WO2023202061A1 - 一种用于超高密度数据存储的纳米存储器及其制备方法 - Google Patents

一种用于超高密度数据存储的纳米存储器及其制备方法 Download PDF

Info

Publication number
WO2023202061A1
WO2023202061A1 PCT/CN2022/132568 CN2022132568W WO2023202061A1 WO 2023202061 A1 WO2023202061 A1 WO 2023202061A1 CN 2022132568 W CN2022132568 W CN 2022132568W WO 2023202061 A1 WO2023202061 A1 WO 2023202061A1
Authority
WO
WIPO (PCT)
Prior art keywords
ultra
data storage
density data
nanomemory
nano
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2022/132568
Other languages
English (en)
French (fr)
Inventor
路建美
李华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University
Original Assignee
Suzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou University filed Critical Suzhou University
Publication of WO2023202061A1 publication Critical patent/WO2023202061A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11C—STATIC STORES
    • G11C5/00—Details of stores covered by group G11C11/00
    • G11C5/02—Disposition of storage elements, e.g. in the form of a matrix array
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/126—Copolymers block
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/143—Side-chains containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

Definitions

  • the invention belongs to the technical field of functional design of organic semiconductor materials and development of new memory devices, and specifically involves the preparation of amphiphilic block copolymer materials, self-assembly to form micelles, preparation of substrate-induced nano memory devices and testing of semiconductor properties.
  • the storage density of memory devices currently in use is about 10 6-8 bit/cm 2 , which is several orders of magnitude different from the ultra-high-density data storage requirements of 10 12 bit/cm 2 .
  • the use of traditional device preparation processes and materials is increasingly unable to meet the ultra-high demand for storage density in current technology.
  • the new generation of memory has higher requirements, and its application in mobile phones, computers and other equipment has many practical needs, such as doubling the working area, doubling the operating speed, and increasing the storage capacity of the storage device.
  • the size directly affects the design composition of the entire device.
  • a common preparation method for organic electrical memory devices is a metal-organic active layer-metal sandwich structure. The size of the memory cells in this structure is still tens of microns, and it still cannot meet the pursuit of ultra-high-density information storage.
  • the object of the present invention is to provide a method for preparing a nanometer memory device.
  • the method provided by the invention is to rationally introduce acceptor groups into amphiphilic block copolymers, self-assemble to form micelles as storage units, and realize the arraying of micelles through the induction of nanoarray substrates to achieve the preparation of nanomemory. .
  • a nano-memory for ultra-high-density data storage including a conductive substrate and a nano-memory unit on the substrate; the nano-memory unit is an amphiphilic block polymer glue beam array.
  • amphiphilic block polymers are self-assembled in a solvent to form micelles, and then the micelles are arrayed on the surface of a conductive substrate to obtain a nanomemory for ultra-high density data storage; preferably, the template method is used Prepare a nanobowl-shaped conductive substrate, and then induce micelles to array on the surface of the conductive substrate to achieve array arrangement of micelles to obtain nanomemory for ultra-high-density data storage.
  • the nano-bowl-shaped conductive substrate consists of a supporting substrate and a nano-bow-shaped conductive layer on its surface.
  • the nano-bow-shaped conductive layer has an indium oxide/metal double-layer structure and is shaped like a nano-bowl; the supporting substrate is indium tin oxide. (ITO) glass.
  • nitrocarbazole monomer, naphthalimide monomer and hydrophilic monomer undergo ring-opening metathesis polymerization in a solvent to obtain an amphiphilic block polymer, which forms a gel through self-assembly in the solvent.
  • the nano-bowl-shaped conductive substrate is prepared by template method, and the micelle array arrangement is realized through substrate induction to realize the preparation of nano-memory.
  • the amphiphilic block polymer is an amphiphilic tri-block polymer, which is composed of a nitrocarbazole segment, a naphthalimide segment and a hydrophilic segment.
  • the hydrophilic monomer is polyethylene glycol monomer.
  • the body is polymerized to obtain the hydrophilic segment of polyethylene glycol; the chemical structural formula of the amphiphilic block polymer is as follows: .
  • n 10-15, n is 5-10, a is 7-12, and b is 10-20; preferably, m is 11-14, n is 6-9, a is 7-10, and b is 10 ⁇ 15.
  • the invention designs and synthesizes a novel tri-block copolymer, in which nitrocarbazole, naphthalimide and polyethylene glycol serve as the main functional groups of the hydrophobic and hydrophilic segments respectively.
  • the nitrocarbazole monomer is polymerized to obtain the nitrocarbazole segment, and then the naphthalimide monomer is added to polymerize to obtain the nitrocarbazole segment naphthalimide segment polymer, and then polyethylene is added.
  • Diol monomer is polymerized to obtain an amphiphilic triblock polymer, that is, an amphiphilic block polymer, which is composed of a nitrocarbazole segment, a naphthalimide segment and a polyethylene glycol segment.
  • the catalyst is Grubbs third-generation catalyst
