Probe for electrochemical microscope and method for manufacturing an electrochemical microscope probe

Abstract

To provide a probe for electrochemical microscope that has a tip part small enough in inner diameter for use for electrochemical microscopic measurement, and a method of manufacturing the probe for electrochemical microscope.SOLUTION: A probe for electrochemical microscope comprises a cylindrical cylinder part 10 made of a glass base material, a tip part 20 connecting with the cylinder part 10 and decreasing in inner diameter from the cylinder part toward an end part E, and an opening part 30 arranged at the end part E, wherein the opening part 30 has an inner diameter of 200 nm or less, and the tip part 20 has its outer surface formed of a resin composition containing highly chemical-resistant organic resin, which has a weight variation rate of ±5°C or less after being dipped in a 30 wt.% aqueous sodium hydride at 23±1°C for one week.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a probe for an electrochemical microscope (hereinafter referred to as an electrochemical microscope, which includes a scanning electrochemical microscope, a scanning ion conductance microscope, a scanning electrochemical cell microscope, a nanoelectrochemical cell microscope, a scanning tunneling microscope for electrochemistry, a scanning atomic force microscope for electrochemistry, and a composite machine of these and a scanning probe microscope) and a method for manufacturing the probe for an electrochemical microscope.

Background Art

[0002] An electrochemical microscope is known as an analytical instrument for detecting and visualizing electrochemical reactions at the nanoscale and microscale.

[0003] In an electrochemical microscope, a micro glass pipette filled with an electrolyte is used as a probe. Electrodes are arranged inside the probe filled with an electrolytic solution and in the electrolytic solution where the sample is placed, and the ionic current generated between the two electrodes is used as a signal. This ionic current decreases when the tip of the probe approaches and is shielded by the sample. Utilizing this phenomenon, the electrode can be scanned to image the three-dimensional shape of the sample surface. The electrochemical microscope is expected to be used for analyzing electrochemical reactions such as lithium-ion batteries, fuel cells, and catalysts.

[0004] The resolution of an electrochemical microscope depends on the inner diameter of the probe. For example, Patent Document 1 discloses a probe made of borosilicate or quartz. [[ID=I22]]

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, probes made of borosilicate or quartz have the problem of being brittle. Furthermore, probes made of borosilicate or quartz present challenges in electrochemical microscopy measurements under strongly alkaline or strongly acidic environments.

[0007] To improve the chemical resistance of probes, probes made of highly chemical-resistant resins can be considered. However, conventional methods such as laser pullers used for sharpening pipettes have the problem of burning the resin, making it impossible to obtain probes with sufficiently small inner diameters required for electrochemical microscopy.

[0008] This invention was made in view of the above circumstances, and aims to provide an electrochemical microscope probe and a method for manufacturing an electrochemical microscope probe, in which the inner diameter of the opening at the tip of the probe is small enough to be used for measurements with an electrochemical microscope, and which has excellent chemical resistance. [Means for solving the problem]

[0009] To solve the aforementioned problems, the present invention proposes the following means. (1) The probe for an electrochemical microscope according to embodiment 1 of the present invention is A cylindrical part made of a glass substrate, A tip portion is continuously connected to the cylindrical portion, and its inner diameter decreases towards the end from the cylindrical portion. An opening located at the end, Equipped with, The inner diameter of the aforementioned opening is 200 nm or less. The outer surface of the tip portion is made of a resin composition containing a highly chemical-resistant organic resin. The aforementioned highly chemical-resistant organic resin is a resin whose weight change rate before and after immersion in a 30 wt% sodium hydroxide aqueous solution at 23 ± 1°C for one week is within ±5%. (2) Aspect 2 of the present invention is the electrochemical microscope probe of Aspect 1, The aforementioned tip portion The glass substrate and, A resin composition layer made of the resin composition is provided on the glass substrate, It may be provided. (3) Embodiment 3 of the present invention is an electrochemical microscope probe according to Embodiment 2, The average thickness of the resin composition layer may be 1 / 2 or less of the inner diameter of the opening. (4) A fourth aspect of the present invention is an electrochemical microscope probe according to aspect 1, wherein in a region where the inner diameter of the tip is 1 μm or less, the tip may be made of the resin composition. (5) Embodiment 5 of the present invention is an electrochemical microscope probe according to any one of Embodiments 1 to 4, wherein the highly chemical-resistant organic resin may be a fluororesin. (6) Embodiment 6 of the present invention is an electrochemical microscope probe according to any one of embodiments 1 to 5, wherein the glass substrate may be lead-doped soda glass, borosilicate, or quartz. (7) The method for manufacturing an electrochemical microscope probe according to aspect 7 of the present invention is: A cylindrical cylindrical part, A tip portion is continuously connected to the cylindrical portion, and its inner diameter decreases towards the end from the cylindrical portion. An opening is located at the end and has an inner diameter of 200 nm or less, A resin composition layer made of a resin composition containing a highly chemical-resistant organic resin is formed at the tip of the hollow member having the above-mentioned features. The hollow member is made of a glass substrate, The aforementioned highly chemical-resistant organic resin is a resin whose weight change rate before and after immersion in a 30 wt% sodium hydroxide aqueous solution at 23 ± 1°C for one week is within ±5%. (8) Aspect 8 of the present invention is the method for manufacturing an electrochemical microscope probe according to aspect 7, wherein the highly chemical-resistant organic resin may be a fluororesin. (9) Aspect 9 of the present invention is a method for manufacturing an electrochemical microscope probe according to aspect 7 or 8, wherein the glass substrate may be lead-doped soda glass, borosilicate, or quartz. (10) Aspect 10 of the present invention is a method for manufacturing an electrochemical microscope probe according to any one of aspects 7 to 9, The resin composition layer may be formed by a spray method. (11)Aspect 11 of the present invention is that the method for manufacturing a probe for an electrochemical microscope according to any one of Aspects 7 to 10 is After forming the resin composition layer, at least a part of the glass substrate at the tip may be dissolved.

