Substrate processing method and substrate processing apparatus

Abstract

The substrate treatment method includes: a first treatment liquid supply step, wherein a first treatment liquid containing one of sulfuric acid and hydrogen peroxide water is coated onto the surface of a substrate; a second treatment liquid supply step, wherein a second treatment liquid containing the other of sulfuric acid and hydrogen peroxide water and having a lower viscosity than the first treatment liquid is supplied to the surface of the substrate coated with the first treatment liquid; a mixture treatment step, wherein the surface of the substrate is treated with a sulfuric acid-hydrogen peroxide-water mixture generated by mixing the first treatment liquid and the second treatment liquid on the surface of the substrate; and a rinsing step, wherein after the mixture treatment step, a rinsing liquid is supplied to the substrate to rinse away the sulfuric acid-hydrogen peroxide-water mixture from the surface of the substrate.

Description

Technical Field

[0001] This application claims priority based on Japanese Patent Application No. 2020-120953, filed on July 14, 2020, the entire contents of which are incorporated herein by reference.

[0002] This invention relates to an apparatus and method for processing substrates. Substrates that are to be processed include, for example, semiconductor wafers, substrates for liquid crystal display devices, substrates for FPD (flat panel display) devices such as organic EL (electroluminescence) display devices, substrates for optical discs, substrates for magnetic disks, substrates for optical disks, substrates for photomasks, ceramic substrates, substrates for solar cells, etc. Background Technology

[0003] A known method involves mixing a first treatment solution and a second treatment solution on a substrate and reacting them, using the reaction product to treat the substrate. Specifically, in resist stripping processes used to remove resist residue from a substrate after dry etching, SPM (sulfuric acid-hydrogen peroxide solution), a mixture of sulfuric acid and hydrogen peroxide water, is sometimes used.

[0004] Patent Document 1 discloses a substrate processing method in which sulfuric acid and hydrogen peroxide water are mixed in a nozzle to prepare SPM, and the SPM is supplied to the surface of a substrate. Patent Document 2 discloses a substrate processing method in which sulfuric acid and hydrogen peroxide water are supplied to a substrate from another nozzle, and the two are mixed on the substrate to generate SPM.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2019-207948

[0008] Patent Document 2: Japanese Patent Application Publication No. 2004-349669 Summary of the Invention

[0009] The problems that the invention needs to solve

[0010] In the substrate processing described in Patent Document 1, the consumption of processing liquid increases because processing is performed while the processing liquid is flowing out. Specifically, SPM needs to be discharged from the nozzle at a flow rate of approximately 0.5 to 2 liters per minute. Therefore, there is still room for improvement in terms of substrate processing cost and environmental impact.

[0011] Patent Document 2 discloses a substrate treatment in which a liquid film of sulfuric acid is formed on the substrate, and hydrogen peroxide water is supplied to the liquid film in a mist-like manner. This treatment is particularly preferred in terms of reducing the consumption of sulfuric acid, but it is difficult to form a liquid film that uniformly covers the entire area of ​​the substrate surface, and it is also difficult to maintain the state of the liquid film covering the entire area of ​​the substrate surface. Therefore, there is still room for improvement in the uniformity of the treatment.

[0012] Therefore, one embodiment of the present invention provides a substrate processing method and a substrate processing apparatus that can uniformly process the substrate surface and reduce the consumption of processing liquid.

[0013] Methods for solving problems

[0014] One embodiment of the present invention provides a substrate treatment method, comprising: a first treatment liquid supply step, wherein a first treatment liquid comprising one of sulfuric acid and hydrogen peroxide water is coated on the surface of a substrate; a second treatment liquid supply step, wherein a second treatment liquid comprising the other of sulfuric acid and hydrogen peroxide water and having a viscosity lower than that of the first treatment liquid is supplied to the surface of the substrate coated with the first treatment liquid; a mixture treatment step, wherein the surface of the substrate is treated with a sulfuric acid-hydrogen peroxide-water mixture generated by mixing the first treatment liquid and the second treatment liquid on the surface of the substrate; and a rinsing step, wherein after the mixture treatment step, a rinsing liquid is supplied to the substrate to rinse away the sulfuric acid-hydrogen peroxide-water mixture from the surface of the substrate.

[0015] According to this method, since a first treatment liquid with a higher viscosity is coated onto the surface of the substrate, the consumption of the first treatment liquid can be suppressed while uniformly coating and adhering it to the surface of the substrate. A second treatment liquid is then supplied to the surface of the substrate coated with the first treatment liquid. Thus, the first and second treatment liquids are mixed on the surface of the substrate to generate a sulfuric acid-hydrogen peroxide-water mixture. Because the first treatment liquid uniformly coats and adheres to the substrate surface, the sulfuric acid-hydrogen peroxide-water mixture can be uniformly coated onto the surface of the substrate without any omissions. Because the second treatment liquid has a lower viscosity, the mixing of the first and second treatment liquids proceeds rapidly. Since the first and second treatment liquids are mixed on the substrate, the heat generated during the mixing reaction can be effectively utilized to treat the surface of the substrate. After treatment with the sulfuric acid-hydrogen peroxide-water mixture, a rinsing liquid can be supplied to the surface of the substrate to rinse away the sulfuric acid-hydrogen peroxide-water mixture, and the treatment is stopped.

[0016] Thus, a substrate processing method is provided that can perform uniform processing on the surface of the substrate and reduce the consumption of processing liquid.

[0017] An example of substrate treatment is the removal of foreign matter present on the substrate surface. Specific examples of foreign matter include residues and films. Film removal can be achieved through film peeling or etching of a portion of the film. An example of a film is a photoresist film.

[0018] In one embodiment of the present invention, the aforementioned first processing liquid includes a thickener. Therefore, since the viscosity of the first processing liquid can be adjusted using the thickener, the first processing liquid can be coated onto the surface of the substrate at a viscosity suitable for processing.

[0019] One embodiment of the present invention provides a substrate treatment method, comprising: a first treatment liquid supply step, wherein a first treatment liquid containing a tackifier is applied to the surface of a substrate; a second treatment liquid supply step, wherein a second treatment liquid is supplied to the surface of the substrate coated with the first treatment liquid; a mixture treatment step, wherein the surface of the substrate is treated with a sulfuric acid-hydrogen peroxide-water mixture generated by mixing the first treatment liquid and the second treatment liquid on the surface of the substrate; and a rinsing step, wherein after the mixture treatment step, a rinsing liquid is supplied to the substrate to rinse away the sulfuric acid-hydrogen peroxide-water mixture from the surface of the substrate.

[0020] According to this method, the first treatment liquid, containing a thickener, can be coated and adhered to the surface of a substrate while suppressing its consumption. A second treatment liquid is then supplied to the surface of the substrate coated with the first treatment liquid. This mixes the first and second treatment liquids on the substrate surface to generate a sulfuric acid-hydrogen peroxide-water mixture. Because the first treatment liquid uniformly coats and adheres to the substrate surface, the sulfuric acid-hydrogen peroxide-water mixture can be uniformly and completely coated onto the substrate surface. Furthermore, since the first and second treatment liquids are mixed on the substrate, the heat generated during their mixing reaction can be effectively utilized to treat the substrate surface. After treatment with the sulfuric acid-hydrogen peroxide-water mixture, a rinsing solution can be supplied to the substrate surface to rinse away the mixture, thus stopping the treatment.

[0021] Similar to the aforementioned embodiments, one example of substrate treatment is the removal of foreign matter present on the substrate surface. Specific examples of foreign matter include residues and films. Film removal can be achieved through film peeling or etching of a portion of the film. An example of a film is a photoresist film.

[0022] One embodiment of the present invention provides a substrate treatment method, comprising: a first treatment liquid supply step, wherein a first treatment liquid comprising hydrogen peroxide water and a thickener is applied to the surface of a substrate; a second treatment liquid supply step, wherein a second treatment liquid comprising sulfuric acid is supplied to the surface of the substrate on which the first treatment liquid is applied; a mixture treatment step, wherein the surface of the substrate is treated with a sulfuric acid-hydrogen peroxide mixture generated by mixing the first treatment liquid and the second treatment liquid on the surface of the substrate; and a rinsing step, wherein after the mixture treatment step, a rinsing liquid is supplied to the substrate to rinse away the sulfuric acid-hydrogen peroxide mixture from the surface of the substrate.

