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 redistribution layer provided with an insulating part having a pattern in which the occurrence of cracks is suppressed and which has excellent resolution, a resin composition for forming an insulating film, and a photosensitive resin composition. A method for manufacturing a semiconductor device according to the present invention comprises a semiconductor element preparation step and a redistribution layer formation step. The redistribution layer formation step comprises: a step 1 for forming an insulating film using a resin composition A; a step 2 for performing a step 2a for forming a via part and a step 2b for forming a trench part to form an insulating part having a recess part configured from the via part and the trench part; a step 3 for forming a metal layer that fills the recess part; and a step 4 for removing a part of the metal layer by CMP processing to obtain a conductive part. In the step 2a and / or the step 2b, dry etching using a resist pattern of a photosensitive resin composition B as a mask is performed.

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, which has an insulating part and a conductive part, is used as an organic interposer from the viewpoint of low cost, etc. Here, multilayering of the redistribution layer is being considered, but if the semi-additive process (SAP) is used to manufacture the redistribution layer, it may be difficult to maintain the flatness of the redistribution layer. Therefore, the manufacture of a redistribution layer by the dual damascene method is being considered. This method involves forming recesses in an insulating film that include trenches (grooves) used to fill with metal to form wiring, and vias (via holes) used to fill with metal to create interlayer conductivity. After filling the recesses with metal to form a metal layer, the surface of the metal layer is then planarized by polishing. When manufacturing a redistribution layer by the dual damascene method, one method for forming recesses including vias and trenches is to form a resist pattern on an insulating layer, and then use the resist pattern as a mask to etch the insulating film to form vias or trenches. Patent Document 1 discloses the use of a composition containing a silicon-containing polymer or the like as a material for forming such a resist pattern.

[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, it is necessary to have excellent resolution of the pattern of the insulating portion. Furthermore, from the viewpoint of improving the reliability of semiconductor devices, it is necessary for the insulating portion of the redistribution layer to have minimal crack occurrence. 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 etched the insulating film using the resist pattern as a mask to form a redistribution layer having an insulating portion. However, they found that the resolution of the pattern of the insulating portion was insufficient, or cracks occurred in the insulating portion, indicating that there is room for improvement.

[0005] Therefore, the present invention aims to provide a method for manufacturing semiconductor devices that can produce a redistribution layer having an insulating portion with a pattern that suppresses crack occurrence and has excellent resolution. 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 study on the above problems, the inventors of this invention 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; and a redistribution layer formation step for forming a redistribution layer connected to the semiconductor element and having an insulating portion and a conductive portion, wherein the redistribution layer formation step comprises: a step 1 for forming an insulating film by applying a resin composition A containing 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 an insulating portion having a recess composed of the via portion and the trench portion by performing a step 2a for forming via portions in the insulating film and a step 2b for forming trench portions in the insulating film; a step 3 for forming a metal layer so as to fill the recess by a plating process; and a step 4 for obtaining the conductive portion by removing a part of the metal layer by a chemical mechanical polishing process, wherein at least one of the following conditions is met: step 2a includes steps a, b, c and d1 below, and step 2b includes steps a, b, c and d2 below. Step a: Apply 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 to form a resist layer. Step b: Pattern exposure of the resist layer. Step c: Treat the resist layer after pattern exposure with a developer solution containing an organic solvent to form a negative resist pattern on the insulating film. Step d1: Dry etching the insulating film using the negative resist pattern as a mask to form the via portion. Step d2: Dry etching the insulating film using the negative resist pattern as a mask to form the trench portion. [2] The method for manufacturing a semiconductor device according to [1], wherein the developer solution in step c 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. [3] The method for manufacturing a semiconductor device according to [1] or [2], wherein the exposure wavelength in step b 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 bonding 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 resin composition A is a photosensitive resin composition comprising at least one of a photopolymerization initiator and a photoacid generator, and the formation of the via portion in step 2a comprises a pattern exposure treatment and a development treatment.

[10] A method for manufacturing a semiconductor device according to any one of [1] to [9], 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).

[11] A 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 photoacid generator that does not contain alkyl fluoride.

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

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

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

[12] , wherein the dry etching in at least one of step d1 and step d2 is reactive ion etching with a gas containing oxygen atoms.

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

[13] , further comprising a step of removing the negative type resist pattern after at least one of step d1 and step d2.

[15] A method for manufacturing a semiconductor device according to any one of [1] to

[14] , comprising an etching stop layer inside the insulating film.

[16] A resin composition for forming an insulating film, used in a method for manufacturing a semiconductor device according to any one of [1] to

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

[17] A photosensitive resin composition, used in a method for manufacturing a semiconductor device according to any one of [1] to

[15] , 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 semiconductor devices can be provided that can produce a redistribution layer having an insulating portion with a pattern that suppresses crack occurrence and has excellent resolution. 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 1A. This is a schematic cross-sectional view illustrating step 2a in step 2. This is a schematic cross-sectional view illustrating 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 d2. This is a schematic cross-sectional view illustrating step e2. 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 1B. This is a schematic cross-sectional view illustrating step a(2a). This is a schematic cross-sectional view illustrating step b(2a). This is a schematic cross-sectional view illustrating step c(2a). This is a schematic cross-sectional view illustrating step d1. This is a schematic cross-sectional view illustrating step e1. This is a schematic cross-sectional view illustrating step d1 in modified example 2. This is a schematic cross-sectional view illustrating step 1C. This is a schematic cross-sectional view illustrating step 2a-1. This is a schematic cross-sectional view illustrating step 2a-2. This is a schematic cross-sectional view illustrating 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 d2. This is a schematic cross-sectional view illustrating step e2. 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 process 1D. This is a schematic cross-sectional view illustrating process a(2a). This is a schematic cross-sectional view illustrating process b(2a). This is a schematic cross-sectional view illustrating process c(2a). This is a schematic cross-sectional view illustrating process d1. This is a schematic cross-sectional view illustrating process e1.

[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 includes the following steps 1 to 4, and at least one of the following is satisfied: step 2a included in step 2 includes the following steps a, b, c and d1; and step 2b included in step 2 includes the following steps a, b, c and d2. Step 1: A step of applying a resin composition A containing at least one resin (A) selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor and polybenzoxazole precursor onto a substrate to form an insulating film. Step 2: A step of performing step 2a to form via portions in the insulating film and step 2b to form trench portions in the insulating film to form the insulating portion having recesses composed of the via portions and the trench portions. Step 3: A step of forming a metal layer so as to fill the recesses by plating. Step 4: Steps to obtain the conductive portion by removing a portion of the metal layer by chemical mechanical polishing. Step a: Steps to form a resist layer by applying a photosensitive resin 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, onto the insulating film. Step b: Steps to pattern expose the resist layer. Step c: Steps to form a negative resist pattern on the insulating film by treating the resist layer after pattern exposure with a developer containing an organic solvent. Step d1: Steps to form the via portion by dry etching the insulating film using the negative resist pattern as a mask. Step d2: Steps to form the trench portion by dry etching the insulating film using the negative resist pattern as a mask.

[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 that suppresses crack generation and has excellent resolution. The reason for this is generally presumed to be as follows. In the semiconductor device manufacturing method of the present invention, in order to form at least one of via portions and trench portions in the insulating film, step 2a, which is the via portion formation step, includes the above-mentioned steps a, b, c and d1, or step 2b, which is the trench portion formation step, includes the above-mentioned steps a, b, c and d2. Here, the resist layer obtained in step a 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 that has high affinity with the highly hydrophobic resist layer (step c). It is presumed that an insulating portion having a pattern with excellent resolution can be obtained by using the resist pattern obtained in this way as a mask (step d1 or step d2). Furthermore, when developing the resist layer, using a developer containing an organic solvent (step c) makes the insulating film beneath the resist layer less susceptible to damage from the developer compared to using an aqueous alkaline developer, thus suppressing the occurrence of cracks in the insulating portion of the redistribution layer. Additionally, during the dry etching of the insulating film in step d1 or step d2, silicon oxide is generated by silicon atoms in the mask resist pattern, causing the resist pattern to function as a hard mask. This suppresses damage to the insulating film beneath the resist pattern due to dry etching, thus suppressing the occurrence of cracks in the insulating portion of the redistribution layer. However, with long-term use of the redistribution layer, damage to the insulating portion from dry etching may become apparent, leading to significant crack formation. Nevertheless, according to the semiconductor device manufacturing method of the present invention, damage from dry etching is reduced for the reasons mentioned above, so the occurrence of cracks in the insulating portion is sufficiently suppressed even with long-term use of the redistribution layer.

[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 first 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 1A, 2, 3, and 4 in this order. Step 1A: A step of applying a photosensitive resin composition A1 (hereinafter also referred to as "composition A1"), which comprises at least one resin (A) selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor, and at least one of a photopolymerization initiator and a photoacid generator, onto a substrate to form an insulating film. Step 2: After performing step 2a to form via portions by applying a pattern exposure treatment and a development treatment to the insulating film, a step 2b including the following steps a, b, c, and d2 is performed to form trench portions in the insulating film and form an insulating portion having recesses composed of the via portions and the trench portions. Step 3: Filling the recesses by a plating treatment. Step 4: Step to form a metal layer to fill the gap Step a: Step to remove a portion of the metal layer by chemical mechanical polishing to obtain the conductive portion Step b: Step to form a resist layer by applying a photosensitive resin composition B (hereinafter also referred to as "composition B"), which contains a resin (B) having repeating units having groups that decompose by the action of an acid to generate polar groups and silicon atoms, and a photoacid generator, onto the insulating film Step c: Step to pattern expose the resist layer Step c: Step to treat the resist layer after pattern exposure with a developer containing an organic solvent to form a negative resist pattern on the insulating film Step d2: Step to dry etch the insulating film using the negative resist pattern as a mask to form the trench portion

[0016] Furthermore, it is preferable that step 2b in the first embodiment further includes a step of removing the negative resist pattern (hereinafter also referred to as "step e2") after step d2.

[0017] The redistribution layer formation process in the first embodiment is simpler than the redistribution layer formation processes in other embodiments described later, and therefore has the advantage of being highly applicable to industrial use.

[0018] 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 assumes that the first embodiment includes step e2, but step e2 is an optional step and may not be performed.

[0019] <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.

[0020] 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).

[0021] <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 1A, 2, 3, and 4 in this order.

[0022] 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.

[0023] (Step 1A) Figure 1A is a schematic cross-sectional view illustrating Step 1A, showing a cross-section along the thickness direction of the substrate 10 and the insulating film 20. In Step 1A, composition A1 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.

[0024] Coating is preferred as a means of applying composition A1 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 A1 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.

[0025] Step 1A may include a drying process (drying treatment) to dry the composition A1 applied to the substrate 10. This removes components such as solvents from the composition A1 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.

[0026] 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).

[0027] 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.

[0028] - Insulating film The insulating film 20 is a film formed on the substrate 10 by composition A1 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.

[0029] Composition A1 is a photosensitive resin composition comprising a resin (A) and at least one of a photopolymerization initiator and a photoacid generator. Details of composition A1 will be described later.

[0030] Resin (A) is at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor. It is preferable that the resin (A) contained in composition A1 has a radical polymerizable group (described later) or a polarity conversion group such as an acid-degradable group (described later). Details of resin (A) will be explained later.

[0031] 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").

[0032]

[0033] In the structure above, * indicates a bonding position.

[0034] 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: crack generation in the insulating portion can be further suppressed, and the film strength of the insulating portion 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 portion can be further improved, and crack generation in the insulating portion can be further suppressed.

[0035] Composition A1 contains at least one of a photopolymerization initiator and a photoacid generator. Details of the photopolymerization initiator and photoacid generator will be described later.

[0036] From the viewpoint of further suppressing crack formation in the insulating portion, composition A1 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.

[0037] From the viewpoint of further suppressing crack formation in the insulating portion, composition A1 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.

[0038] From the viewpoint of further suppressing crack formation in the insulating portion, composition A1 preferably further contains an adhesive containing an alkoxysilyl group. Examples of adhesives containing an alkoxysilyl group include the metal adhesion modifiers (preferably silane coupling agents having an alkoxysilyl group) described in the following section on composition A.

