Method for manufacturing semiconductor device, resin composition for forming insulating film, and photosensitive resin composition

Abstract

The present invention addresses the problem of providing: a method for manufacturing a semiconductor device, the method being capable of manufacturing a rewiring layer which comprises a conductive part and an insulating part having a pattern with excellent resolution and in which peeling at the interface between the insulating part and the conductive part is suppressed; a resin composition for forming an insulating film; and a photosensitive resin composition. This method for manufacturing a semiconductor device includes a semiconductor element preparation step and a rewiring layer formation step. The rewiring layer formation step includes: a step 1 for forming an insulating film using a resin composition A; a step 2 for forming a resist layer on the insulating film using a photosensitive resin composition B; a step 3 for pattern-exposing the resist layer; a step 4 for processing the pattern-exposed resist layer with a developer containing an organic solvent to form a negative resist pattern; a step 5 for dry-etching the insulating film using the negative resist pattern as a mask to form an insulating part having a recess; and a step 6 for forming a conductive part by means of plating.

Description

Method for manufacturing semiconductor devices, resin composition for forming insulating film, and photosensitive resin composition

[0001] The present invention relates to a method for manufacturing semiconductor devices, a resin composition for forming insulating films, 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 sometimes electrically connected via an interposer having conductive parts such as wiring. In addition to Si interposers, a redistribution layer (RDL) made of resin, comprising an insulating part and a conductive part, is used as an organic interposer from the viewpoint of low cost, etc. The application of the semi-additive process (SAP) to the manufacturing of the above redistribution layer is being considered. An example of a method for manufacturing a redistribution layer by the semi-additive process is as follows: First, an insulating film is formed on the surface of a power supply layer (e.g., a copper thin film) formed on a substrate (e.g., a silicon wafer). Next, the insulating film is etched using a resist pattern as a mask to obtain an insulating part having a recess (e.g., a via or trench). After that, a conductive part is formed in the recess of the insulating part by electroplating. In this way, a redistribution layer having an insulating portion and a conductive portion is formed on the substrate. Patent Document 1 discloses the use of a composition containing a silicon-containing polymer or the like as a material used to form a resist pattern when manufacturing such a redistribution layer.

[0003] Special Publication No. 2023-517998

[0004] In recent years, miniaturization has been required not only for wiring manufactured in the front-end process of semiconductor devices, but also for wiring in redistribution layers manufactured in the back-end process of semiconductor devices. Therefore, when manufacturing a redistribution layer with a patterned insulating portion, excellent resolution of the insulating portion pattern is required. Furthermore, from the viewpoint of improving the reliability of semiconductor devices, a redistribution layer in which delamination at the interface between the insulating portion and the conductive portion is suppressed is required. The present inventors, referring to the description in Patent Document 1, formed a resist layer using a photosensitive resin composition containing a resin containing silicon atoms, positive-type developed with an aqueous alkaline developer to form a resist pattern on an insulating film, and then formed a redistribution layer having an insulating portion by etching the insulating film using the resist pattern as a mask. However, they found that the resolution of the insulating portion pattern was insufficient, or delamination at the interface between the insulating portion and the conductive portion was significant, indicating that there is room for improvement.

[0005] Therefore, the present invention aims to provide a method for manufacturing a semiconductor device that can produce a redistribution layer having an insulating portion and a conductive portion, wherein the insulating portion has a pattern with excellent resolution, and peeling at the interface between the insulating portion and the conductive portion is suppressed. The present invention also aims to provide a resin composition for forming an insulating film and a photosensitive resin composition.

[0006] As a result of diligent research into the above problems, the inventors have 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; 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: a step 1 for forming an insulating film by applying a resin composition A, which comprises at least one resin (A) selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor, onto a substrate; a step 2 for forming a resist layer by applying a photosensitive resin composition B, which comprises a resin (B) having repeating units having groups that decompose by the action of an acid to produce polar groups and silicon atoms, and a photoacid generator, onto the insulating film; a step 3 for pattern exposure of the resist layer; a step 4 for treating the resist layer after pattern exposure with a developer containing an organic solvent to form a negative resist pattern on the insulating film; and a step 5 for dry etching the insulating film using the negative resist pattern as a mask to form the insulating portion having a recess. A method for manufacturing a semiconductor device, comprising in this order: step 6, a step of plating the insulating portion having the recess to form the conductive portion. [2] A method for manufacturing a semiconductor device according to [1], wherein the developer in step 4 comprises at least one organic solvent selected from the group consisting of butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclopentanone, cyclohexanone, and mesitylene. [3] A method for manufacturing a semiconductor device according to [1] or [2], wherein the exposure wavelength in step 3 is in the range of 300 to 450 nm. [4] A method for manufacturing a semiconductor device according to any one of [1] to [3], wherein the resin (A) comprises at least one of the following structures. * indicates the bond position. [5] A method for manufacturing a semiconductor device according to any one of [1] to [4], wherein the weight-average molecular weight of the resin (A) is 30,000 to 200,000. [6] A method for manufacturing a semiconductor device according to any one of [1] to [5], wherein the resin composition A further comprises a nitrogen-containing heterocyclic compound. [7] A method for manufacturing a semiconductor device according to any one of [1] to [6], wherein the resin composition A further comprises at least one antioxidant selected from the group consisting of phenol compounds, phosphite ester compounds, thioether compounds, and phosphonite compounds. [8] A method for manufacturing a semiconductor device according to any one of [1] to [7], wherein the resin composition A further comprises an adhesive containing an alkoxysilyl group. [9] A method for manufacturing a semiconductor device according to any one of [1] to [8], wherein the content of silicon atoms in the resin (B) is 5.0% by mass or more based on the total amount of the resin (B).

[10] The method for manufacturing a semiconductor device according to any one of [1] to [9], wherein the photoacid generator contained in the photosensitive resin composition B is a photoacid generator that does not contain an alkyl fluoride.

[11] The method for manufacturing a semiconductor device according to any one of [1] to

[10] , wherein the photoacid generator contained in the photosensitive resin composition B is a nonionic type photoacid generator.

[12] The method for manufacturing a semiconductor device according to any one of [1] to

[11] , wherein the dry etching in step 5 is reactive ion etching with a gas containing oxygen atoms.

[13] The method for manufacturing a semiconductor device according to any one of [1] to

[12] , further comprising a step of removing the negative type resist pattern between step 5 and step 6.

[14] The method for manufacturing a semiconductor device according to any one of [1] to

[13] , wherein the plating treatment in step 6 is electrolytic plating.

[15] A resin composition for forming an insulating film, used in a method for manufacturing a semiconductor device as described in any of [1] to

[14] , comprising at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor.

[16] A photosensitive resin composition used in a method for manufacturing a semiconductor device as described in any of [1] to

[14] , comprising: a resin containing repeating units having groups that decompose by the action of an acid to produce polar groups and silicon atoms; and a photoacid generator.

[0008] According to the present invention, a method for manufacturing a semiconductor device is available that can produce a redistribution layer comprising an insulating portion and a conductive portion, wherein the insulating portion has a pattern with excellent resolution, and peeling at the interface between the insulating portion and the conductive portion is suppressed. Furthermore, according to the present invention, a resin composition for forming an insulating film and a photosensitive resin composition can also be provided.

[0009] This is a schematic cross-sectional view illustrating step 1. This is a schematic cross-sectional view illustrating step 2. This is a schematic cross-sectional view illustrating step 3. This is a schematic cross-sectional view illustrating step 4. This is a schematic cross-sectional view illustrating step 5. This is a schematic cross-sectional view illustrating step a. This is a schematic cross-sectional view illustrating step 6. This is a schematic cross-sectional view illustrating a member obtained by carrying out steps 1 to 5 and step a. This is a schematic cross-sectional view illustrating step b. This is a schematic cross-sectional view illustrating step c. This is a schematic cross-sectional view illustrating step 6. This is a schematic cross-sectional view illustrating step d.

[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 the structural formula represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl 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.

[0011] In this specification, a polyimide precursor is a resin that undergoes a change in chemical structure due to external stimuli to become a polyimide, preferably a resin that undergoes a change in chemical structure due to heat to become a polyimide, and more preferably a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a polyimide. In this specification, a polyimide is a resin having repeating units containing imide groups in its molecular chain, and preferably a resin having repeating units containing imide ring structures in its molecular chain. Furthermore, if the polyimide is a linear resin, it is preferable that the polyimide is a resin having repeating units containing imide groups in its main chain, and more preferably a resin having repeating units containing imide ring structures in its main chain. In this specification, "main chain" refers to the relatively longest bonding chain in the resin molecule, and "side chain" refers to the other bonding chains. In this specification, an imide group is 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 two carbon atoms and nitrogen atoms in the above-mentioned imide as ring member atoms. The imide ring structure is preferably a five-membered ring. The polyimide may also be a so-called polyamide imide, which has an amide group in the molecular chain in addition to the imide group. 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. Also, # 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.

[0012] [Method for Manufacturing Semiconductor Devices] The present invention provides a method for manufacturing semiconductor devices, comprising a preparation step of preparing a semiconductor element, and a redistribution layer formation step of forming a redistribution layer connected to the semiconductor element and having an insulating portion and a conductive portion. In the method for manufacturing semiconductor devices of the present invention, the redistribution layer formation step comprises the following steps 1 to 6 in this order. Step 1: Apply a resin composition A, which includes at least one resin (A) selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor, to a substrate to form an insulating film. Step 2: Apply a photosensitive resin composition B, which includes a resin (B) containing repeating units having groups that decompose upon the action of an acid to generate polar groups and silicon atoms, and a photoacid generator, to the insulating film to form a resist layer. Step 3: Pattern exposure of the resist layer. Step 4: Treatment of the resist layer after pattern exposure with a developer containing an organic solvent to form a negative resist pattern on the insulating film. Step 5: Dry etching of the insulating film using the negative resist pattern as a mask to form the insulating portion having recesses. Step 6: Plating treatment applied to the insulating portion having recesses to form the conductive portion.

[0013] The semiconductor device manufacturing method of the present invention makes it possible to manufacture a redistribution layer having an insulating portion with a pattern with excellent resolution and suppressing delamination at the interface between the insulating portion and the conductive portion. The reason for this is generally presumed to be as follows. The semiconductor device manufacturing method of the present invention includes steps 2 to 5 described above in order to form recesses in the insulating film. Here, the resist layer obtained in step 2 contains a resin (B) containing silicon atoms and is highly hydrophobic, so depending on the type of developer used for developing the resist layer, fine patterning may be difficult. To address this problem, it is thought that a resist pattern with excellent resolution can be obtained by developing the resist layer using a developer containing an organic solvent with high affinity for the highly hydrophobic resist layer (step 4). It is presumed that an insulating portion with a pattern with excellent resolution can be obtained by using the resist pattern obtained in this way as a mask (step 5). Furthermore, it is presumed that by using a developer containing an organic solvent when developing the resist layer (step 4), the insulating film in the layer below the resist layer is less susceptible to damage from the developer compared to when using an aqueous alkaline developer, thus suppressing delamination at the interface between the insulating portion and the conductive portion. In this case, if the redistribution layer is used for a long period of time under high temperature and high humidity conditions, damage to the insulating film may become apparent, and the above-mentioned delamination may become more pronounced. However, according to the semiconductor device manufacturing method of the present invention, for the reasons mentioned above, damage to the insulating film associated with the development process of the resist layer is reduced, so even if the redistribution layer is used for a long period of time under high temperature and high humidity conditions, the occurrence of the above-mentioned delamination is sufficiently suppressed.

[0014] In the following, preferred embodiments of the semiconductor device manufacturing method of the present invention will be described for each embodiment.

[0015] [First Embodiment] The present invention provides a method for manufacturing a semiconductor device, comprising: a preparation step of preparing a semiconductor element; and a redistribution layer formation step of forming a redistribution layer connected to the semiconductor element and having an insulating portion and a conductive portion, wherein the redistribution layer formation step includes the following steps 1, 2, 3, 4, 5, a, and 6 in this order. Step 1: Apply a resin composition A (hereinafter also referred to as "composition A"), which includes at least one resin (A) selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor, to a substrate to form an insulating film. Step 2: Apply a photosensitive resin composition B (hereinafter also referred to as "composition B"), which includes a resin (B) containing repeating units having groups that decompose by the action of an acid to generate polar groups and silicon atoms, and a photoacid generator, to the insulating film to form a resist layer. Step 3: Pattern exposure of the resist layer. Step 4: Treatment of the resist layer after pattern exposure with a developer containing an organic solvent to form a negative resist pattern on the insulating film. Step 5: Dry etching of the insulating film using the negative resist pattern as a mask to form the insulating portion having recesses. Step a: Remove the negative resist pattern. Step 6: Plating treatment is applied to the insulating portion having recesses to form the conductive portion.

[0016] The procedures for each step in the first embodiment will be described in detail below, with reference to the drawings as necessary. Note that the following description will focus on the case where the first embodiment includes step a, but step a is an optional step and does not need to be performed.

