TW202104869A - Resistance measuring machine and resistance measuring method using the same - Google Patents

Abstract

This invention provides a resistance measuring machine including a resistance measuring machine body with a first terminal and a second terminal, and a first electrode electrically connected to the first terminal, wherein the first electrode includes a conductive material and a polymer.

Description

Resistance measuring machine and resistance measuring method using the resistance measuring machine

The present invention relates to a resistance measuring machine and a resistance measuring method using the resistance measuring machine.

The manufacturing method of a semiconductor element has a process (for example, an etching process, a cleaning process) which brings an intermediate product (more specifically, a wafer etc.) into contact with various fluids. For example, in the cleaning process, the wafer is brought into contact with a fluid to remove impurities (more specifically, ionic substances, particulate substances, etc.) adhering to the surface of the wafer. The fluid (cleaning liquid) used in the cleaning process removes impurities by dissolving impurities attached to the surface of the wafer or washing off impurities attached to the surface of the wafer.

Therefore, in addition to pure water, the fluid may also contain various chemicals (acids, alkalis, organic solvents, etc.). Therefore, a coating material with good chemical resistance (such as fluororesin, etc.) should be used to coat the wafer of the semiconductor device manufacturing device. The parts to be processed (more specifically, metal substrates, etc.) are protected from damage by the above-mentioned fluid. In addition, high temperature may be used to clean the wafer, so the coating material may be required to have ultra-high performance such as chemical resistance at high temperature.

[Prior Technical Literature]

[Non-Patent Literature]

(Non-Patent Document 1) Shigeru Aoki "Corrosion Prevention of Organic Materials", Anti-Corrosion Technology, Vol.37,492-500 (1988) (refer especially to "5.3 Inspection of Organic Lining" and "6. Diagnosis after Start of Use")

However, the parts are usually used for a long time in the cleaning process, so the coating material of the covered part will be deteriorated (thermal deterioration, molecular bond breakage). As a result, defects (more specifically, cracks, cracks, swelling, swelling, peeling, and solvent cracking, etc.) may occur in the coating material. When a defect is formed, the member covered by the coating material (more specifically, the metal substrate) is exposed to the cleaning solution, and the substrate may be dissolved in the cleaning solution. Once the substrate is dissolved in the cleaning solution, contamination of the cleaning solution will occur, and the manufactured semiconductor device may be defective.

The method of inspecting the defects of the coating material is known as the pinhole test, etc. However, the method of diagnosing the deterioration of the coating material during the operation of the manufacturing equipment, etc., has hardly been put into practical use (refer to Non-Patent Document 1) .

In order to prevent the occurrence of semiconductor device defects, it has been a conventional practice, for example, to periodically replace the components of the semiconductor device manufacturing apparatus assuming a time when the coating material will deteriorate. The replacement time is mostly determined by the technicians based on experience or feeling. And, when the operation of the semiconductor element manufacturing apparatus is stopped, the coating material of the component of the semiconductor element manufacturing apparatus is visually observed to confirm whether the coating material is defective.

Therefore, if parts are replaced too late, defects often occur, and the substrate has been exposed to the cleaning solution, causing the substrate to dissolve in the cleaning solution. In some cases, when defects are discovered (for example, when the auxiliary device is found to have peeling like blisters), it has already caused the semiconductor device to be defective.

If it takes too long to discover the defects that have been formed, there will be a problem that the substrate component of the part dissolves into the cleaning solution and contaminates the cleaning solution (contamination). In this case, it is necessary not only to replace the deteriorated parts of the coating material of the semiconductor device manufacturing device, but also to stop the process to clean the semiconductor device manufacturing device. Therefore, once a defect is formed, it takes a lot of labor and time to restart the manufacturing device.

Therefore, the object of the present invention is to provide a measuring machine (testing machine or testing device) and a measuring method that can easily, quickly, and preferably timely find defects in the coating material. And, it is best to provide that even in the operation of the device (such as a semiconductor device manufacturing device), the occurrence of contamination inside the device is suppressed, and the best is that it does not occur, and it has good chemical resistance ( In particular, a measuring machine for good chemical resistance at high temperatures and cleanliness and a measuring method using the measuring machine.

In order to solve the above-mentioned problems, the inventors of the present invention have carried out intensive research and investigation. As a result, they have produced an electrode with a specific composition containing carbon nanotubes (carbon nanotubes) and a fluororesin, which has a higher sensitivity than before. New resistance measuring machine. And found that using such a high-sensitivity resistance measuring machine to measure resistance, it detects microscopic defects (more specifically, micro cracks, pinholes, swelling, etc.) at the stage when they occur. It can prevent the occurrence of macro defects, solve the above-mentioned problems, and finally complete the present invention. That is, the present invention includes an innovative resistance measuring machine and a resistance measuring method using the resistance measuring machine, and provides the following aspects.

1. A resistance measuring machine with:

A resistance measuring machine body having a first terminal and a second terminal; and

The first electrode electrically connected to the first terminal,

The first electrode system contains a conductive material and a polymer.

2. The resistance measuring machine according to the above 1 aspect, wherein the conductive material system includes a carbon-based material.

3. The resistance measuring machine according to the above 1 or 2 aspect, wherein when the mass of the first electrode is 100% by mass, the first electrode contains the conductive material in an amount of 0.01 to 2.0% by mass.

4. The resistance measuring machine according to any one of the above 1 to 3 aspects, wherein the polymer system includes at least one selected from a silicon-based polymer, a fluorine-based polymer, a nitrogen-containing polymer, and a polyolefine.

5. The resistance measuring machine described in any one of the above 1 to 4, wherein the conductive material system includes carbon nanotubes, and the polymer system includes fluorine-based polymers.

6. The resistance measuring machine described in any one of the above 1 to 5 aspects is an inline resistance measuring machine.

7. The resistance measuring machine described in any one of the above 1 to 6 aspects, which is used for defect detection of the conductive part covered with the non-conductive part.

