JP2018006521A - Semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a semiconductor device which is arranged so as to be able to adequately suppress the occurrence of delamination in the semiconductor device and to work as a semiconductor even when used at a high temperature above 200°C over a long period of time.SOLUTION: A semiconductor device comprises: a substrate; a semiconductor element; a component originating from a conductive composition including metal particles, and an inorganic component different from the metal particles; and a component originating from a resin composition including a cyanate ester compound and/or a maleimide compound.SELECTED DRAWING: None

Description

The present invention relates to a semiconductor device. More specifically, the present invention relates to a semiconductor device that can be suitably used as a component constituting an electronic device or the like.

A semiconductor device in which a semiconductor is mounted on a substrate is used for various purposes as a component constituting an electronic device. In recent years, as a die attach material for such a semiconductor device, substitution to lead solder has become remarkable. However, Si power devices, light emitting diodes, and the like have a situation in which high temperatures are emitted from the die in order to handle a large current, and high temperature lead solders and conductive adhesives have been used.
Next-generation power semiconductors such as SiC and GaN are expected to operate at higher temperatures than Si power semiconductors. For in-vehicle applications, etc., it is required to operate at 250 ° C. for a long time for the purpose of simplifying the cooling mechanism of the power semiconductor itself. However, if it exceeds 200 ° C., the lead-free solder itself melts or deteriorates due to oxidation. Moreover, since the organic adhesive component of the conductive adhesive is thermally decomposed, the sintered joining of the metal component is regarded as promising as a die attach technique.

As a material containing a metal component that can be used for die attach, a conductive paste or die attach that contains silver particles having a predetermined average particle diameter and a lower alcohol and does not contain an adhesive component is disclosed (Patent Document 1, Non-patent documents 1 and 2). Also disclosed is a conductive material obtained by firing a composition for a conductive material containing silver particles having a predetermined average particle diameter, an inorganic material having a smaller linear expansion coefficient than silver, and a metal oxide at a predetermined temperature, It is described that this material can be used for die attach (see Patent Document 2).
On the other hand, as a resin composition used as a semiconductor sealing material, a cyanate ester-based composition containing a cyanate ester compound and a silane compound having a specific structure is disclosed (see Patent Document 3).

Japanese Patent No. 5207281 Japanese Patent No. 5417861 JP 2014-15603 A

K. 5 people from Suganuma, Macroelectronics Reliability, 52, (2012), 375-380 Soichi Sakamoto and two others, Journal of Materials Science: Materials in Electronics, (2013), 24, 1332-1340.

As described above, it has been studied to use silver sintered bonding as a semiconductor die attach material that is expected to be used at a high temperature exceeding 200 ° C., but silver is used in a high temperature environment exceeding 200 ° C. for a long time. If placed, sintering will progress and the shape will change, and there is a risk that the layer part of the die attach material between the substrate and the semiconductor element will become highly elastic, stress will increase, and adhesive strength will decrease. In addition, there is a risk that it will not function as a semiconductor. In addition, since metals such as silver originally have a poor affinity with organic resins, when a semiconductor is sealed with a known epoxy resin using a metal component as a die attach, it peels off at the metal interface with the sealing material. There is a problem that is likely to occur. For this reason, it has been considered extremely difficult to guarantee the environmental reliability of the power device itself over a long period of time.

The present invention has been made in view of the above situation, and even when used at a high temperature exceeding 200 ° C. for a long period of time, the occurrence of delamination within the semiconductor device is sufficiently suppressed and the semiconductor device can function as a semiconductor. An object is to provide a semiconductor device.

The present inventor has conducted various studies on a semiconductor device that can function as a semiconductor because the occurrence of peeling is sufficiently suppressed even when used at a high temperature exceeding 200 ° C. for a long time. As a result, the metal particles are different from the metal particles. By using a conductive composition containing an inorganic component as a die attach material, the layer portion of the die attach material between the substrate and the semiconductor element can be made highly elastic even when used at a high temperature exceeding 200 ° C. for a long period of time. When the increase in stress and exfoliation are suppressed and the sealing of the semiconductor element using such a die attach material is performed with a resin composition containing a cyanate ester compound and / or a maleimide compound, the temperature exceeds 200 ° C. The occurrence of peeling between the metal particles and the sealing material is suppressed even when used at a high temperature, and it is found that a semiconductor device that can function as a semiconductor is obtained. Conceive that can be admirably solved the problem, it is the present invention has been completed.

That is, the present invention is a semiconductor device including a substrate and a semiconductor element, wherein the semiconductor device includes metal particles and a component derived from a conductive composition containing an inorganic component different from the metal particles. And a component derived from a resin composition containing a cyanate ester compound and / or a maleimide compound.
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

1. Semiconductor device The semiconductor device of the present invention contains a substrate and a semiconductor element, metal particles, a component derived from a conductive composition containing an inorganic component different from the metal particles, and a cyanate ester compound and / or a maleimide compound. And a component derived from a resin composition. The component derived from the conductive composition means a component formed from the conductive composition, and may be the same component as the conductive composition or a component altered from the conductive composition. . The same applies to components derived from a resin composition containing a cyanate ester compound and / or a maleimide compound. In the semiconductor device of the present invention, a conductive composition containing metal particles and an inorganic component different from the metal particles is used as a die attach material, and a resin composition containing a cyanate ester compound and / or a maleimide compound is used as a semiconductor. Since it is used for sealing an element, the component derived from the conductive composition is present between the substrate of the semiconductor device and the semiconductor element, and the component derived from the resin composition is a component derived from the conductive composition. It exists to cover the substrate and the semiconductor element sandwiched between them.
The semiconductor device of the present invention comprises a substrate and a semiconductor element, metal particles, a conductive composition containing an inorganic component different from the metal particles, and a resin composition containing a cyanate ester compound and / or a maleimide compound. However, as long as it is produced using these, materials other than these may be used. Moreover, 1 type may be used for a board | substrate, a semiconductor element, a conductive composition, and a resin composition, respectively, and 2 or more types may be used.
Hereinafter, the conductive composition, the resin composition, the semiconductor element, and the substrate used in the semiconductor device of the present invention will be described in order.

<Conductive composition>
The conductive composition in the present invention is characterized by containing metal particles and an inorganic component different from the metal particles, and such a conductive composition is also one aspect of the present invention.
When metal particle sintered bonding is used as a die attach material for adhering a substrate and a semiconductor element, if the substrate is left at a temperature of 200 ° C. or higher, the fusion of silver particles proceeds and the bonded portion becomes larger. As a result, the shape of the die attach material changes and becomes highly elastic, or stress is generated in the semiconductor device. On the other hand, when a conductive composition containing an inorganic component different from the metal particles is used in addition to the metal particles, the progress of fusion between the metal particles is hindered by the action of the inorganic component different from the metal particles. Thus, the dense structure of the sintered joint between the metal particles is easily maintained, and the die attach material is prevented from changing its form. In addition, when a semiconductor device using a metal die attach material is placed in a high temperature state of 200 ° C. or higher for a long time, the adhesive force between the substrate and the semiconductor element may be reduced. The cause of such a decrease in the adhesive force is that the bonding between the metal particles progresses and the bonding portion becomes larger, and accordingly, components such as copper that originally existed on the substrate are between the metal particles. This is considered to be easy to move to the semiconductor element side along the coupling portion. By the action of the inorganic component different from the metal particles, the progress of the fusion between the metal particles is hindered, and the dense structure of the sintered joint between the metal particles is easily maintained, thereby reducing the movement of copper and the like. Further, it is possible to suppress a decrease in the adhesive force between the substrate and the semiconductor element.

As a metal particle which the electrically conductive composition of this invention contains, 1 type, or 2 or more types of particles, such as silver, copper, nickel, and zinc, can be used.
Among these, silver or copper is preferable from the viewpoint of conductivity and heat dissipation. More preferably, it is silver. Silver atoms have the property of generating surface reactions that move on the surface while reacting with oxygen in an environment of 250 to 300 ° C., so the addition of inorganic components suppresses the progress of the sintering reaction. The action is more effectively exhibited when the metal atom is a silver atom.
The metal particles may be a metal compound or a single metal, but are preferably single metal particles.

The metal particles contained in the conductive composition of the present invention preferably have an average particle diameter (median diameter) of 0.1 to 15 μm. More preferably, it is 0.1-10 micrometers, More preferably, it is 0.3-6 micrometers. By including metal particles having such an average particle size, the conductive composition becomes more suitable as a die attach material.
In the present invention, the average particle diameter (median diameter) of the metal particles can be measured by a laser diffraction method.

