can be constructed in order to achieve efficient charge transfer and localized surface plasmon resonance effects, thereby improving the optical, electrical and chemical properties of the materials, and further affecting the resistive state behavior of the materials.
  • the present invention provides a method for preparing a hydrogen-bonded organic framework nanocomposite material, comprising the following steps:
  • the organic-inorganic nanocomposite materials prepared by this method not only retain the periodicity and mechanical flexibility of the stacking of hydrogen-bonded organic framework materials, but also effectively enhance the molecular charge transfer characteristics between organic and inorganic materials, greatly improving the conductivity and resistive switching properties of the composite materials, thereby realizing a gradual current signal under voltage scanning and pulses, meeting the rigid requirements for the development of artificial simulation of neural synapse devices.
  • step S12 the successful synthesis of the nano-composite material can be identified by naked eyes through sunlight and ultraviolet light irradiation, and confirmed by characterization methods such as dynamic light scattering, ultraviolet light, fluorescence, and transmission electron microscopy.
  • the amount of TBAPy added to the organic solvent is 4-6 mg/mL.
  • the method of heating and mixing is: heating to 70-90° C. under a protective atmosphere and stirring for 12-20 hours.
  • the impurity removal method is: purification by centrifugation, and multiple washing with organic solvents and alcohols.
  • the organic solvent is DMF (N,N-dimethylformamide), DMSO (dimethyl sulfoxide), 1,4-dioxane or THF (tetrahydrofuran).
  • the alcohol is ethanol or isopropanol.
  • the volume ratio of the organic solvent to the alcohol is 35-45:1.
  • the rotation speed used for the centrifugal separation is 7000-9000 rpm and the time is 30 min.
  • the lighting condition is to use a xenon lamp simulating sunlight.
  • the metal salt solution includes an aqueous silver nitrate solution, an aqueous rhodium nitrate solution or an aqueous copper nitrate solution.
  • the reaction temperature is 40-60° C. and the stirring speed is 30-50 rpm.
  • the present invention also provides a hydrogen-bond organic framework nano-composite material prepared by the above preparation method.
  • the present invention also provides a two-terminal structure memristor device, comprising the above hydrogen bond organic framework nanocomposite material.
  • the present invention also provides a method for preparing the above-mentioned two-terminal structure memristor device, comprising the following steps:
  • the molecular weight of the polyvinylpyrrole is 40,000-60,000.
  • the mixed solvent comprises ethanol and chlorobenzene.
  • volume ratio of the ethanol to chlorobenzene is 1:1-2.
  • the indium tin oxide substrate is obtained by magnetron sputtering deposition at a deposition rate of The thickness is 120-180 nanometers.
  • the evaporation method is vacuum evaporation, and the evaporation deposition rate is The thickness is 80-120 nanometers.
  • the metal electrode is a Cu electrode, an Ag electrode, an Au electrode or an Al electrode.
  • the present invention also provides an application of the above two-terminal structure memristor device in simulating the electrical behavior of a bionic artificial synapse device.
  • the present invention discloses a visualized preparation method for hydrogen-bonded organic framework nanocomposites and its application in bionic artificial synapses. Based on TBAPy organic ligand molecules, it has multidentate carboxylate ions and has extremely strong non-covalent bonding between molecules, especially hydrogen bonding and ⁇ - ⁇ interactions.
  • the synthesis method of hydrogen-bonded organic framework materials is optimized. Through sunlight and ultraviolet light irradiation, the successful synthesis of layered nanoassemblies can be identified by the naked eye, and confirmed by characterization methods such as dynamic light scattering, ultraviolet, fluorescence, and transmission electron microscopy. This method can monitor the assembly process of 2D-HOFs in real time and prevent excessive growth of nanomorphology.
  • the present invention discloses a visualized preparation method for hydrogen-bonded organic framework nanocomposites and its application in bionic artificial synapses. Metal nanoparticles are efficiently loaded on two-dimensional layered pure organic conjugated assemblies by means of photoreduction.
  • This organic-inorganic nanocomposite not only retains the periodicity and mechanical flexibility of the stacking of hydrogen-bonded organic framework materials, but also effectively enhances the molecular charge transfer characteristics between organic and inorganic materials, greatly improves the defects of the hydrogen-bonded organic framework materials themselves, and enhances the charge transfer effect between organic-inorganic materials and the localized surface plasmon resonance effect.
  • a top/bottom structure device was prepared, and a gradual current signal was achieved under voltage scanning and pulses, meeting the rigid requirements for the development of artificial simulated neural synapse devices.
  • FIG1 is a schematic diagram of a visualized preparation method of a hydrogen-bonded organic framework nanocomposite material and an electronic device thereof according to the present invention
  • FIG2 is a transmission electron microscopy (TEM) image of the hydrogen-bonded organic framework nanocomposite material of the present invention
  • FIG3 is an atomic force microscope image (AFM) of the hydrogen-bonded organic framework nanocomposite material
  • FIG4 is a scanning electrical performance diagram of a memristor prepared from a hydrogen-bonded organic framework nanocomposite material of the present invention.
