Process substrate manufacturing method, process substrate processing method, pattern forming method, and cleaning liquid

Abstract

The present invention is a method for manufacturing a treated substrate having a surface of which at least a partial region is modified, the method comprising: a step for exposing the surface of a substrate (10) to a surface modifier containing a compound (A) (20) having binding properties with respect to the substrate (10); and a step for cleaning the exposed substrate (10) with a cleaning solution to obtain a treated substrate (100) in which a film is formed by controlling the compound (A) (20) in the plane direction and the height direction of the substrate (10). The method is characterized in that a cleaning solution in which the distance (Ra) between the Hansen solubility parameter of the compound (A) (20) and the Hansen solubility parameter of the cleaning solution satisfies the relationship (Ra) 2 < = 128 is selected.

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.

[0002] This application claims priority based on Japanese Patent Application No. 2022-186637 filed in Japan on November 22, 2022, and incorporates its content herein. Background Art

[0003] In recent years, the trend of high integration and miniaturization of semiconductor devices has increased, and the miniaturization of inorganic patterns formed by organic patterns and etching processes used as masks has been continuously developed, requiring film thickness control at the atomic layer level.

[0004] 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 high step coverage and film thickness controllability compared to general CVD (Chemical Vapor Deposition) methods.

[0005] The ALD method is a thin film formation technique in which two gases mainly composed of elements constituting a film to be formed are alternately supplied to a substrate, and a thin film is formed on the substrate in atomic layer units, and this operation is repeated multiple times to form a film having a desired thickness.

[0006] In the ALD method, the self-limiting function of growth (self-limiting function) is utilized, that is, 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.

[0007] For example, when forming an Al2O3 film on a substrate, a source gas composed of TMA (TriMethyl Aluminum) and an oxidation gas containing O are used. In addition, when forming a nitride film on a substrate, a nitride gas is used instead of the oxidation gas.

[0008] In recent years, methods for selectively forming a film in a surface region of a substrate using the ALD method have been attempted. For example, after subjecting a part of the substrate region to a water-repellent treatment using a surface modifier, atomic layer film formation using the ALD method is performed on the untreated region. In the film formation method, by using the ALD method, film thickness control, step coverage, and miniaturization at the atomic layer level of patterning can be expected.

[0009] In the method of region-selective film formation on the substrate surface, generally, the substrate surface is hydrophobized region-selectively, thereby hindering film formation on the hydrophobized substrate surface. For example, in the case of selectively forming a film on the insulator surface of a substrate surface where a conductor surface and an insulator surface coexist, it is required to hydrophobize the conductor surface selectively.

[0010] For example, in Patent Document 1, it is described that for a surface including two or more regions and adjacent regions among the two or more regions, by forming a self-assembled monolayer film of octadecylphosphonic acid on surfaces with different materials, the contrast between regions with different materials becomes good.

[0011] Prior Art Documents

[0012] Patent Documents

[0013] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2021-014631 Summary of the Invention

[0014] Technical Problem to be Solved by the Invention

[0015] When hydrophobizing the substrate surface region-selectively using a surface modifier, if the remaining surface modifier is deposited on the surface modification layer, uniform film formation on the modification layer cannot be achieved, which causes pattern defects.

[0016] In addition, in the method of Patent Document 1, cleaning with isopropyl alcohol (IPA) is disclosed after exposure to the surface modifier, but the removability of the remaining surface modifier is lacking, and there is room for improvement.

[0017] The present invention has been completed in view of the above circumstances, and its technical problem is to provide a manufacturing method of a processed substrate, a method for processing a substrate that can be used in the manufacturing method, a pattern formation method, and a cleaning liquid. The manufacturing method of the processed substrate is a manufacturing method of a processed substrate having a surface with at least a part of the region modified. By cleaning the substrate exposed to the surface modifier, the remaining surface modifier can be removed, and a processed substrate can be obtained in which the surface modifier is controlled in the plane direction and the height direction for film formation.

[0018] Means for Solving the Above Technical Problem

[0019] To solve the above technical problem, the present invention adopts the following configuration.

[0020] A first aspect of the present invention is a method for manufacturing a processed substrate, which is a method for manufacturing a processed substrate having a surface with at least a partially modified region, including: a step of exposing the surface of the substrate to a surface modifier containing a compound (A) having binding properties to the substrate; and a step of cleaning the exposed substrate with a cleaning liquid to obtain a processed substrate in which the compound (A) is controlled and formed into a film in the plane direction and height direction of the substrate, and selecting a cleaning liquid in which the distance Ra between the Hansen solubility parameter of the compound (A) and the Hansen solubility parameter of the cleaning liquid satisfies (Ra) 2 ≤ 128.

[0021] A second aspect of the present invention is a method for processing a substrate, including: a step of exposing the surface of the substrate to a surface modifier containing a compound (A) having binding properties to the substrate; and a step of cleaning the exposed substrate with a cleaning liquid to control the compound (A) and form a film in the plane direction and height direction of the substrate, and selecting a cleaning liquid in which the distance Ra between the Hansen solubility parameter of the compound (A) and the Hansen solubility parameter of the cleaning liquid satisfies (Ra) 2 ≤ 128.

[0022] A third aspect of the present invention is a method for forming a pattern, including: a step of forming an atomic layer by thin film formation using an evaporation method on the surface of a region of the processed substrate manufactured by the method for manufacturing a processed substrate according to the first aspect, where the surface modifier is not formed into a film.

[0023] A fourth aspect of the present invention is a cleaning liquid, which is a cleaning liquid for the method for manufacturing a processed substrate according to the first aspect or the method for processing a substrate according to the second aspect, and the cleaning liquid 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, dibutyl ether, acetone, cyclopentanone, 2,6-dimethyl-4-heptanone, and propylene glycol monomethyl ether.

[0024] Advantages of the Invention

[0025] According to the present invention, it is possible to provide a method for manufacturing a processed substrate, a method for processing a substrate that can be used in this manufacturing method, a method for forming a pattern, and a cleaning liquid. The method for manufacturing a processed substrate is a method for manufacturing a processed substrate having a surface with at least a partially modified region. By cleaning the substrate exposed to the surface modifier, the remaining surface modifier can be removed, and a processed substrate in which the surface modifier is controlled and formed into a film in the plane direction and height direction can be obtained. Description of the Drawings

[0026] Figure 1It is a schematic diagram showing the state after the surface of the substrate is exposed to the surface modifier (after the exposure process).

[0027] Figure 2 It is a schematic diagram showing the states before and after cleaning the substrate after the exposure process with a cleaning liquid.

[0028] Figure 3A It is an atomic force microscope (AFM) observation image (observation range 1 μm × 1 μm) of the surface of the substrate just after the exposure process.

[0029] Figure 3B It is an AFM observation image (observation range 1 μm × 1 μm) of the surface of the processed substrate manufactured in Example 11.

[0030] Figure 3C It is an AFM observation image (observation range 1 μm × 1 μm) of the surface of the processed substrate manufactured in Comparative Example 1. Detailed Description of the Invention

[0031] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments and can be appropriately modified and implemented within the scope of the object of the present invention.

[0032] (Method for manufacturing a processed substrate)

[0033] The manufacturing method of the processed substrate according to the first aspect of the present invention is a method for manufacturing a processed substrate having a surface with at least a part of the region modified.

[0034] The manufacturing method of the processed substrate includes: a step of exposing the surface of the substrate to a surface modifier containing a compound (A) having binding properties with respect to the substrate (hereinafter also referred to as "exposure step"); and a step of cleaning the exposed substrate with a cleaning liquid to obtain a processed substrate in which the compound (A) is controlled in the plane direction and the height direction of the substrate to form a film (hereinafter also referred to as "cleaning step").

[0035] In the manufacturing method of the processed substrate, a cleaning liquid is selected such that the distance Ra between the Hansen solubility parameter of the compound (A) and the Hansen solubility parameter of the cleaning liquid satisfies (Ra) 2 ≤ 128.

[0036] Figure 1 It is a schematic diagram showing the state after the surface of the substrate is exposed to the surface modifier (after the exposure process).

