CN115915775A - A memristor based on a covalent organic framework (COF) film and its preparation method - Google Patents

A memristor based on a covalent organic framework (COF) film and its preparation method Download PDF

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CN115915775A
CN115915775A CN202310002675.9A CN202310002675A CN115915775A CN 115915775 A CN115915775 A CN 115915775A CN 202310002675 A CN202310002675 A CN 202310002675A CN 115915775 A CN115915775 A CN 115915775A
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memristor
mixed solution
film
covalent organic
organic framework
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陶野
万厚钊
胡婷
范玉舟
汪涵斌
张军
沈谅平
王浩
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Hubei University
Hubei Jiangcheng Laboratory
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Abstract

发明公开了一种基于共价有机框架薄膜的忆阻器,其结构从下至上为:衬底、导电底电极、共价有机框架薄膜、有机聚合物薄膜和导电顶电极。忆阻器制备包括以下步骤:在0‑80℃下,将特定的芳香二醛混合溶液和芳香多胺混合溶液混合,滴加在所需导电底电极上或直接将带有导电底电极的衬底浸于混合溶液中,即可在底电极上得到均匀的共价有机框架薄膜用于忆阻器。之后制备聚合物胶体溶液,将其旋涂于共价有机框架薄膜表面,最后使用掩膜版采用热蒸镀或溅射制备顶电极。本发明首次提出一种新型忆阻器的制备方法,该制备方法过程简单,价格经济,无需高精度的精密仪器,在无需复杂环境的条件下即可在衬底上原位生长制备大面积的共价有机框架(COF)薄膜。

Figure 202310002675

The invention discloses a memristor based on a covalent organic frame film, whose structure from bottom to top is: a substrate, a conductive bottom electrode, a covalent organic frame film, an organic polymer film and a conductive top electrode. The preparation of the memristor includes the following steps: at 0-80°C, mix a specific aromatic dialdehyde mixed solution and an aromatic polyamine mixed solution, drop it on the desired conductive bottom electrode or directly place the substrate with the conductive bottom electrode By immersing the bottom electrode in the mixed solution, a uniform covalent organic framework film can be obtained on the bottom electrode for the memristor. Then a polymer colloid solution is prepared, which is spin-coated on the surface of the covalent organic framework film, and finally the top electrode is prepared by thermal evaporation or sputtering using a mask. The present invention proposes a new type of memristor preparation method for the first time. The preparation method is simple in process, economical in price, does not require high-precision precision instruments, and can grow large-area memristors in situ on a substrate without complicated environments. Covalent organic framework (COF) films.

Figure 202310002675

Description

一种基于共价有机框架(COF)薄膜的忆阻器及其制备方法A memristor based on a covalent organic framework (COF) film and its preparation method

技术领域technical field

本发明属于有机二维材料应用技术领域,具体来说涉及一种基于共价有机框架(COF)薄膜的忆阻器及其制备方法。The invention belongs to the technical field of application of organic two-dimensional materials, and in particular relates to a memristor based on a covalent organic framework (COF) film and a preparation method thereof.

背景技术Background technique

共价有机框架(Covalent Organic Frameworks,COF)材料作为一种新兴的多孔材料,因其有趣的结构优点(如总有机骨架、可调孔隙度和可预测的结构)而受到人们的广泛关注。然而,共价有机框架粉末的不溶性和不可加工特性限制了其应用。目前,共价有机框架材料在气体的储存与分离、非均相催化、储能材料、光电、传感以及药物递送等领域已经有了广泛的研究并展现出优异的应用前景。在此之前,已有一些研究者利用共价有机框架材料制作出可用的忆阻器。As an emerging class of porous materials, covalent organic frameworks (COF) materials have attracted much attention due to their interesting structural advantages such as total organic framework, tunable porosity, and predictable structure. However, the insolubility and non-processability of covalent organic framework powders limit their applications. At present, covalent organic framework materials have been widely studied in the fields of gas storage and separation, heterogeneous catalysis, energy storage materials, optoelectronics, sensing, and drug delivery, and have shown excellent application prospects. Previously, some researchers have used covalent organic framework materials to make usable memristors.

但大多COF的合成方法较为繁琐,反应时间较长,一般都是溶剂热法合成,需要在高温高压的环境下反应数天,如文章Towards High-Performance Resistive SwitchingBehavior through Embedding D-A System into 2D Imine-Linked Covalent OrganicFrameworks合成的COF-TT-BT和COF-TT-TVT薄膜就需要在120℃下反应72h。而且许多利用共价有机框架制备的忆阻器并非原位合成生长,还需进行转移操作(例如专利CN2018102788065),由此会使得制备工艺繁琐。此外,许多利用共价有机框架制备的忆阻器都为三层结构(底电极—薄膜—顶电极)并无阻挡层,顶电极一般都是采用热蒸镀或溅射的方式制备,而有机共价框架薄膜是一种有序的含一维通道的结构,其有较大的孔结构,直接在薄膜表面蒸镀或溅射极易使得金属侵入薄膜内部,相当于减少了薄膜厚度,提高了器件制备的偶然性。However, the synthesis methods of most COFs are cumbersome and the reaction time is long. Generally, they are synthesized by solvothermal method and need to be reacted for several days under high temperature and high pressure environment. For example, the article Towards High-Performance Resistive Switching Behavior through Embedding D-A System into 2D Imine-Linked The COF-TT-BT and COF-TT-TVT films synthesized by Covalent OrganicFrameworks need to be reacted at 120°C for 72h. Moreover, many memristors prepared using covalent organic frameworks are not grown by in-situ synthesis, and need to be transferred (for example, patent CN2018102788065), which will make the preparation process cumbersome. In addition, many memristors prepared using covalent organic frameworks have a three-layer structure (bottom electrode-film-top electrode) without a barrier layer. The top electrode is generally prepared by thermal evaporation or sputtering, while the organic The covalent frame film is an ordered structure with one-dimensional channels, which has a large pore structure. Direct evaporation or sputtering on the surface of the film can easily cause the metal to invade the interior of the film, which is equivalent to reducing the thickness of the film and improving the efficiency of the film. The contingency of device fabrication is eliminated.

基于上述理由,提出本申请。Based on the above reasons, this application is filed.

发明内容Contents of the invention

基于上述理由,针对现有技术中存在的问题或缺陷,本发明的目的在于提供一种基于共价有机框架(COF)薄膜的忆阻器及其制备方法,解决或至少部分解决现有技术中存在的上述技术缺陷。本发明的共价有机框架(COF)可在大气中、在较广的温度范围下,快速原位生长于各种平整衬底表面,并可通过改变芳香二醛混合溶液和芳香多胺混合溶液的浓度、摩尔量和反应时间,即可得到不同厚度的薄膜,便于制作不同厚度结构的忆阻器。Based on the above reasons, in view of the problems or defects in the prior art, the object of the present invention is to provide a memristor based on a covalent organic framework (COF) film and its preparation method, which solves or at least partially solves the existing problems in the prior art. The above-mentioned technical defect of existence. The covalent organic framework (COF) of the present invention can grow rapidly in situ on various flat substrate surfaces in the atmosphere and in a wide temperature range, and can be grown by changing the aromatic dialdehyde mixed solution and the aromatic polyamine mixed solution Films with different thicknesses can be obtained by changing the concentration, molar mass and reaction time, which is convenient for making memristors with different thickness structures.

