Substrate processing method

Abstract

The present invention aims to provide a substrate processing method, which solves the problem that the processing time becomes long if the resist film is to be removed only by the decomposition effect of ozone; the problem that although the peeling is promoted by swelling the resist film, there is still a lot of room for improvement in the degree of swelling, and can suppress the burden of waste liquid treatment and remove the resist film from the substrate in a short time. The substrate processing method comprises: a step of bringing an ozone-containing aqueous solution (920) into contact with the resist film on the substrate (901); and a step of bringing an ammonia-containing aqueous solution (930) containing ammonia at a higher concentration than the ozone-containing aqueous solution (920) into contact with a portion (P1) of the resist film that has been in contact with the ozone-containing aqueous solution (920).

Description

Technical Field

[0001] The present invention relates to a substrate processing method, and in particular to a substrate processing method for removing a resist film from a substrate. Background Art

[0002] After processing using a resist film on a substrate, the resist film is often removed from the substrate. In order to perform this treatment, a method of supplying a sulfuric acid / hydrogen peroxide mixture (SPM) as a cleaning liquid to the substrate surface has been widely used in the past. However, due to the heavy burden of waste liquid treatment, a substrate treatment method that does not use SPM has been sought in recent years.

[0003] Japanese Patent Publication No. 2010-153442 (Patent Document 1) discloses a substrate processing method for removing a resist film on a wafer. As an example, it is recorded that a mixed solution of ammonia water and ozone water is supplied to the wafer to remove the resist film. According to the publication, it is claimed that the resist can be removed at a high speed.

[0004] Japanese Patent Publication No. 2001-144006 (Patent Document 2) proposes to etch a resist film by supplying ozone-dissolved water and an ozone decomposition catalyst liquid to a resist film formed on a semiconductor wafer. As a method shown in an appropriate example, ammonia water as an ozone decomposition catalyst liquid is first sprayed onto the wafer. Next, ozone-dissolved water is sprayed onto the wafer. Thus, in a state where the entire surface of the wafer is covered with the ozone decomposition catalyst liquid, ozone-dissolved water is sprayed onto the surface of the wafer. According to the publication, it is claimed that since ozone can be decomposed instantly on the surface of the wafer, the etching time can be shortened.

[0005] Japanese Patent Publication No. 2001-203182 (Patent Document 3) discloses a method for purifying the surface of an article. Specifically, an alkaline aqueous solution and an ozone aqueous solution are simultaneously supplied to the surface of an article contaminated by attachments. At this time, it is set that the aforementioned surface is continuously in contact with a fresh alkaline aqueous solution and an ozone aqueous solution. Thus, ozone is decomposed on the surface. Thus, the aforementioned attachments are removed. According to the publication, it is claimed that an excellent cleaning effect can be obtained without using a special physical action (such as a high-pressure jet injection) that is dangerous to damage the surface of the article.

[0006] Japanese Patent Publication No. 4-179225 (Patent Document 4) discloses a cleaning method. The following contents are recorded in the publication: As one form of the cleaning method, the object to be cleaned is immersed in a cleaning solution and irradiated with ultraviolet rays, wherein the cleaning solution contains ammonia or amines, and hydrogen peroxide and / or ozone. According to the publication, it is claimed that heating equipment for the liquid is not required as an effect.

[0007] Japanese Patent Publication No. 2003-234323 (Patent Document 5) proposes a substrate processing method for removing organic matter. It should be noted that the organic matter is a reaction product formed on the surface of the substrate by dry etching using a resist as a mask. According to the substrate processing method, a removal liquid is supplied to the surface of the substrate, thereby causing the organic matter to swell. Next, the substrate is rotated, thereby removing the removal liquid attached to the substrate. Next, as described above, the residue of the swollen organic matter is peeled off. The peeling is performed by supplying a cleaning medium to the surface of the substrate. As the above-mentioned removal liquid, a liquid containing an organic alkali solution is exemplified. In addition, as the above-mentioned cleaning medium, warm water is exemplified. It is explained that the reason for removing the removal liquid attached to the substrate before supplying the cleaning medium is to avoid the phenomenon of generating a strong base due to the mixing of the two, thereby eliminating the need to spend time on the treatment of removing such a strong base.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2010-153442

[0011] Patent Document 2: Japanese Patent Application Publication No. 2001-144006

[0012] Patent Document 3: Japanese Patent Application Publication No. 2001-203182

[0013] Patent Document 4: Japanese Patent Application Laid-Open No. 4-179225

[0014] Patent Document 5: Japanese Patent Application Publication No. 2003-234323 Summary of the invention

[0015] Problems to be solved by the invention

[0016] The techniques of Patent Documents 1 to 3 above are intended to accelerate the decomposition of the resist film by promoting the action of ozone. According to the research of the inventors of the present application, when the resist film is to be removed mainly by the decomposition action, the processing time becomes long.

[0017] The technology of the above-mentioned Patent Document 4 intends to remove the resist and the like by irradiating a mixture of several chemical solutions with ultraviolet light. Since the functions of each chemical solution gradually become inactive after mixing, this technology easily hinders the full expression of the functions of each chemical solution. Therefore, the required processing time tends to be prolonged.

[0018] According to the technology of the above-mentioned patent document 5, the peeling is promoted by swelling the resist film. However, according to the research of the inventors of the present application, there is still much room for improvement in the degree of swelling. Therefore, there is still much room for improvement in reducing the processing time.

[0019] The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a substrate processing method capable of reducing the burden of waste liquid processing and removing a resist film from a substrate in a short time.

[0020] Means for solving problems

[0021] To solve the above-mentioned problems, the first method is a substrate processing method, which comprises: a process of bringing an ozone-containing aqueous solution into contact with a resist film on a substrate; and a process of bringing an ammonia-containing aqueous solution into contact with a portion of the resist film that has been in contact with the ozone-containing aqueous solution by the process of bringing the ammonia-containing aqueous solution into contact with the portion of the resist film that has been in contact with the ozone-containing aqueous solution, wherein the ammonia-containing aqueous solution is an aqueous solution containing ammonia at a higher concentration than the ozone-containing aqueous solution.

[0022] According to a second aspect, in the substrate processing method according to the first aspect, the step of bringing the substrate into contact with the ozone-containing aqueous solution is performed by spraying the ozone-containing aqueous solution toward the substrate.

[0023] A third aspect is the substrate processing method according to the first or second aspect, wherein the step of contacting the substrate with the aqueous ammonia solution is performed by spraying the aqueous ammonia solution toward the substrate.

[0024] According to a fourth aspect, in the substrate processing method according to the third aspect, the step of ejecting the aqueous solution containing ammonia includes the step of moving a nozzle ejecting the aqueous solution containing ammonia.

[0025] According to a fifth aspect, in the substrate processing method according to the fourth aspect, the step of moving the nozzle is performed so that the ammonia-containing aqueous solution is sprayed longer toward the peripheral portion of the substrate than toward the central portion of the substrate.

[0026] The sixth method is a substrate processing method described in any one of the first to fifth methods, further comprising: a step of separating, by physical cleaning, the portion of the resist film that has been in contact with the aqueous ammonia solution through the aforementioned contacting step with the aqueous ammonia solution from the aforementioned substrate.