[0037] The substrate 10 includes a region A and a region B.

[0038] The surface modifier contains a compound (A) 20 having binding properties with respect to the region B of the substrate 10.

[0039] In Figure 1 , a surface modifier layer 224 covering the entire surface of the region B of the substrate 10 is formed on the substrate 10. The surface modifier layer 224 is composed of a single-layer portion 22 in which the compound (A) 20 is directly bonded to the surface of the region B of the substrate 10 and a remaining portion 24 in which the compound (A) 20 is deposited on the single-layer portion 22.

[0040] The remaining portion 24 protrudes onto the region A of the substrate 10. In such a state, when an atomic layer is to be formed on the region A of the substrate 10, film formation is hindered, and a C layer (enclosed by a dotted line) with defects d is formed in part.

[0041] Figure 2 is a schematic diagram showing the states before and after cleaning the substrate after the exposure process with a cleaning liquid.

[0042] On the processed substrate 100 after cleaning, a surface modifier layer 220 covering the entire surface of the region B of the substrate 10 is formed on the substrate 10. By cleaning with a cleaning liquid, the remaining portion 24 is removed, and the surface modifier layer 220 is composed only of the single-layer portion 22 in which the compound (A) 20 is directly bonded to the surface of the region B of the substrate 10. That is, a processed substrate 100 is obtained in which the compound (A) 20 is controlled in the plane direction and the height direction of the substrate to form a film.

[0043] "The compound (A) is controlled in the plane direction and the height direction of the substrate to form a film" means that the compound (A) molecules are arranged on the surface of a specific region of the substrate, covering the entire surface of the specific region and not covering the adjacent region to the specific region, thereby forming a film with a certain thickness. In Figure 2 , in the processed substrate 100, the compound (A) molecules are arranged on the surface of the region B in the substrate 10, covering the entire surface of the region B and not covering the adjacent region A to the region B, thereby forming a film (surface modifier layer 220, single-layer portion 22) with a certain thickness L.

[0044] In such a state, when an atomic layer is to be formed on the region A of the substrate 10, film formation is not hindered, and the desired atomic layer can be easily formed.

[0045] According to the manufacturing method of the processed substrate of the first aspect, it is possible to manufacture Figure 2 the processed substrate 100 shown.

[0046] Hereinafter, an embodiment of the manufacturing method of the processed substrate will be described.

[0047] <Exposure process>

[0048] In the exposure step of the present embodiment, the surface of the substrate is exposed in a surface modifier containing a compound (A) having binding properties to the substrate.

[0049] 《Regarding the Substrate》

[0050] Examples of the substrate to be processed in the present embodiment include substrates for manufacturing semiconductor devices. For example, silicon (Si) substrates, silicon nitride (SiN) substrates, silicon oxide film (SiOx) 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, etc. can be cited.

[0051] Examples of the "surface of the substrate" include not only the surface of the substrate itself but also the surface of an inorganic pattern or an organic pattern provided on the substrate, or the surface of an unpatterned inorganic layer or organic layer.

[0052] Examples of the inorganic pattern provided on the substrate include a pattern formed by forming an etching mask on the surface of the inorganic layer existing on the substrate by a photoresist method and then performing an etching process. Examples of the inorganic layer include, in addition to the substrate itself, oxide films of elements constituting the substrate, and films or layers of inorganic substances such as SiN, SiOx, W, Co, TiN, TaN, Ge, SiGe, Al, Al2O3, Ni, Ru, Cu formed on the surface of the substrate.

[0053] There is no particular limitation on such a film or layer, and examples include films or layers of inorganic substances formed during the manufacturing process of semiconductor devices.

[0054] Examples of the organic pattern provided on the substrate include resin patterns formed on the substrate by photolithography using a photoresist or the like. Such an organic pattern can be formed, for example, by forming an organic layer as a photoresist film on the substrate and exposing and developing the organic layer through a photomask. Examples of the organic layer include, in addition to the surface of the substrate itself, an organic layer provided on the surface of a laminated film provided on the surface of the substrate. There is no particular limitation on such an organic layer, and examples include organic films provided for forming an etching mask during the manufacturing process of semiconductor devices.

[0055] In the manufacturing method of the processed substrate of the present embodiment, the surface to be processed of the substrate may include one region or two or more regions. When the surface to be processed includes two or more regions, at least one of the two or more regions includes the substrate surface, and the materials of adjacent regions among the two or more regions are different from each other.

[0056] InFigure 1 In [description], the substrate 10 has a region A and a region B. By exposing the processed surface of the substrate 10 to a surface modifier, the compound (A) 20 is selectively adsorbed on the surface of the region B of the substrate 10. Thus, it is possible to make the contact angles of water with respect to the region surfaces different between the region A and the region B of the substrate 10.

[0057] "Regarding the Surface Modifier"

[0058] In the present embodiment, the surface modifier contains a compound (A) (hereinafter also referred to as "(A) component") having binding properties to the substrate.

[0059] In Figure 1 [description], a surface modifier containing the compound (A) 20 having binding properties to the region B of the substrate 10 is used.

[0060] The (A) component is not particularly limited as long as it is an (A) component having binding properties to the selected substrate. For example, in the case of using a copper (Cu) or cobalt (Co) substrate, an (A) component having a thiol group is preferred; in the case of using a tungsten (W), copper (Cu), cobalt (Co), Al2O3, or TiN substrate, an (A) component having a phosphonic acid group is preferred; in the case of using a TiN substrate, an (A) component having an amino group is preferred; in the case of using a cobalt (Co) substrate, an (A) component having a carboxylic acid group is preferred; in the case of using a SiO2 substrate, an (A) component having a chlorosilyl group or an alkoxysilyl group is preferred.

[0061] As the (A) component when using a copper (Cu) or cobalt (Co) substrate, an alkanethiol compound is preferred. Among alkanethiol compounds, linear or branched alkanethiols are particularly preferred, alkanethiols having 1 to 45 carbon atoms are preferred, alkanethiols having 5 to 30 carbon atoms are more preferred, and alkanethiols having 10 to 25 carbon atoms are further preferred.

[0062] Specific examples of linear or branched alkanethiols include octadecanethiol, hexadecanethiol, tetradecanethiol, dodecanethiol, and decanethiol, and octadecanethiol is preferred.

[0063] The surface modifier may contain components other than the (A) component in addition to the (A) component.

[0064] With respect to the total mass of the surface modifier, the content of the (A) component in the surface modifier is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 99% by mass or more, and may be 100% by mass.

[0065] [Operations of the Exposure Process]

[0066] In the exposure process of the present embodiment, the surface of the substrate 10 is exposed to the above surface modifier.

[0067] The method of exposing the surface of the substrate to the surface modifier containing the component (A) is not particularly limited. For example, it can be, for example, the following method: The surface of the substrate is exposed to a surface modifier that may contain a solvent (typically a liquid surface modifier) by a coating method such as an immersion method, a spin coating method, a roll coating method, or a doctor blade method.

[0068] As the exposure temperature, for example, it is 10°C or higher and 90°C or lower, preferably 20°C or higher and 80°C or lower, and more preferably 20°C or higher and 30°C or lower.

[0069] From the viewpoint of selective surface modification between regions with different materials on the substrate surface, the exposure time is preferably 20 seconds or longer, more preferably 30 seconds or longer, and further preferably 45 seconds or longer. As the upper limit of the above exposure time, there is no particular limitation. For example, it is 2 hours or shorter, typically 1 hour or shorter, preferably 5 minutes or shorter, further preferably 2 minutes or shorter, and particularly preferably 1 minute or shorter.

[0070] In the substrate after being exposed to the surface modifier, depending on the material of each region of the substrate surface, the component (A) contained in the surface modifier is selectively adsorbed in the region.

[0071] In Figure 1 , on the entire surface of region B of the substrate 10, the compound (A) 20 is adsorbed to form a surface modifier layer 224 composed of a monolayer portion 22 and a remaining portion 24 on which the compound (A) 20 is deposited on the monolayer portion 22. The remaining portion 24 protrudes onto region A of the substrate 10.

