Method for manufacturing semiconductor device and photosensitive resin composition

Abstract

The present invention addresses the problem of providing: a method for manufacturing a semiconductor device, the method achieving excellent resolution of a resist pattern and excellent collapse resistance of an obtained plating pattern; and a photosensitive resin composition used in the method. A method for manufacturing a semiconductor device according to the present invention comprises: a preparation step for preparing a semiconductor element; and a redistribution layer formation step for forming a redistribution layer connected to the semiconductor element and provided with an insulation part and a conductive part. The redistribution layer formation step comprises, in the following order: a step 1 for forming a photosensitive resin composition layer containing a resin the polarity of which is changed by the action of an acid and a photoacid generator on a substrate; a step 2 for pattern-exposing the composition layer; a step 3 for removing an unexposed part of the exposed composition layer with a developer containing an organic solvent to obtain a negative type resist pattern; a step 4 for forming a plating layer using the pattern as a mold; and a step 5 for peeling the pattern to obtain a patterned plating layer.

Description

Method for manufacturing semiconductor devices, and photosensitive resin composition

[0001] This invention relates to a method for manufacturing semiconductor devices and a photosensitive resin composition.

[0002] The semiconductor device manufacturing process is divided into a front-end process, in which elements such as transistors and integrated circuits are formed on the surface of a silicon wafer, and a back-end process, in which semiconductor chips obtained by separating the silicon wafer on which integrated circuits etc. are formed are packaged. In the back-end process, multiple semiconductor chips and a package substrate are electrically connected via an interposer having conductive parts such as wiring. Recently, instead of Si interposers, the use of a redistribution layer (RDL) made of resin, which has insulating parts and conductive parts, is being considered from the viewpoint of low cost, etc. As a method for obtaining such a redistribution layer, for example, Patent Document 1 discloses a method in which a chemically amplified positive-type photosensitive resin composition layer is exposed, a mold is created by developing it with an alkaline aqueous solution (alkaline development), and then a patterned plating layer (plating pattern) is obtained by plating it.

[0003] Japanese Patent Publication No. 2020-16796

[0004] In this context, when the present inventors investigated the redistribution layer formation method described in Patent Document 1, it became clear that although the resolution of the resist pattern was excellent, the resulting plating pattern sometimes collapsed.

[0005] Therefore, in view of the above circumstances, the present invention aims to provide a method for manufacturing a semiconductor device and a photosensitive resin composition used therein, which exhibit excellent resolution of the resist pattern and excellent resistance to collapse of the resulting plating pattern.

[0006] The inventors of the present invention conducted thorough research on the above problems and discovered that a photosensitive resin composition layer containing a resin whose polarity changes due to the action of an acid and a photoacid generator can be exposed to light, and then developed with a developer containing an organic solvent to form a negative-type resist pattern. By using this as a template for plating, a plating pattern with excellent resistance to collapse can be obtained, leading to the present invention. In other words, the inventors of the present invention found that the above problems can be solved by the following configuration.

[0007] (1) A method for manufacturing a semiconductor device, comprising: a preparation step for preparing a semiconductor element; and a redistribution layer formation step for forming a redistribution layer connected to the semiconductor element and having an insulating portion and a conductive portion, wherein the redistribution layer formation step comprises, in this order: step 1 for forming a photosensitive resin composition layer on a substrate containing a resin whose polarity changes by the action of an acid and a photoacid generator; step 2 for pattern exposure of the photosensitive resin composition layer; step 3 for obtaining a negative resist pattern by removing the unexposed portion of the exposed photosensitive resin composition layer with a developer containing an organic solvent; step 4 for forming a plating layer using the negative resist pattern as a template; and step 5 for obtaining a patterned plating layer by peeling off the negative resist pattern. (2) The method for manufacturing a semiconductor device according to (1), wherein the developer comprises at least one organic solvent selected from the group consisting of butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, cyclopentanone, cyclohexanone, and mesitylene. (3) The method for manufacturing a semiconductor device according to (1) or (2), wherein the exposure wavelength in step 2 is in the range of 350 to 450 nm. (4) The method for manufacturing a semiconductor device according to any one of (1) to (3), wherein the resin has repeating units represented by formula (B) described later. (5) The method for manufacturing a semiconductor device according to any one of (1) to (4), wherein the photoacid generator is a photoacid generator that generates an acid without a fluoride alkyl group. (6) The method for manufacturing a semiconductor device according to any one of (1) to (5), wherein the photoacid generator is a nonionic type photoacid generator. (7) A method for manufacturing a semiconductor device according to any one of (1) to (6) above, wherein the plating method in step 4 is an electroplating method. (8) A method for manufacturing a semiconductor device according to any one of (1) to (7) above, further comprising a step of forming a seed adhesion layer and a seed layer on the negative resist pattern in that order before step 4. (9) A method for manufacturing a semiconductor device according to (8) above, wherein the seed adhesion layer is a Ti-containing layer and the seed layer is a Cu-containing layer.(10) A method for manufacturing a semiconductor device according to (8) or (9), further comprising the step of removing the seed adhesion layer and the seed layer. (11) A method for manufacturing a semiconductor device according to any one of (1) to (10), wherein the area of ​​the substrate-side surface of the plating layer on the pattern is larger than the area of ​​the other surface. (12) A method for manufacturing a semiconductor device according to any one of (1) to (11), wherein the insulating portion is a resin layer containing at least one resin selected from the group consisting of polyimide and polybenzoxazole. (13) A photosensitive resin composition used in a method for manufacturing a semiconductor device according to any one of (1) to (12), containing a resin whose polarity changes upon the action of an acid and a photoacid generator.

[0008] As shown below, the present invention provides a method for manufacturing a semiconductor device and a photosensitive resin composition used therein, which exhibit excellent resolution of the resist pattern and excellent resistance to collapse of the resulting plating pattern.

[0009] This is a cross-sectional view showing one step of a conventional plating pattern formation method using an alkali-developable positive resist. This is a cross-sectional view showing one step of a conventional plating pattern formation method using an alkali-developable positive resist. This is a cross-sectional view showing one step of a conventional plating pattern formation method using an alkali-developable positive resist. This is a cross-sectional view showing one step of a conventional plating pattern formation method using an alkali-developable positive resist. This is a cross-sectional view showing one step of a conventional plating pattern formation method using an alkali-developable positive resist. This is a cross-sectional view showing step 1 of one embodiment of the redistribution layer formation process in the manufacturing method of the present invention. This is a cross-sectional view showing step 2 of one embodiment of the redistribution layer formation process in the manufacturing method of the present invention. This is a cross-sectional view showing step 3 of one embodiment of the redistribution layer formation process in the manufacturing method of the present invention. This is a cross-sectional view showing step 4 of one embodiment of the redistribution layer formation process in the manufacturing method of the present invention. This is a cross-sectional view showing step 5 of one embodiment of the redistribution layer formation process in the manufacturing method of the present invention.

[0010] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments specified. In this specification, numerical ranges represented by the symbol "~" mean a range that includes the numerical values ​​before and after "~" as the lower and upper limits, respectively. In this specification, the term "process" includes not only independent processes but also processes that are indistinguishable from other processes as long as the intended effect of the process is achieved. In the notation of groups (atomic groups) in this specification, notations that do not specify substituted or unsubstituted include both groups (atomic groups) with substituents and groups (atomic groups) without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include the emission line spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate," "(meth)acrylic" means both or either "acrylic" and "methacrylic," and "(meth)acryloyl" means both or either "acryloyl" and "methacryloyl." In this specification, Me in structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, total solids means the total mass of all components of the composition excluding the solvent. In this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values, unless otherwise specified.In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and connecting Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series as columns. Unless otherwise specified, these molecular weights shall be measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, if NMP is unsuitable as an eluent, such as in cases of low solubility, THF (tetrahydrofuran) may be used. Unless otherwise specified, detection in GPC measurements shall be performed using a UV (ultraviolet) wavelength 254 nm detector. In this specification, when the positional relationship of each layer constituting a laminate is described as "up" or "down," it is sufficient that there are other layers above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the other layers, and the reference layer and the other layers do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up," or, if there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Note that this setting of up and down directions is for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from vertically upward. In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to each component contained in the composition. Also, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, preferred embodiments are more preferred embodiments.In this specification, the resolution of the resist pattern in the redistribution layer formation process is also referred to simply as "resolution," the collapse of the resist pattern that serves as a template when a plating layer is formed using the resist pattern as a template is also referred to as "pattern collapse during plating," the resistance to pattern collapse during plating of the resist pattern that serves as a template is also referred to simply as "plating resistance," the residue after peeling off the resist pattern is also referred to simply as "peeling resistance," the peelability of the resist pattern is also referred to simply as "peeling resistance," the shape of the patterned plating layer (plating pattern) is also referred to simply as "pattern shape," and the resistance to collapse of the plating pattern is also referred to as "the effects of the present invention are excellent."

[0011] The present invention relates to a method for manufacturing a semiconductor device (hereinafter also referred to as "the manufacturing method of the present invention"), which comprises a preparation step for preparing a semiconductor element and a redistribution layer formation step for forming a redistribution layer connected to the semiconductor element and having an insulating portion and a conductive portion, wherein the redistribution layer formation step comprises, in this order: step 1 for forming a photosensitive resin composition layer containing a resin whose polarity changes by the action of an acid and a photoacid generator on a substrate; step 2 for pattern exposure of the photosensitive resin composition layer; step 3 for obtaining a negative resist pattern by removing the unexposed portion of the exposed photosensitive resin composition layer with a developer containing an organic solvent (hereinafter also referred to as "organic solvent developer"); step 4 for forming a plating layer using the negative resist pattern as a template; and step 5 for obtaining a patterned plating layer by peeling off the negative resist pattern.

[0012] First, a comparison is shown between a conventional plating pattern formation method using alkaline development, as disclosed in Patent Document 1, and the redistribution layer formation step using an organic solvent developer in the manufacturing method of the present invention.

[0013] Figures 1A to 1E are cross-sectional views showing a conventional plating pattern formation method using an alkali-developable positive-type resist in order of steps. First, as shown in Figure 1A, a photosensitive resin composition layer 20 is formed on the substrate 10. The photosensitive resin composition layer 20 contains a resin whose polarity changes due to the action of an acid and a photoacid generator. Next, as shown in Figure 1B, when the photosensitive resin composition layer 20 is pattern-exposed (exposed in a pattern), the polarity of the resin in the photosensitive resin composition layer increases in the exposed portion (exposed portion 20a) of the photosensitive resin composition layer 20 due to the acid generated from the photoacid generator. Furthermore, as shown in Figure 1C, the exposed portion 20a, where the polarity of the resin has increased, is removed by alkali development, and the remaining unexposed portion 20b becomes a positive-type resist pattern 20b. Note that a positive-type pattern refers to a pattern formed from the remaining unexposed portion after the exposed portion has been removed. After that, as shown in Figure 1D, a plating layer 30 is formed using the positive-type resist pattern 20b as a template. Furthermore, as shown in Figure 1E, the positive resist pattern 20b is peeled off. In this way, the plating layer 30 becomes the plating pattern 30.

[0014] Here, as shown in Figure 1E, the plated pattern 30 has a shape (tapered) (narrows towards the substrate) where the area of ​​the substrate-side surface 30b is smaller than the area of ​​the other surface (the surface in contact with air) 30t. The reason for this is that when the photosensitive resin composition layer 20 is pattern-exposed, the amount of light is weaker at the bottom of the exposed area 20a (the substrate side), and the unexposed area 20b (positive resist pattern 20b) becomes reverse-tapered. When plating is performed using this as a mold, the resulting plated pattern 30 becomes tapered. A plated pattern 30 with this shape is prone to collapsing.

[0015] In contrast, the redistribution layer formation step in the manufacturing method of the present invention is as follows. Figure 2 is a cross-sectional view showing one aspect of the redistribution layer formation step in the manufacturing method of the present invention in order of steps. First, as shown in Figure 2A, a photosensitive resin composition layer 20 is formed on the substrate 10 (step 1). The photosensitive resin composition layer 20 contains a resin whose polarity changes due to the action of an acid and a photoacid generator. Next, as shown in Figure 2B, the photosensitive resin composition layer 20 is pattern exposed (exposed in a pattern) (step 2). In the exposed portion (exposed portion 20a) of the photosensitive resin composition layer 20, the polarity of the resin in the photosensitive resin composition layer increases due to the acid generated from the photoacid generator. Furthermore, as shown in Figure 2C, the unexposed portion 20b is removed with an organic solvent developer (step 3). The remaining exposed portion 20a becomes a negative-type resist pattern 20a. Note that a negative-type pattern refers to a pattern in which the unexposed portion is removed and the remaining exposed portion becomes the pattern. Subsequently, as shown in Figure 2D, a plating layer 32 is formed using the negative resist pattern 20a as a template (step 4). Furthermore, as shown in Figure 2E, the negative resist pattern 20a is peeled off (step 5). In this way, the plating layer 32 becomes a plating pattern 32.

