JP2012144617A - Die-bonding material for optical semiconductor device and optical semiconductor device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a die-bonding material for optical semiconductor devices, with which bondability during wire bonding is improved and the thermal cracking resistance of a cured material is enhanced.SOLUTION: The die-bonding material for optical semiconductor devices includes: a first silicone resin represented by formula (1) and having an aryl group and a hydrogen atom bonded to silicon atom; a second silicone resin represented by formula (51), having no hydrogen atom bonded to silicon atom and having an aryl group and alkenyl group; a catalyst for hydrosilylation reaction; and silicon oxide particles. In the die-bonding material for optical semiconductor devices, the first silicone resin has no dimethylsiloxane skeleton and the second silicone resin has no dimethylsiloxane skeleton.

Description

  The present invention relates to a die bond material for an optical semiconductor device used for die bonding of an optical semiconductor element such as a light emitting diode (LED) element, and an optical semiconductor device using the die bond material for an optical semiconductor device.

  Optical semiconductor elements such as light emitting diode (LED) elements are widely used as light sources for display devices. An optical semiconductor device using an optical semiconductor element has low power consumption and long life. Moreover, the optical semiconductor device can be used even in a harsh environment. Accordingly, optical semiconductor devices are used in a wide range of applications such as mobile phone backlights, liquid crystal television backlights, automobile lamps, lighting fixtures, and signboards.

Patent Document 1 below discloses an optical semiconductor device in which an LED element is mounted on a substrate. In this optical semiconductor device, the LED element is bonded to the upper surface of the substrate using a die bond material. This die bond material includes an alkenyl group-containing polyorganosiloxane, a polyorganohydrogensiloxane having three or more hydrogen atoms bonded to silicon atoms, a platinum catalyst, and an adhesion promoter. The alkenyl group-containing polyorganosiloxane is a polyorganosiloxane having a hydroxyl group amount of 50 to 3000 ppm bonded to a silicon atom, an average of one or more alkenyl groups bonded to a silicon atom, and SiO _4/2 units. Including.

JP 2009-114365 A

  In obtaining the optical semiconductor device, first, a die bonding material is applied or laminated on a substrate by using a coating device called a die bonder to form a die bonding layer. Next, an optical semiconductor element is laminated on the die bond layer, and the die bond layer is cured. Thereafter, wire bonding is performed to electrically connect the optical semiconductor elements.

  In the conventional die-bonding material as described in Patent Document 1, it is sometimes difficult to perform wire bonding with high accuracy due to the fact that the cured product of the die-bonding material is relatively soft. For example, during wire bonding, the cured product of the die bond material absorbs ultrasonic vibration, which may inhibit bonding and cause wire bonding failure.

  Furthermore, in a conventional optical semiconductor device using a die bond material, when the cured product of the die bond material is exposed to a high temperature due to light emission from the optical semiconductor element, cracks may occur in the cured product.

  An object of the present invention is to provide a die bond material for an optical semiconductor device that can improve bondability at the time of wire bonding and can further improve the heat-resistant crack characteristics of a cured product, and the die bond material for an optical semiconductor device. It is to provide an optical semiconductor device.

  According to a wide aspect of the present invention, the first silicone resin represented by the following formula (1) and having a hydrogen atom bonded to an aryl group and a silicon atom, and represented by the following formula (51) and a silicon atom And a second silicone resin having no aryl atom and alkenyl group, a hydrosilylation catalyst, and silicon oxide particles, wherein the first silicone resin comprises a dimethylsiloxane skeleton. There is provided a die bond material for an optical semiconductor device in which the second silicone resin does not have a dimethylsiloxane skeleton.

In the above formula (1), a, b and c are a / (a + b + c) = 0.05 to 0.50, b / (a + b + c) = 0 to 0.20 and c / (a + b + c) = 0.30. 0.90 is satisfied, R1 to R6 each represents at least one aryl group, at least one represents a hydrogen atom, and R1 to R6 other than the aryl group and the hydrogen atom are hydrocarbon groups having 1 to 8 carbon atoms. Represents. However, in the above formula (1), in the structural unit represented by (R4R5SiO2 _{/ 2} ), both R4 and R5 are not methyl groups and are not dimethylsiloxane structural units.

In the above formula (51), p, q and r are p / (p + q + r) = 0.05 to 0.50, q / (p + q + r) = 0.05 to 0.50 and r / (p + q + r) = 0. R51 to R56, at least one represents an aryl group, at least one represents an alkenyl group, and R51 to R56 other than the aryl group and the alkenyl group are carbon atoms having 1 to 8 carbon atoms. Represents a hydrogen group. However, in the above formula (51), in the structural unit represented by (R54R55SiO _2/2 ), both R54 and R55 are not methyl groups and are not dimethylsiloxane structural units.

  In a specific aspect of the die bond material for an optical semiconductor device according to the present invention, the first silicone resin represented by the above formula (1) is a first silicone resin represented by the following formula (1A).

In the above formula (1A), a, b, c1 and c2 are a / (a + b + c1 + c2) = 0.05 to 0.50, b / (a + b + c1 + c2) = 0 to 0.20, (c1 + c2) / (a + b + c1 + c2) = 0.30-0.90, satisfying c1 / (a + b + c1 + c2) = 0.30-0.90 and c2 / (a + b + c1 + c2) = 0-0.20, R1 to R6 each represents at least one aryl group, At least one represents a hydrogen atom, and R1 to R6 other than the aryl group and the hydrogen atom represent a hydrocarbon group having 1 to 8 carbon atoms. However, in the above formula (1A), the structural unit represented by (R4R5SiO2 _{/ 2} ) is not a methyl group in R4 and R5, and is not a dimethylsiloxane structural unit.

  In another specific aspect of the die bond material for an optical semiconductor device according to the present invention, the second silicone resin represented by the above formula (51) is a second silicone resin represented by the following formula (51A). .

In the above formula (51A), p, q, r1 and r2 are p / (p + q + r1 + r2) = 0.05 to 0.50, q / (p + q + r1 + r2) = 0.05 to 0.50, (r1 + r2) / (p + q + r1 + r2) ) = 0.05 to 0.50, r1 / (p + q + r1 + r2) = 0.05 to 0.40 and r2 / (p + q + r1 + r2) = 0 to 0.50, R51 to R56 are at least one aryl group And at least one represents an alkenyl group, and R51 to R56 other than an aryl group and an alkenyl group represent a hydrocarbon group having 1 to 8 carbon atoms. However, in the above formula (51A), in the structural unit represented by (R54R55SiO _2/2 ), both R54 and R55 are not methyl groups and are not dimethylsiloxane structural units.

  It is preferable that the viscosities at 25 ° C. and 10 rpm measured with the respective E-type viscometers of the first silicone resin and the second silicone resin are 1200 mPa · s or more and 6000 mPa · s or less.

  In another specific aspect of the die bond material for an optical semiconductor device according to the present invention, the first silicone resin is a first silicone resin having an aryl group, a hydrogen atom bonded to a silicon atom, and an alkenyl group. is there.

  An optical semiconductor device according to the present invention includes an optical semiconductor device die-bonding material configured according to the present invention, a connection target member, and an optical semiconductor element connected to the connection target member using the optical semiconductor device die-bonding material. Is provided.

  A die bond material for an optical semiconductor device according to the present invention is represented by the formula (1), a first silicone resin having an aryl group and a hydrogen atom bonded to a silicon atom, a formula (51), and a silicon atom. A second silicone resin having no bonded hydrogen atom and having an aryl group and an alkenyl group; a hydrosilylation reaction catalyst; and silicon oxide particles, wherein the first silicone resin has a dimethylsiloxane skeleton. In addition, since the second silicone resin does not have a dimethylsiloxane skeleton, bondability at the time of wire bonding can be improved, and heat-resistant crack characteristics of the cured product can be further improved.

