Pattern formation method, method for manufacturing an electronic device

Abstract

The present invention aims to provide a pattern forming method capable of forming a pattern with excellent limit resolution, and a method for manufacturing an electronic device. The pattern forming method of the present invention comprises: a process 1 of forming a metal resist film on a substrate using a photosensitive or radiation-sensitive resin composition comprising a metal compound having at least one bond selected from the group consisting of a metal-carbon bond and a metal-oxygen bond; a process 2 of exposing the metal resist film to light; and a process 3 of obtaining a pattern by removing unexposed portions by performing a development treatment on the exposed metal resist film using a developer solution containing an organic solvent, wherein after process 3, a process 4 of cleaning the pattern using a rinse solution containing an organic solvent may be further provided, and the developer solution or rinse solution satisfies a predetermined requirement.

Description

Technology Field

[0001] The present invention relates to a pattern forming method and a method for manufacturing an electronic device. Background Technology

[0002] After the resist for the KrF excimer laser (wavelength 248 nm), a pattern formation method using chemical amplification is being used to compensate for the decrease in sensitivity caused by light absorption.

[0003] In order to miniaturize semiconductor devices, the wavelength of the exposure light source and the numerical aperture (high NA) of the projection lens have been increased, and currently, an exposure machine using an ArF excimer laser with a wavelength of 193 nm as a light source is being developed. In addition, recently, pattern formation methods using extreme ultraviolet (EUV) and electron beam (EB) as light sources are also being considered.

[0004] Under these circumstances, a pattern formation method using a photosensitive or radiation-sensitive resin composition containing a metal compound is being proposed.

[0005] Patent Document 1 discloses a method for forming a pattern by exposing a coating layer formed using a resist material containing a metal compound to light, and then developing it with a specific developer. Prior art literature

[0006] Patent Document 1: U.S. Patent Application Publication No. 2020 / 0326627 The problem to be solved

[0007] The inventors have examined the pattern forming method described in Patent Document 1 and have found that when forming a fine pattern, pattern collapse is likely to occur, or that it is difficult to form a fine pattern in the first place. Hereinafter, a pattern obtained that has minimal pattern collapse and is fine is also referred to as having excellent limiting resolution.

[0008] Accordingly, the present invention aims to provide a pattern forming method capable of forming a pattern with excellent limit resolution.

[0009] In addition, the present invention has the objective of providing a method for manufacturing an electronic device using the pattern forming method described above. means of solving the problem

[0010] The inventors, as a result of careful consideration to solve the above problem, found that the above problem can be solved by the following configuration.

[0011] (1) A process 1 for forming a metal resist film on a substrate using a metal compound having at least one bond selected from the group consisting of metal-carbon bonds and metal-oxygen bonds, and a metal resist film on a substrate using a light-sensitive or radiation-sensitive resin composition.

[0012] Process 2 for exposing a metal resist film, and

[0013] A pattern forming method having process 3, which obtains a pattern by removing unexposed portions by performing a developing treatment on an exposed metal resist film using a developer containing an organic solvent,

[0014] After process 3, process 4 may be further provided for cleaning the pattern using a rinse solution containing an organic solvent, and

[0015] If the pattern formation method does not have process 4 after process 3, the developer is a chemical solution containing two or more organic solvents, and

[0016] In the case where the pattern forming method has process 4 after process 3, at least one of the developer and the rinse solution is a chemical solution containing two or more types of organic solvents, and

[0017] A pharmaceutical solution comprising two or more organic solvents, having at least the polarity term δ in the Hansen solubility parameter P and hydrogen bonding term δ H The sum is 9.8 (J / cm²) 3 )0.5 A pattern forming method comprising an organic solvent of less than

[0018] (2) A chemical solution containing two or more organic solvents, having at least a polar term δ in the Hansen solubility parameter P and hydrogen bonding term δ H The sum is 8.0 (J / cm²) 3 ) 0.5 A pattern forming method described in (1) comprising an organic solvent of less than

[0019] (3) A chemical solution containing two or more organic solvents, comprising organic solvent A and organic solvent B,

[0020] The boiling point of organic solvent A is higher than the boiling point of organic solvent B, and

[0021] Polarity term δ in the Hansen solubility parameter of organic solvent A P and hydrogen bonding term δ H The sum is the polar term δ in the Hansen solubility parameter of organic solvent B. P and hydrogen bonding term δ H A pattern forming method described in (1) or (2) that is smaller than the sum of the.

[0022] (4) A pattern forming method described in any one of (1) to (3), wherein the metal compound comprises at least one selected from the group consisting of a compound represented by formula (1) described below, and a compound represented by formula (2) described below and a condensate thereof.

[0023] (5) A pattern forming method described in any one of (1) to (4), wherein the content of the metal compound is 50 mass% or more relative to the total solid content of the composition.

[0024] (6) A method for manufacturing an electronic device comprising a pattern forming method described in any one of (1) to (5). Effects of the invention

[0025] According to the present invention, a pattern forming method capable of forming a pattern with excellent limit resolution can be provided.

[0026] In addition, according to the present invention, a method for manufacturing an electronic device using the pattern forming method can be provided. Specific details for implementing the invention

[0027] The present invention will be described in detail below.

[0028] The constituent requirements described below may be explained in detail based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0029] Unless otherwise specified, monovalent substituents are preferred.

[0030] In this specification, "active light" or "radiation" means, for example, emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam), etc. In this specification, "light" means active light or radiation.

[0031] Unless otherwise specified, the term "exposure" in this specification includes not only exposure by emission spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also drawing by particle beams such as electron beams and ion beams.

[0032] In this specification, "~" is used to mean including the values ​​listed before and after it as lower and upper limits.

[0033] The bonding direction of the divalent groups indicated in this specification is not limited unless specifically explained. For example, in a compound represented by the formula "XYZ", if Y is -COO-, Y may be -CO-O- or -O-CO-. Also, the compound may be "X-CO-OZ" or "XO-CO-Z".

[0034] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0035] In this specification, the term "solid content" refers to a component that forms a metal resist film and does not include solvents (e.g., organic solvents and water). Furthermore, any component that forms a metal resist film is considered a solid content even if its nature is in a liquid phase.

[0036] In this specification, the boiling point is a value under 1 atmosphere (760 mmHg) and means the standard boiling point.

[0037] [Pattern Formation Method]

[0038] The pattern forming method of the present invention comprises: a step 1 of forming a metal resist film on a substrate using a photosensitive or radiation-sensitive resin composition (hereinafter also referred to as a "metal resist composition") comprising a metal compound having at least one bond selected from the group consisting of metal-carbon bonds and metal-oxygen bonds (hereinafter also referred to as a "specific metal compound"); a step 2 of exposing the metal resist film to light; and a step 3 of obtaining a pattern by removing unexposed portions by performing a development treatment on the exposed metal resist film using a developer solution containing an organic solvent, wherein after step 3, the pattern forming method may further comprise a step 4 of cleaning the pattern using a rinse solution containing an organic solvent; if the pattern forming method does not comprise step 4 after step 3, the developer solution is a chemical solution containing two or more organic solvents; and if the pattern forming method comprises step 4 after step 3, at least one of the developer solution and the rinse solution is a chemical solution containing two or more organic solvents, and two or more organic A pharmaceutical solution containing a solvent, at least the polar term δ in the Hansen solubility parameter P and hydrogen bonding term δ H The sum of (hereinafter, "δ P +δ H It is also written as "") 9.8 (J / cm² 3 ) 0.5 Includes organic solvents less than

[0039] The following is a chemical solution comprising two or more organic solvents, wherein at least δ in the Hansen solubility parameter P +δ H 9.8 (J / cm²) 3 ) 0.5 A chemical solution containing an organic solvent less than (in other words, a chemical solution containing two or more organic solvents, wherein at least one of the organic solvents contained in the chemical solution is δ in the Hansen solubility parameter P +δ H 9.8 (J / cm²) 3 ) 0.5A chemical solution that is an organic solvent with less than [amount] is also called a "specific chemical solution."

[0040] Although the mechanism by which the desired effect is obtained by the above pattern forming method is not necessarily clear, the inventors speculate as follows.

[0041] Features of the pattern forming method of the present invention include using a metal resist composition containing a specific metal compound, and using a specific chemical solution in at least one of the developer in process 3 and the rinse solution in process 4.

