WO2022227229A1 - Method for preparing nanoprobe - Google Patents

Method for preparing nanoprobe Download PDF

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Publication number
WO2022227229A1
WO2022227229A1 PCT/CN2021/098450 CN2021098450W WO2022227229A1 WO 2022227229 A1 WO2022227229 A1 WO 2022227229A1 CN 2021098450 W CN2021098450 W CN 2021098450W WO 2022227229 A1 WO2022227229 A1 WO 2022227229A1
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Prior art keywords
solution
metal
nanoprobe
preparing
mixed solution
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PCT/CN2021/098450
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French (fr)
Chinese (zh)
Inventor
杨树明
程碧瑶
李少博
王飞
邓惠文
赵书浩
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西安交通大学
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Priority to GB2207755.6A priority Critical patent/GB2611841A/en
Publication of WO2022227229A1 publication Critical patent/WO2022227229A1/en

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q60/00—Particular types of SPM [Scanning Probe Microscopy] or microscopes; Essential components thereof
    • G01Q60/24—AFM [Atomic Force Microscopy] or apparatus therefor, e.g. AFM probes
    • G01Q60/38—Probes, their manufacture, or their related instrumentation, e.g. holders
    • 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

Definitions

  • the invention belongs to the technical field of nanometer manufacturing and measurement, in particular to a preparation method of a nanometer probe.
  • Nanotechnology is an emerging field of scientific development in today's world, and its core is nanofabrication technology.
  • the improvement of the level of nanofabrication technology will have a huge impact on aerospace, micro-nano sensing, life science, integrated circuits and other technical fields.
  • Nano-fabrication technology is inseparable from nano-fabrication and measurement. Nano-fabrication and measurement are used to ensure the accuracy of machining. The accuracy is often at least an order of magnitude higher than that of machining. Otherwise, there will be no standards for nano-fabrication to follow. It can be seen that nano-fabrication and measurement will occupy an extremely important position in the development of nanotechnology.
  • the AFM colloidal probe technology developed in recent years is to obtain the surface potential and surface charge density by measuring the force of the colloidal probe in the electrolyte solution on the charged surface.
  • the so-called colloidal probe technology refers to bonding a micron-sized microsphere to the end of the probe cantilever of the AFM as a sensor to measure the interfacial interaction force.
  • the AFM colloid probe technique is an effective means to probe the influence of surface charge by measuring electrostatic interactions at the nanoscale.
  • the size of the colloidal probe is 1-10 microns, the test accuracy is limited, and the measurement at the nanometer scale is lacking.
  • the colloidal probe is pasted by glue, and it is difficult to control the pasting position and affect the accuracy. At the same time, it is often easy to fall off when encountering high temperature or liquid.
  • the purpose of the present invention is to overcome the defects and deficiencies existing in the prior art, and to provide a preparation method of a nano-probe.
  • the present invention adopts following technical scheme to realize:
  • a method for preparing a nanoprobe obtains a nanoprobe by attaching metal nanoparticles to the tip of an AFM microscope probe, and specifically includes the following implementation steps:
  • the metal nanoparticle solution and the metal compound solution containing metal ions are added to the glycine-sodium hydroxide solution for reaction, after mixing evenly, at the set temperature, after a period of reaction, cooled to room temperature, and washed with deionized water several times to obtain a metal nanoparticle solution with a preset concentration;
  • step 1) mix surfactant P123, 1M hydrochloric acid and ethanol, then add silicon tetrachloride and stir to form a solution, pour the solution into an evaporating dish, and let it stand to obtain a semi-solid silicic acid mixed solution; configure in step 1)
  • the good metal nanoparticle solution is added to the semi-solid silicic acid mixed solution formed in 2) to obtain a mixed solution, and the AFM probe is immersed in the mixed solution for a period of time and taken out to obtain a metal nanoprobe.
  • a further improvement of the present invention is that, in step 1), the concentration of the metal nanoparticle solution is 120-150 pM, and silver nanoparticles or gold nanoparticles are selected.
  • a further improvement of the present invention is that, in step 1), the metal particle type is selected from one of copper, lead, zinc, iron, cobalt and nickel in the heavy metal particles, and the concentration is 3-5 ⁇ M.
  • a further improvement of the present invention is that, in step 1), the concentration of glycine-sodium hydroxide is 3-5mM.
