Hybrid bonding insulating film forming material, method for manufacturing a semiconductor device, and semiconductor device.

Abstract

This hybrid bonding insulation film-forming material contains a thermosetting polyamide having a phenolic hydroxyl group in each molecule, and a solvent.

Description

[Technical Field]

[0001] This disclosure relates to a hybrid bonding insulating film forming material, a method for manufacturing a semiconductor device, and a semiconductor device. [Background technology]

[0002] In recent years, three-dimensional packaging of semiconductor chips has been considered to improve the integration density of LSIs (Large Scale Integrated Circuits). Non-patent document 1 discloses an example of three-dimensional packaging of semiconductor chips.

[0003] When performing three-dimensional mounting of semiconductor chips using C2W (Chip-to-Wafer) bonding, the use of hybrid bonding technology, which is used in W2W (Wafer-to-Wafer) bonding, is being considered in order to achieve fine bonding of the wiring between devices.

[0004] In C2W hybrid bonding, there is a risk of misalignment due to thermal expansion of the substrate, chips, etc., caused by heating during bonding. To address this issue, Patent Document 1 discloses an example of a technology that can lower the bonding temperature by using a cyclic olefin resin. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2019-204818 [Non-patent literature]

[0006] [Non-Patent Document 1] FC Chen et al., “System on Integrated Chips(SoIC TM) for 3D Heterogeneous Integration”, 2019 IEEE 69th Electronic Components and Technology Conference (ECTC), p.594-599(2019) [Overview of the project] [Problems that the invention aims to solve]

[0007] The method of C2W bonding using hybrid bonding technology with an organic insulating film is still in the investigation stage and has not yet been put into practical use. When using the cyclic olefin resin described in Patent Document 1, the heat resistance of the resulting organic insulating film is insufficient, and there is a risk of bonding defects occurring at the interface between the substrate and the organic insulating film when exposed to high temperatures during C2W bonding. On the other hand, as mentioned above, the method of C2W bonding using hybrid bonding technology with an insulating film requires a low bonding temperature.

[0008] Generally, resin bonding is performed at temperatures higher than the glass transition temperature of the resin. Furthermore, when thermoplastic resins such as polyimide and polybenzoxazole are used as insulating films, there is a correlation between the resin's glass transition temperature and the bonding temperature; to achieve a low bonding temperature, the resin's glass transition temperature must be lowered. However, lowering the resin's glass transition temperature can lead to problems with heat resistance. Therefore, there is a need for resin materials that can be bonded at temperatures below the glass transition temperature. This disclosure is made in view of the above-mentioned prior circumstances and aims to provide a hybrid bonding insulating film forming material that can be bonded in a temperature range below the glass transition temperature, as well as a semiconductor device using this hybrid bonding insulating film forming material and a method for manufacturing the same. [Means for solving the problem]

[0009] The specific means for achieving the aforementioned objectives are as follows: <1> A hybrid bonding insulating film forming material comprising a thermosetting polyamide having phenolic hydroxyl groups in its molecule and a solvent. <2> Furthermore, it contains a crosslinking agent. <1> Hybrid bonding insulating film forming material as described above. <3> A first semiconductor substrate is prepared, having a first substrate body, a first electrode and a first organic insulating film provided on one surface of the first substrate body. A semiconductor chip is prepared, comprising a semiconductor chip substrate body, a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body, The first electrode and the second electrode are joined together, and the first organic insulating film and the second organic insulating film are bonded together. For the fabrication of at least one of the first organic insulating film and the second organic insulating film, <1> or <2> A method for manufacturing a semiconductor device using the hybrid bonding insulating film forming material described above. <4> After bonding the first organic insulating film and the second organic insulating film, the first electrode and the second electrode are bonded together. <3> A method for manufacturing a semiconductor device as described above. <5> The semiconductor chip is prepared by framing a second semiconductor substrate having a second substrate body, a plurality of second electrodes and a second organic insulating region provided on one surface of the second substrate body. <3> or <4> A method for manufacturing a semiconductor device as described above. <6> The bonding of the first organic insulating film and the second organic insulating film is performed at a temperature such that the temperature difference between the semiconductor chip and the first semiconductor substrate is 10°C or less. <3> ~ <5> A method for manufacturing a semiconductor device as described in any one of the items. <7> In the manufactured semiconductor device, the total thickness of the organic insulating film formed by bonding the first organic insulating film and the second organic insulating film is 0.1 μm or more. <3> ~ <6> A method for manufacturing a semiconductor device as described in any one of the items. <8> Before the bonding of the first electrode and the second electrode, and before the bonding of the first organic insulating film and the second organic insulating film are carried out, at least one of the one surface of the first semiconductor substrate and the side of the one surface of the semiconductor chip are polished. <3> ~ <7> A method for manufacturing a semiconductor device as described in any one of the items. <9> The polishing includes chemical mechanical polishing. <8> A method for manufacturing a semiconductor device as described above. <10> The polishing further includes mechanical polishing. <9> A method for manufacturing a semiconductor device as described above. <11> The thickness of the first electrode is greater than the thickness of the first organic insulating film, and the thickness of the second electrode is greater than the thickness of the second organic insulating film. <3> ~ <10> A method for manufacturing a semiconductor device as described in any one of the items. <12> A first semiconductor substrate having a first substrate body, a first organic insulating film and a first electrode provided on one surface of the first substrate body, The semiconductor chip comprises a semiconductor chip substrate body and a semiconductor chip having a second organic insulating film and a second electrode provided on one side of the semiconductor chip substrate body. The first organic insulating film and the second organic insulating film are joined together, and the first electrode and the second electrode are joined together, At least one of the first organic insulating film and the second organic insulating film is <1> or <2> A semiconductor device which is a cured product of the hybrid bonding insulating film forming material described above. [Effects of the Invention]

[0010] According to this disclosure, it is possible to provide a hybrid bonding insulating film forming material that can be bonded in a temperature range below the glass transition temperature, as well as a semiconductor device using this hybrid bonding insulating film forming material and a method for manufacturing the same. [Brief explanation of the drawing]

[0011] [Figure 1] Figure 1 is a schematic cross-sectional view showing an example of a semiconductor device manufactured by a semiconductor device manufacturing method according to one embodiment. [Figure 2]Figure 2 is a diagram illustrating, step by step, the method for manufacturing the semiconductor device shown in Figure 1. [Figure 3] Figure 3 is a diagram that shows in more detail the bonding method in the semiconductor device manufacturing method shown in Figure 2. [Figure 4] Figure 4 shows a method for manufacturing the semiconductor device shown in Figure 1, and sequentially illustrates the steps after the process shown in Figure 2. [Figure 5] Figure 5 shows an example of applying a semiconductor device manufacturing method according to one embodiment to a chip-to-wafer (C2W) device. [Modes for carrying out the invention]

[0012] The present disclosure is described in detail below. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the components (including elemental steps, etc.) are not essential unless otherwise explicitly stated. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0013] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes, provided that the purpose of such process is achieved. In this disclosure, the numerical range indicated using "~" includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in stages within this disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described within this disclosure, the upper or lower limit of that range may be replaced with the values ​​shown in the examples. In this disclosure, each component may contain multiple types of the corresponding substance. If multiple types of the substance corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple types of substances present in the composition, unless otherwise specified. In this disclosure, each component may include multiple types of particles. If multiple types of particles corresponding to each component are present in the composition, the particle size of each component refers to the value for a mixture of such multiple types of particles present in the composition, unless otherwise specified. In this disclosure, the terms “layer” or “film” include cases where, when the region in which the layer or film exists is observed, it is formed not only over the entire region but also over only a portion of the region. In this disclosure, "(meth)acryloyl" means at least one of acryloyl and methacryloyl, "(meth)acrylic" means at least one of acrylic and methacrylic, and "(meth)acrylate" means at least one of acrylate and methacrylate. In this disclosure, the average thickness of a layer or film is given as the arithmetic mean value obtained by measuring the thickness of five points on the layer or film in question. The thickness of a layer or film can be measured using a micrometer or the like. In this disclosure, if the thickness of a layer or film can be measured directly, it is measured using a micrometer. On the other hand, when measuring the thickness of a single layer or the total thickness of multiple layers, it may be measured by observing the cross-section of the object to be measured using an electron microscope.

[0014] <Hybrid bonding insulating film forming material> The hybrid bonding insulating film forming material of this disclosure (hereinafter, the hybrid bonding insulating film forming material may be simply referred to as the "insulating film forming material") comprises a thermosetting polyamide having phenolic hydroxyl groups in its molecule and a solvent. The insulating film forming material of this disclosure may optionally contain other components such as crosslinking agents and polymerization initiators. According to this disclosure, it becomes possible to provide an insulating film forming material that can be bonded in a temperature range below the glass transition temperature. The reason for this is not clear, but it is presumed to be as follows. The insulating film forming material of this disclosure contains a thermosetting polyamide having phenolic hydroxyl groups in its molecule. When the thermosetting polyamide having phenolic hydroxyl groups in its molecule hardens through a thermosetting reaction and a cured product is formed, some of the phenolic hydroxyl groups are exposed on the surface of the cured product. When the cured products with exposed phenolic hydroxyl groups are heated and pressed together, a hardening reaction occurs between the unreacted thermosetting polyamides having phenolic hydroxyl groups in their molecules that are contained within the cured product. The hardening reaction between the thermosetting polyamides on the surface of the cured product can proceed even below the glass transition temperature. As a result, it is presumed that a strong bond is constructed between the cured products in the temperature range below the glass transition temperature, enabling bonding. Furthermore, when hardened materials with exposed phenolic hydroxyl groups on their surfaces are heated and pressed together, the materials can be joined together due to the contribution of hydrogen bonding. As a result, it is presumed that a strong bond is established between the hardened materials at temperatures below the glass transition temperature, enabling joining.

[0015] Examples of thermosetting polyamides having phenolic hydroxyl groups in the molecule used in this disclosure include polybenzoxazole precursors and polyimide precursors (such as polyamic acid). The location of the phenolic hydroxyl group in the thermosetting polyamide is not particularly limited; it may be at the end of the thermosetting polyamide or within the main chain skeleton.

[0016] The details of the insulating film forming material of this disclosure will be described below. In the following description, the cases in which the thermosetting polyamide having phenolic hydroxyl groups in the molecule is a polybenzoxazole precursor and the cases in which it is a polyimide precursor (polyamic acid) will be described. Hereinafter, the case in which the thermosetting polyamide having phenolic hydroxyl groups in the molecule is a polybenzoxazole precursor may be referred to as the first insulating film forming material, and the case in which the thermosetting polyamide having phenolic hydroxyl groups in the molecule is a polyimide precursor (polyamic acid) may be referred to as the second insulating film forming material.

[0017] [First insulating film forming material] The first insulating film forming material includes (a) a polybenzoxazole precursor as a thermosetting polyamide having phenolic hydroxyl groups in its molecule. In this specification, (a) polybenzoxazole precursors, and at least one compound selected from the group consisting of (b) photosensitive agents, (c) solvents, and (d) heterocyclic compounds, thioureas, and compounds having a mercapto group, may be referred to as component (a), component (b), component (c), and component (d), respectively, as they may be. Furthermore, the first insulating film forming material may contain a polyimide precursor having phenolic hydroxyl groups in its molecule, or it may contain a polyimide precursor not having phenolic hydroxyl groups in its molecule. When the first insulating film forming material contains at least one of a polyimide precursor having phenolic hydroxyl groups in its molecule and a polyimide precursor not having phenolic hydroxyl groups in its molecule, the proportion of the polybenzoxazole precursor having phenolic hydroxyl groups in its molecule to the total of the polybenzoxazole precursor having phenolic hydroxyl groups in its molecule, the polyimide precursor having phenolic hydroxyl groups in its molecule and the polyimide precursor not having phenolic hydroxyl groups in its molecule is preferably 50% by mass or more and less than 100% by mass, more preferably 60% by mass to 90% by mass, and even more preferably 65% ​​by mass to 80% by mass. Furthermore, the first insulating film forming material does not necessarily have to contain a polyimide precursor having a phenolic hydroxyl group in its molecule, nor does it necessarily have to contain a polyimide precursor that does not have a phenolic hydroxyl group in its molecule.

[0018] ((a) Polybenzoxazole precursor) The type of polybenzoxazole precursor is not particularly limited. The polybenzoxazole precursor preferably has a structural unit represented by the following formula (II). [ka] (In formula (II), U is a tetravalent organic group, and V is a divalent organic group.) In formula (II), the amide unit containing a hydroxyl group is converted to an oxazole ring, which has excellent heat resistance, chemical resistance, and electrical properties, by dehydration and ring closure during the heating process.

[0019] Furthermore, in the structural unit represented by formula (II), the amide unit containing a hydroxyl group is effective in improving the solubility of the polymer in alkaline aqueous solutions.

[0020] A polymer having a structural unit represented by formula (II) may contain only one type of structural unit, or it may contain two or more types. When it is a copolymer having two or more types of structural units, it may be a polymer having at least two types of structural units represented by formula (II), or it may be a polymer having a structure represented by formula (III). When a polymer having a structural unit represented by formula (II) has at least two types of structural units represented by formula (II), the combination of structural units represented by formula (II) is not particularly limited. For example, it may be a combination of a structural unit in which the divalent organic group represented by V is a divalent aromatic group and a structural unit in which V is a divalent organic group having an aliphatic structure with 6 to 30 carbon atoms.

[0021] [ka] (In formula (III), U is a tetravalent organic group, and V and W are each independently divalent organic groups. j and k are mole fractions, the sum of j and k is 100 mol%, with j being 60-99.9 mol% and k being 0.1 mol%-40 mol% (preferably j being 80-99.9 mol% and k being 0.1 mol%-20 mol%).)

[0022] In formulas (II) and (III), the tetravalent organic group represented by U is a residue of a diamine used in the synthesis of polyhydroxyamides. The tetravalent organic group represented by U is preferably a tetravalent aromatic group or an organic group having 6 to 40 carbon atoms, and more preferably a tetravalent aromatic group having 6 to 40 carbon atoms. As for the tetravalent aromatic group, it is preferable that all four bonding sites are located on an aromatic ring. Furthermore, an aromatic group refers to a group that contains an aromatic ring.

[0023] Examples of diamines that give a tetravalent organic group represented by U include, but are not limited to, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, and 2,2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

[0024] In formula (III), the divalent organic group represented by W is a residue of a diamine used in the synthesis of polyhydroxyamides. The divalent organic group represented by W is preferably a divalent aromatic group, a divalent aliphatic group, or an organic group having 4 to 20 carbon atoms, and more preferably an aromatic group having 4 to 20 carbon atoms. The divalent organic group represented by W is a residue of a diamine other than the diamines that give rise to the tetravalent organic group represented by U.

[0025] Examples of diamines that give a divalent organic group represented by W include aromatic diamine compounds such as 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, benzicine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, and 1,4-bis(4-aminophenoxy)benzene. Furthermore, examples of diamines containing a silicone group include, but are not limited to, LP-7100, X-22-161AS, X-22-161A, X-22-161B, X-22-161C, and X-22-161E (all manufactured by Shin-Etsu Chemical Co., Ltd., and are trade names).

[0026] In formulas (II) and (III), the divalent organic group represented by V is a residue of a dicarboxylic acid or dicarboxylic acid derivative (hereinafter referred to as dicarboxylic acids) used in the synthesis of polyhydroxyamides. The divalent organic group represented by V is preferably a divalent aromatic group or an organic group having 6 to 40 carbon atoms. From the viewpoint of heat resistance, it is preferable that the group is a divalent aromatic group having 6 to 40 carbon atoms, and as a divalent aromatic group, it is preferable that both bond sites are located on an aromatic ring.

[0027] From the viewpoint of having a high dehydration and ring closure rate during the heating process at low temperatures (e.g., below 200°C), as well as good heat resistance and mechanical strength, it is preferable that V is a divalent organic group having an aliphatic structure with 6 to 30 carbon atoms.

[0028] Dicarboxylic acids that give a divalent organic group represented by V include isophthalic acid, terephthalic acid, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether (4,4'-diphenyl ether dicarboxylic acid), 4,4'-dicarboxytetraphenylsilane, bis(4-carboxyphenyl)sulfone, 2,2-bis(p-carboxyphenyl)propane, 5-tert-butylisophthalic acid, 5 - Aromatic dicarboxylic acids such as bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, and those having an aliphatic linear structure include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succicic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, and 2,3-dimethyl Succinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanediic acid, dodecanediic acid, tridecane Examples include dicarboxylic acids such as diacetic acid, tetradecane diacetic acid, pentadecane diacetic acid, hexadecanedioic acid, heptadecanedioic acid, octadecane diacetic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacondioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and others. Furthermore, dicarboxylic acids represented by the following formulas are also included, but are not limited to these. These compounds can be used individually or in combination of two or more. [ka] (In the formula, Z is an independent hydrocarbon group having 1 to 6 carbon atoms, and i is an integer from 1 to 6.)