[0039] (Step 2) Step 2a Figure 1B is a schematic cross-sectional view illustrating step 2a in step 2, and shows a cross-section of the substrate 10 and the insulating film 20 along the thickness direction. In step 2a, via portions 22A are formed in the insulating film 20 by applying pattern exposure and development processing to the insulating film 20. The following describes the processes that can be carried out in step 2a.

[0040] ...Exposure process (pattern exposure) In step 2a, the insulating film 20 is subjected to pattern exposure. One method of pattern exposure is to selectively expose the insulating film 20. Selective exposure means that only a part of the insulating film 20 is exposed. By selective exposure, the insulating film 20 is divided into exposed areas (exposed areas) and unexposed areas (unexposed areas), which are not shown in the figure.

[0041] The exposure amount is not particularly limited as long as it can cure composition A1 (insulating film 20), 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.

[0042] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0043] 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 (5) excimer laser (wavelength 157 nm), (6) extreme ultraviolet light; EUV (wavelength 13.6 nm), (7) YAG laser with second harmonic 532 nm and third harmonic 355 nm. For composition A1, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with the i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited, and any method in which at least a part of the insulating film 20 is exposed is acceptable, but examples include exposure using a photomask and exposure by laser direct imaging.

[0044] ...The post-exposure heat treatment step 2a may include a post-exposure heat treatment in which the insulating film 20 is heated after pattern exposure. The post-exposure heat treatment can be performed after the exposure treatment and before the development treatment. 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 known examples include 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.

[0045] ...In the development process 2a, the insulating film 20 after pattern exposure is subjected to a development process. One method of development is to develop the insulating film 20 after pattern exposure with a developer to form via portions 22A in the insulating film 20. 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.

[0046] Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents. From the viewpoint of achieving superior effects in the present invention, developing solutions containing organic solvents are preferred.

[0047] 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.

[0048] If the developer contains an organic solvent, the organic solvent may be one of the compounds described in paragraph

[0387] of International Publication No. 2021 / 112189. This 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.

[0049] When the developer contains an organic solvent, one or more organic solvents can be used in mixture form. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is even more preferred.

[0050] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Alternatively, the above content may be 100% by mass.

[0051] The developing solution may further contain other components. Examples of other components include known surfactants and known defoamers.

[0052] ...The rinsing process 2a 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.

[0053] The method of supplying the rinse solution is not particularly limited as long as a desired pattern can be formed. Examples include immersing the insulating film in the rinse solution, supplying the rinse solution to the insulating film by filling it with liquid, supplying the rinse solution to the insulating film with a shower, and continuously supplying the rinse solution onto the insulating film 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 rinse solution during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] The rinse solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0059] ...The heat treatment step 2a may include a heat treatment in which the pattern obtained by the developing process (insulating film 20 on which via portions 22A are formed) is heated. If a rinsing treatment is performed, the heat treatment may be performed on the pattern after rinsing. During the heat treatment, the resin such as the polyimide precursor is cyclized to become a resin such as polyimide. In addition, crosslinking of unreacted crosslinkable groups in resin (A) or crosslinking agents other than resin (A) also proceeds.

[0060] The heating temperature (maximum heating temperature) in the heat treatment is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, particularly preferably 160 to 250°C, and most preferably 160 to 230°C. For the heat treatment, reference can be given to paragraphs

[0326] to

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

[0061] The via portion 22A is a hole that penetrates the insulating film 20 in the thickness direction and is used in the production of a part of the conductive portion of the redistribution layer in steps 3 and 4 described later. The insulating film 20 may have only one via portion 22A or two or more. The cross-sectional shape of the via portion 22A (the shape of the cross section along the thickness direction of the insulating film 20) is a rectangle. The front shape of the via portion 22A (the shape when the via portion 22A is observed from the top surface of the insulating film 20) is a circle or a rectangle. The depth of the via portion 22A is not particularly limited, but is preferably 1 to 20 μm, more preferably 2 to 15 μm, and even more preferably 2 to 10 μm. The diameter of the via portion 22A is preferably 1.0 to 30 μm, more preferably 1.5 to 20 μm, and even more preferably 1.5 to 10 μm.

[0062] • Process 2b Process 2b is carried out after process 2a and includes processes a, b, c, d2 and e2.

[0063] ...Step a Figure 1C is a schematic cross-sectional view illustrating step a, showing cross-sections along the thickness direction of the substrate 10, insulating film 20, and resist layer 30. In step a, composition B, described later, is applied onto the insulating film 20. As a result, the resist layer 30 is formed on the insulating film 20 and on the substrate 10, where a part of the surface is exposed due to the formation of via portions 22A.

[0064] The means for applying composition B onto the insulating film 20 can be the means described in step 1A for applying composition A1 onto the substrate 10, and the preferred embodiment is the same.

[0065] Step a 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. The preferred drying temperature and drying time in the drying treatment of step a are the same as the preferred drying temperature and drying time in the drying treatment of step 1A.

[0066] ...The resist layer 30 is a layer formed by composition B described later, and is used in step c 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.

[0067] Composition B comprises a resin (B) and a photoacid generator. Details of Composition B will be described later.

[0068] 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.

[0069] 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 the occurrence of cracks in the insulating 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.

[0070] 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.

[0071] 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.

[0072] ...Step b Figure 1D is a schematic cross-sectional view illustrating step b, showing a cross-section along the thickness direction of the substrate 10, insulating film 20, and the resist layer 31 after pattern exposure. In step b, the resist layer 30 is pattern exposed. As a result, a resist layer 31 after pattern exposure, including exposed areas 30A and unexposed areas 30B, is formed on a part of the substrate 10 and the insulating film 20.

[0073] 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. Therefore, by selectively exposing the resist layer 30, a resist layer 31 with exposed portions 30A and unexposed portions 30B is formed after pattern exposure. The preferred exposure amount and exposure wavelength in step b are the same as the preferred exposure amount and exposure wavelength in the exposure process of step 2a. In particular, the exposure wavelength in step b 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, from the viewpoint of achieving both resolution and pattern shape.

[0074] Step b may include a post-exposure heat treatment in which the resist layer 31 is heated after pattern exposure. That is, the post-exposure heat treatment can be performed after the exposure treatment in step b and before the development treatment in step c. The preferred mode of the post-exposure heat treatment in step b is the same as the preferred mode of the post-exposure heat treatment in step 2a.

[0075] ...Step c Figure 1E is a schematic cross-sectional view illustrating step c, showing a cross-section along the thickness direction of the substrate 10, insulating film 20, and negative resist pattern 32. In step c, the resist layer 31 after pattern exposure is treated with a developer solution containing an organic solvent (development process). 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.

[0076] The development process in step c is a negative-type development in which the unexposed portion 30B of the resist layer 31 after pattern exposure is removed. The preferred embodiment of the developer solution containing an organic solvent used in step c is the same as the preferred embodiment of the developer solution containing an organic solvent used in the development process in step 2a. In particular, the developer solution used in step c 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, 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.

[0077] Step c may include a rinsing step in which the pattern is washed (rinsed) with a rinsing solution after the developing step. The preferred embodiments of the rinsing step and the rinsing solution in step c are the same as the preferred embodiments of the rinsing step and the rinsing solution in step 2a.

[0078] ...Step d2 Figure 1F is a schematic cross-sectional view illustrating step d2, showing the cross-section when the substrate 10, insulating portion 21, and negative resist pattern 32 are cut along the thickness direction such that the trench portion 22B is exposed along its extending direction. In step d2, 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 composed of via portions 22A and trench portions 22B. The insulating portion 21 is a component corresponding to the insulating film 20.

[0079] Dry etching may be single-step etching or may be multi-step etching. When the etching consists of a plurality of steps, the etching of each step may be the same process or different processes. The dry etching method is not particularly limited, but from the viewpoint of excellent pattern shape, reactive ion etching (RIE) is preferred. The plasma generation mechanism in reactive ion etching is not particularly limited, but methods that can independently control the 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 method can be used for dry etching, and various conditions and the like are appropriately determined according to the composition, use and the like of the insulating film 20. For example, etching can be performed in accordance with Proc. of SPIE, Vol. 6924, 692420 (2008), Japanese Unexamined Patent Publication No. 2009-267112, and the like. It is also possible to follow the method described in "Chapter 4 Etching" of "Semiconductor Process Textbook Fourth Edition, 2007 Publisher: SEMI Japan".

[0080] In particular, the dry etching in step d2 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 makes it easier for the etching of the insulating film 20 to proceed. Specific examples of the oxygen atom-containing gas include O ２ , O ３ , CO, CO ２ , NO, NO ２ , N ２ O, SO, SO ２ , and at least one selected from the group consisting of COS, etc. may be mentioned. In addition to the oxygen atom-containing gas, Ar, He, Xe, Kr, and N as diluent gases ２At 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.

[0081] ...The trench portion 22B is a line-shaped groove formed in the insulating film 20 and is used in the production of a part of the conductive portion of the redistribution layer in steps 3 and 4 described later. In the example of Figure 1F, the trench portion 22B is a line-shaped groove formed so as to pass through the previously formed via portion 22A when the surface of the insulating film 20 (insulating portion 21) opposite to the substrate 10 is viewed from above. The insulating portion 21 may have only one trench portion 22B or two or more. The cross-sectional shape of the trench portion 22B (the cross-section that intersects the extending direction of the trench portion 22B and is along the depth direction of the trench portion 22B) can be a rectangle. The diameter (width) of the trench portion 22B 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.

[0082] ...The recessed portion 22 includes a via portion 22A and a trench portion 22B, and is used in the manufacturing of the conductive portion of the redistribution layer in steps 3 and 4 described later. In the example of Figure 1F, the via portion 22A and the trench portion 22B are formed in the order of via portion 22A and trench portion 22B in the thickness direction of the insulating portion 21, moving away from the substrate 10, and the via portion 22A and the trench portion 22B together constitute the recessed portion 22. The shape of the recessed portion 22 is not particularly limited, but usually it is a shape in which the via portion 22A and the trench portion 22B are integrated.

[0083] ...Step e2 Figure 1G is a schematic cross-sectional view illustrating step e2, showing a cross-section along the thickness direction of the substrate 10 and the insulating portion 21. In step e2, the negative resist pattern 32 placed on the insulating portion 21 is removed. This exposes the surface of the insulating portion 21.

[0084] 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 e2 is not particularly limited, but the reactive ion etching (RIE) described above is preferred. Various conditions for dry etching in step e2 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 d2 above. Among these, the dry etching in step e2 is preferably reactive ion etching using a gas containing fluorine atoms (hereinafter also referred to as "fluorine atom-containing gas"). A specific example of a fluorine atom-containing gas is CF ４ , C ２ F ６ SF ６ These include the following. 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.

[0085] (Step 3) Figure 1H is a schematic cross-sectional view illustrating Step 3, showing cross-sections along the thickness direction of the substrate 10, the insulating portion 21, and the metal layer 40. In Step 3, metal is filled into the recesses 22 by plating. This forms the metal layer 40 on the substrate 10 and the insulating portion 21.

[0086] Known plating methods include electroplating and electroless plating. Below is an example of a method for forming the metal layer 40 by plating. First, a seed layer (for example, a Ti barrier layer made of titanium) is provided on the entire side of the insulating portion 21 where the recess 22 is formed, using a method such as sputtering. Providing a seed layer promotes the uniform growth of the subsequent plating metal and improves the adhesion of the plating metal to the insulating portion 21 and the substrate 10. Next, a power supply layer (copper layer) is provided on the surface of the seed layer by sputtering. Then, the metal layer 40 is formed by performing electroplating using the power supply layer (for example, electrolytic copper plating). Before performing the electroplating, the power supply layer may be pretreated with sulfuric acid treatment and water washing.

[0087] The material constituting the metal layer 40 is not particularly limited, but examples 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.

[0088] (Step 4) Figure 1I is a schematic cross-sectional view illustrating Step 4, showing a cross-section of the substrate 10 and the redistribution layer 50 along the thickness direction. In Step 4, the surface of the metal layer 40 is subjected to chemical mechanical polishing (CMP) to remove a portion of the metal layer 40 until a portion of the surface of the insulating portion 21 is exposed. This forms a redistribution layer 50 including the conductive portion 41 and the insulating portion 21. The conductive portion 41 is a component formed by CMP treatment of the metal layer 40 and is a component containing the aforementioned metal.

