KR102372648B1 - Hydrophobic processing method, hydrophobic processing apparatus, and storage medium therefor - Google Patents

Abstract

Provided are a hydrophobicization treatment method, a hydrophobic treatment apparatus, and a recording medium capable of sufficiently stably imparting an expected degree of hydrophobicity to a substrate according to the heat treatment temperature of the substrate. The hydrophobization treatment method according to the present invention is for hydrophobizing the surface of a substrate, (A) supplying a processing gas for hydrophobization to the surface of the substrate, (B) adding the surface of the substrate to an atmosphere containing the processing gas A step of exposing the substrate over a predetermined period of time; (C) a step of heating the substrate in the presence of a processing gas after the step (B) is provided.

Description

Hydrophobization treatment method, hydrophobization treatment apparatus, and recording medium for hydrophobization treatment

The present invention relates to a method, apparatus and recording medium for hydrophobizing the surface of a substrate.

The process of manufacturing a semiconductor has a process of forming a resist pattern for etching on the surface of a wafer (substrate). The resist pattern is formed by exposing and developing a resist film formed on the surface of the substrate. In order to prevent peeling or collapse of the resist pattern, the resist film needs to be in close contact with the surface of the substrate. In order to ensure the high adhesiveness of a resist film and a board|substrate, hydrophobization process of the wafer surface is performed before formation of a resist film.

HMDS (hexamethyldisilazane, (CH ₃ ) ₃ SiNHSi(CH ₃ ) ₃ ) is known as a compound for hydrophobizing the substrate surface. Patent Document 1 discloses, in response to the problem of reducing the hydrophobicity non-uniformity in the substrate surface, when the substrate is hydrophobized, HMDS gas is intermittently supplied into an airtight container, so that the gas of the substrate is in contact with the supply of the gas. Suppressing that the temperature becomes remarkably low, thereby solving the above problem is disclosed. In paragraph [0008] of Patent Document 1, it is described that 'HMDS gas introduced into the sealed container is lower than the temperature of the wafer W', and in paragraph [0009], 'In the hydrophobic treatment using HMDS gas, the wafer ( The higher the temperature of W), the higher the hydrophobicity of the wafer surface'.

Patent Document 2 discloses a subject that foreign substances may be generated on the substrate surface when HMDS is hydrolyzed by moisture. In order to solve this problem, Patent Document 2 discloses that the process of performing heat treatment for evaporating moisture from the substrate surface to the process of making the substrate surface hydrophobic are performed in a dehumidified atmosphere. In addition, in paragraph [0052] of Patent Document 2, 'The surface of the wafer 10 is exposed to HMDS in a vapor state. In the meantime, the wafer 10 is heated to, for example, 110°C (step S3). In addition, the heating temperature here is not limited to 110 degreeC, What is necessary is just to suppress the re-adsorption of water|moisture content to the wafer 10 surface. For example, it may be 100°C or higher.'

Patent Document 1: Japanese Patent Laid-Open No. 2000-150368 Patent Document 2: Japanese Patent Laid-Open No. 2004-103850

According to the study of the present inventors, if the substrate is heat-treated after being sufficiently exposed to the HMDS gas, as described in Patent Document 1, the higher the heat treatment temperature, the higher the hydrophobicity of the substrate tends to be. However, the present inventors have found that if the substrate is heated for the heat treatment before the substrate is sufficiently exposed to the HMDS gas, the hydrophobicity of the substrate does not increase as expected even when the heat treatment temperature is increased.

An object of the present invention is to provide a hydrophobicization treatment method capable of imparting an expected degree of hydrophobicity to a substrate in a sufficiently stable manner depending on the heat treatment temperature of the substrate, and an apparatus and a recording medium used therefor.

The hydrophobization treatment method according to the present invention is for hydrophobizing the surface of a substrate, (A) supplying a processing gas for hydrophobization to the surface of the substrate, (B) adding the surface of the substrate to an atmosphere containing the processing gas A step of exposing the substrate over a predetermined period of time; (C) a step of heating the substrate in the presence of a processing gas after the step (B) is provided.

According to the hydrophobization treatment method, reactant molecules (eg HMDS molecules) contained in a sufficient amount of processing gas are physically adsorbed on the surface of the substrate under low-temperature conditions (eg 15 to 35° C.) ((A) Step and (B) step), and heat treatment of the substrate (eg, heating temperature of 60 to 180° C.) can be performed ((C) step). It is presumed that physical adsorption of reactant molecules to the substrate surface is dominant under low-temperature conditions of 15 to 35°C, while chemical reactions between reactant molecules and substrate surface are presumed to dominate under high-temperature conditions of 60 to 180°C.

By sufficiently securing a time (eg, 2 to 10 seconds) for physical adsorption of reactant molecules to the substrate surface, hydrophobicity expected according to the heat treatment temperature of the substrate can be sufficiently stably imparted to the substrate. According to the studies of the present inventors, in a conventional hydrophobic treatment apparatus, there is a distance (for example, 5 to 6 m) between the supply source of the processing gas and the chamber in which the hydrophobicization treatment is performed, and the opening/closing valve is located in the pipe connecting them. Due to whether or not to dispose, a difference may occur in the performance of the hydrophobic treatment apparatus when heat treatment is performed at a high temperature (eg, 140° C. or higher).

11A and 11B both show a process gas (here, HMDS solution) from a supply source A (right) of a liquid reactant for hydrophobization (here, HMDS solution) to a chamber C (left) where hydrophobization is performed through a flow path L. It shows a device for supplying nitrogen gas including steam).

11A shows a case where the three-way valve V1 is disposed near the chamber C, and FIG. 11B shows a case where the three-way valve V1 is disposed near the supply source A, respectively. Moreover, the heater H may be provided on the outer side of the flow path La from the supply source A to the three-way valve V1 so that the vapor|steam of HMDS may not condense in the inside. In addition, a pipe for supplying nitrogen gas is connected to the three-way valve V1, and the flow path Lb from the three-way valve V1 to the chamber C and the inside of the chamber C can be purged with nitrogen gas. .

11A, since the three-way valve V1 is close to the chamber C and the flow path La from the supply source A to the three-way valve V1 is usually filled with process gas. , after switching the three-way valve V1 so that the HMDS vapor is introduced into the chamber C, the supply of the HMDS vapor to the chamber C is started within a relatively short time. For this reason, there exists an advantage that it is easy to ensure the time for HMDS molecules to physically adsorb to the substrate surface. On the other hand, since the vapor of HMDS normally remains in the flow path La, there is a disadvantage that a performance difference between treatments tends to occur.

