Method for manufacturing a processed substrate, method for processing a substrate, method for forming a pattern, and cleaning solution

Abstract

To provide a method for manufacturing a treated substrate capable of removing a surplus surface modifier by cleaning a substrate exposed to a surface modifier to obtain the treated substrate having the surface modifier formed controlled in surface and height directions, a method for treating a substrate, a method for forming a pattern, and a cleaning liquid.SOLUTION: A method for manufacturing a treated substrate having at least a partial area modified comprises the steps of: exposing the surface of a substrate 10 to a surface modifier containing a compound (A) 20 having bondability to the substrate 10; and cleaning the exposed substrate 10 with a cleaning liquid to obtain a treated substrate 100 including a compound (A) 20 deposited controlled in the surface and height directions of the substrate 10. The cleaning liquid is selected and used so that a distance Ra between Hansen solubility parameter of the compound (A) 20 and Hansen solubility parameter of the cleaning liquid has a relationship of (Ra)2≤128.SELECTED DRAWING: Figure 2

Description

【Technical Field】 【0001】 The present invention relates to a method for manufacturing a processing substrate, a method for processing a substrate, a method for forming a pattern, and a cleaning liquid. 【Background Art】 【0002】 In recent years, the trend towards higher integration and miniaturization of semiconductor devices has increased, and the miniaturization of organic patterns serving as masks and inorganic patterns formed by etching processes has advanced, and film thickness control at the atomic layer level is required. As a method for forming a thin film at the atomic layer level on a substrate, an atomic layer growth method (ALD (Atomic Layer Deposition) method; hereinafter also simply referred to as the "ALD method") is known. The ALD method is known to have both high step coverage and film thickness controllability compared to a general CVD (Chemical Vapor Deposition) method. 【0003】 The ALD method is a thin film forming technique in which two types of gases mainly composed of elements constituting the film to be formed are alternately supplied onto a substrate, and the formation of a thin film in atomic layer units on the substrate is repeated a plurality of times to form a film having a desired thickness. In the ALD method, during the supply of the source gas, only the components of one or several layers of the source gas are adsorbed on the substrate surface, and the excess source gas does not contribute to growth, and the self-limiting function (self-limiting function) of growth is utilized. For example, when forming an Al2O3 film on a substrate, a source gas composed of TMA (TriMethyl Aluminum) and an oxidizing gas containing O are used. Further, when forming a nitride film on a substrate, a nitride gas is used instead of the oxidizing gas. 【0004】 In recent years, methods for selectively depositing films on substrate surfaces using ALD (Advanced Laser Development) have been explored. For example, a surface modifier is used to make a portion of the substrate water-repellent, and then an atomic layer is deposited on the untreated area using the ALD method. By utilizing the ALD method in film deposition, atomic layer-level film thickness control, step coverage, and miniaturization of patterns can be expected. In region-selective film deposition methods on substrate surfaces, film deposition is generally inhibited on the water-repellent substrate surface by selectively making the substrate surface water-repellent. For example, when selectively depositing a film on the insulating surface of a substrate surface where conductive and insulating surfaces coexist, it is necessary to selectively make the conductive surface water-repellent. For example, Patent Document 1 describes a surface comprising two or more regions, in which a self-assembled monolayer film of octadecylphosphonic acid is formed on adjacent regions of the two or more regions with different materials, thereby improving the contrast between regions of different materials. [Prior art documents] [Patent Documents] 【0005】 [Patent Document 1] Japanese Patent Publication No. 2021-014631 [Overview of the project] [Problems that the invention aims to solve] 【0006】 When selectively making a substrate surface water-repellent using a surface modifier, if excess surface modifier accumulates on the surface modification layer, the modified layer cannot be formed uniformly, leading to pattern defects. Furthermore, while the method described in Patent Document 1 discloses cleaning with isopropyl alcohol (IPA) after exposure to a surface modifier, it has poor removal capabilities for excess surface modifier, leaving room for improvement. 【0007】 The present invention has been made in view of the above circumstances, and aims to provide a method for manufacturing a treated substrate having a surface that has been modified in at least a portion of the area, wherein by washing the substrate exposed to the surface modifier, excess surface modifier can be removed, and a treated substrate can be obtained in which the surface modifier is controlled in the planar and height directions during film formation. The invention also aims to provide a substrate treatment method, a pattern formation method, and a cleaning solution that can be used in this manufacturing method. [Means for solving the problem] 【0008】 To solve the above problems, the present invention employs the following configuration. A first aspect of the present invention is a method for manufacturing a treated substrate having a surface that is modified in at least a portion of its area, comprising the steps of: exposing the surface of the substrate to a surface modifier containing a compound (A) that has bonding properties to the substrate; and washing the substrate after the exposure with a cleaning solution to obtain a treated substrate in which the compound (A) is formed in a film controlled in the planar and height directions of the substrate, wherein the distance Ra between the Hansen solubility parameter of the compound (A) and the Hansen solubility parameter of the cleaning solution is (Ra) 2 This is a method for manufacturing a processed substrate, in which the cleaning solution is selected and used to satisfy the relationship ≤ 128. 【0009】 A second aspect of the present invention includes the steps of: exposing the surface of a substrate to a surface modifier containing a compound (A) that has bonding properties to the substrate; and washing the substrate after the exposure with a cleaning solution to form a film of compound (A) while controlling its distribution in the planar and height directions of the substrate, wherein the distance Ra between the Hansen solubility parameter of compound (A) and the Hansen solubility parameter of the cleaning solution is (Ra) 2 This is a method for processing a substrate, in which a cleaning solution is selected and used that satisfies the relationship ≤ 128. 【0010】 A third aspect of the present invention is a pattern formation method that includes the step of forming an atomic layer on the surface of a processed substrate manufactured by the method for manufacturing a processed substrate according to the first aspect, by forming a thin film using a vapor deposition method, in a region where the surface modifier has not been formed. 【0011】 A fourth aspect of the present invention is a cleaning solution used in a method for manufacturing a processed substrate according to the first aspect, or a method for processing a substrate according to the second aspect, which contains at least one organic solvent selected from the group consisting of decane, tetradecane, cyclohexane, propylene glycol monomethyl ether acetate, isobutanol, 1-octanol, 2-ethyl-1-hexanol, dibutiether, acetone, cyclopentanone, 2,6-dimethyl-4-heptanone, and propylene glycol monomethyl ether. [Effects of the Invention] 【0012】 According to the present invention, a method for manufacturing a treated substrate having a surface modified in at least a portion of its area can be provided, wherein excess surface modifier can be removed by washing the substrate exposed to the surface modifier, and a treated substrate can be obtained in which the surface modifier is controlled in the planar and height directions during film formation. The invention also provides a substrate processing method, a pattern forming method, and a cleaning solution that can be used in this manufacturing method. [Brief explanation of the drawing] 【0013】 [Figure 1] This is a schematic diagram showing the state of the substrate surface after exposure to a surface modifier (after the exposure process). [Figure 2] This is a schematic diagram showing the state of the substrate before and after cleaning with a cleaning solution following the exposure process. [Figure 3A] This is an atomic force microscope (AFM) image of the substrate surface immediately after the exposure process (observation range 1 μm × 1 μm). [Figure 3B] This is an AFM observation image (observation range 1 μm × 1 μm) of the surface of the processed substrate manufactured in Example 11. [Figure 3C] This is an AFM observation image (observation range 1 μm × 1 μm) of the surface of the processed substrate manufactured in Comparative Example 1. [Modes for carrying out the invention] 【0014】 The embodiments of the present invention will be described in detail below, but the present invention is not limited in any way to the embodiments described below, and can be implemented with appropriate modifications within the scope of the object of the present invention. 