[0027] According to a seventh aspect, in the substrate processing method according to the sixth aspect, the physical cleaning includes a step of blowing a gas toward the substrate.

[0028] According to an eighth aspect, in the substrate processing method according to the seventh aspect, the step of blowing the gas toward the substrate includes the step of spraying an aqueous solution containing ammonia toward the substrate using the gas.

[0029] A ninth aspect is the substrate processing method according to the seventh or eighth aspect, wherein the gas is an inert gas.

[0030] A tenth aspect is the substrate processing method according to any one of the first to fifth aspects, wherein the step of contacting the substrate with the ozone-containing aqueous solution includes the step of forming cracks in the resist film using the ozone-containing aqueous solution.

[0031] The 11th method is a substrate processing method described in the 10th method, wherein the step of contacting the aforementioned ammonia-containing aqueous solution includes: allowing the ammonia-containing aqueous solution to penetrate into the interface between the aforementioned substrate and the aforementioned resist film through the cracks formed by the step of forming cracks on the aforementioned resist film, thereby peeling off the aforementioned resist film from the aforementioned substrate.

[0032] A twelfth aspect is the substrate processing method according to any one of the first to eleventh aspects, wherein the ammonia-containing aqueous solution contains hydrogen peroxide.

[0033] A thirteenth aspect is the substrate processing method according to any one of the first to twelfth aspects, further comprising: irradiating the resist film with ultraviolet rays before the step of contacting the ozone-containing aqueous solution.

[0034] According to a fourteenth aspect, in the substrate processing method according to any one of the first to thirteenth aspects, the step of contacting the substrate with the ozone-containing aqueous solution includes the step of supplying the substrate with the ozone-containing aqueous solution instead of supplying the substrate with the ammonia-containing aqueous solution.

[0035] According to a fifteenth aspect, in the substrate processing method according to any one of the first to fourteenth aspects, the step of bringing the substrate into contact with the ozone-containing aqueous solution includes the step of heating the ozone-containing aqueous solution in a pipe away from the substrate.

[0036] A sixteenth aspect is the substrate processing method according to any one of the first to fifteenth aspects, wherein the step of contacting the substrate with the ozone-containing aqueous solution includes a step of heating the ozone-containing aqueous solution on the substrate.

[0037] Effects of the Invention

[0038] According to the first method, the ammonia-containing aqueous solution is brought into contact with the portion of the resist film that has been in contact with the ozone-containing aqueous solution. Since the portion that has been in contact with the ozone-containing aqueous solution has been subjected to the decomposition effect caused by ozone in advance, it is easy to be subjected to the swelling effect caused by the ammonia-containing aqueous solution. Thus, the swelling of the resist film is promoted. Therefore, the resist film can be removed in a short time in the subsequent process. In addition, compared with SPM, the waste liquid treatment burden of the ozone-containing aqueous solution and the ammonia-containing aqueous solution is small. As described above, the burden of waste liquid treatment can be suppressed, and the resist film can be removed from the substrate in a short time. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 It is a plan view schematically showing the structure of a substrate processing apparatus.

[0040] Figure 2 For along Figure 1 Schematic cross-sectional view along line II-II.

[0041] Figure 3 For along Figure 1 Schematic cross-sectional view along line III-III.

[0042] Figure 4 To show Figure 3 A cross-sectional view of an example of the configuration of a spray nozzle.

[0043] Figure 5 The following is a flowchart schematically showing the substrate processing method in the first embodiment of the present invention from the perspective of processing a portion of a resist film.

[0044] Figure 6 It is a partial cross-sectional view schematically showing the first step of the substrate processing method in the first embodiment of the present invention.

[0045] Figure 7 It is a partial cross-sectional view schematically showing the second step of the substrate processing method in the first embodiment of the present invention.

[0046] Figure 8 It is a partial cross-sectional view schematically showing the third step of the substrate processing method in the first embodiment of the present invention.

[0047] Fig. 9 It is a partial cross-sectional view schematically showing the fourth step of the substrate processing method in the first embodiment of the present invention.

[0048] Fig.10 The following is a flowchart schematically showing the operation of the substrate processing apparatus according to the first embodiment of the present invention.

[0049] Fig.11 It is a plan view schematically showing a first operation of the substrate processing apparatus in the first embodiment of the present invention.

[0050] Fig.12 It is a plan view schematically showing the second operation of the substrate processing apparatus in the first embodiment of the present invention.

[0051] Fig.13 It is a plan view schematically showing the third operation of the substrate processing apparatus in the first embodiment of the present invention.

[0052] Fig.14It is a top view schematically showing the fourth operation of the substrate processing apparatus in the first embodiment of the present invention.

[0053] Fig.15 It is a top view schematically showing the fifth operation of the substrate processing apparatus in the first embodiment of the present invention.

[0054] Fig.16 It is a top view schematically showing the sixth operation of the substrate processing apparatus in the first embodiment of the present invention.

[0055] Fig.17 It is a top view schematically showing the seventh operation of the substrate processing apparatus in the first embodiment of the present invention.

[0056] Fig.18 It is a top view schematically showing the eighth operation of the substrate processing apparatus in the first embodiment of the present invention.

[0057] Fig.19 The following is a flowchart schematically showing the operation of the substrate processing apparatus according to the second embodiment of the present invention.

[0058] Fig. 20 It is a plan view schematically showing a first operation of the substrate processing apparatus in accordance with the second embodiment of the present invention.

[0059] Fig.21 It is a plan view schematically showing the second operation of the substrate processing apparatus in the second embodiment of the present invention.

[0060] Fig. 22 It is a top view schematically showing the third operation of the substrate processing apparatus in the second embodiment of the present invention.

[0061] Fig.23 The following is a flowchart schematically showing the operation of the substrate processing apparatus according to the third embodiment of the present invention.

[0062] Fig.24 The following is a flowchart schematically showing the operation of the substrate processing apparatus according to the fourth embodiment of the present invention.

[0063] Fig.25 The following is a flowchart schematically showing the substrate processing method in accordance with the fifth embodiment of the present invention from the perspective of the operation of the substrate processing apparatus.

[0064] Fig.26 A partial cross-sectional view schematically showing one step of a substrate processing method in accordance with a fifth embodiment of the present invention.

[0065] Fig. 27The following is a flowchart schematically showing the operation of the substrate processing apparatus according to the sixth embodiment of the present invention.

[0066] Fig.28 A flowchart schematically shows a substrate processing method in Embodiment 6 of the present invention in order to process a portion of a resist film.

[0067] Fig.29 A partial cross-sectional view schematically showing one step of a substrate processing method in accordance with a sixth embodiment of the present invention. DETAILED DESCRIPTION

[0068] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. It should be noted that in the following drawings, the same or corresponding parts are denoted by the same reference numerals and their description will not be repeated.

[0069] <Substrate processing equipment>

[0070] First, an example of a substrate processing apparatus applicable to the following embodiments 1 to 6 is described below. It should be noted that in each embodiment, it is not necessary to use all the functions of the substrate processing apparatus described below. Therefore, in each embodiment, unnecessary parts of the mechanism of the substrate processing apparatus can be omitted.

