Substrate, selective film deposition method, organic deposited film and organic material

Abstract

A selective film deposition method characterized in that a substrate, having a structure in which both a first surface region including a metal element and a second surface region including a non-metal inorganic material are exposed, is exposed to a solution containing an organic matter represented by general formula (1) and a solvent, to deposit a film of the organic matter in the first surface region selectively rather than in the second surface region. (1): R1(X)m (in general formula (1): R1 is a hydrocarbon group with 4 to 100 carbon atoms that may include a heteroatom or a halogen atom, wherein m hydrogen atoms of the hydrocarbon group are substituted by X; X is -PO3(R2)2, -O-PO3(R2)2, -CO2R2, -SR2, or -SSR1; R2 is each a hydrogen atom or an alkyl group with 1 to 6 carbon atoms; and m is a positive integer where, when the hydrocarbon group includes r carbon atoms, m / r is 0.01 to 0.25)

Description

[Technical Field]

[0001] The present disclosure relates to a substrate, a selective film deposition method for selectively depositing a film on a surface region of a substrate containing a metal element, a deposited film of an organic material, and an organic material. [Background technology]

[0002] In recent years, semiconductor chip structures have become increasingly miniaturized, and conventional lithography methods, which pattern structures by selectively removing portions of the structure, have problems such as the large number of steps and high costs. If chemical vapor deposition (CVD) or atomic layer deposition (ALD) methods could selectively form films in desired locations on a substrate, they would be the optimal processes for forming fine structures, and it is believed that these problems would be resolved.

[0003] However, when using CVD or ALD to selectively deposit a film on a substrate that has multiple surface regions made of different materials, such as metals used for electrodes and wiring, and inorganic dielectrics used for insulating films, it is necessary to selectively deposit a deposition-inhibiting film, but conventional methods did not provide sufficiently high selectivity.

[0004] A known method for selectively forming a film is to deposit a material that inhibits film deposition in an area where the film is not desired. For example, Patent Document 1 discloses a method for forming a pattern of a thin film of an inorganic material such as TiN, AlN, or SiN on a substrate by atomic layer deposition (ALD), which includes forming a pattern of an atomic layer deposition-inhibiting layer on the substrate by screen printing or the like using an atomic layer deposition-inhibiting material composed of a fluorine-containing resin having a fluorine content of 30 atomic % or more, at least one tertiary carbon or quaternary carbon, and no ester group, hydroxyl group, carboxyl group, or imide group, and then forming a layer of inorganic material by atomic layer deposition in an area where the atomic layer deposition-inhibiting layer is not present.

[0005] Patent Document 2 also describes a method for selectively depositing a layer on a substrate having an exposed metal surface and an exposed silicon-containing surface, which includes: (a) growing a first self-assembled monolayer on the exposed metal surface; (b) growing a second organosilane-based self-assembled monolayer on the exposed silicon-containing surface; and (c) heating the substrate to remove the first self-assembled monolayer from the exposed metal surface. (d) selectively depositing a layer, which is a low-k dielectric layer or a metal layer, on the exposed metal surface; and (e) heating the substrate to remove the second self-assembled monolayer from over the exposed silicon-containing surface.

[0006] According to the above method, for a substrate having a first surface and a second surface made of different materials, a film can be selectively deposited on the first surface rather than the second surface by utilizing the difference in the surface conditions of the two surfaces. Furthermore, according to the above method, the number of process steps for forming a microstructure can be reduced.

[0007] Furthermore, for example, Patent Document 3 discloses a process for selectively forming an organic thin film on a substrate having a first surface that is a metallic surface and a second surface that is a dielectric surface, by performing a deposition cycle including a step of contacting a first gas-phase precursor with the substrate and a step of contacting a second gas-phase precursor with the substrate. Example 1 of Patent Document 3 describes that a polyimide film was formed by performing 250 to 1000 deposition cycles using 1,6-diaminohexane (DAH) and pyromellitic dianhydride (PMDA) on a 200 mm silicon wafer having tungsten (W) features alternating with silicon oxide surfaces, and that the thickness of the polyimide film on the metallic tungsten surface was greater than the thickness of the polyimide film on the SiO2 surface.

[0008] Patent Document 4 discloses a method for selectively forming a passivation layer on a first metallic surface using the selective deposition of an organic film described in Patent Document 3, and then forming a layer X only on a second dielectric surface, and further a method for forming a metallization structure of an integrated circuit using this method. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Republished WO2016 / 147941 [Patent Document 2] Special Publication No. 2018-512504 [Patent Document 3] Japanese Patent Application Laid-Open No. 2017-216448 [Patent Document 4] Japanese Patent Application Publication No. 2018-137435 Summary of the Invention [Problem to be solved by the invention]

[0010] However, Patent Document 1 forms a predetermined pattern on a substrate made of a single material using an atomic layer deposition inhibitor material, and does not disclose a method for selectively forming an atomic layer deposition inhibitor layer on a desired surface region of a substrate having multiple surface regions made of different materials.

[0011] The organosilane-based self-assembled monolayer used in Patent Document 2 selectively deposits on silicon-containing surfaces, but does not selectively deposit on metals or metal oxides.

[0012] The methods for selectively forming organic thin films described in Patent Documents 3 and 4 require repeated deposition cycles of switching raw materials and temperatures multiple times, and the formation of organic thin films requires a great deal of effort.

[0013] In view of the above-mentioned problems, the present disclosure aims to provide a selective film deposition method that can selectively deposit an organic film on a surface region containing a metal element rather than on a surface region containing a non-metallic inorganic material on a substrate with a simple operation, a deposited film of an organic material deposited by the above-mentioned method, and the organic material, etc. [Means for solving the problem]

[0014] As a result of extensive research, the inventors have discovered that by using at least one organic substance represented by the general formula (1) described below, a film of the organic substance can be selectively deposited on a surface region of a substrate containing a metal element rather than on a surface region containing a non-metallic inorganic material, and have thus completed the present invention.

[0015] A selective film deposition method according to an embodiment of the present disclosure is characterized in that a substrate having a structure in which both a first surface region containing a metal element and a second surface region containing a non-metallic inorganic material are exposed is exposed to a solution containing an organic substance represented by the following general formula (1) and a solvent, and a film of the organic substance is selectively deposited on the first surface region rather than on the second surface region. R 1 (X) m (1) (In general formula (1), R 1 is a hydrocarbon group having 4 to 100 carbon atoms which may have a heteroatom or a halogen atom, and m hydrogen atoms of the hydrocarbon group are substituted with X. X is -PO3(R 2 )2, -O-PO3(R 2 )2, -CO2R 2 , -SR 2 , or -SSR 1 R 2 are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m is a positive integer, and when the number of carbon atoms in the hydrocarbon group is r, m / r is 0.01 to 0.25.

[0016] According to the selective film deposition method, by using an organic material represented by general formula (1), it is possible to provide a method for selectively depositing an organic material film on a first surface region containing a metal element exposed on a substrate, rather than on a second surface region containing a non-metallic inorganic material exposed on the substrate, through a simple operation. In this specification, a film made of an organic material is also referred to as an organic material film or an organic material deposited film.

[0017] A substrate according to an embodiment of the present disclosure is a substrate having a first surface region containing a metal element and a second surface region containing a non-metallic inorganic material, wherein the first surface region has an organic film represented by the aforementioned general formula (1), and the second surface region does not have the organic film, or the thickness t2 of the organic film on the second surface region is thinner than the thickness t1 of the organic film on the first surface region.

[0018] According to the above substrate, it is possible to provide a substrate on which the organic film is deposited selectively on the first surface region containing a metal element rather than on the second surface region containing a non-metallic inorganic material.

[0019] The organic deposition film according to an embodiment of the present disclosure is an organic deposition film formed by the selective film deposition method described above, and is characterized by being composed of an organic material represented by the aforementioned general formula (1) deposited on a substrate.

[0020] The organic substance according to the embodiment of the present disclosure is characterized in that it is an organic substance represented by the above-mentioned general formula (1) used in the selective film deposition method.

[0021] By using the above organic material, it is possible to selectively deposit an organic film on a first surface region containing a metal element exposed on a substrate rather than on a second surface region containing a non-metallic inorganic material exposed on the substrate with a simple operation.