In the case of the configuration shown in Fig. 11B, since the flow path La in which the vapor of HMDS normally remains is short, there is an advantage that the performance difference between treatments can be suppressed. On the other hand, since the flow path Lb from the three-way valve V1 to the chamber C is purged with nitrogen gas for each treatment, after switching the three-way valve V1 so that the vapor of HMDS is introduced into the chamber C, It takes several seconds until the vapor of HMDS is actually supplied to the chamber (C). When the control to start heating the substrate is performed simultaneously with the switching of the three-way valve V1, the temperature of the substrate surface rises within a few seconds, and the heat treatment of the substrate is performed in a state where physical adsorption of HMDS molecules is insufficient. There is this.

According to the hydrophobization treatment method according to the present invention, there is a merit that, for example, the expected degree of hydrophobicity according to the heat treatment temperature of the substrate can be sufficiently stably provided to the substrate regardless of the difference in the configuration of the apparatus as described above. . That is, the hydrophobization treatment method according to the present invention can contribute to the improvement of the robustness of the hydrophobization treatment apparatus.

From the viewpoint of sufficiently generating physical adsorption of reactant molecules for hydrophobization, steps (A) and (B) may be carried out in a state where the substrate is disposed at a position away from the heating plate for heating. The step (C) may be performed in a state in which the substrate is placed in a position close to the hot plate. In this case, the hydrophobization treatment method may further include a step of moving the substrate to a position close to the hot plate after the step (B) and before the step (C).

From the same viewpoint, the step (A) and the step (B) may be performed in a state in which the substrate is disposed in an upper position spaced apart from the heating plate for heating. The step (C) may be performed in a state in which the substrate is placed in a position close to the hot plate. In this case, the hydrophobization treatment method may further include a step of lowering the substrate to a position close to the hot plate after the step (B) and before the step (C).

(C) You may perform heating of the board|substrate in a process by means other than a hot platen. For example, the step (C) may be performed by supplying a heated processing gas to the surface of the substrate. Alternatively, the heating in the step (C) may be performed by irradiating the substrate with light for radiant heating.

The physical adsorption of the reactant molecules to the substrate surface and the chemical reaction between the reactant molecules and the substrate surface may be performed in different chambers. That is, the process (A) and the process (B) may be implemented in the chamber for physical absorption, and the process (C) may be implemented in the chamber for a chemical reaction which accommodates a hot plate and is located in the transverse direction for the physical absorption. In this case, the hydrophobization treatment method may further include a step of transferring the substrate from the physical adsorption chamber to the chemical reaction chamber after the step (B) and before the step (C).

In order to suppress the adverse effect of the processing gas containing the reactant molecules on other processing, the hydrophobization processing method may further include a step of sucking the processing gas-containing gas from the peripheral side of the substrate. In addition, in order to suppress that the back surface of a board|substrate becomes hydrophobic, you may supply an inert gas or air to the back surface of a board|substrate in (A) process and (B) process. Since the steps (A) and (B) are performed under low-temperature conditions (for example, 15 to 35° C.), even when an inert gas or air is supplied to the back side of the substrate, it is due to the non-uniformity of temperature, which tends to become a problem under high-temperature conditions. The problem of non-uniformity of the process to be carried out is hard to generate|occur|produce. In addition, it is preferable that the temperature of the inert gas or air supplied to the back side of the substrate is also low (for example, 15 to 35°C).

In the hydrophobization treatment method, prior to the execution of the step (A), the processing gas is supplied from the supply source to a flow path connecting the processing gas supply source and the chamber in which the substrate hydrophobicization treatment is performed. A step of filling the region up to the above with a processing gas may be further provided. As described above with respect to FIG. 11B , when the flow path Lb from the three-way valve V1 to the chamber C is filled with nitrogen gas (inert gas), the supply source A and the chamber C are in a conductive state After , it takes several seconds until the process gas is actually supplied to the chamber C. On the other hand, prior to the execution of the step (A), a part of the nitrogen gas in the flow path Lb is substituted with the processing gas, so that the supply source A and the chamber C are electrically connected to perform the step (A). After , the process gas can be introduced into the chamber C within a very short time (refer to FIGS. 12A to 12C ).

The step of substituting a part of the inert gas in the flow path with the processing gas may be performed while the previous substrate hydrophobization treatment is finished and the next substrate hydrophobicization treatment is started. That is, in the hydrophobization treatment method, in the steps (A) to (C), after supplying the processing gas from the supply source to the chamber through a flow passage connecting the supply source of the processing gas and the chamber in which the hydrophobization treatment of the substrate is performed, the processing gas is supplied to the chamber, and then the flow passage In the process of supplying an inert gas to the chamber through You may further provide the process of filling with a process gas (refer FIGS. 13A-13C).

As described above, when an area from the supply source side in the flow path to the front side of the chamber is filled with the processing gas, an excessive amount of processing gas is supplied from the supply source and the processing gas is prevented from flowing into the chamber at an unintended timing. A three-way valve may be provided in the middle of the flow path and in the vicinity of the gas outlet of the chamber (refer to FIGS. 14A and 14B).

The following 1st - 3rd aspects are mentioned as a specific apparatus for implementing the said hydrophobization treatment method. According to the device according to these aspects, it is possible to secure a time for sufficiently physically adsorbing the reactant molecules for hydrophobization to the substrate surface, thereby providing a sufficiently stable hydrophobicity to the substrate, which is expected depending on the heat treatment temperature of the substrate. there is.

An apparatus according to the first aspect includes a supply source of a processing gas for hydrophobization, a lid portion having an inner surface facing the surface of a substrate with a gap therebetween, a gas discharge port formed in the cover portion, and conveying the processing gas from the supply source to the gas discharge port a gas outlet, comprising: a flow path for heating the substrate; a hot plate for heating the substrate; and a plurality of support pins for lifting and lowering the substrate above the hot plate; It is possible to supply a processing gas to the surface of the substrate from the

An apparatus according to a second aspect includes a supply source of a processing gas for hydrophobization, a cover portion having an inner surface facing the surface of a substrate with a gap therebetween, a gas discharge port formed in the cover portion, and conveying the processing gas from the supply source to the gas discharge port a first flow path for venting the gas, a second flow path for conveying the process gas from the supply source to the gas discharge port, and a heater for heating the processing gas transferred to the second flow path, wherein the flow path from the supply source to the gas outlet is the first flow path can be switched to the second flow path.