8. A device comprising the resistance measuring machine described in any one of the above 1 to 7 aspects.

9. A method for measuring resistance, comprising using the resistance measuring machine described in any one of aspects 1 to 7 above.

10. A resistance measurement method, which is a resistance measurement method using the resistance measuring machine described in any one of the above 1 to 7 aspects, including:

(A) Bring the conductive part covered with the non-conductive part into contact with the conductive fluid; and

(C) In the state where the second terminal of the resistance measuring machine is electrically connected to the conductive part of the aforementioned member, the first electrode is brought into contact with the conductive fluid to measure the conductive part covered with the non-conductive part and The resistance between conductive fluids.

11. The measurement method described in the above 10 aspect, which includes before (C):

(B) Electrically connect the first terminal and the second terminal of the resistance measuring machine to the conductive part of the component as far apart as possible to measure the resistance of the conductive part to confirm the conductivity of the conductive part.

12. A method for detecting defects in a non-conductive part, the method comprising: when the operation of the device is temporarily stopped, when the conductive part is covered by the non-conductive part and the part covered by the non-conductive part is not removed from the device The resistance measuring machine described in any one of the above 1 to 7 aspects is used to measure the resistance of the non-conductive part.

13. A method for monitoring the defects of the non-conductive part, the method comprising: during the operation of the device, using the above 1~ when the parts covered by the non-conductive part of the conductive part are not removed from the device during the operation of the device. The resistance measuring machine described in any one of the 7 aspects measures the resistance of the non-conductive part.

According to the present invention, it is possible to provide a measuring machine and a measuring method that can easily, quickly, and preferably timely find defects in the coating material. The above-mentioned measuring machine has good chemical resistance and cleanliness. By using this measuring machine to measure resistance, it is preferable to find defects in the coating material at a very slight stage (the state of microscopic defects), and more preferably What is predictable is the occurrence of mega-defects.

Moreover, it is possible to provide the best that even in the operation of the device (such as a semiconductor device manufacturing device), the occurrence of contamination inside the device is suppressed, and the best is that it does not occur, and it has good chemical resistance. (Especially good chemical resistance at high temperature) and cleanliness measuring machine and measuring method using the measuring machine.

1: Resistance measuring machine

3: Measuring machine body

5, 6: Wiring

7: The first electrode (measurement electrode)

8: second electrode

11: container

15: Liquid medicine (conductive fluid)

20: Wafer cassette (wafer transport part)

22: Substrate

24: Coating layer

25: Conductive part (conductive layer)

26: Non-conductive part (non-conductive layer, insulating layer, PCTFE layer)

30: Lining storage tank

31: body

32: Lining layer

33: Liquid Inlet

34: Liquid medicine outlet

35: Lid

36: First electrode entrance

40: Lining piping

41: Tube

42, 46: Lining

43: Flange (connection part)

45: Three-opening tube

47: flange

Fig. 1 schematically shows an example of a resistance measuring machine according to an embodiment of the present invention.

Fig. 2 schematically shows the method of evaluating the chemical resistance of the first electrode included in the resistance measuring machine according to one embodiment of the present invention.

Fig. 3 schematically shows an example of a wafer cassette (wafer conveying member) to be measured.

Fig. 4 schematically shows an example of a lined storage tank (a metal storage tank lined with a lining layer) as a measurement object.

Fig. 5 schematically shows an example of a lining pipe (a metal pipe lined with a lining layer) to be measured and an example of the connection of these pipes.

Fig. 6 schematically shows an example of a method of confirming the conductivity of the conductive layer of the wafer cassette.

FIG. 7 schematically shows an example of the resistance measurement method (defect detection method) of the non-conductive layer of the wafer cassette.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

<Resistance measuring machine>

The resistance measuring machine of the embodiment of the present invention has:

A resistance measuring machine body having a first terminal and a second terminal; and

The first electrode electrically connected to the first terminal,

The first electrode system contains a conductive material and a polymer.

1. Electrodes

The resistance measuring machine of the embodiment of the present invention has a first electrode. The first electrode is electrically connected to the first terminal of the main body of the resistance measuring machine. The first electrode contains a conductive material and a polymer.

The resistance measuring machine of the embodiment of the present invention may have a second electrode. The second electrode can be electrically connected to the second terminal of the resistance measuring machine body. Therefore, the resistance measuring machine may have a second electrode electrically connected to the second terminal. The second electrode may contain conductive materials and polymers. When the second electrode does not contain conductive materials and polymers, it may contain, for example, brass, copper, stainless steel, iron, aluminum, etc., and the electrode material can be appropriately selected according to the use environment and the like.

The volume resistivity (volume resistivity) of the first electrode and the second electrode may be any suitable value whose resistance can be measured. When the electrode contains conductive materials and polymers, the volume resistivity of the electrode is preferably 1×10 ^-1 to 1×10 ⁷ Ω‧cm, more preferably 1×10 ⁰ to 1×10 ⁵ Ω ‧Cm, more preferably 1×10 ¹ ~1×10 ³ Ω‧cm. The measuring method of volume resistivity will be described in detail in the examples.

The shape and size of the electrode are not particularly limited as long as the resistance measuring machine to be obtained in the present invention can be obtained and the resistance can be measured. The shape can be, for example, a cylindrical shape or a corner column shape (triangular column, quadrangular column, pentagonal column, hexagonal column, etc.), and can be, for example, a size with a bottom area of 0.01-100 cm ² and a length of 0.1-100 cm. In addition, the electrode may have a clip shape, a needle shape, a plate shape, or the like.