[0022] A solution according to an embodiment of the present disclosure is a solution used in the selective film deposition method described above, and is characterized by containing an organic substance represented by the above-described general formula (1) and a solvent.

[0023] By using the above solution, it is possible to selectively deposit the above organic film on a first surface region containing a metal element exposed on a substrate rather than on a second surface region containing a non-metallic inorganic material exposed on the substrate with a simple operation. [Effects of the Invention]

[0024] According to the selective film deposition method of the embodiment of the present disclosure, by using an organic substance represented by the aforementioned general formula (1), it is possible to provide a method for selectively depositing a film of the organic substance on a first surface region containing a metal element exposed on a substrate rather than on a second surface region containing a non-metallic inorganic material exposed on the substrate, with a simple operation.

[0025] According to the substrate according to the embodiment of the present disclosure, it is possible to provide a substrate on which a film of an organic material represented by the aforementioned general formula (1) is deposited selectively on a first surface region containing a metal element exposed on the substrate rather than on a second surface region containing a non-metallic inorganic material exposed on the substrate. DETAILED DESCRIPTION OF THE INVENTION

[0026] The present disclosure will be described in detail below, but the following description of the constituent elements is an example of an embodiment of the present disclosure, and the present disclosure is not limited to these specific details. Various modifications can be made within the scope of the gist of the present disclosure.

[0027] A selective film deposition method according to an embodiment of the present disclosure is characterized in that a substrate having a structure in which both a first surface region containing a metal element and a second surface region containing a non-metallic inorganic material are exposed is exposed to a solution containing an organic substance represented by the following general formula (1) and a solvent, and a film of the organic substance is selectively deposited on the first surface region rather than on the second surface region. R 1 (X) m (1) (In general formula (1), R 1 is a hydrocarbon group having 4 to 100 carbon atoms which may have a heteroatom or a halogen atom, and m hydrogen atoms of the hydrocarbon group are substituted with X. X is -PO3(R2 )2, -O-PO3(R 2 )2, -CO2R 2 , -SR 2 , or -SSR 1 R 2 are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m is a positive integer, and when the number of carbon atoms in the hydrocarbon group is r, m / r is 0.01 to 0.25.

[0028] According to the selective film deposition method, by using an organic material represented by the general formula (1), it is possible to selectively deposit an organic material film on a first surface region containing a metal element exposed on a substrate rather than on a second surface region containing a non-metallic inorganic material exposed on the substrate with a simple operation.

[0029] Here, selectively depositing the organic film on the first surface region rather than on the second surface region means that the organic film is deposited on the first surface region and not on the second surface region, or that the thickness of the organic film on the first surface region is thicker than the thickness of the organic film on the second surface region. Whether or not an organic film has been deposited can be determined mainly by dropping pure water onto the surface of the substrate and measuring the angle (contact angle) between the water droplet and the substrate surface using a contact angle meter.

[0030] When the organic material represented by general formula (1) has poor affinity for water, the contact angle with water of the substrate surface on which the organic material film is deposited increases. In the selective film deposition method according to an embodiment of the present disclosure, the contact angle with water of the first surface region is preferably larger than that of the second surface region. Specifically, the contact angle with water of the first surface region is preferably 10° or more larger than that of the second surface region, more preferably 20° or more larger, and even more preferably 30° or more larger. This makes it possible to determine that an organic film is selectively deposited on the first surface region, which has a large water contact angle, compared to the second surface region, which has a small water contact angle. In the present disclosure, the contact angle of water on the first surface region is preferably 80° or more, more preferably 90° or more, and even more preferably 100° or more. On the other hand, the contact angle of water on the second surface region, to which no organic matter adheres or only a small amount adheres, is preferably about 20 to 70°.

[0031] Whether or not an organic deposition film has been formed on a substrate can also be determined by analyzing the elemental composition of the substrate surface using X-ray photoelectron spectroscopy (XPS). If the organic material contains characteristic atoms such as phosphorus or sulfur, peaks for these elements can be confirmed.

[0032] The ease with which the organic material deposits on the first and second surface regions varies depending on the material of each surface region. However, it is preferable that the thickness t1 of the organic material film on the first surface region is greater than the thickness t2 of the organic material film on the second surface region, and that the value t1 / t2, obtained by dividing t1 by t2, be 5 or greater. Furthermore, the value t1 / t2 is more preferably 10 or greater, and even more preferably 100 or greater. Regarding the film thickness, t1 is preferably 0.3 nm or greater, and more preferably 0.6 nm or greater. Furthermore, t2 is preferably less than 0.3 nm, and more preferably 0 nm, i.e., no organic material is deposited at all. t1 and t2 can be measured using an atomic force microscope (AFM) or the like.

[0033] The metal element may be at least one metal element selected from the group consisting of Cu, Co, Ru, Ni, Pt, Al, Ta, Ti, and Hf. The metal element may exist as a metal or as a compound containing the metal element. The compound containing the metal element may be any compound that is chemically bonded to the metal element, such as a metal oxide, a metal nitride, or an alloy. Metals and metal oxides are particularly preferred. Furthermore, Cu, Co, and Ru are preferred as the metal element.

[0034] Examples of non-metallic inorganic materials include silicon-based materials such as silicon, silicon oxide, silicon nitride, and silicon oxynitride, and germanium-based materials such as germanium, germanium oxide, germanium nitride, and germanium oxynitride. Among them, at least one selected from the group consisting of silicon, silicon oxide, silicon nitride, and silicon oxynitride is preferred. Silicon includes both polycrystalline silicon and single-crystalline silicon. Silicon oxide is SiO x (x is 1 or more and 2 or less), and is typically SiO2. Silicon nitride is SiN x (x is 0.3 or more and 9 or less), and a typical example is Si3N4. Silicon oxynitride is expressed as Si4OxNy (x is 3 or more and 6 or less, y is 2 or more and 4 or less), and an example is Si4O5N3.

[0035] Methods for obtaining a first surface region in which metal is exposed include methods for obtaining a metal film using chemical vapor deposition (CVD), physical vapor deposition (PVD), plating, etc. For example, a substrate having a structure in which both a first surface region containing metal and a second surface region containing nonmetallic inorganic material are exposed can be obtained by forming a metal film on the above-mentioned film of nonmetallic inorganic material and forming the metal film into a predetermined pattern by photolithography, or by forming holes or grooves in a film of nonmetallic inorganic material, filling the grooves with metal, and optionally polishing by CMP (chemical mechanical polishing). In addition, a method for obtaining the first surface region in which the metal is exposed includes a method in which an oxide film on the surface of the metal film is removed by vapor-phase etching or wet etching to expose the metal surface. The oxide film may also be removed mechanically.

[0036] Methods for obtaining a first surface region in which a metal oxide is exposed include methods for obtaining a metal oxide film using chemical vapor deposition, physical vapor deposition, etc., and methods for forming a native oxide film by exposing a metal film obtained by a similar method to the atmosphere. For example, a substrate having a structure in which both a first surface region containing a metal oxide and a second surface region containing a nonmetallic inorganic material are exposed can be obtained by a method of forming a metal oxide film on the above-mentioned nonmetallic inorganic material film and then forming the metal oxide film into a predetermined pattern using a photolithography method, or a method of forming holes or grooves in a nonmetallic inorganic material film, filling the grooves with metal, and forming a native oxide film on the metal.

[0037] The first surface region containing a metal element may contain compounds other than those containing a metal element on which the organic substance represented by general formula (1) can be deposited, but it is desirable that the first surface region contains only compounds containing a metal element, and that only the compounds containing a metal element are exposed on the surface. The second surface region containing the non-metallic inorganic material may contain a compound of the non-metallic inorganic material, or may contain only the non-metallic inorganic material, but it is desirable that it contains only the non-metallic inorganic material and that only the non-metallic inorganic material is exposed on the surface.

[0038] Substrates used in embodiments of the present disclosure include semiconductor device substrates having a metal or metal oxide film in their structure, and substrates on which metal or metal oxide is formed during the patterning process of semiconductor devices. Substrates on which metal wiring having a predetermined pattern is formed in the insulating film of a semiconductor element are particularly preferred. That is, the first surface region corresponds to metal wiring having a surface native oxide film or metal wiring with exposed metal, and the second surface region corresponds to an insulating film made of a non-metallic inorganic material. However, the substrates used in embodiments of the present disclosure are not limited to these.