[0042] When photolithography is performed on the metal resist film in Process 2, at least one bond selected from the group consisting of metal-carbon bonds and metal-oxygen bonds of a specific metal compound is ruptured in the exposed area, and as the specific metal compounds polymerize (crosslink) with respect to the ruptured area, a difference in solubility with respect to an organic solvent (dissolution contrast) is manifested between the exposed and unexposed areas. When a specific chemical solution is applied to at least one of the developer solution in Process 3 and the rinse solution in Process 4, it is presumed that since the specific chemical solution contains multiple organic solvents, it is easy to form solvation with the specific metal compound prior to exposure compared to the polymer derived from the specific metal compound generated by photolithography, and as a result, an effect of excellent dissolution contrast between the exposed and unexposed areas is obtained. Furthermore, the specific chemical solution is at least δ P +δ H 9.8 (J / cm²) 3 ) 0.5 It is presumed that pattern collapse can also be suppressed because it contains an organic solvent of less than 1, which can suppress the penetration of a specific chemical solution into the exposure area in processes 3 and 4. Due to these effects, it is presumed that the limiting resolution is excellent.

[0043] Hereinafter, a higher limit resolution is also referred to as "the effect of the present invention is superior."

[0044] The pattern forming method preferably comprises process 1, process 2, process 3, and optionally process 4 in this order. In addition, the pattern forming method may include other processes described later in addition to processes 1 to 4.

[0045] First, each process in the pattern formation method will be explained in detail below.

[0046] [Process 1 (Metal Resist Film Formation Process)]

[0047] Process 1 is a process of forming a metal resist film using a metal resist composition.

[0048] Methods for forming a metal resist film using a metal resist composition include, for example, applying the metal resist composition onto a substrate or depositing a metal resist component onto a substrate. Additionally, the metal resist composition will be described later.

[0049] As a method for applying a metal resist composition onto a substrate, for example, a method of applying the metal resist composition onto a substrate (e.g., silicon, etc.) used for manufacturing semiconductor devices such as integrated circuits using devices such as a spinner and a coater may be used.

[0050] As for the coating method, spin coating using a spinner is preferred. The rotational speed when performing spin coating is preferably 1,000 to 3,000 rpm.

[0051] A metal resist film may be formed by drying a substrate coated with a metal resist composition.

[0052] As a drying method, for example, a heating method (PreBake) may be used. The heating may be performed using means provided in a known exposure machine and / or a known developer, and a hot plate.

[0053] The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 30 to 800 seconds, and even more preferably 40 to 600 seconds. Heating may be performed once or two or more times.

[0054] The thickness of the metal resist film is preferably 10 to 90 nm, more preferably 10 to 65 nm, and more preferably 15 to 50 nm in order to form a fine pattern with higher precision.

[0055] In addition, an underlayer (e.g., an inorganic film, an organic film, and an anti-reflective film) may be formed between the substrate and the metal resist film.

[0056] The composition for forming the lower limb film preferably includes a known organic material or a known inorganic material.

[0057] The thickness of the lower membrane is preferably 10 to 90 nm, more preferably 10 to 50 nm, and more preferably 10 to 30 nm.

[0058] Examples of compositions for forming a lower membrane include AL412 (manufactured by Brewer Science) and the SHB series (e.g., SHB-A940, manufactured by Shin-Etsu Kagaku High School).

[0059] A top coat may be formed on the side opposite to the substrate of the metal resist film using a top coat composition.

[0060] It is preferable that the top coat composition be applied uniformly to the side opposite to the substrate of the metal resist film without mixing with the metal resist film.

[0061] The top coat composition preferably includes a resin, an additive, and an organic solvent.

[0062] As for a method of forming a top coat, for example, a known method of forming a top coat can be cited, and specifically, a method of forming a top coat described in paragraphs

[0072] to

[0082] of Japanese Patent Publication No. 2014-059543 can be cited.

[0063] As a method for forming a top coat, it is preferable to form a top coat containing a basic compound described in Japanese Patent Publication No. 2013-061648 on the side opposite to the substrate of the metal resist film. Examples of the basic compound include, for instance, the basic compound described in International Publication No. 2017 / 002737.

[0064] In addition, the top coat may also comprise a compound having at least one selected from the group consisting of -O-, -S-, hydroxyl groups, thiol groups, -CO-, and -COO-.

[0065] [Process 2 (Photolithography)]

[0066] Process 2 is a process of exposing a metal resist film. The exposure is performed in a pattern.

[0067] Process 2 is preferably a process of exposing a pattern through a photomask.

[0068] As for the photomask, for example, a known photomask can be used. Additionally, the photomask may be in contact with a metal resist film.

[0069] Examples of exposure light for exposing a metal resist film include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams.

[0070] The wavelength of the exposure light is preferably 250 nm or less, more preferably 220 nm or less, and more preferably 1 to 200 nm. Specifically, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), X-rays, EUV (wavelength 13 nm), or electron beams are preferred, a KrF excimer laser, an ArF excimer laser, EUV, or electron beams are more preferred, and EUV or electron beams are more preferred.

[0071] The exposure amount is not particularly limited as long as it is an amount that reduces the solubility of the exposed metal resist film in a developer containing an organic solvent.

[0072] The exposure method of process 2 may be immersion exposure.

[0073] Process 2 may be performed once or two or more times.

[0074] [Process 3 (Development Process)]

[0075] Process 3 is a process of performing a development treatment on an exposed metal resist film using a developer containing an organic solvent. By performing the development treatment, unexposed areas in the exposed metal resist film are removed, and a pattern is formed.

[0076] If the pattern forming method does not have the following process 4, and if it has the following process 4 and the rinse solution used in process 4 is a chemical solution other than a specific chemical solution, then in process 3, the specific chemical solution is used as the developer.

[0077] Meanwhile, the pattern forming method has process 4 described below, and in addition, if the rinse solution used in process 4 is a specific chemical solution, the developer solution used in process 3 may be a specific chemical solution or any other chemical solution.

[0078] In addition, specific medications and other medications will be described later.

[0079] Development Method

[0080] As for methods of occurrence, for example, known methods of occurrence can be cited.

[0081] Specifically, examples include a method of immersing an exposed metal resist film in a tank filled with a developer solution for a certain period of time (dip method), a method of developing by raising the developer solution on the surface of the exposed metal resist film by surface tension and stopping for a certain period of time (puddle method), a method of spraying the developer solution onto the surface of the exposed metal resist film (spray method), and a method of continuously dispensing the developer solution while scanning a nozzle that dispenses the developer solution at a certain speed onto a substrate having an exposed metal resist film that is rotating at a certain speed (dynamic dispensing method).

[0082] In addition, after the development process, a process to stop the development may be carried out using a solvent other than the developer.

[0083] The development time is preferably 10 to 300 seconds, and more preferably 20 to 120 seconds.

[0084] The temperature of the developer solution during development is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0085] [Process 4 (Rinse Process)]

[0086] Process 4 is a process of cleaning the pattern obtained by Process 3 (development process) using a rinse solution containing an organic solvent.

[0087] Rinse Method

[0088] As for the rinsing method, for example, the same method as the developing method in process 3 above (e.g., dip method, puddle method, spray method, and dynamic dispensing method, etc.) can be cited.

[0089] The processing time is preferably 10 to 300 seconds, and more preferably 10 to 120 seconds.

[0090] The temperature of the rinse solution is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0091] [Other processes]

[0092] The pattern forming method may further include other processes other than the above processes 1 to 4.

[0093] Other processes include, for example, a baking process after exposure, a post-baking process, an etching process, and a purification process.

[0094] Post-exposure baking process

[0095] It is preferable that the pattern formation method includes a Post Exposure Bake (PEB) process after performing Process 2 (exposure process) and before performing Process 3 (development process).

[0096] The heating temperature of the bake after exposure is preferably 80 to 200°C, more preferably 80 to 180°C, and more preferably 80 to 150°C. The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and more preferably 30 to 120 seconds.

[0097] Baking after exposure may be performed using means provided in a known exposure machine and / or developer, and a hot plate. In addition, baking after exposure may be performed once or two or more times.

[0098] Post-bake process

[0099] The pattern forming method preferably includes a process for heating the pattern (post-bake process) after process 4 (rinse process). By the post-bake (PB) process, the developer and rinse solution remaining between and inside the pattern can be removed, and the surface roughness of the pattern can be improved.

[0100] In the post-baking process, the heating temperature is preferably 40 to 250°C, and more preferably 80 to 200°C.

