Package substrates and semiconductor package substrates

Abstract

To provide a package substrate having an insulating layer that has high insulation reliability and is difficult to peel off from a glass core substrate, and a semiconductor package substrate equipped with said package substrate. [Solution] In a package substrate comprising a glass core substrate, a conductor layer, and an insulating layer, the conductor layer is formed to cover at least a portion of the first main surface, at least a portion of the second main surface, and at least a portion of the side walls defining the through holes of the glass core substrate, at least a portion of the conductor layer is covered with an insulating layer, the insulating layer contains polyimide, the imide group concentration of the polyimide is 15% to 38%, the internal stress of the insulating layer is 20 MPa or less, and the surface roughness Ra of the insulating layer is 10 nm or less.

Description

[Technical Field]

[0001] This invention relates to a package substrate and a semiconductor package substrate. [Background technology]

[0002] Package substrates equipped with terminals and wiring contain semiconductor chips and other components sealed in resin materials, and are incorporated into various electrical and electronic devices such as smartphones, notebook PCs, and AI servers. As the performance of these devices improves, the integration of semiconductor package substrates is increasing, and there is a demand for miniaturization and finer wiring in these package substrates.

[0003] A package substrate is a build-up substrate in which a core substrate, wiring layers, and insulating layers are laminated. Glass is increasingly being used for the core substrate because its excellent rigidity, flatness, and smoothness make it easy to miniaturize package substrates and to finen wiring on glass core substrates. Organic materials such as epoxy resin cured products are used as insulating materials.

[0004] Used for mounting semiconductor elements and various electronic components, a glass core substrate with a built-in high-frequency filter has been proposed as a substrate equipped with a glass core substrate (see Patent Document 1). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2021-166257 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, Patent Document 1 only discloses an insulating layer formed using a sheet of silica-containing epoxy resin as an insulating layer for insulating the wiring layer in a glass core substrate with a built-in high-frequency filter. The insulating layer formed using a sheet of silica-containing epoxy resin has problems such as low insulation reliability and the fact that it exhibits a linear thermal expansion coefficient (CTE) considerably higher than that of the glass core substrate, which may cause it to peel off from the glass core substrate depending on the operating temperature.

[0007] The present invention has been made in view of the above problems, and aims to provide a package substrate having an insulating layer that has high insulating reliability and is difficult to peel off from a glass core substrate, and a semiconductor package substrate equipped with the package substrate. [Means for solving the problem]

[0008] Specifically, the present invention relates to the following: (1) A package substrate comprising a glass core substrate, a conductive layer, and an insulating layer, The glass core substrate has a first main surface, a second main surface which is the surface opposite to the first main surface, and through holes. The through-hole penetrates between the first main surface and the second main surface in the glass core substrate. The conductive layer covers a portion of the first main surface, a portion of the second main surface, and at least a portion of the side wall defining the through hole. The insulating layer covers at least a portion of the conductive layer. The insulating layer contains polyimide, The imide group concentration of the polyimide is 15% or more and 38% or less, more preferably 20% or more and 38% or less. The internal stress of the insulating layer is 20 MPa or less. A package substrate in which the surface roughness Ra of the insulating layer is 10 nm or less.

[0009] (2) Polyimide is a polymer of tetracarboxylic dianhydride and diamine, The tetracarboxylic dianhydrides are 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride (BPADA), 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), and bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)-2,2',3,3',5,5'-he It contains one or more selected from the group consisting of xamethylbiphenyl-4,4'-diyl (TAHMBP), 4,4'-oxydiphthalic acid dianhydride (ODPA), spiro[11H-difluoro[3,4-b:3',4'-i]xanthene-11,9'-[9H]fluorene]-1,3,7,9-tetron (SFDA), and 9,9-bis(3,4-dicarboxyphenyl)fluorendiohydride (BPAF), The diamine comprises one or more selected from the group consisting of p-phenylenediamine (PDA), 4-aminophenyl-4-aminobenzoate (4-BAAB), 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB), 2,2'-bis(trifluoromethoxy)benzidine (TFMOB), and diaminodiphenylsulfone (3,3'-DDS). (1) The package substrate described above.

[0010] (3) The package substrate according to (1) or (2), wherein the linear thermal expansion coefficient (CTE) of the insulating layer is 20 ppm / K or less.

[0011] (4) A package substrate as described in any one of (1) to (3), wherein the 5% weight loss temperature (TD5) of the insulating layer is 400°C or higher.

[0012] (5) The package substrate according to any one of claims (1) to (4), wherein the tensile elongation of the insulating layer is 1% or more.

[0013] (6) A semiconductor package substrate having a package substrate as described in any one of (1) to (5), and a semiconductor chip mounted on the package substrate. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a package substrate having an insulating layer with high insulation reliability and difficult to peel from a glass core substrate, and a semiconductor package substrate including the package substrate.

Embodiments for Carrying Out the Invention

[0015] ≪Package Substrate≫ The package substrate is a base in a state where no semiconductor element is mounted, and is used for mounting a semiconductor element. The package substrate includes a glass core substrate, a conductor layer, and an insulating layer. The package substrate may optionally include a silicon interposer, a glass interposer, a silicon bridge, bumps, inductors, and the like.

[0016] <Glass Core Substrate> The glass core substrate has a first main surface, a second main surface opposite to the first main surface, and through holes. The through holes penetrate between the first main surface and the second main surface in the glass core substrate. The number of through holes in the glass core substrate is not particularly limited, but the glass core substrate usually has a plurality of through holes. The through holes can be formed by a method such as etching, laser processing, or electrical discharge machining.

[0017] The material of the glass core substrate is not particularly limited. For example, the material of the glass core substrate includes non-alkali glass, alkali glass, quartz glass, and glass ceramics.

[0018] The thickness of the glass core substrate is not particularly limited. Typically, the thickness of the glass substrate is preferably 1 μm or more and 5000 μm or less, and more preferably 10 μm or more and 2000 μm or less.

[0019] <Conductor Layer> The conductive layer covers at least a portion of the first main surface, at least a portion of the second main surface, and at least a portion of the sidewalls defining the through-holes in the glass core substrate. In the through-holes of the glass core substrate, the conductive layer may cover the sidewalls defining the through-holes in a layered manner, or the conductive layer may fill the voids of the through-holes.