  • FIG5 is a diagram of repeated scanning electrical performance of a memristor prepared from a hydrogen-bonded organic framework nanocomposite material of the present invention.
  • FIG6 is a method for simulating synaptic memory using a memristor prepared from the hydrogen-bonded organic framework nanocomposite material of the present invention.
  • a visualized preparation method of a hydrogen-bonded organic framework nanocomposite material is as follows:
  • the organic ligand TBAPy is generated by reaction.
  • the organic ligand TBAPy is dissolved in anhydrous DMF solvent, then heated at 80°C under ultrasound assistance and nitrogen atmosphere and stirred for 16 hours, an excess of anhydrous ethanol solution is added, and stirred under ultrasound assistance.
  • the assembly process of the two-dimensional hydrogen-bonded organic nanomaterials is monitored in real time with the help of the naked eye and a portable ultraviolet lamp, which effectively prevents the excessive growth of nanobelts.
  • the size of the nanobelt assembly is accurately analyzed using a transmission electron microscope.
  • the synthesized suspension is further purified by centrifugation at 8000 rpm for 30 minutes, and then washed and purified multiple times with DMF and ethanol solvents to obtain 2D-HOFs.
  • 2D-HOFs Under the irradiation of a xenon lamp simulating sunlight, 2D-HOFs were dispersed in a 55°C silver nitrate aqueous solution and stirred at 40 rpm. The photoreduction reaction was used to prepare metal nanoparticles with a particle size distribution of about 2-10 nanometers. They were loaded on a two-dimensional nanosheet structure, and the color change of the nanoassembly suspension could be observed by the naked eye, ultimately obtaining a hydrogen-bonded organic framework nanocomposite material.
  • a method for preparing a two-terminal memristor device is as follows:
  • the hydrogen-bonded organic framework nanocomposite material loaded with nanosilver particles was dispersed in a mixed solvent of ethanol and chlorobenzene (volume ratio 1:2) of polyvinyl pyrrole with a molecular weight of about 50,000, and was spin-coated on the ITO surface to prepare a functional nanofilm.
  • a 100-nanometer-thick metal aluminum electrode is deposited on the surface of the organic functional nanofilm.
  • the deposition rate of the first 10 nanometers is The subsequent deposition rate is Finally, a two-terminal structured memristor device of metal/active layer/metal was prepared to simulate the electrical behavior of bionic artificial synaptic devices.
  • a single device unit was 0.78 mm 2 and the size of the entire device was 2 ⁇ 2 cm 2 .
  • the memristor device was tested with the help of Keithley's 4200-SCS semiconductor electrical and pulse test system. DC voltages of 0 to 3V and 0 to -3V were applied respectively, and the current-voltage curve was obtained by stimulation of cyclic voltage sweep. Repeated positive stimulation and negative stimulation were used to achieve memory erasure and relearning. Further design of reasonable voltage stimulation and algorithm to achieve short-term memory and long-term memory characteristics, and finally the top/bottom structured two-terminal memristor device was used to simulate artificial synaptic behavior.
  • AFM of the hydrogen-bonded organic framework material loaded with nanoparticles showed that the nanobelts and polyvinylpyrrole achieved secondary assembly, presenting a uniform surface morphology and tight stacking behavior, as shown in Figure 3.
  • the electrical performance of the memristor prepared from hydrogen-bonded organic framework nanocomposites is that the current value of the memory device based on the "bottom electrode/organic-inorganic hybrid HOFs film/top electrode” structure shows a gradual change under the continuous voltage scanning, and the resistance state is constantly increasing, thus presenting multiple resistance states, which is similar to the signal changes generated by the release and reception of neurotransmitters at both ends of synaptic neurons, as shown in Figure 4.
  • the performance of the device can be manipulated through electrical stimulation. Repeated positive stimulation causes the current level of the device to gradually decrease and the resistance state to continuously increase, showing a "forgetting" process. Further negative stimulation can increase the current level and achieve a re-learning process, as shown in Figure 5.

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Abstract

A hydrogen bond organic framework nanocomposite material, and a preparation method therefor and the use thereof. A synthesized organic conjugated ligand is dissolved in a mixed solvent; an organic framework material having a nanobelt structure is synthesized under mild conditions; and metal nanoparticles are prepared by means of a photo-reduction reaction and loaded into a two-dimensional hydrogen bond organic assembly structure, such that the nano material can achieve changes in multiple conductive states by means of positive and negative voltage stimulation and effectively construct an artificial synaptic simulation system.

Description

一种氢键有机框架纳米复合材料及其制备方法和应用A hydrogen bond organic framework nanocomposite material and its preparation method and application 技术领域Technical Field
本发明属于仿生人工突触器件领域，具体涉及一种氢键有机框架纳米复合材料及其制备方法和应用。The invention belongs to the field of bionic artificial synaptic devices, and specifically relates to a hydrogen-bond organic framework nanocomposite material and a preparation method and application thereof.
