Substrate processing method and substrate processing device

Abstract

The present invention provides a substrate processing method and a substrate processing device capable of efficiently performing substrate processing using the oxidizing power of a processing liquid. A liquid film (LQ) of a processing liquid containing at least any one of sulfuric acid, sulfate, peroxysulfuric acid and peroxysulfate or a processing liquid containing hydrogen peroxide is formed on a substrate (SB). Plasma (PL) is irradiated on the liquid film (LQ).

Description

Technical Field

[0001] The present invention relates to a substrate processing method and a substrate processing device, and in particular to a substrate processing method and a substrate processing device using plasma. Background Art

[0002] In most cases, the manufacturing method of a semiconductor device is accompanied by a wet treatment process for removing a resist film from a substrate. As a typical process of this kind, there is a method using the oxidizing power of peroxysulfuric acid generated in a mixed solution of sulfuric acid and hydrogen peroxide solution, i.e., a treatment solution. In order to continuously and stably generate peroxysulfuric acid, hydrogen peroxide solution must usually be added to the treatment solution. For this reason, the burden of drainage treatment increases, or the reuse of sulfuric acid becomes difficult.

[0003] On the other hand, in the resist removal method disclosed in Japanese Patent Laid-Open No. 2002-53312 (Patent Document 1), peroxysulfuric acid is generated by irradiating a solution containing sulfuric acid with oxygen plasma. Then, a wafer with a resist formed on the surface is immersed in a solution containing peroxysulfuric acid. According to this method, the generation of peroxysulfuric acid can be promoted by irradiating sulfuric acid with oxygen plasma. According to the publication, it is claimed that the resist removal ability of the mixed solution of sulfuric acid and hydrogen peroxide can be maintained without adding hydrogen peroxide.

[0004] [Prior art literature]

[0005] [Patent Document]

[0006] [Patent Document 1] Japanese Patent Publication No. 2002-53312 Summary of the invention

[0007] [Problems to be solved by the invention]

[0008] The process of removing the resist film from the substrate mostly requires a large amount of time, energy and chemical material consumption, so the efficiency of the process is required. In addition, it is not limited to the substrate processing of removing the resist film, and for other substrate processing, the efficiency is of course also beneficial to the manufacturer.

[0009] The present invention has been made to solve the above problems, and an object of the present invention is to provide a substrate processing method capable of efficiently performing substrate processing using the oxidizing power of a processing liquid.

[0010] [Technical means to solve the problem]

[0011] The first embodiment is a substrate processing method, comprising: forming a liquid film of a processing liquid containing at least any one of sulfuric acid, sulfate, peroxysulfuric acid and peroxysulfate or a processing liquid containing hydrogen peroxide on a substrate; and irradiating the liquid film with plasma.

[0012] A second embodiment is a substrate processing method according to the first embodiment, wherein the step of irradiating the plasma is performed while the substrate is rotated, and using the plasma locally arranged in a circumferential direction with respect to the rotation of the substrate.

[0013] A third embodiment is a substrate processing method according to the second embodiment, wherein the step of irradiating the plasma includes a step of swinging the position of the plasma in a radial direction of the rotation of the substrate.

[0014] A fourth embodiment is a substrate processing method according to the second embodiment, wherein the step of irradiating the plasma is performed using the plasma extending over the entire radial position of the substrate.

[0015] A fifth embodiment is a substrate processing method according to any one of the first to fourth embodiments, wherein the step of irradiating the plasma includes a step of blowing a plasma jet toward the substrate.

[0016] A sixth embodiment is the substrate processing method according to any one of the first to fourth embodiments, wherein the step of irradiating the plasma includes a step of statically maintaining the atmosphere in the plasma.

[0017] The seventh embodiment is a substrate processing method according to any one of the first to sixth embodiments, wherein the process of forming the liquid film includes: a process of starting to supply the processing liquid to the substrate; and a process of stopping supplying the processing liquid to the substrate; and the process of irradiating the plasma is performed after the process of starting to supply the processing liquid and before the process of stopping supplying the processing liquid.

[0018] The eighth embodiment is a substrate processing method according to any one of the first to seventh embodiments, wherein the process of forming the liquid film includes: a process of starting to supply the processing liquid to the substrate; and a process of stopping supplying the processing liquid to the substrate; and the process of irradiating the plasma is performed after the process of stopping supplying the processing liquid.

[0019] The ninth embodiment is a substrate processing device for processing a substrate using a processing liquid containing at least any one of sulfuric acid, sulfate, peroxysulfuric acid and peroxysulfate, or a processing liquid containing hydrogen peroxide, and the substrate processing device includes: a holding portion for holding the substrate; a liquid supply portion for supplying the processing liquid onto the substrate to form a liquid film of the processing liquid on the substrate; and a plasma source for irradiating plasma to the liquid film.

[0020] A tenth embodiment is a substrate processing apparatus according to the ninth embodiment, further comprising a rotation drive unit that rotates the holding unit to rotate the substrate, wherein the plasma source is configured to be able to swing in a radial direction of the rotation of the substrate.