[0020] The material of the conductive layer is typically a metal such as copper, titanium, tin, molybdenum, or aluminum, or an alloy containing these metals, with copper and copper alloys being preferred. The conductive layer is usually formed as a circuit on a glass core substrate. The method for forming the conductive layer as a circuit is not particularly limited and is formed on the glass core substrate according to conventional methods. In a glass core substrate, the circuit formed as a conductive layer on the first main surface and the circuit formed as a conductive layer on the second main surface are usually connected by conductive layers formed within through holes (via holes).

[0021] <Insulating layer> The insulating layer covers at least a portion of the conductive layer. The insulating layer may also cover areas on the glass core substrate where the conductive layer is not formed. The method of covering a portion of the conductor layer with an insulating layer is not particularly limited. For example, an insulating layer can be formed covering a portion or all of the conductor layer by applying a varnish containing polyamic acid or polyimide onto a metal layer using known coating methods such as spin coating, die coating, silkscreen, gravure coating, dip coating, bar coating, knife coating, or roll coating, and then heating the formed coating film. Furthermore, an insulating layer covering a portion of the conductor layer can also be formed by first forming a large insulating layer over a wide area including the area where the insulating layer is to be formed, and then removing unnecessary parts from the large insulating layer using methods such as laser irradiation or etching with an etching mask.

[0022] The insulating layer contains polyimide. In the polyimide, some imide groups may be ring-open to the extent that the desired effect is not impaired. When the imidation rate in the polyimide is defined as 100% when all parts that can form an imide ring are ring-closed, the imidation rate of the polyimide is preferably, for example, 80% or more, more preferably 90% or more, particularly preferably 95% or more, and most preferably 100%.

[0023] Furthermore, polyimides may have carboxylic acid ester bonds or carboxylic acid amide bonds in their molecular chains. In other words, "polyimide" in the specification and claims of this application encompasses so-called "polyesterimide" and "polyamideimide." Polyimides will be discussed in more detail later.

[0024] The imide group concentration of the polyimide is 15% to 38%, preferably 16% to 38%, more preferably 20% to 38%, even more preferably 22% to 35%, and particularly preferably 22% to 30%. The imide group concentration can be adjusted by appropriately adjusting the molecular weight of the monomers used in the synthesis of polyimides. As the amount of high molecular weight monomers used increases, the imide group concentration decreases. Conversely, as the amount of low molecular weight monomers used increases, the imide group concentration increases. The imide group concentration is calculated from the total amount of imide groups (C2O2N) with a molecular weight of 70.0 in the polyimide and the number-average molecular weight of the polyimide using the following formula. Imide group concentration (%) = (Total molecular weight of imide groups) / (Number-average molecular weight of polyimide) × 100

[0025] When the imide group concentration is 15% or higher, the interaction between imide groups in the polyimide molecules contained in the insulating layer is strong, which allows for the formation of an insulating film with a low coefficient of linear thermal expansion. When the imide group concentration is 38% or less, the water absorption rate of the insulating layer is low, and the insulating reliability of the insulating layer is high.

[0026] The insulating layer may contain resins other than polyimide, insofar as the desired effect is not impaired. In this case, the ratio of the mass of polyimide to the total mass of the resin material constituting the insulating layer is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% or more. Specific examples of resins other than polyimide include polybenzoxazole, polyacrylate, and polysiloxane. Due to the ease of forming the insulating layer, it is particularly preferable that the resin material constituting the insulating layer contains only polyimide.

[0027] As described later, the surface roughness Ra of the insulating layer is 10 nm or less. An insulating layer with a surface roughness Ra of 10 nm or less can be formed, and the insulating layer may contain fillers or reinforcing materials to the extent that the desired effect is not impaired. However, from the viewpoint of forming an insulating layer with a surface roughness Ra of 10 nm or less, it is preferable that the materials constituting the insulating layer do not contain fillers or reinforcing materials.

[0028] The internal stress of the insulating layer is 20 MPa or less, and more preferably 10 MPa or less. The internal stress of the insulating layer is measured by the method described later in the examples. Generally, the linear thermal expansion coefficient of glass is smaller than that of resin. Therefore, internal stress occurs in the insulating layer containing polyimide, which is deposited on a glass core substrate. Low internal stress reduces the likelihood of delamination of the insulating layer from the glass core substrate, as well as warping and damage to the glass core substrate, even after the package substrate or semiconductor package substrate is heated and then cooled. The internal stress of an insulating layer tends to be lower the less filler or reinforcing material it contains. In this respect, it is preferable that the insulating layer does not contain fillers or reinforcing materials. Furthermore, if the resin or various materials contained in the insulating layer are not crosslinked, the internal stress of the insulating layer tends to be low. For this reason, the internal stress of the insulating layer can also be reduced by using a resin that does not have crosslinking groups or contains only a small amount of them, or by not including a so-called crosslinking agent with crosslinking groups in the composition for forming the insulating layer, or by including only a small amount of it. Examples of crosslinkable groups include unsaturated bond-containing groups such as vinyl groups, allyl groups, and (meth)acryloyl groups; epoxy groups; isocyanate groups; and hydrolyzable silicon groups such as trimethoxysilyl groups and triethoxysilyl groups.

[0029] The insulating layer can also be formed by attaching a dry film containing polyamic acid or polyimide to a glass core substrate and then heating the dry film. In this case, a varnish containing polyamic acid or polyimide contained in the dry film can be prepared, and the internal stress of the insulating layer can be measured using the obtained varnish according to the method described later in the examples.

[0030] The surface roughness Ra of the insulating layer is 10 nm or less. Preferably, the surface roughness Ra of the insulating layer is 1.0 nm or less, and more preferably 0.4 nm or less. The lower limit of the surface roughness of the insulating layer may be greater than 0 nm and may be 0.1 nm or more. Note that the surface roughness Ra of the insulating layer is the surface roughness Ra of the main surface of the insulating layer that is not in contact with the glass core substrate or the conductive layer.