[0029] In this disclosure, there are no particular limitations on the method for producing component (a). Generally, it can be synthesized using dicarboxylic acids, hydroxyl group-containing diamines, and, if necessary, diamines other than hydroxyl group-containing diamines. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting it with diamines. Dichloride derivatives are preferred as the dihalide derivative.

[0030] Dichloride derivatives can be synthesized by reacting dicarboxylic acids with a halogenating agent in a solvent, or by reacting them in an excess of halogenating agent and then removing the excess by distillation. Common halogenating agents used in acid chloride reactions of carboxylic acids include thionyl chloride, phosphoryl chloride, phosphorus oxychloride, and phosphorus pentachloride. Suitable reaction solvents include N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N,N-dimethylacetamide, N,N-dimethylformamide, toluene, and benzene.

[0031] The amount of halogenating agents used is preferably 1.5 to 3.0 moles, more preferably 1.7 to 2.5 moles, per 1.0 mole of the dicarboxylic acid derivative when reacting in a solvent, and preferably 4.0 to 50 moles, more preferably 5.0 to 20 moles, when reacting in the halogenating agent. The reaction temperature is preferably -10°C to 70°C, more preferably 0°C to 20°C.

[0032] The reaction between dichloride derivatives and diamines is preferably carried out in an organic solvent in the presence of a dehydrohalogenating agent. Organic bases such as pyridine and triethylamine can be used as the dehydrohalogenating agent. Suitable organic solvents include N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N,N-dimethylacetamide, and N,N-dimethylformamide. The reaction temperature is preferably -10°C to 30°C, and more preferably 0°C to 20°C.

[0033] Examples of diamines include aromatic diamines, aliphatic diamines, and alicyclic diamines. Specifically, these include 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diaminoterephthalic acid, bis(4-amino-3-carboxyphenyl)methylene, bis(4-amino-3-carboxyphenyl) ether, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-5,5'-dicarboxy-2,2'-dimethylbiphenyl, 1,3-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, and bis(4 Examples include bis(amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)ether, bis(4-amino-3-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 1,4-diaminocyclohexane, 1,1,3,3-tetramethyl-1,3-bis(4-aminophenyl)disiloxane, poly(propylene glycol)diamine, etc., which can be used individually or in combination of two or more.

[0034] (a) Component may be developed with an alkaline aqueous solution. Therefore, it is preferable that it be soluble in an alkaline aqueous solution. Examples of alkaline aqueous solutions include aqueous solutions of organic ammonium such as tetramethylammonium hydroxide (TMAH) aqueous solution, aqueous solutions of metal hydroxides, and aqueous solutions of organic amines. Generally, it is preferable to use an aqueous TMAH solution with a concentration of 2.38% by mass. Therefore, it is preferable that component (a) is soluble in the aqueous TMAH solution.

[0035] One criterion for determining whether component (a) is soluble in an alkaline aqueous solution is described below. Component (a) is dissolved in any solvent to form a solution, which is then spin-coated onto a substrate such as a silicon wafer to form a resin film with a thickness of approximately 5 μm. This film is then immersed in one of the following solutions: TMAH aqueous solution, metal hydroxide aqueous solution, or organic amine aqueous solution, at 20°C to 25°C. If the component dissolves and forms a solution, then the component (a) used is determined to be soluble in an alkaline aqueous solution.

[0036] (a) The molecular weight of the resin soluble in an alkaline aqueous solution of component (a) is preferably 10,000 to 100,000 in weight-average molecular weight equivalent to polystyrene, more preferably 12,000 to 100,000, and even more preferably 14,000 to 85,000. When the weight-average molecular weight of component (a) is 10,000 or more, adequate solubility in alkaline developer can be ensured. Furthermore, when the weight-average molecular weight of component (a) is 100,000 or less, good solubility in solvents tends to be obtained, and the increase in viscosity of the solution and the resulting decrease in handling ease can be suppressed. The weight-average molecular weight can be measured by gel permeation chromatography and then converted using a standard polystyrene calibration curve. Furthermore, the degree of dispersion, obtained by dividing the weight-average molecular weight by the number-average molecular weight, is preferably 1.0 to 4.0, and more preferably 1.0 to 3.5.

[0037] ((b) component: photosensitive agent) The first insulating film forming material may include a polybenzoxazole precursor or a copolymer of a polybenzoxazole precursor, which is component (a), along with a photosensitive agent, which is component (b). This photosensitive agent reacts to light and has a function for the developing solution of the film formed from the composition. There are no particular limitations on the photosensitive agent used as component (b) in this disclosure, but it is preferable that it generates an acid or radical upon exposure to light.

[0038] When the first insulating film forming material is a positive-type photosensitive resin composition, (b) the photosensitive agent is more preferably one that generates acid upon exposure to light (a photoacid generator). In the positive type, the photoacid generator generates acid upon irradiation with light and has the function of increasing the solubility of the irradiated area in an alkaline aqueous solution. Examples of such photoacid generators include o-quinone diazide compounds, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts, with o-quinone diazide compounds being preferred due to their high sensitivity.

[0039] The above o-quinone diazide compounds can be obtained, for example, by condensing o-quinone diazide sulfonyl chlorides with hydroxy compounds, amino compounds, etc., in the presence of a dehydrochlorinating agent. Examples of the o-quinone diazide sulfonyl chlorides that can be used include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, naphthoquinone-1,2-diazide-4-sulfonyl chloride, etc.

[0040] Examples of the hydroxy compounds that can be used include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,2',3'-pentahydroxybenzophenone, 2,3,4,3',4',5'-hexahydroxybenzophenone, bis(2,3,4-trihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)propane, 4b,5,9b,10-tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethylindeno[2,1-a]inden, tris(4-hydroxyphenyl)methane, and tris(4-hydroxyphenyl)ethane.

[0041] Examples of the amino compounds that can be used include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and bis(4-amino-3-hydroxyphenyl)hexafluoropropane.

[0042] The o-quinone diazidosulfonyl chloride and the hydroxy compound and / or amino compound are preferably blended so that the total amount of hydroxyl groups and amino groups is 0.5 to 1 equivalent per mole of o-quinone diazidosulfonyl chloride. The preferred ratio of the dechlorinating agent to the o-quinone diazidosulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95. The preferred reaction temperature is 0°C to 40°C, and the preferred reaction time is 1 to 10 hours.

[0043] The reaction solvents used in the above reaction include dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, and N-methyl-2-pyrrolidone. Examples of dehydrochlorinating agents include sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, and pyridine.

[0044] Furthermore, if the polybenzoxazole precursor contains a photocrosslinkable group such as an acryloyl group or a methacryloyl group, a radical-generating compound can be used as component (b), or if a compound that can be crosslinked or polymerized by the action of an acid is used as a crosslinking agent, an acid-generating compound can be used as component (b), i.e., a photopolymerization initiator, thereby enabling the first insulating film forming material to be used as a negative-type photosensitive resin composition. This negative-type photosensitive resin composition has the function of reducing the solubility of the light-irradiated area in an alkaline aqueous solution through a crosslinking reaction caused by light irradiation.

[0045] In the first insulating film forming material, the amount of component (b) (photosensitive agent) is preferably 5 to 100 parts by mass, and more preferably 8 to 40 parts by mass, per 100 parts by mass of component (a) (base resin), from the viewpoint of the difference in dissolution rate between the exposed and unexposed areas and the allowable range of sensitivity.

[0046] ((c) Ingredients: Solvent) The first insulating film forming material contains a solvent. Examples of solvents include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, methyl 3-methoxypropionate, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, and 3-methoxy-N,N-dimethylpropanamide.

[0047] These solvents can be used individually or in combination of two or more. While there are no particular restrictions on the amount of solvent used, it is generally preferable to adjust the proportion of the solvent in the first insulating film forming material to 20% to 90% by mass.

[0048] ((d) Component: At least one compound selected from the group consisting of heterocyclic compounds, thioureas, and compounds having a mercapto group) The first insulating film forming material may contain component (d). (d) Among the components, a heterocyclic compound is a cyclic compound in which the ring is composed of atoms of two or more elements (in addition to carbon, nitrogen, oxygen, sulfur, etc.). Examples of heterocyclic compounds include compounds having a triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimididine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, and triazine ring. Among these, compounds having a triazole ring, pyrrole ring, pyrazole ring, thiazole ring, imidazole ring and tetrazole ring containing a carbon atom and a nitrogen atom are preferred.

[0049] (d) Among the components, thioureas include, but are not limited to, monomethylthiourea, thiourea, dimethylthiourea, diethylthiourea, and dibutylthiourea.

[0050] (d) Among the components, specific examples of heterocyclic compounds and compounds having a mercapto group include pyrrole, 3-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, 2-ethylpyrrole, indole, 5-hydroxyindole, pyrazole, 4-methylpyrazole, 3-aminopyrazole, 3-methylpyrazole, 3,5-diisopropylpyrazole, 3-amino-5-hydroxypyrazole, indazole, 5-aminoindazole, 6-aminoindazole, imidazole, 2-methylimidazole, 2-ethylimidazole, 2- Chilimidazole, 4-imidazolecarboxylic acid, 4-methylimidazole, benzimidazole, 5-methylbenzimidazole, 2-aminobenzimidazole, 5,6-dimethylbenzimidazole, 2-mercapto-1,3,4-thiadiazole, 2,5-dimethyl-1,3,4-thiadazole, 4-phenyl-1,2,3-thiadazole, 2-amino-1,3,4-thiadazole, 2-amino-5-ethyl-1,3,4-oxadiazole, thiazole, 2-aminothiazole, 2-methylthiazole, 2-methoxythiazole, 2-ethoxythi Azole, 2-isobutylthiazole, 2-trimethylsilylthiazole, 5-trimethylsilylthiazole, 4-methylthiazole, 4,5-dimethylthiazole, 2-ethylthiazole, 2,4-dimethylthiazole, 2-amino-5-methylthiazole, 2-amino-4-methylthiazole, 2,4,5-trimethylthiazole, benzothiazole, 2-methylbenzothiazole, 2,5-dimethylbenzothiazole, 1,2,4-triazole, 1,2,3-triazole, 1,2,5-triazole, 3-mercapto-4-methyl-4H-1,2 ,4-triazole, 3-mercapto-1,2,4-triazole, 4-amino-3,5-dimethyl-4H-1,2,4-triazole, 4-amino-3,5-dipropyl-4H-1,2,4-triazole, 3-amino-5-isopropyl-1,2,4-triazole, 4-amino-3-mercapto-5-methyl-4H-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 4-amino-1,2,4-triazole, 4-amino-3,5-dimethyl-1,2,Examples include, but are not limited to, 4-triazole, 4-amino-5-methyl-4H-1,2,4-triazole-3-thiol, 3,5-diamino-1H-1,2,4-triazole, benzotriazole, 5-methyl-1H-benzotriazole, 5,6-dimethylbenzotriazole, 5-amino-1H-benzotriazole, benzotrizole-4-sulfonic acid, 1H-tetrazol, 5-methyl-1H-tetrazol, 5-(methylthio)-1H-tetrazol, 5-(ethylthio)-1H-tetrazol, 5-phenyl-1H-tetrazol, 5-amino-1H-tetrazol, 5-nitro-1H-tetrazol, 1-methyl-1H-tetrazol, 5,5'-bis-1H-tetrazol, etc. These are used alone or in combination of two or more types.

[0051] (d) Among the components, at least one selected from the group consisting of 1H-tetrazole, 5-substituted-1H-tetrazole, 1-substituted-1H-tetrazole and its derivatives is preferred, at least one selected from the group consisting of 1,2,3-triazole, 1,2,4-triazole and its derivatives, 1,2,3-benzotriazole, 5-substituted-1H-benzotriazole, 6-substituted-1H-benzotriazole, 5,6-substituted-1H-benzotriazole and its derivatives is more preferred, and 5-methyl-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, or 5,5'-bis-1H-tetrazole is particularly preferred.

[0052] (d) Component is used to prevent corrosion between the photosensitive resin and the substrate (e.g., copper and copper alloys) and to improve adhesion.

[0053] The amount of component (d) added is usually 0.1 to 10 parts by mass per 100 parts by mass of component (a) (base resin), and 0.1 to 10 parts by mass in total when two or more types are combined. More preferably, it is in the range of 0.2 to 5 parts by mass. If the amount is 0.1 parts by mass or more, an effect of improving adhesion to the metal layer tends to be ensured, and if it is 10 parts by mass or less, an effect of improving adhesion corresponding to the amount of component (d) added tends to be enjoyed.

[0054] ((e) component: crosslinking agent that can be crosslinked or polymerized by heating) The first insulating film forming material preferably contains a crosslinking agent that can be crosslinked or polymerized by heating. In the process of applying, exposing, developing, and then heat-treating the first insulating film forming material, the crosslinking compound reacts with the polybenzoxazole precursor or polybenzoxazole, i.e., crosslinks. Alternatively, in the heat-treating process, the crosslinking compound itself polymerizes. This prevents the brittleness of the film that is a concern at relatively low temperatures, for example, below 200°C, and improves mechanical properties, chemical resistance, flux resistance, etc.

[0055] Component (e) is not particularly limited other than being a compound that undergoes crosslinking or polymerization during the heat treatment process, but it is preferably a compound having a methylol group, an alkoxymethyl group, an epoxy group, or a vinyl ether group in its molecule. Compounds in which these groups are bonded to a benzene ring, or melamine resins and urea resins in which the N position is substituted with a methylol group and / or an alkoxymethyl group, are preferred. Compounds in which these groups are bonded to a benzene ring having a phenolic hydroxyl group are even more preferred because they can increase the dissolution rate of the exposed area during development, thereby improving sensitivity. Among these, compounds having two or more methylol groups or alkoxymethyl groups in their molecule are even more preferred in terms of sensitivity, varnish stability, and the ability to prevent melting of the film during curing after pattern formation.

[0056] Such compounds can be represented by the following general formulas (9) to (11).

[0057] [ka] (In the formula, G represents a single bond or a monovalent to tetravalent organic group, R 11 , R 12 Each of the following independently represents a hydrogen atom or a monovalent organic group, o is an integer from 1 to 4, and p and q are each an integer from 0 to 4.

[0058] [ka] (In the formula, each of the two J's is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, which may contain an oxygen atom or a fluorine atom, and R 13 ~R 16 Each of the following independently represents a hydrogen atom or a monovalent organic group, r and s are each independently integers from 1 to 3, and p and q are each independently integers from 0 to 3.

[0059] [ka] (In the formula, R 17 , R 18 Each of these independently represents a hydrogen atom or a monovalent organic group, and there are multiple R 18 (They may have a ring structure and be connected to each other.)

[0060] Examples of the crosslinking agents mentioned above include, but are not limited to, the compound shown in chemical formula (12) below. These compounds can be used individually or in combination of two or more.

[0061] [ka]

[0062] In the first insulating film forming material, the amount of component (e) (a crosslinking agent that can be crosslinked or polymerized by heating) is preferably 1 to 50 parts by mass per 100 parts by mass of component (a) (base resin), from the viewpoint of development time, allowable range of unexposed film percentage, and cured film properties. On the other hand, from the viewpoint of chemical resistance and flux resistance of the cured film at temperatures below 230°C, it is even more preferable to use 20 parts by mass or more, i.e., 20 to 50 parts by mass. If the first insulating film forming material includes at least one of a polyimide precursor having a phenolic hydroxyl group in its molecule and a polyimide precursor not having a phenolic hydroxyl group in its molecule, then the polymerizable monomer (crosslinking agent) described below may be used as the crosslinking agent.

[0063] ((f) component: a thermal acid generator that produces acid when heated) The first insulating film forming material can be a thermal acid generator (thermally latent acid generator) that generates acid upon heating. Using a thermal acid generator is preferable because it efficiently acts as a catalyst when the phenolic hydroxyl group-containing polyamide structure of the polybenzoxazole precursor undergoes a dehydration reaction and cyclization.

[0064] The acid generated from the above-mentioned thermal acid generator (thermal latent acid generator) is preferably a strong acid. Specifically, preferred acids include aryl sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, perfluoroalkyl sulfonic acids such as camphorsulfonic acid, trifluoromethanesulfonic acid, and nonafluorobutanesulfonic acid, and alkyl sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid. These acids efficiently act as catalysts when the phenolic hydroxyl group-containing polyamide structure of the polybenzoxazole precursor undergoes a dehydration reaction and cyclization.