[0021] An eleventh embodiment is a substrate processing apparatus according to the ninth embodiment, further comprising a rotation drive unit that rotates the holding unit to rotate the substrate, wherein the plasma source generates the plasma extending over the entire radial direction of the substrate.

[0022] The twelfth embodiment is a substrate processing device according to any one of the ninth to eleventh embodiments, wherein the plasma source includes: a pipe, including a gas inlet for receiving a supply of gas, and a gas outlet configured in a manner toward the substrate; a first electrode, configured in the pipe; and a second electrode, configured outside the pipe.

[0023] A thirteenth embodiment is the substrate processing apparatus according to the twelfth embodiment, wherein the second electrode is away from a path of the processing liquid supplied onto the substrate.

[0024] A fourteenth embodiment is a substrate processing apparatus according to the twelfth embodiment, wherein the second electrode is connected to a path of the processing liquid supplied onto the substrate.

[0025] The fifteenth embodiment is a substrate processing device according to any one of the ninth to eleventh embodiments, wherein the plasma source includes: a dielectric layer having a first surface facing the liquid film and a second surface opposite to the first surface; a first electrode, arranged on the first surface away from the liquid film; and a second electrode, arranged on the second surface.

[0026] [Effects of the Invention]

[0027] According to the first embodiment, plasma is irradiated on a liquid film of a treatment liquid containing at least any one of sulfuric acid, sulfate, peroxysulfuric acid and peroxysulfate or a treatment liquid containing hydrogen peroxide. Thus, free radicals with strong oxidizing power are generated in the liquid film. Therefore, substrate processing can be effectively performed using the oxidizing power of the treatment liquid.

[0028] According to the second embodiment, plasma partially arranged in the circumferential direction is used. Thus, although the plasma is only partially arranged in the circumferential direction, the plasma can be irradiated in the entire circumferential direction as the substrate rotates.

[0029] According to the third embodiment, the position of the plasma can be swung in the radial direction. Thus, although the plasma is only partially arranged in the radial direction, the plasma can be irradiated in a wide range with the swung plasma and the rotation of the substrate.

[0030] According to the fourth embodiment, plasma extending over the entire radial position is used. Thus, even without causing the position of the plasma to fluctuate in the radial direction, the entire substrate can be irradiated with plasma as the substrate rotates.

[0031] According to the fifth embodiment, a plasma jet is blown toward a substrate, thereby enabling substrate processing using the plasma jet.

[0032] According to the sixth embodiment, the atmosphere in the plasma is kept static, thereby preventing the liquid film from being disturbed by the flow of the atmosphere.

[0033] According to the seventh embodiment, the plasma is irradiated while the processing liquid is supplied. Thus, the processing liquid is replaced during the plasma irradiation. Therefore, the reduction in the processing effect caused by the deterioration of the processing liquid can be suppressed.

[0034] According to the eighth embodiment, the plasma is irradiated after the supply of the processing liquid is stopped, thereby being able to suppress the consumption of the processing liquid.

[0035] According to the ninth embodiment, plasma is irradiated on a liquid film of a treatment liquid containing at least any one of sulfuric acid, sulfate, peroxysulfuric acid and peroxysulfate or a treatment liquid containing hydrogen peroxide. Thus, free radicals with strong oxidizing power are generated in the liquid film. Therefore, substrate processing can be effectively performed using the oxidizing power of the treatment liquid.

[0036] According to the tenth embodiment, the position of the plasma can be swung in the radial direction. Thus, although the plasma is only locally arranged in the radial direction, the plasma can be irradiated in a wide range with the swung plasma and the rotation of the substrate.

[0037] According to the eleventh embodiment, plasma extending over the entire radial position is used. Thus, even without causing the position of the plasma to fluctuate in the radial direction, the entire substrate can be irradiated with plasma as the substrate rotates.

[0038] According to the twelfth embodiment, the plasma source includes a first electrode disposed in a gas pipe and a second electrode disposed outside the pipe, thereby generating a plasma jet using the gas ejected from the pipe.

[0039] According to the thirteenth embodiment, the second electrode is away from the path of the processing liquid supplied onto the substrate, thereby enabling plasma to be generated without the first electrode and the second electrode coming into contact with the processing liquid.

[0040] According to the fourteenth embodiment, the second electrode is connected to the path of the processing liquid supplied onto the substrate, thereby generating plasma extending from the first electrode to the liquid film of the processing liquid.

[0041] According to the fifteenth embodiment, the plasma source includes: a dielectric layer having a first surface facing the liquid film and a second surface opposite to the first surface, a first electrode disposed on the first surface away from the liquid film, and a second electrode disposed on the second surface. Thus, plasma can be generated while the atmosphere in the plasma is statically maintained. Therefore, the liquid film is prevented from being disturbed by the flow of the atmosphere. Therefore, disturbance of the substrate processing caused by the disturbance of the liquid film is avoided. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 It is a plan view schematically showing the structure of the substrate processing system according to the first embodiment of the present invention.