Advantages of the Invention

[0010] According to the above aspect of the present invention, it is possible to provide a probe for an electrochemical microscope in which the inner diameter of the opening at the tip of the probe is small enough to be used for measurement of an electrochemical microscope and which has excellent chemical resistance, and a method for manufacturing a probe for an electrochemical microscope.

Brief Description of the Drawings

[0011] [Figure 1] It is a schematic cross-sectional view of a probe for an electrochemical microscope according to an embodiment of the present invention. [Figure 2] It is an enlarged cross-sectional view of the probe for an electrochemical microscope shown in FIG. 1. [Figure 3] It is a schematic cross-sectional view of a hollow member for manufacturing a probe for an electrochemical microscope according to an embodiment of the present invention. [Figure 4] It is a schematic cross-sectional view of a probe for an electrochemical microscope according to another embodiment of the present invention. [Figure 5] It is an enlarged cross-sectional view of the probe for an electrochemical microscope shown in FIG. 4. [Figure 6] It is a diagram for explaining the chemical resistance test results of Example 1 and Comparative Example 1. [Figure 7] It is a diagram for explaining the relationship between the immersion time and the current value in Example 2 and Comparative Example 1.

Modes for Carrying Out the Invention

[0012] The electrochemical microscope probe described herein will be explained in detail below with reference to the drawings. Note that, for the sake of clarity, the drawings used in the following description may show enlarged versions of key features, and the dimensional ratios of each component may not be the same as those in reality. Furthermore, the materials, dimensions, etc., exemplified in the following description are merely examples, and the present invention is not limited to these; it can be modified as appropriate without altering its essence.

[0013] (First Embodiment) Figure 1 is a schematic cross-sectional view of the electrochemical microscope probe 100 according to the first embodiment. Figure 2 is an enlarged cross-sectional view of the electrochemical microscope probe 100 of Figure 1. As shown in Figures 1 and 2, the electrochemical microscope probe 100 comprises a cylindrical portion 10 made of a glass substrate, a tip portion 20 continuously connected to the cylindrical portion 10 and whose inner diameter decreases from the cylindrical portion 10 toward the end E, and an opening 30 located at the end E. Each part will be described below.

[0014] "Cylindrical section" The cylindrical portion 10 is cylindrical and made of a glass substrate. The cylindrical portion is cylindrical with substantially the same diameter in the longitudinal direction. The inner diameter of the cylindrical portion 10 is not particularly limited as long as it can be measured with an electrochemical microscope. For example, it is 0.5 to 2.0 mm. The outer diameter of the cylindrical portion 10 is not particularly limited as long as it can be measured with an electrochemical microscope. For example, the outer diameter of the cylindrical portion 10 is 0.90 mm to 3.00 mm.

[0015] The glass substrate 50 constituting the cylindrical portion 10 is not particularly limited, but may be, for example, lead-doped soda glass, borosilicate, or quartz.

[0016] "Tip" The tip portion 20 is continuously connected to the cylindrical portion 10, and its inner diameter decreases from the cylindrical portion 10 toward the end portion E. The outer surface of the tip portion 20 is made of a resin composition containing a highly chemical-resistant organic resin. The tip portion 20 of the first embodiment comprises a glass substrate 50 and a resin composition layer 40 provided on the surface of the glass substrate 50 (the outer surface of the tip portion 20).

[0017] <Glass substrate at the tip> In the first embodiment, the glass substrate 50 of the tip portion 20 is the same as the glass substrate of the cylindrical portion 10.