[0039] A specific method for selectively depositing a film of the organic material represented by general formula (1) on the first surface region rather than on the second surface region involves exposing the substrate to a solution containing the organic material and a solvent. This method is described below.

[0040] As the organic substance, an organic substance represented by the following general formula (1) is used. R 1 (X) m (1) (In general formula (1), R 1 is a hydrocarbon group having 4 to 100 carbon atoms which may have a heteroatom or a halogen atom, and m hydrogen atoms of the hydrocarbon group are substituted with X. X is -PO3(R 2 )2, -O-PO3(R 2 )2, -CO2R 2 , -SR 2 , or -SSR 1 R 2 are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m is a positive integer, and when the number of carbon atoms in the hydrocarbon group is r, m / r is 0.01 to 0.25.

[0041] The concept of the organic substance represented by the general formula (1) above includes the concepts of the organic substances represented by the general formulae (2) to (5), and for example, an organic substance represented by at least one selected from the group consisting of the general formulae (2) to (5) can be used.

[0042] The organic substances represented by the general formulas (2) to (5) will be explained below. [Organic substance represented by general formula (2) (including organic substance represented by general formula (6)] General formula (2)[R 3 (PO3(R 4 )2) n ], R 3 is a hydrocarbon group having 4 to 100 carbon atoms which may have a heteroatom or a halogen atom, and n hydrogen atoms of the hydrocarbon group are (PO3(R 4 )2), n is 1 or 2, and R 4 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R 4 is preferably a hydrogen atom. 4 When R is a hydrogen atom, it becomes a phosphonic acid. 4may be the same or may be different.

[0043] Furthermore, the organic substance represented by the general formula (2) [R 3 (PO3(R 4 )2) n ] is represented by the general formula (6) [R 11 In the general formula (6), R 11 is a monovalent hydrocarbon group having 6 to 100 carbon atoms which may have a heteroatom or a halogen atom.

[0044] [Organic substance represented by general formula (3) (including organic substance represented by general formula (7)] General formula (3) [R 5 (O-PO3(R 6 )2) n ], R 5 is a hydrocarbon group having 4 to 100 carbon atoms which may have a heteroatom or a halogen atom, and n hydrogen atoms of the hydrocarbon group are (O-PO3(R 6 )2), n is 1 or 2, and R 6 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R 6 is preferably a hydrogen atom. 6 When R is a hydrogen atom, it becomes a phosphate ester. 6 may be the same or may be different.

[0045] Furthermore, the organic substance represented by the general formula (3) [R 5 (O-PO3(R 6 )2) n ] is represented by the general formula (7) [R 12 In the general formula (7), R 12 is a monovalent hydrocarbon group having 6 to 100 carbon atoms which may have a heteroatom or a halogen atom.

[0046] [Compounds represented by general formula (4) (including compounds represented by general formula (8)] General formula (4)[R 7 (CO2R 8 ) n ], R 7 is a hydrocarbon group having 4 to 100 carbon atoms which may have a heteroatom or a halogen atom, and n hydrogen atoms of the hydrocarbon group are (COR 8 ) n is 1 or 2, and R 8 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R 8 is preferably a hydrogen atom. 8 When R is a hydrogen atom, it becomes a carboxylic acid. 8 may be the same or may be different.

[0047] Furthermore, the organic substance represented by the general formula (4) [R 7 (CO2R 8 ) n ] is represented by the general formula (8) [R 13 In the general formula (8), R 13 is a monovalent hydrocarbon group having 6 to 100 carbon atoms which may have a heteroatom or a halogen atom.

[0048] [Organic substance represented by general formula (5) (including organic substance represented by general formula (9)] General formula (5) [R 9 (SR 10 ) n ], R 9 is a hydrocarbon group having 4 to 100 carbon atoms which may have a heteroatom or a halogen atom, and n hydrogen atoms of the hydrocarbon group are (SR 10 ) n is 1 or 2, and R 10 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or -SR 9 is. R 10 is preferably a hydrogen atom. 10 When R is a hydrogen atom, it becomes a thiol. 10may be the same or may be different.

[0049] Furthermore, the organic compound represented by the general formula (5) [R 9 (SR 10 ) n ] is represented by the following general formula (9) [R 14 In the general formula (9), R 14 is a monovalent hydrocarbon group having 6 to 100 carbon atoms which may have a heteroatom or a halogen atom.

[0050] R 3 , R 5 , R 7 , R 9 , R 11 , R 12 , R 13 , and R 14 Examples of heteroatoms that may be contained in the hydrocarbon group include a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, etc. Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0051] Also, R 3 , R 5 , R 7 , R 9 , R 11 , R 12 , R 13 , and R 14 may have a branched structure or a cyclic structure. A branched structure is one that contains a secondary or tertiary carbon atom and is branched at the carbon atom. The cyclic structure may be an alicyclic hydrocarbon or an aryl group. Examples of the alicyclic hydrocarbon include a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, and a campholoyl group. Examples of the aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a p-hydroxyphenyl group, a 1-naphthyl group, a 1-anthracenyl group, and a benzyl group.

[0052] Examples of the organic substance represented by general formula (2) or general formula (6) include methylphosphonic acid, ethylphosphonic acid, n-propylphosphonic acid, n-butylphosphonic acid, n-pentylphosphonic acid, n-hexylphosphonic acid, n-heptylphosphonic acid, n-octylphosphonic acid, n-nonylphosphonic acid, n-decylphosphonic acid, n-undecylphosphonic acid, n-dodecylphosphonic acid, n-tridecylphosphonic acid, n-tetradecylphosphonic acid, n-pentadecylphosphonic acid, n-hexadecylphosphonic acid, n-heptadecylphosphonic acid, n-octadecylphosphonic acid, and n-nonadecylphosphonic acid. Phosphonic acid, phenylphosphonic acid, (2-phenylethyl)phosphonic acid, (3-phenylpropyl)phosphonic acid, (4-phenylbutyl)phosphonic acid, (5-phenylpentyl)phosphonic acid, (6-phenylhexyl)phosphonic acid, (7-phenylhexyl)phosphonic acid, (8-phenyloctyl)phosphonic acid, (9-phenylnonyl)phosphonic acid, (10-phenyldecyl)phosphonic acid, (11-phenylundecyl)phosphonic acid, (12-phenyldodecyl)phosphonic acid, methylenediphosphonic acid, (4-aminophenyl)phosphonic acid, (4-aminobenzyl)phosphonic acid, benzhydrylphosphonic acid, (4-bromophenyl)phosphonic acid , (2-chloroethyl)phosphonic acid, (3-chloropropyl)phosphonic acid, (4-chlorobutyl)phosphonic acid, (5-chloropentyl)phosphonic acid, (6-chlorohexyl)phosphonic acid, (2-bromoethyl)phosphonic acid, (3-bromopropyl)phosphonic acid, (4-bromobutyl)phosphonic acid, (5-bromopentyl)phosphonic acid, (6-bromohexyl)phosphonic acid, 1,2-ethylenediphosphonic acid, 1,3-propylenediphosphonic acid, 1,4-butanediphosphonic acid perfluorobutyl)ethylphosphonic acid, 2-(perfluorohexyl)ethylphosphonic acid, and 2-(perfluoroheptyl)ethylphosphonic acid.

[0053] Examples of organic substances represented by general formula (3) or general formula (7) include those in which the phosphonyl group (-POH group) of the phosphonic acid exemplified above has been substituted with -OPOH. Examples include n-hexyl phosphate, n-heptyl phosphate, n-octyl phosphate, n-nonyl phosphate, n-decyl phosphate, n-undecyl phosphate, n-dodecyl phosphate, n-tridecyl phosphate, n-tetradecyl phosphate, n-pentadecyl phosphate, n-hexadecyl phosphate, n-heptadecyl phosphate, n-octadecyl phosphate, n-nonadecyl phosphate, phenyl phosphate, benzyl dihydrogen phosphate, 2-phenylethyl phosphate, 3-phenylpropyl phosphate, 4-phenylbutyl phosphate, 5-phenylpentyl phosphate, 6-phenylhexyl phosphate, and 7-phenylheptyl phosphate. Examples of perfluorobutyl phosphate include 8-phenyloctyl phosphate, 9-phenylnonyl phosphate, 10-phenyldecyl phosphate, 11-phenylundecyl phosphate, 12-phenyldodecyl phosphate, diethyl phosphate, dipropyl phosphate, dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, dinonyl phosphate, didecyl phosphate, phenyl phosphate, diphenyl phosphate, dibenzyl phosphate, 2-(perfluorobutyl)ethyl phosphate, 2-(perfluoropentyl)ethyl phosphate, 2-(perfluorohexyl)ethyl phosphate, and 2-(perfluoroheptyl)ethyl phosphate.