[0023] According to this method, since hydrogen peroxide water is coated onto the surface of the substrate as a first treatment solution containing a thickener, the consumption of hydrogen peroxide water can be suppressed while the surface of the substrate is fully coated with hydrogen peroxide water and sealed tightly. A second treatment solution containing sulfuric acid is supplied to the surface of the substrate coated with the first treatment solution (hydrogen peroxide water). Thus, hydrogen peroxide water and sulfuric acid are mixed on the surface of the substrate to generate a sulfuric acid-hydrogen peroxide mixture. Since the first treatment solution uniformly coats and seals the substrate surface, the sulfuric acid-hydrogen peroxide mixture can be uniformly coated onto the surface of the substrate without any omissions. Furthermore, since sulfuric acid and hydrogen peroxide water are mixed on the substrate, the heat generated during the reaction can be effectively utilized to treat the surface of the substrate. After treatment with the sulfuric acid-hydrogen peroxide mixture, a rinsing solution can be supplied to the surface of the substrate to rinse away the sulfuric acid-hydrogen peroxide mixture, and the treatment is stopped.

[0024] Similar to the aforementioned embodiments, one example of substrate treatment is the removal of foreign matter present on the substrate surface. Specific examples of foreign matter include residues and films. Film removal can be achieved through film peeling or etching of a portion of the film. An example of a film is a photoresist film.

[0025] In one embodiment of the present invention, the aforementioned tackifier comprises at least one selected from the group consisting of polyvinylpyrrolidone, polyacrylic acid, sodium polyacrylate, ammonium polyacrylate, cross-linked polyacrylic acid, cross-linked sodium polyacrylate, cross-linked acrylic polymers, and carboxylic acid copolymers.

[0026] The thickener preferably has, for example, heat resistance that allows the viscosity of the first processing solution to remain above a desired value at the temperature of the first processing solution when supplied to the surface of the substrate. In this case, the desired value refers to the ability to uniformly and completely coat the first processing solution onto the surface of the substrate and maintain this coating state for at least a certain period of time, preferably in the range of 30 mPa·s to 3000 mPa·s. The thickener further preferably has heat resistance that allows the viscosity of the sulfuric acid-hydrogen peroxide-water mixture to remain above a desired value at the temperature of the mixture processing step. In this case, the desired value refers to the ability to maintain the state of complete diffusion of the sulfuric acid-hydrogen peroxide-water mixture on the surface of the substrate for at least a certain period of time, preferably in the range of 30 mPa·s to 3000 mPa·s.

[0027] In one embodiment of the present invention, the aforementioned second processing liquid does not contain a thickener. By eliminating the thickener from the second processing liquid, it is possible to supply the second processing liquid to the surface of the substrate at a low viscosity. This, in turn, promotes mixing of the first and second processing liquids on the substrate.

[0028] When the first processing solution contains a viscosity improver, this viscosity improver is present in the sulfuric acid-hydrogen peroxide-water mixture generated on the substrate, increasing its viscosity. Therefore, processing with the sulfuric acid-hydrogen peroxide-water mixture can be performed while ensuring that the mixture adheres completely to the surface of the substrate. This results in uniform treatment of the substrate surface.

[0029] To reduce the consumption of the second treatment solution, a thickener may be included in the second treatment solution. However, its content is preferably limited to a level that does not affect its mixing with the first treatment solution.

[0030] In one embodiment of the present invention, in the aforementioned first processing liquid supply process, the aforementioned first processing liquid is coated onto the surface of the aforementioned substrate, thereby forming a coating film of the aforementioned first processing liquid covering the entire area of ​​the surface of the aforementioned substrate.

[0031] In this method, since the coating film (e.g., a gel-like coating film) of the first treatment liquid covers the entire area of ​​the substrate surface, the first treatment liquid can adhere to the entire area of ​​the substrate surface. Therefore, the sulfuric acid-hydrogen peroxide-water mixture formed by mixing the first treatment liquid and the second treatment liquid can adhere to the entire area of ​​the substrate surface, and the entire surface area of ​​the substrate can be uniformly treated.

[0032] In one embodiment of the present invention, in the aforementioned second processing liquid supply step, the aforementioned second processing liquid is supplied to the surface of the coating film of the aforementioned first processing liquid. In this method, a coating film of the first processing liquid is formed on the surface of a substrate, and the second processing liquid is supplied to the surface of the coating film. Therefore, since it is possible to suppress the first processing liquid from being carried outside the substrate due to the flow of the second processing liquid, the consumption of the first processing liquid can be reduced.

[0033] In one embodiment of the present invention, the aforementioned second processing liquid supply process begins when the supply of the aforementioned first processing liquid to the surface of the aforementioned substrate is stopped.

[0034] In this method, the supply of the second processing liquid is started after the supply of the first processing liquid (more specifically, the supply of a new liquid) is stopped. Therefore, since the first processing liquid can be prevented from being carried away from the substrate due to the flow of the low-viscosity second processing liquid, the consumption of the first processing liquid can be reduced.

[0035] In one embodiment of the present invention, at least a portion of the aforementioned mixture processing step overlaps with at least a portion of the aforementioned second processing liquid supply step.

[0036] The mixing of the first and second processing solutions begins by supplying the second processing solution to the surface of the substrate while the first processing solution is present on the surface of the substrate. Therefore, sometimes the treatment of the substrate surface using a mixture of sulfuric acid and hydrogen peroxide is started during the process of supplying the second processing solution.

[0037] In one embodiment of the present invention, during at least a portion of the aforementioned mixture treatment process, the supply of the aforementioned second treatment liquid to the surface of the aforementioned substrate is stopped.

[0038] In this method, while the supply of the second processing liquid is stopped (specifically, the supply of a new liquid), there is a period during which the substrate surface is treated with a mixture of sulfuric acid and hydrogen peroxide.

[0039] For example, with the substrate surface held horizontally and facing upwards, supplying a second processing liquid to the surface of the substrate to which the first processing liquid is coated can be stopped, thereby achieving a paddle state where a liquid film of a sulfuric acid-hydrogen peroxide-water mixture is supported on the substrate surface. By maintaining this paddle state, substrate processing using the sulfuric acid-hydrogen peroxide-water mixture can be performed without supplying the first and second processing liquids. During such paddle processing, one or both of the first and second processing liquids can be added to the substrate surface as needed.

[0040] In one embodiment of the present invention, the aforementioned first processing solution supply step and the aforementioned second processing solution supply step are alternately repeated. This method allows for the treatment of the substrate with a sulfuric acid-hydrogen peroxide-water mixture while the first and second processing solutions are alternately supplied as needed. Therefore, the surface of the substrate can be adequately treated to avoid insufficient treatment.

[0041] When the first processing liquid supply step is performed again after the second processing liquid supply step, other steps can be added in between. That is, the first processing liquid can be supplied after the second processing liquid supply step, after a mixed liquid treatment step performed without supplying the first and second processing liquids. Alternatively, the first processing liquid supply step can be performed after the aforementioned rinsing step.

[0042] One embodiment of the present invention provides a substrate processing apparatus for implementing the substrate processing method as described above. The substrate processing apparatus includes: a substrate holding mechanism (substrate support) for holding a substrate; a first processing liquid nozzle for supplying the first processing liquid to the substrate held in the substrate holding mechanism; a second processing liquid nozzle for supplying the second processing liquid to the substrate held in the substrate holding mechanism; a rinsing liquid nozzle for supplying the rinsing liquid to the substrate held in the substrate holding mechanism; and a control unit (controller). The control unit controls the supply of the first processing liquid from the first processing liquid nozzle to perform the first processing liquid supply step, controls the supply of the second processing liquid from the second processing liquid nozzle to perform the second processing liquid supply step, and controls the supply of the rinsing liquid from the rinsing liquid nozzle to perform the rinsing step.

[0043] This configuration enables the aforementioned substrate processing method to be implemented. Therefore, a substrate processing apparatus is provided that can uniformly process the surface of a substrate and reduce the consumption of processing liquid.