[0016] Here, as shown in Figure 2E, the plating pattern 32 has a shape (reverse tapered) (wider towards the substrate) where the area of ​​the substrate-side surface 32b is equal to or larger than the area of ​​the other surface (the surface in contact with air) 32t. The reason for this is that when the photosensitive resin composition layer 20 is pattern-exposed, the amount of light becomes weaker at the bottom of the exposed area 20a (the substrate side), causing the exposed area 20a (negative resist pattern 20a) to become tapered. When plating is performed using this as a mold, the resulting plating pattern 32 has a reverse tapered shape. In other words, the resulting plating pattern 32 has the opposite shape to the plating pattern 30 (tapered) in Figure 1E. As described above, in the manufacturing method of the present invention, the plating pattern has a shape (reverse tapered) (wider towards the substrate) where the area of ​​the substrate-side surface 32b is equal to or larger than the area of ​​the other surface (the surface in contact with air) 32t.

[0017] The following describes each step.

[0018] [I] Preparation Step The preparation step is a step of preparing the semiconductor device. Here, the semiconductor device may have a metal wiring layer and terminals electrically connected to the metal wiring layer in order to electrically connect to the redistribution layer described later.

[0019] The function of a semiconductor device is distinguished by its operation. Examples of semiconductor functions include computation (CPU, GPU, etc.), storage (memory, etc.), conversion (converter, etc.), filtering, and sensing. When these functions are integrated into a single chip or unit, the function is identified in that integrated state. If the identified functions differ, they are considered different semiconductor devices.Specific examples of semiconductor devices include logic LSI (Large Scale Integration), ASIC (Application Specific Integrated Circuit), FPGA (Field Programmable Gate Array), ASSP (Application Specific Standard Product), microprocessors (e.g., CPU, GPU, etc.), memory (e.g., DRAM (Dynamic Random Access Memory), SRAM (Static Random Access Memory), HMC (Hybrid Memory Cube), MRAM (Magnetic RAM), PCM (Phase-Change Memory), ReRAM (Resistive RAM), FeRAM (Ferroelectric RAM), flash memory, etc.), LED (Light Emitting Diode), power semiconductor devices, analog IC (Integrated Circuit), DC (Direct Current)-DC (Direct Current) converters, insulated gate bipolar transistors (IGBTs), accelerometers, pressure sensors, oscillators, gyroscopes, and other MEMS (Micro Electro Mechanical Systems), GPS (Global Positioning System), and FM (Frequency Examples include Modulation, NFC (Nearfield Communication), RFEM (RF Expansion Module), MMIC (Monolithic Microwave Integrated Circuit), WLAN (Wireless Local Area Network), discrete components, BSI (Back Side Illumination), CIS (Contact Image Sensor), camera modules, passive devices, SAW (Surface Acoustic Wave) filters, RF (Radio Frequency) filters, RFIPD (Radio Frequency Integrated Passive Devices), and BB (Broadband).

[0020] [II] Redistribution Layer Formation Process The redistribution layer formation process (hereinafter also referred to as "the formation process of the present invention") is a process for forming a redistribution layer that is connected to the semiconductor element and has an insulating portion and a conductive portion, and is a process that has steps 1 to 5 described later in this order. Here, the redistribution layer formed in the redistribution layer formation process has an insulating portion and a conductive portion as described above, but is usually a multilayer wiring structure in which a plurality of redistributions (conductive portions) are separated by a plurality of interlayer insulating films (insulating portions), and refers to a layer consisting of one set of redistributions and an interlayer insulating film formed thereon. Note that there are also cases in which the redistribution layer consists of only one layer.

[0021] In the formation process of the present invention, the resist pattern is formed by chemical amplification using a photoacid generator, resulting in high dissolution contrast. Furthermore, the organic solvent developer used for development has lower surface tension and capillary force compared to alkaline developers, making swelling of the developer less likely. As a result, it exhibits excellent resolution. Moreover, as described above, the plating pattern obtained in the formation process of the present invention has excellent resistance to collapse.

[0022] The following will first describe steps 1 to 5, which are included in the formation process of the present invention, and then describe the conductive part and the insulating part.

[0023] [1] Step 1 Step 1 is a step of forming a photosensitive resin composition layer on a substrate containing a resin whose polarity changes due to the action of an acid and a photoacid generator. Note that the substrate and the photosensitive resin composition layer do not necessarily have to be in direct contact, and there may be another layer in between (for example, an insulating part (interlayer insulating film), a seed adhesion layer, a seed layer, etc., as described later).

[0024] [Substrate] The substrate is a component that supports the redistribution layer obtained by the redistribution layer formation process. Examples of substrates include inorganic substrates, resin substrates, and composite substrates thereof. Specific examples of materials constituting an inorganic substrate include glass, quartz, silicone, and silicon nitride. An inorganic substrate may also be a composite substrate obtained by depositing molybdenum, titanium, aluminum, or copper onto a substrate containing any of these materials. Specific examples of materials constituting a resin substrate include synthetic resins such as polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene and other fluororesins, liquid crystal polymers, acrylic resins, epoxy resins, silicone resins, ionomer resins, cyanate resins, crosslinked fumarate diesters, cyclic polyolefins, aromatic ethers, maleimide-olefins, cellulose, and episulfide compounds. A substrate composed of such a synthetic resin may, for example, take the form of a multilayer laminated structure such as a thin-film transistor (TFT).

[0025] In the present invention, the above-mentioned semiconductor element may be used as a substrate. Similarly, a package substrate may be used as a substrate. Hereinafter, in this specification, a package substrate is a substrate used when mounting a semiconductor element on a motherboard or the like.

[0026] [Photosensitive resin composition layer] The photosensitive resin composition layer contains a resin whose polarity changes due to the action of an acid (hereinafter also referred to as "resin (B)") and a photoacid generator.

[0027] [Resin (B)] Resin (B) is preferably a resin whose polarity increases due to the action of an acid and whose solubility in organic solvent developer decreases, and more preferably a resin having a group that decomposes due to the action of an acid to produce polar groups (hereinafter also called "acid-degradable group") (hereinafter also called "acid-degradable resin"). Polarity refers to an uneven distribution of positive and negative charges. When resin (B) is an acid-degradable resin, the glass transition temperature (Tg) of the exposed area (where polar groups are generated) tends to be higher than that of the unexposed area, so the penetration of the plating solution is suppressed and the resistance to stress during plating formation is increased, thereby improving the plating resistance.

[0028] <Acid-degradable groups> Acid-degradable groups are groups that decompose upon the action of an acid to produce a polar group. Acid-degradable groups preferably have a structure in which the polar group is protected by a leaving group that decomposes and is eliminated upon the action of an acid. The polar groups are not particularly limited as long as they are groups that become poorly soluble or insoluble in a developer solution containing an organic solvent, but examples include acidic groups such as phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and tris(alkylsulfonyl)methylene groups (groups that dissociate in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, which is conventionally used as a developer solution for resists), or alcoholic hydroxyl groups.

[0029] Alcoholic hydroxyl groups refer to hydroxyl groups bonded to a hydrocarbon group, excluding hydroxyl groups directly bonded to an aromatic ring (phenolic hydroxyl groups), and exclude aliphatic alcohols in which the α-position of the hydroxyl group is substituted with an electron-withdrawing group such as a fluorine atom (for example, fluorinated alcohol groups (hexafluoroisopropanol groups, etc.)). Preferably, the alcoholic hydroxyl group has a pKa (acid dissociation constant) of 12 to 20.

[0030] As the polar group, a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferred.

[0031] As the acid-decomposable group, a group obtained by substituting a hydrogen atom of these groups with an acid-leaving group is preferred. Examples of the acid-leaving group (leaving group) include -C(R ３６ )(R ３７ )(R ３８ ), -C(R ３６ )(R ３７ )(OR ３９ ), and -C(R ０１ )(R ０２ )(OR ３９ ), etc. In the formula, R ３６ to R ３９ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ３６ and R ３７ may be bonded to each other to form a ring. R ０１ and R ０２ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[0032] R ３６ to R ３９ , R ０１ and R ０２ are preferably alkyl groups having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and an octyl group. R ３６ to R ３９ , R ０１ and R ０２The cycloalkyl group may be monocyclic or polycyclic. As a monocyclic group, a cycloalkyl group having 3 to 8 carbon atoms is preferred, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As a polycyclic group, a cycloalkyl group having 6 to 20 carbon atoms is preferred, such as an adamantyl group, a norbornyl group, an isobolonyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, a tetracyclododecyl group, and an androstanyl group. At least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom. ３６ ~R ３９ , R ０１ and R ０２ The aryl group is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, and an anthyl group. ３６ ~R ３９ , R ０１ and R ０２ The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, and a naphthylmethyl group. ３６ ~R ３９ , R ０１ and R ０２ The alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms, such as a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group. ３６ and R ３７ The ring formed by the bonding of these groups is preferably a cycloalkyl group (monocyclic or polycyclic). Preferred cycloalkyl groups include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. Monocyclic cycloalkyl groups having 5 to 6 carbon atoms are more preferred, and monocyclic cycloalkyl groups having 5 carbon atoms are even more preferred.

[0033] <Preferred Embodiments> For reasons that the effects of the present invention are superior, the resin (B) preferably has repeating units represented by the following formula (B).

[0034] Formula (B)

[0035] In formula (B), R represents a group that is removed by an acid (leaving group), and X represents a hydrogen atom or a methyl group. Specific examples of the leaving group and preferred embodiments are as described above.

[0036] The resin (B) preferably has repeating units represented by the following formula (AI) as repeating units having acid-degradable groups. The repeating units represented by formula (AI) generate carboxyl groups as polar groups upon the action of an acid, and exhibit high interaction through hydrogen bonding among multiple carboxyl groups.

[0037]

[0038] In formula (AI), Xa １ Rx represents a hydrogen atom, alkyl group, cyano group, or halogen atom. T represents a single bond or divalent linking group. １ ~Rx ３ Each of these independently represents an alkyl group or a cycloalkyl group. Rx １ ~Rx ３ These two may combine to form a ring structure.

[0039] Examples of divalent linking groups for T include alkylene groups, -COO-Rt-, -O-Rt-, and phenylene groups. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or -COO-Rt-. Rt is preferably an alkylene group having 1 to 5 carbon atoms, and -CH ２ -, - (CH ２ ) ２ - or - (CH ２ ) ３ - is more preferable. T is more preferably a single bond.

[0040] X ａ１ The alkyl group may have substituents, and examples of substituents include hydroxyl groups and halogen atoms (preferably fluorine atoms). ａ１The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, hydroxymethyl, and trifluoromethyl groups, with methyl being preferred. ａ１ A hydrogen atom or a methyl group is preferred.

[0041] Rx １ Rx ２ and Rx ３ The alkyl group may be linear or branched, and is preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, or t-butyl group. The number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 1 to 5. Rx １ Rx ２ and Rx ３ Preferred cycloalkyl groups include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups.

[0042] Rx １ Rx ２ and Rx ３ The ring structure formed by the bonding of these two is preferably a monocyclic cycloalkane ring such as a cyclopentyl ring and a cyclohexyl ring, or a polycyclic cycloalkyl group such as a norbornane ring, tetracyclodecane ring, tetracyclododecane ring, and adamantane ring, with a monocyclic cycloalkane ring having 5 or 6 carbon atoms being more preferred.

[0043] Rx １ Rx ２ and Rx ３ Each of these is preferably an alkyl group, and more preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

[0044] Each of the above groups may have substituents, and examples of substituents include alkyl groups (1 to 4 carbon atoms), cycloalkyl groups (3 to 8 carbon atoms), halogen atoms, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms), with a carbon number of 8 or less being preferred. In particular, from the viewpoint of further improving the solubility contrast in developing solutions containing organic solvents before and after acid decomposition, substituents that do not have heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms are more preferred (for example, alkyl groups substituted with hydroxyl groups are more preferred), groups consisting only of hydrogen atoms and carbon atoms are even more preferred, and linear or branched alkyl groups or cycloalkyl groups are particularly preferred.

[0045] In equation (AI), Rx １ ~Rx ３ Each of these is an alkyl group, and Rx １ ~Rx ３ It is preferable that the two do not combine to form a ring structure. This ensures that the -C(Rx) group decomposes and is eliminated by the action of acid. １ ) (Rx ２ ) (Rx ３ This suppresses the increase in volume of the base represented by ), and tends to suppress volume contraction of the exposed area in the exposure process and the post-exposure heating process which may be performed after the exposure process.

[0046] The following are specific examples of repeating units represented by formula (AI), but the present invention is not limited to these specific examples. In the specific examples, Rx is a hydrogen atom, CH ３ CF ３ , or CH ２ This represents an OH group. Rxa and Rxb each independently represent an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms). Xa １ is a hydrogen atom, CH ３ CF ３ , or CH ２ This represents OH. Z represents a substituent, and if there are multiple Zs, they may be the same or different from each other. p represents 0 or a positive integer. Specific and preferred examples of Z are Rx １ ~Rx ３These are similar to the specific examples and preferred examples of substituents that each of the groups may have.

