Substrate processing apparatus, liquid supply apparatus, and substrate processing method

Abstract

To easily adjust the composition of a mixture when generating a mixed liquid required for cleaning and etching a substrate.SOLUTION: A substrate processing apparatus includes a substrate support part for supporting a substrate, and a liquid supply part for supplying a liquid to the surface of the substrate supported by the substrate support part, wherein the liquid supply part supplies a mixed liquid prepared by mixing a main solution, one or more chemicals selected from an additive, an oxidizing agent, and an etching agent, and pure water at a predetermined ratio to the substrate.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a substrate processing apparatus, a liquid supply apparatus, and a substrate processing method. [Background technology]

[0002] There are two types of equipment for cleaning or etching substrates: dry systems that do not use chemicals (chemical solutions), and wet systems that do. In wet systems, the chemicals used are selected based on the type of substrate, the type of film, contaminants and residues on the substrate, etc. In some cases, multiple chemicals are mixed together and used as a mixed solution. When mixing chemicals, the mixture must be adjusted taking into account the concentration of the chemicals and the amount of chemicals used.

[0003] Patent Documents 1 and 2 describe the preparation of a remover solution for removing silicon oxide films on silicon substrates. The remover solution is prepared by mixing a remover stock solution with water containing dissolved in an inert gas, with hydrogen fluoride being used as the remover stock solution. Patent Document 3 describes a cleaning solution used in a regeneration cleaning unit to completely remove contaminants from the substrate surface. It describes that cleaning solutions that can be used include an ammonia-hydrogen peroxide solution mixture, hydrogen fluoride (HF), a mixture of hydrogen fluoride (HF) and nitric acid (HNO3), buffered hydrofluoric acid (BHF), ammonium fluoride, and a mixture of hydrofluoric acid and ethylene glycol (HFEG).

[0004] Patent Document 4 describes a phosphoric acid solution containing silicon as an aqueous solution that selectively etches a silicon nitride film on a substrate where a silicon oxide film and a silicon nitride film are exposed on the surface. Patent Document 5 describes a mixed solution that removes resist from a substrate surface covered with resist on which a hardened layer has been formed. The mixed solution described is an HF-mixed SPM (a mixed solution of sulfuric acid and hydrogen peroxide) that is generated by premixing hydrogen peroxide (H2O2) and hydrogen fluoride (HF) to generate a mixed solution, and then adding sulfuric acid (H2SO4). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-051264 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-146505 [Patent Document 3] Japanese Patent Application Publication No. 2018-049918 [Patent Document 4] Japanese Patent Application Publication No. 2019-091815 [Patent Document 5] Japanese Patent Application Laid-Open No. 2016-181677 Summary of the Invention [Problem to be solved by the invention]

[0006] Patent Documents 1 to 5 describe mixed solutions of multiple chemicals as cleaning solutions and etching solutions, but do not describe the advantages of arbitrarily adjusting the chemical composition. If the chemical composition could be arbitrarily prepared, users could easily and quickly change cleaning solutions and etching solutions. Furthermore, users who purchase chemicals can improve the efficiency of substrate processing if they can accurately control the chemical composition themselves. Therefore, there is a need for a proposal that allows the chemical composition to be arbitrarily adjusted in a substrate processing apparatus or liquid supply apparatus.

[0007] The present invention aims to provide a substrate processing apparatus, a liquid supply apparatus, and a substrate processing method that are capable of easily adjusting the composition of a mixture when generating a mixture required for substrate cleaning and etching processes. [Means for solving the problem]

[0008] In one aspect of the present invention, a substrate processing apparatus is provided, which includes a substrate support section that supports a substrate, and a liquid supply section that supplies a liquid to the surface of the substrate supported by the substrate support section, and the liquid supply section supplies a mixed liquid prepared by adjusting a predetermined ratio of a main solution, one or more chemicals selected from an additive, an oxidizing agent, and an etching agent, and pure water to the substrate.

[0009] An aspect of the present invention provides a liquid supply device that supplies a liquid to the surface of a substrate supported by a substrate support, the liquid supply device supplying a mixture of a main solution, one or more chemicals selected from an additive, an oxidizing agent, and an etching agent, and pure water adjusted in a predetermined ratio to the substrate.

[0010] In one aspect of the present invention, a substrate processing method is provided, which includes generating a mixed solution by adjusting a main solution, one or more chemicals selected from an additive, an oxidizing agent, and an etching agent, and pure water in a predetermined ratio, and supplying the mixed solution to a substrate supported on a substrate support. [Effects of the Invention]