[0054] Examples of organic substances represented by general formula (4) or general formula (8) include those in which the phosphonyl group (-POH group) of the phosphonic acid exemplified above has been substituted with -COH. Examples include n-hexanoic acid, n-heptanoic acid, n-octanoic acid, n-nonanoic acid, n-decanoic acid, n-undecanoic acid, n-dodecanoic acid, n-tridecanoic acid, n-tetradecanoic acid, n-pentadecanoic acid, n-hexadecanoic acid, n-heptadecanoic acid, n-octadecanoic acid, n-nonadecanoic acid, benzoic acid, 2-phenylethanoic acid, 3-phenylpropanoic acid, 4-phenylbutanoic acid, 5-phenylpentanoic acid, 6-phenylhexanoic acid, 7-phenylheptanoic acid, 8-phenyloctanoic acid, 9-phenylhexanoic acid, 10-phenylhexanoic acid, 11-phenylhexanoic acid, 12-phenylhexanoic acid, 13-phenylpropanoic acid, 14-phenylbutanoic acid, 15-phenylpentanoic acid, 16-phenylhexanoic acid, 17-phenylheptanoic acid, 18-phenyloctanoic acid, 19-phenyloctanoic acid, 20-phenylpentanoic acid, 21-phenylhexanoic acid, 22-phenylhexanoic acid, 23-phenylpropanoic acid, 24-phenylbutanoic acid, 25-phenylpentanoic acid, 26-phenylhexanoic acid, 27-phenylheptanoic acid, 28-phenyloctanoic acid, 29-phenylhexanoic acid, 30-phenylhexanoic acid, 31-phenylhexanoic acid, 32-phenylhexanoic acid, 33-phenylpropanoic acid, 34-phenylbutanoic acid, 35-phenylpentanoic Nonanoic acid, 10-phenyldecanoic acid, 11-phenylundecanoic acid, 12-phenyldodecanoic acid, 1,2-ethanedicarboxylic acid, 1,3-propanedicarboxylic acid, 1,4-butanedicarboxylic acid, 1,5-pentanedicarboxylic acid, 1,6-hexanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 1,8-octanedicarboxylic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid Candicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,15-pentadecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,17-heptadecanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, diethylmalonic acid, dipropylmalonic acid, dibutylmalonic acid, dipentylmalonic acid, dihexylmalonic acid, o-phthalic acid, m-phthalic acid, p-phthalic acid, 2-(perfluorobutyl)ethoxy perfluoro-1,6-hexanedioic acid, perfluoro-1,7-heptanedioic acid, perfluoro-1,8-octanedioic acid, 4,4'-bisbenzoic acid, and 4,4'-(hexafluoroisopropylidene)bis(benzoic acid).

[0055] Examples of the organic substance represented by general formula (5) or general formula (9) include those in which the phosphonyl group (-PO3H group) of the phosphonic acid exemplified above is substituted with -SH. For example, n-hexanethiol, n-heptanethiol, n-octanethiol, n-nonanethiol, n-decanethiol, n-undecanethiol, n-dodecanethiol, n-tridecanethiol, n-tetradecanethiol, n-pentadecanethiol, n-hexadecanethiol, n-heptadecanethiol, n-octadecanethiol, n-nonadecanethiol, cyclohexanethiol, thiophenol, phenylmethanethiol, 2-phenylethanethiol, 3-phenylpropanethiol, 4-phenylbutanethiol, 5-phenylpentanethiol, 6-phenylhexanethiol, 7-phenylheptanethiol, 8-phenyloctanethiol, 9-phenylnonanethiol, 10-phenyldecylthiol, 11-phenylundecylthiol, 12-phenyldodecylthiol, ethanedithiol, 1,3-propanedithiol, 1, 4-Butanedithiol, 1,5-Pentanedithiol, 1,6-Hexaneedithiol, 1,7-Heptanedithiol, 1,8-Octanedithiol, 1,9-Nonanedithiol, 1,10-Decanedithiol, 1,11-Undecanedithiol, 1,12-Dodecanedithiol, 1,13-Tridecanedithiol, 1,14-Tetradecanedithiol, 1,15-Pentadecanedithiol, 1,16-Hexadecanedithiol, 1,17- Examples include heptadecanedithiol, 1,18-octadecanedithiol, 1,19-nonadecanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,4-benzenedimethanethiol, 2-(perfluorobutyl)ethanethiol, 2-(perfluoropentyl)ethanethiol, 2-(perfluorohexyl)ethanethiol, and 2-(perfluoroheptyl)ethanethiol.

[0056] R 1 , R 3 , R 5 , R 7 , R 9 , R 11 , R12 , R 13 , and R 14 However, if some or all of the hydrogen atoms are replaced with fluorine atoms, heat resistance can be improved, which is preferable. In particular, it is preferable that the hydrogen atoms are replaced with multiple fluorine atoms, and it is also preferable that the compound further contains a perfluoroalkyl group.

[0057] It can also increase the amount of organic matter deposited, 11 , R 12 , R 13 , and R 14 is preferably a monovalent organic group represented by the following general formula (10). R 15 -(CH2) n - (10) (In equation (10), R 15 is a hydrogen atom or a monovalent hydrocarbon group which may have a heteroatom or a halogen atom. n is an integer of 2 to 20, and the total number of carbon atoms in formula (10) is 6 to 100.

[0058] In addition, it can also increase the amount of organic matter deposited, so R 11 , R 12 , R 13 , and R 14 is preferably a monovalent organic group represented by the following general formula (11). R 16 -OY-((CH2) p O) q -Z-(CH2) r - (11) (In formula (11), R 16 is a hydrogen atom, a methyl group, or a phenyl group. Y and Z are any divalent group or direct bond. p is an integer of 1 to 4, and q and r are positive integers. The total number of carbon atoms in formula (11) is 6 to 100. The repeating unit (CH2) p The order of the O and CH2 in the formula is arbitrary. Furthermore, the above formula (11) is R 16 -O-((CH2) p O) q-(CH2) r The total number of carbon atoms in the formula (11) is preferably 10 to 90, and more preferably 20 to 80.

[0059] Also, R 1 , R 3 , R 5 , R 7 , R 9 , R 11 , R 12 , R 13 , and R 14 is preferably a straight-chain hydrocarbon group containing no branched structure, since it can increase the amount of organic matter deposited. The straight-chain hydrocarbon group may contain a cyclic structure, and the cyclic structure is preferably an aryl group, particularly a phenyl group, and is preferably present at the end of the straight-chain hydrocarbon group.

[0060] In a selective film deposition method according to an embodiment of the present disclosure, a substrate is exposed to a solution containing an organic substance represented by the above-mentioned general formula (1) and a solvent, and a film of the organic substance is selectively deposited on the first surface region rather than on the second surface region. Exposing the substrate to the solution means bringing the surface of the substrate into contact with the solution.

[0061] A specific example of a selective film deposition method is a method in which a substrate having a first surface region and a second surface region is immersed in a solution containing an organic substance represented by general formula (1) and a solvent, thereby contacting the solution with the surface of the substrate and selectively depositing a film of the organic substance on the first surface region of the substrate. This method is referred to as the immersion method.

[0062] As a method for exposing a substrate to a solution, in addition to an immersion method in which the substrate is immersed in the solution, a spin coating method in which the solution is dropped onto a substrate and then rotated at high speed, a spray coating method in which the solution is sprayed onto the substrate, a coating method in which the solution is applied to the substrate, etc. can be used, and the method is not limited to these as long as it is a method that allows the substrate to come into contact with the solution.

[0063] The concentration of the organic substance represented by the general formula (1) contained in the solution is preferably 0.01% by mass or more and 20% by mass or less, more preferably 0.05% by mass or more and 10% by mass or less, still more preferably 0.1% by mass or more and 8% by mass or less, and particularly preferably 0.3% by mass or more and 5% by mass or less, relative to 100% by mass of the total amount of the solution. When the solution contains two or more organic substances, the above concentration range refers to the total concentration of the organic substances.