  • the solvent is methylene chloride
  • the temperature is 20-40°C
  • the environment is an inert gas atmosphere
  • the time of each polymerization is 0.5-5 h, preferably 0.5-2 h.
  • the invention utilizes nitrocarbazole, naphthalimide and polyethylene glycol monomers to obtain an amphiphilic block polymer in a solvent, and the prepared amphiphilic block polymer is self-assembled in the solvent to prepare a micelle solution , the solvents are tetrahydrofuran and water.
  • the present invention uses the air-water interface self-assembly method to prepare single-layer PS pellets.
  • Nanobowl arrays were prepared using PS beads as templates, and the array arrangement of micelles was achieved through substrate induction.
  • Conductive atomic force microscopy (C-AFM) was used to measure the performance of nanomemory devices. Specifically, use indium tin oxide (ITO) glass to pull the polystyrene (PS) pellet dispersion, and then pull the indium nitrate solution, then calcine and spray metal to obtain a nano-bowl-shaped conductive substrate; then drop the micellar solution On the nanobowl-shaped conductive substrate and drying, a nanomemory for ultra-high-density data storage is obtained.
  • ITO indium tin oxide
  • PS polystyrene
  • the polystyrene pellet dispersion is composed of polystyrene pellets, surfactant, organic solvent and water.
  • the organic solvent is a low-boiling point alcohol; the calcination temperature is 500 ⁇ 700°C, the time is 1 ⁇ 3h, and the heating rate is 1 ⁇ 3°C/min.
  • the solution of PS beads is dispersed on the surface of the sodium dodecyl sulfate (SDS) solution, and the single-layer PS beads are pulled using indium tin oxide (ITO) glass.
  • the solution of PS beads is water and ethanol, and the concentration of SDS solution is 0.1mmol/L.
  • the size of the ITO glass piece is 1 cm ⁇ 2 cm.
  • the specific operation is to transfer the single-layer PS balls to the surface of the indium nitrate solution, pull them out, and then calcine them at high temperature to obtain the indium oxide nanobowl array and micellar solution.
  • the array arrangement is achieved under the induction of the substrate.
  • the concentration of indium nitrate solution is 0.2 M.
  • the substrate calcination temperature is 600°C, the calcination time is 2 h, and the heating rate is 2°C/min.
  • the concentration of the micellar solution is 0.0625 mg/mL, and the monodisperse particle size of the PS beads is 50 to 300 nm.
  • the advantages of the present invention are: the micelles formed by self-organization of the amphiphilic block polymer are uniform in size, the resulting micelles can be regularly arranged in arrays under the induction of the substrate, and at the same time, the micelles in the substrate have good semiconductor properties. Characteristics, it can be used as a nano-memory unit in the development of memory devices. This innovative approach significantly reduces the size of storage cells compared to traditional storage devices and opens up new ideas for the further development of ultra-high-density data memories in the future.
  • Figure 1 is a synthesis diagram of amphiphilic block copolymers.
  • Figure 2 shows the hydrogen nuclear magnetic resonance spectrum of the amphiphilic block copolymer.
  • Figure 3 shows the scanning electron microscope morphology of micelles.
  • Figure 4 shows the scanning electron microscope morphology of the single-layer polystyrene pellet template array.
  • Figure 5 is a scanning electron microscope morphology of the indium oxide conductive substrate.
  • Figure 6 is a scanning electron microscope morphology of a nanomemory device.
  • Figure 7 is the current-voltage curve of micelles in nanometer memory devices.
  • Figure 8 shows carbazole monomer without nitro group.
  • Figure 9 shows long chain polyethylene glycol monomers.
  • the test conditions of nuclear magnetic resonance the hydrogen nuclear magnetic resonance spectrum is measured by an INOVA 400MHz FT-NMR spectrometer. The temperature is 25°C. All chemical shifts are based on tetramethylsilicon (TMS). The chemical shift value of the proton is used as a basis and is given in ppm.
  • TMS tetramethylsilicon
  • the amphiphilic block polymer When the prepared amphiphilic block polymer is self-assembled in a solvent to prepare a micellar solution, the amphiphilic block polymer is dissolved in tetrahydrofuran (THF), water is added dropwise under conventional stirring, and then dialyzed , finally forming a micellar solution.
  • THF tetrahydrofuran
  • the adding method of water is 10 ⁇ 100 ⁇ L, 10 ⁇ 200 ⁇ L, 10 ⁇ 400 ⁇ L, 10 ⁇ 800 ⁇ L, and the dropping interval is 30 s.
  • the molecular weight of the dialysis bag is 300 K, and the dialysis time is 24 h.
  • the nanomicelle storage device is fixed on the sample stage of C-AFM, and the current-voltage (I-V) curve of each storage unit is recorded by applying voltage to the nanomicelle storage unit in each nanobowl.
  • the test environment is in the air environment.
  • the measurement mode is contact mode.
  • the conductive probes are platinum/iridium coated silicon probes.
  • Example 1 Synthesis of amphiphilic block copolymers.
  • the synthesis diagram of the amphiphilic block copolymer is shown in Figure 1.
  • the synthesis of naphthalimide monomers, polyethylene glycol monomers, and nitrocarbazole monomers is an existing technology.
  • the carbazole is replaced with 3-nitrocarbazole, and the nitrocarbazole monomer is obtained by the step-by-step reaction.
  • the number of repeating units of PEG monomethyl ether in the existing synthesis method is replaced from 44 to 12, and the polyethylene is obtained by the step-by-step reaction. Diol monomer.