1-1. Conductive materials

Examples of conductive materials include, for example, non-metallic conductive materials (more specifically, carbon-based materials, etc.). Examples of carbon-based materials include graphite, graphene, fullerene, carbon nanotubes (CNT), carbon fiber, silicon carbide, conductive polymers (more Specifically, polyacetylene (polyacetylene), polythiophene (polythiophene, etc.) and these chemical modifications (derivatives). From the viewpoint of further improving chemical resistance and cleaning properties, the conductive material preferably contains a non-metallic conductive material, more preferably contains a carbon-based material, and more preferably contains CNT.

In this manual, the so-called "CNT" is usually understood as CNT (carbon nanotube) The substance may be any substance that can obtain the electrode included in the resistance measuring device to be obtained in the present invention, and there is no particular limitation.

CNTs can be single-layered or multi-layered (for example, double-layered). Commercial products can be used for CNT, and for example, the CNT-uni (trade name) series manufactured by Taiyo Nippon Acid Co., Ltd. can be used.

CNT can be used alone or in combination.

In the embodiment of the present invention, the average length of the CNT is preferably 50 μm or more, more preferably 100 to 200 μm, and even more preferably 150 to 200 μm.

When the average length of the CNT is 50 μm or more, the conductive path is easily formed. In this regard, the conductivity is improved and better.

In this specification, the so-called average length of CNT (or average fiber length) refers to the average length obtained from an image taken by SEM. That is, a part of the electrode containing the conductive material and the polymer is heated to 300°C to 600°C to ash, and a residue (sample for SEM photography) is obtained. Take a SEM image of the residue. The length of each CNT included in the SEM image is obtained by image processing. The average value of the length obtained by the image processing is obtained by calculation, and this average value is referred to as the average length of the CNT.

In the embodiment of the present invention, the content of the conductive material, based on the mass of the electrode containing the conductive material being 100% by mass (standard), is preferably 0.01 to 2.0% by mass, more preferably It is between 0.04 and 1.5% by mass, more preferably between 0.05 and 1.0% by mass, and particularly preferably between 0.05 and 0.5% by mass.

When the content of the conductive material is 0.05 to 0.5% by mass, there will be a sufficient amount to form a conductive path, so the conductivity of the electrode will be improved and better.

1-2. Polymer

Examples of polymers include, for example, chemical-resistant polymers (more specifically, silicon-based polymers, fluorine-based polymers, nitrogen-containing polymers, polyolefine, and other polymers). Examples of silicon-based polymers include silicon resin and silicon rubber. Examples of fluorine-based polymers include fluorine resin and fluorine rubber. Examples of polyolefins include polypropylene and polyethylene. Examples of the nitrogen-containing polymer include polyamide, polyimide, or polyamide-imide. Examples of other polymers include epoxy resins and liquid crystal polymers. From the standpoint of having heat resistance and improving chemical resistance and cleaning properties, the polymer preferably contains a chemical resistant polymer, more preferably contains a fluorine-based resin, and more preferably contains a fluorine resin. .

In this specification, the so-called "fluororesin" refers to a substance generally understood as a fluororesin, and it is not particularly limited as long as it can obtain the electrode included in the resistance measuring device to be obtained by the present invention.

Examples of such fluororesins include those selected from polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkoxy vinyl ether copolymer ( PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), ethylene/tetrafluoroethylene copolymer (ETFE), ethylene/chlorotrifluoroethylene copolymer (ECTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene At least one of the group consisting of vinyl fluoride (PVDF) and polyvinyl fluoride (PVF).

As the fluororesin, for example, polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkoxy vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoroethylene Fluoropropylene copolymer (FEP), ethylene/tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF) are better, polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (PTFE) Fluoroethylene (modified PTFE), tetrafluoroethylene/perfluoroalkoxy vinyl ether copolymer (PFA), and polychlorotrifluoroethylene (PCTFE) are better.

For fluororesin, commercially available products can be used, such as:

For polytetrafluoroethylene (PTFE), M-12 (trade name), M-11 (trade name), and POLYFLON PTFE-M (trade name) manufactured by DAIKIN INDUSTRIES, LTD can be used ,

For modified polytetrafluoroethylene (modified PTFE), Daikin Industry Co., Ltd. M-112 (trade name), M-111 (trade name), and POLYFLON PTFE-M (trade name) can be used,

For polychlorotrifluoroethylene (PCTFE), M-300PL (trade name), M-300H (trade name), and NEOFLON PCTFE (trade name) manufactured by Daikin Industry Co., Ltd. can be used.

For the tetrafluoroethylene/perfluoroalkoxy vinyl ether copolymer (PFA), AP-230 (trade name), AP-210 (trade name) manufactured by Daikin Industry Co., Ltd., and NEOFLON PFA (trade name) can be used. Name) etc.

The fluororesin can be used alone or in combination.

1-3. Manufacturing method of electrode containing conductive material and polymer

The manufacturing method of the electrode is not particularly limited as long as the resistance measuring machine to be obtained by the present invention can be obtained. The electrode can be formed by, for example, forming a conductive material composition containing a conductive material and a polymer.

The polymer contained in the conductive material composition may be in the form of particles. The average particle size of such a particulate polymer is preferably 500 μm or less, more preferably 8 to 250 μm, more preferably 10 to 50 μm, and particularly preferably 10 to 25 μm. When the average particle size of the particulate polymer is 500 μm or less, the conductive material and polymer can be uniformly dispersed in the electrode, so the conductivity of the electrode will be further improved.

_{In this specification, the so-called average particle size refers to the average particle size D 50} obtained by measuring the particle size distribution using a laser diffraction/scattering particle size distribution device ("MT3300II" manufactured by Nikkiso). The cumulative value in the particle size distribution determined by the scattering method is the particle size at 50%).

The electrode of the embodiment of the present invention is preferably manufactured by a manufacturing method including a step of compression molding a polymer composition dispersed with a conductive material (for example, a fluororesin composition dispersed with carbon nanotubes). The compression molding conditions can be appropriately selected.

When the conductive material composition is a fluororesin composition, the method of manufacturing an electrode containing PTFE or modified PTFE, and an electrode containing other fluororesin (such as PFA, FEP, ETFE, ECTFE, PCTFE, PVDF or PVF) The manufacturing method is partly different.

