Semiconductor manufacturing equipment and processing modules

Abstract

To provide a technology that can suppress the formation of natural oxide film on the surface of a substrate.SOLUTION: A method for manufacturing a semiconductor device according to an aspect of the present disclosure has a step for applying a liquid material containing an ionic liquid on a substrate to form a protective film; a step for transporting the substrate on which the protective film is formed into the atmosphere; and a step for removing the protective film from the substrate that has been transported to the atmosphere.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This disclosure ,half Conductor manufacturing equipment and Processing Module Regarding. [Background technology]

[0002] A technique is known in which activated gas species of NF3 gas react with the native oxide film on the surface of a semiconductor wafer to form a protective film, and then the semiconductor wafer is heated to sublimate the protective film, thereby removing the native oxide film from within minute recesses, etc. (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 10-335316 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a technique that can suppress the formation of a native oxide film on the surface of a substrate. [Means for solving the problem]

[0005] A method for manufacturing a semiconductor device according to one aspect of the present disclosure includes a first processing module that applies a liquid material including an ionic liquid onto a substrate to form a protective film, a second processing module that removes the protective film formed on the substrate, and a transfer module that transfers the substrate between the first processing module and the second processing module in the atmosphere. The second processing module is configured to heat the substrate to cause a phase transition of the ionic liquid and to remove the protective film by performing a physical operation on the substrate. . [Effects of the Invention]

[0006] According to the present disclosure, it is possible to suppress the generation of a natural oxide film on the surface of a substrate. [Brief explanation of the drawings]

[0007] [Figure 1] 1A and 1B are diagrams illustrating an example of a method for manufacturing a semiconductor device according to a first embodiment; [Figure 2A] 1A to 1C are cross-sectional views illustrating steps in an example of a manufacturing method for the semiconductor device according to the first embodiment. [Figure 2B] 1A to 1C are cross-sectional views illustrating steps in an example of a manufacturing method for the semiconductor device according to the first embodiment. [Figure 2C] 1A to 1C are cross-sectional views illustrating steps in an example of a manufacturing method for the semiconductor device according to the first embodiment. [Figure 2D] 1A to 1C are cross-sectional views illustrating steps in an example of a manufacturing method for the semiconductor device according to the first embodiment. [Figure 2E] 1A to 1C are cross-sectional views illustrating steps in an example of a manufacturing method for the semiconductor device according to the first embodiment. [Figure 3] Schematic diagram showing an example of a vacuum film-forming device [Figure 4] Schematic diagram showing an example of a spin coater [Figure 5] Schematic diagram showing an example of a slit coater [Figure 6] Schematic diagram showing an example of a slit coater [Figure 7] Schematic diagram showing another example of a slit coater [Figure 8] Schematic diagram showing an example of a peeling device [Figure 9] FIG. 8 is a diagram for explaining the stage of the peeling device of FIG. 7; [Figure 10] FIG. 8 is a diagram for explaining the stage of the peeling device of FIG. 7; [Figure 11] 10A and 10B are diagrams illustrating an example of a method for manufacturing a semiconductor device according to a second embodiment; [Figure 12] Schematic diagram showing an example of a vacuum slit coater [Figure 13] 10A and 10B are diagrams illustrating an example of a manufacturing method of a semiconductor device according to a third embodiment. [Figure 14] 10A and 10B are diagrams illustrating an example of a method for manufacturing a semiconductor device according to a fourth embodiment. [Figure 15A] Cross-sectional views showing an example of a method for filling Cu into vias formed in a laminated film [Figure 15B] Cross-sectional views showing an example of a method for filling Cu into vias formed in a laminated film [Figure 15C] Cross-sectional views showing an example of a method for filling Cu into vias formed in a laminated film [Figure 15D] Cross-sectional views showing an example of a method for filling Cu into vias formed in a laminated film [Figure 15E] Cross-sectional views showing an example of a method for filling Cu into vias formed in a laminated film [Figure 15F] Cross-sectional views showing an example of a method for filling Cu into vias formed in a laminated film [Figure 16] Schematic diagram showing a slit coater of a first modified example. [Figure 17] FIG. 10 is a diagram showing an example of the operation of the slit coater of the first modified example. [Figure 18] FIG. 10 is a diagram showing another example of the operation of the slit coater of the first modified example. [Figure 19] FIG. 1 is a diagram illustrating a mechanism for suppressing contact between an ionic liquid and a cleaning liquid. [Figure 20] FIG. 1 is a diagram illustrating a mechanism for suppressing contact between an ionic liquid and a cleaning liquid. [Figure 21] Schematic diagram showing a slit coater of a second modified example. [Figure 22] Electrical circuit diagram to explain the stage ground circuit [Figure 23] Schematic diagram showing a slit coater of a third modified example. [Figure 24] Electrical circuit diagram to explain the outer casing grounding circuit [Figure 25] Schematic diagram showing a slit coater according to a fourth modified example. [Figure 26] FIG. 10 is a diagram showing an example of the operation of a slit coater according to a fourth modified example. [Figure 27] FIG. 10 is a diagram showing another example of the operation of the slit coater of the fourth modified example. [Figure 28A] FIG. 10 is a diagram for explaining an application example of a slit coater according to a fourth modified example. [Figure 28B] FIG. 10 is a diagram for explaining an application example of a slit coater according to a fourth modified example. [Figure 28C] FIG. 10 is a diagram for explaining an application example of a slit coater according to a fourth modified example. [Figure 29]Schematic diagram showing a slit coater according to a fifth modified example. [Figure 30] FIG. 13 is a diagram showing an example of the operation of a slit coater according to a fifth modified example. [Figure 31] FIG. 13 is a diagram showing an example of the operation of a slit coater according to a fifth modified example. DETAILED DESCRIPTION OF THE INVENTION

[0008] Hereinafter, non-limiting exemplary embodiments of the present disclosure will be described with reference to the accompanying drawings. In all the accompanying drawings, the same or corresponding reference numerals are used to designate the same or corresponding members or components, and redundant descriptions will be omitted.

[0009] [First embodiment] (Method of manufacturing a semiconductor device) An example of a method for manufacturing a semiconductor device according to the first embodiment will be described with reference to Fig. 1. Fig. 1 is a diagram showing an example of a method for manufacturing a semiconductor device according to the first embodiment. Figs. 2A to 2E are cross-sectional views showing steps in the example of the method for manufacturing a semiconductor device according to the first embodiment.

[0010] The method for manufacturing a semiconductor device according to the first embodiment includes a vacuum processing step S11, an atmospheric processing step S12, a protective film forming step S13, a protective film removing step S14, and a vacuum processing step S15. The vacuum processing step S11, the protective film removing step S14, and the vacuum processing step S15 are performed in a vacuum, while the atmospheric processing step S12 and the protective film forming step S13 are performed in the atmosphere. "In the atmosphere" here means that the processing steps are performed under a pressure of approximately 1 atmosphere, and the atmosphere during the processing steps may be an inert gas such as a rare gas or N2 gas.

[0011] The vacuum processing step S11 is a step of subjecting the substrate to various vacuum processes in a vacuum apparatus. Examples of the various vacuum processes include, but are not limited to, a film formation process, an etching process, a chemical oxide removal (COR) process, and a heat treatment process. The COR process includes, for example, a process of supplying a mixed gas containing a halogen-containing gas and a basic gas to the substrate to convert oxides and generate reaction products, and a process of removing the reaction products. In this embodiment, the various vacuum processes may be, for example, a process of forming an insulating film 11 and a conductive film 12, as shown in FIG. 2A, to prepare a substrate 10 including an area 11A where an insulating material is exposed and an area 12A where a conductive material is exposed. Examples of insulating materials include, but are not limited to, low-k films. Examples of conductive materials include, but are not limited to, copper (Cu), ruthenium (Ru), cobalt (Co), polysilicon (Poly-Si), and tungsten (W). The substrate that has undergone various vacuum processes in the vacuum device is transported out of the vacuum device into the atmosphere via a loader of the vacuum device, transported into the atmosphere by a transport device, and then transported into the atmosphere device via the loader of the atmosphere device.

[0012] The atmospheric treatment step S12 is a step performed after the vacuum treatment step S11, and is a step of subjecting the substrate to various atmospheric treatments in an atmospheric device. Examples of the various atmospheric treatments include, but are not limited to, wet treatments, atmospheric pressure film formation treatments, and plating treatments. In this embodiment, the various atmospheric treatments may be, for example, wet treatments, as shown in FIG. 2B, in which a chemical solution 13 containing hydrogen fluoride (HF) is supplied to the substrate 10 in the atmosphere to remove oxides (e.g., native oxide films) on the surface of the substrate 10. Examples of the HF-containing chemical solution 13 include, but are not limited to, diluted hydrofluoric acid (DHF). Methods for supplying the HF-containing chemical solution 13 to the substrate 10 include, but are not limited to, spin coating and slit coating.

[0013] The protective film formation step S13 is a step performed after the atmospheric treatment step S12. It is a step in which a liquid material containing an ionic liquid is applied to the substrate in an atmospheric treatment device to form a protective film on the surface of the substrate. The protective film formation step S13 is performed to protect the clean surface from contamination by impurities such as oxygen (O), water (HO), and organic matter, and to prevent the formation of a native oxide film. Therefore, the protective film formation step S13 is preferably performed immediately after the atmospheric treatment step S12. In this embodiment, as shown in FIG. 1, the protective film formation step S13 is performed immediately after the atmospheric treatment step S12 in the same atmospheric treatment device as the atmospheric treatment step S12. In this embodiment, as shown in FIG. 2C, for example, the protective film formation step S13 involves applying a liquid material containing an ionic liquid to the substrate 10 from which oxides have been removed by the wet treatment in the atmospheric treatment step S12, thereby forming a protective film 14 on the surface of the substrate 10. This results in the surface of the substrate 10 being covered with the protective film 14, thereby suppressing the adsorption of impurities to the surface of the substrate 10. Furthermore, the protective film 14 formed from a liquid material containing an ionic liquid has the property of not easily evaporating even when transferred from the atmosphere to a vacuum. Therefore, even if the next process is performed in a vacuum, the generation of oxides on the surface of the substrate 10 can be suppressed until immediately before processing. Methods for applying the liquid material containing an ionic liquid include, but are not limited to, spin coating and slit coating. Details of the ionic liquid will be described later. The substrate on which the protective film has been formed in the atmospheric device is transferred from the atmospheric device to the atmosphere via the atmospheric device's loader, transferred to the atmosphere by a transfer device, and then transferred into the vacuum device via the vacuum device's loader.

[0014] The protective film removal step S14 is a step performed after the protective film formation step S13, and is a step of removing the protective film formed on the substrate in a vacuum apparatus to expose a clean surface. In this embodiment, in the protective film removal step S14, as shown in FIG. 2D , the substrate 10 is heated in a vacuum to cause a phase transition of the ionic liquid, thereby reducing the adhesion of the protective film 14 to the underlying layers (the insulating film 11 and the conductive film 12). Next, the protective film 14 on the surface of the substrate 10 is peeled off and removed by performing a physical operation on the substrate 10. Examples of the physical operation include horizontally moving, rotating, and tilting the substrate 10. The viscosity of the protective film 14 may be reduced by causing a phase transition of the ionic liquid.

[0015] The vacuum processing step S15 is a step performed after the protective film removal step S14, and is a step of performing various vacuum processing on the substrate in a vacuum apparatus. Examples of various vacuum processing include, but are not limited to, a film formation process, an etching process, a COR process, and a heat treatment. The vacuum processing step S15 is preferably performed immediately after the protective film removal step S14 without exposing the substrate to the atmosphere, so as to prevent impurities from re-adhering to the clean surface. In this embodiment, the vacuum processing step S15 is performed immediately after the protective film removal step S14 in the same vacuum apparatus as the protective film removal step S14. In this embodiment, the various vacuum processing may be, for example, a film formation process for forming an insulating film 15, as shown in FIG. 2E. Note that instead of the insulating film 15, a film formation process for forming a metal film may also be performed.

[0016] As described above, according to the semiconductor device manufacturing method of the first embodiment, a liquid material containing an ionic liquid is applied to the surface of the substrate in advance as a protective film, and the protective film is then removed in a vacuum just before the start of the film formation process. This prevents oxides from being generated on the surface of the substrate, and allows the desired film to be formed on a clean surface where oxide generation has been suppressed. As a result, deterioration of the interface characteristics (e.g., electrical characteristics, mechanical characteristics) between the surface of the substrate and the desired film can be suppressed.