  • G3 catalyst (20.075 mg, 0.0275 mmol) to a 20 mL vial, dissolve it in 2 mL of methylene chloride, and purge it with nitrogen for 2 minutes to remove the air, then add the nitrocarbazole monomer (169.8 mg, 0.33 mmol) in 2 mL of dichloromethane, stirred for 1 h in a nitrogen atmosphere at 28°C for polymerization, then added 2 mL of dichloromethane containing naphthalimide monomer (137.65 mg, 0.275 mmol), and continued the polymerization for 1 h.
  • Example 3 Preparation of single-layer polystyrene (PS) bead array.
  • Single-layer PS pellets were prepared using the self-assembly method at the air-water interface. Take 1 mL of PS beads with a monodisperse particle size of 150 nm and put it into a 5 mL vial, add 1 mL of absolute ethanol, and vibrate with ultrasonic to obtain a PS solution. Pour 0.1 mmol/L sodium dodecyl sulfate (SDS) aqueous solution into a 600 mL glass petri dish and let it stand until there are no bubbles in the liquid surface. Take a 10 cm ⁇ 2 cm glass piece and insert it obliquely into the liquid surface. A micro-injector with a specification of 10 ⁇ L takes the previously prepared PS solution and drops it onto the glass slide.
  • SDS sodium dodecyl sulfate
  • the solution spreads along the glass slide to the liquid surface, and evenly disperses and self-assembles on the liquid surface to form a single layer film.
  • the morphology of the single-layer PS pellet matrix is shown in Figure 4.
  • Indium nitrate solution was used as a precursor to fill the gaps of single-layer PS beads. Pour 25 mL of 0.2 M indium nitrate aqueous solution into a 20 ml petri dish. After the liquid level calms down, use 1 cm ⁇ 2 cm ITO glass to pull up a layer of PS pellet film (method of Example 3), and then Insert it obliquely into the indium nitrate solution, take out the ITO glass after three seconds, dry it on the heating table at 70°C for 0.5 h, then put it into a tube furnace and burn it in the air at 600°C for 2 h, with a heating rate of At 2°C/min, the single-layer PS pellet was burned, and the indium nitrate became indium oxide after burning, and the indium oxide matrix cavity was successfully prepared.
  • Figure 5 is a diagram of the indium oxide nanobowl-shaped substrate array. After the matrix cavity substrate is successfully prepared, in order to ensure its conductivity, a layer of gold is plated on its surface (10 mA, 70 s), and then 0.5 mL of the previously prepared micellar solution (0.0625 mg/mL) is dripped onto the matrix substrate at an angle. and dried at room temperature for 1 h. The nanomicelle beads are dispersed into the nanobowl under the induction of the substrate to form a matrix arrangement, and a nanomicelle storage device is obtained. The morphology of the nanomicelle array is shown in Figure 6.
  • Example 5 Test of electrical storage performance of nanomicelle arrays.
  • the prepared matrix nanomicelle storage device was fixed on the sample stage of the conductive atomic force microscope (C-AFM), and conductive glue was used to connect the platform to the gold conductive layer under the micelle. Under the environment exposed to the air , the measurement mode is the contact mode.
  • the gold-plated nanomatrix cavity base is the bottom electrode
  • the platinum/iridium conductive probe contacting the micelle is the top electrode.
  • Figure 7 shows the I-V curve of the nanomicelles in the prepared nanomemory device. After scanning at 0-(-5 V), the device changes from OFF state to ON state. Testing all memory cells shows that the ternary ratio is 71%. The binary ratio is 29%, indicating that the device can be applied to the development of ternary storage devices.
  • Comparative example Coat a layer of gold (10 mA, 70 s) on the conductive surface of ITO glass with a size of 1 cm
  • the test method, testing all memory cells showed a ternary ratio of 39%.
  • Example 1 The nitrocarbazole monomer in Example 1 was adjusted to the carbazole monomer shown in Figure 8, and the same polymerization was performed to obtain an amphiphilic triblock polymer, which was prepared as a micellar solution using the method of Example 2. , the device was prepared using the method of Example 4, and all memory cells were tested using the test method of Example 5, and no ternary memory cells were found.
  • Example 1 The polyethylene glycol monomer in Example 1 was adjusted to the polyethylene glycol monomer shown in Figure 9, and the same polymerization was performed to obtain an amphiphilic triblock polymer, which was prepared into a gel using the method of Example 2.
  • the beam solution was prepared by using the method of Example 4 to prepare the device. Using the test method of Example 5, all memory cells were tested and showed that the ternary ratio was 53%.
  • the present invention uses self-assembled micelles of amphiphilic block copolymers as nano-storage units, and realizes the device-based preparation of nano-micelles through the induction of the array substrate.
  • the micelles in the resulting nanomemory devices exhibit good semiconductor properties.
  • the disclosed D-A-H triblock amphiphilic polymerization and its nanomicelle-prepared devices use binary as the main storage and almost no ternary.
  • the present invention not only obtains nano-storage units, but also realizes that ternary far exceeds binary
  • the significant progress has provided a new method for the preparation of a new generation of ultra-high-density information storage devices.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Semiconductor Memories (AREA)

