SUBSTRATE PROCESSING METHOD AND SUBSTRATE PROCESSING APPARATUS

Abstract

To provide a technique capable of satisfactorily removing a zirconium oxide film used as a mask from a substrate.SOLUTION: A substrate processing method according to an embodiment of the present disclosure includes a preparation step, a mask removal step, and a drying step. In the preparation step, a zirconium oxide film as a mask is formed on a laminated film, and the substrate is prepared by dry etching into a given shape. In the mask removal step, after the preparation step, a mask removing liquid containing sulfuric acid as a main component is supplied to the substrate to remove the zirconium oxide film. In the drying step, the surface of the substrate that has been wetted with a rinsing liquid is dried after the mask removal step.SELECTED DRAWING: Figure 16

Description

[Technical field]

[0001] The disclosed embodiments relate to a substrate processing method and a substrate processing apparatus. [Background technology]

[0002] Conventionally, there is known a technique for etching a zirconium oxide (ZrO2) film, which is formed on a substrate such as a semiconductor wafer (hereinafter also referred to as a wafer) and is used as a gate oxide film, into a given pattern shape (see Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2005-79316 A Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a technique that can effectively remove a zirconium oxide film used as a mask from a substrate. [Means for solving the problem]

[0005] A substrate processing method according to one aspect of the present disclosure includes a preparation step, a mask removal step, and a drying step. In the preparation step, a substrate is prepared in which a zirconium oxide film is formed as a mask on a laminate film, and the zirconium oxide film is dry-etched into a given shape. In the mask removal step, after the preparation step, a mask removal solution containing sulfuric acid as a main component is supplied to the substrate to remove the zirconium oxide film. In the drying step, after the mask removal step, the surface of the substrate wetted with a rinse solution is dried. Effect of the Invention

[0006] According to the present disclosure, the zirconium oxide film used as a mask can be successfully removed from the substrate. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic diagram showing a schematic configuration of a substrate processing system according to an embodiment. [Diagram 2] FIG. 2 is a schematic diagram showing an example of a specific configuration of the processing unit according to the embodiment. [Diagram 3] FIG. 3 is a diagram illustrating an example of the configuration of a mixed liquid supply unit according to the embodiment. [Figure 4] FIG. 4 is a schematic diagram showing an example of a state of the wafer surface after the preparation process according to the embodiment. [Diagram 5] FIG. 5 is a schematic diagram showing a mask removal process according to the embodiment. [Figure 6] FIG. 6 is a schematic diagram showing an example of a state of the wafer surface after the mask removal process according to the embodiment. [Figure 7] FIG. 7 is a schematic diagram showing the pre-residue removal treatment according to the embodiment. [Figure 8] FIG. 8 is a schematic diagram showing an example of a state of a wafer surface after a pre-residue removal process according to the embodiment. [Figure 9] FIG. 9 is a schematic diagram showing the residue removal process according to the embodiment. [Figure 10] FIG. 10 is a schematic diagram showing an example of a state of the wafer surface after the residue removal process according to the embodiment. [Figure 11] FIG. 11 is a schematic diagram showing the rinsing process and the drying process according to the embodiment. [Figure 12] FIG. 12 is a schematic diagram illustrating an example of a specific configuration of a processing unit according to the first modification of the embodiment. [Figure 13] FIG. 13 is a schematic diagram showing a rinsing process and a drying process according to the first modification of the embodiment. [Figure 14] FIG. 14 is a schematic diagram showing an example of a specific configuration of the dry processing unit according to the second modification of the embodiment. [Figure 15] FIG. 15 is a cross-sectional view showing an example of the configuration of a nozzle according to the third modification of the embodiment. [Figure 16] FIG. 16 is a flowchart showing a procedure of substrate processing executed by the substrate processing system according to this embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Hereinafter, with reference to the attached drawings, an embodiment of the substrate processing method and substrate processing apparatus disclosed in the present application will be described in detail. Note that the present disclosure is not limited to the following embodiment. It should be noted that the drawings are schematic, and the dimensional relationship of each element, the ratio of each element, and the like may differ from reality. Furthermore, there may be parts in which the dimensional relationship and ratio differ between the drawings.

[0009] Conventionally, there is known a technique for etching a zirconium oxide (ZrO2) film, which is formed on a substrate such as a semiconductor wafer (hereinafter also referred to as a wafer) and is used as a gate oxide film, into a given pattern shape.

[0010] On the other hand, when a zirconium oxide film is used as a mask, it is necessary to ultimately remove it completely while minimizing the impact on other films. However, there has been little knowledge about processes for effectively removing the zirconium oxide film used as a mask.

[0011] Therefore, there is a need for a technology that overcomes the above-mentioned problems and enables the zirconium oxide film used as a mask to be effectively removed from a substrate.

[0012] <Outline of the substrate processing system> First, a schematic configuration of a substrate processing system 1 according to an embodiment will be described with reference to Fig. 1. Fig. 1 is a diagram showing a schematic configuration of the substrate processing system 1 according to an embodiment. The substrate processing system 1 is an example of a substrate processing apparatus. In the following, to clarify the positional relationship, an X-axis, a Y-axis, and a Z-axis that are orthogonal to each other are defined, and the positive direction of the Z-axis is defined as a vertically upward direction.

[0013] 1, the substrate processing system 1 includes a loading / unloading station 2 and a processing station 3. The loading / unloading station 2 and the processing station 3 are provided adjacent to each other.

[0014] The carry-in / out station 2 includes a carrier placement section 11 and a transport section 12. On the carrier placement section 11, a plurality of carriers C are placed, each of which accommodates a plurality of substrates, in this embodiment, semiconductor wafers W (hereinafter referred to as wafers W), in a horizontal state.

[0015] The transfer section 12 is provided adjacent to the carrier placement section 11, and includes therein a substrate transfer device 13 and a transfer section 14. The substrate transfer device 13 includes a wafer holding mechanism that holds the wafer W. The substrate transfer device 13 is capable of moving in the horizontal and vertical directions and rotating about a vertical axis, and transfers the wafer W between the carrier C and the transfer section 14 using the wafer holding mechanism.

[0016] The processing station 3 is provided adjacent to the transport section 12. The processing station 3 includes a transport section 15 and a plurality of processing units 16. The plurality of processing units 16 are provided side by side on both sides of the transport section 15.