背景技术Background technique
随着芯片制造产业的进一步发展，借助芯片尺寸微缩化策略以提升其数据存储和计算能力已接近理论极限。为了打破这一瓶颈，受到人脑的启发，开发类脑神经网络计算以及建立人工突触的物理模型受到科学家们的广泛关注。相比于传统的硅基半导体中独立运行的存储和计算器件单元，人脑中的神经突触可以并行实现运算和存储的任务，具备存算一体的能力，高频信息传输和处理速率、超高密度信息存储容量以及较低的器件功耗等特点。因此，开发新型的人工突触器件来构建类脑神经计算的基本结构单元，为下一代机器学习、认知识别、高密度信息存储技术提供了重要的发展前景。当前基于垂直顶/底电极结构的仿生忆阻器件表现出极大的发展潜力，通过调节双端器件的多重电导态，模拟突触前后权重的变化。到目前为止，基于忆阻器的人工突触器件也取得了一系列成果，开发出多种新型忆阻材料体系，用于模拟生物突触的特征功能，如：长期可塑性、短期可塑性、长期抑制、短期抑制、时间依赖性可塑性等等。然而，目前研究最为广泛的忆阻材料仍然是无机过渡金属氧化物材料，但是其性能受制于材料本身的可调谐性和柔韧性，无法应用于当下热门的柔性智能以及可穿戴电子产品。因此，探索兼具机械柔性和突触特性的忆阻材料具有重要的研究意义。With the further development of the chip manufacturing industry, the use of chip size miniaturization strategies to improve its data storage and computing capabilities has reached a theoretical limit. In order to break this bottleneck, inspired by the human brain, the development of brain-like neural network computing and the establishment of physical models of artificial synapses have attracted widespread attention from scientists. Compared with the independent storage and computing device units in traditional silicon-based semiconductors, the neural synapses in the human brain can realize computing and storage tasks in parallel, have the ability to store and compute in one, high-frequency information transmission and processing rate, ultra-high density information storage capacity and low device power consumption. Therefore, the development of new artificial synaptic devices to construct the basic structural unit of brain-like neural computing provides an important development prospect for the next generation of machine learning, cognitive recognition, and high-density information storage technology. At present, bionic memristor devices based on vertical top/bottom electrode structures show great development potential. By adjusting the multiple conductance states of the two-terminal device, the changes in the weights before and after the synapse are simulated. So far, artificial synaptic devices based on memristors have also achieved a series of results, and a variety of new memristor material systems have been developed to simulate the characteristic functions of biological synapses, such as long-term plasticity, short-term plasticity, long-term inhibition, short-term inhibition, time-dependent plasticity, etc. However, the most widely studied memristor materials are still inorganic transition metal oxide materials, but their performance is limited by the tunability and flexibility of the materials themselves and cannot be applied to the current popular flexible smart and wearable electronic products. Therefore, it is of great research significance to explore memristor materials that have both mechanical flexibility and synaptic properties.
二维的氢键有机共轭骨架材料(2D-HOFs)具有较低生产成本、良好的形变耐受性、生物可兼容性、层状自组装结构、周期性分子排列、优异的结晶性等优点，成为当前二维材料领域的研究热点，在生物学、能源环境等领域大放异彩。然而，由于2D-HOFs具有较差的电导率和弱的电荷转移能力，在很大程度上限制了其在电子学领域的应用。因此，借助二维层状材料高比表面的特性，能够构建2D-HOFs与金属材料的纳米异质结，以期实现高效的电荷转移、局域表面等离子体共振效应，从而改善材料的光、电以及化学性能，进一步影响材料的电阻态行为。人工模拟突触的特征功能，借助新型程序算法，以期实现类脑神经计算的基本结构单元。Two-dimensional hydrogen-bonded organic conjugated framework materials (2D-HOFs) have the advantages of low production cost, good deformation tolerance, biocompatibility, layered self-assembly structure, periodic molecular arrangement, excellent crystallinity, etc., and have become a research hotspot in the field of two-dimensional materials, and have shined in the fields of biology, energy and environment. However, due to the poor electrical conductivity and weak charge transfer ability of 2D-HOFs, their application in the field of electronics is largely limited. Therefore, with the help of the high specific surface area of two-dimensional layered materials, nano-heterojunctions of 2D-HOFs and metal materials can be constructed in order to achieve efficient charge transfer and localized surface plasmon resonance effects, thereby improving the optical, electrical and chemical properties of the materials, and further affecting the resistive state behavior of the materials. Artificially simulate the characteristic functions of synapses, with the help of new program algorithms, in order to realize the basic structural unit of brain-like neural computing.