The manufacturing method of electrodes containing PTFE or modified PTFE includes:

Prepare a fluororesin composition in which carbon nanotubes are dispersed in a fluororesin (preferably particulate fluororesin);

Put the fluororesin composition (after appropriate pre-treatment (preparatory drying, granulation, etc.) as necessary) into the mold, preferably 0.1 to 100 MPa, more preferably 1 to 80 MPa, more preferably It is pressurized and compressed at a pressure of 5~50MPa to make a preformed body;

The preform is fired at a temperature higher than the melting point of the fluororesin composition (preferably 345 to 400°C, more preferably 360 to 390°C) for more than 2 hours to produce Shaped body; and

The formed body is processed (preferably cutting processing) to form an electrode.

The manufacturing method of electrodes containing PTFE and fluororesin other than modified PTFE (such as PFA, FEP, ETFE, ECTFE, PCTFE, PVDF or PVF) includes:

Prepare a fluororesin composition in which carbon nanotubes are dispersed in a fluororesin (preferably particulate fluororesin);

Put the fluororesin composition into the mold, perform appropriate pre-treatment (preparatory drying, etc.) as needed, heat it for 1 to 5 hours at a temperature of, for example, 150 to 400°C, and then heat it at a temperature of, for example, 0.1 to 100 MPa (preferably It is 1~80MPa, more preferably 5~50MPa) to pressurize and compress to obtain a molded body; and

The formed body is processed (preferably cutting) to obtain an electrode.

2. The main body of the resistance measuring machine

As long as the main body of the resistance measuring machine has a measuring range, measuring sensitivity, etc. corresponding to the measuring object, the resistance measuring machine to be obtained by the present invention can be obtained, and there is no particular limitation. The best measuring range of the resistance measuring machine is 10MΩ~4000MΩ. This system has a first terminal and a second terminal. The first terminal can function as a high-voltage output side terminal and is electrically connected to the first electrode. The second terminal functions as a ground-side terminal and is electrically connected to the conductive part of the component (measurement object) to be measured. The connection between the second terminal and the conductive part of the measuring object can pass through the second electrode or not pass through the second electrode. The first terminal and the second terminal are both, as long as the resistance measuring machine to be obtained by the present invention can be obtained, and there is no particular limitation, and it may be a terminal commonly used as a terminal of the resistance measuring machine.

Commercial products can be used for the main body of such a resistance measuring machine. Examples of such commercially available products include "Insulation Resistance Meter HIOKI IR 4050S (trade name)" manufactured by Hioki Electric Co., Ltd., and "Micro Checker" manufactured by SANKO ELECTRONIC LABORATORY CO., LTD. KS1" and so on.

3. Wiring

The electrode and the terminal may be electrically connected, and the connection method is not particularly limited, and may be connected by, for example, wiring. The wiring can connect the two electrodes to the main body of the resistance measuring machine (electrically), as long as the resistance measuring machine to be obtained by the present invention can be obtained, and there is no particular limitation.

Depending on the environment in which the resistance measuring machine will be used, etc., wiring may be required to have various properties such as heat resistance, chemical resistance, and light resistance. In such a case, the wiring is required to have an appropriate structure corresponding to the required properties. Examples that can be given include wiring formed by covering the periphery of a copper wire with fluororesin, vinyl chloride, polyethylene, or the like.

Fig. 1 schematically shows an example of the resistance measuring machine according to the embodiment of the present invention. The resistance measuring machine 1 has: a measuring machine body 3 having a first terminal (not shown) and a second terminal (not shown); and a first electrode 7 electrically connected to the first terminal of the measuring machine body 3. And it can have a second electrode 8 that can be connected to a second terminal. The first electrode 7 is connected to the first terminal through the wiring 5, and the second electrode 8 can be connected to the second terminal through the wiring 6. The first electrode 7 may be, for example, a cylindrical shape or a prism shape containing a conductive material and a polymer, and the second electrode may be, for example, a clip, a round rod, etc. made of brass or SUS.

The first terminal system has chemical resistance. Fig. 2 schematically shows the method of evaluating the chemical resistance of the first electrode. The target drug solution 15 is poured into a plastic container 11 that is not corroded by the target drug. The temperature and the like of the medicinal solution 15 can be appropriately selected in consideration of the use conditions and the like of the evaluation target. The first electrode 7 is brought into contact with the chemical solution 15. While maintaining the contact state, the contact portion of the first electrode 7 was visually observed to evaluate the chemical resistance of the first electrode 7. The details will be disclosed in the embodiment.

<Method of Measuring Resistance>

Another object of the present invention is to provide a new resistance measuring method including the use of the resistance measuring machine of the embodiment of the present invention. As long as the resistance measurement is performed using the resistance measurement device of the embodiment of the present invention, the measurement conditions, measurement objects, and the like are not particularly limited.

The resistance measurement method of the embodiment of the present invention can be suitably used in relation to Conductive part and non-conductive part, and the conductive part is covered by the non-conductive part (measurement object) whether the non-conductive part is defective or not.

4. Measurement object

Examples of parts in which the conductive part is covered by the non-conductive part include, for example, a metal storage tank (lined storage tank) lined with a lining layer (non-conductive layer, non-conductive part), lining Metal piping with a lining layer (lining piping), wafer transport parts with a conductive layer covered with a non-conductive layer (e.g., wafer cassette, wafer chuck, wafer pincette, wafer Circular lifter (lifter), etc.

FIG. 3 shows an example of a wafer cassette (wafer transport member) 20 as a measurement target. The right side of Figure 3 schematically shows a part of the cross section of the wafer cassette. Generally speaking, the wafer cassette is a component for storing and transporting silicon wafers, and can store wafers with a diameter of 200 mm, for example.