[0044] In one embodiment of the present invention, the aforementioned substrate holding mechanism includes a spin chuck that holds the surface of the substrate horizontally upward and rotates it. In this case, the aforementioned control unit preferably controls the supply of the first processing liquid from the aforementioned first processing liquid nozzle and the rotation of the aforementioned spin chuck during the aforementioned first processing liquid supply process, so as to spin-coat the aforementioned first processing liquid onto the surface of the aforementioned substrate.

[0045] This configuration allows the first processing liquid to be applied to the surface of the substrate using a spin coating method. As a result, since a small amount of the first processing liquid can be uniformly distributed on the surface of the substrate, the surface of the substrate can be uniformly processed while reducing the consumption of the first processing liquid.

[0046] In one embodiment of the present invention, the aforementioned substrate processing apparatus further includes: a nozzle moving unit that moves the first processing liquid nozzle between a processing position for supplying processing liquid to a substrate held in the aforementioned substrate holding mechanism and a standby position that is retracted from the aforementioned processing position; and a cleaning pot that, in the aforementioned standby position, immerses the outlet of the first processing liquid nozzle in nozzle cleaning liquid.

[0047] According to this configuration, the discharge port can be cleaned in the standby position of the first treatment fluid when the first treatment fluid nozzle is not in use. This allows for the suppression or prevention of discharge port blockage caused by the high viscosity of the first treatment fluid.

[0048] The above or other objects, features, and effects of the present invention will become clear from the description of the embodiments described below with reference to the accompanying drawings. Attached Figure Description

[0049] [ Figure 1A-1E ] Figures 1A to 1E This is a process diagram illustrating a substrate processing method according to one embodiment of the present invention.

[0050] [ Figure 1F-1H ] Figures 1F to 1H This is a process diagram used to illustrate the aforementioned substrate processing method.

[0051] [ Figure 2A-2D ] Figures 2A to 2D It is a graphical cross-sectional view used to illustrate an example of the state of the substrate surface in the main process.

[0052] [ Figure 3 ] Figure 3 This is an illustrative cross-sectional view illustrating an example of the configuration of a substrate processing apparatus for performing the substrate processing method as described above.

[0053] [ Figure 4 ] Figure 4 This is a diagram illustrating an example of the configuration of the first processing liquid supply source.

[0054] [ Figure 5 ] Figure 5 This is a diagram illustrating an example of the configuration of the second treatment fluid supply source.

[0055] [ Figure 6 ] Figure 6 This is a block diagram illustrating the configuration related to the control of each part of the aforementioned substrate processing apparatus.

[0056] [ Figure 7 ] Figure 7 This is a diagram illustrating other configuration examples of the first treatment fluid supply source.

[0057] [ Figure 8 ] Figure 8This is a process diagram illustrating the substrate processing method according to the second embodiment of the present invention. Detailed Implementation

[0058] Figures 1A to 1H This is a process diagram illustrating a substrate processing method according to one embodiment of the present invention. The substrate processing method includes a first processing solution coating step S1 (a first processing solution supply step, Figure 1A-Figure 1B ), the second processing liquid supply process S2 ( Figure 1C ), Mixed liquid treatment process S3 ( Figure 1C-1D ), rinsing process S4 ( Figure 1E ), residue removal process S5 ( Figures 1F-1G ) and drying process S6 ( Figure 1H The substrate W to be processed is a substrate on which a resist film (not shown) is formed on its surface (the upper surface in this embodiment). The substrate W can be a semiconductor substrate or a substrate for a liquid crystal display device. A typical resist film is a resist film used as a mask for dry etching. The substrate processing method in this embodiment involves a resist stripping process to peel off the resist film from the surface of the substrate W. More specifically, the resist is stripped and removed from the surface of the substrate W using a sulfuric acid-hydrogen-peroxide mixture (SPM).

[0059] The substrate W, with a resist film formed on its surface, is moved into the processing chamber 1 (refer to...). Figure 3 The substrate W is held in a horizontal position by a rotating chuck 5. In this position, the substrate W rotates around a vertical axis of rotation A passing through its central portion. The substrate W is held in the rotating chuck 5 with the surface of the substrate W to which the resist film is formed facing upwards.

[0060] The first processing solution coating step S1 is a process in which the first processing solution L1 is supplied to the surface (upper surface) of the substrate W while rotating the substrate W using a rotary chuck 5, and the first processing solution L1 is coated onto the surface of the substrate W (so-called spin coating). In this embodiment, the first processing solution L1 contains one of sulfuric acid and hydrogen peroxide water, which are raw materials for SPM, but does not contain the other. In this embodiment, the first processing solution L1 is a high-viscosity processing solution that also contains a thickener (high viscosity modifier).

[0061] In the first treatment liquid coating process S1, such as Figure 1AAs shown, a predetermined amount of first processing liquid L1 is supplied from the first processing liquid nozzle N1 to the vicinity of the center of the substrate W. After supplying only the predetermined amount, the supply of the first processing liquid L1 from the first processing liquid nozzle N1 is stopped. The first processing liquid L1 supplied to the surface of the substrate W diffuses towards the periphery of the substrate W due to the centrifugal force accompanying the rotation of the substrate W. Thus, as... Figure 1B As shown, a coating film F1 of a first processing liquid L1 is formed, capable of covering the entire area of ​​the surface (upper surface) of a substrate W. A predetermined supply amount of the first processing liquid L1 is determined to be sufficient to form the coating film F1 covering the entire area of ​​the surface (upper surface) of the substrate W by rotating the substrate W. This predetermined supply amount is further preferably determined to be the amount necessary for forming the coating film F1 covering the entire surface (upper surface) of the substrate W, thereby minimizing the consumption of the first processing liquid L1.

[0062] The second processing liquid supply step S2 is performed after the first processing liquid coating step S1. That is, it begins when a coating film F1 of the first processing liquid L1 has been formed over the entire surface (upper surface) of the substrate W. In this embodiment, the second processing liquid L2 contains either sulfuric acid or hydrogen peroxide water, which are raw materials for SPM, or the other of the aforementioned components not included in the first processing liquid L1, and also does not contain the other of the aforementioned components already included in the first processing liquid L1. The second processing liquid L2 is preferably a low-viscosity processing liquid with a viscosity lower than that of the first processing liquid L1. The second processing liquid L2 preferably does not contain a thickener, but may contain a trace amount of a thickener if necessary.

[0063] In the second processing liquid supply process S2, such as Figure 1C As shown, while rotating the substrate W around the rotation axis A using a rotating chuck 5, a second processing liquid L2 is supplied from the second processing liquid nozzle N2 onto the coating film F1 of the first processing liquid L1 formed over the entire area of ​​the surface (upper surface) of the substrate W. This supply can be a continuous supply at a specified flow rate. Figure 1CAs shown, the second processing liquid nozzle N2 can be a straight nozzle that discharges the second processing liquid L2 in a continuous columnar flow. Alternatively, the second processing liquid nozzle N2 can be a spray nozzle that sprays the second processing liquid L2 with a conical profile. Furthermore, the second processing liquid nozzle N2 can be used in a fixed discharge process during the second processing liquid supply step S2, where the liquid application position on the substrate W is substantially maintained in a fixed position (e.g., on the rotation axis A); or it can be used in a moving discharge process during the second processing liquid supply step S2, where the liquid application position on the substrate W is moved. In the moving discharge case, the liquid application position of the second processing liquid L2 discharged from the second processing liquid nozzle N2 moves within a range from the rotation center to the periphery on the surface of the substrate W, thus it is preferable that the liquid application position scans the surface of the substrate W. The second processing liquid supply step S2 is performed within a predetermined time.

[0064] The mixed solution treatment step S3 is a process of stripping the resist film on the surface of the substrate W using a mixed solution, namely SPM, formed by mixing the first treatment solution L1 and the second treatment solution L2 on the substrate W. Specifically, while sulfuric acid and hydrogen peroxide water are mixed on the substrate W to generate a heat-generating reaction, SPM is generated, which etches the resist film on the surface of the substrate W. When the supply of the second treatment solution L2 begins, since the mixing of the first treatment solution L1 and the second treatment solution L2 begins, at least a portion of the second treatment solution supply step S2 can overlap with at least a portion of the mixed solution treatment step S3 (see reference). Figure 1C ).