[0017] (Vacuum film forming equipment) An example of a vacuum film-forming apparatus for carrying out the film-forming processes performed in the vacuum processing steps S11 and S15 will be described with reference to Fig. 3. Fig. 3 is a schematic diagram showing an example of the vacuum film-forming apparatus.

[0018] The vacuum deposition apparatus 100 includes a chamber 110 , a gas supply unit 120 , an exhaust system 130 , and a control unit 190 .

[0019] The chamber 110 defines a sealed processing space 111 for accommodating a wafer W. A mounting table 112 is provided inside the chamber 110.

[0020] The mounting table 112 has a substantially circular shape in a plan view and is fixed to the bottom of the chamber 110. A wafer W is placed in a substantially horizontal state on the mounting table 112. A heater 113 for heating the mounting table 112 and the wafer W is provided inside the mounting table 112.

[0021] A sidewall of the chamber 110 is provided with a loading / unloading port (not shown) for loading / unloading the wafer W into / from the processing space 111. The loading / unloading port is opened and closed by a gate valve (not shown). A shower head 114 having a plurality of outlets for discharging processing gas is provided on the ceiling of the chamber 110.

[0022] The gas supply unit 120 includes a gas supply source 121 and a gas supply path 122. The gas supply source 121 includes a supply source for various processing gases. The gas supply path 122 connects the gas supply source 121 to the shower head 114. The gas supply path 122 is provided with, for example, a valve and a flow rate controller (neither of which are shown). In the gas supply unit 120, various processing gases from the gas supply source 121 are discharged into the processing space 111 via the gas supply path 122 and the shower head 114.

[0023] The exhaust system 130 is connected to, for example, an exhaust port 115 provided at the bottom of the chamber 110. The exhaust system 130 includes, for example, a pressure control valve and a vacuum pump (neither of which are shown), and evacuates the interior of the chamber 110.

[0024] The control unit 190 processes computer-executable instructions that cause the vacuum deposition apparatus 100 to perform the vacuum processing steps S11 and S15. The control unit 190 can be configured to control each element of the vacuum deposition apparatus 100 to perform the vacuum processing steps S11 and S15. The control unit 190 includes, for example, a computer. The computer includes, for example, a CPU (Central Processing Unit), a storage unit, and a communication interface.

[0025] (Coating equipment) A spin coater, which is an example of a coating device for performing the wet treatment performed in the atmospheric treatment step S12 and the application of the liquid material containing an ionic liquid performed in the protective film formation step S13, will be described with reference to Fig. 4. Fig. 4 is a schematic diagram showing an example of a spin coater.

[0026] The spin coater 200 includes a housing 210 , a liquid supply unit 220 , and a control unit 290 .

[0027] The housing 210 forms a sealed processing space 211 for accommodating a wafer W therein. The housing 210 is provided with a loading / unloading port (not shown) for loading / unloading the wafer W into / from the processing space 211. The loading / unloading port is opened and closed by a gate valve (not shown). A mounting table 212 is provided inside the housing 210. The mounting table 212 is connected to the upper end of a rotation shaft 213 that penetrates the bottom of the housing 210 and is configured to be rotatable. The wafer W is placed on the mounting table 212 in a substantially horizontal state. A heater 214 for heating the wafer W is embedded inside the mounting table 212.

[0028] The liquid supply unit 220 includes a liquid supply source 221 and a nozzle 222. The liquid supply source 221 includes a supply source of various liquid materials, such as a chemical liquid containing hydrogen fluoride (HF) and a liquid material containing an ionic liquid. The nozzle 222 is provided to penetrate the ceiling of the housing 210, and supplies various liquid materials from the liquid supply source 221 to the surface of the wafer W placed on the mounting table 212.

[0029] The control unit 290 processes computer-executable instructions that cause the spin coater 200 to perform the wet treatment performed in the atmospheric treatment step S12 and the application of the liquid material including the ionic liquid performed in the protective film formation step S13. The control unit 290 can be configured to control each element of the spin coater 200 to perform the wet treatment performed in the atmospheric treatment step S12 and the application of the liquid material including the ionic liquid performed in the protective film formation step S13. The control unit 290 includes, for example, a computer. The computer includes, for example, a CPU, a storage unit, and a communication interface.

[0030] 5 and 6, a slit coater, which is an example of a coating device for carrying out the wet treatment performed in the atmospheric treatment step S12 and the application of a liquid material containing an ionic liquid performed in the protective film formation step S13, will be described. Figures 5 and 6 are schematic diagrams showing an example of a slit coater. Figures 5 and 6 are a side view and a perspective view of the slit coater, respectively.

[0031] The slit coater 300 includes a stage 310 , a liquid supply unit 320 , and a control unit 390 .

[0032] The stage 310 holds the wafer W in a substantially horizontal position.

[0033] The liquid supply unit 320 includes a liquid supply source 321 and a slit nozzle 322. The liquid supply source 321 includes a supply source for various liquid materials, such as a chemical liquid containing HF and a liquid material containing an ionic liquid. The slit nozzle 322 moves horizontally above the wafer W to supply the liquid material from the liquid supply source 321 to the surface of the wafer W placed on the stage 310.

[0034] The control unit 390 processes computer-executable instructions that cause the slit coater 300 to perform the wet treatment performed in the atmospheric treatment step S12 and the application of the liquid material containing the ionic liquid performed in the protective film formation step S13. The control unit 390 can be configured to control each element of the slit coater 300 to perform the wet treatment performed in the atmospheric treatment step S12 and the application of the liquid material containing the ionic liquid performed in the protective film formation step S13. The control unit 390 includes, for example, a computer. The computer includes, for example, a CPU, a storage unit, and a communication interface.

[0035] Another example of a slit coater, which is an example of a coating device for performing the wet treatment performed in the atmospheric treatment step S12 and the application of a liquid material containing an ionic liquid performed in the protective film formation step S13, will be described with reference to Fig. 7. Fig. 7 is a schematic diagram showing another example of a slit coater.

[0036] The slit coater 400 includes a stage 410 , a liquid supply unit 420 , and a control unit 490 .

[0037] The stage 410 places the wafer W in a substantially horizontal position. The stage 410 is connected to the upper end of a rotation shaft 412 that is rotated by a drive mechanism 411, and is configured to be rotatable. A liquid receiving portion 413 that is open on the upper side is provided around the lower periphery of the stage 410. The liquid receiving portion 413 receives liquid material that spills or is shaken off from the wafer W.

[0038] The liquid supply unit 420 includes a liquid supply source 421 and a slit nozzle 422. The liquid supply source 421 includes a supply source for various liquid materials, such as a chemical liquid containing HF and a liquid material containing an ionic liquid. The slit nozzle 422 moves horizontally above the wafer W to supply the liquid material from the liquid supply source 421 to the surface of the wafer W placed on the stage 410.

[0039] The control unit 490 processes computer-executable instructions that cause the slit coater 400 to perform the wet treatment performed in the atmospheric treatment step S12 and the application of the liquid material containing the ionic liquid performed in the protective film formation step S13. The control unit 490 can be configured to control each element of the slit coater 400 to perform the wet treatment performed in the atmospheric treatment step S12 and the application of the liquid material containing the ionic liquid performed in the protective film formation step S13. The control unit 490 includes, for example, a computer. The computer includes, for example, a CPU, a storage unit, and a communication interface.

[0040] (peeling device) An example of a delamination apparatus for removing the protective film in the protective film removal step S14 will be described with reference to Figures 8 to 10. Figure 8 is a schematic diagram showing an example of the delamination apparatus. Figure 9 is a diagram for explaining the stage of the delamination apparatus of Figure 8, showing a state in which a wafer is placed on the stage and the space between the stage and the wafer is filled with a temperature control fluid. Figure 10 is a diagram for explaining the stage of the delamination apparatus of Figure 8, showing a state in which a wafer is not placed on the stage and the stage is not filled with a temperature control fluid.

[0041] The stripping apparatus 500 includes a chamber 510 , a liquid circulation unit 530 , an exhaust system 540 , and a control unit 590 .

[0042] The chamber 510 forms a sealed processing space 511 therein for accommodating the wafer W. A stage 512 is provided inside the chamber 510.

[0043] The stage 512 holds the wafer W in a substantially horizontal position. The stage 512 includes a holder 512a and a rotating shaft 512b. The rotating shaft 512b is rotatably and vertically supported by an annular support 514a at the bottom of the reaction vessel 514 via, for example, a spline seal bearing 513. The stage 512 is connected to the rotation drive shaft of a motor 515. The stage 512 is also supported by an elevating mechanism 516 so that it can be elevated. Control signals for the motor 515 and the elevating mechanism 516 are output from a control unit 590. The stage 512 is surrounded by the cylindrical reaction vessel 514 with a bottom.

[0044] Reaction tank 514 has, for example, a central bottom 514b and a peripheral bottom 514c that have different depths in a concentric pattern, with central bottom 514b being deeper than peripheral bottom 514c. The liquid in reaction tank 514 flows smoothly from peripheral bottom 514c toward central bottom 514b. Note that the two-step step structure does not have to be the case as long as the structure allows the liquid to flow smoothly; for example, a conical shape with a deeper center or a multi-step structure may be used.

[0045] A drain 517 opens to the central bottom 514b. A return pipe 535 of the liquid circulation unit 530 is connected to the drain 517. A liquid supply flow path 518a opens to the side of the reaction tank 514. A drain flow path 518b opens to the side of the reaction tank 514 at a position lower than the liquid supply flow path 518a. A plurality of exhaust paths 518c communicate with the side of the reaction tank 514 at a position higher than the liquid supply flow path 518a. A heater 519 is embedded in the bottom of the reaction tank 514 to heat the wafers W and the temperature control fluid supplied into the reaction tank 514.

[0046] Additionally, three lift pins 520 are provided above the bottom of the reaction tank 514. When the stage 512 is lowered, the lift pins 520 are inserted into through-holes provided in the stage 512 and protrude from the upper surface of the stage 512, thereby lifting and holding the wafer W.

[0047] Further, stoppers 521 for fixing the wafer W held on the stage 512 are provided on the outer edge of the stage 512. As shown in Figures 9 and 10, for example, three stoppers 521 are provided at equal intervals in the circumferential direction on the outer edge of the stage 512. Fixing the wafer W by the stoppers 521 can prevent the wafer W from coming off the stage 512 when the wafer W is rotated.

[0048] The liquid circulation unit 530 includes a tank 531 , a temperature control mechanism 532 , a supply pipe 533 , a sealing mechanism 534 , and a return pipe 535 .

[0049] The tank 531 stores a temperature control fluid. The temperature control fluid is supplied from the tank 531 to between the upper surface of the stage 512 and the lower surface of the wafer W via a supply pipe 533. This adjusts the temperature of the wafer W to approximately the same temperature as the temperature of the temperature control fluid. From the viewpoint of excellent thermal conductivity, it is preferable to use an ionic liquid as the temperature control fluid. For example, the same ionic liquid as the ionic liquid that constitutes the protective film formed on the surface of the wafer W can be used as the ionic liquid.

[0050] The temperature adjustment mechanism 532 includes a heater and a temperature sensor (neither of which are shown). The temperature adjustment mechanism 532 controls the temperature of the temperature adjustment fluid in the tank 531 by controlling the heater based on the value detected by the temperature sensor.

[0051] The outgoing pipe 533 is provided coaxially with the rotation shaft 512b of the stage 512, and rotates and moves up and down together with the rotation shaft 512b by a motor 515 and an elevating mechanism 516. As shown in FIG. 10 , the upper end of the outgoing pipe 533 is inserted into an opening 512c provided in the center of the stage 512, and the temperature-controlling fluid is supplied onto the stage 512.

[0052] The sealing mechanism 534 rotatably supports the outgoing pipe 533 in an airtight sealed state.

[0053] The return pipe 535 is connected to the drain 517 and recovers the temperature control fluid spilled from the stage 512 into the tank 531 .

[0054] The exhaust system 540 is connected to, for example, the plurality of exhaust paths 518c and includes, for example, a pressure control valve and a vacuum pump (neither of which are shown), and exhausts the interior of the chamber 510.