[0018] <Resin composition layer at the tip> The resin composition layer 40 is made of a resin composition. The resin composition contains a highly chemical-resistant organic resin. The highly chemical-resistant organic resin is a resin whose weight change rate before and after immersion in a 30 wt% sodium hydroxide aqueous solution at 23 ± 1°C for one week is within ±5%. If the weight change rate of the highly chemical-resistant organic resin before and after immersion in a 30 wt% sodium hydroxide aqueous solution at 23 ± 1°C for one week is within ±5%, the chemical resistance of the electrochemical microscope probe 100 is improved, making measurements possible in alkaline and acidic environments. Furthermore, forming the resin composition layer 40 on a glass substrate improves the flexibility of the electrochemical microscope probe 100. More preferably, the resin has a weight change rate of within ±1% before and after immersion in a 30 wt% sodium hydroxide aqueous solution at 23 ± 1°C for one week. The lower the weight change rate of the highly chemical-resistant organic resin, the higher the chemical resistance, so a weight change rate of 0% is most preferable. The resin composition is solid at 20°C to 30°C.

[0019] The highly chemical-resistant organic resin is not particularly limited as long as it satisfies the above-mentioned weight change rate, but for example, fluororesins are preferred as highly chemical-resistant organic resins. Examples of fluororesins include polytetrafluoroethylene (PTFE), copolymer of ethylene and tetrafluoroethylene (ETFE), copolymer of ethylene and chlorotrifluoroethylene (ECTFE), copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA), copolymer of tetrafluoroethylene and hexafluoropropylene (FEP), copolymer of tetrafluoroethylene, perfluoroalkyl vinyl ether and hexafluoropropylene (EPE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), etc. Highly chemical-resistant organic resins may be used individually or in combination of two or more of these.

[0020] The content of the highly chemical-resistant organic resin in the resin composition is preferably, for example, 40% by mass or more. A more preferable content of the highly chemical-resistant organic resin in the resin composition is 60% by mass or more. A still preferable content of the highly chemical-resistant organic resin in the resin composition is 80% by mass or more. The content of the highly chemical-resistant organic resin in the resin composition is preferably 100% by mass or less. More preferably, the content of the highly chemical-resistant organic resin in the resin composition is 90% by mass or less.

[0021] The form of the highly chemical-resistant organic resin in the resin composition is not particularly limited. For example, it may exist in particulate form in the resin composition. When the highly chemical-resistant organic resin is in particulate form, its average particle size is preferably, for example, 1 μm or less. A more preferred particle size for the highly chemical-resistant organic resin is 200 nm or less, even more preferably 20 nm or less, and particularly preferably 5 nm or less. The average particle size of the highly chemical-resistant organic resin can be measured, for example, by laser diffraction in accordance with JIS Z 8825:2013.

[0022] The resin composition may further contain a binder resin to improve the adhesion between the highly chemical-resistant organic resin and the glass substrate. The binder resin is not particularly limited, but examples include acrylic resin, cellulose resin, imide resin, and urethane resin. It is preferable that the binder resin also has chemical resistance. The content of the binder resin is not particularly limited as long as the chemical resistance of the electrochemical microscope probe 100 does not decrease. For example, the content of the binder resin in the resin composition is preferably 10% by mass or more. More preferably, the content of the binder resin in the resin composition is 30% by mass or more. For example, for example, the content of the binder resin in the resin composition is preferably 60% by mass or less. More preferably, the content of the binder resin in the resin composition is 40% by mass or less.

[0023] Depending on the application, the resin composition may contain surfactants, dispersants, rust inhibitors, antioxidants, extreme pressure agents, etc.

[0024] The average thickness of the resin composition layer 40 is not particularly limited. For example, the average thickness of the resin composition layer 40 is 1 / 2 or less of the inner diameter of the opening. Preferably, the lower limit of the average thickness of the resin composition layer 40 is 4 nm or more. The average thickness of the resin composition layer can be measured, for example, by observing the cross-section of the electrochemical microscope probe 100 with a scanning electron microscope (SEM).

[0025] "Opening" The aperture 30 is located at end E. The inner diameter D of the aperture 30 is preferably 10 μm or less. More preferably, the inner diameter D of the aperture 30 is 2 μm or less. The inner diameter is the inner diameter of the aperture, and if the inner shape of the aperture 30 is not a perfect circle, the inner diameter is the longest length between two points on the inside. There is no particular lower limit to the inner diameter D, but for example, it is 1 nm or more. A smaller inner diameter D of the aperture 30 is preferable because it improves the spatial resolution of the electrochemical microscope.

[0026] (Method of manufacturing a probe for an electrochemical microscope) Next, a method for manufacturing the electrochemical microscope probe 100 will be described. In the method for manufacturing the electrochemical microscope probe 100 according to this embodiment, a resin composition layer 40 made of a resin composition containing a highly chemical-resistant organic resin is formed on the tip portion 21 of a hollow member 200 made of a glass substrate. The highly chemical-resistant organic resin forming the resin composition layer 40 is a resin whose weight change rate before and after immersion in a 30 wt% sodium hydroxide aqueous solution at 23 ± 1°C for one week is within ±5%. The requirements will be described below.