【0015】 (Method of manufacturing the processed substrate) A method for manufacturing a processed substrate according to a first aspect of the present invention is a method for manufacturing a processed substrate having a surface in which at least a portion of the area has been modified. The method for manufacturing such a processed substrate includes a step of exposing the surface of the substrate to a surface modifier containing a compound (A) that has bonding properties to the substrate (hereinafter also referred to as the "exposure step"), and a step of washing the substrate after exposure with a cleaning solution to obtain a processed substrate in which the compound (A) is formed in a controlled manner in the planar and height directions of the substrate (hereinafter also referred to as the "cleaning step"). In the manufacturing method of such a processed substrate, the distance Ra between the Hansen solubility parameter of compound (A) and the Hansen solubility parameter of the cleaning solution is (Ra) 2 Select and use the cleaning solution that satisfies the relationship ≤ 128. 【0016】 Figure 1 is a schematic diagram showing the state of the substrate surface after exposure to a surface modifier (after the exposure process). The substrate 10 comprises region A and region B. The surface modifier contains compound (A) 20 which has binding properties to region B of the substrate 10. In Figure 1, a surface modifier layer 224 is formed on the substrate 10, covering the entire area B of the substrate 10. The surface modifier layer 224 consists of a single layer portion 22 on which compound (A) 20 is directly bonded to the surface B of the substrate 10, and an excess portion 24 on which compound (A) 20 is deposited on the single layer portion 22. The excess portion 24 protrudes onto region A of the substrate 10. In this state, when attempting to form an atomic layer on region A of the substrate 10, film formation is inhibited, resulting in the formation of a C layer (outlined by dashed lines) with defects d in some areas. 【0017】 Figure 2 is a schematic diagram showing the state of the substrate before and after cleaning with a cleaning solution following the exposure process. After cleaning, the treated substrate 100 has a surface modifier layer 220 formed on the substrate 10 that covers the entire area B of the substrate 10. The excess portion 24 is washed away by the cleaning solution, and the surface modifier layer 220 consists only of a single layer portion 22 on the surface B of the substrate 10 to which compound (A) 20 is directly bonded. In other words, a treated substrate 100 is obtained in which compound (A) 20 is formed in a controlled manner in both the planar and height directions of the substrate 10. 【0018】 "The compound (A) is deposited in a controlled manner in the planar and height directions of the substrate" means that compound (A) molecules are arranged on the surface of a specific region on the substrate, covering the entire surface of that specific region, and forming a film of a certain thickness without covering the region adjacent to that specific region. In Figure 2, in the processed substrate 100, compound (A) molecules are arranged on the surface of region B on the substrate 10, covering the entire surface of region B, and forming a film (surface modifier layer 220, single layer portion 22) of a certain thickness L without covering the region A adjacent to region B. In this state, when attempting to form an atomic layer on region A of the substrate 10, the desired atomic layer can be easily formed without the film formation being hindered. 【0019】 According to the manufacturing method of the processed substrate according to the first embodiment described above, a processed substrate 100 as shown in Figure 2 can be manufactured. The following describes one embodiment of a method for manufacturing such a processed substrate. 【0020】 <Exposure process> In the exposure step of this embodiment, the surface of the substrate is exposed to a surface modifier containing a compound (A) that has binding properties to the substrate. 【0021】 ≪About the circuit board≫ Examples of substrates to be processed in this embodiment include substrates used for the fabrication of semiconductor devices. For example, silicon (Si) substrates, silicon nitride (SiN) substrates, silicon oxide (Ox) substrates, tungsten (W) substrates, cobalt (Co) substrates, titanium nitride (TiN) substrates, tantalum nitride (TaN) substrates, germanium (Ge) substrates, silicon germanium (SiGe) substrates, aluminum (Al) substrates, nickel (Ni) substrates, ruthenium (Ru) substrates, copper (Cu) substrates, and the like. The term "surface of the substrate" includes not only the surface of the substrate itself, but also the surface of inorganic or organic patterns provided on the substrate, or the surface of an unpatterned inorganic or organic layer. 【0022】 Examples of inorganic patterns formed on a substrate include patterns created by preparing an etching mask on the surface of an inorganic layer present on the substrate using a photoresist method, and then performing an etching process. Examples of inorganic layers include the substrate itself, oxide films of elements constituting the substrate, and films or layers of inorganic materials such as SiN, SiOx, W, Co, TiN, TaN, Ge, SiGe, Al, Al2O3, Ni, Ru, and Cu formed on the surface of the substrate. Such films and layers are not particularly limited, but examples include inorganic films and layers formed during the manufacturing process of semiconductor devices. 【0023】 Examples of organic patterns provided on a substrate include resin patterns formed on the substrate by photolithography using photoresist or the like. Such organic patterns can be formed, for example, by forming an organic layer, which is a photoresist film, on the substrate, exposing this organic layer through a photomask, and developing it. The organic layer may be on the surface of the substrate itself, or on the surface of a multilayer film provided on the substrate surface. Such organic layers are not particularly limited, but examples include organic films provided to form an etching mask during the manufacturing process of semiconductor devices. 【0024】 In the manufacturing method of the processed substrate of this embodiment, the surface of the substrate to be processed may include one region or may include two or more regions. If the surface to be processed includes two or more regions, at least one of the two or more regions includes the substrate surface, and adjacent regions among the two or more regions may be made of different materials. In Figure 1, the substrate 10 comprises region A and region B. By exposing the surface of the substrate 10 to be treated with a surface modifier, compound (A) 20 is selectively adsorbed onto the surface of region B of the substrate 10. This makes it possible to make the contact angles of water with respect to the surface of region A and region B of the substrate 10 different from each other. 【0025】 ≪About surface modifiers≫ In this embodiment, the surface modifier contains a compound (A) that has bonding properties to the substrate (hereinafter also referred to as "component (A)"). In Figure 1, a surface modifier containing compound (A) 20, which has bonding properties to region B of the substrate 10, is used. 【0026】 Component (A) is not particularly limited as long as it has bonding properties to the selected substrate, but for example, when using a copper (Cu) or cobalt (Co) substrate, a component (A) having a thiol group is preferred; when using a tungsten (W), copper (Cu), cobalt (Co), Al2O3, or TiN substrate, a component (A) having a phosphonic acid group is preferred; when using a TiN substrate, a component (A) having an amino group is preferred; when using a cobalt (Co) substrate, a component (A) having a carboxylic acid group is preferred; and when using an SiO2 substrate, a component (A) having a chlorosilane group or an alkoxysilane group is preferred. When using a copper (Cu) or cobalt (Co) substrate, an alkylthiol compound is preferred as component (A). Among alkylthiol compounds, linear or branched alkylthiols are particularly preferred, alkylthiols having 1 to 45 carbon atoms are preferred, alkylthiols having 5 to 30 carbon atoms are more preferred, and alkylthiols having 10 to 25 carbon atoms are even more preferred. 【0027】 Specific examples of linear or branched alkylthiols include octadecanethiol, hexanedecanethiol, tetradecanethiol, dodecanethiol, and decanethiol, with octadecanethiol being preferred. 