[0011] According to an aspect of the present invention, when a mixture required for substrate cleaning or etching is produced, the composition of the mixture can be easily adjusted. As a result, by using an optimal mixture for substrate processing, the cleaning power and etching selectivity for the substrate can be improved, thereby improving the substrate processing efficiency. Furthermore, in semiconductor manufacturing, even if changes in process node, integration, etc., cause changes in user requirements regarding residues (materials to be removed) on the substrate, etching targets, etching selectivity, etc., the mixture can be easily adjusted within the equipment. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is a schematic view showing an example of a substrate processing apparatus according to a first embodiment. [Figure 2] FIG. 2 is a view showing an example of first to fourth containers of the substrate processing apparatus according to the first embodiment. [Figure 3]FIG. 10 is a diagram showing a main part of an example of a substrate processing apparatus according to a second embodiment. [Figure 4] FIG. 11 is a diagram showing a state in which a plurality of types of main solutions are prepared in an example of a substrate processing apparatus according to a third embodiment. [Figure 5] FIG. 11 is a diagram showing a state in which a plurality of types of additives are prepared in an example of a substrate processing apparatus according to a third embodiment. [Figure 6] FIG. 11 is a diagram showing a state in which a plurality of types of oxidizing agents are prepared in an example of a substrate processing apparatus according to a third embodiment. [Figure 7] FIG. 11 is a diagram showing a state in which a plurality of types of etching agents are prepared in an example of a substrate processing apparatus according to a third embodiment. [Figure 8] FIG. 2 is a diagram showing a buffer tank as an example of a mixing unit. [Figure 9] FIG. 2 is a diagram showing an overview of a mixing valve, which is an example of a mixing unit. [Figure 10] FIG. 1 is a diagram illustrating mixing of a main solution, an additive, an oxidizing agent, an etching agent, and pure water using a mixing valve. [Figure 11] FIG. 10 is a diagram showing a main part of an example of a substrate processing apparatus according to a fourth embodiment. [Figure 12] 1 is a flowchart including an example of a substrate processing method according to an embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention is not limited to the contents described below. In addition, in the drawings, in order to make each configuration of the embodiment easier to understand, some parts are enlarged or emphasized, or some parts are simplified or omitted, and the actual structure, shape, scale, etc. may differ.

[0014] <Substrate processing equipment> [First embodiment] FIG. 1 is a schematic diagram showing an example of a substrate processing apparatus according to the first embodiment, and FIG. 2 is a diagram showing an example of a first container 21 to a fourth container 24 of the substrate processing apparatus according to the first embodiment. The substrate processing apparatus 100 is, for example, a substrate cleaning apparatus, an etching apparatus, or the like. In this embodiment, the substrate processing apparatus 100 is a substrate cleaning apparatus. As shown in FIG. 1, the substrate processing apparatus 100 includes a substrate support unit 10 and a liquid supply unit 20. The substrate support unit 10 includes a table 11 and a rotation shaft 12. The substrate support unit 10 is, for example, a spinner chuck that holds the substrate W by suction on the lower surface thereof. The substrate W may have a circular or rectangular shape.

[0015] The table 11 supports the substrate W by suction from the underside of the substrate W using a suction mechanism (not shown) so that the substrate W is horizontal. The table 11 is provided at the upper end of a rotation shaft 12, and rotates about the rotation axis AX as the rotation shaft 12 rotates. The rotation shaft 12 is connected to a drive source (not shown), and when driven by the drive source, the rotation shaft 12 rotates, causing the table 11 and the substrate W suction-held on the table 11 to rotate.

[0016] The liquid supply unit 20 includes a first container 21, a second container 22, a third container 23, a fourth container 24, a pure water supply system 25, a mixer 26, a discharge nozzle 27, a heater H1, and a filter F. The first container 21 contains a main solution A. The second container 22 contains an additive B. The third container 23 contains an oxidizing agent C. The fourth container 24 contains an etching agent D. The "third container" and the "fourth container" are one of the second containers, and in this embodiment, they are referred to as the "third container" and the "fourth container" to distinguish them from the other second containers. The materials used for the first container 21, the second container 22, the third container 23, and the fourth container 24 are chemical-resistant and can be appropriately stored with respect to the chemicals (chemical solutions) contained therein.

[0017] The shapes and sizes of the materials of the first container 21, second container 22, third container 23, and fourth container 24 can be designed appropriately depending on the installation location and the amount of drug used. As shown by the dotted lines in Figure 2, the first container 21, second container 22, third container 23, and fourth container 24 are freely replaceable, and at least one container may be replaceable, or all of the containers may be replaceable. By making each container replaceable, the user can flexibly adjust the drug dosage depending on the usage status of each drug.

[0018] Examples of the main solution A include solutions of pure water, organic solvents, pH adjusters, anticorrosive agents, chelating agents, surfactants, and reaction accelerators. The main solution A may also be a mixed solution in which chemical components such as pure water, organic solvents, pH adjusters, anticorrosive agents, chelating agents, surfactants, and reaction accelerators are mixed in any ratio. For example, if the mixed solution is a mixture in which additive B is mixed with the main solution A, the second container 22 for containing additive B may not be provided. When mixing, at least two or more chemicals selected from the group consisting of the main solution A, additive B, oxidizing agent C, etching agent D, and pure water are mixed. The mixing ratio of each component can be 1:1000 to 2000, and a mixed solution can be produced in any ratio within this range.

[0019] For example, a mixed solution can be produced in which the ratio of main solution A:additive B:oxidizer C:etchant D:pure water is 1-100:0-100:0.1-100:0.1-100:1-100. The concentrations of main solution A, additive B, oxidizer C, and etchant D are not the concentrations when the entire mixed solution is taken as 100, but rather the concentrations of a mixed solution obtained by mixing each chemical at a desired concentration and diluting it with pure water, and a mixed solution of this concentration can be used. Examples of pure water, organic solvents, pH adjusters, corrosion inhibitors, chelating agents, surfactants, and reaction accelerators include known substances. Examples of pure water include purified water, ion-exchanged water, and distilled water.

[0020] Examples of organic solvents include water-soluble substances such as alcohols and glycol ethers. They may also be aprotic polar solvents, such as dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), and dimethylformamide (DMF).

[0021] As the pH adjuster, generally known substances can be used, and examples thereof include inorganic acids, organic acids, inorganic alkalis, and organic alkalis.