[0065] After the second processing liquid supply step S2, that is, after stopping the supply of the second processing liquid L2, as follows: Figure 1D As shown, a mixing reaction (SPM reaction) of the first processing solution L1 and the second processing solution L2 also occurs on the surface of the substrate W, and SPM corrosion of the resist film occurs. After the supply of the second processing solution L2 is stopped, the rotation of the substrate W can be stopped. The substrate W can be rotated at a low speed (refer to) to maintain the first processing solution L1, the second processing solution L2, and the SPM mixture formed therefrom on the substrate W. Figure 1D Thus, the coating film F1 of the first processing liquid L1 is coated with the second processing liquid L2, resulting in a liquid-coated state. Therefore, the SPM formed by their mixture is also liquid-coated on the substrate W. By maintaining this liquid-coated state, resist etching can be performed using the SPM without supplying the first processing liquid L1 and the second processing liquid L2.

[0066] In the mixing process S3 after the supply of the second processing liquid L2 is stopped, the first processing liquid L1 can be replenished to the surface of the substrate W from the first processing liquid nozzle N1, or the second processing liquid L2 can be replenished to the surface of the substrate W from the second processing liquid nozzle N2, as needed. Only one of the first processing liquid L1 and the second processing liquid L2 may be replenished, or both may be replenished. Alternatively, the supply of the second processing liquid L2 may continue throughout the entire mixing process S3 without stopping.

[0067] The rinsing step S4 is performed after the resist film on the substrate W has been sufficiently etched through the mixed solution treatment step S3. Specifically, as follows... Figure 1E As shown, while rotating the substrate W using a rotating chuck 5, a rinsing solution R, such as pure water (deionized water) or carbonated water, is supplied from the rinsing solution nozzle NR to flush away the resist film and SPM etched on the substrate W to the outside of the substrate W surface. The substrate W is preferably rotated at a higher speed than in the mixing solution treatment step S3, and centrifugal force is used to form a flow of rinsing solution R on the surface of the substrate W from the center of rotation to the periphery.

[0068] The first treatment liquid coating step S1, the second treatment liquid supply step S2, the mixed liquid treatment step S3, and the rinsing step S4 can be performed repeatedly in a cyclical manner. That is, the first treatment liquid coating step S1, the second treatment liquid supply step S2, the mixed liquid treatment step S3, and the rinsing step S4 can be performed again after the rinsing step S4. In this case, the viscosity of the first treatment liquid supplied in the second and subsequent first treatment liquid coating steps S1 can be lower than the viscosity of the first treatment liquid used in the first first treatment liquid coating step S1.

[0069] Furthermore, the first treatment liquid coating step S1, the second treatment liquid supply step S2, and the mixed liquid treatment step S3 can be performed repeatedly in a cyclical manner. Moreover, after a predetermined number of repetitions, a rinsing step S4 can be performed. In this case, the viscosity of the first treatment liquid supplied in the second and subsequent first treatment liquid coating steps S1 can be lower than the viscosity of the first treatment liquid used in the first first treatment liquid coating step S1.

[0070] The residue removal process S5 is a cleaning process used to remove foreign matter that was not completely removed in the rinsing process S4. More specifically, the residue removal process S5 removes the products (processing residue) and particles from the surface of the substrate W in the mixture treatment process S3. The residue removal process S5 includes... Figure 1F The cleaning fluid supply process S51 and S52 shown are described. Figure 1G The rinsing step S52 is shown. Depending on the required treatment, the residue removal step S5 can be omitted.

[0071] In the cleaning solution supply process S51, the substrate W is rotated using a rotary chuck 5 while the cleaning solution C (more specifically, the cleaning solution) is supplied to the surface of the substrate W from the chemical nozzle NC. The cleaning solution supply process S51 may be an alkaline cleaning process that uses an ammonia-hydrogen peroxide-water mixture (e.g., SC1) as the cleaning solution C to clean the substrate W.

[0072] The rinsing step S52 is a step that follows the cleaning fluid supply step S51, in which the cleaning fluid C on the surface of the substrate W is replaced with rinsing fluid R, and the cleaning fluid C is rinsed away from the surface of the substrate W. In the rinsing step S52, the substrate W is rotated using a rotary chuck 5 while the rinsing fluid R is supplied to the surface of the substrate W from the rinsing fluid nozzle NR.

[0073] Drying process S6 is followed by rinsing process S52 in residue removal process S5 (see reference). Figure 1G This is performed after the residue removal step S5. If the residue removal step S5 is omitted, the rinsing step S4 (see...) is performed after this step. Figure 1E This is followed by the drying process S6. That is, the drying process S6 is performed after the supply of rinsing solution R to the surface of the substrate W is stopped. For example... Figure 1H As shown, drying step S6 can be a rotary drying process that uses a rotating chuck 5 to rotate the substrate W at high speed and uses centrifugal force to spin-dry the liquid on the substrate W. Through this drying step S6, a series of substrate treatments are completed, from the processing chamber 1 (see reference 1)... Figure 3 The processed substrate W is removed from the processing chamber 1 (refer to...). Figure 3 Remove the substrate W after the resist film has been peeled off the surface and the surface has been cleaned and dried.

[0074] Figures 2A to 2D This is a schematic cross-sectional view illustrating an example of the state of the substrate surface during the main process. In this example, the first processing solution L1 is high-viscosity hydrogen peroxide water, i.e., hydrogen peroxide water containing a thickener. The second processing solution L2 is sulfuric acid. The second processing solution L2 is preferably sulfuric acid with a lower viscosity than the first processing solution L1. For example, the second processing solution L2 is sulfuric acid without a thickener. The viscosity of the first processing solution L1 at the temperature (e.g., room temperature) when supplied to the surface of the substrate W is 30 mPa·s or more, preferably 50 mPa·s or more, more preferably 100 mPa·s or more, and even more preferably 200 mPa·s or more. The upper limit of the viscosity of the first processing solution L1 is any range that allows it to be spin-coated onto the surface of the substrate W, for example, 3000 mPa·s.

[0075] Examples of tackifiers include polyvinylpyrrolidone (PVP) and acrylic tackifiers. Acrylic tackifiers include not only polyacrylic acid, sodium polyacrylate, ammonium polyacrylate, cross-linked polyacrylic acid, and cross-linked sodium polyacrylate, but also cross-linked acrylic polymers and carboxylic acid copolymers (ammonium or sodium salts). One or more of these tackifiers can be used. Tackifiers can be provided in powder, aqueous solution, or emulsion form.

[0076] First processing solution coating process S1 (refer to) Figure 2A In this process, a coating film F1 (e.g., a gel-like film) of high-viscosity hydrogen peroxide water (first treatment solution L1) is formed on the surface of substrate W. The coating film F1 adheres tightly to the entire surface area of ​​substrate W.

[0077] Second processing fluid supply process S2 (refer to) Figure 2B In this process, sulfuric acid (second treatment liquid L2), which has a lower viscosity, is supplied, for example, onto a coating film of high-viscosity hydrogen peroxide water (coating film F1 of the first treatment liquid L1), thereby forming a liquid layer of sulfuric acid. Then, mixing of the high-viscosity hydrogen peroxide water (first treatment liquid L1) and sulfuric acid (second treatment liquid L2) begins.

[0078] Mixture processing step S3 (refer to) Figure 2C In this process, SPM is generated by mixing high-viscosity hydrogen peroxide water with sulfuric acid. This SPM reaches the surface of substrate W, thereby etching the resist film formed on the surface of substrate W. Since the hydrogen peroxide water exists on the surface of substrate W in a high-viscosity state, the reaction proceeds while inhibiting or preventing the SPM from flowing out of substrate W. Thus, by supplying a small amount of high-viscosity hydrogen peroxide water and a small amount of sulfuric acid, the resist film on the surface of substrate W can be etched. If hydrogen peroxide water and / or sulfuric acid are insufficient, they can be replenished as previously described. Because the high-viscosity hydrogen peroxide water coating film F1 adheres tightly to the entire area of ​​substrate W, uniform processing can be performed over the entire area of ​​substrate W, resulting in a substrate processing (resist stripping process) with good uniformity.

[0079] Regarding the thickener contained in the first processing liquid L1, when the first processing liquid L1 and the second processing liquid L2 are mixed on the substrate W to generate SPM, it is preferable that the viscosity of the SPM is 30 mPa·s or more, preferably 50 mPa·s or more, more preferably 100 mPa·s or more, and even more preferably 200 mPa·s or more. Therefore, since the SPM can be easily maintained in a liquid-coated state on the substrate W, the consumption of the first processing liquid L1 and the second processing liquid L2 can be efficiently reduced, and uniform substrate processing can be easily achieved.

