Method for manufacturing substrate material for semiconductor package, prepreg, and application of prepreg
By controlling melt viscosity through a specific resin content and heating conditions in prepregs, the method achieves stable fine wiring with minimal width variations, enhancing high-density connections and chip mounting reliability in semiconductor packages.
Patent Information
- Application Number
- JP2023031146
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Filing Date
- 2023-03-01
- Publication Date
- 2026-01-06
- Estimated Expiration
- 2041-09-15
AI Technical Summary
Wiring substrates for semiconductor packages face challenges in achieving fine wiring with minimal variations in width, which is crucial for high-density connections and reliable chip mounting.
A method involving a laminate of prepregs with a specific resin content and heating conditions to control melt viscosity, ensuring rapid increase in viscosity, resulting in a substrate material with reduced thickness variations and stable fine wiring formation.
Enables stable formation of fine wiring with minimal width variations, facilitating high-density connections and reliable mounting of semiconductor chips with improved productivity and reduced warpage.
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Abstract
Description
[Technical Field]
[0001] The present disclosure relates to a method for manufacturing a substrate material for a semiconductor package having an insulating substrate, a prepreg, and the application of the prepreg to manufacturing a substrate material for a semiconductor package. [Background technology]
[0002] In order to realize high-speed transmission and miniaturization of semiconductor devices, it is necessary to connect wiring substrates for semiconductor packages and semiconductor chips at high density. As wiring substrates for semiconductor packages, those having a structure that can connect different types of semiconductor chips in parallel using a fine wiring layer and a structure that can mount semiconductor chips with fine bumps have been proposed. [Prior art documents] [Patent documents]
[0003] [Patent Document 1] Japanese Patent Application Publication No. 11-126978 [Patent Document 2] Japanese Patent Application Publication No. 8-198982 Summary of the Invention [Problem to be solved by the invention]
[0004] Wiring boards for semiconductor packages on which semiconductor chips are mounted are often manufactured by forming wiring on an insulating substrate of a substrate material for semiconductor packages. Substrate materials for semiconductor packages are generally manufactured by a method including heating and pressurizing a laminate including several stacked prepregs.
[0005] To achieve higher density, wiring substrates for semiconductor packages are often required to have fine wiring with widths of 10 μm or less. However, when forming such fine wiring, minute variations in the wiring width can become a significant problem.
[0006] One aspect of the present disclosure relates to a substrate material for semiconductor packages that enables stable formation of fine wiring while suppressing variations in wiring width. [Means for solving the problem]
[0007] One aspect of the present disclosure relates to a method for producing a substrate material for a semiconductor package having an insulating substrate, the method comprising: forming an insulating substrate from a laminate including two or more prepregs by a molding process that includes increasing the temperature of the laminate while applying pressure to the laminate. The prepreg includes an inorganic fiber base material and a thermosetting resin composition impregnated into the inorganic fiber base material, and the content of the thermosetting resin composition is 40% by mass or more and 80% by mass or less based on the mass of the prepreg. The molding process includes increasing the temperature of the laminate from 55×10 to 150°C from the point at which the melt viscosity of the prepreg reaches its minimum. 3 1000×10 Pa·s / min or faster 3 This involves heating the material to a temperature of 100 Pa·s.
[0008] Generally, the melt viscosity of a prepreg decreases with increasing temperature, reaches a minimum value (minimum melt viscosity), and then increases. The rate of increase in melt viscosity varies depending on the influence of heating conditions, etc. According to the findings of the present inventors, in a molding process for forming a substrate material, when a laminate containing a prepreg with a specific resin content is heated, the rate of increase in the melt viscosity of the prepreg increases from the point at which the minimum melt viscosity is reached to 55 × 10 3 1000×10 Pa·s / min or faster 3 When heated under conditions that increase the thermal conductivity to Pa·s, a substrate material with extremely small thickness variations is formed. When wiring is formed using this substrate material with small thickness variations, the variation in wiring width is suppressed more than before.
[0009] Another aspect of the present disclosure relates to a prepreg comprising an inorganic fiber substrate and a thermosetting resin composition impregnated into the inorganic fiber substrate. The content of the thermosetting resin composition is 40 to 80 mass% based on the mass of the prepreg. The melt viscosity of the prepreg measured at a temperature rising rate of 4°C / min is 55 × 10 from the point at which the melt viscosity reaches its minimum. 3 1000×10 Pa·s / min or faster 3 It rises to Pa·s.
[0010] By using the prepreg according to one aspect of the present disclosure in the above method, it is possible to easily produce a substrate material for a semiconductor package that enables the stable formation of fine wiring while suppressing variations in wiring width. [Effects of the Invention]
[0011] According to one aspect of the present disclosure, there is provided a substrate material for semiconductor packages that enables stable formation of fine wiring while suppressing variation in wiring width. Because variation in wiring width is small, high-density fine wiring can be easily formed. The substrate material for semiconductor packages according to one aspect of the present disclosure is also excellent in terms of reducing warpage. A wiring board formed from the substrate material for semiconductor packages according to one aspect of the present disclosure enables semiconductor chips having fine bumps to be mounted with high reliability and good productivity. [Brief explanation of the drawings]
[0012] [Figure 1] FIG. 1 is a cross-sectional view showing an example of a prepreg. [Figure 2] 1A to 1C are cross-sectional views showing an example of a method for manufacturing a substrate material for a semiconductor package. [Figure 3] 1A to 1C are cross-sectional views showing an example of a method for manufacturing a substrate material for a semiconductor package. DETAILED DESCRIPTION OF THE INVENTION
[0013] The invention is not limited to the examples described below.
[0014] Fig. 1 is a cross-sectional view showing an example of a prepreg. The prepreg 1 shown in Fig. 1 includes an inorganic fiber base material 11 and a thermosetting resin composition 12 impregnated into the inorganic fiber base material 11.
[0015] The inorganic fiber substrate 11 can be, for example, a woven or nonwoven fabric containing inorganic fibers. The inorganic fibers constituting the inorganic fiber substrate 11 may be glass fibers, carbon fibers, or a combination thereof. The inorganic fiber substrate 11 may also be a glass cloth made of glass fibers. The proportion of glass fibers in the inorganic fibers constituting the inorganic fiber substrate may be 80 to 100 mass %, 90 to 100 mass %, 95 to 100 mass %, or 99 to 100 mass %. The glass fibers may be, for example, E-glass, S-glass, or quartz glass. The thickness of the inorganic fiber substrate 11 may be 0.01 to 0.20 μm.
[0016] When measured at a temperature rise rate of 4°C / min, the melt viscosity of prepreg 1 was 55 x 10 3 1000×10 Pa·s / min or faster 3 The melt viscosity may increase from the minimum melt viscosity to 1000×10 Pa·s. 3 This is the average rate of increase in melt viscosity per minute from the time when the melt viscosity reaches the minimum melt viscosity [Pa s] to the time when the melt viscosity reaches the minimum melt viscosity [Pa s]. 3 If the time required for the viscosity to rise to Pa·s is T minutes, the rate of increase in melt viscosity can be calculated using the following formula: Melt viscosity increase rate [Pa·s / min] = (1000×10 3 -Minimum melt viscosity) / T
[0017] From the viewpoint of further suppressing the variation in wiring width, the rate of increase in melt viscosity is set to 60×10 3 Pa·s / min or more, 65×10 3 Pa·s / min or more, 70×10 3 Pa·s / min or more, 75×10 3 Pa·s / min or more, 80×103 Pa·s / min or more, 85×10 3 Pa·s / min or more, 90×10 3 Pa·s / min or more, 95×10 3 Pa·s / min or more, 100×10 3 Pa·s / min or more, 105×10 3 Pa·s / min or more, or 110×10 3 Pa s / min or more, and 200×10 3 Pa·s / min or less, 190×10 3 Pa·s / min or less, 180×10 3 Pa·s / min or less, 170×10 3 Pa·s / min or less, or 160×10 3 It may be less than Pa·s / min.