[0065] These acids are added to the first insulating film forming material as a thermal acid generator, either in the form of a salt such as an onium salt or in the form of a covalent bond such as an imidosulfonate.

[0066] Preferred onium salts include diaryliodonium salts such as diphenyliodonium salt, di(alkylaryl)iodonium salts such as di(t-butylphenyl)iodonium salt, trialkylsulfonium salts such as trimethylsulfonium salt, dialkylmonoarylsulfonium salts such as dimethylphenylsulfonium salt, and diarylmonoalkyliodonium salts such as diphenylmethylsulfonium salt. These are preferred because their decomposition start temperature is in the range of 150°C to 250°C, and they decompose efficiently during the cyclization dehydration reaction of the polybenzoxazole precursor at temperatures below 280°C.

[0067] From the above points, as a thermoacid generator as an onium salt, diaryliodonium salts, di(alkylaryl)iodonium salts, trialkylsulfonium salts, dialkylmonoarylsulfonium salts, or diarymonoalkyliodonium salts of arylsulfonic acid, camphorsulfonic acid, perfluoroalkylsulfonic acid, or alkylsulfonic acid are preferred in terms of storage stability and developability. More specifically, di(t-butylphenyl)iodonium salt of p-toluenesulfonic acid (1% weight loss temperature 180°C, 5% weight loss temperature 185°C), di(t-butylphenyl)iodonium salt of trifluoromethanesulfonic acid (1% weight loss temperature 151°C, 5% weight loss temperature 173°C), trimethylsulfonium salt of trifluoromethanesulfonic acid (1% weight loss temperature 255°C, 5% weight loss temperature 278°C), and dimethylphenylsulfonium salt of trifluoromethanesulfonic acid (1% weight loss temperature 186°C) are preferred. Preferred salts include diphenylmethylsulfonium salt of trifluoromethanesulfonic acid (1% weight loss temperature 154°C, 5% weight loss temperature 179°C), di(t-butylphenyl)iodonium salt of nonafluorobutanesulfonic acid, diphenyliodonium salt of camphorsulfonic acid, diphenyliodonium salt of ethanesulfonic acid, dimethylphenylsulfonium salt of benzenesulfonic acid, and diphenylmethylsulfonium salt of toluenesulfonic acid.

[0068] In addition, examples of the imidosulfonate include phthalimidotosulfonate and naphthoylimidotosulfonate, with naphthoylimidotosulfonate being preferred. Specific examples of naphthoylimidotosulfonate include, for example, 1,8-naphthoylimidotrifluoromethylsulfonate (1% weight loss temperature 189 °C, 5% weight loss temperature 227 °C), 2,3-naphthoylimidotrifluoromethylsulfonate (1% weight loss temperature 185 °C, 5% weight loss temperature 216 °C), etc., which can be mentioned as preferred ones.

[0069] In addition, as the above component (f) (thermal acid generator), as shown in the following chemical formula (13), R 19 R 20 C=N-O-SO2-R 21 A compound having the structure (1% weight loss temperature 204 °C, 5% weight loss temperature 235 °C) can also be used. Here, R 21 Examples of R include aryl groups such as p-methylphenyl group and phenyl group, alkyl groups such as methyl group, ethyl group, and isopropyl group, perfluoroalkyl groups such as trifluoromethyl group and nonafluorobutyl group, etc. Also, R 19 Examples of R include cyano group, and examples of R 20 include, for example, methoxyphenyl group and phenyl group, etc.

[0070]

Chemical formula

[0071] In addition, as the above component (f) (thermal acid generator), as shown in the following chemical formula (14), a compound having an amide structure -HN-SO2-R 22 can also be used. Here, R 22 Examples of R include alkyl groups such as methyl group, ethyl group, and propyl group, aryl groups such as methylphenyl group and phenyl group, perfluoroalkyl groups such as trifluoromethyl group and nonafluorobutyl, etc. Also, -HN-SO2-R 22Examples of groups to which it can bond include 2,2,-bis(4-hydroxyphenyl)hexafluoropropane, 2,2,-bis(4-hydroxyphenyl)propane, and di(4-hydroxyphenyl) ether.

[0072] [ka]

[0073] Furthermore, as component (f) (thermal acid generator) used in this disclosure, a salt formed from a strong acid other than an onium salt and a base may also be used. Preferred strong acids include, for example, aryl sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, perfluoroalkyl sulfonic acids such as camphorsulfonic acid, trifluoromethanesulfonic acid and nonafluorobutanesulfonic acid, and alkyl sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid. Preferred bases include, for example, pyridine, alkylpyridines such as 2,4,6-trimethylpyridine, N-alkylpyridines such as 2-chloro-N-methylpyridine, and halogenated-N-alkylpyridines. More specifically, pyridine salts of p-toluenesulfonic acid (1% weight loss temperature 147°C, 5% weight loss temperature 190°C), dibenzyl L-aspartate salts of p-toluenesulfonic acid (1% weight loss temperature 202°C, 5% weight loss temperature 218°C), 2,4,6-trimethylpyridine salt of p-toluenesulfonic acid, and 1,4-dimethylpyridine salt of p-toluenesulfonic acid are preferred in terms of storage stability and developability. These can also decompose in the cyclization dehydration reaction of polybenzoxazole precursors at temperatures below 280°C and act as catalysts.

[0074] The amount of component (f) (thermal acid generator) is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass, and even more preferably 0.5 to 10 parts by mass, per 100 parts by mass of component (a) (base resin).

[0075] (Other ingredients) In addition to the above components (a) to (f), the first insulating film forming material may also contain other conventionally known components such as (1) a dissolution accelerator, (2) a dissolution inhibitor, (3) an adhesion promoter, and (4) a surfactant or leveling agent.

[0076] [Second insulating film forming material] The second insulating film forming material includes (A) a polyimide precursor as a thermosetting polyamide having phenolic hydroxyl groups in its molecule. The polyimide precursor may have polymerizable unsaturated bonding sites. The second insulating film forming material may also include a polybenzoxazole precursor having phenolic hydroxyl groups in its molecule, or a polyimide precursor not having phenolic hydroxyl groups in its molecule. When the second insulating film forming material contains at least one of a polybenzoxazole precursor having phenolic hydroxyl groups in its molecule and a polyimide precursor not having phenolic hydroxyl groups in its molecule, the proportion of the polyimide precursor having phenolic hydroxyl groups in its molecule to the total of the polyimide precursor having phenolic hydroxyl groups in its molecule, the polyimide precursor having phenolic hydroxyl groups in its molecule and the polyimide precursor not having phenolic hydroxyl groups in its molecule is preferably 50% by mass or more and less than 100% by mass, more preferably 60% by mass to 90% by mass, and even more preferably 65% ​​by mass to 80% by mass. Furthermore, the second insulating film forming material does not necessarily have to contain a polybenzoxazole precursor having a phenolic hydroxyl group in its molecule, nor does it necessarily have to contain a polyimide precursor that does not have a phenolic hydroxyl group in its molecule.

[0077] (A) The polyimide precursor is preferably at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide. Polyamic acid esters and polyamic acid amides are compounds in which at least some of the hydrogen atoms of the carboxyl groups in polyamic acid are replaced with monovalent organic groups, and polyamic acid salts are compounds in which at least some of the carboxyl groups in polyamic acid form a salt structure with a basic compound with a pH of 7 or higher.

[0078] (A) The polyimide precursor preferably contains a compound having a structural unit represented by the following general formula (1). This tends to result in a semiconductor device with an insulating film that exhibits high reliability.

[0079] [ka]

[0080] In general formula (1), X represents a tetravalent organic group and Y represents a divalent organic group. 6 and R 7 Each of these independently represents a hydrogen atom or a monovalent organic group, and R 6 and R 7 At least one of them may have a polymerizable unsaturated bond. The polyimide precursor may have multiple structural units represented by the above general formula (1), and X, Y, R in the multiple structural units 6 and R 7 These may be the same or different. Note, R 6 and R 7 The combination of each is not particularly limited, as long as they are independently hydrogen atoms or monovalent organic groups. For example, R 6 and R 7 At least one of them may be a hydrogen atom, and the rest may be monovalent organic groups as described later, and they may all be the same or different monovalent organic groups, and both may be hydrogen atoms. As mentioned above, when the polyimide precursor has multiple structural units represented by the above general formula (1), the R of each structural unit 6 and R 7 The combinations may be the same or different.

[0081] In general formula (1), the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 5 to 13, and even more preferably 6 to 12 carbon atoms. The tetravalent organic group represented by X may include an aromatic ring from the viewpoint of heat resistance. Examples of aromatic rings include aromatic hydrocarbon groups (for example, aromatic rings with 6 to 20 carbon atoms) and aromatic heterocyclic groups (for example, heterocyclic rings with 5 to 20 atoms). The tetravalent organic group represented by X is preferably an aromatic hydrocarbon group. Examples of aromatic hydrocarbon groups include benzene rings, naphthalene rings, and phenanthrene rings. When the tetravalent organic group represented by X contains an aromatic ring, each aromatic ring may have a substituent or be unsubstituted. Examples of substituents on the aromatic ring include alkyl groups, fluorine atoms, alkyl halides, hydroxyl groups, amino groups, and the like. When the tetravalent organic group represented by X contains a benzene ring, it is preferable that the tetravalent organic group represented by X contains one to four benzene rings, more preferably one to three benzene rings, and even more preferably one or two benzene rings. When the tetravalent organic group represented by X contains two or more benzene rings, each benzene ring may be linked by a single bond, or by an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), or a silylene bond (-Si(R)). A )2-; Two R A Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), Siloxane bond (-O-(Si(R B )2-O-) n ; Two R's B Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more. The rings may be linked by linking groups such as , or by a composite linking group formed by combining at least two of these linking groups. Alternatively, two benzene rings may be linked at two locations by a single bond and at least one of a linking group, forming a five-membered or six-membered ring containing a linking group between the two benzene rings.

[0082] In general formula (1), -COOR 6 The group and the -CONH- group are preferably in the ortho position relative to each other, and -COOR 7It is preferable that the group and the -CO- group are in the ortho position relative to each other.

[0083] Specific examples of the tetravalent organic group represented by X include the groups represented by formulas (A) to (F) below. Among these, the group represented by formula (E) below is preferred from the viewpoint of obtaining an insulating film with excellent flexibility and suppression of void generation at the bonding interface, and more preferably C is a group containing an ether bond, and even more preferably an ether bond. This disclosure is not limited to the specific examples listed below.

[0084] [ka]

[0085] In formula (D), A and B are independently single bonds or divalent groups not conjugated to a benzene ring. However, both A and B cannot be single bonds. Examples of divalent groups not conjugated to a benzene ring include methylene groups, halide methylene groups, halide methylmethylene groups, carbonyl groups, sulfonyl groups, ether bonds (-O-), sulfide bonds (-S-), and silylene bonds (-Si(R)). A )2-; Two R A Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group.) are some examples. Among these, A and B are preferably a methylene group, a bis(trifluoromethyl)methylene group, a difluoromethylene group, an ether bond, a sulfide bond, etc., and an ether bond is more preferred.

[0086] In formula (E), C is an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-OC(=O)-), or a silylene bond (-Si(R) A )2-; Two R A Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), Siloxane bond (-O-(Si(R B )2-O-) n; Two R's B Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more. ) or a divalent group formed by combining at least two of these. C preferably contains an ether bond, and more preferably is an ether bond. Furthermore, C may have a structure represented by the following formula (C1).

[0087] [ka]

[0088] The alkylene group represented by C in formula (E) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms. Specific examples of alkylene groups represented by C in formula (E) include linear alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group; methylmethylene group, methylethylene group, ethylmethylene group, dimethylmethylene group, 1,1-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, ethylethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, and 1,1-dimethyl Examples include branched alkylene groups such as methylene group, 1,2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 2,3-dimethyltetramethylene group, and 1,4-dimethyltetramethylene group. Among these, methylene groups are preferred.

[0089] The halogenated alkylene group represented by C in formula (E) is preferably a halogenated alkylene group having 1 to 10 carbon atoms, more preferably a halogenated alkylene group having 1 to 5 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 3 carbon atoms. Specific examples of the halogenated alkylene group represented by C in formula (E) include alkylene groups in which at least one hydrogen atom in the alkylene group represented by C in formula (E) above is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethylene groups, difluoromethylene groups, and hexafluorodimethylmethylene groups are preferred.

[0090] R included in the above silylene bond or siloxane bond A or R B The alkyl group represented is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. A or R B Specific examples of alkyl groups represented by include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, and the like.

[0091] Specific examples of the tetravalent organic group represented by X may be the groups represented by the following formulas (J) to (O).

[0092] [ka]

[0093] The tetravalent organic group represented by X may include an alicyclic ring from the viewpoint of adjusting the coefficient of thermal expansion when the cured product is formed. When the tetravalent organic group represented by X includes an alicyclic ring, examples include ring structures that do not contain unsaturated bonds, such as cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, cyclooctane rings, decahydronaphthalene rings, norbornane rings, adamantane rings, and bicyclo[2.2.2]octane rings, and ring structures that contain unsaturated bonds, such as cyclohexene rings. Spirocyclic structures that include these ring structures are also examples. The alicyclic ring may have substituents such as oxo groups (=O), alkyl groups, fluorine atoms, alkyl halides, hydroxyl groups, and amino groups, or it may be unsubstituted. A specific example of a case where the tetravalent organic group represented by X has a spiro ring structure is shown in the following formula (P).

[0094] [ka]

[0095] In general formula (1), the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20, and even more preferably 12 to 18 carbon atoms. The skeleton of the divalent organic group represented by Y may be the same as the skeleton of the tetravalent organic group represented by X, and the preferred skeleton of the divalent organic group represented by Y may be the same as the preferred skeleton of the tetravalent organic group represented by X. The skeleton of the divalent organic group represented by Y may be a structure in which two bond positions of the tetravalent organic group represented by X are substituted with atoms (e.g., hydrogen atoms) or functional groups (e.g., alkyl groups). The divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, it is preferable that the divalent organic group represented by Y is a divalent aromatic group. Examples of divalent aromatic groups include divalent aromatic hydrocarbon groups (for example, groups with 6 to 20 carbon atoms constituting the aromatic ring) and divalent aromatic heterocyclic groups (for example, groups with 5 to 20 atoms constituting the heterocycle), with divalent aromatic hydrocarbon groups being preferred.

[0096] Specific examples of divalent aromatic groups represented by Y include the groups represented by the following formulas (G) to (H). Among these, the group represented by the following formula (H) is preferred from the viewpoint of obtaining an insulating film with excellent flexibility and suppression of void generation at the bonding interface, and more preferably the group represented by the following formula (H) in which D contains a single bond or an ether bond, and even more preferably a single bond or an ether bond.

[0097] [ka]

[0098] In formulas (G) to (H), R independently represents an alkyl group, an alkoxy group, a hydroxyl group, an alkyl halide, a phenyl group, or a halogen atom, and n independently represents an integer from 0 to 4. In formula (H), D is a single bond, alkylene group, halogenated alkylene group, carbonyl group, sulfonyl group, ether bond (-O-), sulfide bond (-S-), phenylene group, ester bond (-OC(=O)-), silylene bond (-Si(R) A )2-; Two R A Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), Siloxane bond (-O-(Si(R B )2-O-) n ; Two R's B Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or more. ) or a divalent group formed by combining at least two of these. Furthermore, D may be the structure represented by formula (C1) above. Specific examples of D in formula (H) are a single bond or the same as the specific examples of C in formula (E). In formula (H), D is preferably a single bond, an ether bond, a group containing an ether bond and a phenylene group, or a group containing an ether bond, a phenylene group, and an alkylene group, each independently.

[0099] The alkyl group represented by R in formulas (G) to (H) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. Specific examples of alkyl groups represented by R in formulas (G) to (H) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl groups.

[0100] The alkoxy group represented by R in formulas (G) to (H) is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably an alkoxy group having 1 or 2 carbon atoms. Specific examples of the alkoxy group represented by R in formulas (G) to (H) include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, and t-butoxy groups.

[0101] The halogenated alkyl group represented by R in formulas (G) to (H) is preferably a halogenated alkyl group having 1 to 5 carbon atoms, more preferably a halogenated alkyl group having 1 to 3 carbon atoms, and even more preferably a halogenated alkyl group having 1 or 2 carbon atoms. Specific examples of the halogenated alkyl group represented by R in formulas (G) to (H) include alkyl groups in which at least one hydrogen atom in the alkyl group represented by R in formulas (G) to (H) is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethyl groups, difluoromethyl groups, and trifluoromethyl groups are preferred.