【0028】 The surface modifier may contain components other than component (A) in addition to component (A). The content of component (A) in the surface modifier is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 99% by mass or more, and may be 100% by mass, based on the total mass of the surface modifier. 【0029】 [Exposure process operation] In the exposure step of this embodiment, the surface of the substrate 10 is exposed to the surface modifier described above. The method of exposing the surface of the substrate to a surface modifier containing component (A) is not particularly limited, and examples include exposing the surface of the substrate to a surface modifier (typically a liquid surface modifier) ​​which may contain a solvent, by means of an immersion method or a coating method such as a spin coating method, a roll coating method and a doctor blade method. 【0030】 The exposure temperature is, for example, 10°C to 90°C, preferably 20°C to 80°C, and more preferably 20°C to 30°C. Regarding the exposure time, from the viewpoint of selective surface modification between areas of different materials on the substrate surface, 20 seconds or more is preferred, 30 seconds or more is more preferred, and 45 seconds or more is even more preferred. There is no particular upper limit to the above exposure time, but for example it is 2 hours or less, typically 1 hour or less, preferably 5 minutes or less, more preferably 2 minutes or less, and particularly preferably 1 minute or less. 【0031】 In substrates exposed to a surface modifier, component (A) contained in the surface modifier is adsorbed selectively in each region of the substrate surface, depending on the material of that region. In Figure 1, compound (A) 20 is adsorbed over the entire region B of the substrate 10, forming a surface modifier layer 224 consisting of a single layer 22 and an excess layer 24 on the single layer 22 where compound (A) 20 is deposited. The excess layer 24 protrudes onto region A of the substrate 10. 【0032】 The contact angle of the substrate surface with respect to water after exposure to the surface modifier can be, for example, 50° to 140°. By controlling the substrate surface material, the type and amount of component (A) contained in the surface modifier, and the exposure conditions, the contact angle with water on the substrate surface in the region where component (A) is adsorbed can be set to 50° or more. In this embodiment, the contact angle with water on the substrate surface in the region where component (A) is adsorbed is preferably 60° or more, more preferably 70° or more, and even more preferably 90° or more. There is no particular upper limit to the contact angle with water on the substrate surface in the region where component (A) is adsorbed, but it is, for example, 140° or less, and typically 130° or less. The aforementioned contact angle with water is measured, for example, by dropping a droplet of pure water onto the substrate surface using a contact angle measuring device and waiting for a predetermined time to elapse. 【0033】 <Washing process> In the cleaning step of this embodiment, the substrate after the exposure step is cleaned with a cleaning solution to obtain a processed substrate in which component (A) is controlled to form a film in the planar and height directions of the substrate. 【0034】 ≪About the cleaning solution≫ In the washing process, the Hansen solubility parameter of component (A) and the distance Ra between the Hansen solubility parameters are (Ra) 2 Select and use a cleaning solution that satisfies the relationship ≤ 128. (Ra) 2 From the viewpoint of the ability to remove excess surface modifier, (Ra) 2 ≤126 is preferred. (Ra) 2 The lower limit is 0≦(Ra) from the viewpoint of the ability to remove excess surface modifier. 2 It is preferable that this be the case. 【0035】 The distance Ra between the Hansen solubility parameter of component (A) and that of the cleaning liquid is represented in three-dimensional coordinates, and is calculated by the following formula (1) using the Hansen solubility parameter (δ dA , δ pA , δ hA ) of component (A) and the Hansen solubility parameter (δ dS , δ pS , δ hS ) of the cleaning liquid. 【0036】 (Ra) 2 =(δ dS -δ dA ) 2 +(δ pS -δ pA ) 2 +(δ hS -δ hA ) 2 ···(1) [However, δ dS and δ dA are dispersion terms, δ pS and δ pA are polar terms, and δ hS and δ hA are hydrogen bond terms.] 【0037】 The Hansen solubility parameter can be calculated from predetermined parameters based on the solubility parameter and cohesion characteristics explained by Charles Hansen in, for example, "Hansen Solubility Parameters: A User’s Handbook" by Charles M. Hansen, CRC Press (2007) and "The CRC Handbook and Solubility Parameters and Cohesion Parameters," edited by Allan F.M. Barton (1999) (1999). 【0038】 The Hansen solubility parameter is theoretically calculated as a numerical constant and is a useful tool for predicting the ability of a solvent material to dissolve a specific solute. The Hansen solubility parameters are derived experimentally and theoretically from the following three Hansen solubility parameters (i.e., δ d , δ p and δ h By combining these factors, it can be used as a measure of the overall strength and selectivity of the material. The unit of the Hansen solubility parameter is MPa. 0.5 or (J / cc) 0.5 It is granted by [this method]. δ d : Energy derived from intermolecular dispersion forces (dispersion term) δ p : Energy derived from intermolecular polar forces (polar term) δ h : Energy derived from intermolecular hydrogen bonding forces (hydrogen bonding term) 【0039】 (A) The Hansen solubility parameters for each component and washing solution can be calculated using software such as "Molecular Modeling Pro" software, version 5.1.9 (ChemSW, Fairfield CA, www.chemsw.com), Hansen Solubility from Dynacomp Software, HSPiP, etc. 【0040】 In this embodiment, a cleaning solution containing an organic solvent can be used. The organic solvent may be a single type or two or more types may be used in combination. If the cleaning solution contains two or more organic solvents, the Hansen solubility parameter (δ) of the cleaning solution should be considered. dS ,δ pS ,δ hS This can be calculated from the mixed volume ratio of each organic solvent. For example, when using two organic solvents (S1 and S2) as described below, if the mixed volume ratio of each component is a:b (S1:S2=a:b), the Hansen solubility parameter of the cleaning solution can be calculated using the following equations (1) to (3). 【0041】 δ dS =(a*δ dS1+b*δ dS2 ) / (a+b) (1) δ pS =(a*δ pS1 +b*δ pS2 ) / (a+b) (2) δ hS =(a*δ hS1 +b*δ hS2 ) / (a+b) (3) 【0042】 As the cleaning solution, one containing an organic solvent (S1) selected from the group consisting of polar solvents and hydrocarbon solvents (hereinafter also referred to as "component (S1)") can be preferably used. Examples of polar solvents in component (S1) include ketone solvents, ester solvents, alcohol solvents, and ether solvents. 【0043】 As ketone solvents, those having 3 or more carbon atoms are preferred, and examples include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylamyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate, with acetone, cyclopentanone, and 2,6-dimethyl-4-heptanone being preferred. 【0044】 As for ester solvents, those with 6 or more carbon atoms are preferred, and examples include propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate, with propylene glycol monomethyl ether acetate being preferred. 【0045】 Examples of alcohol-based solvents include those with 4 or more carbon atoms, such as n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, 4-methyl-2-pentanol (methyl isobutylcarbinol; MIBC), n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, and n-decanol; glycol-based solvents such as diethylene glycol and triethylene glycol; and glycol ether-based solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol. Isobutanol, 1-octanol, 2-ethyl-1-hexanol, and 1-methoxy-2-propanol are preferred. 【0046】 As for ether-based solvents, those with 8 or more carbon atoms are preferred. For example, in addition to the glycol ether-based solvents mentioned above, dibutyl ether, dipentyl ether, etc., are examples, with dibutyl ether being preferred. 【0047】 As hydrocarbon solvents, for example, alkanes having 6 or more carbon atoms are preferred, and linear or cyclic alkanes are more preferred. Examples include linear alkanes such as hexane, octane, decane, and undecane, or cyclic alkanes such as cyclohexane, cycloheptane, cyclooctanecyclodecane. Decane, tetradecane, and cyclohexane are preferred, and decane and tetradecane are more preferred. 【0048】 Among the above, the cleaning solution is more preferably one that contains an organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, ether solvents, and hydrocarbon solvents, and even more preferably one that contains at least one organic solvent selected from the group consisting of alkanes having 6 or more carbon atoms, alkylene glycol monoalkyl ether acetates having 6 or more carbon atoms, alcohols having 4 or more carbon atoms, ethers having 8 or more carbon atoms, and ketones having 3 or more carbon atoms. 