[0022] The anticorrosive agent is not particularly limited, but examples thereof include compounds containing a nitrogen-containing heterocycle such as a triazole ring, an imidazole ring, a pyridine ring, a phenanthroline ring, a tetrazole ring, a pyrazole ring, a pyrimidine ring, and a purine ring.

[0023] Examples of the chelating agent include 1-hydroxyethane-1,1-diphosphonic acid tetrasodium solution, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, etidronic acid, ethylenediaminedisuccinic acid, edetic acid, citric acid, gluconic acid, glutamic acid diacetic acid, diethylenetriaminepentaacetic acid, hydroxyethanediphosphonic acid, hydroxyethylethylenediaminetriacetic acid, phytic acid, hexametaphosphoric acid, pentetic acid, and metaphosphoric acid, and sodium salts of these chelating agents may also be used.

[0024] Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. Known substances can be used as the reaction accelerator.

[0025] Additive B may be any chemical that allows for the concentration to be adjusted independently from the components of main solution A, for example, and that allows for further adjustment of its properties. Additive B includes one or more of the following: organic solvent, pH adjuster, anticorrosive, chelating agent, surfactant, reaction accelerator, etc. The organic solvent, pH adjuster, anticorrosive, chelating agent, surfactant, and reaction accelerator may be the same chemicals as those used as the chemical components of main solution A described above. Additive B can be adjusted in concentration independently from main solution A and further diluted with, for example, pure water in mixing section 26 to produce a lower concentration, for example, additive B at a concentration of about ppm. Additive B may also be prepared in a state diluted with main solution A.

[0026] Oxidizing agent C contains either a peroxide or an oxoacid. Examples of peroxides include hydrogen peroxide, peracetic acid, and other commonly known peroxides. Examples of oxoacids include nitric acid, potassium nitrate, cerium ammonium nitrate, permanganate, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, hypobromous acid, bromous acid, bromic acid, perbromic acid, chromic acid, dichromic acid, hypoiodous acid, iodous acid, iodic acid, periodic acid, phosphorous acid, phosphoric acid, sulfurous acid, sulfuric acid, sulfonic acid, sulfinic acid, and other commonly known oxoacids. The concentration of oxidizing agent C can be adjusted independently. Alternatively, the concentration may be adjusted by diluting it with the main solution A, for example, pure water.

[0027] Etching agent D contains at least one of hydrogen halide, hydrogen halide compound, and basic compound. Examples of hydrogen halide include hydrogen fluoride, hydrochloric acid, hydrogen bromide, and hydrogen iodide. Examples of hydrogen halide compounds include hexafluorosilicic acid.

[0028] Examples of basic compounds include ammonium fluoride and tetramethylammonium fluoride. The concentration of the etching agent D can be adjusted independently. As with the oxidizing agent C, the concentration may be adjusted by diluting it with the main solution A, for example, pure water.

[0029] The pure water supply system 25 stores pure water Wa within the system. The pure water Wa may be the same as the pure water used for the main solution A. The pure water supply system 25 may have a known pure water production device inside and supply the produced pure water Wa. Alternatively, the pure water supply system 25 may be configured to purchase pure water Wa and supply the purchased pure water Wa. The system is provided with a pump, a filter, and an adjustment unit (not shown) that adjusts the flow rate of the pure water Wa when it is supplied. Note that known pumps and filters can be used for the pumps and filters.

[0030] The mixing unit 26 prepares (mixes) the main solution A, one or more chemicals selected from the group consisting of an additive B, an oxidizing agent C, and an etching agent D, and pure water Wa in a predetermined ratio to produce a mixed solution. Examples of the mixing unit 26 include a buffer tank T (see FIG. 8) and a mixing valve V (see FIGS. 9 and 10), which will be described later. The mixing unit 26 and the first container 21 are connected by a main solution supply line L1, and a predetermined amount of the main solution A at a predetermined concentration is supplied to the mixing unit 26 via the main solution supply line L1.

[0031] A pump P1 and a filter 21F are provided on the main solution supply line L1, and a predetermined amount of main solution A at a predetermined concentration from which impurities have been removed is supplied to the mixing section 26. The mixing section 26 and the second container 22 are connected by an additive supply line L2, and a predetermined amount of additive B at a predetermined concentration is supplied to the mixing section 26 via the additive supply line L2. A pump P2 and a filter 22F are provided on the additive supply line L2, and a predetermined amount of additive B at a predetermined concentration from which impurities have been removed is supplied to the mixing section 26.

[0032] The mixer 26 and the third container 23 are connected by an oxidizer supply line L3, and a predetermined amount of oxidizer C at a predetermined concentration is supplied to the mixer 26 via the oxidizer supply line L3. A pump P3 and a filter 23F are provided on the oxidizer supply line L3, and a predetermined amount of oxidizer C at a predetermined concentration from which impurities have been removed is supplied to the mixer 26. The mixer 26 and the fourth container 24 are connected by an etching agent supply line L4, and a predetermined amount of etching agent D at a predetermined concentration is supplied to the mixer 26 via the etching agent supply line L4.

[0033] A pump P4 and a filter 24F are provided on the etching agent supply line L4, and a predetermined amount of etching agent D at a predetermined concentration from which impurities have been removed is supplied to the mixer 26. The mixer 26 and the pure water supply system 25 are connected by a pure water supply line L5, and a predetermined amount of pure water Wa is supplied to the mixer 26 via the pure water supply line L5. An adjustment unit (not shown) that adjusts the flow rate of the pure water Wa is provided within the pure water supply system 25, and supplies the predetermined amount of pure water Wa to the mixer 26. Known pumps and filters can be used for the pumps P1 to P4 and filters 21F to 24F.