为了实现本发明的上述第一个目的,本发明采用的技术方案如下:In order to realize above-mentioned first object of the present invention, the technical scheme that the present invention adopts is as follows:

一种基于共价有机框架(COF)薄膜的忆阻器,从下至上依次包括衬底,导电底电极,共价有机框架薄膜,有机聚合物阻挡层和导电顶电极。A memristor based on a covalent organic framework (COF) film, which sequentially includes a substrate, a conductive bottom electrode, a covalent organic framework film, an organic polymer barrier layer, and a conductive top electrode from bottom to top.

进一步地,上述技术方案,所述共价有机框架薄膜的厚度为100-150nm,所述有机聚合物阻挡层的厚度为60-200nm。Further, in the above technical solution, the thickness of the covalent organic framework film is 100-150 nm, and the thickness of the organic polymer barrier layer is 60-200 nm.

进一步地,上述技术方案,所述导电底电极厚度为60-200nm,所述导电顶电极的厚度为50-200nm,所述导电顶电极的厚度优选为60-100nm。Further, in the above technical solution, the thickness of the conductive bottom electrode is 60-200 nm, the thickness of the conductive top electrode is 50-200 nm, and the thickness of the conductive top electrode is preferably 60-100 nm.

进一步地,上述技术方案,所述衬底为玻璃、带有氧化层(SiO2)的硅片、聚对苯二甲酸乙二醇酯(PET)等中的任意一种。Further, in the above technical solution, the substrate is any one of glass, silicon wafer with an oxide layer (SiO 2 ), polyethylene terephthalate (PET), and the like.

进一步地,上述技术方案,所述导电底电极ITO、FTO、金或铂等中的任意一种。Further, in the above technical solution, the conductive bottom electrode is any one of ITO, FTO, gold or platinum.

进一步地,上述技术方案,所述导电顶电极为铝、金、铂、钛、钨、铌、镍、钴、铜、银或石墨烯等中的任意一种。Further, in the above technical solution, the conductive top electrode is any one of aluminum, gold, platinum, titanium, tungsten, niobium, nickel, cobalt, copper, silver, or graphene.

进一步地,上述技术方案,所述共价有机框架薄膜采用下述方法制得:在0-80℃下的大气环境下,将芳香二醛混合溶液和芳香多胺混合溶液混合,快速将所得混合液滴加于导电底电极表面或直接将带有导电底电极的衬底浸于所述混合液中,即可在衬底表面得到一层均匀的共价有机框架薄膜。Further, in the above technical solution, the covalent organic framework film is prepared by the following method: in an atmospheric environment at 0-80°C, mix the aromatic dialdehyde mixed solution and the aromatic polyamine mixed solution, and quickly mix the obtained Droplets are added to the surface of the conductive bottom electrode or the substrate with the conductive bottom electrode is directly immersed in the mixed liquid, so that a layer of uniform covalent organic framework film can be obtained on the substrate surface.

更进一步地,上述所述共价有机框架薄膜采用原位生长方式制得,具体操作步骤如下:Further, the covalent organic framework film described above is prepared by in-situ growth, and the specific operation steps are as follows:

按配比将芳香二醛混合溶液和芳香多胺混合溶液均匀混合后用移液枪取50-300μL滴加在带有导电底电极的衬底表面,等待2-15min,或将带有导电底电极的衬底直接浸于混合均匀的溶液中2-15min,然后取出衬底,用有机溶剂D清洗,去除多余反应物,最后在室温下干燥即可。Mix the aromatic dialdehyde mixed solution and the aromatic polyamine mixed solution evenly according to the ratio, then take 50-300 μL dropwise with a pipette gun on the surface of the substrate with a conductive bottom electrode, wait for 2-15 minutes, or put the conductive bottom electrode The substrate is directly immersed in the uniformly mixed solution for 2-15 minutes, then the substrate is taken out, washed with organic solvent D to remove excess reactants, and finally dried at room temperature.

优选地,上述技术方案,所述芳香二醛混合溶液和所述芳香多胺混合溶液中的芳香二醛和芳香多胺的物质的量的比为:(0.00002755~0.00005964):0.00002755。Preferably, in the above technical solution, the ratio of the amounts of aromatic dialdehydes and aromatic polyamines in the aromatic dialdehyde mixed solution to the aromatic polyamine mixed solution is: (0.00002755-0.00005964):0.00002755.

优选地,上述技术方案,所述芳香二醛混合溶液与芳香多胺混合溶液的体积比为1:1。Preferably, in the above technical solution, the volume ratio of the aromatic dialdehyde mixed solution to the aromatic polyamine mixed solution is 1:1.

优选地,上述技术方案,所述有机溶剂D为乙醇,异丙醇或二氯甲烷等中的任意一种。Preferably, in the above technical solution, the organic solvent D is any one of ethanol, isopropanol or methylene chloride.

优选地,上述技术方案,所述芳香二醛混合溶液采用下述方法配制而成:按配比称量芳香二醛,然后依次加入有机溶剂A、有机溶剂B和有机酸C,充分溶解,得到透明无色的芳香二醛混合溶液,其中,所述芳香二醛混合溶液中芳香二醛的浓度为0.00626~0.01355mol/L,有机酸的体积比为5%~10%。Preferably, in the above technical scheme, the aromatic dialdehyde mixed solution is prepared by the following method: weigh the aromatic dialdehyde according to the proportion, then add organic solvent A, organic solvent B and organic acid C in sequence, fully dissolve, and obtain transparent A colorless aromatic dialdehyde mixed solution, wherein the aromatic dialdehyde concentration in the aromatic dialdehyde mixed solution is 0.00626-0.01355 mol/L, and the volume ratio of the organic acid is 5%-10%.

优选地,上述技术方案,所述芳香多胺混合溶液采用下述方法配制而成:按配比称量芳香多胺,然后依次加入有机溶剂A、有机溶剂B和有机酸C,充分溶解,得到深绿色的芳香多胺混合溶液,其中,所述芳香多胺混合溶液中芳香多胺的浓度为0.00626mol/L,有机酸的体积比为5%-10%。Preferably, in the above technical scheme, the aromatic polyamine mixed solution is prepared by the following method: weigh the aromatic polyamine according to the proportion, then add organic solvent A, organic solvent B and organic acid C in sequence, fully dissolve, and obtain deep A green aromatic polyamine mixed solution, wherein the concentration of the aromatic polyamine in the aromatic polyamine mixed solution is 0.00626 mol/L, and the volume ratio of the organic acid is 5%-10%.

较优选地,上述技术方案,所述芳香二醛为对苯二甲醛、间苯二甲醛或联苯二甲醛等中的任意一种。More preferably, in the above technical solution, the aromatic dialdehyde is any one of terephthalaldehyde, isophthalaldehyde or biphenyldialdehyde.