[0055] The control unit 590 processes computer-executable instructions that cause the peeling apparatus 500 to perform the protective film removal step S14. The control unit 590 can be configured to control each element of the peeling apparatus 500 to perform the protective film removal step S14. The control unit 590 includes, for example, a computer. The computer includes, for example, a CPU, a storage unit, and a communication interface.

[0056] Second Embodiment (Method of manufacturing a semiconductor device) An example of a method for manufacturing the semiconductor device of the second embodiment will be described with reference to Fig. 11. Fig. 11 is a diagram showing an example of a method for manufacturing the semiconductor device of the second embodiment.

[0057] The method for manufacturing a semiconductor device according to the second embodiment includes a vacuum processing step S21, a protective film forming step S22, a protective film removing step S23, and a vacuum processing step S24. The vacuum processing step S21, the protective film forming step S22, the protective film removing step S23, and the vacuum processing step S24 are performed in a vacuum.

[0058] The vacuum processing step S21 is a step of performing various vacuum processes on the substrate in a vacuum device. The vacuum processing step S21 may be the same as the vacuum processing step S11 in the first embodiment, for example.

[0059] The protective film formation step S22 is a step performed after the vacuum processing step S21. It is a step in which a liquid material containing an ionic liquid is applied to a substrate in a vacuum apparatus to form a protective film on the surface of the substrate. The protective film formation step S22 is performed to protect the clean surface from contamination by impurities such as oxygen (O), water (HO), and organic matter, and to prevent the formation of a native oxide film. Therefore, the protective film formation step S22 is preferably performed immediately after the vacuum processing step S21. In this embodiment, the protective film formation step S22 is performed immediately after the vacuum processing step S21 in the same vacuum apparatus as the vacuum processing step S21. The protective film formed from the liquid material containing an ionic liquid does not easily evaporate in a vacuum, so it can be applied in a vacuum. Furthermore, even if the next step is performed in a vacuum, the generation of oxides on the surface of the substrate can be suppressed until immediately before the processing. Methods for applying the liquid material containing an ionic liquid include, but are not limited to, spin coating and slit coating. The substrate on which the protective film has been formed in the vacuum device is transported from the vacuum device into the atmosphere via a loader of the vacuum device, transported to the atmosphere by a transport device, and then transported into another vacuum device via a loader of another vacuum device.

[0060] The protective film removing step S23 is a step performed after the protective film forming step S22, and is a step of removing the protective film formed on the substrate in a vacuum device to expose a clean surface. The protective film removing step S23 may be the same as the protective film removing step S14 in the first embodiment, for example.

[0061] The vacuum processing step S24 is a step performed after the protective film removing step S23, and is a step of performing various vacuum processes on the substrate in a vacuum device. The vacuum processing step S24 may be the same as the vacuum processing step S15 in the first embodiment, for example.

[0062] As described above, according to the semiconductor device manufacturing method of the second embodiment, a liquid material containing an ionic liquid is applied to the surface of the substrate in advance as a protective film, and the protective film is then removed in a vacuum just before the start of the film formation process. This prevents oxides from being generated on the surface of the substrate, and allows the desired film to be formed on a clean surface where oxide generation has been suppressed. As a result, deterioration of the interface characteristics (e.g., electrical characteristics, mechanical characteristics) between the surface of the substrate and the desired film can be suppressed.

[0063] (Vacuum coating equipment) A vacuum slit coater, which is an example of a vacuum coating device for coating the liquid material containing an ionic liquid in the protective film forming step S22, will be described with reference to Fig. 12. Fig. 12 is a schematic diagram showing an example of a vacuum slit coater.

[0064] The vacuum slit coater 600 includes a chamber 610 , a liquid supply unit 620 , a liquid circulation unit 630 and a control unit 690 .

[0065] The chamber 610 forms a sealed processing space 611 for accommodating a wafer W therein. A stage 612 is provided within the chamber 610. The stage 612 holds the wafer W in a substantially horizontal position. The stage 612 is rotatably connected to the upper end of a rotation shaft 614 that is rotated by a drive mechanism 613. A liquid receiving section 615 that is open at the top is provided around the lower periphery of the stage 612. The liquid receiving section 615 receives and stores chemical liquids, liquid materials, etc. that spill or are shaken off from the wafer W. The interior of the chamber 610 is evacuated by an exhaust system (not shown) that includes a pressure control valve, a vacuum pump, etc.

[0066] The liquid supply unit 620 includes a slit nozzle 621. The slit nozzle 621 moves horizontally above the wafer W to supply the liquid material containing the ionic liquid from the liquid circulation unit 630 onto the surface of the wafer W placed on the stage 612.

[0067] The liquid circulation unit 630 recovers the liquid material containing the ionic liquid stored in the liquid receiving unit 615 and supplies it to the slit nozzle 621. The liquid circulation unit 630 includes a compressor 631, a raw liquid tank 632, a carrier gas supply source 633, a cleaning unit 634, and pH sensors 635 and 636.

[0068] Compressor 631 is connected to liquid receiver 615 via pipe 639a, recovers the liquid material containing the ionic liquid stored in liquid receiver 615, and compresses it to, for example, atmospheric pressure or higher. Compressor 631 is connected to raw liquid tank 632 via pipe 639b, and transports the compressed liquid material containing the ionic liquid to raw liquid tank 632 via pipe 639b. Pipe 639a is provided with, for example, a valve and a flow rate controller (neither of which is shown). For example, by controlling the opening and closing of a valve, the liquid material containing the ionic liquid is periodically transported from compressor 631 to raw liquid tank 632.

[0069] The raw liquid tank 632 stores a liquid material containing an ionic liquid. One ends of pipes 639b to 639d are inserted into the raw liquid tank 632. The other end of pipe 639b is connected to a compressor 631, and the liquid material containing an ionic liquid compressed by the compressor 631 is supplied to the raw liquid tank 632 via pipe 639b. The other end of pipe 639c is connected to a carrier gas supply source 633, and a carrier gas such as nitrogen (N2) gas is supplied to the raw liquid tank 632 from the carrier gas supply source 633 via pipe 639c. The other end of pipe 639d is connected to a slit nozzle 621, and the liquid material containing an ionic liquid in the raw liquid tank 632 is transported to the slit nozzle 621 together with the carrier gas via pipe 639d. Pipes 639b to 639d are provided with, for example, valves and flow rate controllers (neither of which is shown).

[0070] The carrier gas supply source 633 is connected to the raw liquid tank 632 via a pipe 639c, and supplies a carrier gas such as N2 gas to the raw liquid tank 632 via the pipe 639c.

[0071] Cleaning unit 634 is provided in pipe 639b. Cleaning unit 634 cleans the liquid material containing the ionic liquid transported from compressor 631. A drain pipe 639e is connected to cleaning unit 634, and the liquid material containing the ionic liquid whose properties have deteriorated is discharged via drain pipe 639e. For example, cleaning unit 634 controls whether to reuse or discharge the liquid material containing the ionic liquid based on the detection value of pH sensor 636. Furthermore, cleaning unit 634 may control whether to reuse or discharge the liquid material containing the ionic liquid based on the detection value of pH sensor 635. Furthermore, cleaning unit 634 may control whether to reuse or discharge the liquid material containing the ionic liquid based on the detection values of pH sensors 635 and 636.

[0072] The pH sensor 635 is provided in the compressor 631 and detects the hydrogen ion concentration (pH) of the liquid material containing the ionic liquid in the compressor 631 .

[0073] The pH sensor 636 is provided in the cleaning section 634 and detects the hydrogen ion concentration (pH) of the liquid material containing the ionic liquid in the cleaning section 634 .

[0074] The control unit 690 processes computer-executable instructions that cause the vacuum slit coater 600 to apply the liquid material containing the ionic liquid in the protective film forming step S22. The control unit 690 can be configured to control each element of the vacuum slit coater 600 to apply the liquid material containing the ionic liquid in the protective film forming step S22. The control unit 690 includes, for example, a computer. The computer includes, for example, a CPU, a storage unit, and a communication interface.

[0075] Third Embodiment (Method of manufacturing a semiconductor device) An example of a method for manufacturing the semiconductor device of the third embodiment will be described with reference to Fig. 13. Fig. 13 is a diagram showing an example of a method for manufacturing the semiconductor device of the third embodiment.

[0076] The method for manufacturing a semiconductor device according to the third embodiment includes a vacuum processing step S31, a protective film forming step S32, a protective film removing step S33, and an atmospheric processing step S34. The vacuum processing step S31 and the protective film forming step S32 are performed in a vacuum, and the protective film removing step S33 and the atmospheric processing step S34 are performed in the atmosphere.

[0077] The vacuum processing step S31 is a step of performing various vacuum processes on the substrate in a vacuum device. The vacuum processing step S31 may be the same as the vacuum processing step S11 in the first embodiment, for example.

[0078] The protective film forming step S32 is a step performed after the vacuum processing step S31, in which a liquid material containing an ionic liquid is applied to a substrate in a vacuum apparatus to form a protective film on the surface of the substrate. In this embodiment, the protective film forming step S32 is performed in a different process module connected to the process module in which the vacuum processing step S31 is performed via a vacuum transfer chamber. The substrate on which the protective film has been formed in the vacuum apparatus is transferred from the vacuum apparatus to the atmosphere via a loader of the vacuum apparatus, transferred to the atmosphere by a transfer apparatus, and then transferred into the atmosphere apparatus via a loader of the atmosphere apparatus.

[0079] The protective film removal step S33 is a step performed after the protective film formation step S32, in which a clean surface is exposed by removing the protective film formed on the substrate in an atmospheric device. In this embodiment, in the protective film removal step S33, the substrate is heated in the atmosphere to cause a phase transition of the ionic liquid, thereby reducing the adhesion of the protective film to the underlying layers (insulating material and conductive material). Next, the protective film on the surface of the substrate is peeled off and removed by performing a physical operation on the substrate. Examples of physical operations include horizontally moving, rotating, and tilting the substrate. Note that the viscosity of the protective film may be reduced by causing a phase transition of the ionic liquid.

[0080] The atmospheric treatment step S34 is a step performed after the protective film removal step S33, and is a step in which various atmospheric treatments are performed on the substrate in an atmospheric device. Examples of various atmospheric treatments include, but are not limited to, wet treatment, atmospheric pressure film formation, and plating. The atmospheric treatment step S34 is preferably performed simultaneously with the protective film removal step S33 or consecutively after the protective film removal step S33 to prevent impurities from re-adhering to the clean surface.

[0081] As described above, according to the semiconductor device manufacturing method of the third embodiment, a liquid material containing an ionic liquid is applied to the surface of a substrate in advance as a protective film, and the protective film is then removed in a vacuum just before the start of the film formation process. This prevents oxides from being generated on the surface of the substrate, and allows the desired film to be formed on a clean surface where oxide generation has been suppressed. As a result, deterioration of the interface characteristics (e.g., electrical characteristics, mechanical characteristics) between the surface of the substrate and the desired film can be suppressed.

[0082] [Fourth embodiment] (Method of manufacturing a semiconductor device) An example of a method for manufacturing the semiconductor device of the fourth embodiment will be described with reference to Fig. 14. Fig. 14 is a diagram showing an example of a method for manufacturing the semiconductor device of the fourth embodiment.

[0083] The method for manufacturing a semiconductor device according to the fourth embodiment includes a vacuum processing step S41, a protective film forming step S42, a protective film removing step S43, and an atmospheric processing step S44. The vacuum processing step S41 and the protective film forming step S42 are performed in a vacuum, and the protective film removing step S43 and the atmospheric processing step S44 are performed in the atmosphere.

[0084] The vacuum processing step S41 is a step of performing various vacuum processes on the substrate in a vacuum device. The vacuum processing step S41 may be the same as the vacuum processing step S11 in the first embodiment, for example.

[0085] The protective film forming step S42 is a step performed after the vacuum processing step S41, in which a liquid material containing an ionic liquid is applied to the substrate in a vacuum apparatus to form a protective film on the surface of the substrate. In this embodiment, the protective film forming step S42 is performed in a different process module connected to the process module in which the vacuum processing step S41 is performed via a load lock chamber (buffer). The load lock chamber is configured so that its interior can be switched between a vacuum atmosphere and an atmospheric atmosphere. The substrate on which the protective film has been formed in the vacuum apparatus is transferred from the vacuum apparatus to the atmosphere via a loader of the vacuum apparatus, transferred to the atmosphere by a transfer device, and then transferred into the atmospheric apparatus via a loader of the atmospheric apparatus.