[0018] The melt viscosity of a prepreg is measured by sandwiching a prepreg specimen between two parallel plates with a diameter of 8 mm and measuring the dynamic viscoelasticity in shear mode at a frequency of 10 Hz while heating from 20°C to 200°C or higher at a predetermined heating rate (e.g., 4°C / min). The thickness of the specimen for measurement is 10 to 400 μm, and if necessary, two or more prepregs may be laminated to prepare the specimen. For measurement, a viscoelasticity measuring device, such as the ARES (Rheometrics Scientific F.E., Inc.), can be used.
[0019] From the viewpoint of further suppressing the variation in wiring width, the minimum melt viscosity of prepreg 1 measured at a temperature rise rate of 4°C / min is 10 × 10 3 Pa·s or less, 9.0×10 3 Pa·s or less, 8.0×10 3 Pa·s or less, 7.0×10 3 Pa·s or less, 6.0×10 3 Pa·s or less, 5.0×10 3 Pa·s or less, or 4.0×10 3 Pa s or less, and 1.0 × 10 3 It may be Pa·s or more.
[0020] The temperature at which prepreg 1 exhibits the minimum melt viscosity may be 80°C or higher from the viewpoint of prepreg handleability, or 120°C or higher from the viewpoint of storage stability. The temperature at which prepreg 1 exhibits the minimum melt viscosity may be 200°C or lower from the viewpoint of productivity, or 180°C or lower from the viewpoint of reducing warpage.
[0021] The content of the thermosetting resin composition 12 in the prepreg 1 may be 40 to 80 mass %. Using a prepreg containing 40 to 80 mass % of the thermosetting resin composition 12, a substrate material for a semiconductor package with little thickness variation can be easily produced by the method described below. The content of the thermosetting resin composition 12 can be adjusted, for example, by the amount of the curable resin composition applied depending on the thickness of the inorganic fiber substrate 11.
[0022] The content of thermosetting resin composition 12 in prepreg 1 can be determined, for example, by a method including dividing a cross-sectional photograph of prepreg 1 into a region of inorganic fiber substrate 11 and a region of thermosetting resin composition 12 by binarization processing and calculating the area of each. In this case, the density of inorganic fiber substrate 11 and the density of thermosetting resin composition 12 may be considered to be the same.
[0023] The thermosetting resin composition 12 may contain an inorganic component in addition to the thermosetting resin component. The proportion of the resin component in the thermosetting resin composition 12 may be 20 to 100 mass% relative to the mass of the thermosetting resin composition 12, or may be 20 to 80 mass% from the viewpoint of reducing the linear expansion coefficient, 30 to 100 mass% from the viewpoint of reducing voids after lamination, or 40 to 100 mass% from the viewpoint of further improving the flatness of the substrate material. Thus, the proportion of the resin component in the thermosetting resin composition 12 may be 40 to 80 mass% relative to the mass of the thermosetting resin composition 12. In other words, the proportion of the resin component in the prepreg 1 may be 16 to 64 mass%.
[0024] The proportion of the resin component contained in the thermosetting resin composition 12 can be calculated by a method such as ash content measurement. Ash content measurement is a method of calculating the proportion of the resin component by carbonizing the resin component at high temperature.
[0025] In the thermosetting resin composition 12, components excluding inorganic components may be considered to be resin components. An example of an inorganic component is an inorganic filler. In the thermosetting resin composition 12, components excluding inorganic fillers may be considered to be resin components.
[0026] The melt viscosity increase rate and minimum melt viscosity of prepreg 1 can be controlled, for example, by the content of the thermosetting resin composition in prepreg 1 and the composition of the resin components. The melt viscosity increase rate and minimum melt viscosity of prepreg 1 can be controlled by adjusting the ratio of inorganic components in the resin components, the molecular weight and glass transition temperature of the high-molecular-weight component contained in the resin components, the type and blending ratio of thermosetting resin, and the type and blending ratio of curing accelerator. The melt viscosity increase rate and minimum melt viscosity of prepreg 1 tend to increase when the content of the thermosetting resin composition is high.
[0027] In particular, the molecular weight and glass transition temperature of the high-molecular-weight component contained in the resin component, as well as the type and blending ratio of the curing accelerator, can significantly affect the behavior of the melt viscosity of the prepreg. For example, the glass transition temperature of the high-molecular-weight component may be lower than the temperature at which the curing reaction of the thermosetting resin composition is activated. The glass transition temperature of the high-molecular-weight component may be the temperature at which the maximum value of tan δ is obtained when the dynamic viscoelasticity of a strip-shaped molded product of the high-molecular-weight component is measured in a temperature range of 40 to 350°C under conditions of a chuck distance of 20 mm, a frequency of 10 Hz, and a heating rate of 5°C / min. A dynamic viscoelasticity measuring device manufactured by UBM, for example, can be used to measure the dynamic viscoelasticity. The temperature at which the curing reaction of the thermosetting resin composition is activated may be the temperature at which the maximum heat generation due to the curing reaction is obtained when differential scanning calorimetry of the thermosetting resin composition is performed in a temperature range of 40 to 350°C at a heating rate of 5°C / min. A differential scanning calorimeter manufactured by PerkinElmer, for example, can be used to measure the differential scanning calorimetry.
[0028] The glass transition temperature of the high molecular weight component may be 10 to 80°C lower than the temperature at which the curing reaction of the thermosetting resin composition is activated. From the viewpoint of reducing the influence of temperature variations when laminating the prepregs, the glass transition temperature of the high molecular weight component may be 20 to 80°C lower than the temperature at which the curing reaction of the thermosetting resin composition is activated. From the viewpoint of suppressing voids when laminating the prepregs, the glass transition temperature of the high molecular weight component may be 10 to 60°C lower than the temperature at which the curing reaction of the thermosetting resin composition is activated. Therefore, the glass transition temperature of the high molecular weight component may be 20 to 60°C lower than the temperature at which the curing reaction of the thermosetting resin composition is activated.
[0029] The thermosetting resin composition 12 may contain a thermoplastic resin as a high-molecular-weight component. The thermoplastic resin is not particularly limited as long as it is a resin that softens when heated, and may have one or more reactive functional groups at the molecular end or in the molecular chain. Examples of the reactive functional group include an epoxy group, a hydroxyl group, a carboxyl group, an amino group, an amide group, an isocyanato group, an acryloyl group, a methacryloyl group, a vinyl group, and a maleic anhydride group.
[0030] The thermoplastic resin may be, for example, at least one selected from an acrylic resin, a polyamide resin, a polyimide resin, and a polyurethane resin.
[0031] The content of the thermoplastic resin may be, for example, 20 to 80 mass % based on the total mass of the components of the thermosetting resin composition 12 other than the inorganic filler.
[0032] To suppress moisture absorption, the thermoplastic resin may contain a resin having a siloxane group. For example, an acrylic resin, a polyamide resin, a polyimide resin, or a polyurethane resin may have a siloxane group. The resin having a siloxane group may be a silicone resin.
[0033] From the viewpoints of suppressing outgassing during heating and improving adhesiveness, the thermoplastic resin may contain a polyimide resin having a siloxane group, which may be, for example, a polymer formed by the reaction of a siloxane diamine with a tetracarboxylic dianhydride or a polymer formed by the reaction of a siloxane diamine with a bismaleimide.
[0034] The siloxane diamine may be, for example, a compound represented by the following general formula (5). [ka] In the formula, Q 4 and Q 9 each independently represents an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and Q 5 , Q 6 , Q 7 and Q 8 each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a phenoxy group; and d represents an integer of 1 to 5.