  • a further improvement of the present invention is that in step 1), the volume ratio of the metal nanoparticle solution, the metal ion solution and the glycine-sodium hydroxide solution is (3-5):(1-1.5):(1-1.5).
  • a further improvement of the present invention is that, in step 1), the reaction temperature is 160-200° C., and the reaction time is 5-10 h.
  • a further improvement of the present invention is that, in step 2), the volume ratio of surfactant P123, 1M hydrochloric acid and ethanol is 1:(0.2-0.5):(2-5):(0.5-1.5).
  • a further improvement of the present invention is that, in step 2), the solution is poured into an evaporating dish and left to stand for 12-24 hours.
  • a further improvement of the present invention is that, in step 2), the AFM probe is immersed in the mixed solution for 15-30 minutes and then taken out to obtain a metal nanoprobe.
  • the present invention provides a method for preparing a nano-probe, which accurately measures the interface in the nanometer-to-micrometer scale, fills the vacancy of the scale, can be used to measure surface potential and surface charge density, and solves important problems in the field of nanotribology technical bottleneck.
  • the tip ball of the spherical probe is in the order of microns, while the probe tip ball prepared by the present invention is in the nanometer scale, so the probe in the present invention is more suitable for various measurement applications in the nanometer scale.
  • Figure 1 is a scanning electron microscope image of a common colloid probe.
  • FIG. 2 is a scanning electron microscope picture of the atomic force microscope probe used in the specific embodiment of the present invention.
  • FIG. 3 is a scanning electron microscope picture of gold nanoparticles grown on the tip of an atomic force microscope probe in a specific embodiment of the present invention.
  • the invention provides a preparation method of nano probe. Specific steps are as follows:
  • the surfactant P123, 1M hydrochloric acid and ethanol are mixed in a certain volume ratio, and the ratio of surfactant P123, 1M hydrochloric acid, ethanol and silicon tetrachloride is 1:(0.2-0.5):(2- 5): 0.5-1.5, configure 200-500mL solution.
  • the AFM probe was immersed in the mixed solution for 15-30 min and then taken out to obtain a metal nanoprobe.
  • the 120 pM gold nanoparticle solution and the iron oxide compound solution containing iron particles at a concentration of 3 ⁇ M were added to a 3 mM glycine-sodium hydroxide solution for reaction.
  • Figure 1 is an SEM image of a common colloid probe
  • Figure 2 is an AFM probe.
  • the surfactant P123, 1M hydrochloric acid and ethanol are mixed in a certain volume ratio.
  • the ratio of surfactant P123, 1M hydrochloric acid, ethanol and silicon tetrachloride is 1:0.2:2:0.5, and 200mL solution is prepared.
  • the solution was poured into an evaporating dish and allowed to stand for 12 h, and the micelles formed by the surfactant were volatilized with ethanol.
  • Add the solution prepared in 1) to the solution formed in 2) to obtain a mixed solution.
  • the AFM probe was immersed in the mixed solution for 15 min and then taken out to obtain the gold nanoprobe as shown in Figure 3.
  • the tip of the nanoparticles greatly reduces the curvature of the tip by half the valence.
  • a 135 pM solution of gold or silver nanoparticles and a solution of lead hydroxide containing lead particles at a concentration of 4 ⁇ M were added to a solution of glycine-sodium hydroxide at a concentration of 4 mM for the reaction.
  • the surfactant P123, 1M hydrochloric acid and ethanol are mixed in a certain volume ratio.
  • the ratio of surfactant P123, 1M hydrochloric acid, ethanol ethanol and silicon tetrachloride is 1:0.3:3:1, and the configuration is 300mL. solution.
  • the solution was poured into an evaporating dish and allowed to stand for 18 h, and the micelles formed by the surfactant were volatilized with the ethanol.
  • the AFM probe was immersed in the mixed solution for 25 min and then taken out to obtain silver nanoprobes.
  • a 150 pM solution of gold or silver nanoparticles and a solution of lead hydroxide containing lead particles at a concentration of 5 ⁇ M were added to a solution of glycine-sodium hydroxide at a concentration of 5 mM for the reaction.
  • the surfactant P123, 1M hydrochloric acid and ethanol are mixed in a certain volume ratio.
  • the ratio of surfactant P123, 1M hydrochloric acid, ethanol and silicon tetrachloride is 1:0.5:5:1.5, and 300mL solution is prepared.
