Substrate cleaning apparatus, substrate cleaning method, and semiconductor device manufacturing method

Abstract

The cleaning apparatus (1) for the substrate (S) includes: an ozone water generation unit (2) that generates ozone water by containing ozone gas with an ozone concentration of 50% by volume or more and an ozone partial pressure of 30 kPa (abs) or less in a gas-liquid mixer (21); an ozone water supply unit (3) that sprays and supplies the ozone water to the substrate (S); and a miscible liquid supply unit (4) that contains a miscible liquid that is miscible with the ozone water and sprays and supplies the heatable liquid to the substrate (S). Furthermore, by spraying the ozone water and the miscible liquid simultaneously or alternately, the two are made to mix on the sprayed side (S1).

Description

Technical Field

[0001] This invention relates to technologies that can contribute to substrate cleaning apparatus, substrate cleaning methods, and semiconductor device manufacturing methods. Background Technology

[0002] In substrates (semiconductor wafer substrates, etc.) used in various electrical equipment, in addition to performing any process (photolithography, etching, film formation, ion implantation, CMP, etc.), the substrate is cleaned as needed after each process so that no unwanted substances such as particles or organic matter remain on the surface of the substrate.

[0003] For example, photolithography, one of the manufacturing processes of semiconductor devices, is a process of forming fine patterns on a substrate. When making a semiconductor device, it is sometimes repeated many times (e.g., dozens to hundreds of times).

[0004] In this photolithography process, a photoresist (photoresist) composed of organic materials is typically used as a photosensitive material. The photoresist is applied to a substrate to form a photoresist layer, or a desired pattern is formed on the photoresist layer. After appropriate use (e.g., after etching, film deposition, ion implantation, etc.), the photoresist layer needs to be cleaned and removed as desired (e.g., completely removed).

[0005] In conventional cleaning, sulfuric acid and hydrogen peroxide water heated to high temperatures are used as cleaning solutions. However, the disposal of these solutions as wastewater can create a significant environmental burden. Therefore, in recent years, methods utilizing ozone water, which has a strong oxidizing power, have been explored as a cleaning method with a very low environmental impact, replacing conventional cleaning (e.g., Patent Documents 1-7, Non-Patent Documents 1-3). Ozone water decomposes appropriately into oxygen and water, thus attracting attention as a cleaning solution with a very low environmental impact as wastewater.

[0006] Ozone water, for example, can be obtained by dissolving ozone gas in a solvent. It is preferable to supply the ozone water to the substrate while maintaining the desired ozone concentration. For example, in Patent Document 4, it is disclosed that by supplying both hot water and pressurized ozone water to the substrate, the ozone concentration of the ozone water can be easily maintained during the period before the two are about to mix, and the mixing of the ozone water raises the temperature, making it easier to exert the desired oxidizing power.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2002-261068

[0010] Patent Document 2: Japanese Patent No. 4444557

[0011] Patent Document 3: Japanese Patent Application Publication No. 2009-297588

[0012] Patent Document 4: Japanese Patent Application Publication No. 2021-034672

[0013] Patent Document 5: Japanese Patent No. 5332052

[0014] Patent Document 6: Japanese Patent No. 7186751

[0015] Patent Document 7: Japanese Patent Application Publication No. 2008-311257

[0016] Non-patent literature

[0017] Non-patent document 1: T. Miura et al, "Novel plasmaless photoresist removal method in gas phase at room temperature", ECS Transactions, Volume 19, Issue 3, pp. 423 (2009).

[0018] Non-patent document 2: T. Miura et al, "Production and Detection of OH Species by a Highly Concentrated Ozone Gas for Thin Film Processing", ACSIN-12&ICSPM21 (2013).

[0019] Non-patent document 3: Ozone Handbook (Revised 2nd Edition) Japan Ozone Association (Ozone Manual (Revised 2nd Edition) Japan Ozone Association) Summary of the Invention

[0020] In methods that simply dissolve ozone gas in a solvent, as described above, it is difficult to obtain high concentrations of ozone water. For example, methods that dissolve ozone gas in a pressurized state in a solvent have also been considered, but these methods are prone to causing rapid self-decomposition of ozone, which may make it difficult to maintain practical safety.

[0021] Furthermore, if only hot water and pressurized ozone water are supplied to the substrate as in Patent Document 4, the ozone water is prone to degassing (foaming) as it rapidly heats up and depressurizes (e.g., returns to normal pressure). This results in a lower ozone concentration in the degassed ozone water, which may prevent it from exerting the desired oxidizing power.

[0022] The present invention was made in view of the above circumstances, and its object is to provide a technique for easily and safely generating high concentrations of ozone water, suppressing the ozone concentration decay of the generated ozone water, and easily exerting the desired oxidizing power.

[0023] The substrate cleaning apparatus, cleaning method, and semiconductor device manufacturing method of the present invention can help solve the above-mentioned problems. In one aspect of the cleaning apparatus, it includes: an ozone water generating unit that generates ozone water by containing ozone gas and a solvent capable of dissolving the ozone gas in a gas-liquid mixer; an ozone water supply unit that sprays out the ozone water; a miscible liquid supply unit that sprays out a miscible liquid having miscibility with the ozone water; and a support unit that supports the substrate in a manner located in the spraying direction of the ozone water from the ozone water supply unit.

[0024] The gas-liquid mixer includes: a solvent flow path for the solvent to flow through; and an ozone gas introduction path connected to the solvent flow path for introducing ozone gas into the solvent flow path. The gas-liquid mixer contains the ozone gas in such a way that the ozone concentration is 50% by volume or more and the ozone partial pressure is 30 kPa (abs) or less.

[0025] The feature is that, when the substrate is located in the ozone water spraying direction of the ozone water supply unit, the miscible liquid supply unit can spray the miscible liquid onto the side of the substrate from which the ozone water is sprayed, i.e., the sprayed side, at a temperature higher than that of the ozone water sprayed from the ozone water supply unit. By simultaneously or alternately spraying the ozone water and the miscible liquid from the ozone water supply unit and the miscible liquid supply unit, the two can be mixed on the sprayed side.

[0026] One aspect of the cleaning method includes: an ozone water generation step, in which ozone gas and a solvent capable of dissolving the ozone gas are contained in a gas-liquid mixer to generate ozone water; an ozone water supply step, in which the ozone water is sprayed onto a substrate supported by a support portion; and a miscible liquid supply step, in which a miscible liquid having miscibility with the ozone water is sprayed onto the substrate.