[0034] By storing the main solution A, additive B, oxidizer C, etchant D, and pure water in the first container 21, second container 22, third container 23, fourth container 24, and pure water supply system 25, respectively, the user can independently adjust the concentration of each chemical. As a result, the concentration of each chemical can be appropriately controlled when finally preparing the mixed solution. Furthermore, the first container 21 can be removed from the main solution supply line L1. The second container 22 can be removed from the additive supply line L2. The third container 23 can be removed from the oxidizer supply line L3. The fourth container 24 can be removed from the etchant supply line L4.

[0035] Therefore, because the first container 21, the second container 22, the third container 23, and the fourth container 24 each have a standardized shape, the first container 21, the second container 22, the third container 23, and the fourth container 24 can be replaced individually. As a result, when replenishing the main solution A, the additive B, the oxidizer C, and the etchant D, the main solution A, the additive B, the oxidizer C, and the etchant D can be replenished by simply replacing the first container 21, the second container 22, the third container 23, and the fourth container 24. Note that the first container 21, the second container 22, the third container 23, and the fourth container 24 shown in the figures are merely examples, and containers of shapes different from those shown in the figures may be used. Furthermore, the first container 21, the second container 22, the third container 23, and the fourth container 24 may be containers of the same shape or different shapes.

[0036] The discharge nozzle 27 supplies the mixed liquid generated in the mixer 26 onto the upper surface of the rotating substrate W. The supplied mixed liquid spreads over the entire surface of the rotating substrate W, and the substrate W is subjected to an etching process or a cleaning process. A known discharge nozzle is used as the discharge nozzle 27, and a spray discharge nozzle is an example of such a discharge nozzle.

[0037] The discharge nozzle 27 and the mixer 26 are connected by a mixed liquid supply line L6, and the mixed liquid produced in the mixer 26 is sent to the discharge nozzle 27 via the mixed liquid supply line L6. A heater H1 and a filter F are provided on the mixed liquid supply line L6, and the mixed liquid is heated to an appropriate temperature to remove impurities and sent to the discharge nozzle 27. The temperature to which the mixed liquid is heated can be set appropriately depending on the types of drugs being mixed, etc. The heater H1 and filter F used can be publicly known heaters and filters.

[0038] [Second embodiment] FIG. 3 illustrates the main components of a substrate processing apparatus 200 according to a second embodiment. Components similar to those in the first embodiment are denoted by the same reference numerals, and a description of those components will be omitted. The following description will focus on differences from the first embodiment. As shown in FIG. 3 , in this embodiment, a first flow rate adjuster 28A, a second flow rate adjuster 28B, a third flow rate adjuster 28C, and a fourth flow rate adjuster 28D are provided on the main solution supply line L1, the additive supply line L2, the oxidizing agent supply line L3, and the etching agent supply line L4. The "third flow rate adjuster" and the "fourth flow rate adjuster" are each a type of second flow rate adjuster, and are referred to as the "third flow rate adjuster" and the "fourth flow rate adjuster" in this embodiment to distinguish them from the other second flow rate adjusters. Although the pure water supply system 25 and the pure water supply line L5 are omitted in FIG. 3 , the pure water supply system 25 includes a pump, a filter, and an adjuster (not shown) for adjusting the flow rate of the pure water Wa when the pure water Wa is supplied, as described above. The adjusting section that adjusts the flow rate of the pure water Wa has the same functions as the first flow rate adjusting section 28A, the second flow rate adjusting section 28B, the third flow rate adjusting section 28C, and the fourth flow rate adjusting section 28D.

[0039] The first flow rate adjustment unit 28A sets the flow rate per unit time of the main solution A and adjusts the amount supplied to the mixing unit 26. The second flow rate adjustment unit 28B sets the flow rate per unit time of the additive B and adjusts the amount supplied to the mixing unit 26. The third flow rate adjustment unit 28C sets the flow rate per unit time of the oxidizing agent C and adjusts the amount supplied to the mixing unit 26. The fourth flow rate adjustment unit 28D sets the flow rate per unit time of the etching agent D and adjusts the amount supplied to the mixing unit 26.

[0040] Furthermore, in order to generate a mixed solution in the mixing section 26, the first flow rate adjustment section 28A, the second flow rate adjustment section 28B, the third flow rate adjustment section 28C, and the fourth flow rate adjustment section 28D adjust the amounts of the main solution A, the additive B, the oxidizing agent C, and the etching agent D to predetermined proportions based on a predetermined mixing ratio of each agent, thereby adjusting the amounts of the supplied agents to the mixing section 26. The adjustment of the supplied amounts may be performed by program control or manually.

[0041] By providing first flow rate adjuster 28A, second flow rate adjuster 28B, third flow rate adjuster 28C, and fourth flow rate adjuster 28D, the user can easily set the mixing ratio of each drug and generate a mixture with an appropriate mixing ratio. First flow rate adjuster 28A, second flow rate adjuster 28B, third flow rate adjuster 28C, and fourth flow rate adjuster 28D are, for example, flow rate adjustment valves, and globe valves, needle valves, gate valves, solenoid valves, and other known valves can be used. The amount of supply to mixer 26 is adjusted based on the mixing ratio at which the mixture is generated in mixer 26, to generate the mixture.