[0017] The transfer section 15 includes a substrate transfer device 17 therein. The substrate transfer device 17 includes a wafer holding mechanism that holds the wafer W. The substrate transfer device 17 is capable of moving in the horizontal and vertical directions and rotating about a vertical axis, and transfers the wafer W between the delivery section 14 and the processing unit 16 using the wafer holding mechanism.

[0018] The processing unit 16 performs a predetermined substrate processing on the wafer W transferred by the substrate transfer device 17 .

[0019] The substrate processing system 1 also includes a control device 4. The control device 4 is, for example, a computer, and includes a control unit 18 and a storage unit 19. The storage unit 19 stores programs for controlling various processes executed in the substrate processing system 1. The control unit 18 controls the operation of the substrate processing system 1 by reading out and executing the programs stored in the storage unit 19.

[0020] Such a program may be recorded in a computer-readable storage medium and installed from that storage medium into the storage unit 19 of the control device 4. Examples of computer-readable storage media include a hard disk (HD), a flexible disk (FD), a compact disk (CD), a magnet optical disk (MO), and a memory card.

[0021] In the substrate processing system 1 configured as described above, first, the substrate transfer device 13 in the loading / unloading station 2 takes out the wafer W from the carrier C placed on the carrier placement part 11, and places the taken-out wafer W on the transfer part 14. The wafer W placed on the transfer part 14 is taken out of the transfer part 14 by the substrate transfer device 17 in the processing station 3, and is carried into the processing unit 16.

[0022] The wafer W carried into the processing unit 16 is processed by the processing unit 16, and then carried out of the processing unit 16 by the substrate transfer device 17 and placed on the delivery section 14. Then, the processed wafer W placed on the delivery section 14 is returned to the carrier C of the carrier placement section 11 by the substrate transfer device 13.

[0023] <Processing unit configuration> Next, the configuration of the processing unit 16 will be described with reference to Fig. 2. Fig. 2 is a schematic diagram showing an example of a specific configuration of the processing unit 16. As shown in Fig. 2, the processing unit 16 includes a chamber 20, a substrate processing section 30, a liquid supply section 40, and a collection cup 50.

[0024] The chamber 20 accommodates a substrate processing unit 30, a liquid supply unit 40, and a collection cup 50. An FFU (Fan Filter Unit) 21 is provided on the ceiling of the chamber 20. The FFU 21 forms a downflow within the chamber 20.

[0025] Substrate processing unit 30 includes a holder 31, a support 32, and a drive unit 33, and performs liquid processing on a placed wafer W. Holder 31 holds wafer W horizontally. Support 32 is a member extending in the vertical direction, with a base end rotatably supported by drive unit 33 and a tip end supporting holder 31 horizontally. Drive unit 33 rotates support 32 about a vertical axis.

[0026] In the substrate processing unit 30, the supporting column 32 is rotated using the driving unit 33, thereby rotating the holding unit 31 supported by the supporting column 32, and thereby rotating the wafer W held by the holding unit 31.

[0027] A holding member 31a for holding the wafer W from the side is provided on the upper surface of the holding part 31 included in the substrate processing unit 30. The wafer W is held horizontally by the holding member 31a while being slightly spaced from the upper surface of the holding part 31. The wafer W is held by the holding part 31 with the surface on which the substrate processing is performed facing upward.

[0028] The liquid supply unit 40 supplies a processing fluid to the wafer W. The liquid supply unit 40 includes a plurality of (three in this example) nozzles 41a to 41c, an arm 42a that horizontally supports the nozzles 41a to 41c, and a swivel and lift mechanism 43a that rotates and raises and lowers the arm 42a. The liquid supply unit 40 further includes a nozzle 41d, an arm 42b that horizontally supports the nozzle 41d, and a swivel and lift mechanism 43b that rotates and raises and lowers the arm 42b.

[0029] The nozzle 41a is connected to a mixed liquid supply unit 60 via a valve 44a and a flow rate regulator 45a. The mixed liquid supply unit 60 will be described in detail later.

[0030] The nozzle 41b is connected to a DIW supply source 46b via a valve 44b, a flow rate regulator 45b, and a heater 47. The DIW supply source 46b is, for example, a tank that stores DIW (DeIonized Water). The DIW is an example of pure water. The heater 47 heats the DIW supplied to the nozzle 41b based on a command from the control unit 18.

[0031] The nozzle 41c is connected to a DHF supply source 46c via a valve 44c and a flow rate regulator 45c. The DHF supply source 46c is, for example, a tank that stores DHF (dilute hydrofluoric acid). Such DHF is an example of an aqueous solution containing a fluoride compound.

[0032] The nozzle 41d is connected to an IPA supply source 46d via a valve 44d and a flow rate regulator 45d. The IPA supply source 46d is, for example, a tank that stores IPA (isopropyl alcohol). Such IPA is an example of a water-soluble alcohol and also an example of an organic solvent.

[0033] From the nozzle 41a, the mask removing liquid L1 (see FIG. 5) supplied from the mixed liquid supply unit 60 is discharged. The details of the mask removing liquid L1 will be described later. From the nozzle 41b, DIW supplied from the DIW supply source 46b or HDIW (Hot DIW) obtained by heating DIW to a given temperature by the heater 47 is discharged.

[0034] DHF supplied from a DHF supply source 46c is discharged from the nozzle 41c, and IPA supplied from an IPA supply source 46d is discharged from the nozzle 41d.

[0035] Collection cup 50 is disposed to surround holding part 31, and collects the processing liquid scattered from wafer W due to rotation of holding part 31. A drainage port 51 is formed in the bottom of collection cup 50, and the processing liquid collected by collection cup 50 is discharged from drainage port 51 to the outside of processing unit 16. In addition, an exhaust port 52 is formed in the bottom of collection cup 50, which discharges gas supplied from FFU 21 to the outside of processing unit 16.

[0036] <Configuration of mixed liquid supply unit> Next, the configuration of the mixed liquid supply unit 60 included in the substrate processing system 1 will be described with reference to Fig. 3. Fig. 3 is a diagram showing an example of the configuration of the mixed liquid supply unit 60 according to an embodiment. Each part of the mixed liquid supply unit 60 described below can be controlled by the control unit 18.

[0037] As shown in FIG. 3, the mixed liquid supply unit 60 according to the embodiment includes a sulfuric acid supply unit 100, a pure water supply unit 120, and a mixer 140.

[0038] The sulfuric acid supply unit 100 supplies sulfuric acid to the mixing unit 140. The sulfuric acid is, for example, concentrated sulfuric acid. The sulfuric acid supply unit 100 includes a sulfuric acid supply source 101a, a valve 101b, a flow rate regulator 101c, a tank 102, a circulation line 103, and a sulfuric acid supply line 110.