The conductive composition of the present invention may contain one kind or two or more kinds of metal particles, but contains two or more kinds of metal particles having different average particle diameters (median diameters). It is preferable.
When two or more kinds of metal particles having different average particle diameters are included, it is preferable that the ratio of those having an average particle diameter of 0.1 to 15 μm in the entire metal particles is 70% by mass or more. More preferably, it is 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass, that is, when two or more kinds of metal particles having different average particle diameters (median diameters) are contained. The average particle diameter (median diameter) is a combination of metal particles each having a range of 0.1 to 15 μm.
The two or more kinds of metal particles having different average particle diameters (median diameters) may be particles of the same metal species or particles of different metal species, but the conductive compositions are the same. It is one of the preferred embodiments of the present invention to include two or more metal particles having different average particle diameters (median diameters).

When the conductive composition of the present invention contains two or more kinds of metal particles having an average particle diameter (median diameter) in the range of 0.1 to 15 μm, the average particle diameter of the metal particles having the largest average particle diameter Is preferably 1.0 to 9.9 μm. Moreover, it is preferable that the average particle diameter of the metal particle with the smallest average particle diameter is 0.1-0.99 micrometer. That is, the conductive composition includes metal particles having a median diameter of 1.0 to 9.9 μm and metal particles having a median diameter of 0.1 to 0.99 μm. Is one of the preferred embodiments of the present invention.
The average particle size of the metal particles having the largest average particle size is more preferably 1.2 to 8 μm, still more preferably 1.4 to 5 μm, and particularly preferably 1.6 to 4 μm. Especially preferably, it is 1.8-3.5 micrometers, Most preferably, it is 2.0-3.2 micrometers.
The average particle size of the metal particles having the smallest average particle size is more preferably 0.1 to 0.9 μm, still more preferably 0.15 to 0.8 μm, and particularly preferably 0.00. It is 2 to 0.7 μm, particularly preferably 0.25 to 0.6 μm, and most preferably 0.3 to 0.5 μm.

When the conductive composition of the present invention includes two or more kinds of metal particles having different average particle diameters (median diameters), the mass ratio of the metal particles having the largest average particle diameter and the metal particles having the smallest average particle diameter is: It is preferably 30/70 to 85/15. More preferably, it is 40 / 60-80 / 20, More preferably, it is 50 / 50-70 / 30.

The metal particles contained in the conductive composition of the present invention preferably have a BET specific surface area of 0.5 to 10 m ² / g measured by the BET method. More preferably, it is 0.6-8.0 m < ² > / g, More preferably, it is 0.6-6.0 m < ² > / g.

The shape of the metal particles included in the conductive composition of the present invention is not particularly limited, and may be any shape such as a spherical shape, a flat shape, or a polyhedral shape, and includes two or more different shapes of metal particles. It may be. When the electrically conductive composition of this invention contains 2 or more types of metal particles from which an average particle diameter differs, the shape of those metal particles may be the same and may differ.

The electrically conductive composition of this invention contains the inorganic component different from the said metal particle. The inorganic component different from the metal particles may be a compound or a single atom.
The inorganic component contains at least one element of Group 1 to 17 of the periodic table excluding the metal element and carbon (C) contained in the metal particles contained in the conductive composition, and contains two or more of these elements. May be. The element may be a metallic element or a nonmetallic element.
As an element of the periodic table group 1-17 excluding the metal element and carbon (C) which the metal particle which an electroconductive composition has, Preferably, it is an element of the periodic table group 3-16, More preferably, It is an element of Groups 4 to 15 of the periodic table.

When the inorganic component is a compound, the compounds include oxides, nitrides, composite oxides, layered double hydroxides, hydroxides, clay compounds, solid solutions, alloys, zeolites, halides, carboxylate compounds, and carbonate compounds. Hydrogen carbonate compound; nitric acid compound; sulfuric acid compound; sulfonic acid compound; phosphoric acid compound such as hydroxyapatite; phosphorous compound; hypophosphorous acid compound, boric acid compound; silicic acid compound; aluminate compound; Salt etc. are mentioned. Preferably, it is any of oxide, nitride, and sulfide, and more preferably, any of oxide and nitride.

The inorganic component different from the metal particles in the conductive composition of the present invention is preferably in the form of particles, and the average particle diameter (median diameter) is preferably 0.05 to 50 μm. . More preferably, it is 0.08-20 micrometers, More preferably, it is 0.1-10 micrometers.
In the present invention, the average particle diameter (median diameter) of an inorganic component different from the metal particles can be measured by a laser diffraction method.

It is preferable that the content rate of the inorganic component different from the said metal particle in the electrically conductive composition of this invention is 0.5-50 mass% with respect to 100 mass% of the whole electrically conductive composition. More preferably, it is 0.8-40 mass%, More preferably, it is 1.0-30 mass%.

The conductive composition of the present invention may contain a solvent. The solvent is not particularly limited, and may be a non-polar aromatic compound such as an alcohol having 1 to 20 carbon atoms, benzene, xylene, toluene, naphthalene, (di) methylnaphthalene; Hydrocarbon compounds up to: ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone; ethyl acetate, butyl acetate, ethyl butyrate, butyl butyrate, ethyl lactate, butyl lactate, propylene glycol methyl ether acetate, γ- Examples include esters such as butyrolactone; ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, monoglyme, diglyme, and triglyme. Of these, an alcohol having 1 to 20 carbon atoms which may have a substituent is most preferable.

About the C1-C20 alcohol which may have the said substituent, as for C1-C20 alcohol, what has 1-3 hydroxyl groups is preferable. It is preferable that a C1-C20 alcohol has a C1-C10 linear or branched alkyl group, and when C1-C20 alcohol has a substituent, it is C1-C1. The thing by which the hydrogen atom of 10 to 10 linear or branched alkyl groups was substituted by the substituent is preferable.
Examples of the alcohol having 1 to 20 carbon atoms having no substituent include methanol, ethanol, ethylene glycol, n-propanol, i-propanol, triethylene glycol, n-butanol, i-butanol, sec-butanol, and t-butanol. , N-pentanol, i-pentanol, sec-pentanol, t-pentanol, 2-methylbutanol, n-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, 4- Examples include methylpentanol, 1-ethylbutanol, 2-ethylbutanol, 1,1-dimethylbutanol, 2,2-dimethylbutanol, 3,3-dimethylbutanol, and 1-ethyl-1-methylpropanol.

The substituent that the alcohol having 1 to 20 carbon atoms may have is preferably at least one selected from the group consisting of an alkoxy group, an amino group, and a halogen atom. As an alkoxy group, a C1-C10 thing is preferable. Examples of the halogen atom include fluorine, bromine, chlorine and iodine.
Examples of the C1-C20 alcohol having a substituent include methoxymethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-chloroethanol, and ethanolamine.
The conductive composition of the present invention may contain one type of solvent or two or more types.

When the conductive composition of the present invention contains a solvent, the mixing ratio (mass ratio) of the metal particles and the solvent is not particularly limited, but the metal particles: solvent is preferably 4: 1 to 16: 1. . When the metal particles are contained in such a ratio, the composition can exhibit better performance as a die attach material. The metal particle: solvent is more preferably 6: 1 to 12: 1, and still more preferably 8: 1 to 10: 1.

When the conductive composition of the present invention is used as a die attach material, the metal particles are melted and fused to the substrate and the semiconductor element, thereby fixing the substrate and the semiconductor element. Therefore, the conductive composition of the present invention does not require an adhesive component for fixing the semiconductor element to the substrate.
Therefore, in the conductive composition of the present invention, the content ratio of the adhesive component is preferably 15% by mass or less with respect to the entire conductive composition. The content ratio of the adhesive component is more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less. It can be said that the adhesive component is substantially not contained when the content ratio of the adhesive component is 3% by mass or less. However, when such an adhesive component is used as the organic component contained in the above-described conductive composition of the present invention, the preferred content of the adhesive component is the same as the content of the inorganic component different from the metal particles described above. It is preferable that
Here, the adhesive component means an organic compound having an action of adhering different substances, and is a compound known as an epoxy-based, phenol-based, acrylic-based, polyimide-based, silicon-based, urethane-based or thermoplastic adhesive. Etc. are included.