FIG. 1 is a front sectional view showing an optical semiconductor device according to an embodiment of the present invention.

  Details of the present invention will be described below.

  The die-bonding material for optical semiconductor devices according to the present invention includes a first silicone resin, a second silicone resin, a hydrosilylation catalyst, and silicon oxide particles. The first silicone resin is represented by the formula (1), and has an aryl group and a hydrogen atom bonded to a silicon atom. The second silicone resin is represented by the formula (51), does not have a hydrogen atom bonded to a silicon atom, and has an aryl group and an alkenyl group. That is, the die bond material for an optical semiconductor device according to the present invention includes a silicone resin capable of hydrosilylation reaction, and the silicone resin capable of hydrosilylation reaction includes the first silicone resin and the second silicone resin. .

  In the die bond material for an optical semiconductor device according to the present invention, the first silicone resin does not have a dimethylsiloxane skeleton, and the second silicone resin does not have a dimethylsiloxane skeleton. That is, the silicone resin capable of hydrosilylation contained in the die bond material for optical semiconductor devices according to the present invention does not have a dimethylsiloxane skeleton.

  By adopting the above composition in the die bond material for optical semiconductor devices according to the present invention, the die bond material for optical semiconductor devices according to the present invention is coated on a coating target member such as a substrate using a coating device such as a die bonder, and the die bond After the optical semiconductor element is laminated on the material and the die bond material is cured, the wire bonding can be performed with high precision when wire bonding is performed in order to electrically connect the optical semiconductor element. That is, by adopting the above composition, bondability during wire bonding can be improved. In particular, the fact that the first silicone resin does not have a dimethylsiloxane skeleton and the second silicone resin does not have a dimethylsiloxane skeleton means that an optical semiconductor element can be obtained without absorbing ultrasonic vibration during wire bonding. It contributes to improving the bondability at the time of wire bonding.

  Furthermore, by adopting the above composition in the die bond material for optical semiconductor devices according to the present invention, both the first and second silicone resins have an aryl group, so that the heat-resistant crack characteristics of the cured product of the die bond material can be improved. it can. In an optical semiconductor device using a die bond material, a cured product of the die bond material is exposed to a high temperature when the optical semiconductor element emits light. Since the hardened | cured material of the die-bonding material for optical semiconductor devices which concerns on this invention does not produce a crack easily even if it exposes to high temperature, the reliability of an optical semiconductor device can be improved.

(First silicone resin)
The 1st silicone resin contained in the die-bonding material for optical semiconductor devices which concerns on this invention is represented by following formula (1), and has an aryl group and the hydrogen atom couple | bonded with the silicon atom. The first silicone resin does not have a dimethylsiloxane skeleton (dimethylsiloxane structural unit). The hydrogen atom is directly bonded to the silicon atom. As said aryl group, an unsubstituted phenyl group and a substituted phenyl group are mentioned. As for the said 1st silicone resin, only 1 type may be used and 2 or more types may be used together.

In the above formula (1), a, b and c are a / (a + b + c) = 0.05 to 0.50, b / (a + b + c) = 0 to 0.20 and c / (a + b + c) = 0.30. 0.90 is satisfied, R1 to R6 each represents at least one aryl group, at least one represents a hydrogen atom, and R1 to R6 other than the aryl group and the hydrogen atom are hydrocarbon groups having 1 to 8 carbon atoms. Represents. However, in the above formula (1), in the structural unit represented by (R4R5SiO2 _{/ 2} ), both R4 and R5 are not methyl groups and are not dimethylsiloxane structural units. In the above formula (1), the structural unit represented by (R4R5SiO _2/2 ) and the structural unit represented by (R6SiO _3/2 ) each may have an alkoxy group, You may have.

  As described above, the first silicone resin does not have a dimethylsiloxane skeleton. Therefore, the first silicone resin represented by the above formula (1) does not have a structural unit represented by the following formula (101).

From the viewpoint of further improving both the heat-resistant crack characteristics and the cold-heat cycle characteristics of the cured product of the die bond material, the first silicone resin represented by the above formula (1) is represented by (CH ₃ SiO _3/2 ). It is preferable to have a structural unit. By introducing this structural unit, even if the cured product of the die bond material is exposed to a thermal cycle, cracks are hardly generated in the cured product.

  From the viewpoint of further improving both the heat-resistant crack characteristics and the cold-heat cycle characteristics of the cured product of the die bond material, the first silicone resin represented by the above formula (1) is the first silicone resin represented by the following formula (1A). 1 is preferable.

In the above formula (1A), a, b, c1 and c2 are a / (a + b + c1 + c2) = 0.05 to 0.50, b / (a + b + c1 + c2) = 0 to 0.20, (c1 + c2) / (a + b + c1 + c2) = 0.30-0.90, satisfying c1 / (a + b + c1 + c2) = 0.30-0.90 and c2 / (a + b + c1 + c2) = 0-0.20, R1 to R6 each represents at least one aryl group, At least one represents a hydrogen atom, and R1 to R6 other than the aryl group and the hydrogen atom represent a hydrocarbon group having 1 to 8 carbon atoms. However, in the above formula (1A), the structural unit represented by (R4R5SiO2 _{/ 2} ) is not a methyl group in R4 and R5, and is not a dimethylsiloxane structural unit. In the above formula (1A), when R6 is other than an aryl group or an alkenyl group, R6 preferably represents a hydrocarbon group having 2 to 8 carbon atoms, not a methyl group. In the above formula (1A), the structural unit represented by (R4R5SiO _2/2 ) and the structural unit represented by (R6SiO _3/2 ) may each have an alkoxy group, and have a hydroxy group. You may have.

  From the viewpoint of obtaining a die bond material that is further excellent in gas barrier properties, the first silicone resin may be a first silicone resin having an aryl group, a hydrogen atom bonded to a silicon atom, and an alkenyl group. preferable. From the viewpoint of obtaining a die bond material that is further excellent in gas barrier properties, in the formula (1) and the formula (1A), at least one of R1 to R6 represents an aryl group, and at least one represents a hydrogen atom. , At least one represents an alkenyl group, and R1 to R6 other than an aryl group, a hydrogen atom and an alkenyl group preferably represent a hydrocarbon group having 1 to 8 carbon atoms.

  The above formula (1) and the above formula (1A) show an average composition formula. The hydrocarbon group in the above formula (1) and the above formula (1A) may be linear or branched. R1 to R6 in the above formula (1) and the above formula (1A) may be the same or different.

In the above formula (1) and the above formula (1A), the oxygen atom part in the structural unit represented by (R4R5SiO _2/2 ) and the oxygen atom part in the structural unit represented by (R6SiO _3/2 ) are respectively An oxygen atom part forming a siloxane bond, an oxygen atom part of an alkoxy group, or an oxygen atom part of a hydroxy group is shown.

  In general, in each structural unit of the above formula (1) and the above formula (1A), the content of alkoxy groups is small, and the content of hydroxy groups is also small. In general, when an organosilicon compound such as an alkoxysilane compound is hydrolyzed and polycondensed in order to obtain a first silicone resin, most of the alkoxy groups and hydroxy groups are converted into partial skeletons of siloxane bonds. Because. That is, most of oxygen atoms of the alkoxy group and oxygen atoms of the hydroxy group are converted into oxygen atoms forming a siloxane bond. When each structural unit of the above formula (1) and the above formula (1A) has an alkoxy group or a hydroxy group, a slight amount of unreacted alkoxy group or hydroxy group that has not been converted into a partial skeleton of a siloxane bond remains. Indicates that The same applies to the case where each structural unit of formula (51) described later and formula (51A) described below has an alkoxy group or a hydroxy group.