[0031] Methods for forming an insulating layer with a surface roughness Ra of 10 nm or less include applying a varnish containing polyamic acid to a glass core substrate to form a coating film, and then imidizing the polyamic acid contained in the coating film, or applying a varnish containing polyimide to a glass core substrate to form a coating film, and then drying the coating film. Spin coating and slit coating are preferred methods for applying the varnish. When forming the insulating layer, it is preferable that the varnish does not contain fillers or reinforcing materials.

[0032] The surface of the glass core substrate is highly smooth. Furthermore, because the surface roughness Ra of the insulating layer is 10 nm or less, the smoothness of both the glass core substrate and the conductive layer formed on the insulating layer is high, which reduces conductor loss and improves transmission loss.

[0033] The linear thermal expansion coefficient (CTE) of the insulating layer is preferably 20 ppm / K or less, and more preferably 10 ppm / K or less. Having such a low CTE value for the insulating layer makes it less prone to warping, less likely to peel off from the glass core substrate and conductor layer, and less likely to cause damage to the glass core substrate due to excessive thermal expansion of the insulating layer. Methods to reduce the linear thermal expansion coefficient (CTE) of an insulating layer include reducing the amount of reinforcing or filler material in the insulating layer, omitting reinforcing or filler material from the insulating layer, and enhancing intermolecular interactions, such as by adopting a structure that facilitates the formation of intermolecular hydrogen bonds in the polyimide or other resins contained in the insulating layer. The linear thermal expansion coefficient (CTE) of an insulating layer can be measured by the method described later in the examples.

[0034] In terms of the heat resistance of the insulating layer, it is preferable that the 5% weight loss temperature (TD5) of the insulating layer be 400°C or higher, more preferably 500°C or higher, and even more preferably 550°C or higher. The 5% weight loss temperature (TD5) can be measured by the method described later in the examples.

[0035] The 5% weight loss temperature (TD5) tends to be higher with increasing imide group concentration. Therefore, the 5% weight loss temperature (TD5) can be adjusted by increasing the imide group concentration within the range of 15% to 38%. Furthermore, the 5% weight loss temperature (TD5) can also be adjusted by reducing the content of low molecular weight compounds or by increasing the linearity of the polyimide.

[0036] In terms of the drop impact resistance of package substrates and semiconductor package substrates, the tensile elongation of the insulating layer is preferably 1% or more, more preferably 10% or more, and even more preferably 20% or more. The tensile elongation of the insulating layer can be measured by the method described later in the examples.

[0037] [Polyimide] The polyimide is not particularly limited as long as it has an imide group concentration of 15% to 38%, an internal stress of 20 MPa or less in the insulating layer, and a surface roughness Ra of 10 nm or less in the insulating layer. Polyimides include structures derived from tetracarboxylic dianhydrides and structures derived from diamines. Preferred examples of tetracarboxylic dianhydrides and diamines are described below.

[0038] Suitable tetracarboxylic dianhydrides include 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), pyromellitic acid dianhydride (PMDA), 4,4'-oxydiphthalic acid dianhydride (ODPA), 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic acid dianhydride (BPADA), 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride (CpODA), and 2,2' ,3,3'-biphenyltetracarboxylic acid dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic acid anhydride (6FDA), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic acid anhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, methylene-4,4'-diphthalic acid dianhydride, 1,1-ethylidene-4,4'-diphthalic acid dianhydride, 2,2-propyridene-4,4'-diphthalic acid dianhydride, 1,2-ethylidene 1,3-Diphthalic acid dianhydride, 1,3-Trimethylene-4,4'-Diphthalic acid dianhydride, 1,4-Tetramethylene-4,4'-Diphthalic acid dianhydride, 1,5-Pentamethylene-4,4'-Diphthalic acid dianhydride, 4,4'-Oxydiphthalic acid dianhydride, p-Phenylenebis(Trimellitate anhydride), Thio-4,4'-Diphthalic acid dianhydride, Sulfonyl-4,4'-Diphthalic acid dianhydride, 1,3-Bis(3,4-Dicarboxyphenyl)benzene dianhydride, 1,3-Bis(3,4-Dicarboxyphenoxy)benzene dianhydride, 1,4-Bis(3, 4-Dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-Bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,3,6,7-anthracenetetracarboxylic acid dianhydride, 1,2,7,8-phenanthrenetetracarboxylic acid dianhydride, bicyclohexyl-3,3',9,9-bis(3,4-dicarboxyphenyl)fluorenediacid anhydride (BPAF), 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, spiro[11H-difluoro[3,4-b:3',4'-i]xanthene- This may include substances selected from the group consisting of 11,9'-[9H]fluorene]-1,3,7,9-tetron (SFDA), p-phenylenebis(trimellitic acid monoester anhydride) (TMHQ), (1,3-dioxoisobenzofuran-5-yl)1,3-dioxoisobenzofuran-5-carboxylate (8CI), bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)-2,2',3,3',5,5'-hexamethylbiphenyl-4,4'-diyl (TAHMBP), etc., and combinations thereof.

[0039] Furthermore, a compound represented by the following chemical formula (t1) can also be suitably used as a tetracarboxylic dianhydride. [ka]

[0040] Suitable diamines include p-phenylenediamine (PDA), m-phenylenediamine, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB), 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-diaminodiphenyl ether, 4-aminophenyl-4-aminobenzoate, 4,4'-diaminobenzanilide, 3,3'-diaminodiphenyl sulfone (3,3'-DDS), 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3' -Diaminodiphenyl sulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bi 4-(4-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl) This may include hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, and selected from the group consisting of 9,9-bis(4-aminophenyl)fluorene (BAFL), 4-aminophenyl-4-aminobenzoate (4-BAAB), 2,2'-bis(trifluoromethoxy)benzidine (TFMOB), etc., and combinations thereof.