较优选地,上述技术方案,所述芳香多胺为三(4-氨基苯基)胺(TAPA)。More preferably, in the above technical solution, the aromatic polyamine is tris(4-aminophenyl)amine (TAPA).

较优选地,上述技术方案,所述有机溶剂A为乙醇或异丙醇。More preferably, in the above technical scheme, the organic solvent A is ethanol or isopropanol.

较优选地,上述技术方案,所述有机溶剂B为均三甲苯。More preferably, in the above technical solution, the organic solvent B is mesitylene.

较优选地,上述技术方案,所述有机酸C为乙酸或丁二酸。More preferably, in the above technical solution, the organic acid C is acetic acid or succinic acid.

进一步地,上述技术方案,所述有机聚合物阻挡层采用下述方法制备而成:Further, in the above technical solution, the organic polymer barrier layer is prepared by the following method:

在80-100℃下,将有机聚合物A溶于液体B中,得到胶状溶液,采用旋涂法将所述胶状溶液旋涂于共价有机框架薄膜表面即可。The organic polymer A is dissolved in the liquid B at 80-100° C. to obtain a colloidal solution, and the colloidal solution is spin-coated on the surface of the covalent organic framework film by a spin coating method.

较优选地,上述技术方案,所述有机聚合物A为聚乙烯醇(PVA)或聚甲基丙烯酸甲酯(PMMA)。More preferably, in the above technical solution, the organic polymer A is polyvinyl alcohol (PVA) or polymethyl methacrylate (PMMA).

较优选地,上述技术方案,所述液体B为去离子水、二氯甲烷、二甲基亚砜、二氯乙烷、三氯甲烷、丙酮、甲乙酮、苯、氯苯或四氢呋喃等中的任意一种。需要说明的是,因PVA几乎不溶于有机溶剂,因此当有机聚合物A为聚乙烯醇(PVA)时,其对应采用的液体B必须是去离子水。More preferably, in the above technical scheme, the liquid B is any one of deionized water, dichloromethane, dimethyl sulfoxide, dichloroethane, chloroform, acetone, methyl ethyl ketone, benzene, chlorobenzene or tetrahydrofuran, etc. A sort of. It should be noted that since PVA is almost insoluble in organic solvents, when the organic polymer A is polyvinyl alcohol (PVA), the corresponding liquid B must be deionized water.

较优选地,上述技术方案,所述胶状溶液中聚合物A与液体B的质量体积比(聚合物质量:液体体积)为1~20mg/mL。More preferably, in the above technical solution, the mass volume ratio of the polymer A to the liquid B in the colloidal solution (polymer mass: liquid volume) is 1-20 mg/mL.

本发明的第二个目的在于提供上述所述基于共价有机框架(COF)薄膜的忆阻器的制备方法,所述方法具体包括如下步骤:The second object of the present invention is to provide a method for preparing the above-mentioned memristor based on a covalent organic framework (COF) film, and the method specifically includes the following steps:

(1)将带有导电底电极的衬底清洗干净,然后干燥;(1) The substrate with the conductive bottom electrode is cleaned, then dried;

(2)在洁净干燥的底电极表面生长共价有机框架薄膜,然后干燥;(2) growing a covalent organic framework film on the surface of the clean and dry bottom electrode, and then drying;

(3)在所述共价有机框架薄膜上旋涂胶体溶液,得到有机聚合物阻挡层;(3) Spin coating a colloidal solution on the covalent organic framework film to obtain an organic polymer barrier layer;

(4)采用热蒸镀或磁控溅射的方式在有机聚合物阻挡层表面制备导电顶电极。(4) Prepare a conductive top electrode on the surface of the organic polymer barrier layer by means of thermal evaporation or magnetron sputtering.

与现有技术相比,本发明的优势在于:Compared with the prior art, the present invention has the advantages of:

(1)本发明可在较广的温度范围下,快速(10min左右)原位生长各种平整衬底表面,且制备方法简单,不涉及精密昂贵的仪器,本发明所使用到的药品也都是工厂可大规模生产的药品,价格经济。(1) The present invention can rapidly (about 10 minutes) in-situ grow various flat substrate surfaces in a wide temperature range, and the preparation method is simple, does not involve sophisticated and expensive instruments, and the medicines used in the present invention are all It is a medicine that can be mass-produced in factories, and the price is economical.

(2)本发明中的忆阻器由5层结构组成,从下至上分别为衬底,导电底电极,共价有机骨架薄膜,有机物阻挡层和导电顶电极。衬底和导电底电极可视为一个部分,例如可以为带ITO的玻璃片或带金属膜的硅片,只起到一个支撑和导电的作用,所以其厚度对于器件的性能并无明显影响;共价有机骨架薄膜是核心结构,其是忆阻器能发生阻变的核心,厚度100nm左右性能最好,最稳定,过薄容易击穿成为导体,过厚难以发生阻变;有机阻挡层主要起到防止金属顶电极侵入的作用,这也是本发明同许多其他发明的不同之处。本发明顶电极采用溅射或热蒸镀的方式制备,若无阻挡层,金属便会随机进入薄膜内部,极大提高器件制备的偶然性,降低器件的稳定性;导电顶电极和底电极都起到导电的作用,但顶电极厚度在60-100nm最佳,过薄容易在测试时被测试针刺穿导致无法测试,而过厚就需要增加溅射或热蒸镀的时间,可能对薄膜有损伤且增加成本。(2) The memristor in the present invention consists of a five-layer structure, which are substrate, conductive bottom electrode, covalent organic framework film, organic barrier layer and conductive top electrode from bottom to top. The substrate and the conductive bottom electrode can be regarded as one part, for example, it can be a glass sheet with ITO or a silicon sheet with a metal film, which only plays a supporting and conductive role, so its thickness has no obvious impact on the performance of the device; The covalent organic framework film is the core structure, which is the core of memristor resistance change. The thickness of about 100nm has the best performance and the most stable. If it is too thin, it is easy to break down and become a conductor. It plays the role of preventing the intrusion of the metal top electrode, which is also the difference between the present invention and many other inventions. The top electrode of the present invention is prepared by sputtering or thermal evaporation. If there is no barrier layer, the metal will randomly enter the inside of the film, which greatly improves the contingency of device preparation and reduces the stability of the device; both the conductive top electrode and the bottom electrode are However, the thickness of the top electrode is 60-100nm. If it is too thin, it is easy to be pierced by the test needle during the test and cannot be tested. If it is too thick, it will need to increase the time of sputtering or thermal evaporation, which may affect the film. damage and increase costs.