[0071] Figure 1 It is a plan view schematically showing the structure of the substrate processing apparatus in Embodiment 1 of the present invention. Figure 2 and Figure 3 Each along Figure 1 The schematic cross-sectional view of the line II-II and line III-III of FIG. The figure also shows a wafer 901 (substrate) processed by the substrate processing device. A resist film (at Figure 1 to Figure 3 The resist film is removed by substrate processing using a substrate processing device. The substrate processing device includes a support unit 10, a spray unit 30, and a spray unit 40.

[0072] The support part 10 has a rotating shaft 16, a rotating base 13, a chuck 12, a back nozzle 11, a warm water supply source 101, a deionized water supply source 102, a valve 111 and a valve 112. The rotating shaft 16 is rotated by a motor (not shown). The rotating base 13 is mounted on the rotating shaft 16. The chuck 12 is mounted near the outer edge of the rotating base 13 and fixes the wafer 901. With these structures, the wafer 901 is supported on the support part 10 in a rotatable manner (see arrow SP). The back nozzle 11 sprays a fluid, especially a liquid, onto the back side of the wafer 901. In order not to hinder the spraying, an opening OP is provided on the rotating base 13. The warm water supply source 101 supplies warm water to the back nozzle 11 via the valve 111. The deionized water supply source 102 supplies deionized water to the back nozzle 11 via the valve 112.

[0073] The ejection unit 30 includes an ejection nozzle 31, an arm 32, a rotating shaft 33, an actuator 34, an ozone water supply unit 301, an additive supply unit 302, an SC1 supply unit 303, a deionized water supply unit 304, a valve 311, a valve 312, a valve 313, a valve 314, a liquid pipe 320, and a heater 331. The ejection nozzle 31 is connected to the liquid pipe 320, and ejects the liquid supplied from the liquid pipe 320 onto the wafer 901. The arm 32 connects the ejection nozzle 31 and the rotating shaft 33. The rotation angle of the rotating shaft 33 is adjusted by the actuator 34. With these structures, the ejection nozzle 31 can perform a scanning action roughly along the radial direction of the wafer 901 (refer to Figure 1 ).

[0074] The ozone water supply unit 301 supplies ozone water to the liquid pipe 320 via a valve 311. The additive supply unit 302 supplies additives to the liquid pipe 320 via a valve 312. The additive may be a liquid. The SC1 supply unit 303 supplies SC1 (Standard Clean 1) cleaning liquid to the liquid pipe 320 via a valve 313. The SC1 cleaning liquid is a mixture of ammonia water, hydrogen peroxide water, and water. The deionized water supply unit 304 supplies deionized water to the liquid pipe 320 via a valve 314.

[0075] The heater 331 is a mechanism for heating the ozone water from the ozone water supply unit 301. The heater 331 is preferably installed between the valve 311 and the liquid pipe 320. Here, the valve 311 may also be the valve closest to the liquid pipe 320 among at least one valve installed between the ozone water supply unit 301 and the liquid pipe 320. The heater 331 may also be arranged in the piping between the ozone water supply unit 301 and the liquid pipe 320, more upstream than the part where the piping from the additive supply unit 302, the SC1 supply unit 303 and the deionized water supply unit 304 merges, or may be arranged more downstream. In the former case, only the ozone water can be selectively heated, and in the latter case, the mixed liquid can be heated. The heater 331 is, for example, a lamp heater or an LED heater.

[0076] The spray section 40 includes a spray nozzle 41, an arm 42, a rotating shaft 43, an actuator 44, an ammonia water supply section 401, a hydrogen peroxide water supply section 402, an SC1 cleaning liquid supply section 403, a gas supply section 409, a valve 411, a valve 412, a valve 413, and a valve 419. The spray nozzle 41 is a two-fluid nozzle that sprays a liquid supplied from a liquid pipe 420 and a gas supplied from a gas pipe 429, that is, a two-fluid nozzle. It is preferred that the two fluids are mixed with each other to generate a flow of gas and liquid droplets dispersed in the gas.

[0077] The arm 42 connects the spray nozzle 41 to the rotating shaft 43. The rotation angle of the rotating shaft 43 is adjusted by the actuator 44. With these structures, the spray nozzle 41 can perform a scanning operation substantially along the radial direction of the wafer 901 (see Figure 1 ).

[0078] The ammonia water supply unit 401 supplies ammonia water to the liquid pipe 420 via a valve 411. The temperature of the supplied ammonia water is preferably above room temperature and below 40°C. The hydrogen peroxide water supply unit 402 supplies hydrogen peroxide water to the liquid pipe 420 via a valve 412. The temperature of the supplied hydrogen peroxide water is preferably above room temperature and below 80°C. The SC1 cleaning liquid supply unit 403 supplies SC1 cleaning liquid to the liquid pipe 420 via a valve 413. The gas supply unit 409 supplies gas to the gas pipe 429 via a valve 419. The gas supplied from the gas supply unit 409 can be an inert gas, such as nitrogen (N2) gas.

[0079] Figure 4 To illustrate the spray nozzle 41 ( Figure 3 ) is a cross-sectional view of an example of the structure of the spray nozzle 41. In order to perform spraying from the spray port OS, the spray nozzle 41 has a liquid nozzle portion 41L, a gas nozzle portion 41G and a gas introduction port 41i.

[0080] The liquid nozzle portion 41L has a through hole HL. One end of the through hole HL is connected to the liquid pipe 20, and the other end of the through hole HL reaches the spray port OS.

[0081] The gas nozzle part 41G has an annular hole HG surrounding the liquid nozzle part 41L. The annular hole HG is connected to the gas inlet port 41i and reaches the spray port OS. The extension direction of the outlet portion of the annular hole HG (see the dotted arrow in the figure) and the extension direction of the outlet portion of the through hole HL (see the solid arrow in the figure) are arranged so as to intersect at the bottom of the spray nozzle 41. With this configuration, the gas ejected from the gas nozzle part 41G collides with the liquid ejected from the liquid nozzle part 41L. As a result, a flow AS of gas and liquid droplets dispersed into the gas is generated.

[0082] It should be noted that, in the above, a case where a mechanism for the scanning action of the jet nozzle 31 and a mechanism for the scanning action of the spray nozzle 41 are separately provided is described, but as a modified example, a common scanning mechanism may be provided for performing scanning actions of both the jet nozzle 31 and the spray nozzle 41. In other words, the jet nozzle 31 and the spray nozzle 41 may also be installed on a common arm that can perform scanning actions. In this case, it is preferred to install the jet nozzle 31 and the spray nozzle 41 in such a manner that an area that directly receives the spray from the jet nozzle 31 and an area that directly receives the spray from the spray nozzle 41 are away from each other. Thus, the fluid flowing from the jet nozzle 31 to the chip 901 and the fluid flowing from the spray nozzle 41 to the chip 901 are prevented from interfering with each other unnecessarily during the path. It should be noted that, even in a case such as Figure 1 When the ejection nozzle 31 and the spray nozzle 41 as shown can perform scanning actions independently, based on the above reasons, it is preferable to control the scanning actions of both in a manner so as to maintain a state in which the area directly receiving the ejection from the ejection nozzle 31 and the area directly receiving the spray from the spray nozzle 41 are separated from each other.