[0047]

[0048]

[0049]

[0050] Furthermore, it is preferable that the resin (B) has repeating units having acid-degradable groups, as described in paragraphs

[0057] to

[0071] of Japanese Patent Application Publication No. 2014-202969.

[0051] Furthermore, resin (B) may have repeating units having acid-degradable groups, which generate alcoholic hydroxyl groups as described in paragraphs

[0072] to

[0073] of Japanese Patent Application Publication No. 2014-202969.

[0052] The repeating unit having an acid-degradable group may be of one type or two or more types may be used in combination.

[0053] The content of repeating units having acid-degradable groups in resin (B) (the total if there are multiple repeating units having acid-degradable groups) is preferably 20 to 90 mol%, and more preferably 40 to 80 mol%, relative to the total repeating units of resin (B), for reasons that the effects of the present invention are superior. In particular, it is preferable that resin (B) has repeating units represented by the above formula (AI), and that the content of repeating units represented by the above formula (AI) relative to the total repeating units of resin (B) is 40 mol% or more.

[0054] Resin (B) may contain other repeating units. Examples of other repeating units include repeating units having at least one selected from the group consisting of lactone structures, sultone structures, and carbonate structures; repeating units having hydroxyl groups or cyano groups; repeating units having acidic groups; and repeating units having an alicyclic hydrocarbon structure without polar groups (e.g., acidic groups, hydroxyl groups, cyano groups, etc.) and not exhibiting acid degradability. Details of such other repeating units can be found in paragraphs

[0121] to

[0161] of International Publication No. 2016 / 208300, which are incorporated herein by reference.

[0055] <Molecular Weight> The weight-average molecular weight (Mw) of resin (B) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, even more preferably 3,000 to 15,000, and particularly preferably 3,000 to 11,000. By setting the weight-average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and deterioration of developability and viscosity that leads to deterioration of film-forming ability can be prevented. The degree of dispersion (molecular weight distribution) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and even more preferably 1.1 to 2.0. The smaller the molecular weight distribution, the better the resolution and resist shape, the smoother the sidewalls of the resist pattern, and the better the roughness. The weight-average molecular weight of resin (B) is the standard polystyrene equivalent value obtained from gel permeation chromatography (GPC) under the following conditions: • Column type: TSK gel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mm ID × 30.0 cm) • Developing solvent: THF (tetrahydrofuran) • Column temperature: 40°C • Flow rate: 1 ml / min • Sample injection volume: 10 μL • Instrument name: HLC-8120 (manufactured by Tosoh Corporation)

[0056] <Content> The content of resin (B) is preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 60% by mass or more, and particularly preferably 80% by mass or more, relative to the total solid content of the photosensitive resin composition layer, for reasons that the effects of the present invention are superior. There is no particular upper limit, but 99% by mass or less is preferred, 97% by mass or less is more preferred, and 95% by mass or less is even more preferred. Resin (B) may be used alone or in combination of multiple types.

[0057] [Photoacid Generator] The photoacid generator is not particularly limited, but it is preferably a compound that generates an organic acid upon irradiation with active light or radiation. The photoacid generator may be contained in the resin (B) and / or a resin other than resin (B) described above. More specifically, the photoacid generator may be linked to resin (B) and / or a resin other than resin (B) via a chemical bond. As the photoacid generator, known compounds and mixtures thereof that generate acid upon irradiation with active light or radiation, used as photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorizers and photocolor changers for dyes, and microresists, can be appropriately selected and used. For example, the compounds described in paragraphs

[0039] to

[0103] of Japanese Patent Application Publication No. 2010-061043 and the compounds described in paragraphs

[0284] to

[0389] of Japanese Patent Application Publication No. 2013-004820 can be cited, but the present invention is not limited thereto. Examples of photoacid generators include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imidosulfonates, oximesulfonates, diazodisulfones, disulfones, and o-nitrobenzylsulfonates.

[0058] For the sake of superior effectiveness of the present invention, the photoacid generator is preferably a photoacid generator that generates an acid without a fluoride alkyl group. When such a photoacid generator is used, the impact on the plating process can be suppressed, resulting in superior performance such as resistance to collapse. For the sake of superior effectiveness of the present invention, the photoacid generator is preferably a nonionic type photoacid generator.

[0059] The photosensitive resin composition layer preferably contains at least one compound selected from the group consisting of oximesulfonate groups and imidosulfonate groups, a compound having at least one cation selected from the group consisting of sulfonium cations and iodonium cations, a diazosulfone compound, and a disulfone compound, for reasons that the effects of the present invention are superior. By using these compounds, the efficiency of acid generation by exposure is improved, and the bonding between the acid group and the vinyl ether group compound described above is thought to proceed more efficiently.

[0060] <Oxime Sulfonate Compounds> Compounds having an oxime sulfonate group (hereinafter also referred to as "oxime sulfonate compounds") are not particularly limited as long as they have an oxime sulfonate group, but it is preferable that they be oxime sulfonate compounds represented by formulas (OS-103), (OS-104), and (OS-105).

[0061]

[0062] In formulas (OS-103) to (OS-105), R １１ R represents an alkyl group, aryl group, or heteroaryl group, and there are multiple R groups. １２ Each of these independently represents a hydrogen atom, alkyl group, aryl group, or halogen atom, and there are multiple R groups. １６ Each of these independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group, where X represents O or S, n represents 1 or 2, and m represents an integer from 0 to 6.

[0063] In the above formulas (OS-103) to (OS-105), R １１ The alkyl group, aryl group, or heteroaryl group represented by may have substituents. In the above formulas (OS-103) to (OS-105), R １１ The alkyl group represented by is preferably an alkyl group having a total of 1 to 30 carbon atoms, which may have substituents. １１Examples of the substituent that the alkyl group represented by may include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group.

[0064] In the above formulas (OS-103) to (OS-105), R １１ Examples of the alkyl group represented by include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group.

[0065] Further, in the above formulas (OS-103) to (OS-105), R １１ As the aryl group represented by, an aryl group having a total of 6 to 30 carbon atoms which may have a substituent is preferable. R １１ Examples of the substituent that the aryl group represented by may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.

[0066] R １１ Preferred examples of the aryl group represented by include a phenyl group, a p-methylphenyl group, a trimethylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, and a p-phenoxyphenyl group.

[0067] Further, in the above formulas (OS-103) to (OS-105), R １１ As the heteroaryl group represented by, a heteroaryl group having a total of 4 to 30 carbon atoms which may have a substituent is preferable. R １１Examples of the substituent that the heteroaryl group represented by may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.

[0068] In the above formulas (OS-103) to (OS-105), R １１ The heteroaryl group represented by only needs to have at least one heteroaromatic ring, and for example, a heteroaromatic ring and a benzene ring may be fused. R １１ Examples of the heteroaryl group represented by include a group obtained by removing one hydrogen atom from a ring selected from the group consisting of an optionally substituted thiophene ring, pyrrole ring, thiazole ring, imidazole ring, furan ring, benzothiophene ring, benzothiazole ring, and benzimidazole ring.

[0069] In the above formulas (OS-103) to (OS-105), R １２ is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group. In the above formulas (OS-103) to (OS-105), among two or more R １２ present in the compound, it is preferable that one or two are an alkyl group, an aryl group or a halogen atom, more preferable that one is an alkyl group, an aryl group or a halogen atom, and particularly preferable that one is an alkyl group and the rest are hydrogen atoms. In the above formulas (OS-103) to (OS-105), the alkyl group or aryl group represented by R １２ may have a substituent. The alkyl group or aryl group represented by R １２ Examples of the substituent that the alkyl group or aryl group represented by may have include the same groups as the substituents that the alkyl group or aryl group in the above R １ may have.

[0070] In the above formulas (OS-103) to (OS-105), R １２The alkyl group represented by is preferably an alkyl group having a total of 1 to 12 carbon atoms, which may have substituents, and more preferably an alkyl group having a total of 1 to 6 carbon atoms, which may have substituents. １２ The alkyl groups that are represented are preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, n-hexyl, allyl, chloromethyl, bromomethyl, methoxymethyl, and benzyl groups; more preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, and n-hexyl groups; even more preferably methyl, ethyl, n-propyl, n-butyl, and n-hexyl groups; and particularly preferably methyl.

[0071] In the above formulas (OS-103) to (OS-105), R １２ The aryl group represented by is preferably an aryl group having a total of 6 to 30 carbon atoms, which may have substituents. １２ The preferred aryl group represented by is a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group. １２ Examples of halogen atoms represented by include fluorine, chlorine, bromine, and iodine. Among these, chlorine and bromine atoms are preferred.

[0072] In the above formulas (OS-103) to (OS-105), X represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing X as a ring member is a 5-membered ring or a 6-membered ring. In the above formulas (OS-103) to (OS-105), n represents 1 or 2, and when X is O, n is preferably 1, and when X is S, n is preferably 2.

[0073] In the above formulas (OS-103) to (OS-105), R １６ The alkyl group and alkyloxy group represented by the above formula (OS-103) to (OS-105) may have substituents. １６The alkyl group represented by is preferably an alkyl group having a total of 1 to 30 carbon atoms, which may have substituents. １６ The substituents that the alkyl group represented by may have include halogen atoms, alkyloxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, and aminocarbonyl groups.

[0074] In the above formulas (OS-103) to (OS-105), R １６ Preferred alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl, and benzyl groups.

[0075] In the above formulas (OS-103) to (OS-105), R １６ The alkyloxy group represented is preferably an alkyloxy group having a total of 1 to 30 carbon atoms, which may have substituents. １６ The substituents that the alkyloxy group represented by may have include halogen atoms, alkyloxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, and aminocarbonyl groups.

[0076] In the above formulas (OS-103) to (OS-105), R １６ The alkyloxy group represented by is preferably a methyloxy group, ethyloxy group, butyloxy group, hexyloxy group, phenoxyethyloxy group, trichloromethyloxy group, or ethoxyethyloxy group. １６ Examples of aminosulfonyl groups in this context include methylaminosulfonyl group, dimethylaminosulfonyl group, phenylaminosulfonyl group, methylphenylaminosulfonyl group, and aminosulfonyl group. １６Examples of alkoxysulfonyl groups represented by include methoxysulfonyl group, ethoxysulfonyl group, propyloxysulfonyl group, and butyloxysulfonyl group.

[0077] Furthermore, in the above formulas (OS-103) to (OS-105), m represents an integer from 0 to 6, preferably an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0078] Furthermore, in the above-mentioned oxime sulfonate compound, the stereostructure (E, Z, etc.) of the oxime and benzothiazole rings may be either one or a mixture of both.

[0079] Specific examples of compounds represented by formula (OS-101) that can be suitably used in the present invention include, but are not limited to, the compounds described in paragraphs 0092 to 0097 of International Publication No. 2015 / 064602. Commercial products include WPAG-336 (manufactured by Wako Pure Chemical Industries, Ltd.), WPAG-443 (structure shown below, manufactured by Wako Pure Chemical Industries, Ltd.), MBZ-101 (structure shown below, manufactured by Midori Chemical Co., Ltd.), and the like.

[0080] <Idomisosulfonate Compounds> Examples of compounds having an imidosulfonate group (hereinafter also referred to as "imidosulfonate compounds") include the compound represented by the general formula (ZV).

[0081]

[0082] In the general formula (ZV), R ２０８ represents an alkyl or aryl group. A represents an alkylene, alkenylene, or arylene group. If the alkyl group is a cyclic alkyl group, it may form a ring via a carbonyl group. R ２０８ The alkyl group is preferably a linear alkyl group or a cyclic alkyl group. ２０８The group is preferably a linear or branched alkyl group or an aryl group. These groups may or may not be substituted. Furthermore, if the alkyl group is a cyclic alkyl group, it may form a ring via a carbonyl group, and the cyclic alkyl group may be polycyclic. Preferably, the group is a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, or pentyl group) and a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl, cyclohexyl, or norbonyl group). ２０８ The alkyl group may be further substituted with, for example, a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, and / or a nitro group.

[0083] R ２０８ The aryl group is preferably a phenyl group or a naphthyl group. ２０８の The aryl group may be further substituted with, for example, a halogen atom, an alkoxy group (e.g., C1-C5), a hydroxyl group, a cyano group and / or a nitro group, but preferably, a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a pentyl group) and a cycloalkyl group having 3 to 10 carbon atoms (a cyclopentyl group, a cyclohexyl group, or a norbonyl group).

[0084] Examples of alkylene groups in A include alkylene groups having 1 to 12 carbon atoms (e.g., methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), examples of alkenylene groups in A include alkenylene groups having 2 to 12 carbon atoms (e.g., etenylene group, propenylene group, butenylene group, etc.), and examples of arylene groups in A include arylene groups having 6 to 10 carbon atoms (e.g., phenylene group, torylene group, naphthylene group, etc.). Among these, the naphthylene group is a preferred example when the i-line is used as the exposure wavelength. Specific examples of imidosulfonate compounds include, but are not limited to, the compounds described in paragraphs 0092 to 0097 of International Publication No. 2015 / 064602.