  • the solution was poured into an evaporating dish and allowed to stand for 24 hours, and the micelles formed by the surfactant were volatilized with ethanol.
  • the AFM probes were immersed in the mixed solution for 30 min and then taken out to obtain silver nanoprobes.

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  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Radiology & Medical Imaging (AREA)
  • Health & Medical Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

A method for preparing a nanoprobe, the method comprising steps: 1) adding a metal nanoparticle solution and a metal compound solution containing metal ions to a glycine-sodium hydroxide solution for reaction, uniformly mixing same, then reacting same for a period of time at a set temperature, cooling same to room temperature, and washing same with deionized water several times to obtain a metal nanoparticle solution with a preset concentration; and 2) first, mixing a surfactant of P123, 1M hydrochloric acid and ethanol, then, adding silicon tetrachloride and stirring same to form a solution, pouring the solution into an evaporation dish, and leaving same to stand to obtain a semi-solid silicic acid mixed solution; and adding the metal nanoparticle solution prepared in step 1) to the semi-solid silicic acid mixed solution formed in step 2) to obtain a mixed solution, immersing an AFM probe in the mixed solution for a period of time, and then taking same out to obtain the metal nanoprobe. The prepared probe tip ball is nano-scale, which is suitable for various nano-scale measurement applications.

Description

一种纳米探针的制备方法A kind of preparation method of nanometer probe 技术领域technical field
本发明属于纳米制造测量技术领域，具体涉及一种纳米探针的制备方法。The invention belongs to the technical field of nanometer manufacturing and measurement, in particular to a preparation method of a nanometer probe.
背景技术Background technique
纳米技术作为当今世界科学发展的一个新兴领域，其核心是纳米加工技术。纳米加工技术水平的提高将对航空航天、微纳传感、生命科学、集成电路等技术领域产生巨大的影响。而纳米加工技术离不开纳米制造与测量，纳米制造与测量用来保证加工的精度，其精度往往至少要高于加工一个数量级，否则纳米加工将无标准可遵循。可见纳米制造与测量在纳米加工将在纳米技术的发展中占有极其重要的地位。近年来，随着原子力显微镜（AFM）技术的发展和应用，使得纳米尺度下的实验研究得到更为精确的实验数据成为可能。近年来发展起来的 AFM 胶体探针技术，即通过测量电解质溶液中胶体探针受到带电表面的作用力，获得表面电势和表面电荷密度。所谓胶体探针技术是指将一个微米尺寸的微球粘结到 AFM 的探针悬臂梁末端作为传感器，实现界面相互作用力的测量。AFM 胶体探针技术是在纳米尺度测量静电作用探索表面电荷影响的有效手段。但是胶体探针尺寸在1-10微米，测试精度有限，缺乏在纳米尺度的测量。与此同时，胶体探针是通过胶水粘贴，本身粘贴位置就很难把控影响精确度，同时遇到高温或液体常常容易脱落。Nanotechnology is an emerging field of scientific development in today's world, and its core is nanofabrication technology. The improvement of the level of nanofabrication technology will have a huge impact on aerospace, micro-nano sensing, life science, integrated circuits and other technical fields. Nano-fabrication technology is inseparable from nano-fabrication and measurement. Nano-fabrication and measurement are used to ensure the accuracy of machining. The accuracy is often at least an order of magnitude higher than that of machining. Otherwise, there will be no standards for nano-fabrication to follow. It can be seen that nano-fabrication and measurement will occupy an extremely important position in the development of nanotechnology. In recent years, with the development and application of atomic force microscopy (AFM) technology, it has become possible to obtain more accurate experimental data for experimental research at the nanoscale. The AFM colloidal probe technology developed in recent years is to obtain the surface potential and surface charge density by measuring the force of the colloidal probe in the electrolyte solution on the charged surface. The so-called colloidal probe technology refers to bonding a micron-sized microsphere to the end of the probe cantilever of the AFM as a sensor to measure the interfacial interaction force. The AFM colloid probe technique is an effective means to probe the influence of surface charge by measuring electrostatic interactions at the nanoscale. However, the size of the colloidal probe is 1-10 microns, the test accuracy is limited, and the measurement at the nanometer scale is lacking. At the same time, the colloidal probe is pasted by glue, and it is difficult to control the pasting position and affect the accuracy. At the same time, it is often easy to fall off when encountering high temperature or liquid.