[0101] The heating time in the post-baking process is preferably 10 to 180 seconds, and more preferably 30 to 120 seconds.

[0102] <Etching Process>

[0103] The pattern forming method may include an etching process that etches a substrate using the formed pattern as a mask.

[0104] As for the etching method, known etching methods can be cited, for example. Specifically, the method described in Proc. of SPIE Vol. 6924, 692420 (2008), "Chapter 4 Etching" of "Semiconductor Process Manual, 4th Edition, 2007, Publisher: SEMI Japan" and Japanese Patent Publication No. 2009-267112 can be cited.

[0105] <Refining Process>

[0106] The pattern forming method may have a purification process for purifying the metal resist composition, developer, rinse solution, and / or other various components (e.g., a composition for forming a substrate film and a composition for forming a top coat, etc.) used in the pattern forming method.

[0107] As for purification methods, known purification methods may be cited, and methods using a filter or using an adsorbent are preferred.

[0108] The pore diameter of the filter is often 1 μm or less, preferably 500 nm or less, more preferably less than 100 nm, more preferably 10 nm or less, and particularly preferably 5 nm or less. The lower limit is often 0.01 nm or more.

[0109] The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. The filter may be composed of a composite material combining the filter material and an ion exchange medium. The filter may be a filter that has been pre-cleaned with an organic solvent.

[0110] In the method of filtration using filters, multiple types of filters may be connected in series or in parallel. When using multiple types of filters, filters with different hole diameters and / or materials may be combined. In addition, the material to be purified may be filtered once or two or more times. In the case of filtering two or more times, filtration may be performed while circulating.

[0111] The method of using the adsorbent may involve using only the adsorbent, or using a combination of the filter and the adsorbent.

[0112] Examples of adsorbents include known adsorbents, specifically inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

[0113] In the preparation of a metal resist composition, for example, it is preferable to dissolve various components, such as specific metal compounds that may be included in the metal resist composition, in an organic solvent and then filter them while circulating them using multiple filters of different materials. Specifically, a polyethylene filter with a pore diameter of 50 nm, a nylon filter with a pore diameter of 10 nm, and a polyethylene filter with a pore diameter of 3 nm may be connected in this sequence and filtered 10 or more times.

[0114] It is preferable that the metal resist composition be filtered using a filter and then filled into a clean container. From the perspective of suppressing deterioration over time, it is more preferable that the metal resist composition filled into the container be refrigerated.

[0115] Liquids containing organic solvents, such as developing solution and rinsing solution, may contain a conductive compound in order to prevent failure of chemical piping and various parts (e.g., filters, O-rings, tubes, etc.) associated with electrostatic charging and electrostatic discharge.

[0116] Examples of conductive compounds include methanol. In terms of maintaining developing performance or rinsing performance, the content of the conductive compound in the developer solution is preferably 10 mass% or less with respect to the total mass of the developer solution, or the content of the conductive compound in the rinsing solution is preferably 5 mass% or less with respect to the total mass of the rinsing solution. The lower limit is often 0.01 mass% or more.

[0117] [Specific medicine solution]

[0118] A specific drug solution is a drug solution comprising two or more organic solvents, and at least δ in the Hansen solubility parameter P +δ H 9.8 (J / cm²) 3 ) 0.5 Includes organic solvents less than

[0119] In other words, the specific chemical solution is a chemical solution comprising two or more organic solvents, and δ in the Hansen solubility parameter of at least one organic solvent among the organic solvents comprising the specific chemical solution P +δ H a, 9.8 (J / cm²) 3 ) 0.5 It is a drug solution with a value less than δ in the Hansen solubility parameter. In addition, for a specific drug solution, δ in the Hansen solubility parameter P +δ H 9.8 (J / cm²) 3 ) 0.5 If it contains an organic solvent less than (hereinafter also referred to as "organic solvent X"), δ in the Hansen solubility parameter P +δ H 9.8 (J / cm²) 3 ) 0.5 It may contain an organic solvent of the above degree (hereinafter also referred to as "organic solvent Y").

[0120] A suitable embodiment of a specific drug solution is a drug solution comprising two or more organic solvents, wherein at least δ in the Hansen solubility parameter P +δ H 8.0 (J / cm²)3 ) 0.5 An embodiment comprising an organic solvent of less than δ is preferred, and the drug solution comprises two or more organic solvents, and at least δ in the Hansen solubility parameter P +δ H 5.0 (J / cm²) 3 ) 0.5 An embodiment including an organic solvent as described below is more preferable.

[0121] δ in the above Hansen solubility parameter P +δ H The lower limit of is not specifically restricted, but 0 (J / cm²) 3 ) 0.5 Ideally, this is desirable.

[0122] In addition, another suitable embodiment of a specific chemical solution is a chemical solution containing two or more organic solvents, and an embodiment containing organic solvent X described later and organic solvent Y described later is also preferred.

[0123] In this specification, the Hansen solubility parameter refers to the Hansen solubility parameter described in "Hansen Solubility Parameters: A Users Handbook, Second Edition" (pp. 1-310, CRC Press, 2007). That is, the Hansen solubility parameter represents solubility as a multidimensional vector (variance term: δ D , polar term: δ P and hydrogen bonding term: δ H It is represented as ), and their three parameters also represent the coordinates of a point in a three-dimensional space called Hansen space. In addition, the unit of each term of the Hansen solubility parameter is (J / cm²). 3 ) 0.5 am.

[0124] Therefore, δ P +δ H is the polar term (δ in the Hansen solubility parameter). P ) and hydrogen bonding term (δ H It is the sum of ).

[0125] δ in the Hansen solubility parameter of organic solvent X P +δ H is 9.8 (J / cm²) 3 ) 0.5 Less than 8.0 (J / cm²) 3 ) 0.5 Less than is desirable, and 5.0 (J / cm²) 3 ) 0.5 The following is more preferable, and 1.0 (J / cm²) 3 ) 0.5 The following is more desirable. The lower limit is 0 (J / cm²). 3 ) 0.5 Ideally, this is desirable.

[0126] δ in the Hansen solubility parameter of organic solvent X D is 0.0~30.0(J / cm²) 3 ) 0.5 It is desirable to have 10.0~20.0 (J / cm²). 3 ) 0.5 It is more desirable.

[0127] δ in the Hansen solubility parameter of organic solvent X P is 0.0~9.0 (J / cm²) 3 ) 0.5 It is desirable to have 0.0~4.0 (J / cm²). 3 ) 0.5 is more desirable, and 0.0~2.0 (J / cm²) 3 ) 0.5 It is more desirable, and 0.0~1.0 (J / cm²) 3 ) 0.5 It is particularly desirable.

[0128] δ in the Hansen solubility parameter of organic solvent X H is 0.0~9.0 (J / cm²) 3 ) 0.5 It is desirable, and 0.0~5.5 (J / cm²) 3 ) 0.5 is more desirable, and 0.0~2.0 (J / cm²) 3 ) 0.5 It is more desirable, and 0.0~1.0 (J / cm²) 3 ) 0.5It is particularly desirable.

[0129] The boiling point of organic solvent X is preferably 100°C or higher, and more preferably 150°C or higher. The upper limit is often 260°C or lower, and preferably 220°C or lower.

[0130] δ in the Hansen solubility parameter of organic solvent Y P +δ H is 9.8 (J / cm²) 3 ) 0.5 That is all. The upper limit is 30.0 (J / cm²). 3 ) 0.5 The following is preferable, and 20.0 (J / cm²) 3 ) 0.5 The following is more desirable.

[0131] δ in the Hansen solubility parameter of organic solvent Y D is 0.0~30.0(J / cm²) 3 ) 0.5 It is desirable to have 10.0~20.0 (J / cm²). 3 ) 0.5 It is more desirable.

[0132] δ in the Hansen solubility parameter of organic solvent Y P is 0.0~20.0(J / cm²) 3 ) 0.5 It is desirable to have 0.0~10.0 (J / cm²). 3 ) 0.5 It is more desirable.

[0133] δ in the Hansen solubility parameter of organic solvent Y H is 0.0~20.0(J / cm²) 3 ) 0.5 It is desirable to have 3.0~15.0 (J / cm²). 3 ) 0.5 It is more desirable.

[0134] The boiling point of organic solvent Y is preferably 100°C or higher, and more preferably 110°C or higher. The upper limit is often 260°C or lower, and preferably 200°C or lower.

[0135] Certain chemical solutions may be a mixture of an organic solvent and water.