An apparatus according to a third aspect includes: a supply source of a processing gas for hydrophobization; a chamber for accommodating a substrate; It has a hot plate for heating, a chamber for a chemical reaction in which the substrate is heated, and a transport plate for transferring the substrate from the chamber for physical adsorption to the chamber for chemical reaction. In order to suppress the physical adsorption of reactant molecules to the back surface of the substrate in the physical adsorption chamber, the carrier plate supports the substrate when the substrate is in the physical adsorption chamber and supplies an inert gas or air to the back side of the substrate. may have The temperature of the board|substrate at the time of the process in the chamber for physical adsorption is 15-35 degreeC, for example, The temperature of the board|substrate at the time of the process in the chamber for chemical reaction is 60-180 degreeC, for example.

The present invention provides a computer-readable recording medium for hydrophobicization in which a program for executing the hydrophobicization processing method is recorded in a hydrophobicization processing apparatus.

According to the present invention, the hydrophobicity expected according to the heat treatment temperature of the substrate can be sufficiently stably provided to the substrate.

1 is a perspective view of a substrate processing system to which a hydrophobization processing apparatus (hydrophobization processing unit) according to the present invention is applied.
FIG. 2 is a cross-sectional view taken along line II - II in FIG. 1 .
FIG. 3 is a cross-sectional view taken along line III - III in FIG. 2 .
4 is a cross-sectional view showing a schematic configuration of a hydrophobization processing unit according to the first embodiment.
5 is a cross-sectional view showing a state in which the process (A) and the process (B) are performed in an open state in the chamber of the hydrophobicization treatment unit.
6 is a cross-sectional view showing a state in which step (C) is performed in a state in which the chamber of the hydrophobicization unit is closed.
7 is a cross-sectional view showing a state in which a gas replacement process is performed in a state in which the chamber of the hydrophobicization unit is closed.
8 is a cross-sectional view showing a state in which steps (A) and (B) are performed in the hydrophobicization treatment unit according to the second embodiment.
9 is a cross-sectional view showing a state in which step (C) is performed in the hydrophobization treatment unit according to the second embodiment.
10A to 10D are cross-sectional views schematically showing a state in which a hydrophobization treatment is performed by a hydrophobization treatment unit according to a third embodiment.
11A and 11B are schematic diagrams illustrating a mechanism for supplying a processing gas from a supply source of processing gas to a chamber through a flow path.
12A to 12C are schematic diagrams illustrating an example of a process including a step of replacing a part of the inert gas in the flow path with the processing gas.
13A to 13C are schematic diagrams illustrating another example of a process including a step of replacing a part of the inert gas in the flow path with the processing gas.
14A and 14B, FIG. 14A is a schematic diagram illustrating a state in which the processing gas from the supply source is transferred from the three-way valve to the exhaust side, and FIG. 14B is a schematic diagram showing the state in which the processing gas from the supply source is supplied from the three-way valve to the chamber am.
15A and 15B are schematic diagrams for explaining a contact angle of a water droplet, which is an index of hydrophobicity on the surface of a substrate.

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described in detail, referring drawings. In the description, the same elements or elements having the same function are given the same reference numerals, and overlapping descriptions are omitted. The hydrophobization processing unit (hydrophobization processing apparatus) of the present embodiment is an apparatus for hydrophobizing the surface of a wafer in a substrate processing system. In addition, as an index indicating the hydrophobicity (or hydrophilicity) of the wafer, the contact angle of water droplets dropped on the surface of the wafer is generally used. As shown in Fig. 15, an angle formed by a line (dotted-dotted line) connecting one of the left and right end points of the water droplet D and the apex and the surface of the wafer W is θ, and this angle is doubled. (2θ) is the contact angle. 15A shows a state in which a water droplet D is dropped on a wafer W having a high surface hydrophobicity, while FIG. 15B shows a state in which a water droplet D is dropped on a wafer W having a low surface hydrophobicity.

(Configuration of substrate processing system)

First, the substrate processing system 1 is demonstrated with reference to FIGS. The substrate processing system 1 includes a coating and developing apparatus 2 and an exposure apparatus 3 . The exposure apparatus 3 performs exposure processing of the resist film. Specifically, an energy ray is irradiated to an exposure target portion of a resist film (photosensitive film) by a method such as immersion exposure. Examples of the energy ray include ArF excimer laser, KrF excimer laser, g-ray, i-ray, or extreme ultraviolet (EUV).

The coating and developing apparatus 2 performs a process of forming a resist film on the surface of the wafer W (substrate) before exposure treatment by the exposure apparatus 3 , and develops the resist film after the exposure process. In the present embodiment, the wafer W has a disk shape, but a wafer in which a part of a circle is notched or a wafer having a shape other than a circle such as a polygon may be used. The wafer W may be, for example, a semiconductor substrate, a glass substrate, a mask substrate, an FPD (Flat Panel Display) substrate, or other various substrates.

1 to 3 , the coating and developing apparatus 2 includes a carrier block 4 , a processing block 5 , and an interface block 6 . The carrier block 4 , the processing block 5 and the interface block 6 are arranged in the horizontal direction.

The carrier block 4 has a carrier station 12 and a carry-in/out unit 13 . The carry-in/out unit 13 is interposed between the carrier station 12 and the processing block 5 . The carrier station 12 supports a plurality of carriers 11 . The carrier 11 accommodates, for example, a plurality of circular wafers W in a sealed state, and has an opening/closing door (not shown) for loading and unloading the wafers W on the side surface 11a side (FIG. 3). Reference). The carrier 11 is detachably installed on the carrier station 12 so that the side surface 11a may face the carrying-in/out part 13 side. The carry-in/out unit 13 has a plurality of opening/closing doors 13a respectively corresponding to the plurality of carriers 11 on the carrier station 12 . By simultaneously opening the opening/closing door and the opening/closing door 13a of the side surface 11a, the inside of the carrier 11 and the inside of the carrying-in/out part 13 communicate with each other. The carrying-in/out part 13 has the delivery arm A1 built-in. The transfer arm A1 takes out the wafer W from the carrier 11 and delivers it to the processing block 5 , and receives the wafer W from the processing block 5 and returns it into the carrier 11 .