The electrically conductive composition of this invention may contain other components other than the various components mentioned above.
Examples of other components include a coupling agent.
The content of these other components is preferably 10% by mass or less with respect to 100% by mass of the entire conductive composition. More preferably, it is 8 mass% or less, More preferably, it is 5 mass% or less.

<Resin composition containing cyanate ester compound and / or maleimide compound>
The resin composition containing the cyanate ester compound and / or maleimide compound in the present invention contains either one or both of a cyanate ester compound and a maleimide compound. Each of the cyanate ester compound and the maleimide compound contained in the resin composition may be one kind or two or more kinds.
Below, a cyanate ester compound and a maleimide compound are demonstrated in order, and the other component which a resin composition may contain after that is demonstrated.
[Cyanate ester compounds]
The cyanate ester compound contained in the resin composition in the present invention has at least two cyanato groups (—OCN) in one molecule. For example, a compound represented by the following general formula (1) is preferable. is there.

(In the general formula (1), R ¹ and R ² are the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group, or a halogen group (X). R ³ Are the same or different and each represents an organic group represented by the following chemical formula: R ⁴ is the same or different and represents an organic group represented by the following chemical formula: m ¹ is 0 or 1 N ¹ represents an integer of 0 to 10.)

Although it does not specifically limit as a compound represented by the said General formula (1), For example, bis (4-cyanatophenyl) methane, bis (3, 5- dimethyl- 4-cyanatophenyl) methane, bis (3- Methyl-4-cyanatophenyl) methane, bis (4-cyanatophenyl) -1,1-ethane, bis (4-cyanatophenyl) -2,2-ethane, 2,2-bis (4-cyanato) Phenyl) propane, 2,2-bis (3,5-dimethyl-4-cyanatophenyl) methane, di (4-cyanatophenyl) ether, di (4-cyanatophenyl) thioether, 4,4- {1 , 3-phenylenebis (1-methylethylidene)} bisphenylcyanato, 4,4-dicyanatophenyl, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3- Hexafluoro Lopan, 1,1′-bis- (p-cyanatophenyl) -ethane, 2,2′-bis (p-cyanatophenyl) propane, 4,4′-methylenebis (2,6-dimethylphenylcyanato) 2,2′-bis (p-cyanatophenyl) hexafluoropropane, α, α′-bis (4-cyanatophenyl) -m-diisopropylbenzene and the like, cyanate esters of dihydric phenols; Cyanate esters of trihydric phenols such as cyanate phenyl) -1,1,1-ethane, bis (3,5-dimethyl-4-cyanatephenyl) -4-cyanatephenyl-1,1,1-ethane; phenol novolac Type cyanate ester, cresol novolac type cyanate ester, dicyclopentadiene bisphenol type cyanate ester, etc. That. Among these, 2,2-bis (4-cyanatophenyl) propane and phenol novolac-type cyanate are preferable from the viewpoints of dielectric properties and curability of the cured product.

As the cyanate ester compound, a multimer (for example, trimer, pentamer) formed by cyclization of a cyanate group of the compound represented by the general formula (1) to form a triazine ring structure is used. You can also Among these, a trimer is preferable from the viewpoint of operability and solubility in other curable resins. A technique for obtaining a multimer may be performed by a normal technique.

The cyanate ester compound may be liquid or solid, but in consideration of melt kneading with other curable resins, it has high compatibility, or has a melting point or softening point of 120 ° C. or lower. It is suitable to have. More preferably, it has a melting point or softening point of 100 ° C. or lower.
The melting point means the temperature (° C.) at which the crystals melt and become liquid in an inert atmosphere. Therefore, amorphous compounds and those already in liquid form at room temperature do not have a melting point.
The melting point of the cyanate ester compound can be measured, for example, by differential scanning calorimetry (DSC). The softening point (° C.) is a value measured according to JIS K7234 (1986). For example, it can be measured using a thermal softening temperature measuring device (product name “ASP-MG4”, manufactured by Meitec). it can.

When the resin composition in this invention contains a cyanate ester compound, it is preferable that the compounding ratio of a cyanate ester compound is 5-95 mass% with respect to 100 mass% of total mass of the organic component contained in a resin composition. . With such a blending ratio, both durability against heat and humidity and handling properties as a semiconductor sealing material can be achieved, and excellent reliability can be given to a semiconductor package using the same. More preferably, it is 10-90 mass%, More preferably, it is 15-85 mass%.

[Maleimide compound]
When the resin composition in the present invention contains a maleimide compound, the handling property of the resin composition is improved.
As the maleimide compound, bismaleimide such as N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N′-m-phenylene bismaleimide, N, N′-p-phenylene bismaleimide 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis [4- (4-maleimidophenoxy) phenyl] methane, 1,1,1,3,3,3-hexafluoro-2, 2-bis [4- (4-maleimidophenoxy) phenyl] propane, N, N′-p, p′-diphenyldimethylsilylbismaleimide, N, N′-4,4′-diphenyl ether bismaleimide, N, N ′ -Methylenebis (3-chloro-p-phenylene) bismaleimide, N, N'-4,4'-diphenylsulfone bismaleimide, N, N'-4, '-Dicyclohexylmethane bismaleimide, N, N'-dimethylenecyclohexane bismaleimide, N, N'-m-xylene bismaleimide, N, N'-4,4'-diphenylcyclohexane bismaleimide, N-phenylmaleimide and formaldehyde Cocondensates with aldehyde compounds such as acetaldehyde, benzaldehyde and hydroxyphenylaldehyde are preferred. Moreover, the following general formula (2):

(Wherein R ⁵ is

Or

Represents a divalent group. Q ¹ is a group directly connected to two aromatic rings, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group, and an oxide. It represents at least one group selected from the group consisting of groups. The bismaleimide compound represented by) is preferred.
Specifically, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,2- [4- (3-maleimidophenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl ] Butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (3-maleimidophenoxy) phenyl] sulfide, bis [4- (3-male Midofenokishi) phenyl] sulfoxide, bis [4- (3-maleimido phenoxy) phenyl] sulfone, bis [4- (3-maleimido phenoxy) phenyl] ether, the following general formula (3):

(Wherein, Q ² is, .n ² representing a divalent group consisting of aromatic ring which may have a substituent, the number of repetitions, average the number of 0.) Represented by Compounds and the like are preferred. Specifically, the Q ² is preferably a divalent group such as a phenyl group, a biphenyl group, or a naphthyl group (such as a phenylene group, a biphenylene group, or a naphthylidene group).

When the maleimide compound in the present invention is a polymer compound, the maleimide compound preferably has a weight average molecular weight of 200 to 5,000. When the molecular weight of the maleimide compound is in such a range, a cured product having excellent heat resistance and the like can be obtained. More preferably, it is 220-4500, More preferably, it is 250-4000.
The weight average molecular weight of the maleimide compound can be measured by GPC under the conditions described in the examples.

When the resin composition in this invention contains a maleimide compound, it is preferable that the content rate is 10-90 mass% with respect to 100 mass% of total mass of the organic component contained in a resin composition. More preferably, it is 15-85 mass%, More preferably, it is 20-80 mass%.

The resin composition in the present invention preferably contains both a cyanate ester compound and a maleimide compound.
When the resin composition in the present invention contains a cyanate ester compound and a maleimide compound, the blending ratio of the maleimide compound is 5 to 500% by mass with respect to 100% by mass of the cyanate ester compound in the curable resin composition. Is preferred. By using at such a ratio, the resin composition can be made excellent in heat resistance and sufficiently improved in handling properties. More preferably, it is 5-400 mass% with respect to 100 mass% of cyanate ester compounds, More preferably, it is 5-300 mass%.

[Siloxane compound]
The resin composition in the present invention further has the following average composition formula (4):
XaYbZcSiOd (4)
(Wherein X is the same or different and represents an organic skeleton containing an imide bond. Y is the same or different and represents at least one selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom and an OR group. Z is the same or different and represents an organic group containing no imide bond, and R is the same or different and is at least one selected from the group consisting of an alkyl group, an acyl group, an aryl group, and an unsaturated aliphatic residue. Represents a species and may have a substituent, a, b and c are 0 or a number less than 3, and d is a non-zero number less than 2 and a + b + c + 2d = 4. It is preferable to contain a siloxane compound.
By including such a siloxane compound, the resin composition is further excellent in heat resistance.