[0102] In equations (G) to (H), n is independently preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0103] Specific examples of divalent aliphatic groups represented by Y include linear or branched alkylene groups, cycloalkylene groups, and divalent groups having a polyalkylene oxide structure.

[0104] The linear or branched alkylene group represented by Y is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms. Specific examples of alkylene groups represented by Y include tetramethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, 2-methylpentamethylene, 2-methylhexamethylene, 2-methylheptamethylene, 2-methyloctamethylene, 2-methylnonamethylene, and 2-methyldecamethylene.

[0105] The cycloalkylene group represented by Y is preferably a cycloalkylene group having 3 to 10 carbon atoms, and more preferably a cycloalkylene group having 3 to 6 carbon atoms. Specific examples of cycloalkylene groups represented by Y include cyclopropylene and cyclohexylene.

[0106] The unit structure contained in the divalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, and even more preferably an alkylene oxide structure having 1 to 4 carbon atoms. Among these, polyethylene oxide structure or polypropylene oxide structure is preferred as the polyalkylene oxide structure. The alkylene group in the alkylene oxide structure may be linear or branched. The unit structure in the polyalkylene oxide structure may be one type or two or more types.

[0107] The divalent organic group represented by Y may be a divalent group having a polysiloxane structure. Examples of a divalent group having a polysiloxane structure represented by Y include a divalent group having a polysiloxane structure in which the silicon atom in the polysiloxane structure is bonded to a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Specific examples of C1-C20 alkyl groups that bond to silicon atoms in the polysiloxane structure include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-octyl, 2-ethylhexyl, and n-dodecyl groups. Among these, the methyl group is preferred. The aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent. Specific examples of substituents on the aryl group include halogen atoms, alkoxy groups, and hydroxyl groups. Specific examples of aryl groups having 6 to 18 carbon atoms include phenyl groups, naphthyl groups, and benzyl groups. Among these, the phenyl group is preferred. The alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be one type or two or more types. The silicon atoms constituting the divalent group having a polysiloxane structure represented by Y may be bonded to the NH group in general formula (1) via an alkylene group such as a methylene group or an ethylene group, or an arylene group such as a phenylene group, etc.

[0108] The group represented by formula (G) is preferably the group represented by the following formula (G'), and the group represented by formula (H) is preferably the group represented by the following formula (H'), formula (H''), or formula (H''').

[0109] [ka]

[0110] In formula (H'''), R independently represents an alkyl group, an alkoxy group, an alkyl halide, a phenyl group, a hydroxyl group, or a halogen atom. R is preferably an alkyl group, and more preferably a methyl group.

[0111] The combination of the tetravalent organic group represented by X and the divalent organic group represented by Y in general formula (1) is not particularly limited. Examples of such combinations include a combination where X is the group represented by formula (E) and Y is the group represented by formula (H).

[0112] R 6 and R 7 Each of these independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an organic group having an unsaturated double bond, more preferably one of the groups represented by the following general formula (2), an ethyl group, an isobutyl group, or a t-butyl group, and even more preferably contains an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2). When the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), the transmittance of i-rays is high, and good cured products tend to be formed even when curing at low temperatures of 400°C or below. Furthermore, when the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), at least a portion of the unsaturated double bond portion is removed by the (C) compound.

[0113] Specific examples of aliphatic hydrocarbon groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl groups, with ethyl, isobutyl, and t-butyl groups being preferred.

[0114] [ka]

[0115] In general formula (2), R 8 ~R10 Each of these independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R x This represents a divalent linking group.

[0116] R in general formula (2) 8 ~R 10 The aliphatic hydrocarbon group represented by has 1 to 3 carbon atoms, preferably 1 or 2. 8 ~R 10 Specific examples of the aliphatic hydrocarbon group represented by include the methyl group, ethyl group, n-propyl group, isopropyl group, etc., with the methyl group being preferred.

[0117] R in general formula (2) 8 ~R 10 As for combinations, R 8 and R 9 is a hydrogen atom, and R 10 A combination of hydrogen atoms or methyl groups is preferred.

[0118] R in general formula (2) x The linking group is a divalent linking group, preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of hydrocarbon groups having 1 to 10 carbon atoms include linear or branched alkylene groups. R x The number of carbon atoms in the compound is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.

[0119] In general formula (1), R 6 and R 7 At least one of them may be a group represented by the general formula (2), R 6 and R 7 Both of the groups may be represented by the general formula (2).

[0120] (A) If the polyimide precursor contains a compound having a structural unit represented by the general formula (1) above, the R of all structural units contained in the compound 6 and R 7 The group R, represented by the general formula (2) for the sum of6 and R 7 The proportion is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more. There is no particular upper limit, and it may be 100 mol%. Furthermore, the aforementioned percentage may be between 0 mol% and less than 60 mol%.

[0121] The group represented by general formula (2) is preferably the group represented by the following general formula (2').

[0122] [ka]

[0123] In general formula (2'), R 8 ~R 10 Each of these independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and q represents an integer from 1 to 10.

[0124] In general formula (2'), q is an integer between 1 and 10, preferably between 2 and 5, and more preferably 2 or 3.

[0125] The content of the structural unit represented by general formula (1) in a compound having the structural unit represented by general formula (1) is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more, relative to the total structural units. The upper limit of the aforementioned content is not particularly limited and may be 100 mol%.

[0126] (A) The polyimide precursor may be synthesized using a tetracarboxylic dianhydride and a diamine compound. In this case, in general formula (1), X corresponds to a residue derived from the tetracarboxylic dianhydride, and Y corresponds to a residue derived from the diamine compound. Note that (A) the polyimide precursor may also be synthesized using a tetracarboxylic acid instead of a tetracarboxylic dianhydride.

[0127] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, and 2,3,5,6-pyridinetetracarboxylic dianhydride. Carboxylic acid dianhydrides, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3- Xafluoro-2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3, Examples include 3,3-hexafluoro-2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4'-oxydiphthalic acid dianhydride, 4,4'-sulfonyldiphthalic acid dianhydride, and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride. Tetracarboxylic acid dianhydrides may be used individually or in combination of two or more types.

[0128] Specific examples of diamine compounds include 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, and 2 ,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,4'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 2,4'-diaminodiphenyl sulfide, 2,2'-diaminodiphenyl sulfide, o-tolidine, o-tolidine sulfone, 4,4'-methylenebis(2,6- Diethylaniline), 4,4'-methylenebis(2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenonediamine, bis-{4-(4'-aminophenoxy)phenyl}sulfone, 2,2-bis{4-(4'-aminophenoxy)phenyl}propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis{4-(3'-aminophenoxy)phenyl}sulfone, 2,2-bis(4-A Minophenyl)propane, 9,9-bis(4-aminophenyl)fluorene, 1,3-bis(3-aminophenoxy)benzene, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2-methyl-1,Examples include 9-diaminononane, 2-methyl-1,10-diaminodecane, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and diaminopolysiloxane. Preferred diamine compounds include 2,2'-dimethylbiphenyl-4,4'-diamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, and 1,3-bis(3-aminophenoxy)benzene. Diamine compounds may be used individually or in combination of two or more.

[0129] It has a structural unit represented by general formula (1), and R in general formula (1) 6 and R 7 A compound in which at least one of the groups is a monovalent organic group can be obtained, for example, by the following method (a) or (b). (a) A tetracarboxylic dianhydride (preferably a tetracarboxylic dianhydride represented by the following general formula (8)) is reacted with a compound represented by R-OH in an organic solvent to form a diester derivative, and then the diester derivative is subjected to a condensation reaction with a diamine compound represented by H2N-Y-NH2. (b) A tetracarboxylic dianhydride is reacted with a diamine compound represented by H2N-Y-NH2 in an organic solvent to obtain a polyamic acid solution, and a compound represented by R-OH is added to the polyamic acid solution and reacted in an organic solvent to introduce an ester group. Here, Y in the diamine compound represented by H2N-Y-NH2 is the same as Y in general formula (1), and the specific examples and preferred examples are also the same. Also, R in the compound represented by R-OH represents a monovalent organic group, and the specific examples and preferred examples are the same as R in general formula (1). 6 and R 7 This is the same as in the previous case. The tetracarboxylic dianhydride represented by general formula (8), the diamine compound represented by H2N-Y-NH2, and the compound represented by R-OH may each be used individually or in combination of two or more. Examples of the aforementioned organic solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, dimethoxyimidazolidinone, and 3-methoxy-N,N-dimethylpropionamide, among which 3-methoxy-N,N-dimethylpropionamide is preferred. A polyimide precursor may be synthesized by reacting a dehydrating condensation agent with a compound represented by R-OH in a polyamic acid solution. The dehydrating condensation agent preferably contains at least one selected from the group consisting of trifluoroacetic anhydride, N,N'-dicyclohexylcarbodiimide (DCC), and 1,3-diisopropylcarbodiimide (DIC).

[0130] (A) The aforementioned compounds contained in the polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, then reacting it with a chlorinating agent such as thionyl chloride to convert it to an acid chloride, and then reacting the acid chloride with a diamine compound represented by H2N-Y-NH2. (A) The aforementioned compounds contained in the polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, and then reacting the diester derivative with a diamine compound represented by H2N-Y-NH2 in the presence of a carbodiimide compound. (A) The aforementioned compounds contained in the polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a diamine compound represented by H2N-Y-NH2 to form a polyamic acid, then isoimidizing the polyamic acid in the presence of a dehydrating condensation agent such as trifluoroacetic anhydride, and then reacting it with a compound represented by R-OH. Alternatively, a portion of the tetracarboxylic dianhydride may be reacted with a compound represented by R-OH beforehand, and the partially esterified tetracarboxylic dianhydride may be reacted with a diamine compound represented by H2N-Y-NH2.

[0131] [ka]

[0132] In general formula (8), X is the same as X in general formula (1), and the specific examples and preferred examples are also the same.

[0133] (A) The compound represented by R-OH used in the synthesis of the aforementioned compound contained in the polyimide precursor is the R group represented by general formula (2). x The compound may be one in which a hydroxyl group is bonded to the group, or one in which a hydroxyl group is bonded to the terminal methylene group of the group represented by general formula (2'). Specific examples of compounds represented by R-OH include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate, among which 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are preferred.

[0134] (A) There are no particular restrictions on the molecular weight of the polyimide precursor, but for example, it is preferably 10,000 to 200,000 in weight-average molecular weight, and more preferably 10,000 to 100,000. (A) The weight-average molecular weight of the polyimide precursor can be determined by the same method as for (a) the polybenzoxazole precursor.

[0135] The second insulating film forming material may further contain a dicarboxylic acid, and the (A) polyimide precursor contained in the second insulating film forming material may have a structure in which some of the amino groups in the (A) polyimide precursor react with the carboxyl groups in the dicarboxylic acid. For example, when synthesizing the polyimide precursor, some of the amino groups of the diamine compound may be reacted with the carboxyl groups of the dicarboxylic acid. The dicarboxylic acid may be a dicarboxylic acid having a (meth)acrylic group, for example, a dicarboxylic acid represented by the following formula. In this case, when synthesizing the (A) polyimide precursor, a methacrylic group derived from the dicarboxylic acid can be introduced into the (A) polyimide precursor by reacting a portion of the amino group of the diamine compound with the carboxyl group of the dicarboxylic acid.

[0136] [ka]

[0137] The second insulating film forming material may contain a polyimide resin in addition to (A) the polyimide precursor. By combining the polyimide precursor and the polyimide resin, it is possible to suppress the generation of volatile substances due to dehydration cyclization during imide ring formation, and thus tend to suppress the generation of voids. The polyimide resin referred to here is a resin in which all or part of the resin skeleton has an imide skeleton. It is preferable that the polyimide resin is soluble in the solvent in the insulating film forming material using the polyimide precursor.

[0138] The polyimide resin is not particularly limited as long as it is a polymer compound having multiple structural units containing imide bonds. For example, it is preferable to include a compound having a structural unit represented by the following general formula (X). This tends to result in a semiconductor device with an insulating film that exhibits high reliability.

[0139] [ka]

[0140] In general formula (X), X represents a tetravalent organic group and Y represents a divalent organic group. Preferred examples of substituents X and Y in general formula (X) are the same as preferred examples of substituents X and Y in general formula (1) described above.

[0141] When the second insulating film forming material contains a polyimide resin, the ratio of the polyimide resin to the total of the polyimide precursor and the polyimide resin may be 15% to 50% by mass, or 10% to 20% by mass.

[0142] The second insulating film forming material may contain other resins besides (A) the polyimide precursor and polyimide resin. Examples of other resins, from the viewpoint of heat resistance, include the polybenzoxazole precursor, novolac resin, acrylic resin, polyethernitrile resin, polyethersulfone resin, epoxy resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyvinyl chloride resin, etc. The other resins may be used individually or in combination of two or more.

[0143] In the second insulating film forming material, the content of (A) polyimide precursor relative to the total amount of resin components is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, and even more preferably 90% to 100% by mass.

[0144] ((B) Solvent) The second insulating film forming material contains (B) solvent (hereinafter also referred to as "component (B)"). Component (B) preferably contains at least one compound selected from the group consisting of compounds represented by the following formulas (3) to (7).

[0145] [ka]

[0146] In formulas (3) to (7), R 1 , R 2 , R 8 and R 10 Each of these is an alkyl group having 1 to 4 carbon atoms, and R 3 ~R 7 and R 9Each is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. s is an integer from 0 to 8, t is an integer from 0 to 4, r is an integer from 0 to 4, and u is an integer from 0 to 3.

[0147] In formula (3), s is preferably 0. In formula (4), R 2 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. t is preferably 0, 1 or 2, and more preferably 1. In formula (5), R 3 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group, an ethyl group, a propyl group or a butyl group. R 4 and R 5 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. In formula (6), R 6 ~R 8 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. r is preferably 0 or 1, and more preferably 0. In formula (7), R 9 and R 10 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. u is preferably 0 or 1, and more preferably 0.

[0148] Component (B) may be, for example, at least one of the compounds represented by formulas (4), (5), (6) and (7), or may be the compound represented by formula (5) or the compound represented by formula (7).

[0149] Specific examples of component (B) include the following compounds.

[0150]

Chemical formula

[0151] The component (B) included in the second insulating film forming material is not limited to the aforementioned compounds, but may be other solvents. Component (B) may be an ester solvent, an ether solvent, a ketone solvent, a hydrocarbon solvent, an aromatic hydrocarbon solvent, a sulfoxide solvent, and the like.

[0152] Solvents for esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates such as methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate and ethyl ethoxyacetate), alkyl 3-alkoxypropionates such as methyl 3-alkoxypropionate and ethyl 3-alkoxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate). Examples include alkyl 2-alkoxypropionates such as ethyl toxypropionate, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, and propyl 2-alkoxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate), methyl 2-alkoxy-2-methylpropionate such as methyl 2-methoxy-2-methylpropionate, ethyl 2-alkoxy-2-methylpropionate such as ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, and ethyl 2-oxobutanoate.

[0153] Examples of ether solvents include diethylene 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, and propylene glycol monopropyl ether acetate. Examples of solvents for ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone (NMP). Examples of hydrocarbon solvents include limonene. Examples of solvents for aromatic hydrocarbons include toluene, xylene, and anisole. Examples of solvents for sulfoxides include dimethyl sulfoxide.

[0154] (B) Preferred solvents for component (B) include γ-butyrolactone, cyclopentanone, and ethyl lactate.

[0155] In the second insulating film forming material, from the viewpoint of reducing toxicity such as reproductive toxicity and reducing environmental burden, the NMP content may be 1% by mass or less relative to the total amount of the insulating film forming material, or 3% by mass or less relative to the total amount of the (A) polyimide precursor.

[0156] In the second insulating film forming material, the content of component (B) is preferably 1 to 10,000 parts by mass, and more preferably 50 to 10,000 parts by mass, per 100 parts by mass of polyimide precursor (A).

[0157] Component (B) preferably contains at least one of the following: solvent (1), which is selected from the group consisting of compounds represented by formulas (3) to (6); and solvent (2), which is selected from the group consisting of ester solvents, ether solvents, ketone solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, and sulfoxide solvents. Furthermore, the content of solvent (1) may be 5% to 100% by mass, or 5% to 50% by mass, relative to the total of solvent (1) and solvent (2). The content of solvent (1) may be 10 to 1000 parts by mass, 10 to 100 parts by mass, or 10 to 50 parts by mass per 100 parts by mass of polyimide precursor (A).