[0041] Furthermore, a compound represented by the following chemical formula (d1) can also be suitably used as the diamine. [ka]

[0042] With respect to the tetracarboxylic dianhydride mentioned above, the amount of residues derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) is preferably 70 mol% to 95 mol% of the total amount of residues derived from tetracarboxylic dianhydride in the polyimide. The amount of residues derived from 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride (BPADA) is preferably 60 mol% to 100 mol% relative to the total amount of residues derived from tetracarboxylic dianhydrides in the polyimide. The amount of residues derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) is preferably 10 mol% to 40 mol% relative to the total amount of residues derived from tetracarboxylic dianhydride in the polyimide. The amount of residues derived from bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)-2,2',3,3',5,5'-hexamethylbiphenyl-4,4'-diyl (TAHMBP) is preferably 40 mol% to 60 mol% of the total amount of residues derived from tetracarboxylic dianhydride in the polyimide. The amount of residues derived from 4,4'-oxydiphthalic acid dianhydride (ODPA) is preferably 5 mol% to 30 mol% relative to the total amount of residues derived from tetracarboxylic acid dianhydride in the polyimide. The amount of residues derived from spiro[11H-difluoro[3,4-b:3',4'-i]xanthene-11,9'-[9H]fluorene]-1,3,7,9-tetron (SFDA) is preferably 1 mol% to 10 mol% relative to the total amount of residues derived from tetracarboxylic dianhydrides in the polyimide. The amount of residues derived from bicyclohexyl-3,3',9,9-bis(3,4-dicarboxyphenyl)fluorendiohydride (BPAF) is preferably 3 mol% to 20 mol% relative to the total amount of residues derived from tetracarboxylic dianhydride in the polyimide. The amount of residues derived from the compound represented by the above chemical formula (t1) is preferably 70 mol% to 100 mol% relative to the total amount of residues derived from tetracarboxylic dianhydride in the polyimide.

[0043] With respect to the above-mentioned diamine, the amount of residues derived from p-phenylenediamine (PDA) is preferably 70 mol% to 95 mol% of the total amount of residues derived from diamine in the polyimide. The amount of residues derived from 4-aminophenyl-4-aminobenzoate (4-BAAB) is preferably 5 mol% to 100 mol% relative to the total amount of residues derived from diamines in the polyimide. The amount of residues derived from 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) is preferably 70 mol% to 95 mol% of the total amount of residues derived from diamines in the polyimide. The amount of residues derived from 2,2'-bis(trifluoromethoxy)benzidine (TFMOB) is preferably 70 mol% to 100 mol% relative to the total amount of residues derived from diamines in the polyimide. The amount of residues derived from 3,3'-diaminodiphenylsulfone (3,3'-DDS) is preferably 5 mol% to 30 mol% relative to the total amount of residues derived from diamines in the polyimide. The amount of residues derived from the compound represented by the above chemical formula (d1) is preferably 70 mol% to 100 mol% relative to the total amount of residues derived from the diamine in the polyimide.

[0044] From the perspective of the environmental persistence of organic fluorine compounds (PFAS), the total content of fluorine atoms contained in the tetracarboxylic dianhydride having a specific fluorine-containing structure and the total content of fluorine atoms contained in the diamine having a specific fluorine-containing structure are preferably less than 500 mg, more preferably less than 300 mg, still more preferably less than 100 mg, and particularly preferably less than 50 mg per 1 kg of polyimide.

[0045] Here, the acid dianhydride and diamine having a specific fluorine-containing structure refer to substances excluding those containing only the structural elements of the following formulas (A1) and (A2) from the tetracarboxylic dianhydride having a trifluoromethyl group (-CF3) and / or a difluoromethylene group (-CF2-), and the diamine having a trifluoromethyl group (-CF3) and / or a difluoromethylene group (-CF2-). CF3-X (A1) X-CF2-X’ (A2) (In formulas (A1) and (A2), X is -OR ,

[0047] ,

[0046] , , a3 , , a4 , or -NR a1 R a2 X’ is a hydrogen atom, a methyl group, an aromatic group, -C(O)-, -OR a3 -SR a3 or -NR a3 R a4 R a1 R a2 R a3 and R a4 are each independently a hydrogen atom, a methyl group, -CH2-, an aromatic group, or -C(O)-)

[0046] More preferably, the content of the tetracarboxylic dianhydride component having a trifluoromethyl group directly bonded to an aromatic ring or -C(CF3)2- directly bonded to an aromatic ring is less than 0.5 mol% in all the tetracarboxylic dianhydride components, and the content of the diamine component having a trifluoromethyl group directly bonded to an aromatic ring or -C(CF3)2- directly bonded to an aromatic ring is less than 0.5 mol% in all the diamine components.

[0047] Examples of tetracarboxylic dianhydrides and diamines include 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 9,9-bis(trifluoromethyl)xanthenetetracarboxylic dianhydride, 9-trifluoromethylxanthenetetracarboxylic dianhydride, 2,2'-bis(trifluoromethyl)benzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

[0048] Polyamic acid, a precursor to polyimide, is obtained by the reaction of tetracarboxylic dianhydride with a diamine. Polyimide is obtained by dehydration cyclization (imidization) of polyamic acid. The method for preparing polyamic acid is not particularly limited, and any known method can be applied. For example, a polyamic acid solution can be obtained by dissolving a diamine and a tetracarboxylic dianhydride in approximately equimolar amounts (molar ratio of 90:100 to 110:100) in an organic solvent and stirring.

[0049] The temperature conditions for the reaction between a diamine and a tetracarboxylic dianhydride, i.e., the synthesis reaction of polyamic acid, are not particularly limited, but are, for example, in the range of 10°C to 150°C. The reaction time for the synthesis reaction of polyamic acid is not particularly limited, but is, for example, in the range of 10 minutes to 30 hours.

[0050] The concentration of the polyamic acid solution is typically 5 to 35% by weight, preferably 10 to 30% by weight. Within this concentration range, the polyamic acid obtained by polymerization has an appropriate molecular weight, and the polyamic acid solution has an appropriate viscosity.

[0051] As a polymerization method for polyamic acids, a method of adding a tetracarboxylic dianhydride to a diamine is preferred in order to suppress ring-opening of the acid dianhydride. When adding multiple types of diamines or multiple types of tetracarboxylic dianhydrides, they may be added all at once or in multiple steps. The various properties of the polyimide can also be controlled by adjusting the order of monomer addition.