[0039] The sulfuric acid supply source 101a is connected to the tank 102 via the valve 101b and the flow rate regulator 101c. This allows the sulfuric acid supply source 101a to supply sulfuric acid to the tank 102 via the valve 101b and the flow rate regulator 101c, and store the sulfuric acid in the tank 102.

[0040] The circulation line 103 is a circulation line that exits from the tank 102 and returns to the tank 102. In the circulation line 103, a pump 104, a filter 105, a flow rate regulator 106, a heater 107, a thermocouple 108, and a switching unit 109 are provided in this order from the upstream side with respect to the tank 102.

[0041] A pump 104 forms a circulation flow of sulfuric acid that leaves the tank 102, passes through a circulation line 103, and returns to the tank 102. A filter 105 removes contaminants such as particles contained in the sulfuric acid circulating in the circulation line 103. A flow regulator 106 regulates the flow rate of the circulation flow of sulfuric acid through the circulation line 103.

[0042] The heater 107 heats the sulfuric acid circulating in the circulation line 103. The thermocouple 108 measures the temperature of the sulfuric acid circulating in the circulation line 103. Therefore, the control unit 18 can control the temperature of the sulfuric acid circulating in the circulation line 103 by using the heater 107 and the thermocouple 108.

[0043] The switching unit 109 is connected to the mixing unit 140 of the mixed liquid supply unit 60 via a sulfuric acid supply line 110 , and can switch the direction of the sulfuric acid circulating in the circulation line 103 between the tank 102 and the mixing unit 140 .

[0044] In the sulfuric acid supply line 110, a flow meter 111, an electric needle valve 112, a valve 113, and a branching portion 114 are provided in this order from the upstream side with respect to the switching portion 109.

[0045] The flow meter 111 measures the flow rate of the sulfuric acid flowing through the sulfuric acid supply line 110. The needle valve 112 adjusts the flow rate of the sulfuric acid flowing through the sulfuric acid supply line 110. The branch portion 114 is connected via a valve 115 to a drain portion DR.

[0046] The control unit 18 then performs feedback control of the needle valve 112 using the value measured by the flow meter 111, thereby making it possible to supply sulfuric acid to the mixing unit 140 at a highly accurate flow rate.

[0047] Further, a pure water supply source 116a, a valve 116b, a flow rate regulator 116c, and a valve 116d are provided in the tank 102. The tank 102 is connected to a drain section DR via the valve 116d, and the pure water supply source 116a is connected between the tank 102 and the valve 116d via the valve 116b and the flow rate regulator 116c.

[0048] As a result, when replacing the sulfuric acid in the tank 102, the control unit 18 can control the valve 116b, the flow regulator 116c, and the valve 116d to dilute the concentrated sulfuric acid in the tank 102 to a given concentration before discharging it into the drain unit DR.

[0049] The pure water supply unit 120 supplies DIW to the mixer 140. The pure water supply unit 120 includes a pure water supply source 121a, a valve 121b, a flow rate regulator 121c, a tank 122, and a pure water supply line 123.

[0050] The pure water supply source 121a is connected to the tank 122 via the valve 121b and the flow rate regulator 121c. This allows the pure water supply source 121a to supply pure water to the tank 122 via the valve 121b and the flow rate regulator 121c, and store the pure water in the tank 122.

[0051] The pure water supply line 123 is provided with a valve 124, a flow meter 125, an electric needle valve 126, a valve 127, and a branching portion 128 in this order from the upstream side with respect to the tank 122.

[0052] The flow meter 125 measures the flow rate of the pure water flowing through the pure water supply line 123. The needle valve 126 adjusts the flow rate of the pure water flowing through the pure water supply line 123. The branch portion 128 is connected via a valve 129 to a drain portion DR.

[0053] The control unit 18 then performs feedback control of the needle valve 126 using the value measured by the flow meter 125, thereby making it possible to supply the pure water to the mixer 140 at a highly accurate flow rate.

[0054] In addition, the tank 122 is connected to the drain section DR via a valve 130. This allows the control section 18 to control the valve 130 to discharge the pure water in the tank 122 to the drain section DR, for example, when replacing the pure water in the tank 122.

[0055] The mixer 140 mixes the sulfuric acid supplied from the sulfuric acid supply unit 100 and the pure water supplied from the pure water supply unit 120 to generate a mask removing liquid L1 (see FIG. 5). In the embodiment, the mixer 140 is provided at a location where the sulfuric acid supply line 110 and the pure water supply line 123 join together.

[0056] The mixer 140 is connected to the processing unit 16 via a mixed liquid supply line 160. The mixed liquid supply line 160 is provided with the above-mentioned valve 44a and flow rate regulator 45a. This allows the mixed liquid supply unit 60 to supply the mask removal liquid L1 having a mixture ratio set by the user to the processing unit 16.

[0057] As described above, the sulfuric acid supplying part 100 is provided with the heater 107, and the temperature of the mask removing solution L1 is increased by the reaction between the sulfuric acid and the pure water in the mixing part 140. As a result, the mixed solution supplying part 60 of the embodiment can heat the mask removing solution L1 to a desired temperature and supply it to the processing unit 16.

[0058] For example, the mixed solution supplying unit 60 uses the heater 107 of the sulfuric acid supplying unit 100 to increase the temperature of the concentrated sulfuric acid to about 120° C. Then, the mixed solution supplying unit 60 heats the mask removing solution L1 to about 150° C. by the heat of reaction generated when the sulfuric acid and the DIW are mixed in the mixing unit 140.

[0059] Although not shown in FIG. 3, the circulation line 103 and the like may be provided with a separate valve or the like.

[0060] <Substrate processing details> Next, details of the substrate processing of the wafer W in the processing unit 16 will be described with reference to Fig. 4 to Fig. 11. In the substrate processing according to the embodiment, first, a wafer W having a surface structure as shown in Fig. 4 is prepared. Fig. 4 is a schematic diagram showing an example of a state of the surface of the wafer W after the preparation processing according to the embodiment.

[0061] 4, a multilayer film ML and a mask M are formed on the surface of a wafer W. The multilayer film ML is formed on the surface of a base layer F0. The base layer F0 is made of, for example, silicon oxide (SiO2).

[0062] The multilayer film ML includes, for example, a first layer F1, a second layer F2, and a third layer F3, which are arranged in this order from the surface of the underlayer F0. The first layer F1 is made of, for example, polysilicon. The second layer F2 is made of, for example, tungsten. The third layer F3 is made of, for example, silicon nitride (SiN).