[0086] The protective film removing step S43 is a step performed after the protective film forming step S42, and is a step of removing the protective film formed on the substrate in an atmospheric device to expose a clean surface. The protective film removing step S43 may be the same as the protective film removing step S33 in the third embodiment.

[0087] The atmospheric treatment step S44 is a step performed after the protective film removal step S43, and is a step of subjecting the substrate to various atmospheric treatments in an atmospheric device. The atmospheric treatment step S44 may be the same as the atmospheric treatment step S34 in the third embodiment.

[0088] As described above, according to the semiconductor device manufacturing method of the fourth embodiment, a liquid material containing an ionic liquid is applied to the surface of a substrate in advance as a protective film, and the protective film is then removed in a vacuum just before the start of the film formation process. This prevents oxides from being generated on the surface of the substrate, and allows the desired film to be formed on a clean surface where oxide generation has been suppressed. As a result, deterioration of the interface characteristics (e.g., electrical characteristics, mechanical characteristics) between the surface of the substrate and the desired film can be suppressed.

[0089] [Ionic Liquid] Ionic liquids are ionic compounds that are liquid at room temperature and are composed of positive ions (cations) and negative ions (anions). The ionic liquids used in the embodiments are ionic liquids whose physical properties change depending on environmental factors. The environmental factors include, for example, temperature. The physical properties include, for example, at least one of viscosity and adhesiveness.

[0090] As an example of an ionic liquid used in the embodiments, an ionic liquid that undergoes a reversible phase transition depending on the temperature can be suitably used. By changing the temperature of the substrate, a phase transition occurs in the ionic liquid, and the adhesion between the ionic liquid and the substrate can be changed. In other words, by controlling the temperature of the ionic liquid, it is possible to change the state of the ionic liquid between one that adheres to the substrate (wafer) as a viscous film and one that is easily peeled off from the substrate (wafer).

[0091] For example, when forming a protective film by applying a liquid material containing an ionic liquid to a substrate, the temperature of the substrate is set to a first temperature so that the adhesion between the ionic liquid and the substrate is high. As a result, the liquid material applied to the substrate remains on the substrate, forming a protective film. On the other hand, when removing the protective film formed on the substrate, the temperature of the substrate is set to a second temperature different from the first temperature so that the adhesion between the ionic liquid and the substrate is reduced. As a result, the protective film, which has reduced adhesion to the substrate, is easily peeled off from the substrate when the substrate is subjected to physical operations such as horizontal movement, rotation, or tilting.

[0092] Examples of cations that constitute ionic liquids include cations containing quaternary nitrogen, such as pyridinium, imidazolium, ammonium, pyrrolidinium, and piperidinium, as well as cations containing quaternary phosphorus, such as phosphonium. These cations have alkyl groups -(CH2) as side chains. n Contains CH3.

[0093] Examples of pyridinium-type cations include C2py represented by the chemical formula (C1-1). + , C4py represented by the chemical formula (C1-2) + These include, but are not limited to:

[0094] [ka]

[0095] The imidazolium type cation is, for example, C2mim represented by the chemical formula (C2-1). + , C4mim represented by the chemical formula (C2-2) + , C6mim represented by the chemical formula (C2-3) + , C8mim represented by the chemical formula (C2-4) + These include, but are not limited to:

[0096] [ka]

[0097] The ammonium cation is, for example, N represented by the chemical formula (C3-1). 3,1,1,1 + , N represented by the chemical formula (C3-2) 4,1,1,1 + , N represented by the chemical formula (C3-3) 6,1,1,1 + , N represented by the chemical formula (C3-4) 2,2,1,(2O1) + , represented by the chemical formula (C3-5) Ch + These include, but are not limited to:

[0098] [ka]

[0099] Examples of pyrrolidinium-type cations include Pyr represented by the chemical formula (C4-1). 1,3 + , Pyr represented by the chemical formula (C4-2) 1,4 + These include, but are not limited to:

[0100] [ka]

[0101] Examples of piperidinium-type cations include Pip 1,3 + , Pip represented by the chemical formula (C5-2) 1,4 + These include, but are not limited to:

[0102] [ka]

[0103] Examples of phosphonium cations include P 5,2,2,2 + , P represented by the chemical formula (C6-2) 6,6,6,14 + These include, but are not limited to:

[0104] [ka]

[0105] The anion constituting the ionic liquid is TfO, which is represented by the chemical formula (A1). - , Tf2N represented by chemical formula (A2) - (TFSA - ), Tf3C represented by chemical formula (A3) - , FSA represented by chemical formula (A4) - , CH3COO represented by chemical formula (A5) - , CF3COO represented by the chemical formula (A6) - , BF4 represented by chemical formula (A7) - , PF6 represented by chemical formula (A8) - , represented by the chemical formula (A9) (CN)N - , AlCl4 represented by the chemical formula (A10) - , Al2Cl7 represented by the chemical formula (A11) - These include, but are not limited to:

[0106] [ka]

[0107] Specific examples of ionic liquids include tributylhexadecylphosphonium 3-(trimethylsilyl)-1-propanesulfonate (BHDP·DSS) and N,N-diethyl-N-methyl-N(2-methoxyethyl)ammonium tetrafluoroborate (DEME·BF4).

[0108] [Example] 15A to 15F, an example of application of the semiconductor device manufacturing method of the embodiment will be described, taking as an example a case where Cu is embedded in a via in a back end of line (BEOL) process. 15A to 15F are cross-sectional views showing steps in an example of a method for embedding Cu in a via formed in a laminated film.

[0109] First, as shown in FIG. 15A, a substrate 20 is prepared in which an insulating film 26 is formed on a lower wiring 21. An etching stop layer 23 is formed between the lower wiring 21 and the insulating film 26. The lower wiring 21 is embedded in a trench 22 formed in an interlayer insulating film 24 with a barrier metal film 25 sandwiched therebetween. The lower wiring 21 may be, for example, a Cu wiring, but is not limited thereto. The etching stop layer 23 may be, for example, a silicon carbonitride film (SiCN film), but is not limited thereto. The interlayer insulating film 24 may be, for example, a low-k film, but is not limited thereto. The barrier metal film 25 may be, for example, a tantalum nitride (TaN) film, but is not limited thereto. In addition, a via 27 and a trench 28 are formed in the insulating film 26.

[0110] 15B, a TaN film 29 is conformally formed as a barrier metal film inside the via 27 and the trench 28. The TaN film 29 may be formed by, for example, an ALD method performed in a vacuum device, but is not limited to this.

[0111] 15C, a Cu seed film 30 is conformally formed as a seed film on the TaN film 29. The Cu seed film 30 can be formed by, for example, a PVD method, but is not limited to, this. The Cu seed film is formed in a different module within the same vacuum apparatus as that for forming the TaN film 29.

[0112] 15D, a liquid material containing an ionic liquid is applied to the substrate 20 to form a protective film 31 so as to cover the surface of the Cu seed film 30. The protective film 31 is formed, for example, in a different module within the same vacuum apparatus that forms the TaN film 29 and the Cu seed film 30. Examples of ionic liquids include, but are not limited to, ionic liquids that undergo reversible phase transition depending on the temperature.

[0113] 15E, with the adhesion between the Cu seed film 30 and the protective film 31 reduced, the protective film 31 is peeled off and removed from the surface of the Cu seed film 30 by performing physical operations such as horizontally moving, rotating, or tilting the substrate 20. One method for removing the protective film 31 is to use a spin coater in an atmospheric device. For example, the protective film 31 can be removed by rotating the substrate 20 with a spin coater while the adhesion of the protective film 31 to the Cu seed film 30 is reduced by heating the substrate 20.

[0114] Next, as shown in FIG. 15F , Cu 32 is embedded inside the via 27 and the trench 28. The embedding process of Cu 32 is performed, for example, using the same atmospheric equipment that removes the protective film 31. By removing the protective film 31 covering the surface of the Cu seed film 30 immediately before embedding Cu 32, Cu 32 can be embedded on the Cu seed film 30, whose surface oxidation has been suppressed. This suppresses a decrease in adhesion between the Cu seed film 30 and Cu 32, thereby improving resistance to stress migration (SM) and electromigration (EM). In contrast, if the protective film 31 is not used, the surface of the Cu seed film 30 is likely to be oxidized before embedding Cu 32, which reduces adhesion between the Cu seed film 30 and Cu 32 and makes SM defects and EM defects more likely to occur. Embedding Cu 32 can be performed, for example, by plating, but is not limited thereto. Examples of plating methods include electroless deposition (ELD) and electrochemical deposition (ECD). The filling of the vias 27 and the trenches 28 with Cu 32 is performed in the same module (spin coater) as the atmospheric device used to remove the protective film 31.

[0115] As described above, according to the embodiment, after the Cu seed film 30 is formed, a liquid material containing an ionic liquid is applied to the surface of the Cu seed film 30 to form the protective film 31, and the protective film 31 is removed immediately before embedding Cu 32. This makes it possible to prevent a natural oxide film from being formed on the surface of the Cu seed film 30.

[0116] In the above embodiment, the TaN film 29 and the Cu seed film 30 are formed inside the via 27 and the trench 28, and then the protective film 31 is formed, and after the protective film 31 is removed, Cu 32 is embedded. However, the present disclosure is not limited to this. For example, the Cu seed film 30 may be omitted.

[0117] [Modification of slit coater] The configuration of the slit coater of the first modified example will be described with reference to Fig. 16. Fig. 16 is a schematic diagram showing the slit coater of the first modified example.

[0118] The slit coater 700 includes a stage 710 , a liquid supply unit 720 , a substage 730 , a concentration measurement nozzle 740 , and a control unit 790 .

[0119] The stage 710 places the wafer W in a substantially horizontal position. The stage 710 is connected to the upper end of a rotation shaft 712 that is rotated by a drive mechanism 711, and is configured to be rotatable. A liquid receiving portion 713 that is open on the upper side is provided around the lower periphery of the stage 710. The liquid receiving portion 713 receives liquid material that spills or is shaken off from the wafer W.

[0120] The liquid supply unit 720 includes an ionic liquid supply source 721 , an ionic liquid supply pipe 722 , a cleaning liquid supply source 723 , a cleaning liquid supply pipe 724 , and a slit nozzle 725 .

[0121] The ionic liquid supply source 721 supplies the ionic liquid IL to the slit nozzle 725 via the ionic liquid supply pipe 722. The ionic liquid IL may be the ionic liquid described above.

[0122] The ionic liquid supply pipe 722 is a pipe that supplies the ionic liquid IL from the ionic liquid supply source 721 to the slit nozzle 725. The ionic liquid supply pipe 722 is formed of, for example, a conductive member.

[0123] A cleaning liquid supply source 723 supplies cleaning liquid CL to a slit nozzle 725 via a cleaning liquid supply pipe 724. The cleaning liquid CL is preferably a liquid material containing isopropyl alcohol (IPA) that is commonly used in semiconductor cleaning processes, but may also be a cleaning agent used in other semiconductor processes (for example, an acidic cleaning agent such as phosphoric acid, hydrofluoric acid, hydrochloric acid, or nitric acid, or an alkaline cleaning liquid such as SC1 (NH4OH / HO2 / HO)).

[0124] The cleaning liquid supply pipe 724 is a pipe that supplies the cleaning liquid CL from the cleaning liquid supply source 723 to the slit nozzle 725. The cleaning liquid supply pipe 724 is formed of, for example, a conductive member.

[0125] Slit nozzle 725 moves horizontally above wafer W to supply ionic liquid IL and cleaning liquid CL to the surface of wafer W placed on stage 710. Slit nozzle 725 also moves above substage 730 to supply ionic liquid IL and cleaning liquid CL onto substage 730. Slit nozzle 725 includes a main body 725a, an outer shell 725b, an ionic liquid supply port 725c, and a cleaning liquid supply port 725d.