The processing block 5 includes a BCT module (underlayer film forming module) 14, a COT module (resist film forming module) 15, a TCT module (upper layer film forming module) 16, and a DEV module (developing). processing module) (17). These modules are arranged in the order of the DEV module 17 , the BCT module 14 , the COT module 15 , and the TCT module 16 from the bottom side.

The BCT module 14 is for forming an underlayer film (eg, an antireflection film) on the surface of the wafer W, and as shown in FIG. 3 , an application unit U1, a heat treatment unit U2, A hydrophobization processing unit U5 and a transfer arm A2 for transferring the wafer W to these units are incorporated. The application unit U1 is configured to apply a coating liquid for forming an underlayer film to the surface of the wafer W. The heat treatment unit U2 is configured to heat the wafer W with a hot plate, cool the heated wafer W with a cooling plate, for example, and perform heat treatment. Specific examples of the heat treatment performed in the BCT module 14 include heat treatment for curing the underlayer film. The hydrophobization processing unit U5 is configured to perform a hydrophobization treatment on the surface of the wafer W on which the antireflection film is formed. The detail of the hydrophobization processing unit U5 is mentioned later.

The COT module 15 is configured to form a thermosetting and photosensitive resist film on the underlayer film. The COT module 15 incorporates a plurality of coating units (not shown), a plurality of heat treatment units (not shown), and a transfer arm A3 for transferring the wafer W to these units. The application unit is configured to apply a processing liquid for forming a resist film (made of a resist) onto the underlayer film. The heat treatment unit is configured to heat the wafer W by, for example, a hot plate, and to perform heat treatment by cooling the heated wafer W by, for example, a cooling plate. Specific examples of the heat treatment performed in the COT module 15 include heat treatment (PAB: Pre Applied Bake) for curing the resist film.

The TCT module 16 is configured to form an upper layer film on a resist film. The TCT module 16 includes a plurality of coating units (not shown), a plurality of heat treatment units (not shown), and a transport arm A4 for transporting the wafer W to these units. The application unit is configured to apply a coating liquid for forming an upper layer film to the surface of the wafer W. The heat treatment unit is configured to heat the wafer W by, for example, a hot plate, and to perform heat treatment by cooling the heated wafer W by, for example, a cooling plate. Specific examples of the heat treatment performed in the TCT module 16 include heat treatment for curing the upper layer film.

The DEV module 17 is configured to perform development processing of the exposed resist film. The DEV module 17 includes a plurality of developing units (not shown), a plurality of heat treatment units (not shown), a transfer arm A5 that transfers the wafer W to these units, and does not pass through these units. It has a built-in direct transfer arm A6 for transferring the wafer W without it (refer to Fig. 2). The developing unit is configured to partially remove the resist film to form a resist pattern. The heat treatment unit heats the wafer W with, for example, a hot plate, and cools the heated wafer W with, for example, a cooling plate to perform heat treatment. Specific examples of the heat treatment performed in the DEV module 17 include heat treatment before development (PEB: Post Exposure Bake), heat treatment after development (PB: Post Bake), and the like.

A shelf unit U10 is provided on the carrier block 4 side in the processing block 5 (refer to FIGS. 2 and 3). The shelf unit U10 is provided so as to reach the TCT module 16 from the bottom surface, and is partitioned into a plurality of cells arranged in the vertical direction. A lifting arm A7 is provided in the vicinity of the shelf unit U10. The lifting arm A7 raises and lowers the wafer W between cells of the shelf unit U10 .

A shelf unit U11 is provided on the interface block 6 side in the processing block 5 (refer to Figs. 2 and 3). The shelf unit U11 is provided so as to reach the upper part of the DEV module 17 from the bottom surface, and is divided into a plurality of cells arranged in the vertical direction.

The interface block 6 has a built-in transfer arm A8 and is connected to the exposure apparatus 3 . The transfer arm A8 takes out the wafer W of the shelf unit U11 and delivers it to the exposure apparatus 3 , receives the wafer W from the exposure apparatus 3 and returns to the shelf unit U11 . Consists of.

(Configuration of hydrophobic treatment unit)

With reference to FIGS. 4-7, the hydrophobization processing unit (hydrophobization processing apparatus) U5 which concerns on 1st Embodiment is demonstrated in detail. As shown in FIG. 4 , the hydrophobization processing unit U5 includes an upper case (cover part) 21 , a lower case 22 , an opening/closing unit 30 , a hot plate 40 , and an air supply unit 60 . and an exhaust unit 70 , a lifting unit 80 , and a control unit 90 .

The upper case 21 has a circular top plate 21a arranged horizontally, and a peripheral wall 21b protruding downward from the periphery of the top plate 21a. The lower case 22 has a circular bottom plate 22a arranged horizontally, a peripheral wall 22b protruding upward from the periphery of the bottom plate 22a, and provided on the outer periphery of the upper end of the peripheral wall 22b. It has a flange 22c and is arrange|positioned just below the upper case 21. The outer diameter of the lower case 22 is smaller than the outer diameter of the upper case 21 . The upper case 21 and the lower case 22 are spaced apart from each other.

The opening/closing unit 30 includes a shutter 31 and a shutter driver 32 , and opens and closes between the periphery of the upper case 21 and the periphery of the lower case 22 . The shutter 31 has an upper flange 31a in contact with the lower end of the peripheral wall 21b of the upper case 21 , a lower flange 31b in contact with the lower surface of the flange 22c of the lower case, and the upper flange It has a cylindrical peripheral wall 31c which connects the inner edge of 31a and the outer edge of the lower flange 31b. The upper flange 31a is provided with a packing P1, and the packing P1 seals a gap between the upper surface of the upper flange 31a and the lower end surface of the peripheral wall 21b. The lower flange 31b is provided with a packing P2, and the packing P2 seals a gap between the upper surface of the lower flange 31b and the lower surface of the flange 22c.

The shutter driver 32 is, for example, an air cylinder, and has a lifting rod 32a protruding upward. The distal end of the lifting rod 32a is fixed to the shutter 31 . The shutter driver 32 raises and lowers the shutter 31 via the lifting rod 32a.

The upper case 21 and the lower case 22 form a processing space R1 therebetween. The wafer W to be hydrophobized is horizontally arranged in the processing space R1 so that the front surface Wa faces upward (the back surface Wb faces downward). In the following description, 'wafer (W)' means a wafer W disposed in the processing space R1.