发明内容Summary of the invention
为了解决现有技术存在的问题，本发明提供一种氢键有机框架纳米复合材料的制备方法，包括如下步骤：In order to solve the problems existing in the prior art, the present invention provides a method for preparing a hydrogen-bonded organic framework nanocomposite material, comprising the following steps:
S11：将TBAPy(1,3,6,8-四苯甲酸-芘)加入有机溶剂中，加热混合，得到前驱体溶液；S11: adding TBAPy (1,3,6,8-tetrabenzoic acid-pyrene) into an organic solvent, heating and mixing, to obtain a precursor solution;
S12：向所述前驱体溶液中加入醇或水，除杂，得到纳米级2D-HOFs；S12: adding alcohol or water to the precursor solution to remove impurities and obtain nanoscale 2D-HOFs;
S13：光照条件下，将纳米级2D-HOFs加入金属盐溶液中反应，得到所述氢键有机框架纳米复合材料。S13: Under light conditions, adding nanoscale 2D-HOFs to a metal salt solution for reaction to obtain the hydrogen-bonded organic framework nanocomposite material.
该方法制备的有机-无机纳米复合材料既保留了氢键有机框架材料堆积的周期性和机械柔韧性，又有效增强了有机和无机材料之间分子电荷转移特性，极大的提升了复合材料的导电性和阻变特性，从而在电压扫描和脉冲下实现渐变式电流信号，满足开发人工模拟神经突触器件的硬性要求。The organic-inorganic nanocomposite materials prepared by this method not only retain the periodicity and mechanical flexibility of the stacking of hydrogen-bonded organic framework materials, but also effectively enhance the molecular charge transfer characteristics between organic and inorganic materials, greatly improving the conductivity and resistive switching properties of the composite materials, thereby realizing a gradual current signal under voltage scanning and pulses, meeting the rigid requirements for the development of artificial simulation of neural synapse devices.
同时，在所述步骤S12中，通过日光以及紫外光照射，可以利用肉眼识别纳米级复合材料的成功合成，并被动态光散射、紫外、荧光、透射电子显微镜等表征手段证实。Meanwhile, in step S12, the successful synthesis of the nano-composite material can be identified by naked eyes through sunlight and ultraviolet light irradiation, and confirmed by characterization methods such as dynamic light scattering, ultraviolet light, fluorescence, and transmission electron microscopy.
优选的，所述步骤S11中，TBAPy在有机溶剂中的加入量为4-6mg/mL。Preferably, in step S11, the amount of TBAPy added to the organic solvent is 4-6 mg/mL.
优选的，所述步骤S11中，加热混合的方法为：于保护气氛下加热至70-90℃，搅拌12-20h。Preferably, in step S11, the method of heating and mixing is: heating to 70-90° C. under a protective atmosphere and stirring for 12-20 hours.
优选的，所述步骤S12中，所述除杂的方法为：离心分离提纯，用有机溶剂和醇多次清洗。Preferably, in step S12, the impurity removal method is: purification by centrifugation, and multiple washing with organic solvents and alcohols.
优选的，所述有机溶剂为DMF(N,N-二甲基甲酰胺)，DMSO(二甲基亚砜)，1,4二氧六环或THF(四氢呋喃)。Preferably, the organic solvent is DMF (N,N-dimethylformamide), DMSO (dimethyl sulfoxide), 1,4-dioxane or THF (tetrahydrofuran).
优选的，所述醇为乙醇或异丙醇。Preferably, the alcohol is ethanol or isopropanol.
优选的，所述有机溶剂和醇的体积比为35-45：1。Preferably, the volume ratio of the organic solvent to the alcohol is 35-45:1.
优选的，所述离心分离所用的转速为7000-9000转/min，时间为30min。Preferably, the rotation speed used for the centrifugal separation is 7000-9000 rpm and the time is 30 min.
优选的，所述步骤S12中，光照条件为使用模拟太阳光氙灯。Preferably, in step S12, the lighting condition is to use a xenon lamp simulating sunlight.
优选的，所述金属盐溶液包括硝酸银水溶液，硝酸铑水溶液或硝酸铜水溶液。Preferably, the metal salt solution includes an aqueous silver nitrate solution, an aqueous rhodium nitrate solution or an aqueous copper nitrate solution.
优选的，所述步骤S13中，反应的温度为40-60℃，搅拌速度为30-50转/min。Preferably, in step S13, the reaction temperature is 40-60° C. and the stirring speed is 30-50 rpm.
本发明还提供一种上述制备方法制备得到的氢键有机框架纳米复合材料。The present invention also provides a hydrogen-bond organic framework nano-composite material prepared by the above preparation method.
本发明还提供一种双端结构忆阻器件，包括上述氢键有机框架纳米复合材料。The present invention also provides a two-terminal structure memristor device, comprising the above hydrogen bond organic framework nanocomposite material.
本发明还提供一种上述双端结构忆阻器件的制备方法，包括如下步骤：The present invention also provides a method for preparing the above-mentioned two-terminal structure memristor device, comprising the following steps:
S21：将氢键有机框架纳米复合材料和聚乙烯基吡咯于混合溶剂中混合后，分离得到上层分散液；S21: mixing the hydrogen-bonded organic framework nanocomposite material and polyvinyl pyrrole in a mixed solvent, and separating to obtain an upper dispersion;
S22：将所述上层分散液涂覆于氧化铟锡基底上，干燥，得到有机功能纳米薄膜复合层；S22: coating the upper dispersion on an indium tin oxide substrate and drying to obtain an organic functional nano-thin film composite layer;
S23：向所述有机功能纳米薄膜复合层涂覆上层分散液的一侧表面蒸镀金属电极，得到所述双端结构忆阻器件。S23: evaporating a metal electrode onto the surface of one side of the organic functional nano-thin film composite layer coated with the upper dispersion liquid to obtain the two-terminal structure memristor device.