[0043] Figure 2 It is a rough representation Figure 1 A block diagram of a structure of a control unit included in a substrate processing system.

[0044] Figure 3 This is a side view schematically showing the structure of the substrate processing apparatus according to the first embodiment of the present invention.

[0045] Figure 4 It is a brief description Figure 1 A plan view showing the arrangement of a liquid supply unit and a plasma source included in a substrate processing apparatus.

[0046] Figure 5 is along Figure 4 A schematic partial cross-sectional view along line VV in FIG.

[0047] Figure 6 is along Figure 5 A schematic partial cross-sectional view along line VI-VI.

[0048] Figure 7 So with Figure 5 The corresponding field of view schematically shows a partial cross-sectional view of the structure of the substrate processing apparatus in Embodiment 2 of the present invention.

[0049] Figure 8 is along Figure 7 A schematic partial cross-sectional view along line VIII-VIII in FIG.

[0050] Fig. 9 This is a plan view schematically illustrating the arrangement of a liquid supply unit and a plasma source included in a substrate processing apparatus according to a third embodiment of the present invention.

[0051] Fig.10 is along Fig. 9 A schematic partial cross-sectional view along line XX in FIG.

[0052] Fig.11 is along Fig.10 A schematic partial cross-sectional view along line XI-XI in FIG.

[0053] Fig.12 So with Figure 5 The corresponding field of view schematically shows a partial cross-sectional view of the structure of the substrate processing apparatus in Embodiment 4 of the present invention.

[0054] Fig.13 is along Fig.12 A schematic partial cross-sectional view along line XIII-XIII in FIG.

[0055] [Explanation of Symbols]

[0056] 10: Substrate holder (holding part)

[0057] 11, 52: Axis

[0058] 12: Rotation motor (rotation drive unit)

[0059] 20, 20B: Liquid nozzle (liquid supply unit)

[0060] 29: Liquid delivery unit

[0061] 30, 30A~30C: Plasma source

[0062] 31, 31A~31C: first electrode

[0063] 32, 32A to 32C: second electrode

[0064] 33, 33B: Piping

[0065] 33C: Dielectric layer

[0066] 36, 36A~36C, 37C: Insulation coating

[0067] 39: Gas delivery unit

[0068] 40: AC power supply (power supply)

[0069] 50: Scanning mechanism

[0070] 51: Arm

[0071] 53: Angle actuator (scanning drive unit)

[0072] 80: Chamber

[0073] 90: Control Department

[0074] 91: CPU (Central Processing Unit)

[0075] 92: ROM (read-only memory)

[0076] 93: RAM (Random Access Memory)

[0077] 94: Storage device

[0078] 94P: Processor

[0079] 95: Bus

[0080] 96: Input

[0081] 97: Display unit

[0082] 98: Ministry of Communications

[0083] 100: Substrate processing system

[0084] 101~104: Substrate processing device

[0085] C: Carrier

[0086] CR: Center Robot

[0087] DP: Circumferential

[0088] DR: Radius direction

[0089] DS: Arrow

[0090] F1: Lower surface (first surface)

[0091] F2: Upper surface (second surface)

[0092] IR: Indexer Robot

[0093] LP: Loading Port

[0094] LQ: Liquid film

[0095] PL: Plasma

[0096] PS: Substrate mounting part

[0097] SB: Substrate

[0098] UT: Processing Unit DETAILED DESCRIPTION

[0099] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In the following drawings, the same or corresponding parts are denoted by the same reference numerals, and their description will not be repeated.

[0100] <Implementation method 1>

[0101] Figure 1 1 is a plan view schematically showing an example of the structure of the substrate processing system 100 according to the first embodiment. The substrate processing system 100 includes a load port LP, an indexer robot IR, a center robot CR, a control unit 90, and at least one processing unit UT ( Figure 1 There are four processing units in the figure). The plurality of processing units UT are used to process a substrate SB (wafer), at least one of which corresponds in detail to a substrate processing device 101 described later. The substrate processing device 101 is a single-chip device that can be used for substrate processing, specifically, a single-chip device that can be used for processing to remove organic matter attached to the substrate SB. This organic matter is typically a used resist film. This resist film is used, for example, as an implantation mask for an ion implantation process. The substrate processing device 101 may have a chamber 80. In this case, the atmosphere in the chamber 80 can be controlled to perform substrate processing in a desired atmosphere.

[0102] The control unit 90 can control the operation of each unit included in the substrate processing system 100. Each carrier C is a container for accommodating a substrate SB. The loading port LP is a container holding mechanism for holding a plurality of carriers C. The indexer robot IR can transport the substrate SB between the loading port LP and the substrate mounting portion PS. The central robot CR can transport the substrate SB from any one of the substrate mounting portion PS and at least one processing unit UT to another processing unit UT. Through the above structure, the indexer robot IR, the substrate mounting portion PS and the central robot CR function as a transport mechanism for transporting the substrate SB between each processing unit UT and the loading port LP.