附图说明Description of drawings

图1为本发明的基于共价有机框架(COF)薄膜的忆阻器的结构示意图;Fig. 1 is the structural representation of the memristor based on covalent organic framework (COF) film of the present invention;

图2为实施例1制备的忆阻器的开关特性曲线;Fig. 2 is the switching characteristic curve of the memristor prepared in embodiment 1;

图3为实施例1制备的忆阻器的的循环稳定性测试结果;Fig. 3 is the cycle stability test result of the memristor prepared in embodiment 1;

图4为实施例2制备的忆阻器的开关特性曲线;Fig. 4 is the switching characteristic curve of the memristor prepared in embodiment 2;

图5为实施例2制备的忆阻器的的循环稳定性测试结果;Fig. 5 is the cycle stability test result of the memristor prepared in embodiment 2;

图6为实施例3制备的忆阻器的开关特性曲线;Fig. 6 is the switching characteristic curve of the memristor prepared in embodiment 3;

图7为实施例3制备的忆阻器的的循环稳定性测试结果;Fig. 7 is the cycle stability test result of the memristor prepared in embodiment 3;

图8为实施例4制备的忆阻器的开关特性曲线;Fig. 8 is the switching characteristic curve of the memristor prepared in embodiment 4;

图9为实施例4制备的忆阻器的的循环稳定性测试结果;Fig. 9 is the cycle stability test result of the memristor prepared in embodiment 4;

图10为实施例2制备的共价有机框架薄膜的扫描电镜图像;Figure 10 is a scanning electron microscope image of the covalent organic framework film prepared in Example 2;

图11为实施例4制备的共价有机框架薄膜薄膜的扫描电镜图像。FIG. 11 is a scanning electron microscope image of the covalent organic framework film prepared in Example 4.

具体实施方式Detailed ways

下面通过实施案例对本发明作进一步详细说明。The present invention will be described in further detail below through examples of implementation.

为了更好地理解本发明而不是限制本发明的范围,在本申请中所用的表示用量、百分比的所有数字、以及其他数值,在所有情况下都应理解为以词语“大约”所修饰。因此,除非特别说明,否则在说明书中所列出的数字参数都是近似值,其可能会根据试图获得的理想性质的不同而加以改变。各个数字参数至少应被看作是根据所报告的有效数字和通过常规的四舍五入方法而获得的。In order to better understand the present invention but not to limit the scope of the present invention, all figures representing dosage, percentage, and other numerical values used in this application should be understood as being modified by the word "about" in all cases. Accordingly, unless otherwise indicated, the numerical parameters set forth in the specification are approximations that may vary depending upon different properties sought to be obtained. At a minimum, each numerical parameter should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

本发明提供了一种基于共价有机框架薄膜的忆阻器,其结构从下至上为:衬底、导电底电极、共价有机框架薄膜、有机聚合物薄膜和导电顶电极。忆阻器制备包括以下步骤:在0-80℃下,将特定的芳香二醛混合溶液和芳香多胺混合溶液混合,滴加在所需导电底电极上或直接将带有导电底电极的衬底浸于混合溶液中,即可在底电极上得到均匀的共价有机框架薄膜用于忆阻器。之后制备聚合物胶体溶液,将其旋涂于共价有机框架薄膜表面,最后使用掩膜版采用热蒸镀或溅射制备顶电极。本发明首次提出一种新型忆阻器的制备方法,该制备方法过程简单,价格经济,无需高精度的精密仪器,在无需复杂环境的条件下即可在衬底上原位生长制备大面积的共价有机框架(COF)薄膜。The invention provides a memristor based on a covalent organic frame film, which has a structure from bottom to top: a substrate, a conductive bottom electrode, a covalent organic frame film, an organic polymer film and a conductive top electrode. The preparation of the memristor includes the following steps: at 0-80°C, mix a specific aromatic dialdehyde mixed solution and an aromatic polyamine mixed solution, drop it on the desired conductive bottom electrode or directly put the substrate with the conductive bottom electrode By immersing the bottom electrode in the mixed solution, a uniform covalent organic framework film can be obtained on the bottom electrode for the memristor. Then a polymer colloid solution is prepared, which is spin-coated on the surface of the covalent organic framework film, and finally the top electrode is prepared by thermal evaporation or sputtering using a mask. The present invention proposes a new type of memristor preparation method for the first time. The preparation method is simple in process, economical in price, does not require high-precision precision instruments, and can grow large-area memristors in situ on a substrate without complicated environments. Covalent organic framework (COF) films.

在本发明的具体实施方式中,所涉及的仪器如下:In the specific embodiment of the present invention, involved instrument is as follows:

超声清洗仪Ultrasonic cleaner

旋涂仪Spin coater

热蒸发镀膜仪Thermal evaporation coater

Agilent Techolodies B1500A半导体器件分析仪和探针台Agilent Technologies B1500A Semiconductor Device Analyzer and Probe Station

扫描电子显微镜scanning electron microscope

所涉及的药品购买源为:The drug purchase sources involved are:

芳香二醛和芳香多胺购自上海源叶生物科技有限公司,其余试剂购自国药集团,纯度为分析纯。Aromatic dialdehydes and aromatic polyamines were purchased from Shanghai Yuanye Biotechnology Co., Ltd., and other reagents were purchased from Sinopharm Group, and the purity was analytically pure.

测试方法说明:Description of test method:

开关特性曲线:利用Agilent Techolodies B1500A半导体器件分析仪和探针台进行测试,在导电顶电极上施加电压,导电底电极接地,测试电压施加方式为0V→负截止电压→0V→正截止电压→0V,与测试结果对应,以图2为例,0V→负截止电压对应图中的1,负截止电压→0V对应图中的2,0V→正截止电压对应图中的3,正截止电压→0V对应图中的4。正电压扫描(即0V→正截止电压→0V)过程中的步长为正截止电压/100,负电压扫描(即0V→负截止电压→0V)过程中的步长为负截止电压/100。Switching characteristic curve: use Agilent Techolodies B1500A semiconductor device analyzer and probe station to test, apply voltage on the conductive top electrode, and ground the conductive bottom electrode. The test voltage application method is 0V→negative cut-off voltage→0V→positive cut-off voltage→0V , corresponding to the test results, taking Figure 2 as an example, 0V→negative cut-off voltage corresponds to 1 in the figure, negative cut-off voltage→0V corresponds to 2 in the figure, 0V→positive cut-off voltage corresponds to 3 in the figure, positive cut-off voltage→0V Corresponding to 4 in the figure. The step size in the process of positive voltage scanning (ie 0V→positive cut-off voltage→0V) is positive cut-off voltage/100, and the step size in the process of negative voltage scan (ie 0V→negative cut-off voltage→0V) is negative cut-off voltage/100.

循环稳定性测试:即重复进行开关特性测试,一次开关特性曲线(即电压0V→负截止电压→0V→正截止电压→0V的扫描)视为一次循环,利用半导体分析仪自带的循环测试功能测试重复进行开关特性测试,之后根据不同器件本身性能选取所有循环某一电压点的两个电阻值进行绘图。以实施例1为例,选取0.25V时的高阻态和低阻态的两个点的电阻值,对所有循环都取0.25V时的电阻值,再进行绘图,即可得循环稳定性测试散点图。Cyclic stability test: repeat the switching characteristic test, a switching characteristic curve (i.e. voltage 0V → negative cut-off voltage → 0V → positive cut-off voltage → 0V scan) is regarded as a cycle, using the cycle test function that comes with the semiconductor analyzer The test repeats the switching characteristic test, and then selects two resistance values at a certain voltage point in all cycles according to the performance of different devices for drawing. Taking Example 1 as an example, select the resistance values of the two points of the high-resistance state and the low-resistance state at 0.25V, and take the resistance value at 0.25V for all cycles, and then draw the graph to obtain the cycle stability test scatterplot.