[0136] The water content is preferably less than 50 mass% with respect to the total mass of the specific liquid, more preferably less than 20 mass%, more preferably less than 10 mass%, and particularly preferably not substantially water-free (e.g., less than 1 mass%).

[0137] The content of the organic solvent in the specific drug solution is preferably 50 to 100 mass% with respect to the total mass of the specific drug solution, more preferably 80 to 100 mass%, more preferably 90 to 100 mass%, and particularly preferably 95 to 100 mass%.

[0138] The content of organic solvent X in a specific drug solution is preferably 1 to 80 mass% with respect to the total mass of the specific drug solution, more preferably 1 to 50 mass%, and more preferably 5 to 30 mass%.

[0139] The content of organic solvent Y in a specific drug solution is preferably 20 to 99 mass% with respect to the total mass of the specific drug solution, more preferably 50 to 99 mass%, and more preferably 70 to 95 mass%.

[0140] The organic solvent included in the specific chemical solution is preferably at least one selected from the group consisting of ester-based solvents, hydrocarbon-based solvents, alcohol-based solvents, ether-based solvents, ketone-based solvents, and amide-based solvents, and more preferably at least one selected from the group consisting of ester-based solvents, hydrocarbon-based solvents, alcohol-based solvents, ether-based solvents, ketone-based solvents, and amide-based solvents.

[0141] In addition, at least one of the organic solvents included in the specific chemical solution is preferably an ester-based solvent, a hydrocarbon-based solvent, an alcohol-based solvent, an ether-based solvent, or a ketone-based solvent, and the organic solvent included in the specific chemical solution is more preferably an ester-based solvent, an alcohol-based solvent, an ether-based solvent, or a ketone-based solvent, and a hydrocarbon-based solvent.

[0142] A specific chemical solution comprises organic solvent A and organic solvent B, wherein the boiling point of organic solvent A is higher than the boiling point of organic solvent B, and δ in the Hansen solubility parameter of organic solvent A P +δ H a. δ in the Hansen solubility parameter of organic solvent B H +δ P It is preferable to be smaller.

[0143] In other words, regarding the specific chemical solution having a more superior effect of the present invention, among two types of organic solvents arbitrarily selected, the boiling point of one organic solvent is higher than the boiling point of the other organic solvent, and furthermore, the δ of the one organic solvent P +δ H a, δ in the Hansen solubility parameter of the organic solvent of the other party mentioned above P +δ H It is desirable for it to be lower.

[0144] Among organic solvents A and B, the one with a lower content has a higher boiling point, and also, regarding the Hansen solubility parameter δ P +δ H It is more desirable for it to be smaller.

[0145] <Specific examples of ester-based solvents, hydrocarbon-based solvents, alcohol-based solvents, ether-based solvents and ketone-based solvents>

[0146] Hereinafter, specific examples of ester-based solvents, hydrocarbon-based solvents, alcohol-based solvents, ether-based solvents, ketone-based solvents, and amide-based solvents that can be suitably used as organic solvents included in specific chemical solutions will be described in detail.

[0147] (Ester-based solvent)

[0148] The carbon number of the ester-based solvent is preferably 2 to 12, and more preferably 5 to 10.

[0149] The ester-based solvent has heteroatoms. For example, oxygen atoms may be cited as the heteroatoms, and it is preferable that the ester-based solvent has only oxygen atoms as heteroatoms.

[0150] The number of heteroatoms in the ester-based solvent is preferably 2 to 6, more preferably 2 to 3, and more preferably 2. In addition, the ester-based solvent may have one or more -COO- groups, and it is preferable to have only one -COO- group.

[0151] As ester-based solvents, for example, methyl acetate, butyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, hexyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 1-methoxy-2-propyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butanoate, 2-methyl hydroxyisobutyrate, isoamyl butyrate, Examples include isobutyl isobutyrate, ethyl propionate, propyl propionate, butyl propionate, and isobutyl propionate.

[0152] The ester-based solvent is preferably propyl acetate, butyl acetate, hexyl acetate, PGMEA, ethyl lactate, isoamyl butyrate, ethyl propionate, propyl propionate, butyl propionate, or isobutyl propionate.

[0153] The boiling point of the ester-based solvent is preferably 100 to 200°C, more preferably 120 to 200°C, and more preferably 120 to 180°C.

[0154] (Hydrocarbon solvent)

[0155] Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. The aliphatic hydrocarbon solvent may be a saturated aliphatic hydrocarbon solvent or an unsaturated aliphatic hydrocarbon solvent, and a saturated aliphatic hydrocarbon solvent is preferred.

[0156] The carbon number of the hydrocarbon solvent is preferably 3 to 20, more preferably 8 to 12, and more preferably 9 to 11.

[0157] Aliphatic hydrocarbon solvents may be straight-chain, branched-chain, or cyclic, and straight-chain is preferred. Aromatic hydrocarbon solvents may be either monocyclic or polycyclic.

[0158] Examples of hydrocarbon solvents include saturated aliphatic hydrocarbon solvents such as pentane, hexane, octane, nonene, decaine, undecane, dodecane, hexadecane, 2,2,4-trimethylpentane and 2,2,3-trimethylhexane; and aromatic hydrocarbon solvents such as mesitylene, cumene, pseudocumene, 1,2,4,5-tetramethylbenzene, p-cymene, toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene and dipropylbenzene.

[0159] The hydrocarbon solvent is preferably a saturated aliphatic hydrocarbon solvent, more preferably at least one selected from the group consisting of octane, nonene, decane, undecane, and dodecane, and more preferably at least one selected from the group consisting of nonene, decane, and undecane.

[0160] The boiling point of the hydrocarbon solvent is preferably 100 to 260°C, more preferably 120 to 240°C, more preferably 125 to 220°C, and particularly preferably 140 to 220°C.

[0161] (Ketone solvents)

[0162] The carbon number of the ketone solvent is preferably 3 to 20, more preferably 3 to 15, and even more preferably 3 to 12.

[0163] Examples of ketone-based solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetone monoacetone, ionone, diacetone monoalcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, isophorone, and propylene carbonate.

[0164] Ketone solvents are preferably cyclohexanone, 2-heptanone, or diisobutylketone.

[0165] The boiling point of the ketone-based solvent is preferably 100 to 200°C, more preferably 120 to 180°C, and even more preferably 150 to 180°C.

[0166] (Alcohol-based solvent)

[0167] Examples of alcohol-based solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol, and 4-methyl-2-pentanol is preferred.

[0168] The boiling point of the alcohol-based solvent is preferably 80 to 180°C, more preferably 80 to 160°C, and more preferably 80 to 150°C.

[0169] (Ether-based solvents)

[0170] Examples of ether-based solvents include dioxane, tetrahydrofuran, and diisobutyl ether, and diisobutyl ether is preferred.

[0171] The boiling point of the ether-based solvent is preferably 100 to 180°C, more preferably 100 to 160°C, and more preferably 100 to 140°C.

[0172] (Amid-based solvents)

[0173] Examples of amide solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphorictriamide, and 1,3-dimethyl-2-imidazolidinone.

[0174] The boiling point of the amide solvent is preferably 140 to 250°C, and more preferably 150 to 230°C.

[0175] <An example of a suitable mode of composition of an organic solvent in a specific chemical solution>

[0176] Below is an example of a suitable mode of composition of an organic solvent in a specific chemical solution.

[0177] (Mode 1)

[0178] A specific chemical solution comprises at least a first organic solvent and a second organic solvent, and

[0179] δ in the Hansen solubility parameter of at least one of the first organic solvent and the second organic solvent P +δ H a, 9.8 (J / cm²) 3 ) 0.5 Less than,

[0180] The second organic solvent is an organic solvent selected from the group consisting of hydrocarbon solvents, ester solvents, alcohol solvents, ether solvents, and ketone solvents (provided that the ester solvent in the second organic solvent is of a different type from the ester solvent of the first organic solvent), and

[0181] The content of the first organic solvent is 40 mass% or more (preferably 50 mass% or more, more preferably 60 mass% or more) with respect to the total content of the first organic solvent and the second organic solvent. The upper limit is preferably 95 mass% or less, and more preferably 90 mass% or less.