[0027] The gas-liquid mixer includes: a solvent flow path for the solvent to flow through; and an ozone gas introduction path connected to the solvent flow path for introducing ozone gas into the solvent flow path. The gas-liquid mixer contains the ozone gas in such a way that the ozone concentration is 50% by volume or more and the ozone partial pressure is 30 kPa (abs) or less.

[0028] The feature is that, when the substrate is located in the ozone water spraying direction in the ozone water supply process, the miscible liquid supply process can spray the miscible liquid at a higher temperature than the ozone water sprayed through the ozone water supply process onto the side of the substrate from which the ozone water is sprayed, i.e., the sprayed side. By performing the ozone water supply process and the miscible liquid supply process simultaneously or alternately, the ozone water and the miscible liquid are mixed on the sprayed side.

[0029] One method of manufacturing a semiconductor device is characterized by using a substrate cleaned by a cleaning method to manufacture the semiconductor device.

[0030] As shown above, according to the present invention, it is possible to easily and safely generate high-concentration ozone water, suppress the ozone concentration decay of the generated ozone water, and easily obtain the desired oxidizing power. Attached Figure Description

[0031] Figure 1 This is a schematic structural diagram illustrating an example of the ozone water supply device used to explain the embodiments.

[0032] Figure 2 This is a schematic structural diagram used to illustrate regions R1 to R3 formed on substrate S.

[0033] Figure 3 This is a schematic structural diagram illustrating the ejection structure of Example 1.

[0034] Figure 4 This is a schematic structural diagram illustrating the regions R1 to R3 formed on the substrate S by the ejection structure of Example 1.

[0035] Figure 5 This is a schematic structural diagram illustrating the ejection structure of Example 2.

[0036] Figure 6 This is a schematic structural diagram illustrating an example of nozzle H (a diagram facing the nozzle supply surface H11).

[0037] Figure 7 This is a schematic structural diagram used to illustrate another example of nozzle H (a diagram facing the nozzle supply surface H12).

[0038] Figure 8 This is a schematic structural diagram illustrating the ejection structure of Example 2. Detailed Implementation

[0039] The substrate cleaning apparatus, cleaning method, and semiconductor device manufacturing method of the embodiments of the present invention are completely different from the structure shown in Patent Document 4, which supplies hot water and pressurized ozone water to the substrate for cleaning.

[0040] That is, in this embodiment, ozone gas and a solvent capable of dissolving the ozone gas (hereinafter appropriately referred to as solvent) are contained in a gas-liquid mixer to generate ozone water, and the ozone water is sprayed onto a substrate that is the target of the ozone water supply and supplied with the ozone water. The gas-liquid mixer contains ozone gas in such a way that the ozone concentration is 50% by volume or more and the ozone partial pressure is 30 kPa (abs) or less.

[0041] Furthermore, the system is configured to spray and supply a miscible liquid (hereinafter referred to as the miscible liquid) having miscibility with ozone water onto the side of the substrate from which the ozone water is sprayed, i.e., the sprayed side (hereinafter appropriately referred to as the sprayed side), at a temperature higher than that of the sprayed ozone water (hereinafter appropriately referred to as the heatable temperature). Moreover, by simultaneously (together) or alternately spraying the ozone water and the heatable temperature miscible liquid (hereinafter appropriately referred to as the heatable liquid), the two can be made miscible in the sprayed side.

[0042] With this structure, ozone water is generated by containing high-concentration ozone gas in a state where the ozone partial pressure is sufficiently reduced. Therefore, rapid self-decomposition reactions within the ozone gas can be effectively suppressed, maintaining practical safety. Furthermore, the ozone gas contained as described above readily dissolves in solvents in a gas-liquid mixer, enabling the safe generation of high-concentration (e.g., 100 ppm or higher) ozone water.

[0043] Furthermore, when ozone water is sprayed onto the substrate (the ejected side) and supplied, it is not necessary to pressurize the ozone water as in Patent Document 4, thus suppressing the degassing of the ozone water. Therefore, compared to the structure in Patent Document 4, the ozone concentration decay of the ozone water can be sufficiently suppressed.

[0044] Furthermore, the ozone water sprayed onto the sprayed side of the substrate (the ozone water remaining on the sprayed side) mixes with the heatable liquid and heats up, easily exerting the desired oxidizing power. Thus, the desired cleaning effect can be obtained.

[0045] The substrate cleaning apparatus, cleaning method, and semiconductor device manufacturing method of this embodiment only require the use of ozone water generated by containing high-concentration ozone gas in a state where the ozone partial pressure is sufficiently reduced, as described above, and the configuration to mix the ozone water sprayed onto the substrate with a heatable liquid and then heat it. That is, technical knowledge from various fields (e.g., ozone field, cleaning field, semiconductor field, etc.) can be appropriately applied, and design modifications can be made as needed, referring to existing technical documents, etc. Examples of this can be listed later.

[0046] Furthermore, in the embodiments described later, the same reference numerals will be used for identical content, thereby appropriately omitting detailed descriptions. Additionally, in the figures, hollow arrows indicate the spraying state of ozone water, and black arrows indicate the spraying state of heatable liquids.

[0047] "refer to"

[0048] For example, in the case of conventional ozone gas generating devices (ozone generators), the ozone gas that can be generated is sometimes a low concentration (e.g., ozone concentration of 20% by volume or less), containing a large amount of components other than ozone (e.g., oxygen) (hereinafter appropriately referred to as non-ozone components). Even when using such low concentration ozone gas, it is difficult to generate high concentrations of ozonated water, as a large amount of non-ozone components are dissolved.

[0049] Furthermore, ozone water, which is produced by dissolving low-concentration ozone gas in a solvent under high pressure to achieve a high concentration, also contains non-ozone components dissolved in a supersaturated state, in addition to the ozone component. When such ozone water is released into the atmosphere, the non-ozone components easily degas (e.g., generate bubbles and disperse into the atmosphere), and the ozone component also easily disperses, thus making it impossible to maintain the high concentration of the ozone water.

[0050] In recent years, by using methods such as adsorption concentration (using surface adsorption of silica gel, etc.) and cooling concentration to concentrate ozone gas generated by ozone generators, it has been possible to generate ozone gas with high concentrations (e.g., ozone concentration of 50% or more by volume).