实施例1Example 1

本实施例的一种基于共价有机框架(COF)薄膜的忆阻器,从下至上依次包括衬底,导电底电极,共价有机框架薄膜,有机聚合物阻挡层和导电顶电极;其中:所述衬底、导电底电极、共价有机框架薄膜、有机聚合物阻挡层和导电顶电极的厚度依次为1cm、100nm、150nm、50nm和60nm。A memristor based on a covalent organic framework (COF) film in this embodiment includes a substrate, a conductive bottom electrode, a covalent organic framework film, an organic polymer barrier layer, and a conductive top electrode from bottom to top; wherein: The thicknesses of the substrate, conductive bottom electrode, covalent organic framework film, organic polymer barrier layer and conductive top electrode are 1 cm, 100 nm, 150 nm, 50 nm and 60 nm in sequence.

上述所述基于共价有机框架(COF)薄膜的忆阻器采用下述方法制备而成,具体步骤如下:The above-mentioned memristor based on covalent organic framework (COF) film is prepared by the following method, and the specific steps are as follows:

(1)将2cm×2cm×1cm的ITO玻璃清洗干净,放在玻璃清洗架上,将其浸于超纯水超声清洗30min,之后换成丙酮超声清洗30min,最后换成无水乙醇超声清洗30min,最后取出,放在60℃的干燥箱内干燥6h。(1) Clean the 2cm×2cm×1cm ITO glass, put it on the glass cleaning rack, immerse it in ultrapure water for ultrasonic cleaning for 30 minutes, then replace it with acetone for ultrasonic cleaning for 30 minutes, and finally replace it with absolute ethanol for 30 minutes , and finally take it out and dry it in a drying oven at 60°C for 6 hours.

(2)在小称量瓶内称量8mg的对苯二甲醛,先后加入2ml的无水乙醇、2ml的均三甲苯和400μL的乙酸;在另一个小称量瓶内称量8mg的三(4-氨基苯基)胺(TAPA),加入2ml的乙醇、2ml的均三甲苯和400μL的乙酸,待其充分溶解后,将两瓶溶液混合均匀;取200μL滴加于水平放置的ITO表面,待其反应10min后,用乙醇冲洗未反应完的溶液,在室温下干燥12h,得到共价有机框架薄膜;其中:(2) Weigh 8 mg of terephthalaldehyde in a small weighing bottle, successively add 2 ml of absolute ethanol, 2 ml of mesitylene and 400 μL of acetic acid; weigh 8 mg of tris( 4-Aminophenyl) amine (TAPA), add 2ml of ethanol, 2ml of mesitylene and 400μL of acetic acid, after it is fully dissolved, mix the two bottles of solution evenly; take 200μL dropwise on the surface of ITO placed horizontally, After reacting for 10 minutes, rinse the unreacted solution with ethanol, and dry at room temperature for 12 hours to obtain a covalent organic framework film; wherein:

对苯二甲醛混合溶液和TAPA混合溶液中的对苯二甲醛与TAPA的物质的量的比为0.00005964:0.00002755。The ratio of the amount of terephthalaldehyde to TAPA in the terephthalaldehyde mixed solution and the TAPA mixed solution is 0.00005964:0.00002755.

(3)制备PVA胶状液体:取0.2g聚乙烯醇(PVA)(分子量为1750±50)在90℃下溶于10ml超纯水,得到胶状溶液;取40μL所述胶状溶液旋涂于共价有机框架薄膜表面,旋涂参数为3000rmp,旋涂时间为20s,得到有机聚合物阻挡层。(3) Preparation of PVA colloidal liquid: take 0.2g polyvinyl alcohol (PVA) (molecular weight is 1750 ± 50) and dissolve in 10ml ultrapure water at 90°C to obtain a colloidal solution; take 40 μL of the colloidal solution for spin coating On the surface of the covalent organic framework film, the spin coating parameter is 3000rmp, and the spin coating time is 20s to obtain an organic polymer barrier layer.

(4)用掩膜版在有机聚合物阻挡层表面蒸镀Al电极。(4) Evaporate an Al electrode on the surface of the organic polymer barrier layer with a mask.

用半导体器件分析仪测试本实施例制备的基于共价有机框架(COF)薄膜的忆阻器器件的I-V特性。The I-V characteristics of the covalent organic framework (COF) film-based memristor device prepared in this example were tested with a semiconductor device analyzer.

图2即为实施例1制备的忆阻器的开关特性曲线,其曲线变化方向如箭头所示,忆阻器的初始阻态为高阻态,同许多忆阻器不同的是,该忆阻器需要用负扫描电压使其进入低阻态。如图2所示,开始以0V→-1.5V→0V的电压扫描,限制电流为A,在电压为-0.25V时,会使忆阻器由高阻态转换为低阻态。之后以0V→1V→0V的电压扫描,在电压为0.7V时,会使忆阻器由低阻态转换为高阻态。Fig. 2 is the switching characteristic curve of the memristor prepared in Example 1, and the direction of the change of the curve is shown by the arrow, and the initial resistance state of the memristor is a high resistance state. Unlike many memristors, the memristor The device requires a negative scan voltage to bring it into a low-impedance state. As shown in Figure 2, start scanning with a voltage of 0V→-1.5V→0V, limit the current to A, and when the voltage is -0.25V, the memristor will be converted from a high-impedance state to a low-impedance state. Afterwards, the voltage of 0V→1V→0V is scanned, and when the voltage is 0.7V, the memristor will be converted from a low resistance state to a high resistance state.

图3为实施例1制备的忆阻器的的循环稳定性测试结果,对其进行反复擦除和写入的过程,发现其具有良好的稳定性,开关比约为100,可进行33次正常操作。Fig. 3 is the cycle stability test result of the memristor prepared in Example 1, it is repeatedly erased and written in the process, it is found that it has good stability, the on-off ratio is about 100, and it can be normal for 33 times operate.

实施例2Example 2

本实施例的一种基于共价有机框架(COF)薄膜的忆阻器,从下至上依次包括衬底,导电底电极,共价有机框架薄膜,有机聚合物阻挡层和导电顶电极;其中:所述衬底、导电底电极、共价有机框架薄膜、有机聚合物阻挡层和导电顶电极的厚度依次为2cm、100nm、90nm、50nm和60nm。A memristor based on a covalent organic framework (COF) film in this embodiment includes a substrate, a conductive bottom electrode, a covalent organic framework film, an organic polymer barrier layer, and a conductive top electrode from bottom to top; wherein: The thicknesses of the substrate, conductive bottom electrode, covalent organic framework film, organic polymer barrier layer and conductive top electrode are 2cm, 100nm, 90nm, 50nm and 60nm in sequence.