【0049】 The cleaning solution may contain an organic solvent (S2) other than component (S1) (hereinafter also referred to as "component (S2)"). Component (S2) is not particularly limited, and any organic solvent that is miscible with component (S1) can be used. The content of component (S1) in the cleaning solution is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and may also be 100% by mass, based on the total mass of the cleaning solution. 【0050】 [Washing process operation] In the cleaning step of this embodiment, the substrate after the exposure step is cleaned with a cleaning solution. The method for cleaning the substrate after the exposure process using a cleaning solution is not particularly limited, but specifically includes a dipping method in which a cleaning tank is filled with cleaning solution and the substrate is immersed, a spinning method in which the substrate is rotated at high speed while cleaning solution is flowed onto the substrate from a nozzle, and a spray method in which the substrate is cleaned by spraying the solution onto it. Apparatus for performing such cleaning includes a batch cleaning apparatus that cleans multiple substrates contained in a cassette simultaneously, and a single-wafer cleaning apparatus that cleans a single substrate mounted in a holder. 【0051】 The temperature conditions during washing are, for example, 10°C to 90°C, preferably 20°C to 80°C, and more preferably 20°C to 30°C. Regarding the washing time, from the viewpoint of removing excess surface modifier, 20 seconds or more is preferable, 30 seconds or more is more preferable, and 45 seconds or more is even preferable. There is no particular upper limit to the above washing time, but for example it is 5 minutes or less, typically 2 minutes or less, and 1 minute or less is preferable. 【0052】 In the cleaning process of this embodiment, after cleaning with a cleaning solution, a processed substrate is obtained in which component (A) is controlled in the planar and height directions of the substrate to form a film. In Figure 2, the treated substrate 100 after cleaning has a surface modifier layer 220 formed on the substrate 10, consisting only of a single layer 22 that covers the entire area B of the substrate 10. The excess portion 24 that had accumulated on the single layer 22 and protruded onto area A of the substrate 10 before cleaning has been washed away by the cleaning solution. 【0053】 In one embodiment of the method for manufacturing a processed substrate as described above, a processed substrate can be manufactured by including the steps of: exposing the surface of a substrate to a surface modifier containing a compound (A) that has bonding properties to the substrate; and washing the substrate after the exposure with a cleaning solution to obtain a processed substrate in which the compound (A) is deposited in a film controlled in the planar and height directions of the substrate. According to the manufacturing method of this embodiment, the distance Ra between the Hansen solubility parameter of compound (A) and the Hansen solubility parameter of the washing solution is (Ra) 2 By using the cleaning solution that satisfies the relationship ≤ 128 to clean a substrate exposed to compound (A), a treated substrate can be obtained in which compound (A) is deposited in a film controlled in both the planar and height directions of the substrate. In the processed substrate obtained in this way, when attempting to form an atomic layer on a specific region of the substrate where the compound (A) has not been deposited, the desired atomic layer can be easily formed without the deposition being hindered. 【0054】 In the processed substrate manufactured by the manufacturing method of this embodiment, it can be confirmed that compound (A) was deposited in a controlled manner in both the planar and height directions of the substrate, as follows. 【0055】 The controlled deposition of compound (A) in the planar direction of the substrate can be confirmed by measuring the "water contact angle" on the treated surface of the substrate. The "water contact angle" is measured, for example, by dropping a droplet of pure water onto the substrate surface using a contact angle measuring device and waiting for a predetermined time. If the "water contact angle" on the treated surface of the substrate remains almost unchanged between the time the substrate surface is exposed to the surface modifier and the time it is cleaned with the cleaning solution, it can be determined that compound (A) is being deposited in a controlled manner in the planar direction of the substrate. In the processed substrate manufactured by the manufacturing method of this embodiment, the "water contact angle" on the processed surface of the substrate is maintained at, for example, 50° to 140°, preferably 60° to 130°, more preferably 70° to 130°, and even more preferably 90° to 130°. 【0056】 The fact that compound (A) was deposited in a controlled manner in the height direction of the substrate can be confirmed by measuring the proportion (remaining rate) of compound (A) that exists above a certain height from the substrate surface. Here, the "proportion (remaining rate) of compound (A)" is expressed as the area percentage covering the monolayer surface by compound (A) molecules, for example, by observing the treated substrate from above with an atomic force microscope (AFM) and detecting compound (A) molecules that exist above the substrate surface at a height exceeding the thickness of the monolayer in which compound (A) molecules are arranged (i.e., deposited on the monolayer). The lower the "percentage of compound (A) present (residual rate)" on the processed surface of the substrate, the higher the cleaning and removal efficiency of compound (A) by the cleaning solution, and it can be determined that compound (A) is being controlled and deposited in the height direction of the substrate. In the processed substrate manufactured by the manufacturing method of this embodiment, the "residual rate of compound (A)" on the processed surface of the substrate is lower than, for example, when conventional general-purpose isopropanol (IPA) is used as the cleaning solution. For example, when a copper substrate is used as the substrate and octadecanethiol (ODT) is used as compound (A), the "residual rate of compound (A)" on the processed surface of the substrate is less than 8.2%, preferably 7.5% or less, more preferably 6% or less, and even more preferably 5% or less. 【0057】 <Regarding other embodiments> In the above-described embodiment of the method for manufacturing a processed substrate, a case including an exposure step and a cleaning step was explained. However, the method for manufacturing a processed substrate according to the first aspect of the present invention is not limited thereto, and may further include other steps other than the exposure step and the cleaning step as needed. Examples of other steps include a pretreatment step, a surface treatment step, a rinsing step, and a drying step. 【0058】 Regarding the pre-treatment process: In the pretreatment step, the substrate surface is pretreated. The pretreatment of the substrate surface is preferably a treatment that can impart hydroxyl groups to the substrate surface. Examples of pretreatment methods include ozone treatment and treatment with a pretreatment oxidizing agent described later. From the viewpoint of improving the adsorption of the surface modifier to the substrate surface, at least one pretreatment oxidizing agent selected from the group consisting of hydrogen peroxide and perhalic acid is preferred. The pretreatment temperature is not particularly limited, but is typically 10 to 35°C, preferably 15 to 30°C, and more preferably 20 to 25°C. When the pretreatment temperature is within the above preferred range, it is easier to remove the native oxide film on the substrate surface and to impart hydroxyl groups to the substrate surface. The processing time for pretreatment is not particularly limited, but is typically 10 seconds to 10 minutes, preferably 20 seconds to 5 minutes, and more preferably 30 seconds to 3 minutes. When the processing time for pretreatment is within the above preferred range, it is easier to remove the native oxide film on the substrate surface and to impart hydroxyl groups to the substrate surface. 【0059】 Regarding the surface treatment process: In the surface treatment step, the substrate surface before the exposure step is treated with diluted hydrofluoric acid using a known method. By further providing a surface treatment step before the exposure step, organic residue adhering to the substrate surface can be removed, and the film formation of the surface modifier in the planar direction of the substrate can be improved. 