[0182] (Mode 2)

[0183] A specific chemical solution comprises at least a first organic solvent and a second organic solvent, and

[0184] δ in the Hansen solubility parameter of at least one of the first organic solvent and the second organic solvent P +δ H a, 9.8 (J / cm²) 3 ) 0.5 Less than,

[0185] The first organic solvent is a hydrocarbon-based solvent, and

[0186] The second organic solvent is an organic solvent selected from the group consisting of hydrocarbon solvents, ester solvents, alcohol solvents, ether solvents, and ketone solvents (provided that the hydrocarbon solvent in the second organic solvent is of a different type from the hydrocarbon solvent of the first organic solvent), and

[0187] The content of the first organic solvent is 30 mass% or less (preferably 20 mass% or less) with respect to the total content of the first organic solvent and the second organic solvent. The lower limit is preferably 10 mass% or more, and more preferably 15 mass% or more.

[0188] (Mode 3)

[0189] A specific chemical solution comprises at least a first organic solvent and a second organic solvent, and

[0190] δ in the Hansen solubility parameter of at least one of the first organic solvent and the second organic solvent P +δ H a, 9.8 (J / cm²) 3 ) 0.5 Less than,

[0191] The first organic solvent is a ketone-based solvent, and

[0192] The second organic solvent is an organic solvent selected from the group consisting of alcohol-based solvents and ketone-based solvents (provided that the ketone-based solvent in the second organic solvent is of a different type from the ketone-based solvent of the first organic solvent), and

[0193] The content of the first organic solvent is 30 to 70 mass% (preferably 40 to 60 mass%) with respect to the total content of the first organic solvent and the second organic solvent.

[0194] (Mode 4)

[0195] A specific chemical solution comprises at least a first organic solvent and a second organic solvent, and

[0196] δ in the Hansen solubility parameter of at least one of the first organic solvent and the second organic solvent P +δ H a, 9.8 (J / cm²) 3 ) 0.5 Less than,

[0197] The first organic solvent is an ester-based solvent, and

[0198] The second organic solvent is a hydrocarbon-based solvent, and

[0199] The mass ratio of the content of the first organic solvent to the content of the second organic solvent (content of the first organic solvent / content of the second organic solvent) is 1 to 50 (preferably 3 to 20, more preferably 6 to 15).

[0200] In the above embodiments 1 to 4, the total content of the first organic solvent and the second organic solvent is preferably 80 to 100 mass% with respect to the total content of the organic solvent in the specific chemical solution, more preferably 90 to 100 mass%, and more preferably 95 to 100 mass%. In addition, if the specific chemical solution includes other organic solvents other than the first organic solvent and the second organic solvent, other known organic solvents other than those mentioned above may be used as the other organic solvents.

[0201] In the above embodiments 1 to 4, δ in the boiling point and Hansen solubility parameter of the first organic solvent and the second organic solvent P +δ H In terms of the relationship, one of the first organic solvent and the second organic solvent has a higher boiling point than the other organic solvent, and also, δ in the Hansen solubility parameter P +δ H It is desirable that α is small. Among the first organic solvent and the second organic solvent, the one with a lower content has a higher boiling point, and also δ in the Hansen solubility parameter P +δ H It is more desirable for it to be smaller.

[0202] In addition, in the above embodiments 1 to 4, the boiling points of the first organic solvent and the second organic solvent are both preferably 100°C or higher, and more preferably 120°C or higher.

[0203] In addition, it is preferable that the specific chemical solution substantially does not contain an organic solvent containing 50 mass% or more of fluorine atoms. "Substantially not containing" means that the content of the organic solvent containing 50 mass% or more of fluorine atoms is 5 mass% or less with respect to the total mass of the specific chemical solution, and 3 mass% or less is preferable, 1 mass% or less is more preferable, and 0 mass% is more preferable.

[0204] <Acid component>

[0205] Certain medicinal solutions may contain acidic components.

[0206] The acidic component may exist as an ion after ionization in the drug solution.

[0207] As for the acid component, it is preferable to have at least one type consisting of a group selected from organic acids or inorganic acids.

[0208] Examples of organic acids include the organic acids described below.

[0209] Examples of inorganic acids include boric acid, nitric acid, sulfuric acid, phosphoric acid, and hydrochloric acid.

[0210] (Organic acid)

[0211] It is preferable that the treatment solution contains organic acids.

[0212] Organic acids may be dissociated in the treatment solution or may form salts.

[0213] The content of organic acid is 1.00 mass% or more with respect to the total mass of the treatment solution, and 3.00 mass% or more is preferable and 5.00 mass% or more is more preferable in terms of superior pattern resolution.

[0214] The content of organic acid is less than 40.00 mass% with respect to the total mass of the treatment solution, and less than 30.00 mass% is more preferable and less than 20.00 mass% is more preferable in terms of superior pattern resolution.

[0215] Examples of organic acids include carboxylic acid-based organic acids such as aliphatic carboxylic acid-based organic acids and aromatic carboxylic acid-based organic acids, and phosphonic acid-based organic acids; carboxylic acid-based organic acids are preferred, and monocarboxylic acids are more preferred.

[0216] Carboxylic acid organic acids are compounds having one or more carboxyl groups.

[0217] Carboxylic acid-based organic acids may have additional hydroxyl groups in addition to carboxyl groups.

[0218] The number of carboxyl groups in a carboxylic acid-based organic acid is preferably 1 to 10, more preferably 1 to 5, and more preferably 1.

[0219] Examples of aliphatic carboxylic acid organic acids include acetic acid, formic acid, propionic acid, butyric acid, glycolic acid, lactic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimetic acid, sebacic acid, maleic acid, malic acid, citric acid, tartaric acid, and gluconic acid.

[0220] Examples of aromatic carboxylic acid-based organic acids include phthalic acid, isophthalic acid, terephthalic acid, gallic acid, trimellitic acid, melittic acid, and cinnamic acid.

[0221] Examples of phosphonic acid-based organic acids include compounds described in paragraphs

[0026] to

[0036] of International Publication No. 2018 / 020878 and compounds described in paragraphs

[0031] to

[0046] of International Publication No. 2018 / 030006, the contents of which are incorporated herein by reference.

[0222] It is preferable that the organic acid comprises at least one organic acid selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, and lactic acid.

[0223] Organic acids may be used alone or in combination with inorganic acids.

[0224] Other ingredients

[0225] Certain medicinal solutions may contain components other than organic solvents and acidic components.

[0226] Other ingredients include, for example, known surfactants.

[0227] The content of the surfactant is preferably 0.001 to 5 mass% with respect to the total mass of the specific drug solution, more preferably 0.005 to 2 mass%, and even more preferably 0.01 to 0.5 mass%.

[0228] [Other medicines]

[0229] As described above, when the pattern forming method has process 4, a specific chemical solution is used in at least one of the developer solution of process 3 and the rinsing solution of process 4. A specific chemical solution may be used in either the developer solution of process 3 or the rinsing solution of process 4, or a specific chemical solution may be used in one of the developer solution of process 3 and the rinsing solution of process 4, and other chemical solutions may be used in the other.

[0230] Other chemical solutions are chemical solutions other than specific chemical solutions, and known developing solutions and rinsing solutions may be applied.

[0231] Other organic solvents included in the chemical solution include, for example, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents that may be included in the organic solvent of the specific chemical solution.

[0232] Other chemical solutions may be a mixture of an organic solvent and water.

[0233] Other medicinal solutions may contain other ingredients other than the above ingredients.

[0234] Other ingredients may include, for example, known organic solvents other than those mentioned above and known surfactants.

[0235] [Metal Resist Composition]

[0236] The metal resist composition used in Process 1 is described below.

[0237] Specific metal compounds

[0238] The metal resist composition includes a specific metal compound.

[0239] A specific metal compound is a metal compound having at least one bond selected from the group consisting of metal-carbon bonds (MC) and metal-oxygen bonds (MO). M represents a metal atom.

[0240] A metal-carbon bond refers to a state in which at least one metal atom and at least one carbon atom in a specific metal compound are bonded by a covalent bond, a coordinate bond, an ionic bond, a van der Waals bond, etc. In the case of bonding by the above covalent bond, the covalent bond may be any of a single bond, a double bond, or a triple bond. Furthermore, a metal-oxygen bond refers to a state in which at least one metal atom and at least one oxygen atom in a specific metal compound are bonded by a covalent bond, a coordinate bond, an ionic bond, a van der Waals bond, etc. In the case of bonding by the above covalent bond, the covalent bond may be any of a single bond or a double bond.

[0241] In addition, if a specific metal compound has a metal-carbon bond, that specific metal compound is a so-called organometallic compound.