[0085] <Compounds having at least one cation selected from the group consisting of sulfonium cations and iodonium cations> Compounds having at least one cation selected from the group consisting of sulfonium cations and iodonium cations are preferably compounds in which the anion is non-nucleophilic and which produce an organic acid with a pKa of -1 or less upon photodegradation, and more preferably compounds having a sulfonic acid anion, a sulfonylimide anion, a bis(alkylsulfonyl)imide anion, or a tris(alkylsulfonyl)methyl anion as the anion. More preferably, compounds represented by the following general formula (ZI) or (ZII) can be listed.

[0086]

[0087] In the above general formula (ZI), R ２０１ , R ２０２ and R ２０３ Each of these independently represents an organic group. ２０１ , R ２０２ and R ２０３ The number of carbon atoms in the organic group is generally 1 to 30, preferably 1 to 20. Also, R ２０１ ~R ２０３ Two of these may bond together to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. ２０１ ~R ２０３ Examples of groups formed by the bonding of two of these include alkylene groups (e.g., butylene groups, pentylene groups). － Examples include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphor sulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, tris(alkylsulfonyl)methide anions, etc.

[0088] The aliphatic moiety in aliphatic sulfonate anions and aliphatic carboxylic acid anions may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms.

[0089] The aromatic group in aromatic sulfonic acid anions and aromatic carboxylic acid anions is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, a naphthyl group, etc.

[0090] The alkyl and aryl groups listed above may have substituents. Specific examples include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), alkoxycarbonyl groups (preferably having 2 to 7 carbon atoms), acyl groups (preferably having 2 to 12 carbon atoms), alkoxycarbonyloxy groups (preferably having 2 to 7 carbon atoms), alkylthio groups (preferably having 1 to 15 carbon atoms), alkylsulfonyl groups (preferably having 1 to 15 carbon atoms), alkyliminosulfonyl groups (preferably having 1 to 15 carbon atoms), aryloxysulfonyl groups (preferably having 6 to 20 carbon atoms), alkylaryloxysulfonyl groups (preferably having 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl groups (preferably having 10 to 20 carbon atoms), alkyloxyalkyloxy groups (preferably having 5 to 20 carbon atoms), and cycloalkylalkyloxyalkyloxy groups (preferably having 8 to 20 carbon atoms). Regarding the aryl group and ring structure of each group, alkyl groups (preferably having 1 to 15 carbon atoms) can be further used as substituents.

[0091] The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylbutyl group, and the like.

[0092] An example of a sulfonyliimide anion is the saccharin anion.

[0093] The alkyl group in bis(alkylsulfonyl)imido anions and tris(alkylsulfonyl)methide anions is preferably an alkyl group having 1 to 5 carbon atoms. Substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or alkyl groups substituted with fluorine atoms being preferred. Furthermore, the alkyl groups in bis(alkylsulfonyl)imido anions may bond to each other to form a ring structure. This increases the acid strength. － Preferably, the cation contains an aromatic ring group having an alkyl group with 3 or more carbon atoms as a substituent. The alkyl group preferably has 6 or more carbon atoms, and more preferably 8 or more. The alkyl group may be linear, branched, or cyclic, and specific examples include n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-amyl, i-amyl, tert-amyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, n-octyl, and 2-ethylhexyl. Similarly, the anion is preferably a sulfonate containing an alkyl group with 6 or more carbon atoms, or a sulfonate containing an aromatic ring having an alkyl group with 3 or more carbon atoms as a substituent.

[0094] Z － Particularly preferred is the anion represented by the following general formula (AN1).

[0095]

[0096] In the formula, Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. １ , R ２ Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group, and when multiple Rs are present, the R is used. １ , R ２These can be the same or different. L represents a divalent linking group, and if there are multiple Ls, they can be the same or different. A represents a cyclic organic group. x represents an integer from 0 to 20, y represents an integer from 0 to 10, and z represents an integer from 0 to 10.

[0097] The general formula (AN1) will be explained in more detail. The alkyl group in the alkyl group substituted with a fluorine atom of Xf preferably has 1 to 10 carbon atoms, and more preferably has 1 to 4 carbon atoms. Furthermore, the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include a fluorine atom and CF ３ , C ２ F ５ , C ３ F ７ , C ４ F ９ ,CH ２ CF ３ ,CH ２ CH ２ CF ３ ,CH ２ C ２ F ５ ,CH ２ CH ２ C ２ F ５ ,CH ２ C ３ F ７ ,CH ２ CH ２ C ３ F ７ ,CH ２ C ４ F ９ ,CH ２ CH ２ C ４ F ９ These include, among others, fluorine atoms, CF ３ This is preferable. In particular, it is preferable that both Xf atoms are fluorine atoms.

[0098] R １ , R ２The alkyl group may have substituents (preferably fluorine atoms), and is preferably one with 1 to 4 carbon atoms. More preferably, it is a perfluoroalkyl group with 1 to 4 carbon atoms. １ , R ２ Specific examples of alkyl groups having substituents include CF ３ , C ２ F ５ , C ３ F ７ , C ４ F ９ , C ５ F １１ , C ６ F １３ , C ７ F １５ , C ８ F １７ ,CH ２ CF ３ ,CH ２ CH ２ CF ３ ,CH ２ C ２ F ５ ,CH ２ CH ２ C ２ F ５ ,CH ２ C ３ F ７ ,CH ２ CH ２ C ３ F ７ ,CH ２ C ４ F ９ ,CH ２ CH ２ C ４ F ９ Among them, CF ３ This is preferable. １ , R ２ Preferably, it is a fluorine atom or CF ３ That is the case.

[0099] x is preferably 0 to 10, more preferably 0 to 2. y is preferably 0 to 8, more preferably 0 to 6. z is preferably 0 to 5, more preferably 0 to 3. The divalent linking group of L is not particularly limited and can be -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ２Examples include alkylene groups, cycloalkylene groups, alkenylene groups, or linked groups formed by linking multiple thereof, with linked groups having a total of 12 or fewer carbon atoms being preferred. Among these, -COO-, -OCO-, -CO-, and -O- are preferred, and -COO- and -OCO- are more preferred.

[0100] The cyclic organic group A is not particularly limited as long as it has a cyclic structure, and examples include alicyclic groups, aryl groups, and heterocyclic groups (including not only aromatic but also non-aromatic ones). Alicyclic groups may be monocyclic or polycyclic, and monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl groups, and polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups are preferred. Among these, alicyclic groups with a bulky structure having 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred from the viewpoint of improving MEEF because they can suppress diffusion in the film during the post-exposure heating process. Examples of aryl groups include benzene rings, naphthalene rings, phenanthrene rings, and anthracene rings. Examples of heterocyclic groups include those derived from furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Among these, those derived from furan rings, thiophene rings, and pyridine rings are preferred.

[0101] The above-mentioned cyclic organic group may have substituents, and examples of such substituents include linear or branched alkyl groups (which may be linear, branched, or cyclic, and preferably have 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, and preferably have 3 to 20 carbon atoms), aryl groups (preferably have 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups, sulfonic acid ester groups, and the like. The carbon atoms constituting the cyclic organic group (carbon atoms that contribute to ring formation) may be carbonyl carbons.

[0102] R ２０１ , R ２０２ and R２０３ Examples of organic groups include aryl groups, alkyl groups, and cycloalkyl groups. ２０１ , R ２０２ and R ２０３ It is preferable that at least one of these is an aryl group, and more preferably that all three are aryl groups. In addition to phenyl and naphthyl groups, heteroaryl groups such as indole and pyrrole residues are also possible as aryl groups. ２０１ ~R ２０３ Preferably, the alkyl and cycloalkyl groups include linear or branched alkyl groups having 1 to 10 carbon atoms, and cycloalkyl groups having 3 to 10 carbon atoms. More preferably, alkyl groups include methyl, ethyl, n-propyl, i-propyl, and n-butyl groups. More preferably, cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl groups. These groups may further have substituents. Examples of substituents include, but are not limited to, nitro, halogen atoms such as fluorine, carboxy, hydroxyl, amino, cyano, alkoxy (preferably C1 to C15), cycloalkyl groups (preferably C3 to C15), aryl groups (preferably C6 to C14), alkoxycarbonyl groups (preferably C2 to C7), acyl groups (preferably C2 to C12), and alkoxycarbonyloxy groups (preferably C2 to C7).

[0103] The divalent linking groups of Za include alkylene groups, arylene groups, carbonyl groups, sulfonyl groups, carbonyloxy groups, carbonylamino groups, sulfonylamide groups, ether bonds, thioether bonds, amino groups, disulfide groups, and -(CH ２ ) ｎ -CO-, -(CH ２ ) ｎ -SO ２ Examples include -, -CH=CH-, aminocarbonylamino group, aminosulfonylamino group, etc. (n is an integer from 1 to 3).

[0104] Note R ２０１ , R２０２ and R ２０３ In cases where at least one of the groups is not an aryl group, preferred structures include cationic structures such as those described in paragraphs 0046 to 0048 of Japanese Patent Publication No. 2004-233661, paragraphs 0040 to 0046 of Japanese Patent Publication No. 2003-35948, the compounds exemplified as formulas (I-1) to (I-70) in U.S. Patent Application Publication No. 2003 / 0224288A1, and the compounds exemplified as formulas (IA-1) to (IA-54) and (IB-1) to (IB-24) in U.S. Patent Application Publication No. 2003 / 0077540A1.

[0105] In general formula (ZII), R ２０４ ~R ２０５ R represents an aryl group. ２０４ ~R ２０５ As for the aryl group, the R in the aforementioned compound (ZI) ２０１ ~R ２０３ This is similar to the aryl group described as an aryl group. ２０４ ~R ２０５ The aryl group may have substituents. These substituents may also be R in the aforementioned compound (ZI). ２０１ ~R ２０３ Examples of aryl groups that may be present include:

[0106] Specific examples of compounds having at least one cation selected from the group consisting of sulfonium cations and iodonium cations include, but are not limited to, the compounds described in paragraphs 0128-0133 of International Publication No. 2015 / 064602.

[0107] <Content> The content of the photoacid generator is preferably 0.1 to 20% by mass, and more preferably 0.5 to 18% by mass, relative to the total solid content of the photosensitive resin composition layer, for the sake of superior effects of the present invention. The photoacid generator may be contained alone or in combination of two or more types. When the photosensitive resin composition layer contains two or more types of photoacid generators, it is preferable that their total content be within the above range.

[0108] [Other Additives] The photosensitive resin composition layer may contain components other than those listed above (hereinafter also referred to as "other additives"). Examples of such additives include crosslinking agents, hydrophobic resins (preferably different from resin (B)), acid diffusion inhibitors, surfactants, onium carboxylates, and the like. For other additives, refer to paragraphs

[0204] to

[0332] of International Publication No. 2016 / 208300, which are incorporated herein by reference.

[0109] [Thickness] The thickness of the photosensitive resin composition layer is not particularly limited, but for reasons that the effects of the present invention are superior, it is preferably 0.1 to 100 μm, more preferably 1 to 50 μm, and even more preferably 5 to 20 μm.

[0110] [Method of Formation] The method for forming a photosensitive resin composition layer on a substrate is not particularly limited, but examples include applying a photosensitive resin composition containing a solvent onto the substrate, or attaching a film-like photosensitive resin composition onto the substrate.

[0111] [Solvent] Any known solvent can be used. Organic solvents are preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0112] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), and 2-alkyloxy Suitable examples include alkyl propionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate).

[0113] Suitable ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0114] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0115] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, as well as cyclic terpenes such as limonene.

[0116] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0117] Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0118] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0119] Suitable alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0120] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0121] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more of these, is preferred. The combined use of dimethyl sulfoxide and γ-butyrolactone, or the combined use of N-methyl-2-pyrrolidone and ethyl lactate, is more preferred.

[0122] In a photosensitive resin composition, the solvent content is preferably such that the total solids concentration is 10 to 90% by mass, and more preferably 50 to 80% by mass, from the viewpoint of coatability. If two or more solvents are included, it is preferable that their total concentration is within the above range.

[0123] [Application Method] The method for applying the photosensitive resin composition onto a substrate is not particularly limited, but specific examples include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating is preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating or slit coating is more preferred. By adjusting the solid content concentration of the composition and the application conditions according to the method applied, a film of the desired thickness can be obtained. Alternatively, a method can be applied in which a coating film formed in advance on a temporary support using the above application method is transferred onto the substrate.

[0124] [Soft baking] A heat treatment (soft baking) may be performed on the photosensitive resin composition applied to the substrate. This removes components such as solvents from the photosensitive resin composition applied to the substrate. The heating temperature in the heat treatment is preferably 50 to 150°C, and more preferably 80 to 130°C. Heating may also be performed under reduced pressure. The heating time is preferably 10 seconds to 10 minutes, and more preferably 30 seconds to 5 minutes.

[0125] [Preferred Embodiments] In one preferred embodiment, step 1 is a step in which an insulating film (insulating portion) is formed on a substrate, and then a photosensitive resin composition layer is formed on the insulating film. Specific examples of the insulating film (insulating portion) and preferred embodiments are described below. In another preferred embodiment, step 1 is a step in which a seed adhesion layer and a seed layer are formed in this order on the substrate or on the insulating film, and then a photosensitive resin composition layer is formed on the seed layer.