[0080] After the mixed liquid treatment step S3, the process proceeds to the rinsing step S4 (see reference). Figure 2D Replace the SPM on the substrate W with the rinsing solution R, and remove it from the surface of the substrate W together with the etched resist film.

[0081] For the case where high-viscosity sulfuric acid (i.e., sulfuric acid with added thickener) is used in the first processing solution L1 and hydrogen peroxide water (preferably hydrogen peroxide water with a lower viscosity than the first processing solution L1) is used in the second processing solution L2, it is sufficient to simply exchange the "hydrogen peroxide water" and "sulfuric acid" as described above. In this case, substrate processing (resist stripping processing) with good uniformity can also be achieved.

[0082] Figure 3 This is an illustrative cross-sectional view illustrating an example configuration of a substrate processing apparatus 100 (processing unit) for performing the substrate processing method as described above. The substrate processing apparatus 100 includes a rotary chuck 5 (as an example of a substrate holding mechanism, a first processing liquid nozzle N1), a second processing liquid nozzle N2, a chemical solution nozzle NC, a rinsing liquid nozzle NR, and a standby tank 3, all housed within a processing chamber 1. The substrate processing apparatus 100 also includes a first processing liquid supply source 15 and a second processing liquid supply source 25 disposed outside the processing chamber 1. The substrate processing apparatus 100 further includes a chemical solution supply source 35 disposed outside the processing chamber 1.

[0083] The rotary chuck 5 is a substrate holding and rotating device that holds a substrate W in a horizontal position within a processing chamber 1, allowing the substrate W to rotate around a vertical rotation axis A passing through the center of the substrate W. The rotary chuck 5 includes a rotation shaft 51 extending along the rotation axis A, a rotation base 52 attached to the upper end of the rotation shaft 51, and a rotary motor 53 for rotating the rotation shaft 51. The rotation base 52 has a disk shape held horizontally at the upper end of the rotation shaft 51. A plurality of clamping pins 54 spaced circumferentially are arranged at the periphery of the rotation base 52. The plurality of clamping pins 54 are configured to contact and clamp the substrate W at its peripheral end face. A vacuum chuck that adsorbs and holds the substrate W at the center of its lower surface can be used instead of such a mechanical chuck.

[0084] The first processing liquid nozzle N1 is a nozzle that supplies the first processing liquid L1 to the surface (upper surface) of the substrate W held in the rotary chuck 5. The first processing liquid nozzle N1 has the form of a movable nozzle that moves between a processing position (shown in solid lines) and a standby position (shown in double-dotted lines). The processing position is the position where the first processing liquid L1 is discharged onto the surface of the substrate W held in the rotary chuck 5, and the standby position is the position set on the side of the rotary chuck 5. More specifically, the first processing liquid nozzle N1 is moved by a first nozzle moving unit 11. The first nozzle moving unit 11 includes, for example, a horizontally extending first swing arm 12, at which the first processing liquid nozzle N1 is attached. Although detailed illustrations are omitted, the first nozzle moving unit 11 also includes a swing drive mechanism attached to the base end of the first swing arm 12, which causes the first swing arm 12 to swing about a vertical swing axis passing through the base end of the first swing arm 12. Therefore, the first processing liquid nozzle N1 moves between the processing position and the standby position. As mentioned above, the first processing liquid L1 is a high-viscosity processing liquid. The processing position can be the position where the first processing liquid L1 is applied at the center of rotation of the substrate W. The first processing liquid L1 applied at the center of rotation of the substrate W is spread to the entire surface area of ​​the substrate W by the centrifugal force generated by the rotation of the substrate W.

[0085] The second processing liquid nozzle N2 is a nozzle that supplies the second processing liquid L2 to the surface (upper surface) of the substrate W held in the rotary chuck 5. The second processing liquid nozzle N2 has a movable nozzle configuration that moves between a processing position and a standby position. The processing position is the position where the second processing liquid L2 is discharged onto the surface of the substrate W held in the rotary chuck 5, and the standby position is the position set on the side of the rotary chuck 5. More specifically, the second processing liquid nozzle N2 is moved by a second nozzle moving unit 21. The second nozzle moving unit 21 has, for example, the same configuration as the first nozzle moving unit 11. That is, the second nozzle moving unit 21 includes, for example, a horizontally extending second swing arm 22, at the swing end of which the second processing liquid nozzle N2 is attached. Similar to the first nozzle moving unit 11, the second nozzle moving unit 21 has a swing drive mechanism that swings the second swing arm 22. The second processing liquid nozzle N2 can operate as a scanning nozzle that simultaneously discharges the second processing liquid L2 and scans the liquid-covered position on the substrate W. In this case, the processing position varies between the rotation center and the periphery of the substrate W.

[0086] The cleaning nozzle NC supplies cleaning fluid C (cleaning solution) to the surface (upper surface) of the substrate W held in the rotary chuck 5. The cleaning nozzle NC is a movable nozzle that moves between a processing position and a standby position. The processing position is where the cleaning fluid C is discharged to the surface of the substrate W held in the rotary chuck 5, and the standby position is a position set on the side of the rotary chuck 5. More specifically, the cleaning nozzle NC is moved by a third nozzle moving unit 31. The third nozzle moving unit 31 has, for example, the same configuration as the first nozzle moving unit 11. That is, the third nozzle moving unit 31 includes, for example, a horizontally extending third swing arm 32, at the swing end of which the cleaning nozzle NC is attached. Similar to the first nozzle moving unit 11, the third nozzle moving unit 31 has a swing drive mechanism for swinging the third swing arm 32. As mentioned above, the cleaning fluid C is, for example, a mixture of ammonia and hydrogen peroxide (e.g., SC1). The cleaning nozzle NC can function as a scanning nozzle that simultaneously discharges the cleaning solution C and scans the liquid-covered areas on the substrate W. That is, the processing position can move between the rotation center and the periphery of the substrate W.

[0087] The rinsing fluid nozzle NR is a nozzle that supplies rinsing fluid R to the surface (upper surface) of the substrate W held in the rotating chuck 5. In this embodiment, the rinsing fluid nozzle NR has a fixed nozzle configuration. Alternatively, the rinsing fluid nozzle NR can also have a movable nozzle configuration that moves between a processing position and a standby position. The processing position is the position where rinsing fluid R is discharged to the surface of the substrate W held in the rotating chuck 5, and the standby position is a position set on the side of the rotating chuck 5. In this embodiment, the rinsing fluid nozzle NR is fixed in such a way that it discharges rinsing fluid R towards the rotation center of the substrate W. Typically, the rinsing fluid R is pure water (deionized water).

[0088] Standby tank 3 is positioned in the standby position of the first processing fluid nozzle N1. Figure 3 (Shown with double-dotted lines) This is an example of a cleaning tank for cleaning the outlet 10 of the first processing fluid nozzle N1. The standby tank 3 may be shaped like a container for storing nozzle cleaning fluid for cleaning the outlet 10 of the first processing fluid nozzle N1. In the standby position, the outlet 10 of the first processing fluid nozzle N1 is immersed in the nozzle cleaning fluid in the standby tank 3. This suppresses the solidification of the high-viscosity first processing fluid L1, thereby preventing clogging of the outlet 10 of the first processing fluid nozzle N1.

[0089] The first processing fluid nozzle N1 is connected to the first processing fluid supply source 15 via the first processing fluid piping 13. A first processing fluid valve 14 is installed in the middle of the first processing fluid piping 13. The first processing fluid valve 14 opens and closes the flow path of the first processing fluid piping 13.

[0090] The second processing fluid nozzle N2 is connected to the second processing fluid supply source 25 via the second processing fluid piping 23. A second processing fluid valve 24 is installed midway through the second processing fluid piping 23. The second processing fluid valve 24 opens and closes the flow path of the second processing fluid piping 23.