[0083] <Implementation method 1>

[0084] Figure 5 is from the portion P1 ( Figure 6 ) is performed on the substrate and a flowchart of the substrate processing method in this embodiment 1 is roughly shown. Figure 6 to Figure 9 1 and 2 are partial cross-sectional views schematically showing the first to fourth steps of the substrate processing method in the first embodiment.

[0085] Reference Figure 6First, a wafer 901 having a resist film 902 including a portion P1 is prepared. It should be noted that the resist film 902 may have a pattern shape (not shown) on the wafer 901. In addition, the resist film 902 may be a film that has been modified, for example, to be used as an etching mask or an implantation mask. Generally, due to the modification, the removal of the resist film becomes more difficult.

[0086] Reference Figure 7 , in step T21( Figure 5 ), the ozone-containing aqueous solution 920 is brought into contact with at least a portion P1 of the resist film 902. For this purpose, the ozone-containing aqueous solution 920 is sprayed toward the wafer 901. The portion P1 of the resist film 902 that has been in contact with the ozone-containing aqueous solution 920 is subjected to a decomposition effect caused by ozone. Specifically, the C (carbon)-C bonds in the resist film 902 are cut by ozone radicals. It is preferred that the decomposition effect of the ozone-containing aqueous solution 920 be utilized to form cracks on the resist film 902. In other words, it is preferred that the decomposition effect caused by the ozone-containing aqueous solution 920 be applied to the resist film 902 until cracks are generated on the resist film 902. Here, it is preferred that the ozone-containing aqueous solution 920 does not substantially contain ammonia water, and it is also preferred that the ozone-containing aqueous solution 920 does not substantially contain hydrogen peroxide water, and for example, it may be simple ozone water generated by dissolving ozone in deionized water.

[0087] Reference Figure 8 Next, in step T31 ( Figure 5 ), the ammonia-containing aqueous solution is brought into contact with a portion P1 of the resist film 902. For this purpose, the ammonia-containing aqueous solution is sprayed toward the wafer 901. Specifically, a droplet 930S of the ammonia-containing aqueous solution is brought into contact with the portion P1. Compared with the ozone-containing aqueous solution 920, the ammonia-containing aqueous solution contains ammonia at a high concentration. It should be noted that, as described above, the ozone-containing aqueous solution 920 may not contain ammonia. The resist film 902 that has been in contact with the ammonia-containing aqueous solution is subjected to a swelling effect caused by NH4OH in the ammonia-containing aqueous solution. Preferably, the swelling effect is accompanied by the intrusion of the ammonia-containing aqueous solution into the cracks of the resist film 902 formed in the above-mentioned step T21.

[0088] It should be noted that, in other parts on the wafer 901, the ammonia-containing aqueous solution and the ozone-containing aqueous solution 920 ( Figure 7 ) contact, thereby temporarily activating the decomposition effect caused by ozone in the ozone-containing aqueous solution 920. In addition, the ammonia-containing aqueous solution may also contain hydrogen peroxide water, thereby enhancing the above-mentioned swelling effect and temporarily activating the above-mentioned decomposition effect.

[0089] As described above, step T21 and step T31 are performed. Thereafter, the combination of step T21 and step T31 may be repeated any number of times.

[0090] Reference Fig. 9 Next, in step T32 ( Figure 5 ), the portion P1 of the resist film 902 is separated (peeled off) from the wafer 901 by physical cleaning. Here, the so-called physical cleaning mainly refers to cleaning based on mechanical action. The physical cleaning process preferably includes a process of blowing a gas toward the wafer 901, and more preferably a process of spraying droplets 930S containing an ammonia solution toward the wafer 901 using a gas. The gas is preferably an inert gas, such as N2 gas.

[0091] By performing the above-mentioned steps T21, T31 and T32 ( Figure 5 ), thereby the desired part (typically, the entirety) of the resist film 902 is peeled off. Thus, the peeling process of the resist film 902 is completed.

[0092] Step T21, step T31 and step T32 ( Figure 5 ) need not be performed simultaneously on the entire resist film 902, and may be performed at any time on each portion of the resist film 902. In view of this situation, the following is an example of a substrate processing apparatus ( Figure 1 to Figure 3 ) is used as an example to illustrate the substrate processing.

[0093] Fig.10 From the substrate processing device ( Figure 1 to Figure 3 )'s actions are schematically shown in the flowchart of the substrate processing method in this embodiment 1. Figures 11 to 18 Each of them is a top view schematically showing the first to eighth operations of the substrate processing apparatus in the first embodiment. Figures 11 to 18 In the substrate processing device ( Figure 1 to Figure 3 ) The positions of the ejection nozzle 31 and the spray nozzle 41 are only indicated by dots, and the illustration of other structures is omitted.

[0094] Reference Fig.11 , a wafer 901 ( Figure 6 ) is installed in the substrate processing device ( Figure 1 to Figure 3 ). The wafer 901 is rotated (see arrow SP in the figure). As a result, the position of the portion P1 rotates around the center of the wafer 901. The number of rotations per minute is, for example, about 800 rpm.

[0095] Reference Fig.12 In step S20( Fig.10 ), the ozone-containing aqueous solution 920 ( Figure 7) of ozone water. At this time, the spray nozzle 31 is preferably arranged near the center of the chip 901. The ozone-containing aqueous solution 920 gradually expands outward on the chip 901 by centrifugal force. From the perspective of shortening the time required for peeling off the resist film 902 and suppressing unnecessary etching of the chip 901 as the base of the resist film 902, the ozone concentration of the ozone water is preferably set to a sufficiently high concentration, for example, about 100 ppm. The spraying amount of ozone water is preferably less than 3 liters / minute. The ozone water as the ozone-containing aqueous solution 920 can also be supplied to the ozone water supply unit 301 ( Figure 2 ) and the ejection nozzle 31 and in a pipe away from the chip 901 by a heater 331 ( Figure 2 ) heating. The heating may continue during the period of spraying the ozone-containing aqueous solution 920. It should be noted that the ozone-containing aqueous solution 920 may be heated on the wafer 901 instead of being heated in the above-mentioned piping, or may be heated on the wafer 901 and heated in the above-mentioned piping. For this purpose, a heater for radiating heat to the upper surface of the wafer 901 may be provided in the substrate processing apparatus. The heater may also be away from the piping. As described later, the back nozzle 11 ( Figure 3 ) to heat the wafer 901 instead of the heater, or the heater and the back nozzle 11 ( Figure 3 ) is used to heat the wafer 901. Thus, the liquid on the wafer 901 is also heated. In the first embodiment, the process of bringing the ozone-containing aqueous solution 920 into contact with the portion P1 in step S20 is performed by supplying the ozone-containing aqueous solution 920 to the wafer 901 from the ejection nozzle 31, rather than supplying the ammonia-containing aqueous solution to the wafer 901 from the spray nozzle 41.