[0027] (Hollow member) Figure 3 is a schematic cross-sectional view of the hollow member 200. The hollow member 200 comprises a cylindrical portion 11, a tip portion 21 continuously connected to the cylindrical portion 11 and whose inner diameter decreases from the cylindrical portion 11 toward the end E1, and an opening 31 with an inner diameter of 200 nm located at the end E1. The hollow member may be made using a probe made of a glass substrate for electrochemical microscopy, or it may be manufactured from a cylindrical glass capillary by a known method. As a method of manufacturing from a glass capillary, for example, the tip shape of the pipette can be adjusted by using a laser puller device and controlling the laser irradiation intensity, irradiation range, tensile strength, etc.

[0028] The glass substrate constituting the hollow member 200 may be lead-doped soda glass, borosilicate, or quartz. Quartz is preferred to reduce the inner diameter of the opening 31.

[0029] (Formation of resin composition layer) A resin composition layer 40 is formed on the tip portion 21 of the hollow member 200. The method for forming the resin composition layer 40 is not particularly limited. For example, it may be formed by applying a paint in which a highly chemical-resistant organic resin is dispersed or dissolved in a solvent. Methods for applying the paint include spraying and dipping. Spraying is particularly preferred.

[0030] "paint" The coating used in the method for manufacturing an electrochemical microscope probe according to this embodiment preferably contains a solvent and a highly chemical-resistant organic resin that is dispersed or dissolved in the solvent.

[0031] The highly chemical-resistant organic resin dispersed or dissolved in the paint is a resin whose weight change rate before and after immersion in a 30 wt% sodium hydroxide aqueous solution at 23 ± 1°C for one week is within ±5%. When the weight change rate before and after immersion in a 30 wt% sodium hydroxide aqueous solution at 23 ± 1°C for one week is within ±5%, the chemical resistance of the electrochemical microscope probe 100 is improved, enabling measurements in alkaline and acidic environments. The highly chemical-resistant organic resin is not particularly limited as long as it satisfies the above weight change rate, but fluororesins are preferred, for example. Examples of fluororesins used as highly chemical-resistant organic resins include polytetrafluoroethylene (PTFE), copolymers of ethylene and tetrafluoroethylene (ETFE), copolymers of ethylene and chlorotrifluoroethylene (ECTFE), copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA), copolymers of tetrafluoroethylene and hexafluoropropylene (FEP), copolymers of tetrafluoroethylene, perfluoroalkyl vinyl ether, and hexafluoropropylene (EPE), polychlorotrifluoroethylene (PCTFE), and polyvinylidene fluoride (PVDF). These highly chemical-resistant organic resins may be used individually or in combination of two or more. From the viewpoint of chemical resistance and flexibility, polyethylene tetrafluoroethylene is particularly preferred as the highly chemical-resistant organic resin in solvents.

[0032] The mass ratio of the highly chemical-resistant organic resin to the total solids in the paint is preferably, for example, 40% by mass or more. A more preferable mass ratio of the highly chemical-resistant organic resin to the total solids in the paint is 60% by mass or more. An even more preferable mass ratio of the highly chemical-resistant organic resin to the total solids in the paint is 80% by mass or more. The mass ratio of the highly chemical-resistant organic resin to the total solids in the paint is preferably 100% by mass or less. More preferably, the content of the highly chemical-resistant organic resin to the total solids in the paint is 90% by mass or less.

[0033] The form of the highly chemical-resistant organic resin in the paint is not particularly limited. The highly chemical-resistant organic resin may be dissolved in the paint or dispersed. If the highly chemical-resistant organic resin is dispersed in the paint, it may be in particulate form. If the highly chemical-resistant organic resin is in particulate form, its average particle size is preferably, for example, 1 μm or less. A more preferable particle size for the highly chemical-resistant organic resin is 400 nm or less. The average particle size of the highly chemical-resistant organic resin can be measured by laser diffraction, for example, in accordance with JIS Z 8825:2013.

[0034] The paint may further contain a binder resin to improve the adhesion between the highly chemical-resistant organic resin and the glass substrate. The binder resin is not particularly limited, but examples include acrylic resin, cellulose resin, imide resin, and urethane resin. It is preferable that the binder resin also has chemical resistance. The mass ratio of the binder resin to the total solid content of the paint is not particularly limited, as long as the chemical resistance of the electrochemical microscope probe 100 does not decrease. For example, it is preferable that the mass ratio of the binder resin to the total solid content of the paint is 10% by mass or more. More preferably, it is 30% by mass or more. For example, it is preferable that the mass ratio of the binder resin to the total solid content of the paint is 60% by mass or less. More preferably, it is 40% by mass or less.

[0035] Depending on the application, surfactants, dispersants, rust inhibitors, antioxidants, extreme pressure agents, etc., may be added to the paint.

[0036] The solvent used in the paint is not particularly limited, as long as it can dissolve or disperse the highly chemical-resistant organic resin. Examples include hydrofluoroethers such as methyl perfluoroether, methyl nonafluorobutyl ether, and methyl nonafluoroisobutyl ether.