[0072] The contact angle of the surface of the substrate after being exposed to the surface modifier with respect to water can be set, for example, to 50° or more and 140° or less.

[0073] By controlling the material of the substrate surface, the type and usage amount of the component (A) contained in the surface modifier, and the exposure conditions, etc., the contact angle of the surface of the region where the component (A) is adsorbed with respect to water can be set to 50° or more. In the present embodiment, the contact angle of the surface of the region where the component (A) is adsorbed with respect to water is preferably 60° or more, more preferably 70° or more, and further preferably 90° or more. As the upper limit value of the contact angle of the surface of the region where the component (A) is adsorbed with respect to water, there is no particular limitation. For example, it is 140° or less, typically 130° or less.

[0074] For example, using a contact angle measuring device, a pure water droplet is dropped onto the substrate surface, and the contact angle with respect to water is measured after a specified time.

[0075] <Cleaning process>

[0076] In the cleaning process of the present embodiment, the substrate after the exposure process is cleaned with a cleaning liquid to obtain a processed substrate on which the component (A) is formed into a film with controlled surface direction and height direction on the substrate.

[0077] "Regarding the cleaning liquid"

[0078] In the cleaning process, a cleaning liquid is selected such that the distance Ra between the Hansen solubility parameter of the component (A) and the Hansen solubility parameter of the cleaning liquid satisfies the relationship of (Ra) 2 ≤ 128.

[0079] Regarding (Ra) 2 , from the viewpoint of the removal performance of the remaining surface modifier, (Ra) 2 ≤ 126 is preferred. Regarding the lower limit of (Ra) 2 , from the viewpoint of the removal performance of the remaining surface modifier, it is preferably 0 ≤ (Ra) 2 .

[0080] The distance Ra between the Hansen solubility parameter of the component (A) and the Hansen solubility parameter of the cleaning liquid is calculated using the Hansen solubility parameter of the component (A) (δ dA , δ pA , δ hA ) represented by three-dimensional coordinates and the Hansen solubility parameter of the cleaning liquid (δ dS , δ pS , δ hS ) through the following mathematical formula (1).

[0081] Mathematical formula (1): (Ra) 2 = (δ dS - δ dA ) 2 + (δ pS - δ pA ) 2 + (δ hS - δ hA ) 2

[0082] [wherein, 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.]

[0083] Hansen solubility parameters can be calculated, for example, according to the parameters specified for solubility parameters and cohesion characteristics set forth by Charles Hansen in 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).

[0084] The Hansen solubility parameter, which can be theoretically calculated as a numerical constant, is a useful tool for predicting the ability of a solvent material to dissolve a specific solute.

[0085] The Hansen solubility parameter can be used as an indicator of the overall strength and selectivity of a material by combining the following three Hansen solubility parameters (i.e., δ d 、δ p and δ h ) derived from experiments and theory.

[0086] The unit of the Hansen solubility parameter is given by MPa 0.5 or (J / cc) 0.5 .

[0087] δ d : The energy from the dispersion force between molecules (dispersion term)

[0088] δ p : The energy from the polar force between molecules (polar term)

[0089] δ h : The energy from the hydrogen bond force between molecules (hydrogen bond term)

[0090] (A) The Hansen solubility parameters of the components and the cleaning liquid can be calculated using software such as “Molecular Modeling Pro”, version 5.1.9 (ChemSW, Fairfield CA, www.chemsw.com) or software such as Hansen Solubility and HSPiP from Dynacomp Software.

[0091] In the present embodiment, as the cleaning liquid, a cleaning liquid containing an organic solvent can be used. The organic solvent here can be used alone or in combination of two or more.

[0092] When the cleaning liquid contains two or more organic solvents, the Hansen solubility parameter (δ dS , δ pS , δ hS ) of the cleaning liquid can be calculated from the mixing volume ratio of each organic solvent.

[0093] For example, when using the following organic solvent (S1) and organic solvent (S2) in combination, when the mixing volume ratio of each component is a:b (S1:S2 = a:b), the Hansen solubility parameter of the cleaning liquid can be calculated by the following formulas (1) to (3).

[0094] δ dS = (a * δ dS1 + b * δ dS2 ) / (a + b) (1)

[0095] δ pS = (a * δ pS1 + b * δ pS2 ) / (a + b) (2)

[0096] δ hS = (a * δ hS1 + b * δ hS2 ) / (a + b) (3)

[0097] As the cleaning liquid, a cleaning liquid containing an organic solvent (S1) selected from the group consisting of a polar solvent and a hydrocarbon solvent (hereinafter also referred to as the "(S1) component") can be suitably used.

[0098] Examples of the polar solvent in the (S1) component include ketone solvents, ester solvents, alcohol solvents, ether solvents, etc.

[0099] As the ketone solvent, it is preferably a ketone having 3 or more carbon atoms. For example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl pentyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetone alcohol, acetylmethanol, acetophenone, methylnaphthone, isophorone, propylene carbonate can be cited. Preferred are acetone, cyclopentanone, 2,6-dimethyl-4-heptanone.

[0100] As the ester solvent, it is preferably an ester having 6 or more carbon atoms. For example, 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, 3-methyl-3-methoxybutyl acetate can be cited. Preferred is propylene glycol monomethyl ether acetate.

[0101] As the alcohol solvent, those having 4 or more carbon atoms are preferred, and examples thereof include: alcohols such as n-butanol, sec-butanol, tert-butanol, isobutanol, 4-methyl-2-pentanol (methyl isobutyl carbinol; MIBC), n-hexanol, n-heptanol, n-octanol, n-decanol, etc.; glycol solvents such as diethylene glycol, triethylene glycol, etc.; glycol ether 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, methoxymethyl butanol, etc. Isobutanol, 1-octanol, 2-ethyl-1-hexanol, and 1-methoxy-2-propanol are preferred.

[0102] As the ether solvent, those having 8 or more carbon atoms are preferred. For example, in addition to the above-mentioned glycol ether solvents, dibutyl ether, dipentyl ether, etc. can be cited, and dibutyl ether is preferred.

[0103] As the hydrocarbon solvent, for example, alkanes having 6 or more carbon atoms are preferred, and linear or cyclic alkanes are more preferred. Examples thereof include linear alkanes such as hexane, octane, decane, undecane, etc., or cyclic alkanes such as cyclohexane, cycloheptane, cyclooctane, cyclodecane, etc. Decane, tetradecane, and cyclohexane are preferred, and decane and tetradecane are more preferred.

[0104] Among the above, as the cleaning liquid, a cleaning liquid containing an organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, an ether solvent, and a hydrocarbon solvent is more preferred, and a cleaning liquid containing at least one organic solvent selected from the group consisting of an alkane having 6 or more carbon atoms, an alkylene glycol monoalkyl ether acetate having 6 or more carbon atoms, an alcohol having 4 or more carbon atoms, an ether having 8 or more carbon atoms, and a ketone having 3 or more carbon atoms is further preferred.

[0105] The cleaning liquid may also contain an organic solvent (S2) other than the component (S1) (hereinafter also referred to as the “component (S2)”). The component (S2) is not particularly limited, and an organic solvent having miscibility with the component (S1) can be used.

[0106] The content of the component (S1) in the cleaning liquid is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, particularly preferably 95% by mass or more, and may be 100% by mass, based on the total mass of the cleaning liquid.

[0107] [Operation of the cleaning process]

[0108] In the cleaning process of the present embodiment, the substrate after the exposure process is cleaned with the cleaning liquid.

[0109] The method for cleaning the substrate after the exposure process using a cleaning liquid is not particularly limited. Specifically, examples include an immersion method in which the cleaning liquid is filled in a cleaning tank and the substrate is immersed, a rotary method in which the cleaning liquid is made to flow from a nozzle onto the substrate while the substrate is rotated at high speed, a spraying method in which a liquid is sprayed onto the substrate for cleaning, and the like. As a device for performing such cleaning, there are a batch-type cleaning device for simultaneously cleaning a plurality of substrates stored in a cassette, a single-sheet type cleaning device for mounting a single substrate on a holder for cleaning, and the like.