[0126] [Seed layer and seed adhesion layer] The seed layer is a layer that acts as a power supply layer for the plating layer formed in step 4, which will be described later. The seed adhesion layer is a layer that improves the adhesion of the seed layer. The seed layer and seed adhesion layer are formed by, for example, sputtering or vapor deposition, and the materials used are, for example, Cu, Ni, Al, Ti, Cr, Mo, W, Ta, Au, Ir, Ru, Pd, Pt, AlSi, AlSiCu, AiCu, NIFe, ITO, IZO, AZO, ZnO, PZT, TiN, Cu ３ N ４ Cu alloys or combinations thereof can be applied. For reasons that the effects of the present invention are superior, it is preferable that the seed adhesion layer is a Ti-containing layer and the seed layer is a Cu-containing layer.

[0127] <Thickness> The thickness of the seed layer is not particularly limited, but for reasons that the effects of the present invention are better, it is preferably 10 to 1000 nm, more preferably 50 to 500 nm, and even more preferably 100 to 200 nm. The thickness of the seed adhesion layer is not particularly limited, but for reasons that the effects of the present invention are better, it is preferably 5 to 200 nm, and more preferably 10 to 100 nm.

[0128] [2] Step 2 Step 2 is a step of pattern exposure of the photosensitive resin composition layer formed in Step 1. One method of pattern exposure is to selectively expose the photosensitive resin composition layer. Selective exposure means exposing only a part of the photosensitive resin composition layer. By selective exposure, exposed and unexposed areas are formed in the photosensitive resin composition layer.

[0129] [Exposure Amount] The exposure amount is not particularly limited as long as it can cure the photosensitive resin composition, but for example, it is 50 to 10,000 mJ / cm in terms of exposure energy at a wavelength of 365 nm. ２ Preferably, 200 to 8,000 mJ / cm² ２ This is preferable.

[0130] [Exposure Wavelength] The exposure wavelength is preferably 190 to 1,000 nm, and more preferably 350 to 450 nm, for the reasons that the effects of the present invention are superior.

[0131] [Light Source] In relation to the light source, the exposure wavelength can be (1) semiconductor laser (e.g., wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-line (wavelength 436nm), h-line (wavelength 405nm), i-line (wavelength 365nm), broad (three wavelengths of g, h, and i lines), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F ２ Examples include excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, and (7) YAG laser with second harmonic 532 nm and third harmonic 355 nm. For composition A1, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with the i-line is more preferred from the viewpoint of exposure sensitivity.

[0132] [Exposure Method] The exposure method is not particularly limited and any method in which at least a portion of the photosensitive resin composition layer is exposed is acceptable, but examples include exposure using a photomask and exposure by laser direct imaging.

[0133] [PEB] Step 2 may include a Post Exposure Bake (PEB) in which the photosensitive resin composition layer is heated after pattern exposure. The Post Exposure Bake can be performed after exposure and before development. The heating temperature in the Post Exposure Bake is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the Post Exposure Bake is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. The heating rate in the Post Exposure Bake is preferably 1 to 12°C / min from the starting temperature to the maximum heating temperature, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The heating rate may also be changed as appropriate during heating. The heating means in the Post Exposure Bake is not particularly limited, and known examples include hot plates, ovens, and infrared heaters. Furthermore, it is preferable to carry out the heating process in a low-oxygen atmosphere by flowing inert gases such as nitrogen, helium, and argon through the system.

[0134] [3] Step 3 Step 3 is a step in which a negative resist pattern is obtained by removing the unexposed portion of the photosensitive resin composition layer exposed in Step 2 with a developer solution containing an organic solvent.

[0135] [Developer] The developer used in step 3 contains an organic solvent. Examples of organic solvents included in the developer are the compounds described in paragraph

[0387] of International Publication No. 2021 / 112189, which are incorporated herein by reference. Suitable alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutylcarbinol, and triethylene glycol, while suitable amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide. The organic solvent included in the developer can be used individually or in a mixture of two or more.

[0136] The developer preferably contains at least one organic solvent selected from the group consisting of butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, cyclopentanone, cyclohexanone, and mesitylene, for which the effects of the present invention are superior.

[0137] The content of organic solvent in the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the developer. Alternatively, the above content may be 100% by mass.

[0138] The developing solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0139] [Rinsing Process] Step 3 may include a rinsing process in which the pattern is washed (rinsed) with a rinsing solution after obtaining the negative-type resist pattern. Alternatively, methods such as supplying the rinsing solution before the developer solution remaining on the negative-type resist pattern dries completely may be employed.

[0140] There are no particular restrictions on the method of supplying the rinsing solution. These methods include immersing the negative resist pattern in the rinsing solution, supplying the rinsing solution to the negative resist pattern by adding liquid, supplying the rinsing solution to the negative resist pattern with a shower, and continuously supplying the rinsing solution onto the negative resist pattern using means such as a straight nozzle. The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0141] As a rinsing solution, for example, a solvent different from the solvent contained in the developer (e.g., water, or an organic solvent different from the organic solvent contained in the developer) can be used. Examples of organic solvents different from the organic solvent contained in the developer include organic solvents similar to those exemplified above as organic solvents contained in the developer. Among these, an organic solvent with lower pattern solubility than the organic solvent contained in the developer is preferred.

[0142] If the rinsing solution contains an organic solvent, the content of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, relative to the total mass of the rinsing solution. Alternatively, the organic solvent may be 100% by mass relative to the total mass of the rinsing solution.

[0143] The rinse solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0144] [Post-bake] Step 3 may include a heat treatment (post-bake) in which the obtained negative resist pattern is heated. If a rinsing treatment is performed, the heat treatment may be performed on the negative resist pattern after rinsing.

[0145] For the heating temperature (maximum heating temperature) in the heat treatment, 50 to 300°C is preferred, 180 to 200°C is more preferred, and 100 to 150°C is even more preferred. For further details on the heat treatment, please refer to paragraphs

[0326] to

[0332] of International Publication No. 2023 / 190064, which are incorporated herein by reference.

[0146] [Negative Resist Pattern] In step 3, the exposed portion of the photosensitive resin composition layer is obtained as a negative resist pattern. The preferred range of thickness for the negative resist pattern is the same as that for the photosensitive resin composition layer described above.

[0147] [4] Step 4 Step 4 is a step in which a plating layer is formed using the negative resist pattern formed in Step 3 as a template.

[0148] [Formation Method] The method for forming the plating layer is not particularly limited, but known plating treatments such as electroplating and electroless plating can be used. The material constituting the plating layer is not particularly limited, but can be copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Among these, copper or aluminum is preferred, and copper is more preferred. When forming the plating layer by electroplating, it is preferable to provide the seed adhesion layer and seed layer on the substrate and / or on the negative-type resist pattern in this order. In this case, it is preferable to include a step before step 4 in which the seed adhesion layer and seed layer are formed on the substrate and / or on the negative-type resist pattern in this order. For example, as described above, the seed adhesion layer and seed layer may be formed on the substrate in step 1 beforehand, or the seed adhesion layer and seed layer may be formed in this order on the negative-type resist pattern (including the surface of the recess (exposed area removed by the developer) created by the formation of the negative-type resist pattern) between step 3 and step 4. A plating layer is formed by applying an electroplating treatment (e.g., electrolytic copper plating) to the seed layer. Prior to the plating treatment, the seed layer may be subjected to pretreatment such as sulfuric acid treatment and water washing.

[0149] [Thickness] The thickness of the plating layer is not particularly limited, but is preferably 0.1 to 100 μm, more preferably 1 to 50 μm, and even more preferably 3 to 10 μm.

[0150] [5] Step 5 Step 5 is a step in which a patterned plating layer (plating pattern) is obtained by peeling off the negative resist pattern. Methods for removing the remaining resist pattern include, for example, removal by chemical treatment, and a method using a stripping solution is preferred. Methods for removing the remaining resist pattern include, for example, removal by known methods such as the spray method, shower method and paddle method using a stripping solution.

[0151] [Stripping Solution] Examples of stripping solutions include those obtained by dissolving an alkaline compound in at least one selected from the group consisting of water, dimethyl sulfoxide, and N-methylpyrrolidone. Examples of alkaline compounds (compounds that dissolve in water and exhibit alkalinity) include alkaline inorganic compounds such as sodium hydroxide and potassium hydroxide, and alkaline organic compounds such as primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0152] [Preferred Embodiments] A preferred embodiment of the removal method is to immerse a substrate having the pattern to be removed in a stripping solution that is being stirred and has a liquid temperature of 50 to 80°C for 1 to 30 minutes. It is also preferable that the stripping solution does not dissolve the plating pattern.

[0153] [Rinsing Treatment, etc.] After removing the resist pattern with the stripping solution, it is also preferable to perform a rinsing treatment to remove any remaining stripping solution. Water or the like can be used for the rinsing treatment. After removing the resist pattern with the stripping solution and / or rinsing treatment, a drying treatment may be performed to remove any excess liquid from the substrate.

[0154] [Removal of Seed Adhesion Layer and Seed Layer] If a seed adhesion layer and seed layer are formed on the substrate, it is preferable to remove these layers. These layers can be removed, for example, by treatment with an etching solution (alkaline, acidic, etc.).

[0155] [6] Conductive part The patterned plating layer (plating pattern) formed in step 5 described above becomes the conductive part. The preferred thickness of the plating pattern is the same as that of the plating layer described above. The area of ​​the substrate-side surface of the plating pattern is preferably larger than the area of ​​the other surface (the interface in contact with air). That is, the plating pattern is preferably in the shape of an inverse taper (widening towards the substrate). More specifically, when the length of the substrate-side interface of the plating pattern (length in the width direction) is Lb and the length of the interface of the plating pattern in contact with air (length in the width direction) is Lt, Lb / Lt is preferably 1.00 or more, and more preferably 1.05 or more.

[0156] [7] Insulating part As described above, the redistribution layer formed in the formation process of the present invention comprises an insulating part and a conductive part. Typically, the insulating part is an interlayer insulating film for separating the plating pattern (conductive part) formed in step 5 described above. The insulating part is not particularly limited as long as it can insulate the conductive part, but for reasons that the effects of the present invention are superior, it is preferable that the insulating part is a resin layer containing at least one resin selected from the group consisting of polyimide and polybenzoxazole. It is preferable that the polyimide is obtained from a polyimide precursor, and it is preferable that the polybenzoxazole is obtained from a polybenzoxazole precursor. Here, a polyimide precursor is a resin that undergoes a change in chemical structure due to external stimuli to become polyimide, and it is preferable that the resin undergoes a change in chemical structure due to heat to become polyimide, and it is even more preferable that the resin undergoes a ring-closing reaction due to heat to form a ring structure to become polyimide. Furthermore, polyimide is a resin having repeating units containing imide groups in the molecular chain, and it is preferable that the resin has repeating units containing imide ring structures in the molecular chain. Furthermore, when the polyimide is a linear resin, it is preferable that the polyimide is a resin having repeating units containing imide groups in the main chain, and more preferably a resin having repeating units containing imide ring structures in the main chain. In this specification, "main chain" refers to the relatively longest bonding chain in the resin molecule, and "side chains" refers to the other bonding chains. In this specification, an imide group refers to a structure represented by *-C(=O)N(-*)C(=O)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. In this specification, an imide ring structure refers to a ring structure that includes all of the carbon atoms and nitrogen atoms in the above imide as ring member atoms. The imide ring structure is preferably a five-membered ring. In addition to imide groups, the polyimide may also be a so-called polyamide imide, which has amide groups in the molecular chain. In this specification, an amide group refers to a structure represented by *-C(=O)N(-#)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom.Furthermore, the '#' symbol represents a bonding site with another structure, preferably a bonding site with a hydrogen atom or a carbon atom, and more preferably a bonding site with a hydrogen atom.

[0157] [Preferred Embodiments] The insulating portion is preferably formed from a composition (hereinafter also referred to as "resin composition A") containing at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor (hereinafter also referred to as "resin (A)"). Resin composition A may be in the form of a film or a liquid, but it is preferably in the form of a liquid.

[0158] [Resin (A)] Resin (A) is at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor. Among these, polyimide and polyimide precursor are preferred, and polyimide precursor is more preferred. Resin (A) preferably has polymerizable groups, and more preferably contains radical polymerizable groups. If resin (A) has radical polymerizable groups, resin composition A preferably contains a photopolymerization initiator (especially a radical polymerization initiator), and more preferably contains a photopolymerization initiator (especially a radical polymerization initiator) and a polymerizable compound (especially a radical crosslinking agent). Furthermore, a sensitizer may be included as needed. For example, a negative-type photosensitive film can be formed from such a resin composition A. Resin (A) may also have polarity conversion groups such as acid-degradable groups. If resin (A) has acid-degradable groups, resin composition A preferably contains a photoacid generator. From such a resin composition A, for example, a chemically amplified positive-type or negative-type photosensitive film can be formed.