[0042] [Third embodiment] 4 to 7 are diagrams showing main parts of a substrate processing apparatus 300 according to a third embodiment. Components similar to those in the first and second embodiments are denoted by the same reference numerals, and descriptions of those components will be omitted. The following description will focus on the differences from the first and second embodiments. FIG. 4 is a diagram showing a state in which a plurality of different main solutions, namely, main solution A1, main solution A2, main solution A3,..., main solution An, are prepared in an example of a substrate processing apparatus 300 according to a third embodiment. One or more of the main solutions A can be selected. The main solutions A1, A2, A3,..., and An are contained in first containers 211, 212, 213,..., 21n.

[0043] The main solution A1, main solution A2, main solution A3,... main solution An may be contained in all or any of the first containers 211, 212, 213... 21n as different types of main solutions, i.e., as mixed solutions in which different chemicals are mixed at a predetermined mixing ratio. Also, only one chemical may be contained in any of the first containers 211, 212, 213... 21n as a chemical adjusted to a predetermined concentration. Note that if the mixed chemicals are the same but the mixing ratios are different, they are different types of main solutions.

[0044] The first containers 211, 212, 213...21n and the main solution supply line L1 are connected by branch main solution supply lines L11, L12, L13...L1n. The main solutions A1, A2, A3...An are supplied to the main solution supply line L1 via the branch main solution supply lines L11, L12, L13...L1n. In addition, first flow rate adjusters 28A1, 28A2, 28A3...28An having the same function as the first flow rate adjuster 28A of the second embodiment are provided on the branch main solution supply lines L11, L12, L13...L1n.

[0045] Therefore, one or more main solutions can be selected to be supplied to the main solution supply line L1. For example, when supplying main solution A1 and main solution A2 to the main solution supply line L1, first flow rate adjusters 28A1 and 28A2 are opened, and the other first flow rate adjusters 28A3...28An are closed. By providing different selectable main solutions, a variety of mixed solutions with different concentrations and mixing ratios can be produced in the mixer 26.

[0046] 5 is a diagram showing a state in which a plurality of different additives, namely, additive B1, additive B2, additive B3,..., additive Bn, are prepared in an example of a substrate processing apparatus 300 according to the third embodiment. One or more of the additives B can be selected. The additives B1, additive B2, additive B3,..., additive Bn are contained in second containers 221, 222, 223,..., 22n. The additives B1, additive B2, additive B3,..., additive Bn are different types of additives.

[0047] The additive may be a mixed additive produced by mixing additives at a predetermined mixing ratio, or may be only one type of additive. Also, additives of the same type but with different concentrations are considered different types of additives. Also, a mixed additive may be contained in all of the second containers 221, 222, 223,... 22n, or only one type of additive may be contained in all of the second containers 221, 222, 223,... 22n. Furthermore, at least one of the second containers 221, 222, 223,... 22n may contain only one type of additive, and the remaining second containers may contain a mixed additive.

[0048] The second containers 221, 222, 223...22n and the additive supply line L2 are connected by branch additive supply lines L21, L22, L23...L2n. Additives B1, Additive B2, Additive B3...Additive Bn are supplied to the additive supply line L2 via the branch additive supply lines L21, L22, L23...L2n.

[0049] Additionally, second flow rate adjusters 28B1, 28B2, 28B3, . . . 28Bn having the same function as the second flow rate adjuster 28B of the second embodiment are provided on the branch additive supply lines L21, L22, L23, . . . L2n. This allows one or more additives to be selected for supply to the additive supply line L2. For example, when supplying additive B1 and additive B2 to the additive supply line L2, the second flow rate adjusters 28B1 and 28B2 are opened, and the other second flow rate adjusters 28B3, . . . 28Bn are closed. By providing different selectable additives, a variety of mixed solutions with different concentrations and mixing ratios can be produced in the mixing unit 26.

[0050] 6 is a diagram showing a state in which a plurality of different oxidizing agents, namely, oxidizing agent C1, oxidizing agent C2, oxidizing agent C3, oxidizing agent Cn, are prepared in an example of a substrate processing apparatus 300 according to the third embodiment. One or more of the oxidizing agents C can be selected. The oxidizing agents C1, oxidizing agent C2, oxidizing agent C3, oxidizing agent Cn are contained in third containers 231, 232, 233, . . . 23n. The oxidizing agents C1, oxidizing agent C2, oxidizing agent C3, oxidizing agent Cn are different types of oxidizing agents. Furthermore, even if the oxidizing agents are the same type, if the concentrations are different, they are considered to be different types of additives.

[0051] The third containers 231, 232, 233...23n are connected to the oxidant supply line L3 by branched oxidant supply lines L31, L32, L33...L3n. The oxidant C1, oxidant C2, oxidant C3...oxidant Cn are supplied to the oxidant supply line L3 via the branched oxidant supply lines L31, L32, L33...L3n.

[0052] Additionally, third flow rate adjusters 28C1, 28C2, 28C3, . . . 28Cn, which have the same function as the third flow rate adjuster 28C of the second embodiment, are provided on the branch oxidant supply lines L31, L32, L33, . . . L3n. This allows one or more oxidants to be selected for supply to the oxidant supply line L3. For example, when oxidant C1 and oxidant C2 are to be supplied to the oxidant supply line L3, the third flow rate adjusters 28C1 and 28C2 are opened, and the other third flow rate adjusters 28C3, . . . 28Cn are closed. By providing different selectable oxidants, a variety of mixed solutions with different concentrations and mixing ratios can be generated in the mixer 26.