[0096] Reference Fig.13 As described above, the ozone-containing aqueous solution 920 expands, and as a result, the ozone-containing aqueous solution 920 contacts the portion P1 ( Figure 5 : Step T21). In addition, as shown in the figure, the ozone-containing aqueous solution 920 preferably covers the entire upper surface of the wafer 901.

[0097] Reference Fig.14 In step S30( Fig.10 ), using N2 as gas, an aqueous ammonia peroxide solution (a mixed solution of aqueous ammonia and aqueous hydrogen peroxide) as an aqueous ammonia solution is sprayed from the spray nozzle 41. In other words, the droplets 930S ( Figure 8) is sprayed. Thus, an ammonia-containing aqueous solution 930 is locally supplied to the wafer 901 near the spray nozzle 41. During the spraying, an ozone-containing aqueous solution 920 can be continuously sprayed from the spray nozzle 31. The spraying amount is preferably 20 ml / min or more and 300 ml / min or less. The rotation speed per minute of the wafer 901 in step S30 can be lower than the rotation speed per minute in the aforementioned step S20, for example, about 500 rpm.

[0098] By receiving the spray, the ozone-containing aqueous solution 920 is substantially excluded from the area near the spray nozzle 41 on the upper surface of the wafer 901 (the area directly receiving the spray). In addition, the ammonia-containing aqueous solution 930 that extends outside the area near the spray nozzle 41 is mixed with the ozone-containing aqueous solution 920. Fig.14 At the time point shown, portion P1 has not yet come into contact with the aqueous ammonia solution 930 .

[0099] In the above process, ozone water from the ejection nozzle 31 and an aqueous ammonia peroxide solution (ammonia water and hydrogen peroxide solution) from the spray nozzle 41 are supplied to the chip 901. The ratio (volume ratio) of ammonia water and hydrogen peroxide solution can be the same. In this case, the ratio (volume ratio) of ozone water: ammonia water: hydrogen peroxide solution is, for example, about 2000:10:10 under conditions with more ozone water, and about 500:125:125 under conditions with less ozone water. The ammonia water referred to here has a concentration of, for example, about 28% by weight, and the hydrogen peroxide solution has a concentration of, for example, about 30% by weight. It should be noted that an ammonia-containing aqueous solution that does not contain hydrogen peroxide solution can also be used, for example, ammonia water can be used instead of the aqueous ammonia peroxide solution.

[0100] Reference Fig.15 , along with the rotation of the wafer 901, when viewed from above ( Fig.15 When the position of the portion P1 in the field of view of the spray nozzle 41 is sufficiently close to the position of the spray nozzle 41, the portion P1 contacts the ammonia-containing aqueous solution 930 ( Figure 5 :Step T31).

[0101] Reference Fig.16 , along with the rotation of the wafer 901, when viewed from above ( Fig.16 When the position of the portion P1 in the field of view of the spray nozzle 41 is sufficiently far away from the position of the spray nozzle 41, the portion P1 contacts the ozone-containing aqueous solution 920 again ( Figure 5 :Step T21). By repeating this action, the steps corresponding to step T21 and step T31 ( Figure 5 )of Fig.15 and Fig.16 process.

[0102] Reference Fig.17When the position of the spray nozzle 41 is shifted to a certain extent from the position of the portion P1 in the radial direction as the spray nozzle 41 spraying the ammonia solution moves, i.e., scans, the spray of the ammonia solution is not supplied to the portion P1. Instead, the spray of the ammonia solution is supplied to the other portion P2. Thus, the same treatment as that in the portion P1 can be performed in the portion P2.

[0103] Reference Fig.18 , with the scanning action of the spray nozzle 41 again, the spray containing the ammonia solution is again supplied from the spray nozzle 41 to the portion P1. The spray and the droplets 930S ( Fig. 9 ). In other words, the aerosol flow of the droplet 930S toward the resist film 902 collides. Therefore, the spray acts on the resist film 902 as physical cleaning. The portion P1 is separated (peeled off) from the wafer 901 by this physical cleaning.

[0104] As the spray nozzle 41 scans, the portion P2 ( Fig.17 ) are also separated in the same manner. The scanning action is preferably performed in a manner that the ammonia-containing aqueous solution 930 is sprayed toward the peripheral portion of the wafer 901 for a longer time than the central portion of the wafer 901. In other words, the spray nozzle 41 that sprays the ammonia-containing aqueous solution 930 is preferably located above the peripheral portion of the wafer 901 for a longer time than the time it is located above the central portion of the wafer 901. For example, Fig.17 Compared with the configuration of the spray nozzle 41 shown, the Fig.18 The configuration of the spray nozzle 41 shown is longer. Fig.17 Compared with the configuration of the spray nozzle 41 shown in Fig.18 In the arrangement of the spray nozzles shown, the spray nozzles 41 are arranged closer to the peripheral edge in the radial direction.

[0105] As described above, the resist film 902 ( Figure 6 ) Overall peeling process.

[0106] It should be noted that, in the above description, the scanning action of the spray nozzle 41 is described, but for example, the arrow SN ( Figure 14 to Figure 18 ), the ejection nozzle 31 may also perform a scanning action. When both the spray nozzle 41 and the ejection nozzle 31 perform a scanning action, the relative position of the spray nozzle 41 and the ejection nozzle 31 may be fixed or variable. When the relative position of the spray nozzle 41 and the ejection nozzle 31 is fixed, a common mechanism for performing a scanning action can be used; when the relative position of the spray nozzle 41 and the ejection nozzle 31 is variable, the degree of freedom for optimizing the scanning action can be increased.

[0107] Here, in at least a portion of the period during which the liquid is supplied from both the ejection nozzle 31 and the spray nozzle 41, the ejection nozzle 31 is preferably located closer to the center of the wafer 901 than the spray nozzle 41. More preferably, the ejection nozzle 31 is located closer to the center of the wafer 901 than the spray nozzle 41 during more than half of the above period. During the above period, the ejection nozzle 31 may always be located closer to the center of the wafer 901 than the spray nozzle 41. Thus, the range in which the ozone-containing aqueous solution 920 from the ejection nozzle 31 spreads due to the centrifugal force becomes easy to include the position of the spray nozzle 41 in the radial direction. Therefore, the probability that the region that has been in contact with the ozone-containing aqueous solution 920 receives the spray from the spray nozzle 41 can be increased.

[0108] Regarding the above-mentioned period of supplying liquid from both the jet nozzle 31 and the spray nozzle 41, it may be a period during which liquid is simultaneously sprayed from the jet nozzle 31 and the spray nozzle 41, or it may be a period during which liquid is alternately supplied from the jet nozzle 31 and the spray nozzle 41 at short intervals in a manner that the liquids from the two nozzles fully coexist on the chip 901, instead of or at the same time.

[0109] In addition, during the above treatment, the back nozzle 11 ( Figure 2 and Figure 3 ) Warm water is supplied to the back side of the wafer 901. This can increase the temperature of the wafer 901 being processed. For example, warm water of about 80° C. is sprayed at about 2 liters / minute.