[0089] The apparatus and conditions used for the CMP treatment in step 4 are not particularly limited, and known apparatus and conditions may be used. Preferably, the CMP treatment in step 4 is carried out such that a part of the surface of the insulating portion 21 is exposed and metal remains only within the recess 22 (see Figure 1G). In particular, if the CMP treatment is carried out until the surface 21a of the insulating portion 21 and the surface 41a of the conductive portion 41 form the same surface, a laminate with excellent flatness is likely to be obtained when a laminate is manufactured by stacking multiple redistribution layers 50.

[0090] If the above-mentioned seed layer or power supply layer (not shown) is formed between the insulating portion 21 and the metal layer 40, the power supply layer present in portions of the insulating portion 21 other than the recess 22 may be removed by the CMP treatment in step 4.

[0091] 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 a semiconductor element and a package substrate. In the example of Figure 1I, the redistribution layer 50 includes an insulating portion 21 and a conductive portion 41 that fills a recess 22 (see Figure 1G) in the insulating portion 21. In the example of Figure 1I, the surface 21a of the insulating portion 21 and the surface 41a of the conductive portion 41 form the surface of the redistribution layer 50.

[0092] (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.

[0093] 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.

[0094] In this embodiment, the series of steps 1A to 4 described above may be repeated in this order to create a multilayer redistribution layer.

[0095] [Second Embodiment] The second embodiment of the method for manufacturing a semiconductor device of the present invention is the same as the first embodiment described above, except that the above-described step 1 uses a non-photosensitive resin composition A2 (step 1B described later), and step 2a includes steps a, b, c and d1.

[0096] Specifically, the second embodiment is a method for manufacturing a semiconductor device, comprising: a preparation step for preparing a semiconductor element; and a redistribution layer formation step for forming a redistribution layer connected to the semiconductor element and having an insulating portion and a conductive portion, wherein the redistribution layer formation step includes the following steps 1B, 2, 3, and 4 in this order. Step 1B: A step of applying a resin composition A2 (hereinafter also referred to as "composition A2") containing the above-mentioned resin (A) and not photosensitive onto a substrate to form an insulating film. Step 2: After performing step 2a, which includes the following steps a, b, c, and d1, to form via portions in the insulating film, step 2b, which includes the following steps a, b, c, and d2, to form trench portions in the insulating film, thereby forming an insulating portion having recesses composed of the via portions and the trench portions. Step 3: A step of forming a metal layer so as to fill the recesses by a plating process. Step 4: A step of removing a part of the metal layer by a chemical mechanical polishing process to obtain the conductive portion. Step a: By the action of an acid Steps to form a resist layer by applying a photosensitive resin composition B (hereinafter also referred to as "composition B"), which comprises a resin (B) containing repeating units having groups that decompose to produce polar groups and silicon atoms, and a photoacid generator, onto the insulating film: Step b: Pattern exposure of the resist layer Step c: Treatment of the resist layer after pattern exposure with a developer solution containing an organic solvent to form a negative resist pattern on the insulating film Step d1: Dry etching of the insulating film using the negative resist pattern as a mask to form the via portion Step d2: Dry etching of the insulating film using the negative resist pattern as a mask to form the trench portion

[0097] In the second embodiment, step 2a preferably further includes a step to remove the negative resist pattern (hereinafter also referred to as "step e1") after step d1. In addition, in the second embodiment, step 2b preferably further includes the above-described step e2 after step d2.

[0098] The redistribution layer formation process in the second embodiment has the advantage of being able to easily achieve both industrial applicability and resolution compared to the redistribution layer formation process in other embodiments.

[0099] 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 e1 and e2, but steps e1 and e2 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.

[0100] <Preparation Process> The preparation process for the second embodiment is the same as that for the first embodiment.

[0101] <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 1B, 2, 3, and 4 in this order.

[0102] (Step 1B) Figure 2A is a schematic cross-sectional view illustrating Step 1B, showing a cross-section along the thickness direction of the substrate 10 and the insulating film 120. In Step 1B, composition A2 is applied to the substrate 10 to form the insulating film 120 on the substrate 10. Step 1B is the same as Step 1A of the first embodiment, except that composition A2, described later, is used instead of composition A1.

[0103] Composition A2 is a non-photosensitive resin composition comprising resin (A). 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 composition A2, which is 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 A2 will be described later.

[0104] Resin (A) is at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor. Details of resin (A) will be described later.

[0105] 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.

[0106]

[0107] In the structure above, * indicates a bonding position.

[0108] 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: crack generation in the insulating portion can be further suppressed, and the film strength of the insulating portion 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 portion can be further improved, and crack generation in the insulating portion can be further suppressed.

[0109] From the viewpoint of further suppressing crack formation in the insulating portion, composition A2 preferably further contains a nitrogen-containing heterocyclic compound. Details of the nitrogen-containing heterocyclic compounds that may be included in composition A2 are the same as those of the nitrogen-containing heterocyclic compounds that may be included in composition A1 described above.

[0110] From the viewpoint of further suppressing crack formation in the insulating portion, composition A2 preferably further contains at least one antioxidant selected from the group consisting of phenol compounds, phosphite compounds, thioether compounds, and phosphonite compounds. Details of the antioxidants that may be included in composition A2 are the same as those described above for the antioxidants that may be included in composition A1.

[0111] From the viewpoint of further suppressing crack formation in the insulating portion, composition A2 preferably further contains an adhesive containing an alkoxysilyl group. Details of the alkoxysilyl group-containing adhesive that may be included in composition A2 are the same as those of the alkoxysilyl group-containing adhesive that may be included in composition A1.

[0112] (Process 2) Process 2a Process 2a includes processes a, b, c, d1 and e1. In the following description, processes a, b and c included in process 2a may be referred to as process a(2a), process b(2a) and process c(2a), respectively.

[0113] ...Step a(2a) Figure 2B is a schematic cross-sectional view illustrating step a(2a), showing cross-sections along the thickness direction of the substrate 10, insulating film 120, and resist layer 130. In step a(2a), composition B is applied to the insulating film 120 to form a resist layer 130 on the insulating film 120. Step a(2a) is the same as step a of the first embodiment, except that a resist layer 130 is formed on the insulating film 120.

[0114] ...The resist layer 130 is a layer formed by composition B described later, and is used in step c(2a) described later to form a negative resist pattern. The preferred thickness of the resist layer 130 is the same as the preferred thickness of the resist layer 30 in the first embodiment. The details and preferred embodiments of composition B used in the second embodiment are the same as those of composition B used in the first embodiment.

[0115] ...Step b(2a) Figure 2C is a schematic cross-sectional view illustrating step b(2a), showing a cross-section along the thickness direction of the substrate 10, the insulating film 120, and the resist layer 131 after pattern exposure. In step b(2a), the resist layer 130 is pattern exposed. This forms a resist layer 131 on the insulating film 120, including exposed areas 130A and unexposed areas 130B. The method of pattern exposure in step b(2a) is the same as the method of pattern exposure in step b of the first embodiment. However, a photomask with a different pattern than that of step b of the first embodiment may be used, for example, so that via areas 22A (see Figure 2E, etc.) are formed in step d1 described later. Preferred exposure amounts and exposure wavelengths in step b(2a) are the same as preferred exposure amounts and exposure wavelengths in step b of the first embodiment.

[0116] Step b(2a) may include a post-exposure heat treatment in which the resist layer 131 is heated after pattern exposure. That is, the post-exposure heat treatment can be performed after the exposure treatment in step b(2a) and before the development treatment in step c(2a). A preferred embodiment of the post-exposure heat treatment in step b(2a) is the same as a preferred embodiment of the post-exposure heat treatment in step b of the first embodiment.

[0117] ...Step c(2a) Figure 2D is a schematic cross-sectional view illustrating step c(2a), showing cross-sections along the thickness direction of the substrate 10, insulating film 120, and negative resist pattern 132. In step c(2a), the resist layer 131 after pattern exposure is developed with a developer solution containing an organic solvent. This removes the unexposed areas 130B, and a negative resist pattern 132 consisting of exposed areas 130A is formed on a part of the insulating film 120.

[0118] The development process in step c(2a) is a negative-type development in which the unexposed portion 130B of the resist layer 131 after pattern exposure is removed. The preferred embodiment of the developer solution containing the organic solvent used in step c(2a) is the same as the preferred embodiment of the developer solution containing the organic solvent in step c of the first embodiment.

[0119] Step c(2a) may include a rinsing process in which the pattern is washed (rinsed) with a rinsing solution after the developing process. The preferred embodiments of the rinsing process and rinsing solution in step c(2a) are the same as the preferred embodiments of the rinsing process and rinsing solution in step c of the first embodiment.

[0120] ...Step d1 Figure 2E is a schematic cross-sectional view illustrating step d1, showing cross-sections along the thickness direction of the substrate 10, insulating film 120, and negative resist pattern 132. In step d1, a portion of the insulating film 120 is removed by dry etching of the insulating film 120 using the negative resist pattern 132 as a mask. As a result, via portions 22A are formed in the insulating film 120. Also, as a result of the formation of via portions 22A, a portion of the surface of the substrate 10 is exposed.

[0121] The dry etching method in step d1 is the same as the dry etching method in step d2 of the first embodiment. However, the dry etching conditions can be appropriately adjusted according to known conditions so that via portions 22A are formed.

[0122] The via portion 22A in the second embodiment is the same as the via portion 22A in the first embodiment, except that its manufacturing method is different. The insulating portion 120 may have only one via portion 22A or two or more.

[0123] ...Step e1 Figure 2F is a schematic cross-sectional view illustrating step e1, showing a cross-section along the thickness direction of the substrate 10 and the insulating film 120. In step e1, the negative-type resist pattern 132 placed on the insulating film 120 is removed. This exposes the surface of the insulating film 120. The method for removing the negative-type resist pattern 132 is the same as in step e2 in the first embodiment.

[0124] Step 2b: Step 2b of the second embodiment is the same as step 2b of the first embodiment, except that it is performed after step 2a of the second embodiment, so its description is omitted.

[0125] (Steps 3 and 4) Steps 3 and 4 of the second embodiment are the same as steps 3 and 4 of the first embodiment, except that they are performed after step 2 of the second embodiment, so their description will be omitted.

[0126] (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.

[0127] <Modification 1> In the second embodiment described above, a configuration in which the trench portion is formed after the via portion is formed (i.e., a configuration in which step 2b is performed after step 2a) was shown, but the invention is not limited thereto. For example, Modification 1 of the second embodiment described above is a configuration in which the via portion is formed after the trench portion is formed (i.e., a configuration in which step 2a is performed after step 2b).

[0128] <Modification 2> In the second embodiment described above, a configuration was shown in which dry etching was performed in step d1 until a part of the surface of the substrate 10 was exposed to form the via portion 22A, but the invention is not limited thereto. For example, as modification 2 of the second embodiment described above, dry etching may be completed in step d1 of step 2a before the surface of the substrate 10 is exposed (see Figure 3A), and then in step d2 of step 2b, which is performed thereafter, dry etching may be performed until a part of the surface of the substrate 10 is exposed.

[0129] Specifically, Figure 3A is a schematic cross-sectional view illustrating step d1 in Modification 2, and shows a cross-section of the substrate 10 and the insulating film 120 along the thickness direction. In step d1 of Modification 2, dry etching of the insulating film 120 is performed using the negative resist pattern 132 as a mask, and the dry etching of the insulating film 120 is completed before the surface of the substrate 10 is exposed. As a result, a first via portion 22a is formed in the insulating film 120. The first via portion 22a constitutes a part of the via portion (recess).

[0130] After step d1 in Modified Example 2, the above-described steps 2b (steps a, b, c, d2, and e2) are carried out. However, in step d2 in Modified Example 2, the insulating film 120 at the bottom of the first via portion 22a shown in Figure 3A is dry-etched until the surface of the substrate 10 is exposed. In this way, a redistribution layer with a structure similar to that shown in Figure 1F in the first embodiment is obtained.