[0126] The main body 725a has an ionic liquid flow channel 725e therein. The ionic liquid flow channel 725e is connected to the ionic liquid supply pipe 722 via an ionic liquid supply port 725c formed in the upper part of the main body 725a. As a result, the ionic liquid IL from the ionic liquid supply source 721 is supplied to the ionic liquid flow channel 725e via the ionic liquid supply pipe 722 and the ionic liquid supply port 725c, and is discharged from the lower end of the ionic liquid flow channel 725e. The main body 725a is formed, for example, from an insulating material. The flow channel cross-sectional area of the ionic liquid flow channel 725e is optimized depending on the viscosity and contact angle (wettability) of the ionic liquid IL.

[0127] The outer cover 725b is provided outside the main body 725a so as to form a cleaning liquid flow path 725f between itself and the outer surface of the main body 725a. The cleaning liquid flow path 725f is connected to the cleaning liquid supply pipe 724 via a cleaning liquid supply port 725d. As a result, the cleaning liquid CL from the cleaning liquid supply source 723 is supplied to the cleaning liquid flow path 725f via the cleaning liquid supply pipe 724 and the cleaning liquid supply port 725d and is discharged from the lower end of the cleaning liquid flow path 725f. The outer cover 725b is formed of, for example, a conductive material. The flow path cross-sectional area of the cleaning liquid flow path 725f is optimized depending on the viscosity and contact angle (wettability) of the cleaning liquid CL.

[0128] In this way, slit nozzle 725 has a double piping structure including ionic liquid flow path 725e and cleaning liquid flow path 725f formed by main body 725a and outer cover 725b. This allows ionic liquid IL and cleaning liquid CL to be applied with a single slit nozzle 725.

[0129] The substage 730 is provided separately from the stage 710 at a position where the ionic liquid IL and cleaning liquid CL can be applied by the liquid supply unit 720. In the example of FIG. 16, the substage 730 is provided to the side of the stage 710. A plate-like member 731 having an opening 731a is provided on the upper surface of the substage 730 in the area where the ionic liquid IL and cleaning liquid CL are applied. The temperature of the upper surface of the substage 730 can be adjusted by heating means or cooling means. The heating means may be, for example, a heater embedded inside the substage 730. The cooling means may be, for example, a refrigerant flow path formed inside the substage 730.

[0130] The concentration measurement nozzle 740 is formed, for example, by a tubular member. One end of the concentration measurement nozzle 740 is positioned so as to come into contact with the ionic liquid IL and cleaning liquid CL applied to the substage 730. As a result, when the ionic liquid IL and cleaning liquid CL are applied to the substage 730 by the liquid supply unit 720, a portion of the applied ionic liquid IL and cleaning liquid CL is sucked up from one end of the tubular member. That is, the concentration measurement nozzle 740 can recover a portion of the ionic liquid IL and cleaning liquid CL applied to the substage 730 by the liquid supply unit 720. The concentrations of the ionic liquid IL and cleaning liquid CL recovered by the concentration measurement nozzle 740 can be confirmed by performing various measurements on the ionic liquid IL and cleaning liquid CL. Examples of such measurements include resistivity measurement, chromatographic measurement, and optical measurement (e.g., FT-IR). In the case of ionic liquid IL for plating applications, examples of such measurements include colorimetric measurement and non-contact conductivity measurement.

[0131] The control unit 790 controls each element of the slit coater 700. For example, the control unit 790 processes computer-executable instructions that cause the slit coater 700 to perform the wet treatment performed in the atmospheric treatment step S12 and the application of the liquid material containing the ionic liquid IL performed in the protective film formation step S13. The control unit 790 can be configured to control each element of the slit coater 700 to perform the wet treatment performed in the atmospheric treatment step S12 and the application of the liquid material containing the ionic liquid IL performed in the protective film formation step S13. The control unit 790 includes, for example, a computer. The computer includes, for example, a CPU, a storage unit, and a communication interface.

[0132] An example of the operation of the slit coater 700 of the first modified example will be described with reference to Fig. 17. Fig. 17 is a diagram showing an example of the operation of the slit coater 700 of the first modified example, and shows an example of the operation when measuring the concentration of the ionic liquid IL after applying the ionic liquid IL to a wafer W placed on a stage 710.

[0133] First, the control unit 790 moves the slit nozzle 725 horizontally above the wafer W placed on the stage 710, while discharging the ionic liquid IL from the slit nozzle 725 toward the wafer W. As a result, the ionic liquid IL is applied onto the wafer W placed on the stage 710, as shown in the left diagram of FIG.

[0134] Next, the control unit 790 moves the slit nozzle 725 to a position above the substage 730, corresponding to the opening 731a of the plate-like member 731. The control unit 790 also ejects the ionic liquid IL from the slit nozzle 725 toward the substage 730. As a result, the ionic liquid IL is applied onto the substage 730, as shown in the right diagram of FIG.

[0135] At this time, a portion of the ionic liquid IL discharged onto the substage 730 is sucked up by the concentration measurement nozzle 740. Therefore, by performing various measurements on the ionic liquid IL sucked up by the concentration measurement nozzle 740, the concentration of the ionic liquid IL can be confirmed.

[0136] Furthermore, when checking the concentration of the ionic liquid IL, it is preferable to adjust the temperature of the substage 730 in order to reduce the surface tension (viscosity) of the ionic liquid and make it easier to measure the concentration.

[0137] Another example of the operation of the slit coater 700 of the first modified example will be described with reference to Fig. 18. Fig. 18 is a diagram showing another example of the operation of the slit coater 700 of the first modified example, and shows an example of the operation when the slit nozzle 725 is automatically cleaned after the ionic liquid IL is applied onto the wafer W placed on the stage 710.

[0138] First, the control unit 790 moves the slit nozzle 725 horizontally above the wafer W placed on the stage 710, while discharging the ionic liquid IL from the slit nozzle 725 toward the wafer W. As a result, the ionic liquid IL is applied onto the wafer W placed on the stage 710, as shown in the left diagram of FIG.

[0139] Next, control unit 790 moves slit nozzle 725 to a position above substage 730 corresponding to opening 731a of plate-like member 731. Control unit 790 also ejects cleaning liquid CL from slit nozzle 725 onto substage 730. As a result, as shown in the right diagram of FIG. 18 , cleaning liquid CL is applied onto substage 730, and the tip of slit nozzle 725 is cleaned.

[0140] 19 and 20, a mechanism for preventing contact between the ionic liquid IL and the cleaning liquid CL in the slit coater 700 of the first modified example will be described.

[0141] FIG. 19 is a diagram for explaining a mechanism for suppressing contact between the ionic liquid IL and the cleaning liquid CL, and shows an example of the operation when the liquid material discharged from the slit nozzle 725 is switched from the ionic liquid IL to the cleaning liquid CL.

[0142] First, as shown in FIG. 19(a), the control unit 790 stops the slit nozzle 725 from discharging the ionic liquid IL.

[0143] Subsequently, as shown in FIG. 19(b), the control unit 790 sucks the ionic liquid IL back upward in the ionic liquid flow channel 725e, for example, by a suck-back operation.

[0144] Next, as shown in FIG. 19(c), the control unit 790 moves the slit nozzle 725 to a position above the substage 730, corresponding to the opening 731a of the plate-like member 731. The control unit 790 also ejects the cleaning liquid CL from the slit nozzle 725 onto the substage 730. At this time, some of the cleaning liquid CL flows into the ionic liquid flow path 725e, but the ionic liquid IL is sucked back into the ionic liquid flow path 725e due to a suck-back operation. Therefore, an air pocket AP is formed between the ionic liquid IL and the cleaning liquid CL in the ionic liquid flow path 725e. As a result, mixing of the ionic liquid IL into the cleaning liquid CL can be suppressed.

[0145] Furthermore, a portion of the cleaning liquid CL is sucked up by the concentration measurement nozzle 740. Therefore, by performing various measurements on the cleaning liquid CL sucked up by the concentration measurement nozzle 740, the concentration of the cleaning liquid CL can be confirmed. The concentration of the cleaning liquid CL shows different values depending on whether or not the ionic liquid IL is mixed in. Therefore, by checking the concentration of the cleaning liquid CL, it can be confirmed whether or not the ionic liquid IL is mixed in the cleaning liquid CL.

[0146] 19(d), the control unit 790 discharges the cleaning liquid CL from the slit nozzle 725 toward the wafer W while moving the slit nozzle 725 horizontally above the wafer W placed on the stage 710. As a result, the cleaning liquid CL is applied onto the wafer W placed on the stage 710.

[0147] As described above, the slit coater 700 of the first modified example can prevent the ionic liquid IL from coming into contact with the cleaning liquid CL when switching the liquid material discharged from the slit nozzle 725 from the ionic liquid IL to the cleaning liquid CL. As a result, it is possible to prevent the concentration of the cleaning liquid CL from becoming unstable after switching from the ionic liquid IL to the cleaning liquid CL.

[0148] FIG. 20 is a diagram for explaining a mechanism for suppressing contact between the ionic liquid IL and the cleaning liquid CL, and shows an example of the operation when the liquid material discharged from the slit nozzle 725 is switched from the cleaning liquid CL to the ionic liquid IL.

[0149] First, as shown in FIG. 20(a), the control unit 790 stops the slit nozzle 725 from discharging the cleaning liquid CL.

[0150] Subsequently, as shown in FIG. 20(b), the control unit 790 sucks the cleaning liquid CL back upward in the cleaning liquid flow path 725f, for example, by a suck-back operation.

[0151] Next, as shown in FIG. 20(c), the control unit 790 moves the slit nozzle 725 to a position above the substage 730, corresponding to the opening 731a of the plate-like member 731. The control unit 790 also ejects the ionic liquid IL from the slit nozzle 725 onto the substage 730. At this time, some of the ionic liquid IL flows into the cleaning liquid flow path 725f, but the cleaning liquid CL is sucked back into the cleaning liquid flow path 725f by a suck-back operation. Therefore, an air pocket AP is formed between the cleaning liquid CL and the ionic liquid IL in the cleaning liquid flow path 725f. As a result, mixing of the cleaning liquid CL with the ionic liquid IL can be suppressed.

[0152] Furthermore, a portion of the ionic liquid IL is sucked up into the concentration measurement nozzle 740. The concentration of the ionic liquid IL can be confirmed by performing various measurements on the ionic liquid IL sucked up by the concentration measurement nozzle 740. The concentration of the ionic liquid IL exhibits different values depending on whether or not the cleaning liquid CL is mixed in. Therefore, by checking the concentration of the ionic liquid IL, it is possible to confirm whether or not the cleaning liquid CL is mixed into the ionic liquid IL.

[0153] 20(d), the control unit 790 ejects the ionic liquid IL from the slit nozzle 725 toward the wafer W while moving the slit nozzle 725 horizontally above the wafer W placed on the stage 710. As a result, the ionic liquid IL is applied onto the wafer W placed on the stage 710.

[0154] As described above, the slit coater 700 of the first modified example can prevent the cleaning liquid CL from coming into contact with the ionic liquid IL when switching the liquid material discharged from the slit nozzle 725 from the cleaning liquid CL to the ionic liquid IL. As a result, it is possible to prevent the concentration of the ionic liquid IL from becoming unstable after switching from the cleaning liquid CL to the ionic liquid IL.

[0155] The configuration of a slit coater according to a second modified example will be described with reference to Figures 21 and 22. Figure 21 is a schematic diagram showing the slit coater according to the second modified example. Figure 22 is an electric circuit diagram for explaining a stage ground circuit.

[0156] The slit coater 800 includes a stage 810 , a liquid supply unit 820 , a substage 830 , a concentration measurement nozzle 840 , a stage ground circuit 850 , a nozzle position adjustment unit 860 , and a control unit 890 .

[0157] The stage 810, liquid supply unit 820, substage 830, concentration measurement nozzle 840, and control unit 890 may have the same configuration as the stage 710, liquid supply unit 720, substage 730, concentration measurement nozzle 740, and control unit 790 in the slit coater 700.

[0158] The stage 810 places the wafer W in a substantially horizontal position. The stage 810 is connected to the upper end of a rotation shaft 812 that is rotated by a drive mechanism 811, and is configured to be rotatable. A liquid receiving portion 813 that is open on the upper side is provided around the lower periphery of the stage 810. The liquid receiving portion 813 receives liquid material that spills or is shaken off from the wafer W.