The cassette 20 covers the insulating base material 22 with a coating layer 24 (conductive layer 25 and insulating layer 26), for example. In Fig. 3, the conductive layer 25 is indicated by diagonal lines. The wafer cassette 20 is brought into contact with the chemical solution for a long time, and the insulating layer 26 is formed with defects (for example, pinholes). The pinhole test described later confirmed the existence of the defect. However, defects cannot be confirmed visually.

The wafer cassette 20 may use a conductive substrate (for example, a stainless steel substrate) instead of the insulating substrate 22. If a conductive base material is used, the conductive layer 25 is not required, so the coating layer 24 includes only the insulating layer 26. The same is true in this case. It can be kept in contact with the chemical solution for a long time to make it defective and use it as a measurement object.

Fig. 4 schematically shows an example of the lining tank 30 as a measurement object. The lining tank 30 has a cylindrical metal main body 31 and a non-conductive lining layer 32 lining the inner side of the main body 31, and a plurality of ports are provided on the upper part of the main body 31. For example, a medicine lined with a lining layer 32 The liquid inlet 33, the medical liquid outlet 34 lined with the lining layer 32, the lid 35 lined with the lining layer 32, and the first electrode inlet 36 lined with the lining layer 32. The medicinal liquid 15 can be poured into the lining tank 30 from the medicinal liquid inlet 33, and the measuring electrode 7 of the measuring machine can be inserted into the tank from the first electrode inlet 36, so that the measuring electrode 7 and the medicinal liquid 15 can be in contact with each other.

Fig. 5 schematically shows an example in which at least three lining pipes 40 as the measurement target are connected. The lining pipe 40 may have, for example, a metal pipe 41, a non-conductive lining 42 on the inner side of the pipe, and metal flanges (connecting portions) 43 at both ends of the pipe. The pipe 41 is a straight pipe with two openings, but it can also be a bent pipe or has three openings. The lining pipe 40 may have, for example, a metal three-opening pipe 45, a non-conductive lining 46 on the inner side of the pipe, and metal flanges 47 at the three ends of the pipe. These lining pipes can be connected to each other by flanges. The first electrode of the measuring machine can be inserted into the liner piping from the three-opening pipe, and the first electrode can be brought into contact with the chemical solution 15.

The resistance measurement method of the embodiment of the present invention may include, for example:

(A) Bring the conductive part covered by the non-conductive part (measurement object) in contact with the conductive fluid; and

(C) In a state where the second terminal of the resistance measuring device is electrically connected to the conductive part of the component, the first electrode is brought into contact with the conductive fluid to measure the conductive part covered by the non-conductive part and the conductive part. The electrical resistance between sexual fluids.

The resistance measurement method of the embodiment of the present invention may further include before (C) (before or after (A)):

(B) Electrically connect the first terminal and the second terminal of the resistance measuring machine to the conductive part of the component as far apart as possible to measure the resistance of the conductive part to confirm the conductivity of the conductive part.

The electrical connection of the first terminal to the conductive part of the component and the electrical connection of the second terminal Separate the parts connected to the conductive part of the part as much as possible to confirm that the conductive part of the whole part is conductive, so that the defect of the non-conductive part of the whole part can be detected.

With reference to FIGS. 6 and 7, the resistance measurement method and defect detection method of the non-conductive part of the measurement object using the resistance measurement machine 1 will be described.

As shown in Fig. 6, the container 11 is filled with a chemical solution (conductive fluid) 15, and then, for example, the above-mentioned wafer cassette 20 (base material 22 is covered by a coating layer 24 (conductive layer 25 and insulating layer 26) The portion) is in contact with the medicinal solution 15 as an example of the measurement target.

The first electrode 7 and the second electrode 8 are in contact with the conductive layer (conductive portion) 25 (the substrate 22 when the substrate is conductive) of the wafer cassette 20 so as to be separated as much as possible, and with The conductive layer 25 is connected. In this state, the resistance of the conductive part of the cassette 20 was measured. This confirms the conductivity of the conductive layer of the cassette 20. Confirmation of conductivity can also be performed before the wafer cassette is immersed in the chemical solution (not immersed in the chemical solution), or after the resistance value of the insulating layer (non-conductive layer or non-conductive part) is measured.

Next, as shown in FIG. 7, the first electrode 7 is separated from the conductive layer of the wafer cassette 20 and the first electrode 7 is brought into contact with the chemical solution 15. The distance between the surface of the first electrode 7 and the surface of the wafer cassette 20 is about 5 cm. In this state, the resistance value is measured. Apply a voltage of 1000V for 10 seconds. Based on the measured resistance value, the defect detectability of the insulating layer (non-conductive part) of the measurement object is evaluated.

The same is true for other measuring objects. The first electrode is brought into contact with the liquid medicine and the second electrode is brought into contact with the conductive part of the measuring object. Resistance measurement and defect detection of the non-conductive part can also be performed.

<Device with resistance measuring device>

The resistance measuring device of the embodiment of the present invention can be used in combination with various devices. For example, it can be combined with a manufacturing device (such as a semiconductor manufacturing device (such as a pattern forming device, a cleaning device, a peeling device)). Equipment), chemical manufacturing equipment, etc.), conveying equipment (e.g., chemical conveying equipment, etc.). More specifically, these devices may be devices that can process chemical liquids (including water, acidic and alkaline media, organic solvents, etc.).

The resistance measuring device of the embodiment of the present invention can be used for "inline use".

In this manual, the so-called "online use" has the following meaning:

(1) When the operation (or operation) of the device is temporarily stopped, the non-conductive part can be detected by the resistance measuring device when the conductive part is covered by the non-conductive part and the part is not removed from the device. The presence or absence of defects; and

(2) During the operation (or operation) of the device, a resistance measuring device can be used to monitor the presence or absence of defects in the non-conductive part of the component covered by the non-conductive part.