[0131] [Third Embodiment] The third 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 1C, 2, 3, and 4 in this order. Step 1C: After applying the above-mentioned composition A2 to a substrate to form a first insulating layer, an etching stop layer is formed on the first insulating layer, and then the above-mentioned composition A1 is applied on the etching stop layer to form a second insulating layer, thereby forming an insulating film in which the first insulating layer, the etching stop layer and the second insulating layer are stacked in this order. Step 2: Step 2a-1, which includes pattern exposure and development processing, is performed on the second insulating layer so that a part of the surface of the etching stop layer is exposed, thereby forming a first via portion. Next, step 2a-2 is performed to remove the etching stop layer at the bottom of the first via portion so that a part of the surface of the first insulating layer is exposed, thereby forming a second via portion including the first via portion. Next, step 2b, which includes steps a, b, c, and d2 below, is performed to form a trench in the insulating film, and step 2a-3 is performed to remove the first insulating layer at the bottom of the second via so that a part of the surface of the substrate is exposed, thereby forming a via including the second via, thereby forming the insulating part having a recess composed of the via and the trench. Step 3: A metal layer is formed to fill the recess by a plating process. Step 4: A part of the metal layer is removed by a chemical mechanical polishing process to obtain the conductive part. Step a: The composition B is applied to the insulating film to form a resist layer. Step b: The resist layer is pattern exposed. Step c: The resist layer after pattern exposure is treated with a developer containing an organic solvent to form a negative resist pattern on the insulating film. Step d2: The insulating film is dry etched using the negative resist pattern as a mask to form the trench.

[0132] Furthermore, it is preferable that step 2b in the third embodiment further includes step e2 described above.

[0133] The redistribution layer formation process in the third embodiment has the advantage of being able to easily achieve both industrial applicability and reliability compared to the redistribution layer formation processes in the other embodiments.

[0134] The procedures for each step in the third embodiment will be described in detail below, with reference to the drawings as necessary. In the following description, the third embodiment will be described in the case where step e2 is included, but step e2 is an optional step and does not need to be performed. Here, in the description of the third embodiment, the differences from the above-described embodiments will be mainly described, and the descriptions of steps and components that are the same as in the above-described embodiments may be omitted. Also, in the drawings used in the description of the third embodiment, components that are the same as those in the above-described embodiments may be denoted by the same reference numerals and their descriptions may be omitted.

[0135] <Preparation Steps> The preparation steps for the third embodiment are the same as those for the first embodiment.

[0136] <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 1C, 2, 3, and 4.

[0137] (Step 1C) Figure 4A is a schematic cross-sectional view illustrating Step 1C, showing a cross-section along the thickness direction of the substrate 10 and the insulating film 220. In Step 1C, the above-mentioned composition A2 is applied to the substrate 10 to form a first insulating layer 220A, then an etching stop layer 220B is formed on the first insulating layer 220A, and then the above-mentioned composition A1 is applied on the etching stop layer 220B to form a second insulating layer 220C. This results in an insulating film 220 including the first insulating layer 220A, the etching stop layer 220B, and the second insulating layer 220C.

[0138] The method for forming the first insulating layer 220A is the same as in step 1B of the second embodiment. The thickness of the first insulating layer 220A is preferably 1.0 to 15 μm, and more preferably 1.5 to 10 μm. The details and preferred embodiments of composition A2 used for forming the first insulating layer 220A are the same as those of composition A2 used in the second embodiment, including preferred embodiments.

[0139] The method for forming the etching stop layer 220B is not particularly limited, but examples include chemical vapor deposition methods such as CVD (Chemical Vapor Deposition), and physical vapor deposition methods such as sputtering, vacuum deposition, and ion plating. The thickness of the etching stop layer 220B is preferably 10 to 200 nm, and more preferably 20 to 100 nm. The etching stop layer 220B is not particularly limited as long as it is a layer that can suppress etching of the first insulating layer 220A. Specific examples of materials constituting the etching stop layer 220B include SiN, SiON, and SiOCN-based materials, as well as metal oxides such as aluminum oxide (AlOx; x is a number represented by 1 to 3), with SiN being preferred.

[0140] The method for forming the second insulating layer 220C is the same as in step 1A of the first embodiment, except that composition A1 is applied on the etching stop layer 220B. The thickness of the second insulating layer 220C is preferably 1.0 to 15 μm, and more preferably 1.5 to 10 μm. The details and preferred embodiments of composition A1 used for forming the second insulating layer 220C are the same as those of composition A1 used in the first embodiment.

[0141] (Step 2) Step 2a-1 Figure 4B is a schematic cross-sectional view illustrating Step 2a-1, showing a cross-section along the thickness direction of the substrate 10 and the insulating film 220. In Step 2a-1, the second insulating layer 220C is subjected to pattern exposure and development processing so that a part of the surface of the etching stop layer 220B is exposed, thereby forming the first via portion 222a. The first via portion 222a constitutes a part of the recess 222 (see Figure 4G, etc.) described later. The method for forming the first via portion 222a can be the same as the method used in Step 2a of the first embodiment.

[0142] Step 2a-2: Figure 4C is a schematic cross-sectional view illustrating step 2a-2, showing a cross-section along the thickness direction of the substrate 10 and the insulating film 220. In step 2a-2, the etching stop layer 220B at the bottom of the first via portion 222a is removed so that a part of the surface of the first insulating layer 220A is exposed, thereby forming the second via portion 222b. The second via portion 222b includes the first via portion 222a described above and constitutes a part of the recess 222 (see Figure 4G, etc.) described later. The method for forming the second via portion 222b (i.e., the method for removing the etching stop layer 220B at the bottom of the first via portion 222a) can be the same as the method used in step e2 of the first embodiment.

[0143] - Steps 2b and 2a-3 After step 2a-2, step 2b is performed, which includes steps a, b, c, d2, and e2. By performing step 2b, an insulating portion including a trench is obtained. Here, as will be described in detail in the description of step d2 below, performing step d2 of the third embodiment may also result in the performance of step 2a-3. In the following description, we will show the case in which the performance of step d2 also results in the performance of step 2a-3, but we are not limited to this, and steps d2 and 2a-3 may be performed separately.

[0144] ...Step a Figure 4D is a schematic cross-sectional view illustrating step a, showing cross-sections along the thickness direction of the substrate 10, insulating film 220, and resist layer 230. In step a, composition B, described later, is applied to the insulating film 220. This forms a resist layer 230 on the insulating film 220 (specifically, the first insulating layer 220A and the second insulating layer 220C). Step a is the same as step a of the first embodiment, except that the resist layer 230 is formed on the insulating film 220.

[0145] ...The resist layer 230 is a layer formed by composition B described later, and is used in step c described later to form a negative resist pattern. The preferred thickness of the resist layer 230 is the same as the preferred thickness of the resist layer 30 in the first embodiment. The details and preferred embodiments of composition B used in the third embodiment are the same as those of composition B used in the first embodiment.

[0146] ...Step b Figure 4E is a schematic cross-sectional view illustrating step b, showing a cross-section along the thickness direction of the substrate 10, the insulating film 220, and the resist layer 231 after pattern exposure. In step b, the resist layer 230 is pattern exposed. This forms a resist layer 231 after pattern exposure, which includes a part of the unexposed portion 230B formed on the first insulating layer 220A, a part of the unexposed portion 230B formed on the second insulating layer 220C, and an exposed portion 230A formed on the second insulating layer 220C. The method of pattern exposure of the resist layer 230 is the same as the method of pattern exposure in step b of the first embodiment. The preferred modes of exposure amount and exposure wavelength in step b are the same as the preferred modes of exposure amount and exposure wavelength in step b of the first embodiment.

[0147] Step b may include a post-exposure heat treatment in which the resist layer 231 is heated after pattern exposure. That is, the post-exposure heat treatment can be performed after the exposure treatment in step b and before the development treatment in step c. A preferred embodiment of the post-exposure heat treatment in step b is the same as a preferred embodiment of the post-exposure heat treatment in step b of the first embodiment.

[0148] ...Step c Figure 4F is a schematic cross-sectional view illustrating step c, showing cross-sections along the thickness direction of the substrate 10, insulating film 220, and negative-type resist pattern 232. In step c, the resist layer 231 after pattern exposure is developed with a developer solution containing an organic solvent. This removes the unexposed areas 230B, and a negative-type resist pattern 232 consisting of exposed areas 230A is formed on a part of the insulating film 220 (specifically, the second insulating layer 220C).

[0149] The development process in step c is a negative-type development in which the unexposed portion 230B of the resist layer 231 after pattern exposure is removed. The preferred embodiment of the developer solution containing the organic solvent used in step c is the same as the preferred embodiment of the developer solution containing the organic solvent in step c of the first embodiment.

[0150] Step c may include a rinsing process in which the pattern is washed (rinsed) with a rinsing solution after the developing process. The preferred embodiments of the rinsing process and rinsing solution in step c are the same as those of the preferred embodiments of the rinsing process and rinsing solution in step c of the first embodiment.

[0151] ...Step d2 Figure 4G is a schematic cross-sectional view illustrating step d2, showing the cross-section when the substrate 10, insulating portion 221, and negative resist pattern 232 are cut along the thickness direction such that the trench portion 222B is exposed along its extending direction. In step d2, a portion of the insulating film 220 is removed by dry etching of the insulating film 220 using the negative resist pattern 232 as a mask, forming an insulating portion 221 having a recess 222 composed of via portion 222A and trench portion 222B. In step d2, a portion of the second insulating layer 220C and, if applicable, a portion of the etching stop layer 220B are removed, as well as the first insulating layer 220A at the bottom of the second via portion 222b. As a result, a recess 222 including the trench portion 222B and via portion 222A is formed. In other words, by carrying out step d2, step 2a-3 is also carried out.

[0152] The dry etching method in step d2 is the same as the dry etching method in step d2 of the first embodiment. However, the dry etching conditions can be appropriately adjusted according to known conditions so that the recess 222 is formed.

[0153] The insulating portion 221 is a component corresponding to the insulating film 220, and has a recess 222 formed therein. The insulating portion 221 includes a first insulating layer 220A, an etching stop layer 220B, and a second insulating layer 220C. The insulating portion 221 may have only one trench portion 222B, or two or more. The insulating portion 221 may also have only one via portion 222A, or two or more. The details of the via portion 222A and the trench portion 222B are the same as those of the via portion 22A and the trench portion 22B in the first embodiment.

[0154] ...Step e2 Figure 4H is a schematic cross-sectional view illustrating step e2, showing a cross-section along the thickness direction of the substrate 10 and the insulating portion 221. In step e2, the negative-type resist pattern 232 placed on the insulating film 221 (specifically, the second insulating layer 220C) is removed. This exposes the surface of the second insulating layer 220C. The method for removing the negative-type resist pattern 232 is the same as in step e2 of the first embodiment.

[0155] (Step 3) Figure 4I is a schematic cross-sectional view illustrating Step 3, showing cross-sections along the thickness direction of the substrate 10, the insulating portion 221, and the metal layer 240. In Step 3, metal is filled into the recesses 222 by a plating process. This forms a metal layer 240 on the substrate 10 and the insulating film 221. The plating method is the same as in Step 3 of the first embodiment. The material constituting the metal layer 240 is the same as the metal layer 40 of the first embodiment.

[0156] (Step 4) Figure 4J is a schematic cross-sectional view illustrating Step 4, showing a cross-section along the thickness direction of the substrate 10 and the redistribution layer 250. In Step 4, the surface of the metal layer 240 is subjected to CMP treatment to remove a portion of the metal layer 40 until the surface of the second insulating layer 220C is exposed. This forms a redistribution layer 250 including a conductive portion 241 and an insulating portion 221. The conductive portion 241 is a component formed by CMP treatment of the metal layer 240 and is a component containing the aforementioned metal. The apparatus and conditions used for CMP treatment are the same as those in Step 4 of the first embodiment.

[0157] If the above-mentioned power supply layer (not shown) is formed between the insulating portion 221 and the metal layer 240, the power supply layer present in portions other than the recess 222 (see Figure 4H) of the insulating portion 221 may be removed by the CMP treatment in step 4.