[0158] ((C) compound) The second insulating film forming material may contain compound (C). Compound (C) acts on the polymerizable unsaturated bond sites of the polyimide precursor (A) and promotes the detachment of the polymerizable unsaturated bond sites. (C) Examples of compounds include nitrogen-containing compounds. Nitrogen-containing compounds may also be thermal base generators. Thermal base generators generate bases when heated, and these bases promote the detachment of unsaturated bond sites from the (A) polyimide precursor.

[0159] Specific examples of nitrogen-containing compounds include anilinediacetic acid, 2-(methylphenylamino)ethanol, 2-(ethylanilino)ethanol, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, 4-aminobenzamide, 2-aminobenzamide, nicotinamide, 4-amino-N-methylbenzamide, 4-aminoacetanilide, 4-aminoacetophenone, diazabicycloundecene, and salts thereof. Among these, anilinediacetic acid, 4-aminobenzamide, nicotinamide, diazabicycloundecene, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, and salts thereof are preferred. Nitrogen-containing compounds may be used individually or in combination of two or more.

[0160] The nitrogen-containing compound preferably includes a compound represented by the following formula (17) or a compound represented by the following formula (18).

[0161] [ka]

[0162] In equations (17) and (18), R 31A ~R 33A Each of these is independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxyl group, or a monovalent aromatic group, R 31A ~R 33A At least one (preferably one) of these is a monovalent aromatic group. 31A ~R 33A The groups may form a ring structure with adjacent groups. Examples of the formed ring structure include five-membered rings, six-membered rings, etc., which may have substituents such as methyl groups and phenyl groups. The hydrogen atoms of the monovalent aliphatic hydrocarbon group may be substituted with functional groups other than hydroxyl groups.

[0163] In equations (17) and (18), R 31A ~R 33A It is preferable that at least one (preferably one) of these is a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxyl group, or a monovalent aromatic group.

[0164] In equations (17) and (18), R 31A ~R 33A The monovalent aliphatic hydrocarbon group has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. The monovalent aliphatic hydrocarbon group is preferably a methyl group, an ethyl group, etc.

[0165] In equations (17) and (18), R 31A ~R 33A A monovalent aliphatic hydrocarbon group having a hydroxyl group is R 31A ~R 33A Preferably, the group is a monovalent aliphatic hydrocarbon group to which one or more hydroxyl groups are bonded, and more preferably, a group to which one to three hydroxyl groups are bonded. Specific examples of monovalent aliphatic hydrocarbon groups having hydroxyl groups include methylol group and hydroxyethyl group, with the hydroxyethyl group being preferred.

[0166] R in equations (17) and (18) 31A ~R 33A Examples of monovalent aromatic groups include monovalent aromatic hydrocarbon groups and monovalent aromatic heterocyclic groups, with monovalent aromatic hydrocarbon groups being preferred. For monovalent aromatic hydrocarbon groups, those with 6 to 12 carbon atoms are preferred, and those with 6 to 10 carbon atoms are more preferred. Examples of monovalent aromatic hydrocarbon groups include phenyl groups and naphthyl groups.

[0167] R in equations (17) and (18) 31A ~R 33A The monovalent aromatic group may have substituents. Substituents include R of formulas (17) and (18). 31A ~R 33AThe monovalent aliphatic hydrocarbon group, and the R of formulas (17) and (18) described above. 31A ~R 33A Examples include monovalent aliphatic hydrocarbon groups having a hydroxyl group.

[0168] (C) The content of compound is preferably 0.1 to 20 parts by mass per 100 parts by mass of polyimide precursor (A), more preferably 0.3 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, from the viewpoint of storage stability.

[0169] The second insulating film forming material comprises (A) a polyimide precursor and (B) a solvent, and optionally includes (C) a compound, (D) a photopolymerization initiator, (E) a polymerizable monomer, (F) a thermal polymerization initiator, (G) a polymerization inhibitor, an antioxidant, a coupling agent, a surfactant, a leveling agent, a rust inhibitor, etc., and may also include other components and unavoidable impurities to the extent that they do not impair the effects of the present disclosure. Preferably, the second insulating film forming material further comprises components (D) and (E). Hereinafter, (C) compound will also be referred to as component (C), (D) photopolymerization initiator as component (D), (E) polymerizable monomer as component (E), (F) thermal polymerization initiator as component (F), and (G) polymerization inhibitor as component (G).

[0170] For example, the second insulating film forming material has an amount of 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass. (A) Polyimide precursor ~ (B) Component, (A) Polyimide precursor ~ (C) Component, (A) Polyimide precursor ~ (E) Component, (A) Polyimide precursor ~ (F) Component, (A) Polyimide precursor ~ (G) Component, (A) Polyimide precursors ~ (G) Components and at least one selected from the group consisting of antioxidants, coupling agents, surfactants, leveling agents, and rust inhibitors. It may consist of [something]. The preferred forms of each component are described below.

[0171] ((D) Photopolymerization initiator) The second insulating film forming material preferably contains (D) a photopolymerization initiator. This reduces the number of steps required to fabricate electrodes in the semiconductor device manufacturing process, thereby reducing the overall cost of the semiconductor device manufacturing process.

[0172] (D)Specific examples of components include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, 4,4'-bis(diethylamino)benzophenone, o-methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibe Benzophenone derivatives such as benzoyl ketone and fluorenone; acetophenone derivatives such as acetophenone, 2,2-diethoxyacetophenone, 3'-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, and diethylthioxanthone; benzyl, benzyl Benzyl derivatives such as zyldimethyl ketal and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, and propyl benzoin; 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O- Oxime derivatives such as toxycarbonyl oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime); N-arylglycines such as N-phenylglycine; peroxides such as benzoyl perchloride;Aromatic biimidazoles such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazole dimer; acylphosphine oxide derivatives such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, Irgacure OXE03 (manufactured by BASF), Irgacure OXE04 (manufactured by BASF), etc. The component (D) may be used alone or in combination of two or more. Among these, an oxime compound derivative is preferable from the viewpoints of not containing a metal element and having high reactivity and high sensitivity.

[0173] When the second insulating film forming material contains the component (D), the content of the component (D) is preferably 0.1 part by mass to 20 parts by mass, more preferably 1 part by mass to 15 parts by mass, and still more preferably 5 parts by mass to 15 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor from the viewpoint that photocrosslinking is likely to be uniform in the film thickness direction.

[0174] The second insulating film forming material may contain an antireflection agent that suppresses reflected light from the substrate direction from the viewpoint of improving photosensitivity.

[0175] ((E) Polymerizable monomer (crosslinking agent)) The second insulating film forming material preferably contains an (E) polymerizable monomer. The component (E) preferably has at least one group containing a polymerizable unsaturated double bond, and more preferably has at least one (meth)acrylic group from the viewpoint of being preferably polymerizable by combination with a photoinitiator. From the viewpoints of improving crosslinking density and photosensitivity, it is preferable to have 2 to 6 groups containing a polymerizable unsaturated double bond, and more preferably 2 to 4 groups. The polymerizable monomer may be used alone or in combination of two or more.

[0176] Polymerizable monomers having a (meth)acrylic group are not particularly limited, and include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetra Examples include acrylates, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isocyanurate triacrylate, ethoxylated isocyanurate trimethacrylate, acryloyloxyethyl isocyanurate, methacryloyloxyethyl isocyanurate, tricyclodecanedimethanol diacrylate, 2-hydroxyethyl (meth)acrylate, 1,3-bis((meth)acryloyloxy)-2-hydroxypropane, ethylene oxide (EO)-modified bisphenol A diacrylate, and ethylene oxide (EO)-modified bisphenol A dimethacrylate.

[0177] Polymerizable monomers other than those having a (meth)acrylic group are not particularly limited, and include, for example, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, methylenebisacrylamide, N,N-dimethylacrylamide, and N-methylolacrylamide.

[0178] Component (E) is not limited to compounds having a polymerizable unsaturated double bond group, but may also be a compound having a polymerizable group other than an unsaturated double bond group (for example, an oxirane ring).

[0179] If the second insulating film forming material contains component (E), the content of component (E) is not particularly limited, but is preferably 1 to 100 parts by mass, more preferably 1 to 75 parts by mass, and even more preferably 1 to 50 parts by mass, per 100 parts by mass of polyimide precursor (A).

[0180] ((F) Thermal polymerization initiator) The second insulating film forming material preferably contains (F) a thermal polymerization initiator, from the viewpoint of improving the physical properties of the cured product.

[0181] (F)Specific examples of component include ketone peroxides such as methyl ethyl ketone peroxide, peroxyketals such as 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, and 1,1-di(t-butylperoxy)cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, and diisopropylbenzene hydroperoxide, and dialdehydes such as dicumyl peroxide and di-t-butyl peroxide. Examples include diacyl peroxides such as quill peroxide, dilauroyl peroxide, and dibenzoyl peroxide; peroxydicarbonates such as di(4-t-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate; peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate; and bis(1-phenyl-1-methylethyl)peroxide. The thermal polymerization initiator may be used alone or in combination of two or more.

[0182] If the second insulating film forming material contains component (F), the content of component (F) may be 0.1 to 20 parts by mass, 1 to 15 parts by mass, or 1 to 10 parts by mass per 100 parts by mass of the polyimide precursor.

[0183] ((G) Polymerization inhibitors) The second insulating film forming material may contain component (G) from the viewpoint of ensuring good storage stability. Examples of polymerization inhibitors include radical polymerization inhibitors and radical polymerization suppressants.

[0184] Specific examples of component (G) include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthaquinone, N-phenyl-2-naphthylamine, cuperone, 2,5-tholquinone, tannic acid, parabenzylaminophenol, nitrosamines, hindered phenol compounds, etc. Polymerization inhibitors may be used alone or in combination of two or more. Combining two or more polymerization inhibitors tends to make it easier to adjust the photosensitive properties due to differences in reactivity. Hindered phenol compounds may have both the function of a polymerization inhibitor and the function of an antioxidant described later, or they may have only one of the functions.

[0185] The hindered phenol compounds are not particularly limited, and include, for example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t- [Butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1, 3,5-Tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-s-butyl-3 -Hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-Dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3, 5-Tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1, 3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl- Examples include 3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and N,N'-hexane-1,6-diyrbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide]. Among these, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] is preferred.

[0186] If the second insulating film forming material contains component (G), the content of component (G) is preferably 0.01 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the (A) polyimide precursor, from the viewpoint of storage stability of the insulating film forming material and heat resistance of the resulting cured product.

[0187] The second insulating film forming material may further include an antioxidant, a coupling agent, a surfactant, a leveling agent, or a rust inhibitor.

[0188] (Antioxidant) The second insulating film forming material may contain an antioxidant, from the viewpoint of suppressing a decrease in adhesion by capturing oxygen radicals and peroxide radicals generated during high-temperature storage, reflow processing, etc. The inclusion of an antioxidant in the second insulating film forming material can suppress oxidation of the electrodes during insulation reliability testing.

[0189] Specific examples of antioxidants include the compounds exemplified above as hindered phenol compounds, N,N'-bis[2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl]oxamide, N,N'-bis-3-(3,5-di-tert-butyl-4'-hydroxyphenyl)propionylhexamethylenediamine, 1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid. Antioxidants may be used individually or in combination of two or more types.

[0190] If the second insulating film forming material contains an antioxidant, the antioxidant content is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the polyimide precursor (A).

[0191] (Coupling agent) The second insulating film forming material may contain a coupling agent. During heat treatment, the coupling agent reacts with (A) the polyimide precursor to crosslink, or the coupling agent itself polymerizes. This tends to improve the adhesion between the resulting cured product and the substrate.

[0192] Specific examples of coupling agents are not particularly limited. Examples of coupling agents include 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamidoic acid, and benzophenone-3,3'-bis(N-[3-triethoxy Examples include silane coupling agents such as sisilyl)propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, N,N'-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane; and aluminum-based adhesive aids such as aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate. The coupling agent may be used alone or in combination of two or more types.

[0193] When the second insulating film forming material contains a coupling agent, the content of the coupling agent is preferably 0.1 part by mass to 20 parts by mass, more preferably 0.3 part by mass to 10 parts by mass, and still more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the polyimide precursor (A).

[0194] (Surfactant and leveling agent) The second insulating film forming material may contain at least one of a surfactant and a leveling agent. By including at least one of a surfactant and a leveling agent in the insulating film forming material, the coating property (for example, suppression of striation (non-uniformity of film thickness)), improvement of adhesion, and compatibility of compounds in the insulating film forming material can be improved.

[0195] Examples of the surfactant or the leveling agent include polyoxyethylene urethyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like.

[0196] The surfactant and the leveling agent may be used alone or in combination of two or more.

[0197] When the second insulating film forming material contains at least one of a surfactant and a leveling agent, the total content of the surfactant and the leveling agent is preferably 0.01 part by mass to 10 parts by mass, more preferably 0.05 part by mass to 5 parts by mass, and still more preferably 0.05 part by mass to 3 parts by mass with respect to 100 parts by mass of the polyimide precursor (A).

[0198] (Rust preventive agent) The second insulating film forming material may contain a rust preventive agent from the viewpoints of suppressing corrosion of metals such as copper and copper alloys and suppressing discoloration of the metals. Examples of the rust preventive agent include azole compounds and purine derivatives.

[0199] Specific examples of azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, and 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benz Examples include zotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazol, 5-methyl-1H-tetrazol, 5-phenyl-1H-tetrazol, 5-amino-1H-tetrazol, and 1-methyl-1H-tetrazol.

[0200] Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, and 8-amino Examples include adenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, and their derivatives.

[0201] Rust inhibitors may be used individually or in combination of two or more types.

[0202] If the second insulating film forming material contains a rust inhibitor, the amount of rust inhibitor is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of (A) polyimide precursor. In particular, when the amount of rust inhibitor is 0.1 parts by mass or more, discoloration of the surface of copper or copper alloy is suppressed when the second insulating film forming material is applied to the surface of copper or copper alloy.

[0203] (Properties of insulating film forming materials) From the viewpoint of bonding at low temperatures, the insulating film forming material of this disclosure preferably has a glass transition temperature of 100°C to 400°C when cured, and more preferably 150°C to 350°C.

[0204] The glass transition temperature of the cured material is measured as follows. First, the insulating film forming material is heated in a nitrogen atmosphere for 2 hours at a predetermined curing temperature (e.g., 150°C to 375°C) at which the curing reaction can occur to obtain a cured material. The obtained cured material is cut to create a rectangular parallelepiped measuring 5 mm × 50 mm × 3 mm, and the dynamic viscoelasticity is measured using a dynamic viscoelasticity measuring device (e.g., RSA-G2, manufactured by TA Instruments) with a tensile jig, under the conditions of frequency: 1 Hz and heating rate: 5°C / min, in the temperature range of 50°C to 350°C. The glass transition temperature (Tg) is defined as the temperature of the peak top portion of tanδ, which is obtained from the ratio of storage modulus to loss modulus obtained by the above method.

[0205] The insulating film forming material of this disclosure may be a negative-type photosensitive insulating film forming material or a positive-type photosensitive insulating film forming material. Furthermore, the negative-type photosensitive insulating film forming material or the positive-type photosensitive insulating film forming material may be used for at least one of the following: providing a plurality of through holes for arranging a plurality of terminal electrodes in a first organic insulating film provided on one surface of a first substrate body, as described later, and providing a plurality of through holes for arranging a plurality of terminal electrodes in a second organic insulating film provided on one surface of a second substrate body.

[0206] The insulating film forming material of this disclosure preferably has a thermal expansion coefficient of 150 ppm / K or less when cured, more preferably 100 ppm / K or less, and even more preferably 70 ppm / K or less. As a result, the thermal expansion coefficient of the cured insulating film and the thermal expansion coefficient of the electrode are equal to or close to each other, so that even if heat generation occurs during use of the semiconductor device, damage to the semiconductor device due to the difference in thermal expansion coefficients between the insulating layer and the electrode can be suppressed. Thermal expansion coefficient is the rate at which the length of the cured material expands per unit temperature due to the rise in temperature. The thermal expansion coefficient can be calculated by measuring the change in the length of the cured material at 100°C to 150°C using a thermomechanical analyzer or the like.

[0207] <Semiconductor device> The semiconductor device of the present disclosure comprises a first semiconductor substrate having a first substrate body, a first organic insulating film and a first electrode provided on one side of the first substrate body, and a semiconductor chip having a semiconductor chip substrate body, a second organic insulating film and a second electrode provided on one side of the semiconductor chip substrate body, wherein the first organic insulating film and the second organic insulating film are bonded together, the first electrode and the second electrode are bonded together, and at least one of the first organic insulating film and the second organic insulating film is a cured product of the insulating film forming material of the present disclosure. The semiconductor device of this disclosure has excellent heat resistance of the insulating film because at least one of the first organic insulating film and the second organic insulating film (insulating film portion) is a cured product of the insulating film forming material of this disclosure.