优选的，所述聚乙烯基吡咯的分子量为40000-60000。Preferably, the molecular weight of the polyvinylpyrrole is 40,000-60,000.
优选的，所述混合溶剂包括乙醇和氯苯。Preferably, the mixed solvent comprises ethanol and chlorobenzene.
进一步地，所述乙醇和氯苯的体积比为1：1-2。Furthermore, the volume ratio of the ethanol to chlorobenzene is 1:1-2.
优选的，所述氧化铟锡基底是利用磁控溅射沉积得到，沉积速率为
Figure PCTCN2022132126-appb-000001
厚度为120-180纳米。 Preferably, the indium tin oxide substrate is obtained by magnetron sputtering deposition at a deposition rate of
Figure PCTCN2022132126-appb-000001
The thickness is 120-180 nanometers.
优选的，所述步骤S23中，蒸镀的方法为真空蒸发法，蒸镀沉积的速率为
Figure PCTCN2022132126-appb-000002
厚度为80-120纳米。 Preferably, in step S23, the evaporation method is vacuum evaporation, and the evaporation deposition rate is
Figure PCTCN2022132126-appb-000002
The thickness is 80-120 nanometers.
优选的，所述金属电极为Cu电极，Ag电极，Au电极或Al电极。Preferably, the metal electrode is a Cu electrode, an Ag electrode, an Au electrode or an Al electrode.
本发明还提供一种上述双端结构忆阻器件在模拟仿生人工突触器件的电学行为的应用。The present invention also provides an application of the above two-terminal structure memristor device in simulating the electrical behavior of a bionic artificial synapse device.
本发明的技术方案相比现有技术具有以下优点：The technical solution of the present invention has the following advantages over the prior art:
1、本发明一种用于氢键有机框架纳米复合材料的可视化制备方法及其在仿生人工突触的应用。基于TBAPy有机配体分子，具备多齿羧酸根离子，分子之间具有极强的非共价键作用，尤其是氢键作用和π-π相互作用。在此，优化了氢键有机框架材料的合成方法，通过日光以及紫外光照射，可以利用肉眼识别层状纳米组装体的成功合成，并被动态光散射、紫外、荧光、透射电子显微镜等表征手段得以证实。此方法可以实时监测2D-HOFs的组装过程，防止纳米形貌的过度生长。1. The present invention discloses a visualized preparation method for hydrogen-bonded organic framework nanocomposites and its application in bionic artificial synapses. Based on TBAPy organic ligand molecules, it has multidentate carboxylate ions and has extremely strong non-covalent bonding between molecules, especially hydrogen bonding and π-π interactions. Here, the synthesis method of hydrogen-bonded organic framework materials is optimized. Through sunlight and ultraviolet light irradiation, the successful synthesis of layered nanoassemblies can be identified by the naked eye, and confirmed by characterization methods such as dynamic light scattering, ultraviolet, fluorescence, and transmission electron microscopy. This method can monitor the assembly process of 2D-HOFs in real time and prevent excessive growth of nanomorphology.
2、本发明一种用于氢键有机框架纳米复合材料的可视化制备方法及其在仿生人工突触的应用。借助光还原的方法在二维层状纯有机共轭组装体上，高效负载金属纳米颗粒。这一有机-无机纳米复合材料既保留了氢键有机框架材料堆积的周期性和机械柔韧性，又有效增强了有机和无机材料之间分子电荷转移特性，大大改善了氢键有机框架材料本身的缺陷，增强了有机-无机材料间的电荷转移作用以及局域表面等离子体共振效应。制备了顶/底结构的器件，在电压扫描和脉冲下实现渐变式电流信号，满足开发人工模拟神经突触器件的硬性要求。2. The present invention discloses a visualized preparation method for hydrogen-bonded organic framework nanocomposites and its application in bionic artificial synapses. Metal nanoparticles are efficiently loaded on two-dimensional layered pure organic conjugated assemblies by means of photoreduction. This organic-inorganic nanocomposite not only retains the periodicity and mechanical flexibility of the stacking of hydrogen-bonded organic framework materials, but also effectively enhances the molecular charge transfer characteristics between organic and inorganic materials, greatly improves the defects of the hydrogen-bonded organic framework materials themselves, and enhances the charge transfer effect between organic-inorganic materials and the localized surface plasmon resonance effect. A top/bottom structure device was prepared, and a gradual current signal was achieved under voltage scanning and pulses, meeting the rigid requirements for the development of artificial simulated neural synapse devices.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明氢键有机框架纳米复合材料的可视化制备方法及其电子器件的示意图；FIG1 is a schematic diagram of a visualized preparation method of a hydrogen-bonded organic framework nanocomposite material and an electronic device thereof according to the present invention;
图2为本发明氢键有机框架纳米复合材料的透射电镜图(TEM)；FIG2 is a transmission electron microscopy (TEM) image of the hydrogen-bonded organic framework nanocomposite material of the present invention;
图3为本氢键有机框架纳米复合材料的原子力显微镜图(AFM)；FIG3 is an atomic force microscope image (AFM) of the hydrogen-bonded organic framework nanocomposite material;
图4为本发明氢键有机框架纳米复合材料所制备的忆阻器的扫描电学性能图；FIG4 is a scanning electrical performance diagram of a memristor prepared from a hydrogen-bonded organic framework nanocomposite material of the present invention;
图5为本发明氢键有机框架纳米复合材料所制备的忆阻器的重复扫描电学性能图；FIG5 is a diagram of repeated scanning electrical performance of a memristor prepared from a hydrogen-bonded organic framework nanocomposite material of the present invention;
图6为本发明氢键有机框架纳米复合材料所制备的忆阻器用于模拟突触记忆的方法。FIG6 is a method for simulating synaptic memory using a memristor prepared from the hydrogen-bonded organic framework nanocomposite material of the present invention.