【0060】 Regarding the rinsing process: After the exposure process, the exposed substrate may be cleaned as needed (for example, by washing with water, deionized water, or an activator rinse). For example, for cleaning the substrate surface having an inorganic or organic pattern, which may be performed as needed, the cleaning solution conventionally used for cleaning inorganic or organic patterns can be used as is. Examples of cleaning solutions for inorganic patterns include SPM (sulfuric acid-hydrogen peroxide solution) and APM (ammonia-hydrogen peroxide solution), while examples of cleaning solutions for organic patterns include water and surfactant rinses. 【0061】 Regarding the drying process: In the drying step, the substrate is dried. In the method for manufacturing a processed substrate according to this embodiment, a drying step may be further provided after the exposure step or the cleaning step. By providing a drying step, the cleaning solution remaining on the substrate can be efficiently removed. The method for drying the substrate is not particularly limited, and known methods such as spin drying, heat drying, hot air drying, and vacuum drying can be used. For example, spin drying under an inert gas (such as nitrogen gas) blow is a preferred example. Furthermore, if necessary, the substrate may be subjected to additional heat treatment at a temperature between 100°C and 300°C after drying following exposure. 【0062】 In the method for manufacturing a processed substrate according to this embodiment, for example, two types of surface modifiers may be used. In an embodiment in which two types of surface modifiers are used, when a substrate having region A and region B is used, region A of the substrate is exposed to the first surface modifier to surface modify region A, and then the exposed substrate is cleaned with a suitable cleaning solution that satisfies the relationship of the present invention. Subsequently, region B of the substrate after cleaning is exposed to the second surface modifier using the same procedure to surface modify region B, and then the substrate after the second exposure is cleaned with a suitable cleaning solution that satisfies the relationship of the present invention. In this way, even when two or more types of surface modifiers are used, a processed substrate in which each region of the substrate is modified by a different surface modifier can be obtained by repeating the exposure step and the cleaning step. 【0063】 In the manufacturing method of the processed substrate according to the above embodiment, compound (A) 20 is selectively adsorbed onto the surface of region B of the substrate 10 by exposing the surface to be treated of the substrate 10 to a surface modifier. This makes it possible to make the contact angles of water with respect to the surface of regions A and B of the substrate 10 different from each other. Regarding the substrate that can be used in the manufacturing method of the processed substrate according to this embodiment, a region in the substrate that tends to have a higher water contact angle (preferably a lower surface free energy) than the other region is a region composed of a conductor. 【0064】 The conductor is not particularly limited as long as it is a material that has electrical conductivity. Examples of conductors include materials containing metal atoms. Examples of conductors include metals (e.g., elemental metals), alloys, and metal compounds (e.g., nitrides). If the conductor is a metal, the surface of the conductor is a metallic surface. If the conductor is an alloy, the surface of the conductor is an alloy surface. If the conductor is a metal compound, the surface of the conductor is a conductive metal compound surface. Examples of metals included in the metal surface include at least one selected from the group consisting of tungsten (W), cobalt (Co), aluminum (Al), titanium nitride (TiN), tantalum nitride (TaN), nickel (Ni), ruthenium (Ru), and copper (Cu). In particular, it is preferable to include at least one selected from the group consisting of tungsten, ruthenium, copper, and cobalt, and more preferably at least one selected from the group consisting of tungsten and ruthenium. The region having the substrate surface may be a region composed of a substrate containing these metals. 【0065】 The conductive surface may be pre-treated with an oxidizing agent. Examples of oxidizing agents for pre-treating the conductive surface (hereinafter referred to as "pre-treatment oxidizing agent") include those that can remove the native oxide film present on the conductive surface and impart hydroxyl groups to the conductive surface. Examples of pre-treatment oxidizing agents include peroxides such as hydrogen peroxide, perhalates such as periodic acid, and oxoacids such as nitric acid and hypochlorous acid. Among these, at least one selected from the group consisting of hydrogen peroxide and perhalates is preferred as the pre-treatment oxidizing agent from the viewpoint of adsorption properties of compound (A). At least one selected from the group consisting of hydrogen peroxide and perhalates is also preferred from the viewpoint of treating the conductive surface without damaging inorganic materials such as SiO2 and Al2O3 when such inorganic materials coexist with the conductive surface. The pretreatment oxidizing agent may be used alone or in combination of two or more types. The conductive surface may be treated with ozone, or it may be treated with a pre-treatment oxidizing agent after ozone treatment. The conductive surface, treated with at least one of pretreatment with an oxidizing agent and / or ozone treatment, is modified with hydroxyl groups. 【0066】 The substrate used in the manufacturing method of the processed substrate of this embodiment may have a surface that includes two or more regions made of different materials, and at least one of the two or more regions may be a conductive surface. If a substrate has at least one region with a conductive surface, then two or more regions may have conductive surfaces. If a substrate has two or more regions with conductive surfaces, those regions may contain the same conductor or different conductors. 【0067】 Among the two or more regions, a region in which the water contact angle tends to be smaller (preferably, the surface free energy is higher) than that of the other region is a region that does not have a conductive surface (for example, a region made of an insulator (hereinafter referred to as the "insulating region"). The surface of the substrate to be treated may include one insulating region or two or more. When there are two or more insulating regions, these regions may be made of the same material or different materials. The surface of the substrate to be treated preferably includes one or more regions having a conductive surface and one or more regions having an insulating surface. 【0068】 The insulator constituting the insulating region is composed of insulating compounds. Examples of insulating compounds include oxides such as aluminum oxide (Al2O3), titanium oxide (TiO2), zirconium oxide (ZrO2), hafnium oxide (HfO2), tantalum oxide (Ta2O5), silicon oxide (SiOx (1≦x≦2)), fluorine-containing silicon oxide (SiOF), and carbon-containing silicon oxide (SiOC); nitrides such as silicon nitride (SiN) and boron nitride (BN); carbides such as silicon carbide (SiC); carbonitrides such as silicon carbonitride (SiCN); oxynitrides such as silicon oxynitride (SiON); oxycarbonitrides such as silicon oxycarbonitride (SiOCN); and insulating resins such as polyimide, polyester, and plastic resins. 【0069】 The surface of the substrate to be treated may include two or more regions containing a conductive surface, and adjacent regions among the two or more said regions may have different materials. 【0070】 If the surface to be treated includes two regions, the surface to be treated may include a first region containing a conductive surface and a second region adjacent to the first region (e.g., an insulating region) which is made of a different material from the first region. In this case, "adjacent regions" refers to the first region and the second region. The first and second regions may or may not be divided into multiple regions. 【0071】 If the surface to be treated includes three or more regions, the surface to be treated may include a first region containing a conductive surface, a second region adjacent to the first region and made of a different material (e.g., an insulating region), and a third region adjacent to the second region and made of a different material. In this case, "adjacent regions" may refer to the first and second regions (i.e., adjacent regions), or to the first and third regions (i.e., the region immediately adjacent). If the materials of the first region and the third region are the same (i.e., both the first region and the third region contain a conductive surface), then the "adjacent regions" are the first region and the second region, or the second region and the third region (i.e., adjacent regions). The first, second, and third regions may or may not be divided into multiple regions. The same approach can be applied when the surface to be treated includes a fourth or higher region. There is no particular upper limit to the number of regions with different materials, as long as the effects of the present invention are not impaired, but for example, it is 7 or less or 6 or less, and typically 5 or less. 