[0091] The cleaning solution nozzle NC is connected to the cleaning solution supply source 35 via a cleaning solution piping 33. A cleaning solution valve 34 is installed midway through the cleaning solution piping 33. The cleaning solution valve 34 opens and closes the flow path of the cleaning solution piping 33. Although not shown in the figure, the cleaning solution supply source 35 includes a cleaning solution tank for storing cleaning solution (e.g., a mixture of ammonia and hydrogen peroxide), and a cleaning solution pump that delivers the cleaning solution from the cleaning solution tank toward the cleaning solution nozzle NC and into the cleaning solution piping 33. The cleaning solution is stored in the cleaning solution tank. More specifically, a cleaning solution containing ammonia and hydrogen peroxide is mixed in a prescribed ratio to prepare the cleaning solution, and the solution is stored in the cleaning solution tank. If necessary, a heater for heating the cleaning solution to an appropriate temperature may be installed in the cleaning solution tank or the cleaning solution piping 33.

[0092] The flushing fluid nozzle NR is connected to the flushing fluid supply source 45 via flushing fluid piping 43. A flushing fluid valve 44 is installed midway through the flushing fluid piping 43. The flushing fluid valve 44 opens and closes the flow path of the flushing fluid piping 43. The flushing fluid supply source 45 can be a plant utility that supplies flushing fluids such as deionized water.

[0093] Figure 4 This diagram illustrates an example of the configuration of the first processing liquid supply source 15. The first processing liquid supply source 15 includes: a first processing liquid tank 16 for storing the first processing liquid L1; and a first processing liquid pump 17 for discharging the first processing liquid L1 from the first processing liquid tank 16 toward the first processing liquid nozzle N1 and into the first processing liquid piping 13. A first filter 18 for removing foreign matter from the first processing liquid L1 may be installed in the first processing liquid piping 13. The first processing liquid tank 16 stores a pre-prepared high-viscosity first processing liquid L1. The high-viscosity first processing liquid L1 is prepared by mixing one of sulfuric acid and hydrogen peroxide water with a viscosity-increasing agent. When the first processing liquid L1 contains sulfuric acid, it is preferable to install a first processing liquid heater 19 in the first processing liquid tank 16 or the first processing liquid piping 13. This allows the first processing liquid L1 to be heated to a temperature higher than room temperature (e.g., approximately 120°C to 130°C). When the first processing solution L1 contains hydrogen peroxide water, such a first processing solution heater 19 is not required. The first processing solution L1 at room temperature (ambient temperature, generally 0°C to 30°C, for example, around 25°C) is supplied to the first processing solution nozzle N1 and discharged.

[0094] Figure 5This diagram illustrates an example of the configuration of the second processing liquid supply source 25. The second processing liquid supply source 25 includes: a second processing liquid tank 26 for storing the second processing liquid L2; and a second processing liquid pump 27 for discharging the second processing liquid L2 from the second processing liquid tank 26 toward the second processing liquid nozzle N2 and into the second processing liquid piping 23. A second filter 28 for removing foreign matter from the second processing liquid L2 may be installed in the second processing liquid piping 23. The second processing liquid tank 26 stores the second processing liquid L2 (preferably a second processing liquid L2 with a lower viscosity than the first processing liquid L1). In this embodiment, the second processing liquid L2 contains either sulfuric acid or hydrogen peroxide water and does not contain a thickener. If the second processing liquid L2 contains sulfuric acid, a second processing liquid heater 29 is provided in the second processing liquid tank 26 or the second processing liquid piping 23. This allows the second processing liquid L2 to be heated to a temperature higher than room temperature (e.g., approximately 120°C to 130°C). When the second processing liquid L2 contains hydrogen peroxide water, such a second processing liquid heater 29 is not required. The second processing liquid L2 at room temperature (ambient temperature, generally 0°C to 30°C, for example, around 25°C) is supplied to the second processing liquid nozzle N2 and discharged.

[0095] Figure 6 This is a block diagram illustrating the control-related configuration of each part of the substrate processing apparatus 100. The substrate processing apparatus 100 includes a controller 2, which serves as a control unit for controlling its various parts. The controller 2 includes a processor (CPU) 2a and a memory 2b. The processor 2a executes programs stored in the memory 2b to implement various functions of the controller 2. In other words, the controller 2 is configured (programmed) to perform various functions. The controller 2 controls the opening and closing of the first processing liquid valve 14, the second processing liquid valve 24, the chemical liquid valve 34, and the rinsing liquid valve 44. Furthermore, the controller 2 controls the rotation of the rotary chuck 5, the operation of the first nozzle moving unit 11, the second nozzle moving unit 21, and the third nozzle moving unit 31, etc. Additionally, the controller 2 controls the operation of the first processing liquid supply source 15, the second processing liquid supply source 25, and the chemical liquid supply source 35.

[0096] Therefore, controller 2 controls the supply and stopping of the first processing liquid L1, the second processing liquid L2, the cleaning liquid C, and the rinsing liquid R. Additionally, controller 2 controls the rotation of the substrate W (rotation / stop and rotation speed, etc.). Furthermore, controller 2 controls the positions of the first processing liquid nozzle N1, the second processing liquid nozzle N2, and the chemical solution nozzle NC. Controller 2 executes the aforementioned first processing liquid coating process S1, second processing liquid supply process S2, mixed liquid treatment process S3, rinsing process S4, residue removal process S5, and drying process S6 through such control.

[0097] When the untreated substrate W is transferred to the rotary chuck 5 by a substrate transfer robot (not shown), the controller 2 executes the first processing liquid coating process S1 (see reference). Figure 1A and Figure 1B That is, while the controller 2 rotates the rotary chuck 5 at the first processing liquid coating speed (e.g., 500 rpm to 1500 rpm), the controller 2 positions the first processing liquid nozzle N1 in the processing position and opens the first processing liquid valve 14, discharging a predetermined amount of the first processing liquid L1 from the first processing liquid nozzle N1 towards the center of rotation of the surface (upper surface) of the substrate W. The first processing liquid L1 in contact with the surface of the substrate W diffuses towards the periphery of the substrate W using centrifugal force, thereby spreading to the entire surface of the substrate W. Thus, a coating film F1 of the first processing liquid L1 covering the entire area of ​​the surface of the substrate W is formed.

[0098] After the first processing liquid coating process S1, the controller 2 executes the second processing liquid supply process S2 (see reference). Figure 1C That is, controller 2 moves the first processing fluid nozzle N1 to the standby position. Figure 3 Instead of showing the first processing liquid nozzle (indicated by a double-dotted line), the second processing liquid nozzle N2 is moved to the processing position. The outlet 10 of the first processing liquid nozzle N1 is immersed in nozzle cleaning liquid in the standby tank 3 in the standby position, thereby cleaning the outlet 10. The controller 2 rotates the rotary chuck 5 at the second processing liquid processing speed (e.g., 300 rpm to 800 rpm). The second processing liquid processing speed is preferably equal to or lower than the first processing liquid coating speed. Furthermore, the controller 2 positions the second processing liquid nozzle N2, for example, at the center of rotation of the surface of the substrate W where the second processing liquid L2 is applied.

[0099] The controller 2 can keep the second processing liquid nozzle N2 stationary while the second processing liquid L2 is at the center of rotation on the surface of the substrate W, and then perform the second processing liquid supply step S2. Alternatively, the controller 2 can perform the second processing liquid supply step S2 while moving the second processing liquid nozzle N2, scanning the contact position of the second processing liquid L2 between the center of rotation and the periphery of the substrate W surface. When the second processing liquid nozzle N2 is a spray nozzle, it is sometimes appropriate to keep the contact position stationary while performing the second processing liquid supply step S2. Conversely, when the second processing liquid nozzle N2 is a straight nozzle, it is sometimes appropriate to scan the contact position while performing the second processing liquid supply step S2.

[0100] After the second processing liquid supply step S2, the controller 2 stops the supply of the second processing liquid L2 from the second processing liquid nozzle N2 and moves the second processing liquid nozzle N2 to the standby position. Additionally, the controller 2 sets the rotation speed of the rotary chuck 5 to the mixing liquid processing speed (e.g., 0 rpm to 50 rpm). The mixing liquid processing speed is preferably lower than the second processing liquid supply speed, but can also be zero (i.e., rotation stops). By supplying the second processing liquid L2 onto the coating film F1 of the first processing liquid L1, they can be mixed to generate SPM. Therefore, the processing step utilizing SPM begins immediately after the supply of the second processing liquid L2, i.e., the mixing liquid processing step S3 begins (see reference). Figure 1C and Figure 1D Since the mixing of the high-viscosity first processing liquid L1 and the second processing liquid L2 continues on the surface of the substrate W even after the supply of the second processing liquid L2 is stopped, the mixing liquid processing step S3 continues even after the supply of the second processing liquid L2 is stopped.