[0017] <Preparation Process> The preparation process is the process of preparing the semiconductor device. 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.

[0018] 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).

[0019] <Redistribution Layer Formation Process> The redistribution layer formation process is a process of forming a redistribution layer that is connected to the semiconductor element and has an insulating portion and a conductive portion, and includes the following steps 1, 2, 3, 4, 5, a, and 6 in this order.

[0020] The method of connecting the semiconductor element and the redistribution layer is not particularly limited, and known methods can be used. Specifically, methods using bonding wires or solder balls are examples of such methods. The semiconductor element and the redistribution layer are electrically connected by the redistribution layer formation process.

[0021] (Step 1) Figure 1A is a schematic cross-sectional view illustrating Step 1, showing a cross-section along the thickness direction of the substrate 10 and the insulating film 20. In Step 1, composition A is applied to the substrate 10 to form the insulating film 20 on the substrate 10. In the example of Figure 1A, an example is shown in which the insulating film 20 is formed in contact with the substrate 10, but it is not limited to this, and the insulating film 20 may be formed on the substrate 10 via other layers not shown. In the example of Figure 1A, an example is shown in which the insulating film 20 is formed over the entire surface of one side of the substrate 10, but it is not limited to this, and the insulating film 20 may be formed on at least a part of one side of the substrate 10. Furthermore, the insulating film 20 may be formed on both sides of the substrate 10.

[0022] Coating is preferred as a means of applying composition A onto the substrate 10. Specific application methods 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 composition A and the coating conditions according to the application method, 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 10.

[0023] Step 1 may include a drying process (drying treatment) to dry the composition A applied to the substrate 10. This removes components such as solvents from the composition A applied to the substrate 10. The drying temperature in the drying treatment is preferably 50 to 150°C. Drying may also be performed under reduced pressure. The drying time is preferably 30 seconds to 20 minutes.

[0024] The substrate 10 is a component that supports the redistribution layer obtained by the redistribution layer formation process. Examples of substrates 10 include inorganic substrates, resin substrates, and composite substrates thereof. Specific examples of materials constituting the inorganic substrate include glass, quartz, silicon, and silicon nitride. The 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 this embodiment, a substrate containing the semiconductor elements described above may be used as the substrate 10. Alternatively, in this embodiment, a package substrate may be used as the substrate 10. Hereinafter, a package substrate is a substrate used when mounting semiconductor elements onto a motherboard or the like.

[0026] - Insulating film The insulating film 20 is a film formed on the substrate 10 by composition A, and corresponds to the insulating portion in the redistribution layer described later. The thickness of the insulating film 20 is preferably 1 to 20 μm, and more preferably 2 to 15 μm.

[0027] Composition A comprises resin (A). Preferably, composition A is a non-photosensitive resin composition. Examples of non-photosensitive resin compositions include those that do not contain components having polarity-changing groups (e.g., acid-degradable groups described later), and those that do not contain photopolymerization initiators (described later) and photoacid generators (described later). When a non-photosensitive resin composition is used and resin (A) is a polyimide precursor, the curing of resin (A) proceeds well, so an insulating part with excellent film strength (e.g., Young's modulus or elongation at break) can be obtained. Note that resin (A) may have polymerizable groups. Details of composition A will be described later.

[0028] Resin (A) is at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor. It is preferable that resin (A) contained in composition A does not have any radical polymerizable groups (described later) or polarity-converting groups such as acid-degradable groups (described later). Details of resin (A) will be explained later.

[0029] From the viewpoint of further improving the film strength of the insulating portion, the resin (A) preferably contains at least one of the following structures (hereinafter also referred to as "specific ring structure X").

[0030]

[0031] In the structure above, * indicates a bonding position.

[0032] The weight-average molecular weight (Mw) of resin (A) is preferably 30,000 to 200,000, more preferably 35,000 to 150,000, and even more preferably 40,000 to 100,000. If the Mw of resin (A) is above the lower limit, at least one of the following can be achieved: delamination at the interface between the insulating and conductive parts can be further suppressed, and the film strength of the insulating part can be further improved. If the Mw of resin (A) is below the upper limit, at least one of the following can be achieved: the resolution of the insulating part can be further improved, and delamination at the interface between the insulating and conductive parts can be further suppressed.

[0033] From the viewpoint of further suppressing delamination at the interface between the insulating and conductive parts, composition A preferably further contains a nitrogen-containing heterocyclic compound. Specific examples of nitrogen-containing heterocyclic compounds include the migration inhibitor and the rust inhibitor used as the migration inhibitor in the later description of composition A.

[0034] From the viewpoint of further suppressing peeling at the interface between the insulating portion and the conductive portion, composition A preferably further contains at least one antioxidant selected from the group consisting of phenol compounds, phosphite ester compounds, thioether compounds, and phosphonite compounds. Regarding phenol compounds, phosphite ester compounds, and thioether compounds, the contents of paragraphs

[0433] to

[0443] of Japanese Patent Application Publication No. 2025-020376 can be referenced, and these contents are incorporated herein. Furthermore, regarding phosphonite compounds, the contents of paragraphs

[0041] to

[0043] of Japanese Patent Application Publication No. 2012-255142 can be referenced, and these contents are incorporated herein.

[0035] From the viewpoint of further suppressing delamination at the interface between the insulating and conductive parts, composition A preferably further contains an adhesive containing an alkoxysilyl group. Examples of adhesives containing an alkoxysilyl group include metal adhesion modifiers (preferably silane coupling agents having an alkoxysilyl group) as described in the following section on composition A.

[0036] (Step 2) Figure 1B is a schematic cross-sectional view illustrating Step 2, showing cross-sections along the thickness direction of the substrate 10, insulating film 20, and resist layer 30. In Step 2, composition B is applied to the insulating film 20 to form the resist layer 30 on the insulating film 20.

[0037] The means for applying composition B onto the insulating film 20 can be the same as the means for applying composition A onto the substrate 10 in step 1, and the preferred embodiment is also the same.

[0038] Step 2 may include a drying process (drying treatment) of composition B applied on the insulating film 20. This removes components such as solvents from composition B applied on the insulating film 20. Preferred drying temperature and drying time in the drying treatment of Step 2 are the same as preferred drying temperature and drying time in the drying treatment of Step 1.

[0039] The resist layer 30 is a layer formed by composition B described later, and is used in step 3 described later to form a negative resist pattern. The thickness of the resist layer 30 is preferably 0.05 to 1 μm, and more preferably 0.10 to 0.50 μm.

[0040] Composition B comprises a resin (B) and a photoacid generator. Details of Composition B will be described later.

[0041] Resin (B) is a resin containing repeating units that have groups that decompose upon the action of an acid to produce polar groups, and silicon atoms. Details of resin (B) will be explained later.

[0042] The silicon atom (Si atom) content in resin (B) is preferably 5.0% by mass or more, more preferably 7.0% by mass or more, and even more preferably 9.0% by mass or more, based on the total amount of resin (B), from the viewpoint of further improving the performance as an etching mask for the negative resist pattern described later and further suppressing peeling at the interface between the insulating part and the conductive part. The silicon atom (Si atom) content in resin (B) is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, based on the total amount of resin (B), from the viewpoint of having better resolution. Details of the Si atom content based on the total amount of resin (B) will be explained later.

[0043] Details of the photoacid generator contained in Composition B will be described later. From the viewpoint of reducing environmental impact and from the viewpoint of achieving superior effects of the present invention, it is preferable that the photoacid generator contained in Composition B is a photoacid generator that does not contain alkyl fluoride.

[0044] From the viewpoint of achieving superior effects of the present invention, the photoacid generator contained in Composition B is preferably a nonionic photoacid generator. Details of the nonionic photoacid generator will be described later.

[0045] (Step 3) Figure 1C is a schematic cross-sectional view illustrating Step 3, showing cross-sections along the thickness direction of the substrate 10, the insulating film 20, and the resist layer 31 after pattern exposure. In Step 3, the resist layer 30 is pattern exposed. This forms a resist layer 31 on the insulating film 20, including exposed areas 30A and unexposed areas 30B.

[0046] One method of pattern exposure is to selectively expose the resist layer 30. Selective exposure means exposing only a portion of the resist layer 30. By selective exposure, the resist layer 31 after pattern exposure is divided into exposed areas 30A and unexposed areas 30B.

[0047] The exposure amount is not particularly limited as long as it can cure composition B (resist layer 30), 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.

[0048] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and from the viewpoint of achieving both resolution and pattern shape, it is preferably in the range of 300 to 450 nm, more preferably in the range of 340 to 420 nm, and even more preferably in the range of 355 to 405 nm.

[0049] In relation to the light source, the exposure wavelength can be found in: (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-line (wavelength 436nm), h-line (wavelength 405nm), i-line (wavelength 365nm), broad (three wavelengths: g, h, i), (4) excimer lasers, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F ２ Examples include excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, and (7) YAG laser with second harmonic 532 nm and third harmonic 355 nm. For composition B, 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. The exposure method is not particularly limited, and any method in which at least a part of the resist layer 30 is exposed is acceptable, but examples include exposure using a photomask and exposure by laser direct imaging.

[0050] - The post-exposure heat treatment step 3 may include a post-exposure heat treatment to heat the resist layer 31 after pattern exposure. The post-exposure heat treatment can be performed after the exposure treatment in step 3 and before the development treatment in step 4. The heating temperature in the post-exposure heat treatment is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heat treatment is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. The heating rate in the post-exposure heat treatment 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 heat treatment is not particularly limited and includes known hot plates, ovens, and infrared heaters. It is also preferable to perform the heating in a low-oxygen atmosphere by flowing inert gases such as nitrogen, helium, and argon.

[0051] (Step 4) Figure 1D is a schematic cross-sectional view illustrating Step 4, showing cross-sections along the thickness direction of the substrate 10, insulating film 20, and negative resist pattern 32. In Step 4, the resist layer 31 after pattern exposure is developed with a developer solution containing an organic solvent. This removes the unexposed areas 30B, and a negative resist pattern 32 consisting of exposed areas 30A is formed on a part of the insulating film 20.

[0052] Here, development in which the unexposed parts of the film are removed by the development process is called negative development, and development in which the exposed parts of the film are removed by the development process is called positive development. The development process in step 4 is negative development in which the unexposed parts 30B of the resist layer 31 after pattern exposure are removed.

[0053] As the organic solvent contained in the developer, compounds described in paragraph

[0387] of International Publication No. 2021 / 112189 can be used. This content is 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.

[0054] In particular, the developer preferably contains at least one organic solvent selected from the group consisting of butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclopentanone, cyclohexanone, and mesitylene, from the viewpoint of superior resolution and development uniformity; more preferably contains at least one organic solvent selected from the group consisting of butyl acetate, propylene glycol monomethyl ether acetate, and cyclopentanone; and even more preferably contains at least one organic solvent selected from the group consisting of butyl acetate and propylene glycol monomethyl ether acetate. The organic solvent contained in the developer can be used as a mixture of one or more types.

[0055] The content of the organic solvent 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.

[0056] The developing solution may further contain other components. Examples of other components include known surfactants and known defoamers.

[0057] - Rinsing step 4 may include a rinsing process in which the pattern is washed (rinsed) with a rinsing solution after the developing process. Alternatively, methods such as supplying the rinsing solution before the developing solution in contact with the pattern has completely dried may be employed.

[0058] The method of supplying the rinsing solution is not particularly limited as long as the desired pattern can be formed. Examples include immersing the negative resist pattern 32 in the rinsing solution, supplying the rinsing solution to the negative resist pattern 32 by adding liquid, supplying the rinsing solution to the negative resist pattern 32 with a shower, and continuously supplying the rinsing solution onto the negative resist pattern 32 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.

[0059] 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.

[0060] When the rinsing solution contains an organic solvent, the organic solvent can be the same as the organic solvent exemplified above when the developer contains an organic solvent. Preferably, the organic solvent in the rinsing solution is different from the organic solvent in the developer, and more preferably, it is an organic solvent with lower pattern solubility than the organic solvent in the developer.

[0061] If the rinsing solution contains an organic solvent, one or more organic solvents may be used in mixture form. Preferred organic solvents include cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA (propylene glycol monomethyl ether acetate), or PGME (propylene glycol monomethyl ether). Cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, or PGME are more preferred, and cyclohexanone or PGMEA are even more preferred.

[0062] When the rinsing solution contains an organic solvent, the amount 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 amount of the organic solvent may be 100% by mass, relative to the total mass of the rinsing solution.

[0063] The rinse solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0064] (Step 5) Figure 1E is a schematic cross-sectional view illustrating Step 5, showing cross-sections along the thickness direction of the substrate 10, the insulating portion 21, and the negative resist pattern 32. In Step 5, a portion of the insulating film 20 is removed by dry etching of the insulating film 20 using the negative resist pattern 32 as a mask. This results in an insulating portion 21 having a recess 22. As a result of the formation of the recess 22, a portion of the surface of the substrate 10 is exposed. The insulating portion 21 is a component corresponding to the insulating film 20. Since the insulating portion 21 has a recess 22, it is used as a mold when forming the conductive portion in Step 6, which will be described later.