具体实施方式Detailed ways
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it, but the embodiments are not intended to limit the present invention.
实施例1Example 1
一种氢键有机框架纳米复合材料的可视化制备方法，具体如下：A visualized preparation method of a hydrogen-bonded organic framework nanocomposite material is as follows:
基于成熟的合成步骤反应生成有机配体TBAPy，将有机配体TBAPy溶于无水DMF溶剂中，然后在超声辅助以及氮气氛围下80℃加热下搅拌16h，加入过量无水乙醇溶液，在超声辅助下搅拌，借助肉眼和手提式紫外灯，实时监测二维氢键有机纳米材料的组装过程，有效防止纳米带的过度生长，并利用透射电子显微镜精准分析纳米带组装体的尺寸，合成好的悬浮液进一步以8000转/分钟，30分钟做离心分离提纯，随后用DMF和乙醇溶剂多次清洗纯化得到2D-HOFs。Based on the mature synthesis steps, the organic ligand TBAPy is generated by reaction. The organic ligand TBAPy is dissolved in anhydrous DMF solvent, then heated at 80°C under ultrasound assistance and nitrogen atmosphere and stirred for 16 hours, an excess of anhydrous ethanol solution is added, and stirred under ultrasound assistance. The assembly process of the two-dimensional hydrogen-bonded organic nanomaterials is monitored in real time with the help of the naked eye and a portable ultraviolet lamp, which effectively prevents the excessive growth of nanobelts. The size of the nanobelt assembly is accurately analyzed using a transmission electron microscope. The synthesized suspension is further purified by centrifugation at 8000 rpm for 30 minutes, and then washed and purified multiple times with DMF and ethanol solvents to obtain 2D-HOFs.
在模拟太阳光氙灯的照射下，将2D-HOFs分散于55℃硝酸银水溶液中，40转/min搅拌反应，利用光还原反应实现金属纳米颗粒的制备，纳米颗粒的粒径分布在2-10纳米左右，将其负载于二维纳米片结构上，肉眼可以观测纳米组装体悬浮液的颜色变化，最终得到氢键有机框架纳米复合材料。Under the irradiation of a xenon lamp simulating sunlight, 2D-HOFs were dispersed in a 55°C silver nitrate aqueous solution and stirred at 40 rpm. The photoreduction reaction was used to prepare metal nanoparticles with a particle size distribution of about 2-10 nanometers. They were loaded on a two-dimensional nanosheet structure, and the color change of the nanoassembly suspension could be observed by the naked eye, ultimately obtaining a hydrogen-bonded organic framework nanocomposite material.
实施例2Example 2
一种双端结构忆阻器件的制备方法，具体如下：A method for preparing a two-terminal memristor device is as follows:
将负载纳米银颗粒的氢键有机框架纳米复合材料分散在分子量50000左右聚乙烯基吡咯的乙醇和氯苯的混合溶剂中(体积比1：2)，并经过旋涂在ITO表面实现功能纳米薄膜的制备。The hydrogen-bonded organic framework nanocomposite material loaded with nanosilver particles was dispersed in a mixed solvent of ethanol and chlorobenzene (volume ratio 1:2) of polyvinyl pyrrole with a molecular weight of about 50,000, and was spin-coated on the ITO surface to prepare a functional nanofilm.
高真空度条件下，在有机功能纳米薄膜的表面沉积一层100纳米厚的金属铝电极，前10纳米的沉积速率为
Figure PCTCN2022132126-appb-000003
后续沉积速率为
Figure PCTCN2022132126-appb-000004
最终制备得到金属/活性层/金属的双端结构忆阻器件，用于模拟仿生人工突触器件的电学行为，单个器件单元为0.78mm 2器件，整片器件的尺寸大小为2×2cm 2。 Under high vacuum conditions, a 100-nanometer-thick metal aluminum electrode is deposited on the surface of the organic functional nanofilm. The deposition rate of the first 10 nanometers is
Figure PCTCN2022132126-appb-000003
The subsequent deposition rate is
Figure PCTCN2022132126-appb-000004
Finally, a two-terminal structured memristor device of metal/active layer/metal was prepared to simulate the electrical behavior of bionic artificial synaptic devices. A single device unit was 0.78 mm 2 and the size of the entire device was 2×2 cm 2 .