[0101] After the supply of the second treatment liquid L2 is stopped, if a predetermined reaction time has elapsed, controller 2 executes the rinsing step S4 (refer to...). Figure 1E That is, controller 2 moves the rinsing fluid nozzle NR to the processing position. Then, controller 2 rotates the rotary chuck 5 at a specified rinsing speed (e.g., 300 rpm to 1000 rpm). In this state, controller 2 opens the rinsing fluid valve 44, discharging rinsing fluid R from the rinsing fluid nozzle NR to the substrate W. In this embodiment, the contact position of the rinsing fluid R on the surface of the substrate W is fixed at the center of the substrate W. However, a rinsing fluid nozzle NR in the form of a movable nozzle can also be used to move (scan) the contact position of the rinsing fluid R between the center and the periphery of the substrate W.

[0102] After a predetermined rinsing time, controller 2 stops the discharge of rinsing fluid R from rinsing fluid nozzle NR, thereby ending rinsing process S4 and moving rinsing fluid nozzle NR to standby position.

[0103] Then, controller 2 executes residue removal process S5 (refer to...) Figure 1F and Figure 1G That is, controller 2 moves the cleaning solution nozzle NC to the processing position. Then, controller 2 rotates the rotary chuck 5 at a specified cleaning solution processing speed (e.g., 500 rpm to 1500 rpm). In this state, controller 2 opens the cleaning solution valve 34 to discharge the cleaning solution C (e.g., a mixture of ammonia and hydrogen peroxide) to the substrate W, thereby executing the cleaning solution supply step S51 (see reference). Figure 1FThe contact position of the cleaning liquid C on the surface of the substrate W can be fixed at the center of the substrate W, or it can move (scan) between the center and the periphery of the substrate W. After the cleaning liquid C is supplied for a predetermined time, the controller 2 stops the discharge of the cleaning liquid C from the liquid nozzle NC and moves the liquid nozzle NC to the standby position.

[0104] Then, controller 2 executes the rinsing process S52 after cleaning fluid treatment (refer to...). Figure 1G This rinsing step S52 can be performed immediately after the mixing treatment step S3 (see reference). Figure 1E They are essentially the same.

[0105] After a predetermined rinsing time, controller 2 stops the discharge of rinsing liquid R from rinsing liquid nozzle NR, thus ending rinsing step S52. Then, controller 2 executes drying step S6 (rotary drying): the rotary chuck 5 is accelerated to a drying rotation speed (e.g., 2500 rpm to 4000 rpm), and the rinsing liquid R on the substrate W is spun dry (see reference). Figure 1H After the drying process S6 has been performed for the specified time, the controller 2 stops the rotation of the rotating chuck 5, thus ending the process.

[0106] The processed substrate W is received from the rotary chuck 5 and removed from the processing chamber 1 by a substrate transfer robot (not shown).

[0107] Figure 7 This is a diagram illustrating other configuration examples of the first processing liquid supply source 15.

[0108] The foregoing Figure 4 In the illustrated configuration of the first processing liquid supply source 15, the adjusted first processing liquid L1 can be supplied to the first processing liquid tank 16, or the first processing liquid L1 can be prepared within the first processing liquid tank 16. Specifically, the first processing liquid L1 prepared by mixing one of sulfuric acid or hydrogen peroxide water with a thickener is supplied to the first processing liquid tank 16, or such preparation is performed within the first processing liquid tank 16.

[0109] In contrast, Figure 7 In the example of the configuration of the first processing liquid supply source 15 shown, one of sulfuric acid or hydrogen peroxide water and a thickener are mixed midway through the first processing liquid piping 13.

[0110] Specifically, in the first treatment liquid piping 13, a first treatment liquid component distribution pipe 131, which supplies the first treatment liquid component L1a (either sulfuric acid or hydrogen peroxide water), is connected to a thickener piping 132, which supplies a liquid thickener. Therefore, the first treatment liquid component L1a and the thickener merge and mix at the first treatment liquid piping 13. To promote mixing, a pipe mixer 133 is provided within the first treatment liquid piping 13.

[0111] The pipeline mixer 133, for example, has a stirring element that agitates the fluid flowing through the first treatment fluid piping 13, thereby ensuring thorough mixing of the first treatment fluid component L1a with the thickener to aid in the generation of a high-viscosity first treatment fluid L1. Not only agitation-type pipeline mixers can be used, but also dispersion-type pipeline mixers can be used, which disperse and discharge fluid from mixing nozzles into the main flow path when the first treatment fluid component L1a and the thickener merge, thereby achieving dispersion mixing.

[0112] The first processing liquid supply source 15 in this configuration example is particularly suitable when the thickener is a liquid or emulsion. When the thickener is a solid (powder, etc.), Figure 4 The first processing liquid supply source 15 shown is more suitable.

[0113] As described above, according to this embodiment, a first processing liquid L1, which is a high-viscosity liquid with added thickener, is coated onto the entire surface (upper surface) of the substrate W. This suppresses the consumption of the first processing liquid L1 and ensures that the first processing liquid L1 is uniformly and tightly coated across the entire surface of the substrate W. By supplying a second processing liquid L2 to the surface of the substrate W coated with the first processing liquid L1, the first processing liquid L1 and the second processing liquid L2 are mixed on the substrate W to generate SPM. Since the first processing liquid L1 is uniformly and completely coated across the entire surface of the substrate W and tightly coated, the SPM can be uniformly and completely coated across the entire surface of the substrate W. Therefore, processing using SPM (the process of etching the resist) can be uniformly performed across the entire surface of the substrate W. Furthermore, since the first processing liquid L1 and the second processing liquid L2 are mixed on the substrate W, the heat of reaction during their mixing can be utilized, thereby enabling efficient processing. The process using SPM can be stopped by replacing SPM with rinsing fluid R supplied to the surface of substrate W.

[0114] Since the mixing of the first treatment solution L1 and the second treatment solution L2 proceeds rapidly as long as the second treatment solution L2 has a lower viscosity (e.g., lower than the viscosity of the first treatment solution L1), a mixture of them, i.e., SPM, can be generated quickly. As a result, more efficient processing can be performed.

[0115] Since the viscosity of the first processing solution L1 can be appropriately adjusted according to the thickener, an appropriate viscosity can be set considering factors such as the spreadability when coated on the surface of the substrate W, the retention of the coating film F1 on the surface of the substrate W, and the degree of mixing with the second processing solution L2. As a result, the consumption of the first processing solution L1 can be reduced and the substrate W can be treated uniformly.

[0116] In particular, by using a liquid containing hydrogen peroxide and a thickener as the first treatment solution L1 and a liquid containing sulfuric acid as the second treatment solution L2, the consumption of hydrogen peroxide can be reduced, and therefore it is preferred.

[0117] In the first processing liquid coating step S1, as long as a coating film F1 (e.g., a gel-like coating film) is formed on the surface of the substrate W, the first processing liquid L1 can reliably adhere to the entire area of ​​the surface of the substrate W. Accordingly, since the SPM generated by supplying the second processing liquid L2 can reliably adhere to the entire area of ​​the surface of the substrate W, efficient and uniform processing can be performed.

[0118] Preferably, the second processing liquid supply step S2 is performed while the supply of the first processing liquid L1 is stopped (new liquid supply). This reliably reduces the consumption of the first processing liquid L1. Furthermore, since the second processing liquid L2 can be supplied onto the coating film F1 of the first processing liquid L1, the flow of the second processing liquid L2 can prevent the first processing liquid L1 from being carried away from the substrate W.

[0119] Preferably, the supply of the second processing liquid L2 (the supply of new liquid) is stopped during at least a portion of the mixing liquid processing step S3. This further suppresses the consumption of the second processing liquid L2. That is, by performing a coating process in which the second processing liquid L2 is mixed on the coating film F1 of the first processing liquid L1, substrate processing using SPM as the mixture of the two liquids can be performed. At this time, since neither the first processing liquid L1 nor the second processing liquid L2 is supplied, the consumption of any processing liquid can be reduced.