[0065] Dry etching refers to an etching process that does not use liquid, and means performing etching by a chemical or physical method. Dry etching may be single-step etching or multi-step etching. When etching consists of multiple steps, the etching of each step may be the same process or different processes. The method of dry etching is not particularly limited, but reactive ion etching (RIE) is preferred from the viewpoint of excellent pattern shape. The plasma generation mechanism in reactive ion etching is not particularly limited, but methods capable of independently controlling plasma density and bias voltage, such as inductively coupled plasma (ICP) type, capacitively coupled plasma (CCP) type, and electron cyclotron resonance (ECR) type are preferred. Any known dry etching method can be used, and various conditions are appropriately determined depending on the composition and use of the insulating film 20. For example, etching can be performed in accordance with Proc. of SPIE Vol. 6924, 692420 (2008), Japanese Patent Application Laid-Open No. 2009-267112, etc. In addition, the method described in "Chapter 4 Etching" of "Semiconductor Process Textbook Fourth Edition, 2007, Publisher: SEMI Japan" can also be followed.

[0066] Among others, the dry etching in step 5 is preferably plasma etching using a gas containing oxygen atoms (oxygen atom-containing gas), and more preferably reactive ion etching using a gas containing oxygen atoms. This facilitates the progress of etching of the insulating film 20. Specific examples of the oxygen atom-containing gas include O ２ , O ３ , CO, CO ２ , NO, NO ２ , N ２ O, SO, SO ２This includes at least one selected from the group consisting of , and COS, etc. In addition to oxygen atom-containing gases, Ar, He, Xe, Kr, and N are used as diluent gases. ２ At least one selected from the group consisting of the following may be used, and furthermore, Cl may be used as an additive gas. ２ HBr, BCl ３ ,CH ４ , and NH ４ At least one selected from the group consisting of the following may be used. When an oxygen atom-containing gas is used, the etching of the insulating film 20 is promoted by the irradiation effect of oxygen radicals and oxygen ions generated in the plasma, while the etching resistance of the negative-type resist pattern 32 containing silicon components is increased by the oxidation and aggregation of silicon components in the resist film, making it possible to increase the selectivity ratio between the negative-type resist pattern 32 and the insulating film 20.

[0067] The recessed portion 22 is used in the manufacturing of the conductive portion of the redistribution layer in step 6, which will be described later. The insulating portion 21 may have only one recessed portion 22, or it may have two or more. The recessed portion 22 may be a via portion or a trench portion.

[0068] ...The via portion is a hole that penetrates the insulating portion 21 in the thickness direction. The cross-sectional shape of the via portion (the shape of the cross section along the thickness direction of the insulating portion 21) can be a rectangle. The front shape of the via portion (the shape when the recess 22 is observed from the upper surface of the insulating portion 21 if the recess 22 is a via portion) can be a circle or a rectangle. The diameter of the via portion is preferably 1.0 to 20 μm, more preferably 1.5 to 15 μm, and even more preferably 1.5 to 10 μm. The depth of the via portion is not particularly limited, but is preferably 1.0 to 20 μm, more preferably 2.0 to 15 μm, and even more preferably 2.0 to 10 μm.

[0069] The trench portion is a linear groove formed in the insulating portion 21. The cross-sectional shape of the trench portion (the cross-section that intersects the extending direction of the trench portion and is aligned with the depth direction of the trench portion) can be a rectangle. The diameter (width) of the trench portion is preferably 1.0 to 20 μm, more preferably 1.5 to 15 μm, and even more preferably 1.5 to 10 μm. The depth of the trench portion 22B is preferably 0.5 to 10 μm, more preferably 1.0 to 7.5 μm, and even more preferably 1.0 to 5.0 μm.

[0070] (Step a) Figure 1F is a schematic cross-sectional view illustrating step a, showing a cross-section along the thickness direction of the substrate 10 and the insulating portion 21. In step a, the negative resist pattern 32 placed on the insulating portion 21 is removed. This exposes the surface of the insulating portion 21.

[0071] The method for removing the negative resist pattern 32 is not particularly limited, but dry etching is one example. The dry etching method in step a is not particularly limited, but the reactive ion etching (RIE) described above is preferred. Various conditions for dry etching in step a are appropriately determined according to the composition and application of the negative resist pattern 32. For example, it is also possible to follow the method described in the literature shown in step 5 above. In particular, the dry etching in step a is preferably reactive ion etching using a gas containing fluorine atoms (hereinafter also referred to as "fluorine atom-containing gas"). Specific examples of fluorine atom-containing gases include CF ４ , C ２ F ６ SF ６ These include, for example. In addition, at least one of the above-mentioned diluent gas and additive gas may be used in addition to the fluorine atom-containing gas.

[0072] (Step 6) Figure 1G is a schematic cross-sectional view illustrating step 6, showing cross-sections along the thickness direction of the substrate 10, the insulating portion 21, and the conductive portion 41. In step 6, metal is filled into the recesses 22 by plating. As a result, the conductive portion 41 is formed on the substrate 10 and the insulating portion 21, and a redistribution layer 50 including the conductive portion 41 and the insulating portion 21 is obtained.

[0073] As for the plating method, known plating methods such as electroplating and electroless plating can be mentioned, and electroplating is preferred from the viewpoint of superior productivity and adhesion. As an example of a method for forming the conductive part 41 by electroplating, a method using a substrate 10 having a power supply layer on its surface can be mentioned. Specifically, electroplating (e.g., electrolytic copper plating) is performed using the power supply layer (e.g., a metal layer such as a thin copper film, not shown) on the surface of the substrate 10 exposed at the bottom of the recess 22. As a result, the conductive part 41 is formed in the recess 22. Before performing the electroplating, pretreatment such as sulfuric acid treatment and water washing may be performed on the power supply layer. Here, when a substrate having a power supply layer on its surface is used and electroplating is performed using the power supply layer in step 6, the redistribution layer formation step in the first embodiment can be said to be a step using a semi-additive method.

[0074] The materials constituting the conductive part 41 are not particularly limited, but include 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.

[0075] The redistribution layer 50, as described above, comprises an insulating portion 21 and a conductive portion 41. Typically, it refers to a multilayer wiring structure in which multiple redistributions (conductive portions) are separated by multiple interlayer insulating films (insulating portions), and is a layer consisting of one set of redistributions and an interlayer insulating film formed thereon. There are also cases in which the redistribution layer consists of only one layer. The redistribution layer 50 is suitably used as a so-called interposer, which is used to electrically connect semiconductor elements and package substrates.

[0076] (Other steps) If the substrate 10 described above is not a package substrate, this embodiment may include a package substrate connection step for connecting the package substrate and the redistribution layer. Preferably, the package substrate is formed on the side of the redistribution layer opposite to the side on which the semiconductor elements are formed. A known method can be used to connect the package substrate and the redistribution layer, specifically, a method using bonding wires or solder balls. This electrically connects the package substrate and the redistribution layer.

[0077] If the substrate 10 described above does not correspond to a semiconductor element or a package substrate, this embodiment may include a step of peeling off the substrate 10. The method for peeling off the substrate 10 is not particularly limited, and known methods can be used.

[0078] In this embodiment, the series of steps 1 to 6 described above may be repeated in this order to create a multilayer redistribution layer.

[0079] [Second Embodiment] The second embodiment of the semiconductor device manufacturing method of the present invention is a semiconductor device manufacturing method comprising a preparation step of preparing a semiconductor element and a redistribution layer formation step of forming a redistribution layer connected to the semiconductor element and having an insulating portion and a conductive portion, wherein the redistribution layer formation step includes the following steps 1, 2, 3, 4, 5, a, b, c, 6, and d in this order. Step 1: Apply the above-mentioned composition A to a substrate to form an insulating film. Step 2: Apply the above-mentioned composition B to the insulating film to form a first resist layer. Step 3: Pattern exposure of the first resist layer. Step 4: After pattern exposure, treat the first resist layer with a developer containing an organic solvent to form a first negative-type resist pattern on the insulating film. Step 5: Dry etching the insulating film using the first negative-type resist pattern as a mask to form the insulating portion having recesses. Step a: Remove the first negative-type resist pattern. Step b: Apply a photosensitive resin composition to the insulating portion to form a second resist layer. Step c: Pattern exposure and development treatment are performed on the second resist layer to form a second resist pattern on the insulating portion having openings that communicate with the recesses. Step 6: Plating treatment is performed on the insulating portion having recesses to form the conductive portion. Step d: Remove the second resist pattern.

[0080] The procedures for each step in the second embodiment will be described in detail below, with reference to the drawings as necessary. Note that the following description will focus on the case where the second embodiment includes steps a and d, but steps a and d are optional and do not need to be performed. The following description of the second embodiment will primarily focus on the differences from the first embodiment, and descriptions of steps and components similar to those in the first embodiment may be omitted. Furthermore, in the drawings used to describe the second embodiment, components identical to those in the first embodiment may be denoted by the same reference numerals, and their descriptions may be omitted.

[0081] <Preparation Process> The preparation process for the second embodiment is the same as that for the first embodiment.

[0082] <Redistribution Layer Formation Process> The redistribution layer formation process is a process of forming a redistribution layer that is connected to the semiconductor element described above and has an insulating portion and a conductive portion, and includes the following steps 1, 2, 3, 4, 5, a, b, c, 6, and d in this order.

[0083] (Steps 1 to 5 and step a) Figure 2A is a schematic cross-sectional view of the member obtained by carrying out steps 1 to 5 and step a, and shows a cross-section along the thickness direction of the substrate 10 and the insulating portion 21. The insulating portion 21 has a recess 22. Steps 1 to 5 and step a of the second embodiment are the same as steps 1 to 5 and step a of the first embodiment, so their explanation is omitted. The first resist layer, the first resist layer after pattern exposure, and the first negative resist pattern described in any of steps 2 to 5 and step a of the second embodiment are the same members as the resist layer 30, the resist layer 31 after pattern exposure, and the negative resist pattern 32 described in any of steps 2 to 5 and step a of the first embodiment.

[0084] (Step b) Figure 2B is a schematic cross-sectional view illustrating step b, showing cross-sections along the thickness direction of the substrate 10, the insulating portion 21, and the second resist layer 130. In step b, the photosensitive resin composition is applied onto the insulating portion 21. As a result, the second resist layer 130 is formed on the insulating portion 21 and on the substrate 10, where a part of the surface is exposed due to the formation of the recess 22.

[0085] The means for applying the photosensitive resin composition onto the insulating portion 21 can be the same as the means for applying composition A onto the substrate 10 in step 1 of the first embodiment, and the preferred embodiment is the same.

[0086] Step b may include a drying process (drying treatment) for the photosensitive resin composition applied to the insulating portion 21. This removes components such as solvents from the photosensitive resin composition applied to the insulating portion 21. The preferred drying temperature and drying time in the drying treatment of step b are the same as the preferred drying temperature and drying time in the drying treatment of step 1 of the first embodiment.

[0087] The second resist layer 130 is a layer formed from a photosensitive resin composition and is used to form the second resist pattern in step c described later. The thickness of the second resist layer 130 is preferably 0.5 to 20 μm, and more preferably 1.0 to 10 μm.

[0088] The photosensitive resin composition used to form the second resist layer 130 is not particularly limited, and known photosensitive resin compositions can be used. The photosensitive resin composition may be for negative-type development or for positive-type development. The definitions of negative-type development and positive-type development are as described below. An example of a photosensitive resin composition for negative-type development is a composition comprising an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator. An example of a photosensitive resin composition for positive-type development is a composition comprising a resin whose solubility changes with the action of an acid (preferably an acid-degradable resin, i.e., a polymer having constituent units having acid groups protected by acid-degradable groups) and a compound that generates acid upon irradiation with active light. Furthermore, the above-described composition B may be used as the photosensitive resin composition.

[0089] (Step c) Figure 2C is a schematic cross-sectional view illustrating step c, showing the cross-section when the substrate 10, the insulating portion 21, and the second resist pattern 132 are cut along the thickness direction. In step c, the second resist pattern 132 is formed on a part of the insulating portion 21 by applying a pattern exposure and development process to the second resist layer 130. The second resist pattern 132 has an opening 23 that communicates with the recess 22. Since the second resist pattern 132 has an opening 23, it is used as a mold together with the insulating portion 21 having the recess 22 when forming the conductive portion in step 6 described later. The processes that can be carried out in step c will be described below.

[0090] - Exposure treatment (pattern exposure) In step c, the second resist layer 130 is subjected to pattern exposure. One method of pattern exposure is to selectively expose the second resist layer 130. Selective exposure means that only a part of the second resist layer 130 is exposed. By selective exposure, the second resist layer 130 is formed with exposed areas (exposed areas) and unexposed areas (non-exposed areas) which are not shown. The preferred exposure amount and exposure wavelength in the pattern exposure of step c are the same as the preferred exposure amount and exposure wavelength in step 3 of the first embodiment.