In the siloxane compound, the structure of the siloxane skeleton (main chain skeleton in which a siloxane bond is essential) is preferably, for example, a chain (straight or branched), ladder, network, ring, cage, cubic, etc. Illustrated. Especially, since the effect is easily exhibited even if the addition amount of the siloxane compound is small, a ladder shape, a net shape, or a cage shape is preferable. That is, as the siloxane compound, those containing polysilsesquioxane are particularly suitable.
In addition, it is preferable that the ratio for which the siloxane skeleton in the said siloxane compound accounts is 10-80 mass% in 100 mass% of siloxane compounds. More preferably, it is 15-70 mass%, More preferably, it is 20-50 mass%.

In the above average composition formula (4), preferred forms of X are as described later, and as Y, a hydroxyl group or an OR group is preferred. Among them, an OR group is more preferable, and an OR group in which R is an alkyl group having 1 to 8 carbon atoms is more preferable. Z is preferably at least one selected from the group consisting of aromatic residues such as alkyl groups, aryl groups and aralkyl groups, and unsaturated aliphatic residues (these have a substituent). You may). More preferably, it is a C1-C8 alkyl group which may have a substituent, or aromatic residues, such as an aryl group and an aralkyl group. The coefficient a of X is a number 0 ≦ a <3, the coefficient b of Y is a number 0 ≦ b <3, the coefficient c of Z is a number 0 ≦ c <3, The coefficient d of O is a number 0 <d <2. The coefficient a of X is preferably a number 0 <a <3. In other words, the coefficient a of X is preferably a non-zero number less than 3.

The siloxane compound is, for example, the following general formula (5):

(In the formula, X, Y and Z are the same as above. N ³ and n ⁴ represent the degree of polymerization. N ³ is a non-zero positive integer, and n ⁴ is 0 or positive. It is an integer.)
"Y / Z-" represents that Y or Z is bonded, " _X1-2- " represents that one or two Xs are bonded, and "(Z / "Y) _1-2 " represents that one Z or Y is bonded, two Z or Y are bonded, or two Z and Y are bonded in total. “Si— (X / Y / Z) ₃ ” indicates that any three selected from X, Y, and Z are bonded to a silicon atom.
In the general formula (5), Si-Om ³ and Si-Om ⁴ is not intended to define the binding order of Si-Om ³ and Si-Om ^4, for example, Si-Om ³ and Si-Om ⁴ is A form in which they are co-condensed alternately or randomly, a form in which a polysiloxane composed of Si—Om ³ and a polysiloxane of Si—Om ⁴ are bonded are suitable, and the condensed structure is arbitrary.

The siloxane compound can be represented by the above average composition formula (4), a siloxane skeleton which the siloxane compound has (main chain essentially containing siloxane bond) can also be expressed as (SiO _{m) n.} The structure other than (SiO _m ) _n in such a siloxane compound is an organic skeleton having an imide bond (a structure in which an imide bond is essential) X, Y such as a hydrogen atom or a hydroxyl group, and an organic group not containing an imide bond. Z, which are bonded to the silicon atom of the main chain skeleton.
X, Y and Z may or may not be included in the repeating unit in the form of a “chain”. For example, one or more Xs may be contained in one molecule as a side chain. In the above (SiO _m ) _n , n represents the degree of polymerization, and the degree of polymerization represents the degree of polymerization of the main chain skeleton, and n organic skeletons having an imide bond may not necessarily exist. In other words, an organic skeleton having one imide bond in one unit of (SiO _m ) _n is not necessarily present. In addition, one or more organic skeletons having an imide bond may be included in one molecule, but when a plurality of organic skeletons are included, as described above, an organic skeleton having two or more imide bonds in one silicon atom. It may be bonded. The same applies to the following.

In the main chain skeleton (SiO _m ) _n , m is preferably a number of 1 or more and less than 2. More preferably, m = 1.5 to 1.8.
The above n represents the degree of polymerization and is preferably 1 to 5000. More preferably, it is 1-2000, More preferably, it is 1-1000, Most preferably, it is 1-200.
As the silane compound when n is 2, the structural unit (hereinafter also referred to as “structural unit (I)”) in which at least one organic skeleton (X) having an imide bond is bonded to a silicon atom is 2 And a form in which only one structural unit (I) is contained. Specifically, the following general formula (6):

(Wherein A is Y or Z, and X, Y and Z are each the same as above) and the like, and a homopolymer form containing two identical structural units (I), There are a homopolymer form containing two different structural units (I) and a copolymer form (cocondensed structure form) containing only one of the structural units (I).

In the said average composition formula (4), it is preferable that it is 20-100 mol with respect to 100 mol of silicon atoms contained in a silane compound as a ratio for which the organic skeleton which has an imide bond accounts. More preferably, it is 50-100 mol, More preferably, it is 70-100 mol.

X in the average composition formula (4) is preferably a structural unit represented by the following general formula (7). That is, in the siloxane compound of the present invention, X in the average composition formula (4) is represented by the following general formula (7):

(Wherein R ⁶ represents at least one structure selected from the group consisting of aromatic, heterocyclic and alicyclic rings. X and z are the same or different and are integers of 0 or more and 5 or less, y Is 0 or 1. It is preferable that the siloxane compound which is a structural unit represented by this is included. By including such a siloxane compound having a ring structure in the structure, the heat resistance of the cured product obtained from the resin composition in the present invention is further improved.

In the structural unit represented by the general formula (7), x and z are the same or different and are integers of 0 or more and 5 or less. Moreover, y is 0 or 1, and is preferably 0. x + z may be an integer of 0 or more and 10 or less, but is preferably 3 to 7, more preferably 3 to 5, and particularly preferably 3.

In the general formula (7), R ⁶ represents at least one structure selected from the group consisting of aromatic, heterocyclic and alicyclic rings. That is, R ⁶ comprises a group having a ring structure (aromatic ring) of an aromatic compound, a group having a ring structure (heterocycle) of a heterocyclic compound, and a group having a ring structure (alicyclic ring) of an alicyclic compound. It represents at least one group selected from the group.
Specifically, R ⁶ is preferably a phenylene group, naphthylidene group, norbornene divalent group, (alkyl) cyclohexylene group, cyclohexenyl group or the like.
The structural unit represented by the general formula (7) is a structural unit represented by the following general formula (7-1) when R ⁶ is a phenylene group, and R ⁶ is (alkyl) cyclohexylene. When it is a group, it becomes a structural unit represented by the following general formula (7-2). When R ⁶ is a naphthylidene group, it becomes a structural unit represented by the following general formula (7-3), and R ⁶ When is a norbornene divalent group, the structural unit is represented by the following general formula (7-4). When R ⁶ is a cyclohexenyl group, the structural unit is represented by the following general formula (7-5). It becomes a structural unit.

In the general formulas (7-1) to (7-5), x, y, and z are the same as x, y, and z in the general formula (7), respectively.
In the general formula (7-1), R ^{7 to} R ¹⁰ are the same or different and represent at least one structure selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom and an aromatic. As said R < ⁷ > -R < ¹⁰ >, the form whose all are hydrogen atoms is preferable.
In the general formula (7-2), R ^{11 to} R ¹⁴ and R ^{11 ′} to R ^{14 ′} are the same or different and are at least one selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom, and an aromatic. Represents the structure of As the ^R 11 ^{to R 14} and ^R 11' ^{to R 14',} forms all ^{R 12} or ^{R 13} are the remaining methyl group is a hydrogen atom, ^or, R 11 ^{to R 14} and ^R 11' ^{to R 14 'all} are hydrogen atom form ^or embodiment R 11 ^{to R 14} and ^R 11' ^{to R 14'} all are a fluorine atom is preferable. More preferably, R ¹² or R ¹³ is a methyl group and the rest are all hydrogen atoms.

In the general formula (7-3), R ^{15 to} R ²⁰ are the same or different and represent at least one structure selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom and an aromatic. As said R < ¹⁵ > -R < ²⁰ >, the form whose all are hydrogen atoms or the form whose all are fluorine atoms is preferable. More preferred is a form in which all are hydrogen atoms.
In the general formula (7-4), R ^{21 to} R ²⁶ are the same or different and represent at least one structure selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom, and an aromatic. As said R < ²¹ > -R < ²⁶ >, the form in which all are a hydrogen atom, the form that all are fluorine atoms, or the form in which all are chlorine atoms is preferable. More preferred is a form in which all are hydrogen atoms.
In formula ^{(7-5), R 27 ~R 30} , R 27' and ^{R 30'} are the same or different, a hydrogen atom, an alkyl group, at least one selected from the group consisting of halogen atoms and the aromatic Represents the structure of As the ^R 27 ^{to R 30, R 27 'and R 30',} it forms all are hydrogen atom, and all are a fluorine atom form or any form of embodiment all is a chlorine atom is preferable. More preferred is a form in which all are hydrogen atoms.