[0051] For example, the ozone gas generator manufactured by Meidensha and using a cooling and concentration method (trade name: Pure Ozone Generator (Japanese: ピュアオゾンジェネレータ)) can generate ozone gas at extremely high concentrations (over 90% by volume) approaching approximately 100%, and has also obtained international safety standard SEMI-S2 certification, achieving practical safety.

[0052] However, in concentrated ozone gas as described above, it is necessary to maintain a reduced pressure to prevent a rapid self-decomposition reaction. Therefore, it is difficult to apply to structures that contain ozone gas under high pressure in a gas-liquid mixer to generate ozone water.

[0053] On the other hand, in this embodiment, as described later in the ozone water generation unit 2, ozone gas is contained in a gas-liquid mixer under reduced pressure (ozone partial pressure is 30 kPa (abs) or less). Therefore, it is also possible to safely utilize the extremely high concentration of ozone gas as described above to fully generate the desired high concentration of ozone water.

[0054] As a specific example, when the ozone concentration of the ozone gas contained in the gas-liquid mixer is 90% or more by volume and the oxygen concentration is less than 10% by volume, the ozone gas can be safely maintained by setting it to a depressurization state (i.e., a state where the ozone partial pressure is 30kPa(abs) or less) where the total pressure of the ozone gas is 30kPa(abs) or less.

[0055] In addition, in the case of ozone gas with an ozone concentration of 50% or more and an oxygen concentration of less than 50% by volume, the ozone gas can be safely maintained by setting it to a depressurization state with a total pressure of 60 kPa (abs) or less (i.e., a state with an ozone partial pressure of 30 kPa (abs) or less).

[0056] Example

[0057] <Main Structure of Cleaning Device 1 in the Embodiment>

[0058] Figure 1 This is a schematic structural diagram illustrating the structure of the substrate cleaning apparatus 1 used in the embodiment. The apparatus 1 includes an ozone water generating unit 2, an ozone water supply unit 3, and a miscible liquid supply unit 4 as its main components. The ozone water generating unit 2 contains ozone gas and a solvent in a gas-liquid mixer 21 to generate ozone water. The ozone water supply unit 3 sprays and supplies the ozone water to the substrate S. The miscible liquid supply unit 4 contains a miscible liquid and sprays it onto the substrate S, supplying a heatable liquid.

[0059] The device 1 can, for example, be operated by a control unit (not shown) that appropriately controls the ozone water generating unit 2, the ozone water supply unit 3, and the miscible liquid supply unit 4. As an example of the control unit, the following structure can be described: appropriately obtaining the states of the ozone water generating unit 2, the ozone water supply unit 3, and the miscible liquid supply unit 4 (e.g., the temperature, flow rate, pressure, etc. of the solvent, ozone water, and miscible liquid respectively; hereinafter appropriately referred to as device states), controlling the device states, or controlling the spraying of the ozone water and the heatable liquid (e.g., controlling the simultaneous or alternating spraying of ozone water and the heatable liquid as described later).

[0060] The solvent in the ozone water generation unit 2, the flow path of the ozone water (e.g., the flow paths indicated by arrows Y1 and Y2), the flow path of the ozone water in the ozone water supply unit 3 (not shown), and the flow path of the miscible liquid in the miscible liquid supply unit 4 (not shown) can be configured in various ways. For example, configurations using various piping can be listed. However, the flow paths of the ozone water in the ozone water supply unit 3 and the miscible liquid in the miscible liquid supply unit 4 are designed as independent structures (i.e., structures that are not interconnected).

[0061] In the flow paths described above, in addition to using piping as mentioned, other methods may also be used, for example, as shown in the example below. Figure 1 Temperature adjustment units (e.g., heaters, coolers) 22, 31, 41, etc., are provided as shown, or various flow path devices (e.g., on / off valves, pumps, storage tanks, measuring instruments, etc.) are provided. Furthermore, in cases where impurities (such as metal ions generated due to dissolution of the inner circumferential surface of the pipe in the case of metal piping) may be introduced into the aforementioned flow paths, it is preferable to configure the flow path to suppress such introduction. For example, temperature adjustment units 22, 31, 41 can be provided on the outer circumference of each flow path (e.g., the outer circumference of the pipe) and configured to indirectly adjust the temperature of the inner circumference of that flow path. Additionally, in the case of metal piping, methods such as coating the inner circumferential surface of the pipe with Teflon (registered trademark) can be employed.

[0062] exist Figure 1 In the apparatus 1, ozone water is generated by the ozone water generating unit 2 (ozone water generating process). When the ejected side S1 of the substrate S is located in the ozone water ejection direction of the ozone water supply unit 3 and the heatable liquid ejection direction of the miscible liquid supply unit 4, the ozone water and the heatable liquid are ejected simultaneously or alternately (ozone water supply process and miscible liquid supply process described later).

[0063] Therefore, for example Figure 2 As shown, on the ejected side S1 of the substrate S, there is a region R1 containing ozone water, a region R2 containing a heatable liquid, and a region R3 where regions R1 and R2 overlap. That is, the ozone water in region R1 and the heatable liquid in region R2 are miscible in region R3, thereby the ozone water present in region R3 (and its surrounding area) absorbs heat from the heatable liquid and heats up. Furthermore, the oxidizing power of the heated ozone water increases.

[0064] Ozone water heated as described above sometimes produces OH radicals due to ozone decomposition. While these OH radicals are highly reactive, their lifespan is shorter than that of ozone, and they tend to disappear immediately after generation (due to their low selectivity, they react with surrounding substances and disappear quickly). However, according to... Figure 2 As shown, the OH radicals generated in the ejected side S1 are more likely to have an effective effect on the ejected side S1 before they disappear.

[0065] Therefore, the ozone water sprayed from side S1 has a reaction rate constant that is easily increased (e.g., by several orders of magnitude) due to the generation of OH free radicals, and thus has sufficient oxidizing power even when diluted with a heatable liquid.

[0066] <Structural Example of Ozone Water Generation Unit 2>

[0067] Figure 1 The ozone water generating unit 2 shown is configured such that, in a gas-liquid mixer 21, while a solvent is contained, ozone gas is contained at an ozone concentration of 50% by volume or more and an ozone partial pressure of 30 kPa (abs) or less, thereby dissolving the ozone gas in the solvent to generate ozone water with a high concentration (e.g., 100 ppm or more). Furthermore, it is configured to allow the generated ozone water to be discharged relative to the subsequent ozone water supply unit 3 (e.g., discharged as indicated by arrow Y1).