[0091] Step c may include a post-exposure heat treatment in which the second resist layer 130 is heated after pattern exposure. That is, the post-exposure heat treatment can be performed after the exposure treatment and before the development treatment. A preferred embodiment of the post-exposure heat treatment in step c is the same as a preferred embodiment of the post-exposure heat treatment in step 3 of the first embodiment.

[0092] In development step c, the second resist layer 130 after pattern exposure is subjected to development. One method of development is to develop the second resist layer 130 after pattern exposure with a developer to form openings 23 in the second resist layer 130. Here, development in which the unexposed parts of the film are removed by development is called negative development, and development in which the exposed parts of the film are removed by development is called positive development. The development in step c may be negative development or positive development.

[0093] Examples of developing solutions used in the developing process of step c include alkaline aqueous solutions or developing solutions containing organic solvents.

[0094] When the developer is an alkaline aqueous solution, the basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, preferably those described in paragraph

[0300] of International Publication No. 2023 / 190064, and more preferably TMAH (tetramethylammonium hydroxide). The content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the developer.

[0095] The preferred embodiment of the developer containing the organic solvent is the same as the preferred embodiment of the developer containing the organic solvent in the developing process of step 4 of the first embodiment.

[0096] The developing solution may further contain other components. Examples of other components include known surfactants and known defoamers.

[0097] - Rinsing step c may include a rinsing process in which the pattern is washed (rinsed) with a rinsing solution after the developing process. Alternatively, a method such as supplying the rinsing solution before the developing solution in contact with the pattern has completely dried may be employed. The preferred mode of rinsing in step c is the same as the preferred mode of rinsing in step 4.

[0098] If the developer is an alkaline aqueous solution, water can be used as the rinsing solution. If the developer contains an organic solvent, a solvent different from the solvent contained in the developer (for example, water, or an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0099] When the rinsing solution contains an organic solvent, the organic solvent can be the same as the organic solvent exemplified above when the developer contains an organic solvent. Preferably, the organic solvent in the rinsing solution is different from the organic solvent in the developer, and more preferably, it is an organic solvent with lower pattern solubility than the organic solvent in the developer.

[0100] If the rinsing solution contains an organic solvent, one or more organic solvents may be used in mixture form. Preferred organic solvents include cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA (propylene glycol monomethyl ether acetate), or PGME (propylene glycol monomethyl ether). Cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, or PGME are more preferred, and cyclohexanone or PGMEA are even more preferred.

[0101] When the rinsing solution contains an organic solvent, the amount 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 amount of the organic solvent may be 100% by mass, relative to the total mass of the rinsing solution.

[0102] The rinse solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0103] - The opening 23 is an opening in the second resist pattern 132 placed on the insulating portion 21, and is used in the manufacturing of the conductive portion of the redistribution layer in step 6 described later. The opening 23 is preferably a trench portion. Details of the trench portion are as described above, so their explanation will be omitted. When the opening 23 is a trench portion, Figure 2C is a cross-section when the substrate 10, insulating portion 21, and second resist pattern 132 are cut along the thickness direction such that the trench portion is exposed along its extending direction. In the example of Figure 2C, in the thickness direction of the insulating portion 21 and the second resist pattern 132, the recess 22 and the opening 23 are arranged in the order of recess 22 and opening 23 in the direction away from the substrate 10, and the recess 22 and the opening 23 are in communication and have an integrated shape. For example, if the recess 22 is a via portion and the opening 23 is a trench portion, the via portion and the trench portion will have an integrated shape.

[0104] (Step 6) Figure 2D is a schematic cross-sectional view illustrating Step 6, showing cross-sections along the thickness direction of the substrate 10, insulating portion 21, second resist pattern 132, and conductive portion 141. In Step 6, metal is filled into the recesses 22 and openings 23 by plating. This forms the conductive portion 141 on the substrate 10 and the insulating portion 21, and a redistribution layer 150 including the conductive portion 141 and the insulating portion 21 is obtained. The plating method is the same as in Step 6 of the first embodiment. The material constituting the conductive portion 141 is the same as that of the conductive portion 41 in the first embodiment. Here, if a substrate having a power supply layer on its surface is used, and electrolytic plating is performed using the power supply layer in Step 6, the redistribution layer formation step in the second embodiment can be said to be a step using a semi-additive method.

[0105] (Step d) Figure 2E is a schematic cross-sectional view illustrating step d, showing a cross-section along the thickness direction of the substrate 10 and the redistribution layer 150. In step d, the second resist pattern 132 placed on the insulating portion 21 is removed. This exposes a part of the surface of the insulating portion 21. The method for removing the second resist pattern 132 is not particularly limited, but is similar to, for example, step a in the first embodiment.

[0106] (Other steps) Other steps that may be included in the second embodiment are the same as the other steps in the first embodiment described above, so their explanation will be omitted.

[0107] [Semiconductor Device] The semiconductor device obtained by each of the embodiments described above (hereinafter also referred to as "the semiconductor device") includes the semiconductor element described above and the redistribution layer described above, and preferably further includes the package substrate described above. When the semiconductor device includes a package substrate, the semiconductor device has a structure in which the semiconductor element, the redistribution layer, and the semiconductor package substrate are stacked in this order.

[0108] The semiconductor device manufacturing method of the present invention can be applied to CoWoS (Chip on Wafer on Substrate) technology. CoWoS technology is a technology for mounting multiple semiconductor devices (semiconductor chips) on a single package substrate. When the semiconductor device manufacturing method of the present invention is applied to CoWoS technology, the semiconductor device will have a structure in which multiple semiconductor devices are mounted on a semiconductor package substrate via a redistribution layer.

[0109] Specific structures of this semiconductor device include those in which the redistribution layer 105 and insulating layer 115 described in paragraphs

[0213] to

[0218] of Japanese Patent Application Publication No. 2016-027357 and in Figure 1 are replaced with the redistribution layer obtained in each of the above embodiments. The contents other than the redistribution layer 105 and insulating layer 115 of the above publication are incorporated into this specification.

[0110] [Resin Composition A] The resin composition A used in the semiconductor device manufacturing method of the present invention (hereinafter also referred to as "resin composition A" or "composition A") is a resin composition containing the above-mentioned resin (A). Preferably, resin composition A is an insulating film forming resin composition used in the semiconductor device manufacturing method described above. Resin composition A may be in the form of a film or a liquid, but it is preferably in the form of a liquid. The components contained in resin composition A and components that may be contained will be described below.

[0111] [Resin (A)] Resin (A) is at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor. Resin composition A preferably contains polyimide or polyimide precursor as resin (A). Resin (A) preferably has polymerizable groups, and more preferably contains radical polymerizable groups. Resin (A) may also have polarity conversion groups such as acid-degradable groups.

[0112] <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).

[0113]

[0114] In formula (2), A １ and A ２ Each of these is independently an oxygen atom or -NR ｚ - represents R １１１ represents a divalent organic group, R 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.

[0115] 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.

[0116] Also, R １１１ From the viewpoint of i-ray transmittance, a divalent organic group represented by formula (51) or formula (61) below is preferred, and in particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferred.

[0117] Formula (51)

[0118]

[0119] In formula (51), R ５０ ~R ５７ Each of these is independently a hydrogen atom, a fluorine atom, or a monovalent organic group, R ５０ ~R ５７ At least one of them is a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents a bonding site with the nitrogen atom in formula (2). ５０ ~R ５７Examples of monovalent organic groups include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

[0120]

[0121] In formula (61), R ５８ and R ５９ Each of these is independently a fluorine atom, a methyl group, or a trifluoromethyl group, and each of these independently represents a bonding site with the nitrogen atom in formula (2). Examples of diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used individually or in combination of two or more.

[0122] 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.

[0123]

[0124] 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 It is more preferable that the group is selected from -CH ２ -, -C(CF ３ ) ２ -, -C(CH ３ ) ２ -, -O-, -CO-, -S-, and -SO ２It is even more preferable that the group is a divalent group selected from the group consisting of -.

[0125] 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.

[0126] 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.

[0127] R in equation (2) １１３ and R １１４ Each 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.

[0128]

[0129] 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 -CH ２ 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.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] As the repeating unit represented by formula (2), a repeating unit represented by formula (2-A) is preferable. That is, it is preferable that at least one type of polyimide precursor used in the present invention is a precursor having a repeating unit represented by formula (2-A). When the polyimide precursor contains the repeating unit represented by formula (2-A), it is possible to further widen the range of exposure latitude.

[0135] Formula (2-A)

[0136]

[0137] In formula (2-A), A １ and A ２ each represent an oxygen atom, and R １１１ and R １１２ each independently represent a divalent organic group, R １１３ and R １１４ each independently represent a hydrogen atom or a monovalent organic group, at least one of R １１３ and R １１４ is a group containing a polymerizable group, and it is preferable that both are groups containing a polymerizable group.

[0138] A １ , A ２ , R １１１ , R １１３ and R １１４ each independently have the same definition as A １ , A ２ , R １１１ , R １１３ and R １１４ in formula (2), and the preferred ranges are also the same. R １１２ has the same definition as R １１２ in formula (5), and the preferred ranges are also the same.

[0139] The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types thereof. It may also contain structural isomers of the repeating unit represented by formula (2). In addition to the repeating unit of formula (2) above, the polyimide precursor may also contain other types of repeating units.

[0140] 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).

[0141] 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 molecular weight dispersion 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 molecular weight dispersion 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, molecular weight dispersion 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.

[0142] <Polyimide> The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide soluble in a developer containing an organic solvent as a main component. In the present specification, the alkali-soluble polyimide refers to a polyimide that dissolves in an amount of 0.1 g or more at 23°C in 100 g of a 2.38 mass% tetramethylammonium hydroxide aqueous solution. From the viewpoint of pattern formability, a polyimide that dissolves in an amount of 0.5 g or more is preferable, and a polyimide that dissolves in an amount of 1.0 g or more is more preferable. The upper limit of the dissolution amount is not particularly limited, but is preferably 100 g or less. As the polyimide, a polyimide having a plurality of imide structures in the main chain is preferable from the viewpoints of the film strength and insulating properties of the obtained film.

[0143] (Fluorine Atom) From the viewpoint of the film strength of the obtained film, the polyimide preferably also has a fluorine atom. The fluorine atom is contained, for example, in R in the repeating unit represented by formula (4) described later １３２ , or in R in the repeating unit represented by formula (4) described later １３１ , and it is preferable that the fluorine atom is contained in R in the repeating unit represented by formula (4) described later １３２ , or in R in the repeating unit represented by formula (4) described later １３１ as a fluorinated alkyl group, and such an embodiment is more preferable. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5 mass% or more, and is preferably 20 mass% or less.

[0144] (Silicon Atom) From the viewpoint of the film strength of the obtained film, the polyimide preferably also has a silicon atom. The silicon atom is preferably contained, for example, in R in the repeating unit represented by formula (4) described later １３１ , and it is preferable that the silicon atom is contained in R in the repeating unit represented by formula (4) described later １３１ as an organically modified (poly)siloxane structure described later, and such an embodiment is more preferable. The aforementioned silicon atom or the aforementioned organically modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1 mass% or more, and more preferably 20 mass% or less.

[0145] (Ethylene-unsaturated bond) From the viewpoint of the film strength of the resulting film, it is preferable that the polyimide has an ethylenically unsaturated bond. The polyimide may have an ethylenically unsaturated bond at the end of the main chain or in the side chains, but it is preferable that it has one in the side chains. It is preferable that the above ethylenically unsaturated bond has radical polymerizability. The ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. １３２ or R １３１ Preferably, it is included in R １３２ or R １３１ It is more preferable that it be included as a group having an ethylenically unsaturated bond. Among these, the ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. １３１ Preferably, it is included in R １３１ It is more preferable that the group contains an ethylenically unsaturated bond. Examples of groups containing an ethylenically unsaturated bond include vinyl groups, allyl groups, and vinylphenyl groups, which have a vinyl group that is directly bonded to an aromatic ring and may be substituted, (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (IV).

[0146]

[0147] In formula (IV), R ２０ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred.

[0148] In formula (IV), R ２１ This is an alkylene group having 2 to 12 carbon atoms, -O-CH ２ CH(OH)CH ２The characters represent -, -C(=O)O-, -O(C=O)NH-, a (poly)alkylene oxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 or 3; the repeating number of the alkylene oxy group preferably has 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3), or a group formed by combining two or more of these. The alkylene group having 2 to 12 carbon atoms may be linear, branched, cyclic, or a combination thereof. The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

[0149] Among these, R ２１ Preferably, the group is represented by any of the following formulas (R1) to (R3), and more preferably by the group represented by formula (R1).