[0110] As the temperature condition during cleaning, for example, it is 10°C or higher and 90°C or lower, preferably 20°C or higher and 80°C or lower, and more preferably 20°C or higher and 30°C or lower.

[0111] As the cleaning time, from the viewpoint of the removal performance of the remaining surface modifier, it is preferably 20 seconds or longer, more preferably 30 seconds or longer, and further preferably 45 seconds or longer. As the upper limit of the above cleaning time, there is no particular limitation. For example, it is 5 minutes or shorter, typically 2 minutes or shorter, and preferably 1 minute or shorter.

[0112] In the cleaning process of the present embodiment, after cleaning with the cleaning liquid, a treated substrate is obtained in which the component (A) is formed into a film with controlled orientation in the plane direction and height direction of the substrate.

[0113] In Figure 2 , on the treated substrate 100 after cleaning, a surface modifier layer 220 is formed which is composed of only a single-layer portion 22 covering the entire surface of the region B of the substrate 10. The remaining portion 24 that protrudes onto the region A of the substrate 10 and is deposited on the single-layer portion 22 before cleaning is removed by the cleaning liquid.

[0114] In one embodiment of the method for manufacturing the treated substrate described above, it includes: a step of exposing the surface of the substrate to a surface modifier containing a compound (A) having binding properties to the substrate; and a step of cleaning the exposed substrate with a cleaning liquid to obtain a treated substrate in which the compound (A) is formed into a film with controlled orientation in the plane direction and height direction of the substrate, whereby a treated substrate having a surface with at least a partially modified region can be manufactured.

[0115] According to the manufacturing method of the present embodiment described above, by using a cleaning liquid in which the distance Ra between the Hansen solubility parameter of the compound (A) and the Hansen solubility parameter of the cleaning liquid satisfies the relationship of (Ra) 2 ≤128 to clean the substrate exposed to the compound (A), a treated substrate in which the compound (A) is formed into a film with controlled orientation in the plane direction and height direction of the substrate can be obtained.

[0116] In the thus obtained processed substrate, when an atomic layer is to be formed on a specific region of the substrate where the compound (A) is not formed into a film, the desired atomic layer can be easily formed without hindering film formation.

[0117] In the processed substrate produced by the manufacturing method of the present embodiment, it can be confirmed as follows that the compound (A) is formed into a film while being controlled in the plane direction and the height direction of the substrate.

[0118] Regarding the fact that the compound (A) is formed into a film while being controlled in the plane direction of the substrate, it can be confirmed by measuring the "contact angle of water" on the processed surface of the substrate. The "contact angle of water" mentioned here can be obtained, for example, by using a contact angle measuring device to drop a pure water droplet onto the substrate surface and measuring it after a specified time.

[0119] If the "contact angle of water" on the processed surface of the substrate hardly changes during the period after the substrate surface is exposed to the surface modifier and after being cleaned with the cleaning liquid, it can be judged that the compound (A) is formed into a film while being controlled in the plane direction of the substrate.

[0120] In the processed substrate produced by the manufacturing method of the present embodiment, the "contact angle of water" on the processed surface of the substrate is, for example, maintained at 50° or more and 140° or less, preferably maintained at 60° or more and 130° or less, more preferably maintained at 70° or more and 130° or less, and further preferably maintained at 90° or more and 130° or less.

[0121] Regarding the fact that the compound (A) is formed into a film while being controlled in the height direction of the substrate, it can be confirmed by measuring the existence ratio (survival rate) of the compound (A) existing at a certain height above the substrate surface. The "existence ratio (survival rate) of the compound (A)" mentioned here is represented by an area ratio, which is, for the processed substrate, when observing from above it with an atomic force microscope (AFM), detecting the compound (A) molecules existing at a height exceeding the thickness of the monolayer of the molecular arrangement of the compound (A) formed on the substrate (that is, deposited on the monolayer), and the area ratio of the surface of the monolayer covered by the compound (A) molecules.

[0122] The lower the "existence ratio (survival rate) of the compound (A)" on the processed surface of the substrate, the higher the cleaning removability of the compound (A) with the cleaning liquid, and it can be judged that the compound (A) is formed into a film while being controlled in the height direction of the substrate.

[0123] In the processing substrate manufactured by the manufacturing method of the present embodiment, the "residual ratio of compound (A)" in the processing surface of the substrate is, for example, lower than that in the case of using conventional isopropyl alcohol (IPA) as a cleaning liquid. For example, when a copper substrate is used as the substrate and octadecanethiol (ODT) is used as compound (A), the "residual ratio of compound (A)" in the processing surface of the substrate is less than 8.2%, preferably 7.5% or less, more preferably 6% or less, and still more preferably 5% or less.

[0124] <Regarding other embodiments>

[0125] In the manufacturing method of the processing substrate of the above embodiment, the case including an exposure step and a cleaning step has been described, but the manufacturing method of the processing substrate of the first aspect of the present invention is not limited thereto, and other steps other than the exposure step and the cleaning step may also be included as needed. As other steps, a pretreatment step, a surface treatment step, a rinsing step, and a drying step can be exemplified.

[0126] Regarding the pretreatment step:

[0127] In the pretreatment step, pretreatment of the substrate surface is performed. The pretreatment of the substrate surface is preferably a treatment capable of imparting hydroxyl groups to the substrate surface. As a pretreatment method, for example, ozone treatment, treatment with a pretreatment oxidant described later, etc. can be exemplified. From the viewpoint of improving the adsorptivity of the surface modifier to the substrate surface, the pretreatment oxidant is preferably at least one selected from the group consisting of hydrogen peroxide and perhalic acid.

[0128] The treatment temperature of the pretreatment is not particularly limited, and is typically 10 to 35 °C, preferably 15 to 30 °C, and more preferably 20 to 25 °C. If the treatment temperature of the pretreatment is within the above preferred range, it is easy to remove the natural oxide film on the substrate surface and easy to impart hydroxyl groups to the substrate surface.

[0129] The treatment time of the pretreatment is not particularly limited, and is typically 10 seconds to 10 minutes, preferably 20 seconds to 5 minutes, and more preferably 30 seconds to 3 minutes. If the treatment time of the pretreatment is within the above preferred range, it is easy to remove the natural oxide film on the substrate surface and easy to impart hydroxyl groups to the substrate surface.

[0130] Regarding the surface treatment step:

[0131] In the surface treatment step, the substrate surface before the above exposure step is treated with diluted hydrofluoric acid by using a known method. By further providing a surface treatment step before the above exposure step, it is possible to remove the residue derived from organic matter adhering to the substrate surface and improve the film-forming property of the surface modifier in the plane direction of the substrate.

[0132] Regarding the rinsing step:

[0133] After the exposure process, the exposed substrate can be cleaned as needed (for example, cleaned by rinsing with water, deionized water, surfactant, etc.).

[0134] For example, in the cleaning of the surface of a substrate having an inorganic pattern or an organic pattern as needed, the cleaning liquids conventionally used in the cleaning treatment of inorganic patterns or organic patterns can be directly used as they are. Examples of the cleaning liquid for the cleaning treatment of inorganic patterns include SPM (sulfuric acid / hydrogen peroxide water), APM (ammonia / hydrogen peroxide water), etc., and examples of the cleaning liquid for the cleaning treatment of organic patterns include water, surfactant rinsing, etc.

[0135] Regarding the drying process:

[0136] In the drying process, the substrate is dried. In the method for manufacturing a processed substrate of the present solution, a drying process can also be provided after the exposure process or the cleaning process. By providing the drying process, the cleaning liquid remaining on the substrate can be efficiently removed.

[0137] The drying method of 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 blowing of an inert gas (such as nitrogen) can be preferably exemplified.

[0138] In addition, a heat treatment at 100°C or higher and 300°C or lower can be additionally performed on the dried substrate after exposure as needed.