[0103] The unprocessed substrate SB is taken out from the carrier C by the indexer robot IR and transferred to the central robot CR via the substrate placement part PS. The central robot CR carries the unprocessed substrate SB into the processing unit UT. The processing unit UT processes the substrate SB. The processed substrate SB is taken out from the processing unit UT by the central robot CR, and after passing through other processing units UT as needed, it is transferred to the indexer robot IR via the substrate placement part PS. The indexer robot IR carries the processed substrate SB into the carrier C. Based on the above, the substrate SB is processed.

[0104] Figure 2 is a schematic diagram showing the control unit 90 ( Figure 1) is a block diagram of the structure. The control unit 90 can be composed of a general-purpose computer having a circuit. Specifically, the control unit 90 includes a central processing unit (CPU) 91, a read-only memory (ROM) 92, a random access memory (RAM) 93, a storage device 94, an input unit 96, a display unit 97, a communication unit 98, and a bus 95 that connects these.

[0105] ROM 92 stores basic programs. RAM 93 is provided as a work area when CPU 91 executes specified processing. Storage device 94 is composed of non-volatile storage devices such as flash memory or hard disk device. Input unit 96 is composed of various switches or touch screens, etc., and receives input setting instructions for processing program libraries, etc. from the operator. Display unit 97 is composed of, for example, a liquid crystal display device and a lamp, etc., and displays various information under the control of CPU 91. Communication unit 98 has a data communication function via a local area network (LAN) and the like. Storage device 94 is pre-set with information for components constituting substrate processing system ( Figure 1 ) of each device. One of the above-mentioned multiple modes is selected by CPU 91 executing processing program 94P, and each device is controlled by this mode. In addition, processing program 94P can be stored in a recording medium. As long as this recording medium is used, processing program 94P can be installed in control unit 90. In addition, part or all of the functions executed by control unit 90 do not necessarily need to be implemented by software, and can also be implemented by hardware such as dedicated logic circuits.

[0106] Figure 3 It is a side view schematically showing the structure of the substrate processing apparatus 101 according to the first embodiment. Figure 4 It is a plan view schematically illustrating the arrangement of the liquid supply unit 20 and the plasma source 30 included in the substrate processing apparatus 101 . Figure 5 is along Figure 4 A schematic partial cross-sectional view along line VV in FIG. Figure 6 is along Figure 5 1 is a schematic partial cross-sectional view taken along line VI-VI in FIG. The substrate processing apparatus 101 is used to process the substrate SB using a processing liquid. Specifically, the substrate processing apparatus 101 is used to remove a resist film (not shown) from the substrate SB using a processing liquid.

[0107] Figure 3 The structures shown in the following figures can be chamber 80 ( Figure 1) is surrounded. The pressure in the chamber 80 may be approximately atmospheric pressure (e.g., above 0.5 atmospheres and below 2 atmospheres). In other words, each plasma source described later may be an atmospheric pressure plasma source. The atmosphere in the chamber 80 is, for example, air or an inert gas. In the case of air, since no special gas is required, the process cost can be reduced. In the case of an inert gas, it is prevented that oxygen atoms (especially oxygen free radicals) in the gas have an adverse effect on substrate processing. An inert gas is, for example, nitrogen or a rare gas. An example of a rare gas is argon.

[0108] The substrate processing device 101 includes a substrate holder 10 (holding part), a liquid nozzle 20 (liquid supply part), a liquid delivery part 29, a plasma source 30, a gas delivery part 39 and an AC power supply 40 (power supply). The substrate holder 10 holds the substrate SB. The liquid delivery part 29 delivers the processing liquid to the liquid nozzle 20. The processing liquid is a liquid containing at least any one of sulfuric acid, sulfate, peroxysulfuric acid and peroxysulfate, or a liquid containing hydrogen peroxide, preferably a liquid containing sulfuric acid. The processing liquid is typically an aqueous solution. The liquid nozzle 20 supplies the processing liquid to the substrate SB to form a liquid film LQ of the processing liquid on the substrate SB. The gas delivery part 39 delivers gas to the plasma source 30. This gas, for example, contains at least any one of H2, O2, N2, Ar or He. For example, when the gas contains O2, oxygen plasma can be generated. The plasma source 30 irradiates the liquid film LQ with plasma PL.

[0109] The substrate processing apparatus 101 includes a shaft 11 and a rotary motor 12 (rotation drive unit). The shaft 11 is mounted at the center of the substrate holder 10. The rotary motor 12 rotates the shaft. With this structure, the substrate holder 10 can be rotated, so that the substrate SB can be rotated.