[0208] <Manufacturing method for semiconductor devices> The semiconductor device manufacturing method of the present disclosure involves manufacturing a semiconductor device using the insulating film forming material of the present disclosure. Specifically, the semiconductor device manufacturing method of the present disclosure involves preparing a first semiconductor substrate having a first substrate body, a first electrode and a first organic insulating film provided on one surface of the first substrate body, preparing a semiconductor chip having a semiconductor chip substrate body, a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body, bonding the first electrode and the second electrode, and bonding the first organic insulating film and the second organic insulating film, and using the insulating film forming material of the present disclosure to produce at least one of the first organic insulating film and the second organic insulating film.

[0209] Hereinafter, an embodiment of the semiconductor device of the present disclosure and an embodiment of the method for manufacturing the semiconductor device of the present disclosure will be described in detail with reference to the drawings. In the following description, the same or corresponding parts will be denoted by the same reference numerals, and redundant descriptions will be omitted. Furthermore, unless otherwise specified, positional relationships such as up, down, left, and right will be based on the positional relationships shown in the drawings. In addition, the dimensional ratios in the drawings are not limited to those shown.

[0210] (An example of a semiconductor device) Figure 1 is a schematic cross-sectional view showing an example of a semiconductor device of the present disclosure. As shown in Figure 1, the semiconductor device 1 is, for example, an example of a semiconductor package, and comprises a first semiconductor chip 10 (first semiconductor substrate), a second semiconductor chip 20 (semiconductor chip), a pillar portion 30, a redistribution layer 40, a substrate 50, and a circuit board 60.

[0211] The first semiconductor chip 10 is a semiconductor chip such as an LSI (Large-Scale Integrated Circuit) chip or a CMOS (Complementary Metal Oxide Semiconductor) sensor, and has a three-dimensional mounting structure with the second semiconductor chip 20 mounted downwards. The second semiconductor chip 20 is a semiconductor chip such as an LSI or memory, and is a chip component with a smaller area in a planar view than the first semiconductor chip 10. The second semiconductor chip 20 is chip-to-chip (C2C) bonded to the back surface of the first semiconductor chip 10. The first semiconductor chip 10 and the second semiconductor chip 20 are firmly and finely bonded to each other by hybrid bonding, which will be described in detail later, with their respective terminal electrodes and the insulating films around them being joined together.

[0212] The pillar portion 30 is a connection portion in which a plurality of pillars 31 made of a metal such as copper (Cu) are sealed with resin 32. The plurality of pillars 31 are conductive members that extend from the upper surface to the lower surface of the pillar portion 30. The plurality of pillars 31 may have a cylindrical shape with a diameter of 3 μm or more and 20 μm or less (5 μm in one example), and may be arranged so that the distance between the centers of each pillar 31 is 15 μm or less. The plurality of pillars 31 make a flip-chip connection between the lower terminal electrode of the first semiconductor chip 10 and the upper terminal electrode of the redistribution layer 40. By using the pillar portion 30, the semiconductor device 1 can form connection electrodes without using a technique called TMV (Through mold via), which involves drilling holes in a mold and soldering the connections. The pillar portion 30 has a thickness of approximately the same as the second semiconductor chip 20, and is arranged horizontally to the side of the second semiconductor chip 20. Alternatively, multiple solder balls may be placed in place of the pillar portion 30, and the solder balls may be used to electrically connect the lower terminal electrode of the first semiconductor chip 10 to the upper terminal electrode of the redistribution layer 40.

[0213] The redistribution layer 40 is a wiring layer that has the function of terminal pitch conversion, which is a function of the package substrate. It is a layer in which a redistribution pattern is formed on the insulating film on the underside of the second semiconductor chip 20 and on the underside of the pillar portion 30 using polyimide or polybenzoxazole and copper wiring, etc. The redistribution layer 40 is formed with the first semiconductor chip 10, the second semiconductor chip 20, etc. inverted (see Figure 4(d)).

[0214] The redistribution layer 40 electrically connects the terminal electrodes on the underside of the second semiconductor chip 20 and the terminal electrodes of the first semiconductor chip 10 via the pillar portion 30 to the terminal electrodes of the substrate 50. The terminal pitch of the substrate 50 is wider than the terminal pitch of the pillar 31 and the terminal pitch of the second semiconductor chip 20. Various electronic components 51 may be mounted on the substrate 50. If there is a large difference in terminal pitch between the redistribution layer 40 and the substrate 50, an inorganic interposer or the like may be used to make an electrical connection between the redistribution layer 40 and the substrate 50.

[0215] The circuit board 60 is a substrate on which the first semiconductor chip 10 and the second semiconductor chip 20 are mounted, and which has a plurality of through electrodes inside that are electrically connected to the substrate 50 to which the first semiconductor chip 10, the second semiconductor chip 20 and electronic components 51 are connected. In the circuit board 60, the terminal electrodes of the first semiconductor chip 10 and the second semiconductor chip 20 are electrically connected to terminal electrodes 61 provided on the back surface of the circuit board 60 by the plurality of through electrodes.

[0216] (An example of a semiconductor device manufacturing method) Next, an example of a method for manufacturing the semiconductor device 1 will be described with reference to Figures 2 to 4. Figure 2 is a diagram showing the method for manufacturing the semiconductor device shown in Figure 1 in sequence. Figure 3 is a diagram showing the bonding method (hybrid bonding) in the method for manufacturing the semiconductor device shown in Figure 2 in more detail. Figure 4 is a diagram showing the method for manufacturing the semiconductor device shown in Figure 1, sequentially following the steps shown in Figure 2.

[0217] The semiconductor device 1 can be manufactured, for example, through the following steps (a) to (n). (a) A step of preparing a first semiconductor substrate 100 corresponding to the first semiconductor chip 10. (b) A step of preparing a second semiconductor substrate 200 corresponding to the second semiconductor chip 20. (c) A step of polishing the first semiconductor substrate 100. (d) A step of polishing the second semiconductor substrate 200. (e) A step of separating the second semiconductor substrate 200 into individual pieces and obtaining a plurality of semiconductor chips 205. (f) A step of aligning the terminal electrodes 203 of each of the multiple semiconductor chips 205 with respect to the terminal electrodes 103 of the first semiconductor substrate 100. (g) A step of bonding the insulating film 102 of the first semiconductor substrate 100 and each insulating film portion 202b of the plurality of semiconductor chips 205 to each other (see Figure 3(b)). (h) A step of joining the terminal electrodes 103 of the first semiconductor substrate 100 to the terminal electrodes 203 of each of the multiple semiconductor chips 205 (see Figure 3(c)). (i) A step of forming a plurality of pillars 300 (corresponding to pillars 31) between a plurality of semiconductor chips 205 on the connection surface of the first semiconductor substrate 100. (j) A step of obtaining a semi-finished product M1 by molding resin 301 onto the connection surface of the first semiconductor substrate 100 so as to cover the semiconductor chip 205 and the pillar 300. (k) A process in which the resin 301 side of the semi-finished product M1 molded in process (j) is ground down to thin it and obtain a semi-finished product M2. (l) A step of forming a wiring layer 400 corresponding to the rewiring layer 40 on the semi-finished product M2 thinned in step (k). (m) A step of cutting the semi-finished product M3, which has a wiring layer 400 formed in step (l), along the cutting line A so that it becomes each semiconductor device 1. (n) A step in which the semiconductor device 1a, which has been individualized in step (m), is inverted and placed on the substrate 50 and the circuit board 60 (see Figure 1).

[0218] The insulating film forming material of this disclosure may be an insulating film forming material used for producing at least one of the first organic insulating film and the second organic insulating film in a semiconductor device manufacturing method comprising at least one step corresponding to step (f) and steps (i) to (n).

[0219] [Process (a) and Process (b)] Step (a) is a step of preparing a first semiconductor substrate 100, which is a silicon substrate on which integrated circuits consisting of semiconductor elements and wiring connecting them are formed, corresponding to a plurality of first semiconductor chips 10. In step (a), as shown in Figure 2(a), a plurality of terminal electrodes 103 (first electrodes) made of copper, aluminum, etc. are provided at predetermined intervals on one surface 101a of the first substrate body 101 made of silicon, etc., and an insulating film 102 (first insulating film), which is a cured product of the insulating film forming material of this disclosure, is provided in the space between them. The insulating film 102 may be provided on one surface 101a of the first substrate body 101 and then the plurality of terminal electrodes 103 may be provided, or the plurality of terminal electrodes 103 may be provided on one surface 101a of the first substrate body 101 and then the insulating film 102 may be provided. A predetermined interval is provided between the plurality of terminal electrodes 103 in order to form pillars 300 in a step described later, and another terminal electrode (not shown) connected to the pillars 300 is formed in between.

[0220] Step (b) is a step of preparing a second semiconductor substrate 200, which is a silicon substrate on which an integrated circuit comprising semiconductor elements and wiring connecting them is formed, corresponding to a plurality of second semiconductor chips 20. In step (b), as shown in Figure 2(a), a plurality of terminal electrodes 203 (a plurality of second electrodes) made of copper, aluminum, etc. are continuously provided on one surface 201a of the second substrate body 201 made of silicon, etc., and an insulating film 202 (a second insulating film, an organic insulating region) which is a cured product of the insulating film forming material of this disclosure is provided. The insulating film 202 may be provided on one surface 201a of the second substrate body 201 and then the plurality of terminal electrodes 203 may be provided, or the plurality of terminal electrodes 203 may be provided on one surface 201a of the second substrate body 201 and then the insulating film 202 may be provided.

[0221] Even if both the insulating films 102 and 202 used in steps (a) and (b) are cured products of the insulating film forming material of this disclosure, one of the insulating films 102 and 202 may be a cured product of the insulating film forming material of this disclosure and the other may be another cured product. Examples of insulating film forming materials for forming other cured products include insulating film forming materials containing polyamide-imide, benzocyclobutene (BCB), etc. The tensile modulus of insulating films 102 and 202 at 25°C is preferably 7.0 GPa or less, more preferably 5.0 GPa or less, even more preferably 3.0 GPa or less, and particularly preferably 2.5 GPa or less.

[0222] The thermal expansion coefficients of the insulating films 102 and 202 are preferably 150 ppm / K or less, more preferably 100 ppm / K or less, and even more preferably 90 ppm / K or less.

[0223] The thickness of insulating films 102 and 202 is preferably 0.1 μm to 50 μm, and more preferably 1 μm to 15 μm. This ensures uniformity of the insulating film thickness while shortening the processing time in subsequent polishing steps.

[0224] From the viewpoint of making the work in steps (c) and (d) easier to perform and simplifying these steps, it is preferable that at least one of the following conditions be met (preferably both conditions be met): the polishing rate of the insulating film 102 is 0.1 to 5 times the polishing rate of the terminal electrode 103, and the polishing rate of the insulating film 202 is 0.1 to 5 times the polishing rate of the terminal electrode 203. For example, if the terminal electrode 103 or 203 is made of copper and the polishing rate of the copper is 50 nm / min, the polishing rate of the insulating film 102 or 202 is preferably 200 nm / min or less (four times or less the polishing rate of copper), more preferably 100 nm / min or less (twice the polishing rate of copper) and even more preferably 50 nm / min or less (equivalent to or less the polishing rate of copper).

[0225] Next, a method for manufacturing an insulating film will be described. The insulating film is obtained by curing an insulating film forming material. Examples of the above-mentioned methods for manufacturing an insulating film include (α) a method comprising the steps of applying and drying an insulating film forming material onto a substrate to form a resin film, and heat-treating the resin film, and (β) a method comprising the steps of forming an insulating film with a constant thickness on a film that has been subjected to a release treatment using an insulating film forming material, then transferring the resin film to a substrate by a lamination method, and heat-treating the resin film formed on the substrate after the transfer. From the viewpoint of flatness, method (α) is preferred.

[0226] Examples of coating methods for insulating film-forming materials include spin coating, inkjet coating, and slit coating.

[0227] In the spin coating method, for example, the insulating film forming material may be spin-coated under conditions such as a rotation speed of 300 rpm (revolutions per minute) to 3,500 rpm, preferably 500 rpm to 1,500 rpm, an acceleration of 500 rpm / second to 15,000 rpm / second, and a rotation time of 30 seconds to 300 seconds.

[0228] The process may include a drying step after applying the insulating film forming material to a support, film, etc. Drying may be performed using a hot plate, oven, etc. The drying temperature is preferably 75°C to 130°C, and more preferably 90°C to 120°C from the viewpoint of improving the flatness of the insulating film. The drying time is preferably 30 seconds to 5 minutes. Drying may be performed two or more times. This makes it possible to obtain a resin film in which the above-mentioned insulating film forming material is formed in a film-like manner.

[0229] In the slit coating method, for example, the insulating film forming material may be slit coated under the following conditions: chemical dispensing speed of 10 μL / sec to 400 μL / sec, chemical dispensing section height of 0.1 μm to 1.0 μm, stage speed (or chemical dispensing section speed) of 1.0 mm / sec to 50.0 mm / sec, stage acceleration of 10 mm / sec to 1000 mm / sec, ultimate vacuum level of 10 Pa to 100 Pa during reduced-pressure drying, reduced-pressure drying time of 30 seconds to 600 seconds, drying temperature of 60°C to 150°C, and drying time of 30 seconds to 300 seconds.

[0230] The formed resin film may be heat-treated. The heating temperature is preferably 150°C to 450°C, and more preferably 150°C to 350°C. By heating the temperature within the above range, damage to the substrate, device, etc., is suppressed, energy saving in the process is achieved, and an insulating film can be suitably produced.

[0231] The heating time is preferably 5 hours or less, and more preferably 30 minutes to 3 hours. By keeping the heating time within the above range, the crosslinking reaction or the dehydration ring-closing reaction can be carried out sufficiently. The heat treatment can be performed in the atmosphere of air or in an inert atmosphere such as nitrogen, but a nitrogen atmosphere is preferred from the viewpoint of preventing oxidation of the resin film.

[0232] Examples of equipment used for heat treatment include quartz tube furnaces, hot plates, rapid thermal annealing, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, and microwave curing furnaces.

[0233] When using the insulating film forming material of this disclosure, which is a negative-type photosensitive insulating film forming material or a positive-type photosensitive insulating film forming material, when the insulating film 202 is provided on one surface 201a of the second substrate body 201 and then a plurality of terminal electrodes 203 are provided, for example, a method may be used that includes the steps of: coating the insulating film forming material onto the substrate; drying to form a resin film; pattern exposure of the resin film, developing with a developer to obtain a patterned resin film; and heat treatment of the patterned resin film. This makes it possible to obtain a cured patterned insulating film.

[0234] Alternatively, when providing the insulating film 202 on one surface 201a of the second substrate body 201 and then providing the multiple terminal electrodes 203, a method may be used that includes, for example, the steps of: applying an insulating film forming material other than the insulating film forming material of the present disclosure onto the substrate; drying to form a resin film; applying and drying the insulating film forming material of the present disclosure, which is a negative-type photosensitive insulating film forming material or a positive-type photosensitive insulating film forming material, onto the resin film, then pattern exposure, developing with a developer to obtain a patterned resin film; and heat-treating the patterned resin film. This makes it possible to obtain a cured patterned insulating film.

[0235] Pattern exposure involves exposing a predetermined pattern to light, for example, through a photomask. The active light to be irradiated can be i-rays, broadband ultraviolet light, visible light, or radiation, with i-rays being preferred. Exposure equipment can include parallel exposure machines, projection exposure machines, steppers, scanner exposure machines, etc.

[0236] A patterned resin film, which is a resin film with a pattern formed on it, can be obtained by developing it after exposure. If the insulating film forming material of this disclosure is a negative-type photosensitive insulating film forming material, the unexposed areas are removed with a developer. The organic solvent used as a developer for negative film can be a good solvent for photosensitive resin films, either alone or by appropriately mixing a good solvent with a poor solvent. Examples of good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, cyclopentanone, cyclohexanone, and cycloheptanone. Examples of poor solvents include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

[0237] If the insulating film forming material of this disclosure is a positive-type photosensitive insulating film forming material, the exposed area is removed with a developer. Examples of solutions used as developer for positive film include tetramethylammonium hydroxide (TMAH) solution and sodium carbonate solution.

[0238] At least one of the negative-type developer and the positive-type developer may contain a surfactant. The surfactant content is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the developer.