[0150]

[0151] In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, or a (poly)alkylene oxy group having 2 to 30 carbon atoms, or a group having two or more of these bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents R in formula (IV). ２１ This represents the bonding site with the oxygen atom to which it is bonded. In formulas (R1) to (R3), a preferred embodiment of L is an alkylene group having 2 to 12 carbon atoms, or a (poly)alkylene oxy group having 2 to 30 carbon atoms, as shown in formula (IV) R ２１The preferred embodiment is the same as that of an alkylene group having 2 to 12 carbon atoms, or a (poly)alkylene oxy group having 2 to 30 carbon atoms. In formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * is the same as * in formula (IV), and the preferred embodiment is the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate).

[0152] In formula (IV), * represents a binding site with another structure, and is preferably a binding site with the polyimide main chain.

[0153] The amount of ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0154] (Polymerizable groups other than those having ethylenically unsaturated bonds) Polyimide may have polymerizable groups other than those having ethylenically unsaturated bonds. Examples of polymerizable groups other than those having ethylenically unsaturated bonds include epoxy groups and cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups. Polymerizable groups other than those having ethylenically unsaturated bonds include, for example, R in the repeating unit represented by formula (4) described later. １３１ It is preferable that it be included in [the specified form]. The amount of polymerizable groups other than those having ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0155] (Polarity-changing group) Polyimide may have polarity-changing groups such as acid-degradable groups. The acid-degradable group in polyimide is R in formula (2) above. １１３ and R １１４ The acid-degradable group is the same as described above, and the preferred embodiment is also the same. The polarity-converting group is, for example, R in the repeating unit represented by formula (4) described later. １３１ , R １３２ It is found in the ends of polyimides, etc.

[0156] (Acid Value) When polyimide is subjected to development using a developer mainly composed of an organic solvent (for example, "solvent development"), the acid value of the polyimide is preferably 1 to 35 mg KOH / g, more preferably 2 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. As for the acid group contained in the polyimide, from the viewpoint of achieving both storage stability and developability, an acid group with a pKa of 0 to 10 is preferred, and an acid group with a pKa of 3 to 8 is more preferred. pKa is the equilibrium constant Ka, expressed by its negative common logarithm pKa, considering the dissociation reaction in which hydrogen ions are released from the acid. In this specification, unless otherwise specified, pKa is the value calculated by ACD / ChemSketch®. The pKa value may be based on the values ​​listed in the "Revised 5th Edition Chemical Handbook: Basic Section" edited by the Chemical Society of Japan. When the acid group is a polyvalent acid such as phosphoric acid, the above pKa is the first dissociation constant. As such an acid group, polyimide preferably contains at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0157] 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).

[0158] In formula (4), R １３１ represents a divalent organic group, R 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.

[0159] Formula (4-1)

[0160]

[0161] In formula (4-1), R １３３ is a polymerizable group, and the other groups are equivalent to formula (4).

[0162] Formula (4-2)

[0163] 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).

[0164] 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:

[0165] 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.

[0166] 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.

[0167] 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.

[0168] 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.

[0169] 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.

[0170] (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

[0171] Polyimide is a material in which all repeating units are R １３１ and R １３２ The 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.

[0172] 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 flexural resistance of the cured film 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.

[0173] <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.

[0174] <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.

[0175] <Polyamide-imide precursors> Examples of polyamide-imide precursors include the compounds described in paragraphs

[0104] to

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

[0176] <Polyamideimides> Examples of polyamideimides include the compounds described in paragraphs

[0125] to

[0138] of International Publication No. 2022 / 145355. The foregoing description is incorporated herein by reference.

[0177] <Method for producing polyimide precursors, etc.> Polyimide precursors, etc. are produced, for example, by the method described in paragraphs

[0134] to

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

[0178] <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.

[0179] 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.

[0180] [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.

[0181] 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.

[0182] [Polymerizable Compound] Resin composition A preferably contains a polymerizable compound. Examples of polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[0183] <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.

[0184] 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.

[0185] 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.

[0186] 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.

[0187] 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.

[0188] 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.

[0189] 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.

[0190] 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).

[0191] 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.

[0192] 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.

[0193] 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.

[0194] 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.

[0195] 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.

[0196] If 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.

[0197] 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.

[0198] <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.

[0199] 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 other crosslinking agent or two or more. If it contains two or more, it is preferable that the total amount is within the above range.

[0200] [Polymerization Initiator] Resin composition A may contain 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.

[0201] 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.

[0202] 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.

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] 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.

[0208] 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.

[0209] 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.

[0210] 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.

[0211]

[0212] 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.

[0213]

[0214] As the photoradical polymerization initiator, for example, an oxime compound having a fluorene ring, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, and an oxime compound having a fluorine atom described in paragraphs

[0169] to

[0171] of International Publication No. WO 2021 / 112189 can also be used. In addition, an oxime compound having a nitro group, an oxime compound having a benzofuran skeleton, and an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton described in paragraphs

[0208] to

[0210] of International Publication No. WO 2021 / 020359 can also be used. The contents of these documents are incorporated herein by reference.

[0215] In addition, as the photopolymerization initiator, the compounds described in paragraphs

[0113] to

[0117] of Japanese Unexamined Patent Publication No. 2023-058585 can also be used. This description is incorporated into the specification of the present application by reference.

[0216] When the 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, still more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the resin composition A. The resin composition A may contain only one type of polymerization initiator, or may contain two or more types thereof. When two or more types are contained, the total amount preferably falls within the above range. It should be noted that since a photopolymerization initiator may also function as a thermal polymerization initiator in some cases, crosslinking by the photopolymerization initiator can be further promoted by heating with an oven, a hot plate or the like in some cases.

[0217] [Sensitizer] Resin composition A may contain a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. The sensitizer in the electronically excited state comes into contact with thermal radical polymerization initiators, photoradical polymerization initiators, etc., causing electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiator and photoradical polymerization initiator undergo chemical changes and decompose, generating radicals, acids, or bases. Examples of sensitizers include compounds such as benzophenone, Michlaz ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazoleazomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds.Examples of sensitizers include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyrideneindanone, and p-dimethylaminobenzylideneindanone. 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin 3-Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-Methoxycarbonyl-7-diethylaminocoumarin, 3-Ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate Examples of sensitizing dyes include 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide. Other sensitizing dyes may also be used. For details of sensitizing dyes, refer to paragraphs

[0161] to

[0163] of Japanese Patent Application Publication No. 2016-027357, which are incorporated herein by reference.

[0218] When Resin Composition A contains a sensitizer, the content of the sensitizer is preferably from 0.01 to 20% by mass, more preferably from 0.1 to 15% by mass, and still more preferably from 0.5 to 10% by mass, relative to the total solid content of Resin Composition A. Resin Composition A may contain only one type of sensitizer, or may contain two or more types thereof. When two or more types are contained, the total amount is preferably within the above range.

[0219] [Base Generator] Resin Composition A may contain a base generator. Herein, the base generator is a compound capable of generating a base through a physical or chemical action. Preferred examples of base generators include thermal base generators and photobase generators. In particular, when Resin Composition A contains a precursor of a cyclized resin, Resin Composition A preferably contains a base generator. When Resin Composition A contains a thermal base generator, for example, heating can promote the cyclization reaction of the precursor, resulting in a cured product having favorable mechanical properties and chemical resistance, and consequently exhibiting favorable performance as an interlayer insulating film for a rewiring layer contained in, for example, a semiconductor package. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. Any known base generator can be used as the base generator. Examples of the base generator include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of the nonionic base generator include the compounds described in paragraphs

[0249] to

[0277] of International Publication No. WO 2022 / 145355, the description of which is incorporated herein by reference.

[0220] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0221] Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs

[0148] to

[0163] of International Publication No. 2018 / 038002, and the compounds described in paragraphs

[0280] to

[0281] of International Publication No. 2022 / 145355.

[0222] When resin composition A contains a base generating agent, the amount of base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of resin in resin composition A. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. Resin composition A may contain only one type of base generating agent, or it may contain two or more types. When it contains two or more types, it is preferable that the total amount is within the above range.

[0223] [Solvent] Resin composition A preferably contains a solvent. Any known solvent can be used. An organic solvent is preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0224] 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).

[0225] 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.

[0226] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0227] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, as well as cyclic terpenes such as limonene.

[0228] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0229] 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.

[0230] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0231] 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.

[0232] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0233] 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.

[0234] From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of resin composition A 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.

[0235] [Metal Adhesion Modifier] From the viewpoint of improving adhesion to metal materials used in electrodes and wiring, etc., resin composition A preferably contains a metal adhesion modifier. Examples of metal adhesion modifiers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[0236] <Silane Coupling Agents> Examples of silane coupling agents include the compounds described in paragraph

[0316] of International Publication No. 2021 / 112189 and the compounds described in paragraphs

[0067] to

[0078] of Japanese Patent Application Publication No. 2018-173573, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs

[0050] to

[0058] of Japanese Patent Application Publication No. 2011-128358. The following compounds are also preferred as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group. In addition, R below represents a structure derived from a blocking agent in the blocked isocyanate group. The blocking agent can be selected according to the elimination temperature, but examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and activated methylene compounds. For example, from the viewpoint of wanting the desorption temperature to be 160 to 180°C, caprolactam is preferred. Examples of commercially available compounds of this type include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0237]

[0238] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-( Examples include aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more. Furthermore, oligomeric compounds having multiple alkoxysilyl groups can also be used as silane coupling agents. Examples of such oligomeric compounds include compounds containing a repeating unit represented by the following formula (S-1).

[0239]

[0240] In formula (S-1), R Ｓ１ represents a monovalent organic group, R Ｓ２ R represents a hydrogen atom, a hydroxyl group, or an alkoxy group, and n represents an integer between 0 and 2. Ｓ１It is preferable that the structure includes polymerizable groups. Examples of polymerizable groups include groups having ethylenically unsaturated bonds, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. Examples of groups having ethylenically unsaturated bonds 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, etc. Vinylphenyl groups, (meth)acrylamide groups, or (meth)acryloyloxy groups are preferred, vinylphenyl groups or (meth)acryloyloxy groups are more preferred, and (meth)acryloyloxy groups are even more preferred. Ｓ２ n is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group. n represents an integer from 0 to 2, and is preferably 1. Here, the structures of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound may all be the same. Here, it is preferable that n is 1 or 2 in at least one of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two. Commercial products can be used as such oligomer-type compounds, and an example of a commercial product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0241] When resin composition A contains a metal adhesion improver, the content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of resin (A). A content above the lower limit ensures good adhesion between the pattern and the metal layer (conductive part), while a content below the upper limit ensures good heat resistance and mechanical properties of the pattern. Resin composition A may contain only one type of metal adhesion improver, or it may contain two or more types. If it contains two or more types, the total amount is preferably within the above range.

[0242] [Migration Inhibitor] It is preferable that the resin composition A further contains a migration inhibitor. By including a migration inhibitor, for example, when the resin composition A is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions originating from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0243] There are no particular limitations on the migration inhibitors, but examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, and 6H-pyran ring, triazine ring), thioureas and compounds having sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, or tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0244] As a migration inhibitor, an ion trapping agent that captures anions such as halogen ions can also be used.

[0245] Other migration inhibitors that can be used include the rust inhibitor described in paragraph

[0094] of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs

[0073] to

[0076] of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph

[0052] of Japanese Patent Publication No. 2011-059656, the compounds described in paragraphs

[0114] ,

[0116] and

[0118] of Japanese Patent Publication No. 2012-194520, the compounds described in paragraph

[0166] of International Publication No. 2015 / 199219, and the like, which are incorporated herein by reference.

[0246] Specific examples of migration inhibitors include the following compounds.

[0247]

[0248] When Resin Composition A contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and still more preferably 0.1 to 1.0% by mass, based on the total solid content of Resin Composition A. Resin Composition A may contain only one migration inhibitor, or may contain two or more migration inhibitors. When two or more migration inhibitors are contained, the total amount thereof preferably falls within the above range.

[0249] [Polymerization Inhibitor] It is preferable that Resin Composition A contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0250] Specific examples of the polymerization inhibitor compound include the compounds described in paragraph

[0310] of International Publication No. WO 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, and 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide. The content of the above document is incorporated herein by reference.

[0251] When Resin Composition A contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and still more preferably 0.05 to 10% by mass, based on the total solid content of Resin Composition A. Resin Composition A may contain only one polymerization inhibitor, or may contain two or more polymerization inhibitors. When two or more polymerization inhibitors are contained, the total amount thereof preferably falls within the above range.

[0252] [Light Absorber] Resin composition A may also preferably contain a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure. Examples of light absorbers include the compounds described in paragraphs

[0159] to

[0183] of International Publication No. 2022 / 202647, and the compounds described in paragraphs

[0088] to

[0108] of Japanese Patent Application Publication No. 2019-206689. These contents are incorporated herein by reference.

[0253] If resin composition A contains a light absorber, the amount of light absorber is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass, relative to the total solid content of resin composition A.