[0037] (Second Embodiment) Figure 4 is a schematic cross-sectional view of the electrochemical microscope probe 100A according to the second embodiment. Figure 5 is an enlarged cross-sectional view of the electrochemical microscope probe 100 of Figure 4. As shown in Figures 4 and 5, the electrochemical microscope probe 100A comprises a cylindrical portion 10 made of a glass substrate, a tip portion 20A continuously connected to the cylindrical portion 10 and whose inner diameter decreases from the cylindrical portion 10 toward the end E2, and an opening 30A located at the end E2. The parts will be described below. In the following description, components having the same or similar functions will be denoted by the same reference numerals. Components having the same or similar functions may not be described repeatedly.

[0038] "Tip" The tip portion 20A is continuously connected to the cylindrical portion 10, and its inner diameter decreases from the cylindrical portion 10 toward the end portion E2. The outer surface of the tip portion 20A is made of a resin composition 40A containing a highly chemical-resistant organic resin. In the second embodiment, at least in the region where the inner diameter of the tip portion 20A is 1 μm or less, the tip portion 20A is made of the resin composition 40A. In the region where the inner diameter of the tip portion 20A is greater than 1 μm, the composition of the tip portion 20A is not particularly limited and may consist only of the resin composition 40A, or it may consist of a glass substrate 50 and a resin composition layer provided on the surface of the glass substrate 50 (the outer surface of the tip portion 20A), as in the first embodiment. The glass substrate 50 is the same as the glass substrate of the cylindrical portion 10.

[0039] <Resin composition for the tip> In the region where the inner diameter of the tip portion 20A is 1 μm or less, the tip portion 20A is made of resin composition 40A. Since the tip portion 20A is made of resin composition 40A in the region where the inner diameter of the tip portion 20A is 1 μm or less, the flexibility of the electrochemical microscope probe 100A is improved, and its chemical resistance is also improved. Resin composition 40A contains a highly chemical-resistant organic resin. The highly chemical-resistant organic resin is a resin in which the weight change rate of the highly chemical-resistant organic resin before and after immersion in a 30 wt% sodium hydroxide aqueous solution at 23 ± 1°C for one week is within ±5%. If the weight change rate of the highly chemical-resistant organic resin before and after immersion in a 30 wt% sodium hydroxide aqueous solution at 23 ± 1°C for one week is within ±5%, the chemical resistance of the electrochemical microscope probe 100 is improved, and measurements can be taken in alkaline and acidic environments. More preferably, the resin has a weight change rate of ±1% or less before and after immersion in a 30 wt% sodium hydroxide aqueous solution at 23±1°C for one week. The lower the weight change rate, the higher the chemical resistance, so a weight change rate of 0% is most preferable.

[0040] The highly chemical-resistant organic resin is not particularly limited as long as it satisfies the above-mentioned weight change rate and maintains sufficient strength so that the tip portion 20A can maintain its shape during measurement. For example, fluororesins are preferred as highly chemical-resistant organic resins. Examples of fluororesins include polytetrafluoroethylene (PTFE), copolymer of ethylene and tetrafluoroethylene (ETFE), copolymer of ethylene and chlorotrifluoroethylene (ECTFE), copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA), copolymer of tetrafluoroethylene and hexafluoropropylene (FEP), copolymer of tetrafluoroethylene, perfluoroalkyl vinyl ether and hexafluoropropylene (EPE), polychlorotrifluoroethylene (PCTFE), and polyvinylidene fluoride (PVDF). Highly chemical-resistant organic resins may be used individually or in combination of two or more of these.

[0041] The content of the highly chemical-resistant organic resin in the resin composition 40A is preferably, for example, 40% by mass or more. A more preferable content of the highly chemical-resistant organic resin in the resin composition 40A is 60% by mass or more. A still preferable content of the highly chemical-resistant organic resin in the resin composition 40A is 80% by mass or more. The content of the highly chemical-resistant organic resin in the resin composition 40A is preferably 100% by mass or less. More preferably, the content of the highly chemical-resistant organic resin in the resin composition 40A is 90% by mass or less.

[0042] The form of the highly chemical-resistant organic resin in the resin composition 40A is not particularly limited. For example, the highly chemical-resistant organic resin may be present in particulate form in the resin composition 40A. When the highly chemical-resistant organic resin is in particulate form, its average particle size is preferably, for example, 1 μm or less. A more preferable particle size for the highly chemical-resistant organic resin is 400 nm or less. The average particle size of the highly chemical-resistant organic resin can be measured, for example, by laser diffraction in accordance with JIS Z 8825:2013.

[0043] The resin composition 40A may further contain a binder resin to improve the adhesion between the highly chemical-resistant organic resin and the glass substrate. The binder resin is not particularly limited, but examples include acrylic resin, cellulose resin, imide resin, and urethane resin. It is preferable that the binder resin also has chemical resistance. The amount of binder resin is not particularly limited as long as the chemical resistance of the electrochemical microscope probe 100 does not decrease. For example, the content of the binder resin in the resin composition 40A is preferably 10% by mass or more. More preferably, the content of the binder resin in the resin composition 40A is 30% by mass or more. For example, for example, the content of the binder resin in the resin composition 40A is preferably 60% by mass or less. More preferably, the content of the binder resin in the resin composition 40A is 40% by mass or less.