[0063] The mask M is formed on the surface of the multilayer film ML (specifically, on the surface of the third layer F3). The mask M is made of zirconium oxide. That is, the mask M is a zirconium oxide film.

[0064] The mask M according to the embodiment is formed, for example, by applying a raw material liquid containing zirconium oxide to the surface of the wafer W and then annealing the wafer W at a given temperature (for example, about 450° C.).

[0065] 4, the multilayer film ML and the mask M are dry etched into a given shape with a high aspect ratio so that a part of the surface of the underlayer F0 is exposed. In the present disclosure, the configurations of the underlayer F0 and the multilayer film ML are not limited to the example in FIG.

[0066] Next, the wafer W having the surface structure described above is loaded into the chamber 20 of the processing unit 16 by the substrate transfer device 17. The wafer W is then held by the holding member 31a of the substrate processing unit 30 with the surface to be processed facing upward. Thereafter, the control unit 18 (see FIG. 1) controls the driving unit 33 to rotate the holding member 31a together with the wafer W at a given rotation speed.

[0067] Then, in the processing unit 16, a mask removal process is performed using a mask removing liquid L1, as shown in Fig. 5. Fig. 5 is a schematic diagram showing the mask removal process according to the embodiment. In the mask removal process, the control unit 18 moves the nozzle 41a of the liquid supply unit 40 (see Fig. 2) to above the center of the wafer W.

[0068] Thereafter, the control unit 18 opens the valve 44a for a given time to supply the mask removing solution L1 containing concentrated sulfuric acid to the surface of the wafer W. This allows the control unit 18 to etch only the mask M among the multiple films formed on the surface of the wafer W with high selectivity.

[0069] Therefore, according to the embodiment, the zirconium oxide film used as the mask M can be removed from the wafer W satisfactorily.

[0070] The mask removing solution L1 according to the embodiment may be, for example, a mixture of concentrated sulfuric acid (for example, a concentration of 96%) and pure water in a ratio of 4:1 to 1:0. This allows only the mask M, out of the multiple films formed on the surface of the wafer W, to be etched with even higher selectivity.

[0071] Therefore, according to the embodiment, the zirconium oxide film used as the mask M can be removed from the wafer W more satisfactorily.

[0072] In the mask removal process according to the embodiment, the mask removal solution L1 may be heated by the heat of reaction generated when sulfuric acid and DIW are mixed together, so that the mask removal process can be performed at a higher temperature, and therefore only the mask M among the multiple films formed on the surface of the wafer W can be etched with higher selectivity.

[0073] Therefore, according to the embodiment, the zirconium oxide film used as the mask M can be removed from the wafer W more satisfactorily.

[0074] In the embodiment, the mask M may be made of a zirconium oxide film formed by a wet method, not a vapor phase synthesis method. This allows the mask M to be removed more effectively by the mask remover L1, which is a mixture of sulfuric acid and pure water, than a zirconium film formed by a vapor phase synthesis method.

[0075] Therefore, according to the embodiment, the zirconium oxide film used as the mask M can be removed from the wafer W more satisfactorily.

[0076] Furthermore, in the embodiment, the mask M can be removed by a wet process using the mask removal liquid L1 rather than a dry process, and therefore the film quality of the multilayer film ML can be maintained in a good condition compared to the case where the mask M is removed by a dry process.

[0077] For example, when the mask M is removed by a dry process, the dry process may affect not only the mask M but also the multilayer film ML, causing problems such as rounding of corners of the third layer F3 adjacent to the mask M. However, in the embodiment, the mask M can be removed by wet etching using the mask removing liquid L1, so that such problems can be prevented.

[0078] 6 is a schematic diagram showing an example of a state of the surface of the wafer W after the mask removal process according to the embodiment. As shown in FIG. 6, in the embodiment, after the mask removal process, the mask M is satisfactorily removed from the surface of the wafer W, but residues R1 and R2 may remain.

[0079] The residue R1 is a residue resulting from the zirconium oxide film that is the mask M (see FIG. 4). Specifically, the residue R1 includes silicide that is formed at the interface between the third layer F3 and the mask M when a raw material liquid containing zirconium oxide is applied to the surface of the wafer W and then annealed to form the mask M.

[0080] The residue R2 is a residue resulting from the mask removing liquid L1. Specifically, the residue R2 is a particle containing a sulfur (S) component contained in the mask removing liquid L1.

[0081] Therefore, in the embodiment, a pre-residue removal process and a residue removal process are performed to remove the residues R1 and R2 from the wafer W. The pre-residue removal process is an example of another residue removal process. Fig. 7 is a schematic diagram showing the pre-residue removal process according to the embodiment, and Fig. 8 is a schematic diagram showing an example of the state of the wafer W surface after the pre-residue removal process according to the embodiment.

[0082] 7, in the pre-residue removal process, the control unit 18 (see FIG. 1) moves the nozzle 41b of the liquid supply unit 40 (see FIG. 2) to above the center of the wafer W. Thereafter, the control unit 18 opens the valve 44b for a given time, thereby supplying HDIW heated to a given temperature to the surface of the wafer W.

[0083] Furthermore, the control unit 18 stops the operation of the heater 47 (see FIG. 2) to supply DIW that is not heated (for example, at room temperature) to the surface of the wafer W. This allows the control unit 18 to remove a large amount of residue R2 from the surface of the wafer W, as shown in FIG.

[0084] Since the multilayer film ML is not etched by HDIW and DIW, the pre-residue removal process according to the embodiment does not affect the film quality of the multilayer film ML.

[0085] Following this pre-residue removal process, in the embodiment, a residue removal process is performed. Fig. 9 is a schematic diagram showing the residue removal process according to the embodiment, and Fig. 10 is a schematic diagram showing an example of a state of the surface of the wafer W after the residue removal process according to the embodiment.

[0086] 9, in the residue removal process, the control unit 18 (see FIG. 1) moves the nozzle 41c of the liquid supply unit 40 (see FIG. 2) to above the center of the wafer W. Thereafter, the control unit 18 opens the valve 44c for a given time period to supply DHF to the surface of the wafer W. This allows the control unit 18 to satisfactorily remove the residues R1 and R2 from the surface of the wafer W, as shown in FIG.