Among the general formulas (7-1) to (7-5), the general formula (7-4) or (7-5) is preferable. When a siloxane compound having a reactive carbon-carbon unsaturated bond in such a side chain is used, reaction of the siloxane compound with a maleimide compound or the like during curing of the resin composition prevents the siloxane compound from being raised on the surface of the cured product. The appearance of the cured product can be made favorable.

Among the structural units represented by the general formula (7), the following general formula (7-6):

(Wherein R ³¹ represents a structural unit represented by at least one structure selected from the group consisting of aromatic, heterocyclic and alicyclic rings). That is, the siloxane compound of the present invention preferably includes a siloxane compound in which X in the average composition formula (4) is a structural unit represented by the general formula (7-6). Incidentally, ^{R 31} in the general formula (7-6) in is preferably the same as ^{R 6} as described in the general formula (7).

Particularly preferable forms of the siloxane compound include poly (γ-phthalimidopropylsilsesquioxane) in which R ³¹ is a phenylene group; poly {γ- (hexahydro-4-methyl) in which R ³¹ is a methylcyclohexylene group. Phthalimido) propylsilsesquioxane}; poly {γ- (1,8-naphthalimido) propylsilsesquioxane} in which R ³¹ is a naphthylidene group; poly {γ- (R ³¹ is a norbornene divalent group) 5-norbornene-2,3-imido) propylsilsesquioxane}; poly [(cis-4-cyclohexene-1,2-imido) propylsilsesquioxane] in which R ³¹ is a cyclohexenyl group.
The structures of these compounds can be identified by measuring ¹ H-NMR, ¹³ C-NMR, and MALDI-TOF-MS.

The molecular weight of the siloxane compound is preferably a number average molecular weight of 100 to 10,000. If the polymer compound exceeds 10,000, there is a possibility that it cannot be sufficiently mixed with the cyanate ester compound or the maleimide compound. Moreover, there exists a possibility that heat resistance etc. may not become enough that it is less than 100. More preferably, it is 500-5000, More preferably, it is 1000-5000. The weight average molecular weight is preferably 100 to 10,000. More preferably, it is 500-5000, More preferably, it is 1000-5000.
The molecular weight (number average molecular weight and weight average molecular weight) of the siloxane compound can be measured under the conditions described in Examples by GPC (gel permeation chromatography) measurement.

In the said resin composition, it is preferable that a siloxane compound is mix | blended with the resin composition containing a maleimide compound, and the compounding ratio in that case is 30-350 mass with respect to 100 mass% of maleimide compounds which a resin composition contains. % Is preferred. More preferably, it is 35-350 mass%, More preferably, it is 40-300 mass%.

Although it does not specifically limit as a method to obtain the said siloxane compound, For example, the following manufacturing method (I) and (II) etc. are mentioned.
(I) An intermediate (consisting of a siloxane compound) represented by an average composition formula X′aYbZcSiOd having an organic skeleton X ′ having an amide bond corresponding to the organic skeleton X containing an imide bond in the siloxane compound and a siloxane bond The manufacturing method including the process of imidating.
(II) Hydrolysis / condensation of an intermediate composed of a siloxane compound in which the organic skeleton having an imide bond corresponding to the organic skeleton X containing an imide bond in the siloxane compound is bonded to a silicon atom and having a hydrolyzable group The manufacturing method including the process to make.

[Carbodiimide compound]
The resin composition in the present invention preferably further contains a carbodiimide compound. The carbodiimide compound has higher reactivity with water than the cyanate ester compound, and when mixed with the resin composition containing the cyanate ester compound, it reacts preferentially with water and becomes a urea compound as shown in the following formula (8). Thus, since the carbodiimide compound consumes water in preference to the cyanate ester compound, by adding the carbodiimide compound to the cyanate ester compound, generation of carbon dioxide due to hydrolysis of the cyanate ester compound and carbamate compounds due to side reactions Can be suppressed.
Furthermore, since the urea compound formed by the reaction of the carbodiimide compound with water can react with the cyanate ester compound at the active hydrogen site, it is consumed to form a crosslinked structure at the time of curing of the resin composition, such as mechanical strength. Does not inhibit the physical properties of the cured product. For this reason, the resin composition in the present invention can form a cured product that is sufficiently suppressed from generating non-uniform structures such as bubbles and gels and that has excellent physical properties.

The carbodiimide compound contained in the resin composition in the present invention may be a compound having at least one carbodiimide group represented by (—N═C═N—) in the molecule, but the following general formula (9):

^(Wherein, R ^{32, R 34} are the same or different, ^{.R 33} representing a monovalent hydrocarbon group which may 1 to 50 carbon atoms which may have a substituent are the same or different, substituted Represents a divalent hydrocarbon group having 1 to 50 carbon atoms which may have a group, and n ⁵ is preferably a compound represented by a number of 0 to 10,000.

In the said General formula (9), carbon number of the hydrocarbon group of R < ³² > -R < ³⁴ > becomes like this. Preferably it is 1-40, More preferably, it is 1-30, More preferably, it is 1-20. .
Examples of the monovalent hydrocarbon group for R ³² and R ³⁴ include an aliphatic group, a linear or cyclic alkyl group, an alkenyl group, an alkynyl group; an aryl group that is an aromatic group; or two or more thereof Any of the groups in which
The divalent hydrocarbon group for R ³³ may be any divalent group obtained by taking one hydrogen atom from the above monovalent hydrocarbon group.
In the general formula (9), R ^{32 to} R ³⁴ may have a substituent, and examples of the substituent include a hydroxyl group, an amino group, a nitro group, and a halogen atom.
R ^{32 to} R ³⁴ may have one of these substituents, or may have two or more. Moreover, you may have 1 type of substituents and may have 2 or more types.
In the general formula (9), ^{n 5} is preferably 0 to 200, more preferably from 0 to 150, more preferably from 0 to 100.

Specific examples of the carbodiimide compound include N, N′-diphenylcarbodiimide, N, N′-dicyclohexylcarbodiimide, N, N′-di-2,6-dimethylphenylcarbodiimide, N, N′-diisopropylcarbodiimide, N, N′-dioctyldecylcarbodiimide, N, N′-di-o-toluylcarbodiimide, N, N′-di-p-toluylcarbodiimide, N, N′-di-p-nitrophenylcarbodiimide, N, N ′ -Di-p-aminophenylcarbodiimide, N, N'-di-p-hydroxyphenylcarbodiimide, N, N'-di-p-chlorophenylcarbodiimide, N, N'-di-o-chlorophenylcarbodiimide, N, N′-di-3,4-dichlorophenylcarbodiimide, N, N′-di-2,5-dic Ruphenylcarbodiimide, N, N'-p-phenylene-bis-o-toluylcarbodiimide, N, N'-p-phenylene-bis-dicyclohexylcarbodiimide, N, N'-p-phenylene-bis-di-p-chloro Phenylcarbodiimide, N, N′-2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide, N, N′-hexamethylene-bis-cyclohexylcarbodiimide, N, N′-ethylene-bis-diphenylcarbodiimide, N, N′-ethylene-bis-dicyclohexylcarbodiimide, N-toluyl-N′-cyclohexylcarbodiimide, N, N′-di-2,6-diisopropylphenylcarbodiimide, N, N′-di-2,6-di-tert- Butylphenylcarbodiimide, N-toluyl-N'-fur Nylcarbodiimide, N, N′-benzylcarbodiimide, N-octadecyl-N′-phenylcarbodiimide, N-benzyl-N′-phenylcarbodiimide, N-octadecyl-N′-tolylcarbodiimide, N-cyclohexyl-N′-tolylcarbodiimide N-phenyl-N′-tolylcarbodiimide, N-benzyl-N′-tolylcarbodiimide, N, N′-di-o-ethylphenylcarbodiimide, N, N′-di-p-ethylphenylcarbodiimide, N, N '-Di-o-isopropylphenylcarbodiimide, N, N'-di-p-isopropylphenylcarbodiimide, N, N'-di-o-isobutylphenylcarbodiimide, N, N'-di-p-isobutylphenylcarbodiimide, N , N'-di-2,6-diethylfe Nylcarbodiimide, N, N′-di-2-ethyl-6-isopropylphenylcarbodiimide, N, N′-di-2-isobutyl-6-isopropylphenylcarbodiimide, N, N′-di-2,4,6- Monocarbodiimide compounds such as trimethylphenylcarbodiimide, N, N′-di-2,4,6-triisopropylphenylcarbodiimide, N, N′-di-2,4,6-triisobutylphenylcarbodiimide; poly (1,6 -Hexamethylenecarbodiimide), poly (4,4'-methylenebiscyclohexylcarbodiimide), poly (1,3-cyclohexylenecarbodiimide), poly (1,4-cyclohexylenecarbodiimide), poly (4,4'-diphenylmethanecarbodiimide) ), Poly (3,3′-dimethyl-4,4′-diph Nylmethanecarbodiimide), poly (naphthylene carbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (tolylcarbodiimide), poly (diisopropylcarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly And polycarbodiimide compounds such as (triethylphenylenecarbodiimide) and poly (triisopropylphenylenecarbodiimide). These carbodiimide compounds may be used alone or in combination of two or more.