【0072】 (Method for processing circuit boards) A second aspect of the present invention relates to a substrate processing method, which includes a step of exposing the surface of the substrate to a surface modifier containing a compound (A) that has bonding properties to the substrate (exposure step), and a step of washing the substrate after exposure with a cleaning solution to form a film of compound (A) while controlling its distribution in the planar and height directions of the substrate (cleaning step). In the substrate processing method, the distance Ra between the Hansen solubility parameter of compound (A) and the Hansen solubility parameter of the cleaning solution is (Ra) 2 Select and use the cleaning solution that satisfies the relationship ≤ 128. The exposure step and cleaning step in the processing method for such substrates are the same as the description of the <exposure step> and <cleaning step> in one embodiment of the (method for manufacturing a processed substrate) described above. 【0073】 According to the substrate processing method of this embodiment, the surface of the substrate can be modified by including the steps of: exposing the surface of the substrate to a surface modifier containing a compound (A) that has bonding properties to the substrate; and washing the substrate after the exposure with a cleaning solution to form a film of compound (A) while controlling its distribution in the planar and height directions of the substrate. In addition, the distance Ra between the Hansen solubility parameter of compound (A) and the Hansen solubility parameter of the washing solution is (Ra) 2 By selecting and using the aforementioned washing solution that satisfies the relationship ≤ 128, the washing and removal efficiency of excess compound (A) is improved, making it possible to form a modified layer of uniform thickness. 【0074】 (Pattern formation method) A third aspect of the present invention relates to a pattern formation method which includes a step of forming an atomic layer on the surface of a processed substrate manufactured by the manufacturing method of the first aspect, in a region where the surface modifier has not been formed, by thin film formation using a vapor deposition method. 【0075】 <Process of forming an atomic layer by thin film formation using vapor deposition> In this step, an atomic layer is formed on the surface of the processed substrate, manufactured by the manufacturing method of the above-described embodiment, in a region where the surface modifier has not been deposited, by thin film formation using vapor deposition. For example, in Figure 2, an atomic layer is formed on region A of the processed substrate 100 after cleaning by thin film formation using vapor deposition. Vapor deposition is a method that uses a gas containing the raw materials for the thin film, and a method that utilizes chemical reactions in the gas phase to form the thin film is preferably used. 【0076】 Examples of deposition methods include atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), pulse laser deposition (PLD), molecular beam epitaxy (MBE), and ion plating. Among these, ALD or CVD is preferred, with ALD being more preferred. 【0077】 Examples of CVD methods include thermal CVD, plasma CVD, photo-CVD, reduced-pressure CVD, laser CVD, and metal-organic CVD (MOCVD). Examples of ALD methods include thermal ALD and plasma ALD. 【0078】 Examples of the formed atomic layer (Y) include a metal layer, a metal oxide layer, a metal nitride layer, a nonmetal oxide layer, a nonmetal nitride layer, a metal-nonmetal oxide layer, and a metal-nonmetal nitride layer. 【0079】 [About the formation of atomic layers by the ALD method] In this embodiment, the ALD method is preferred as the vapor deposition method. The substrate surface in the region where the surface modifier film is deposited exhibits selectively improved water repellency compared to the surface in the region where the surface modifier film is not deposited. As a result, the amount of material depositing the film can be selectively varied between two or more regions on the substrate surface. This selective improvement in water repellency can be confirmed by measuring the contact angle of water with respect to the surface of the region. Specifically, among the two or more regions, adsorption (preferably chemiadsorption) of the atomic layer-forming material by the ALD method becomes difficult in the region containing the substrate surface. As a result, a difference in the amount of atomic layer-forming material deposited occurs between the two or more regions. In other words, the amount of atomic layer-forming material deposited by the ALD method differs region by region. Specifically, the amount of atomic layer-forming material deposited in the region containing the substrate surface is lower than the amount deposited in the insulating region. Examples of chemical adsorption of the atomic layer-forming material include chemical adsorption with hydroxyl groups applied to the substrate surface by pretreatment. 【0080】 Among the two or more regions mentioned above, a region in which the water contact angle tends to be larger (preferably smaller) than that of the other region includes at least one element selected from the group consisting of W, Co, Al, Ni, Ru, and Cu. The region having a substrate surface may also include these elements. Among the two or more regions mentioned above, a region in which the water contact angle tends to be smaller (preferably, the surface free energy is higher) than that of the other region includes at least one selected from the group consisting of Si, Al2O3, SiN, SiOx, Ge, SiGe, TEOS, Low-k materials, and ILD. The insulating region may be composed of materials containing the insulating compound, in addition to the insulating compound itself. 【0081】 There are no particular restrictions on the atomic layer formation method using the ALD method, but it is preferable to use a thin film formation method by adsorption (preferably chemiadsorption) using at least two gas-phase reactants (hereinafter simply referred to as "precursor gases"). Specifically, this includes a method comprising the following steps (a) and (b), and repeating steps (a) and (b) at least once (1 cycle) until the desired film thickness is obtained. Step (a) Exposing the surface-modified substrate to a pulse of a first precursor gas, and Step (b) After step (a), the step of exposing the substrate to a pulse of a second precursor gas. 【0082】 After step (a) and before step (b), the process may or may not include a plasma treatment step, a step of removing or purging the first precursor gas and its reactants with a carrier gas, a second precursor gas, etc. After step (b) above, the process may or may not include a plasma treatment step, a step of removing or purging the second precursor gas and its reactants with a carrier gas, etc. Examples of carrier gases include inert gases such as nitrogen, argon, and helium. 【0083】 Each pulse and each layer formed in each cycle is preferably self-regulating, and it is more preferable that each formed layer is a single atomic layer. The thickness of the single atomic layer can be, for example, 5 nm or less, preferably 3 nm or less, more preferably 1 nm or less, and even more preferably 0.5 nm or less. 【0084】 Examples of the first precursor gas include organometallic compounds, metal halides, and metal oxide halides. Specifically, examples include tantalum pentaethoxide, tetrakis(dimethylamino)titanium, pentakis(dimethylamino)tantalum, tetrakis(dimethylamino)zirconium, tetrakis(dimethylamino)hafnium, tetrakis(dimethylamino)silane, copper hexafluoroacetylacetonate vinyltrimethylsilane, Zn(C2H5)2, Zn(CH3)2, TMA (trimethylaluminum), TaCl5, WF6, WOCl4, CuCl, ZrCl4, AlCl3, Al(CH3)3, TiCl4, SiCl4, and HfCl4. 【0085】 Examples of the second precursor gas include precursor gases that can decompose the first precursor or precursor gases that can remove ligands from the first precursor. Specifically, examples include H2O, H2O2, O2, O3, NH3, H2S, H2Se, PH3, AsH3, C2H4, or Si2H6. 【0086】 There are no particular restrictions on the exposure temperature in step (a), but for example, it is 100°C or more and 800°C or less, preferably 150°C or more and 650°C or less, more preferably 180°C or more and 500°C or less, and even more preferably 200°C or more and 375°C or less. There are no particular restrictions on the exposure temperature in process (b), but it should be substantially equal to or higher than the exposure temperature in process (a). There are no particular restrictions on the films formed by the ALD method, but examples include films containing pure elements (e.g., Si, Cu, Ta, W), films containing oxides (e.g., SiO2, GeO2, HfO2, ZrO2, Ta2O5, TiO2, Al2O3, ZnO, SnO2, Sb2O5, B2O3, In2O3, WO3), films containing nitrides (e.g., Si3N4, TiN, AlN, BN, GaN, NbN), films containing carbides (e.g., SiC), films containing sulfides (e.g., CdS, ZnS, MnS, WS2, PbS), films containing selenides (e.g., CdSe, ZnSe), films containing phosphides (GaP, InP), films containing arsenides (e.g., GaAs, InAs), or mixtures thereof. 