实施例3Example 3
双端结构忆阻器件在仿生人工突触的应用，具体如下：The application of two-terminal memristor devices in bionic artificial synapses is as follows:
在25℃、30％湿度的温和条件下，借助吉时利公司(Keithley)生产的4200-SCS半导体电学和脉冲测试系统对忆阻器件进行测试。分别施加0到3V和0到-3V的直流电压，通过 循环电压扫描的刺激得到电流-电压曲线。分别采用重复的正向刺激和负向刺激，实现记忆的擦除和再学习。进一步设计合理的电压刺激和算法以实现短期记忆和长时记忆特征，最终借助顶/底结构的双端忆阻器件用于模拟人工突触行为。Under mild conditions of 25°C and 30% humidity, the memristor device was tested with the help of Keithley's 4200-SCS semiconductor electrical and pulse test system. DC voltages of 0 to 3V and 0 to -3V were applied respectively, and the current-voltage curve was obtained by stimulation of cyclic voltage sweep. Repeated positive stimulation and negative stimulation were used to achieve memory erasure and relearning. Further design of reasonable voltage stimulation and algorithm to achieve short-term memory and long-term memory characteristics, and finally the top/bottom structured two-terminal memristor device was used to simulate artificial synaptic behavior.
效果评价Evaluation
氢键有机框架材料的合成步骤以及光还原负载金属纳米颗粒，将有机-无机杂化材料利用旋涂的工艺制备成有机纳米薄膜，并制备形成顶/底结构的仿生柔性器件，如图1所示。The synthesis steps of hydrogen-bonded organic framework materials and photoreduction-loaded metal nanoparticles are used to prepare organic-inorganic hybrid materials into organic nanofilms using a spin coating process, and to prepare bionic flexible devices with top/bottom structures, as shown in Figure 1.
氢键有机框架材料负载纳米颗粒后的TEM可以看出纳米条带状氢键材料被成功制备，并实现了纳米颗粒的均匀负载，薄膜在微观尺度上表现出较好的均一性，如图2所示。TEM after the hydrogen-bonded organic framework material was loaded with nanoparticles showed that the nano-strip hydrogen-bonded material was successfully prepared and the uniform loading of nanoparticles was achieved. The film showed good uniformity at the microscopic scale, as shown in Figure 2.
氢键有机框架材料负载纳米颗粒后的AFM表明纳米带与聚乙烯基吡咯实现了二次组装，呈现出均匀的表面形貌和紧密的堆积行为，如图3所示。AFM of the hydrogen-bonded organic framework material loaded with nanoparticles showed that the nanobelts and polyvinylpyrrole achieved secondary assembly, presenting a uniform surface morphology and tight stacking behavior, as shown in Figure 3.
氢键有机框架纳米复合材料所制备的忆阻器的电学性能，是基于“底电极/有机-无机杂化HOFs薄膜/顶电极”结构的存储器件在电压的持续扫描下，器件的电流值呈现渐变的特征，电阻态在不断的升高，从而呈现出多重电阻态，类似于突触神经元两端释放和接受神经介质所产生的信号变化，如图4所示。The electrical performance of the memristor prepared from hydrogen-bonded organic framework nanocomposites is that the current value of the memory device based on the "bottom electrode/organic-inorganic hybrid HOFs film/top electrode" structure shows a gradual change under the continuous voltage scanning, and the resistance state is constantly increasing, thus presenting multiple resistance states, which is similar to the signal changes generated by the release and reception of neurotransmitters at both ends of synaptic neurons, as shown in Figure 4.
器件的性能可以通过电学刺激的方式来操控，重复的正向刺激使得器件的电流水平逐渐下降，阻态不断升高，表现出“遗忘”的过程，进一步通过负向刺激，可以提升电流水平，达到再学习的过程，如图5所示。The performance of the device can be manipulated through electrical stimulation. Repeated positive stimulation causes the current level of the device to gradually decrease and the resistance state to continuously increase, showing a "forgetting" process. Further negative stimulation can increase the current level and achieve a re-learning process, as shown in Figure 5.
通过电学测试结果结合合理的算法，提出利用正反向交替的电学刺激可以实现模拟人工突触器件的短期记忆和长期记忆，实现忆阻器的生物学应用，如图6所示。By combining the electrical test results with a reasonable algorithm, it is proposed that the use of alternating positive and reverse electrical stimulation can simulate the short-term memory and long-term memory of artificial synaptic devices and realize the biological application of memristors, as shown in Figure 6.
显然，上述实施例仅仅是为清楚地说明所作的举例，并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。Obviously, the above embodiments are merely examples for clear explanation and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from these are still within the protection scope of the invention.