[0242] The number of bonds selected from the above group having a specific metal compound is preferably 2 or more, and more preferably 3 or more. The upper limit is preferably 10 or less, and more preferably 5 or less.

[0243] As metal atoms constituting a specific metal compound, examples include metal atoms of groups 3 to 16 of the periodic table, and tin, antimony, tellurium, indium, hafnium, tantalum, tungsten, bismuth, titanium, cobalt, nickel, zirconium, or palladium are preferred, and tin is more preferred.

[0244] In addition, in this specification, silicon atoms are included in metal atoms.

[0245] Examples of specific metal compounds include compounds represented by formula (1).

[0246] [Chemical Formula 1]

[0247]

[0248] In Equation (1), M represents a metal atom. R 1 R represents an alkyl group that may have substituents, an aliphatic unsaturated hydrocarbon group that may have substituents, or an aryl group that may have substituents. 2 ne, -OCOR r1 or -OR r2 It represents. R r1 It represents silver, a hydrogen atom, an alkyl group that may have substituents, an aliphatic unsaturated hydrocarbon group that may have substituents, or an aryl group that may have substituents. R r2 represents an alkyl group that may have a substituent, an aliphatic unsaturated hydrocarbon group that may have a substituent, or an aryl group that may have a substituent. n1+m1 represents the valence of the metal atom represented by M.

[0249] In equation (1), M represents a metal atom.

[0250] M may be a metal atom constituting the specific metal compound, and is preferably tin, antimony, tellurium, indium, hafnium, tantalum, tungsten, bismuth, titanium, cobalt, nickel, zirconium, or palladium, and is more preferably tin.

[0251] In Equation (1), R 1 It represents an alkyl group that may have a substituent, an aliphatic unsaturated hydrocarbon group that may have a substituent, or an aryl group that may have a substituent.

[0252] The above alkyl group may be any of a straight chain, a branched chain, or a cyclic group.

[0253] The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 16, and even more preferably 1 to 5. R 1 In the case where the alkyl group represented by is an alkyl group having a substituent, the number of carbons includes the number of carbons of the substituent.

[0254] Examples of the above alkyl groups include methyl, ethyl, propyl, and butyl groups.

[0255] Examples of substituents that the above alkyl group may have include halogen atoms, hydroxyl groups, cyano groups, nitro groups, amino groups, and aromatic groups. A phenyl group is preferred as the aromatic group. A benzyl group is preferred as the alkyl group having a phenyl group.

[0256] The above-mentioned aliphatic unsaturated hydrocarbon group is an aliphatic hydrocarbon group having an unsaturated group within it.

[0257] Examples of unsaturated groups include double and triple bonds.

[0258] The above aliphatic unsaturated hydrocarbon group may be any of a straight chain, a branched chain, or a cyclic form.

[0259] The number of carbon atoms in the above aliphatic unsaturated hydrocarbon group is preferably 2 to 30, more preferably 2 to 16, and even more preferably 2 to 5. R 1 In the case where the aliphatic unsaturated hydrocarbon group represented by is an aliphatic unsaturated hydrocarbon group having a substituent, the number of carbons includes the number of carbons of the substituent.

[0260] Examples of the above-mentioned aliphatic unsaturated hydrocarbon groups include, for instance, a vinyl group, an ethyne group, an allyl group, a 1-propene group, a 1-methyl-1-propene group, a 2-propene group, a 2-methyl-2-propene group, a 1-propane group, a 1-methyl-1-propane group, a 2-propane group, a 2-methyl-2-propane group, a 1-butene group, a 2-butene group, a 3-butene group, a 1-butyne group, a 2-butyne group, and a 3-butyne group, and a vinyl group or an allyl group is preferred.

[0261] Examples of substituents that the above-mentioned aliphatic unsaturated hydrocarbon group may have include halogen atoms, hydroxyl groups, cyano groups, nitro groups, amino groups, and aromatic groups.

[0262] The above aryl group may be either a monocyclic or polycyclic group.

[0263] The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 12, and even more preferably 6 to 8. R 1 In the case where the aryl group represented by is an aryl group having a substituent, the number of carbon atoms is a number that includes the number of carbon atoms of the substituent.

[0264] Examples of the above aryl groups include phenyl groups, naphthyl groups, anthryl groups, pyreneyl groups, phenanthrenyl groups, methylphenyl groups, dimethylphenyl groups, biphenyl groups, and fluorenyl groups, and phenyl groups or naphthyl groups are preferred.

[0265] Examples of substituents that the above aryl group may have include alkyl groups, halogen atoms, hydroxyl groups, cyano groups, nitro groups, amino groups, and aromatic groups.

[0266] In Equation (1), R 2 ne, -OCOR r1 or -OR r2 It represents. R r1 It represents silver, a hydrogen atom, an alkyl group that may have substituents, an aliphatic unsaturated hydrocarbon group that may have substituents, or an aryl group that may have substituents. R r2 represents an alkyl group that may have a substituent, an aliphatic unsaturated hydrocarbon group that may have a substituent, or an aryl group that may have a substituent.

[0267] R 2 As, -OCOR r1 This is desirable.

[0268] R r1 or R r2 The alkyl group that may have a substituent, the aliphatic unsaturated hydrocarbon group that may have a substituent, and the aryl group that may have a substituent, represented as, for example, each of the above R 1Examples include alkyl groups that may have substituents, aliphatic unsaturated hydrocarbon groups that may have substituents, and aryl groups that may have substituents.

[0269] In Equation (1), n1+m1 represents the valence of the metal atom represented by M.

[0270] n1+m1 is appropriately selected to match the valence that the metal atom represented by M can take. In other words, n1+m1 is a value that varies depending on the type of metal atom represented by M. Note that n1+m1 represents an integer greater than or equal to 1.

[0271] n1 is preferably an integer from 0 to 2, and more preferably 1.

[0272] m1 is preferably an integer from 0 to 4, and 3 is more preferable.

[0273] R 1 If this plural exists, R 1 They may be identical or different. R 2 If there are multiple instances of , R 2 They may be identical or different.

[0274] Specific metal compounds include compounds represented by formula (2) and their condensates.

[0275] [Chemical Formula 2]

[0276]

[0277] In Equation (2), R 3 represents a hydrocarbon group that may have a substituent. z and x represent numbers that satisfy the relationship in Equation (2-1) and the relationship in Equation (2-2).

[0278] Examples of the above hydrocarbon groups include an alkyl group that may have a substituent, an aliphatic unsaturated hydrocarbon group that may have a substituent, and an aryl group that may have a substituent. Furthermore, suitable modes of the above alkyl group, the above aliphatic unsaturated hydrocarbon group, and the above aryl group are R 1 Various suitability modes of each stage can be cited.

[0279] R 3 If this plural exists, R 3 They may be identical or different.

[0280] As specific metal compounds, compounds represented by formula (3) can also be cited.

[0281] [Chemical Formula 3]

[0282]

[0283] In Equation (3), M represents a metal atom. L represents a single bond or a divalent linker. R 4 and R 6 Each represents, independently, an alkyl group that may have substituents, an aliphatic unsaturated hydrocarbon group that may have substituents, or an aryl group that may have substituents. R 5 and R 7 une, each independently, -OCOR r3 or -OR r4 It represents. R r3 It represents silver, a hydrogen atom, an alkyl group that may have substituents, an aliphatic unsaturated hydrocarbon group that may have substituents, or an aryl group that may have substituents. R r4 represents an alkyl group that may have a substituent, an aliphatic unsaturated hydrocarbon group that may have a substituent, or an aryl group that may have a substituent. n2+m2 and n3+m3 each independently represent the valence -1 of the metal atom represented by M.

[0284] In Equation (3), M can be, for example, a metal atom represented by M in Equation (1).

[0285] In Equation (3), R 4 and R 6 As for, for example, the above R 1 One can cite the energy that appears as.

[0286] In Equation (3), R 5 and R 7 As such, for example, the above R 2 One can cite the energy that appears as.

[0287] In Equation (3), R r3 and R r4 As such, for example, each of the above R r1 and the above R r2 One can cite the energy that appears as.

[0288] R 4 If there are multiple instances of , R 4 They may be identical or different. R 5 If there are multiple instances of , R 5 They may be identical or different. R 6 If this plural exists, R 6 They may be identical or different. R 7 If this plural exists, R 7 They may be identical or different.

[0289] In equation (3), L represents a single link or a divalent linker.