  It does not specifically limit as a C1-C8 hydrocarbon group in the said Formula (1) and said Formula (1A), For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group N-hexyl group, n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group, cyclohexyl group , Vinyl group and allyl group.

  When there is an alkenyl group in the formula (1) and the formula (1A), examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. From the viewpoint of further enhancing the gas barrier property, the alkenyl group in the first silicone resin and the alkenyl group in the above formula (1) and the above formula (1A) are preferably vinyl groups or allyl groups. More preferably.

  It is preferable that the content ratio of the aryl group calculated | required from the following formula (X1) in the said 1st silicone resin is 3 mol% or more and 30 mol% or less. When the content ratio of the aryl group is 3 mol% or more, the gas barrier property is further enhanced. When the content ratio of the aryl group is 30 mol% or less, the die bond material is hardly peeled off. From the viewpoint of further improving the gas barrier properties, the content ratio of the aryl group is more preferably 5 mol% or more. From the viewpoint of making the peeling of the die bond material more difficult to occur, the content ratio of the aryl group is more preferably 20 mol% or less.

  Aryl group content ratio (mol%) = (average number of aryl groups contained in one molecule of the first silicone resin × molecular weight of aryl group / number average molecular weight of the first silicone resin) × 100・ Formula (X1)

  In the above formula (X1), “first silicone resin” means “first silicone resin whose average composition formula is represented by the above formula (1) or the above formula (1A)”.

  When using the 1st silicone resin which has a phenyl group, the aryl group in the said formula (X1) shows a phenyl group, and the content rate of an aryl group shows the content rate of a phenyl group.

In the first silicone resin represented by the above formula (1) or the above formula (1A), the structural unit represented by (R4R5SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) is represented by the following formula (1 -2), that is, a structure in which one of oxygen atoms bonded to a silicon atom in the bifunctional structural unit constitutes a hydroxy group or an alkoxy group may be included.

(R4R5SiXO _1/2 ) (Formula (1-2))

The structural unit represented by (R4R5SiO _2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (1-b), and is further represented by the following formula (1-2b). A portion surrounded by a broken line of the structural unit may be included. That is, a structural unit having a group represented by R4 and R5 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R4R5SiO _2/2 ). Specifically, when the alkoxy group is converted into a partial skeleton of a siloxane bond, the structural unit represented by (R4R5SiO _2/2 ) is a broken line of the structural unit represented by the following formula (1-b) The part enclosed by is shown. When an unreacted alkoxy group remains, or when the alkoxy group is converted to a hydroxy group, the structural unit represented by (R4R5SiO _2/2 ) having the remaining alkoxy group or hydroxy group has the following formula: The part enclosed with the broken line of the structural unit represented by (1-2-b) is shown. In the structural unit represented by the following formula (1-b), the terminal oxygen atom generally forms a siloxane bond with an adjacent silicon atom, and shares an oxygen atom with the adjacent structural unit. Therefore, one oxygen atom at the terminal is defined as “O _1/2 ”.

  In the above formulas (1-2) and (1-2-b), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. R4 and R5 in the above formulas (1-b), (1-2) and (1-2b) are the same groups as R4 and R5 in the above formula (1) or the above formula (1A). .

In the first silicone resin represented by the above formula (1) or the above formula (1A), the structural unit represented by (R6SiO _3/2 ) (hereinafter also referred to as trifunctional structural unit) is represented by the following formula (1 -3) or (1-4), that is, a structure in which two oxygen atoms bonded to a silicon atom in the trifunctional structural unit each constitute a hydroxy group or an alkoxy group, or a trifunctional structural unit One of the oxygen atoms bonded to the silicon atom therein may include a structure constituting a hydroxy group or an alkoxy group.

(R6SiX ₂ O _1/2 ) Formula (1-3)
(R6SiXO _2/2 ) Formula (1-4)

The structural unit represented by (R6SiO _3/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (1-c), and further includes the following formula (1-3-c) or (1 The part enclosed with the broken line of the structural unit represented by -4-c) may be included. That is, a structural unit having a group represented by R6 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R6SiO _3/2 ).

  In the above formulas (1-3), (1-3-c), (1-4) and (1-4-c), X represents OH or OR, and OR represents a linear or branched group. An alkoxy group having 1 to 4 carbon atoms is represented. R6 in the above formulas (1-c), (1-3), (1-3-c), (1-4) and (1-4-c) represents the above formula (1) or the above formula (1A). It is the same group as R6 in).

  The above formulas (1-b) and (1-c), formulas (1-2) to (1-4), and formulas (1-2b), (1-3-c) and (1-4- In c), the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an isopropoxy group, and an isobutoxy group. , Sec-butoxy group and t-butoxy group.

  A / (a + b + c) in the formula (1) and a / (a + b + c1 + c2) in the formula (1A) are 0.05 or more and 0.50 or less. When a / (a + b + c) and a / (a + b + c1 + c2) are not less than the above lower limit and not more than the above upper limit, the heat resistance of the die bond material can be further enhanced, and peeling of the die bond material can be further suppressed. A / (a + b + c) in the above formula (1) and a / (a + b + c1 + c2) in the above formula (1A) are preferably 0.10 or more, more preferably 0.15 or more, preferably 0.45 or less. Preferably it is 0.40 or less.

B / (a + b + c) in the above formula (1) and b / (a + b + c1 + c2) in the above formula (1A) are 0 or more and 0.20 or less. When b / (a + b + c) and b (a + b + c1 + c2) are less than or equal to the above upper limit, the storage elastic modulus at a high temperature is increased. b / (a + b + c) and b (a + b + c1 + c2) may exceed 0, and may be 0.01 or more. In the above formula (1) and the above formula (1A), even if the structural unit of (R4R5SiO _2/2 ) is present, the bondability of the cured product of the die bond material can be improved and the heat cracking property can be improved. it can. When b is 0 and b / (a + b + c) and b / (a + b + c1 + c2) are 0, there is no structural unit of (R4R5SiO _2/2 ) in the above formula (1) and the above formula (1A). .

  C / (a + b + c) in the above formula (1) and (c1 + c2) / (a + b + c1 + c2) in the above formula (1A) are 0.30 or more and 0.90 or less. When c / (a + b + c) and (c1 + c2) / (a + b + c1 + c2) are equal to or higher than the lower limit, the storage elastic modulus at a high temperature of the die bond material is increased. When c / (a + b + c) is not more than the above upper limit, the heat resistance of the die bond material is increased. C / (a + b + c) in the above formula (1) and (c1 + c2) / (a + b + c1 + c2) in the above formula (1A) are preferably 0.40 or more, more preferably 0.50 or more, preferably 0.80 or less. More preferably, it is 0.75 or less.

In the above formula (1A), c1 / (a + b + c1 + c2) is 0.30 or more and 0.90 or less, and c2 / (a + b + c1 + c2) is 0 or more and 0.20 or less. When c1 / (a + b + c1 + c2) and c2 / (a + b + c1 + c2) are not less than the above lower limit and not more than the above upper limit, both the heat-resistant crack characteristics and the cold-heat cycle characteristics of the cured product of the die bond material can be greatly enhanced. C1 / (a + b + c1 + c2) in the above formula (1A) is preferably 0.35 or more, more preferably 0.40 or more, preferably 0.80 or less, more preferably 0.75 or less. c2 / (a + b + c1 + c2) may exceed 0 or may be 0.01 or more. In addition, when c2 is 0 and c2 / (a + b + c1 + c2) is 0, the structural unit of (R6SiO _3/2 ) does not exist in the above formula (1A).