The hot plate 40 is for heat-treating the wafer W, and is accommodated in the lower case 22 . The heating plate 40 has a built-in heating wire (not shown), and the temperature is increased by supplying electric power to the heating wire.

The air supply unit 60 has a gas supply source 62 and a flow path 62a. The distal end of the flow path 62a is connected to a gas discharge port 21c provided in the center of the upper case 21 . The gas supply source 62 supplies only the inert gas to the processing space R1 by switching the three-way valve from a state in which an inert gas (for example, nitrogen gas) containing the vapor of the hydrophobic treatment liquid is supplied to the processing space R1. state can be changed (see FIGS. 11A and 11B ). The hydrophobization treatment gas is, for example, a gas obtained by mixing a vaporized component of HMDS (hexamethyldisilazane) with nitrogen gas. HMDS reacts with silanol groups present on the wafer surface and hydrophobizes the wafer surface by covering it with methyl groups. In addition, although the number of gas outlets 21c provided in the upper case 21 is set to one in FIG. 4 , a plurality of gas outlets 21c may be provided and the process gas may be introduced into the processing space R1 from these outlets. .

The exhaust unit 70 has a gas outlet 71 and an exhaust pump 72 . The gas outlet 71 penetrates through the periphery of the upper case 21 and is opened at the lower end surface of the peripheral wall 21b. The exhaust pump 72 includes, for example, an electric fan or the like, and is connected to the gas exhaust port 71 via an exhaust pipe 72a. The exhaust unit 70 draws in the gas in the processing space R1 and discharges it outside by driving the exhaust pump 72 . In addition, although the case where the gas outlet 71 was opened in the lower end surface of the circumferential wall 21b in FIG. 4 was shown, the gas outlet 71 may be opened in the inner surface of the circumferential wall 21b.

The elevating unit 80 includes an elevating body 81 and an elevating body driver 82 . The elevating body 81 has an elevating plate 81a horizontally arranged below the center of the lower case, and three supporting pins 81b protruding upward from the elevating plate 81a. In addition, in FIG. 4, only the two support pins 81b are shown. The three support pins 81b penetrate the bottom plate 22a and the hot plate 40 of the lower case 22 , and support the wafer W on the hot plate 40 . Four or more may be sufficient as the number of the support pins 81b.

The elevating body actuator 82 is, for example, an air cylinder, and has the elevating rod 82a protruding upward. The distal end of the lifting rod 82a is fixed to the lifting plate 81a. The elevating body driver 82 raises and lowers the elevating body 81 via the elevating rod 82a, and elevates the wafer W supported by the support pin 81b.

The control unit 90 is a computer for control, and includes a display unit (not shown) for displaying a setting screen of the subdivision processing condition, an input unit (not shown) for inputting the subdivision processing condition, and a computer-readable recording medium. It has a reading unit (not shown) for reading. In the recording medium, a program for causing the control unit 90 to execute the decimalization process is recorded, and the program is read by the reading unit of the control unit 90 . As a recording medium, a hard disk, a compact disk, a flash memory, a flexible disk, a memory card etc. are mentioned, for example. The control unit 90 includes the opening/closing unit 30, the hot plate 40, the air supply unit 60, the exhaust unit 70 and the lifting unit ( 80), and perform a hydrophobicization process.

(Control of the hydrophobicization processing unit (hydrophobicization processing method))

Hereinafter, the hydrophobization processing method executed by the control unit 90 will be described. First, the control unit 90 controls the opening/closing unit 30 to lower the shutter 31 to open a gap between the periphery of the upper case 21 and the periphery of the lower case 22 (see FIG. 5 ). In this state, the wafer W is loaded into the processing space R1. The wafer W is supported by the support pins 81b in a raised state, so that the wafer W is horizontally disposed in the processing space R1 so that the surface Wa faces upward.

Next, in a state in which the periphery of the processing space R1 is opened and the support pin 81b is raised, the control unit 90 controls the air supply unit 60 to control the supply of the processing gas as shown in FIG. 5 . ((A) step). That is, the processing gas is supplied in a state in which the wafer W is disposed at an upper position spaced apart from the hot plate 40 . Accordingly, the surface of the wafer W can be exposed to the atmosphere containing the processing gas over a predetermined period of time (step (B)).

In step (A), the temperature of the processing gas introduced from the gas outlet 21c is preferably 15 to 35°C, more preferably 15 to 30°C, and still more preferably 15 to 20°C. When this temperature is 35° C. or less, a sufficient amount of HMDS can be physically adsorbed on the surface of the wafer W. In addition, in order to make this temperature into less than 15 degreeC, it is easy to generate|occur|produce the necessity of preparing a cooling means separately. From the same viewpoint, in the step (B), the atmospheric temperature of the wafer W is preferably 15 to 35°C, more preferably 15 to 30°C, still more preferably 15 to 20°C. From the viewpoint of physically adsorbing HMDS to the surface of the wafer W more reliably, the temperature of the surface of the wafer W may be lower than the temperature of the processing gas.

From the viewpoint of sufficiently physically adsorbing HMDS molecules to the surface of the wafer W and achieving high throughput, the processing time of the step (B) is preferably 2 to 10 seconds, more preferably 5 to 8 seconds am.

As described above, since the process (A) and the process (B) are performed with the periphery of the processing space R1 open, there is a risk that HMDS discharged from the processing space R1 may adversely affect other processes. . In order to prevent this, the control unit 90 executes control for discharging HMDS-containing gas from the gas outlet 71 by operating the exhaust pump 72 while the steps (A) and (B) are being executed. You can do it. In addition, from the viewpoint of reducing the amount of processing gas, it is desirable to make the gap between the periphery of the wafer W and the inner surface of the peripheral wall 21b of the upper case 21 as small as possible. For example, by holding the wafer W with the support pins 81b in a raised state, the height position of the back surface Wb of the wafer W is adjusted so that the wafer W is accommodated in the upper case 21 . What is necessary is just to make it higher than the lower surface of the peripheral wall 21b.