[0068] Examples of applications for the gas-liquid mixer 21 include ejectors, aspirators, and jet pumps, but it is not limited to these and various other methods can be used. That is, the gas-liquid mixer 21 can be configured to have a solvent flow path (not shown) for the solvent contained therein to flow through and an ozone gas introduction path (not shown) connected to the solvent flow path and introducing the ozone gas contained therein into the solvent flow path.

[0069] According to the gas-liquid mixer 21 configured to have a solvent flow path and an ozone gas inlet path, in the ozone gas inlet path, an attraction pressure based on Bernoulli's theorem is generated according to the flow rate (velocity) of the solvent flowing in the solvent flow path. Additionally, vapor corresponding to the saturated vapor pressure of the solvent is generated in the ozone gas inlet path. For example, when the solvent is water, it has properties equivalent to water (saturated vapor pressure characteristics, water vapor pressure characteristics).

[0070] Based on the properties of such solvents and the pressure at which ozone gas is contained in the gas-liquid mixer 21 (hereinafter appropriately referred to as the containment pressure), a range of solvent temperatures where the vapor pressure of the ozone gas inlet path of the gas-liquid mixer 21 is less than the containment pressure can be derived (hereinafter appropriately referred to as the attractable range). This attractable range is preferably set appropriately taking into account the general solubility characteristics of the gas relative to the solvent (the tendency for solubility to increase as the solvent temperature decreases) (for example, set to 25°C or less as in paragraph

[0023] of Japanese Patent No. 4296393). Therefore, if the solvent temperature deviates from the attractable range, for example, the solvent temperature can be pre-adjusted in the stage before the solvent is contained in the gas-liquid mixer 21 (for example, by adjusting it through a temperature adjustment unit not shown), or the solvent temperature can be adjusted by operating the temperature adjustment unit 22.

[0071] The ozone water generated by the gas-liquid mixer 21 can be supplemented with a concentration-adjusting gas to stabilize the ozone concentration before being discharged to the ozone water supply unit 3 in the downstream section. Alternatively, it can be circulated within the ozone water generation unit 2 (for example, circulated by feedback to the upstream side of the gas-liquid mixer 21 as shown by arrow Y2) or temporarily stored. In the case of achieving a high concentration through the concentration-adjusting gas, for example, adding carbon dioxide or the like to the ozone water to acidify it can be used.

[0072] Any solvent capable of dissolving ozone gas can be appropriately used; examples include raw water, pure water, and ultrapure water. Additionally, depending on the need, the purity of the solvent can be increased using a pure water manufacturing device (not shown).

[0073] Ozone gas can be generated by various ozone gas generating devices. When contained in the gas-liquid mixer 21, it is sufficient as long as the ozone concentration is 50% by volume or more and the ozone partial pressure is 30 kPa (abs) or less. As an example of an ozone gas generating device, an ozone gas generating device manufactured by Meidensha (trade name: Pure Ozone Generator) can be cited.

[0074] According to this ozone water generating unit 2, ozone water with a high concentration of 100 ppm or more (e.g., 300 to 400 ppm) can be safely generated.

[0075] <Structural Example of Ozone Water Supply Unit 3>

[0076] Figure 1 The ozone water supply unit 3 shown is configured to spray ozone water introduced from the ozone water generation unit 2 from the spraying unit 30. However, in this spraying structure, it is sufficient to configure it to spray and supply ozone water to the sprayed side S1 of the substrate S, and various methods can be applied. As an example, the structure shown in Embodiments 1 to 3 described later can be cited as an example of spraying through the spray nozzle 32 and the spray outlet 33 of the nozzle H.

[0077] In addition, the ozone water in the ozone water supply unit 3 can be temperature-adjusted (e.g., cooled by the temperature adjustment unit 31) to maintain the ozone concentration before being sprayed onto the substrate S, or it can be temporarily stored in the ozone water supply unit 3.

[0078] The temperature of the ozone water sprayed onto the substrate S can be set appropriately based on the range that it does not become solidified and can be heated by the heat-generating liquid.

[0079] <Structural Example of Miscible Liquid Supply Unit 4>

[0080] Figure 1 The miscible liquid supply section 4 shown is configured to contain the miscible liquid and eject the heatable liquid from the ejection section 40. However, in this ejection structure, it is sufficient to configure it to eject and supply the liquid to the ejected side S1 of the substrate S, and various methods can be applied. As an example, the structure shown in Embodiments 1 to 3 described later can be cited, which ejects the liquid through the ejection nozzle 42 and the ejection outlet 43 of the nozzle H.

[0081] Furthermore, the miscible liquid in the miscible liquid supply section 4 may be temperature-adjusted (e.g., heated by the temperature adjustment section 41) to a temperature that can be heated before being sprayed onto the sprayed side S1 of the substrate S (before reaching the sprayed side S1). However, if the liquid has already reached a temperature that can be heated while it is being contained in the miscible liquid supply section 4, it may be sprayed directly. Alternatively, it may be temporarily stored in the ozone water supply section 3.

[0082] Miscible liquids only need to be miscible with ozone water and can be appropriately applied. Examples include raw water, pure water, ultrapure water, ion-exchanged water, alkaline aqueous solutions, and acidic aqueous solutions. However, while organic solvents such as lower alcohols are miscible with ozone water, it is believed that the C-C bonds of these organic solvents will be broken by ozone, so they are not preferred if they may have some impact on the substrate S. Alternatively, tap water can be used, but it is preferable to use it after increasing the purity of the water using a pure water production apparatus (not shown) as needed (e.g., depending on the type of substrate S).

[0083] The scalable temperature of a miscible liquid can be appropriately set. For example, when the ozone water is at room temperature (e.g., 5°C to 35°C), the scalable temperature can be set to a temperature higher than room temperature (e.g., above 40°C). By setting the scalable temperature in this way, the heat energy of the miscible liquid (the scalable liquid) can be provided to the ozone water, resulting in the promotion of OH free radical generation. Furthermore, when the miscible liquid is raw water, pure water, ultrapure water, or ion-exchanged water, the upper limit of the scalable temperature can be set to 100°C.

[0084] <An example of substrate S>

[0085] The substrate S can be positioned in the direction of ozone water spraying from the ozone water supply section 3 and in the direction of heatable liquid spraying from the miscible liquid supply section 4, as long as the oxidizing power of the ozone water can be utilized to achieve the desired effect, and various methods can be applied. As an example, various substrates (e.g., semiconductor substrates, glass substrates) that can be cleaned, such as those shown in Patent Documents 1-7, Non-Patent Documents 1-3, Japanese Patent Application Publication No. 2017-173461, and Japanese Patent Application Publication No. 2017-123402, can be listed.