[0035] Examples of siloxane diamines represented by formula (5) where d is 1 include 1,1,3,3-tetramethyl-1,3-bis(4-aminophenyl)disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis(4-aminoethyl)disiloxane, 1,1,3,3-tetraphenyl-1,3-bis(2-aminoethyl)disiloxane, and 1,1,3,3-tetraphenyl-1,3-bis(3-amino propyl)disiloxane, 1,1,3,3-tetramethyl-1,3-bis(2-aminoethyl)disiloxane, 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane, 1,1,3,3-tetramethyl-1,3-bis(3-aminobutyl)disiloxane, and 1,3-dimethyl-1,3-dimethoxy-1,3-bis(4-aminobutyl)disiloxane. Examples of siloxane diamines represented by formula (5) where d is 2 include 1,1,3,3,5,5-hexamethyl-1,5-bis(4-aminophenyl)trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethyl-1,5-bis(3-aminopropyl)trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis(4-aminobutyl)trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis(5-aminopentyl)trisiloxane, and 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis( 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis(4-aminobutyl)trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis(5-aminopentyl)trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis(3-aminopropyl)trisiloxane, 1,1,3,3,5,5-hexaethyl-1,5-bis(3-aminopropyl)trisiloxane, and 1,1,3,3,5,5-hexapropyl-1,5-bis(3-aminopropyl)trisiloxane.
[0036] Examples of commercially available siloxane diamines include "PAM-E" (amino group equivalent weight 130 g / mol), "KF-8010" (amino group equivalent weight 430 g / mol), "X-22-161A" (amino group equivalent weight 800 g / mol), "X-22-161B" (amino group equivalent weight 1500 g / mol), "KF-8012" (amino group equivalent weight 2200 g / mol), "KF-8008" (amino group equivalent weight 5700 g / mol), and "X-22-94 Examples of suitable siloxane diamines include "BY-16-09" (amino group equivalent 700 g / mol, side chain phenyl type), "X-22-1660B-3" (amino group equivalent 2200 g / mol, side chain phenyl type) (all manufactured by Shin-Etsu Chemical Co., Ltd.), "BY-16-853U" (amino group equivalent 460 g / mol), "BY-16-853" (amino group equivalent 650 g / mol), and "BY-16-853B" (amino group equivalent 2200 g / mol) (all manufactured by Dow Corning Toray Co., Ltd.). These can be used alone or in combination of two or more. Among these, siloxane diamines may be selected from "PAM-E", "KF-8010", "X-22-161A", "X-22-161B", "BY-16-853U", and "BY-16-853" in terms of reactivity with maleimide groups. In terms of dielectric properties, siloxane diamines may be selected from "PAM-E," "KF-8010," "X-22-161A," "BY-16-853U," and "BY-16-853." In terms of varnish compatibility, siloxane diamines may be selected from "KF-8010," "X-22-161A," and "BY-16-853."
[0037] The content of siloxane groups in the siloxane group-containing polyimide resin is not particularly limited, but may be 5 to 50 mass% based on the mass of the polyimide resin from the viewpoints of reactivity and compatibility, 5 to 30 mass% from the viewpoint of heat resistance, and 10 to 30 mass% from the viewpoint of further reducing moisture absorption.
[0038] The polyimide resin may be a polymer synthesized from a diamine other than siloxane diamine, or may be a polymer synthesized from a combination of siloxane diamine and other diamine.
[0039] Other diamines used as raw materials for polyimide resins are not particularly limited, and examples thereof include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethenemethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4- Amino-3,5-diisopropylphenyl)methane, 3,3'-diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenyl Ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis(3-aminophenyl)propane, 2,2'-(3,4'-diaminodiphenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-(3,4'-diaminodiphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 1,3-bis(3-aminophenoxy)benzene, 1, 4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,3'-(1,4-phenylenebis(1-methylethylidene))bisaniline, 3,4'-(1,4-phenylenebis(1-methylethylidene))bisaniline, 4,4'-(1,4-phenylenebis(1-methylethylidene))bisaniline, 2,2-bis(4-(3-aminophenoxy)phenyl)propane, 2,2-bis(4-(3-aminophenoxy)phenyl)hexafluoropropane, 2,Examples of the diamine include aromatic diamines such as 2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, bis(4-(3-aminophenoxy)phenyl)sulfide, bis(4-(4-aminophenoxy)phenyl)sulfide, bis(4-(3-aminophenoxy)phenyl)sulfone, bis(4-(4-aminophenoxy)phenyl)sulfone, 3,3'-dihydroxy-4,4'-diaminobiphenyl, and 3,5-diaminobenzoic acid, 1,3-bis(aminomethyl)cyclohexane, 2,2-bis(4-aminophenoxyphenyl)propane, aliphatic ether diamines represented by the following general formula (4), aliphatic diamines represented by the following general formula (11), and diamines having a carboxyl group and / or a hydroxyl group. [ka] In formula (4), Q 1 , Q 2 and Q 3 each independently represents an alkylene group having 1 to 10 carbon atoms; and b represents an integer of 2 to 80. [ka] In the formula (11), c represents an integer of 5 to 20.
[0040] Examples of the aliphatic ether diamine represented by the general formula (4) include those represented by the following general formula: [ka] and aliphatic ether diamines represented by the following general formula (12). [ka] In the formula (12), e represents an integer of 0 to 80.
[0041] Examples of the aliphatic diamine represented by the general formula (11) include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and 1,2-diaminocyclohexane.
[0042] The diamines exemplified above can be used alone or in combination of two or more.
[0043] Tetracarboxylic dianhydrides can be used as raw materials for polyimide resins. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, Bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,2',3'-benzophenonetetracarboxylic dianhydride, 3,3,3',4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine -2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,4,3',4'-biphenyltetracarboxylic dianhydride, 2,3,2',3'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)dimethylsilane dianhydride, bis(3,4-dicarboxyphenyl)methylphenylsilane dianhydride, bis(3,4-dicarboxyphenyl)diphenylsilane dianhydride, 1,4-bis(3,4-Dicarboxyphenyldimethylsilyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylene bis(trimellitate anhydride), ethylene tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexachloro Dronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis(exo-bicyclo[2,2,1]heptane-2,3-dicarboxylic dianhydride, bicyclo-[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis( 3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenyl)phenyl]propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenyl)phenyl]hexafluoropropane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 1,4-bis(2-hydroxyhexafluoroisopropyl)benzenebis(trimellitic anhydride), 1,3-bis(2-hydroxyhexafluoroisopropyl)benzenebis(trimellitic anhydride), 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride, and tetracarboxylic acid dianhydrides represented by the following general formula (7): [ka] In the formula (7), a represents an integer of 2 to 20.
[0044] Examples of tetracarboxylic dianhydrides represented by the general formula (7) above include those that can be synthesized from trimellitic anhydride monochloride and the corresponding diol, and specifically include 1,2-(ethylene)bis(trimellitate anhydride), 1,3-(trimethylene)bis(trimellitate anhydride), 1,4-(tetramethylene)bis(trimellitate anhydride), 1,5-(pentamethylene)bis(trimellitate anhydride), and 1,6-(hexamethylene)bis(trimellitate anhydride). , 1,7-(heptamethylene)bis(trimellitate anhydride), 1,8-(octamethylene)bis(trimellitate anhydride), 1,9-(nonamethylene)bis(trimellitate anhydride), 1,10-(decamethylene)bis(trimellitate anhydride), 1,12-(dodecamethylene)bis(trimellitate anhydride), 1,16-(hexadecamethylene)bis(trimellitate anhydride), and 1,18-(octadecamethylene)bis(trimellitate anhydride).
[0045] The tetracarboxylic dianhydride may include a tetracarboxylic dianhydride represented by the following general formula (6) or (8) from the viewpoint of imparting good solubility in a solvent and moisture resistance reliability. [ka] [ka]
[0046] The above-mentioned tetracarboxylic dianhydrides can be used alone or in combination of two or more.