[0158] (Other steps) Other steps that may be included in the third embodiment are the same as the other steps in the first embodiment described above, so their explanation will be omitted.

[0159] [Fourth Embodiment] The fourth 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 1D, 2, 3, and 4 in this order. Step 1D: After applying the above-mentioned composition A2 onto a substrate to form a first insulating layer, an etching stop layer is formed on the first insulating layer, and then the above-mentioned composition A2 is applied on the etching stop layer to form a second insulating layer, thereby forming an insulating film in which the first insulating layer, the etching stop layer and the second insulating layer are stacked in this order. Step 2: Step 2a-11, including the following steps a, b, c and d1, is performed to form a first via portion on the second insulating layer so that a part of the surface of the etching stop layer is exposed, and Step 2a-12 is performed to remove the etching stop layer at the bottom of the first via portion so that a part of the surface of the first insulating layer is exposed, thereby forming a second via portion including the first via portion. Next, step 2b, which includes steps a, b, c, and d2 below, is performed to form a trench in the insulating film, and step 2a-13 is performed to remove the first insulating layer at the bottom of the second via so that a part of the surface of the substrate is exposed, thereby forming a via including the second via, thereby forming the insulating film having a recess composed of the via and the trench. Step 3: A metal layer is formed to fill the recess by a plating process. Step 4: A part of the metal layer is removed by a chemical mechanical polishing process to obtain the conductive part. Step a: The composition B is applied to the insulating film to form a resist layer. Step b: The resist layer is pattern exposed. Step c: The resist layer after pattern exposure is treated with a developer containing an organic solvent to form a negative resist pattern on the insulating film. Step d1: The insulating film is dry-etched using the negative resist pattern as a mask to form the via. Step d2: The insulating film is dry-etched using the negative resist pattern as a mask to form the trench.

[0160] In the fourth embodiment, step 2a-11 preferably further includes step e1 described above. Also, in the fourth embodiment, step 2b preferably further includes step e2 described above.

[0161] The redistribution layer formation process in the fourth embodiment has the advantage of being able to achieve both resolution and reliability compared to the redistribution layer formation process in the other embodiments.

[0162] The procedures for each step in the fourth embodiment will be described in detail below, with reference to the drawings as necessary. In the following description, the fourth embodiment will be described in the case where steps e1 and e2 are included, but steps e1 and e2 are optional steps and do not need to be performed. Here, in the description of the fourth embodiment, the differences from the above-described embodiments will be mainly described, and the descriptions of steps and components that are the same as in the above-described embodiments may be omitted. Also, in the drawings used in the description of the fourth embodiment, components that are the same as those in the above-described embodiments may be denoted by the same reference numerals and their descriptions may be omitted.

[0163] <Preparation Steps> The preparation steps for the fourth embodiment are the same as those for the first embodiment.

[0164] <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 1D, 2, 3, and 4.

[0165] (Step 1D) Figure 5A is a schematic cross-sectional view illustrating Step 1D, showing a cross-section along the thickness direction of the substrate 10 and the insulating film 220. In Step 1D, the above-described composition A2 is applied to the substrate 10 to form a first insulating layer 320A, then an etching stop layer 320B is formed on the first insulating layer 320A, and then the above-described composition A2 is applied on the etching stop layer 320B to form a second insulating layer 320C. In this way, an insulating film 320 including the first insulating layer 320A, the etching stop layer 320B and the second insulating layer 320C is obtained.

[0166] The method for forming the first insulating layer 320A is the same as the method for forming the first insulating layer 220A in the third embodiment. The thickness of the first insulating layer 320A is the same as the thickness of the first insulating layer 220A in the third embodiment. The details and preferred embodiments of composition A2 used for forming the first insulating layer 320A are the same as those of composition A2 used in the second embodiment, including preferred embodiments.

[0167] The method for forming the etching stop layer 320B is the same as the method for forming the etching layer 220B in the third embodiment. The material constituting the etching stop layer 320B is the same as the material constituting the etching layer 220B in the third embodiment.

[0168] The method for forming the second insulating layer 320C is the same as the method for forming the second insulating layer 220C in the third embodiment, except that composition A2 is used. The thickness of the second insulating layer 320C is the same as the thickness of the second insulating layer 220C in the third embodiment. The details and preferred embodiments of composition A2 used for forming the second insulating layer 320C are the same as those of composition A2 used in the second embodiment, including preferred embodiments.

[0169] (Step 2) Steps 2a-11 and 2a-12 In Step 2, first, Step 2a-11, which includes Steps a, b, c, d1 and e1, is carried out so that a part of the surface of the etching stop layer 320B is exposed, thereby forming a first via portion 322a (see Figure 5E) on the second insulating layer 320C. In the following description, Steps a, b and c included in Step 2a-11 may be referred to as Step a(2a), Step b(2a) and Step c(2a), respectively. Here, as will be described in detail in the description of Step e1 below, Step 2a-12 may be carried out as a result of carrying out Step e1 of the fourth embodiment. In the following description, the case in which Step 2a-12 is carried out by carrying out Step e1 is shown, but it is not limited to this, and Step e1 and Step 2a-12 may be carried out separately.

[0170] ...Step a(2a) Figure 5B is a schematic cross-sectional view illustrating step a(2a), showing cross-sections along the thickness direction of the substrate 10, insulating film 320, and resist layer 330. Specifically, it shows the state in which the resist layer 330 is formed on the second insulating film 320C. In step a(2a), composition B, described later, is applied to the insulating film 320. As a result, the resist layer 330 is formed on the insulating film 320 (specifically, the second insulating layer 320C). Step a(2a) is the same as step a of the first embodiment, except that the resist layer 330 is formed on the second insulating film 320C.

[0171] ...The resist layer 330 is a layer formed by composition B described later, and is used in step c(2a) described later to form a negative resist pattern. The preferred thickness of the resist layer 330 is the same as the preferred thickness of the resist layer 30 in the first embodiment. The details and preferred embodiments of composition B used in the fourth embodiment are the same as those of composition B used in the first embodiment.

[0172] ...Step b(2a) Figure 5C is a schematic cross-sectional view illustrating step b(2a), showing a cross-section along the thickness direction of the substrate 10, the insulating film 320, and the resist layer 331 after pattern exposure. In step b(2a), the resist layer 330 is pattern exposed. This forms a resist layer 331 after pattern exposure, which includes exposed areas 330A and unexposed areas 330B formed on the second insulating layer 320C. The method of pattern exposure of the resist layer 330 is the same as the method of pattern exposure in step b of the first embodiment. The preferred exposure amount and exposure wavelength in step b(2a) are the same as the preferred exposure amount and exposure wavelength in step b of the first embodiment.

[0173] Step b(2a) may include a post-exposure heat treatment in which the resist layer 331 is heated after pattern exposure. That is, the post-exposure heat treatment can be performed after the exposure treatment in step b(2a) and before the development treatment in step c(2a). A preferred mode of the post-exposure heat treatment in step b(2a) is the same as a preferred mode of the post-exposure heat treatment in step b of the first embodiment.

[0174] ...Step c(2a) Figure 5D is a schematic cross-sectional view illustrating step c(2a), showing a cross-section along the thickness direction of the substrate 10, insulating film 320, and negative resist pattern 332. In step c(2a), the resist layer 331 after pattern exposure is developed with a developer solution containing an organic solvent. This removes the unexposed areas 330B, and a negative resist pattern 332 consisting of the exposed areas 330A is formed on a part of the second insulating layer 320C.

[0175] The development process in step c(2a) is a negative-type development in which the unexposed portion 330B of the resist layer 331 after pattern exposure is removed. The preferred embodiment of the developer solution containing the organic solvent used in step c(2a) is the same as the preferred embodiment of the developer solution containing the organic solvent in step c of the first embodiment.

[0176] Step c(2a) may include a rinsing process in which the pattern is washed (rinsed) with a rinsing solution after the developing process. The preferred embodiments of the rinsing process and rinsing solution in step c(2a) are the same as the preferred embodiments of the rinsing process and rinsing solution in step c of the first embodiment.

[0177] ...Step d1 Figure 5E is a schematic cross-sectional view illustrating step d1, showing a cross-section along the thickness direction of the substrate 10 and the insulating film 320. In step d1, a negative resist pattern 332 is used as a mask to dry etch the second insulating layer 320C so that a part of the surface of the etching stop layer 320B is exposed, thereby forming a first via portion 322a. The first via portion 322a constitutes a part of a recess (not shown) formed in the insulating portion (not shown) obtained by step 2. The dry etching method in step d1 is the same as the dry etching method in step d1 of the second embodiment.

[0178] ...Step e1 Figure 5F is a schematic cross-sectional view illustrating step e1, and shows a cross-section along the thickness direction of the substrate 10 and the insulating film 320.

[0179] In step e1, the negative resist pattern 332 placed on the second insulating layer 320C is removed. This exposes the surface of the second insulating layer 320C. In step e1, the negative resist pattern 332 is removed, as is the etching stop layer 320B at the bottom of the first via portion 322a. This forms the second via portion 322b, which includes the first via portion 322a. In other words, the execution of step e1 also executes step 2a-12. The second via portion 322b includes the first via portion 322a and constitutes a part of the recess (not shown) formed in the insulating portion (not shown) obtained by step 2.

[0180] The method for removing the negative resist pattern 332 and the etching stop layer 320B is the same as in step e1 in the first embodiment.

[0181] Step 2b Steps 2b and 2a-13 of the fourth embodiment are the same as steps 2b and 2a-3 of the third embodiment, except that they are performed after both steps 2a-11 and 2a-12 of the fourth embodiment have been completed, so their explanation is omitted.

[0182] (Steps 3 and 4) Steps 3 and 4 of the fourth embodiment are the same as steps 3 and 4 of the third embodiment, except that they are performed after step 2 of the fourth embodiment, so their description will be omitted.

[0183] (Other steps) Other steps that may be included in the fourth embodiment are the same as the other steps in the third embodiment described above, so their explanation will be omitted.

[0184] [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.

[0185] 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.

[0186] 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.

[0187] [Resin Composition A] The resin composition A used in the method for manufacturing the semiconductor device 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 method for manufacturing the semiconductor device described above. One embodiment of resin composition A is the above-mentioned composition A1 and composition A2. 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.

[0188] [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 a polyimide precursor as resin (A). Resin (A) preferably has polymerizable groups, and more preferably contains radical polymerizable groups. If resin (A) has radical polymerizable groups, resin composition A preferably contains a photopolymerization initiator (especially a radical polymerization initiator), and more preferably contains a photopolymerization initiator (especially a radical polymerization initiator) and a polymerizable compound (especially a radical crosslinking agent). Furthermore, a sensitizer may be included as needed. For example, a negative-type photosensitive film can be formed from such a resin composition A. Resin (A) may also have polarity conversion groups such as acid-degradable groups. If resin (A) has acid-degradable groups, resin composition A preferably contains a photoacid generator. From such a resin composition A, for example, a chemically amplified positive-type or negative-type photosensitive film can be formed.

[0189] <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).

[0190]

[0191] 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.

[0192] 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. ｚR 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.

[0193] 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.

[0194] Formula (51)

[0195]

[0196] 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 ５７ Examples 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).

[0197]

[0198] 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.

[0199] 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.

[0200]

[0201] 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 ２ It is even more preferable that the group is a divalent group selected from the group consisting of -.

[0202] 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.

[0203] 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.

[0204] R in equation (2) １１３ and R １１４Each of these independently represents a hydrogen atom or a monovalent organic group. Preferably, the monovalent organic group includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene oxy group. Also, R １１３ and R １１４ It is preferable that at least one of them contains a polymerizable group, and more preferably that both contain a polymerizable group. １１３ and R １１４ It is also preferable that at least one of the components contains two or more polymerizable groups. The polymerizable groups are groups that can undergo crosslinking reactions by the action of heat and radicals, and radical polymerizable groups are preferred. Examples of polymerizable groups include groups having an ethylenically unsaturated bond, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. As radical polymerizable groups of the polyimide precursor, groups having an ethylenically unsaturated bond are preferred. Examples of groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (III), with groups represented by the following formula (III) being preferred.