Abstract

一种用于超高密度数据存储的纳米存储器及其制备方法，在两亲性嵌段共聚物中合理引入给受体基团，自组装形成胶束作为存储单元，通过纳米阵列基底的诱导实现胶束的阵列化来实现纳米存储器的制备。其优点是：两亲性嵌段聚合物自组装形成的胶束尺寸均匀，所得的胶束能够规则地在基底的诱导下实现阵列化排布，同时基底中的胶束具有良好的半导体特性，可作为纳米存储单元应用到存储器件的开发。与传统的存储设备相比，这种方法大大缩小了存储单元的尺寸，并为未来进一步发展超高密度数据存储器开辟了新的思路。

Description

一种用于超高密度数据存储的纳米存储器及其制备方法 技术领域
本发明属于有机半导体材料的功能化设计，新型存储器件开发的技术领域，具体涉及制备两亲性嵌段共聚物材料，自组装形成胶束，基底诱导纳米存储器件的制备以及半导体性能的测试。
 背景技术
现在使用的存储器件的存储密度约为10 6-8 bit/cm 2，与10 12 bit/cm 2的超高密度数据存储要求相差几个数量级。传统器件制备工艺与材料的使用已经越来越不能满足当前科技对存储密度的超高需求。随着科学技术的发展，新代存储器有着更高的要求，应用在手机、计算机等设备中有很多现实的需求，如工作面积的成倍减小，操作速度的成倍提升，并且存储设备的大小直接影响整个设备的设计组成。近些年的常见有机电存储器件的制备方法为金属-有机活性层-金属的三明治结构，这种结构存储单元的尺寸仍有几十个微米，还仍不能满足超高密度信息存储的寻求。
因此，科学家们从两个方面努力提高有机器件的数据存储密度，一是开发多级数据存储器件，将存储密度从2 n提高到3 n或4 n及以上；二是通过将单元尺寸从微米级降到纳米级来实现。从2010年第一篇关于基于小分子的三进制器件的报道开始，研究者们已经在分子内/分子间电荷转移、构象变化和电荷陷阱机制的指导下构建了数十个小分子和高分子多级存储器件。其中，高分子材料具有易加工、自旋涂层和功能可调控等优点，甚至适合于构建高密度存储器件，但是存储单元的尺寸偏大且以二进制为主，因此，如何设计一种新型的功能性聚合物自组装成纳米级的存储单元，是进一步提高三元数据存储密度的关键问题。
技术问题
本发明的目的是提供一种纳米存储器件的制备方法。本发明提供的方法是在两亲性嵌段共聚物中合理引入给受体基团，自组装形成胶束作为存储单元，通过纳米阵列基底的诱导实现胶束的阵列化来实现纳米存储器的制备。
 技术解决方案
为达到上述目的，本发明采用如下技术方案：一种用于超高密度数据存储的纳米存储器，包括导电基底与基底上的纳米存储单元；所述纳米存储单元为两亲性嵌段聚合物胶束阵列。
本发明中，将两亲性嵌段聚合物在溶剂中自组装形成胶束，然后将胶束在导电基底表面阵列化，得到用于超高密度数据存储的纳米存储器；优选的，以模板法制备纳米碗状导电基底，然后再诱导胶束在导电基底表面阵列化，实现胶束阵列化排布，得到用于超高密度数据存储的纳米存储器。优选的，纳米碗状导电基底由支撑基材及其表面的纳米碗状导电层组成，纳米碗状导电层为氧化铟/金属双层结构，形状为纳米碗状；支撑基材为氧化铟锡（ITO）玻璃。
本发明中，硝基咔唑单体、萘酰亚胺单体和亲水单体在溶剂中通过开环易位聚合反应，得到两亲性嵌段聚合物，通过在溶剂中自组装形成胶束，以模板法制备纳米碗状导电基底，通过基底诱导实现胶束阵列化排布，实现纳米存储器的制备。所述两亲性嵌段聚合物为两亲性三嵌段聚合物，由硝基咔唑链段、萘酰亚胺链段与亲水链段组成，亲水单体为聚乙二醇单体，聚合得到聚乙二醇亲水链段；所述两亲性嵌段聚合物的化学结构式如下： 。
其中，m为10～15，n为5～10，a为7～12，b为10～20；优选的，m为11～14，n为6～9，a为7～10，b为10～15。
本发明设计合成新颖的三嵌段共聚物，硝基咔唑、萘酰亚胺和聚乙二醇分别作为疏水和亲水段的主要功能基团。首先将硝基咔唑单体进行聚合，得到硝基咔唑链段，再加入萘酰亚胺单体，进行聚合得到硝基咔唑链段萘酰亚胺链段聚合物，再加入聚乙二醇单体，进行聚合得到两亲性三嵌段聚合物，即两亲性嵌段聚合物，为硝基咔唑链段、萘酰亚胺链段与聚乙二醇链段组成的两亲性三嵌段聚合物。优选的，聚合时，催化剂为Grubbs 第三代催化剂，溶剂为二氯甲烷，温度为20～40℃，环境为惰性气体氛围；每次聚合的时间为0.5～5 h，优选0.5～2 h。
本发明利用硝基咔唑、萘酰亚胺和聚乙二醇单体在溶剂中得到两亲性嵌段聚合物，将制备的两亲性嵌段聚合物在溶剂中自组装制备胶束溶液，溶剂为四氢呋喃与水。