[0053] FIG. 7 is a diagram showing a state in which a plurality of different etching agents are prepared as etching agent D1, etching agent D2, etching agent D3, and etching agent Dn in an example of a substrate processing apparatus 300 according to the third embodiment. Any one or more of the etching agents D can be selected. The etching agents D1, D2, D3, and Dn are contained in fourth containers 241, 242, 243, and so on 24n. The etching agents D1, D2, D3, and Dn are different types of etching agents. Furthermore, etching agents of the same type but with different concentrations are considered different types of etching agents.

[0054] The fourth containers 241, 242, 243...24n and the etching agent supply line L4 are connected by branch etching agent supply lines L41, L42, L43...L4n. The etching agents D1, D2, D3...Dn are supplied to the etching agent supply line L4 via the branch etching agent supply lines L41, L42, L43...L4n.

[0055] Additionally, the branch etching agent supply lines L41, L42, L43,..., L4n are provided with fourth flow rate adjusters 28D1, 28D2, 28D3..., 28Dn, which have the same function as the fourth flow rate adjuster 28D of the second embodiment. This allows one or more etching agents to be selected for supply to the etching agent supply line L4. For example, when supplying etching agent D1 and etching agent D2 to the etching agent supply line L4, the fourth flow rate adjusters 28D1 and 28D2 are opened, and the other fourth flow rate adjusters 28D3..., 28Dn are closed. By providing different selectable etching agents, the mixer 26 can generate a variety of mixed solutions with different concentrations and mixing ratios.

[0056] 8 is a diagram showing a buffer tank T, which is an example of the mixing unit 26. The buffer tank T is a device that mixes predetermined concentrations and amounts of the main solution A, additive B, oxidizing agent C, etching agent D, and pure water Wa, which are supplied from the main solution supply line L1, additive supply line L2, oxidizing agent supply line L3, etching agent supply line L4, and pure water supply line L5, to generate a mixed solution in which each chemical is uniformly mixed.

[0057] The mixed solution is prepared in advance in the buffer tank T before being supplied to the substrate W. The buffer tank T has a cylindrical shape with a bottom and an open top. The shape is not limited to a cylindrical shape, and may be a box-like rectangular shape. The buffer tank T may be made of any known material as long as it is resistant to corrosion by the chemicals to be introduced. Examples include stainless steel and titanium alloy.

[0058] The buffer tank T is equipped with a stirrer P and a heater H2. The stirrer P stirs the main solution A, additive B, oxidizer C, etchant D, and pure water Wa supplied to the buffer tank T to create a uniform mixture. Examples of the stirrer P include propeller blades, paddle blades, and the like as stirring blades. The propeller blades, paddle blades, and the like have a rotating shaft (not shown) connected to their centers and are rotated by a motor (not shown) to which the rotating shaft is attached. The heater H2 is provided on a part of the side of the buffer tank T and is connected to a heat source (not shown), heating the mixture inside to a constant temperature.

[0059] It should be noted that, when the heater H1 is provided on the mixed liquid supply line L6, the heater H2 does not necessarily have to be provided in the buffer tank T. The bottom surface of the buffer tank T is connected to the mixed liquid supply line L6, and the mixed liquid in the buffer tank T is sent to the mixed liquid supply line L6.

[0060] FIG. 9 is a diagram illustrating a mixing valve V, which is an example of the mixing unit 26, and FIG. 10 is a diagram illustrating the mixing of a main solution A, an additive B, an oxidizer C, an etching agent D, and pure water Wa in the mixing valve V. The mixing valve V adjusts the mixing ratio of the main solution A, the additive B, the oxidizer C, the etching agent D, and the pure water Wa, which are supplied from the main solution supply line L1, the additive supply line L2, the oxidizer supply line L3, the etching agent supply line L4, and the pure water supply line L5, at predetermined concentrations and in predetermined amounts, to generate a mixed solution in which each chemical is uniformly mixed. The mixed solution is generated in the mixing valve V before being supplied to the substrate W. Note that a known mixing valve can be used for the mixing valve V.

[0061] 10, the mixing valve V includes mixing valves V1, V2, V3, and V4. The mixing valve V1 mixes the main solution A and the additive B supplied from the main solution supply line L1 and the additive supply line L2 to generate a mixed solution M1. The mixing valve V2 mixes the mixed solution M1 generated by the mixing valve V1 with the oxidizer C supplied from the oxidizer supply line L3 to generate a mixed solution M2.

[0062] The mixing valve V3 mixes the mixed solution M2 produced in the mixing valve V2 with the etching agent D supplied from the etching agent supply line L4 to produce a mixed solution M3. The mixing valve V4 mixes the mixed solution M3 produced in the mixing valve V3 with the pure water Wa supplied from the pure water supply line L5 to produce a mixed solution M. The mixing valve V4 is connected to the mixed solution supply line L6, and the mixed solution M is finally sent to the mixed solution supply line L6 as a mixed solution of the main solution A, the additive B, the oxidizing agent C, the etching agent D, and the pure water Wa.

[0063] [Fourth embodiment] 11 is a diagram showing the main parts of a substrate processing apparatus 400 according to the fourth embodiment. Components similar to those in the first to third embodiments are denoted by the same reference numerals, and a description of those components will be omitted. The following description will focus on the differences from the first to third embodiments. In this embodiment, the main solution supply line L1, the additive supply line L2, the oxidizing agent supply line L3, the etching agent supply line L4, and the pure water supply line L5 are connected to the discharge nozzles 27A, 27B, 27C, 27D, and 27Wa corresponding to the respective supply lines.