[0064] The solvent used in the solution of the present disclosure is not particularly limited, and any conventionally known solvent can be used as long as it can dissolve the above organic substances and cause little damage to the surface of the object to be treated. From the viewpoint of being able to dissolve the organic substances and causing little damage to the surface of the object to be treated, it is preferable to contain an organic solvent (non-aqueous solvent) other than water, and from the viewpoint of the solubility of the organic substances, it is preferable to contain an organic solvent (non-aqueous solvent) other than hydrocarbon solvents.

[0065] Suitable non-aqueous solvents other than the hydrocarbon solvents include, for example, esters, ethers, ketones, sulfoxide solvents, sulfone solvents, lactone solvents, carbonate solvents, alcohol solvents, polyhydric alcohol derivatives, nitrogen-containing solvents, silicone solvents, and mixtures thereof.

[0066] Examples of the esters include ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl acetate, i-pentyl acetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, n-pentyl formate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl n-octanoate, methyl decanoate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, dimethyl adipate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl ethoxyacetate.

[0067] Examples of the ethers include di-n-propyl ether, ethyl-n-butyl ether, di-n-butyl ether, ethyl-n-amyl ether, di-n-amyl ether, ethyl-n-hexyl ether, di-n-hexyl ether, di-n-octyl ether, as well as ethers having a branched hydrocarbon group such as diisopropyl ether and diisoamyl ether corresponding to the carbon numbers of these ethers, dimethyl ether, diethyl ether, methyl ethyl ether, methyl cyclopentyl ether, diphenyl ether, tetrahydrofuran, dioxane, methyl perfluoropropyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, methyl perfluorohexyl ether, and ethyl perfluorohexyl ether.

[0068] Examples of the ketones include acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, cyclohexanone, and isophorone.

[0069] Examples of the sulfoxide solvents include dimethyl sulfoxide, and examples of the sulfone solvents include dimethyl sulfone, diethyl sulfone, bis(2-hydroxyethyl) sulfone, and tetramethylene sulfone.

[0070] Examples of the lactone solvent include β-propiolactone, γ-butyrolactone, γ-valerolactone, γ-hexanolactone, γ-heptanolactone, γ-octanolactone, γ-nonanolactone, γ-decanolactone, γ-undecanolactone, γ-dodecanolactone, δ-valerolactone, δ-hexanolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone, δ-undecanolactone, δ-dodecanolactone, and ε-hexanolactone.

[0071] Examples of the carbonate solvents include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, and propylene carbonate. Examples of the alcohol solvents include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, triethylene glycol, tripropylene glycol, tetraethylene glycol, tetrapropylene glycol, and glycerin.

[0072] Examples of the derivatives of the polyhydric alcohols include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether. polyhydric alcohol derivatives having an OH group, such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tetrapropylene glycol monomethyl ether, and butylene glycol monomethyl ether; or ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate;Diethylene glycol diacetate, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol monomethyl ether acetate, tetraethylene glycol monoethyl ether acetate, tetraethylene glycol monobutyl ether acetate, tetraethylene glycol diacetate, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, propylene glycol monomethyl ether acetate (propylene glycol 1-monomethyl ether 2-acetate), propylene glycol monoethyl ether acetate, Propylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, dipropylene glycol diacetate, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol diacetate, tetrapropylene glycol dimethyl ether, tetrapropylene glycol monomethyl ether acetate, tetrapropylene glycol diacetate, butylene glycol dimethyl ether, butylene glycol monomethyl ether acetate,Examples of such polyhydric alcohol derivatives include butylene glycol diacetate, glycerin triacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl propionate.

[0073] Examples of the nitrogen-containing solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone, triethylamine, and pyridine.

[0074] Examples of silicone solvents include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane.

[0075] Furthermore, from the viewpoint of the solubility of organic substances, the organic solvent is preferably a polar organic solvent, and preferably contains at least one selected from the group consisting of esters, ethers, ketones, alcohol-based solvents, and derivatives of polyhydric alcohols. In particular, an alcohol-based solvent is preferred, and ethanol or isopropyl alcohol (IPA) can be suitably used.

[0076] The solvent may contain water, and in this case, the concentration of water is preferably 40% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, relative to 100% by mass of the solution of the present disclosure.

[0077] Furthermore, in order to promote the formation of a deposited film of an organic substance, a catalyst such as an acidic compound such as hexafluoroisopropanol, trifluoroacetic acid, trifluoroacetic anhydride, trifluoromethanesulfonic acid, or trifluoromethanesulfonic anhydride, or a basic compound such as pyridine, N,N-dimethyl-4-aminopyridine, ammonia, or imidazole may be added to the solution of the present disclosure. The amount of catalyst added is preferably 0.01 to 50% by mass relative to 100% by mass of the total amount of the organic substance.

[0078] The temperature of the solution in the above immersion method or the like is preferably 0 to 80°C, and the time for immersing the substrate in the solution is preferably 10 seconds to 48 hours, and preferably 1 minute to 24 hours. When immersing the substrate in the solution, the solution may be stirred with a stirring blade or the like.

[0079] Furthermore, it is preferable to carry out a cleaning step in which the substrate is cleaned with a solvent after exposing the substrate to a solution containing an organic substance to deposit an organic film. Examples of solvents that can be used in the cleaning step include the organic solvents described above. A preferred cleaning method involves immersing the substrate in the solvent at 0 to 80°C for 1 to 1000 seconds. When the substrate is immersed in a solution containing an organic substance, the substrate is removed from the solution and cleaned with the solvent.

[0080] After the above cleaning step, it is preferable to dry the substrate by spraying an inert gas such as nitrogen or argon onto the substrate. The temperature of the sprayed inert gas is preferably 0 to 80°C.

[0081] In a selective film deposition method according to an embodiment of the present disclosure, a substrate having a structure in which both the first surface region and the second surface region are exposed is exposed to a solution containing an organic substance represented by general formula (1) and a solvent, and a film of the organic substance is selectively deposited on the first surface region rather than the second surface region. When exposing the substrate to the solution, the substrate may be exposed to one type of solution, and a film of the organic substance may be selectively deposited on the first surface region rather than the second surface region, or two or more types of solutions may be prepared, and the substrate may be exposed to each solution in turn, and a film of the organic substance may be selectively deposited on the first surface region rather than the second surface region.

[0082] In this case, it is desirable to expose the substrate to the first solution, then wash with the above-mentioned solvent and dry, then expose the substrate to the second solution, and similarly wash with the above-mentioned solvent and dry. Even when three or more types of solutions are prepared, it is desirable to sequentially perform the steps of washing with the above-mentioned solvent and drying after exposing the substrate to a solution and before exposing the substrate to the next solution. However, in some cases, the above-mentioned washing and drying steps may be omitted.

[0083] In addition, the organic matter contained in the solution to be exposed to the substrate after the second time is 1 The number of carbon atoms in the organic matter contained in the solution to be initially exposed is 1 However, it is desirable to set the number of carbon atoms in the organic matter contained in the second or subsequent solutions to be exposed to the substrate to be greater than or equal to the number of carbon atoms in the organic matter contained in the first solution to be exposed. The above R in the organic matter contained in the solution exposed to the substrate after the second 1 The number of carbon atoms in the organic matter contained in the solution to be initially exposed is 1 When the number of carbon atoms is greater than or equal to 1, the resulting substrate has a higher contact angle, allowing a thicker film of the organic material to be selectively deposited on the first surface region.

[0084] When exposing the substrate to the solution, two or more types of the solution are prepared and the substrate is sequentially exposed to each solution, so that even if the time for exposing the substrate to the solution, i.e., the time for immersing the substrate in the solution, is shortened, the organic film can be selectively deposited on the first surface region rather than the second surface region.

[0085] [Substrate after selective deposition of organic film] A substrate according to an embodiment of the present disclosure is a substrate having a first surface region containing a metal element and a second surface region containing a non-metallic inorganic material, wherein the first surface region has an organic film represented by the aforementioned general formula (1), and the second surface region does not have the organic film, or the thickness t2 of the organic film on the second surface region is thinner than the thickness t1 of the organic film on the first surface region. The contact angle of water on the first surface region is preferably larger than the contact angle of water on the second surface region, more preferably by 10° or more.