本发明利用空气-水界面自组装的方法制备单层PS小球。以PS小球为模板制备纳米碗阵列，通过基底诱导实现胶束的阵列化排布，利用导电原子力显微镜（C-AFM）测量纳米存储器件性能。具体的，用氧化铟锡（ITO）玻璃提拉聚苯乙烯（PS）小球分散液，再提拉硝酸铟溶液，然后煅烧，喷金属，得到纳米碗状导电基底；再将胶束溶液滴在纳米碗状导电基底上，干燥，得到用于超高密度数据存储的纳米存储器。聚苯乙烯小球分散液由聚苯乙烯小球、表面活性剂、有机溶剂以及水组成，有机溶剂为低沸点醇；煅烧的温度为500～700℃，时间为1～3h，升温速率为1～3℃/min。
上述方案中，PS小球的溶液分散到十二烷基硫酸钠（SDS）溶液表面，用氧化铟锡（ITO）玻璃提拉单层PS小球。PS小球的溶液为水和乙醇，SDS溶液浓度为0.1mmol/L。ITO玻璃片的规格为1 cm×2 cm。然后利用硝酸铟溶液作为填充单层PS小球空隙的前驱体，具体操作为，将单层PS球转移到硝酸铟溶液表面，提拉取出，经过高温煅烧得到氧化铟纳米碗阵列，胶束溶液滴入基底中，在基底的诱导下实现阵列化排布。优选的，硝酸铟溶液浓度为0.2 M。基底煅烧温度为600℃，煅烧时间为2 h，升温速率为2℃/min。胶束溶液浓度为0.0625 mg/mL，PS小球的单分散粒径为50～300nm。
 有益效果
本发明的优点是：两亲性嵌段聚合物自组形成的胶束尺寸均匀，所得的胶束能够规则地在基底的诱导下实现阵列化排布，同时基底中的胶束具有良好的半导体特性，可作为纳米存储单元应用到存储器件的开发。与传统的存储设备相比，这种创新的方法大大缩小了存储单元的尺寸，并为未来进一步发展超高密度数据存储器开辟了新的思路。
 附图说明
图1为两亲性嵌段共聚物的合成图。
图2为两亲性嵌段共聚物的核磁共振氢谱图。
图3为胶束的扫描电子显微镜形貌图。
图4为单层聚苯乙烯小球模板阵列扫描电子显微镜形貌图。
图5为氧化铟导电基底的扫描电子显微镜形貌图。
图6为纳米存储器件的扫描电子显微镜形貌图。
图7为纳米存储器件中胶束的电流-电压曲线图。
图8为不含硝基的咔唑单体。
图9为长链聚乙二醇单体。
 本发明的实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将对本发明的各实施方式进行详细的阐述。然而，本领域的普通技术人员可以理解，在本发明各实施方式中，为了使读者更好地理解本申请而提出了许多技术细节。但是，即使没有这些技术细节和基于以下各实施方式的种种变化和修改，也可以实现本申请各权利要求所要求保护的技术方案。下文将结合附图和具体实施例来进一步说明本发明的技术方案。除非另有说明，下列实施例中所使用的试剂、材料、仪器等均可通过商业手段获得，G3催化剂来自罗恩试剂。具体制备操作以及实验方法都为本领域常规方法，核磁的测试条件：核磁共振氢谱通过INOVA 400MHz FT-NMR光谱仪进行测量，温度为25℃，所有化学位移都是以四甲基硅（TMS）质子的化学位移值为基准，以ppm为单位给出。
本发明将制备的两亲性嵌段聚合物在溶剂中自组装制备胶束溶液时，两亲性嵌段聚合物溶解在四氢呋喃（THF）中，在常规搅拌作用下逐滴加入水，经透析，最终形成胶束溶液。优选的，水的加入方式为10×100 μL、10×200 μL、10×400 μL、10×800 μL，滴加间隔为30 s。透析袋分子量为300 K，透析时间为24 h。
本发明中，纳米胶束存储器件固定在C-AFM的样品台上，通过对每个纳米碗中的纳米胶束存储单元施加电压，从而记录下每个存储单元的电流-电压（I-V）曲线。测试环境为在空气环境。测量模式为接触模式。导电探针为铂/铱涂层的硅探针。
实施例1：两亲性嵌段共聚物的合成。
两亲性嵌段共聚物的合成图如图1所示，萘酰亚胺单体、聚乙二醇单体、硝基咔唑单体的合成为现有技术，比如将现有合成方法中的咔唑更换为3-硝基咔唑，按步反应得到硝基咔唑单体，比如将现有合成方法中的PEG单甲醚由重复单元数44替换为12，按步反应得到聚乙二醇单体。在20 mL小瓶中加入G3催化剂（20.075 mg，0.0275 mmol），用2 mL的二氯甲烷溶解，并且用氮气排气2分钟除去其中空气，然后加入含有硝基咔唑单体（169.8 mg，0.33 mmol）的2 mL二氯甲烷，在28℃下氮气氛围中搅拌1 h进行聚合，再加入含萘酰亚胺单体（137.65 mg，0.275 mmol）的2 mL二氯甲烷，继续聚合反应1 h，再加入含聚乙二醇单体（267.07 mg，0.33 mmol）的2 mL二氯甲烷，继续聚合反应1 h；反应结束后加入1 mL的乙烯基乙醚再次搅拌0.5 h终止聚合；将最终反应液倒入200 mL的冷乙醚中，搅拌有灰色沉淀析出，抽滤得到固体，把固体用5 mL的二氯甲烷溶解，再次倒入200 mL的冷乙醚中，再以同样的方式溶解沉淀提纯聚合物两次，以此得到纯的两亲性三嵌段聚合物，烘干后为红黑色固体（0.3597 g，62%），该两亲性嵌段共聚物的核磁图如图2。