[0290] Examples of the above divalent linkers include alkylene groups and arylene groups.

[0291] In Equation (3), n2+m2 and n3+m3 each independently represent the valence -1 of the metal atom represented by M.

[0292] n2+m2 and n3+m3 are "valence of the metal atom represented by M - 1", and are appropriately selected to match the valence that the metal atom represented by M can take.

[0293] Specific metal compounds include the compound represented by formula (4), its hydrolysate, and the condensate of its hydrolysate.

[0294] [Chemical Formula 4]

[0295]

[0296] In Equation (4), R 8 represents a hydrocarbon group that may have a substituent. X represents a hydrolytic group. nz represents 1 or 2.

[0297] As for the above hydrocarbon group, for example, the above R 1 One can cite the energy that appears as.

[0298] As for X, for example, -NHR x1 , -NR x1 R x2 , -OSiR x1 R x2 R x3 , -N(SiR x1 3)(R x2 ), -N(SiR x1 3)(SiR x2 3), Azid, -C≡CR x1 , -NH(COR x1 ), -NR x1 (COR x2 ), -NR x1 C(NR x2 )R x3 Examples include (amidinate group) and imide group, -NHR x1 or -NR x1 R x2 It is desirable. R x1 ~R x3 Each independently represents a hydrocarbon group having 1 to 10 carbon atoms. R x1 ~R x3 As for, an alkyl group having 1 to 10 carbon atoms is preferred.

[0299] R 8 If this plural exists, R 8 They may be identical or different. If there are multiple Xs, they may be identical or different.

[0300] As for specific metal compounds, compounds represented by formula (5) are preferred.

[0301] [Chemical Formula 5]

[0302]

[0303] In Equation (5), R 9 represents an alkyl group that may have substituents, an aliphatic unsaturated hydrocarbon group that may have substituents, or an aryl group that may have substituents. R 10 silver, -OCOR r5 or -OR r6 It represents. R r5 represents a hydrogen atom, an alkyl group that may have substituents, an aliphatic unsaturated hydrocarbon group that may have substituents, or an aryl group that may have substituents. R r6 It represents an alkyl group that may have a substituent, an aliphatic unsaturated hydrocarbon group that may have a substituent, or an aryl group that may have a substituent.

[0304] In Equation (5), R 9 , R 10 , R r5 and R r6 Each, in Equation (1), R 1 , R 2 , R r1 and R r2 It has the same meaning as and the mode of suitability is also the same.

[0305] R that exists in multiple places 10 They may be identical or different.

[0306] As for the specific metal compound, it is preferable to include at least one selected from the group consisting of the compound represented by Formula (1), the compound represented by Formula (2), and the condensate thereof, more preferable to include at least one selected from the group consisting of the compound represented by Formula (5), the compound represented by Formula (2), and the condensate thereof, and more preferable to include the compound represented by Formula (5).

[0307] Specific metal compounds include, for example, the specific metal compounds described in Japanese Patent Publication No. 2021-047426, Japanese Patent Publication No. 2021-179606, Japanese Patent Publication No. 6805244 and International Publication No. 2019 / 111727.

[0308] Specific metal compounds may be used as a single type or in two or more types.

[0309] The content of a specific metal compound is preferably 50 to 100 mass% with respect to the total solid content of the metal resist composition, and more preferably 80 to 100 mass%.

[0310] Organic acid

[0311] The metal resist composition may include an organic acid.

[0312] Examples of organic acids include carboxylic acids, sulfonic acids, sulfinic acids, organic phosphinic acids, organic phosphonic acids, phenols, enols, thiols, imidic acids, oximes, and sulfonamides.

[0313] Examples of carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butanoic acid, pentoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, 2-ethylhexanoic acid, oleic acid, acrylic acid, methacrylic acid, trans-2,3-dimethylacrylic acid, stearic acid, linoleic acid, linolenic acid, arachidonic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, gallic acid, and shikimic acid; dicarboxylic acids such as oxalic acid, malonic acid, maleic acid, methylmalonic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, and tartaric acid; and carboxylic acids having three or more carboxyl groups such as citric acid.

[0314] Organic acids may be used as a single type or as two or more types.

[0315] The content of the organic acid is preferably 0 to 10 mass% with respect to the total solid content of the metal resist composition, and more preferably 1 to 5 mass%.

[0316] Surfactants

[0317] The metal resist composition may include a surfactant.

[0318] When a metal resist composition includes a surfactant, it can form a pattern with better adhesion and fewer development defects.

[0319] The surfactant is preferably a fluorine-based surfactant or a silicone-based surfactant.

[0320] Examples of fluorine-based surfactants and silicone-based surfactants include the surfactants described in paragraphs

[0218] and

[0219] of International Publication No. 2018 / 193954.

[0321] Surfactants may be used as a single type or as two or more types.

[0322] When the metal resist composition includes a surfactant, the content of the surfactant is preferably 0.0001 to 2 mass% with respect to the total solid content of the metal resist composition, and more preferably 0.0005 to 1 mass%.

[0323] Organic solvents

[0324] The metal resist composition may include an organic solvent.

[0325] Examples of organic solvents include organic solvents that may be included in the specific drug solution and the other drug solution mentioned above.

[0326] The content of the organic solvent in the metal resist composition is preferably such that the solid content concentration is 0.5 to 30 mass%, and more preferably such that it is 1 to 20 mass%. In the above embodiment, the coating properties of the metal resist composition can be improved.

[0327] Other Additives

[0328] The metal resist composition may include other additives such as water, a dissolution inhibitor, a dye, a plasticizer, a photosensitizer, a light absorber, and a compound that promotes solubility in a developer (e.g., a phenol compound with a molecular weight of 1000 or less, and a cycloaliphatic or aliphatic compound containing a carboxylic acid group, etc.).

[0329] The metal resist composition is suitably used as a photosensitive composition for EUV light or electron beams.

[0330] EUV light has a wavelength of 13.5 nm, which is shorter than that of ArF light (wavelength 193 nm), so the number of incident photons is lower when exposed with the same sensitivity. Consequently, the influence of "photon shot noise," where the number of photons becomes non-uniform probabilistically, is significant, leading to a deterioration of LER (Line Edge Roughness) and bridge defects. To reduce photon shot noise, one method is to increase the exposure amount to increase the number of incident photons, but this comes at a trade-off with the requirement for high sensitivity.

[0331] Furthermore, although I explained exposure to EUV light as an example, the same problem often occurs when exposure is performed with electron beams.

[0332] [Method for manufacturing an electronic device]

[0333] The present invention also relates to a method for manufacturing an electronic device comprising the pattern forming method.

[0334] The above electronic device is suitably mounted in electrical and electronic devices (e.g., home appliances, OA (Office Automation), media-related devices, optical devices and communication devices, etc.).

[0335] Examples

[0336] The present invention will be described in more detail below based on the examples. The materials, usage amounts, ratios, processing details, and processing procedures shown in the following examples may be appropriately modified without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be interpreted as being limited by the examples shown below.

[0337] [Preparation of Metal Resist Composition]

[0338] [Metal Resist Composition R-1]

[0339] A metal resist precursor solution was prepared by adding monobutyl tin oxide hydrate (BuSnOOH) powder (0.209 g, TCI America) to 4-methyl-2-pentanol (10 mL). The solution was placed in a closed vial and stirred for 24 hours. The resulting mixture was centrifuged at 4000 rpm for 15 minutes and filtered through a 0.45 μm PTFE (polytetrafluoroethylene) syringe filter to remove insoluble material, thereby obtaining metal resist composition R-1.

[0340] In addition, the organic solvent in the metal resist composition R-1 was removed and calcined at 600°C, and the Sn content in the residual mass of SnO2 was 0.093 M. Furthermore, dynamic light scattering (DLS) of the metal resist precursor solution was analyzed using a Moebius instrument (Wyatt Technology). The results were consistent with the monomodal distribution of particles having an average particle size of 2 nm and were consistent with the diameter reported for the dimeric butyltin hydroxide oxide polyatomic cation (Eychenne-Baron et al., Organometallics, 19, 1940-1949 (2000)).

[0341] [Metal Resist Composition R-2]

[0342] Compound 1 (2.4 g) synthesized by a known method and citric acid (0.1 g) were dissolved in 1-methoxy-2-propyl acetate (97.5 g), and the resulting solution was filtered through a 0.1 μm PTFE syringe filter to obtain metal resist composition R-2.