When the first silicone resin is subjected to ²⁹ Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) based on tetramethylsilane (hereinafter referred to as TMS), although the above formula shows a slight variation depending on the type of substituent. The peak corresponding to the structural unit represented by (R1R2R3SiO _1/2 ) in (1) and the above formula (1A) appears in the vicinity of +10 to −5 ppm, and in the above formula (1) and the above formula (1A), Each peak corresponding to the bifunctional structural unit of (R4R5SiO2 _{/ 2} ) and (1-2) appears in the vicinity of −10 to −50 ppm, and (R6SiO3 _{/ 2} ) in the above formula (1) and the above formula (1A). , (CH ₃ SiO _3/2 ), and peaks corresponding to the trifunctional structural units of (1-3) and (1-4) appear in the vicinity of −50 to −80 ppm.

Therefore, the ratio of each structural unit in the above formula (1) and the above formula (1A) can be measured by measuring ²⁹ Si-NMR and comparing the peak areas of the respective signals.

However, in the case where the structural unit in the above formula (1) and the above formula (1A) cannot be distinguished by the ²⁹ Si-NMR measurement based on the TMS, not only the ²⁹ Si-NMR measurement result but also ¹ By using the measurement results of H-NMR as necessary, the ratio of each structural unit in the above formula (1) and the above formula (1A) can be distinguished.

(Second silicone resin)
The 2nd silicone resin contained in the die-bonding material for optical semiconductor devices which concerns on this invention is represented by following formula (51), and has an aryl group and an alkenyl group. The second silicone resin does not have a dimethylsiloxane skeleton (dimethylsiloxane structural unit). The alkenyl group is directly bonded to the silicon atom. The carbon atom in the carbon-carbon double bond of the alkenyl group may be bonded to the silicon atom, and the carbon atom different from the carbon atom in the carbon-carbon double bond of the alkenyl group is bonded to the silicon atom. It may be. As said aryl group, an unsubstituted phenyl group and a substituted phenyl group are mentioned. As for the said 2nd silicone resin, only 1 type may be used and 2 or more types may be used together.

In the above formula (51), p, q and r are p / (p + q + r) = 0.05 to 0.50, q / (p + q + r) = 0.05 to 0.50 and r / (p + q + r) = 0. R51 to R56, at least one represents an aryl group, at least one represents an alkenyl group, and R51 to R56 other than the aryl group and the alkenyl group are carbon atoms having 1 to 8 carbon atoms. Represents a hydrogen group. However, in the above formula (51), in the structural unit represented by (R54R55SiO _2/2 ), both R54 and R55 are not methyl groups and are not dimethylsiloxane structural units. In the above formula (51), the structural unit represented by (R54R55SiO _2/2 ) and the structural unit represented by (R56SiO _3/2 ) may each have an alkoxy group, and have a hydroxy group. You may have.

  As described above, the second silicone resin does not have a dimethylsiloxane skeleton. Therefore, the second silicone resin represented by the above formula (51) does not have a structural unit represented by the following formula (101).

From the viewpoint of further enhancing both the heat cracking characteristics and the thermal cycle resistance characteristics of the cured product of the die bond material, the second silicone resin represented by the above formula (51) is represented by (CH ₃ SiO _3/2 ). It is preferable to have a structural unit. By introducing this structural unit, even if the cured product of the die bond material is exposed to a thermal cycle, cracks are hardly generated in the cured product.

  From the standpoint of further enhancing both the heat-resistant crack characteristics and the cold-heat cycle characteristics of the cured product of the die bond material, the second silicone resin represented by the above formula (51) is a second silicone resin represented by the following formula (51A). 2 is preferable.

In the above formula (51A), p, q, r1 and r2 are p / (p + q + r1 + r2) = 0.05 to 0.50, q / (p + q + r1 + r2) = 0.05 to 0.50, (r1 + r2) / (p + q + r1 + r2) ) = 0.05 to 0.50, r1 / (p + q + r1 + r2) = 0.05 to 0.40 and r2 / (p + q + r1 + r2) = 0 to 0.50, R51 to R56 are at least one aryl group And at least one represents an alkenyl group, and R51 to R56 other than an aryl group and an alkenyl group represent a hydrocarbon group having 1 to 8 carbon atoms. However, in the above formula (51A), in the structural unit represented by (R54R55SiO _2/2 ), both R54 and R55 are not methyl groups and are not dimethylsiloxane structural units. In the above formula (51A), when R56 is other than an aryl group and an alkenyl group, R56 preferably represents a hydrocarbon group having 2 to 8 carbon atoms, not a methyl group. In the formula (51A), the structural unit represented by (R54R55SiO _2/2 ) and the structural unit represented by (R56SiO _3/2 ) may each have an alkoxy group, You may have.

  The above formula (51) and the above formula (51A) show the average composition formula. The hydrocarbon group in the above formula (51) and the above formula (51A) may be linear or branched. R51 to R56 in the above formula (51) and the above formula (51A) may be the same or different.

  In the above formula (51) and the above formula (51A), examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. From the viewpoint of further enhancing the gas barrier properties, the alkenyl group in the second silicone resin and the alkenyl group in the above formula (51) and the above formula (51A) are preferably vinyl groups or allyl groups, More preferably.

  It does not specifically limit as a C1-C8 hydrocarbon group in the said Formula (51) and said Formula (51A), For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group N-hexyl group, n-heptyl group, n-octyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group, cyclohexyl group , Vinyl group and allyl group.

  It is preferable that the content ratio of the aryl group calculated | required from the following formula (X51) in the said 2nd silicone resin is 3 mol% or more and 30 mol% or less. When the content ratio of the aryl group is 3 mol% or more, the gas barrier property is further enhanced. When the content ratio of the aryl group is 30 mol% or less, the die bond material is hardly peeled off. From the viewpoint of further improving the gas barrier properties, the content ratio of the aryl group is more preferably 5 mol% or more. From the viewpoint of making peeling more difficult, the aryl group content is more preferably 20 mol% or less.

  Aryl group content ratio (mol%) = (average number of aryl groups contained in one molecule of second silicone resin × molecular weight of aryl group / number average molecular weight of second silicone resin) × 100 Formula (X51)

  In the above formula (X51), “second silicone resin” indicates “second silicone resin whose average composition formula is represented by the above formula (51) or the above formula (51A)”.

  When the second silicone resin represented by the above formula (51) or the above formula (51A) and having a phenyl group is used, the aryl group in the above formula (X51) represents a phenyl group, and the content ratio of the aryl group is The content ratio of the phenyl group is shown.

In the second silicone resin represented by the above formula (51) or the above formula (51A), the structural unit represented by (R54R55SiO _2/2 ) (hereinafter also referred to as a bifunctional structural unit) has the following formula (51 -2), that is, a structure in which one of oxygen atoms bonded to a silicon atom in the bifunctional structural unit constitutes a hydroxy group or an alkoxy group may be included.

(R54R55SiXO _1/2 ) Formula (51-2)

The structural unit represented by (R54R55SiO _2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (51-b), and is further represented by the following formula (51-2-b). A portion surrounded by a broken line of the structural unit may be included. That is, a structural unit having a group represented by R54 and R55 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R54R55SiO _2/2 ).

  In the above formulas (51-2) and (51-2-b), X represents OH or OR, and OR represents a linear or branched alkoxy group having 1 to 4 carbon atoms. R54 and R55 in the above formulas (51-b), (51-2) and (51-2-b) are the same groups as R54 and R55 in the above formula (51) or the above formula (51A). .

In the second silicone resin represented by the above formula (51) or the above formula (51A), the structural unit represented by (R56SiO _3/2 ) (hereinafter also referred to as trifunctional structural unit) is represented by the following formula (51 -3) or (51-4), that is, a structure in which two oxygen atoms bonded to a silicon atom in a trifunctional structural unit each constitute a hydroxy group or an alkoxy group, or a trifunctional structural unit One of the oxygen atoms bonded to the silicon atom therein may include a structure constituting a hydroxy group or an alkoxy group.