[0047] Bismaleimide can be used as a raw material for polyimide resin. Although the bismaleimide is not particularly limited, examples thereof include bis(4-maleimidophenyl)methane, polyphenylmethane maleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, and 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane. These can be used alone or in combination of two or more. The bismaleimide may be selected from bis(4-maleimidophenyl)methane, bis(4-maleimidophenyl)sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, and 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, which are highly reactive and can improve dielectric properties and wireability; from 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, bis(4-maleimidophenyl)methane, and 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane in terms of solubility in solvents; from bis(4-maleimidophenyl)methane in terms of inexpensiveness; and from the viewpoint of wireability, from 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane and BMI-3000 (product name) by Desiigner Molecules, Inc.
[0048] The thermosetting resin composition 12 includes a thermosetting resin, which is a compound that forms a crosslinked polymer upon heating. The thermosetting resin typically has a reactive functional group that undergoes a crosslinking reaction. The reactive functional group may be, for example, an epoxy group, a hydroxyl group, a carboxyl group, an amino group, an amide group, an isocyanato group, an acryloyl group, a methacryloyl group, a vinyl group, a maleic anhydride group, or a combination thereof.
[0049] The content of the thermosetting resin may be, for example, 20 to 80 mass % based on the total mass of the components of the thermosetting resin composition 12 other than the inorganic filler.
[0050] The thermosetting resin composition 12 may contain an epoxy resin as a thermosetting resin. The epoxy resin may be a compound containing two or more epoxy groups. The epoxy resin may be a phenol glycidyl ether type epoxy resin in terms of curability and cured product properties. Examples of phenol glycidyl ether type epoxy resins include biphenylaralkyl type epoxy resins, bisphenol A type (or AD type, S type, or F type) glycidyl ethers, hydrated bisphenol A type glycidyl ethers, ethylene oxide adduct bisphenol A type glycidyl ethers, propylene oxide adduct bisphenol A type glycidyl ethers, phenol novolac resin glycidyl ethers, cresol novolac resin glycidyl ethers, bisphenol A novolac resin glycidyl ethers, naphthalene resin glycidyl ethers, trifunctional (or tetrafunctional) glycidyl ethers, and dicyclopentadiene phenol resin glycidyl ethers. Other examples of epoxy resins include glycidyl esters of dimer acids, trifunctional (or tetrafunctional) glycidyl amines, and glycidyl amines of naphthalene resins, which may be used alone or in combination of two or more.
[0051] The thermosetting resin composition 12 may contain an acrylate compound as a thermosetting resin. The acrylate compound may have two or more (meth)acryloyl groups. Examples of the acrylate compound include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, and pentaerythritol triacrylate. Examples of the acrylate include methyl acrylate, methyl methacrylate, ... [ka]
[0052] In formula (13), R 41 and R 42each independently represents a hydrogen atom or a methyl group, and f and g each independently represent an integer of 1 or greater. A radiation-polymerizable compound having a glycol skeleton as represented by formula (13) can impart solvent resistance after curing. Urethane acrylate, urethane methacrylate, isocyanuric acid-modified di / triacrylate, and methacrylate can impart high adhesiveness after curing.
[0053] The thermosetting resin composition 12 may contain a thermosetting elastomer selected from styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic elastomers, and silicone-based elastomers. Thermosetting elastomers are composed of hard segment components and soft segment components, with the hard segment components generally contributing to heat resistance and strength, and the soft segment components contributing to flexibility and toughness. These thermosetting elastomers may be used alone or in combination of two or more. The thermosetting elastomer may be selected from styrene-based elastomers, olefin-based elastomers, polyamide-based elastomers, and silicone-based elastomers in terms of heat resistance and insulation reliability, or from styrene-based elastomers and olefin-based elastomers in terms of dielectric properties.
[0054] The thermosetting elastomer has a reactive functional group at the molecular end or in the molecular chain. Examples of the reactive functional group include an epoxy group, a hydroxyl group, a carboxyl group, an amino group, an amide group, an isocyanato group, an acryloyl group, a methacryloyl group, a vinyl group, and a maleic anhydride group. From the viewpoints of compatibility and wireability, the reactive functional group of the thermosetting elastomer may be an epoxy group, an amino group, an acryloyl group, a methacryloyl group, a vinyl group, or a maleic anhydride group, or may be an epoxy group, an amino group, or a maleic anhydride group. The content of the thermosetting elastomer may be 10 to 70 mass% based on the mass of the thermosetting resin composition, or may be 20 to 60 mass% from the viewpoints of dielectric properties and varnish compatibility.
[0055] The thermosetting resin composition may optionally contain a curing accelerator that accelerates the curing reaction of the thermosetting resin. Examples of the curing accelerator include peroxides, imidazole compounds, organic phosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. These may be used alone or in combination of two or more. When the thermosetting resin is an epoxy resin, the curing accelerator may be, for example, an imidazole compound.
[0056] The content of the curing accelerator may be 0.1 to 10 mass% based on the total mass of the components other than the inorganic filler in the thermosetting resin composition, or may be 0.5 to 5 mass%, or 0.75 to 3 mass% from the viewpoints of dielectric properties and handling properties of the prepreg.
[0057] The thermosetting resin composition 12 may contain an adhesion aid, such as a silane coupling agent, a triazole compound, or a tetrazole compound.
[0058] The silane coupling agent may be a compound having a nitrogen atom to improve adhesion to metal. Examples of the silane coupling agent include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, and 3-isocyanatepropyltriethoxysilane.
[0059] The content of the silane coupling agent may be 0.1 to 20 mass % based on the total mass of components other than the inorganic filler in the thermosetting resin composition 12, from the viewpoints of the effect of addition, heat resistance, production costs, and the like.
[0060] Examples of the triazole compound include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenone], and 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenone]. ol], 6-(2-benzotriazolyl)-4-tert-octyl-6'-tert-butyl-4'-methyl-2,2'-methylenebisphenol, 1,2,3-benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, carboxybenzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole, and 2,2'-[[(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol.
[0061] Examples of tetrazole compounds include 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 1-methyl-5-ethyl-1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-phenyl-5-mercapto-1H-tetrazole, 1-(2-dimethylaminoethyl)-5-mercapto-1H-tetrazole, 2-methoxy-5-(5-trifluoromethyl-1H-tetrazol-1-yl)-benzaldehyde, 4,5-di(5-tetrazolyl)-[1,2,3]triazole, and 1-methyl-5-benzoyl-1H-tetrazole.
[0062] The content of the triazole compound and the tetrazole compound may be 0.1 to 20 mass % based on the total mass of the components other than the inorganic filler in the thermosetting resin composition 12, from the viewpoints of the effect of addition, heat resistance, and production costs.
[0063] The silane coupling agent, the triazole compound, and the tetrazole compound may be used alone or in combination.
[0064] The thermosetting resin composition 12 may contain an ion scavenger. The ion scavenger adsorbs ionic impurities in the organic insulating layer, thereby improving insulation reliability during moisture absorption. Examples of ion scavenger include compounds known as copper inhibitors for preventing copper from ionizing and dissolving, such as triazine thiol compounds and phenol-based reducing agents, as well as inorganic compounds based on bismuth, antimony, magnesium, aluminum, zirconium, calcium, titanium, tin, or mixtures thereof.
[0065] Examples of commercially available ion scavengers include inorganic ion scavengers manufactured by Toagosei Co., Ltd. (trade names: IXE-300 (antimony-based), IXE-500 (bismuth-based), IXE-600 (antimony and bismuth mixed), IXE-700 (magnesium and aluminum mixed), IXE-800 (zirconium-based), and IXE-1100 (calcium-based)). These may be used alone or in combination of two or more.
[0066] The content of the ion scavenger may be 0.01 to 10 mass % based on the total mass of the components of the thermosetting resin composition 12 other than the inorganic filler, from the viewpoints of the effect of addition, heat resistance, production costs, and the like.
[0067] The thermosetting resin composition 12 may contain a filler to impart low moisture absorption and low moisture permeability. The filler may be an inorganic filler, an organic filler, or a combination thereof. The inorganic filler can be added to the insulating substrate for the purpose of imparting thermal conductivity, low thermal expansion, low moisture absorption, etc., to the insulating substrate. The organic filler can be added to the insulating substrate for the purpose of imparting toughness, etc., to the insulating substrate.