[0044] Depending on the application, the resin composition 40A may contain surfactants, dispersants, rust inhibitors, antioxidants, extreme pressure agents, and the like.

[0045] The average thickness of the resin composition 40A is not particularly limited, as long as the strength necessary for measurement is maintained. For example, the average thickness of the resin composition 40A is 1 / 2 or less of the inner diameter of the opening. Preferably, the lower limit of the average thickness of the resin composition layer 40A is 100 nm or more.

[0046] "Opening" The aperture 30A is located at end E2. The inner diameter D of aperture 30A is 400 nm or less. The lower limit of the inner diameter D is not particularly limited, but for example, it is 1 nm or more. A smaller inner diameter D1 of aperture 30A is preferable because it improves the spatial resolution of the electrochemical microscope.

[0047] (Method of manufacturing a probe for an electrochemical microscope) Next, a method for manufacturing the electrochemical microscope probe 100A will be described. In the method for manufacturing the electrochemical microscope probe 100A according to this embodiment, a resin composition layer 40 made of a resin composition 40A containing a highly chemical-resistant organic resin is formed on the tip portion 21 of a hollow member 200 made of a glass substrate (Figure 2). The weight change rate of the highly chemical-resistant organic resin before and after immersion of the highly chemical-resistant organic resin forming the resin composition layer 40 in a 30 wt% sodium hydroxide aqueous solution at 23 ± 1°C for one week is within ±5%. The following describes each requirement.

[0048] (Hollow member) The hollow member 200 comprises a cylindrical portion 11, a tip portion 21 continuously connected to the cylindrical portion 11 and whose inner diameter decreases from the cylindrical portion 11 toward the end E1, and an opening 31 with an inner diameter of 200 nm located at the end E. The hollow member may be made using a probe made of a glass substrate for electrochemical microscopy, or it may be manufactured from a cylindrical glass capillary by a known method. As a method of manufacturing from a glass capillary, for example, the tip shape of the pipette can be adjusted by using a laser puller device and controlling the laser irradiation intensity, irradiation range, tensile strength, etc.

[0049] The glass substrate constituting the hollow member 200 may be lead-doped soda glass, borosilicate, or quartz. Quartz is preferred to reduce the inner diameter of the opening 31.

[0050] (Formation of resin composition layer) A resin composition layer 40 is formed on the tip portion 21 of the hollow member 200. The method for forming the resin composition layer 40 is not particularly limited. For example, it may be formed by applying a paint in which a highly chemical-resistant organic resin is dispersed or dissolved in a solvent. Methods for applying the paint include spraying and dipping. Spraying is particularly preferred.

[0051] "paint" The coating used in the method for manufacturing an electrochemical microscope probe according to this embodiment preferably contains a solvent and a highly chemical-resistant organic resin that is dispersed or dissolved in the solvent.

[0052] The highly chemical-resistant organic resin dispersed or dissolved in the paint is a resin whose weight change rate before and after immersion in a 30 wt% sodium hydroxide aqueous solution at 23 ± 1°C for one week is within ±5%. When the weight change rate before and after immersion in a 30 wt% sodium hydroxide aqueous solution at 23 ± 1°C for one week is within ±5%, the chemical resistance of the electrochemical microscope probe 100 is improved, enabling measurements in alkaline and acidic environments. The highly chemical-resistant organic resin is not particularly limited as long as it satisfies the above weight change rate, but fluororesins are preferred, for example. Examples of fluororesins used as highly chemical-resistant organic resins include polytetrafluoroethylene (PTFE), copolymers of ethylene and tetrafluoroethylene (ETFE), copolymers of ethylene and chlorotrifluoroethylene (ECTFE), copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA), copolymers of tetrafluoroethylene and hexafluoropropylene (FEP), copolymers of tetrafluoroethylene, perfluoroalkyl vinyl ether, and hexafluoropropylene (EPE), polychlorotrifluoroethylene (PCTFE), and polyvinylidene fluoride (PVDF). Highly chemical-resistant organic resins may be used individually or in combination of two or more of these.

[0053] The mass ratio of the highly chemical-resistant organic resin to the total solids in the paint is preferably, for example, 40% by mass or more. A more preferable mass ratio of the highly chemical-resistant organic resin to the total solids in the paint is 60% by mass or more. An even more preferable mass ratio of the highly chemical-resistant organic resin to the total solids in the paint is 80% by mass or more. The mass ratio of the highly chemical-resistant organic resin to the total solids in the paint is preferably 100% by mass or less. More preferably, the content of the highly chemical-resistant organic resin to the total solids in the paint is 90% by mass or less.