Next, the control unit 90 controls the elevating unit 80 to lower the elevating body 81 to place the wafer W on the hot plate 40 (refer to FIG. 6 ). Further, by controlling the opening/closing portion 30 to raise the shutter 31 , between the periphery of the upper case 21 and the periphery of the lower case 22 is closed. The control unit 90 increases the temperature of the hot plate 40 by starting power supply to the hot plate 40 . Thereby, the surface temperature of the wafer W is heated to 60-180 degreeC ((C) process). Since the process (C) is performed in a state in which the processing space R1 is sealed, the exhaust pump 72 is stopped. The supply of the processing gas by the air supply unit 60 continues even after the start of the process (C). In addition, if it seems that a sufficient amount of HMDS exists in the processing space R1, the supply of the processing gas may be stopped after a predetermined time has elapsed (for example, 5 to 10 seconds later) from the start of the process (C), Alternatively, the processing gas may be intermittently introduced into the processing space R1 by repeating the stop and restart of the supply of the processing gas. (C) The processing time of a process becomes like this. Preferably it is 20 to 90 second, More preferably, it is 30 to 70 second.

Next, the control part 90 performs gas substitution control as shown in FIG. That is, the control unit 90 supplies nitrogen gas into the processing space R1 by controlling the air supply unit 60 while maintaining the closed state of the processing space R1 , and also operates the exhaust pump 72 to supply nitrogen gas. A gas containing HMDS is discharged from the outlet 71 .

As described above, the hydrophobicization process is completed, and the control unit 90 controls the opening/closing unit 30 to lower the shutter 31 (see FIG. 5 ). Accordingly, the gap between the periphery of the upper case 21 and the periphery of the lower case 22 is opened again, and the wafer W is unloaded.

<Second embodiment>

(Configuration of hydrophobic treatment unit)

With reference to FIGS. 8 and 9, the hydrophobization processing unit U15 which concerns on 2nd Embodiment is demonstrated. Here, differences from the above-described first embodiment will be mainly described. The hydrophobization processing unit U15 does not include the hot plate 40 , but includes a mechanism for heating the processing gas introduced into the processing space R1 . By introducing the heated processing gas into the processing space R1 through the plurality of gas discharge ports 21c, the temperature of the wafer W is increased.

As shown in FIG. 8 , the hydrophobization processing unit U15 includes a first flow path 62a for supplying a process gas containing HMDS vapor to the gas outlet 21c, and a second flow path different from the flow path 62a. (62b) is provided. The second flow path 62b is also a flow path for supplying a gas containing HMDS vapor to the gas outlet 21c. The second flow path 62b includes a heater 62h that heats the process gas in the flow path. The flow path from the gas supply source 62 to the gas discharge port 21c is switchable from the first flow path 62a to the second flow path 62b by the control unit 90 . Moreover, you may provide the heater (not shown) for heat retention for preventing dew condensation of HMDS in flow paths other than the part in which the heater 62h in the 2nd flow path 62b was provided.

(Control of the hydrophobicization processing unit (hydrophobicization processing method))

Hereinafter, the hydrophobization processing method executed by the control unit 90 will be described. Also here, differences from the above-described first embodiment will be mainly described.

First, the control unit 90 controls the opening/closing unit 30 to lower the shutter 31 to open a gap between the periphery of the upper case 21 and the periphery of the lower case 22 (see FIG. 5 ). In this state, the wafer W is loaded into the processing space R1. The wafer W is horizontally disposed in the processing space R1 so that the surface Wa faces upward. The control unit 90 controls the elevating unit 80 to raise the elevating body 81 , and supporting the wafer W by the support pins 81b of the elevating unit 81 . Thereafter, the shutter 31 is raised by controlling the opening/closing portion 30 to close between the periphery of the upper case 21 and the periphery of the lower case 22 .

Next, the control unit 90 changes the support pin 81b from the raised state to the lowered state. Thereafter, by controlling the air supply unit 60 , as shown in FIG. 8 , supply control of the processing gas through the first flow path 62a is performed (step (A)). Accordingly, the surface of the wafer W can be exposed to the atmosphere containing the processing gas over a predetermined period of time (step (B)). In addition, although the case where (A) and (B) process is implemented in the state where the support pin 81b is lowered is illustrated here, you may implement these processes in a raised state, and the protrusion amount of the support pin 81b is exemplified. You may arrange the wafer W at any height by adjusting.

In step (A), the temperature of the processing gas introduced through the first flow path 62a is preferably 15 to 35°C, more preferably 15 to 30°C, and still more preferably 15 to 20°C. . When this temperature is 35° C. or less, a sufficient amount of HMDS can be physically adsorbed on the surface of the wafer W.

Next, by controlling the air supply unit 60 , the control unit 90 switches the flow path of the process gas from the first flow path 62a to the second flow path 62b including the heater 62h as shown in FIG. 9 . . By discharging the heated processing gas from the plurality of gas discharge ports 21c, the surface temperature of the wafer W is heated to 60 to 180°C (step (C)). (C) The processing time of a process becomes like this. Preferably it is 20 to 90 second, More preferably, it is 30 to 70 second. Incidentally, the step (C) may be carried out in a state in which the support pins 81b are raised or in a lowered state, or the amount of protrusion of the support pins 81b so that the wafer W can be heated as uniformly as possible. may be adjusted to arrange the wafer W at an arbitrary height.

Then, the control part 90 performs gas substitution control similarly to 1st Embodiment. As described above, the hydrophobicization process is completed, and the control unit 90 controls the opening/closing unit 30 to lower the shutter 31 . Accordingly, the gap between the periphery of the upper case 21 and the periphery of the lower case 22 is opened again, and the wafer W is unloaded.

<Third embodiment>

(Configuration of hydrophobic treatment unit)

A hydrophobization processing unit U25 according to the third embodiment will be described with reference to FIGS. 10A to 10D . Also here, differences from the above-described first embodiment will be mainly described. The hydrophobicization processing unit U25 includes a physical adsorption chamber C1 that mainly promotes physical adsorption of HMDS to the wafer W, and a chemical reaction chamber that mainly advances a chemical reaction between HMDS and the surface of the wafer W. (C2) is provided. The physical adsorption chamber (C1) and the chemical reaction chamber (C2) are arranged in a horizontal direction.

Both the physical adsorption chamber (C1) and the chemical reaction chamber (C2) can accommodate the wafer (W), a common lower case 45, and two upper cases (covers) 41 that can be lifted independently of each other , 42). In the physical adsorption chamber C1, the surface of the wafer W is exposed to the processing gas in the presence of the processing gas under the condition of a temperature of 15 to 35°C. In the chemical reaction chamber C2, the surface of the wafer W is exposed to the processing gas in the presence of the processing gas under conditions of a temperature of 60 to 180°C. The lower case 45 has a hot plate 50 at a position corresponding to the upper case 42 .