[0086] The organic film (deposited film) may be physically adsorbed on the first surface region or chemically bonded to a component contained in the substrate. It is presumed that groups containing phosphorus, oxygen, or sulfur atoms in the molecules of the organic material interact with the metal or metal oxide contained in the substrate to form the organic film. In this case, it is presumed that the organic film has a monolayer structure. The substrate surface before the organic material is deposited is often hydrophilic due to the metal or metal oxide contained in the substrate, whereas the substrate surface after the organic material is deposited is often hydrophobic due to the organic film. When the organic material described above is used as the organic material, it is presumed that the phosphorus, oxygen, or sulfur atoms interact with the metal or metal oxide, exposing hydrocarbon groups such as alkyl groups on the surface of the organic film, and thus the first surface region is hydrophobic due to the deposition of the organic film. For this reason, if pure water is dropped onto the first surface region after the organic substance has been deposited and the angle (contact angle) between the water droplet and the wafer surface is measured with a contact angle meter, it is estimated that the contact angle of the first surface region will be larger than that of the second surface region. [Example]

[0087] Examples that more specifically disclose embodiments of the present disclosure are given below, but the present disclosure is not limited to these examples.

[0088] [Example 1] (Solution preparation) Isopropyl alcohol (IPA) was used as the solvent, and n-octadecanoic acid was used as the organic substance. The organic substance was mixed and dissolved so that the content was 1% by mass, to prepare a solution containing n-octadecanoic acid and the solvent.

[0089] (Preparing the substrate) A silicon substrate with a 100 nm thick cobalt film was irradiated with UV / O3 for 30 minutes (lamp: EUV200WS, distance from lamp: 10 mm, ozone is generated from oxygen in the air by UV irradiation) to oxidize the surface, resulting in a substrate with a cobalt oxide (CoOx) film on the surface.

[0090] A silicon substrate having a 100 nm thick cobalt film was immersed in a 0.5 mass % HF aqueous solution at 22° C. for 1 minute to remove the native oxide film on the surface, thereby obtaining a substrate having a cobalt (Co) film on the surface.

[0091] A silicon substrate with a 100 nm thick copper film was cleaned by UV / O3 irradiation (lamp: EUV200WS, distance from lamp: 10 mm, ozone is generated from oxygen in the air by UV irradiation) for 30 minutes to obtain a substrate with a copper oxide film (CuOx) on the surface.

[0092] A silicon substrate having a copper film with a thickness of 100 nm was immersed in a 0.5 mass % HF aqueous solution at 22° C. for 1 minute to remove the native oxide film on the surface, thereby obtaining a substrate having a copper film (Cu) on the surface.

[0093] A silicon substrate having a silicon oxide film with a thickness of 100 nm was immersed in a 0.5 mass % HF aqueous solution at 22° C. for 1 minute to clean the surface, thereby obtaining a substrate having a silicon oxide (SiOx) film on the surface.

[0094] A silicon substrate having a silicon nitride film with a thickness of 30 nm was immersed in a 0.5 mass % HF aqueous solution at 22°C for 1 minute to remove the native oxide film on the surface, thereby obtaining a substrate having a silicon nitride film (SiN) on the surface.

[0095] The silicon substrate was immersed in a 0.5 mass % HF aqueous solution at 22° C. for 1 minute to remove the native oxide film on the surface, thereby obtaining a substrate with a silicon surface (Si substrate).

[0096] (Surface treatment using a solution containing organic matter) The seven substrates prepared by the above process were each immersed in the above solution for 24 hours at 22°C to perform surface treatment of the substrates, and organic matter was deposited on the surface of each substrate.The substrates were then immersed in IPA for 60 seconds twice, and dried by spraying nitrogen gas for 60 seconds.

[0097] (Measurement of water contact angle) Approximately 1 μl of pure water was placed on the surfaces of seven substrates according to Example 1 that had been subjected to surface treatment with a solution containing an organic substance, and the angle (contact angle) between the water droplet and the wafer surface was measured using a contact angle meter (DM-301, manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Table 1.

[0098] [Table 1]

[0099] As a result of measuring the contact angles using the above method, as shown in Table 1, the CuOx substrate, Cu substrate, CoOx substrate, and Co substrate had higher contact angles than the Si substrate, SiN substrate, and SiOx substrate, demonstrating that by using carboxylic acid as the organic substance, an organic film can be selectively deposited on the surface of a metal or metal oxide.

[0100] [Examples 2 to 20] The same procedures as in Example 1 were carried out and evaluation was carried out, except that the type of material on the substrate surface, the type of organic substance, the type of solvent, the solution concentration (concentration of organic substance), etc. were changed as shown in Table 2. That is, in the above example, a CoOx substrate, a Co substrate, and an SiOx substrate were prepared. The results are shown in Table 2. [Comparative Examples 1 to 2] In Comparative Example 1, an IPA solution not containing the above-mentioned organic substance was used, as shown in Table 2. In Comparative Example 2, PGMEA was used as the solvent and trimethylsilyldimethylamine was used as the organic substance, as shown in Table 2, and they were mixed and dissolved so that the concentration of the organic substance became the concentration shown in Table 2, to prepare a solution containing the organic substance and the solvent. Note that trimethylsilyldimethylamine does not fall under the category of organic substances represented by the above-mentioned general formula (1).

[0101] (Substrate preparation and surface treatment with solutions) In Comparative Examples 1-2, the same substrates as in Examples 2-20 were prepared, and surface treatment with a solution was carried out in the same manner as in Examples 2-20.

[0102] (Measurement of water contact angle) Approximately 1 μl of pure water was placed on the substrate surfaces of Comparative Examples 1 and 2, and the angle (contact angle) between the water droplet and the wafer surface was measured using a contact angle meter (DM-301, manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Table 2.

[0103] [Table 2]

[0104] As is clear from the results shown in Table 2, in Examples 2 to 20, the Co substrate or CoOx substrate had a higher contact angle than the SiOx substrate, and it was found that by using an organic substance represented by general formula (1) as the organic substance, an organic film can be selectively deposited on the surface of a metal or metal oxide. On the other hand, in Comparative Examples 1 and 2, which did not use an organic substance or used another organic substance, the contact angles of the Co substrate and the CoOx substrate did not increase. In particular, in Comparative Example 2, the contact angle of the SiOx substrate was higher than that of the CoOx substrate and the Co substrate, which suggests that trimethylsilyldimethylamine was selectively deposited on the SiOx substrate.

[0105] (Elemental composition analysis of the substrate obtained in the example by X-ray photoelectron spectroscopy (XPS)) Of the above-mentioned examples, the elemental composition of the substrate surface was analyzed by X-ray photoelectron spectroscopy (XPS) for the substrates obtained in the examples numbered in Table 3 below. The results are shown in Table 3.

[0106] [Table 3]

[0107] As is clear from the results shown in Table 3, characteristic elements contained in the organic substances used, i.e., in the case of phosphonic acid, a strong peak of the P element was observed on the surface of the Co substrate and CoOx substrate obtained in the examples shown in Table 3, and in the case of thiol, a strong peak of the S element was observed. On the other hand, no peaks of the P element or S element were observed on the surface of the SiOx substrate. Therefore, it is presumed that a film of phosphonic acid or thiol is formed on the Co substrate and the CoOx substrate.

[0108] [Examples 21 to 27] (Evaluation of heat resistance) A substrate on which an organic film was formed on the surface of a CoOx film using the organic materials shown in Table 4 in the same manner as in Example 1 was placed in a quartz tube, and after evacuating the tube with an oil pump for 1 hour, the substrate was heated by heating the quartz tube. Heating was stopped one hour after the substrate temperature reached the specified temperature, and the substrate was cooled for 30 minutes before being removed. The water contact angle of the heated substrate was measured using the method described above in "Measurement of Water Contact Angle." The heating temperature was increased by 50°C from 100°C, and the maximum heating temperature at which the contact angle decreased by 10° or less upon heating was defined as the heat-resistant temperature. Note that when the maximum heating temperature (heat-resistant temperature) was 100°C, the difference between the contact angle of the substrate before heating and the contact angle upon heating to 100°C was 10°C or less, but the contact angle decreased by more than 10°C upon heating to 150°C.