[0068] Examples of inorganic fillers include alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, crystalline silica, amorphous silica, boron nitride, titania, glass, iron oxide, ceramic, and carbon. Examples of organic fillers include rubber-based fillers. These inorganic or organic fillers can be used alone or in combination of two or more. The thermosetting resin composition 12 may contain a silica filler and / or an alumina filler.
[0069] The average particle size of the filler may be 10 μm or less or 5 μm or less. The maximum particle size of the filler may be 30 μm or less or 20 μm or less. If the average particle size exceeds 10 μm and the maximum particle size exceeds 30 μm, it tends to be difficult to obtain the effect of improving fracture toughness. There are no particular restrictions on the lower limits of the average particle size and the maximum particle size, but they are usually 0.001 μm.
[0070] The filler may have both an average particle size of 10 μm or less and a maximum particle size of 30 μm or less. Fillers with a maximum particle size of 30 μm or less but an average particle size of more than 10 μm tend to relatively reduce adhesive strength. Fillers with an average particle size of 10 μm or less but a maximum particle size of more than 30 μm tend to increase variability in adhesive strength.
[0071] The average particle size and maximum particle size of the filler can be measured, for example, by using a scanning electron microscope (SEM) to measure the particle size of fillers on the order of 1000 particles. In the case of a measurement method using an SEM, for example, a cured product obtained by heat-curing a thermosetting resin composition may be produced, and the cross section of the central part of the cured product may be observed with the SEM. The probability of the presence of fillers with particle sizes of 30 μm or less may be 80% or more of all fillers.
[0072] The content of the filler (particularly the inorganic filler) may be, for example, 40 to 300 mass % based on the total mass of the components of the thermosetting resin composition 12 other than the filler.
[0073] The thermosetting resin composition may contain an antioxidant to improve storage stability, prevent electromigration, and prevent corrosion of the metal conductor circuit. Examples of antioxidants include benzophenone-based, benzoate-based, hindered amine-based, benzotriazole-based, and phenol-based antioxidants. The content of the antioxidant may be 0.01 to 10% by mass based on the total mass of the components of the thermosetting resin composition 12 other than the inorganic filler, in terms of the effect of addition, heat resistance, cost, etc.
[0074] The dielectric constant of the cured product of the thermosetting resin composition 12 at 10 GHz may be 3.0 or less, and may be 2.8 or less to further improve the reliability of electrical signals. The dielectric loss tangent of the cured product of the thermosetting resin composition 12 at 10 GHz may be 0.005 or less. The dielectric constant can be measured using a test piece of the cured product of the thermosetting resin composition, which is 60 mm long, 2 mm wide, and 300 μm thick. The test piece may be vacuum dried at 30°C for 6 hours before measurement. The dielectric loss tangent can be calculated from the resonant frequency and unloaded Q value obtained at 10 GHz. The measurement device may be a Keysight Technologies vector network analyzer E8364B, a Kanto Electronics Application Development CP531 (10 GHz resonator), and a CPMAV2 (program). The measurement temperature may be 25°C.
[0075] The glass transition temperature of the cured product formed by thermal curing of the thermosetting resin composition 12 may be 120°C or higher in order to suppress cracking during temperature cycling, or 140°C or higher in order to alleviate stress on wiring. The glass transition temperature of the cured product may be 240°C or lower in order to enable lamination at low temperatures, or 220°C or lower in order to suppress cure shrinkage.
[0076] The width of the prepreg 1 may be, for example, 200 to 1,300 mm. The thickness of the prepreg 1 may be, for example, 15 to 300 μm. If the thickness of the prepreg 1 is less than 15 μm, unevenness resulting from the inorganic fiber base material 11 tends to remain, resulting in a relatively reduced flatness. If the thickness of the prepreg 1 is more than 300 μm, warpage tends to increase.
[0077] The prepreg 1 can be obtained, for example, by a method including impregnating an inorganic fiber substrate 11 with a resin varnish containing a thermosetting resin composition 12 and a solvent, and removing the solvent from the resin varnish.
[0078] 2 and 3 are cross-sectional views showing an example of a method for producing a substrate material for a semiconductor package. The method shown in Figures 2 and 3 includes a step of forming a substrate material for a semiconductor package 100 having an insulating substrate 10 formed by integrating two or more prepregs 1 through a molding process that includes increasing the temperature of a laminate 5 having a metal foil 3, two or more prepregs 1, and the metal foil 3 stacked in this order, while applying pressure to the laminate 5. The insulating substrate 10 has metal foils 3 provided on both sides of the insulating substrate 10. An insulating resin layer may be provided between the metal foil 3 and the laminate 5.
[0079] In the molding process for forming the semiconductor package substrate material 100, the melt viscosity of the prepreg 1 is increased by 55×10 from the point where the melt viscosity of the prepreg 1 is at its minimum. 3 1000×10 Pa·s / min or faster 3 The laminate 5 is heated and pressurized under heating conditions that increase the pressure to Pa·s. By using a molding process under such heating conditions, a semiconductor package substrate material 100 with small thickness variations can be easily manufactured. Using the semiconductor package substrate material 100, semiconductor devices that transmit high-frequency signals and that have fine wiring and chips with fine bumps connected thereto can be manufactured with high reliability and productivity. The resulting semiconductor package substrate material 100 also excels in reducing warpage.
[0080] From the viewpoint of further suppressing the variation in wiring width, the melt viscosity increase rate exhibited by the prepreg 1 under the heating conditions of the molding process for forming the semiconductor package substrate material 100 is set to 60×10 3 Pa·s / min or more, 65×10 3 Pa·s / min or more, 70×10 3 Pa·s / min or more, 75×10 3 Pa·s / min or more, 80×10 3 Pa·s / min or more, 85×10 3 Pa·s / min or more, 90×10 3 Pa·s / min or more, 95×10 3 Pa·s / min or more, 100×10 3 Pa·s / min or more, 105×10 3 Pa·s / min or more, or 110×10 3 Pa s / min or more, and 200×10 3 Pa·s / min or less, 190×10 3 Pa·s / min or less, 180×10 3 Pa·s / min or less, 170×10 3 Pa·s / min or less, or 160×10 3 It may be less than Pa·s / min.
[0081] From the viewpoint of further suppressing the variation in wiring width, the minimum melt viscosity exhibited by the prepreg 1 under the heating conditions of the molding process for forming the semiconductor package substrate material 100 is 10×10 3 Pa·s or less, 9.0×10 3 Pa·s or less, 8.0×10 3 Pa·s or less, 7.0×10 3 Pa·s or less, 6.0×10 3 Pa·s or less, 5.0×10 3 Pa·s or less, or 4.0×10 3 Pa s or less, and 1.0 × 10 3 It may be Pa·s or more.
[0082] The temperature at which the prepreg 1 exhibits the minimum melt viscosity during the molding process may be 80°C or higher or 120°C or higher, and may be 200°C or lower or 180°C or lower.
[0083] The two or more prepregs 1 may be the same or different from one another. When two or more different prepregs 1 are used, the melt viscosity increase rate and minimum melt viscosity of at least the prepreg 1 located on the outermost side (the side closest to the metal foil 3) may be within the above ranges.
[0084] Under the heating conditions of the molding process for forming the semiconductor package substrate material 100, the melt viscosity of the prepreg 1 decreases to the minimum melt viscosity and then increases as the curing reaction progresses. Generally, a high temperature rise rate tends to lower the minimum melt viscosity of the prepreg 1. The temperature rise rate may be, for example, 2°C / min or more, 3°C / min or more, or 4°C / min or more, or 8°C / min or less, 7°C / min or less, or 6°C / min or less. The temperature rise rate may be constant or variable. The temperature of the laminate 5 may be increased, for example, starting from a temperature in the range of 20 to 120°C.