The hydrophobization processing unit U25 further includes a conveying plate P for conveying the wafer W from the physical adsorption chamber C1 to the chemical reaction chamber C2. 10A to 10D , the transfer plate P has a flow path Q for supplying an inert gas (eg nitrogen gas) or air to the rear surface Wb side of the wafer W. As shown in FIGS. The lower case 45 has a flow path 45a leading to the flow path Q. Gas supply through the flow path Q and the flow path 45a is implemented when the conveyance plate P is accommodated in the chamber C1 for physical absorption. By suppressing the physical adsorption of HMDS to the back surface of the wafer W, hydrophobization of the back surface of the wafer W can be suppressed. Since the steps (A) and (B) are performed under a low-temperature condition of 15 to 35°C, for example, if an inert gas or air at a temperature of 15 to 35°C is supplied to the back surface of the substrate, the treatment resulting from the temperature non-uniformity The problem of non-uniformity does not occur.

(Control of the hydrophobicization processing unit (hydrophobicization processing method))

First, as shown in Fig. 10A, the upper case 41 of the physical absorption chamber C1 is positioned above and the support pin is raised. The wafer W is loaded into the Thereafter, the chamber C1 for physical absorption is closed by lowering the upper case 41 . In this state, as shown in FIG. 10B , a processing gas is supplied to the front side of the wafer W (step (A)), and the back surface Wb of the wafer W is passed through the flow path Q and the flow path 45a. Inert gas or air is supplied to the side. In the step (A), the temperature of the processing gas introduced into the physical adsorption chamber C1 is preferably 15 to 35° C., more preferably 15 to 30° C., and still more preferably 15 to 20° C. . Accordingly, the surface of the wafer W can be exposed to the atmosphere containing the processing gas over a predetermined period of time (step (B)). By maintaining this state for preferably 2 to 10 seconds, more preferably 5 to 8 seconds, HMDS can be sufficiently physically adsorbed onto the surface of the wafer W. Moreover, the chamber C1 for physical adsorption is provided with a gas discharge port (not shown), and is comprised so that the gas inside can be discharged|emitted suitably.

Next, as shown in Fig. 10C, after opening the physical adsorption chamber C1 by raising the upper case 41, the upper case 42 of the chemical reaction chamber C2 by the conveying plate P The wafer W is loaded downward. Thereafter, as shown in FIG. 10D , the wafer W is placed on the hot plate 50 by lowering the upper case 42 and the support pins, and the hot plate 50 is supplied while supplying a processing gas to the surface of the wafer W. ) to heat the surface temperature of the wafer W to 60 to 180° C. by increasing the temperature (step (C)). (C) The processing time of a process becomes like this. Preferably it is 20 to 90 second, More preferably, it is 30 to 70 second.

As a result, the hydrophobicization process is completed, and thereafter, the upper case 42 is opened and the support pin is raised. Thereby, the wafer W will be in a state which can be carried out by the conveyance plate P from the chamber C2 for chemical reaction.

As mentioned above, although embodiment of this invention was described in detail, this invention is not limited to the said embodiment, Various changes are possible in the range which does not deviate from the summary. For example, in the first and second embodiments, the configuration in which sealing and opening of the processing space R1 are switched is exemplified when the shutter 31 moves up and down. However, when the upper case 21 moves up and down, the processing space R1 ) may be configured to switch between sealing and opening.

In the above embodiment, the flow path connecting the supply source of the processing gas and the chamber in which the hydrophobization treatment of the wafer W is performed is filled with nitrogen gas (inert gas) (the processing gas in the flow path is purged with nitrogen gas) Although the case of starting the process (A) is exemplified from the above, the process (A) may be started after a part of the nitrogen gas in the flow path is replaced with the process gas. 12A is a diagram illustrating a state in which the flow path L is filled with nitrogen gas before the process (A) is performed. FIG. 12B shows the three-way valve V1 from the state of FIG. 12A is operated to supply process gas from the supply source A to the flow path L, so that the front side of the chamber C from the supply source A side in the flow path L It is a figure which shows the state which replaced the nitrogen gas with the process gas with respect to the area|region up to. The boundary B shown in FIG. 12B schematically shows the boundary between the process gas and the nitrogen gas in the flow path L. As shown in FIG. The distance from the boundary B to the inlet (gas outlet) of the chamber C is preferably within 1 m, more preferably within 0.6 m. 12C is a view showing a state in which the supply source (A) and the chamber (C) are conducted in order to perform the process (A) from the state shown in FIG. 12B.

As shown in FIG. 12B , after the supply of the process gas from the supply source A to the chamber C is started by allowing the process gas to reach the position of the boundary B in advance, within a very short time (for example, A process gas can be introduced into the chamber (C) within 1 second). When replacing the nitrogen gas in the flow path L with the processing gas, an excess amount of the processing gas is supplied from the supply source A to the flow path L, and the processing gas is not introduced into the chamber C at an unintended timing. , a process gas in an amount smaller than the internal volume of the flow path L may be supplied from the supply source A to the flow path L. In steps (A) to (C), after the processing gas is supplied from the supply source A to the chamber C through the flow path L, the processing gas in the flow path L is replaced with nitrogen gas again. In addition, at the timing of replacing the gas in the flow path L ( FIG. 12B ), the chamber C may be opened to accommodate the wafer W to be hydrophobized.

The step of replacing a part of the nitrogen gas in the flow path L with the processing gas may be performed while the hydrophobization treatment of the previous wafer W is completed and the hydrophobization treatment of the next wafer W is started. . 13A is a diagram illustrating a state in which a processing gas is supplied from the supply source A to the chamber C through the flow path L in steps (A) to (C). 13B is a diagram illustrating a state in which the three-way valve V1 is operated and nitrogen gas is supplied to the chamber C through the flow path L after hydrophobization of the wafer W is performed. 13C is a diagram illustrating a state in which the three-way valve V1 is operated again from the state of FIG. 13B and a part of the nitrogen gas in the flow path L is substituted with the processing gas. The boundary B shown in FIG. 13C schematically shows the boundary between the process gas and the nitrogen gas in the flow path L. As shown in FIG. The distance from the boundary B to the inlet (gas outlet) of the chamber C is preferably within 1 m, more preferably within 0.6 m.