实施例2：胶束的制备。
取1 mg两亲性嵌段共聚物溶解在1 mL的四氢呋喃中，以水为选择性溶剂在搅拌过程中逐滴加入，分别以10×100 μL、10×200 μL、10×400 μL、10×800 μL 的过程滴加，滴加间隔为30 s，直至滴加完毕，溶液浓度为0.0625 mg/mL，继续搅拌0.5 h，然后放入分子量为300 k的透析袋，再放入2 L的去离子水中透析，每隔8h换一次水，重复三次，得到胶束溶液。胶束的形貌图如图3。
实施例3：单层聚苯乙烯（PS）小球阵列的制备。
利用空气-水界面自组装的方法制备单层PS小球。取1 mL单分散粒径为150 nm的PS小球放入5 mL的小瓶中，加入1 mL无水乙醇，超声震荡，得到PS溶液。将0.1 mmol/L十二烷基硫酸钠（SDS）水溶液倒入600 mL的玻璃培养皿中，静置直到液面没有气泡，取10 cm×2 cm的玻璃片斜插入液面之中，用规格为10 μL的微量进样器取之前配好的PS溶液并滴入玻璃片上，溶液沿着玻璃片扩散到液面之上，并且在液面上均匀分散自组装形成单层膜。利用1 cm×2 cm规格的ITO玻璃片，从液面内斜提拉上来，使单层PS小球附着在玻璃上，静置干燥。单层PS小球矩阵的形貌图如图4。
实施例4：纳米胶束阵列的制备。
利用硝酸铟溶液作为填充单层PS小球空隙的前驱体。取25 mL 0.2 M的硝酸铟水溶液倒入20ml的培养皿中，待液面平静后，用1 cm×2 cm规格的ITO玻璃提拉一层PS小球膜（实施例3的方法），然后斜插入硝酸铟溶液中，三秒钟后取出ITO玻璃，在加热台70℃下烘干0.5 h，然后放入管式炉中，在空气中，600℃的条件下灼烧2 h，升温速率为2℃/min，单层PS小球被烧掉，硝酸铟在灼烧后成为氧化铟，成功制备出氧化铟矩阵空洞。图5为氧化铟纳米碗状基底阵列图。矩阵空洞基底制备成功后，为了保证其导电性，在其表面镀一层金（10 mA，70 s），然后取之前制备的0.5 mL胶束溶液（0.0625 mg/mL）倾斜滴加到矩阵基底上，常温条件下干燥1 h。纳米胶束小球在基底的诱导下分散到纳米碗中构成矩阵排列，得到纳米胶束存储器件。纳米胶束阵列的形貌图如图6。
实施例5：纳米胶束阵列的电存储性能测试。
将制备好的矩阵型纳米胶束存储器件固定在导电原子力显微镜（C-AFM）的样品台上，用导电胶将平台与胶束下面的金导电层相连接，在暴露于空气中的环境下，测量模式为接触模式，在纳米级别上进行胶束的电性能测试中，镀金的纳米矩阵空洞基底为底电极，接触胶束的铂/铱导电探针为顶电极，通过导电探针（铂/铱涂层的硅探针）对每个纳米碗中的纳米胶束存储器施加电压，从而记录下每个存储器的电流-电压（I-V）曲线，以获得其存储性能。图7显示了制备的纳米存储器件中纳米胶束的I-V曲线，经0-（-5 V）的扫描，器件由OFF态转变为ON态，测试所有存储单元表明三进制比率为71%、二进制比率为29%，说明该器件可以应用到三进制的存储设备的开发中。
对比例：在1 cm×2 cm规格的ITO玻璃导电面镀一层金（10 mA，70 s），然后滴涂0.5 mL胶束溶液（实施例2），干燥得到器件，采用实施例5的测试方法，测试所有存储单元表明三进制比率为39%。
将实施例1中的硝基咔唑单体调整为图8所示的咔唑单体，进行同样的聚合，得到两亲性三嵌段聚合物，采用实施例2的方法制备为胶束溶液，采用实施例4的方法制备得到器件，采用实施例5的测试方法，测试所有存储单元，没有发现三进制存储单元。
将实施例1中的聚乙二醇单体调整为图9所示的聚乙二醇单体，进行同样的聚合，得到两亲性三嵌段聚合物，采用实施例2的方法制备为胶束溶液，采用实施例4的方法制备得到器件，采用实施例5的测试方法，测试所有存储单元表明三进制比率为53%。
综上所述，本发明通过两亲性嵌段共聚物自组装的胶束作为纳米存储单元，通过阵列基底的诱导实现纳米胶束的器件化制备。所得的纳米存储器件中的胶束表现出良好的半导体特性。现有技术，公开的D-A-H三嵌段两亲性聚合及其纳米胶束制备的器件以二进制为主要存储，几乎没有三进制，本发明不仅得到纳米存储单元，而且实现三进制远超过二进制的显著进步，为新一代超高密度信息存储器件的制备提供了新的方法。