[0110] In addition, the substrate processing device includes an arm 51, a shaft 52, and an angle actuator 53 (scanning drive unit). The angle actuator 53 adjusts the angle of the shaft 52 around the axis. One end of the arm 51 is fixed to the shaft 52, and the other end of the arm 51 is arranged away from the axis of the shaft 52. By installing the plasma source 30 at the other end, the plasma source 30 is slanted in the radial direction DR ( Figure 4 ) as shown by arrow DS( Figure 4 ) is shown in the figure, and is configured to be swingable. Furthermore, the moving direction of the plasma source 30 caused by the swing only needs to have a component in the radial direction DR, and does not need to be strictly parallel to the radial direction DR.

[0111] In the present embodiment, the plasma source 30 and the liquid nozzle 20 are fixed to each other. Thus, the liquid nozzle 20 also swings in conjunction with the swing of the plasma source 30. Furthermore, as a modified example, the position of the liquid nozzle 20 may be fixed, or a swing mechanism for the liquid nozzle 20 may be provided separately from the swing mechanism for the plasma source 30.

[0112] The plasma source 30 includes a pipe 33, a first electrode 31, and a second electrode 32. In addition, the plasma source 30 preferably includes an insulating cover 36. The pipe 33 includes a gas inlet ( Figure 5 ), and a gas outlet ( Figure 5 At least a portion of the first electrode 31 is disposed in the pipe 33. Figure 5 As shown, the first electrode 31 may protrude from the gas inlet. On the other hand, the first electrode 31 preferably does not protrude from the gas outlet. In other words, the first electrode 31 is preferably arranged above the gas outlet. The second electrode 32 is arranged outside the pipe 33. In addition, the second electrode 32 is away from the path of the processing liquid supplied to the substrate SB. Specifically, the second electrode 32 is mounted on the side of the pipe 33, and faces the first electrode 31 via the pipe 33, the internal space of the pipe 33 and the insulating coating 36. The insulating coating 36 covers the first electrode 31 in a manner that separates the space where the plasma PL is generated from the first electrode 31.

[0113] The AC power source 40 applies an AC voltage between the first electrode 31 and the second electrode 32. In this case, the potential of the second electrode 32 may be a reference potential. As a modified example, a DC pulse power source may be used instead of the AC power source 40. In this case, for example, the first electrode 31 becomes an anode and the second electrode 32 becomes a cathode.

[0114] Next, a substrate processing method using the substrate processing apparatus 101 will be described below.

[0115] The substrate holder 10 holds the substrate SB. The substrate SB is rotated by the rotation of the substrate holder 10. The liquid delivery unit 29 delivers the processing liquid to the liquid nozzle 20. Thus, the processing liquid is ejected from the liquid nozzle 20 onto the substrate SB. As a result, a liquid film LQ of the processing liquid is formed on the substrate SB. Here, the thickness of the liquid film LQ is preferably in the range of 0.3 mm to 2.0 mm, and more preferably about 1 mm.

[0116] like Figure 5As shown by the arrow, the gas delivery unit 39 delivers gas to the pipe 33 of the plasma source 30, and the AC power supply 40 applies an AC voltage between the first electrode 31 and the second electrode 32. As a result, the plasma source 30 generates plasma PL. The plasma PL extends from the gas outlet of the pipe 33 to the liquid film LQ together with the flow of the gas. As a result, the plasma PL is irradiated to the liquid film LQ. In other words, a plasma jet is blown toward the substrate SB.

[0117] The irradiation is performed along with the rotation of the substrate SB, and the irradiation is performed in the circumferential direction DP ( Figure 4 ) is performed by locally configuring the plasma PL on the substrate SB. In addition, the irradiation is performed while making the position of the plasma PL in the radial direction DR ( Figure 4 ) while swinging upwards.

[0118] The formation of the liquid film LQ starts by starting to supply the processing liquid onto the substrate SB, and stops by stopping the supply of the processing liquid onto the substrate SB. Furthermore, after stopping the supply of the processing liquid, if the substrate SB is not rotating at a high speed, the liquid film LQ can be maintained. The irradiation of the plasma PL is performed after starting to supply the processing liquid and before stopping the supply of the processing liquid. Thus, a process of irradiating the plasma PL while supplying the processing liquid is performed.

[0119] Radicals are generated in the liquid film LQ by irradiation with the plasma PL. The oxidizing power of the radicals accelerates the processing of the substrate SB. Specifically, the removal of the resist film (not shown) from the substrate SB is accelerated.

[0120] After the substrate treatment, a rinsing process and a drying process of the substrate SB are usually performed. For example, the rinsing process is performed by spraying pure water onto the substrate SB, and the drying process is performed by drying with isopropyl alcohol (IPA).

[0121] According to the present embodiment, the plasma PL is irradiated onto the liquid film LQ of the processing liquid containing at least any one of sulfuric acid, sulfate, peroxysulfuric acid and peroxysulfate or the processing liquid containing hydrogen peroxide. Figure 5 ). Thus, free radicals with strong oxidizing power are generated in the liquid film LQ. Therefore, substrate processing using the oxidizing power of the processing liquid can be effectively performed. Specifically, the resist film can be effectively removed from the substrate SB.