[0086] As a specific example, when various substrates that can be cleaned are designated as substrate S, the apparatus 1 can be appropriately applied to clean the substrate during various processes (photolithography, etching, film deposition, ion implantation, CMP, etc.) as needed. This allows for the cleaning of the substrate surface to prevent unwanted substances such as particles and organic matter from remaining on the substrate surface.

[0087] For example, by photolithography, a photoresist layer (e.g., the coating layers S1a and S1b described later) is formed by coating a photoresist on the ejected side S1 of the substrate S (photoresist layer formation process), and the photoresist layer is cleaned by the apparatus 1 (photoresist layer removal process), the photoresist layer can be removed as desired.

[0088] Alternatively, a cured layer can be formed on the surface of the resist layer by ion implantation of impurity ions. In resist layers with such cured layers, for example, in Patent Document 5, a method is proposed to remove the remaining portion by pre-removing the cured layer through plasma treatment, but this may lead to larger and more complex cleaning equipment, or increased cleaning costs. Furthermore, Patent Document 6 proposes a method to clean the resist layer by pre-forming cracks in the cured layer through high-temperature steam treatment, allowing ozone water to penetrate the resist layer through these cracks. However, since the cured layer itself cannot be dissolved, the removal rate of the resist layer may be extremely low.

[0089] On the other hand, according to device 1, the high oxidizing power of ozone water can be utilized by the cured layer as described above, so the resist layer containing the cured layer can be sufficiently removed even without performing the plasma treatment of Patent Document 5 or the high-temperature steam treatment of Patent Document 6. Furthermore, device 1 can also be used in combination with the plasma treatment of Patent Document 5 and the high-temperature steam treatment of Patent Document 6, in which case the removal of the resist layer containing the cured layer may become easier.

[0090] In ion implantation of the resist layer, the target resist layer can be appropriately set. For example, when a P-type layer or an N-type layer is formed on the ejected side S1 of the substrate S, ions such as P, As, and B can be used as impurity ions. The ion type can be implanted with any accelerating voltage (e.g., around several hundred kV) and implantation amount (e.g., 10 kV). 13 ~10 15 pcs / cm 2 Ion implantation was performed.

[0091] Furthermore, when the substrate S is porous, the ozone water and heatable liquid sprayed from the device 1 may exist not only on the surface of the sprayed side S1, but also on the surface of the micropores formed on the inner side of the substrate S. That is, on the surface of these micropores, etc., a layer of liquid may also form... Figure 1 In regions R1 to R3 as shown, the desired effect is obtained from the oxidizing power of ozone water.

[0092] <Other>

[0093] In the ozone water ejected from the ozone water supply unit 3 and the heatable liquid ejected from the miscible liquid supply unit 4, the ejection direction, ejection flow rate (velocity), and ejection force can be appropriately set. For example, the ejection directions of the ozone water and the heatable liquid may not be as described later. Figure 3 , Figure 5 , Figure 8 That is, it is only set to a direction orthogonal to the substrate S (the upper or lower side in the vertical direction in the figure), while it is set to a direction that is tilted at a specified angle relative to the substrate S.

[0094] Furthermore, based on the viewpoint of optimizing the miscibility efficiency of ozone water and the heatable liquid, and thereby optimizing the OH radical generation efficiency (exerting a higher oxidation-promoting effect), it is preferable to be able to appropriately change the angles of the ozone water and the heatable liquid relative to the substrate S in their respective ejection directions (hereinafter appropriately referred to as the ozone water ejection angle and the heatable liquid ejection angle, respectively). For example, in device 1, an angle adjustment function unit that can change the ozone water ejection angle and the heatable liquid ejection angle separately can be included.

[0095] The spray flow rate and spray force of ozone water and heatable liquid can be appropriately set according to the positional relationship between the device 1 and the substrate S. However, it is preferable to set the spray flow rate and spray force of ozone water within a range that does not cause degassing of ozone water after spraying.

[0096] Furthermore, when both ozone water and the heatable liquid are in a spraying state, it can be exemplified that the spraying of ozone water begins after a predetermined time (e.g., a few seconds to tens of seconds) following the initial spraying of the heatable liquid. In this case, similar to the spraying structure of Example 1 shown in Verification Examples 1 and 2 described later, the sprayed side S1 of the substrate S can be preheated with the heatable liquid (heating is performed before the spraying of ozone water begins), thus easily generating OH free radicals, which can promote oxidation and potentially achieve a higher oxidizing power.

[0097] Alternatively, the substrate S can be appropriately supported by the support portion 6 as shown in Embodiments 1 to 3 described later, or it can be appropriately housed in the container 5.

[0098] <Example 1>

[0099] Figure 3 , Figure 4 Example 1 illustrates an example of the ejection structure using tubular ejection nozzles 32 and 42. Figure 3 In this container, the nozzle 32 is positioned vertically above the container (such as an atmospheric pressure chamber) 5, which is capable of housing the substrate S, in an inward-outward direction, penetrating through the container 5. The nozzle 32 is configured such that one end is connected in communication with the spray section 30 of the ozone water supply section 3, thereby enabling the ozone water from the ozone water supply section 3 to be sprayed vertically downward relative to the inside of the container 5.

[0100] The nozzle 42 is positioned at a predetermined distance from the nozzle 32, above the container 5 in the vertical direction, and in a manner that penetrates the container 5 in the inward and outward directions. The nozzle 42 is configured such that one end of the nozzle 42 is connected in communication with the ejection portion 40 of the miscible liquid supply unit 4, thereby enabling the heatable liquid of the miscible liquid supply unit 4 to be ejected vertically downward relative to the inside of the container 5.

[0101] Figure 3 , Figure 4 The substrate S shown is flat, and a coating layer S1a, such as a resist layer, is provided on the ejected side S1 of one end in the thickness direction (the side facing the ejection nozzles 32 and 42). In addition, the substrate S is supported by the support 6 in the position where the coating layer S1a faces the ejection nozzles 32 and 42, so that it can rotate freely.

[0102] exist Figure 3 In the case of the support portion 6, it is composed of a support platform 61 supporting the substrate S and a rotation shaft 62 extending from the center of the support platform 61 downward in the vertical direction and rotating the support platform 61. In the support platform 61, when the support platform 61 is rotated, it is preferable to have a structure that can support the substrate S in a way that does not cause positional displacement. As an example, a structure that supports the substrate S by a vacuum chuck can be cited.