上述所述基于共价有机框架(COF)薄膜的忆阻器采用下述方法制备而成,具体步骤如下:The above-mentioned memristor based on covalent organic framework (COF) film is prepared by the following method, and the specific steps are as follows:

(1)将2cm×2cm×2cm的ITO玻璃清洗干净,放在玻璃清洗架上,将其浸于超纯水超声清洗30min,之后换成丙酮超声清洗30min,最后换成无水乙醇超声清洗30min,最后取出,放在60℃的干燥箱内干燥6h。(1) Clean the 2cm×2cm×2cm ITO glass, put it on the glass cleaning rack, immerse it in ultrapure water for ultrasonic cleaning for 30 minutes, then replace it with acetone for ultrasonic cleaning for 30 minutes, and finally replace it with absolute ethanol for 30 minutes , and finally take it out and dry it in a drying oven at 60°C for 6 hours.

(2)在小称量瓶内称量10mg的联苯二甲醛,先后加入2ml的无水乙醇、2ml的均三甲苯和400μL的乙酸;在另一个小称量瓶内称量8mg的三(4-氨基苯基)胺(TAPA),加入2ml的乙醇、2ml的均三甲苯和400μL的乙酸,待其充分溶解后,将两瓶溶液混合,取200μL滴加于水平放置的ITO表面,待其反应7min后,用乙醇冲洗未反应完的溶液,在室温下干燥12h,得到共价有机框架薄膜;其中:(2) Weigh 10 mg of biphenyldiformaldehyde in a small weighing bottle, successively add 2 ml of absolute ethanol, 2 ml of mesitylene and 400 μL of acetic acid; weigh 8 mg of tris( 4-Aminophenyl)amine (TAPA), add 2ml of ethanol, 2ml of mesitylene and 400μL of acetic acid, after it is fully dissolved, mix the two bottles of solutions, take 200μL dropwise on the surface of ITO placed horizontally, wait After reacting for 7 minutes, the unreacted solution was rinsed with ethanol, and dried at room temperature for 12 hours to obtain a covalent organic framework film; wherein:

联苯二甲醛混合溶液和TAPA混合溶液中的联苯二甲醛与TAPA的物质的量的比为0.0000439:0.00002755。The ratio of the amount of biphenyldiformaldehyde to TAPA in the biphenyldiformaldehyde mixed solution and the TAPA mixed solution is 0.0000439:0.00002755.

(3)制备PVA胶状液体:取0.1g PVA在90℃下溶于10ml超纯水,得到胶状溶液,取40μL所述胶状溶液旋涂于共价有机框架薄膜表面,旋涂参数为3000rmp,旋涂时间为20s,得到有机聚合物阻挡层。(3) Preparation of PVA colloidal liquid: Take 0.1g PVA and dissolve it in 10ml ultrapure water at 90°C to obtain a colloidal solution. Take 40 μL of the colloidal solution and spin-coat it on the surface of the covalent organic framework film. The spin-coating parameters are 3000rmp, spin-coating time is 20s to obtain an organic polymer barrier layer.

(4)用掩膜版在有机框架薄膜PVA表面溅射钨电极。(4) Sputtering a tungsten electrode on the surface of the organic frame film PVA with a mask.

用半导体器件分析仪测试本实施例制备的基于共价有机框架(COF)薄膜的忆阻器器件的I-V特性。The I-V characteristics of the covalent organic framework (COF) film-based memristor device prepared in this example were tested with a semiconductor device analyzer.

图4即为实施例2制备的忆阻器的开关特性曲线,其曲线变化方向如箭头所示(箭头顺序同图2一致),忆阻器的初始阻态为高阻态,同许多忆阻器不同的是,该忆阻器需要用负扫描电压使其进入低阻态。如图4所示,开始以0V→-1.2V→0V的电压扫描,限制电流为A,在电压为-1.15V时,会使忆阻器由高阻态转换为低阻态。之后以0V→2V→0V的电压扫描,在电压为0.4V时,会使忆阻器由低阻态转换为高阻态。Fig. 4 is the switching characteristic curve of the memristor prepared in Example 2, and the direction of the curve change is as shown by the arrows (the order of the arrows is consistent with that in Fig. 2), and the initial resistance state of the memristor is a high resistance state, which is the same as that of many memristors. Unlike memristors, this memristor requires a negative sweep voltage to bring it into a low-impedance state. As shown in Figure 4, start scanning with a voltage of 0V→-1.2V→0V, limit the current to A, and when the voltage is -1.15V, the memristor will switch from a high-impedance state to a low-impedance state. Afterwards, the voltage of 0V→2V→0V is scanned, and when the voltage is 0.4V, the memristor will be converted from a low-resistance state to a high-resistance state.

图5为实施例2制备的忆阻器的的循环稳定性测试结果,对其进行反复擦除和写入的过程,发现其具有良好的稳定性,开关可进行65次正常操作。Fig. 5 is the cycle stability test result of the memristor prepared in Example 2. It is found that the memristor has good stability after repeated erasing and writing, and the switch can perform 65 normal operations.

实施例3Example 3

本实施例的一种基于共价有机框架(COF)薄膜的忆阻器,从下至上依次包括衬底,导电底电极,共价有机框架薄膜,有机聚合物阻挡层和导电顶电极;其中:所述衬底、导电底电极、共价有机框架薄膜、有机聚合物阻挡层和导电顶电极的厚度依次为1cm、100nm、150nm、50nm和60nm。A memristor based on a covalent organic framework (COF) film in this embodiment includes a substrate, a conductive bottom electrode, a covalent organic framework film, an organic polymer barrier layer, and a conductive top electrode from bottom to top; wherein: The thicknesses of the substrate, conductive bottom electrode, covalent organic framework film, organic polymer barrier layer and conductive top electrode are 1 cm, 100 nm, 150 nm, 50 nm and 60 nm in sequence.

上述所述基于共价有机框架(COF)薄膜的忆阻器采用下述方法制备而成,具体步骤如下:The above-mentioned memristor based on covalent organic framework (COF) film is prepared by the following method, and the specific steps are as follows:

(1)将2cm×2cm×1cm的ITO玻璃清洗干净,放在玻璃清洗架上,将其浸于超纯水超声清洗30min,之后换成丙酮超声清洗30min,最后换成无水乙醇超声清洗30min,最后取出,放在60℃的干燥箱内干燥6h。(1) Clean the 2cm×2cm×1cm ITO glass, put it on the glass cleaning rack, immerse it in ultrapure water for ultrasonic cleaning for 30 minutes, then replace it with acetone for ultrasonic cleaning for 30 minutes, and finally replace it with absolute ethanol for 30 minutes , and finally take it out and dry it in a drying oven at 60°C for 6 hours.

(2)在小称量瓶内称量8mg的对苯二甲醛,先后加入2ml的无水乙醇、2ml的均三甲苯和400μL的乙酸;在另一个小称量瓶内称量8mg的三(4-氨基苯基)胺(TAPA),加入2ml的乙醇、2ml的均三甲苯和400μL的乙酸,待其充分溶解后,将两瓶溶液混合,取200μL滴加于水平放置的ITO表面,待其反应10min后,用乙醇冲洗未反应完的溶液,在室温下干燥12h,得到共价有机框架薄膜;其中:(2) Weigh 8 mg of terephthalaldehyde in a small weighing bottle, successively add 2 ml of absolute ethanol, 2 ml of mesitylene and 400 μL of acetic acid; weigh 8 mg of tris( 4-Aminophenyl)amine (TAPA), add 2ml of ethanol, 2ml of mesitylene and 400μL of acetic acid, after it is fully dissolved, mix the two bottles of solutions, take 200μL dropwise on the surface of ITO placed horizontally, wait After reacting for 10 minutes, rinse the unreacted solution with ethanol, and dry at room temperature for 12 hours to obtain a covalent organic framework film; wherein:

对苯二甲醛混合溶液和TAPA混合溶液中的对苯二甲醛与TAPA的物质的量的比为0.00005964:0.00002755。The ratio of the amount of terephthalaldehyde to TAPA in the terephthalaldehyde mixed solution and the TAPA mixed solution is 0.00005964:0.00002755.