[0122] The treatment liquid preferably contains sulfuric acid. In this case, peroxymonosulfuric acid (peroxomonosulfuric acid) can be generated by plasma irradiation of sulfuric acid. By utilizing plasma irradiation, the generation can be performed without using hydrogen peroxide. In this case, the burden of drainage treatment can be reduced, or the regeneration of sulfuric acid can be facilitated. Here, when using a treatment liquid containing sulfuric acid, the concentration of sulfuric acid is preferably in the range of 94% to 98%, and more preferably about 96%.

[0123] Plasma PL ( Figure 5 ) in the circumferential DP( Figure 4 In this way, although the plasma PL only locally arranged in the circumferential direction DP is used, the plasma PL can be irradiated in the entire circumferential direction DP as the substrate SB rotates.

[0124] In the radial direction DR( Figure 4 ) on the plasma source 30, i.e., the position of the plasma PL ( Figure 5 Thus, although the plasma PL only partially arranged in the radial direction DR is used, the plasma PL can be irradiated over a wide range along with the oscillation of the plasma PL and the rotation of the substrate SB.

[0125] The processing liquid is supplied during the irradiation of the plasma PL. Thus, the processing liquid is replaced during the irradiation of the plasma PL. Therefore, it is possible to suppress a decrease in the processing effect caused by the deterioration of the processing liquid.

[0126] The irradiation of the plasma PL is performed by blowing a plasma jet toward the substrate SB. That is, the substrate can be processed using the plasma jet.

[0127] The plasma source 30 includes a first electrode 31 disposed in a gas pipe 33 and a second electrode 32 disposed outside the pipe 33. Thus, a plasma jet using the gas ejected from the pipe 33 can be generated.

[0128] The second electrode 32 is separated from the path of the processing liquid supplied onto the substrate SB. Thus, the plasma PL can be generated in a state where neither the first electrode 31 nor the second electrode 32 is in contact with the processing liquid.

[0129] Furthermore, the formation of the liquid film LQ is started by starting to supply the processing liquid onto the substrate SB, and is stopped by stopping the supply of the processing liquid onto the substrate SB. After stopping the supply of the processing liquid, if the substrate SB is not rotating at a high speed, the liquid film LQ can be maintained. In this case, the plasma PL can be irradiated after stopping the supply of the processing liquid. Thus, the plasma PL is irradiated without adding the processing liquid onto the substrate SB. Therefore, the consumption of the processing liquid can be suppressed.

[0130] As a modified example, the substrate SB may not rotate but stop during the irradiation of the plasma PL. In this case, the plasma source 30 is preferably in a direction opposite to the swing direction ( Figure 4 Thus, even if the substrate SB does not rotate, the plasma PL can be irradiated to a wide range on the substrate SB by swinging the plasma source 30. In this case, the mechanism for rotating the substrate SB can be omitted.

[0131] <Implementation method 2>

[0132] Figure 7 So with Figure 5 The corresponding field of view schematically shows a partial cross-sectional view of the structure of the substrate processing apparatus 102 in the second embodiment. Figure 8 is along Figure 7 The substrate processing device 102 includes a plasma source 30A instead of the plasma source 30 ( Figure 5 and Figure 6 :Implementation method 1).

[0133] The plasma source 30A has a first electrode 31A and a second electrode 32A. In addition, the plasma source 30A preferably has an insulating covering portion 36A. The first electrode 31A and the insulating covering portion 36A can be arranged in the same manner as the first electrode 31 and the insulating covering portion 36A. Figure 5 and Figure 6 : Embodiment 1) is the same. However, it is preferred that the surface of the first electrode 31A facing the liquid film LQ has a large area. In order to ensure such a large area, the cross section of the pipe 33 perpendicular to the flow direction of the gas ( Figure 8 In the area of ​​the first electrode 31A in the field of view, the area of ​​the first electrode 31A may be more than half of the area of ​​the internal space of the pipe 33. The second electrode 32A is arranged outside the pipe 33 and connected to the path of the processing liquid supplied to the substrate SB. Specifically, at least a portion of the second electrode 32A is arranged in the liquid nozzle 20. Figure 7 As shown, the second electrode 32A may protrude from the liquid inlet of the liquid nozzle 20 .

[0134] In addition, since the configuration other than the above is substantially the same as that of the first embodiment, the same reference numerals are given to the same or corresponding elements, and the description thereof will not be repeated.

[0135] According to the present embodiment, the second electrode 32A is in contact with the path of the processing liquid supplied onto the substrate SB, thereby generating the plasma PL extending from the first electrode 31A to the liquid film LQ of the processing liquid.