[0110] Next, in step S80, the discharge nozzle 31 discharges deionized water. Thus, the wafer 901 is washed with water. During this treatment, the back nozzle 11 ( Figure 2 and Figure 3 ) Deionized water is supplied to the back side of the wafer 901. In addition, the spraying from the spray nozzle 41 may be stopped during this treatment. The rotational speed of the wafer 901 in step S80 may be higher than that in the aforementioned step S30, for example, about 800 rpm.

[0111] Next, in step S90, the deionized water is stopped from being ejected from the ejection nozzle 31 and the back nozzle 11, and the wafer 901 is rotated at a high speed of, for example, about 2500 rpm. Thus, the liquid on the wafer 901 is removed by centrifugal force. That is, the wafer 901 is dried. It should be noted that the drying process may also include a process of ejecting a volatile liquid such as isopropyl alcohol from the ejection nozzle 31, thereby suppressing the generation of water stains.

[0112] As described above, the substrate processing device ( Figure 1 to Figure 3 ) action( Fig.10 ).

[0113] According to this embodiment, the ammonia-containing aqueous solution 930 ( Fig.14 ) and the resist film 902 ( Figure 6 ) has been mixed with an ozone-containing aqueous solution 920 ( Figure 7 ) contact part P1( Fig.13 ) is in contact with the wafer 901. Since the portion P1 is previously subjected to the decomposition effect caused by the ozone, it is easy to be subjected to the swelling effect caused by the ammonia-containing aqueous solution 930. As a result, the swelling of the resist film 902 can be promoted. Therefore, the resist film 902 can be removed in a short time in the subsequent process. In addition, compared with SPM, the burden of waste liquid treatment of the ozone-containing aqueous solution 920 and the ammonia-containing aqueous solution 930 is small. As described above, the burden of waste liquid treatment can be suppressed and the resist film 902 can be removed from the wafer 901 in a short time.

[0114] It should be noted that when the resist film is to be decomposed as a whole by relying on the decomposition effect of ozone, if the thickness of the resist film is large enough, the processing time will become very long. This situation is particularly problematic in single-chip substrate processing. In this embodiment, the resist film is not decomposed as a whole, but the residue of the swollen resist film 902 is peeled off (see Fig. 9 ). Thus, it is not necessary to decompose the resist film until the resist film disappears entirely. Therefore, the treatment can be performed in a short time as described above.

[0115] Step of contacting the ozone-containing aqueous solution 920 ( Fig.13 ) by ejecting from the nozzle 31 ( Figure 1 and Figure 2 ) is performed by spraying the ozone-containing aqueous solution 920 toward the wafer 901. Thus, the ozone-containing aqueous solution 920 can be used in a method suitable for single-wafer substrate processing.

[0116] The step of contacting the aqueous solution containing ammonia 930 ( Fig.15 ) by spraying from the spray nozzle 41 ( Figure 1 and Figure 3 ) is performed by spraying the ammonia-containing aqueous solution 930 toward the wafer 901. Thus, the ammonia-containing aqueous solution 930 can be used in a method suitable for single-wafer substrate processing.

[0117] Step of spraying the ammonia-containing aqueous solution 930 ( Fig.17 and Fig.18 ) includes a step of moving the spray nozzle 41 that sprays the ammonia-containing aqueous solution 930, specifically, includes a step of performing a scanning action. As a result, the ammonia-containing aqueous solution 930 can be locally and concentratedly supplied to the wafer 901 at each time point, and the ammonia-containing aqueous solution 930 can also be supplied to a wide range on the wafer 901 by moving the spray nozzle 41. Therefore, the stripping effect can be locally enhanced, and the stripping process can be performed in a wide range on the wafer 901.

[0118] The step of moving the spray nozzle 41 is preferably performed in such a manner that the ammonia-containing aqueous solution 930 is sprayed longer toward the peripheral portion of the wafer 901 than toward the central portion of the wafer 901. Fig.17 and Fig.18 ) on the wafer 901. Therefore, the wafer 901 can be processed more evenly.

[0119] By physical cleaning ( Fig. 9 ) The process of making the resist film 902 contact with the aqueous ammonia solution 930 ( Fig.13 ) and the portion P1 that has been in contact with the aqueous ammonia solution 930 is separated from the wafer 901. Since the resist film 902 has been subjected to the swelling process ( Figure 8 ) and is fully swollen, so it is easily peeled off by physical cleaning. Therefore, the resist film 902 can be peeled off in a shorter time.

[0120] Physical cleaning ( Fig. 9 ) includes from the spray nozzle 41 ( Figure 1 and Figure 3 ) A step of blowing a jet of gas toward the wafer 901. Thus, compared with the case of blowing a fluid consisting only of a liquid or a fluid containing a solid, sufficient cleaning power can be ensured and damage to the wafer 901 can be suppressed.

[0121] The step of blowing gas toward the wafer 901 includes spraying droplets 930S (containing an aqueous ammonia solution) of the wafer 901 with gas. Figure 8 and Fig. 9 ) process. As a result, the droplets 930S dispersed in the gas collide with the wafer 901. Figure 8 In the process, the ammonia-containing aqueous solution is pressed deeper into the resist film 902 by gas pressure. Therefore, swelling is easily performed even in the deep part of the resist film 902. In addition, the ozone-containing aqueous solution 920 is removed from the portion of the upper surface of the wafer 901 that is directly touched by the airflow by gas pressure. This prevents the swelling effect of the ammonia-containing aqueous solution 930 from being hindered by the effect of ozone in this portion. Therefore, the swelling can be promoted. In addition, in Fig. 9 In the process, since the air flow contains droplets 930S, the effect of physical cleaning can be improved.

[0122] The gas is preferably an inert gas, thereby avoiding unnecessary chemical reactions between the gas and the wafer 901 .

[0123] Regarding the step of contacting the ozone-containing aqueous solution 920 ( Figure 7), it is preferable to include a step of forming cracks on the resist film 902 using the ozone-containing aqueous solution 920. Thus, the ammonia-containing aqueous solution 930 ( Fig.15 ) penetrates from the cracks. Therefore, it is possible to promote the swelling of the resist film 902 caused by the ammonia-containing aqueous solution 930 (refer to Figure 8 ).

[0124] The ammonia-containing aqueous solution 930 preferably contains hydrogen peroxide. Thus, the swelling of the resist film 902 caused by the ammonia-containing aqueous solution 930 can be promoted (see Figure 8 ). In addition, the ammonia-containing aqueous solution 930 ( Fig.15 ) spreads on the wafer 901, and is thereby mixed into the ozone-containing aqueous solution 920. Thus, the decomposition action of the resist film 902 caused by the ozone-containing aqueous solution 920 can be activated.

[0125] Step of contacting the ozone-containing aqueous solution 920 ( Fig.12 ) includes: not supplying the ammonia-containing aqueous solution 930 to the wafer 901 ( Fig.14 ), but rather a process of supplying an ozone-containing aqueous solution 920 to the wafer 901 ( Fig.10 : Step S20). Thus, a large amount of ozone-containing aqueous solution 920 can be supplied to wafer 901 before being acted upon by ammonia-containing aqueous solution 930. Therefore, in step S30 ( Fig.10 ) before the resist film 902 ( Figure 7 ) The decomposition effect caused by ozone is fully applied in advance.