[0159] <Polyimide Precursor> The polyimide precursor used in the present invention is not particularly limited in terms of type, but it is preferable that it contains repeating units represented by the following formula (2).

[0160]

[0161] In formula (2), A １ and A ２Each of these is independently an oxygen atom or -NR ｚ - represents R １１１ R represents a divalent organic group. １１５ represents a tetravalent organic group, R １１３ and R １１４ Each of these independently represents a hydrogen atom or a monovalent organic group, R ｚ represents a hydrogen atom or a monovalent organic group.

[0162] A in equation (2) １ and A ２ Each of these is independently an oxygen atom or -NR ｚ R represents a negative sign, and an oxygen atom is preferred. ｚ R represents a hydrogen atom or a monovalent organic group, with a hydrogen atom being preferred. １１１ R represents a divalent organic group. １１１ It is preferable that the base is one of the bases described in paragraphs

[0042] to

[0053] of Japanese Patent Publication No. 2023-003421.

[0163] Also, R １１１ Examples of such groups include the following. Among these, AR-8 is preferred because it exhibits superior effects compared to the present invention. Note that the hydrogen atoms in these structures may be further substituted with known substituents such as hydroxyl groups and hydrocarbon groups.

[0164]

[0165] In the formula, A represents a single bond or a divalent linking group, and is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO ２ Preferably, the group is -, -NHCO-, or a combination thereof, and is a C1-C3 alkylene group, -O-, -C(=O)-, -S-, or -SO- which may be substituted with a single bond or a fluorine atom. ２ - More preferably, the group is selected from -CH ２ -, -O-, -S-, -SO ２ -, -C (CF ３ ) ２ -, or -C(CH ３ ) ２It is even more preferable that it is -. In the formula, * represents a bonding site with another structure.

[0166] R in equation (2) １１５ * represents a tetravalent organic group. A tetravalent organic group containing an aromatic ring is preferred, and a group represented by formula (5) or formula (6) below is more preferred. In formula (5) or formula (6), * independently represents a bonding site with another structure.

[0167]

[0168] In formula (5), R １１２ The linking group is a single bond or a divalent linking group, and may be a single bond or a carbon-1 to carbon-10 aliphatic hydrocarbon group, -O-, -CO-, -S-, -SO- which may be substituted with a fluorine atom. ２ Preferably, the group is selected from -, -NHCO-, and combinations thereof, and is a C1- to C3 alkylene group, -O-, -CO-, -S-, and -SO- which may be single-bonded or substituted with a fluorine atom. ２ - More preferably, the group is selected from -CH ２ -, -C (CF ３ ) ２ -, -C(CH ３ ) ２ -, -O-, -CO-, -S-, and -SO ２ It is even more preferable that the group is a divalent group selected from the group consisting of -.

[0169] R １１５ Preferably, the tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride described in paragraphs

[0055] to

[0057] of Japanese Patent Application Publication No. 2023-003421 is preferred.

[0170] In equation (2), R １１１ and R １１５ It is also possible that at least one of them has an OH group. More specifically, R １１１ Examples include residues of bisaminophenol derivatives.

[0171] R in equation (2) １１３ and R １１４Each of these independently represents a hydrogen atom or a monovalent organic group. Preferably, the monovalent organic group includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene oxy group. Also, R １１３ and R １１４ It is preferable that at least one of them contains a polymerizable group, and more preferably that both contain a polymerizable group. １１３ and R １１４ It is also preferable that at least one of the components contains two or more polymerizable groups. The polymerizable groups are groups that can undergo crosslinking reactions by the action of heat and radicals, and radical polymerizable groups are preferred. Examples of polymerizable groups include groups having an ethylenically unsaturated bond, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. As radical polymerizable groups of the polyimide precursor, groups having an ethylenically unsaturated bond are preferred. Examples of groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (III), with groups represented by the following formula (III) being preferred.

[0172]

[0173] In equation (III), R ２００ R represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred. In formula (III), * represents a bonding site with other structures. In formula (III), R ２０１ This is an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２ - represents a cycloalkylene group or a polyalkylene oxy group. ２０１ Examples include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, as well as 1,2-butanediyl, 1,3-butanediyl, and -CH２ CH(OH)CH ２ -, or a polyalkylene oxy group is preferred, and alkylene groups such as ethylene groups and propylene groups, -CH ２ CH(OH)CH ２-, cyclohexyl groups, or polyalkylene oxy groups are more preferred, and alkylene groups such as ethylene groups and propylene groups, or polyalkylene oxy groups are even more preferred. In the present invention, a polyalkylene oxy group refers to a group in which two or more alkylene oxy groups are directly bonded. The alkylene groups in the multiple alkylene oxy groups contained in the polyalkylene oxy group may be the same or different. When the polyalkylene oxy group contains multiple types of alkylene oxy groups with different alkylene groups, the arrangement of the alkylene oxy groups in the polyalkylene oxy group may be random, have blocks, or have patterns such as alternating arrangements. The number of carbon atoms in the alkylene group (including the number of carbon atoms of substituents if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. The alkylene group may also have substituents. Preferred substituents include alkyl groups, aryl groups, or halogen atoms. The number of alkylene oxy groups in the polyalkylene oxy group (number of repeating polyalkylene oxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkylene oxy group is preferably a polyethylene oxy group, a polypropylene oxy group, a polytrimethylene oxy group, a polytetramethylene oxy group, or a group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, more preferably a polyethylene oxy group or a polypropylene oxy group, and even more preferably a polyethylene oxy group. In the group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, the ethylene oxy groups and propylene oxy groups may be arranged randomly, in blocks, or in alternating patterns. The preferred number of repeating ethylene oxy groups in these groups is as described above.

[0174] In equation (2), R １１３ If R is a hydrogen atom, １１４When is a hydrogen atom, the polyimide precursor may form a pair salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0175] In equation (2), R １１３ and R １１４ At least one of the groups may be a polarity-converting group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it decomposes under the action of acid to produce alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups, but acetal groups, ketal groups, silyl groups, silyl ether groups, or tertiary alkyl ester groups are preferred, and from the viewpoint of exposure sensitivity, acetal groups or ketal groups are more preferred. Examples of acid-degradable groups include tert-butoxycarbonyl groups, isopropoxycarbonyl groups, tetrahydropyranyl groups, tetrahydrofuranyl groups, ethoxyethyl groups, methoxyethyl groups, ethoxymethyl groups, trimethylsilyl groups, tert-butoxycarbonylmethyl groups, and trimethylsilyl ether groups. From the viewpoint of exposure sensitivity, ethoxyethyl groups or tetrahydrofuranyl groups are preferred.

[0176] The polyimide precursor may also preferably contain fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less, based on the total mass of the polyimide precursor.

[0177] Furthermore, to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane as the diamine.

[0178] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having the repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to further widen the exposure latitude.

[0179] Formula (2-A)

[0180]

[0181] In formula (2-A), A １ and A ２ represents an oxygen atom, R １１１ and R １１２ Each of these independently represents a divalent organic group, R １１３ and R １１４ Each of these independently represents a hydrogen atom or a monovalent organic group, R １１３ and R １１４ Preferably, at least one of the groups is a polymerizable group, and both are polymerizable groups.

[0182] A １ A ２ , R １１１ , R １１３ and R １１４ Each of these independently corresponds to A in equation (2). １ A ２ , R １１１ , R １１３ and R １１４ This is synonymous with the following, and the preferred range is also similar. １１２ R in equation (5) is １１２ This is synonymous with the same thing, and the preferred range is also similar.

[0183] The polyimide precursor may contain one type of repeating unit represented by formula (2), or it may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). In addition to the repeating unit of formula (2), the polyimide precursor may also contain other types of repeating units.

[0184] One embodiment of the polyimide precursor in the present invention is one in which the content of repeating units represented by formula (2) is 50 mol% or more relative to the total number of repeating units. More preferably, the content is 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the content is not particularly limited, and all repeating units in the polyimide precursor except for the terminals may be repeating units represented by formula (2).

[0185] (Molecular Weight) The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 300,000, more preferably 5,000 to 100,000, even more preferably 10,000 to 50,000, and particularly preferably 15,000 to 40,000. The number-average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The degree of dispersion of the molecular weight of the above polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no particular upper limit for the degree of dispersion of the molecular weight of the polyimide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. In this specification, the degree of dispersion of molecular weight is a value calculated by weight-average molecular weight / number-average molecular weight. When resin composition A contains multiple types of polyimide precursors as resin (A), it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimide precursors are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polyimide precursors as a single resin are, respectively, within the above ranges.

[0186] <Polyimide> The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable that it contains repeating units represented by the following formula (4).

[0187]

[0188] In formula (4), R １３１ R represents a divalent organic group. １３２R represents a tetravalent organic group. If it has a polymerizable group, the polymerizable group is R １３１ and R １３２ It may be located at least one of the two, or it may be located at the end of the polyimide as shown in formula (4-1) or formula (4-2) below.

[0189] Formula (4-1)

[0190]

[0191] In formula (4-1), R １３３ is a polymerizable group, and the other groups are equivalent to formula (4).

[0192] Formula (4-2)

[0193] R １３４ and R １３５ At least one of the groups is a polymerizable group, and if it is not a polymerizable group, it is a monovalent organic group, and the other group is equivalent to formula (4).

[0194] Examples of polymerizable groups include groups containing the ethylenically unsaturated bond described above, or polymerizable groups other than those having the ethylenically unsaturated bond described above. １３１ R represents a divalent organic group. As an example of a divalent organic group, R in formula (2) is １１１ Similar examples are given, and the preferred range is also similar. １３１ Examples include diamine residues remaining after the removal of the amino group of a diamine. Examples of diamines include aliphatic diamines, cyclic aliphatic diamines, and aromatic diamines. A specific example is R in formula (2) of the polyimide precursor. １１１ Examples include:

[0195] R １３１ It is preferable that the diamine residue has at least two alkylene glycol units in its main chain, in order to more effectively suppress the occurrence of warping during firing. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule, and even more preferably, it is the above-mentioned diamine residue that does not contain an aromatic ring.

[0196] Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule include Jeffermin® KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0197] R １３２ R represents a tetravalent organic group. As an example of a tetravalent organic group, R in formula (2) is １１５ Similar examples are given, and the preferred range is also similar. For example, R １１５ The four bonders of the tetravalent organic group, as exemplified, bond with the four -C(=O)- parts in formula (4) to form a fused ring.

[0198] R １３２ Examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from a tetracarboxylic dianhydride. １３２ A specific example of this is R in formula (2) of the polyimide precursor. １１５ Examples include: From the standpoint of film strength, R １３２ Preferably, the aromatic diamine residue has one to four aromatic rings.

[0199] R １３１ and R １３２ It is also preferable that at least one of them has an OH group. More specifically, R １３１ Preferred candidates include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

[0200] Polyimide is a material in which all repeating units are R １３１ and R １３２The combination of R may include the repeating unit represented by the above formula (4), which is the same. １３１ and R １３２ The polyimide may contain repeating units represented by formula (4) above, which include two or more different combinations of elements. In addition to the repeating units represented by formula (4), the polyimide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by formula (2) above.

[0201] (Imidization rate (ring closure rate)) The imidization rate (also called the "ring closure rate") of polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting film. There is no particular upper limit to the above imidization rate, and it is sufficient if it is 100% or less. The above imidization rate is measured by, for example, the following method: The infrared absorption spectrum of the polyimide is measured, and the absorption peak originating from the imide structure is 1377 cm⁻¹. －１ The peak intensity P1 in the vicinity is determined. Next, the polyimide is heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum is measured again, at 1377 cm⁻¹. －１ Determine the nearby peak intensity P2. Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be calculated based on the following formula: Imidization rate (%) = (Peak intensity P1 / Peak intensity P2) × 100

[0202] (Molecular Weight) The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 300,000, more preferably 5,000 to 100,000, even more preferably 10,000 to 50,000, and particularly preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the bending resistance of the film after curing can be improved. To obtain a film with excellent mechanical properties (e.g., elongation at break), the weight-average molecular weight is preferably 15,000 or more. The number-average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The degree of dispersion of the molecular weight of the above polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no specific upper limit for the degree of dispersion of the molecular weight of polyimide, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. When resin composition A contains multiple types of polyimide as resin (A), it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polyimide are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the above multiple types of polyimide are treated as a single resin are each within the above range.

[0203] <Polybenzoxazole precursors> Examples of polybenzoxazole precursors include the compounds described in paragraphs

[0073] to

[0095] of International Publication No. 2022 / 145355. The foregoing description is incorporated herein by reference.

[0204] <Polybenzoxazoles> Examples of polybenzoxazoles include the compounds described in paragraphs

[0101] to

[0108] of International Publication No. 2022 / 145355. The foregoing description is incorporated herein by reference.