[0136] <Implementation method 3>

[0137] Fig. 9 1 is a plan view schematically illustrating the arrangement of the liquid nozzle 20B and the plasma source 30B of the substrate processing apparatus 103 according to the third embodiment. The liquid nozzle 20B and the plasma source 30B replace the liquid nozzle 20 and the plasma source 30A ( Figure 7 and Figure 8 : Implementation method 2) is set in the substrate processing device 103. Fig.10 is along Fig. 9 A schematic partial cross-sectional view along line XX in FIG. Fig.11 is along Fig.10 A schematic partial cross-sectional view along line XI-XI in FIG.

[0138] The plasma source 30B has a pipe 33B, a first electrode 31B, and a second electrode 32B. In addition, the plasma source 30B preferably has an insulating coating 36B. Figure 7 and Figure 8 : Embodiment 2) Similarly, at least a portion of the second electrode 32B is disposed in the liquid nozzle 20B. The insulating covering portion 36B covers the first electrode 31B so as to separate the space where the plasma PL is generated from the first electrode 31B.

[0139] The plasma source 30B is configured to generate a plasma in the radial direction DR ( Fig. 9 ) position and extends as a whole. Fig.10 ). For this reason, Fig. 9 As shown, it is preferred that the plasma source 30B extends over the radial direction DR ( Fig. 9 ) position, and more preferably, the first electrode 31B extends throughout the radial direction DR ( Fig. 9 )'s position as a whole.

[0140] By the above structure, the plasma source 30B is located above the central position of the substrate SB (substrate holder 10). The liquid nozzle 20B is preferably arranged to deviate from the central position and has a posture in which its ejection port is directed toward one side of the central position. In other words, it is preferred that the extension direction of the liquid nozzle 20B is inclined in a manner that the ejection port is directed toward one side of the central position. Thus, even if the liquid nozzle 20B is not arranged at the central position, the processing liquid can be supplied to the central position.

[0141] The plasma irradiation in the substrate processing method using the substrate processing apparatus 103 is performed while the substrate SB is rotated, using the plasma PL extending over the entire position in the radial direction DR of the substrate SB. Therefore, the substrate processing apparatus 103 has the mechanism for rotating the substrate SB described in the first embodiment, but the plasma PL is not swung, so the mechanism for this may be omitted.

[0142] In addition, since the configuration other than the above is substantially the same as that of the first embodiment or the second embodiment, the same reference numerals are given to the same or corresponding elements, and the description thereof will not be repeated.

[0143] According to this embodiment, the radial direction DR ( Fig. 9 ) position and extends as a whole. Fig.10 ). Thus, even if the position of the plasma PL is not swung in the radial direction DR, the entire substrate SB can be irradiated with the plasma PL as the substrate SB rotates.

[0144] <Implementation method 4>

[0145] Fig.12 So with Figure 5 The corresponding field of view schematically shows a partial cross-sectional view of the structure of the substrate processing apparatus 104 in the fourth embodiment. Fig.13 is along Fig.12 A schematic partial cross-sectional view along line XIII-XIII in FIG.

[0146] The substrate processing apparatus 104 includes a plasma source 30C instead of the plasma source 30 ( Figure 5 and Figure 6 : Embodiment 1). The plasma source 30C includes a dielectric layer 33C, a first electrode 31C, and a second electrode 32C. In addition, the plasma source 30C preferably has an insulating covering portion 36C and an insulating covering portion 37C. The dielectric layer 33C has a lower surface F1 (first surface) facing the liquid film LQ and an upper surface F2 (a second surface opposite to the first surface). The first electrode 31C is disposed on the lower surface F1 away from the liquid film LQ. The second electrode 32C is disposed on the upper surface F2. Fig.13 As shown in FIG. 1 , the first electrode 31C and the second electrode 32C are preferably a pair of comb-teeth electrodes meshing with each other in a planar layout parallel to the dielectric layer 33C. The insulating covering portion 36C covers the first electrode 31C in a manner that separates the space where the plasma PL is generated from the first electrode 31C. The insulating covering portion 37C covers the second electrode 32C in a manner that separates the space where the plasma PL is generated from the second electrode 32C.

[0147] The generation of plasma PL in the substrate processing method using the substrate processing apparatus 104 is performed by plasmatizing the atmosphere around the plasma source 30C. Therefore, in the embodiment, the gas delivery unit 39 ( Figure 3 : Embodiment 1). The atmosphere around the plasma source 30C may be substantially static. Furthermore, the chamber 80 ( Figure 1 ) is significantly smaller than the flow used to generate the plasma jet in the first to third embodiments. Therefore, in this specification, the state in which the static state is slightly disturbed by the flow of the former is also regarded as the static state. The irradiation of the plasma PL in this embodiment is performed while the atmosphere in the plasma PL is kept static.