[0139] In the method for manufacturing a processed substrate of the present solution, for example, two surface modifiers can be used. In an embodiment in the case of using two surface modifiers, in the case of using a substrate having regions A and B, after surface-modifying region A of the substrate by exposing region A of the substrate in the first surface modifier, the exposed substrate is cleaned with an appropriate cleaning liquid satisfying the relationship of the present invention. Then, in the same manner, after surface-modifying region B of the cleaned substrate by exposing region B of the substrate in the second surface modifier, the substrate after the second exposure is cleaned with an appropriate cleaning liquid satisfying the relationship of the present invention. Thus, in the case of using two or more surface modifiers, by repeating the exposure process and the cleaning process, a processed substrate in which each region of the substrate is modified with different surface modifiers can also be obtained.

[0140] In the method for manufacturing a processed substrate of the above embodiment, by exposing the surface to be processed of the substrate 10 in the surface modifier, the compound (A) 20 is selectively adsorbed on the surface of region B of the substrate 10. Thereby, the contact angles of water with respect to the region surfaces can be made different between region A and region B of the substrate 10.

[0141] Regarding a substrate that can be used in the method for manufacturing a processing substrate of the present solution, as a region where the contact angle of water tends to be larger (preferably the surface free energy becomes smaller) between two or more regions in the substrate than in another region, an example is a region composed of a conductor.

[0142] The conductor may be any material having conductivity and is not particularly limited. As the conductor, examples of materials containing metal atoms can be cited. As the conductor, for example, metals (such as monomers of metal elements), alloys, and metal compounds (such as nitrides, etc.) can be cited. When the conductor is a metal, the surface of the conductor becomes a metal surface. When the conductor is an alloy, the surface of the conductor becomes an alloy surface. When the conductor is a metal compound, the surface of the conductor becomes a conductive metal compound surface.

[0143] Examples of the metal contained 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). Among them, it is preferable to contain at least one selected from the group consisting of tungsten, ruthenium, copper, and cobalt, and more preferably to contain at least one selected from the group consisting of tungsten and ruthenium. The region having the substrate surface may also be a region composed of a substrate containing these metals.

[0144] The surface of the conductor can be pretreated with an oxidizing agent. As the oxidizing agent for pretreating the surface of the conductor (hereinafter referred to as "pretreatment oxidizing agent"), examples include oxidizing agents that can remove the natural oxide film present on the surface of the conductor and can impart hydroxyl groups to the surface of the conductor. As the pretreatment oxidizing agent, for example, peroxides such as hydrogen peroxide, perhalic acids such as periodic acid, and oxyacids such as nitric acid or hypochlorous acid can be cited. Among them, as the pretreatment oxidizing agent, from the viewpoint of the adsorbability of compound (A), at least one selected from the group consisting of hydrogen peroxide and perhalic acid is preferable. In the case where the surface of inorganic substances such as SiO2 and Al2O3 coexists with the surface of the conductor, from the viewpoint of treating the surface of the conductor without damaging the inorganic substance, at least one selected from the group consisting of hydrogen peroxide and perhalic acid is also preferable.

[0145] The pretreatment oxidizing agent can be used alone or in combination of two or more.

[0146] The surface of the conductor can be subjected to ozone treatment, or it can also be treated with a pretreatment oxidizing agent after ozone treatment.

[0147] The surface of the conductor after at least one of the pretreatment with the pretreatment oxidizing agent and the ozone treatment is modified with hydroxyl groups.

[0148] The substrate used in the method for manufacturing a processing substrate according to this embodiment may also be a substrate having a surface including two or more regions with different materials, and at least one of the two or more regions has a conductive surface.

[0149] In the case of a substrate in which at least one region has a conductive surface, two or more regions may have a conductive surface. In the case of a substrate having two or more regions with a conductive surface, these regions may include the same conductor as each other or may include different conductors.

[0150] As a region where the contact angle of water is smaller (preferably the surface free energy becomes higher) between the above two or more regions than another region, a region without a conductive surface (for example, a region composed of an insulator (hereinafter referred to as "insulator region")) can be cited. The surface to be processed of the substrate may include one insulator region or may include two or more. In the case of two or more insulator regions, these regions may be composed of the same material as each other or may be composed of different materials.

[0151] The surface to be processed of the substrate preferably includes one or more regions with a conductive surface and insulator regions, respectively.

[0152] The insulator constituting the insulator region is composed of an insulating compound. As the insulating compound, for example, oxides such as alumina (Al2O3), titanium oxide (TiO2), zirconium oxide (ZrO2), hafnium oxide (HfO2), tantalum oxide (Ta2O5), silicon oxide (SiOx (1≤x≤2)), fluorine-containing silicon oxide (SiOF), carbon-containing silicon oxide (SiOC); nitrides such as silicon nitride (SiN), boron nitride (BN); carbides such as silicon carbide (SiC); carbonitrides such as silicon carbonitride (Si CN); oxynitrides such as silicon oxynitride (SiON); carbon oxynitrides such as silicon carbon oxynitride (Si OCN); insulating resins such as polyimide, polyester, and plastic resin, etc.

[0153] The surface to be processed of the substrate may include two or more regions containing a conductive surface, and the materials of the adjacent regions among the two or more regions may also be different from each other.

[0154] In the case where the surface to be processed includes two regions, the surface to be processed may include a first region containing a conductive surface and a second region (for example, an insulator region) adjacent to the first region and having a material different from that of the first region. In this case, the "adjacent regions" are the first region and the second region.

[0155] The first region and the second region may each be divided into a plurality of regions or may not be divided.

[0156] In the case where the surface to be processed includes three or more regions, the surface to be processed may include: a first region containing a conductor surface; a second region (e.g., an insulator region) having a different material from the first region and adjacent to the first region; and a third region having a different material from the second region and adjacent to the second region. In this case, the "adjacent regions" may be the first region and the second region (i.e., the adjacent regions), or the first region and the third region (i.e., the regions adjacent with one region in between).

[0157] In the case where the materials of the first region and the third region are not different (i.e., when both the first region and the third region contain a conductor surface), the "adjacent regions" are the first region and the second region, or the second region and the third region (i.e., the adjacent regions).

[0158] The first region, the second region, and the third region may each be divided into a plurality of regions or may not be divided.

[0159] The same concept can also be applied to the case where the surface to be processed includes four or more regions.

[0160] As the upper limit value of the number of regions with different materials, there is no particular limitation as long as the effects of the present invention are not impaired. For example, it is 7 or less, or 6 or less, and typically 5 or less.

[0161] (Method for processing a substrate)

[0162] The method for processing a substrate according to the second aspect of the present invention is a method including the following steps: a step of exposing the surface of the substrate in a surface modifier containing a compound (A) having adhesiveness to the substrate (exposure step); and a step of cleaning the exposed substrate with a cleaning liquid to control the compound (A) in the plane direction and the height direction of the substrate and form a film (cleaning step).

[0163] In the method for processing the substrate, the cleaning liquid is selected such that the distance Ra between the Hansen solubility parameter of the compound (A) and the Hansen solubility parameter of the cleaning liquid satisfies the relationship of (Ra) 2 ≤ 128.

[0164] Regarding the exposure step and the cleaning step in the method for processing the substrate, the descriptions are the same as those of the <exposure step> and the <cleaning step> in an embodiment of the above (method for manufacturing a processed substrate).

[0165] According to the method for treating a substrate of the present solution, by including a step of exposing the surface of the substrate in a surface modifier containing a compound (A) having binding properties to the substrate and cleaning the exposed substrate with a cleaning liquid, and a step of controlling the compound (A) in the plane direction and height direction of the substrate and forming a film, the surface of the target substrate can be surface-modified.

[0166] In addition, by selecting a cleaning liquid such that the distance Ra between the Hansen solubility parameter of the compound (A) and the Hansen solubility parameter of the cleaning liquid satisfies the relationship (Ra) 2 ≤128, the cleaning removability of the remaining compound (A) can be improved, and a modified layer with uniform thickness can be formed.

[0167] (Pattern formation method)

[0168] The pattern formation method according to the third aspect of the present invention is a method including the following steps: a step of forming an atomic layer on the surface of the area of the treated substrate manufactured by the manufacturing method of the first aspect, where the surface modifier is not formed.