[0239] The development time can be, for example, twice the time it takes for a photosensitive resin film to completely dissolve when immersed in the developer. The development time may be adjusted according to the thermosetting polyamide having phenolic hydroxyl groups in the molecules contained in the insulating film forming material of this disclosure, for example, preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and even more preferably 20 seconds to 5 minutes from the viewpoint of productivity.

[0240] The pattern resin film may be washed with a rinsing solution after development. As the rinsing solution, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. may be used individually or in appropriate mixtures, or these may be used in a stepwise combination.

[0241] In addition, other organic materials constituting the insulating films 102 and 202, besides the cured product of the insulating film forming material of this disclosure, may be photosensitive resins, thermosetting non-conductive films (NCF), or thermosetting resins. This organic material may also be an underfill material. Furthermore, the organic material constituting the insulating films 102 and 202 may be a heat-resistant resin.

[0242] [Step (c) and step (d)] Step (c) is a step of polishing the first semiconductor substrate 100. In step (c), as shown in Figure 3(a), one side 101a of the surface of the first semiconductor substrate 100 is polished using chemical mechanical polishing (CMP) so that each surface 103a of the terminal electrode 103 is at the same position as or slightly higher (protruding) than the surface 102a of the insulating film 102. In step (c), the first semiconductor substrate 100 can also be polished by CMP under conditions that selectively and deeply grind the terminal electrode 103, which is made of copper or the like. In step (c), the terminal electrode 103 may be polished by CMP so that each surface 103a of the terminal electrode 103 coincides with the surface 102a of the insulating film 102. The polishing method is not limited to CMP, and back grinding or the like may be used. Prior to polishing by CMP, mechanical polishing may be performed using a polishing device such as a surface planer. When each surface 103a of the terminal electrode 103 is slightly higher than the surface 102a of the insulating film 102 (i.e., when the thickness of the first electrode, the terminal electrode 103, is greater than the thickness of the first insulating film, the insulating film 102), the height difference between each surface 103a and surface 102a (the thickness difference between the terminal electrode 103 and the insulating film 102) may be 1 nm to 150 nm, or 1 nm to 80 nm. In this disclosure, the height difference between the insulating film (surface 102a, etc.) and the electrode (surface 103a, etc.) refers to the arithmetic mean obtained when measuring five points in a measurement target such as a wafer using an atomic force microscope (AFM).

[0243] Step (d) is a step of polishing the second semiconductor substrate 200. In step (d), as shown in Figure 3(a), one side 201a of the surface of the second semiconductor substrate 200 is polished using the CMP method so that each surface 203a of the terminal electrode 203 is at the same position as or slightly higher (protruding) than the surface 202a of the insulating film 202. In step (d), the second semiconductor substrate 200 is polished using the CMP method under conditions that selectively and deeply grind the terminal electrode 203, which is made of, for example, copper. In step (d), the terminal electrode 203 may be polished using the CMP method so that each surface 203a of the terminal electrode 203 coincides with the surface 202a of the insulating film 202. The polishing method is not limited to the CMP method, and back grinding or the like may be employed. When each surface 203a of the terminal electrode 203 is slightly higher than the surface 202a of the insulating film 202 (i.e., when the thickness of the second electrode, the terminal electrode 203, is greater than the thickness of the second insulating film, the insulating film 202), the height difference between each surface 203a and surface 202a (the thickness difference between the terminal electrode 203 and the insulating film 202) may be 1 nm to 150 nm, or 1 nm to 80 nm.

[0244] In steps (c) and (d), the insulating film 102 and the insulating film 202 may be polished to the same thickness, or for example, the insulating film 202 may be polished to a thickness greater than that of the insulating film 102. Alternatively, the insulating film 202 may be polished to a thickness less than that of the insulating film 102. When the insulating film 202 is thicker than that of the insulating film 102, much of the foreign matter adhering to the bonding interface when the second semiconductor substrate 200 is pieced or when chip mounting can be contained by the insulating film 202, further reducing bonding defects. On the other hand, when the insulating film 202 is thinner than that of the insulating film 102, the height of the mounted semiconductor chip 205, i.e., the semiconductor device 1, can be reduced. Steps (c) and (d) may be performed at least one of the two, and it is preferable to perform both steps (c) and (d).

[0245] [Step (e)] Step (e) is a step in which the second semiconductor substrate 200 is divided into individual pieces to obtain a plurality of semiconductor chips 205. In step (e), as shown in Figure 2(b), the second semiconductor substrate 200 is divided into a plurality of semiconductor chips 205 by a cutting means such as dicing. When dicing the second semiconductor substrate 200, a protective material may be applied to the insulating film 202 before dividing it into individual pieces. In step (e), the insulating film 202 of the second semiconductor substrate 200 is divided into insulating film portions 202b corresponding to each semiconductor chip 205. Examples of dicing methods for dividing the second semiconductor substrate 200 include plasma dicing, stealth dicing, and laser dicing. As a surface protective material for the second semiconductor substrate 200 during dicing, for example, a thin film such as an organic film that can be removed with water, TMAH, etc., or a carbon film that can be removed with plasma, etc. may be provided. In this embodiment, a large-area second semiconductor substrate 200 is prepared and then fragmented to obtain multiple semiconductor chips 205, but the method of preparing the semiconductor chips 205 is not limited to this. The semiconductor chip 205 includes a semiconductor chip substrate body, a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body.

[0246] [Process (f)] Step (f) is a step in which the terminal electrodes 203 of each of the multiple semiconductor chips 205 are aligned with respect to the terminal electrodes 103 of the first semiconductor substrate 100. In step (f), as shown in Figure 2(c), each semiconductor chip 205 is aligned so that the terminal electrodes 203 of each semiconductor chip 205 face the corresponding multiple terminal electrodes 103 of the first semiconductor substrate 100. Alignment marks or the like may be provided on the first semiconductor substrate 100 for this alignment.

[0247] [Process (g)] Step (g) is a step in which the insulating film 102 of the first semiconductor substrate 100 and each insulating film portion 202b of the multiple semiconductor chips 205 are bonded to each other. In step (g), after removing organic matter, metal oxides, etc. adhering to the surface of each semiconductor chip 205, the semiconductor chips 205 are aligned with the first semiconductor substrate 100 as shown in Figure 2(c), and then the insulating film portions 202b of each of the multiple semiconductor chips 205 are bonded to the insulating film 102 of the first semiconductor substrate 100 as a hybrid bonding (see Figure 3(b)). At this time, the insulating film portions of the multiple semiconductor chips 205 and the insulating film 102 of the first semiconductor substrate 100 may be uniformly heated before bonding. By bonding while heating, the insulating film 102 and insulating film portions 202b expand more than the terminal electrodes 103 and 203 due to the difference in thermal expansion coefficients between the insulating film 102 and insulating film portions 202b and the terminal electrodes 103 and 203. In step (c), the first semiconductor substrate 100 may be polished so that the height of the insulating film 102 becomes approximately equal to or greater than the height of the terminal electrode 103 due to thermal expansion caused by heating, and in step (d), the second semiconductor substrate 200 may be polished so that the height of the insulating film portion 202b becomes approximately equal to or greater than the height of the terminal electrode 203. The temperature difference between the semiconductor chip 205 and the first semiconductor substrate 100 during bonding is preferably, for example, within 10°C. By heating and bonding at such a highly uniform temperature, an insulating bond portion S1 is formed in which the insulating film 102 and the insulating film portion 202b are bonded, and multiple semiconductor chips 205 are mechanically firmly attached to the first semiconductor substrate 100. Furthermore, because the heating and bonding is performed at a highly uniform temperature, misalignment at the bonding location is less likely to occur, and high-precision bonding can be achieved. At this attachment stage, the terminal electrode 103 of the first semiconductor substrate 100 and the terminal electrode 203 of the semiconductor chip 205 are spaced apart from each other and are not connected (however, alignment is performed). The semiconductor chip 205 may be bonded to the first semiconductor substrate 100 by other bonding methods, such as room temperature bonding.

[0248] The total thickness of the organic insulating film, which is the insulating junction portion where the insulating film 102 and the insulating film portion 202b are joined, is not particularly limited and may be, for example, 0.1 μm or more, or from the viewpoint of suppressing the influence of foreign matter and from the viewpoint of device design, it may be 1 μm to 20 μm, and preferably 1 μm to 5 μm.

[0249] [Process (h)] Step (h) is a step in which the terminal electrodes 103 of the first semiconductor substrate 100 are joined to the terminal electrodes 203 of each of the multiple semiconductor chips 205. In step (h), as shown in Figure 2(d), once the bonding in step (g) is completed, heat H, pressure, or both are applied to join the terminal electrodes 103 of the first semiconductor substrate 100 to each of the terminal electrodes 203 of the multiple semiconductor chips 205 as a hybrid bond (see Figure 3(c)). If the terminal electrodes 103 and 203 are made of copper, the annealing temperature in step (g) is preferably 150°C to 400°C, and more preferably 200°C to 300°C. Through this joining process, the terminal electrodes 103 and their corresponding terminal electrodes 203 are joined to form an electrode joint portion S2, and the terminal electrodes 103 and 203 are firmly joined mechanically and electrically. Note that the electrode bonding in step (h) may be performed after the bonding in step (g), or it may be performed simultaneously with the bonding in step (g).

[0250] As described above, multiple semiconductor chips 205 are electrically and mechanically positioned with high precision at predetermined locations on the first semiconductor substrate 100. At the semi-finished product stage shown in Figure 2(d), for example, a product reliability test (such as a connection test) may be performed, and only good products may be used in subsequent processes. Next, an example of a manufacturing method for a semiconductor device using such a semi-finished product will be described with reference to Figure 4.

[0251] [Step (i)] Step (i) is a step of forming a plurality of pillars 300 between a plurality of semiconductor chips 205 on the connection surface 100a of the first semiconductor substrate 100. In step (i), as shown in Figure 4(a), a plurality of pillars 300 made of, for example, copper are formed between the plurality of semiconductor chips 205. The pillars 300 can be formed from copper plating, conductive paste, copper pins, etc. One end of the pillar 300 is formed to be connected to a terminal electrode of the first semiconductor substrate 100 that is not connected to the terminal electrode 203 of the semiconductor chip 205, and the other end extends upward. The pillar 300 has, for example, a diameter of 10 μm or more and 100 μm or less, and a height of 10 μm or more and 1000 μm or less. Note that, for example, one to 10,000 pillars 300 may be provided between a pair of semiconductor chips 205.

[0252] [Process (j)] Step (j) is a step of molding resin 301 onto the connection surface 100a of the first semiconductor substrate 100 so as to cover the multiple semiconductor chips 205 and the multiple pillars 300. In step (j), as shown in Figure 4(b), epoxy resin or the like is molded to completely cover the multiple semiconductor chips 205 and the multiple pillars 300. Examples of molding methods include compression molding, transfer molding, and lamination of a film-like epoxy film. This resin molding fills the spaces between the multiple pillars 300 and the spaces between the pillars 300 and the semiconductor chips 205 with resin 301. This forms a semi-finished product M1 filled with resin. Note that a curing treatment may be performed after molding with epoxy resin or the like. Furthermore, when steps (i) and (j) are performed almost simultaneously, i.e., when the pillar 300 is formed at the same time as the resin molding, the pillar may be formed using a fine transfer method called imprinting and a conductive paste or electroplating.

[0253] [Process (k)] Step (k) is a process in which a semi-finished product M1, which consists of a resin 301 molded in step (j), a plurality of pillars 300, and a plurality of semiconductor chips 205, is thinned by grinding from the resin 301 side to obtain a semi-finished product M2. In step (k), as shown in Figure 4(c), the first semiconductor substrate 100 etc., which is molded in resin, is thinned by polishing the upper part of the semi-finished product M1 with a grinder or the like to obtain a semi-finished product M2. Through polishing in step (k), the thickness of the semiconductor chips 205, pillars 300, and resin 301 is thinned to, for example, several tens of micrometers, the semiconductor chips 205 take on a shape corresponding to the second semiconductor chip 20, and the pillars 300 and resin 301 take on a shape corresponding to the pillar portion 30.

[0254] [Process (l)] Step (l) is a step in which a wiring layer 400 corresponding to the rewiring layer 40 is formed on the semi-finished product M2 that was thinned in step (k). In step (l), as shown in Figure 4(d), a rewiring pattern is formed on the second semiconductor chip 20 and pillar portion 30 of the ground semi-finished product M2 using polyimide or polybenzoxazole, copper wiring, etc. This forms a semi-finished product M3 having a wiring structure with widened terminal pitch of the second semiconductor chip 20 and pillar portion 30.

[0255] [Process (m) and process (n)] Step (m) is a process in which the semi-finished product M3, on which the wiring layer 400 was formed in step (l), is cut along the cutting line A so that it becomes each semiconductor device 1. In step (m), as shown in Figure 4(d), the semiconductor device substrate is cut along the cutting line A so that it becomes each semiconductor device 1 by dicing or the like. Then, in step (n), the semiconductor devices 1a that were individualized in step (m) are inverted and placed on the substrate 50 and the circuit board 60 to obtain multiple semiconductor devices 1 as shown in Figure 1.

[0256] According to the above embodiment, which is an example of a semiconductor device manufacturing method, the insulating film 102 of the first semiconductor substrate 100 and the insulating film 202 of the second semiconductor substrate 200 are cured products of the insulating film forming material of this disclosure. Since the cured products of the insulating film forming material of this disclosure have high heat resistance, deterioration of the insulating film caused by heating such as bonding is suppressed, and the occurrence of peeling, degradation, etc. of the insulating film is suppressed. Furthermore, since it is possible to lower the bonding temperature by using the insulating film forming material of this disclosure, the occurrence of defects such as deterioration of the insulating film is further reduced.

[0257] Although one embodiment of the semiconductor device manufacturing method of the present disclosure has been described in detail above, the present disclosure is not limited to the above embodiment. For example, in the above embodiment, in the process shown in Figure 4, the steps of forming the pillar 300 (i), molding the resin 301 (j), and grinding the resin 301 to thin it (k) were performed in order. However, the step of molding the resin 301 onto the connection surface of the first semiconductor substrate 100 (j) may be performed first, followed by the step of grinding the resin 301 to a predetermined thickness to thin it (k), and then the step of forming the pillar 300 (i). In this case, the work of grinding the pillar 300 can be reduced, and the portion of the pillar 300 that is to be ground is no longer needed, thus reducing material costs.

[0258] Furthermore, although the above embodiment describes a C2C bonding example, this disclosure may also be applied to Chip-to-Wafer (C2W) bonding as shown in Figure 5. In C2W, a semiconductor wafer 410 (first semiconductor substrate) is prepared having a substrate body 411 (first substrate body), an insulating film 412 (first insulating film) provided on one side of the substrate body 411, and a plurality of terminal electrodes 413 (first electrodes). Simultaneously, a semiconductor substrate (second semiconductor substrate) is prepared before the individualization of a plurality of semiconductor chips 420, having a substrate body 421 (second substrate body), an insulating film portion 422 (second insulating film) provided on one side of the substrate body 421, and a plurality of terminal electrodes 423 (second electrodes). Then, one side of the semiconductor wafer 410 and one side of the second semiconductor substrate before individualization into semiconductor chips 420 are polished by CMP or the like, in the same manner as in steps (c) and (d) above. Subsequently, the same fragmentation process as in step (e) is performed on the second semiconductor substrate to obtain multiple semiconductor chips 420.

[0259] Next, as shown in Figure 5(a), the terminal electrode 423 of the semiconductor chip 420 is aligned with the terminal electrode 413 of the semiconductor wafer 410 (step (f)). Then, the insulating film 412 of the semiconductor wafer 410 and the insulating film portion 422 of the semiconductor chip 420 are bonded together (step (g)), and the terminal electrode 413 of the semiconductor wafer 410 and the terminal electrode 423 of the semiconductor chip 420 are joined together (step (h)), obtaining the semi-finished product shown in Figure 5(b). This creates an insulating joint portion S3 where the insulating film 412 and the insulating film portion 422 are joined, and the semiconductor chip 420 is mechanically firmly and precisely attached to the semiconductor wafer 410. Furthermore, an electrode joint portion S4 is created where the terminal electrode 413 and its corresponding terminal electrode 423 are joined together, and the terminal electrode 413 and the terminal electrode 423 are mechanically and electrically firmly joined.

[0260] Subsequently, as shown in Figures 5(c) and 5(d), a semiconductor device 401 is obtained by bonding multiple semiconductor chips 420 to a semiconductor wafer 410 in the same manner. Note that the multiple semiconductor chips 420 may be bonded to the semiconductor wafer 410 one by one by hybrid bonding, or they may be bonded together to the semiconductor wafer 410 by hybrid bonding.