[0205]

[0206] In equation (III), R ２００ R represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred. In formula (III), * represents a bonding site with other structures. In formula (III), R ２０１ This is an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２ - represents a cycloalkylene group or a polyalkylene oxy group. ２０１ Examples include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, as well as 1,2-butanediyl, 1,3-butanediyl, and -CH２ CH(OH)CH ２ -, or a polyalkylene oxy group is preferred, and alkylene groups such as ethylene groups and propylene groups, -CH ２ CH(OH)CH ２-, cyclohexyl groups, or polyalkylene oxy groups are more preferred, and alkylene groups such as ethylene groups and propylene groups, or polyalkylene oxy groups are even more preferred. In the present invention, a polyalkylene oxy group refers to a group in which two or more alkylene oxy groups are directly bonded. The alkylene groups in the multiple alkylene oxy groups contained in the polyalkylene oxy group may be the same or different. When the polyalkylene oxy group contains multiple types of alkylene oxy groups with different alkylene groups, the arrangement of the alkylene oxy groups in the polyalkylene oxy group may be random, have blocks, or have patterns such as alternating arrangements. The number of carbon atoms in the alkylene group (including the number of carbon atoms of substituents if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. The alkylene group may also have substituents. Preferred substituents include alkyl groups, aryl groups, or halogen atoms. The number of alkylene oxy groups in the polyalkylene oxy group (number of repeating polyalkylene oxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkylene oxy group is preferably a polyethylene oxy group, a polypropylene oxy group, a polytrimethylene oxy group, a polytetramethylene oxy group, or a group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, more preferably a polyethylene oxy group or a polypropylene oxy group, and even more preferably a polyethylene oxy group. In the group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, the ethylene oxy groups and propylene oxy groups may be arranged randomly, in blocks, or in alternating patterns. The preferred number of repeating ethylene oxy groups in these groups is as described above.

[0207] In equation (2), R １１３ If R is a hydrogen atom, １１４When is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. Examples of the tertiary amine compound having such an ethylenically unsaturated bond include N,N-dimethylaminopropyl methacrylate.

[0208] 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 becomes possible to further widen the exposure latitude.

[0209] Formula (2-A)

[0210]

[0211] 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.

[0212] A １ , A ２ , R １１１ , R １１３ and R １１４ each independently have the same meaning 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 meaning as R １１２ in formula (5), and the preferred range is also the same.

[0213] 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.

[0214] As one embodiment of the polyimide precursor in the present invention, an embodiment is mentioned in which the content of the repeating unit represented by formula (2) is 50 mol% or more based on all repeating units. The content is more preferably 70 mol% or more, still 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 excluding terminal ends may be the repeating unit represented by formula (2).

[0215] The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 300,000, more preferably 5,000 to 100,000, still 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 still more preferably 4,000 to 20,000. The molecular weight dispersity of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0 or more. Although the upper limit of the molecular weight dispersity of the polyimide precursor is not particularly specified, it is, for example, preferably 7.0 or less, more preferably 6.5 or less, and still more preferably 6.0 or less. In the present specification, the molecular weight dispersity is a value calculated by weight average molecular weight / number average molecular weight. When resin composition A contains a plurality of types of polyimide precursors as resin (A), it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polyimide precursor fall within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the plurality of types of polyimide precursors as a single resin each fall within the above ranges.

[0216] <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 term "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% aqueous tetramethylammonium hydroxide solution. From the viewpoint of pattern formability, a polyimide that dissolves in an amount of 0.5 g or more is preferred, and a polyimide that dissolves in an amount of 1.0 g or more is more preferred. 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 preferred from the viewpoints of film strength and insulation properties of the obtained film.

[0217] (Ethylenically Unsaturated Bond) From the viewpoint of the film strength of the obtained film, the polyimide preferably has an ethylenically unsaturated bond. The polyimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, but preferably has it in a side chain. The ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later １３２ or R １３１ is preferably contained in, and R １３２ or R １３１ is more preferably contained as a group having an ethylenically unsaturated bond in. Among these, the ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later １３１ is preferably contained in, and R １３１ is more preferably contained as a group having an ethylenically unsaturated bond in. Examples of the group having an ethylenically unsaturated bond include groups having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, and a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).

[0218]

[0219] In formula (IV), R ２０represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred.

[0220] In formula (IV), R ２１ This is an alkylene group having 2 to 12 carbon atoms, -O-CH ２ CH(OH)CH ２ The 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.

[0221] 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).

[0222]

[0223] 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).

[0224] In formula (IV), * represents a binding site with another structure, and is preferably a binding site with the polyimide main chain.

[0225] 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.

[0226] (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.

[0227] (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.

[0228] (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.

[0229] 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).

[0230] 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.

[0231] Formula (4-1)

[0232]

[0233] In formula (4-1), R １３３ is a polymerizable group, and the other groups are equivalent to formula (4).

[0234] Formula (4-2)

[0235] 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).

[0236] 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:

[0237] 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.

[0238] 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.

[0239] 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.

[0240] 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.

[0241] (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. －１Determine 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

[0242] 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.

[0243] 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.

[0244] <Polybenzoxazole Precursor> Examples of the polybenzoxazole precursor include the compounds described in paragraphs

[0073] to

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

[0245] <Polybenzoxazole> Examples of the polybenzoxazole include the compounds described in paragraphs

[0101] to

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

[0246] <Polyamideimide Precursor> Examples of the polyamideimide precursor include the compounds described in paragraphs

[0104] to

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

[0247] <Polyamideimide> Examples of the polyamideimide include the compounds described in paragraphs

[0125] to

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

[0248] <Method for Producing Polyimide Precursor, etc.> The polyimide precursor and the like are produced, for example, by the method described in paragraphs

[0134] to

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

[0249] <Content> The content of the resin (A) in the resin composition A is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass or more, based on the total solid content of the resin composition A. Further, the content of the resin in the resin composition A is preferably 99.5% by mass or less, more preferably 99% by mass or less, still 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 the resin composition A. The resin composition A may contain only one type of the resin (A), or may contain two or more types thereof. When two or more types are contained, the total amount preferably falls within the above range.

[0250] 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.

[0251] [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.

[0252] 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.

[0253] [Polymerizable Compound] Resin composition A preferably contains a polymerizable compound. Examples of polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[0254] <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.

[0255] 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.

[0256] 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.

[0257] 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.

[0258] 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.

[0259] 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.

[0260] 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.

[0261] 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).

[0262] 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.

[0263] 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.

[0264] 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.

[0265] 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.

[0266] 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.

[0267] 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.

[0268] 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.

[0269] <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.

[0270] 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.

[0271] [Polymerization Initiator] Resin composition A preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but a photopolymerization initiator is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, it may be an activator that acts with a photoexcited sensitizer to generate active radicals.

[0272] 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.

[0273] 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.

[0274] 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.

[0275] 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.

[0276] 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.

[0277] 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.

[0278] 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.

[0279] 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.

[0280] 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.

[0281] 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.

[0282]

[0283] 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.

[0284]

[0285] As photoradical polymerization initiators, for example, oxime compounds having a fluorene ring as described in paragraphs

[0169] to

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

[0208] to

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

[0286] In addition, as a photopolymerization initiator, compounds described in paragraphs

[0113] to

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

[0287] If resin composition A contains a polymerization initiator, the content of the polymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, relative to the total solid content of resin composition A. Resin composition A may contain only one type of polymerization initiator or two or more types. If it contains two or more types, it is preferable that the total amount is within the above range. Note that since photopolymerization initiators may also function as thermal polymerization initiators, crosslinking by the photopolymerization initiator may be further advanced by heating with an oven or hot plate, etc.

[0288] [Photoacid Generator] Resin composition A may contain a photoacid generator. Details of the photoacid generator in resin composition A are the same as those of the photoacid generator in composition B described later, so the explanation is omitted. When resin composition A contains a photoacid generator, the content of the photoacid generator is preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass, even more preferably 0.3 to 10% by mass, and even more preferably 0.5 to 5% by mass, based on the total solid content of resin composition A. Resin composition A may contain only one type of photoacid generator, 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.

[0289] [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.

[0290] If resin composition A contains a sensitizer, the sensitizer content is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 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 two or more types. If it contains two or more types, it is preferable that the total amount is within the above range.

[0291] [Base Generator] Resin composition A may contain a base generator. Here, a base generator is a compound that can generate a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. In particular, if resin composition A contains a precursor of a cyclized resin, it is preferable that resin composition A contains a base generator. By containing a thermal base generator in resin composition A, the cyclization reaction of the precursor can be promoted by heating, for example, resulting in good mechanical properties and chemical resistance of the cured product, and good performance as an interlayer insulating film for redistribution layers contained in semiconductor packages, for example. The base generator may be an ionic base generator or a nonionic base generator. Examples of bases generated from the base generator include secondary amines and tertiary amines. Known base generators can be used as the base generator. Examples of base-generating agents include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of nonionic base-generating agents include the compounds described in paragraphs

[0249] to

[0277] of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0292] 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.

[0293] 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.

[0294] 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.

[0295] [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.

[0296] 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).

[0297] 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.

[0298] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0299] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, as well as cyclic terpenes such as limonene.

[0300] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0301] 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.

[0302] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0303] 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.

[0304] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0305] 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.

[0306] 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.

[0307] [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.

[0308] <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.).

[0309]

[0310] 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).

[0311]

[0312] 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.).

[0313] 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, 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.

[0314] [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.

[0315] 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.

[0316] As a migration inhibitor, an ion trapping agent that captures anions such as halogen ions can also be used.

[0317] 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.

[0318] Specific examples of migration inhibitors include the following compounds.

[0319]

[0320] 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 even more preferably 0.1 to 1.0% by mass, relative to the total solid content of resin composition A. Resin composition A may contain only one type of migration inhibitor or two or more types. When it contains two or more types, it is preferable that the total amount is within the above range.

[0321] [Polymerization Inhibitor] Resin composition A preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0322] Specific examples of polymerization inhibitors include the compounds described in paragraph

[0310] of International Publication No. 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]nona-2-ene-N,N-dioxide. This information is incorporated herein by reference.

[0323] If 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 even more preferably 0.05 to 10% by mass, relative to the total solid content of resin composition A. Resin composition A may contain only one polymerization inhibitor or two or more. If it contains two or more, it is preferable that the total amount is within the above range.

[0324] [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.

[0325] 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.

[0326] [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.

[0327] 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.

[0328] 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.

[0329] 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.

[0330] [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, anti-flocculation 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.

[0331] [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.

[0332] [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).

[0333] 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).

[0334] <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.

[0335] 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.

[0336] The above cage-type silsesquioxane structure is preferably a siloxane structure represented by the following formula (S).

[0337]

[0338] 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.

[0339] The repeating unit having Si atoms is preferably represented by the following formula (I).

[0340]

[0341] 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.

[0342]

[0343] 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).

[0344]

[0345]

[0346] 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.

[0347] The repeating units containing Si atoms in resin (B) may be of one type or two or more types may be used in combination.

[0348] 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%.

[0349] 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.

[0350] <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.

[0351] 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.

[0352] 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.

[0353] Preferred polar groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups.

[0354] 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.

[0355] 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.

[0356] 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 ).

[0357]

[0358] 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.

[0359] 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.

[0360] 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.

[0361] 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.

[0362] 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 the entire alkyl group substituted with an aryl group, i.e., the aralkyl group, 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.

[0363] 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.

[0364] 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.

[0365] 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.

[0366] 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.

[0367]

[0368] 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.

[0369] 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.

[0370] 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.

[0371]

[0372] 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.

[0373] 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.

[0374] 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.

[0375] 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.

[0376] 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.

[0377] 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.

[0378] 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.

[0379] 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.

[0380] 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.

[0381]

[0382]

[0383]

[0384] 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.

[0385] 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.

[0386] The repeating unit having an acid-degradable group may be of one type or two or more types may be used in combination.

[0387] 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.

[0388] <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.

[0389] 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)

[0390] 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.

[0391] [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.

[0392] 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.

[0393] 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.

[0394] <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).

[0395]

[0396] 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.

[0397] 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.