[0109] [Table 4]

[0110] As is clear from Table 4, the organic substances used in Examples 21 to 27 were found to have excellent heat resistance, being less likely to disappear from the substrate due to decomposition or desorption even when heated after being deposited on the substrate. Among these, the substrates on which n-octadecylphosphonic acid used in Example 24 and 2-(perfluorohexyl)ethylphosphonic acid used in Example 25 were deposited were found to have particularly excellent heat resistance, and even when heated to 250°C or higher, the organic substances deposited on the substrate did not decompose and disappear, but remained on the substrate, demonstrating particularly high heat resistance.

[0111] Furthermore, when Examples 22 and 23 are compared, even though the carboxylic acids have the same number of carbon atoms, Example 23, which uses 2-(perfluorohexyl)propanoic acid in which hydrogen atoms are substituted with fluorine atoms, has higher heat resistance. Similarly, when Examples 24 and 25, and Examples 26 and 27 are compared, the heat resistance of phosphonic acid and thiol was also improved by substituting hydrogen atoms with fluorine atoms.

[0112] [Example 28] (Solution preparation) Ethanol (EtOH) was used as the solvent and n-octadecylphosphonic acid was used as the organic substance, and the organic substance was mixed and dissolved to make the concentration 1% by mass to prepare solution A. Furthermore, ethanol (EtOH) was used as the solvent and n-octadecanethiol was used as the organic substance, and the organic substance was mixed and dissolved to make the concentration 1% by mass to prepare solution B. (Surface treatment using a solution containing organic matter) The CoOx-containing substrate, Co-containing substrate, and SiOx-containing substrate prepared by the method described in the "Substrate Preparation" section above were each immersed in Solution A at 22°C for 0.5 hours, and then immersed in IPA twice for 60 seconds. The substrates were then further immersed in Solution B at 22°C for 0.5 hours to perform surface treatment, and organic matter was deposited on the surface of each substrate. The substrates were then immersed in IPA twice for 60 seconds, and dried by spraying nitrogen gas for 60 seconds.

[0113] [Examples 29 to 31] The same procedure as in Example 28 was carried out and evaluation was carried out, except that the type of organic substance, the types of solutions A and B, and the immersion times in solutions A and B were changed as shown in Table 5.

[0114] (Measurement of water contact angle) Approximately 1 μl of pure water was placed on the surface of the substrates in Examples 28 to 31, and the angle (contact angle) between the water droplet and the wafer surface was measured using a contact angle meter (DM-301, manufactured by Kyowa Interface Science Co., Ltd.) The results are shown in Table 5, along with the results of Example 3.

[0115] [Table 5]

[0116] As is clear from the results shown in Table 5, in Examples 28 to 31, the substrates containing Co and the substrates containing CoOx had higher contact angles than the substrates containing SiOx, and it was found that by using two types of solutions containing an organic substance represented by general formula (1) as the organic substance, an organic film can be selectively deposited on the surface of a metal or metal oxide.

[0117] Furthermore, when Example 3 is compared with Examples 28 to 31, when two types of solutions containing organic substances are used, the contact angles of the substrate having Co and the substrate having CoOx after a short treatment time of one hour are almost the same as those in Example 3. Furthermore, when Example 28 is compared with Example 31, the contact angle is higher when the organic substance contained in Solution B has a larger carbon number than the organic substance contained in Solution A.

[0118] [Example 32] (Solution preparation) Ethanol (EtOH) was used as a solvent, and (10-phenyldecyl)phosphonic acid was used as an organic substance, and the organic substance was mixed and dissolved so that the content of the organic substance was 1% by mass to prepare a solution. (Surface treatment using a solution containing organic matter) The CoOx-containing substrate, Co-containing substrate, and SiOx-containing substrate prepared by the method described in the "Substrate Preparation" above were immersed in the above solution for 1 hour at 22°C to perform surface treatment of the substrates, and organic substances were deposited on the surfaces of the substrates. The substrates were then immersed in IPA for 60 seconds twice, and dried by spraying nitrogen gas for 60 seconds.

[0119] (Measurement of water contact angle) Approximately 1 μl of pure water was placed on the surface of the substrate in Example 32, and the angle (contact angle) between the water droplet and the wafer surface was measured using a contact angle meter (DM-301, manufactured by Kyowa Interface Science Co., Ltd.) The results are shown in Table 6 together with the results of Example 3.

[0120] [Examples 33 and 34] The same procedure as in Example 32 was carried out and evaluation was carried out, except that polyethylene glycol methyl ether phosphonic acid-15 of the following formula (12) and polyethylene glycol methyl ether phosphonic acid-11 of the following formula (13) were used as the organic substances. The results are shown in Table 6. CH3-O-(CH2CH2O) 11 -CH2CH2-PO3H2(12) CH3-O-(CH2CH2O) 15 -CH2CH2-PO3H2(13)

[0121] [Table 6]

[0122] As is clear from the results shown in Table 6, in Examples 32 to 34, the substrates containing Co and the substrates containing CoOx had higher contact angles than the substrates containing SiOx, and it was found that by using an organic substance represented by general formula (10) or (11) as the organic substance, an organic film can be selectively deposited on the surface of a metal or metal oxide.

[0123] This application claims priority under the Paris Convention or the laws of countries transitioning to it, based on Japanese Patent Application No. 2021-014552 filed on February 1, 2021. The contents of that application are incorporated herein by reference in their entirety.

Claims

1. a substrate having a structure in which both a first surface region containing a metal element and a second surface region containing a non-metallic inorganic material are exposed, is exposed to a solution containing an organic substance represented by the following general formula (1) and a solvent, and a film of the organic substance is selectively deposited on the first surface region rather than on the second surface region; the solvent is at least one selected from the group consisting of esters, ethers, ketones, sulfoxide solvents, sulfone solvents, lactone solvents, carbonate solvents, alcohol solvents, polyhydric alcohol derivatives, nitrogen-containing solvents, and silicone solvents; the alcohol-based solvent is at least one selected from the group consisting of methanol, ethanol, propanol, pentanol, hexanol, heptanol, octanol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, triethylene glycol, tripropylene glycol, tetraethylene glycol, tetrapropylene glycol, and glycerin; Examples of the derivatives of polyhydric alcohols include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, di ... ethylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tetrapropylene glycol monomethyl ether, butylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, triethylene glycol diethyl ether,Triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol monomethyl ether acetate, tetraethylene glycol monoethyl ether acetate, tetraethylene glycol monobutyl ether acetate, tetraethylene glycol diacetate, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, propylene glycol monomethyl ether acetate (propylene glycol 1-monomethyl ether 2-acetate), propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol dipropylene glycol dimethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, dipropylene glycol diacetate, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol diacetate, tetrapropylene glycol dimethyl ether, tetrapropylene glycol monomethyl ether acetate, tetrapropylene glycol diacetate, butylene glycol dimethyl ether, butylene glycol monomethyl ether acetate, butylene glycol diacetate, glycerin triacetate, 3-methoxybutyl acetate,at least one selected from the group consisting of 3-methyl-3-methoxybutyl acetate and 3-methyl-3-methoxybutyl propionate; By exposing the substrate to the solution, a substrate is obtained in which the contact angle of water on the first surface region is at least 10° greater than that on the second surface region. R １ (X) ｍ (1) (In general formula (1), R １ is a hydrocarbon group having 4 to 100 carbon atoms which may have a heteroatom or a halogen atom, and m hydrogen atoms of the hydrocarbon group are substituted with X. X is -PO ３ (R ２ ) ２ , -O-PO ３ (R ２ ) ２ , -CO ２ R ２ , -SR ２ , or -SSR １ It is. ２ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m is a positive integer, and when r is the number of carbon atoms in the hydrocarbon group, m / r is 0.01 to 0.