[0126] Step of contacting the ozone-containing aqueous solution 920 ( Figures 12 to 18 ) may include a step of heating the ozone-containing aqueous solution 920 in a pipe away from the chip 901. Thus, the resist film 902 ( Figure 7 ) decomposition effect.

[0127] The process of contacting with an ozone-containing aqueous solution ( Figures 12 to 18 ) may include a step of heating the ozone-containing aqueous solution 920 on the wafer 901. Thus, the resist film 902 ( Figure 7 ) and the case where the ozone-containing aqueous solution 920 is heated before being supplied onto the wafer 901 (for example, by using the heater 331 ( Figure 2 ) Compared with the case where heating is performed, the deactivation of ozone caused by the passage of time after heating can be suppressed.

[0128] <Implementation method 2>

[0129] Fig.19 From the substrate processing device ( Figure 1 to Figure 3) is schematically shown as a flowchart of the substrate processing method in the second embodiment. This flowchart is different from the flowchart in the first embodiment except that step S20 ( Fig.10 ) corresponds to the process of Implementation 1. Therefore, only the differences associated with the omissions are described below, and the description of the same features as Implementation 1 is omitted.

[0130] Figure 20 to Figure 22 Each of them is a top view schematically showing the first to third operations of the substrate processing apparatus in the second embodiment. Figure 20 to Figure 22 In the substrate processing device ( Figure 1 to Figure 3 ), only the positions of the ejection nozzle 31 and the spray nozzle 41 are indicated by dots, and the illustration of other structures is omitted.

[0131] Reference Fig. 20 First, a wafer 901 ( Figure 6 ) is installed in the substrate processing device ( Figure 1 to Figure 3 ). The wafer 901 is rotated (see arrow SP in the figure). As a result, the positions of the portion P1a and the portion P1b rotate around the center of the wafer 901. In step S30 ( Fig.19 ), the ozone-containing aqueous solution 920 ( Figure 7 ) of ozone water. At substantially the same time, spraying of an aqueous ammonia peroxide solution (a mixed solution of aqueous ammonia and aqueous hydrogen peroxide) as an aqueous ammonia solution 930 is started from the spray nozzle 41 using N2 as a gas.

[0132] Reference Fig.21 , the portion P1a is not initially in contact with the aqueous solution containing ammonia 930 but is in contact with the aqueous solution containing ozone 920. This situation is different from the situation of the portion P1 ( Fig.13 Therefore, the treatment of the portion P1a is substantially the same as the treatment of the portion P1 in Embodiment 1. On the other hand, the portion P1b is not initially in contact with the ozone-containing aqueous solution 920 but is in contact with the ammonia-containing aqueous solution 930.

[0133] Reference Fig. 22 Next, the portion P1b is first contacted with the ozone-containing aqueous solution 920. In other words, step T21 ( Figure 5 ). The subsequent treatment of the portion P1b is substantially the same as the treatment of the portion P1. That is, the portion P1b is also subjected to substantially the same treatment as the treatment of the portion P1, except that it is not initially contacted with the ozone-containing aqueous solution 920 but with the ammonia-containing aqueous solution 930.

[0134] According to this embodiment, compared with the case of embodiment 1 ( Fig.12) is different from the step of contacting the ozone-containing aqueous solution ( Fig. 20 ) is performed by supplying the ammonia-containing aqueous solution 930 to the wafer 901 and supplying the ozone-containing aqueous solution 920 to the wafer 901. Thus, step S20 ( Fig.10 : Embodiment 1). In this embodiment, although it is difficult to supply a large amount of ozone-containing aqueous solution 920 to wafer 901 before wafer 901 is acted upon by ammonia-containing aqueous solution 930, substantially the same effect as in Embodiment 1 can be obtained by sufficiently supplying ozone-containing aqueous solution 920 thereafter.

[0135] <Implementation method 3>

[0136] Fig.23 From the substrate processing device ( Figure 1 to Figure 3 ) is schematically shown as a flowchart of the substrate processing method in the third embodiment. In the present embodiment, in step S20 ( Fig.10 : Implementation method 1) before, to the resist film 902 ( Figure 6 ) irradiates ultraviolet light (UV). The wavelength of ultraviolet light is preferably less than 190nm, for example, 172nm. The irradiation of ultraviolet light can be performed using a substrate processing device ( Figure 1 to Figure 3 ) is implemented by different devices. It should be noted that since the configuration other than the above is substantially the same as that of the above-mentioned embodiment 1, the same reference numerals are given to the same or corresponding elements without repeating the description. As a modified example, step S10 ( Fig.23 ) can also be performed in step S30 ( Fig.19 :Implementation method 2) is performed before.

[0137] According to this embodiment, it is possible to supply the ammonia-containing aqueous solution 930 ( Fig.15 ) time point, the resist film 902 is decomposed by ultraviolet irradiation (refer to Figure 7 ) can be accelerated, specifically, a crack can be more reliably formed on the resist film 902. Therefore, the swelling of the resist film caused by the ammonia-containing aqueous solution 930 can be promoted (see Figure 8 ). Therefore, the resist film 902 can be removed in a shorter time.

[0138] <Implementation method 4>

[0139] Fig.24 From the substrate processing device ( Figure 1 to Figure 3) operation aspect. In this embodiment, step S50 is performed between step S30 and step S80. In step S50, the spray nozzle 31 sprays SC1 cleaning liquid or deionized water while the spray nozzle 41 sprays SC1 cleaning liquid. Thus, the chip 901 is cleaned. The flow rate of the spray nozzle 31 is, for example, about 500 ml / min, and the flow rate of the spray nozzle 41 is, for example, about 100 ml / min. The rotation speed of the chip 901 in step S80 can be the same as the rotation speed in the aforementioned step S30, for example, about 500 rpm. During this treatment, the back nozzle 11 ( Figure 2 and Figure 3 ) SC1 cleaning solution or deionized water is supplied to the back side of the wafer 901. It should be noted that since the configuration other than the above is substantially the same as any one of the above-mentioned embodiments 1 to 3, the same or corresponding elements are denoted by the same reference numerals and are not described repeatedly.

[0140] <Implementation method 5>

[0141] Fig.25 From the substrate processing device ( Figure 1 to Figure 3 ) is schematically shown as a flowchart of the substrate processing method in this embodiment 5. In this embodiment, first, similar to the embodiment 3 ( Fig.23 ) Perform steps S10 and S20 in the same manner.

[0142] Fig.26 FIG. 1 is a partial cross-sectional view schematically showing one process of the substrate processing method in the fifth embodiment. Fig.25 ), from the ejection nozzle 31 ( Figure 2 ) to spray 930L of mixed liquid of ozone water and additives. In other words, open valve 311 and valve 312 ( Figure 2 ) Both. The additives include ammonia water and hydrogen peroxide water. With ozone-containing aqueous solution 920 ( Figure 7 ) compared to the ozone-containing aqueous solution 920. It should be noted that, as mentioned above, the ozone-containing aqueous solution 920 may not contain ammonia. The mixed solution 930L is supplied in step S25, thereby producing both a decomposition effect and a swelling effect on the resist film 902. The decomposition effect caused by the ozone in the ozone-containing aqueous solution is temporarily more activated by mixing ammonia water and hydrogen peroxide water. Although the temporarily increased activity decreases with the passage of time, the influence of the decreased activity can be suppressed by sufficiently supplying a new mixed solution from the spray nozzle 31.