[0398] 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.

[0399] 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.

[0400] 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.

[0401] 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.

[0402] 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.

[0403] 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.

[0404] 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.

[0405] 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.

[0406] 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.

[0407] 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.

[0408] 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.

[0409] 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.

[0410] 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.

[0411] 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.

[0412] 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.

[0413] 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.

[0414] <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).

[0415]

[0416] 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.

[0417] 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).

[0418] 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.

[0419] <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.

[0420]

[0421] 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.

[0422] 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.

[0423] 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.

[0424] 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.

[0425] 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.

[0426] An example of a sulfonyliimide anion is the saccharin anion.

[0427] 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.

[0428] Z － Particularly preferred is the anion represented by the following general formula (AN1).

[0429]

[0430] 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.

[0431] 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.

[0432] 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.

[0433] 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.

[0434] 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.

[0435] 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.

[0436] 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).

[0437] 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).

[0438] 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.

[0439] 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:

[0440] 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.

[0441] <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.

[0442] [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.

[0443] 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.

[0444] [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).

[0445] [Synthesis of Resins (A-2) to (A-11)] 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 listed in the table below.

[0446] The structure of the repeating units contained in resins (A-1) to (A-11) is shown below.

[0447]

[0448]

[0449]

[0450]

[0451]

[0452]

[0453]

[0454]

[0455]

[0456]

[0457]

[0458]

[0459] [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.

[0460] [Synthesis of resins (B-2) to (B-8)] Resins (B-2) to (B-8) are synthesized using the same procedure as resin (B-1), or using a known procedure.

[0461] The structures of resins (B-1) to (B-8) 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).

[0462]

[0463]

[0464]

[0465]

[0466]

[0467]

[0468]

[0469]

[0470]

[0471] [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.

[0472]

[0473]

[0474] [Polymerizable compound] ・C-1: NK ester 4G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0475] [Photopolymerization Initiators] ・D-1: Compound with the following structure ・D-2: Compound with the following structure

[0476]

[0477] [Antioxidants] ・E-1: Compounds with the following structure (corresponds to phenolic compounds)

[0478]

[0479] [Metal Adhesion Modifiers] ・F-1: Compounds with the following structure (correspond to adhesives containing alkoxysilyl groups)

[0480]

[0481] [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)

[0482]

[0483] [Metal complexes] ・H-1: Compounds with the following structure

[0484]

[0485] [Thermal base generating agent] • I-1: Compound with the following structure • I-2: Compound with the following structure

[0486]

[0487] [Thermal polymerization initiator] ・M-1: Compound with the following structure

[0488]

[0489] [Photoacid Generator] ・J-1: Compound with the following structure ・J-2: Compound with the following structure ・J-3: Compound with the following structure

[0490]

[0491] [Acid diffusion control agent] ・K-1: Trioctylamine

[0492] [Solvents] ・L-1: Dimethyl sulfoxide ・L-2: γ-Butyrolactone ・L-3: Propylene glycol monomethyl ether acetate (PGMEA) ・L-4: Propylene glycol monomethyl ether (PGME)

[0493] [Developer and Rinse Solution] The developer and rinse solution used in the examples and comparative examples are as follows: Dev-1: Cyclopentanone Dev-2: Propylene glycol monomethyl ether acetate (PGMEA) Dev-3: Butyl acetate Dev-4: 2.38% by mass aqueous solution of tetramethylammonium hydroxide Dev-5: Pure water

[0494] [Method for Forming a Redistribution Layer 1] [Examples 1-20, Comparative Examples 1-2] An insulating film forming resin composition is applied to a silicon wafer on which a thin copper layer has been formed on the surface by spin coating and dried at 110°C for 5 minutes. The resulting dried coating is subjected to a 300 mJ / cm² test using an i-line stepper (Canon: FPA-5520iV, NA=0.16, σ=0.7) with a mask in which a 3 μm circle via pattern is arranged at 3 μm intervals vertically and horizontally. ２The film is exposed to light. Next, it is developed with cyclopentanone until the unexposed areas are removed, rinsed with PGMEA for 30 seconds, and then heated at a rate of 10°C / min under a nitrogen atmosphere to 230°C for 2 hours. This forms a 4 μm thick insulating film with 3 μm circle vias patterned on it (see Figure 1B). Then, an etching mask resin composition is applied to the resulting insulating film by spin coating and dried at 110°C for 1 minute to form a resist layer with a post-formation thickness of 200 nm (see Figure 1C). Subsequently, using a line-and-space mask with 1, 2, and 3 μm space patterns formed in a line-to-space ratio of 1:1, an i-line stepper (Canon: FPA-5520iV, NA=0.16, σ=0.7) is used to apply 200 mJ / cm² of etching. 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 in which line and space patterns are formed on an insulating film with 3 μm circle vias (see Figure 1E). Next, using the obtained resist pattern (line and space pattern) as a mask, the insulating film is etched using Plasma Systems' parallel plate type reactive ion etching apparatus DES-245R under etching condition 1 below. Etching is stopped when the film has been processed to a height of 2 μm from the top (see Figure 1F), and then the resist pattern (line and space pattern) is removed under etching condition 2 below. This results in an insulating portion with recesses (see Figure 1G). Here, the recesses formed in the insulating portion have a shape in which trenches corresponding to the line and space patterns are formed on the circle vias. Next, a Ti barrier layer with a thickness of 50 nm is formed on the entire surface of the recessed side by sputtering. Then, a copper layer with a thickness of 200 nm is formed on top of the Ti barrier layer, also by sputtering. After that, sulfuric acid treatment (contact with a 10% by mass sulfuric acid aqueous solution for 60 seconds) is performed, followed by rinsing with water. Then, the silicon wafer having the insulating portion with the Ti barrier layer and copper layer formed 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, forming plated copper on the entire surface of the recessed side of the insulating portion and filling the recess with plated copper (see Figure 1H). Next, CMP treatment is performed so that a part of the surface of the insulating portion is exposed and plated copper remains only in the recess, removing the plated copper formed on the insulating portion and the Ti barrier layer present in parts of the insulating portion other than the recess 22 (see Figure 1I). As a result, a redistribution layer comprising a conductive portion containing plated copper and an insulating portion is formed on the silicon wafer.

[0495] (Etching condition 1) Etching gas: O２ Pressure: 20 mTorr; Applied power: 100 mW / cm² ２

[0496] (Etching condition 2) Etching gas: CF ４ Pressure: 20 mTorr; Applied power: 100 mW / cm² ２

[0497] [Resolution Evaluation] The redistribution layer obtained by the above redistribution layer formation method 1 is observed using a cross-sectional SEM (Hitachi: S4800). For the trenches formed on the upper part of the insulating part, the minimum trench width in which the insulating part and the copper-plated part are clearly separated and resolved is determined according to the evaluation criteria below. The evaluation results are recorded in the "Resolution" column of Table 5.

[0498] -Evaluation Criteria- A: Minimum trench width is 1 μm B: Minimum trench width is 2 μm C: Minimum trench width is 3 μm D: None of the trenches are open

[0499] [Crack Evaluation] The redistribution layer obtained by the above redistribution layer formation method 1 is subjected to 500 thermal cycles from -40°C to 125°C under conditions of 85% RH humidity, according to the method specified in JIS C 60068-2-14. After that, the redistribution layer is cut along the thickness direction so that the trenches of the obtained redistribution layer are exposed along the extension direction, and the cut surface is observed over a length of 100 μm using a cross-sectional SEM (Hitachi: S4800). The occurrence of cracks in the insulating film is judged according to the following criteria. The evaluation results are recorded in the "Cracks" column of Table 5. A smaller number of cracks indicates higher reliability of the redistribution layer.

[0500] -Evaluation Criteria- A: No cracks in the insulation B: One or more, but less than five, in the insulation C: Five or more, but less than ten, in the insulation D: Ten or more, in the insulation

[0501] [Evaluation of Young's Modulus] The insulating film-forming resin compositions prepared in each example and comparative example are applied to a silicon wafer by spin coating to form a coating film. The silicon wafer with the obtained film is 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. Thereafter, 800 mJ / cm² is measured using a parallel light mask aligner (PLA-501FA type, 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.

[0502] -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

[0503] [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.

[0504] -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%

[0505] The evaluation results for Examples 1 to 20 and Comparative Examples 1 to 2 are shown in Table 5 below.

[0506]

[0507] From the above results, it can be seen that by using the redistribution layer formation process of the present invention, a redistribution layer is obtained that has an insulating portion having a pattern (including vias and trenches) with excellent resolution and in which crack occurrence 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), an insulating portion with excellent Young's modulus and elongation at break can be obtained. 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 is obtained that has an insulating portion having a pattern with excellent resolution. Comparing Examples 4 and 5, it can be seen 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), crack occurrence is further suppressed and a redistribution layer is obtained that has an insulating portion having a pattern with excellent resolution. 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), crack occurrence is further suppressed, and a redistribution layer with an insulating portion having a pattern superior in resolution is obtained. 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), crack occurrence is further suppressed. A comparison of Examples 4 and 17 shows that when the insulating film forming resin composition contains an antioxidant (especially a phenol compound) (Example 4), crack occurrence is further suppressed. A comparison of Examples 4 and 18 shows that when the insulating film forming resin composition contains a metal adhesion improver (especially an adhesive containing an alkoxysilyl group) (Example 4), crack occurrence is further suppressed. A comparison of Examples 4 and 19 shows that when the insulating film forming resin composition contains a rust inhibitor (especially a nitrogen-containing heterocyclic compound) (Example 4), crack occurrence is further suppressed.A comparison of Examples 4 and 20 shows that when resin A in the insulating film forming resin composition contains the above-mentioned specific ring structure X (Example 4), an insulating portion with superior Young's modulus and elongation at break can be obtained.

[0508] On the other hand, when a resist layer formed using an etching mask formation 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 the occurrence of cracks in the insulating portion cannot be sufficiently suppressed, and the resolution of the insulating portion is also insufficient (Comparative Example 1). Furthermore, when a negative resist pattern formed using an etching mask formation resin composition that does not contain silicon atoms is used as a mask for etching the insulating film, it is found that the occurrence of cracks in the insulating portion cannot be sufficiently suppressed, and the resolution of the insulating portion is also insufficient (Comparative Example 2).

[0509] [Method for Forming a Redistribution Layer 2] [Example 21] On a silicon wafer with a copper thin layer formed on its surface, the insulating film formation resin composition PI-13 is applied by spin coating. Next, the wafer is heated at a rate of 10°C / min under a nitrogen atmosphere and heated at 230°C for 2 hours to form an insulating layer with a film thickness of 4 μm after film formation (see Figure 2A). Then, the etching mask formation resin composition PR-1 is applied on the obtained insulating film by spin coating and dried at 110°C for 1 minute to form a resist layer with a film thickness of 200 nm after film formation (see Figure 2B). Subsequently, using a mask in which a 3 μm circle via pattern is arranged at intervals of 3 μm vertically and horizontally, an i-line stepper (Canon: FPA-5520iV, NA=0.16, σ=0.7) is used to apply 300 mJ / cm². ２Exposure is performed with the specified exposure amount. Subsequently, the wafer is developed by paddled with butyl acetate for 30 seconds, and the wafer is rotated at a rotation speed of 4000 rpm for 30 seconds to obtain a resist pattern on the insulating film in which a 3 μm circle via pattern is formed (see Figure 2D). Next, using the obtained resist pattern as a mask, the insulating film is etched using Plasma Systems' parallel plate type reactive ion etching apparatus DES-245R under etching condition 1 below. Etching is stopped when the insulating film has been processed to the bottom (see Figure 2E), and then the resist pattern is removed under etching condition 2 (see Figure 2F). This forms an insulating film with a thickness of 4 μm in which 3 μm circle vias are patterned. Next, an insulating portion having recesses is obtained in the same manner as in Example 1 of "Method for Forming a Redistribution Layer 1" described above, except that the etching mask formation resin composition PR-1 is applied again to the obtained insulating film. Here, the recesses formed in the insulating portion have a shape in which trenches corresponding to a line and space pattern are formed on the circle vias. Aside from using a silicon wafer having an insulating portion formed in this manner, a redistribution layer is formed on the silicon wafer in the same manner as in Example 1 of the "Method for Forming a Redistribution Layer 1" described above.