(R56SiX ₂ O _1/2 ) (Formula (51-3)
(R56SiXO _2/2 ) Formula (51-4)

The structural unit represented by (R56SiO _3/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula (51-c), and further includes the following formula (51-3-c) or (51 The part enclosed with the broken line of the structural unit represented by -4-c) may be included. That is, a structural unit having a group represented by R56 and having an alkoxy group or a hydroxy group remaining at the terminal is also included in the structural unit represented by (R56SiO _3/2 ).

  In the above formulas (51-3), (51-3-c), (51-4) and (51-4-c), X represents OH or OR, and OR represents a linear or branched group. An alkoxy group having 1 to 4 carbon atoms is represented. R56 in the above formulas (51-c), (51-3), (51-3-c), (51-4) and (51-4-c) represents the above formula (51) and the above (51A). It is the same group as R56 in the inside.

  The above formulas (51-b) and (51-c), formulas (51-2) to (51-4), and formulas (51-2-b), (51-3-c) and (51-4-) In c), the linear or branched alkoxy group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an isopropoxy group, and an isobutoxy group. , Sec-butoxy group and t-butoxy group.

  P / (p + q + r) in the above formula (51) and p / (p + q + r1 + r2) in the above formula (51A) are 0.05 or more and 0.50 or less. When p / (p + q + r) and p / (p + q + r1 + r2) are not less than the above lower limit and not more than the upper limit, the heat resistance of the die bond material can be further enhanced, and peeling of the die bond material can be further suppressed. P / (p + q + r) in the above formula (51) and p / (p + q + r1 + r2) in the above formula (51A) are preferably 0.10 or more, more preferably 0.15 or more, preferably 0.45 or less, more Preferably it is 0.40 or less.

  Q / (p + q + r) in the above formula (51) and q / (p + q + r1 + r2) in the above formula (51A) are 0.05 or more and 0.50 or less. When q / (p + q + r) and q / (p + q + r1 + r2) are not more than the above upper limits, the storage elastic modulus at a high temperature of the die bond material is increased. Q / (p + q + r) in the above formula (51) and q / (p + q + r1 + r2) in the above formula (51A) are preferably 0.40 or less, more preferably 0.35 or less.

  R / (p + q + r) in the above formula (51) and (r1 + r2) / (p + q + r1 + r2) in the above formula (51A) are 0.05 or more and 0.50 or less. When r / (p + q + r) and (r1 + r2) / (p + q + r1 + r2) are equal to or higher than the lower limit, the storage elastic modulus at a high temperature of the die bond material is increased. When r / (p + q + r) and (r1 + r2) / (p + q + r1 + r2) are less than or equal to the above upper limit, the heat resistance of the die bond material is increased.

In the above formula (51A), r1 / (p + q + r1 + r2) is 0.05 or more and 0.40 or less, and r2 / (p + q + r1 + r2) is 0 or more and 0.50 or less. When r1 / (p + q + r1 + r2) and r2 / (p + q + r1 + r2) are not less than the above lower limit and not more than the above upper limit, both the heat-resistant crack characteristics and the cold-heat cycle characteristics of the cured product of the die bond material can be greatly enhanced. r2 / (p + q + r1 + r2) may exceed 0 or 0.01 or more. Note that when r2 is 0 and r2 / (p + q + r1 + r2) is 0, there is no structural unit of (R56SiO _3/2 ) in the above formula (51A).

For the second silicone resin, when ²⁹ Si-nuclear magnetic resonance analysis (hereinafter referred to as NMR) is performed with reference to tetramethylsilane (hereinafter referred to as TMS), although some variation is observed depending on the type of substituent, the above formula (51) and the peak corresponding to the structural unit represented by (R51R52R53SiO _1/2 ) in the formula (51A) appears in the vicinity of +10 to −5 ppm, and in the formula (51) and the formula (51A) ( R54R55SiO _2/2 ) and peaks corresponding to the bifunctional structural units of (51-2) appear in the vicinity of −10 to −50 ppm, and (R56SiO _3/2 ) in the above formula (51) and the above formula (51A). , (CH ₃ SiO _2/2 ) and the peaks corresponding to the trifunctional structural units of (51-3) and (51-4) appear in the vicinity of −50 to −80 ppm.

Therefore, by measuring ²⁹ Si-NMR and comparing the peak areas of the respective signals, the ratio of each structural unit in the above formula (51) and the above formula (51A) can be measured.

However, in the case where the structural unit in the above formula (51) and the above formula (51A) cannot be distinguished by the ²⁹ Si-NMR measurement based on the above TMS, not only the ²⁹ Si-NMR measurement result but also ¹ By using the measurement result of H-NMR as necessary, the ratio of each structural unit in the above formula (51) and the above formula (51A) can be distinguished.

  The content of the second silicone resin with respect to 100 parts by weight of the first silicone resin is preferably 10 parts by weight or more, more preferably 30 parts by weight or more, preferably 400 parts by weight or less, more preferably 200 parts by weight. Less than parts by weight. When the content of the first and second silicone resins is not less than the above lower limit and not more than the above upper limit, a die bond material having a higher storage elastic modulus at a high temperature and more excellent gas barrier properties can be obtained.

(Other properties of the first and second silicone resins and their synthesis methods)
The alkoxy group content of the first and second organopolysiloxanes is preferably 0.5 mol% or more, more preferably 1 mol% or more, preferably 10 mol% or less, more preferably 5 mol% or less. is there. When the content of the alkoxy group is not less than the above lower limit and not more than the above upper limit, the adhesion of the die bond material can be improved. The adhesiveness of a die-bonding material can be improved as content of an alkoxy group is more than the said minimum. When the alkoxy group content is not more than the above upper limit, the storage stability of the first and second silicone resins and the die bond material is increased, and the heat resistance of the die bond material is further increased.

  The content of the alkoxy group means the amount of the alkoxy group contained in the average composition formula of the first and second silicone resins.

  The first and second silicone resins preferably do not contain silanol groups. When the first and second silicone resins do not contain silanol groups, the storage stability of the first and second silicone resins and the die bond material is increased. The silanol group can be reduced by heating under vacuum. The content of silanol groups can be measured using infrared spectroscopy.

  The number average molecular weight (Mn) of the first and second silicone resins is preferably 500 or more, more preferably 800 or more, still more preferably 1000 or more, preferably 50000 or less, more preferably 15000 or less. When the number average molecular weight is equal to or more than the above lower limit, the volatile components are reduced at the time of thermosetting, and the thickness of the cured product of the die bond material is hardly reduced under a high temperature environment. When the number average molecular weight is not more than the above upper limit, viscosity adjustment is easy.

  The number average molecular weight (Mn) is a value obtained by using polystyrene as a standard substance using gel permeation chromatography (GPC). The number average molecular weight (Mn) was measured using two measuring devices manufactured by Waters (column: Shodex GPC LF-804 (length: 300 mm) manufactured by Showa Denko KK), measuring temperature: 40 ° C., flow rate: 1 mL / min, solvent: Tetrahydrofuran, standard substance: polystyrene) means a value measured.

  The method for synthesizing the first and second silicone resins is not particularly limited, and examples thereof include a method in which an alkoxysilane compound is hydrolyzed and subjected to a condensation reaction, and a method in which a chlorosilane compound is hydrolyzed and condensed. Especially, the method of hydrolyzing an alkoxysilane compound from a viewpoint of control of reaction is preferable.

  Examples of the method for hydrolyzing and condensing the alkoxysilane compound include a method of reacting the alkoxysilane compound in the presence of water and an acidic catalyst or a basic catalyst. Further, the disiloxane compound may be hydrolyzed and used.