[0169]

[0170] In this step, an atomic layer is formed by thin film formation using vapor deposition on the surface of the area of the treated substrate manufactured by the manufacturing method of the treated substrate in the above embodiment, where the surface modifier is not formed. For example, in Figure 2 In the area A surface of the cleaned treated substrate 100, an atomic layer is formed by thin film formation using vapor deposition.

[0171] Vapor deposition is a method of using a gas containing a raw material for a thin film, and preferably a method of forming a thin film by a chemical reaction in the gas phase.

[0172] Examples of vapor deposition methods include an atomic layer deposition (ALD) method, a chemical vapor deposition (CVD) method, a physical vapor deposition (PVD) method, a pulse laser deposition (PLD) method, a molecular beam epitaxy (MBE) method, an ion plating method, etc. Among them, the ALD method or the CVD method is preferred, and the ALD method is more preferred.

[0173] As the CVD method, for example, thermal CVD, plasma CVD, photo-CVD, reduced-pressure CVD, laser CVD, metalorganic CVD (MOCVD), etc. can be cited.

[0174] As the ALD method, for example, thermal ALD method, plasma ALD method, etc. can be cited.

[0175] As the formed atomic layer (Y), for example, a metal layer, a metal oxide layer, a metal nitride layer, a non-metal oxide layer, a non-metal nitride layer, a metal-non-metal oxide layer, a metal-non-metal nitride layer, etc. can be cited.

[0176] [Regarding the formation of atomic layers using the ALD method]

[0177] As the vapor deposition method in the present embodiment, the ALD method is preferably used.

[0178] Compared with the surface of the region without the surface modifier film formed, the water repellency of the substrate surface in the region with the surface modifier film formed is selectively improved. As a result, between the above two or more regions, the deposition amount of the material for forming the above film can be selectively different in the regions of the substrate surface. The selective improvement of the water repellency can be confirmed by measuring the contact angle of water with respect to the surface of the region.

[0179] Specifically, in the region having the substrate surface between the above two or more regions, it is difficult to adsorb (preferably chemisorb) the atomic layer forming material by the ALD method. As a result, a difference in the deposition amount of the atomic layer forming material occurs between the above two or more regions. That is, the deposition amount of the atomic layer forming material by the ALD method is selectively different in different regions. Specifically, the deposition amount of the atomic layer forming material in the region having the substrate surface is lower than that in the insulator region.

[0180] As the chemisorption of the atomic layer forming material, chemisorption with the hydroxyl group imparted to the substrate surface by pretreatment, etc. can be cited.

[0181] Between the above two or more regions, as the region where the contact angle of water is larger (preferably the surface free energy becomes smaller) than that of another region, a region containing at least one selected from the group consisting of W, Co, Al, Ni, Ru, and Cu can be cited. The region having the substrate surface can also be a region containing them.

[0182] Among the two or more regions, as a region where the contact angle inclined to water is smaller than another region (preferably with a higher surface free energy), examples include a region containing at least one selected from the group consisting of Si, Al2O3, SiN, SiOx, Ge, SiGe, TEOS, Low-k materials, and ILD. The insulator region can be not only a region composed of the insulating compound but also a region composed of a material containing these.

[0183] As an atomic layer formation method using the ALD method, there is no particular limitation, and examples include a thin film formation method based on adsorption (preferably chemisorption) using at least two gaseous reactants (hereinafter simply referred to as "precursor gases").

[0184] Specifically, examples include a method that includes the following steps (a) and (b), and repeats the following steps (a) and (b) at least once (one cycle) until the desired film thickness is obtained.

[0185] Step (a): A step of exposing the surface-modified substrate to a pulse of the first precursor gas; and

[0186] Step (b): After the step (a), a step of exposing the substrate to a pulse of the second precursor gas.

[0187] After the step (a) and before the step (b), it may or may not include a plasma treatment step, a step of removing or exhausting (purging) the first precursor gas and its reactants using a carrier gas, the second precursor gas, etc.

[0188] After the step (b), it may or may not include a plasma treatment step, a step of removing or purging the second precursor gas and its reactants using a carrier gas, etc.

[0189] Examples of the carrier gas include inert gases such as nitrogen, argon, and helium.

[0190] Each pulse of each cycle and each layer formed are preferably self-controlled, and each layer formed is more preferably a single atomic layer.

[0191] As the film thickness of the single atomic layer, for example, it can be set to 5 nm or less, preferably 3 nm or less, more preferably 1 nm or less, and further preferably 0.5 nm or less.

[0192] As the first precursor gas, organometals, metal halides, metal oxyhalides, etc. can be cited. Specifically, tantalum pentaethoxide, titanium tetrakis(dimethylamino), tantalum pentakis(dimethylamino), zirconium tetrakis(dimethylamino), hafnium tetrakis(dimethylamino), 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, HfCl4, etc. can be cited.

[0193] As the second precursor gas, a precursor gas capable of decomposing the first precursor or a precursor gas capable of removing the ligand of the first precursor can be cited. Specifically, H2O, H2O2, O2, O3, NH3, H2S, H2Se, PH3, AsH3, C2H4, or Si2H6, etc. can be cited.

[0194] As the exposure temperature in step (a), there is no particular limitation. For example, it is 100 °C or higher and 800 °C or lower, preferably 150 °C or higher and 650 °C or lower, more preferably 180 °C or higher and 500 °C or lower, and further preferably 200 °C or higher and 375 °C or lower.

[0195] As the exposure temperature in step (b), there is no particular limitation, and a temperature substantially equal to or higher than the exposure temperature in step (a) can be cited.

[0196] As the film formed by ALD method, there is no particular limitation, and films containing pure elements (such as Si, Cu, Ta, W), films containing oxides (such as SiO2, GeO2, HfO2, ZrO2, Ta2O5, TiO2, Al2O3, ZnO, SnO2, Sb2O5, B2O3, In2O3, WO3), films containing nitrides (such as Si3N4, TiN, AlN, BN, GaN, NbN), films containing carbides (such as SiC), films containing sulfides (such as CdS, ZnS, MnS, WS2, PbS), films containing selenides (such as CdSe, ZnSe), films containing phosphides (GaP, InP), films containing arsenides (such as GaAs, InAs), or their mixtures, etc. can be cited.

[0197] In the method of the present embodiment, for a processed substrate that is manufactured by the manufacturing method of the above-described first aspect and whose surface is modified using a surface modifier, an atomic layer is formed by ALD. In the processed substrate after surface modification, the water repellency of the region having the substrate surface is selectively improved. Therefore, in the region having the substrate surface, the deposition of the atomic layer forming material based on the ALD method is hindered. As a result, in the region having the substrate surface, the deposition amount of the atomic layer forming material based on the ALD method is less than that in the insulator region. Thereby, it is possible to perform film formation based on the ALD method on the insulator region in a region-selective manner.

[0198] According to the pattern forming method of the present embodiment, an atomic layer can be formed by thin film formation using an evaporation method on the surface of a region of a processed substrate manufactured by the manufacturing method of the first aspect where the surface modifier is not formed. Therefore, the pattern forming method of the present embodiment can be suitably applied to selective atomic layer formation.

[0199] (Cleaning liquid)

[0200] The cleaning liquid of the fourth aspect of the present invention is a cleaning liquid for the method of the first aspect or the second aspect. Regarding this cleaning liquid, it is the same as the description of "Regarding the cleaning liquid" in one embodiment of the above (manufacturing method of the processed substrate).

[0201] The cleaning liquid of the present embodiment may contain one organic solvent (S1) alone, or may contain two or more kinds.

[0202] As the organic solvent (S1), decane, tetradecane, cyclohexane, 2-methoxy-1-methylethyl acetate, isobutanol, 1-octanol, 2-ethyl-1-hexanol, dibutyl ether, acetone, cyclopentanone, 2,6-dimethyl-4-heptanone, and 1-methoxy-2-propanol are preferable.