Among the carbodiimide compounds, polycarbodiimide compounds are preferable. Examples of the polycarbodiimide compound include an aliphatic polycarbodiimide in which R ³³ in the general formula (9) is an aliphatic group, and an aromatic polycarbodiimide in which R ³³ has an aromatic group, and an aliphatic polycarbodiimide. Is preferable because it is easier to bleed than aromatic polycarbodiimide, and the aliphatic group is preferably linear rather than branched.

When a polycarbodiimide compound is used as the carbodiimide compound, the weight average molecular weight is preferably 100 or more and 100,000 or less, more preferably 500 or more and 10,000 or less from the viewpoint of safety and ease of handling. .
The weight average molecular weight of the carbodiimide compound can be determined by GPC (gel permeation chromatography) measurement under the following measurement conditions.
Measuring instrument: HLC-8120GPC (trade name, manufactured by Tosoh Corporation)
Molecular weight column: TSK-GEL GMHXL-L and TSK-GELG5000HXL (both manufactured by Tosoh Corporation) are connected in series. Eluent: Tetrahydrofuran (THF)
Standard material for calibration curve: Polystyrene (manufactured by Tosoh Corporation)
Measurement method: The measurement object is dissolved in THF so that the solid content is about 0.2% by mass, and the molecular weight is measured using an object obtained by filtration through a filter as a measurement sample.

The carbodiimide compound can be produced, for example, by heating an organic isocyanate in the presence of a suitable catalyst to cause a decarboxylation reaction to form a carbodiimide bond group.
Formation of the carbodiimide bonding group can be confirmed by disappearance of the absorption peak of the isocyanate group of 2260 cm ⁻¹ and generation of the absorption peak of the carbodiimide bonding group.

In addition to the above basic production method, the carbodiimide compound is disclosed in, for example, U.S. Pat. No. 2,941,956, Japanese Patent Publication No. 47-33279, Japanese Patent Laid-Open No. 5-178954, and Japanese Patent Laid-Open No. 7-330849. And the method disclosed in J. et al. Org. Chem. , 28, 2069 (1963), Chem. , Review 81, 619 (1981). Further, it can be carried out in the absence of a solvent as disclosed in JP-A Nos. 5-178954 and 6-56950.

A commercial item can also be used as said carbodiimide compound. Commonly available commercially available aliphatic polycarbodiimide compounds include Carbodilite LA-1, Carbodilite HMV-8CA, Carbodilite V-05, Carbodilite V-07, Carbodilite HMV-15CA and Carbodilite V-03 not containing an isocyanate group. And Carbodilite V-09 (manufactured by Nisshinbo Chemical Co., Ltd.). Moreover, as a commercial item of an aromatic polycarbodiimide compound, stabaxol P, stavaxol P-400, stavaxol I (above, manufactured by Rhein Chemie Co., Ltd.) and the like can be mentioned.

In the curable resin composition of the present invention, the mixing ratio of the carbodiimide compound is preferably 0.01 to 5% by mass with respect to 100% by mass of the cyanate ester compound in the curable resin composition. By using it in such a ratio, generation | occurrence | production of a heterogeneous structure can be suppressed more fully, and a hardened | cured material can also be made excellent in the external appearance. More preferably, it is 0.05-4 mass% with respect to 100 mass% of cyanate ester compounds, More preferably, it is 0.1-3 mass%.

[Inorganic filler]
The resin composition in the present invention preferably further contains an inorganic filler. It does not specifically limit as an inorganic filler, What is necessary is just to use what is used by the sealing material etc. of a normal mounting board | substrate. For example, a silica filler etc. are mentioned.

As a content rate of the inorganic filler in the said resin composition, it is suitable to set it as 50-95 mass% with respect to 100 mass% of total amounts of a resin composition. More preferably, it is 60-93 mass%, More preferably, it is 70-90 mass%. By using a large amount of the inorganic filler in this way, for example, when used for obtaining a sealing material for a mounting substrate, it is possible to sufficiently prevent the substrate from being warped after curing.

[Other ingredients]
The resin composition in the present invention may also contain other components other than the components described above, if necessary. For example, curing agents; curing accelerators; inorganic fillers; volatile components such as organic solvents and diluents; flame retardants; reinforcing materials; coupling agents; stress relieving agents; Examples include a flexible agent; various rubber-like materials; a photosensitizer; a pigment; and the like, and one or more of these can be used.
Since the resin composition in the present invention may cause problems when it contains a large amount of volatile components, it is desired that the resin composition does not contain volatile components. For example, the resin composition contains 100% by mass of the volatile components. The ratio is preferably 10% by mass or less. More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less, Most preferably, it does not contain a volatile component substantially.

<Board>
As the substrate included in the semiconductor device of the present invention, a substrate generally used as a substrate can be used. For example, aluminum oxide, aluminum nitride, silicon nitride, zirconium oxide, zirconium nitride, titanium oxide, titanium nitride, silicon oxide, sapphire or One kind of ceramic substrate containing these mixtures, metal substrate containing Cu, Fe, Ni, Cr, Al, Ag, Au, Ti or alloys thereof, glass epoxy substrate, BT resin substrate, glass substrate, resin substrate, etc. Two or more kinds can be used.

<Semiconductor element>
The semiconductor element used in the semiconductor device of the present invention is not particularly limited. However, as described above, the semiconductor device of the present invention does not cause peeling in the semiconductor device even when used at a high temperature exceeding 200 ° C. for a long period of time. It is one of the preferred embodiments of the present invention to use next-generation power semiconductors such as SiC and GaN, which are sufficiently suppressed so that they have a high temperature exceeding 200 ° C. during use.

2. The present invention also relates to a method for manufacturing a semiconductor device including a substrate and a semiconductor element, the manufacturing method including metal particles and an inorganic component different from the metal particles. After applying the conductive composition on the substrate, the step of installing a semiconductor element on the substrate, and the step of heating the substrate on which the semiconductor element is installed at 150 ° C. to 300 ° C. in the atmosphere or oxygen gas atmosphere are included. This is also a method for manufacturing a semiconductor device.

The method for applying the conductive composition in the step of applying the conductive composition on the substrate is not particularly limited, and includes a screen printing method, an offset printing method, an ink jet printing method, a flexographic printing method, a gravure printing method, stamping, dispensing, Any method such as squeegee printing, silk screen printing, spraying, and brush coating may be used. Among these methods, screen printing, stamping and dispensing are preferable.

The film thickness of the coating film formed on the substrate in the step of applying the conductive composition on the substrate is preferably 20 to 500 μm. More preferably, it is 30-300 micrometers, More preferably, it is 50-200 micrometers.
The film thickness of the coating film can be measured by a non-contact type laser microscope, a contact type surface roughness measuring device, a light interference type film thickness measuring device, an ellipsometer or the like.

The step of heating the substrate provided with the semiconductor element in the atmosphere or oxygen gas atmosphere may be performed at 150 ° C. to 300 ° C., but is preferably performed at 200 to 300 ° C. More preferably, it is performed at 250 to 300 ° C.
The time for heating at 150 ° C. to 300 ° C. is not particularly limited, but is preferably 5 to 300 minutes. More preferably, it is 10 to 150 minutes.
The heating at 150 ° C. to 300 ° C. may be performed while pressurizing the substrate on which the semiconductor element is installed. In addition, the heating step may include a step of volatilizing the solvent before heating at 150 ° C. to 300 ° C., and the heating temperature in that case may be a temperature lower than 150 ° C. The heating temperature in the step of volatilizing the solvent may be appropriately selected depending on the solvent to be used, and may be, for example, room temperature to 100 ° C.