  Examples of the organosilicon compound for introducing an aryl group into the first and second silicone resins include triphenylmethoxysilane, triphenylethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methyl (phenyl) dimethoxysilane, and Examples thereof include phenyltrimethoxysilane.

  Examples of organosilicon compounds for introducing alkenyl groups into the first and second silicone resins include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, methoxydimethylvinylsilane, vinyldimethylethoxysilane, and 1,3. -Divinyl-1,1,3,3-tetramethyldisiloxane and the like.

  Examples of the organosilicon compound for introducing a hydrogen atom bonded to a silicon atom into the first silicone resin include trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane, and 1,1,3,3. -Tetramethyldisiloxane and the like.

  Examples of other organosilicon compounds that can be used to obtain the first and second silicone resins include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and isopropyl (methyl) dimethoxysilane. Cyclohexyl (methyl) dimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, and octyltrimethoxysilane.

  Examples of the acidic catalyst include inorganic acids, organic acids, acid anhydrides of inorganic acids and derivatives thereof, and acid anhydrides of organic acids and derivatives thereof.

  Examples of the inorganic acid include hydrochloric acid, phosphoric acid, boric acid, and carbonic acid. Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, lactic acid, malic acid, tartaric acid, citric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid and oleic acid. Is mentioned.

  Examples of the basic catalyst include alkali metal hydroxides, alkali metal alkoxides, and alkali metal silanol compounds.

  Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, and cesium hydroxide. Examples of the alkali metal alkoxide include sodium-t-butoxide, potassium-t-butoxide, and cesium-t-butoxide.

  Examples of the alkali metal silanol compound include a sodium silanolate compound, a potassium silanolate compound, and a cesium silanolate compound. Of these, a potassium-based catalyst or a cesium-based catalyst is preferable.

  The viscosities at 25 ° C. and 10 rpm measured with the respective E-type viscometers of the first silicone resin and the second silicone resin are preferably 1200 mPa · s or more and 6000 mPa · s or less. . When the viscosity is within this range, both the stringing and bleeding of the die bond material can be suppressed. From the viewpoint of further suppressing both stringing and bleeding of the die bond material, the viscosity at 10 rpm at 25 ° C. measured using the E-type viscometer of the second silicone resin is preferably 1300 mPa · s. As mentioned above, Preferably it is 4000 mPa * s or less.

  Moreover, the viscosity η1 at 10 rpm at 25 ° C. measured using the E-type viscometer of the die bond material for optical semiconductor devices according to the present invention is preferably 8000 mPa · s or more, preferably 30000 mPa · s or less. Furthermore, at 25 ° C. measured using an E-type viscometer having a viscosity η2 (mPa · s) at 1 rpm at 25 ° C. measured using an E-type viscometer of a die bond material for an optical semiconductor device according to the present invention. The ratio (η2 / η1) to the viscosity η1 (mPa · s) at 10 rpm is preferably 1.5 or more, and preferably 4.0 or less. When the die bond material for optical semiconductor devices according to the present invention has the specific viscosity, both the stringing and bleeding of the die bond material can be remarkably suppressed.

  From the viewpoint of further suppressing both stringing and bleeding of the die bond material, the viscosity η1 is more preferably 12000 mPa · s or more, and more preferably 25000 mPa · s or less. From the viewpoint of further suppressing both the stringing and bleeding of the die bond material, the ratio (η2 / η1) is more preferably 1.6 or more, and more preferably 2.8 or less.

  In addition, the said "viscosity" in the silicone resin and the die bond material for optical semiconductor devices is a value measured using an E-type viscometer (TV-22 type, manufactured by Toki Sangyo Co., Ltd.).

(Catalyst for hydrosilylation reaction)
The hydrosilylation reaction catalyst contained in the die bond material for optical semiconductor devices according to the present invention includes a hydrogen atom bonded to a silicon atom in the first silicone resin, and an alkenyl group in the second silicone resin. Is a catalyst for hydrosilylation reaction.

  As the hydrosilylation reaction catalyst, various catalysts that cause the hydrosilylation reaction to proceed can be used. As for the said catalyst for hydrosilylation reaction, only 1 type may be used and 2 or more types may be used together.

  Examples of the hydrosilylation reaction catalyst include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. A platinum-based catalyst is preferable because the transparency of the die-bonding material can be increased.

  Examples of the platinum-based catalyst include platinum powder, chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex. In particular, a platinum-alkenylsiloxane complex or a platinum-olefin complex is preferable.

  Examples of the alkenylsiloxane in the platinum-alkenylsiloxane complex include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1,3,5,7-tetramethyl-1,3,5. , 7-tetravinylcyclotetrasiloxane and the like. Examples of the olefin in the platinum-olefin complex include allyl ether and 1,6-heptadiene.

  Since the stability of the platinum-alkenylsiloxane complex and platinum-olefin complex can be improved, alkenylsiloxane, organosiloxane oligomer, allyl ether or olefin is added to the platinum-alkenylsiloxane complex or platinum-olefin complex. Is preferred. The alkenylsiloxane is preferably 1,3-divinyl-1,1,3,3-tetramethyldisiloxane. The organosiloxane oligomer is preferably a dimethylsiloxane oligomer. The olefin is preferably 1,6-heptadiene.

  The content of the hydrosilylation reaction catalyst in 100% by weight of the die bond material is preferably 0.01% by weight or more, more preferably 0.02% by weight or more, preferably 0.5% by weight or less, more preferably 0%. .3% by weight or less. When the content of the catalyst for hydrosilylation reaction is not less than the above lower limit, it is easy to sufficiently cure the die bond material, and the gas barrier property of the die bond material can be further enhanced. When the content of the catalyst for hydrosilylation reaction is not more than the above upper limit, the die bond material is more difficult to discolor.

(Silicon oxide particles)
By including silicon oxide particles in the die bond material for an optical semiconductor device according to the present invention, the viscosity of the die bond material before curing is within an appropriate range without impairing the heat resistance and light resistance of the cured product of the die bond material. Can be adjusted. Therefore, the handleability of the die bond material can be improved.

  The primary particle diameter of the silicon oxide particles is preferably 5 nm or more, more preferably 8 nm or more, preferably 200 nm or less, more preferably 150 nm or less. When the primary particle diameter of the silicon oxide particles is not less than the above lower limit, the dispersibility of the silicon oxide particles is further increased, and the transparency of the cured product of the die bond material is further increased. When the primary particle diameter of the silicon oxide particles is not more than the above upper limit, it is possible to sufficiently obtain the effect of increasing the viscosity at 25 ° C. and to suppress the decrease in the viscosity due to the temperature increase.

  The primary particle diameter of the silicon oxide particles is measured as follows. The cured product of the die bond material for an optical semiconductor device is observed using a transmission electron microscope (trade name “JEM-2100”, manufactured by JEOL Ltd.). The size of the primary particles of 100 silicon oxide particles in the visual field is measured, and the average value of the measured values is defined as the primary particle diameter. The primary particle diameter means an average value of the diameters of the silicon oxide particles when the silicon oxide particles are spherical, and an average value of the major diameters of the silicon oxide particles when the silicon oxide particles are non-spherical.

The BET specific surface area of the silicon oxide particles is preferably 30 m ² / g or more, and preferably 400 m ² / g or less. When the BET specific surface area of the silicon oxide particles is 30 m ² / g or more, the viscosity of the die bond material at 25 ° C. can be controlled within a suitable range, and the decrease in viscosity due to temperature rise can be suppressed. When the BET specific surface area of the silicon oxide particles is 400 m ² / g or less, the aggregation of the silicon oxide particles hardly occurs, the dispersibility can be increased, and the transparency of the cured product of the die bond material can be further increased. can do.