技术问题technical problem
本发明的目的是克服现有技术中存在的缺陷和不足，提供了一种纳米探针的制备方法。The purpose of the present invention is to overcome the defects and deficiencies existing in the prior art, and to provide a preparation method of a nano-probe.
技术解决方案technical solutions
本发明采用如下技术方案来实现:The present invention adopts following technical scheme to realize:
一种纳米探针的制备方法，该方法通过在AFM显微镜探针的尖端附着金属纳米粒子得到纳米探针，具体包括以下实现步骤：A method for preparing a nanoprobe, the method obtains a nanoprobe by attaching metal nanoparticles to the tip of an AFM microscope probe, and specifically includes the following implementation steps:
1）制备金属纳米粒子溶液1) Preparation of metal nanoparticle solution
将金属纳米粒子溶液与含有金属离子的金属化合物溶液加入到氨基乙酸-氢氧化钠溶液中进行反应，混合均匀后，在设定温度下，反应一段时间后，冷却至室温，用去离子水洗涤数次，得到预设浓度的金属纳米粒子溶液；The metal nanoparticle solution and the metal compound solution containing metal ions are added to the glycine-sodium hydroxide solution for reaction, after mixing evenly, at the set temperature, after a period of reaction, cooled to room temperature, and washed with deionized water several times to obtain a metal nanoparticle solution with a preset concentration;
2）在AFM探针尖端组装金属纳米粒子2) Assembly of metal nanoparticles at the tip of the AFM probe
首先将表面活性剂P123、1M氢氯酸和乙醇混合，再加入四氯化硅搅拌成为溶液，将溶液倒入蒸发皿中，静置，得到半固态硅酸混合溶液；将步骤1）中配置好的金属纳米粒子溶液加入2）形成的半固态硅酸混合溶液中得到混合溶液，将AFM探针浸入混合溶液一段时间后取出得到金属纳米探针。First, mix surfactant P123, 1M hydrochloric acid and ethanol, then add silicon tetrachloride and stir to form a solution, pour the solution into an evaporating dish, and let it stand to obtain a semi-solid silicic acid mixed solution; configure in step 1) The good metal nanoparticle solution is added to the semi-solid silicic acid mixed solution formed in 2) to obtain a mixed solution, and the AFM probe is immersed in the mixed solution for a period of time and taken out to obtain a metal nanoprobe.
本发明进一步的改进在于，步骤1）中，金属纳米粒子溶液的浓度为120-150pM，选择银纳米粒子或金纳米粒子。A further improvement of the present invention is that, in step 1), the concentration of the metal nanoparticle solution is 120-150 pM, and silver nanoparticles or gold nanoparticles are selected.
本发明进一步的改进在于，步骤1）中，金属粒子类型选择重金属粒子中的铜、铅、锌、铁、钴和镍的一中，浓度为3-5μM。A further improvement of the present invention is that, in step 1), the metal particle type is selected from one of copper, lead, zinc, iron, cobalt and nickel in the heavy metal particles, and the concentration is 3-5 μM.
本发明进一步的改进在于，步骤1）中，氨基乙酸-氢氧化钠的浓度为3-5mM。A further improvement of the present invention is that, in step 1), the concentration of glycine-sodium hydroxide is 3-5mM.
本发明进一步的改进在于，步骤1）中，金属纳米粒子溶液、金属离子溶液以及氨基乙酸-氢氧化钠溶液的体积比为(3-5):(1-1.5):(1-1.5)。A further improvement of the present invention is that in step 1), the volume ratio of the metal nanoparticle solution, the metal ion solution and the glycine-sodium hydroxide solution is (3-5):(1-1.5):(1-1.5).
本发明进一步的改进在于，步骤1）中，反应温度为160-200℃，反应时间为5-10h。A further improvement of the present invention is that, in step 1), the reaction temperature is 160-200° C., and the reaction time is 5-10 h.
本发明进一步的改进在于，步骤2）中，表面活性剂P123、1M氢氯酸和乙醇的体积比为1:(0.2-0.5):(2-5):(0.5-1.5)。A further improvement of the present invention is that, in step 2), the volume ratio of surfactant P123, 1M hydrochloric acid and ethanol is 1:(0.2-0.5):(2-5):(0.5-1.5).