[0159] Liquid supply unit 820 includes an ionic liquid supply source 821, an ionic liquid supply pipe 822, a cleaning liquid supply source 823, a cleaning liquid supply pipe 824, and a slit nozzle 825. Slit nozzle 825 has a main body 825a, an outer shell 825b, an ionic liquid supply port 825c, a cleaning liquid supply port 825d, an ionic liquid flow path 825e, and a cleaning liquid flow path 825f.

[0160] On the upper surface of the substage 830, a plate-like member 831 having an opening 831a in the area where the ionic liquid IL and cleaning liquid CL are to be applied is provided.

[0161] The stage ground circuit 850 includes a power supply 851 , an ammeter 852 , and wiring 853 .

[0162] The power supply 851 applies a direct current (DC) voltage between the ionic liquid supply pipe 822 and the stage 810 via wiring 853. This causes a small current to flow from the ionic liquid supply pipe 822 to the stage 810 via the ionic liquid IL. The power supply 851 also applies a DC voltage between the ionic liquid supply pipe 822 and the substage 830 via wiring 853. This causes a small current to flow from the ionic liquid supply pipe 822 to the substage 830 via the ionic liquid IL. The power supply 851 may superimpose an alternating current (AC) component on the DC voltage.

[0163] An ammeter 852 is provided on the wiring 853. The ammeter 852 measures the minute current flowing from the ionic liquid supply pipe 822 to the stage 810 via the ionic liquid IL. The value of this minute current changes depending on the volume of the liquid mound T1 formed by the ionic liquid IL on the wafer W placed on the stage 810. Therefore, by monitoring the value of the minute current measured by the ammeter 852, the volume of the liquid mound T1 formed by the ionic liquid IL on the wafer W can be determined. The ammeter 852 also measures the minute current flowing from the ionic liquid supply pipe 822 to the substage 830 via the ionic liquid IL. The value of this minute current changes depending on the volume of the liquid mound T2 formed by the ionic liquid IL on the substage 830. Therefore, by monitoring the value of the minute current measured by the ammeter 852, the volume of the liquid mound T2 formed by the ionic liquid IL on the substage 830 can be determined.

[0164] The wiring 853 electrically connects the power supply 851 with the ionic liquid supply pipe 822, the stage 810, and the substage 830.

[0165] The nozzle position adjustment unit 860 controls the height position of the slit nozzle 825 based on the measurement value of the ammeter 852 so that the volume of the liquid mound T1 formed by the ionic liquid IL on the wafer W placed on the stage 810 is constant. Furthermore, the nozzle position adjustment unit 860 controls the height position of the slit nozzle 825 based on the measurement value of the ammeter 852 so that the volume of the liquid mound T2 formed by the ionic liquid IL on the substage 830 is constant. Furthermore, the nozzle position adjustment unit 860 may control the height position of the slit nozzle 825 based on the resistance value of the ionic liquid IL calculated based on the DC voltage applied by the power supply 851 and the minute current measured by the ammeter 852. The nozzle position adjustment unit 860 includes a feedback control circuit 861 and an actuator 862.

[0166] The feedback control circuit 861 controls the actuator 862 based on the measurement value of the ammeter 852. For example, the feedback control circuit 861 controls the actuator 862 so that the measurement value of the ammeter 852 becomes constant. This makes it possible to maintain a substantially constant distance between the upper surface of the wafer W and the tip of the slit nozzle 825. Furthermore, it is possible to maintain a substantially constant distance between the upper surface of the substage 830 and the tip of the slit nozzle 825. The feedback control circuit 861 may be included in the control unit 890.

[0167] The actuator 862 moves the slit nozzle 825 up and down based on a signal from the feedback control circuit 861 .

[0168] As described above, in the slit coater 800 of the second modified example, the nozzle position adjustment unit 860 controls the height position of the slit nozzle 825 based on the measurement value of the ammeter 852 so that the volume of the liquid heap T1 on the wafer W placed on the stage 810 is constant. This allows the ionic liquid IL to be applied onto the wafer W from the slit nozzle 825 while maintaining a substantially constant distance between the upper surface of the wafer W and the tip of the slit nozzle 825. As a result, the in-plane uniformity of the thickness of the ionic liquid IL applied onto the wafer W is improved.

[0169] Furthermore, in the slit coater 800 of the second modified example, the nozzle position adjustment unit 860 controls the height position of the slit nozzle 825 based on the measurement value of the ammeter 852 so that the volume of the liquid heap T2 on the substage 830 is constant. This allows the ionic liquid IL to be applied from the slit nozzle 825 onto the substage 830 while maintaining a substantially constant distance between the upper surface of the substage 830 and the tip of the slit nozzle 825.

[0170] Furthermore, the slit coater 800 of the second modified example has a power supply 851 that applies a DC voltage between the ionic liquid supply pipe 822 and the stage 810. As a result, by applying a DC voltage between the ionic liquid supply pipe 822 and the stage 819 by the power supply 851 while supplying the ionic liquid IL for plating from the slit nozzle 825, electrolytic plating can be performed using the slit coater 800.

[0171] The configuration of a slit coater according to a third modified example will be described with reference to Figures 23 and 24. Figure 23 is a schematic diagram showing the slit coater according to the third modified example. Figure 24 is an electric circuit diagram for explaining an outer skin grounding circuit.

[0172] The slit coater 900 includes a stage 910 , a liquid supply unit 920 , a substage 930 , a concentration measurement nozzle 940 , an outer skin grounding circuit 950 , a nozzle position adjustment unit 960 , and a control unit 990 .

[0173] The stage 910, liquid supply unit 920, substage 930, concentration measurement nozzle 940, and control unit 990 may have the same configuration as the stage 710, liquid supply unit 720, substage 730, concentration measurement nozzle 740, and control unit 790 in the slit coater 700.

[0174] The stage 910 places the wafer W in a substantially horizontal position. The stage 910 is connected to the upper end of a rotation shaft 912 that is rotated by a drive mechanism 911, and is configured to be rotatable. A liquid receiving portion 913 that is open on the upper side is provided around the lower periphery of the stage 910. The liquid receiving portion 913 receives liquid material that spills or is shaken off from the wafer W.

[0175] Liquid supply unit 920 includes an ionic liquid supply source 921, an ionic liquid supply pipe 922, a cleaning liquid supply source 923, a cleaning liquid supply pipe 924, and a slit nozzle 925. Slit nozzle 925 has a main body 925a, an outer shell 925b, an ionic liquid supply port 925c, a cleaning liquid supply port 925d, an ionic liquid flow path 925e, and a cleaning liquid flow path 925f.

[0176] On the upper surface of the substage 930, a plate-like member 931 having an opening 931a in the area where the ionic liquid IL and cleaning liquid CL are to be applied is provided.

[0177] The outer skin ground circuit 950 includes a power supply 951 , an ammeter 952 and wiring 953 .

[0178] Power supply 951 applies a DC voltage between ionic liquid supply pipe 922 and outer skin 925b via wiring 953. This causes a small current to flow from ionic liquid supply pipe 922 to outer skin 925b via ionic liquid IL. Note that power supply 951 may superimpose an AC component on the DC voltage.

[0179] An ammeter 952 is provided on the wiring 953. The ammeter 952 measures the minute current flowing from the ionic liquid supply pipe 922 through the ionic liquid IL to the outer skin 925b. The value of this minute current changes depending on the volume of the liquid mound T1 formed by the ionic liquid IL on the wafer W placed on the stage 910. Therefore, by monitoring the value of the minute current measured by the ammeter 952, the volume of the liquid mound T1 formed by the ionic liquid IL on the wafer W can be determined. Furthermore, the value of this minute current changes depending on the volume of the liquid mound T2 formed by the ionic liquid IL on the substage 930. Therefore, by monitoring the value of the minute current measured by the ammeter 952, the volume of the liquid mound T2 formed by the ionic liquid IL on the substage 930 can be determined.

[0180] Wiring 953 electrically connects power supply 951 with ionic liquid supply pipe 922 and outer skin 925b.

[0181] The nozzle position adjustment unit 960 controls the height position of the slit nozzle 925 based on the measurement value of the ammeter 952 so that the volume of the liquid mound T1 formed by the ionic liquid IL on the wafer W placed on the stage 910 is constant. Furthermore, the nozzle position adjustment unit 960 controls the height position of the slit nozzle 925 based on the measurement value of the ammeter 952 so that the volume of the liquid mound T2 formed by the ionic liquid IL on the substage 930 is constant. Furthermore, the nozzle position adjustment unit 960 may control the height position of the slit nozzle 925 based on the resistance value of the ionic liquid IL calculated based on the DC voltage applied by the power supply 951 and the minute current measured by the ammeter 952. The nozzle position adjustment unit 960 includes a feedback control circuit 961 and an actuator 962.

[0182] The feedback control circuit 961 controls the actuator 962 based on the measurement value of the ammeter 952. For example, the feedback control circuit 961 controls the actuator 962 so that the measurement value of the ammeter 952 becomes constant. This makes it possible to maintain a substantially constant distance between the upper surface of the wafer W and the tip of the slit nozzle 925. Also, it makes it possible to maintain a substantially constant distance between the upper surface of the substage 930 and the tip of the slit nozzle 925. The feedback control circuit 961 may be included in the control unit 990.

[0183] The actuator 962 raises and lowers the slit nozzle 925 based on a signal from the feedback control circuit 961 .

[0184] As described above, in the slit coater 900 of the third modified example, the nozzle position adjustment unit 960 controls the height position of the slit nozzle 925 based on the measurement value of the ammeter 952 so that the volume of the liquid heap T1 on the wafer W placed on the stage 910 is constant. This allows the ionic liquid IL to be applied onto the wafer W from the slit nozzle 925 while maintaining a substantially constant distance between the upper surface of the wafer W and the tip of the slit nozzle 925. As a result, the in-plane uniformity of the thickness of the ionic liquid IL applied onto the wafer W is improved.

[0185] Furthermore, in the slit coater 900 of the third modified example, the nozzle position adjustment unit 960 controls the height position of the slit nozzle 925 based on the measurement value of the ammeter 952 so that the volume of the liquid heap T2 on the substage 930 is constant. This allows the ionic liquid IL to be applied from the slit nozzle 925 onto the substage 930 while maintaining a substantially constant distance between the upper surface of the substage 930 and the tip of the slit nozzle 925.

[0186] The configuration of the slit coater of the fourth modified example will be described with reference to Fig. 25. Fig. 25 is a schematic diagram showing the slit coater of the fourth modified example.

[0187] The slit coater 1000 includes a stage 1010 , an edge liquid supply unit 1020 , and a control unit 1090 .

[0188] The stage 1010 and the control unit 1090 may have the same configuration as the stage 701 and the control unit 790 in the slit coater 700 .

[0189] The stage 1010 places the wafer W in a substantially horizontal position. The stage 1010 is connected to the upper end of a rotation shaft 1012 that is rotated by a drive mechanism 1011, and is configured to be rotatable. A liquid receiving portion 1013 that is open on the upper side is provided around the lower periphery of the stage 1010. The liquid receiving portion 1013 receives liquid material that spills or is shaken off from the wafer W.

[0190] The edge liquid supply unit 1020 applies a liquid material to the edge of the wafer W. The edge liquid supply unit 1020 includes an ionic liquid supply source 1021, an ionic liquid supply pipe 1022, a cleaning liquid supply source 1023, a cleaning liquid supply pipe 1024, and a slit nozzle 1025.

[0191] The ionic liquid supply source 1021 , the ionic liquid supply pipe 1022 , the cleaning liquid supply source 1023 , and the cleaning liquid supply pipe 1024 may have the same configuration as the ionic liquid supply source 721 , the ionic liquid supply pipe 722 , the cleaning liquid supply source 723 , and the cleaning liquid supply pipe 724 .

[0192] The slit nozzle 1025 is configured to be movable on the side of the wafer W between a position approaching the wafer W and a position spaced apart from the wafer W. By moving to a position approaching the wafer W, the slit nozzle 1025 supplies the ionic liquid IL and the cleaning liquid CL to the edge of the wafer W placed on the stage 1010. The slit nozzle 1025 includes a main body 1025a, an outer shell 1025b, an ionic liquid supply port 1025c, a cleaning liquid supply port 1025d, an ionic liquid flow path 1025e, and a cleaning liquid flow path 1025f.