Claims (10)

  1. 一种氢键有机框架纳米复合材料的制备方法，其特征在于，包括如下步骤：A method for preparing a hydrogen-bonded organic framework nanocomposite material, characterized in that it comprises the following steps:
    S11：将TBAPy加入有机溶剂中，加热混合，得到前驱体溶液；S11: adding TBAPy to an organic solvent, heating and mixing, to obtain a precursor solution;
    S12：向所述前驱体溶液中加入醇或水，除杂，得到纳米级2D-HOFs；S12: adding alcohol or water to the precursor solution to remove impurities and obtain nanoscale 2D-HOFs;
    S13：光照条件下，将纳米级2D-HOFs加入金属盐溶液中反应，得到所述氢键有机框架纳米复合材料。S13: Under light conditions, adding nanoscale 2D-HOFs to a metal salt solution for reaction to obtain the hydrogen-bonded organic framework nanocomposite material.
  2. 如权利要求1所述的制备方法，其特征在于，所述步骤S11中，加热混合的方法为：于保护气氛下加热至70-90℃，搅拌12-20h。The preparation method according to claim 1 is characterized in that in the step S11, the heating and mixing method is: heating to 70-90° C. under a protective atmosphere and stirring for 12-20 hours.
  3. 如权利要求1所述的制备方法，其特征在于，所述有机溶剂为DMF，DMSO，1,4-二氧六环或THF。The preparation method according to claim 1, characterized in that the organic solvent is DMF, DMSO, 1,4-dioxane or THF.
  4. 如权利要求1所述的制备方法，其特征在于，所述步骤S13中，反应的温度为40-60℃。The preparation method according to claim 1, characterized in that in step S13, the reaction temperature is 40-60°C.
  5. 如权利要求1所述的制备方法，其特征在于，所述金属盐溶液包括硝酸银水溶液，硝酸铑水溶液或硝酸铜水溶液。The preparation method according to claim 1, characterized in that the metal salt solution comprises an aqueous solution of silver nitrate, an aqueous solution of rhodium nitrate or an aqueous solution of copper nitrate.
  6. 一种权利要求1-5中任一项所述制备方法制备得到的氢键有机框架纳米复合材料。A hydrogen-bonded organic framework nanocomposite material prepared by the preparation method according to any one of claims 1 to 5.
  7. 一种双端结构忆阻器件，其特征在于，包括权利要求6所述的氢键有机框架纳米复合材料。A two-terminal structured memristor device, characterized by comprising the hydrogen-bonded organic framework nanocomposite material according to claim 6.
  8. 一种权利要求7所述双端结构忆阻器件的制备方法，其特征在于，包括如下步骤：A method for preparing a two-terminal memristor device according to claim 7, characterized in that it comprises the following steps:
    S21：将氢键有机框架纳米复合材料和聚乙烯基吡咯于混合溶剂中混合后，分离得到上层分散液；S21: mixing the hydrogen-bonded organic framework nanocomposite material and polyvinyl pyrrole in a mixed solvent, and separating to obtain an upper dispersion;
    S22：将所述上层分散液涂覆于氧化铟锡基底上，干燥，得到有机功能纳米薄膜复合层；S22: coating the upper dispersion on an indium tin oxide substrate, and drying to obtain an organic functional nano-thin film composite layer;
    S23：向所述有机功能纳米薄膜复合层涂覆上层分散液的一侧表面蒸镀金属电极，得到所述双端结构忆阻器件。S23: evaporating a metal electrode onto the surface of one side of the organic functional nano-thin film composite layer coated with the upper dispersion liquid to obtain the two-terminal structure memristor device.
  9. 如权利要求8所述的制备方法，其特征在于，所述混合溶剂包括乙醇和氯苯。The preparation method according to claim 8, characterized in that the mixed solvent comprises ethanol and chlorobenzene.
  10. 权利要求7所述双端结构忆阻器件在模拟仿生人工突触器件的电学行为的应用。Application of the two-terminal memristor device described in claim 7 in simulating the electrical behavior of bionic artificial synaptic devices.
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CN108727605A (en) * 2018-03-16 2018-11-02 中国科学院福建物质结构研究所 Hydrogen bond organic framework materials, preparation method and the application constructed based on condensed ring ligand
CN109904316A (en) * 2019-03-01 2019-06-18 南京大学 A kind of inorganic-organic of analog neuron cynapse/inorganic hybridization double-layer nanometer film memristor and preparation method thereof
US20210119159A1 (en) * 2019-10-22 2021-04-22 Iucf-Hyu (Industry-University Cooperation Foundation Hanyang University) Neuron behavior-imitating electronic synapse device and method of fabricating the same
US20220036170A1 (en) * 2021-08-04 2022-02-03 Beihang University Optoelectronic synaptic memristor
CN114628579A (en) * 2022-03-03 2022-06-14 南京邮电大学 Proton type memristor based on water-soluble polymer and preparation thereof
CN115141380A (en) * 2022-06-09 2022-10-04 复旦大学 Silver nanoparticle loaded hydrogen bond organic framework composite material and preparation method and application thereof

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