As shown in FIG. 13C , by allowing the processing gas to reach the boundary B in advance, the supply of the processing gas from the supply source A to the chamber C is reduced in the subsequent hydrophobization treatment of the wafer W. After initiation, the process gas can be introduced into the chamber C in a very short time (eg within 1 second). The gas in the flow path L may be replaced while the chamber C is closed, for example, while the hydrophobized wafer W is being cooled in the chamber C. After the hydrophobicization treatment is completed, the wafer W is removed from the chamber C, and the next wafer W is loaded into the chamber C.

You may further provide a three-way valve in the vicinity of the chamber C in the middle of the flow path L shown to FIGS. 12A-13C. 14A and 14B , by providing the three-way valve V2 in the vicinity of the chamber C, when a part of the nitrogen gas in the flow path L is replaced with the processing gas, an excess amount from the supply source A of the process gas is supplied, and it is possible to prevent the process gas from flowing into the chamber C at an unintended timing. That is, the process gas from the supply source A is supplied to the three-way valve V2. By operating the three-way valve V2, the supply destination of the process gas can be switched to the chamber C or the discharge side (not shown). 14A is a schematic diagram showing a state in which the processing gas from the supply source A is transferred from the three-way valve V2 to the discharge side. By doing this, the area up to the three-way valve V2 in the flow path L is filled with the processing gas. From this state, by switching the three-way valve V2 in the execution of the step (A), the processing gas can be introduced into the chamber C within a very short time (for example, within 1 second). The distance from the three-way valve V2 to the inlet (gas outlet) of the chamber C is preferably within 1 m, more preferably within 0.6 m. 14B is a schematic diagram showing a state in which the processing gas from the supply source A is supplied to the chamber C from the three-way valve V2. In addition, the process shown in FIGS. 12A to 14B is for continuously hydrophobizing the plurality of wafers W, and since the time for which the processing gas remains in the flow path L is very short, the entire flow path L is heated with a heater. There is no need to take measures such as warming with

In the above embodiment, a gas containing HMDS vapor is exemplified as the gas for the hydrophobic treatment, but a suitable processing gas may be selected according to the material of the substrate. In the second embodiment, the case where a heated process gas is used for the heat treatment of the wafer W is exemplified. In this case, light for radiant heating may be used in combination as a heat source. Various light emitting elements can be used as a light source for radiant heating. Examples of the light emitting element include LED, semiconductor laser, halogen lamp, and xenon flash. What is necessary is just to arrange a light emitting element on the inner surface of the top plate 21a, and to irradiate light toward the surface Wa of the wafer W.

21, 41, 42: upper case (cover part)
21c: gas outlet
40, 50: hot plate
62: gas supply source (source of processing gas)
62a: Euro (1st Euro)
62b: Euro (2nd Euro)
62h: heater
81b: support pin
A: Source of processing gas
C: chamber
L: Euro
C1 : Chamber for physical adsorption
C2 : Chamber for chemical reaction
P: conveying plate
Q: Euro
U5, U15, U25: hydrophobization processing unit (hydrophobicization processing unit)
V2: three-way valve
W: wafer (substrate)
Wa : surface of wafer
Wb: back side of wafer

Claims (20)

A hydrophobization treatment method for hydrophobizing the surface of a substrate, comprising:
(A) supplying a process gas for hydrophobization to the surface of the substrate;
(B) exposing the surface of the substrate to an atmosphere containing the processing gas over a predetermined period of time;
(C) after step (B), heating the substrate in the presence of the processing gas;
The step (A) and the step (B) are carried out in a chamber for physical adsorption,
The process (C) is carried out in a chamber for chemical reaction that accommodates a hot plate,
The hydrophobization treatment method further comprising the step of transferring the substrate from the physical adsorption chamber to the chemical reaction chamber after the step (B) and before the step (C). The method of claim 1,
The said predetermined time in the said (B) process is a hydrophobization treatment method of 2 to 10 seconds. delete delete delete delete delete 3. The method according to claim 1 or 2,
The hydrophobization treatment method further comprising the step of sucking the gas containing the processing gas from the peripheral side of the substrate. 3. The method according to claim 1 or 2,
In the step (A) and the step (B), a hydrophobicization treatment method in which an inert gas or air is supplied to the back surface of the substrate. 3. The method according to claim 1 or 2,
The temperature of the said board|substrate in the said (A) process and the said (B) process is 15-35 degreeC, The hydrophobization treatment method. 3. The method according to claim 1 or 2,
The temperature of the atmosphere in the step (B) is 15 to 35°C, and the heating temperature of the substrate in the step (C) is 60 to 180°C. 3. The method according to claim 1 or 2,
Prior to the execution of the step (A), the processing gas is supplied from the supply source to a passage connecting the supply source of the processing gas and the chamber in which the hydrophobicization treatment of the substrate is performed. The hydrophobization treatment method further comprising the step of filling a region up to the front side of the with the processing gas. 3. The method according to claim 1 or 2,
In the steps (A) to (C), after supplying the processing gas from the supply source to the chamber through a flow path connecting the supply source of the processing gas and the chamber in which the substrate hydrophobization treatment is performed,
supplying an inert gas to the chamber through the flow path;
Before starting the next hydrophobicization treatment of the substrate, the process gas is supplied from the supply source of the process gas to the flow path, thereby filling an area in the flow path from the supply source side to the front side of the chamber with the processing gas. Hydrophobization treatment method further comprising. delete delete delete A hydrophobization treatment apparatus for hydrophobizing the surface of a substrate, comprising:
a source of processing gas for hydrophobization;
a physical adsorption chamber capable of accommodating the substrate and exposing a surface of the substrate to the processing gas by supplying the processing gas;
A chemical reaction chamber capable of accommodating the substrate and having a hot plate for heating the substrate, wherein the substrate is heated;
and a transport plate for transporting the substrate from the physical adsorption chamber to the chemical reaction chamber. 18. The method of claim 17,
The transport plate has a flow path for supporting the substrate and supplying an inert gas or air to a rear surface of the substrate when the substrate is in the physical adsorption chamber. 19. The method according to claim 17 or 18,
The temperature of the substrate at the time of processing in the chamber for physical adsorption is 15 to 35°C, and the heating temperature of the substrate at the time of processing in the chamber for chemical reaction is 60 to 180°C. A computer-readable recording medium for hydrophobization in which a program for causing a hydrophobicization processing apparatus to execute the hydrophobicization processing method according to claim 1 or 2 is recorded.

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