【0087】 In the method of this embodiment, an atomic layer is formed by ALD on a surface-modified substrate manufactured by the manufacturing method according to the first embodiment, using a surface modifier. In the surface-modified substrate, the water repellency of the region having the substrate surface is selectively improved. Therefore, the deposition of the atomic layer-forming material by ALD is inhibited in the region having the substrate surface. As a result, the amount of atomic layer-forming material deposited by ALD is less in the region having the substrate surface compared to the insulating region. This makes it possible to selectively form a film by ALD on the insulating region. 【0088】 According to the pattern formation method of this embodiment, an atomic layer can be formed on the surface of a processed substrate manufactured by the manufacturing method according to the first embodiment, in a region where the surface modifier has not been deposited, by thin film formation using a vapor deposition method. Therefore, the pattern formation method of this embodiment can be suitably applied to selective atomic layer formation. 【0089】 (Cleaning solution) The cleaning solution according to the fourth aspect of the present invention is a cleaning solution used in the method according to the first or second aspect of the present invention. The description of such a cleaning solution is the same as the description of the cleaning solution in the above-described embodiment of the (method for manufacturing a processed substrate). 【0090】 The cleaning solution of this embodiment may contain one type of organic solvent (S1) alone, or it may contain two or more types. Preferred organic solvents (S1) include decane, tetradecane, cyclohexane, 2-methoxy-1-methylethyl acetate, isobutanol, 1-octanol, 2-ethyl-1-hexanol, dibutiether, acetone, cyclopentanone, 2,6-dimethyl-4-heptanone, and 1-methoxy-2-propanol. 【0091】 The content of component (S1) in the washing solution is such that the distance Ra between the Hansen solubility parameter of compound (A) and the Hansen solubility parameter of the washing solution is (Ra) 2 While not particularly limited as long as the relationship ≤128 is satisfied, it is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and may be 100% by mass, relative to the total mass of the cleaning solution. 【0092】 The cleaning solution of this embodiment may contain an organic solvent (S2) other than component (S1) (hereinafter also referred to as "component (S2)"). Component (S2) is not particularly limited, and any organic solvent that is miscible with component (S1) can be used. 【0093】 The cleaning solution may contain optional components in addition to the organic solvent. Examples of optional components include water and impurities. 【0094】 The cleaning solution in this embodiment may contain water. The water may contain trace components that inevitably become mixed in. As water, purified water such as distilled water, ion-exchanged water, and ultrapure water is preferred, and it is preferable to use ultrapure water which is commonly used in semiconductor manufacturing. If the cleaning solution contains water, the water content is preferably 0.01 to 25% by mass, more preferably 0.03 to 20% by mass, and even more preferably 0.05 to 15% by mass, relative to the total mass of the cleaning solution. The cleaning solution in this embodiment may not contain water. 【0095】 The cleaning solution of this embodiment may contain metallic impurities, such as metal atoms including Fe atoms, Cr atoms, Ni atoms, Zn atoms, Ca atoms, or Pb atoms. The total content of metal atoms in the cleaning solution of this embodiment is preferably 100 ppt by mass or less, relative to the total mass of the cleaning solution. The lower limit of the total content of metal atoms is preferable as it is lower, but for example, 0.001 ppt by mass or more is acceptable. For example, the total content of metal atoms may be between 0.001 ppt by mass and 100 ppt by mass. By keeping the total content of metal atoms below the upper limit of the preferred range, the removal performance of excess surface modifier is improved. By keeping the total content of metal atoms above the lower limit of the preferred range, metal atoms are less likely to be released into the system, which is thought to reduce the adverse effect on the overall manufacturing yield of the cleaned product. The content of metal impurities can be adjusted, for example, by purification treatment such as filtering. This purification treatment may be performed on some or all of the raw materials before preparing the washing solution, or after preparing the washing solution. 【0096】 The cleaning solution of this embodiment may contain, for example, impurities of organic origin (organic impurities). The total content of the organic impurities in the cleaning solution of this embodiment is preferably 5000 ppm by mass or less. The lower limit of the organic impurity content is preferable as it is lower, but for example, 0.1 ppm by mass or more is acceptable. For example, the total content of organic impurities may be between 0.1 ppm by mass and 5000 ppm by mass. 【0097】 The cleaning solution of this embodiment may contain countable particles of a size that can be counted by, for example, a light scattering type liquid particle counter. The size of the countable particles is, for example, 0.04 μm or larger. The number of countable particles in the cleaning solution of this embodiment is, for example, 1,000 or less per 1 mL of cleaning solution, with a lower limit of, for example, 1 or more. It is believed that the removal performance of excess surface modifier is improved when the number of countable particles in the cleaning solution is within the above range. 【0098】 The method for storing the cleaning solution in this embodiment is not particularly limited, and conventionally known storage containers can be used. The porosity of the container and the type of gas used to fill the voids should be set appropriately to ensure the stability of the cleaning solution. For example, the porosity of the storage container can be approximately 0.01 to 30 volume percent. 【0099】 According to the cleaning solution of this embodiment, in the method according to the first or second embodiment, the distance Ra between the Hansen solubility parameter of compound (A) and the Hansen solubility parameter is (Ra) 2 By selecting and using components that satisfy the relationship ≤ 128, excess (A) deposited after exposure to the surface modifier can be removed with a high cleaning and removal rate. [Examples] 【0100】 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. 【0101】 The substrate, surface modifier, and cleaning solution used in this embodiment are described below. 【0102】 (Pre-treatment of substrates) For the substrate, we used a coupon made by cutting a blanket substrate with a 200nm thick copper film onto an 8-inch silicon substrate into a 2cm x 2cm piece. All substrates used were treated with diluted hydrofluoric acid. Specifically, each substrate was pre-treated by immersing it in a 25 ppm HF aqueous solution at 25°C for 1 minute. The water contact angle on the substrate surface after pre-treatment, as measured by the method described later, was 30.0°. After the above pretreatment, each substrate was washed with deionized water for 1 minute. After washing, each substrate was dried with a nitrogen stream. 【0103】 (Preparation of surface modifier) Octadecanthiol (ODT) 100% by mass was used as the surface modifier. 【0104】 (Preparation of cleaning solution) As the cleaning solution, 100% by mass of the following organic solvent (S1) was used. The standard cleaning solution was 100% by mass of isopropanol. (S1)-1: Acetone (S1)-2: Propylene glycol monomethyl ether (S1)-3: Deccan (S1)-4: Tetradecane (S1)-5: Cyclohexane (S1)-6:1-Octanol (S1)-7: Isobutanol (S1)-8:2-ethyl-1-hexanol (S1)-9: Dibutyl ether (S1)-10:2,6-dimethyl-4-heptanone (S1)-11: Cyclopentanone (S1)-12: Propylene glycol monomethyl ether acetate For the organic solvent (S1), the distance Ra between the Hansen solubility parameter of ODT and the Hansen solubility parameter of the organic solvent (S1) is (Ra) 2 We selected a solution that satisfies the relationship ≤ 128 and used it as the cleaning solution. 【0105】 [(Ra) 2 [Calculation method] (Ra) 2 For example, when (S1)-1 was used, the calculation was performed using the parameter values ​​listed in Table 1. 【0106】 [Table 1] 【0107】 (Ra) 2 =( δ dS -δ dA ) 2 +( δ pS -δ pA ) 2 +( δ hS -δ hA ) 2 ...(1) [However, δ dS and δ dA is the variance term, δ pS and δ pA is a polar term, δ hS and δ hA This is the hydrogen bond term. 【0108】 From the above formula (1), the (Ra) when using (S1)-1 is as follows: 2 The result was calculated. (Ra) 2 =(15.7-16.4) 2 +(9.1-2.3) 2 +(6.5-2.6) 2 =61.9 (S1)-2 to (S1)-12, and the respective (Ra) when using isopropanol 2 The same method was used to calculate the values ​​of each parameter and (Ra) 2 This is shown in Table 2. 