[0193] The main body 1025a, outer skin 1025b, ionic liquid supply port 1025c, cleaning liquid supply port 1025d, ionic liquid flow path 1025e, and cleaning liquid flow path 1025f may have the same configuration as the main body 725a, outer skin 725b, ionic liquid supply port 725c, cleaning liquid supply port 725d, ionic liquid flow path 725e, and cleaning liquid flow path 725f in the slit nozzle 725.

[0194] The slit nozzle 1025 may be configured to supply the ionic liquid IL and the cleaning liquid CL to the surface of the wafer W placed on the stage 1010 by moving horizontally above the wafer W.

[0195] An example of the operation of the slit coater 1000 of the fourth modified example will be described with reference to Fig. 26. Fig. 26 is a diagram showing an example of the operation of the slit coater 1000 of the fourth modified example, and shows an example of the operation when applying ionic liquid IL to the edge of a wafer W placed on a stage 1010.

[0196] 26 , when applying the ionic liquid IL to the edge of the wafer W placed on the stage 1010, the control unit 1090 moves the slit nozzle 1025 to a position close to the wafer W. Next, the control unit 1090 causes the driving mechanism 1011 to rotate the stage 1010 and the wafer W placed on the stage 1010 via the rotation shaft 1012 while discharging the ionic liquid IL from the slit nozzle 1025 toward the edge of the wafer W. This causes the ionic liquid IL to be applied to the entire circumference of the edge of the wafer W placed on the stage 1010.

[0197] Another example of the operation of the slit coater 1000 of the fourth modified example will be described with reference to Fig. 27. Fig. 27 is a diagram showing another example of the operation of the slit coater 1000 of the fourth modified example, and shows an example of the operation when applying cleaning liquid CL to the edge of the wafer W placed on the stage 1010.

[0198] 27 , when the cleaning liquid CL is to be applied to the edge of the wafer W placed on the stage 1010, the control unit 1090 moves the slit nozzle 1025 to a position close to the wafer W. Next, the control unit 1090 causes the driving mechanism 1011 to rotate the stage 1010 and the wafer W placed on the stage 1010 via the rotation shaft 1012 while discharging the cleaning liquid CL from the slit nozzle 1025 toward the edge of the wafer W. As a result, the cleaning liquid CL is applied to the entire circumference of the edge of the wafer W placed on the stage 1010.

[0199] 28A to 28C, an application example of the fourth modified slit coater 1000 will be described. Figures 28A to 28C are diagrams for explaining an application example of the fourth modified slit coater 1000. Below, as an application example of the slit coater 1000, a film formation method for forming an oxide film on a wafer W will be described.

[0200] First, as shown in Fig. 28A, an ionic liquid IL is selectively applied to the edge of a wafer W using a slit coater 1000 (ionic liquid application step). As the ionic liquid IL, an ionic liquid in which an element that inhibits adsorption of a precursor used in the film formation step described below is coordinated on the surface can be used. Examples of such elements include halogens such as fluorine (F), chlorine (Cl), bromine (Br), iodine (I), astatine (At), and tennessine (Ts).

[0201] Next, as shown in FIG. 28B, a vacuum film-forming apparatus (for example, the vacuum film-forming apparatus 100 described above) is used to form an oxide film Ox on the wafer W whose edges have been coated with the ionic liquid IL in the ionic liquid coating process (film-forming process). Methods for forming the oxide film Ox include, for example, atomic layer deposition (ALD) and chemical vapor deposition (CVD). In the film-forming process, if OH groups are present on the surface of the wafer W, precursors are adsorbed to these groups, thereby depositing an oxide film. However, the aforementioned halogens inhibit the adsorption of precursors by substituting the OH groups on the surface of the wafer W. Therefore, no oxide film Ox is formed on the edges of the wafer W, or even if a film is formed, only a small amount of oxide film Ox is formed.

[0202] Next, a cleaning liquid CL is selectively applied to the edge of the wafer W using a slit coater 1000 (cleaning liquid application step). As a result, as shown in FIG. 28C, the ionic liquid IL applied to the edge of the wafer W is washed away by the cleaning liquid CL. As a result, an oxide film Ox remains on the wafer W in the region other than the edge. At this time, even if a small amount of oxide film Ox is formed on the ionic liquid IL at the edge of the wafer W during the film formation step, the oxide film Ox is washed away and removed together with the ionic liquid IL. The cleaning liquid CL is preferably a liquid material containing isopropyl alcohol (IPA) that is frequently used in semiconductor cleaning steps, but may also be other cleaning agents used in semiconductor processes (e.g., acidic cleaning agents such as phosphoric acid, hydrofluoric acid, hydrochloric acid, and nitric acid, or alkaline cleaning liquids such as SC1 (NH4OH / HO2 / HO)).

[0203] According to the film forming method described above, film formation on the edge (for example, bevel portion) of the wafer W can be prevented, and therefore dust generation from the edge of the wafer W can be suppressed.

[0204] 28A to 28C have been described with reference to an example in which an oxide film Ox is formed on a wafer W, but the present invention is not limited to this. For example, the present invention can be similarly applied to a case in which a nitride film is formed on a wafer W. In this case, the halogen substitutes for NH groups on the surface of the wafer W, thereby inhibiting the adsorption of the precursor.

[0205] Furthermore, the slit coater 1000 of the fourth modified example may be provided with a stage ground circuit and a nozzle position adjustment unit similar to the stage ground circuit 850 and the nozzle position adjustment unit 860 in the slit coater 800 of the second modified example. This allows the ionic liquid IL to be applied to the edge of the wafer W from the slit nozzle 1025 while maintaining a substantially constant distance between the edge of the wafer W and the tip of the slit nozzle 1025. As a result, the circumferential uniformity of the thickness of the ionic liquid IL applied to the edge of the wafer W is improved.

[0206] Furthermore, the slit coater 1000 of the fourth modified example may be provided with an outer surface grounding circuit and a nozzle position adjusting unit similar to the outer surface grounding circuit 950 and the nozzle position adjusting unit 960 of the slit coater 900 of the third modified example. This allows the ionic liquid IL to be applied to the edge of the wafer W from the slit nozzle 1025 while maintaining a substantially constant distance between the edge of the wafer W and the tip of the slit nozzle 1025. As a result, the circumferential uniformity of the thickness of the ionic liquid IL applied to the edge of the wafer W is improved.

[0207] The configuration of the slit coater of the fifth modified example will be described with reference to Fig. 29. Fig. 29 is a schematic diagram showing the slit coater of the fifth modified example.

[0208] The slit coater 1100 includes a stage 1110 , an edge liquid supply unit 1120 , a substage 1130 , a concentration measurement nozzle 1140 , and a control unit 1190 .

[0209] The stage 1110 and the control unit 1190 may have the same configuration as the stage 710 and the control unit 790 in the slit coater 700 .

[0210] The stage 1110 places the wafer W in a substantially horizontal position. The stage 1110 is connected to the upper end of a rotation shaft 1112 that is rotated by a drive mechanism 1111, and is configured to be rotatable. A liquid receiving portion 1113 that is open on the upper side is provided around the lower periphery of the stage 1110. The liquid receiving portion 1113 receives liquid material that spills or is shaken off from the wafer W.

[0211] The edge liquid supply unit 1120 applies a liquid material to the edge of the wafer W. The edge liquid supply unit 1120 includes an ionic liquid supply source 1121, an ionic liquid supply pipe 1122, a cleaning liquid supply source 1123, a cleaning liquid supply pipe 1124, and a slit nozzle 1125. The ionic liquid supply source 1121, the ionic liquid supply pipe 1122, the cleaning liquid supply source 1123, the cleaning liquid supply pipe 1124, and the slit nozzle 1125 may have the same configuration as the ionic liquid supply source 1021, the ionic liquid supply pipe 1022, the cleaning liquid supply source 1023, the cleaning liquid supply pipe 1024, and the slit nozzle 1025 in the slit coater 1000.

[0212] Slit nozzle 1125 includes a main body 1125a, an outer shell 1125b, an ionic liquid supply port 1125c, a cleaning liquid supply port 1125d, an ionic liquid channel 1125e, and a cleaning liquid channel 1125f. Main body 1125a, outer shell 1125b, ionic liquid supply port 1125c, cleaning liquid supply port 1125d, ionic liquid channel 1125e, and cleaning liquid channel 1125f may have the same configuration as main body 725a, outer shell 725b, ionic liquid supply port 725c, cleaning liquid supply port 725d, ionic liquid channel 725e, and cleaning liquid channel 725f of slit nozzle 725.

[0213] The substage 1130 is provided separately from the stage 1110 at a position where the ionic liquid IL and cleaning liquid CL can be applied by the edge liquid supply unit 1120. The substage 1130 is configured to be movable between an application position and a retracted position. The application position is a position where the slit nozzle 1125 can apply the liquid material to the application surface of the substage 1130 when the slit nozzle 1125 moves to a position away from the wafer W. The retracted position is a position where the slit nozzle 1125 does not come into contact with the wafer W when moving between a position approaching the wafer W and a position away from the wafer W. Note that FIG. 29 shows the substage 1130 moved to the retracted position. The application surface of the substage 1130 is provided with a plate-like member 1131 having an opening 1131a in the area where the ionic liquid IL and cleaning liquid CL are applied. The temperature of the application surface of the substage 1130 can be adjusted by heating or cooling means. The heating means may be, for example, a heater embedded inside the substage 1130. The cooling means may be, for example, a coolant flow path formed inside the substage 1130.

[0214] The concentration measurement nozzle 1140 is formed, for example, from a tubular member. One end of the concentration measurement nozzle 1140 is positioned so that it comes into contact with the ionic liquid IL and cleaning liquid CL applied to the application surface of the substage 1130. As a result, when the ionic liquid IL and cleaning liquid CL are applied to the application surface of the substage 1130 by the end liquid supply unit 1120, some of the applied ionic liquid IL and cleaning liquid CL are sucked up from one end of the tubular member. In other words, the concentration measurement nozzle 1140 can recover some of the ionic liquid IL and cleaning liquid CL applied to the application surface of the substage 1130 by the end liquid supply unit 1120. The concentrations of the ionic liquid IL and cleaning liquid CL recovered by the concentration measurement nozzle 1140 can be confirmed by performing various measurements on the ionic liquid IL and cleaning liquid CL. Examples of such measurements include resistivity measurement, chromatographic measurement, and optical measurement (e.g., FT-IR). In the case of ionic liquid IL for plating applications, examples of such measurements include colorimetric measurement and non-contact conductivity measurement.

[0215] An example of the operation of the slit coater 1100 of the fifth modified example will be described with reference to Figures 30 and 31. Figures 30 and 31 are diagrams showing an example of the operation of the slit coater 1100 of the fifth modified example, and show an example of the operation when measuring the concentration of the ionic liquid IL after applying the ionic liquid IL to the edge of the wafer W placed on the stage 1110.

[0216] 30 , the control unit 1190 moves the slit nozzle 1125 to a position close to the wafer W. Next, the control unit 1190 causes the driving mechanism 1111 to rotate the stage 1110 and the wafer W placed on the stage 1110 via the rotation shaft 1112 while discharging the ionic liquid IL from the slit nozzle 1125 toward the edge of the wafer W. As a result, the ionic liquid IL is applied to the entire periphery of the edge of the wafer W placed on the stage 1110.

[0217] 31, the control unit 1190 moves the slit nozzle 1125 to a position away from the wafer W, and also moves the substage 1130 from the retracted position to the application position. The control unit 1190 also ejects the ionic liquid IL from the slit nozzle 1125 toward the substage 1130. As a result, the ionic liquid IL is applied onto the substage 1130.

[0218] At this time, a portion of the ionic liquid IL discharged onto the substage 1130 is sucked up by the concentration measurement nozzle 1140. Therefore, by performing various measurements on the ionic liquid IL sucked up by the concentration measurement nozzle 1140, the concentration of the ionic liquid IL can be confirmed.

[0219] Furthermore, when checking the concentration of the ionic liquid IL, it is preferable to adjust the temperature of the substage 1130 in order to reduce the surface tension (viscosity) of the ionic liquid IL and make it easier to measure the concentration.