[0085] The heating conditions for the molding process to form the semiconductor package substrate material 100 may include increasing the temperature of the laminate 5 to a molding temperature at a predetermined temperature increase rate and maintaining the temperature of the laminate 5 at the molding temperature. In this case, the molding temperature may be, for example, 100 to 250°C, or 150 to 00°C. The heating and pressurizing time at the molding temperature may be, for example, 0.1 to 5 hours.
[0086] During the molding process, pressure is usually continuously applied to the laminate 5. The pressure applied to the laminate 5 during the molding process may be, for example, 0.2 to 10 MPa.
[0087] From the viewpoint of electrical conductivity, the metal foil 3 may contain copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements. The metal foil 3 may be a copper foil, an aluminum foil, or a copper foil. An insulating resin layer may be provided on the surface of the metal foil 3 facing the prepreg 1.
[0088] The device for the molding process of heating and pressurizing the laminate 5 can be a heat press device, and may be, for example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, or an autoclave molding machine.
[0089] When the inorganic fiber substrate 11 constituting the prepreg 1 is a woven fabric containing inorganic fibers, two or more prepregs may be laminated with the inorganic fibers oriented in the same direction, or with the inorganic fibers oriented at right angles to each other.
[0090] When the molding process for forming the semiconductor package substrate material is a heat press, a metal plate may be placed on the surface of the metal foil 3 opposite to the prepreg 1. The thickness of the metal plate may be 0.5 mm to 7 mm. If the metal plate is thinner than 0.5 mm, the metal plate may be easily moved. If the metal plate is thicker than 7 mm, handling may be impaired. The metal plate may be, for example, a stainless steel plate.
[0091] The standard deviation of the thickness measured at any number of points in an area of any size within the metal plate may be 4 μm or less. The standard deviation of the thickness of the metal plate may be, for example, T1, T2, . . . , T3, T4, T5, T6, T7, T8, T9, T10, T11, T12, T13, T14, T15, T16, T17, T18, T19, T20, T n and the average thickness of the metal plate is T, it can be calculated using the following formula.
number
[0092] In the hot press for forming the substrate material for a semiconductor package, a cushioning material may be placed on the surface of the metal foil 3 opposite to the prepreg 1. The cushioning material may be, for example, a paper material with a thickness of about 0.2 mm. Both the cushioning material and the metal plate may be used.
[0093] The molding process for forming a semiconductor package substrate material may be performed in multiple steps. For example, a method for producing a semiconductor package substrate material may further include the steps of laminating one or more additional prepregs on an insulating substrate formed by a first molding process to form a second laminate, and forming an insulating substrate after the second lamination, including a portion formed from the additional prepregs, by a molding process including increasing the temperature of the second laminate while applying pressure to the second laminate. In this case, the additional prepreg may also include an inorganic fiber substrate and a thermosetting resin composition impregnated into the inorganic fiber substrate. The content of the thermosetting resin composition may be 40% by mass or more and 80% by mass or less based on the mass of the additional prepreg. The additional prepreg may be the same as or different from the prepreg constituting the laminate in the first molding process. In the molding process for forming an insulating substrate after the second lamination, the temperature of the second laminate may be increased by 55 × 10 from the point at which the melt viscosity of the additional prepreg shows the minimum melt viscosity. 3 1000×10 Pa·s / min or faster 3 The heating conditions are increased to increase the thermal conductivity to Pa·s. Typically, the metal foil is removed from the first laminate before additional prepregs are laminated to the insulating substrate.
[0094] From the viewpoint of productivity, the width of the substrate material 100 for a semiconductor package may be 200 to 1,300 mm, and the thickness of the substrate material 100 for a semiconductor package may be 200 to 1,500 μm.
[0095] The semiconductor package substrate material 100 can have a thickness with little variation. For example, the standard deviation of the thickness of the semiconductor package substrate material may be 4 μm or less, 3.5 μm or less, 3 μm or less, 2.5 μm or less, or 2 μm or less, or may be 0.1 μm or more. The standard deviation of the thickness of the semiconductor package substrate material 100 can be determined by a method including: dividing the entire main surface of the semiconductor package substrate material into multiple square areas with sides of 50 mm, measuring the thickness at four locations 2 mm inward from the four corners of each area, calculating the standard deviation of the thickness using the thickness values measured at the four locations in each area as a population, and determining the maximum of the standard deviations of the thickness calculated for each area as the standard deviation of the thickness of the semiconductor package substrate material 100. The thickness is measured using, for example, a micrometer.
[0096] The substrate material 100 for semiconductor packages can be used, for example, as a core material for forming a wiring substrate for semiconductor packages on which a semiconductor chip is mounted. By utilizing the metal foil 3 of the substrate material 100 for semiconductor packages or by removing the metal foil 3 and forming wiring on the exposed insulating substrate, a wiring substrate for semiconductor packages having fine wiring can be manufactured.
[0097] The wiring board for semiconductor packages can be obtained, for example, by a method including forming wiring on metal foil 3 by a subtractive method, or by a method including forming wiring by a semi-additive method after removing metal foil 3 as needed. If necessary, through holes penetrating insulating substrate 10 may be formed, and conductive vias may be formed to fill the through holes.
[0098] A semiconductor package is manufactured by mounting a semiconductor chip, memory, etc., at a predetermined position on a wiring substrate for a semiconductor package. The wiring substrate for a semiconductor package obtained using the substrate material for a semiconductor package according to the present disclosure has small thickness variations, which tends to improve the yield of the process of mounting the semiconductor chip. Furthermore, a semiconductor chip having minute solder bumps can be more easily mounted on the wiring substrate.
[0099] A build-up layer may be formed on the wiring substrate for a semiconductor package. In this case, wiring connected to the semiconductor chip may be formed on the build-up layer. The build-up layer may be formed by, for example, a subtractive method, a full-additive method, a semi-additive method (SAP: Semi-Additive Process), a modified semi-additive method (m-SAP: Modified Semi-Additive Process), or a trench method.
[0100] The trench method involves forming a build-up material or photosensitive insulating material layer having a pattern including grooves on a wiring substrate and filling the grooves with a conductive material. The conductive material formed outside the grooves is removed by methods such as CMP or fly-cutting. If the thickness of the substrate material for semiconductor packages is small, the conductive material formed outside the grooves can be easily removed while leaving the conductive material filled in the grooves. [Example]
[0101] The present invention is not limited to the following examples.
[0102] 1.Prepreg Preparation Prepreg A 24 g of zircone diamine (trade name "KF-8010", manufactured by Shin-Etsu Silicones), 240 g of bis(4-maleimidophenyl)methane, and 400 g of propylene glycol monomethyl ether were placed in a flask equipped with a stirrer, a thermometer, and a nitrogen purge device. The reaction solution was heated at 115°C for 4 hours to produce polyimide resin 1. The reaction solution was then heated to 130°C under atmospheric pressure and concentrated to obtain a polyimide resin solution with a concentration of 60% by mass.
[0103] The resulting polyimide resin solution (polyimide resin content: 50 g) was mixed with an epoxy resin solution prepared by dissolving 40 g of biphenylaralkyl epoxy resin (product name "NC-3000-H" manufactured by Nippon Kayaku Co., Ltd.) in propylene glycol monomethyl ether, 0.5 g of a curing accelerator (product name "2P4MHZ-PW" manufactured by Shikoku Kasei Co., Ltd.), a silica slurry containing 40 g of silica filler (product name "SC2050-KNK" manufactured by Admatechs Co., Ltd.), and N-methylpyrrolidone. The mixture was stirred for 30 minutes to obtain a resin varnish. The total concentration of the polyimide resin and epoxy resin in the resin varnish was 65% by mass. The resulting resin varnish was impregnated into a glass cloth (thickness: 0.1 mm) made of E-glass fiber and dried by heating at 150°C for 10 minutes to obtain prepreg A with a resin content (content of the thermosetting resin composition) of 50% by mass.