本发明进一步的改进在于，步骤2）中，溶液倒入蒸发皿后静置12-24h。A further improvement of the present invention is that, in step 2), the solution is poured into an evaporating dish and left to stand for 12-24 hours.
本发明进一步的改进在于，步骤2）中，将AFM探针浸入混合溶液15-30min后取出，得到金属纳米探针。A further improvement of the present invention is that, in step 2), the AFM probe is immersed in the mixed solution for 15-30 minutes and then taken out to obtain a metal nanoprobe.
有益效果beneficial effect
本发明具有如下有益的技术效果:The present invention has following beneficial technical effect:
本发明提供的一种纳米探针的制备方法，该制备方法精准测量纳米到微米尺度范围的界面，填补了该尺度空缺，可用来测量表面电势及表面电荷密度，以及解决纳米摩擦学领域的重要技术瓶颈。现有技术中，球形探针的尖端小球成微米量级，而本发明制备出来的探针尖端小球为纳米尺度，则本发明中的探针更适合纳米尺度的各种测量应用。The present invention provides a method for preparing a nano-probe, which accurately measures the interface in the nanometer-to-micrometer scale, fills the vacancy of the scale, can be used to measure surface potential and surface charge density, and solves important problems in the field of nanotribology technical bottleneck. In the prior art, the tip ball of the spherical probe is in the order of microns, while the probe tip ball prepared by the present invention is in the nanometer scale, so the probe in the present invention is more suitable for various measurement applications in the nanometer scale.
附图说明Description of drawings
图1为普通胶体探针扫描电子显微镜图片。Figure 1 is a scanning electron microscope image of a common colloid probe.
图2为本发明具体实施例中使用的原子力显微镜探针扫描电子显微镜图片。FIG. 2 is a scanning electron microscope picture of the atomic force microscope probe used in the specific embodiment of the present invention.
图3为本发明具体实施例中原子力显微镜探针尖端生长有金纳米颗粒的扫描电子显微镜图片。FIG. 3 is a scanning electron microscope picture of gold nanoparticles grown on the tip of an atomic force microscope probe in a specific embodiment of the present invention.
本发明的最佳实施方式BEST MODE FOR CARRYING OUT THE INVENTION
以下结合附图和实施例对本发明进一步解释说明。The present invention will be further explained below in conjunction with the accompanying drawings and embodiments.
本发明提供的一种纳米探针的制备方法。具体步骤如下：The invention provides a preparation method of nano probe. Specific steps are as follows:
1）制备金属纳米粒子溶液1) Preparation of metal nanoparticle solution
将120-150pM（M即mol/L）的金或银纳米粒子溶液与含有重金属粒子如铜、铅、锌、铁、钴、镍的金属化合物溶液浓度为3-5μM加入到浓度为3-5mM的氨基乙酸-氢氧化钠溶液中进行反应。按照金属纳米粒子溶液、金属离子溶液以及氨基乙酸-氢氧化钠溶液的体积比为(3-5):(1-1.5):(1-1.5)进行混合。混合均匀后，在160-200℃温度下，反应5-10h后，冷却至室温，用去离子水洗涤数次，得到一定浓度的金属纳米粒子溶液。Add 120-150pM (M is mol/L) gold or silver nanoparticle solution and metal compound solution containing heavy metal particles such as copper, lead, zinc, iron, cobalt, nickel at a concentration of 3-5μM to a concentration of 3-5mM. The reaction was carried out in glycine-sodium hydroxide solution. Mix according to the volume ratio of metal nanoparticle solution, metal ion solution and glycine-sodium hydroxide solution as (3-5):(1-1.5):(1-1.5). After mixing evenly, react at 160-200°C for 5-10 hours, then cool to room temperature and wash with deionized water several times to obtain a metal nanoparticle solution with a certain concentration.