(3)制备PMMA胶状液体:取0.1g PMMA在90℃下溶于20ml氯苯,得到胶状溶液,取40μL所述胶状溶液旋涂于共价有机框架薄膜表面,旋涂参数为3000rmp,旋涂时间为20s,得到有机聚合物阻挡层。(3) Preparation of PMMA colloidal liquid: get 0.1g PMMA and dissolve it in 20ml chlorobenzene at 90°C to obtain a colloidal solution, get 40 μL of the colloidal solution and spin-coat it on the surface of the covalent organic framework film, and the spin-coating parameter is 3000rmp , and the spin coating time was 20s to obtain an organic polymer barrier layer.

(4)用掩膜版在有机聚合物阻挡层PMMA表面溅射钨电极。(4) Sputtering a tungsten electrode on the surface of the organic polymer barrier layer PMMA with a mask.

用半导体器件分析仪测试本实施例制备的基于共价有机框架(COF)薄膜的忆阻器器件的I-V特性。The I-V characteristics of the covalent organic framework (COF) film-based memristor device prepared in this example were tested with a semiconductor device analyzer.

图6即为实施例3制备的忆阻器的开关特性曲线,其曲线变化方向如箭头所示(箭头顺序同图2一致),忆阻器的初始阻态为高阻态,同许多忆阻器不同的是,该忆阻器需要用负扫描电压使其进入低阻态。如图6所示,开始以0V→-2V→0V的电压扫描,限制电流为A,会使忆阻器由高阻态转换为低阻态。之后以0V→2.2V→0V的电压扫描,会使忆阻器由低阻态转换为高阻态。Fig. 6 is the switching characteristic curve of the memristor prepared in Example 3, and the change direction of the curve is as shown by the arrows (the order of the arrows is consistent with that in Fig. 2), and the initial resistance state of the memristor is a high resistance state, which is the same as that of many memristors. Unlike memristors, this memristor requires a negative sweep voltage to bring it into a low-impedance state. As shown in Figure 6, start to scan with a voltage of 0V→-2V→0V, and limit the current to A, which will make the memristor switch from a high-impedance state to a low-impedance state. Afterwards, a voltage sweep of 0V→2.2V→0V will cause the memristor to switch from a low-resistance state to a high-resistance state.

图7为实施例3制备的忆阻器的的循环稳定性测试结果,对其进行反复擦除和写入的过程,发现其具有良好的稳定性,开关比约为100,可进行105次正常操作。Figure 7 shows the cycle stability test results of the memristor prepared in Example 3. It was repeatedly erased and written, and it was found to have good stability. The on-off ratio is about 100, and 105 times of normal operate.

实施例4Example 4

本实施例的一种基于共价有机框架(COF)薄膜的忆阻器,从下至上依次包括衬底,导电底电极,共价有机框架薄膜,有机聚合物阻挡层和导电顶电极;其中:所述衬底、导电底电极、共价有机框架薄膜、有机聚合物阻挡层和导电顶电极的厚度依次为2cm、100nm、800nm、50nm和60nm。A memristor based on a covalent organic framework (COF) film in this embodiment includes a substrate, a conductive bottom electrode, a covalent organic framework film, an organic polymer barrier layer, and a conductive top electrode from bottom to top; wherein: The thicknesses of the substrate, conductive bottom electrode, covalent organic framework film, organic polymer barrier layer and conductive top electrode are 2cm, 100nm, 800nm, 50nm and 60nm in sequence.

上述所述基于共价有机框架(COF)薄膜的忆阻器采用下述方法制备而成,具体步骤如下:The above-mentioned memristor based on covalent organic framework (COF) film is prepared by the following method, and the specific steps are as follows:

(1)将2cm×2cm×2cm的ITO玻璃清洗干净,放在玻璃清洗架上,将其浸于超纯水超声清洗30min,之后换成丙酮超声清洗30min,最后换成无水乙醇超声清洗30min,最后取出,放在60℃的干燥箱内干燥6h。(1) Clean the 2cm×2cm×2cm ITO glass, put it on the glass cleaning rack, immerse it in ultrapure water for ultrasonic cleaning for 30 minutes, then replace it with acetone for ultrasonic cleaning for 30 minutes, and finally replace it with absolute ethanol for 30 minutes , and finally take it out and dry it in a drying oven at 60°C for 6 hours.

(2)在小称量瓶内称量10mg的联苯二甲醛,先后加入2ml的无水乙醇、2ml的均三甲苯和400μL的乙酸;在另一个小称量瓶内称量8mg的三(4-氨基苯基)胺(TAPA),加入2ml的乙醇、2ml的均三甲苯和400μL的乙酸,待其充分溶解后,将两瓶溶液混合,取300μL滴加于水平放置的ITO表面,待其反应15min后,用乙醇冲洗未反应完的溶液,在室温下干燥12h,得到共价有机框架薄膜;其中:(2) Weigh 10 mg of biphenyldiformaldehyde in a small weighing bottle, successively add 2 ml of absolute ethanol, 2 ml of mesitylene and 400 μL of acetic acid; weigh 8 mg of tris( 4-Aminophenyl)amine (TAPA), add 2ml of ethanol, 2ml of mesitylene and 400μL of acetic acid, after it is fully dissolved, mix the two bottles of solutions, take 300μL dropwise on the surface of ITO placed horizontally, wait After reacting for 15 minutes, the unreacted solution was rinsed with ethanol, and dried at room temperature for 12 hours to obtain a covalent organic framework film; wherein:

联苯二甲醛混合溶液和TAPA混合溶液中的联苯二甲醛与TAPA的物质的量的比为0.0000549:0.00002755。The ratio of the amount of biphenyldiformaldehyde to TAPA in the biphenyldiformaldehyde mixed solution and the TAPA mixed solution is 0.0000549:0.00002755.

(3)制备PVA胶状液体:取0.2g聚乙烯醇(PVA)(分子量为1750±50)在90℃下溶于10ml超纯水,得到胶状溶液,取40μL所述胶状溶液旋涂于共价有机框架薄膜表面,旋涂参数为3000rmp,旋涂时间为20s,得到有机聚合物阻挡层。(3) Preparation of PVA colloidal liquid: take 0.2g polyvinyl alcohol (PVA) (molecular weight: 1750±50) and dissolve it in 10ml ultrapure water at 90°C to obtain a colloidal solution, and take 40 μL of the colloidal solution for spin coating On the surface of the covalent organic framework film, the spin coating parameter is 3000rmp, and the spin coating time is 20s to obtain an organic polymer barrier layer.