[0054] The form of the highly chemical-resistant organic resin in the paint is not particularly limited. The highly chemical-resistant organic resin may be dissolved in the paint or dispersed. When the highly chemical-resistant organic resin is dispersed in the paint, it is preferably in particulate form. When the highly chemical-resistant organic resin is in particulate form, its average particle size is preferably, for example, 1 μm or less. A more preferable particle size for the highly chemical-resistant organic resin is 400 nm or less. The average particle size of the highly chemical-resistant organic resin can be measured, for example, by laser diffraction in accordance with JIS Z 8825:2013.

[0055] The paint may further contain a binder resin to improve the adhesion between the highly chemical-resistant organic resin and the glass substrate. The binder resin is not particularly limited, but examples include acrylic resin, cellulose resin, imide resin, and urethane resin. It is preferable that the binder resin also has chemical resistance. The mass ratio of the binder resin to the total solid content of the paint is not particularly limited, as long as the chemical resistance of the electrochemical microscope probe 100 does not decrease. For example, it is preferable that the mass ratio of the binder resin to the total solid content of the paint is 10% by mass or more. More preferably, it is 30% by mass or more. For example, it is preferable that the mass ratio of the binder resin to the total solid content of the paint is 60% by mass or less. More preferably, it is 40% by mass or less.

[0056] Depending on the application, surfactants, dispersants, rust inhibitors, antioxidants, extreme pressure agents, etc., may be added to the paint.

[0057] The solvent used in the paint is not particularly limited, as long as it can dissolve or disperse the highly chemical-resistant organic resin. Examples include hydrofluoroethers such as methyl perfluoroether, methyl nonafluorobutyl ether, and methyl nonafluoroisobutyl ether.

[0058] Next, after forming the resin composition layer 40, the glass substrate 50 located at a certain distance from the end of the tip portion 21 is dissolved. Specifically, after dissolving the glass substrate 50, the glass substrate 50 is dissolved in a region where the inner diameter of the tip portion 20A is 1 μm or less, so that the constituent material consists only of the resin composition 40A.

[0059] The method for dissolving the glass substrate 50 is not particularly limited. For example, it may be dissolved by immersing the tip 21 in an aqueous sodium hydroxide solution.

[0060] It should be noted that the technical scope of the present invention is not limited to the embodiments described above, and various modifications can be made without departing from the spirit of the invention. For example, in the first embodiment, the cylindrical portion 10 and the tip portion 20 used the same glass substrate, but different glass substrates may be used.

[0061] Furthermore, without departing from the spirit of the present invention, the components in the above embodiments may be replaced with well-known components as appropriate, and the above embodiments may be combined as appropriate. [Examples]

[0062] Next, embodiments of the present invention will be described. The conditions in the embodiments are merely examples of conditions adopted to confirm the feasibility and effectiveness of the present invention, and the present invention is not limited to these examples of conditions. The present invention can adopt various conditions as long as they do not depart from the spirit of the invention and achieve the objectives of the present invention.

[0063] (Resin composition layer formed on a glass slide) Four 1cm wide strips of glass slide (Matsunami Glass S1112 83-0277, size 72 x 26mm, thickness 1.0mm~1.2mm) were cut, and a polytetrafluoroethylene (fluororesin) spray (FC-250) manufactured by Fine Chemical Japan was sprayed onto them for 2 seconds to form a resin composition layer, thereby obtaining a glass slide with a resin composition layer.

[0064] (Evaluation slide) Four 1cm wide strips of microscope slide glass (Matsunami Glass S1112 83-0277, size 72 x 26mm, thickness 1.0mm-1.2mm) were cut to obtain evaluation slide glass.

[0065] (Chemical resistance test of resin) The above resin composition layer-forming slide glass and evaluation slide glass were immersed in a sodium hydroxide aqueous solution (30 wt%) at room temperature (20°C to 25°C) for 5 days. The weight before and after immersion was measured using an electronic balance, and the change in weight was examined.

[0066] Neither the resin composition layer-formed slide nor the regular slide showed any change in appearance when immersed in a sodium hydroxide aqueous solution. The weight change of the resin composition layer-formed slide was 0%, while the weight change rate of the evaluation slide was 0.1%. Therefore, regarding fluororesin, there was no weight change, and the chemical resistance of the resin composition layer-formed slide with a resin composition layer made of fluororesin was confirmed.

[0067] (Example 1) Hollow members with an inner diameter of 100 nm at the opening were fabricated using glass capillaries (HARVARD CAPILLARIES series and SUTTER QUARTZ GLASS) with a laser puller (SUTTER MODEL P-2000). Subsequently, a fluororesin spray (FC-250) manufactured by Fine Chemical Japan was sprayed onto the tip of the hollow member for 2 seconds to form a resin composition layer, thereby fabricating the electrochemical microscope probe of Example 1. When the film was fabricated on a glass slide under the same conditions, the film thickness was approximately 3.5 nm.