[0103] According to the ejection structure of this embodiment 1, by simultaneously or alternately performing the ozone water ejection process (ejecting ozone water through the ejection nozzle 32) and the miscible liquid ejection process (ejecting a heatable liquid through the ejection nozzle 42), for example, as... Figure 4 As shown, a cladding layer S1a is formed on substrate S with... Figure 2 The same regions R1 to R3. Therefore, the oxidizing power of ozone water can be applied to the coating layer S1a of the substrate S, and the substrate S can be cleaned using a single-piece processing method.

[0104] Furthermore, during the simultaneous or alternating execution of the ozone water spraying process and the miscible liquid spraying process as described above, a rotation process in which the substrate S is rotated by the support portion 6 can also be performed. By appropriately executing this rotation process, the ozone water and the heatable liquid sprayed through the ozone water spraying process and the miscible liquid spraying process are easily distributed along the surface of the coating layer S1a by the centrifugal force of the rotation, and regions R1 to R3 are also easily expanded. As a result, the oxidizing power of ozone water can be widely and evenly exerted on the coating layer S1a.

[0105] Alternatively, when alternating between the ozone water spraying process and the miscible liquid spraying process, a rotation process can be performed during the period when one of the processes is stopped and the other is switched (i.e., the period during which both processes are stopped). In this case, the ozone water and the heatable liquid tend to expand and distribute along the surface of the coating layer S1a each time they are sprayed, and region R3 may expand more easily. As a result, it may be more likely that the oxidizing power of the ozone water can be exerted more evenly relative to the coating layer S1a.

[0106] When the spraying of both ozone water and the heatable liquid stops, and the substrate S is continuously rotated by the support part 6, the ozone water and the heatable liquid remaining in the coating layer S1a are removed by the centrifugal force of the rotation, for example, by being discharged through the discharge part 51 provided in the container 5.

[0107] As a specific example, one could exemplify a cycle in which the ozone water spraying process and the miscible liquid spraying process are alternately performed, and a rotational process is repeatedly performed between these two states, with the ozone water supply process, the miscible liquid supply process, and the states where both the ozone water supply process and the miscible liquid supply process are stopped. By repeatedly performing such a cycle, it is possible to easily, efficiently, and evenly utilize the oxidizing power of the ozone water.

[0108] The ozone water discharged from the discharge section 51 decomposes over time, so even when released into the natural environment, it can effectively suppress (for example, compared to the use of sulfuric acid, pharmaceutical solutions, etc.) the load on the natural environment.

[0109] <Example 2>

[0110] Figures 5-7 Example 2 illustrates an example of the ejection structure when using nozzle H. Figure 5 In the container 5, a nozzle H is provided on the side facing the substrate S in the vertical direction. On the nozzle H, i.e., the nozzle supply surface H1, multiple ozone water spray outlets 33 and multiple miscible liquid spray outlets 43 are respectively provided.

[0111] Furthermore, connecting parts (connectors, etc.) 34 and 44 are provided on the outside of the container 5 in the nozzle H, respectively, and can be connected to the spraying parts 30 and 40. The connecting part 34 is connected to the spraying outlet 33 via the ozone water flow path (not shown) inside the nozzle H, and the connecting part 44 is connected to the spraying outlet 43 via the heatable liquid flow path (not shown) inside the nozzle H. However, the ozone water flow path and the heatable liquid flow path are set as independent structures (i.e., structures that are not connected to each other). Thus, it is configured to spray ozone water and heatable liquid through the spraying outlets 33 and 43 respectively.

[0112] The shapes of the nozzle supply surface H1, nozzle outlets 33 and 43 are not particularly limited and can be set appropriately.

[0113] For example, the nozzle supply surface H1 is formed to be larger than the surface in the covering layer S1a facing the nozzle supply surface H1 (hereinafter appropriately referred to as the sprayed side facing surface), so that ozone water and heatable liquid can be sprayed throughout the entire area of ​​the sprayed side facing surface.

[0114] As a specific example, when the shape of the opposing sides of the ejected parts is circular, examples such as... Figure 6 The nozzle supply surface H11 shown is circular, and multiple nozzle outlets 33 and 43 are arranged in dispersed positions relative to this nozzle supply surface H11. Various methods can be applied when the nozzle outlets 33 and 43 are arranged in dispersed positions. Figure 6In this case, the nozzles are arranged in such a way that multiple nozzles 33 are dispersed relative to the nozzle supply surface H11, and nozzles 43 are provided around each nozzle 33.

[0115] Furthermore, even for example, Figure 7 As shown, the nozzle supply surface H12 is in the shape of a strip extending. As long as the multiple nozzles 33 and 43 are arranged alternately at predetermined intervals in the extending direction (along a straight line along the nozzle supply surface H12), ozone water and heatable liquid can be sprayed throughout the entire area of ​​the sprayed side facing each other by appropriately performing the ozone water spraying process, the miscible liquid spraying process and the rotation process in the same way as in Example 1.

[0116] The shapes of the nozzles 33 and 43 can be appropriately set; for example, circular, rectangular, elliptical, and slit-shaped nozzles can be used. Furthermore, in... Figure 6 , Figure 7 For convenience, the nozzles 33 and 43 are depicted with different shapes (nozzle 33 is depicted as a circle and nozzle 43 is depicted as a rectangle), but they can also be the same shape.

[0117] According to this embodiment 2, in addition to achieving the same effects as in embodiment 1, it also achieves the following effects: Ozone water and the heat-generating liquid are easily sprayed and distributed across the entire area of ​​the sprayed side facing surface. Therefore, region R3 is easily formed relative to the entire area of ​​the sprayed side facing surface, making it possible to easily and evenly exert the oxidizing power of the ozone water.

[0118] <Example 3>

[0119] Figure 8 Example 3 illustrates an example of the ejection structure using a pair of nozzles Ha and Hb. Figure 8 The nozzles Ha and Hb shown are the same shape as nozzle H in Example 2, and are arranged on the upper and lower sides of the container 5 in the vertical direction, respectively, with the substrate S in between.

[0120] exist Figure 8 In the case of substrate S, a coating layer S1a and S1b corresponding to the ejected side S1 are respectively provided on one side and the other side in the thickness direction. In addition, the support portion 6 supporting substrate S has a holding portion 63 that holds the outer periphery of substrate S, and is configured to support substrate S in a position where the coating layers S1a and S1b are facing the nozzles Ha and Hb respectively.