[0052] The organic solvent used for polymerization of polyamic acid is not particularly limited, as long as it does not react with diamines and tetracarboxylic dianhydrides and can dissolve polyamic acid. Examples of organic solvents include urea-based solvents such as methylurea and N,N-dimethylethylurea; sulfoxide-based solvents such as dimethyl sulfoxide, diphenyl sulfone, and tetramethylsulfone; and sulfone-based solvents; amide-based solvents such as 3-methoxy-N,N'-dimethylpropanamide (MPA), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), N,N'-diethylacetamide, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, and hexamethylphosphate triamide; alkyl halide-based solvents such as chloroform and dichloromethane; aromatic hydrocarbon-based solvents such as benzene and toluene; and ether-based solvents such as tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, dimethyl ether, diethyl ether, and p-cresol methyl ether. These solvents are typically used individually or in combination of two or more as needed. From the viewpoint of polyamic acid solubility and polymerization reactivity, MPA, DMAc, DMF, NMP, etc., are preferably used.

[0053] Polyimides can be obtained by the dehydration and cyclization of polyamic acids. One method for preparing polyimides from a polyamic acid solution (varnish) is to add a dehydrating agent, an imidation catalyst, etc., to the polyamic acid solution and allow imidation to proceed in the solution. To accelerate the progression of imidation, the polyamic acid solution may be heated. Note that imidation of polyamic acids can also proceed by heating alone. By mixing the solution containing the polyimide produced by the imidation of polyamic acids with a poor solvent, the polyimide precipitates as a solid. By isolating the polyimide as a solid, impurities generated during the synthesis of polyamic acids, residual dehydrating agents, and imidation catalysts can be washed and removed with the poor solvent, preventing discoloration and increased yellowness of the polyimide. Furthermore, by isolating the polyimide as a solid, solvents suitable for film formation, such as low-boiling point solvents, can be applied when preparing solutions for producing molded products such as films.

[0054] One method for forming an insulating layer on a glass core substrate is to apply a varnish containing polyamic acid or a solvent-soluble polyimide to the glass core substrate to form a coating film, and then heat the formed coating film. Suitable examples of solvents to be included in the varnish are similar to the suitable examples of organic solvents used in the polymerization of polyamic acids mentioned above. Furthermore, the coating film formed using the above-mentioned varnish can be used as a B-stage film (dry film) in a so-called semi-cured state. After attaching the B-stage film to the main surface of the glass core substrate, an insulating layer can be formed by heating the B-stage film to completely cure it.

[0055] The solid content concentration of the varnish containing polyamic acid or a solvent-soluble polyimide is preferably 1% to 40% by mass, and more preferably 5% to 30% by mass, due to the ease of application by spin coating or slit die coating. Furthermore, the viscosity of the varnish containing polyamic acid or a solvent-soluble polyimide is preferably 1 cP to 50,000 cP at 25°C, and more preferably 100 cP to 5,000 cP, due to the ease of application by spin coating or slit die coating.

[0056] The molecular weight of the polyimide (number-average molecular weight in polystyrene terms, measured by gel permeation chromatography (GPC)) is preferably 5,000 to 300,000, more preferably 6,000 to 200,000, and even more preferably 70,000 to 100,000.

[0057] Although not essential, varnishes containing polyamic acid or solvent-soluble polyimide can contain various additives, as long as they do not impair the effects of the present invention. For example, organometallic compounds are suitable as additives because they can more effectively lower the coefficient of linear thermal expansion (CTE) of the insulating layer formed using the varnish.

[0058] More specifically, examples of organometallic compounds include organometallic compounds having an atom of titanium (Ti), zirconium (Zr), or aluminum (Al), namely organotitanium compounds, organozirconium compounds, and organoaluminum compounds, which can be preferably used. Furthermore, it is more preferable that the organometallic compound be fibrous, as being a fibrous organometallic compound results in a lower coefficient of thermal expansion and an improved modulus of elasticity.

[0059] The content of organometallic compounds is not particularly limited, but is preferably 0.1% to 7% by mass, more preferably 0.5% to 5% by mass, and even more preferably 1% to 3% by mass, based on 100% by mass of solids in the varnish.

[0060] ≪Semiconductor Package Substrates≫ A semiconductor package substrate comprises the aforementioned package substrate and a semiconductor chip mounted on the package substrate. In addition to the package substrate and the semiconductor chip, the semiconductor package substrate may also have various other configurations that a semiconductor package substrate may conventionally possess. The mounting of semiconductor chips onto the package substrate may be done via an interposer such as a silicon interposer, or it may be done directly on the package substrate without the use of an interposer. [Examples]

[0061] The present invention will be described in detail below in the following examples, but the present invention is not limited to the following examples.

[0062] <Examples 1-6 and Comparative Examples 1-4> In each example and comparative example, varnishes were prepared by dissolving the polyamic acid or polyamide-containing varnish obtained using the monomers listed in Table 1 in the solvents listed in Table 1 such that the viscosity at 25°C was approximately 3000 cP. Table 1 shows the imide group concentrations of the polyamic acid contained in the varnishes used in each example and comparative example.

[0063] In the examples and comparative examples, the following TCA1 to TCA9 were used as tetracarboxylic dianhydrides. Although TCA9 is not a tetracarboxylic dianhydride, it is listed as such for convenience.

[0064] TCA1: 3,3',4,4'-biphenyltetracarboxylic dianhydride TCA2: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride TCA3: 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride TCA4: 1,2,3,4-cyclobutanetetracarboxylic dianhydride TCA5: Bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)-2,2',3,3',5,5'-hexamethylbiphenyl-4,4'-diyl TCA6: 4,4'-Oxydiphthalic anhydride TCA7: Spiro[11H-difluoro[3,4-b:3',4'-i]xanthene-11,9'-[9H]fluorene]1,3,7,9Tetron TCA8: 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride TCA9: A reaction product obtained by reacting 1 mole of 4,4'-oxydiphthalic anhydride with 2 moles of 2-hydroxyethyl methacrylate. TCA10: A tetracarboxylic dianhydride represented by the following chemical formula (t1). [ka]

[0065] In the examples and comparative examples, the following DA1 to DA6 were used as diamines.