[0064] Predetermined concentrations and amounts of main solution A, additive B, oxidizer C, etchant D, and pure water Wa are supplied from the main solution supply line L1, additive supply line L2, oxidizer supply line L3, etchant supply line L4, and pure water supply line L5 to corresponding discharge nozzles 27A, 27B, 27C, 27D, and 27Wa, respectively, and are supplied toward the center O of the substrate W. The main solution A, additive B, oxidizer C, etchant D, and pure water Wa are mixed at the center O of the substrate W to form a mixed liquid, which is spread over the entire surface of the substrate W by the centrifugal force of the rotating substrate W. Note that the main solution A, additive B, oxidizer C, etchant D, and pure water Wa do not necessarily have to be supplied toward the center O of the substrate W; they may be supplied to the same or nearly the same location on the substrate W. The angles of the multiple discharge nozzles 27A, 27B, 27C, 27D, and 27Wa relative to the substrate can be set as appropriate.

[0065] The main solution A, additive B, oxidizing agent C, etching agent D, and pure water Wa can be supplied onto the substrate W at predetermined concentrations and amounts separately from the discharge nozzles 27A, 27B, 27C, 27D, and 27Wa, allowing the user to set the concentration and discharge amount of each chemical and accurately supply them onto the substrate W. The supplied chemicals become a mixed liquid at an appropriate mixing ratio on the substrate W. In other words, a mixed liquid can be generated on the substrate.

[0066] <Liquid supply device> The liquid supply device 30 has a similar configuration to the liquid supply unit 20. That is, the liquid supply device 30 includes a first container 21, a second container 22, a third container 23, a fourth container 24, a pure water supply system 25, a mixer 26, a discharge nozzle 27, a heater H1, and a filter F. The first container 21 contains a main solution A. The second container 22 contains an additive B. The third container 23 contains an oxidizer C. The fourth container 24 contains an etching agent D. The pure water supply system 25 contains pure water Wa within the system. The mixer 26 and the first container 21 are connected by a main solution supply line L1. The mixer 26 and the second container 22 are connected by an additive supply line L2. The mixer 26 and the third container 23 are connected by an oxidizer supply line L3. The mixing section 26 and the fourth container 24 are connected by an etching agent supply line L4. The mixing section 26 and the pure water supply system 25 are connected by a pure water supply line L5.

[0067] The mixer 26 mixes a main solution A, an additive B, an oxidizing agent C, an etching agent D, and pure water Wa in predetermined concentrations and amounts that have been selected in advance to generate a mixed liquid. The mixer 26 sends the generated mixed liquid to the discharge nozzle 27 via a mixed liquid supply line L6. The discharge nozzle 27 supplies the mixed liquid onto the substrate W. The main solution A, the additive B, the oxidizing agent C, the etching agent D, and the pure water Wa used in the liquid supply device 30 are the same as those in the liquid supply device 20 described in the first embodiment. The liquid supply device 30 can be installed in an existing substrate processing apparatus as a device for supplying liquid to substrates, for example, or can replace an existing liquid supply device.

[0068] <Substrate processing method> FIG. 12 is a flowchart illustrating an example of a substrate processing method according to an embodiment. In this embodiment of the substrate processing method, first, a substrate W is supported on the table 11 of the substrate support unit 10 (S01). A drive source (not shown) of the substrate support unit 10 is driven to rotate the substrate W. Meanwhile, to supply a mixed liquid onto the substrate W, the ratio (mixing ratio) of the main solution A, additive B, oxidizing agent C, etching agent D, and pure water Wa is determined (S02). The main solution A, additive B, oxidizing agent C, etching agent D, and pure water Wa, which are chemicals, may be mixed all together, or only the necessary chemicals may be selected and mixed. Next, chemicals with predetermined concentrations and amounts are mixed in the mixer 26 based on the determined ratio to generate a mixed liquid (S03). The generated mixed liquid is then supplied to the substrate W from the discharge nozzle 27 (S04).

[0069] Thus, according to this embodiment, even a user can arbitrarily control the chemical composition when generating a mixed solution required for substrate cleaning processing, etching processing, etc., and as a result, a substrate processing apparatus, liquid supply apparatus, and substrate processing method are provided that optimize the cleaning power and etching selectivity for the substrate. Furthermore, in semiconductor manufacturing, even if there are changes in user requirements regarding residues on the substrate (substances to be removed), etching targets, etching selectivity, etc. due to changes in process nodes, integration, etc., it becomes possible to control the chemical composition within the apparatus.