The manufacturing method further includes the step of injecting a molten resin composition containing a cyanate ester compound and / or a maleimide compound into a mold in which the substrate after the heating step is disposed, and a substrate on which a semiconductor element is installed. It is preferable to include the process of sealing.
When sealing is performed using a resin composition containing a cyanate ester compound and / or a maleimide compound, by using such a method, a good sealing film having high adhesion to a substrate on which a semiconductor element is installed can be obtained. Can be formed.
As a method for performing such a sealing step, a transfer mold molding method using a transfer molding machine is preferable.

When performing the said sealing process, it is preferable that the viscosity in 150 degreeC of the resin composition containing the fuse | melted cyanate ester compound and / or maleimide compound is 0.1-60 Pa.s. When the resin composition has such an appropriate viscosity, for example, it becomes excellent in handling properties when applied. More preferably, it is 0.2 to 40 Pa · s. Moreover, when casting at normal temperature, it is liquid at normal temperature and it is preferable that it is 5-1000 Pa.s. This is because if the viscosity is too low, the inorganic filler may settle, and if the viscosity is too high, the irregularities to be sealed may not be filled. More preferably, it is 10-500 Pa.s. In addition, the preferable range of the viscosity at 175 ° C. of the resin composition is the same as the preferable range of the viscosity at 150 ° C. described above.
The viscosity of the resin composition can be measured using, for example, an E-type viscometer (manufactured by Brookfield) or a flow tester CFT-500D (manufactured by Shimadzu Corporation).

In the sealing step, the method for curing the resin composition injected under pressure is not particularly limited. For example, it can be cured by thermosetting. The curing method is not particularly limited, and a normal thermosetting method may be adopted. For example, 70-250 degreeC is suitable for thermosetting temperature, More preferably, it is 100-250 degreeC. Moreover, 1-15 hours are suitable for hardening time, More preferably, it is 2-10 hours.

The cured product preferably has a glass transition temperature of 180 ° C. or higher by a thermomechanical analyzer (DMA). Thereby, for example, it can be suitably used for an electronic packaging material such as a sealing material for a mounting board. More preferably, it is 190 degreeC or more, More preferably, it is 195 degreeC or more, Most preferably, it is 200 degreeC or more.

The method for producing a semiconductor device of the present invention may include a step of installing a semiconductor element on the substrate after applying the conductive composition on the substrate, and other steps other than the sealing step, Examples of the other steps include a step of wire bonding between the semiconductor element and the terminal after the step of installing the semiconductor element on the substrate.

The semiconductor device of the present invention has the above-described configuration, and uses a conductive composition in which an inorganic component different from the metal particle is added to the metal particle as a die attach material, and further includes a semiconductor element using the die attach material. By performing sealing with a resin composition containing a cyanate ester compound and / or a maleimide compound, the occurrence of peeling in the semiconductor device is sufficiently suppressed even when used at a high temperature exceeding 200 ° C. for a long period of time. Therefore, in particular, it can be suitably used for various applications as a semiconductor device including next-generation power semiconductors such as SiC and GaN.

It is the figure which showed the outline of the evaluation system of the power cycle characteristic evaluation in an Example. It is the figure which showed the ultrasonic flaw test result of the semiconductor package of the comparative example 1 before the heat cycle (left) and after the heat cycle (right). It is the figure which showed the ultrasonic flaw test result of the semiconductor package of the comparative example 2 before the heat cycle (left) and after the heat cycle (right). It is the figure which showed the ultrasonic flaw test result of the semiconductor package of Example 1 before the heat cycle (left) and after the heat cycle (right).

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

<Molecular weight measurement>
The number average molecular weight and weight average molecular weight of the siloxane compound were determined by GPC (gel permeation chromatography) measurement under the following measurement conditions.
Measuring instrument: HLC-8120GPC (trade name, manufactured by Tosoh Corporation)
Molecular weight column: TSK-GEL GMHXL-L and TSK-GELG5000HXL (both manufactured by Tosoh Corporation) are connected in series. Eluent: Tetrahydrofuran (THF)
Standard material for calibration curve: Polystyrene (manufactured by Tosoh Corporation)
Measurement method: The measurement object is dissolved in THF so that the solid content is about 0.2% by mass, and the molecular weight is measured using an object obtained by filtration through a filter as a measurement sample.

<Measurement of glass transition temperature (Tg)>
The glass transition temperature of the resin composition was measured using a dynamic viscoelasticity measuring device (device name: DMA7100, manufactured by Hitachi High-Tech Science Co., Ltd.). The measurement temperature range was −100 ° C. to 400 ° C., the heating rate was 5 ° C./min, and the measurement was performed in a nitrogen atmosphere.

Synthesis example 1
Synthesis of poly {γ- (5-norbornene-2,3-imido) propylsilsesquioxane} In a 500 mL four-necked flask equipped with a stirrer, a temperature sensor, and a condenser tube, 87.9 g of diglyme previously dried with molecular sieves. Then, 142.5 g of 3-aminopropyltrimethoxysilane was added, and the temperature was raised to 100 ° C. under a flow of dry nitrogen while stirring to remove moisture in the system. Next, 131.8 g of 5-norbornene-2,3-dicarboxylic anhydride was added in four portions over 30 minutes while maintaining the reaction solution temperature at 100 ° C. It was confirmed by high performance liquid chromatography that 5-norbornene-2,3-dicarboxylic anhydride was completely consumed in 9 hours after the completion of the addition.
Subsequently, 42.9 g of deionized water was added all at once, and the temperature was raised so that by-product methanol was refluxed in the cooling pipe. After holding at 95 ° C. for 10 hours, the temperature was raised again by replacing the cooling pipe with a partial condenser. The reaction liquid temperature was allowed to reach 120 ° C. over 3 hours while collecting by-product methanol and condensed water. When reaching 120 ° C., 0.65 g of cesium carbonate is added and heating is started as it is. Recovered by condensing water, reaching 160 ° C. over 3 hours, holding at that temperature for 2 hours and cooling to room temperature. Product A was obtained.
The reaction product A was a dark brown high-viscosity liquid with a non-volatile content of 70.0%, and its molecular weight was measured by GPC to be a number average molecular weight 2340 and a weight average molecular weight 2570. ¹ H-NMR and ¹³ C-NMR were measured, and it was confirmed that the compound of formula (10) (siloxane compound 1) was contained.
¹ H-NMR: 0.25-0.45 (bs, 2H), 1.2-1.45 (bs, 2H), 1.47 (dd, 2H), 3.0-3.2 (bs, 4H), 3.4-3.6 (bs, 2H), 5.8-6.0 (bs, 2H)
¹³ C-NMR: 9.7, 21.5, 40.4, 44.9, 45.7, 50.1, 134.2, 178.0

Synthesis example 2
Synthesis of poly {(cis-4-cyclohexene-1,2-imido) propylsilsesquioxane} In place of 131.8 g of 5-norbornene-2,3-dicarboxylic anhydride in Synthesis Example 1, cis-4-cyclohexene Reaction product B was obtained in the same manner as in Synthesis Example 1 except that 122.2 g of -1,2-dicarboxylic anhydride was used. Reaction product B was a dark brown high-viscosity liquid with a non-volatile content of 70.0%. The molecular weight measured by GPC was a number average molecular weight of 2041 and a weight average molecular weight of 2838. ¹ H-NMR and ¹³ C-NMR were measured, and it was confirmed that the compound of formula (11) (siloxane compound 2) was contained.
¹ H-NMR: 0.25-0.55 (bs, 2H), 1.3-1.5 (bs, 2H), 2.0-2.5 (dd, 4H), 2.9-3. 1 (bs, 2H), 3.2-3.35 (bs, 2H), 5.65-5.8 (bs, 2H)
¹³ C-NMR: 10.0, 21.0, 23.8, 39.0, 41.1, 127.8, 180.5

Preparation Example 1 (Preparation of semiconductor encapsulant composition)
Each raw material was weighed with the composition shown in Table 1 below, and then kneaded using a heating roll kneader to obtain a compound. The surface temperature of the kneading roll was set to 72 ° C., and the kneading time was set to 5 minutes. The compound was made into a powder of 1 mm or less using a pulverizer, and then made into a tablet shape having a diameter of 18 mm and a weight of 7 g using a tableting machine, and used as a semiconductor sealing material.