[0104] Prepreg B Prepreg B was produced in the same manner as prepreg A, except that the resin content was changed to 70 mass %.
[0105] Prepreg C A flask equipped with a stirrer, thermometer, and nitrogen purge device was charged with 10.3 g of 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4.1 g of 1,4-butanediol bis(3-aminopropyl)ether (trade name "B-12" manufactured by Tokyo Chemical Industry Co., Ltd.), and 101 g of N-methylpyrrolidone. Next, 20.5 g of 1,2-(ethylene)bis(trimellitate anhydride) was added. The reaction solution was stirred at room temperature for 1 hour, and then a reflux condenser with a water receiver was attached to the flask. The reaction solution was heated to 180°C while blowing in nitrogen gas, and the temperature was maintained for 5 hours while removing water to allow the reaction to proceed, producing polyimide resin 2. The polyimide resin solution was then cooled to room temperature.
[0106] The resulting polyimide resin solution (polyimide resin content: 50 g) was mixed with an epoxy resin solution prepared by dissolving 40 g of biphenylaralkyl epoxy resin (product name "NC-3000-H" manufactured by Nippon Kayaku Co., Ltd.) in N-methylpyrrolidone, 0.5 g of a curing accelerator (imidazole compound, product name "2P4MHZ-PW" manufactured by Shikoku Kasei Co., Ltd.), 40 g of silica filler-containing silica slurry (product name "SC2050-KNK" manufactured by Admatechs Co., Ltd.), and N-methylpyrrolidone. The mixture was stirred for 30 minutes to obtain a resin varnish. The total concentration of polyimide resin and epoxy resin in the resin varnish was 65% by mass. The resulting resin varnish was impregnated into a glass cloth (thickness: 0.1 mm) made of E-glass fiber and dried by heating at 150°C for 10 minutes to obtain prepreg C with a resin content of 50% by mass.
[0107] Prepreg D Prepreg D was produced in the same manner as prepreg C, except that the resin content was changed to 70% by mass.
[0108] Prepreg E Prepreg E was produced in the same manner as prepreg A, except that the resin content was changed to 35% by mass.
[0109] Prepreg F A polyimide solution containing polyimide resin 1 (polyimide content: 50 g), an epoxy resin solution prepared by dissolving 60 g of biphenylaralkyl epoxy resin (product name "NC-3000-H" manufactured by Nippon Kayaku Co., Ltd.) in propylene glycol monomethyl ether, 1.5 g of a curing accelerator (imidazole compound, product name "2P4MZ" manufactured by Shikoku Kasei Co., Ltd.), a silica slurry containing 50 g of silica filler (product name "SC2050-KNK" manufactured by Admatechs Co., Ltd.), and N-methylpyrrolidone were mixed together and stirred for 30 minutes to obtain a resin varnish. The total concentration of polyimide resin and epoxy resin in the resin varnish was 65% by mass. The resulting resin varnish was impregnated into a glass cloth (thickness: 0.1 mm) made of E-glass fiber, and the resulting resin varnish was dried by heating at 150°C for 10 minutes to obtain prepreg F with a resin content of 50% by mass.
[0110] Prepreg G Prepreg G was produced in the same manner as prepreg A, except that the resin content was changed to 40% by mass.
[0111] Prepreg H Prepreg H was produced in the same manner as prepreg A, except that the resin content was changed to 80 mass %.
[0112] 2. Minimum melt viscosity and rate of increase in melt viscosity of prepreg The prepared prepreg was sandwiched between two parallel plates with a diameter of 8 mm, and the melt viscosity (complex viscosity) of the laminate was measured in shear mode at a frequency of 10 Hz under the temperature rising condition A below using a viscoelasticity measuring device (ARES, manufactured by Rheometrics Scientific F.E. Co., Ltd.). The minimum melt viscosity was calculated from the measurement results. Furthermore, the melt viscosity was measured by 1000 x 10 3 The rate of increase in melt viscosity per minute was determined while the viscosity rose to Pa·s. For prepregs A and D, the minimum melt viscosity and rate of increase in melt viscosity were measured when the temperature rise conditions were changed to condition B below. The measurement results are shown in Table 1. Condition A: Heat from 20°C to 250°C at a rate of 4°C / min Condition B: Heating rate 6°C / min from 20°C to 250°C The temperatures at which prepreg A showed the minimum melt viscosity were 135°C under condition A and 145°C under condition B.
[0113] [Table 1]
[0114] 3. Preparation of Substrate Materials One of prepregs A to H was cut into a square with sides of 250 mm. Four cut prepregs were stacked, and copper foil (MT18EX-5, manufactured by Mitsui Mining & Smelting Co., Ltd.) was placed on both sides of the stack. The prepreg and copper foil laminate was pressed at a pressure of 3 MPa and a vacuum of 40 hPa using a heat press machine (MHPC-VF-350-350-3-70, manufactured by Meiki Seisakusho Co., Ltd.) with five 0.2 mm-thick cushioning materials (KS190, manufactured by Oji Paper Co., Ltd.) sandwiched between the laminate and the stack. While applying pressure, the temperature of the heat press machine was raised to a molding temperature of 230°C under conditions A or B below. Then, the laminate was heated and pressed for 2 hours while maintained at 230°C. Then, 25 mm-wide edges along the four sides of the laminate were cut off using a cut-off saw, and the insulating substrate and the copper foil laminated on both sides of the insulating substrate were removed to obtain a substrate material with a square main surface with sides of 200 mm. Table 2 shows the combinations of prepregs and temperature rise conditions used in each example or comparative example. Condition A: Heat from room temperature (approximately 25°C) to 230°C at a rate of 4°C / min Condition B: Heat from room temperature (approximately 25°C) to 230°C at a rate of 6°C / min
[0115] 4. Evaluation of substrate materials The flatness (thickness variation), warpage, solder bump connectivity, fine wiring formability, and wiring width variation of the substrate material were evaluated by the following methods. The evaluation results are shown in Table 2. The minimum melt viscosity and melt viscosity rise rate of the prepreg shown in Table 2 are values measured under temperature rise conditions corresponding to those used in each example or comparative example.
[0116] Flatness (thickness variation) The main surface of the substrate material was divided into 16 square areas with sides of 50 mm, and the thickness of each area was measured at four locations 2 mm inward from the four corners using a micrometer (Mitutoyo, ID-C112X). The difference between the maximum and minimum thickness values measured at each of the 16 areas was calculated, and the average value of the differences between the maximum and minimum thickness values for the 16 areas (average thickness difference) was calculated. The thickness values measured at the four locations for each of the 16 areas were used as the population to calculate the standard deviation of the thickness. The maximum of the standard deviations of the thickness for each of the 16 areas was recorded as the standard deviation of the substrate material.
[0117] warp The substrate material was placed on a horizontal table, and the distances between the four sides of the 200 mm square substrate material and the surface of the table were measured. The maximum of the four measured distances was recorded as the value of the warpage of the substrate material.
[0118] Solder Bump Connectivity Test substrate materials with square main surfaces measuring 50 mm on a side were cut from the substrate material by dicing. The substrate material was immersed in a 10% by weight sulfuric acid solution for 1 minute. After rinsing with water, a fluxing agent (SPARKLEFLUX WF-6317, manufactured by Senju Metal Industry Co., Ltd.) was applied to the surface of the substrate material. A semiconductor chip with solder bumps was placed on the fluxing surface of the substrate material and heated in a reflow machine (SNR-1065GT, manufactured by Senju Metal Industry Co., Ltd.) set to a maximum temperature of 260°C under a nitrogen atmosphere to mount the semiconductor chip to the substrate material. The semiconductor chip used here had copper pillars with a diameter of 75 μm and a height of 45 μm, and 15 μm-high solder bumps (SnAg) provided on them, with connection terminals arranged at a 150 μm pitch. The semiconductor chip had a square main surface with a side length of 25 mm, obtained by dicing a silicon wafer (manufactured by Waltz, FBW150-00SnAg01JY) with a thickness of 725 μm.