[0070] Although the embodiments of the present invention have been described above, the technical scope of the present invention is not limited to the aspects described in the above-described embodiments. It will be apparent to those skilled in the art that various modifications and improvements can be made to the above-described embodiments. Furthermore, such modifications and improvements are also within the technical scope of the present invention. For example, while the present embodiment describes a substrate processing apparatus as a substrate cleaning apparatus, it may also be an embodiment in which a mixed liquid is supplied to an etching tank of an etching apparatus. Note that one or more of the requirements described in the above-described embodiments may be omitted. Furthermore, the requirements described in the above-described embodiments may be combined as appropriate. Furthermore, the order of execution of each operation shown in the embodiments can be implemented in any order, as long as the results of a previous operation are not used in a subsequent operation. Furthermore, even if the operations in the above-described embodiments are described using terms such as "first," "next," and "subsequently" for convenience, it is not necessary to perform them in this order. [Explanation of symbols]

[0071] 100, 200, 300, 400... Substrate processing equipment 10. Substrate support part 11. Table 12 Rotation axis 20...Liquid supply section 21...1st container 22...Second container 23...Third container 24...4th container 25 Pure Water Supply System 26...Mixing section 27. Discharge nozzle 28A...1st flow rate adjustment section 28B...Second flow rate adjustment section 28C...Third flow rate adjustment section 28D...4th flow rate adjustment section 30...Liquid supply device A: Main solution B... Additives C···oxidizing agent D...etching agent F···Filter H1, H2 heaters L1: Main solution supply line L2 Additive supply line L3: Oxidizer supply line L4: Etching agent supply line L5: Pure water supply line T···Buffer Tank V, V1, V2, V3, V4...Mixing valves Wa: Pure water

Claims

1. a substrate support portion that supports a substrate; a liquid supply unit that supplies a liquid to the surface of the substrate supported by the substrate support unit, The liquid supply unit The main solution, an agent selected from one or more of an additive, an oxidizing agent, and an etching agent; Pure water and and supplying the mixed liquid, which is prepared by adjusting the ratio of the above-mentioned components to the substrate.

2. The liquid supply unit includes: a first container containing the main solution; A second container containing the drug; a pure water supply system; The substrate processing apparatus according to claim 1 , wherein the main solution taken out from the first container, the chemical taken out from the second container, and the pure water from the supply system are adjusted in a predetermined ratio.

3. The substrate processing apparatus according to claim 2 , wherein one or both of the first container and the second container are replaceable.

4. The liquid supply unit includes: a first flow rate adjusting unit that sets a flow rate per unit time of the main solution; a second flow rate adjusting unit that sets the flow rate of the drug per unit time; a pure water supply system; 2 . The substrate processing apparatus according to claim 1 , wherein the flow rates of the first flow rate adjuster, the second flow rate adjuster, and the pure water supplied by the supply system are set, so that the main solution, the chemicals, and the pure water are adjusted to a predetermined ratio.

5. The liquid supply unit includes: The substrate processing apparatus according to claim 1 , wherein a plurality of types of the main solution are prepared, and one or more of the main solutions can be selected.

6. 2. The substrate processing apparatus according to claim 1, wherein the main solution is a mixture of any of pure water, an organic solvent, a pH adjuster, a corrosion inhibitor, a chelating agent, a surfactant, a reaction accelerator, and the like.

7. The liquid supply unit includes: The substrate processing apparatus according to claim 1 , wherein a plurality of types of additives are prepared as the chemicals, and one or more of them can be selected.

8. The substrate processing apparatus according to claim 1 , wherein the additive includes at least one of an organic solvent, a pH adjuster, an anticorrosive, a chelating agent, a surfactant, and a reaction accelerator.

9. The substrate processing apparatus according to claim 1 , wherein the additive is prepared in a state of being diluted with the main solution.

10. The liquid supply unit includes: The substrate processing apparatus according to claim 1 , wherein a plurality of types of oxidizing agents are prepared as the chemicals, and one or more of them can be selected.

11. The substrate processing apparatus according to claim 1 , wherein the oxidizing agent includes one of a peroxide and an oxoacid.

12. The liquid supply unit includes: The substrate processing apparatus according to claim 1 , wherein a plurality of types of etching agents are prepared as the chemicals, and one or more of the etching agents can be selected.

13. The substrate processing apparatus of claim 1 , wherein the etching agent includes at least one of a hydrogen halide, a hydrogen halide compound, and a basic compound.

14. The liquid supply unit includes: The substrate processing apparatus according to claim 1 , further comprising a buffer tank into which predetermined amounts of the main solution, the chemical, and pure water are respectively introduced to generate the mixed solution before being supplied to the substrate.

15. The liquid supply unit includes: The substrate processing apparatus of claim 1 , further comprising a mixing valve for mixing the main solution, the chemical, and the deionized water before supplying them to the substrate.

16. When the liquid supply unit generates the mixed liquid by adjusting the main solution, the additive, the oxidizing agent, the etching agent, and pure water in a predetermined ratio, 2. The substrate processing apparatus according to claim 1, wherein the predetermined ratio of the main solution: the additive: the oxidizing agent: the etching agent: the pure water is 1-100:0-100:0.1-100:0.1-100:1-100.

17. The liquid supply unit includes: a plurality of discharge nozzles for respectively supplying the main solution, the chemical, and the pure water to the substrate; 2. The substrate processing apparatus according to claim 1, wherein the plurality of discharge nozzles each supply the main solution, the chemical, and the pure water at a predetermined flow rate to the same or nearly the same location on the substrate, thereby generating the mixed solution adjusted to a predetermined ratio on the substrate.

18. A liquid supplying apparatus that supplies a liquid to a surface of a substrate supported by a substrate support, The main solution, an agent selected from one or more of an additive, an oxidizing agent, and an etching agent; Pure water and a liquid supplying device that supplies a mixed liquid prepared by adjusting the ratio of the above to a predetermined ratio onto the substrate.

19. The main solution, an agent selected from one or more of an additive, an oxidizing agent, and an etching agent; Pure water and and generating a mixed solution in a predetermined ratio. supplying the mixed liquid to a substrate supported by a substrate support.

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