[0205] <Polyamide-imide precursors> Examples of polyamide-imide precursors include the compounds described in paragraphs

[0104] to

[0119] of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0206] <Polyamideimides> Examples of polyamideimides include the compounds described in paragraphs

[0125] to

[0138] of International Publication No. 2022 / 145355. The above description is incorporated herein by reference. Polyimide precursors, etc., are produced, for example, by the methods described in paragraphs

[0134] to

[0136] of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0207] <Content> The content of resin (A) in resin composition A is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more, based on the total solid content of resin composition A. Furthermore, the content of resin in resin composition A is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, particularly preferably 97% by mass or less, and most preferably 95% by mass or less, based on the total solid content of resin composition A. Resin composition A may contain only one type of resin (A) or may contain two or more types. When containing two or more types, it is preferable that the total amount is within the above range.

[0208] The resin composition A may also preferably contain at least two types of resins. Specifically, the resin composition A may contain a total of two or more types of resin (A) and other resins described later, or it may contain two or more types of resin (A), but it is preferable that it contains two or more types of resin (A). When the resin composition A contains two or more types of resin (A), for example, a polyimide precursor with a structure derived from a dianhydride (R in formula (2) above) １１５ Preferably, the polyimide precursor contains two or more different types of polyimide precursors.

[0209] [Other Resins] Resin composition A may contain the resin (A) described above and other resins different from resin (A) (hereinafter also simply referred to as "other resins"). Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. For example, by further adding (meth)acrylic resin, resin composition A with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, in place of the polymerizable compound described later, or in addition to the polymerizable compound described later, a polymerizable compound with a high polymerizability value and a weight-average molecular weight of 20,000 or less (for example, the molar amount of polymerizable groups per 1 g of resin is 1 × 10) may be used. －３ By adding (meth)acrylic resin (in a quantity of mol / g or more) to resin composition A, the coatability of resin composition A, the solvent resistance of the pattern (cured product), and other properties can be improved.

[0210] If resin composition A contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, particularly preferably 2% by mass or more, even more preferably 5% by mass or more, and most preferably 10% by mass or more, relative to the total solid content of resin composition A. The content of other resins in resin composition A is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, particularly preferably 60% by mass or less, and most preferably 50% by mass or less, relative to the total solid content of resin composition A. A preferred embodiment of resin composition A is one in which the content of other resins is low. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, particularly preferably 5% by mass or less, and most preferably 1% by mass or less, relative to the total solid content of resin composition A. The lower limit of the above content is not particularly limited and may be 0% by mass or more. Resin composition A may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, it is preferable that the total amount is within the above range.

[0211] [Polymerizable Compound] Resin composition A preferably contains a polymerizable compound. Examples of polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[0212] <Radical Crosslinking Agent> Resin composition A preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the above-mentioned groups containing an ethylenically unsaturated bond include vinyl group, allyl group, vinylphenyl group, (meth)acryloyl group, maleimide group, and (meth)acrylamide group. Among these, (meth)acryloyl group, (meth)acrylamide group, or vinylphenyl group is preferred, and from the viewpoint of reactivity, the (meth)acryloyl group is more preferred.

[0213] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more. The radical crosslinking agent may also have three or more ethylenically unsaturated bonds. As for the compound having two or more ethylenically unsaturated bonds, it is preferable that it has 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6. From the viewpoint of the film strength of the resulting pattern (cured product), it is also preferable that resin composition A contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0214] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0215] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid) or their esters and amides, preferably esters of unsaturated carboxylic acids with polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with polyhydric amine compounds. Addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxys are also suitably used. Dehydration condensation reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional carboxylic acids are also suitably used. Addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also suitably used. Furthermore, substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also preferred. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, or allyl ethers. For specific examples, refer to paragraphs

[0113] to

[0122] of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0216] The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph

[0203] of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0217] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs

[0204] to

[0208] of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0218] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and structures in which the (meth)acryloyl groups of these are linked via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0219] Examples of commercially available radical crosslinking agents include SR-494, a tetrafunctional acrylate having four ethylene oxy chains; SR-209, 231, and 239, difunctional methacrylates having four ethylene oxy chains (all manufactured by Sartomer Co., Ltd.); DPCA-60, a hexafunctional acrylate having six pentylene oxy chains; and TPA-330, a trifunctional acrylate having three isobutylene oxy chains (both manufactured by Nippon Kayaku Co., Ltd.); and urethane oligomers. Examples include UAS-10, UAB-140 (both manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Bremmer PME400 (manufactured by NOF Corporation).

[0220] Suitable radical crosslinking agents include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Unexamined Patent Publication No. 62-039418. Compounds having an amino structure or a sulfide structure in the molecule, as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238, can also be used as radical crosslinking agents.

[0221] The radical crosslinking agent may be a radical crosslinking agent having acidic groups such as carboxyl groups and phosphate groups. As a radical crosslinking agent having acidic groups, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group is more preferred. As a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group, a compound in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol is preferred. Examples of commercially available products include polybasic acid-modified acrylic oligomers such as M-510 and M-520 manufactured by Toagosei Co., Ltd.

[0222] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mg KOH / g, and more preferably 1 to 100 mg KOH / g. When the acid value of the radical crosslinking agent is within the above range, it exhibits excellent handling properties during manufacturing and excellent developability. It also exhibits good polymerization properties. The above acid value is measured in accordance with the description in JIS K 0070:1992.

[0223] As radical crosslinking agents, radical crosslinking agents having at least one selected from the group consisting of urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U") are also preferred. Examples of crosslinking agent U include compounds described in paragraphs

[0133] to

[0143] of International Publication No. 2023 / 190064. This content is incorporated herein by reference.

[0224] As radical crosslinking agents, bifunctional methacrylates or acrylates are preferred from the viewpoint of pattern resolution and film stretchability. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1 Examples include ,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, ethylene oxide (EO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, difunctional acrylates having urethane bonds, and difunctional methacrylates having urethane bonds. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the molecular weight of the polyethylene glycol chain is about 200. As a radical crosslinking agent, a monofunctional radical crosslinking agent is preferred from the viewpoint of suppressing warping of the pattern (cured product).Examples of monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate, as well as N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether. As monofunctional radical crosslinking agents, compounds with a boiling point of 100°C or higher under normal pressure are also preferred in order to suppress volatilization before exposure. Other examples of bifunctional or more functional radical crosslinking agents include diallyl phthalate and allyl compounds such as triallyl trimellitate.

[0225] (Content) When resin composition A contains a radical crosslinking agent, the content of the radical crosslinking agent is preferably more than 0% by mass and 60% by mass or less, relative to the total solid content of resin composition A. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0226] A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more agents are used in combination, it is preferable that their total amount be within the above range.

[0227] <Other Crosslinking Agents> Resin composition A may also preferably contain other crosslinking agents different from the radical crosslinking agents described above. Other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having multiple groups in their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products upon exposure to a photoacid generator or photobase generator, and more preferably compounds having multiple groups in their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of an acid or base. As the acid or base, it is preferable that the acid or base is generated from the photoacid generator or photobase generator in the exposure step. Examples of other crosslinking agents include the compounds described in paragraphs

[0179] to

[0207] of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0228] (Content) If resin composition A contains other crosslinking agents, the content of the other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, relative to the total solid content of resin composition A. Resin composition A may contain only one type of other crosslinking agent, or it may contain two or more types. If it contains two or more types, it is preferable that the total amount is within the above range.

[0229] [Polymerization Initiator] Resin composition A preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but a photopolymerization initiator is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, it may be an activator that acts with a photoexcited sensitizer to generate active radicals.

[0230] The photoradical polymerization initiator is present in an amount of at least about 50 L / mol with a wavelength in the range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１It is preferable to include at least one compound having a molar extinction coefficient. The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0231] Any known compound can be used as a photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, and compounds having a trihalomethyl group), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For further details, refer to paragraphs

[0165] to

[0182] of Japanese Patent Application Publication No. 2016-027357 and paragraphs

[0138] to

[0151] of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs

[0065] to

[0111] of Japanese Patent Publication No. 2014-130173, the compounds described in Japanese Patent No. 6301489, the peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019, the photopolymerization initiators described in International Publication No. 2018 / 221177, the photopolymerization initiators described in International Publication No. 2018 / 110179, the photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, the photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and the peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are incorporated herein by reference.

[0232] Examples of ketone compounds include the compounds described in paragraph

[0087] of Japanese Patent Publication No. 2015-087611, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

[0233] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds are preferred as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Publication No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and this is incorporated herein by reference.

[0234] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

[0235] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0236] As aminoacetophenone initiators, acylphosphine oxide initiators, and metallocene compounds, for example, compounds described in paragraphs

[0161] to

[0163] of International Publication No. 2021 / 112189 can also be suitably used. This information is incorporated herein.

[0237] Oxime compounds are preferred as photoradical polymerization initiators. Using oxime compounds makes it possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0238] As for oxime compounds, the compounds described in Japanese Patent Publication No. 2001-233842, the compounds described in Japanese Patent Publication No. 2000-080068, the compounds described in Japanese Patent Publication No. 2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Perkin II (1979, pp. 156-162), and the Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs

[0025] to

[0038] of International Publication No. 2017 / 164127, and compounds described in International Publication No. 2013 / 167515, the like, which are incorporated herein by reference.

[0239] As oxime compounds, for example, compounds with the following structures are preferred: 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, or 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In resin composition A, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a >C=N-O-C(=O)- linking group in its molecule.

[0240]

[0241] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA optomer N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arclus NCI-730, NCI-831, and ADEKA Arclus NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemix Co., Ltd.), and SpeedCure PDO (SARTOMER Examples include those manufactured by ARKEMA. Additionally, oxime compounds with the following structures can also be used.

[0242]

[0243] As photoradical polymerization initiators, for example, oxime compounds having a fluorene ring as described in paragraphs

[0169] to

[0171] of International Publication No. 2021 / 112189, oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring, and oxime compounds having a fluorine atom may be used. Also, oxime compounds having a nitro group as described in paragraphs

[0208] to

[0210] of International Publication No. 2021 / 020359, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxyl group is attached to the carbazole skeleton may be used. These contents are incorporated herein by reference.

[0244] In addition, as a photopolymerization initiator, compounds described in paragraphs

[0113] to

[0117] of Japanese Patent Application Publication No. 2023-058585 may be used. This description is incorporated into the present specification.

[0245] <Content> When resin composition A contains a polymerization initiator, the content of the polymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, relative to the total solid content of resin composition A. Resin composition A may contain only one type of polymerization initiator or two or more types. When two or more types are included, it is preferable that the total amount be within the above range. Note that since photopolymerization initiators may also function as thermal polymerization initiators, crosslinking by the photopolymerization initiator may be further advanced by heating with an oven or hot plate, etc.

[0246] [Solvent] Resin composition A preferably contains a solvent. Specific examples of the solvent are the same as those for the photosensitive resin composition described above, but for reasons that the effects of the present invention are superior, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more such solvents, is preferred. The combined use of dimethyl sulfoxide and γ-butyrolactone, or the combined use of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

[0247] <Solvent Content> From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the composition is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the application method. If two or more solvents are included, it is preferable that their total is within the above range.

[0248] [Other Additives] Resin composition A may contain other additives. Such additives may include, for example, photoacid generators, sensitizers, chain transfer agents, base generators, metal adhesion modifiers (e.g., silane coupling agents, aluminum-based adhesion aids), migration inhibitors, polymerization inhibitors, light absorbers, surfactants, metal complexes, higher fatty acid derivatives, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers and flame retardants). By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs

[0183] onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph

[0237] of the corresponding U.S. Patent Application Publication No. 2013 / 0034812), paragraphs

[0101] to

[0104] ,

[0107] to

[0109] of Japanese Patent Application Publication No. 2008-250074, and the contents of these are incorporated herein. When these additives are incorporated, their total content is preferably 20% by mass or less of the solid content of resin composition A, more preferably 10% by mass or less, and even more preferably 3% by mass or less.

[0249] [Thickness] The thickness of the insulating portion (insulating film) is not particularly limited, but for reasons that the effects of the present invention are superior, it is preferably 0.1 to 100 μm, more preferably 1 to 50 μm, and even more preferably 5 to 20 μm.

[0250] [III] Other steps The redistribution layer formation step may include steps other than those described above. For example, if the substrate is not a package substrate, the redistribution layer formation step may include a package substrate connection step that connects the package substrate and the redistribution layer. It is preferable that the package substrate is formed on the side opposite to the side on which the semiconductor elements in the redistribution layer are formed. Known methods can be used to connect the package substrate and the redistribution layer, and specifically, methods using bonding wires or solder balls can be used. This electrically connects the package substrate and the redistribution layer.