[0087] The DHF used in the residue removal process has a certain degree of etching performance not only for the residue R1 containing silicide, but also for the multilayer film ML. However, in the embodiment, the zirconium oxide film other than the silicide film is removed by the mask removal process, so the time for the residue removal process itself can be shortened. Therefore, according to the embodiment, the film quality of the multilayer film ML can be maintained good even after the residues R1 and R2 are removed.

[0088] In addition, in the embodiment, a pre-residue removal process is performed before the residue removal process, so that a large amount of the residue R2 can be removed before the residue removal process. This can further shorten the time for the residue removal process itself. Therefore, according to the embodiment, even after the residues R1 and R2 are removed, the film quality of the multilayer film ML can be maintained even better.

[0089] In the above example, the residue removal process is performed using DHF, but the processing liquid used in the residue removal process is not limited to DHF, and various aqueous solutions containing fluoride compounds may be used. In the above example, the residue removal process may be performed using an aqueous solution containing a given ratio of ammonia (i.e., ammonia water). These methods can also effectively remove the residues R1 and R2.

[0090] Following the residue removal process, a rinsing process and a drying process are performed in this embodiment. Fig. 11 is a schematic diagram showing the rinsing process and the drying process according to this embodiment.

[0091] 11(a), in the rinsing process, the control unit 18 (see FIG. 1) moves the nozzle 41c of the liquid supply unit 40 (see FIG. 2) to above the center of the wafer W. Thereafter, the control unit 18 opens the valve 44c for a given time period to supply DIW to the surface of the wafer W.

[0092] As a result, the DHF supplied in the previous residue removal process is removed from the surface of the wafer W, and a layer of DIW (a so-called puddle) is formed on the surface of the wafer W, as shown in FIG. 11(a).

[0093] In the drying process performed following the rinsing process, first, as shown in (b) of Fig. 11, the control unit 18 moves the nozzle 41d of the liquid supply unit 40 to above the center of the wafer W. Thereafter, the control unit 18 opens the valve 44d for a given time to supply IPA to the surface of the wafer W. As a result, the paddle of DIW on the surface of the wafer W is replaced with a paddle of IPA, as shown in (b) of Fig. 11.

[0094] Then, in the embodiment, the control unit 18 increases the rotation speed of the wafer W on which the puddle of IPA is formed, to shake off the puddle of IPA from the surface of the wafer W. This completes the drying process of the wafer W.

[0095] Thus, in an embodiment, after the residue removal process, while the surface of the wafer W that has been subjected to the rinsing process is still wet, the DIW paddle is replaced with an IPA paddle on the surface of the wafer W, and then the shake-off process is performed.

[0096] This makes it possible to prevent the pattern of the multilayer film ML formed on the wafer W with a high aspect ratio from collapsing due to the surface tension of the DIW during drying. Therefore, according to the embodiment, the yield of the wafer W can be improved.

[0097] In the above example, the DIW paddle is replaced with the IPA paddle, but the processing liquid used in the replacement process is not limited to IPA, and various water-soluble alcohols may be used. This also makes it possible to prevent the pattern of the multilayer film ML formed on the wafer W with a high aspect ratio from collapsing due to the surface tension of the DIW during drying.

[0098] In the embodiment, the removal process of the mask M may be performed by a single wafer processing device such as the processing unit 16. This allows the mask M to be removed more evenly from the entire surface of the wafer W, as compared to a batch process in which a plurality of wafers W are processed at once.

[0099] <Variation 1> Next, various modified examples of the substrate processing according to the embodiment will be described with reference to Fig. 12 to Fig. 15. Fig. 12 is a schematic diagram showing an example of a specific configuration of a processing unit 16 according to Modification 1 of the embodiment.

[0100] 12, the processing unit 16 according to the first modification is different from the above-described embodiment (see FIG. 2) in that a nozzle 41e is added to an arm 42b. Specifically, the nozzle 41e is connected to a water repellent supply source 46e via a valve 44e and a flow rate regulator 45e.

[0101] The water repellent agent supply source 46e is, for example, a tank that stores the water repellent agent L2 (see FIG. 13). The water repellent agent L2 supplied from the water repellent agent supply source 46e is discharged from the nozzle 41e.

[0102] Here, the water repellent agent L2 is, for example, a water repellent agent diluted with thinner to a predetermined concentration for making the surface of the wafer W water repellent. As the raw material water repellent agent, for example, a silylation agent (or a silane coupling agent) can be used.

[0103] Specifically, for example, TMSDMA (trimethylsilyldimethylamine), DMSDMA (dimethylsilyldimethylamine), TMSDEA (trimethylsilyldiethylamine), HMDS (hexamethyldiphenylamine), etc. can be used as the raw water repellent agent.

[0104] As the thinner, an ether solvent, an organic solvent belonging to ketone, etc., can be used. Specifically, for example, PGMEA (propylene glycol monomethyl ether acetate), cyclohexanone, HFE (hydrofluoroether), etc. can be used as the thinner.

[0105] The processing unit 16 according to the first modified example is similar to the above embodiment except for the above points, and therefore a description of the other parts will be omitted.

[0106] 13 is a schematic diagram showing a rinsing process and a drying process according to Modification 1 of the embodiment. In the substrate processing according to Modification 1, the preparation process, the mask removal process, the pre-residue removal process, and the residue removal process are similar to those in the above embodiment, and therefore detailed descriptions thereof will be omitted.

[0107] 13(a), in the rinsing process, the control unit 18 (see FIG. 1) moves the nozzle 41c of the liquid supply unit 40 (see FIG. 2) to above the center of the wafer W. Thereafter, the control unit 18 opens the valve 44c for a given time period to supply DIW to the surface of the wafer W.

[0108] As a result, the DHF supplied in the previous residue removal process is removed from the surface of the wafer W, and a puddle of DIW is formed on the surface of the wafer W, as shown in FIG. 13(a).

[0109] In the drying process performed following the rinsing process, first, as shown in (b) of Fig. 13, the control unit 18 moves the nozzle 41d of the liquid supply unit 40 to above the center of the wafer W. Thereafter, the control unit 18 opens the valve 44d for a given time to supply IPA to the surface of the wafer W. As a result, the paddle of DIW on the surface of the wafer W is replaced with a paddle of IPA, as shown in (b) of Fig. 13.

[0110] 13(c), the control unit 18 moves the nozzle 41e of the liquid supply unit 40 to above the center of the wafer W. Thereafter, the control unit 18 opens the valve 44e for a given time to supply the water repellent agent L2 to the surface of the wafer W. As a result, as shown in FIG. 13(c), the puddle of IPA on the surface of the wafer W is replaced with a puddle of the water repellent agent L2, and the surface of the wafer W is made water repellent.