[0510] [Comparative Example 3] In Comparative Example 3, the resin composition for etching mask formation was changed to PR-9, the developer used for patterning the resist layer formed by the resin composition for etching mask formation was changed to a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, and pure water was used as the rinse solution after development. In addition, a redistribution layer was formed on a silicon wafer in the same manner as in Example 21.

[0511] [Method for Forming a Redistribution Layer 3] [Example 22] On a silicon wafer with a thin copper layer formed on its surface, the insulating film forming resin composition PI-14 is applied by spin coating. Next, the wafer is heated at a rate of 10°C / min under a nitrogen atmosphere and heated at 230°C for 2 hours to form a first insulating layer with a film thickness of 2 μm. An etching stop layer made of SiN with a film thickness of 50 nm is formed on the obtained first insulating layer by CVD. Then, the insulating film forming resin composition PI-15 is applied on the obtained SiN layer by spin coating and dried at 110°C for 5 minutes to obtain a second insulating layer (see Figure 4A). The obtained second insulating layer is subjected to 300 mJ / cm using an i-line stepper (Canon: FPA-5520iV, NA=0.16, σ=0.7) with a mask in which a 3 μm circle via pattern is arranged at intervals of 3 μm vertically and horizontally. 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 forms a second insulating layer with a thickness of 2 μm on which 3 μm circle vias are patterned on the SiN layer (see Figure 4B). Next, the SiN layer in contact with the bottom of the circle vias is etched using a Plasma Systems parallel plate type reactive ion etching apparatus DES-245R under etching condition 2 below. Etching is stopped when the processing reaches the very bottom of the SiN layer (see Figure 4C). Next, the etching mask formation resin composition PR-1 is applied to the second insulating layer with the patterned circle vias by spin coating, dried at 110°C for 1 minute, and a resist layer with a thickness of 200 nm after film formation is formed (see Figure 4D). Subsequently, using a line-and-space mask in which 1, 2, and 3 μm space patterns were formed with a line-to-space ratio of 1:1, an i-line stepper (Canon FPA-5520iV, NA=0.16, σ=0.7) was used to measure 200 mJ / cm². ２Exposure is performed with the specified exposure dose. After that, the wafer is baked at 120°C for 2 minutes (Post Exposure Bake; PEB), then developed by paddled with butyl acetate for 30 seconds, and the wafer is rotated at 4000 rpm for 30 seconds to obtain a resist pattern with a line and space pattern formed on the second insulating layer (see Figure 4F). Next, using the obtained resist pattern (line and space pattern) as a mask, the second insulating layer is etched using Plasma Systems' parallel plate type reactive ion etching apparatus DES-245R under etching condition 1 below. At this time, the SiN layer on which the circle via pattern has been processed acts as a mask, and the circle via pattern is also transferred to the first insulating layer located below the SiN layer. Etching is stopped when both the first and second insulating layers have been processed to the bottom (see Figure 4G), and then the resist pattern (line and space pattern) is removed under etching condition 2 below (see Figure 4H). This results in an insulating portion with a recess. Here, the insulating portion includes a first insulating layer, an etching stop layer, and a second insulating layer. Furthermore, the recesses formed in the insulating portion have a shape in which trenches corresponding to line-and-space patterns are formed on the circular vias. Except for using a silicon wafer having the insulating portion formed in this way, the redistribution layer is formed on the silicon wafer in the same manner as in Example 1 of the "Method for Forming a Redistribution Layer 1" described above.

[0512] (Etching condition 1) Etching gas: O ２ Pressure: 20 mTorr; Applied power: 100 mW / cm² ２

[0513] (Etching condition 2) Etching gas: CF ４ Pressure: 20 mTorr; Applied power: 100 mW / cm² ２

[0514] [Comparative Example 4] In Comparative Example 4, the resin composition for etching mask formation was changed to PR-9, the developer used for patterning the resist layer formed by the resin composition for etching mask formation was changed to a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, and pure water was used as the rinse solution after development. In addition, a redistribution layer was formed on a silicon wafer in the same manner as in Example 22.

[0515] [Method for Forming a Redistribution Layer 4] [Example 23] On a silicon wafer with a thin copper layer formed on its surface, the insulating film forming resin composition PI-14 is applied by spin coating. Next, the temperature is increased at a rate of 10°C / min under a nitrogen atmosphere and heated at 230°C for 2 hours to form a first insulating layer with a film thickness of 2 μm after film formation. On the obtained first insulating layer, an etching stop layer made of SiN with a film thickness of 50 nm is formed by CVD. Next, the insulating film forming resin composition PI-14 is again applied on the obtained SiN layer by spin coating. Next, the temperature is increased at a rate of 10°C / min under a nitrogen atmosphere and heated at 230°C for 2 hours to form a second insulating layer with a film thickness of 2 μm after film formation (see Figure 5A). Next, the etching mask forming resin composition PR-1 is applied on the obtained second insulating layer by spin coating and dried at 110°C for 1 minute to form a resist layer with a film thickness of 200 nm after film formation (see Figure 5B). Subsequently, using a mask with a 3 μm circle via pattern arranged at 3 μm intervals vertically and horizontally, an i-line stepper (Canon FPA-5520iV, NA=0.16, σ=0.7) was used to measure 300 mJ / cm². ２Exposure is performed with the specified exposure amount. Subsequently, the wafer is developed by paddled with butyl acetate for 30 seconds, and the wafer is rotated at a rotation speed of 4000 rpm for 30 seconds to obtain a resist pattern on the second insulating layer in which a 3 μm circle via pattern is formed (see Figure 5D). Next, using the obtained resist pattern (circle via pattern) as a mask, the second insulating layer is etched using Plasma Systems' parallel plate type reactive ion etching apparatus DES-245R under etching condition 1 below. Etching is stopped when the processing reaches the bottom of the second insulating layer, that is, the point where it contacts the SiN layer (see Figure 5E). Next, the resist pattern (circle via pattern) is removed under etching condition 2 below. At this time, the SiN layer present at the bottom of the circle vias is also removed by etching (see Figure 5F). Next, the etching mask forming resin composition PR-1 is applied again to the second insulating layer on which the circle vias have been processed by spin coating, and dried at 110°C for 1 minute to form a resist layer with a film thickness of 200 nm after film formation. Subsequently, using a line-and-space mask in which 1, 2, and 3 μm space patterns were formed with a line-to-space ratio of 1:1, an i-line stepper (Canon FPA-5520iV, NA=0.16, σ=0.7) was used to measure 200 mJ / cm². ２Exposure is performed with the specified exposure dose. After that, the wafer is baked at 120°C for 2 minutes (Post Exposure Bake; PEB), then developed by paddled with butyl acetate for 30 seconds, and the wafer is rotated at 4000 rpm for 30 seconds to obtain a resist pattern with a line and space pattern formed on the second insulating layer. Next, using the obtained resist pattern (line and space pattern) as a mask, the second insulating layer is etched using a Plasma Systems parallel plate type reactive ion etching apparatus DES-245R under etching condition 1 below. At this time, the SiN layer on which the circle via pattern has been processed acts as a mask, and the circle via pattern is transferred to the second insulating layer located below the SiN layer. Etching is stopped when both the first insulating layer and the second insulating layer have been processed to the bottom, and then the resist pattern (line and space pattern) is removed under etching condition 2 below. This results in an insulating portion having a recess. Here, the insulating portion includes the first insulating layer, the etching stop layer, and the second insulating layer. Furthermore, the recesses formed in the insulating portion have a shape in which trenches corresponding to line-and-space patterns are formed on the circular vias. Except for using a silicon wafer having the insulating portion formed in this manner, the redistribution layer is formed on the silicon wafer in the same manner as in Example 1 of "Method for Forming a Redistribution Layer 1" described above.

[0516] (Etching condition 1) Etching gas: O ２ Pressure: 20 mTorr; Applied power: 100 mW / cm² ２

[0517] (Etching condition 2) Etching gas: CF ４ Pressure: 20 mTorr; Applied power: 100 mW / cm² ２

[0518] [Comparative Example 5] In Comparative Example 5, the resin composition for etching mask formation was changed to PR-9, the developer used for patterning the resist layer formed by the resin composition for etching mask formation was changed to a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, and pure water was used as the rinse solution after development. In addition, a redistribution layer was formed on a silicon wafer in the same manner as in Example 23.

[0519] Even when the redistribution layer formation process described in Examples 21, 22, and 23 is carried out, a redistribution layer is obtained that has an insulating portion with a pattern (including vias and trenches) with excellent resolution and suppressed crack occurrence, similar to when the redistribution layer formation process described in Examples 1 to 20 is carried out. The insulating portion in Examples 21 and 23 is formed using a non-photosensitive insulating film forming resin composition, and the insulating portion in Example 22 includes an insulating layer formed using a non-photosensitive insulating film forming resin composition. Therefore, the insulating portions in Examples 21 to 23 have better Young's modulus and elongation at break compared to the insulating portions in Examples 1 to 20 (formed using a photosensitive insulating film forming resin composition). On the other hand, when the redistribution layer formation process described in Comparative Examples 3, 4, and 5 is carried out, for the same reasons as in Comparative Example 1, the occurrence of cracks in the insulating portion cannot be sufficiently suppressed, and the resolution of the insulating portion is also insufficient.

[0520] 10 Substrate 20, 120, 220, 320 Insulating film 21, 221 Insulating part 21a Surface 22, 222 Recessed parts 22a, 222a, 322a First via part 22A, 222A Via part 22B, 222B Trench part 30, 130, 230, 330 Resist layer 30A, 130A, 230A, 330A Exposed part 30B, 130B, 230B, 330B Unexposed part 31, 131, 331 Resist layer after pattern exposure 32, 132, 232, 332 Negative resist pattern 40, 240 Metal layer 41, 241 Conductive layer 41a Surface 50, 250 Redistribution layer 222b, 322b Second via part 220A, 320A: First insulating layer 220B, 320B: Etching stop layer 220C, 320C: Second insulating layer

Claims

1. A method for manufacturing a semiconductor device, comprising: a preparation step for preparing a semiconductor element; and a redistribution layer formation step for forming a redistribution layer connected to the semiconductor element and having an insulating portion and a conductive portion, wherein the redistribution layer formation step comprises: a step 1 for forming an insulating film by applying a resin composition A containing 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 an insulating portion having a recess composed of the via portion and the trench portion by performing a step 2a for forming via portions in the insulating film and a step 2b for forming trench portions in the insulating film; a step 3 for forming a metal layer so as to fill the recess by a plating process; and a step 4 for obtaining the conductive portion by removing a part of the metal layer by a chemical mechanical polishing process, wherein step 2a includes the following steps a, b, c and d1, and step 2b includes the following steps a, b, c and d2, at least one of these. Step a: 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, onto the insulating film to form a resist layer. Step b: Pattern exposure of the resist layer. Step c: 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 d1: Dry etching of the insulating film using the negative resist pattern as a mask to form the via portion. Step d2: Dry etching of the insulating film using the negative resist pattern as a mask to form the trench portion.

2. The method for manufacturing a semiconductor device according to claim 1, wherein the developer in step c 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 b 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. * represents a bonding site.

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 resin composition A is a photosensitive resin composition comprising at least one of a photopolymerization initiator and a photoacid generator, and the formation of the via portion in step 2a comprises a pattern exposure process and a development process.

10. 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).

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 photoacid generator that does not contain an alkyl fluoride group.

12. 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 photoacid generator.

13. The method for manufacturing a semiconductor device according to claim 1, wherein the dry etching in at least one of step d1 and step d2 is reactive ion etching with a gas containing oxygen atoms.

14. A method for manufacturing a semiconductor device according to claim 1, further comprising a step of removing the negative resist pattern after at least one of the steps d1 and d2.

15. A method for manufacturing a semiconductor device according to claim 1, wherein the insulating film has an etching stop layer inside it.

16. 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 15, comprising at least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor.

17. A photosensitive resin composition used in a method for manufacturing a semiconductor device according to any one of claims 1 to 15, 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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