[0254] [Surfactants] Resin composition A preferably contains a surfactant. Various surfactants can be used as the surfactant, such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0255] By including a surfactant in resin composition A, the liquid properties (especially fluidity) of resin composition A when it is prepared are further improved, the uniformity of the coating thickness and the liquid saving efficiency can be further improved, and the ability of the composition to follow steps is increased. In other words, when forming a film using resin composition A containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability to the surface to be coated and improving the coatability to the surface to be coated. As a result, air bubbles are less likely to be incorporated in the stepped areas, and it is possible to more favorably form a uniform film with less thickness variation.

[0256] Examples of silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include compounds described in paragraphs

[0329] to

[0334] of International Publication No. 2021 / 112189, respectively, which are incorporated herein by reference.

[0257] If resin composition A contains a surfactant, the surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition. Resin composition A may contain only one type of surfactant or two or more types. If it contains two or more types, it is preferable that the total amount is within the above range.

[0258] [Other Additives] Resin composition A may contain various additives as needed, to the extent that the effects of the present invention can be obtained, such as metal complexes, higher fatty acid derivatives, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, photoacid generators, 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 documents are incorporated herein. When these additives are incorporated, it is preferable that their total content be 3% by mass or less of the solid content of resin composition A.

[0259] [Composition B] Composition B, used in the semiconductor device manufacturing method of the present invention, is a photosensitive resin composition comprising the resin (B) described above and a photoacid generator. Since Composition B is used as an etching mask for an insulating film formed using Composition A in the semiconductor device manufacturing method of the present invention, it may be referred to as an etching mask forming resin composition in this specification. The components included in Composition B, and components that may be included, will be described below.

[0260] [Resin (B)] Resin (B) preferably contains repeating units having groups that decompose upon the action of an acid to produce polar groups (hereinafter also referred to as "acid-degradable groups"), and silicon atoms, and preferably also contains structural units having acid-degradable groups and repeating units containing Si atoms (silicon atoms).

[0261] The Si atom content is preferably 1.0 to 30% by mass, more preferably 3.0 to 25% by mass, and even more preferably 5.0 to 20% by mass, based on the total amount of resin (B). Here, the Si atom content based on the total amount of resin (B) corresponds to the sum of the atomic weights of all Si atoms in resin (B) relative to the sum of the atomic weights of all atoms constituting resin (B). The sum of the atomic weights of all atoms constituting resin (B) is calculated based on the molecular weight of each monomer corresponding to each repeating unit constituting resin (B) and the molar ratio of each repeating unit in resin (B). The sum of the atomic weights of all Si atoms in resin (B) is calculated based on the sum of the atomic weights of all Si atoms contained in each of the above monomers and the molar ratio of each repeating unit in resin (B).

[0262] <Repeating units having Si atoms> The resin (B) preferably contains repeating units having Si atoms. The repeating units having Si atoms are not particularly limited as long as they have Si atoms. For example, silane-based repeating units (-SiR ２ -: R is an organic group), siloxane repeating unit (-SiR ２ Examples include (meth)acrylate repeating units having Si atoms (-O-: R is an organic group), vinyl repeating units having Si atoms, etc. Furthermore, it is preferable that the repeating units having Si atoms do not have acid-degradable groups (details will be described later). Since the repeating units having Si atoms are hydrophobic, they exhibit high solubility in developing solutions containing organic solvents. This reduces development defects.

[0263] The repeating units having Si atoms preferably have a silsesquioxane structure. The silsesquioxane structure may be present in the main chain or in the side chains, but it is preferable to have it in the side chains. Having the silsesquioxane structure in the side chains improves the storage stability of the resin. Examples of silsesquioxane structures include cage-type silsesquioxane structures, ladder-type silsesquioxane structures, and random-type silsesquioxane structures. Among these, the cage-type silsesquioxane structure is preferred. Here, a cage-type silsesquioxane structure is a silsesquioxane structure having a cage-like skeleton. The cage-type silsesquioxane structure may be a complete cage-type silsesquioxane structure or an incomplete cage-type silsesquioxane structure, but it is preferable to be a complete cage-type silsesquioxane structure. Furthermore, a ladder-type silsesquioxane structure is a silsesquioxane structure having a ladder-like skeleton. Furthermore, a random-type silsesquioxane structure is a silsesquioxane structure in which the skeleton is random.

[0264] The above cage-type silsesquioxane structure is preferably a siloxane structure represented by the following formula (S).

[0265]

[0266] In formula (S), R represents a monovalent organic group. Multiple Rs may be the same or different. There are no particular limitations on the monovalent organic group, but specific examples include halogen atoms, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, amino groups, mercapto groups, blocked mercapto groups (e.g., mercapto groups blocked (protected) with an acyl group), acyl groups, imide groups, phosphino groups, phosphinyl groups, silyl groups, vinyl groups, hydrocarbon groups which may contain heteroatoms, (meth)acrylic group-containing groups, and epoxy group-containing groups. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of heteroatoms in hydrocarbon groups which may contain heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, and phosphorus atoms. Examples of hydrocarbon groups in hydrocarbon groups which may contain heteroatoms include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups which are combinations thereof. Aliphatic hydrocarbon groups may be linear, branched, or cyclic. Specific examples of aliphatic hydrocarbon groups include linear or branched alkyl groups (especially those with 1 to 30 carbon atoms), linear or branched alkenyl groups (especially those with 2 to 30 carbon atoms), and linear or branched alkynyl groups (especially those with 2 to 30 carbon atoms). Examples of aromatic hydrocarbon groups include aromatic hydrocarbon groups with 6 to 18 carbon atoms, such as phenyl groups, tolyl groups, xylyl groups, and naphthyl groups.

[0267] The repeating unit having Si atoms is preferably represented by the following formula (I).

[0268]

[0269] In formula (I) above, L represents a single bond or a divalent linking group. Examples of divalent linking groups include an alkylene group, -COO-Rt-, and -O-Rt-. In the formula, Rt represents an alkylene group or a cycloalkylene group. L 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. In the above formula (I), X represents a hydrogen atom or an organic group. Examples of organic groups include alkyl groups which may have substituents such as a fluorine atom and a hydroxyl group, and hydrogen atoms, methyl groups, trifluoromethyl groups, or hydroxymethyl groups are preferred. In the above formula (I), A represents a Si-containing group. Among these, the group represented by the following formula (a) or (b) is preferred.

[0270]

[0271] In formula (a) above, R represents a monovalent organic group, and * represents the bond position with L. Multiple Rs may be the same or different. Specific examples and preferred embodiments of R are the same as those in formula (S) above. When A in formula (I) above is the group represented by formula (a), formula (I) above is represented by the following formula (I-a).

[0272]

[0273]

[0274] In the above formula (b), R ｂ represents a hydrocarbon group which may have a heteroatom, and * represents the bond position with L. Specific examples and preferred embodiments of the hydrocarbon group which may have a heteroatom are the same as R in formula (S) described above.

[0275] The repeating units containing Si atoms in resin (B) may be of one type or two or more types may be used in combination.

[0276] The content of repeating units having Si atoms relative to the total repeating units of resin (B) is not particularly limited, but is preferably 1 to 100 mol%, and more preferably 3 to 50 mol%.

[0277] When synthesizing monomers containing Si atoms, any known synthesis method can be employed, but examples include the methods described in Japanese Patent Publication No. 2008-523220 and International Publication No. 01 / 10871.

[0278] <Repeating units having acid-degradable groups> Resin (B) contains repeating units having acid-degradable groups. Repeating units having acid-degradable groups may or may not have Si atoms, but it is preferable that they do not have Si atoms. In this specification, repeating units having both Si atoms and acid-degradable groups are considered to fall under both the category of repeating units having Si atoms and repeating units having acid-degradable groups. For example, a resin consisting only of repeating units having both Si atoms and acid-degradable groups falls under the category of a resin containing repeating units having Si atoms and repeating units having acid-degradable groups.

[0279] An acid-degradable group is a group that decomposes upon the action of an acid to produce a polar group. Preferably, the acid-degradable group has 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.

[0280] 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.

[0281] Preferred polar groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups.

[0282] As acid-degradable groups, groups in which the hydrogen atoms of these groups are replaced with groups that are eliminated by acid are preferred. Examples of groups that are eliminated by acid (leaving groups) include -C(R ３６ ) (Caution ３７ ) (Caution ３８ ), -C(R ３６ ) (Caution ３７ ) ( OR ３９ ), and -C(R ０１ ) (Caution ０２ ) ( OR ３９ Examples include the following. In the formula, R ３６ ~R ３９ Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. ３６ and R ３７ These elements may be joined together to form a ring. ０１ and R ０２ Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0283] R ３６ ~R ３９ , R ０１ and R ０２ The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, and octyl group. ３６ ~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.

[0284] The repeating unit having an acid-degradable group is preferably a repeating unit having a carboxyl group protected by an acetal, or a carboxyl group protected by a ketal. Furthermore, the acid-degradable group is preferably a carboxyl group protected by an acetal or ketal represented by the following formula (a1-1). When the carboxyl group is a acetal or ketal protected by the following formula (a1-1), the acid-degradable group as a whole is -(C=O)-O-CR １ R ２ (OR ３ It has the structure of ).

[0285]

[0286] In the above formula (a1-1), R １ and R ２ Each of these independently represents a hydrogen atom or an alkyl group, except R １ and R ２ Except when both are hydrogen atoms. ３ R represents an alkyl group. １ or R ２ And, R ３ These may be linked together to form a cyclic ether.

[0287] In formula (a1-1), R １ ~R ３ Each of these independently represents either a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched, or cyclic. Here, R １ and R ２ Neither of them represents a hydrogen atom, R １ and R ２ At least one of them represents an alkyl group.

[0288] In equation (a1-1), R １ , R ２ and R ３When represents an alkyl group, the alkyl group may be linear, branched, or cyclic. The number of carbon atoms in a linear or branched alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. Examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, texyl (2,3-dimethyl-2-butyl), n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl groups.

[0289] The number of carbon atoms in the cyclic alkyl group is preferably 3 to 12, more preferably 4 to 8, and even more preferably 4 to 6. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, and isobornyl.

[0290] The alkyl group may have substituents, and examples of substituents include halogen atoms, aryl groups, and alkoxy groups. When a halogen atom is present as a substituent, R １ , R ２ , R ３ R becomes a haloalkyl group, and if it has an aryl group as a substituent, １ , R ２ , R ３This becomes an aralkyl group. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine or chlorine atoms being preferred. The number of carbon atoms in the aryl group is preferably 6 to 20, and more preferably 6 to 12. Examples of aryl groups include phenyl, α-methylphenyl, and naphthyl groups, and examples of alkyl groups substituted with aryl groups, i.e., aralkyl groups, include benzyl, α-methylbenzyl, phenethyl, and naphthylmethyl groups. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and even more preferably a methoxy or ethoxy group. Furthermore, if the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and if the alkyl group is a linear or branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent. These substituents may be further substituted with the substituents mentioned above.

[0291] In the above formula (a1-1), R １ , R ２ and R ３ When represents an aryl group, the number of carbon atoms in the aryl group is preferably 6 to 12, and more preferably 6 to 10. The aryl group may have substituents, and alkyl groups having 1 to 6 carbon atoms are preferred as substituents. Examples of aryl groups include phenyl, tolyl, silyl, cumenyl, and 1-naphthyl groups.

[0292] Also, R １ , R ２ and R ３ These atoms may bond to each other and, together with the carbon atoms to which they are bonded, form a ring. １ and R ２ , R １ and R ３ or R ２ and R ３Examples of ring structures when bonded include cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, tetrahydrofuranyl group, adamantyl group, and tetrahydropyranyl group.

[0293] Note that in equation (a1-1), R １ and R ２ It is preferable that one of them is a hydrogen atom or a methyl group.

[0294] Preferred examples of monomer units (a1-1) having a residue in which the carboxyl group is protected by an acid-degradable group include the monomer units listed below. Note that R represents a hydrogen atom or a methyl group.

[0295]

[0296] When a repeating unit having a structure in which a polar group is protected by a leaving group that decomposes and is removed by the action of an acid has a Si atom, that is, when a repeating unit having a Si atom has a structure in which a polar group is protected by a leaving group that decomposes and is removed by the action of an acid, it is preferable that the leaving group does not contain a Si atom.

[0297] Preferred acid-degradable groups include cumyl ester groups, enol ester groups, acetal ester groups, or tertiary alkyl ester groups, with tertiary alkyl ester groups being more preferred.

[0298] 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 since multiple carboxyl groups exhibit high interaction through hydrogen bonding, the negative pattern formed can be more reliably insoluble or sparingly soluble in the solvent in the composition of the present invention described above.

[0299]

[0300] 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.

[0301] 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.

[0302] X ａ１ The alkyl group may have substituents, and examples of substituents include hydroxyl groups and halogen atoms (preferably fluorine atoms). ａ１ The 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.

[0303] 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.

[0304] 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.

[0305] 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.

[0306] 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.

[0307] 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.

[0308] 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 ３ These are similar to the specific examples and preferred examples of substituents that each of the groups may have.

[0309]

[0310]

[0311]

[0312] 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.

[0313] 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.

[0314] The repeating unit having an acid-degradable group may be of one type or two or more types may be used in combination.