  The silicon oxide particles are not particularly limited, and examples thereof include silica produced by a dry method such as fumed silica and fused silica, and silica produced by a wet method such as colloidal silica, sol-gel silica and precipitated silica. It is done. Among these, fumed silica is preferably used as the silicon oxide particles from the viewpoint of obtaining a die-bonding material with less volatile components and higher transparency.

Examples of the fumed silica include Aerosil 50 (specific surface area: 50 m ² / g), Aerosil 90 (specific surface area: 90 m ² / g), Aerosil 130 (specific surface area: 130 m ² / g), Aerosil 200 (specific surface area). : 200 m ² / g), Aerosil 300 (specific surface area: 300 m ² / g), Aerosil 380 (specific surface area: 380 m ² / g) (all manufactured by Nippon Aerosil Co., Ltd.) and the like.

  The silicon oxide particles are preferably surface-treated with an organosilicon compound. By this surface treatment, the dispersibility of the silicon oxide particles becomes very high, and it is possible to further suppress the decrease in viscosity due to the temperature increase of the die bond material before curing.

  The organosilicon compound is not particularly limited. For example, a silane compound having an alkyl group, a silicon compound having a siloxane skeleton such as dimethylsiloxane, a silicon compound having an amino group, and a silicon compound having a (meth) acryloyl group. Examples thereof include a compound and a silicon compound having an epoxy group. The “(meth) acryloyl group” means an acryloyl group and a methacryloyl group.

  From the viewpoint of further enhancing dispersibility of the silicon oxide particles, the organosilicon compound used for the surface treatment is at least one of an organosilicon compound having a trimethylsilyl group and an organosilicon compound having a polydimethylsiloxane group. It is preferable. The silicon oxide particles are preferably surface-treated with at least one of an organosilicon compound having a trimethylsilyl group and an organosilicon compound having a polydimethylsiloxane group.

  As an example of a method for surface treatment with an organosilicon compound, when an organosilicon compound having a trimethylsilyl group is used, the silicon oxide particles are surface treated using, for example, hexamethyldisilazane, trimethylsilyl chloride, trimethylmethoxysilane, or the like. A method is mentioned. In the case of using an organosilicon compound having a polydimethylsiloxane group, a method of surface-treating silicon oxide particles using a compound having a silanol group at the terminal of the polydimethylsiloxane group, cyclic siloxane, or the like can be mentioned.

Commercially available silicon oxide particles surface-treated with the above organosilicon compound having a trimethylsilyl group include RX200 (specific surface area: 140 m ² / g) and R8200 (specific surface area: 140 m ² / g) (both from Nippon Aerosil Co., Ltd.) Manufactured) and the like.

RY200 (specific surface area: 120 m ² / g) (manufactured by Nippon Aerosil Co., Ltd.) and the like can be mentioned as a commercial product of silicon oxide particles surface-treated with an organosilicon compound having a polydimethylsiloxane group.

  The method for surface-treating the silicon oxide particles with the organosilicon compound is not particularly limited. As this method, for example, a dry method in which silicon oxide particles are added to a mixer and an organosilicon compound is added while stirring, a slurry method in which an organosilicon compound is added to a slurry of silicon oxide particles, and silicon oxide particles And a direct treatment method such as a spray method in which an organosilicon compound is sprayed after drying. Examples of the mixer used in the dry method include a Henschel mixer and a V-type mixer. In the dry method, the organosilicon compound is added directly or as an alcohol aqueous solution, an organic solvent solution or an aqueous solution.

  When preparing a die bond material for an optical semiconductor device in order to obtain silicon oxide particles surface-treated with the organosilicon compound, the silicon oxide particles are mixed with a matrix resin such as the first and second silicone resins. Sometimes, an integral blend method or the like in which an organosilicon compound is directly added may be used.

  In 100% by weight of the die bond material for an optical semiconductor device, the content of the silicon oxide particles is preferably 5% by weight or more, preferably 30% by weight or less, more preferably 25% by weight or less. When the content of the silicon oxide particles is not less than the above lower limit, the viscosity of the die bond material before curing can be adjusted to an appropriate range without impairing the heat resistance and light resistance of the cured product of the die bond material. When the content of the silicon oxide particles is not more than the above upper limit, the viscosity of the die bond material can be controlled to a more appropriate range, and the transparency of the die bond material can be further enhanced. In the die bond material for an optical semiconductor device according to the present invention, even when the content of the silicon oxide particles is 30% by weight or less, the storage elastic modulus at a high temperature is increased.

  The die bond material for an optical semiconductor device according to the present invention contains the silicon oxide particles surface-treated with the organosilicon compound, whereby the second silicone resin having an aryl group or the first silicone resin having an aryl group Even if it contains, the viscosity at the high temperature of a die-bonding material can be maintained at sufficient height. Thereby, the viscosity when the die bond material is heated to a high temperature can be adjusted to an appropriate range, and the dispersed state of the silicon oxide particles in the die bond material can be improved. For this reason, the transparency of the die bond material can be further enhanced.

(Coupling agent)
The die bond material for optical semiconductor devices according to the present invention may further contain a coupling agent in order to impart adhesiveness.

  It does not specifically limit as said coupling agent, For example, a silane coupling agent etc. are mentioned. Examples of the silane coupling agent include vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-methacryloxypropyltrimethoxy. Examples include silane, γ-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane. As for a coupling agent, only 1 type may be used and 2 or more types may be used together.

(Other ingredients)
The die bond material for an optical semiconductor device according to the present invention includes an ultraviolet absorber, an antioxidant, a solvent, a colorant, a filler, an antifoaming agent, a surface treatment agent, a flame retardant, a viscosity modifier, and a dispersant as necessary. , A dispersion aid, a surface modifier, a plasticizer, an antifungal agent, a leveling agent, a stabilizer, a coupling agent, an anti-sagging agent, or a phosphor.

(Details and applications of die bond materials for optical semiconductor devices)
The die bond material for optical semiconductor devices according to the present invention may be in the form of a paste or a film. The die bond material for an optical semiconductor device according to the present invention is preferably in a paste form.

  The first silicone resin, the second silicone resin, and the hydrosilylation reaction catalyst are prepared separately in a liquid containing one or more of them, and a plurality of liquids are prepared immediately before use. The die-bonding material for optical semiconductor devices according to the present invention may be prepared by mixing. In this case, the silicon oxide particles and the coupling agent may be added to the liquid A or the liquid B, respectively. For example, the liquid A containing the second silicone resin and the hydrosilylation reaction catalyst and the liquid B containing the first silicone resin are prepared separately, and the liquid A and the liquid B are mixed immediately before use. A die bond material may be prepared. In this case, the silicon oxide particles and the coupling agent may be added to the A liquid or may be added to the B liquid. Thus, the storage stability is improved by separately forming the second silicone resin and the hydrosilylation reaction catalyst and the first silicone resin into two liquids of the first liquid and the second liquid. Can be made.

  The method for producing a die bond material for an optical semiconductor device according to the present invention is not particularly limited. For example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, a triple roll or a bead mill, Or the method of mixing the said 1st silicone resin, said 2nd silicone resin, the said catalyst for hydrosilylation reaction, and the other component mix | blended as needed under a heating etc. is mentioned.

  The die bond material for an optical semiconductor device according to the present invention is disposed on a connection target member such as a substrate or disposed on the lower surface of the optical semiconductor element, and the connection target member and the optical semiconductor element are connected via the die bond material. Thus, an optical semiconductor device can be obtained.

  The curing temperature of the die bond material for optical semiconductor devices according to the present invention is not particularly limited. The curing temperature of the die bond material for optical semiconductor devices is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, preferably 200 ° C. or lower, and more preferably 180 ° C. or lower. When the curing temperature is equal to or higher than the above lower limit, the die bond material is sufficiently cured. When the curing temperature is not more than the above upper limit, thermal deterioration of the die bond material and the member bonded by the die bond material hardly occurs.