[0119] The substrate material and the chip mounted thereon were cleaned using an ultrasonic cleaner at a frequency of 45 kHz for 10 minutes to remove the fluxing agent, and then dried at 100°C for 30 minutes. Next, underfill was injected between the substrate material and the semiconductor chip on a hot plate heated to 110°C, and the package was further heated at 150°C for 2 hours to obtain a semiconductor package for evaluation. Ten cross-sections of each solder bump located at the four corners of the semiconductor chip in the resulting semiconductor package were observed using a scanning electron microscope to confirm the connection between the solder bump and the copper foil of the substrate material. A total of 120 locations were observed for three semiconductor packages fabricated using the same procedure. The percentage of locations where connection between the solder bump and the copper foil of the substrate material was confirmed was calculated. A percentage of 90% or more was rated "A," and a percentage of less than 90% was rated "B."
[0120] Fine wiring formability Test substrate materials with square main surfaces measuring 50 mm on a side were cut from the substrate material by dicing. The copper foil was removed from the substrate material by etching in an ammonium persulfate solution. A photosensitive insulating material (Hitachi Chemical, AR5100) was applied to the exposed insulating substrate using a slit coater. The coating was dried by heating at 120°C for 1 minute and then cured by heating at 230°C for 2 hours in a nitrogen atmosphere to form a 5 μm-thick insulating resin layer. A seed layer consisting of a titanium layer (50 nm thick) and a copper layer (150 nm thick) was formed on the insulating resin layer by sputtering. A photoresist layer (Hitachi Chemical, RY-5107UT) was then formed on the seed layer, and a 70 mm square area of the photoresist was exposed to UV light using a projection exposure system (Therma Precision, S6Ck exposure system). The exposed photoresist was developed by spraying a 1% by mass aqueous solution of sodium carbonate using a spin developer (Blue Ocean Technology, Inc., ultra-high-pressure spin developer). This exposure and development process resulted in the formation of 20 patterns, each consisting of 20 400 μm-long straight lines arranged with a resist width / space width of 2 μm / 2 μm. The exposed seed layer surface was treated with oxygen plasma for 1 minute using a plasma asher (Nordson Advanced Technology, AP Series batch plasma processing system) at 500 W power, 150 mTorr pressure, and 100 sccm gas flow. A 3 μm-thick copper plating was then formed on the seed layer by electrolytic copper plating. The photoresist was stripped using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. The exposed seed layer was then washed for 30 seconds at 23°C using an aqueous solution prepared by mixing a copper etchant (Mitsubishi Gas Chemical, WLC-C2) and pure water in a 1:1 mass ratio. The copper and titanium layers were then removed by immersion for 10 minutes in a 23°C aqueous solution prepared by mixing a titanium etchant (Mitsubishi Gas Chemical Company, WLC-T) and a 23% aqueous ammonia solution in a mass ratio of 50:1. This procedure resulted in the formation of 20 sets of wiring, each consisting of 20 straight segments. The percentage of the 400 straight segments of the formed wiring that had been confirmed to have collapsed was calculated.If this ratio was between 80% and 100%, it was judged as "A", if this ratio was between 50% and less than 80%, it was judged as "B", and if this ratio was between 0% and less than 50%, it was judged as "C".
[0121] Wiring width variation Wiring was formed on the substrate material in the same manner as in the evaluation of "fine wiring formability," except that the resist width / space width was changed to 5 μm / 5 μm. The cross section of the wiring was observed using a scanning electron microscope (Hitachi High-Technologies Corporation, SU8200 scanning electron microscope), and the width was measured at three arbitrary points on the wiring, and the standard deviation was calculated.
[0122] [Table 2]
[0123] As shown in Table 2, the rate of increase in the melt viscosity of the prepreg was 55 × 10 3 It was confirmed that by using the substrate materials of each example formed under heating conditions of Pa·s / min or higher, it was possible to stably form fine wiring while suppressing variations in wiring width. [Explanation of symbols]
[0124] 1...prepreg, 3...metal foil, 5...laminate, 10...insulating substrate, 11...inorganic fiber base material, 12...thermosetting resin composition, 100...substrate material for semiconductor package.
Claims
1. forming an insulating substrate from the prepregs by a molding process that includes increasing the temperature of a laminate including two or more laminated prepregs while applying pressure to the laminate; the prepreg comprises an inorganic fiber substrate and a thermosetting resin composition impregnated into the inorganic fiber substrate, and the content of the thermosetting resin composition is 40% by mass or more and 80% by mass or less based on the mass of the prepreg; The molding process is performed by increasing the temperature of the laminate by 55×10 from the time when the melt viscosity of the prepreg shows the minimum melt viscosity. 3 At a melt viscosity increase rate of 1000 x 10 Pa s / min or more 3 the melt viscosity is increased by heating the laminate under heating conditions in which the melt viscosity increases to 1000×10 3 Pa·s, and the melt viscosity increase rate is an average value of the rate of increase of the melt viscosity per minute from the time when the melt viscosity shows the minimum melt viscosity until the melt viscosity increases to 1000×10 3 Pa·s; The prepreg exhibits the minimum melt viscosity at a temperature of 80°C or higher and 200°C or lower during the molding process. A method for manufacturing a substrate material for a semiconductor package having an insulating substrate.
2. The heating conditions are such that the melt viscosity of the prepreg is 200×10 3 At a melt viscosity increase rate of 1000 x 10 Pa·s / min or less 3 The method according to claim 1, wherein the viscosity is increased to 100 Pa·s.
3. The heating conditions are such that the prepreg is 10×10 3 3. The method according to claim 1 or 2, wherein the minimum melt viscosity is 0.1 Pa·s or less.
4. The heating conditions are that the prepreg is 5.0 × 10 3 3. The method according to claim 1 or 2, wherein the minimum melt viscosity is 0.1 Pa·s or less.
5. The heating conditions are that the prepreg is 1.0 × 10 3 The method according to claim 3 or 4, wherein the minimum melt viscosity is Pa·s or more.
6. The method comprises: laminating one or more additional prepregs on the formed insulating substrate to form a second laminate; forming an insulating substrate after two laminations, including a portion formed from the additional prepreg, by a second molding process including increasing the temperature of the second laminate while applying pressure to the second laminate; Further comprising: the additional prepreg comprises an inorganic fiber substrate and a thermosetting resin composition impregnated into the inorganic fiber substrate, and the content of the thermosetting resin composition is 40% by mass or more and 80% by mass or less based on the mass of the additional prepreg; The second molding process is performed by increasing the temperature of the second laminate by 55×10 from the time when the melt viscosity of the additional prepreg shows the minimum melt viscosity. 3 At a melt viscosity increase rate of 1000 x 10 Pa·s / min or more 3 The method of any one of claims 1 to 5, comprising increasing the viscosity by heating the laminate under heating conditions that increase the viscosity to Pa·s.
7. A prepreg comprising an inorganic fiber substrate and a thermosetting resin composition impregnated into the inorganic fiber substrate, the content of the thermosetting resin composition is 40 to 80% by mass based on the mass of the prepreg, The melt viscosity of the prepreg was measured at a temperature rise rate of 4°C / min. The melt viscosity was measured at a temperature rise rate of 55 x 10 3 At a melt viscosity increase rate of 1000 x 10 Pa·s / min or more 3 the melt viscosity rises to 1000×10 3 Pa·s, and the melt viscosity rise rate is the average rate of the melt viscosity rise per minute from the time when the melt viscosity shows the minimum melt viscosity until the melt viscosity rises to 1000×10 3 Pa·s, The prepreg has a minimum melt viscosity measured at a temperature rise rate of 4°C / min at a temperature of 80°C or higher and 200°C or lower.
8. The prepreg according to claim 7, which is used as a prepreg for producing a substrate material for a semiconductor package by the method according to any one of claims 1 to 6.
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