[0315] 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). 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.

[0316] <Other Repeating Units> The 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.

[0317] 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 formation 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)

[0318] 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, based on the total solid content of composition B. There is no particular upper limit, but it is preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less. Resin (B) may be used alone or in combination of multiple types.

[0319] [Photoacid Generator] Composition B contains a 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.

[0320] As mentioned above, 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 better performance such as resistance to collapse. Furthermore, as mentioned above, the photoacid generator is preferably a nonionic type photoacid generator.

[0321] Furthermore, the photoacid generator preferably includes at least one compound selected from the group consisting of an oximesulfonate group and an imidosulfonate group, a compound having at least one cation selected from the group consisting of a sulfonium cation and an iodonium cation, a diazosulfone compound, and a disulfone compound. It is believed that using these compounds improves the efficiency of acid generation by exposure, and facilitates the efficient bonding between the acid group and the vinyl ether group compound.

[0322] <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).

[0323]

[0324] 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.

[0325] 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. １１ 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.

[0326] In the above formulas (OS-103) to (OS-105), R １１Examples of alkyl groups that can be represented include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, and benzyl group.

[0327] Furthermore, in the above formulas (OS-103) to (OS-105), R １１ The aryl group represented by is preferably an aryl group having a total of 6 to 30 carbon atoms, which may have substituents. １１ The substituents that the aryl group represented by may have include halogen atoms, alkyl groups, alkyloxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, aminocarbonyl groups, sulfonic acid groups, aminosulfonyl groups, and alkoxysulfonyl groups.

[0328] R １１ Preferred aryl groups represented by are phenyl group, p-methylphenyl group, trimethylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group.

[0329] Furthermore, in the above formulas (OS-103) to (OS-105), R １１ The heteroaryl group represented by is preferably a heteroaryl group having a total of 4 to 30 carbon atoms, which may have substituents. １１ The substituents that the heteroaryl group represented by may have include halogen atoms, alkyl groups, alkyloxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, aminocarbonyl groups, sulfonic acid groups, aminosulfonyl groups, and alkoxysulfonyl groups.

[0330] 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, for example, a heteroaromatic ring and a benzene ring may be fused together.１１ Examples of heteroaryl groups represented by include groups obtained by removing one hydrogen atom from a ring selected from the group consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzimidazole ring, which may have substituents.

[0331] In the above formulas (OS-103) to (OS-105), R １２ R is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group. In the above formulas (OS-103) to (OS-105), two or more R are present in the compound. １２ Preferably, one or two of them are alkyl groups, aryl groups, or halogen atoms; more preferably, one is an alkyl group, aryl group, or halogen atom; and particularly preferably, one is an alkyl group and the rest are hydrogen atoms. In the above formulas (OS-103) to (OS-105), R １２ The alkyl or aryl group represented by may have substituents. １２ The substituents that the alkyl or aryl group represented by may have are the above R １ Examples of substituents similar to those that the alkyl or aryl group in the above can have include.

[0332] In the above formulas (OS-103) to (OS-105), R １２ The alkyl group represented 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.

[0333] 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 atoms. Among these, chlorine and bromine atoms are preferred.

[0334] 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.

[0335] 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. １６ The 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.

[0336] In the above formulas (OS-103) to (OS-105), R １６Preferred 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.

[0337] 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.

[0338] 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. １６ Examples of alkoxysulfonyl groups represented by include methoxysulfonyl group, ethoxysulfonyl group, propyloxysulfonyl group, and butyloxysulfonyl group.

[0339] 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.

[0340] 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.

[0341] 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. Commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), WPAG-443 (structure shown below, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), MBZ-101 (structure shown below, manufactured by Midori Chemical Co., Ltd.), and the like.

[0342] <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).

[0343]

[0344] In the general formula (ZV), R ２０８ represents an alkyl group or aryl group. A represents an alkylene group, an alkenylene group, or an 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. ２０８ The 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.

[0345] 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).

[0346] 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.

[0347] <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.

[0348]

[0349] In the above general formula (ZI), R ２０１ , R ２０２ and R ２０３Each 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 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.

[0350] 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.

[0351] 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.

[0352] 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.

[0353] 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.

[0354] An example of a sulfonyliimide anion is the saccharin anion.

[0355] In bis(alkylsulfonyl)imido anions and tris(alkylsulfonyl)methide anions, the alkyl group is preferably a C1-C5 alkyl group. Substituents for these alkyl groups include halogen atoms, halogen-substituted alkyl groups, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or fluorine-substituted alkyl groups being preferred. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imido anion may bond to each other to form a ring structure. This increases the acid strength. Z － Preferably, the cation contains an aromatic ring group having an alkyl group with 3 or more carbon atoms as a substituent. The alkyl group 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.

[0356] Z － Particularly preferred is the anion represented by the following general formula (AN1).

[0357]

[0358] In the formula, Xf each 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.

[0359] 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 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.

[0360] 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.

[0361] 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.

[0362] 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.

[0363] 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.

[0364] 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).

[0365] 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).

[0366] 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.

[0367] 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:

[0368] 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.

[0369] <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 composition B. The photoacid generator may be contained alone or in combination of two or more types. When composition B contains two or more types of photoacid generators, it is preferable that their total content be within the above range.

[0370] [Other Additives] Composition B may contain components other than those listed above (hereinafter also referred to as "other additives"). Examples of other additives include crosslinking agents, hydrophobic resins (preferably resins different from resin (B)), acid diffusion inhibitors, solvents, surfactants, and onium carboxylate salts. For other additives, refer to paragraphs

[0204] to

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

[0371] 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.

[0372] [Resin A] [Synthesis of Resin (A-1)] 21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyclyme (diethylene glycol dimethyl ether) are mixed and stirred at 60°C for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture is cooled to -10°C, and while maintaining the temperature at -10±5°C, 17.0 g of thionyl chloride is added over 60 minutes. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 90 minutes at -12±3°C, and the mixture is stirred at room temperature for 3 hours. Next, 6000 g of water is added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) is stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring is filtered and dissolved in 500 g of tetrahydrofuran. 6000 g of water (poor solvent) is added to the resulting solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) is stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring is filtered again and dried under reduced pressure at 45°C for 3 days. 46.6 g of the dried powder is dissolved in 419.6 g of tetrahydrofuran, then 2.3 g of triethylamine is added and the mixture is stirred at room temperature for 35 minutes. After that, it is added to 3000 g of ethanol, and the precipitate is filtered. The obtained precipitate is dissolved in 281.8 g of tetrahydrofuran. To this, 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by AmberTec) were added and the mixture was stirred for 4 hours. After that, the ion exchange resin was removed by filtration, and the resulting polymer solution was added to a mixed solution of 4500 g of heptane and 500 g of ethyl acetate to obtain a precipitate. The precipitate was filtered off and dried under reduced pressure at 45°C for 24 hours to obtain 45.1 g of resin (A-1). The molecular weight of resin (A-1) was measured by gel permeation chromatography (standard polystyrene equivalent). The weight-average molecular weight (Mw) was 25,000. The structure of resin (A-1) is presumed to be the structure represented by the following formula (A-1).

[0373] [Synthesis of Resins (A-2) to (A-10)] Resins (A-2) to (A-11) are synthesized in the same manner as resin (A-1), except that the type of acid anhydride and diamine used as raw materials and the charging ratio are appropriately changed. The weight-average molecular weight (Mw) of these resins is shown in the table below.

[0374] The structure of the repeating units contained in resins (A-1) to (A-11) is shown below.

[0375]

[0376]

[0377]

[0378]

[0379]

[0380]

[0381]

[0382]

[0383]

[0384]

[0385]

[0386]

[0387] [Resin (B)] [Synthesis of Resin (B-1)] 194.3 g of cyclohexanone is placed in a three-necked flask under a nitrogen atmosphere and heated to 80°C. 18.0 g, 17.8 g, and 17.0 g of monomers corresponding to each repeating unit of resin (B-1) shown below are added dropwise from left to right, and a solution of polymerization initiator V-601 (Wako Pure Chemical Industries, 3.17 g) dissolved in 105 g of cyclohexanone is added dropwise 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 off and dried to obtain the following resin (B-1) (31.6 g) containing repeating units with Si atoms and repeating units with acid-degradable groups. The composition ratio (molar ratio) of the repeating units determined by NMR (nuclear magnetic resonance) is 10 / 50 / 40 from left to right. The weight-average molecular weight of the resulting resin (B-1) is 10,000, calculated from standard polystyrene equivalents using GPC.

[0388] [Synthesis of resins (B-2) to (B-7)] Resins (B-2) to (B-7) are synthesized using the same procedure as resin (B-1), or using a known procedure.

[0389] The structures of resins (B-1) to (B-7) are shown below. In Table 2 below, the composition ratios are shown from left to right as the content of each repeating unit in the structure below, and the Si atom content refers to the Si atom content (mass%) relative to the total amount of resin (B).

[0390]

[0391]

[0392]

[0393]

[0394]

[0395]

[0396]

[0397]

[0398] [Preparation of Resin Compositions] The insulating film forming resin composition and etching mask forming resin composition used in the examples and comparative examples are obtained by mixing the components listed in Tables 3 and 4 below. The content of each component listed in the table is the amount (parts by mass) indicated in the "parts by mass" column for each column in the table. Specifically, after mixing the components listed in the table, the insulating film forming resin composition and etching mask forming resin composition are obtained by pressure filtration using a polytetrafluoroethylene filter with a pore size of 0.5 μm.

[0399]

[0400]

[0401] [Polymerizable compound] ・C-1: NK ester 4G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0402] [Photopolymerization initiator] ・D-1: Compound with the following structure

[0403]

[0404] [Antioxidants] ・E-1: Compounds with the following structure (corresponds to phenolic compounds)

[0405]

[0406] [Metal Adhesion Modifiers] ・F-1: Compounds with the following structure (correspond to adhesives containing alkoxysilyl groups)

[0407]

[0408] [Rust Inhibitors] ・G-1: Compounds with the following structure (corresponding to nitrogen-containing heterocyclic compounds) ・G-2: Compounds with the following structure (corresponding to nitrogen-containing heterocyclic compounds)

[0409]

[0410] [Metal complexes] ・H-1: Compounds with the following structure

[0411]

[0412] [Thermal base generating agent] • I-1: Compound with the following structure • I-2: Compound with the following structure

[0413]

[0414] [Thermal polymerization initiator] ・M-1: Compound with the following structure

[0415]

[0416] [Photoacid Generator] ・J-1: Compound with the following structure ・J-2: Compound with the following structure ・J-3: Compound with the following structure

[0417]

[0418] [Acid diffusion control agent] ・K-1: Trioctylamine

[0419] [Solvents] ・L-1: Dimethyl sulfoxide ・L-2: γ-Butyrolactone ・L-3: Propylene glycol monomethyl ether acetate (PGMEA) ・L-4: Propylene glycol monomethyl ether (PGME)

[0420] [Developer and Rinse Solution] The developer and rinse solution used in the examples and comparative examples are as follows: Dev-1: Butyl acetate Dev-2: Propylene glycol monomethyl ether acetate (PGMEA) Dev-3: 2.38% by mass aqueous solution of tetramethylammonium hydroxide Dev-4: Pure water

[0421] [Examples 1-21, Comparative Example 1] An insulating film formation resin composition is applied to a silicon wafer with a copper thin layer formed on its surface by spin coating and dried at 110°C for 5 minutes. Next, the temperature is increased at a rate of 10°C / min under a nitrogen atmosphere and heated to 230°C for 2 hours to form an insulating film with a thickness of 5 μm after film formation (see Figure 1A). Then, an etching mask formation resin composition is applied to the obtained insulating film by spin coating and dried at 110°C for 1 minute to form a resist layer with a thickness of 200 nm after film formation (see Figure 1B). Subsequently, using a square via mask with patterns of 2, 3, 4, and 5 μm (diameter) formed on it, an i-line stepper (Canon: FPA-5520iV, NA=0.16, σ=0.7) is used to apply 200 mJ / cm². ２Exposure is performed with the specified exposure dose. Then, after baking (Post Exposure Bake; PEB) under the conditions shown in Table 5, the wafer is developed by paddled for 30 seconds with the developer shown in Table 5, and if specified, rinsed by paddled with the rinse solution shown in Table 5. Finally, the wafer is rotated at 4000 rpm for 30 seconds to obtain a resist pattern with a square via pattern (see Figure 1D). Next, using the obtained resist pattern (square via pattern) as a mask, the insulating film is etched using a Plasma System parallel plate type reactive ion etching apparatus DES-245R under the following etching conditions. Etching is stopped when the insulating film has been processed to the bottom (see Figure 1E). This yields an insulating portion with recesses. Here, the recesses are in the shape of the square via pattern. Next, using the insulating portion with recesses as a mold, electroplating is performed using the following method to fill the recesses with metal and manufacture a conductive portion. First, as a pretreatment before plating, the recessed side of the insulating portion is subjected to an oxygen plasma ashing treatment (output 100W, oxygen flow rate 100 ml, treatment time 60 seconds), followed by sulfuric acid treatment (contact with 10% by mass sulfuric acid aqueous solution for 60 seconds), and then rinsed with water. The silicon wafer with the pretreated insulating portion is 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 The device is set to a specific setting, and electroplating is performed for 10 minutes, filling the inside of the recess formed by the 5 μm mask with plated copper up to a height of 4 μm. In this way, a redistribution layer comprising a conductive portion containing plated copper and an insulating portion is formed on the silicon wafer.