[0251] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0252] [Synthesis of resins for photosensitive resin compositions]

[0253] [Synthesis of Resin A-1] 194.3 g of cyclohexanone is placed in a three-necked flask under a nitrogen atmosphere and heated to 80°C. 19.5 g, 23.9 g, and 6.6 g of monomers corresponding to each repeating unit of Resin A-1 (described below) are added dropwise from left to right, along with a solution of polymerization initiator V-601 (Wako Pure Chemical Industries, 3.17 g) dissolved in 105 g of cyclohexanone, over 6 hours. After the dropwise addition is complete, the reaction is continued at 80°C for another 2 hours. After the reaction solution has cooled, it is added dropwise to a methanol-water mixture over 20 minutes. The precipitated powder is filtered and dried to obtain Resin A-1 (31.6 g), which is an acid-degradable resin. The composition ratio (molar ratio) of the repeating units, determined by NMR (nuclear magnetic resonance) spectroscopy, is 40 / 50 / 10. The weight-average molecular weight of the obtained Resin A-1 is 20,000 in standard polystyrene equivalent, as determined by GPC.

[0254] [Synthesis of Resins A-2 to A-5] Resins A-2 to A-5 are synthesized using the same procedure or a known procedure. The structures of resins A-1 to A-5 are shown below. Table 1 below summarizes the Mw and composition ratio (molar ratio) of each resin.

[0255]

[0256] [Preparation of Photosensitive Resin Compositions] The photosensitive resin compositions PR-1 to PR-9 used in the examples and comparative examples are obtained by mixing the components listed in Table 2 below. Specifically, the content of each component listed in Table 2 shall be the amount (parts by mass) indicated in the "parts by mass" column for each column in Table 2. The obtained compositions are subjected to pressure filtration using a polytetrafluoroethylene filter with a pore size of 0.5 μm.

[0257]

[0258] Each component in Table 2 is as follows.

[0259] [Resin] A-1 to A-5 are as described above.

[0260] [Photosensitive agent] ・B-1: a compound having the structure shown below ・B-2: a compound having the structure shown below ・B-3: a compound having the structure shown below ・B-4: a compound having the structure shown below

[0261] [Acid diffusion controller] ・C-1: trioctylamine ・C-2: tetrabutylammonium hydroxide

[0262] [Crosslinking agent] ・D-1: NK Ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0263] [Polymerization inhibitor] ・E-1: 4-methoxyphenol

[0264] [Solvent] ・L-1: propylene glycol monomethyl ether acetate (PGMEA) ・L-2: propylene glycol monomethyl ether (PGME)

[0265] [Examples 1 to 14]

[0266] [Step 1] The following polyimide precursor resin composition is applied onto a silicon wafer by spin coating, and dried at 110°C for 5 minutes. The temperature is further increased at a rate of 10°C / minute under a nitrogen atmosphere, and heated at 230°C for 2 hours. Thereby, a polyimide insulating film with a film thickness of 5 μm is formed. Next, a Ti barrier layer (seed adhesion layer) with a film thickness of 50 nm and a Cu seed layer with a film thickness of 150 nm are formed in this order on the obtained polyimide insulating film by sputtering. The photosensitive resin composition described in the "Composition" column of Table 3 is applied onto the obtained laminate by spin coating, and soft-baked under the conditions described in the "SB" column of Table 3, thereby forming a 12 μm-thick photosensitive resin composition layer.

[0267] <Polyimide Precursor Resin Composition> Resin: 24 parts by mass of resin consisting of the following repeating unit structure Crosslinking agent: 5 parts by mass of NK ester 4G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) Thermal polymerization initiator: Perbutyl P (manufactured by NOF Corporation) 1 part by mass Solvent: 20 parts by mass of dimethyl sulfoxide Solvent: 50 parts by mass of γ-butyrolactone

[0268] [Step 2] Subsequently, using a line and space mask in which a 3 μm space pattern is formed with a line-to-space ratio of 1:1, an i-line stepper (Canon: FPA-5520iV, NA=0.16, σ=0.7) is used to perform exposure processing at the exposure amount indicated in the "Exposure Amount" column of Table 3. After that, bake (Post Exposure Bake; PEB) is performed under the conditions shown in the "PEB" column of Table 3.

[0269] [Step 3] Next, develop the wafer by paddle for 30 seconds with the developer listed in the "Developer" column of Table 3, and then rotate the wafer at a rotation speed of 4000 rpm (revolutions per minute) for 30 seconds. After that, perform post-bake under the conditions listed in the "Post-bake" column of Table 3 to obtain a line and space pattern (negative resist pattern).

[0270] [Step 4] Next, the parts are treated with sulfuric acid (contact with a 10% by mass sulfuric acid aqueous solution for 60 seconds), followed by rinsing with water. Then, they are immersed in 300 mL of copper plating solution (product name "CU8502", manufactured by Dow Chemical), with a plating bath temperature of 25°C and a current density of 2 A / dm². ２ Set the parameters to the specified value and perform electroplating for 10 minutes to form plated copper (plating layer) up to a height of 6 μm in the space areas of the line and space pattern.

[0271] [Step 5] Next, the negative resist pattern is removed by immersing the material in a resist stripping solution (JELK-001, manufactured by Kanto Chemical Co., Ltd.) at 60°C for 5 minutes, and then rinsing it with pure water (rinsing solution). Furthermore, the Cu seed layer and Ti barrier layer are wet-etched by sequentially treating them with Cu seed etching solution and Ti seed etching solution. In this way, a patterned plating layer (plating pattern) is obtained.

[0272] [Comparative Example 1] A patterned plating layer (plating pattern) is obtained by following the same procedure as in Example 1 described above, except that PR-8 is used as the photosensitive resin composition, Dev-3 is used as the developer, and after development, the plate is rinsed by paddle with a rinsing solution (Dev-4). In Comparative Example 1, the resist pattern is positive type.

[0273] [Comparative Example 2] PR-9 was used as the photosensitive resin composition, and the exposure dose was 400 mJ / cm². ２ Except for not performing PEB, a patterned plating layer (plating pattern) is obtained by following the same procedure as in Example 3 described above.

[0274] [Evaluation] The following evaluation was conducted.

[0275] [Resolution] In each example, the thickness of the photosensitive resin composition layer was set to 8 μm, and a line and space mask was used to form space patterns of 1, 2, and 3 μm in a line-to-space ratio of 1:1 to obtain line and space patterns (Examples 1 to 14 and Comparative Example 2: negative resist pattern, Comparative Example 1: positive resist pattern). The obtained line and space patterns were observed using a cross-sectional SEM (Hitachi: S4800). The smallest space mask dimension in which the line pattern was not collapsed and no bridge residue was generated in the space areas was measured and judged according to the evaluation criteria below. The results are shown in Table 3. The smaller the minimum mask dimension, the better the resolution. From the viewpoint of resolution, A or B is preferable, and A is more preferable.

[0276] -Evaluation Criteria- A: The smallest space mask dimension is 1 μm. B: The smallest space mask dimension is 2 μm. C: The smallest space mask dimension is 3 μm.

[0277] [Pattern Collapse During Plating] After forming plated copper (plating layer) up to a height of 6 μm in the space areas of the line-and-space pattern in step 4, the composite film consisting of the photosensitive resin composition and plated copper is observed using a cross-sectional SEM (Hitachi S4800), and the degree of collapse of the photosensitive resin composition pattern that serves as the template is determined according to the evaluation criteria below. The results are shown in Table 3. The less pattern interfacial peeling and the less shape change is observed before and after the plating process, the higher the plating resistance and the better the template is.

[0278] -Evaluation Criteria- A: No interfacial delamination or shape change is observed. B: Either interfacial delamination or shape change occurs. C: Both interfacial delamination and shape change occur.

[0279] [Residue during peeling] After peeling the resist pattern in step 5, the frequency of residue generation is determined using an optical microscope. Specifically, 200 arbitrary locations on the entire wafer surface are imaged with a 50 μm square field of view, and the percentage of images showing residue due to poor peeling of the photosensitive resin composition is examined and judged according to the evaluation criteria below. The results are shown in Table 3. A lower residue generation rate indicates a mold with superior peeling properties.

[0280] -Evaluation Criteria- A: Residue generation rate is 1% or less. B: Residue generation rate is greater than 1% but 5% or less. C: Residue generation rate is greater than 5%.

[0281] [Pattern Shape] The shape of the copper wiring (plating pattern) obtained in step 5 is observed using a cross-sectional SEM (Hitachi S4800). The interface length (Lb) of the lower part of the copper wiring on the substrate side and the interface length (Lt) of the upper part of the copper wiring in contact with air are measured. The ratio of these two is calculated and judged according to the following criteria. The larger Lb is relative to Lt, the larger the area of ​​the substrate-side surface of the plating pattern is compared to the area of ​​the other surface, which indicates that the copper wiring is less likely to collapse and that it is a good pattern. From the viewpoint of collapse resistance, A or B is preferable, and A is more preferable.

[0282] -Evaluation Criteria- A: The value calculated by Lb / Lt is 1.05 or higher. B: The value calculated by Lb / Lt is 1.00 or higher and less than 1.05. C: The value calculated by Lb / Lt is less than 1.00.

[0283]

[0284] [Composition] In Table 3, PR-1 to PR-9 are as described above.

[0285] [Developer and Rinse Solution] In Table 3, the developer and rinse solution are as follows: Dev-1: Propylene glycol monomethyl ether acetate (PGMEA) Dev-2: Butyl acetate Dev-3: 2.38% by mass aqueous solution of tetramethylammonium hydroxide Dev-4: Pure water Dev-5: 4-methyl-2-pentanol Dev-6: 2-heptanone

[0286] [Summary of Results] As can be seen from Table 3, Examples 1 to 14, which correspond to the formation process of the present invention, exhibit excellent resolution, plating resistance, peelability, and collapse resistance. Comparing Examples 3 and 10 to 14 (comparison of embodiments that differ only in the type of photosensitive resin composition), Examples 3, 10, 12, and 14, in which the resin (B) has repeating units represented by formula (B) and the photoacid generator is a photoacid generator that generates an acid without a fluoride alkyl group, show better collapse resistance. Among these, Examples 3, 10, and 14, in which the photoacid generator is a nonionic type photoacid generator, show even better resolution and peelability.

[0287] On the other hand, in Comparative Example 1, where a positive resist pattern is obtained using an alkaline developer in step 3, the resulting plating pattern has a small Lb / Lt ratio and insufficient resistance to collapse. Furthermore, in Comparative Example 2, where a resin other than resin (B) and a crosslinking agent are used in step 1, the resolution is insufficient.

[0288] 10 Substrate 20 Photosensitive resin composition layer 20a Exposed area 20b Unexposed area 30 Plating layer 30b Substrate-side surface of plating layer 30 30t Other surface of plating layer 30 (surface in contact with air) 32 Plating layer 32b Substrate-side surface of plating layer 32 32t Other surface of plating layer 32 (surface in contact with air) M Line and space mask

Claims

1. A method for manufacturing a semiconductor device, comprising: a preparation step for preparing a semiconductor element; and a redistribution layer formation step for forming a redistribution layer connected to the semiconductor element and having an insulating portion and a conductive portion, wherein the redistribution layer formation step comprises, in this order: step 1 for forming a photosensitive resin composition layer on a substrate containing a resin whose polarity changes by the action of an acid and a photoacid generator; step 2 for pattern exposure of the photosensitive resin composition layer; step 3 for obtaining a negative resist pattern by removing the unexposed portion of the exposed photosensitive resin composition layer with a developer containing an organic solvent; step 4 for forming a plating layer using the negative resist pattern as a template; and step 5 for obtaining a patterned plating layer by peeling off the negative resist pattern.

2. The method for manufacturing a semiconductor device according to claim 1, wherein the developing solution contains at least one organic solvent selected from the group consisting of butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, cyclopentanone, cyclohexanone, and mesitylene.

3. The method for manufacturing a semiconductor device according to claim 1, wherein the exposure wavelength in step 2 is in the range of 350 to 450 nm.

4. The method for manufacturing a semiconductor device according to claim 1, wherein the resin has repeating units represented by the following formula. In the formula, R represents a group that is eliminated by an acid, and X represents a hydrogen atom or a methyl group.

5. The method for manufacturing a semiconductor device according to claim 1, wherein the photoacid generator is a photoacid generator that generates an acid that does not have an alkyl fluoride group.

6. The method for manufacturing a semiconductor device according to claim 1, wherein the photoacid generator is a nonionic photoacid generator.

7. The method for manufacturing a semiconductor device according to claim 1, wherein the plating method in step 4 is an electroplating method.

8. A method for manufacturing a semiconductor device according to claim 1, comprising the step of forming a seed adhesion layer and a seed layer on the negative resist pattern in that order, prior to step 4.

9. The method for manufacturing a semiconductor device according to claim 8, wherein the seed adhesion layer is a layer containing Ti, and the seed layer is a layer containing Cu.

10. A method for manufacturing a semiconductor device according to claim 8, comprising the step of removing the seed adhesion layer and the seed layer.

11. The method for manufacturing a semiconductor device according to claim 1, wherein the area of ​​the substrate-side surface of the plating layer on the pattern is larger than the area of ​​the other surface.

12. The method for manufacturing a semiconductor device according to claim 1, wherein the insulating portion is a resin layer comprising at least one resin selected from the group consisting of polyimide and polybenzoxazole.

13. A photosensitive resin composition used in a method for manufacturing a semiconductor device according to any one of claims 1 to 12, comprising a resin whose polarity changes upon the action of an acid and a photoacid generator.

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