[0111] 13(d), the control unit 18 moves the nozzle 41d of the liquid supply unit 40 to above the center of the wafer W. Thereafter, the control unit 18 opens the valve 44d for a given time to supply IPA to the surface of the wafer W. As a result, the paddle of the water repellent agent L2 on the surface of the wafer W is replaced with a paddle of IPA, as shown in FIG.

[0112] Then, in the first modification, the control unit 18 increases the rotation speed of the wafer W on which the puddle of IPA is formed, so as to shake off the puddle of IPA from the surface of the wafer W. This completes the drying process of the wafer W.

[0113] In this manner, in variant example 1, after the residue removal process, while the surface of the wafer W that has been subjected to the rinsing process is still wet, the surface of the wafer W is made water-repellent with a water-repellent agent L2 and then replaced with a paddle of IPA, after which a shake-off process is performed.

[0114] This effectively prevents the pattern of the multilayer film ML formed on the wafer W with a high aspect ratio from collapsing due to the surface tension of the DIW during drying. Therefore, according to the first modification, the yield of the wafer W can be further improved.

[0115] <Variation 2> Modification 2 differs from the above-described embodiment in that a drying processing unit 70 that performs drying processing on a wafer W is provided in addition to the processing units 16 in the substrate processing system 1. Fig. 14 is a schematic diagram showing an example of a specific configuration of the drying processing unit 70 according to Modification 2 of the embodiment.

[0116] 14, the dry processing unit 70 has a main body 201, a holding plate 202, and a lid member 203. The housing-like main body 201 has an opening 204 for loading and unloading a wafer W. The holding plate 202 holds the wafer W to be processed in a horizontal direction. The lid member 203 supports the holding plate 202 and seals the opening 204 when the wafer W is loaded into the main body 201.

[0117] The main body 201 is a container having a processing space formed therein capable of accommodating one wafer W, and has a wall provided with supply ports 205, 206 and a discharge port 207. The supply ports 205, 206 and the discharge port 207 are connected to a supply flow path and a discharge flow path, respectively, for circulating a supercritical fluid to the drying processing unit 70.

[0118] Supply port 205 is connected to the side surface of housing-like main body 201 opposite to opening 204. Supply port 206 is connected to the bottom surface of main body 201. Discharge port 207 is connected to the lower side of opening 204. Note that, although two supply ports 205, 206 and one discharge port 207 are illustrated in Fig. 14, the numbers of supply ports 205, 206 and discharge ports 207 are not particularly limited.

[0119] Further, inside the main body 201, fluid supply headers 208, 209 and a fluid discharge header 210 are provided. The fluid supply headers 208, 209 are formed with a plurality of supply ports aligned in the longitudinal direction of the fluid supply headers 208, 209, and the fluid discharge header 210 is formed with a plurality of discharge ports aligned in the longitudinal direction of the fluid discharge header 210.

[0120] The fluid supply header 208 is connected to the supply port 205, and is provided adjacent to the side surface opposite the opening 204 inside the housing-like main body 201. In addition, a plurality of supply ports formed in line in the fluid supply header 208 face the opening 204 side.

[0121] The fluid supply header 209 is connected to the supply port 206, and is provided at the center of the bottom surface inside the housing-like main body 201. Furthermore, a plurality of supply ports formed side by side in the fluid supply header 209 face upward.

[0122] Fluid discharge header 210 is connected to discharge port 207, and is provided inside housing-like main body 201 adjacent to the side surface on the opening 204 side and below opening 204. In addition, a plurality of discharge ports formed next to fluid discharge header 210 face upward.

[0123] The fluid supply headers 208 and 209 supply the supercritical fluid into the main body 201. The fluid discharge header 210 guides the supercritical fluid in the main body 201 to the outside of the main body 201 and discharges it. The supercritical fluid discharged to the outside of the main body 201 via the fluid discharge header 210 contains IPA liquid that has been dissolved in the supercritical fluid in a supercritical state from the surface of the wafer W.

[0124] In the drying process according to the second modification, first, as shown in (b) of FIG. 11, the control unit 18 (see FIG. 1) moves the nozzle 41d of the liquid supply unit 40 (see FIG. 2) to above the center of the wafer W. Thereafter, the control unit 18 opens the valve 44d for a given time to supply IPA to the front surface of the wafer W. As a result, the paddle of DIW on the front surface of the wafer W is replaced with a paddle of IPA, as shown in (b) of FIG.

[0125] Next, the control unit 18 transports the wafer W on which the IPA paddle is formed from the processing unit 16 to the drying processing unit 70 using the substrate transport device 17. Then, the control unit 18 controls the drying processing unit 70 to perform a supercritical drying process on the wafer W on which the IPA paddle is formed.

[0126] Specifically, the dry processing unit 70 brings the wafer W on which the IPA puddles are formed into contact with a processing fluid (e.g., CO2) in a supercritical state. Then, the IPA liquid between the patterns formed on the wafer W comes into contact with the supercritical fluid in a high pressure state (e.g., 16 MPa) and gradually dissolves into the supercritical fluid, and the spaces between the patterns are gradually replaced by the supercritical fluid. Finally, the spaces between the patterns are filled only with the supercritical fluid.

[0127] Furthermore, after the IPA liquid is removed from between the patterns, the pressure inside the main body 201 is reduced from a high pressure state to atmospheric pressure, causing the processing fluid CO2 to change from a supercritical state to a gaseous state, and the spaces between the patterns are occupied only by gas. In this way, the IPA liquid between the patterns is removed, and the drying process of the wafer W is completed.

[0128] As described above, in the second modification, after the residue removal process, the surface of the wafer W that has been subjected to the rinsing process is replaced with a puddle of IPA, and the surface of the wafer W is further dried using the processing fluid in a supercritical state.

[0129] This effectively prevents the pattern of the multilayer film ML formed on the wafer W with a high aspect ratio from collapsing due to the surface tension of the DIW during drying. Therefore, according to the second modification, the yield of the wafer W can be further improved.

[0130] <Variation 3> In this modified example 3, the configuration of a nozzle 41a that discharges the mask removing liquid L1 onto the wafer W is different from that of the above embodiment. Fig. 15 is a cross-sectional view showing an example of the configuration of a nozzle 41a according to modified example 3 of the embodiment.

[0131] The nozzle 41a according to the third modification is, for example, a bar nozzle. As shown in Fig. 15, one sulfuric acid supply passage 301 and two water vapor supply passages 302 are inserted into the nozzle 41a and aligned along the longitudinal direction of the nozzle 41a.