[0120] Figure 8 This is a process diagram illustrating the substrate processing method according to the second embodiment of the present invention. In this embodiment, a pretreatment step S0 is performed before the first processing liquid coating step S1. Subsequent steps S1 to S6 are the same as those described in the first embodiment (see...). Figures 1A to 1H )same.

[0121] The pretreatment step S0 is a step in which a second treatment liquid (preferably a second treatment liquid L2 with a lower viscosity than the first treatment liquid L1) is supplied to the surface of the substrate W before the high-viscosity first treatment liquid L1 is coated onto the surface of the substrate W. In the pretreatment step S0, the substrate processing apparatus 100 can perform substantially the same operation as the second treatment liquid supply step S2.

[0122] In the pretreatment step S0, since there is no coating film F1 of the first processing liquid L1 on the substrate W, the second processing liquid L2 is supplied to the surface of the substrate W instead of to the coating film F1 of the first processing liquid L1. The controller 2 causes the rotary chuck 5 to rotate at the processing speed of the second processing liquid, and in this state, the second processing liquid L2 is discharged from the second processing liquid nozzle N2 to the surface of the substrate W.

[0123] After such a pretreatment step S0, the second processing liquid nozzle N2 is moved to a standby position, thereby performing the first processing liquid coating step S1. Since the first processing liquid L1 supplied to the surface of the substrate W comes into contact with the second processing liquid L2 already present on the substrate W, mixing of the first processing liquid L1 and the second processing liquid L2 occurs (SPM reaction). Therefore, the mixing liquid treatment step S3 can be started on the surface of the substrate W immediately after the supply of the first processing liquid L1.

[0124] By performing a pretreatment step S0 before the first treatment liquid coating step S1, the high-viscosity first treatment liquid L1 can be easily spread over the entire surface area of ​​the substrate W, and the mixed liquid treatment at the surface of the substrate W can be promoted, thus enabling more efficient resist stripping treatment.

[0125] The above description pertains to two embodiments of the present invention, but the present invention can be further implemented in other ways. For example, the foregoing embodiments mainly described the process of supplying room temperature hydrogen peroxide water and sulfuric acid at a higher temperature to the surface of substrate W. However, room temperature hydrogen peroxide water and room temperature sulfuric acid can also be supplied to the surface of substrate W. In this case, a high-temperature SPM can be generated on substrate W through the exothermic reaction when hydrogen peroxide water and sulfuric acid are mixed, thereby causing the resist on the surface of substrate W to be etched. To promote the reaction on substrate W, substrate W can be heated using a heater. The heater can be built into the rotating chuck 5, or other heat sources such as halogen heaters can be used.

[0126] Furthermore, the foregoing embodiments described a single-piece substrate processing method in which substrate W is held and processed one by one, but the present invention can also be applied to batch substrate processing method in which multiple substrates are processed together.

[0127] The embodiments of the present invention have been described in detail, but these are merely specific examples used to clarify the technical content of the present invention. The present invention should not be construed as being limited to these specific examples, and the scope of the present invention is defined only by the appended claims.

[0128] Explanation of reference numerals in the attached figures

[0129] S1 First Processing Solution Coating Process

[0130] S2 Second Processing Liquid Supply Process

[0131] S3 Mixture Processing Step

[0132] S4 rinsing process

[0133] S5 Residue Removal Process

[0134] S6 Drying process

[0135] W substrate

[0136] L1 First Treatment Solution

[0137] L2 Second Treatment Solution

[0138] R Rinse Fluid

[0139] C Cleaning solution

[0140] F1 First Treatment Solution Coating Film

[0141] N1 First Processing Fluid Nozzle

[0142] N2 Second Processing Fluid Nozzle

[0143] NR flushing fluid nozzle

[0144] NC liquid nozzle

[0145] 100 Substrate Processing Apparatus

[0146] 1 Processing chamber

[0147] 2 Controllers

[0148] 3 Standby tank

[0149] 5. Rotary chuck

[0150] 10 discharge outlets

[0151] 14 First processing fluid valve

[0152] 15. First-stage treatment fluid supply source

[0153] 24 Second processing fluid valve

[0154] 25 Second Processing Fluid Supply Source

[0155] 44. Flushing fluid valve

Claims

1. A substrate processing method comprising: a first treatment liquid supplying step of applying a first treatment liquid containing one of sulfuric acid and hydrogen peroxide water and a tackifier to a surface of a substrate, thereby forming an applied film covering an entire area of the surface of the substrate; a second treatment liquid supplying step of supplying a second treatment liquid containing the other of sulfuric acid and hydrogen peroxide water and having a lower viscosity than the first treatment liquid to a surface of the applied film of the first treatment liquid formed on the surface of the substrate; a mixed liquid processing step of processing an entire area of the surface of the substrate with a hydrogen peroxide water sulfuric acid mixed liquid generated by mixing the first treatment liquid and the second treatment liquid on the surface of the substrate; a rinsing step of supplying a rinsing liquid to the substrate after the mixed liquid processing step, thereby washing away the hydrogen peroxide water sulfuric acid mixed liquid from the surface of the substrate.

2. The substrate processing method according to claim 1, wherein the first treatment liquid contains hydrogen peroxide water and the tackifier, the second treatment liquid contains sulfuric acid. the tackifier contains at least one selected from the group consisting of polyvinylpyrrolidone, polyacrylic acid, sodium polyacrylate, ammonium polyacrylate, cross-linked polyacrylic acid, cross-linked sodium polyacrylate, cross-linked acrylic acid-based polymers, and carboxylic acid-based copolymers.

3. The substrate processing method as claimed in claim 1 or 2, wherein, the second treatment liquid does not contain a tackifier.

4. The substrate processing method as claimed in claim 1 or 2, wherein, in the second treatment liquid supplying step, the second treatment liquid is supplied to the surface of the applied film of the first treatment liquid, thereby forming a liquid film of the second treatment liquid on the applied film of the first treatment liquid.

5. The substrate processing method as claimed in claim 1 or 2, wherein, the second treatment liquid supplying step is started in a state where the supply of the first treatment liquid to the surface of the substrate is stopped.

6. The substrate processing method as claimed in claim 1 or 2, wherein, at least a part of the mixed liquid processing step overlaps at least a part of the second treatment liquid supplying step.

7. The substrate processing method as claimed in claim 1 or 2, wherein, in at least a part of the mixed liquid processing step, the supply of the second treatment liquid to the surface of the substrate is stopped.

8. The substrate processing method as claimed in claim 1 or 2, wherein, the first treatment liquid supplying step and the second treatment liquid supplying step are alternately repeatedly performed.

9. The substrate processing method as claimed in claim 1 or 2, wherein, 10. A substrate processing apparatus for implementing the substrate processing method according to claim 1 or 2, the substrate processing apparatus comprising: a substrate holding mechanism that holds a substrate; a first treatment liquid nozzle that supplies the first treatment liquid to a substrate held by the substrate holding mechanism; a second treatment liquid nozzle that supplies the second treatment liquid to a substrate held by the substrate holding mechanism; a rinsing liquid nozzle that supplies the rinsing liquid to a substrate held by the substrate holding mechanism; and a control unit that controls the supply of the first treatment liquid from the first treatment liquid nozzle to perform the first treatment liquid supplying step, controls the supply of the second treatment liquid from the second treatment liquid nozzle to perform the second treatment liquid supplying step, and controls the supply of the rinsing liquid from the rinsing liquid nozzle to perform the rinsing step. the substrate holding mechanism includes a rotary chuck that holds a surface of a substrate horizontally upward and rotates the surface, ​ 11. The substrate processing apparatus as recited in claim 10, wherein, ​ The control unit controls the supply of the first treatment liquid from the first treatment liquid nozzle and the rotation of the rotary chuck in the first treatment liquid supply step, thereby spin-coating the first treatment liquid on the surface of the substrate.

12. The substrate processing apparatus according to claim 10, further comprising: a nozzle moving unit that moves the first treatment liquid nozzle between a treatment position for supplying a treatment liquid to a substrate held by the substrate holding mechanism and a standby position that retreats from the treatment position; and a cleaning tank that dips the discharge port of the first treatment liquid nozzle in a nozzle cleaning liquid at the standby position.

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