[0121] As a specific example of the holding part 63, a structure that holds the outer periphery of the substrate S in the thickness direction of the substrate S, and a structure that holds the substrate S by pressing a plurality of claws disposed on the radially outer side of the substrate S toward the radially inner side relative to the outer periphery of the substrate S (for example, a structure that uses so-called edge clamps for holding).

[0122] According to this embodiment 3, in addition to achieving the same effects as in embodiments 1 and 2, it can also achieve the following effects: that is, ozone water and heatable liquid can be sprayed appropriately (either simultaneously or alternately) onto each of the sprayed sides S1 on one side and the other side of the substrate S, thereby improving work efficiency (shortening work time, etc.).

[0123] Furthermore, the support portion 6, which has a structure with a holding portion 63, can properly hold and support the substrate S to avoid contact with one side or the other side in the thickness direction of the substrate S. Thus, the substrate S can be supported without contaminating one side or the other side while being thoroughly cleaned using a single-piece processing method.

[0124] Verification Example 1

[0125] In this verification example 1, the oxidizing power of ozone water relative to the substrate S was verified by applying the ejection structure of Example 1 (hereinafter appropriately referred to as the ejection structure of Example 1) in apparatus 1. As verification conditions, a 20mm × 20mm square chip obtained by cutting a commercially available semiconductor wafer was used as the substrate S. In addition, after forming a 2μm thick coating layer S1a of phenolic varnish resin photoresist on one end of the square chip in the thickness direction (after baking), it was set to a state of being supported on the support platform 61 of the support part 6 (in a non-rotating state). In addition, in the ozone water generation part 2, ozone water with an ozone concentration of about 300ppm was generated by absorbing ozone gas generated by an ozone gas generation device (trade name: pure ozone generator) manufactured by Meidensha (ozone concentration of 90% by volume and ozone partial pressure of 10kPa (abs)) without adding concentration adjustment gas.

[0126] The spray nozzle 32 is configured such that the ozone water is sprayed in the center of the coating layer S1a and the ozone water spray angle is approximately 90°. The spray nozzle 42 is configured such that the heatable liquid is sprayed in the diagonal direction of the coating layer S1a (the heatable liquid after spraying is configured to flow from one diagonal direction of the coating layer S1a to the other side) and the heatable liquid spray angle is approximately 10°.

[0127] Furthermore, for the coating layer S1a of the square chip, a heatable liquid at a temperature of 80°C was first ejected from the ejection nozzle 42 at a flow rate of 300 cc / min. Then, after 30 seconds, ozone water at a temperature of 4°C was ejected from the ejection nozzle 32 at a flow rate of 300 cc / min, and the surface state of the coating layer S1a was observed. The result was that within one minute of the start of the ozone water ejection (e.g., after several tens of seconds), the surface near the center of the coating layer S1a (e.g., near the center) showed improved surface condition. Figure 4 The area near R3 (as shown in the figure) began to peel off and was removed, with a removal rate of 3.5 μm / min observed.

[0128] On the other hand, as a comparative example of the ejection structure (hereinafter appropriately referred to as the comparative example ejection structure), for the coating layer S1a of the square chip, only ozone water at a temperature of 80°C was ejected from the ejection nozzle 32 at a flow rate of 300cc / min, and the surface state of the coating layer S1a was observed. As a result, after a few minutes from the start of the ozone water ejection, the coating layer S1a began to peel off near the center and was removed, and the removal rate was 0.7μm / min.

[0129] Therefore, based on the observation results of the ejection structure of Example 1 and the observation results of the ejection structure of the comparative example, the following can be stated. First, it can be seen that the ozone water in the ejection structure of the comparative example is in a high-temperature state (80°C) before ejection, and the ozone concentration has been reduced (e.g., halved) at the time of ejection, thereby reducing the removal rate.

[0130] On the other hand, in the ozone water of the spray structure of Example 1, the ozone water is diluted by mixing with the heatable liquid in the central part of the coating layer S1a, and the ozone concentration decreases in the same way as in the ozone water of the spray structure of the comparative example. Therefore, from the viewpoint of ozone water concentration, it can be expected that the removal rate will be the same as that of the ozone water in the spray structure of the comparative example, but in actual observation, it becomes a good removal rate. It can be seen that in the case of the ozone water in the spray structure of Example 1, the coating layer S1a absorbs heat from the heatable liquid and heats up (for example, heats up to about 50°C), and the reaction rate constant increases by the generation of OH free radicals. That is, it can be confirmed that the ozone water in the spray structure of Example 1 obtains a promoting oxidation effect from a sufficient amount of OH free radicals in the coating layer S1a, thereby exerting a high oxidizing power.

[0131] Verification Example 2

[0132] In this verification example 2, firstly, for the square chip used in verification example 1, a cladding layer S1a with a thickness of 0.5 μm was formed by coating one end of the chip in the thickness direction with a KrF laser photoresist. Then, ion implantation was performed on the surface of the cladding layer S1a (with an accelerating voltage of 150 kV and an implantation depth of 5 × 10⁻⁶ kV). 14 pcs / cm 2Phosphorus is seeded by ion implantation, thereby forming a cured layer on the surface side of the coating layer S1a.

[0133] Furthermore, under the same verification conditions as in Verification Example 1, for the coating layer S1a (cured layer side) of the square chip, a heatable liquid at a temperature of 80°C was first ejected from the ejection nozzle 42 at a flow rate of 300 cc / min. Then, after 30 seconds, ozone water at a temperature of 4°C was ejected from the ejection nozzle 32 at a flow rate of 300 cc / min, and the surface state of the coating layer S1a was observed. The result was similar to Verification Example 1; within one minute of the start of ozone water ejection (e.g., after several tens of seconds), the surface near the center of the coating layer S1a (e.g., near the center) showed signs of curing. Figure 4 The area near R3 (as shown in the figure) begins to peel off and is removed at a rate of 0.5 μm / min.

[0134] Similarly, using the comparative example ejection structure, for the coating layer S1a of the square chip, only ozone water at a temperature of 80°C was ejected from the ejection nozzle 32 at a flow rate of 300cc / min, and the surface state of the coating layer S1a was observed. However, even after several minutes (after 10 minutes) from the start of the ozone water ejection, the coating layer S1a did not peel off.