[0132] Sulfuric acid heated to a given temperature (e.g., 120° C.) is supplied from a sulfuric acid supply source (not shown) via a valve (not shown) and a flow rate regulator (not shown) to the sulfuric acid supply path 301. Water vapor is supplied from a water vapor generator (not shown) to the water vapor supply path 302 via a valve (not shown) and a flow rate regulator (not shown).

[0133] Furthermore, a discharge passage 304 is connected between a discharge port 303 formed in the lower surface of the nozzle 41 a and the sulfuric acid supply passage 301 , and a discharge passage 305 is connected between the discharge port 303 and the water vapor supply passage 302 .

[0134] That is, sulfuric acid is supplied to the outlet 303 of the nozzle 41 a through an outlet passage 304 , and water vapor V is supplied to the outlet passage 305 .

[0135] In the nozzle 41a according to the third modification, the sulfuric acid and the water vapor V are mixed at the discharge port 303 to generate the mask removing liquid L1. That is, in the present disclosure, the mask removing liquid L1 is generated by mixing the sulfuric acid and the water vapor V after they are discharged from the nozzle 41a and before they reach the wafer W. Note that a plurality of discharge ports 303 are arranged in a line along the longitudinal direction of the nozzle 41a.

[0136] As a result, the nozzle 41a according to the third modification can discharge the mask removing liquid L1, which is generated by mixing the sulfuric acid and the water vapor V, onto the wafer W from the multiple discharge ports 303. In addition, the mask removing liquid L1 is heated (for example, to 160° C. to 180° C.) by the heat of reaction generated when the water vapor V and the sulfuric acid are mixed.

[0137] This allows for even higher selectivity etching of only the mask M among the multiple films formed on the surface of the wafer W. Therefore, according to the third modification, the zirconium oxide film used as the mask M can be more effectively removed from the wafer W.

[0138] The substrate processing apparatus (substrate processing system 1) according to the embodiment includes a holder 31, a liquid supply unit 40, and a controller 18. The holder 31 holds and rotates a substrate (wafer W). The liquid supply unit 40 supplies a processing liquid to the substrate (wafer W) held by the holder 31. The controller 18 controls each unit. The controller 18 also supplies a mask removing liquid L1 containing sulfuric acid as a main component to the substrate (wafer W) on which a zirconium oxide film serving as a mask M is formed on a laminated film ML and which has been dry-etched into a given shape, thereby removing the zirconium oxide film. After removing the zirconium oxide film, the controller 18 also dries the surface of the substrate (wafer W) wetted with the rinse liquid. This allows the zirconium oxide film used as the mask M to be satisfactorily removed from the wafer W.

[0139] <Substrate processing procedure> Next, a procedure for substrate processing according to the embodiment will be described with reference to Fig. 16. Fig. 16 is a flow chart showing the procedure for substrate processing executed by the substrate processing system 1 according to the embodiment.

[0140] In the substrate processing according to the embodiment, a preparation process is first performed (step S101). In the preparation process, as shown in FIG. 4, a zirconium oxide film is formed as a mask M on a laminated film ML, and a wafer W is dry-etched into a given shape.

[0141] Next, the control unit 18 controls the processing unit 16 and the like to perform a holding process of holding the wafer W in the holding unit 31 (step S102). Then, the control unit 18 controls the liquid supply unit 40 and the like to supply a mask removing liquid L1 containing sulfuric acid as a main component to the wafer W, and performs a mask removing process of removing the mask M made of a zirconium oxide film (step S103).

[0142] The mask removal process is performed, for example, with a mask removing liquid L1 in which concentrated sulfuric acid (for example, concentration 96%) and pure water are mixed in a ratio of 4:1 to 1:0. The mask removal process is performed, for example, with a processing time of 30 (seconds) to 600 (seconds), a discharge amount of the mask removing liquid L1 of 600 (mL / m) to 2000 (ml / m), and a rotation speed of the wafer W of 200 (rpm) to 2000 (rpm).

[0143] Next, the control unit 18 controls the liquid supply unit 40 and the like to supply HDIW to the wafer W, and performs a pre-residue removal process to remove the residue R2 (step S104).

[0144] Next, the control unit 18 controls the liquid supply unit 40 and the like to supply DHF or ammonia water to the wafer W to perform a residue removal process for removing at least one of the residues R1 and R2 (step S105).

[0145] When such a residue removal process is performed using DHF, the residue removal process is performed, for example, using DHF in which hydrofluoric acid and pure water are mixed at a ratio of 1:400 to 1:200. The residue removal process is performed, for example, with a processing time of 10 seconds to 300 seconds, a discharge rate of DHF of 1000 mL / m to 2000 ml / m, and a rotation speed of the wafer W of 200 rpm to 2000 rpm.

[0146] Next, the control unit 18 controls the liquid supply unit 40 and the like to perform a rinse process on the wafer W with DIW (step S106). Then, the control unit 18 controls the processing unit 16 to perform a drying process on the wafer W (step S107), completing a series of substrate processing operations.

[0147] The drying process may be, for example, a shaking off process after replacing the surface of the wafer W wetted with DIW with IPA. Also, the drying process may be, for example, a shaking off process after making the surface of the wafer W water-repellent with a water-repellent agent L2 and replacing it with a puddle of IPA.

[0148] Furthermore, the drying process may be performed by, for example, replacing the surface of the wafer W that has been subjected to the rinsing process with a puddle of IPA, and further drying the surface of the wafer W using a processing fluid in a supercritical state.

[0149] The substrate processing method according to the embodiment includes a preparation step (step S101), a mask removal step (step S103), and a drying step (step S107). In the preparation step (step S101), a zirconium oxide film serving as a mask M is formed on a laminated film ML, and a substrate (wafer W) is prepared by dry etching the substrate into a given shape. In the mask removal step (step S103), after the preparation step (step S101), a mask removal liquid L1 containing sulfuric acid as a main component is supplied to the substrate (wafer W) to remove the zirconium oxide film. In the drying step (step S107), after the mask removal step (step S103), the surface of the substrate (wafer W) wetted with the rinsing liquid (DIW) is dried. This allows the zirconium oxide film used as the mask M to be satisfactorily removed from the wafer W.

[0150] Moreover, the substrate processing method according to the embodiment further includes a residue removing step (step S105). In the residue removing step, after the mask removing step (step S103), an aqueous solution (DHF) containing a fluoride compound is supplied to the substrate (wafer W) to remove residues R1 and R2 resulting from at least one of the zirconium oxide film and the mask removing solution L1. This allows the residues R1 and R2 to be satisfactorily removed from the surface of the wafer W.