[0148] The plasma source 30C and the plasma source 30 ( Figure 4 : Embodiment 1) is similarly swung. By performing such oscillation and rotation of the substrate SB, the plasma PL can be irradiated to a wide range on the substrate SB. As a first modification, the plasma source 30C and the plasma source 30B ( Fig. 9 : Embodiment 3) Similarly, a plasma PL extending over the entire position of the radial direction DR of the substrate SB can be generated. In this case, it is preferred that the plasma source 30C extends over the entire position of the radial direction DR of the substrate SB. In this modification, the plasma source 30C is not required to swing. As a second modification, the plasma source 30C can generate a plasma PL that substantially covers the entire surface of the substrate SB. In this case, it is preferred that the plasma source 30C substantially covers the entire surface of the substrate SB. In this modification, from the perspective of plasma irradiation, rotation of the substrate SB is also not required. However, from the perspective of formation of the liquid film LQ, the substrate SB can be rotated. Furthermore, by enlarging the plasma source in the same manner as the first and second modifications in the present embodiment 4, in the other embodiments described, the swinging can be omitted or both the swinging and the rotation can be omitted.

[0149] In addition, since the configuration other than the above is substantially the same as that of any one of the first to third embodiments, the same or corresponding elements are denoted by the same reference numerals and their description will not be repeated.

[0150] According to the present embodiment, the plasma PL can be generated while the atmosphere in the plasma PL is statically maintained. This prevents the liquid film LQ from being disturbed by the flow of the atmosphere. Therefore, it prevents the substrate processing from being disturbed by the disturbance of the liquid film LQ.

[0151] The present invention has been described in detail, but the description is illustrative in all aspects and the present invention is not limited thereto. It is understood that numerous unillustrated variations can be envisioned without departing from the scope of the present invention. The various structures described in the various embodiments and various variations can be appropriately combined or omitted as long as they do not contradict each other.

Claims

1. A substrate processing method, comprising: A step of forming a liquid film of a treatment liquid containing at least any one of sulfuric acid, sulfate, peroxysulfuric acid and peroxysulfate, or a treatment liquid containing hydrogen peroxide on a substrate; as well as a step of irradiating the liquid film with plasma to generate free radicals in the liquid film, The step of irradiating the plasma includes: applying a voltage to a first electrode and a second electrode in the atmosphere to plasmatize the atmosphere to generate plasma; and a process of statically maintaining the atmosphere in the plasma.

2. The substrate processing method according to claim 1, wherein: The step of irradiating the plasma is performed while the substrate is rotated, using the plasma that is locally arranged in a circumferential direction with respect to the rotation of the substrate.

3. The substrate processing method according to claim 2, wherein: The step of irradiating the plasma includes the step of swinging the position of the plasma in a radial direction with respect to the rotation of the substrate.

4. The substrate processing method according to claim 2, wherein: The step of irradiating the plasma is performed using the plasma extending over the entire radial position of the substrate.

5. The substrate processing method according to any one of claims 1 to 4, wherein: The process of forming the liquid film comprises: starting the process of supplying the processing liquid onto the substrate; and stopping the process of supplying the processing liquid onto the substrate; and The step of irradiating the plasma is performed after the step of starting to supply the processing liquid and before the step of stopping the supply of the processing liquid.

6. The substrate processing method according to any one of claims 1 to 4, wherein: The process of forming the liquid film comprises: starting the process of supplying the processing liquid onto the substrate; and stopping the process of supplying the processing liquid onto the substrate; and The step of irradiating the plasma is performed after the step of stopping the supply of the processing liquid.

7. A substrate processing device for processing a substrate using a processing liquid containing at least any one of sulfuric acid, sulfate, peroxysulfuric acid and peroxysulfate or a processing liquid containing hydrogen peroxide, comprising: A holding portion that holds the substrate; a liquid supply unit, supplying the processing liquid onto the substrate to form a liquid film of the processing liquid on the substrate; as well as a plasma source, irradiating the liquid film with plasma to generate free radicals in the liquid film, The plasma source comprises: a first electrode and a second electrode; and a power source for applying a voltage between the first electrode and the second electrode, The plasma source statically maintains an atmosphere around the plasma source, and turns the atmosphere around the plasma source into plasma by applying a voltage to the first electrode and the second electrode disposed in the atmosphere.

8. The substrate processing apparatus according to claim 7, further comprising a rotation driving unit configured to rotate the holding unit to rotate the substrate. The plasma source is configured to be able to swing in a radial direction with respect to the rotation of the substrate.

9. The substrate processing apparatus according to claim 7, further comprising a rotation driving unit configured to rotate the holding unit to rotate the substrate. The plasma source generates the plasma extending over the entire radial position of the substrate.

10. A substrate processing device for processing a substrate using a processing liquid containing at least any one of sulfuric acid, sulfate, peroxysulfuric acid and peroxysulfate or a processing liquid containing hydrogen peroxide, comprising: A holding portion that holds the substrate; a liquid supply unit, supplying the processing liquid onto the substrate to form a liquid film of the processing liquid on the substrate; as well as a plasma source, irradiating the liquid film with plasma, The plasma source comprises: A dielectric layer including a first surface facing the liquid film and a second surface opposite to the first surface; A first electrode, disposed on the first surface away from the liquid film; and The second electrode is disposed on the second surface.

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