[0066] DA1: p-phenylenediamine DA2: 4-aminophenyl-4-aminobenzoate DA3:2,2'-bis(trifluoromethyl)benzidine DA4:2,2'-Bis(trifluoromethoxy)benzidine DA5:3,3'-Diaminodiphenylsulfone DA6:4,4'-diaminodiphenyl ether DA7: A diamine represented by the following chemical formula (d1). [ka]

[0067] In Example 6, the following organometallic compounds and aminosilane compounds were used as other additives. Organometallic compound: Alumina sol 10F (manufactured by Kawaken Fine Chemicals Co., Ltd.) Aminosilane compound: VD-5 (manufactured by Shikoku Chemicals Co., Ltd.)

[0068] The method for producing the polyimide film for each example and each comparative example is shown below.

[0069] (Example 1) 85.0 g of MPA was placed in a 300 mL reaction vessel (glass separable flask) equipped with a stirrer fitted with a stainless steel stirring rod and a nitrogen inlet tube, as the organic solvent for polymerization. Next, at a temperature of 23°C, 3.44 g of DA1 and 0.81 g of DA2 were added to the reaction vessel while stirring the MPA and dissolved. Then, 8.83 g of TCA1, 1.10 g of TCA2, and 0.83 g of TCA7 were added to the reaction mixture in the reaction vessel. Subsequently, the reaction mixture in the reaction vessel was stirred at a temperature of 40°C for 4 hours. Next, the reaction mixture in the reaction vessel was stirred at a temperature of 23°C for 24 hours. Then, 50.0 g of MPA was added to the reaction vessel, and the reaction mixture was stirred at room temperature for 1 hour to obtain a homogeneous polyamic acid solution with a viscosity of approximately 3,000 cP. This polyamic acid solution was applied to a Corning glass substrate (product name: Eagle XG, material: alkali-free glass, thickness: 0.7 mm, size: 100 mm x 100 mm) using a spin coater. The formed coating film was heated in air at 80°C for 30 minutes, and then heated in a nitrogen atmosphere at 350°C (curing temperature) for 60 minutes to obtain a polyimide film with a thickness of 6 μm. The imide group concentration was 36%. The properties of the obtained polyimide film are shown in Table 2.

[0070] (Example 2) The polyimide film of Example 2 was obtained by the same method as in Example 1, except that the tetracarboxylic dianhydride used, its charging ratio, the diamine used, its charging ratio, the solvent used, the curing temperature, and the imide group concentration were as shown in Table 1. The properties of the obtained polyimide film are shown in Table 2.

[0071] (Example 3) 85.0 g of N,N-dimethylformamide (DMF) was placed in a 300 mL reaction vessel (glass separable flask) equipped with a stirrer fitted with a stainless steel stirring rod and a nitrogen inlet tube, as the organic solvent for polymerization. Next, at a temperature of 23°C, 5.82 g of DA3 and 0.50 g of DA5 were added to the reaction vessel while stirring the DMF and dissolved. Then, 6.24 g of TCA5, 1.25 g of TCA2, and 1.19 g of TCA4 were added to the reaction mixture in the reaction vessel, and the reaction mixture in the reaction vessel was stirred at a temperature of 40°C for 4 hours. Next, the reaction mixture in the reaction vessel was stirred at a temperature of 23°C for 8 hours to obtain a polyamic acid solution. Subsequently, 4.7 g of pyridine as an imidization catalyst and 0.91 g of acetic anhydride were added to the obtained polyamic acid solution. The polyamic acid solution containing the imidization catalyst was stirred at 90°C for 4 hours to obtain a polyimide solution. While stirring a polyimide solution cooled to room temperature, 260 g of 2-propyl alcohol (IPA) was added to the polyimide solution to precipitate the polyimide. The precipitated crude polyimide was recovered by suction filtration using a Kiriyama funnel. The obtained solid crude polyimide was washed six times with 130 g of IPA, and then dried in a vacuum oven set to 120°C for 8 hours to obtain polyimide. The obtained polyimide was dissolved in the organic solvent NMP to obtain a homogeneous polyimide solution with a viscosity of approximately 3,000 cP. This polyimide solution was coated onto a Corning glass substrate (product name: Eagle XG, material: alkali-free glass, thickness: 0.7 mm, size: 100 mm × 100 mm) using a spin coater, heated in air at 80°C for 30 minutes, and then heated in a nitrogen atmosphere at 200°C (curing temperature) for 60 minutes to obtain a polyimide film with a thickness of 6 μm. The imide group concentration was 24%. The properties of the obtained polyimide film are shown in Table 2.

[0072] (Example 4) The polyimide film of Example 4 was obtained by the same method as in Example 1, except that the tetracarboxylic dianhydride used, its charging ratio, the diamine used, its charging ratio, the solvent used, the curing temperature, and the imide group concentration were as shown in Table 1. The properties of the obtained polyimide film are shown in Table 2.

[0073] (Example 5) The polyimide film of Example 5 was obtained by the same method as in Example 3, except that the tetracarboxylic dianhydride used, its charging ratio, the diamine used, its charging ratio, the solvent used, the curing temperature, and the imide group concentration were as shown in Table 1. The properties of the obtained polyimide film are shown in Table 2.

[0074] (Example 6) A polyimide solution was obtained in the same manner as in Example 3, except that the tetracarboxylic dianhydride used, its charging ratio, the diamine used, its charging ratio, the solvent used, the curing temperature, and the imide group concentration were as shown in Table 1. Then, while stirring the obtained polyimide solution, the organometallic compound and the aminosilane compound, which were additives, were added and mixed. The polyimide film of Example 6 was obtained from the polyimide solution thus obtained. The properties of the obtained polyimide film are shown in Table 2.

[0075] (Comparative Example 1) A polyimide film of Comparative Example 1 was obtained by the same method as in Example 1, except that the tetracarboxylic dianhydride used, its charging ratio, the diamine used, its charging ratio, and the imide group concentration were as shown in Table 1. The properties of the obtained polyimide film are shown in Table 2.

[0076] (Comparative Example 2 and Comparative Example 3) Polyimide films of Comparative Examples 2 and 3 were obtained by the same method as in Example 3, except that the tetracarboxylic dianhydride used, its charging ratio, the diamine used, its charging ratio, the solvent used, the curing temperature, and the imide group concentration were as shown in Table 1, and 40% by mass of silica filler (product name: NMP-ST, manufactured by Nissan Chemical Corporation) was added relative to the total mass of polyamic acid and silica. The properties of the obtained polyimide films are shown in Table 2.