[0203] Regarding the content of the (S1) component in the cleaning liquid, as long as the distance Ra between the Hansen solubility parameter of the compound (A) and the Hansen solubility parameter of the cleaning liquid satisfies (Ra) 2 ≤128, there is no particular limitation. It is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and can be 100% by mass with respect to the total mass of the cleaning liquid.

[0204] The cleaning liquid of the present embodiment may also contain an organic solvent (S2) other than the (S1) component (hereinafter also referred to as the "(S2) component"). The (S2) component is not particularly limited, and an organic solvent having miscibility with the (S1) component can be used.

[0205] In addition to organic solvents, the cleaning liquid may contain any components. Examples of the optional components include water and impurities.

[0206] The cleaning liquid of the present embodiment may also contain water. The water may contain trace components inevitably mixed therein. As the water, purified water such as distilled water, ion-exchanged water, and ultrapure water is preferred, and ultrapure water commonly used in semiconductor manufacturing is preferably used.

[0207] When the cleaning liquid contains water, the content of water is preferably 0.01 to 25% by mass, more preferably 0.03 to 20% by mass, and still more preferably 0.05 to 15% by mass with respect to the total mass of the cleaning liquid.

[0208] The cleaning liquid of the present embodiment may also not contain water.

[0209] The cleaning liquid of the present embodiment may contain, for example, metal impurities containing metal atoms such as Fe atoms, Cr atoms, Ni atoms, Zn atoms, Ca atoms, or Pb atoms.

[0210] The total content of the above metal atoms in the cleaning liquid of the present embodiment is preferably 100 mass ppt or less with respect to the total mass of the cleaning liquid. The lower the lower limit value of the total content of the metal atoms, the more preferable, and examples thereof include 0.001 mass ppt or more. The total content of the metal atoms is, for example, 0.001 mass ppt or more and 100 mass ppt or less.

[0211] By making the total content of the metal atoms be equal to or less than the upper limit value of the above preferred range, the removal performance of the remaining surface modifier is improved. It is considered that by making the total content of the metal atoms be equal to or more than the lower limit value of the above preferred range, the metal atoms are less likely to exist in a free state in the system and are less likely to have an adverse effect on the overall manufacturing yield of the object to be cleaned.

[0212] The content of the metal impurities can be adjusted by purification treatment such as filtration. The purification treatment such as filtration can be performed on a part or all of the raw materials before preparing the cleaning liquid, or can be performed after preparing the cleaning liquid.

[0213] The cleaning liquid of the present embodiment may contain, for example, impurities derived from organic substances (organic impurities). The total content of the above organic impurities in the cleaning liquid of the present embodiment is preferably 5000 mass ppm or less. The lower the lower limit of the content of the organic impurities, the more preferable, and examples thereof include 0.1 mass ppm or more. As the total content of the organic impurities, for example, 0.1 mass ppm or more and 5000 mass ppm or less are exemplified.

[0214] In the cleaning liquid of the present embodiment, for example, a counted object having a size that can be counted by a light scattering type particle counter in liquid may also be included. The size of the counted object is, for example, 0.04 μm or more. The number of counted objects in the cleaning liquid of the present embodiment is, for example, 1,000 or less per 1 mL of the cleaning liquid, and the lower limit value is, for example, 1 or more. It is considered that by making the number of counted objects in the cleaning liquid within the above range, the removal performance of the remaining surface modifier is improved.

[0215] The storage method of the cleaning liquid of the present embodiment is not particularly limited, and a conventionally well-known storage container can also be used. In order to ensure the stability of the cleaning liquid, it is only necessary to appropriately set the void ratio in the container when storing in the container and the type of gas filling the void portion. For example, as the void ratio in the storage container, about 0.01 to 30% by volume can be cited.

[0216] According to the cleaning liquid of the present embodiment, in the method of the first aspect or the second aspect, a substance is selected such that the distance Ra between the Hansen solubility parameter of the compound (A) and the Hansen solubility parameter of the cleaning liquid satisfies (Ra) 2 ≤128, so that the excess deposited (A) component after exposure to the surface modifier can be removed with a high cleaning removal rate.

[0217] Examples

[0218] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0219] The substrates, surface modifiers, and cleaning liquids used in this example are as follows.

[0220] (Pretreatment of the substrate)

[0221] As the substrate, a coupon made by cutting a blanket substrate having a copper film with a thickness of 200 nm on an 8-inch silicon substrate into 2 cm × 2 cm was used. As the substrates used, all were substrates treated with diluted hydrofluoric acid.

[0222] Specifically, each substrate was pretreated by immersing it in an HF aqueous solution with a concentration of 25 ppm at 25 °C for 1 minute. In addition, the contact angle of water on the surface of the substrate after the pretreatment measured by the method described later was 30.0°.

[0223] After the above pretreatment, each substrate was washed with deionized water for 1 minute. Each substrate after the water wash was dried using a nitrogen gas stream.

[0224] (Preparation of the surface modifier)

[0225] As a surface modifier, 100% by mass of octadecanethiol (ODT) was used.

[0226] (Preparation of cleaning solution)

[0227] As the cleaning solution, 100% by mass of the following organic solvent (S1) was used. In addition, the reference cleaning solution was 100% isopropyl alcohol.

[0228] (S1)-1: Acetone

[0229] (S1)-2: Propylene glycol monomethyl ether

[0230] (S1)-3: Decane

[0231] (S1)-4: Tetradecane

[0232] (S1)-5: Cyclohexane

[0233] (S1)-6: 1-Octanol

[0234] (S1)-7: Isobutanol

[0235] (S1)-8: 2-Ethyl-1-hexanol

[0236] (S1)-9: Dibutyl ether

[0237] (S1)-10: 2,6-Dimethyl-4-heptanone

[0238] (S1)-11: Cyclopentanone

[0239] (S1)-12: Propylene glycol monomethyl ether acetate

[0240] Among the organic solvents (S1), a substance with the distance Ra between the Hansen solubility parameter of 0DT and the Hansen solubility parameter of the organic solvent (S1) being (Ra) 2 ≤128 was used as the cleaning solution.

[0241] [(Calculation method of (Ra) 2

[0242] For (Ra) 2 , for example, when using (S1)-1, the calculation was performed using the respective parameter values recorded in Table 1.

[0243] [Table 1]

[0244] Composition <![CDATA[δ d > <![CDATA[δ p > <![CDATA[δ h > Surface modifier 0DT 16.4 2.3 2.6 Cleaning solution (S1)-1 15.7 9.1 6.5

[0245] Mathematical formula (1): (Ra) 2 =(δ dS -δ dA ) 2 +(δpS -δ pA ) 2 +(δ hS -δ hA ) 2

[0246] [wherein, 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.]

[0247] According to the above mathematical formula (1), (Ra) in the case of using (S1)-1 is calculated as described below. 2 .

[0248] (Ra) 2 =(15.7 - 16.4) 2 +(9.1 - 2.3) 2 +(6.5 - 2.6) 2 =61.9

[0249] (Ra) for each case of using (S1)-2 to (S1)-12 and isopropyl alcohol is calculated in the same manner. The respective parameter values and (Ra) are shown in Table 2. 2 2 are shown in Table 2.

[0250] [Table 2]

[0251] Cleaning solution Organic solvent <![CDATA[δ d > <![CDATA[δ p > <![CDATA[δ h > <![CDATA[(Ra) 2 > (S1)-1 Acetone 15.7 9.1 6.5 61.9 (S1)-2 Propylene glycol monomethyl ether 16.4 6.7 6.1 31.6 (S1)-3 Decane 15.6 0.1 0.1 11.7 (S1)-4 Tetradecane 15.8 0.1 0.1 11.5 (S1)-5 Cyclohexane 16.6 0.1 0.1 11.1 (S1)-6 1 - Octanol 16.1 4.4 12.3 98.6 (S1)-7 Isobutanol 15.5 6.1 12.5 113.3 (S1)-8 2 - Ethyl - 1 - hexanol 15.5 3.1 3.0 64.7 (S1)-9 Dibutyl ether 18.0 8.6 5.1 1.61 (S1)-10 2,6 - Dimethyl - 4 - heptanone 15.5 4.2 2.5 4.43 (S1)-11 Cyclopentanone 18.0 8.6 5.1 48.5 (S1)-12 Propylene glycol monomethyl ether acetate 16.3 7.5 12.5 125.1 Reference Isopropyl alcohol 15.5 7.2 12.8 128.9

[0252] [Manufacturing method of treated substrate]

[0253] (Examples 1 to 12, Comparative Example 1)

[0254] A treated substrate is obtained by a manufacturing method including an exposure step of exposing the surface of the substrate in the surface modifier ODT and a cleaning step of cleaning the substrate after the exposure step with a cleaning liquid. Specifically, it is carried out as follows.