[0151] Moreover, the substrate processing method according to the embodiment further includes a residue removing step (step S105). In the residue removing step, after the mask removing step (step S103), an aqueous solution containing ammonia is supplied to the substrate (wafer W) to remove residues R1 and R2 resulting from at least one of the zirconium oxide film and the mask removing solution L1. This allows the residues R1 and R2 to be satisfactorily removed from the surface of the wafer W.

[0152] Moreover, the substrate processing method according to the embodiment further includes another residue removal step (pre-residue removal process) (step S104). In the another residue removal step, heated deionized water (HDIW) is supplied to the substrate (wafer W) between the mask removal step (step S103) and the residue removal step (step S105) to remove the residue R2 resulting from the mask removal solution L1. This makes it possible to maintain the film quality of the multilayer film ML even better after the residues R1 and R2 are removed.

[0153] In the substrate processing method according to the embodiment, the drying process (step S107) replaces the surface of the substrate (wafer W) wetted with the rinsing liquid (DIW) with water-soluble alcohol (IPA) and then dries the surface. This makes it possible to prevent the pattern of the multilayer film ML formed on the wafer W with a high aspect ratio from collapsing due to the surface tension of the DIW during drying.

[0154] In the substrate processing method according to the embodiment, the drying step (step S107) dries the surface of the substrate (wafer W) using a processing fluid in a supercritical state. This effectively prevents the pattern of the multilayer film ML formed on the wafer W with a high aspect ratio from collapsing due to the surface tension of the DIW during drying.

[0155] In addition, in the substrate processing method according to the embodiment, the drying step (step S107) includes a first replacement step, a water repellent step, a second replacement step, and a shake-off step. In the first replacement step, the surface of the substrate (wafer W) wetted with the rinsing liquid (DIW) is replaced with an organic solvent (IPA). In the water repellent step, a water repellent agent L2 is supplied to the surface of the substrate (wafer W) after the first replacement step. In the second replacement step, the surface of the substrate (wafer W) is replaced with an organic solvent (IPA) after the water repellent step. In the shake-off step, the organic solvent (IPA) located on the surface of the substrate (wafer W) is shaken off after the second replacement step. This effectively prevents the pattern of the multilayer film ML formed on the wafer W with a high aspect ratio from collapsing due to the surface tension of the DIW during drying.

[0156] In the substrate processing method according to the embodiment, in the mask removing step (step S103), the mask removing solution L1 is heated by heat of reaction generated when sulfuric acid and deionized water (DIW) are mixed, whereby the zirconium oxide film used as the mask M can be more effectively removed from the wafer W.

[0157] In the substrate processing method according to the embodiment, in the mask removing step (step S103), the mask removing solution L1 is heated by heat of reaction generated when sulfuric acid is mixed with water vapor V. This makes it possible to more effectively remove the zirconium oxide film used as the mask M from the wafer W.

[0158] Although the embodiments of the present disclosure have been described above, the present disclosure is not limited to the above-described embodiments, and various modifications are possible without departing from the spirit of the present disclosure.

[0159] The disclosed embodiments should be considered to be illustrative and not restrictive in all respects. Indeed, the above-described embodiments may be embodied in various forms. Furthermore, the above-described embodiments may be omitted, substituted, or modified in various forms without departing from the scope and spirit of the appended claims. [Explanation of symbols]

[0160] W wafer (example of substrate) 1. Substrate processing system (an example of a substrate processing apparatus) 16 Processing Unit 18 Control Unit 31 Holding part 40 Liquid supply section L1 Mask Remover L2 Water repellent agent M Mask ML laminated film V. Water Vapor

Claims

1. a preparation step of preparing a substrate in which a zirconium oxide film is formed as a mask on a laminated film, silicide is formed between the laminated film and the zirconium oxide film, and the substrate is dry-etched into a given shape; a mask removing step of supplying a mask removing liquid containing a mixture of sulfuric acid and pure water, the mixture being mainly composed of sulfuric acid, to the substrate after the preparation step, to remove the zirconium oxide film from the surface of the substrate; a residue removing step of supplying an aqueous solution containing a fluoride compound to the substrate after the mask removing step, and removing residue containing at least one of a silicide and a sulfur component from the surface of the substrate; a drying step of drying the surface of the substrate wetted with the rinsing liquid after the residue removing step; A substrate processing method comprising:

2. The method further includes a residue removing step of supplying heated pure water to the substrate between the mask removing step and the residue removing step to remove the residue. The method of claim 1 .

3. The drying step is a step of replacing the surface of the substrate wetted with the rinsing liquid with a water-soluble alcohol and then drying the surface. The substrate processing method according to claim 1 .

4. The drying step dries the surface of the substrate using a processing fluid in a supercritical state. The substrate processing method according to claim 1 .

5. The drying step includes: a first replacement step of replacing the surface of the substrate wetted with the rinsing liquid with an organic solvent; a water repellent step of supplying a water repellent agent to the surface of the substrate after the first replacement step; a second substitution step of substituting the surface of the substrate with an organic solvent after the water repellency step; After the second replacement step, a shaking-off step of shaking off the organic solvent present on the surface of the substrate is included. The substrate processing method according to claim 1 .

6. In the mask removing step, the mask removing solution is heated by heat of reaction generated when sulfuric acid and pure water are mixed. The substrate processing method according to any one of claims 1 to 5.

7. In the mask removing step, the mask removing solution is heated by the heat of reaction generated when sulfuric acid and water vapor are mixed. The substrate processing method according to any one of claims 1 to 6.

8. a holder that holds and rotates the substrate; a liquid supplying unit that supplies a processing liquid to the substrate held by the holding unit; A control unit for controlling each unit; Equipped with The control unit is a mask removing liquid containing sulfuric acid as a main component and a mixture of sulfuric acid and pure water is supplied to the substrate, which has a zirconium oxide film as a mask formed on a laminated film, a silicide formed between the laminated film and the zirconium oxide film, and has been dry-etched into a given shape, to remove the zirconium oxide film from the surface of the substrate; After removing the zirconium oxide film, an aqueous solution containing a fluoride compound is supplied to the substrate to remove residues containing at least one of silicide and sulfur components from the surface of the substrate; After removing the residue, the surface of the substrate wetted with the rinsing liquid is dried. Substrate processing equipment.

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