When the resistance measuring device of this embodiment is combined with the above-mentioned device, the defect detection can be performed continuously or intermittently while the above-mentioned device is in operation. Therefore, the operation of the device does not need to be temporarily stopped or suspended for a long time in order to detect defects, and the operation rate of the device can be improved.

In addition, the resistance measuring device of this embodiment can detect microscopic and slight defects, so the defect can be detected before serious contamination of the device occurs, and, at best, the device will not be substantially contaminated. It can ensure the stable operation of the device.

[Example]

Hereinafter, examples and comparative examples are used to describe the present invention specifically and in detail. However, these examples are only one aspect of the present invention, and the present invention is not limited by these examples in any way.

The components constituting the resistance measuring machine used in the Examples and Comparative Examples, the chemical solution used in the evaluation of the components, the measurement target used in the evaluation, and the like are disclosed below.

<Parts>

(Measuring machine body)

Resistance measuring machine body: "Insulation resistance tester HIOKI IR4050S (trade name)" by Nikkei

(Wiring)

Wiring: Wiring attached to the "Insulation Resistance Tester HIOKI IR4050S (trade name)" manufactured by Nikkei

(electrode)

Electrode (1): Polychlorotrifluoroethylene (PCTFE) electrode containing 0.1% by mass of carbon nanotubes (CNT)

Electrode (2): Polytetrafluoroethylene (PTFE) electrode containing 0.1% by mass of CNT

Electrode (3): PCTFE electrode (not containing CNT)

Electrode (4): Brass electrode attached to Nikkei's "Insulation Resistance Meter HIOKI IR4050S (trade name)"

(Manufacturing of electrodes (1)~(3))

The electrodes (1) to (3) were manufactured in the following manner.

(Electrode(1))

In 2000 parts of CNT dispersion (dispersant 0.15%, CNT 0.025%, solvent: water), 3500 parts of ethanol are added to dilute. Then, 1000 parts of PCTFE particles ("NEOFLON PCTFE, manufactured by Daikin Industry") were added to prepare a mixed slurry.

This mixed slurry is supplied to a pressure-resistant container, and then liquefied carbon dioxide is supplied at a feed rate of 0.03 g/min relative to 1 mg of the dispersant contained in the mixed slurry in the pressure-resistant container to make the pressure in the pressure-resistant container The pressure was increased to 20 MPa, and the temperature was increased to 50°C. While maintaining the above pressure and temperature for 3 hours, make carbon dioxide, solvent (water, ethanol) and dispersant dissolved in carbon dioxide from The pressure container is discharged.

The pressure and temperature in the pressure-resistant container were reduced to atmospheric pressure and normal temperature, respectively, to remove carbon dioxide in the pressure-resistant container, and a PCTFE composition (1) containing 0.1% CNT was obtained.

Put the PCTFE composition (1) into a mold, and perform appropriate pretreatment (preparatory drying, etc.) as necessary. The PCTFE composition (1) was melted by heating the mold with a hot air circulation type electric furnace set at 200 degrees or more for 2 hours or more. After heating for a predetermined time, take out the mold from the electric furnace, press and compress with a hydraulic press at ^{a surface pressure of 25kg/cm 2} or more, and wait until the mold is cooled to near normal temperature, and obtain PCTFE containing 0.1% CNT The formed body of the composition, namely the electrode (1).

(Electrode(2))

Electrode (2) is based on the above-mentioned electrode (1) manufacturing method, except that the PCTFE particles are changed to PTFE particles (POLYFLON PTFE-M manufactured by Daikin Industries), and the same method is used to obtain a PTFE composition containing 0.1% CNT物(2).

The PTFE composition (2) was compressed by applying pressure at 15 MPa and holding it for a certain period of time to obtain a preliminary molded body. The obtained pre-formed body was taken out of the forming mold and fired in a hot air circulating electric furnace set at 345°C or higher for 2 hours or more, and then slowly cooled and then taken out from the electric furnace to obtain 0.1% CNT The formed body of the PTFE composition, namely the electrode (2).

(Electrode(3))

The mold is heated in a hot air circulation type electric furnace set at 200 degrees or more for 2 hours or more to melt the PCTFE particles ("NEOFLON PCTFE" manufactured by Daikin Industry Co., Ltd.). After heating for a predetermined period of time, the mold is taken out from the electric furnace and compressed with a hydraulic press at ^{a surface pressure of 25 kg/cm 2} or more while waiting until the mold is cooled to near normal temperature, a molded body of PCTFE particles is obtained. , Which is the electrode (3). The electrode (3) does not contain CNT.

<Medicinal Solution>

SPM: 97% sulfuric acid (EL grade for Lin Chunyao electronics industry) and 30% hydrogen peroxide water (EL grade for Lin Chunyao electronics industry") mixed chemical solution (mixing ratio (mass ratio) sulfuric acid: hydrogen peroxide water =2: 1)

SC2: 35% hydrochloric acid (EL grade used by Lin Chunyao Electronics Industry), 30% hydrogen peroxide water, and deionized water (mixing ratio (mass ratio) hydrochloric acid: hydrogen peroxide water: deionized water = 1 :1:5)

<Measurement target>

Wafer box (1):

A wafer box with a conductive layer (PCTFE layer containing CNT) and an insulating layer (PCTFE layer) formed on a quartz glass ("GE124 grade" manufactured by HIMEJI RIKA.CO., LTD.) substrate.

Wafer box (2):

A wafer cassette with an insulating layer (PCTFE layer) formed on a stainless steel ("SUS304" manufactured by Imoto Kogyo) substrate. (The metal base material also serves as a conductive layer.)

(Preparation of measurement objects)

The wafer cassettes (1) and (2) to be measured are prepared in the following manner.