2）在AFM探针尖端组装金属纳米粒子2) Assembly of metal nanoparticles at the tip of the AFM probe
首先将表面活性剂P123、1M氢氯酸和乙醇按一定的体积比混合，表面活性剂P123、1M氢氯酸、乙醇和四氯化硅的比例为1:(0.2-0.5):(2-5):0.5-1.5，配置200-500mL溶液。将溶液倒入蒸发皿中，静置12-24h，表面活性剂形成的胶束随着乙醇的挥发。将1）中配置好的溶液加入2）形成的溶液中得到混合溶液。将AFM探针浸入混合溶液15-30min后取出得到金属纳米探针。Firstly, the surfactant P123, 1M hydrochloric acid and ethanol are mixed in a certain volume ratio, and the ratio of surfactant P123, 1M hydrochloric acid, ethanol and silicon tetrachloride is 1:(0.2-0.5):(2- 5): 0.5-1.5, configure 200-500mL solution. Pour the solution into an evaporating dish and let it stand for 12-24 hours, the micelles formed by the surfactant will volatilize with the ethanol. Add the solution prepared in 1) to the solution formed in 2) to obtain a mixed solution. The AFM probe was immersed in the mixed solution for 15-30 min and then taken out to obtain a metal nanoprobe.
实施例1Example 1
1）制备金纳米粒子溶液1) Preparation of gold nanoparticle solution
将120pM的金纳米粒子溶液与含有铁粒子的氧化铁化合物溶液浓度为3μM加入到浓度为3mM的氨基乙酸-氢氧化钠溶液中进行反应。按照金纳米粒子溶液、氧化铁溶液以及氨基乙酸-氢氧化钠溶液的体积比为3:1:1进行混合。混合均匀后，在160℃温度下，反应5h后，冷却至室温，用去离子水洗涤数次，得到一定浓度的金纳米粒子溶液。The 120 pM gold nanoparticle solution and the iron oxide compound solution containing iron particles at a concentration of 3 μM were added to a 3 mM glycine-sodium hydroxide solution for reaction. Mix according to the volume ratio of gold nanoparticle solution, iron oxide solution and glycine-sodium hydroxide solution as 3:1:1. After mixing evenly, react at 160°C for 5 hours, then cool to room temperature and wash with deionized water several times to obtain a gold nanoparticle solution with a certain concentration.
2）在AFM探针尖端组装金纳米粒子2) Assemble gold nanoparticles at the tip of the AFM probe
如图1为普通胶体探针SEM图像，图2为AFM的探针。首先将表面活性剂P123、1M氢氯酸和乙醇按一定的体积比混合，表面活性剂P123、1M氢氯酸、乙醇和四氯化硅的比例为1:0.2:2:0.5，配置200mL溶液。将溶液倒入蒸发皿中，静置12h，表面活性剂形成的胶束随着乙醇的挥发。将1）中配置好的溶液加入2）形成的溶液中得到混合溶液。将AFM探针浸入混合溶液15min后取出得到金纳米探针如图3所示。相比于图1尖端的纳米颗粒极大的缩小了针尖的曲率半价。Figure 1 is an SEM image of a common colloid probe, and Figure 2 is an AFM probe. Firstly, the surfactant P123, 1M hydrochloric acid and ethanol are mixed in a certain volume ratio. The ratio of surfactant P123, 1M hydrochloric acid, ethanol and silicon tetrachloride is 1:0.2:2:0.5, and 200mL solution is prepared. . The solution was poured into an evaporating dish and allowed to stand for 12 h, and the micelles formed by the surfactant were volatilized with ethanol. Add the solution prepared in 1) to the solution formed in 2) to obtain a mixed solution. The AFM probe was immersed in the mixed solution for 15 min and then taken out to obtain the gold nanoprobe as shown in Figure 3. Compared to Fig. 1, the tip of the nanoparticles greatly reduces the curvature of the tip by half the valence.
实施例2Example 2
1）制备金纳米粒子溶液1) Preparation of gold nanoparticle solution
将135pM的金或银纳米粒子溶液与含有铅粒子的氢氧化铅溶液浓度为4μM加入到浓度为4mM的氨基乙酸-氢氧化钠溶液中进行反应。按照金属纳米粒子溶液、金属离子溶液以及氨基乙酸-氢氧化钠溶液的体积比为4:1.2:1.2进行混合。混合均匀后，在180℃温度下，反应8h后，冷却至室温，用去离子水洗涤数次，得到一定浓度的银纳米粒子溶液。A 135 pM solution of gold or silver nanoparticles and a solution of lead hydroxide containing lead particles at a concentration of 4 μM were added to a solution of glycine-sodium hydroxide at a concentration of 4 mM for the reaction. Mix according to the volume ratio of metal nanoparticle solution, metal ion solution and glycine-sodium hydroxide solution as 4:1.2:1.2. After mixing uniformly, react at 180° C. for 8 hours, cool to room temperature, and wash with deionized water several times to obtain a solution of silver nanoparticles with a certain concentration.