The cyanate ester compound, maleimide compound, carbodiimide compound, epoxy compound, aromatic amine compound, phenol compound, imidazole compound, and silane coupling agent described in Table 1 are as follows.
Cyanate ester compound: Phenol novolac-type cyanate ester compound represented by the following formula (12) (product name “Primerset PT30”, manufactured by Lonza Japan)
Maleimide compound: bismaleimide compound having a structure represented by the following formula (13) (product name “Bismaleimide BMI80”, manufactured by KAI Kasei Co., Ltd.)
Carbodiimide compound: Aliphatic polycarbodiimide compound (Product name “Carbodilite V-05”, manufactured by Nisshinbo Chemical Co., Ltd.)
Epoxy compound: Tris (hydroxyphenyl) methane type epoxy resin (product name “EPPN-501HY”, manufactured by Nippon Kayaku Co., Ltd.)
Aromatic amine compound: 4,4′-diaminodiphenyl sulfone (product name “Seika Cure S”, manufactured by Wakayama Seika Kogyo Co., Ltd.)
Phenol compound: Phenol novolak curing agent (Product name “TD-2131”, manufactured by DIC Corporation)
Imidazole compound: 2-Phenyl-4-methyl-5-hydroxymethylimidazole (product name “CUREZOL 2P4MHZ”, manufactured by Shikoku Kasei Kogyo Co., Ltd.)
Silane coupling agent: N-phenyl-3-aminopropyltrimethoxysilane (product name “KBM573”, manufactured by Shin-Etsu Chemical Co., Ltd.)

Preparation Example 2 (Preparation of die attach material)
The following two types of silver powder and two types of inorganic particles are mixed in the composition shown in Table 2 and washed with ethanol. After drying, the mixture is mixed with an ethylene glycol solvent and made into a paste using a rotation / revolution type stirring mixer, The syringe was filled and defoamed and used as a sintered silver die attach material.
<Silver powder>
(1) Product name “AgC-239” manufactured by Fukuda Metal Foil Industry Co., Ltd .: average particle diameter (median diameter) of 6 μm, BET specific surface area of 5.0 m ² / g
(2) Product name “FHD: Average particle diameter (median diameter) is 0.3 μm, BET specific surface area is 1.70 m ² / g, manufactured by Mitsui Mining & Smelting Co., Ltd.
<Inorganic particles>
(3) Super Graphite, product name “HSC059”: material is SiC, average particle size (median diameter) is 0.6 μm, polygonal shape (4) “KE-P30”, Nippon Shokubai Co., Ltd .: material is silica, average Particle size 0.3μm, spherical shape

Examples 1 to 4, Comparative Examples 1 and 2 (production of semiconductor package)
The die attach materials 1 to 3 shown in Table 2 were applied onto the pad area of the copper TO247 lead frame. Thereafter, a 1.5 mm □ SiC Schottky barrier diode was placed on the die attach material and left in an air atmosphere for 30 minutes on a hot plate whose surface temperature was adjusted to 250 ° C. After cooling, the diode element and the terminal were wire-bonded with an aluminum wire having a diameter of 350 μm, and components were mounted on the substrate by ultrasonic cleaning in ethanol.
The substrate with components and the sealing materials 1 to 3 were set in a low-pressure transfer molding machine, and a TO247 type semiconductor package was produced by insert molding of a copper lead frame. The molding conditions were set such that the mold temperature was 180 ° C., the clamp pressure was 294 KN, the preheating time was 5 seconds, the injection pressure was 15 KN, the injection speed was 0.5 mm / s, the transfer time was 28 seconds, and the curing time was 360 seconds. The obtained molded product was left to stand in an inert oven in a nitrogen flow state at 270 ° C. for 5 hours to perform a post-cure treatment to obtain a power device for evaluation.

<Reliability evaluation 1 (heat cycle test)>
In order to evaluate the reliability of the semiconductor packages of Examples and Comparative Examples, a heat cycle test was conducted to examine the influence on the internal structure of the package due to the generation of internal stress when repeatedly exposed to a cold environment. The heat cycle test conditions were a cooling lower limit condition of -50 ° C for 30 minutes, a heating upper limit condition of 250 ° C for 30 minutes, a cooling / heating time of about 3 minutes, and 500 cycles.
Check the internal structure of the package using an ultrasonic flaw detector (FineSATIII, manufactured by Hitachi Power Solutions Co., Ltd.). If there is peeling at the interface between the built-in component and the sealing material inside the package, ×, no bubbles or gels, but no peeling Δ was given when many non-uniform structures such as a product were observed, and ◎ was given when there was no peeling and there were few non-uniform structures.

<Reliability evaluation 2 (power cycle characteristic evaluation)>
(Power cycle evaluation)
The system used for the measurement is shown in FIG. Connect a DC power supply to the power device for evaluation, attach a thermocouple to the surface of the power device, track the temperature change with a multimeter, stop the current when the specified temperature is reached while flowing a constant current by computer control Then, the power device was air-cooled and returned to room temperature as one cycle, and this was repeated, and the number of cycles in which current stopped flowing was investigated. As power cycle conditions, the upper limit of the case temperature (power device surface temperature, Tc) is 250 ° C., the lower limit is room temperature, a forward current value of 8A is applied to generate heat, and after reaching Tc = 250 ° C., the current value is set to 2A. Set to hold for 10 seconds. The number of tests was 15 in each sample, and the ratio of passing the test of 500 cycles, 1000 cycles, and 3000 cycles was examined.
Evaluation system overview:
DC power supply: manufactured by Takasago Seisakusho Co., Ltd., product name “ZX-400LAN”
Multimeter: Product name “2701 multimeter” manufactured by KEITHLEY

Table 3 shows the types of die attach materials and sealing materials used in the examples and comparative examples, and the results of the heat cycle test and power cycle test. 2 to 4 show the ultrasonic flaw detection test results of the power device internal structure before and after the heat cycle test.

In the heat cycle test, regardless of whether inorganic particles are added to the die attach material, the use of an imide-based material as the sealing material will cause peeling or cracking inside the package against thermal shock at severe temperature differences. It was possible to suppress physical damage such as.
However, in the power cycle test, in the comparative example, about 20% to 30% of the samples do not function in about 500 cycles corresponding to the initial stage of the cycle test, whereas in the example, the cycle is as long as 3000 cycles. The function was not impaired even in the cycle, and it was possible to work as a power device.
Not only is it thought that electrochemical changes occur around the chip, die attach material, and wire due to the current, but there are also effects such as the uneven distribution of thermal stress due to the temperature gradient between the chip periphery and the sealing material surface. Although it is considered, it can be expected that these effects can be suppressed to a minimum by adding inorganic particles to the die attach material.

Claims (6)

A semiconductor device comprising a substrate and a semiconductor element,
The semiconductor device includes metal particles and a component derived from a conductive composition containing an inorganic component different from the metal particles;
And a component derived from a resin composition containing a cyanate ester compound and / or a maleimide compound. The semiconductor device according to claim 1, wherein the conductive composition has an adhesive component content of 15% by mass or less with respect to the entire conductive composition. The conductive composition includes metal particles having a median diameter of 1.0 to 9.9 μm and metal particles having a median diameter of 0.1 to 0.99 μm. The semiconductor device according to claim 1, wherein the semiconductor device is characterized. The resin composition has the following average composition formula (4):
XaYbZcSiOd (4)
(Wherein X is the same or different and represents an organic skeleton containing an imide bond. Y is the same or different and represents at least one selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom and an OR group. Z is the same or different and represents an organic group containing no imide bond, and R is the same or different and is at least one selected from the group consisting of an alkyl group, an acyl group, an aryl group, and an unsaturated aliphatic residue. Represents a species and may have a substituent, a, b and c are 0 or a number less than 3, and d is a non-zero number less than 2 and a + b + c + 2d = 4. The semiconductor device according to claim 1, further comprising a siloxane compound. A method of manufacturing a semiconductor device including a substrate and a semiconductor element,
The manufacturing method includes a step of installing a semiconductor element on a substrate after applying a conductive composition containing a metal particle and an inorganic component different from the metal particle on the substrate;
And a step of heating the substrate provided with the semiconductor element at 150 ° C. to 300 ° C. in the atmosphere or in an oxygen gas atmosphere. The manufacturing method further includes the step of injecting a molten resin composition containing a cyanate ester compound and / or a maleimide compound into a mold on which the substrate after the heating step is disposed, and a substrate on which a semiconductor element is installed. The method for manufacturing a semiconductor device according to claim 5, further comprising a step of sealing.