Claims (10)

  1. 一种用于超高密度数据存储的纳米存储器，包括导电基底与基底上的纳米存储单元，其特征在于，所述纳米存储单元为两亲性嵌段聚合物胶束阵列。
  2. 根据权利要求1所述用于超高密度数据存储的纳米存储器，其特征在于，所述两亲性嵌段聚合物由硝基咔唑链段、萘酰亚胺链段与亲水链段组成。
  3. 根据权利要求2所述用于超高密度数据存储的纳米存储器，其特征在于，所述两亲性嵌段聚合物的化学结构式如下：
     
    其中，m为10～15，n为5～10，a为7～12，b为10～20。
  4. 根据权利要求1所述用于超高密度数据存储的纳米存储器，其特征在于，导电基底为纳米碗状导电基底。
  5. 根据权利要求4所述用于超高密度数据存储的纳米存储器，其特征在于，纳米碗状导电基底由支撑基材及其表面的纳米碗状导电层组成。
  6. 权利要求1所述用于超高密度数据存储的纳米存储器的制备方法，其特征在于，将硝基咔唑单体、萘酰亚胺单体和亲水单体在溶剂中通过开环易位聚合反应，得到两亲性嵌段聚合物，然后在溶剂中自组装形成胶束；以模板法制备纳米碗状导电基底，然后通过纳米碗状导电基底诱导胶束实现阵列化排布，得到用于超高密度数据存储的纳米存储器。
  7. 根据权利要求6所述用于超高密度数据存储的纳米存储器的制备方法，其特征在于，用导电玻璃提拉聚苯乙烯小球分散液，再提拉硝酸铟溶液，然后煅烧，喷金属，得到纳米碗状导电基底；再将胶束溶液滴在纳米碗状导电基底上，干燥，得到用于超高密度数据存储的纳米存储器。
  8. 根据权利要求7所述用于超高密度数据存储的纳米存储器的制备方法，其特征在于，聚苯乙烯小球分散液由聚苯乙烯小球、表面活性剂、有机溶剂以及水组成；煅烧的温度为500～700℃，时间为1～3h，升温速率为1～3℃/min。
  9. 两亲性嵌段聚合物在制备权利要求1所述用于超高密度数据存储的纳米存储器中的应用，其特征在于，所述两亲性嵌段聚合物由硝基咔唑链段、萘酰亚胺链段与亲水链段组成。
  10. 权利要求1所述用于超高密度数据存储的纳米存储器在制备有机存储器件中的应用。
PCT/CN2022/132568 2022-04-18 2022-11-17 一种用于超高密度数据存储的纳米存储器及其制备方法 Ceased WO2023202061A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210403832.2 2022-04-18
CN202210403832.2A CN114913884B (zh) 2022-04-18 2022-04-18 一种用于超高密度数据存储的纳米存储器及其制备方法

Publications (1)

Publication Number Publication Date
WO2023202061A1 true WO2023202061A1 (zh) 2023-10-26

Family

ID=82765559

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/132568 Ceased WO2023202061A1 (zh) 2022-04-18 2022-11-17 一种用于超高密度数据存储的纳米存储器及其制备方法

Country Status (2)