[0135] Therefore, according to the ozone water sprayed in the structure of Example 1, even when a cured layer is formed on the surface side of the coating layer S1a, it can be confirmed that the coating layer S1a has a high oxidizing power and a promoting effect brought about by a sufficient amount of OH free radicals.

[0136] The above description only details specific examples. However, it is obvious to those skilled in the art that various modifications can be made within the scope of the technical concept of the present invention, and such modifications are of course within the scope of the claims.

[0137] For example, in Figure 3 , Figure 5 , Figure 8 In the case of the substrate S shown, it is configured to be supported in a horizontally extending position within the container 5, but it is not limited to this and can be supported in various positions. For example, the case in which the substrate S is supported in a vertically extending position within the container 5 can be cited, but in this case, the device 1 can be appropriately modified so that the ejection directions of the nozzles 32 and 42 and the ejection directions of the nozzles H, Ha, and Hb are respectively horizontal (that is, so that the ejected side S1 is located in the respective ejection directions of ozone water and heated liquid).

Claims

1. A substrate cleaning apparatus, characterized in that, have: The ozone water generating unit contains ozone gas and a solvent capable of dissolving the ozone gas in a gas-liquid mixer to generate ozone water. An ozone water supply unit that sprays out ozone water; A miscible liquid supply unit sprays out a miscible liquid that is miscible with the ozone water; as well as A support portion that supports the substrate in the direction in which the ozone water is ejected from the ozone water supply portion. The gas-liquid mixer includes: a solvent flow path for the solvent to flow through; and an ozone gas introduction path connected to the solvent flow path to introduce ozone gas into the solvent flow path. The gas-liquid mixer contains the ozone gas in a manner that ensures an ozone concentration of 50% or more by volume and an ozone partial pressure of 30 kPa (abs) or less. When the substrate is located in the ozone water ejection direction of the ozone water supply section, the miscible liquid supply section can eject the miscible liquid at a higher temperature than the ozone water ejected from the ozone water supply section onto the side of the substrate from which the ozone water is ejected, i.e., the ejection side. By simultaneously or alternately spraying ozone water and the miscible liquid from the ozone water supply unit and the miscible liquid supply unit, the two can be mixed on the sprayed side.

2. The substrate cleaning apparatus according to claim 1, characterized in that, The miscible liquid supply unit sprays the miscible liquid at a temperature of 40°C or higher.

3. The substrate cleaning apparatus according to claim 1, characterized in that, The substrate cleaning device also includes a nozzle that is respectively provided with a plurality of ozone water spray outlets and a plurality of miscible liquid spray outlets. The ozone water spray outlets spray ozone water through the ozone water supply section, and the miscible liquid spray outlets spray the miscible liquid through the miscible liquid supply section.

4. The substrate cleaning apparatus according to claim 1, characterized in that, The substrate cleaning device further includes a pair of nozzles, each of which is provided with multiple ozone water spray outlets and multiple miscible liquid spray outlets. The ozone water spray outlets spray ozone water through the ozone water supply unit, and the miscible liquid spray outlets spray the miscible liquid through the miscible liquid supply unit. The pair of nozzles are positioned facing each other across the substrate.

5. The substrate cleaning apparatus according to claim 1, characterized in that, The support portion supports the substrate so that it can rotate freely.

6. The substrate cleaning apparatus according to claim 1, characterized in that, A resist layer is formed on the ejected side of the substrate.

7. The substrate cleaning apparatus according to claim 6, characterized in that, A cured layer is formed on the resist layer.

8. A method for cleaning a substrate, characterized in that, have: The ozone water generation process involves containing ozone gas and a solvent capable of dissolving the ozone gas in a gas-liquid mixer to generate ozone water. An ozone water supply process, wherein ozone water is sprayed onto a substrate supported by a support portion; and In the miscible liquid supply process, a miscible liquid having miscibility with the ozone water is sprayed onto the substrate. The gas-liquid mixer includes: a solvent flow path for the solvent to flow through; and an ozone gas introduction path connected to the solvent flow path to introduce ozone gas into the solvent flow path. The gas-liquid mixer contains the ozone gas in a manner that ensures an ozone concentration of 50% or more by volume and an ozone partial pressure of 30 kPa (abs) or less. When the substrate is located in the ozone water ejection direction during the ozone water supply process, the miscible liquid supply process can eject the miscible liquid at a higher temperature than the ozone water ejected through the ozone water supply process onto the side of the substrate from which the ozone water is ejected, i.e., the ejection side. By simultaneously or alternately performing the ozone water supply process and the miscible liquid supply process, the ozone water and the miscible liquid are mixed on the sprayed side.

9. The substrate cleaning method according to claim 8, characterized in that, The miscible liquid supply process involves spraying the miscible liquid at a temperature of 40°C or higher.

10. The substrate cleaning method according to claim 8, characterized in that, The nozzles are equipped with multiple ozone water spray outlets and multiple miscible liquid spray outlets. The ozone water spray outlets spray ozone water through the ozone water supply process, and the miscible liquid spray outlets spray the miscible liquid through the miscible liquid supply process.

11. The substrate cleaning method according to claim 8, characterized in that, A pair of nozzles is used, each of which is provided with multiple ozone water spray outlets and multiple miscible liquid spray outlets. The ozone water spray outlets spray ozone water through the ozone water supply process, and the miscible liquid spray outlets spray the miscible liquid through the miscible liquid supply process. The pair of nozzles are positioned facing each other across the substrate.

12. The substrate cleaning method according to claim 8, characterized in that, The support portion supports the substrate so that it can rotate freely.

13. The substrate cleaning method according to claim 12, characterized in that, While alternating between the ozone water supply process and the miscible liquid supply process, a rotation process is performed multiple times, in which the substrate is rotated while both the ozone water supply process and the miscible liquid supply process are stopped.

14. The substrate cleaning method according to claim 8, characterized in that, A resist layer is formed on the ejected side of the substrate.

15. The substrate cleaning method according to claim 14, characterized in that, A cured layer is formed on the resist layer.

16. A method for manufacturing a semiconductor device, characterized in that, A semiconductor device is manufactured using the substrate cleaned by the substrate cleaning method of claim 8.

17. The method for manufacturing a semiconductor device according to claim 16, characterized in that, A resist layer is formed on the ejected side of the substrate.

18. The method for manufacturing a semiconductor device according to claim 17, characterized in that, A cured layer is formed on the resist layer.

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