The wafer cassette (1) 20 has the structure shown in Figure 3, and the base material 22 made of quartz glass is composed of a coating layer 24 (conductive layer 25 and insulating layer 26: specifically, a PCTFE layer 25 and a PCTFE layer containing CNTs). 26) Covered. The wafer cassette 20 is connected to the chemical solution 15 (SPM) for a long period of time (about 90 days) at 130°C (SPM) Contact, the insulating layer 26 is formed with defects (for example, pinholes). The contacting system is carried out while always supplying hydrogen peroxide water to maintain the composition ratio of SC2 and SPM. The following pinhole test was performed to confirm the existence of defects. The existence of the defect cannot be confirmed visually. This wafer cassette (1) 20 was used in the evaluation of any of the resistance measuring machines of Examples 1 to 2 and Comparative Examples 1 to 2. Therefore, the evaluation of all resistance measuring devices is performed using the same wafer transport unit.

The same is true for the wafer transport member (2) 20, and the insulating layer 26 (PCTFE layer 26) was formed to be defective by the same method, and then used for the evaluation of the resistance measuring devices of Examples 1 and 2 and Comparative Examples 1 and 2.

Since the wafer transport member (2) has a stainless steel base material that also serves as the conductive layer 25, the coating layer 24 includes only the insulating layer 26.

(Pinhole test)

The pinhole test is carried out in accordance with the Japanese Industrial Standards (JIS K 6766: 2008).

<Resistance measuring machine>

Prepare the resistance measuring machine as shown in Figure 1. The resistance measuring machine 1 has a measuring machine body 3 having a first terminal and a second terminal, a first electrode 7 electrically connected to the first terminal of the measuring machine body 3, and a second electrode 8 connected to the second terminal. The first electrode 7 is connected to the first terminal by the wire 5, and the second electrode 8 is connected to the second terminal by the wire 6. The first electrode 7 corresponds to the electrodes (1), (2), (3), and (4) in the order of the resistance measuring machines of Examples 1, 2, and Comparative Examples 1, 2. The second electrode corresponds to the electrode (4) regardless of the resistance measuring machine.

<Evaluation Method of Electrode>

(1. Evaluation of the chemical resistance of the electrode)

Figure 2 shows the method of evaluating the chemical resistance of the electrode.

Pour a chemical solution (SPM or SC2) 15 with a liquid temperature of 130°C into a 20L polypropylene container 11. The first electrode 7 is brought into contact with the chemical solution 15. Maintaining the contact state, the contact portion of the first electrode 7 was visually observed. Based on the following evaluation criteria, the chemical resistance of the first electrode 7 was evaluated from the observation results. In the cases where the electrodes (1) to (4) were used as the first electrode 7, the evaluation results of each case are shown in Table 1.

(Evaluation criteria)

A (Excellent): No bubbles are observed on the surface of the electrode (dissolution of the electrode).

B (Bad): Air bubbles were observed on the surface of the electrode.

(2. Evaluation of the electrical conductivity of the electrode)

The wiring 6 not connected to the second electrode 8 is brought into contact with the end of the first electrode 7 connected to the wiring 5, and the resistance value of the first electrode 7 is measured. The lower limit of the detection limit of the measuring machine itself is 10MΩ, and the upper limit is 4000MΩ. The electrical conductivity of the first electrode 7 was evaluated from the measured resistance value based on the following evaluation criteria. In the cases where the electrodes (1) to (4) were used as the first electrode 7, the evaluation results of each case are shown in Table 1.

(Evaluation criteria)

A (Excellent): The resistance value of the electrode is less than 10 MΩ.

B (bad): The resistance value of the electrode is more than 10MΩ.

(3. The method of using the resistance measuring machine to detect the defect of the non-conductive part of the measuring object: (Method of measuring resistance value)

With reference to Figs. 6 and 7, a method of detecting defects in non-conductive parts using the resistance measuring machine 1 will be described.

As shown in Figure 6, the container 11 is filled with a chemical solution 15 (SPM or SC2), so that the above-mentioned wafer cassette 20 (base material 22 is composed of a coating layer 24 (conductive layer (conductive portion)) 25 and a non-conductive layer (Non-conductive part) 26) Covered part) is in contact with the liquid medicine 15.

The first electrode 7 and the second electrode 8 are respectively in contact with the conductive portion 25 of the wafer cassette 20 (when the substrate is conductive, the substrate 22 is contacted), and the first electrode 7 and the second electrode 8 are connected to the measuring machine. The body 3 is connected. The resistance of the wafer cassette 20 is measured. This confirms the conductivity of the conductive portion of the cassette 20.

Next, as shown in FIG. 7, the first electrode 7 is separated from the wafer cassette 20, and the first electrode 7 is brought into contact with the chemical solution 15 in the chemical solution 15. The distance between the surface of the first electrode 7 and the surface of the wafer cassette 20 is about 5 cm. In this state, the resistance value was measured. Apply a voltage of 1000V for 10 seconds. Based on the following evaluation criteria, the defect detection property of the non-conductive part of the measurement target of the resistance measuring machine 1 is evaluated from the measured resistance value. The results are shown in Table 1.

(Evaluation criteria)

A (Excellent): The resistance value exceeds 4000MΩ.

B (bad): The resistance value is below 4000MΩ.

In addition, the resistance of the wafer cassette before the occurrence of defects in the insulating layer 26 was measured in advance by the method shown in FIG. 7, and the resistance value obtained was a resistance value exceeding the upper limit of the detection limit (4000MΩ). Therefore, after confirming that the insulating layer 26 has no defects, the defects are generated before they are used for the evaluation of defect detection.

(4. Evaluation of electrode cleanliness (pollution prevention))

Determination of the amount of metal leached out of the electrode

ICP mass analyzer (perkinElmer made "ELAN DRCII") was used to measure 17 metal elements (Li, Na, Mg, Al, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Cd and Pb) metal elution amount to evaluate the degree of metal contamination in the electrode.