[0077] (Comparative Example 4) 6.2 g of TCA6 was placed in a 300 mL reaction vessel (glass separable flask) equipped with a stirrer fitted with a stainless steel stirring rod and a nitrogen inlet tube. Next, 5.4 g of TCA9 and 16 g of γ-butyrolactone were added to the reaction vessel. While stirring the contents of the reaction vessel at room temperature, 3.2 g of pyridine was added to the reaction vessel. The contents of the reaction vessel were then stirred at room temperature for 16 hours. Next, under ice cooling, a solution of 8.1 g of dicyclohexylcarbodiimide (DCC) dissolved in 8 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring the reaction mixture. Subsequently, a suspension of 3.6 g of DA6 suspended in 11 g of γ-butyrolactone was added to the reaction mixture over 60 minutes while stirring the reaction mixture. After stirring the reaction mixture at room temperature for 4 hours, 1.6 g of ethyl alcohol was added to the reaction mixture. After stirring the reaction mixture for 1 hour, 40 g of γ-butyrolactone was added to the reaction mixture to form a precipitate. The precipitate was removed by filtration to obtain a solution of the reaction mixture. The obtained reaction mixture was added to 160 g of ethyl alcohol to form a precipitate consisting of a crude polymer. After filtering off the crude polymer, the obtained crude polymer was dissolved in 100 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 1000 g of water to precipitate the polymer. After filtering off the precipitate, it was vacuum-dried to obtain a polyamide resin, which is a polycondensate of DADPE and a diphenyl ether dicarboxylic acid having an oxycarbonyl group (CH2=C(CH3)CO-O-CH2CH2-O-CO-), which is a reaction product of ODPA and HEMA. 75.0 g of NMP, 24.5 g of the polyamide resin obtained above, and 0.49 g of photopolymerization initiator (product name: TR-PBG-305, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) were added to a newly prepared flask. The mixture in the flask was stirred at room temperature for 1 hour to obtain a homogeneous resin solution with a viscosity of approximately 3,000 cP. This resin solution was coated onto a Corning glass substrate (product name: Eagle XG, material: alkali-free glass, thickness: 0.7 mm, size: 100 mm × 100 mm) using a spin coater. The formed coating film was heated in air at 80°C for 30 minutes, followed by an integrated exposure of 300 mJ / cm².2 The entire surface of the coating film was exposed by irradiating it with ultraviolet light under the specified conditions. Subsequently, the exposed coating film was heated in a nitrogen atmosphere at 200°C (curing temperature) for 60 minutes to obtain a resin film with a thickness of 6 μm. The properties of the obtained resin film are shown in Table 2.

[0078] The number-average molecular weights of the polyimide and polyamide resins formed in Examples 1 to 6 and Comparative Examples 1 to 4 are as follows. The number-average molecular weights are polystyrene-converted values ​​measured by gel permeation chromatography. Example 1: 49,000 Example 2: 47,000 Example 3: 50,000 Example 4: 13,000 Example 5: 65,000 Example 6: 36,000 Comparative Example 1: 35,000 Comparative Example 2: 51,000 Comparative Example 3: 50,000 Comparative Example 4: 14,000

[0079] The curing temperature for the polyimide film was set to a temperature at which the solvent dries sufficiently, no degradation of the polyimide occurs, and the imide formation of the polyamic acid proceeds sufficiently.

[0080] For each example and comparative example, the package substrates obtained, or the insulating layers formed using the varnishes obtained in each example and comparative example, were evaluated for water absorption, internal stress, linear thermal expansion coefficient (CTE), surface roughness Ra, 5% weight loss temperature (TD5), tensile elongation, and warpage. These evaluation methods are shown below.

[0081] (Water absorption rate) The weight W1 of the insulating layer sample was measured immediately after drying it at 150°C for 30 minutes. Next, the dried sample was immersed in distilled water for 24 hours, after which the sample was removed from the distilled water and the distilled water was wiped off the surface of the sample. The weight W2 of the sample from which the distilled water had been wiped off was measured. The water absorption rate was calculated from W1 and W2 based on the following formula. Water absorption rate (%)=(W2-W1)÷W1×100

[0082] (Internal stress) First, a varnish containing polyamic acid or polyimide was applied to a Corning-manufactured alkali-free glass substrate (trademark: Eagle XG, 0.7 mm thick, 100 mm x 100 mm) using a spin coater to form a coating film. The amount of warpage of the alkali-free glass substrate was measured in advance. Next, the formed coating film was heated at 80°C for 30 minutes in an air atmosphere, and then fired at 350°C for 60 minutes in a nitrogen atmosphere to form an insulating layer with a thickness of 6 μm on an alkali-free glass substrate. To eliminate the effect of water absorption in the insulating layer, the laminate consisting of an alkali-free glass substrate and an insulating layer was dried at 120°C for several minutes. Subsequently, the warpage of the laminate at 25°C under a nitrogen atmosphere was measured using a thin-film stress measuring device (FLX-2320-S, manufactured by KLA-Tencor). Using the warpage of the alkali-free glass substrate and the warpage of the laminate, measured by the methods described above, the internal stress generated between the glass substrate and the insulating layer was calculated using Stoney's formula.

[0083] (Coefficient of linear thermal expansion (CTE)) First, an insulating layer was formed on a glass core substrate, and then the insulating layer was peeled off the glass core substrate. From the obtained insulating layer, strip-shaped test pieces measuring 3 mm in width and 10 mm in length were cut out. The film thickness of the obtained test pieces was measured, and the cross-sectional area in the width direction of the test pieces was calculated. The linear thermal expansion coefficient (CTE) was measured using a thermomechanical analyzer. A Hitachi High-Tech Science Corporation "TMA / SS7100" thermomechanical analyzer was used. Specifically, a load of 29.4 mN was applied to the lengthwise direction of the sample, and the temperature was increased from 10°C to 350°C at a rate of 10°C / min. Then, the temperature was decreased at 40°C / min, and data on the change in strain per unit temperature between 100°C and 300°C during the cooling process was obtained. The linear thermal expansion coefficient was determined based on the obtained data on the change in strain.