2）在AFM探针尖端组装银纳米粒子2) Assembly of silver nanoparticles at the tip of the AFM probe
首先将表面活性剂P123、1M氢氯酸和乙醇按一定的体积比混合，表面活性剂P123、1M氢氯酸、乙醇乙醇和四氯化硅的比例为1:0.3:3:1，配置300mL溶液。将溶液倒入蒸发皿中，静置18h，表面活性剂形成的胶束随着乙醇的挥发。将1）中配置好的溶液加入2）形成的溶液中得到混合溶液。将AFM探针浸入混合溶液25min后取出得到银纳米探针。Firstly, the surfactant P123, 1M hydrochloric acid and ethanol are mixed in a certain volume ratio. The ratio of surfactant P123, 1M hydrochloric acid, ethanol ethanol and silicon tetrachloride is 1:0.3:3:1, and the configuration is 300mL. solution. The solution was poured into an evaporating dish and allowed to stand for 18 h, and the micelles formed by the surfactant were volatilized with the ethanol. Add the solution prepared in 1) to the solution formed in 2) to obtain a mixed solution. The AFM probe was immersed in the mixed solution for 25 min and then taken out to obtain silver nanoprobes.
实施例3Example 3
1）制备银纳米粒子溶液1) Preparation of silver nanoparticle solution
将150pM的金或银纳米粒子溶液与含有铅粒子的氢氧化铅溶液浓度为5μM加入到浓度为5mM的氨基乙酸-氢氧化钠溶液中进行反应。按照金属纳米粒子溶液、金属离子溶液以及氨基乙酸-氢氧化钠溶液的体积比为5:1.5:1.5进行混合。混合均匀后，在200℃温度下，反应10h后，冷却至室温，用去离子水洗涤数次，得到一定浓度的银纳米粒子溶液。A 150 pM solution of gold or silver nanoparticles and a solution of lead hydroxide containing lead particles at a concentration of 5 μM were added to a solution of glycine-sodium hydroxide at a concentration of 5 mM for the reaction. Mix according to the volume ratio of metal nanoparticle solution, metal ion solution and glycine-sodium hydroxide solution as 5:1.5:1.5. After mixing evenly, react at 200°C for 10 hours, then cool to room temperature and wash with deionized water for several times to obtain a solution of silver nanoparticles with a certain concentration.
2）在AFM探针尖端组装银纳米粒子2) Assembly of silver nanoparticles at the tip of the AFM probe
首先将表面活性剂P123、1M氢氯酸和乙醇按一定的体积比混合，表面活性剂P123、1M氢氯酸、乙醇和四氯化硅的比例为1:0.5:5:1.5，配置300mL溶液。将溶液倒入蒸发皿中，静置24h，表面活性剂形成的胶束随着乙醇的挥发。将1）中配置好的溶液加入2）形成的溶液中得到混合溶液。将AFM探针浸入混合溶液30min后取出得到银纳米探针。Firstly, the surfactant P123, 1M hydrochloric acid and ethanol are mixed in a certain volume ratio. The ratio of surfactant P123, 1M hydrochloric acid, ethanol and silicon tetrachloride is 1:0.5:5:1.5, and 300mL solution is prepared. . The solution was poured into an evaporating dish and allowed to stand for 24 hours, and the micelles formed by the surfactant were volatilized with ethanol. Add the solution prepared in 1) to the solution formed in 2) to obtain a mixed solution. The AFM probes were immersed in the mixed solution for 30 min and then taken out to obtain silver nanoprobes.
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection of the present invention. within the range.