(4)用自制掩膜版在有机聚合物阻挡层PVA表面溅射钨电极。(4) A tungsten electrode was sputtered on the surface of the organic polymer barrier layer PVA with a self-made mask.

用半导体器件分析仪测试本实施例制备的基于共价有机框架(COF)薄膜的忆阻器器件的I-V特性。The I-V characteristics of the covalent organic framework (COF) film-based memristor device prepared in this example were tested with a semiconductor device analyzer.

图8即为实施例4制备的忆阻器的开关特性曲线,其曲线变化方向如箭头所示,忆阻器的初始阻态为高阻态,由于反应单体的物质的量增加,反应时间也延长,所以薄膜厚度增加,需要用正扫描电压使其进入低阻态。如图8所示,开始以0V→3V→0V的电压扫描,会使忆阻器由高阻态转换为低阻态,未限制电流,组态变化和实施例2不同,是缓变而非突变。之后以0V→-3V→0V的电压扫描,会使忆阻器由低阻态转换为高阻态。Fig. 8 is the switching characteristic curve of the memristor prepared in Example 4, and the direction of the change of the curve is as shown by the arrow. The initial resistance state of the memristor is a high resistance state. Due to the increase in the amount of the reacting monomer, the reaction time It is also extended, so the thickness of the film increases, and it is necessary to use a positive scanning voltage to make it enter a low-resistance state. As shown in Figure 8, starting to scan with a voltage of 0V→3V→0V will cause the memristor to switch from a high-resistance state to a low-resistance state without limiting the current. mutation. Afterwards, a voltage sweep of 0V→-3V→0V will cause the memristor to switch from a low-resistance state to a high-resistance state.

图9为实施例4制备的忆阻器的的循环稳定性测试结果,对其进行反复擦除和写入的过程,发现其具有良好的稳定性,开关可进行34次正常操作。Fig. 9 shows the cycle stability test results of the memristor prepared in Example 4. After repeated erasing and writing, it is found that it has good stability, and the switch can perform 34 normal operations.

与实施例2相比,实施例4增加了反应溶液的量(200μL→300μL),增加了反应时间(7min→15min),从测试结果来看,实施例4的循环稳定性较差,尤其是高阻的保持特性较差,且循环次数明显小于实施例2。分别对其进行SEM表征发现,实施例2(图10)的共价有机框架薄膜厚度约为90nm,且表面较为平整,整体厚度较为均匀;而实施例4(图11)的共价有机框架薄膜厚度约为800nm,且厚度不均匀,在表面还有许多团聚物,因此可看出改变反应时间和反应物的量可改变薄膜厚度,推测厚度和均匀度应是决定其性能差异的原因。Compared with Example 2, Example 4 increased the amount of reaction solution (200 μ L → 300 μ L), increased the reaction time (7min → 15min), from the test results, the cycle stability of Example 4 is relatively poor, especially The retention characteristic of high resistance is poor, and the number of cycles is significantly smaller than that of Example 2. SEM characterization was carried out on them, and it was found that the thickness of the covalent organic framework film in Example 2 (Figure 10) was about 90nm, and the surface was relatively smooth, and the overall thickness was relatively uniform; The thickness is about 800nm, and the thickness is not uniform, and there are many aggregates on the surface. Therefore, it can be seen that changing the reaction time and the amount of reactants can change the thickness of the film. It is speculated that the thickness and uniformity should be the reason for the difference in performance.

以上对本发明做了示例性的描述,应该说明的是,在不脱离本发明核心的情况下,任何简单的变形、修改或者其他本领域技术人员能够不花费创造性劳动的等同替换均落入本发明的保护范围。The present invention has been exemplarily described above, and it should be noted that any simple deformation, modification or other equivalent replacements that those skilled in the art can do without creative work all fall within the scope of the present invention without departing from the core of the present invention. scope of protection.

Claims (10)

1. A memristor based on Covalent Organic Framework (COF) thin film is characterized in that: the organic solar cell comprises a substrate, a conductive bottom electrode, a covalent organic framework film, an organic polymer barrier layer and a conductive top electrode from bottom to top in sequence.
2. The memristor according to claim 1, wherein: the thickness of the covalent organic framework film is 100-150nm, and the thickness of the organic polymer barrier layer is 60-200nm.
3. The memristor according to claim 1, wherein: the covalent organic framework film is prepared by adopting the following method: mixing the aromatic dialdehyde mixed solution and the aromatic polyamine mixed solution at 0-80 ℃ in an atmospheric environment, quickly dripping the obtained mixed solution on the surface of a conductive bottom electrode or directly soaking a substrate with the conductive bottom electrode in the mixed solution to obtain a layer of uniform covalent organic framework film on the surface of the substrate.
4. The memristor according to claim 1, wherein: the ratio of the amounts of the aromatic dialdehyde and the aromatic polyamine in the aromatic dialdehyde mixed solution and the aromatic polyamine mixed solution is as follows: (0.00002755-0.00005964): 0.00002755.
5. the memristor according to claim 1, wherein: the aromatic dialdehyde mixed solution is prepared by adopting the following method: weighing aromatic dialdehyde according to a ratio, then sequentially adding an organic solvent A, an organic solvent B and an organic acid C, and fully dissolving to obtain a transparent colorless aromatic dialdehyde mixed solution, wherein the concentration of the aromatic dialdehyde in the aromatic dialdehyde mixed solution is 0.00626-0.01355 mol/L, and the volume ratio of the organic acid is 5-10%.
6. The memristor according to claim 1, wherein: the aromatic polyamine mixed solution is prepared by adopting the following method: weighing aromatic polyamine according to a ratio, then sequentially adding an organic solvent A, an organic solvent B and an organic acid C, and fully dissolving to obtain a dark green aromatic polyamine mixed solution, wherein the concentration of the aromatic polyamine in the aromatic polyamine mixed solution is 0.00626mmol/L, and the volume ratio of the organic acid is 5-10%.
7. The memristor according to claim 1, wherein: the organic polymer barrier layer is prepared by the following method:
and (2) dissolving the organic polymer A in the liquid B at 80-100 ℃ to obtain a colloidal solution, and spin-coating the colloidal solution on the surface of the covalent organic framework film by adopting a spin-coating method.
8. The memristor of claim 7, wherein: the organic polymer A is polyvinyl alcohol or polymethyl methacrylate.
9. The memristor of claim 7, wherein: the mass-volume ratio of the polymer A to the liquid B in the colloidal solution is 1-20 mg/mL.
10. A method of making a memristor as in any of claims 1-9, wherein: the method specifically comprises the following steps:
(1) Cleaning the substrate with the conductive bottom electrode, and then drying;
(2) Growing a covalent organic framework film on the surface of the clean and dry bottom electrode, and then drying;
(3) Spinning the colloid solution on the covalent organic framework film to obtain an organic polymer barrier layer;
(4) And preparing the conductive top electrode on the surface of the organic polymer barrier layer by adopting a thermal evaporation or magnetron sputtering mode.
CN202310002675.9A 2023-01-03 2023-01-03 A memristor based on a covalent organic framework (COF) film and its preparation method Pending CN115915775A (en)

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