[0343] [Chemical Formula 6]

[0344] Compound 1

[0345] [Pattern formation by EUV exposure]

[0346] A composition for forming a substrate film, SHB-A940 (manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.), was applied to a silicon wafer with a diameter of 300 mm and baked at 205°C for 60 seconds to form a substrate film with a thickness of 20 nm. On top of this, a metal resist composition R-1 or R-2 was applied, and a metal resist film was formed under the conditions (film thickness and PreBake) shown in Tables 2 and 3. Thus, a silicon wafer having a metal resist film was formed.

[0347] For the silicon wafer having the above resist film, pattern exposure was performed while varying the exposure amount using an EUV scanner NXE3400 (NA0.33, manufactured by ASML). Additionally, a hexagonal array contact hole mask with a pitch of 36 nm and an aperture dimension of 21 nm was used as the reticle. Subsequently, after exposure and baking (PEB) under the conditions shown in Tables 2 and 3, negative type development was performed by puddle for 30 seconds with the developer shown in Tables 2 and 3. If a substrate was present, the wafer was additionally rotated at a rotation speed of 1000 rpm while rinsing with the rinse solution shown in Tables 2 and 3 for 10 seconds, and then the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds to obtain a filler pattern with a pitch of 36 nm.

[0348] [Developer or Rinse Solution]

[0349] The properties of the organic solvents used as the developer and rinse solutions are shown in the table below.

[0350] In addition, "boiling point" in the table refers to the boiling point (standard boiling point) under 1 atmosphere (760 mmHg). Also, the values ​​of each element in the Hansen solubility parameter for organic solvents are values ​​obtained by the method shown above.

[0351] PGMEA: Propylene glycol monomethyl ether acetate

[0352] [Table 1]

[0353]

[0354] [evaluation]

[0355] Using a field scanning electron microscope (CG6300, manufactured by Hitachi High Technology Corporation), 2,000 randomly selected pillars at each exposure level were observed, and the average pillar diameter and pattern completeness were evaluated. The average pillar diameter at the minimum exposure level that satisfies the condition that no collapsed pillars occur among the 2,000 observed pillars was defined as the limiting resolution. A smaller value indicates superior resolution.

[0356] [result]

[0357] The evaluation results are shown in Tables 2 and 3.

[0358] The description in parentheses accompanying various solvents indicates the content (mass%) of the solvent relative to the total mass of the developer or rinse solution containing the solvent. Specifically, the developer in Example 1 contains D-1 and D-2 as solvents, and the content of D-1 is 80 mass% relative to the total mass of the developer in Example 1, and the content of D-2 is 20 mass% relative to the total mass of the developer in Example 1.

[0359] [Table 2]

[0360]

[0361] [Table 3]

[0362]

[0363] From the results of Tables 2 and 3, it was confirmed that the pattern forming method of the present invention exhibits the desired effect.

[0364] From the comparison of Examples 1–4 and Examples 5–8, a drug solution containing two or more organic solvents, δ in the Hansen dissolution parameter P +δ H a, 8.0 (J / cm²) 3 ) 0.5 It was confirmed that when containing organic solvents with a lower limit, the limit resolution is superior.

[0365] From the comparison of Examples 5–8 and Examples 9–18, a chemical solution containing two or more organic solvents comprises organic solvent A and organic solvent B, wherein the boiling point of organic solvent A is higher than the boiling point of organic solvent B, and δ in the Hansen solubility parameter of organic solvent A P +δ H a. δ in the Hansen solubility parameter of organic solvent B H +δ P It was confirmed that in the case of a smaller size, the limiting resolution is superior.

[0366] In addition, except for changing the thickness of the metal resist film from 22 nm to 25 nm, the pattern was formed according to the same procedure as in Example 11, and the same result as in Example 11 was obtained.

[0367] In addition, except for changing the prebaking conditions from 100℃ / 90 seconds to 120℃ / 90 seconds, the pattern was formed according to the same procedure as in Example 11, and the same result as in Example 11 was obtained.

[0368] In addition, except for changing the PEB conditions from 150℃ / 90 seconds to 120℃ / 90 seconds, the pattern was formed according to the same procedure as in Example 11, and the same result as in Example 11 was obtained.

[0369] In addition, except for changing the PEB conditions from 150℃ / 90 seconds to 150℃ / 60 seconds, the pattern was formed according to the same procedure as in Example 11, and the same result as in Example 11 was obtained.

[0370] In addition, except for changing the development time from 30 seconds to 15 seconds, the pattern was formed according to the same procedure as in Example 11, and the same result as in Example 11 was obtained.

[0371] In addition, except for changing the development time from 30 seconds to 60 seconds, the pattern was formed according to the same procedure as in Example 11, and the same result as in Example 11 was obtained.

[0372] In addition, except for changing the rinsing time from 10 seconds to 15 seconds, the pattern was formed according to the same procedure as in Example 11, and the same result as in Example 11 was obtained.

[0373] In addition, except for changing the rinsing time from 10 seconds to 60 seconds, the pattern was formed according to the same procedure as in Example 11, and the same result as in Example 11 was obtained.

Claims

Claim 1 A pattern forming method comprising: a process 1 of forming a metal resist film on a substrate using a photosensitive or radiation-sensitive resin composition comprising a metal compound having at least one bond selected from the group consisting of metal-carbon bonds and metal-oxygen bonds; a process 2 of exposing the metal resist film to light; and a process 3 of obtaining a pattern by removing unexposed portions by performing a development treatment on the exposed metal resist film using a developer solution containing an organic solvent, wherein after process 3, the pattern forming method may further include a process 4 of cleaning the pattern using a rinse solution containing an organic solvent; if the pattern forming method does not include process 4 after process 3, the developer solution is a chemical solution containing two or more organic solvents; if the pattern forming method includes process 4 after process 3, at least one of the developer solution and the rinse solution is a chemical solution containing two or more organic solvents; and the chemical solution containing two or more organic solvents comprises at least a first organic solvent and a second organic solvent, and The polar term δ in the Hansen solubility parameter of at least one of the first organic solvent and the second organic solvent P and hydrogen bonding term δ H The sum is 9.8 (J / cm²) 3 ) 0.5 A pattern forming method having less than, wherein the first organic solvent is an ester-based solvent and the second organic solvent is a hydrocarbon-based solvent, the ester-based solvent of the first organic solvent is butyl acetate, and the content of the first organic solvent is 40 mass% or more and 95 mass% or less with respect to the total content of the first organic solvent and the second organic solvent. Claim 2 In claim 1, the chemical solution comprising two or more organic solvents has a polar term δ in at least the Hansen solubility parameter. P and hydrogen bonding term δ H The sum is 8.0 (J / cm²) 3 ) 0.5 A pattern forming method comprising an organic solvent of less than Claim 3 In claim 1, the boiling point of the second organic solvent is higher than the boiling point of the first organic solvent, and the polar term δ in the Hansen solubility parameter of the second organic solvent P and hydrogen bonding term δ H The sum is the polar term δ in the Hansen solubility parameter of the first organic solvent. P and hydrogen bonding term δ H A pattern forming method that is smaller than the sum of. Claim 4 A pattern forming method according to claim 1, wherein the metal compound comprises at least one selected from the group consisting of a compound represented by formula (1), a compound represented by formula (2), and a condensate of a compound represented by formula (2). [Chemical Formula 1] In Equation (1), M represents a metal atom. R 1 R represents an alkyl group that may have substituents, an aliphatic unsaturated hydrocarbon group that may have substituents, or an aryl group that may have substituents. 2 ne, -OCOR r1 or -OR r2 It represents. R r1 It represents silver, a hydrogen atom, an alkyl group that may have substituents, an aliphatic unsaturated hydrocarbon group that may have substituents, or an aryl group that may have substituents. R r2 represents an alkyl group that may have a substituent, an aliphatic unsaturated hydrocarbon group that may have a substituent, or an aryl group that may have a substituent. n1+m1 represents the valence of the metal atom. [Chemical Formula 2] In Equation (2), R 3 represents a hydrocarbon group that may have a substituent. z and x represent numbers that satisfy the relationship in Equation (2-1) and the relationship in Equation (2-2). Claim 5 A pattern forming method according to claim 1, wherein the content of the metal compound is 50 mass% or more with respect to the total solid content of the composition. Claim 6 A method for manufacturing an electronic device comprising a pattern forming method described in any one of claims 1 to 5. Claim 7 delete

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