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2. The selective film deposition method according to claim 1, wherein the organic substance represented by the general formula (1) includes at least one organic substance selected from the group consisting of the following general formulas (2) to (5): R ３ (PO ３ (R ４ ) ２ ) ｎ (2) (In general formula (2), R ３ is a hydrocarbon group having 4 to 100 carbon atoms which may have a heteroatom or a halogen atom, and n hydrogen atoms of the hydrocarbon group are (PO ３ (R ４ ) ２ ) and n is 1 or 2. R ４ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ４ may be the same or different.) R ５ (O-PO ３ (R ６ ) ２ ) ｎ (3) (In general formula (3), R ５ is a hydrocarbon group having 4 to 100 carbon atoms which may have a heteroatom or a halogen atom, and n hydrogen atoms of the hydrocarbon group are (O-PO ３ (R ６ ) ２ ) and n is 1 or 2. R ６ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ６ may be the same or different.) R ７ (CO) ２ R ８ ) ｎ (4) (In general formula (4), R ７ is a hydrocarbon group having 4 to 100 carbon atoms which may have a heteroatom or a halogen atom, and n hydrogen atoms of the hydrocarbon group are (CO ２ R ８ ) and n is 1 or 2. R ８ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ８ may be the same or different.) R ９ (SR) １０ ) ｎ (5) (In general formula (5), R ９ is a hydrocarbon group having 4 to 100 carbon atoms which may have a heteroatom or a halogen atom, and n hydrogen atoms of the hydrocarbon group are (SR １０ ) and n is 1 or 2. R １０ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or -S-R ９ A plurality of R １０ may be the same or different.)

3. In the general formulas (2) to (5), R ４ , R ６ , R ８ , and R １０ The selective film deposition method according to claim 2, wherein is a hydrogen atom.

4. the metal element is contained as a metal or a metal oxide, 4. The selective film deposition method according to claim 1, wherein the metal is at least one selected from the group consisting of Cu, Co, Ru, Ni, Pt, Al, Ta, Ti, and Hf, and the metal oxide is an oxide of at least one metal selected from the group consisting of Cu, Co, Ru, Ni, Pt, Al, Ta, Ti, and Hf.

5. 5. The selective film deposition method according to claim 1, wherein the non-metallic inorganic material is at least one selected from the group consisting of silicon, silicon oxide, silicon nitride, and silicon oxynitride.

6. 6. The selective film deposition method according to claim 1, wherein the concentration of the organic substance represented by the general formula (1) contained in the solution is 0.01 mass % or more and 20 mass % or less with respect to 100 mass % of the total amount of the solution.

7. 7. The selective film deposition method according to claim 1, wherein the solvent comprises ethanol or isopropyl alcohol.

8. The selective film deposition method according to any one of claims 1 to 7, wherein the organic substance represented by the general formula (1) includes at least one organic substance selected from the group consisting of the following general formulas (6) to (9): R １１ -PO ３ H ２ (6) (In general formula (6), R １１ is a monovalent hydrocarbon group having 6 to 100 carbon atoms which may have a heteroatom or a halogen atom. R １２ -O-PO ３ H ２ (7) (In general formula (7), R １２ is a monovalent hydrocarbon group having 6 to 100 carbon atoms which may have a heteroatom or a halogen atom. R １３ -. ２ H (8) (In general formula (8), R １３ is a monovalent hydrocarbon group having 6 to 100 carbon atoms which may have a heteroatom or a halogen atom. R １４ -SMH (9) (In general formula (9), R １４ is a monovalent hydrocarbon group having 6 to 100 carbon atoms which may have a heteroatom or a halogen atom.

9. 9. The selective film deposition method according to claim 8, wherein the organic substance represented by the general formula (1) includes at least one organic substance represented by the general formula (6) and the general formula (7).

10. The selective film deposition method according to claim 8 , wherein the organic substance represented by the general formula (1) includes an organic substance represented by the general formula (8).

11. 9. The selective film deposition method according to claim 8, wherein the organic substance represented by the general formula (1) includes an organic substance represented by the general formula (9).

12. The R １１ , R １２ , R １３ , and R １４ 12. The selective film deposition method according to claim 8, wherein is a hydrocarbon group in which some or all of the hydrogen atoms have been replaced with fluorine atoms.

13. The R １１ , R １２ , R １３ , and R １４ The selective film deposition method according to any one of claims 8 to 11, wherein is a monovalent organic group represented by the following general formula (10): R １５ -(CH ２ ) ｎ - (10) (In formula (10), R １５ is a hydrogen atom or a monovalent hydrocarbon group which may have a heteroatom or a halogen atom. n is an integer of 2 to 20, and the total number of carbon atoms in formula (10) is 6 to 100.

14. The R １１ , R １２ , R １３ , and R １４ The selective film deposition method according to any one of claims 8 to 11, wherein is a monovalent organic group represented by the following general formula (11): R １６ -O-Y-((CH ２ ) ｐ O) ｑ -Z-(CH ２ ) ｒ - (11) (In formula (11), R １６ is a hydrogen atom, a methyl group, or a phenyl group. Y and Z are each any divalent group or a direct bond. p is an integer of 1 to 4, and q and r are positive integers. The total number of carbon atoms in formula (11) is 6 to 100. The repeating unit (CH ２ ) ｐ O and CH ２ The order of occurrence of is arbitrary in the formula.)

15. The selective film deposition method according to any one of claims 1 to 14, wherein after a film of the organic material represented by the general formula (1) is selectively deposited on the substrate, the substrate is washed with a solvent.

16. The selective film deposition method according to any one of claims 1 to 15, wherein two or more types of solutions are prepared, and the substrate is exposed to each solution in turn.

17. The organic matter contained in the solution to be exposed to the substrate after the second time is １ The number of carbon atoms in the R １ 17. The method of claim 16, wherein the number of carbon atoms is greater than or equal to:

18. A solution used in the selective film deposition method according to any one of claims 1 to 17, characterized in that it comprises an organic substance represented by the following general formula (1) and a solvent: the solvent is at least one selected from the group consisting of esters, ethers, ketones, sulfoxide solvents, sulfone solvents, lactone solvents, carbonate solvents, alcohol solvents, polyhydric alcohol derivatives, nitrogen-containing solvents, and silicone solvents; the alcohol-based solvent is at least one selected from the group consisting of methanol, ethanol, propanol, pentanol, hexanol, heptanol, octanol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, triethylene glycol, tripropylene glycol, tetraethylene glycol, tetrapropylene glycol, and glycerin; Examples of the derivatives of polyhydric alcohols include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, di ... ethylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tetrapropylene glycol monomethyl ether, butylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, triethylene glycol diethyl ether,Triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol monomethyl ether acetate, tetraethylene glycol monoethyl ether acetate, tetraethylene glycol monobutyl ether acetate, tetraethylene glycol diacetate, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, propylene glycol monomethyl ether acetate (propylene glycol 1-monomethyl ether 2-acetate), propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol dipropylene glycol dimethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, dipropylene glycol diacetate, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol diacetate, tetrapropylene glycol dimethyl ether, tetrapropylene glycol monomethyl ether acetate, tetrapropylene glycol diacetate, butylene glycol dimethyl ether, butylene glycol monomethyl ether acetate, butylene glycol diacetate, glycerin triacetate, 3-methoxybutyl acetate,A solution of at least one selected from the group consisting of 3-methyl-3-methoxybutyl acetate and 3-methyl-3-methoxybutyl propionate. R １ (X) ｍ (1) (In general formula (1), R １ is a hydrocarbon group having 4 to 100 carbon atoms which may have a heteroatom or a halogen atom, and m hydrogen atoms of the hydrocarbon group are substituted with X. X is -PO ３ (R ２ ) ２ , -O-PO ３ (R ２ ) ２ , -CO ２ R ２ , -SR ２ , or -SSR １ It is. ２ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m is a positive integer, and when r is the number of carbon atoms in the hydrocarbon group, m / r is 0.01 to 0.

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19. The solvent contains ethanol or isopropyl alcohol, and the concentration of the organic substance represented by the general formula (1) is 0.01% by mass or more and 20% by mass or less with respect to 100% by mass of the total amount of the solution. The solution according to claim 18.

20. An organic substance represented by the following general formula (1), which is used in the selective film deposition method according to any one of claims 1 to 17: R １ (X) ｍ (1) (In general formula (1), R １ is a hydrocarbon group having 4 to 100 carbon atoms which may have a heteroatom or a halogen atom, and m hydrogen atoms of the hydrocarbon group are substituted with X. X is -PO ３ (R ２ ) ２ , -O-PO ３ (R ２ ) ２ , -CO ２ R ２ , -SR ２ , or -SSR １ It is. ２ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m is a positive integer, and when r is the number of carbon atoms in the hydrocarbon group, m / r is 0.01 to 0.25.

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