[0084] (Surface roughness Ra) The surface roughness was measured using an optical interferometry surface roughness meter (ZYGO NewView 5030 system) under the following conditions. (Measurement conditions) Objective lens: 50x mirror Image zoom: 2 FDA Res: Normal (Analysis conditions) Remove: Cylinder Filter: High Pass Filter Low Waven: 0.002mm

[0085] (5% weight loss temperature (TD5)) First, an insulating layer was formed on a glass core substrate, and a sample was taken from the formed insulating layer. Using the acquired sample, the 5% weight loss temperature (TD5) was determined by measurement using a differential thermogravimetric / thermogravimetric analyzer (TG / DTA). The TGDTA7200 manufactured by Hitachi High-Tech Science Corporation was used as the differential thermogravimetric analyzer (TG / DTA). Specifically, TG / DTA measurements were performed in the range of 25 to 600°C at a heating rate of 20°C / min. Considering the effect of moisture in the sample, the temperature at which the sample weight was reduced to 95% of the reference weight was used, and the 5% weight loss temperature (TD5) was obtained.

[0086] (Tensile elongation) The tensile elongation was measured by performing a tensile test using an autograph under the following conditions. The autograph used was the "AGS-J" manufactured by Shimadzu Corporation. Sample measurement range: 15mm width Distance between gripping parts: 50mm Test speed: 10 mm / min Specimen shape: Strip-shaped

[0087] (Amount of curvature) The amount of warpage of the laminate was evaluated using the same method as the internal stress measurement method described above.

[0088] The criteria for each evaluation are as follows.

[0089] (Water absorption rate) The following is a rating system using four levels: A through D. A, B, and C are considered passing grades. A: 0.5% or less B: More than 0.5% and less than 0.8% C: More than 0.8% and less than 1.5% D: More than 1.5%

[0090] (Internal stress) The following is a rating system using four levels: A through D. A and B are considered passing grades. A: 10MPa or less B: More than 10MPa and less than 20MPa C: More than 20MPa and less than 30MPa D: Over 30MPa

[0091] (Coefficient of linear thermal expansion (CTE)) The following is a rating system using four levels: A through D. A and B are considered passing grades. A: 10ppm / K or less B: More than 10ppm / K and less than 20ppm / K C: More than 20ppm / K and less than 30ppm / K D: More than 30ppm / K

[0092] (Surface roughness Ra) The following is a rating system using four levels: A through D. A, B, and C are considered passing grades. A: 0.4nm or less B: More than 0.4nm and less than 1.0nm C: More than 1.0nm and less than 10nm D: More than 10nm

[0093] (5% weight loss temperature (TD5)) The following is a rating system using four levels: A through D. A, B, and C are considered passing grades. A: Above 550℃ B: 500℃ or higher but less than 550℃ C: 400℃ or higher, less than 500℃ D: Below 400℃

[0094] (Tensile elongation) The following is a rating system using four levels: A through D. A, B, and C are considered passing grades. A: 20% or more B: 10% or more but less than 20% C: 1% or more, less than 10% D: Less than 1%

[0095] (Amount of curvature) The following is a rating system using four levels: A through D. A and B are considered passing grades. A: 6μm or less B: More than 6μm and less than 12μm C: More than 12μm and less than 18μm D: More than 18μm

[0096] [Table 1]

[0097] [Table 2]

[0098] Tables 1 and 2 show that in a package substrate comprising a glass core substrate, a conductor layer, and an insulating layer, the conductor layer is formed to cover a portion of the first main surface, a portion of the second main surface, and at least a portion of the side walls defining the through holes of the glass core substrate, at least a portion of the conductor layer is covered with an insulating layer, the insulating layer contains polyimide, the imide group concentration of the polyimide is 15% to 38%, the internal stress of the insulating layer is 20 MPa or less, and the surface roughness Ra of the insulating layer is 10 nm or less, thereby enabling the manufacture of a package substrate with an insulating layer that has low water absorption and CTE, resulting in high insulation reliability, resistance to warping, and resistance to peeling from the glass core substrate.

Claims

1. A package substrate comprising a glass core substrate, a conductive layer, and an insulating layer, The glass core substrate has a first main surface, a second main surface which is the surface opposite to the first main surface, and through holes. The through hole penetrates between the first main surface and the second main surface in the glass core substrate. The conductor layer covers at least a portion of the first main surface, at least a portion of the second main surface, and at least a portion of the side wall defining the through hole. The insulating layer covers at least a portion of the conductive layer. The insulating layer contains polyimide, The imide group concentration of the polyimide is 15% or more and 38% or less. The internal stress of the insulating layer is 20 MPa or less. A package substrate having a surface roughness Ra of 10 nm or less for the insulating layer.

2. The aforementioned polyimide is a polymer of tetracarboxylic dianhydride and diamine. The tetracarboxylic dianhydride is 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic acid anhydride (BPADA), 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)-2,2',3,3',5,5'-hexamethylbiphenyl It contains one or more compounds selected from the group consisting of ru-4,4'-diyl (TAHMBP), 4,4'-oxydiphthalic acid dianhydride (ODPA), spiro[11H-difluoro[3,4-b:3',4'-i]xanthene-11,9'-[9H]fluorene]-1,3,7,9-tetron (SFDA), 9,9-bis(3,4-dicarboxyphenyl)fluorenodioanhydride (BPAF), and compounds represented by the following chemical formula (t1), 【Chemistry 1】 The diamine comprises one or more compounds selected from the group consisting of p-phenylenediamine (PDA), 4-aminophenyl-4-aminobenzoate (4-BAAB), 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB), 2,2'-bis(trifluoromethoxy)benzidine (TFMOB), diaminodiphenylsulfone (3,3'-DDS), and compounds represented by the following chemical formula (d1). 【Chemistry 2】 The package substrate according to claim 1.

3. The package substrate according to claim 1, wherein the coefficient of linear expansion (CTE) of the insulating layer is 20 ppm / K or less.

4. The package substrate according to claim 1, wherein the 5% weight loss temperature (TD5) of the insulating layer is 400°C or higher.

5. The package substrate according to claim 1, wherein the tensile elongation of the insulating layer is 1% or more.

6. A semiconductor package substrate comprising a package substrate according to any one of claims 1 to 5, and a semiconductor chip mounted on the package substrate.

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