[0143] Next, with step S30 ( Fig.10 :Implementation 1) is similar to the case in step S35 ( Fig.25 ) is sprayed from the spray nozzle 41. The physical cleaning ( Fig. 9 ), the resist film 902 is separated from the wafer 901. During the spraying, the mixed liquid is continuously sprayed from the spray nozzle 31. By receiving the spraying, the mixed liquid is substantially removed from the vicinity of the spray nozzle 41 on the upper surface of the wafer 901. In addition, the ammonia-containing aqueous solution 930 that has spread to the outside of the vicinity is mixed with the mixed liquid, thereby further activating the ozone in the mixed liquid 930L.

[0144] Since the subsequent process is different from the implementation method 3 ( Fig.23 ) are the same, so the description thereof is omitted. In this embodiment, step S25 and step S35 are performed instead of step S30 ( Fig.23 ). Such a step replacement is performed not only in Embodiment 3, but also in the other embodiments described above.

[0145] In this embodiment, in step S25 ( Fig.25 ), the liquid ejected from the ejection nozzle 31 includes ozone water, ammonia water, and hydrogen peroxide water. Thus, the decomposition effect caused by the ozone activated by the ammonia water and the hydrogen peroxide water and the swelling effect caused by the ammonia water can be obtained at the same time. Thus, the resist film 902 can be removed from the wafer 901 in a short time.

[0146] <Implementation method 6>

[0147] Fig. 27 From the substrate processing device ( Figure 1 to Figure 3 ) is schematically shown as a flowchart of the substrate processing method in the sixth embodiment. In the present embodiment, the aforementioned step S35 ( Fig.25 : Embodiment 5) in the physical cleaning step ( Fig. 9 In order to compensate for the omission of physical cleaning, the contact with the mixed solution in step S25 is performed for a longer time ( Fig.26 ). It should be noted that, since the mixed solution contains ammonia water, the mixed solution is a kind of ammonia water solution.

[0148] Fig.28 The following is a flowchart schematically showing the substrate processing method in the sixth embodiment from the perspective of processing a portion of a resist film. Fig.29 A partial cross-sectional view schematically showing one step of the substrate processing method in the sixth embodiment.

[0149] In step U10( Fig.28 ), in the resist film 902 ( Figure 6 and Figure 7 ) forms cracks. Fig.28 ) can be used as steps S10 and S20 ( Fig. 27 ) for implementation.

[0150] Reference Fig.29 , then in step U11( Fig.28 ), the mixed solution 930L, especially the ammonia water contained in the mixed solution 930L, penetrates into the interface between the wafer 901 and the resist film 902 through the above-mentioned cracks. Thus, the resist film 902 is peeled off from the wafer 901.

[0151] According to this embodiment, although the time required for step S25 is slightly longer than that of embodiment 5, the resist film 902 can be peeled off from the wafer 901 without using physical cleaning (see Fig.29 ). Therefore, it is preferred to use the present embodiment 6 when physical cleaning is omitted first, and to use the aforementioned embodiment 5 when shortening the processing time is preferred. According to the experimental example made by the inventor of the present application, the time required for stripping the resist film is about 4 minutes in the case of embodiment 5 and about 6 minutes in the case of embodiment 6. It should be noted that, as a modified example, step S50 ( Fig.24 :Implementation method 4).

[0152] Although the present invention has been described in detail, the above description is illustrative in all cases, and the present invention is not limited to these cases. It should be understood that countless variations that are not illustrative are not outside the scope of the present invention. Each structure described by the above-mentioned embodiments and each variation can be appropriately combined or omitted as long as they do not contradict each other.

[0153] Description of Reference Numerals

[0154] 11 Back nozzle

[0155] 31 Spray nozzle

[0156] 41 Spray Nozzle

[0157] 901 wafer (substrate)

[0158] 331 Heater

[0159] 902 Resist Film

[0160] 920 Ozone-containing aqueous solution

[0161] 930 Ammonia-containing aqueous solution

[0162] 930L mixed liquid

[0163] 930S Droplet

Claims

1. A substrate processing method, comprising: Step (a) bringing the ozone-containing aqueous solution into contact with the resist film on the substrate, The step (a) comprises: Step (a-1) spraying the ozone-containing aqueous solution onto the rotating substrate so that the ozone-containing aqueous solution covers the entire upper surface of the substrate, The substrate processing method further comprises: step (b) bringing an ammonia-containing aqueous solution into contact with a portion of the resist film that has been in contact with the ozone-containing aqueous solution in the step of contacting the ozone-containing aqueous solution, wherein the ammonia-containing aqueous solution is an aqueous solution containing ammonia at a higher concentration than the ozone-containing aqueous solution, The step (b) comprises: Step (b-1) causes the ammonia-containing aqueous solution to collide with a gas through a spray nozzle located above the substrate, thereby spraying droplets of the ammonia-containing aqueous solution onto a portion of the resist film that has been in contact with the ozone-containing aqueous solution, The step (b-1) includes the step of moving the spray nozzle in a radial direction above the substrate.

2. The substrate processing method according to claim 1, wherein: The step of moving the spray nozzle is performed so that the ammonia-containing aqueous solution is sprayed toward the peripheral portion of the substrate for a longer time than toward the central portion of the substrate.

3. The substrate processing method according to claim 1 or 2, further comprising: A step of separating the portion of the resist film that has come into contact with the aqueous ammonia solution in the step (b) from the substrate by physical cleaning.

4. The substrate processing method according to claim 3, wherein: The physical cleaning includes a step of blowing the gas toward the substrate.

5. The substrate processing method according to claim 1 or 2, wherein: The gas is an inert gas.

6. The substrate processing method according to claim 1 or 2, wherein: The step (b) includes a step of forming cracks on the resist film using the ozone-containing aqueous solution.

7. The substrate processing method according to claim 6, wherein: The step (b) includes the step of allowing an aqueous ammonia solution to penetrate into an interface between the substrate and the resist film through cracks formed in the step of forming cracks in the resist film, thereby peeling the resist film from the substrate.

8. The substrate processing method according to claim 1 or 2, wherein: The aqueous ammonia solution contains hydrogen peroxide.

9. The substrate processing method according to claim 1 or 2, further comprising: Prior to the step (a), a step of irradiating the resist film with ultraviolet rays.

10. The substrate processing method according to claim 1 or 2, wherein: The step (a) includes a step of supplying an ozone-containing aqueous solution to the substrate instead of supplying an ammonia-containing aqueous solution to the substrate.

11. The substrate processing method according to claim 1 or 2, wherein: The step (a) includes a step of heating the ozone-containing aqueous solution in a pipe away from the substrate.

12. The substrate processing method according to claim 1 or 2, wherein: The step (a) includes: a step of heating the ozone-containing aqueous solution on the substrate.

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