[0255] Exposure step:

[0256] The dried substrate in the above (pretreatment of the substrate) is immersed in the surface modifier ODT at 25°C for 1 minute to perform surface modification of the substrate.

[0257] In addition, the contact angle of water on the surface of the substrate after the exposure step measured by the method described later is 104.5°.

[0258] Cleaning step:

[0259] ​The substrate after the exposure process was immersed in each of the above cleaning liquids at 25°C for 1 minute for cleaning. After cleaning the substrate after the cleaning process with ion-exchanged distilled water at 25°C for 1 minute, it was dried using a nitrogen gas flow to manufacture a surface-modified treated substrate.

[0260] <Evaluation>

[0261] For the treated substrates manufactured by the manufacturing methods of each example, the ODT residual rate and the water contact angle were measured respectively by the methods shown below.

[0262] [ODT Residual Rate]

[0263] The ODT residual rate was measured for the treated substrates manufactured in Examples 1 to 12 and Comparative Example 1.

[0264] Regarding the ODT residual rate, for the treated substrates manufactured in each example, atomic force microscopy (AFM) observation was performed from above, and surface modifier ODT molecules existing at a height exceeding the thickness of the monolayer of the surface modifier ODT molecular arrangement formed on the substrate surface (i.e., deposited on the monolayer) were detected. The ODT residual rate was calculated based on the area ratio of the surface modifier ODT molecules covering the monolayer surface. The results are shown in Table 3.

[0265] In addition, the ODT residual rate (%) shown in Table 3 is the value obtained by performing AFM observation at three arbitrary locations on the treated substrate surface, calculating the ODT residual rate within the observation range at each location, and taking their average.

[0266] The ODT residual rate was obtained by calculating the ratio (%) of the area of the remaining part 24 to the total area of the AFM observation image (observation range 1 μm × 1 μm).

[0267] The thickness L of the monolayer formed by arranging the surface modifier ODT molecules on the substrate was set to 2 nm.

[0268] Figure 3A It is an AFM observation image (observation range 1 μm × 1 μm) of the substrate surface just after the exposure process. Figure 3B It is an AFM observation image (observation range 1 μm × 1 μm) of the surface of the treated substrate manufactured in Example 11. Figure 3C It is an AFM observation image (observation range 1 μm × 1 μm) of the surface of the treated substrate manufactured in Comparative Example 1.

[0269] In Figure 3AIn the AFM observation image shown, reference numeral 100A is a processed substrate. Reference numeral 22A is a monolayer portion where the surface modifier ODT is directly bonded to the substrate surface. Reference numeral 24A is a remaining portion where the surface modifier ODT is deposited on the monolayer portion 22A.

[0270] In Figure 3B In the AFM observation image shown, reference numeral 100B is a processed substrate. Reference numeral 22B is a monolayer portion where the surface modifier ODT is directly bonded to the substrate surface. Reference numeral 24B is a remaining portion where the surface modifier ODT is deposited on the monolayer portion 22B.

[0271] In Figure 3C In the AFM observation image shown, reference numeral 100C is a processed substrate. Reference numeral 22C is a monolayer portion where the surface modifier ODT is directly bonded to the substrate surface. Reference numeral 24C is a remaining portion where the surface modifier ODT is deposited on the monolayer portion 22C.

[0272] [Table 3]

[0273]

[0274] From the results shown in Table 3, it can be seen that the cleaning liquid used in the manufacturing methods of Examples 1 to 12 has a lower ODT residual rate than the reference cleaning liquid used in the manufacturing method of Comparative Example 1, that is, the cleaning removability of the remaining ODT is high.

[0275] In particular, it can be seen that in the manufacturing methods of Examples 3 to 5, the ODT residual rate is particularly low, and the cleaning removability of the remaining ODT is significantly improved.

[0276] [Contact angle of water]

[0277] The contact angle of water was measured for the processed substrates manufactured in Examples 1 to 12 and Comparative Example 1.

[0278] For the contact angle of water, using Dropmaster 700 (manufactured by Kyowa Interface Science Co., Ltd.), a pure water droplet (2.0 μL) was dropped onto the surface of the substrate after surface modification, and the contact angle of water 2 seconds after the drop was measured. The results are shown in Table 4.

[0279] [Table 4]

[0280]

[0281] From the results shown in Table 4, it can be confirmed that in the manufacturing methods of Examples 1 to 12, the contact angle of water in the processed substrate after drying in the cleaning process is 102.7 to 109.9°, which is of the same level as the contact angle of water on the substrate surface after the exposure process, 104.5°.

[0282] This indicates that the ODT layer is maintained at a certain thickness on the substrate surface before and after the cleaning process. Therefore, the results shown in Table 4 teach that only the remaining ODT is efficiently removed.

[0283] The preferred embodiments of the present invention have been described above, but the present invention is not limited to these embodiments. Without departing from the gist of the present invention, additions, omissions, substitutions, and other changes to the structure can be made. The present invention is not limited by the above description and is only limited by the appended claims.

[0284] Explanation of reference numerals

[0285] 10 Substrate

[0286] 20 Compound (A)

[0287] 22 Single-layer part

[0288] 24 Remaining part

[0289] 100 Processed substrate

[0290] 220 Surface modifier layer

[0291] 224 Surface modifier layer.

Claims

1. A manufacturing method of a processed substrate, which is a manufacturing method of a processed substrate having a surface with at least a part of the region modified, characterized in that, Comprising: a step of exposing the surface of the substrate in a surface modifier containing a compound (A) having binding property to the substrate; and a step of cleaning the exposed substrate with a cleaning liquid to obtain a processed substrate on which the compound (A) is controlled and formed into a film in the plane direction and the height direction of the substrate, Select the cleaning liquid such that the distance Ra between the Hansen solubility parameter of the compound (A) and the Hansen solubility parameter of the cleaning liquid satisfies (Ra) 2 ≤ 128 2. The manufacturing method of a processing substrate according to claim 1, wherein, wherein the compound (A) is an alkanethiol compound.

3. The manufacturing method of a processing substrate according to claim 2, wherein, The cleaning liquid 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.

4. The manufacturing method of the processing substrate according to claim 3, characterized in that, The content of the organic solvent in the cleaning liquid is 70% by mass or more relative to the total mass of the cleaning liquid.

5. A method for processing a substrate, characterized in that, Comprising: a step of exposing the surface of the substrate in a surface modifier containing a compound (A) having binding property to the substrate; and a step of cleaning the exposed substrate with a cleaning liquid to control the compound (A) and form a film in the plane direction and the height direction of the substrate, Select the cleaning liquid such that the distance Ra between the Hansen solubility parameter of the compound (A) and the Hansen solubility parameter of the cleaning liquid satisfies (Ra) 2 ≤ 128 6. A pattern forming method, characterized in that, Comprising: a step of forming an atomic layer by thin film formation using a vapor deposition method on the surface of the region of the processed substrate manufactured by the manufacturing method according to any one of claims 1 to 4 where the surface modifier is not formed into a film.

7. A cleaning liquid, which is a cleaning liquid for the manufacturing method of the processed substrate according to any one of claims 1 to 4 or the processing method of the substrate according to claim 5, characterized in that it 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, dibutyl ether, acetone, cyclopentanone, 2,6-dimethyl-4-heptanone, and propylene glycol monomethyl ether.

8. The cleaning solution according to claim 7, wherein, The content of the organic solvent in the cleaning liquid is 70% by mass or more relative to the total mass of the cleaning liquid.

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