【0109】 [Table 2] 【0110】 <Manufacturing method for processed substrates> (Examples 1-12, Comparative Example 1) A treated substrate was obtained by each example of a manufacturing method that included an exposure step of exposing the surface of the substrate to a surface modifier ODT, and a cleaning step of cleaning the substrate with a cleaning solution after the exposure step. Specifically, the process was carried out as follows. 【0111】 Exposure process: The substrate, after drying as described above (substrate pretreatment), was immersed in the surface modifier ODT at 25°C for 1 minute to modify the substrate's surface. Furthermore, the water contact angle on the substrate surface after the exposure process, as measured by the method described later, was 104.5°. 【0112】 Cleaning process: After the exposure process, the substrates were immersed in each of the above-mentioned cleaning solutions for 1 minute at 25°C to perform a cleaning treatment. After the cleaning treatment, the substrates were washed with ion-exchanged distilled water for 1 minute at 25°C, and then dried with a nitrogen stream to produce surface-modified treated substrates. 【0113】 <Rating> For the processed substrates manufactured using the manufacturing method of each example, the ODT remaining rate and the water contact angle were measured using the method described below. 【0114】 [ODT residual rate] The ODT remaining rate was measured for the processed substrates manufactured in Examples 1 to 12 and Comparative Example 1. The ODT retention rate was determined by observing the treated substrates manufactured in each example from above using an atomic force microscope (AFM). Surface modifier ODT molecules existing at a height above the substrate surface that exceeds the thickness of the single layer formed on the substrate (i.e., deposited on the single layer) were detected. The ODT retention rate was calculated from the area percentage covering the single-layer surface by these surface modifier ODT molecules. The results are shown in Table 3. The ODT retention rate (%) shown in Table 3 is calculated by performing AFM observations at three arbitrary points on the treated substrate surface, determining the ODT retention rate within the observation range of each point, and then taking the average of these values. The ODT remaining rate was determined by calculating the percentage of the area occupied by the excess portion 24 relative to the total area of ​​the AFM observation image (observation range 1 μm × 1 μm). The thickness L of the single layer in which surface modifier ODT molecules are arranged on the substrate was set to 2 nm. 【0115】 Figure 3A shows the AFM observation image of the substrate surface immediately after the exposure process (observation range 1 μm × 1 μm). Figure 3B shows the AFM observation image of the treated substrate surface manufactured in Example 11 (observation range 1 μm × 1 μm). Figure 3C shows the AFM observation image of the treated substrate surface manufactured in Comparative Example 1 (observation range 1 μm × 1 μm). In the AFM observation image shown in Figure 3A, reference numeral 100A denotes the processed substrate. Reference numeral 22A denotes a single layer portion in which the surface modifier ODT is directly bonded to the substrate surface. Reference numeral 24A denotes the excess portion in which the surface modifier ODT is deposited on the single layer portion 22A. In the AFM observation image shown in Figure 3B, reference numeral 100B denotes the processed substrate. Reference numeral 22B denotes a single layer portion in which the surface modifier ODT is directly bonded to the substrate surface. Reference numeral 24B denotes the excess portion in which the surface modifier ODT is deposited on the single layer portion 22B. In the AFM observation image shown in Figure 3C, reference numeral 100C denotes the processed substrate. Reference numeral 22C denotes a single layer portion in which the surface modifier ODT is directly bonded to the substrate surface. Reference numeral 24C denotes an excess portion in which the surface modifier ODT is deposited on the single layer portion 22C. 【0116】 [Table 3] 【0117】 The results shown in Table 3 indicate that the cleaning solutions used in the manufacturing methods of Examples 1 to 12 had a lower ODT retention rate compared to the standard cleaning solution used in the manufacturing method of Comparative Example 1, meaning they had a higher cleaning and removal efficiency for excess ODT. In particular, the manufacturing methods in Examples 3 to 5 show a particularly low residual ODT rate, indicating a significant improvement in the cleaning and removal of excess ODT. 【0118】 [Water contact angle] The water contact angle was measured for the processed substrates manufactured in Examples 1 to 12 and Comparative Example 1. The water contact angle was measured using a Dropmaster 700 (manufactured by Kyowa Interface Science Co., Ltd.) by dropping a 2.0 μL drop of pure water onto the surface of a surface-modified substrate and measuring the water contact angle 2 seconds after dropping. The results are shown in Table 4. 【0119】 [Table 4] 【0120】 As shown in Table 4, the water contact angle on the dried treated substrate after the washing step was 102.7 to 109.9° in the manufacturing methods of Examples 1 to 12, which was confirmed to be about the same as the water contact angle of 104.5° on the substrate surface after the exposure step. This clearly shows that the ODT layer is maintained at a constant thickness on the substrate surface before and after the cleaning process. Therefore, the results shown in Table 4 suggest that only excess ODT is efficiently removed. [Explanation of symbols] 【0121】 10 circuit boards 20 Compound (A) 22 Single layer 24 Surplus 100 processed substrates 220 Surface modifier layer 224 Surface modifier layer

Claims

[Claim 1] A method for manufacturing a processed substrate having a surface in which at least a portion of the area is modified, A step of exposing the surface of the substrate to a surface modifier containing a compound (A) that has bonding properties to the substrate, The process involves cleaning the substrate after the exposure with a cleaning solution to obtain a processed substrate in which the compound (A) is deposited in a controlled manner in the planar and height directions of the substrate. Includes, The distance Ra between the Hansen solubility parameter of compound (A) and the Hansen solubility parameter of the washing solution is (Ra) ２ A method for manufacturing a processed substrate, comprising selecting and using the cleaning solution that satisfies the relationship ≤ 128. [Claim 2] The method for producing a processed substrate according to claim 1, wherein the compound (A) is an alkylthiol compound. [Claim 3] The method for producing a treated substrate according to claim 2, wherein the cleaning solution contains at least one organic solvent selected from the group consisting of alkanes having 6 or more carbon atoms, alkylene glycol monoalkyl ether acetates having 6 or more carbon atoms, alcohols having 4 or more carbon atoms, ethers having 8 or more carbon atoms, and ketones having 3 or more carbon atoms. [Claim 4] The method for manufacturing a processed substrate according to claim 3, wherein the content of the organic solvent in the cleaning solution is 70% by mass or more with respect to the total mass of the cleaning solution. [Claim 5] A step of exposing the surface of the substrate to a surface modifier containing a compound (A) that has bonding properties to the substrate, The process involves cleaning the substrate after the aforementioned exposure with a cleaning solution to form a film of compound (A) while controlling its distribution in the planar and height directions of the substrate. Includes, The distance Ra between the Hansen solubility parameter of compound (A) and the Hansen solubility parameter of the washing solution is (Ra) ２ A method for processing a substrate, wherein the cleaning solution is selected and used such that the relationship is ≤ 128. [Claim 6] A pattern forming method comprising the step of forming an atomic layer on the surface of a processed substrate manufactured by the manufacturing method described in any one of claims 1 to 4, in a region where the surface modifier has not been formed, by thin film formation using a vapor deposition method. [Claim 7] A cleaning solution used in a method for manufacturing a processed substrate according to any one of claims 1 to 4, or a method for processing a substrate according to claim 5, A cleaning solution containing at least one organic solvent selected from the group consisting of decane, tetradecane, cyclohexane, propylene glycol monomethyl ether acetate, isobutanol, 1-octanol, 2-ethyl-1-hexanol, dibutiether, acetone, cyclopentanone, 2,6-dimethyl-4-heptanone, and propylene glycol monomethyl ether. [Claim 8] The cleaning solution according to claim 7, wherein the content of the organic solvent in the cleaning solution is 70% by mass or more with respect to the total mass of the cleaning solution.