Country Link
CN (1) CN114913884B (zh)
WO (1) WO2023202061A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114913884B (zh) * 2022-04-18 2026-02-24 苏州大学 一种用于超高密度数据存储的纳米存储器及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030232904A1 (en) * 2002-06-14 2003-12-18 Canon Kabushiki Kaisha Particle composition, recording method, and recording apparatus using the particle composition
US20170181979A1 (en) * 2014-03-31 2017-06-29 Shimadzu Corporation Process for producing nanoparticles
CN111269523A (zh) * 2019-11-19 2020-06-12 武汉理工大学 一种两亲性共聚物自组装复合纳米银粒子的方法
CN114913884A (zh) * 2022-04-18 2022-08-16 苏州大学 一种用于超高密度数据存储的纳米存储器及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1152941C (zh) * 2000-01-25 2004-06-09 华东理工大学 一类含多功能团嵌段式电致发光聚合物及其应用
JP5216995B2 (ja) * 2006-02-03 2013-06-19 国立大学法人北海道大学 ブロック共重合体からなるナノディスク
CN101417996B (zh) * 2008-12-09 2013-04-10 苏州大学 具有对称结构的含咔唑和萘酰亚胺基团的化合物、其制备方法及用途
CN107403718A (zh) * 2017-08-17 2017-11-28 中国科学院长春应用化学研究所 纳米结构的引导组装方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030232904A1 (en) * 2002-06-14 2003-12-18 Canon Kabushiki Kaisha Particle composition, recording method, and recording apparatus using the particle composition
US20170181979A1 (en) * 2014-03-31 2017-06-29 Shimadzu Corporation Process for producing nanoparticles
CN111269523A (zh) * 2019-11-19 2020-06-12 武汉理工大学 一种两亲性共聚物自组装复合纳米银粒子的方法
CN114913884A (zh) * 2022-04-18 2022-08-16 苏州大学 一种用于超高密度数据存储的纳米存储器及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEN YAN-MING, ZUO XIAO-WEI, LI SAN-XI: "Research Status of Semiconductor Nanoparticles Prepared by Amphiphilic Block Polymer Template", GAOFENZI-CAILIAO-KEXUE-YU-GONGCHENG = POLYMER MATERIALS SCIENCE AND ENGINEERING, CHENGDU KEJI DAXUE GAOFENZI YANJIUSUO, CN, vol. 26, no. 09, 15 September 2010 (2010-09-15), CN , pages 155 - 158, XP009549738, ISSN: 1000-7555, DOI: 10.16865/j.cnki.1000-7555.2010.09.041 *

Also Published As

Publication number Publication date
CN114913884A (zh) 2022-08-16
CN114913884B (zh) 2026-02-24

Similar Documents

Publication Publication Date Title
Lei et al. Tuning of the morphology of core− shell− corona micelles in water. I. Transition from sphere to cylinder
JP6042986B2 (ja) シリコンオキサイドのナノパターン形成方法、金属ナノパターンの形成方法およびこれを用いた情報貯蔵用磁気記録媒体
CN104854020A (zh) 使用共聚物封端剂制备银纳米线的方法
WO2023202061A1 (zh) 一种用于超高密度数据存储的纳米存储器及其制备方法
US10121971B2 (en) Cellulose-polymer composites for solar cells
CN111548444A (zh) 一种表面离子液体功能化聚合物微球的制备方法
CN111426674A (zh) 一种增强sers活性的太阳花纳米阵列结构及其制备方法
CN108735349B (zh) 一种含离子液体的银纳米线透明导电薄膜及其制备方法
Wang et al. Nanomicelles array for ultrahigh‐density data storage
CN111944177B (zh) 一种聚合物超薄膜成膜体系以及聚合物超薄膜
CN105241928A (zh) 一种电活性双亲聚合物分子印迹传感器的制备方法
CN119954728B (zh) 一种有机d-a型多进制共轭小分子的分子组装方法和应用
CN113321200B (zh) 一种氮掺杂或铁氮共掺杂多级孔碳球的制备方法及其在电催化氧还原反应中的应用
WO2022242132A1 (zh) 一种电池隔膜用材料、材料制备方法及电池隔膜
CN110317309A (zh) 基于二维聚合物薄膜的忆阻器及其制备方法
CN119264353A (zh) 一种离聚物、其制备方法及用于电解水制氢的催化层浆料和膜电极
CN111234216B (zh) 一种锌金属卟啉共聚酰亚胺及其作为光电信息存储材料的应用
CN111777057A (zh) 一种富微孔炭球及其制备方法和应用
CN113788477B (zh) 一种褶皱石墨烯涂层及其制备方法
CN112201752B (zh) 柔性电存储器件的制备方法及其应用
CN110563904B (zh) 一种聚合物包覆碳纳米管复合材料、制备方法和应用
Liu et al. Preparation of Langmuir-Blodgett composite films based on Bisphenol fluorene and Epoxy bisphenol fluorene with photovoltaic properties
CN111320201A (zh) 一种电化学传感器用硫化银石墨烯复合材料及其制备方法
CN115839031B (zh) 一种有序化导电聚合物复合材料及其制备方法、应用
Yu et al. Polymerization-induced self-assembly: engineered nanomaterials for advanced biomolecule detection and multifaceted biomedical applications

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22938280

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22938280

Country of ref document: EP

Kind code of ref document: A1