[0422] (Etching conditions) Etching gas: O ２ Pressure: 20 mTorr; Applied power: 100 mW / cm² ２

[0423] [Comparative Examples 2 and 3] An insulating film-forming resin composition was applied to a silicon wafer with a copper thin layer formed on its surface by spin coating and dried at 110°C for 5 minutes. The resulting insulating film was subjected to a 300 mJ / cm² injection using an i-line stepper (Canon FPA-5520iV, NA=0.16, σ=0.7) with a square via mask having patterns of 2, 3, 4, and 5 μm (diameter) formed on it. ２ Exposure is performed with the specified exposure dose. Subsequently, the material is developed with cyclopentanone until the unexposed areas are removed, rinsed with PGMEA for 30 seconds, and then heated in a nitrogen atmosphere at a heating rate of 10°C / min to 230°C for 2 hours. This yields an insulating layer with recesses (film thickness 5 μm). Here, the recesses are in the shape of square vias. A redistribution layer is formed on a silicon wafer in the same manner as in Examples 1 to 21 and Comparative Example 1 described above, except that a silicon wafer having the insulating layer formed in this manner is used.

[0424] [Resolution Evaluation] The insulating portion with recesses obtained in the above-described examples and comparative examples (before plating) was observed using a cross-sectional SEM (Hitachi S4800) and evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Resolution" column of Table 5.

[0425] -Evaluation Criteria- A: Minimum aperture mask diameter is 2 μm B: Minimum aperture mask diameter is 3 μm C: Minimum aperture mask diameter is 4 μm D: Minimum aperture mask diameter is 5 μm, or none of the mask diameters are open.

[0426] [Evaluation of Peelability] The redistribution layers obtained in the above-described examples and comparative examples were stored for 264 hours under conditions of 130°C and 85% RH humidity. After that, the obtained redistribution layers were observed using a cross-sectional SEM (Hitachi S4800). For 10 conductive parts, the lengths of the normally bonded parts and abnormally peeled parts at the interface between the insulating part and the conductive part were measured, and the average value was judged according to the following criteria. The smaller the ratio of the length of the peeled part to the length of the bonded part, the more effectively peeling at the interface between the insulating part and the conductive part is suppressed, indicating higher reliability of the redistribution layer. The evaluation results are recorded in the "Peelability" column of Table 5.

[0427] -Evaluation Criteria- A: The total length of the delamination at the interface between the insulating and conductive parts is 5% or less of the total length of the adhesive parts. B: The total length of the delamination at the interface between the insulating and conductive parts is greater than 5% but 10% or less of the total length of the adhesive parts. C: The total length of the delamination at the interface between the insulating and conductive parts is greater than 10% but 20% or less of the total length of the adhesive parts. D: The total length of the delamination at the interface between the insulating and conductive parts is greater than 20% of the total length of the adhesive parts.

[0428] [Evaluation of Young's Modulus] The insulating film-forming resin compositions prepared in Examples 1 to 21 and Comparative Example 1 were applied to silicon wafers by spin coating to form coating films. The silicon wafers with the obtained coating films were dried on a hot plate at 110°C for 5 minutes to obtain a dried coating film with a uniform thickness of approximately 10 μm on the silicon wafer. Subsequently, a temperature-boosting programmable curing furnace (VF-2000 model, manufactured by Koyo Lindbergh) was used to heat the dried coating film at 230°C for 2 hours under a nitrogen atmosphere to obtain a cured product. On the other hand, when using the insulating film-forming resin compositions in Comparative Examples 2 and 3, after obtaining the dried coating film by the above method, a 300 mJ / cm² treatment was performed using a parallel light mask aligner (PLA-501FA model, manufactured by Canon Corporation). ２ The entire surface is exposed to light, and a cured coating is obtained by heating it at 230°C for 2 hours under a nitrogen atmosphere using a temperature-boosting curing furnace (VF-2000 model, manufactured by Koyo Lindbergh). The obtained cured material is immersed in a 4.9 mass% hydrofluoric acid aqueous solution and peeled off from the silicon wafer. The peeled cured material is punched out using a punching machine to prepare test specimens with a sample width of 3 mm and a sample length of 30 mm. The longitudinal elongation of the obtained test specimens is measured using a tensile testing machine (Tensilon) according to ASTM D882-09 and evaluated according to the following criteria. The evaluation results are recorded in the "Young's Modulus" column of Table 5.

[0429] -Evaluation Criteria- A: Young's modulus of 4.0 GPa or higher B: Young's modulus of 3.0 GPa or higher but less than 4.0 GPa C: Young's modulus of less than 3.0 GPa

[0430] [Evaluation of Elongation at Break] Test specimens are prepared using the same method as for measuring Young's modulus as described above. The longitudinal elongation of the obtained test specimens is measured using a tensile testing machine (Tensilon) in accordance with JIS-K6251, under conditions of a crosshead speed of 300 mm / min, 25°C, and 65% RH (relative humidity). Each measurement is performed five times, and the arithmetic mean of the elongation at break (elongation at break) at the time of fracture in the five measurements is used as the index value. The evaluation is performed according to the evaluation criteria below, and the evaluation results are recorded in the "Elongation at Break" column of Table 5. The larger the index value, the better the film strength of the cured material.

[0431] -Evaluation Criteria- A: The above indicator value is 70% or higher B: The above indicator value is 40% or higher but less than 70% C: The above indicator value is less than 40%

[0432] The evaluation results for Examples 1 to 21 and Comparative Examples 1 to 3 are shown in Table 5 below.

[0433]

[0434] From the above results, it can be seen that by using the redistribution layer formation process of the present invention, a redistribution layer can be obtained that has an insulating portion with a pattern (recess) with excellent resolution and in which peeling at the interface between the insulating portion and the conductive portion is suppressed. Furthermore, by using the redistribution layer formation process of the present invention, an insulating portion with excellent elongation at break can be obtained. Comparing Examples 1 to 4, it can be seen that when the Mw of resin (A) contained in the insulating film forming resin composition is 30,000 or more (Examples 3 and 4), a redistribution layer can be obtained in which peeling at the interface between the insulating portion and the conductive portion is further suppressed. Comparing Examples 4, 15 and 16, it can be seen that when the Mw of resin (A) is 200,000 or less (Examples 4 and 15), a redistribution layer can be obtained that has an insulating portion with a pattern with even better resolution. A comparison of Examples 4 and 5 shows that when the photoacid generator contained in the etching mask forming resin composition is a photoacid generator that does not contain alkyl fluoride (Example 4), a redistribution layer is obtained that has an insulating portion with a pattern superior in resolution and in which peeling at the interface between the insulating portion and the conductive portion is further suppressed. A comparison of Examples 4 and 6 shows that when the photoacid generator contained in the etching mask forming resin composition is a nonionic type photoacid generator (Example 4), a redistribution layer is obtained that has an insulating portion with a pattern superior in resolution and in which peeling at the interface between the insulating portion and the conductive portion is further suppressed. A comparison of Examples 4 and 9 shows that when the silicon atom content in resin (B) is 5.0% by mass or more based on the total amount of resin (B) (Example 4), a redistribution layer is obtained that in which peeling at the interface between the insulating portion and the conductive portion is further suppressed. A comparison of Examples 4 and 18 shows that when resin A contained in the insulating film forming resin composition contains the above-mentioned specific ring structure X (Example 4), an insulating portion superior in Young's modulus and elongation at break is obtained. A comparison of Examples 4 and 19 shows that by including an antioxidant (particularly a phenolic compound) in the insulating film-forming resin composition (Example 4), a redistribution layer with more suppressed delamination at the interface between the insulating and conductive parts can be obtained.A comparison of Examples 4 and 20 shows that by including a metal adhesion modifier (particularly an adhesive containing an alkoxysilyl group) in the insulating film-forming resin composition (Example 4), a redistribution layer with further suppressed delamination at the interface between the insulating and conductive parts can be obtained. A comparison of Examples 4 and 21 shows that by including a rust inhibitor (particularly a nitrogen-containing heterocyclic compound) in the insulating film-forming resin composition (Example 4), a redistribution layer with further suppressed delamination at the interface between the insulating and conductive parts can be obtained.

[0435] On the other hand, when a resist layer formed using an etching mask resin composition is subjected to pattern exposure and alkaline development, and the resulting positive resist pattern is used as a mask for etching the insulating film, it is found that delamination at the interface between the insulating and conductive parts cannot be sufficiently suppressed, and the resolution of the insulating part is also insufficient (Comparative Example 1). Furthermore, when patterning the insulating film is performed without using etching, it is found that delamination at the interface between the insulating and conductive parts cannot be sufficiently suppressed, and the resolution of the insulating part is also insufficient (Comparative Examples 2 and 3). Thus, when patterning the insulating film is performed by development without using etching, it is thought that components such as adhesives and rust inhibitors present on the surface of the insulating film dissolve during development, making it impossible to sufficiently suppress delamination at the interface between the insulating and conductive parts.

[0436] 10 Substrate 20 Insulating film 21 Insulating portion 22 Recess 23 Aperture 30 Resist layer (first resist layer) 30A Exposed portion 30B Unexposed portion 31 Resist layer after pattern exposure (first resist layer after pattern exposure) 32 Negative resist pattern (first negative resist pattern) 41, 141 Conductive portion 41a Surface 50, 150 Redistribution layer 130 Second resist layer 132 Second resist pattern

Claims

1. A method for manufacturing a semiconductor device, comprising: a preparation step for preparing a semiconductor element; 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: a step 1 for forming an insulating film by applying a resin composition A, which includes at least one resin (A) selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor, onto a substrate; a step 2 for forming a resist layer by applying a photosensitive resin composition B, which includes a resin (B) having repeating units having groups that decompose by the action of an acid to produce polar groups and silicon atoms, and a photoacid generator, onto the insulating film; a step 3 for pattern exposure of the resist layer; a step 4 for treating the resist layer after pattern exposure with a developer containing an organic solvent to form a negative resist pattern on the insulating film; and a step 5 for dry etching the insulating film using the negative resist pattern as a mask to form the insulating portion having a recess. A method for manufacturing a semiconductor device, comprising, in this order, a step 6 of applying a plating treatment to the insulating portion having the recess to form the conductive portion.

2. The method for manufacturing a semiconductor device according to claim 1, wherein the developer in step 4 comprises at least one organic solvent selected from the group consisting of butyl acetate, propylene glycol monomethyl 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 3 is in the range of 300 to 450 nm.

4. The method for manufacturing a semiconductor device according to claim 1, wherein the resin (A) comprises at least one of the following structures. * indicates the joining position.

5. The method for manufacturing a semiconductor device according to claim 1, wherein the weight-average molecular weight of the resin (A) is 30,000 to 200,000.

6. The method for manufacturing a semiconductor device according to claim 1, wherein the resin composition A further comprises a nitrogen-containing heterocyclic compound.

7. The method for manufacturing a semiconductor device according to claim 1, wherein the resin composition A further comprises at least one antioxidant selected from the group consisting of phenol compounds, phosphite compounds, thioether compounds, and phosphonite compounds.

8. The method for manufacturing a semiconductor device according to claim 1, wherein the resin composition A further comprises an adhesive containing an alkoxysilyl group.

9. The method for manufacturing a semiconductor device according to claim 1, wherein the content of silicon atoms in the resin (B) is 5.0% by mass or more, based on the total amount of the resin (B).

10. The method for manufacturing a semiconductor device according to claim 1, wherein the photoacid generator contained in the photosensitive resin composition B is a photoacid generator that does not contain an alkyl fluoride.

11. The method for manufacturing a semiconductor device according to claim 1, wherein the photoacid generator contained in the photosensitive resin composition B is a nonionic type photoacid generator.

12. The method for manufacturing a semiconductor device according to claim 1, wherein the dry etching in step 5 is reactive ion etching with a gas containing oxygen atoms.

13. The method for manufacturing a semiconductor device according to claim 1, further comprising a step of removing the negative resist pattern between step 5 and step 6.

14. The method for manufacturing a semiconductor device according to claim 1, wherein the plating process in step 6 is an electroplating process.

15. A resin composition for forming an insulating film, used in a method for manufacturing a semiconductor device according to any one of claims 1 to 14, comprising at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor.

16. A photosensitive resin composition used in a method for manufacturing a semiconductor device according to any one of claims 1 to 14, comprising: a resin containing repeating units having groups that decompose upon the action of an acid to produce polar groups and silicon atoms; and a photoacid generator.

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