[0220] Furthermore, the slit coater 1100 of the fifth modified example may be provided with a stage ground circuit and a nozzle position adjustment unit similar to the stage ground circuit 850 and the nozzle position adjustment unit 860 in the slit coater 800 of the second modified example. This allows the ionic liquid IL to be applied to the edge of the wafer W from the slit nozzle 1125 while maintaining a substantially constant distance between the edge of the wafer W and the tip of the slit nozzle 1125. As a result, the circumferential uniformity of the thickness of the ionic liquid IL applied to the edge of the wafer W is improved.

[0221] Furthermore, the slit coater 1100 of the fifth modified example may be provided with an outer surface grounding circuit and a nozzle position adjusting unit similar to the outer surface grounding circuit 950 and the nozzle position adjusting unit 960 of the slit coater 900 of the third modified example. This allows the ionic liquid IL to be applied to the edge of the wafer W from the slit nozzle 1125 while maintaining a substantially constant distance between the edge of the wafer W and the tip of the slit nozzle 1125. As a result, the circumferential uniformity of the thickness of the ionic liquid IL applied to the edge of the wafer W is improved.

[0222] The embodiments disclosed herein should be considered to be illustrative in all respects and not restrictive, and the above-described embodiments may be omitted, substituted, or modified in various ways without departing from the scope and spirit of the appended claims.

[0223] The following additional notes are further disclosed regarding the above embodiment. (Appendix 1) A step of applying a liquid material containing an ionic liquid onto a substrate to form a protective film; transferring the substrate on which the protective film is formed to the atmosphere; removing the protective film from the substrate transferred in the atmosphere; The method for manufacturing a semiconductor device includes the steps of: (Appendix 2) The step of forming the protective film is carried out in the atmosphere. A method for manufacturing the semiconductor device described in Appendix 1. (Appendix 3) The step of forming the protective film is carried out in a vacuum. A method for manufacturing the semiconductor device described in Appendix 1. (Appendix 4) The step of removing the protective film is carried out in a vacuum. 4. A method for manufacturing a semiconductor device according to any one of claims 1 to 3. (Appendix 5) The method further includes a step of forming a film on the substrate in a vacuum without exposing the substrate to the atmosphere, the step being performed after the step of removing the protective film. 5. A method for manufacturing a semiconductor device according to claim 4. (Appendix 6) The step of removing the protective film is carried out in the atmosphere. 4. A method for manufacturing a semiconductor device according to any one of claims 1 to 3. (Appendix 7) The method further includes a step of forming a film on the substrate in the atmosphere, the step being performed after the step of removing the protective film. 7. A method for manufacturing a semiconductor device according to claim 6. (Appendix 8) In the step of forming the film, the film is formed by a plating method. 8. A method for manufacturing a semiconductor device according to claim 7. (Appendix 9) The method further includes a step of removing oxides generated on the substrate before the step of forming the protective film. 9. A method for manufacturing a semiconductor device according to any one of claims 1 to 8. (Appendix 10) The step of removing the oxide is carried out in air. 10. A method for manufacturing a semiconductor device according to claim 9. (Appendix 11) The step of removing the oxides includes a step of removing the oxides with a chemical solution containing hydrogen fluoride (HF). 11. A method for manufacturing a semiconductor device according to claim 10. (Appendix 12) The oxide removing step is carried out in a vacuum. 10. A method for manufacturing a semiconductor device according to claim 9. (Appendix 13) The step of removing the oxide includes: supplying a mixed gas containing a gas containing a halogen element and a basic gas to the substrate to transform the oxide and generate a reaction product; removing the reaction product; Including, 13. A method for manufacturing a semiconductor device according to claim 12. (Appendix 14) The physical properties of the ionic liquid change depending on environmental factors. 14. A method for manufacturing a semiconductor device according to any one of claims 1 to 13. (Appendix 15) The environmental factors include temperature. 15. A method for manufacturing a semiconductor device according to claim 14. (Appendix 16) The physical properties include at least one of viscosity and adhesion. 16. A method for manufacturing a semiconductor device according to claim 14 or 15. (Appendix 17) The ionic liquid has the property of not evaporating in a vacuum. 17. A method for manufacturing a semiconductor device according to any one of claims 1 to 16. (Appendix 18) the substrate has a region on its surface where a conductive material is exposed; 18. A method for manufacturing a semiconductor device according to any one of claims 1 to 17. (Appendix 19) a first processing module for applying a liquid material containing an ionic liquid onto a substrate to form a protective film; a second processing module for removing the protective film formed on the substrate; a transfer module that transfers the substrate between the first processing module and the second processing module in the atmosphere; A semiconductor manufacturing apparatus comprising: (Appendix 20) a first processing apparatus for applying a liquid material containing an ionic liquid onto a substrate to form a protective film; a second processing device that removes the protective film formed on the substrate; a transfer device that transfers the substrate between the first processing device and the second processing device in an atmospheric environment; A system comprising: (Appendix 21) a stage on which a substrate is placed; a liquid supply unit that applies a liquid material to the surface of the substrate placed on the stage; and the liquid supply unit includes an ionic liquid flow path that discharges an ionic liquid and a cleaning liquid flow path that discharges a cleaning liquid; Coating equipment. (Appendix 22) the cleaning liquid flow path is provided around the ionic liquid flow path; 22. The applicator of claim 21. (Appendix 23) The liquid supply unit further includes a sub-stage provided at a position where the liquid material can be applied by the liquid supply unit, separate from the stage. 23. The coating device according to claim 21 or 22. (Appendix 24) The temperature of the surface of the substage onto which the liquid material is applied can be adjusted. 24. The applicator of claim 23. (Appendix 25) a concentration measurement nozzle for recovering a portion of the liquid material applied to the substage; 25. The coating device of claim 23 or 24. (Appendix 26) the concentration measurement nozzle is formed of a tubular member, and one end of the tubular member is provided at a position where it comes into contact with the liquid material applied to the substage; 26. The applicator of claim 25. (Appendix 27) a measuring unit that measures a resistance value of the liquid material applied to the surface of the substrate placed on the stage by the liquid supply unit; 27. The coating device according to any one of claims 21 to 26. (Appendix 28) a position adjusting unit that controls a height position of the liquid supply unit based on the resistance value measured by the measuring unit; 28. The applicator of claim 27. (Appendix 29) the position adjustment unit controls the height position of the liquid supply unit so that the resistance value measured by the measurement unit is constant. 29. The applicator of claim 28. (Appendix 30) The position adjustment unit an actuator that raises and lowers the liquid supply unit; a feedback control circuit that controls the actuator based on the resistance value measured by the measurement unit; Including, 30. The coating device of claim 28 or 29. (Appendix 31) a rotatable stage on which a substrate is placed; an edge liquid supply unit that applies a liquid material to an edge of the substrate placed on the stage; and the end liquid supply unit includes an ionic liquid flow path that discharges an ionic liquid and a cleaning liquid flow path that discharges a cleaning liquid; Coating equipment. (Appendix 32) the cleaning liquid flow path is provided around the ionic liquid flow path; 32. The applicator of claim 31. (Appendix 33) The liquid supply device further includes a sub-stage provided at a position where the liquid material can be applied by the end liquid supply unit, separate from the stage. 33. The coating device of claim 31 or 32. (Appendix 34) The temperature of the surface of the substage onto which the liquid material is applied can be adjusted. 34. The applicator of claim 33. (Appendix 35) a concentration measurement nozzle for recovering a portion of the liquid material applied to the substage; 35. The coating device of claim 33 or 34. (Appendix 36) the concentration measurement nozzle is formed of a tubular member, and one end of the tubular member is provided at a position where it comes into contact with the liquid material applied to the substage; 36. The applicator of claim 35. (Appendix 37) a measuring unit that measures a resistance value of the liquid material applied to the surface of the substrate placed on the stage by the edge liquid supply unit; 37. The coating device of any one of appendixes 31 to 36. (Appendix 38) a position adjusting unit that controls a height position of the end liquid supply unit based on the resistance value measured by the measuring unit; 38. The applicator of claim 37. (Appendix 39) the position adjustment unit controls the height position of the end liquid supply unit so that the resistance value measured by the measurement unit is constant. 39. The applicator of claim 38. (Appendix 40) The position adjustment unit an actuator that raises and lowers the end liquid supply unit; a feedback control circuit that controls the actuator based on the resistance value measured by the measurement unit; Including, 40. The coating device of claim 38 or 39. (Appendix 41) selectively applying an ionic liquid to an edge of a substrate; supplying a precursor to the substrate having the edge coated with the ionic liquid to form an oxide film or a nitride film; a step of selectively applying a cleaning liquid for removing the ionic liquid to an edge of the substrate on which the oxide film or the nitride film is formed; and the ionic liquid contains an element that inhibits adsorption of the precursor; A method for manufacturing a semiconductor device.

[0224] This international application claims priority based on Japanese Patent Application No. 2020-079705, filed on April 28, 2020, and Japanese Patent Application No. 2020-212880, filed on December 22, 2020, the entire contents of which are incorporated herein by reference. [Explanation of symbols]

[0225] 10 Substrate 14 Protective film

Claims

1. a first processing module for applying a liquid material containing an ionic liquid onto a substrate to form a protective film; a second processing module for removing the protective film formed on the substrate; a transfer module that transfers the substrate between the first processing module and the second processing module in the atmosphere; Equipped with the second processing module is configured to heat the substrate to cause a phase transition of the ionic liquid and to remove the protective film by performing a physical operation on the substrate; Semiconductor manufacturing equipment.

2. the physical manipulation includes movement of the substrate; The semiconductor manufacturing apparatus according to claim 1 .

3. The movement of the substrate is horizontal movement of the substrate. The semiconductor manufacturing apparatus according to claim 2 .

4. the physical manipulation comprises rotating the substrate; The semiconductor manufacturing apparatus according to any one of claims 1 to 3.

5. the physical manipulation includes tilting the substrate; The semiconductor manufacturing apparatus according to any one of claims 1 to 4.

6. The physical properties of the ionic liquid change depending on environmental factors. The semiconductor manufacturing apparatus according to any one of claims 1 to 5.

7. The environmental factors include temperature. The semiconductor manufacturing apparatus according to claim 6 .

8. The physical properties include at least one of viscosity and adhesion.

8. The semiconductor manufacturing apparatus according to claim 6 or 7.

9. The ionic liquid is tributylhexadecylphosphonium 3-(trimethylsilyl)-1-propanesulfonate (BHDP·DSS) or N,N-diethyl-N-methyl-N(2-methoxyethyl)ammonium tetrafluoroborate (DEME·BF ４ ) The semiconductor manufacturing apparatus according to any one of claims 1 to 8.

10. a protective film containing an ionic liquid formed on the substrate is subjected to a phase transition by heating the substrate, and the protective film is removed by performing a physical operation on the substrate; The ionic liquid is tributylhexadecylphosphonium 3-(trimethylsilyl)-1-propanesulfonate (BHDP·DSS) or N,N-diethyl-N-methyl-N(2-methoxyethyl)ammonium tetrafluoroborate (DEME·BF 4 ); Processing module.

11. the physical manipulation includes movement of the substrate; The processing module of claim 10.

12. The movement of the substrate is horizontal movement of the substrate. The processing module of claim 11 .

13. the physical manipulation comprises rotating the substrate; A processing module according to any one of claims 10 to 12.

14. the physical manipulation includes tilting the substrate; A processing module according to any one of claims 10 to 13.

15. The physical properties of the ionic liquid change depending on environmental factors. A processing module according to any one of claims 10 to 14.

16. The environmental factors include temperature.

16. The processing module of claim 15.

17. The physical properties include at least one of viscosity and adhesion.

17. A processing module according to claim 15 or 16.

18. a chamber forming a processing space; a stage for holding a substrate on which a protective film containing an ionic liquid is formed; a heating mechanism for heating the substrate to cause a phase transition of the ionic liquid; a stage rotation mechanism for rotating the stage holding the substrate and removing the protective film; a drain for draining the ionic liquid out of the chamber; A processing module comprising:

19. the heating mechanism includes a temperature control fluid supplied between the stage and the substrate; 20. The processing module of claim 18.

20. The heating mechanism includes: a tank for storing the ionic liquid flowing out from the drain; a temperature control mechanism for adjusting the temperature of the ionic liquid in the tank; a supply mechanism that supplies the ionic liquid in the tank between the stage and the substrate; Including, 20. The processing module of claim 18.

21. a stopper that prevents the substrate held by the stage from being separated from the stage; A processing module according to any one of claims 18 to 20.

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