[0068] (Example 2) A hollow member with an inner diameter of 100 nm at the opening was fabricated using a laser puller (SUTTER MODEL P-2000) with glass capillaries (HARVARD CAPILLARIES series and SUTTER QUARTZ GLASS). Subsequently, a fluororesin spray (FC-250) manufactured by Fine Chemical Japan was sprayed twice for 2 seconds each onto the tip of the hollow member to form a resin composition layer, thereby fabricating the electrochemical microscope probe of Example 1. When the film was fabricated on a glass slide under the same conditions, the film thickness was approximately 7 nm.

[0069] (Comparative example) A glass capillary (HARVARD CAPILLARIES series and SUTTER QUARTZ GLASS) was used to fabricate an electrochemical microscope probe for Comparative Example 1 with an inner aperture diameter of 100 nm using a laser puller.

[0070] (Chemical resistance test) The electrochemical microscope probes from Example 1 and Comparative Example 1 were immersed in a 30 wt% sodium hydroxide aqueous solution at room temperature (20°C to 25°C) for one day. The electrochemical microscope probes were observed with a scanning electron microscope before and after immersion.

[0071] (Current value measurement) The electrochemical microscope probes from Example 2 and Comparative Example 1 were immersed in a 30 wt% sodium hydroxide aqueous solution at room temperature (20°C to 25°C) for 20 hours. Then, the probes immersed for 0 hours and 20 hours were attached to an electrochemical microscope, and the current values ​​(reference electrode Ag / AgCl, applied voltage 0.2V) were measured in phosphate buffer.

[0072] As shown in Figure 6, the electrochemical microscope probe of Example 1 showed no change in shape even after being immersed in an aqueous sodium hydroxide solution. On the other hand, the electrochemical microscope probe of Comparative Example 1 showed a change in the shape of its tip after being immersed for one day.

[0073] Figure 7 shows the measurement results of the current values ​​for each probe. As shown in Figure 7, the current value change rate of the electrochemical microscope probe of Example 1 (with coating in Figure 7) after immersion in a sodium hydroxide aqueous solution for 20 hours was 120%. On the other hand, the current value change rate of the electrochemical microscope probe of Comparative Example 1 (without coating in Figure 7) after immersion in a sodium hydroxide aqueous solution for 20 hours was 273%. This increase in current value indicates that the inner diameter of the probe has increased. From the above, it has been confirmed that the electrochemical microscope probe 100 of this disclosure has excellent chemical resistance. [Explanation of Symbols]

[0074] 10 Cylindrical section, 20 Tip section, 30 Opening, 40 Resin composition layer, 100 Probe for electrochemical microscope

Claims

1. A cylindrical part made of a glass substrate, A tip portion is continuously connected to the cylindrical portion, and its inner diameter decreases towards the end from the cylindrical portion. An opening located at the end, Equipped with, The inner diameter of the aforementioned opening is 200 nm or less. The outer surface of the tip portion is made of a resin composition containing a highly chemical-resistant organic resin. The aforementioned highly chemical-resistant organic resin is a resin whose weight change rate before and after immersion in a 30 wt% sodium hydroxide aqueous solution at 23 ± 1°C for one week is within ±5%, and is used for a probe for an electrochemical microscope.

2. The aforementioned tip portion The glass substrate and, A resin composition layer made of the resin composition is provided on the glass substrate, A probe for an electrochemical microscope according to claim 1, comprising the features described above.

3. The electrochemical microscope probe according to claim 2, wherein the average thickness of the resin composition layer is 1 / 2 or less of the inner diameter of the opening.

4. The electrochemical microscope probe according to claim 1, wherein in the region where the inner diameter of the tip portion is 1 μm or less, the tip portion is made of the resin composition.

5. The electrochemical microscope probe according to claim 1 or 2, wherein the highly chemical-resistant organic resin is a fluororesin.

6. The electrochemical microscope probe according to claim 1 or 2, wherein the glass substrate is lead-doped soda glass, borosilicate, or quartz.

7. A cylindrical cylindrical part, A tip portion is continuously connected to the cylindrical portion, and its inner diameter decreases towards the end from the cylindrical portion. An opening is located at the end and has an inner diameter of 200 nm or less, A resin composition layer made of a resin composition containing a highly chemical-resistant organic resin is formed at the tip of the hollow member having the above-mentioned features. The hollow member is made of a glass substrate, The method for manufacturing an electrochemical microscope probe is a method for manufacturing an electrochemical microscope probe, wherein the highly chemical-resistant organic resin is a resin whose weight change rate before and after immersion in a 30 wt% sodium hydroxide aqueous solution at 23 ± 1°C for one week is within ±5%.

8. The method for manufacturing an electrochemical microscope probe according to claim 7, wherein the highly chemical-resistant organic resin is a fluororesin.

9. The method for manufacturing an electrochemical microscope probe according to claim 7 or 8, wherein the glass substrate is lead-doped soda glass, borosilicate, or quartz.

10. The method for manufacturing an electrochemical microscope probe according to claim 7 or 8, wherein the resin composition layer is formed by a spray method.

11. A method for manufacturing an electrochemical microscope probe according to claim 7 or 8, wherein, after forming the resin composition layer, at least a portion of the glass substrate at the tip is dissolved.

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