A test piece of 10mm×20mm×50mm was obtained by cutting. After immersing the test piece in 0.5L of 3.6% hydrochloric acid (EL-UM grade manufactured by Kanto Chemical Co., Ltd.) for about 1 hour, rinse it with ultrapure water (resistance value: ≧18.0MΩ‧cm). In addition, the entire test piece was immersed in 0.1 L of 3.6% hydrochloric acid and kept at room temperature for 24 hours and 168 hours. After a predetermined time has elapsed, the immersion liquid is fully recovered (all the hydrochloric acid used for immersion is collected), and the concentration of metal impurities in the immersion liquid is analyzed. Prepare three test pieces, and use the maximum value of them as the detection amount.

The evaluation criteria are as follows.

A: The detected amount of all metals is less than 5ppb.

B: The detection levels of Al, Cr, Cu, Fe, Ni, Zn, Ca, K and Na are less than 5ppb.

C: The detected amount of Al, Cr, Cu, Fe, Ni and Zn is less than 5ppb.

D: The detection amount of any one of Al, Cr, Cu, Fe, Ni, and Zn is 5 ppb or more.

The results are shown in Table 1.

Measurement of electrode carbon shedding

A total organic carbon meter ("TOCvwp" manufactured by Shimadzu Corporation) was used to measure TOC (total organic carbon) to evaluate the degree of carbon nanotube separation from the electrode. Specifically, the 10mm×20mm×50mm test piece obtained by cutting is immersed in 0.5L of 3.6% hydrochloric acid (EL-UM grade manufactured by Kanto Chemical) for about 1 hour, After an hour, take it out and rinse with ultrapure water (resistance value: ≧18.0MΩ‧cm), then immerse the test piece in ultrapure water and store it at room temperature for 24 hours and 168 hours . After a predetermined period of time, the immersion liquid was completely recovered (all the ultrapure water used for immersion was collected), and total organic carbon analysis was performed on the immersion liquid. Prepare three test pieces, and use the maximum value of them as the detection amount.

The evaluation criteria are as follows.

A: The detected amount of total organic carbon is less than 50ppb.

D: The detected amount of total organic carbon is more than 50ppb.

(Example 2, Comparative Examples 1 to 2)

The same method as in Example 1 was used except that the electrode (1) was changed to the electrodes (2) to (4), and the electrodes and resistance measuring devices of Example 2 and Comparative Examples 1-2 were evaluated, respectively. The results are shown in Table 1.

(to sum up)

Examples 1 to 2 are excellent in any of chemical resistance, electrical conductivity, detectability, and cleanliness. In Comparative Examples 1 to 2, at least one of chemical resistance, electrical conductivity, detection and cleanliness is poor. Therefore, it can be seen that Examples 1-2 have better chemical resistance, electrical conductivity, detectability, and cleanliness than Comparative Examples 1-2.

[Table 1]

[Industrial Utilization Possibility]

The resistance measuring device and the resistance measuring method of the present invention can be used in combination with a semiconductor device manufacturing device in particular, but are not limited to this use.

[Associated Application Case]

This application claims the priority of the basic application under Article 4 of the Paris Convention with the application number 2019-7341 filed in Japan on January 18, 2019. In this manual, the basis The content of the application is incorporated for reference.

1: Resistance measuring machine

3: Measuring machine body

5, 6: Wiring

7: The first electrode

8: second electrode

Claims (13)

A resistance measuring machine, which has: A resistance measuring machine body having a first terminal and a second terminal; and The first electrode electrically connected to the first terminal, The first electrode system contains a conductive material and a polymer. The resistance measuring machine described in item 1 of the scope of patent application, wherein: The conductive material system includes a carbon-based material. Such as the resistance measuring machine described in item 1 or 2 of the scope of patent application, wherein: When the mass of the first electrode is 100% by mass, the first electrode system contains the conductive material in an amount of 0.01 to 2.0% by mass. The resistance measuring machine described in any one of items 1 to 3 in the scope of the patent application, wherein: The polymer system includes at least one selected from silicon-based polymers, fluorine-based polymers, nitrogen-containing polymers, and polyolefins. The resistance measuring machine described in any one of items 1 to 4 of the scope of patent application, wherein: The conductive material system includes carbon nanotubes, and the polymer system includes fluorine-based polymers. The resistance measuring machine described in any one of items 1 to 5 in the scope of the patent application is an on-line resistance measuring machine. The resistance measuring machine described in any one of items 1 to 6 in the scope of the patent application is used for defect detection of parts covered by non-conductive parts with conductive parts. A device containing: The resistance measuring machine described in any one of items 1 to 7 in the scope of patent application. A method for measuring resistance, which includes: Use the resistance measuring machine described in any one of items 1 to 7 in the scope of the patent application. A method for measuring resistance, which uses the resistance measuring method of the resistance measuring machine described in any one of items 1 to 7 of the scope of patent application, and comprising: (A) Bring the conductive part covered with the non-conductive part into contact with the conductive fluid; and (C) In the state where the second terminal of the resistance measuring machine is electrically connected to the conductive part of the aforementioned member, the first electrode is brought into contact with the conductive fluid to measure the conductive part covered with the non-conductive part and The resistance between conductive fluids. The resistance measurement method described in item 10 of the scope of patent application, which includes before (C): (B) Electrically connect the first terminal and the second terminal of the resistance measuring machine to the conductive part of the component as far apart as possible to measure the resistance of the conductive part to confirm the conductivity of the conductive part. A method for detecting defects in non-conductive parts. The method includes: when the operation of the device is temporarily stopped, the application is applied when the conductive part is covered by the non-conductive part and the parts covered by the non-conductive part are not removed from the device. The resistance measuring machine described in any one of items 1 to 7 of the scope of the patent is used to measure the resistance of the non-conductive part. A method is to monitor the defects of the non-conductive part. The method includes: during the operation of the device, when the parts covered by the conductive part with the non-conductive part are not removed from the device, use the first of the scope of patent application To the resistance measuring machine described in any one of items 7 to measure the resistance of the non-conductive part.

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