Claims (9)

  1. 一种纳米探针的制备方法，其特征在于，该方法通过在AFM显微镜探针的尖端附着金属纳米粒子得到纳米探针，具体包括以下实现步骤：A method for preparing a nanoprobe, characterized in that the method obtains a nanoprobe by attaching metal nanoparticles to the tip of an AFM microscope probe, and specifically includes the following implementation steps:
    1）制备金属纳米粒子溶液1) Preparation of metal nanoparticle solution
    将金属纳米粒子溶液与含有金属离子的金属化合物溶液加入到氨基乙酸-氢氧化钠溶液中进行反应，混合均匀后，在设定温度下，反应一段时间后，冷却至室温，用去离子水洗涤数次，得到预设浓度的金属纳米粒子溶液；The metal nanoparticle solution and the metal compound solution containing metal ions are added to the glycine-sodium hydroxide solution for reaction, after mixing evenly, at the set temperature, after a period of reaction, cooled to room temperature, and washed with deionized water several times to obtain a metal nanoparticle solution with a preset concentration;
    2）在AFM探针尖端组装金属纳米粒子2) Assembly of metal nanoparticles at the tip of the AFM probe
    首先将表面活性剂P123、1M氢氯酸和乙醇混合，再加入四氯化硅搅拌成为溶液，将溶液倒入蒸发皿中，静置，得到半固态硅酸混合溶液；将步骤1）中配置好的金属纳米粒子溶液加入2）形成的半固态硅酸混合溶液中得到混合溶液，将AFM探针浸入混合溶液一段时间后取出得到金属纳米探针。First, mix surfactant P123, 1M hydrochloric acid and ethanol, then add silicon tetrachloride and stir to form a solution, pour the solution into an evaporating dish, and let it stand to obtain a semi-solid silicic acid mixed solution; configure in step 1) The good metal nanoparticle solution is added to the semi-solid silicic acid mixed solution formed in 2) to obtain a mixed solution, and the AFM probe is immersed in the mixed solution for a period of time and taken out to obtain a metal nanoprobe.
  2. 根据权利要求1所述的一种纳米探针的制备方法，其特征在于，步骤1）中，金属纳米粒子溶液的浓度为120-150pM，选择银纳米粒子或金纳米粒子。The method for preparing a nanoprobe according to claim 1, wherein in step 1), the concentration of the metal nanoparticle solution is 120-150 pM, and silver nanoparticles or gold nanoparticles are selected.
  3. 根据权利要求1所述的一种纳米探针的制备方法，其特征在于，步骤1）中，金属粒子类型选择重金属粒子中的铜、铅、锌、铁、钴和镍的一中，浓度为3-5μM。The method for preparing a nanoprobe according to claim 1, wherein in step 1), the metal particle type is selected from one of copper, lead, zinc, iron, cobalt and nickel in the heavy metal particles, and the concentration is 3-5 μM.
  4. 根据权利要求1所述的一种纳米探针的制备方法，其特征在于，步骤1）中，氨基乙酸-氢氧化钠的浓度为3-5mM。The method for preparing a nanoprobe according to claim 1, wherein in step 1), the concentration of glycine-sodium hydroxide is 3-5mM.
  5. 根据权利要求1所述的一种纳米探针的制备方法，其特征在于，步骤1）中，金属纳米粒子溶液、金属离子溶液以及氨基乙酸-氢氧化钠溶液的体积比为(3-5):(1-1.5):(1-1.5)。The method for preparing a nanoprobe according to claim 1, wherein in step 1), the volume ratio of the metal nanoparticle solution, the metal ion solution and the glycine-sodium hydroxide solution is (3-5) :(1-1.5):(1-1.5).
  6. 根据权利要求1所述的一种纳米探针的制备方法，其特征在于，步骤1）中，反应温度为160-200℃，反应时间为5-10h。The method for preparing a nanoprobe according to claim 1, wherein in step 1), the reaction temperature is 160-200°C, and the reaction time is 5-10h.
  7. 根据权利要求1所述的一种纳米探针的制备方法，其特征在于，步骤2）中，表面活性剂P123、1M氢氯酸和乙醇的体积比为1:(0.2-0.5):(2-5):(0.5-1.5)。The method for preparing a nanoprobe according to claim 1, wherein in step 2), the volume ratio of surfactant P123, 1M hydrochloric acid and ethanol is 1:(0.2-0.5):(2 -5):(0.5-1.5).
  8. 根据权利要求1所述的一种纳米探针的制备方法，其特征在于，步骤2）中，溶液倒入蒸发皿后静置12-24h。The method for preparing a nanoprobe according to claim 1, wherein in step 2), the solution is poured into an evaporating dish and left to stand for 12-24 hours.
  9. 根据权利要求1所述的一种纳米探针的制备方法，其特征在于，步骤2）中，将AFM探针浸入混合溶液15-30min后取出，得到金属纳米探针。The method for preparing a nanoprobe according to claim 1, wherein in step 2), the AFM probe is immersed in the mixed solution for 15-30min and then taken out to obtain the metal nanoprobe.
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