[0261] In this method for manufacturing the semiconductor device 401, similar to the method for manufacturing the semiconductor device 1 described above, at least one of the insulating film 412 of the semiconductor wafer 410 and the insulating film portion 422 of the semiconductor chip 420 is an insulating film that is a cured product of the insulating film forming material of this disclosure. Therefore, even if foreign matter generated by dicing during the individualization of the semiconductor chip 420 adheres to the insulating film, the insulating film around the foreign matter can be easily deformed, and the foreign matter can be contained within the insulating film without creating large voids in the insulating film. In other words, the effect of foreign matter can be suppressed by the insulating film. Thus, in the manufacturing method relating to C2W described above, similar to C2C, it is possible to reduce bonding defects while performing fine bonding of the semiconductor wafer 410 and the semiconductor chip 420.

[0262] Furthermore, in the above-described method for manufacturing a semiconductor device, inorganic materials may be included in a portion of the insulating film 102 of the semiconductor substrate 100, the insulating film 202 of the semiconductor chip 205, etc., to the extent that the effects of this disclosure are achieved. [Examples]

[0263] The present disclosure will be described in more detail below based on examples and comparative examples. However, the present disclosure is not limited to the examples described below.

[0264] (Synthesis of thermosetting polyamide A1 having phenolic hydroxyl groups in the molecule) In a 0.5-liter flask equipped with a stirrer and thermometer, 15.48 g of 4,4'-diphenyl ether dicarboxylic acid and 90 g of N-methyl-2-pyrrolidone were charged. After cooling the flask to 5°C, 12.64 g of thionyl chloride was added dropwise, and the mixture was reacted for 30 minutes to obtain a solution of 4,4'-diphenyl ether dicarboxylic acid chloride. Next, in a 0.5-liter flask equipped with a stirrer and thermometer, 87.5 g of N-methyl-2-pyrrolidone was charged, and 18.30 g of bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added and stirred until dissolved. Then, 8.53 g of pyridine was added, and while maintaining the temperature at 0-5°C, the solution of 4,4'-diphenyl ether dicarboxylic acid chloride was added dropwise over 30 minutes, followed by stirring for another 30 minutes. The obtained solution was added to 3 liters of water, the precipitate was collected, washed three times with pure water, and then dried under reduced pressure to obtain polyhydroxyamide (polybenzoxazole precursor) (hereinafter referred to as polymer A1). The weight-average molecular weight of polymer A1, determined by the GPC method on a standard polystyrene basis, was 15,000. The structural formula of polymer A1 is shown below.

[0265] [ka]

[0266] (Synthesis of thermosetting polyamide A2 having phenolic hydroxyl groups in the molecule) In a 0.2-liter flask equipped with a stirrer and thermometer, 60 g of N-methyl-2-pyrrolidone was charged, and 13.92 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added and stirred until dissolved. Subsequently, while maintaining the temperature of this solution at 0-5°C, 8.12 g of dodecanediolate dichloride and 2.24 g of 4,4'-diphenyl ether dicarboxylic acid dichloride (molar ratio of dodecanediolate dichloride to 4,4'-diphenyl ether dicarboxylic acid dichloride was 8:2) were added dropwise over 10 minutes, and stirring was continued for 60 minutes. The resulting solution was added to 3 liters of water, the precipitate was collected, washed three times with pure water, and then reduced in pressure to obtain polyhydroxyamide (polybenzoxazole precursor) (hereinafter referred to as polymer A2). The weight-average molecular weight of polymer A2, calculated using the GPC method on a standard polystyrene basis, was 33,000. The structural formula of polymer A2 is shown below.

[0267] [ka]

[0268] (Synthesis of polyimide precursor A3 that does not contain phenolic hydroxyl groups in its molecule) 7.07 g of 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride (ODPA) and 4.12 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) were dissolved in 30 g of N-methyl-2-pyrrolidone (NMP). The resulting solution was stirred at 30°C for 4 hours to obtain polyamic acid. 9.45 g of trifluoroacetic anhydride was added at room temperature (25°C), followed by 7.08 g of 2-hydroxyethyl methacrylate (HEMA), and the mixture was stirred at 45°C for 10 hours. This reaction mixture was added dropwise to distilled water, the precipitate was filtered off and collected, and dried under reduced pressure to obtain polyimide precursor A3 (hereinafter referred to as polymer A3). The weight-average molecular weight of polymer A3, calculated using the GPC method on a standard polystyrene basis, was 20,000. Furthermore, the esterification rate was calculated from the NMR results using the measurement conditions described later. The esterification rate of polymer A3 was 70%, and the proportion of unreacted carboxyl groups was 30 mol%. (Measurement conditions) Measuring instrument: Bruker BioSpin AV400M Magnetic field strength: 400MHz Reference substance: Tetramethylsilane (TMS) Solvent: Dimethyl sulfoxide (DMSO)

[0269] (Synthesis of polyimide precursor A4 that does not contain phenolic hydroxyl groups in the molecule) 6.71 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 1.97 g of paraphenylenediamine were dissolved in 100 g of 3-methoxy-N,N-dimethylpropanamide while stirring. After stirring overnight at 30°C, the reaction solution was added dropwise to dehydrated ethanol, the precipitate was filtered off, and the mixture was dried under reduced pressure to obtain polyimide precursor A4 (hereinafter referred to as polymer A4). The weight-average molecular weight of polymer A4, calculated using the GPC method on a standard polystyrene basis, was 20,000.

[0270] (Synthesis of polyimide precursor A5 that does not contain phenolic hydroxyl groups in its molecule) In the synthesis of polyimide precursor A3, which does not contain phenolic hydroxyl groups in its molecule, the same procedure was followed except that DMAP was replaced with 3.6 g of 4,4'-diaminodiphenyl ether (ODA) and 0.2 g of m-phenylenediamine (MPD) to obtain polyimide precursor A5 (hereinafter referred to as polymer A5). The weight-average molecular weight of polymer A5, determined by GPC method on a standard polystyrene basis, was 25,000.

[0271] (Synthesis of polyimide precursor A6 that does not contain phenolic hydroxyl groups in its molecule) Polyimide precursor A6 was obtained by performing the same procedure as in the synthesis of polyimide precursor A3, except that DMAP was replaced with 3.89 g of ODA (hereinafter referred to as polymer A6). The weight-average molecular weight of polymer A6 was 21,000. The esterification rate of polymer A6 was calculated by NMR measurement under the aforementioned conditions. The esterification rate was 70 mol%, and the proportion of unreacted carboxyl groups was 30 mol%.

[0272] (Synthesis of polyimide precursor A7 that does not contain phenolic hydroxyl groups in its molecule) In the synthesis of polyimide precursor A3, the same procedure was followed except that ODPA was replaced with 6.71 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and DMAP was replaced with 3.89 g of ODA to obtain polyimide precursor A7 (hereinafter referred to as polymer A7). The weight-average molecular weight of polymer A7 was 20,000. The esterification rate of polymer A7 was calculated by NMR measurement under the aforementioned conditions. The esterification rate was 60 mol%, and the proportion of unreacted carboxyl groups was 40 mol%.

[0273] The weight-average molecular weight was determined using gel permeation chromatography (GPC) on a standard polystyrene basis. Specifically, a solution prepared by dissolving 0.5 mg each of polymers A1 to A7 in 1 mL of solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)] was used, and the measurement was performed under the following conditions.

[0274] (Measurement conditions) Measuring device: Shimadzu Corporation SPD-M20A Pump: Shimadzu Corporation LC-20AD Column Oven: Shimadzu Corporation: CTO-20A Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 Eluent: THF / DMF=1 / 1 (volume ratio) LiBr(0.03mol / L), H3PO4(0.06mol / L) Flow rate: 1.0 mL / min, Detector: UV270 nm, Column temperature: 40°C Calibration curves were created using standard polystyrene: TSKgel standard Polystyrene Type F-1, F-4, F-20, F-80, and A-2500 manufactured by Tosoh Corporation.

[0275] [Examples 1-6, Comparative Examples 1-2] (Preparation of insulating film forming material) The insulating film-forming materials for Examples 1-6 and Comparative Examples 1-2 were prepared as follows, using the components and amounts shown in Table 1. The units for the amounts of each component in Table 1 are parts by mass. Blank spaces in Table 1 indicate that the corresponding component was not included. In each example and comparative example, the mixture of each component was kneaded overnight at room temperature (25°C) in a general solvent-resistant container, and then pressure filtered using a 0.2 μm pore filter. The obtained insulating film-forming materials were evaluated as follows.

[0276] The components listed in Table 1 are as follows: • Polyimide precursor or polybenzoxazole derivative Polymers A1 to A7 mentioned above ·solvent B1: 3-Methoxy-N,N-dimethylpropanamide B2: γ-Butyrolactone B3: Dimethyl sulfoxide • Polymerizable monomers C1:2,2-Bis(3,5-bis(hydroxylmethyl)-4-hydroxyphenyl)-1,1,1,3,3,3-Hexafluoropropane(TML-BPAF) C2: Tetraethylene glycol dimethacrylate (TEGDMA) C3: Tricyclodecanedimethanol diacrylate (A-DCP) • Rust inhibitor D1: Benzotriazole (BT) • Polymerization initiator E1: The following compound (TPPA428)

[0277] [ka]

[0278] E2: 8-Methoxypyrene-1,3,6-trisulfonic acid trisodium salt (MPTS) E3: Bis(1-phenyl-1-methylethyl)peroxide (Percumyl D) E4: 1-Phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime (PDO) E5: 4,4'-Bis(diethylamino)benzophenone (EMK)

[0279] (Measurement of the glass transition temperature (Tg) of the cured film) Using the insulating film forming materials of Examples 1-6 and Comparative Examples 1-2, cured films were formed as follows, and then the glass transition temperature was measured. First, an insulating film forming material was spin-coated onto a Si substrate, heated and dried on a hot plate at 95°C for 120 seconds, and then dried again at 105°C for 120 seconds to form a resin film with a thickness of approximately 10 μm after drying. The obtained resin film was cured in a vertical diffusion furnace μ-TF under a nitrogen atmosphere at 350°C for 2 hours to obtain a cured product with a thickness of 10 μm. The obtained cured product was immersed in a 4.9 mass% hydrofluoric acid aqueous solution and peeled off from the Si substrate. The peeled cured film was then shaped using a razor to a sample length of 15 mm and a sample width of 4 mm. Using a Hitachi High-Tech Science TMA7100 model and a tensile jig, the elongation (expansion) of the sample was measured in the temperature range of 50°C to 350°C under the conditions of an initial sample length of 10 mm, a heating rate of 5°C / min, and a load of 10 g. The glass transition temperature (Tg) was defined as the temperature at the start of the change, which was determined by the tangent method at the point where a rapid change in the expansion rate occurred in the curve obtained by the above method.

[0280] (Preparation of a hardened film with a tip) The insulating film forming materials of Examples 1-6 and Comparative Examples 1-2 were spin-coated onto an 8-inch Si wafer using a spin coater, heated and dried on a hot plate at 95°C for 120 seconds, and then dried again at 105°C for 120 seconds to form a resin film with a thickness of approximately 10 μm after drying. For Comparative Examples 1 and 2, the obtained resin films were exposed to an exposure dose of 600 mJ / cm² using a mask aligner MA-8 (manufactured by Suss Microtec). 2Broadband (BB) exposure was performed. The exposed resin film was then developed with cyclopentanone using a Mikasa AD1200 developer to achieve a total development time of 20 seconds. The obtained resin film was cured in a vertical diffusion furnace μ-TF under a nitrogen atmosphere at 350°C for 2 hours to obtain a cured film.

[0281] A portion of the resulting cured film was cut into 5mm square pieces using a blade dicer (DISCO DFD-6362) to obtain resin-coated chips. The obtained resin-coated chips were then pressed onto the cured film using a thermocompression press (manufactured by Showa Denko Materials Co., Ltd.) at a predetermined pressure and bonding temperature shown in Table 1 for 15 seconds to produce a cured film with chips. For each insulating film forming material, five chips pressed onto the cured film were evaluated as described below.

[0282] (evaluation) When a chip was bonded using a heat-sealing machine and then detached when force was applied with tweezers, it was determined to be a bond defect. -Evaluation Criteria for Joining Results- A: Of the five chips, two or fewer showed bonding defects. B: More than two out of five chips showed bonding defects.

[0283] [Table 1]

[0284] As shown in Table 1, Examples 1 to 6 demonstrate that bonding is possible even when the bonding temperature is below the glass transition temperature of the resin, compared to Comparative Examples 1 to 2.

[0285] The disclosure of Japanese Patent Application No. 2022-063655, filed on April 6, 2022, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted as being incorporated by reference. [Explanation of Symbols]

[0286] 1,1a,401…Semiconductor device, 10…First semiconductor chip, 20…Second semiconductor chip, 30…Pillar portion, 40…Redistribution layer, 50…Substrate, 60…Circuit board, 61…Terminal electrode, 100…First semiconductor substrate, 101…First substrate body, 101a…One side, 102…Insulating film (First insulating film), 103…Terminal electrode (First electrode), 103a…Surface, 200…Second semiconductor substrate, 201…Second substrate body, 201a…One side, 202…Insulating film (Second insulating film), 203…Terminal electrode (Second electrode), 203a…Surface, 20 5...Semiconductor chip, 300...Pillar, 301...Resin, 410...Semiconductor wafer (first semiconductor substrate), 411...Substrate body (first substrate body), 412...Insulating film (first insulating film), 413...Terminal electrode (first electrode), 420...Semiconductor chip (second semiconductor substrate), 421...Substrate body (second substrate body), 422...Insulating film portion (second insulating film), 423...Terminal electrode (second electrode), A...Cutting line, H...Heat, M1~M3...Semi-finished product, S1...Insulating joint portion, S2...Electrode joint portion, S3...Insulating joint portion, S4...Electrode joint portion

Claims

1. It comprises a thermosetting polyamide having phenolic hydroxyl groups in its molecule, and a solvent. The thermosetting polyamide is a hybrid bonding insulating film forming material having the following structural units. 【Chemistry 1】

2. The hybrid bonding insulating film forming material according to claim 1, further comprising a crosslinking agent.

3. A first semiconductor substrate is prepared, having a first substrate body, a first electrode and a first organic insulating film provided on one surface of the first substrate body. A semiconductor chip is prepared, comprising a semiconductor chip substrate body, a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body, The first electrode and the second electrode are joined together, and the first organic insulating film and the second organic insulating film are bonded together. A method for manufacturing a semiconductor device, using the hybrid bonding insulating film forming material described in claim 1 or claim 2 for the production of at least one of the first organic insulating film and the second organic insulating film.

4. A method for manufacturing a semiconductor device according to claim 3, wherein the first electrode and the second electrode are bonded together after the first organic insulating film and the second organic insulating film are bonded together.

5. The method for manufacturing a semiconductor device according to claim 3, wherein the semiconductor chip is prepared by framing a second semiconductor substrate having a second substrate body, a plurality of second electrodes provided on one surface of the second substrate body, and a second organic insulating region.

6. The method for manufacturing a semiconductor device according to claim 3, wherein the bonding of the first organic insulating film and the second organic insulating film is performed at a temperature such that the temperature difference between the semiconductor chip and the first semiconductor substrate is 10°C or less.

7. The method for manufacturing a semiconductor device according to claim 3, wherein the total thickness of the organic insulating film formed by bonding the first organic insulating film and the second organic insulating film in the manufactured semiconductor device is 0.1 μm or more.

8. The method for manufacturing a semiconductor device according to claim 3, wherein, before either bonding the first electrode and the second electrode, or bonding the first organic insulating film and the second organic insulating film, one surface of the first semiconductor substrate and at least one side of the one surface of the semiconductor chip are polished.

9. The method for manufacturing a semiconductor device according to claim 8, which includes chemical mechanical polishing.

10. The method for manufacturing a semiconductor device according to claim 9, further comprising mechanical polishing.

11. A method for manufacturing a semiconductor device according to claim 3, wherein the thickness of the first electrode is greater than the thickness of the first organic insulating film, and the thickness of the second electrode is greater than the thickness of the second organic insulating film.

12. A first semiconductor substrate having a first substrate body, a first organic insulating film and a first electrode provided on one surface of the first substrate body, The semiconductor chip comprises a semiconductor chip substrate body and a semiconductor chip having a second organic insulating film and a second electrode provided on one side of the semiconductor chip substrate body. The first organic insulating film and the second organic insulating film are joined together, and the first electrode and the second electrode are joined together, A semiconductor device in which at least one of the first organic insulating film and the second organic insulating film is a cured product of the hybrid bonding insulating film forming material according to claim 1 or claim 2.

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