  Although it does not specifically limit as a hardening method, It is preferable to use a step cure system. The step cure method is a method in which the resin is temporarily cured at a low temperature and then cured at a high temperature. By using the step cure method, curing shrinkage of the die bond material can be suppressed.

(Optical semiconductor device)
An optical semiconductor device according to the present invention includes a die bond material for an optical semiconductor device, a connection target member, and an optical semiconductor element connected to the connection target member using the die bond material for an optical semiconductor device.

  Specific examples of the optical semiconductor device according to the present invention include a light emitting diode device, a semiconductor laser device, and a photocoupler. Such optical semiconductor devices include, for example, backlights such as liquid crystal displays, illumination, various sensors, light sources such as printers and copiers, vehicle measuring instrument light sources, signal lights, indicator lights, display devices, and light sources for planar light emitters. , Displays, decorations, various lights, switching elements and the like.

  The light-emitting element that is the optical semiconductor element is not particularly limited as long as it is a light-emitting element using a semiconductor. Structure is mentioned. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.

  Examples of the material for the substrate include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. Further, a buffer layer may be formed between the substrate and the semiconductor material as necessary. Examples of the material of the buffer layer include GaN and AlN.

  FIG. 1 is a front sectional view showing an optical semiconductor device according to an embodiment of the present invention.

  The optical semiconductor device 1 of the present embodiment includes a housing 2 that is a connection target member and an optical semiconductor element 3. An optical semiconductor element 3 that is an LED element is mounted in the housing 2. The optical semiconductor element 3 is surrounded by an inner surface 2 a having light reflectivity of the housing 2. In the present embodiment, the optical semiconductor element 3 is used as a light emitting element formed of an optical semiconductor.

  The inner surface 2a of the housing 2 is formed so that the diameter of the inner surface 2a increases toward the opening end. Accordingly, among the light emitted from the optical semiconductor element 3, the light B <b> 1 that has reached the inner surface 2 a is reflected by the inner surface 2 a and travels forward of the optical semiconductor element 3.

  The optical semiconductor element 3 is connected to a lead electrode 4 provided in the housing 2 using a die bond material 5. The die bond material 5 is a die bond material for optical semiconductor devices. A bonding pad (not shown) provided on the optical semiconductor element 3 and the lead electrode 4 are electrically connected by a bonding wire 6. A sealing agent 7 is filled in a region surrounded by the inner surface 2 a so as to seal the optical semiconductor element 3 and the bonding wire 6.

  The die bond material 5 may be disposed so as to protrude from the bottom of the optical semiconductor element 3 and surround the periphery thereof, or may be disposed so as not to protrude from the bottom of the optical semiconductor element 3. The thickness of the die bond material 5 is preferably in the range of 2 to 50 μm.

  In the optical semiconductor device 1, when the optical semiconductor element 3 is driven, light is emitted as indicated by a broken line A. In this case, not only the light irradiated from the optical semiconductor element 3 to the side opposite to the upper surface of the lead electrode 4, that is, the upper side, but also the light that reaches the die bond material 5 is reflected as indicated by the arrow B 2.

  The structure shown in FIG. 1 is merely an example of an optical semiconductor device according to the present invention, and can be appropriately modified to the mounting structure of the optical semiconductor element 3.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples.

(First and second silicone resin)
The first and second silicone resins were synthesized as follows.

(Synthesis Example 1) Synthesis of first silicone resin In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 40 g of 1,1,3,3-tetramethyldisiloxane, 185 g of ethyltrimethoxysilane, and 120 g of phenyltrimethoxysilane was added and stirred at 50 ° C. Into this, a solution of 1.2 g of hydrochloric acid and 83 g of water was slowly added dropwise. After the addition, the solution was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by removing the volatile component under reduced pressure. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (A) was obtained.

The number average molecular weight (Mn) of the obtained polymer (A) was 1500. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (A) had the following average composition formula (A1).

(HMe ₂ SiO _1/2 ) _0.20 (EtSiO _3/2 ) _0.50 (PhSiO _3/2 ) _0.30 ... Formula (A1)

  In the above formula (A1), Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group.

  The phenyl group content ratio (aryl group content ratio) of the obtained polymer (A) was 15.6 mol%.

In addition, the molecular weight of each polymer obtained in Synthesis Example 1 and Synthesis Examples 2 to 9 was measured by GPC measurement by adding 1 mL of tetrahydrofuran to 10 mg, stirring until dissolved. In GPC measurement, a measuring device manufactured by Waters (column: Shodex GPC manufactured by Showa Denko KK)
LF-804 (length: 300 mm) × 2, measurement temperature: 40 ° C., flow rate: 1 mL / min, solvent: tetrahydrofuran, standard substance: polystyrene) were used.

(Synthesis Example 2) Synthesis of first silicone resin In a 1000 mL separable flask equipped with a thermometer, a dropping device, and a stirrer, 40 g of 1,1,3,3-tetramethyldisiloxane, 165 g of methyltrimethoxysilane, and 120 g of phenyltrimethoxysilane was added and stirred at 50 ° C. Into this, a solution of 1.2 g of hydrochloric acid and 83 g of water was slowly added dropwise. After the addition, the solution was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by removing the volatile component under reduced pressure. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (B) was obtained.

The number average molecular weight (Mn) of the obtained polymer (B) was 1500. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (B) had the following average composition formula (B1).

(HMe ₂ SiO _1/2 ) _0.20 (MeSiO _3/2 ) _0.50 (PhSiO _3/2 ) _0.30 ... Formula (B1)

  In said formula (B1), Me shows a methyl group and Ph shows a phenyl group.

  The obtained polymer (B) had a phenyl group content (aryl group content) of 15.6 mol%.

(Synthesis Example 3) Synthesis of first silicone resin In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 40 g of 1,1,3,3-tetramethyldisiloxane, 26 g of vinylmethyldimethoxysilane, methyl 132 g of trimethoxysilane and 40 g of phenyltrimethoxysilane were added and stirred at 50 ° C. Into this, a solution of 1.2 g of hydrochloric acid and 83 g of water was slowly added dropwise. After the addition, the solution was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by removing the volatile component under reduced pressure. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (C) was obtained.

The number average molecular weight (Mn) of the obtained polymer (C) was 1300. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (C) had the following average composition formula (C1).

(HMe ₂ SiO _1/2 ) _0.20 (ViMeSiO _2/2 ) _0.10 (MeSiO _3/2 ) _0.60 (PhSiO _3/2 ) _0.10 Formula (C1)

  In the above formula (C1), Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group.

  The phenyl group content ratio (aryl group content ratio) of the obtained polymer (C) was 6 mol%.

(Synthesis Example 4) Synthesis of Second Silicone Resin 62 g of trimethylmethoxysilane, 78 g of vinylmethyldimethoxysilane, and 81 g of phenyltrimethoxysilane were placed in a 1000 mL separable flask equipped with a thermometer, a dropping device, and a stirrer. Stir at ° C. A solution obtained by dissolving 0.8 g of potassium hydroxide in 114 g of water was slowly dropped therein, and after the dropwise addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, 0.9 g of acetic acid was added to the reaction solution, the pressure was reduced to remove volatile components, and potassium acetate was removed by filtration to obtain a polymer (D).

The number average molecular weight (Mn) of the obtained polymer (D) was 2000. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (D) had the following average composition formula (D1).

(Me ₃ SiO _1/2 ) _0.30 (ViMeSiO _2/2 ) _0.30 (PhSiO _3/2 ) _0.40 ... Formula (D1)

  In the above formula (D1), Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group.

  The polymer group (D) had a phenyl group content (aryl group content) of 15.6 mol%.

(Synthesis Example 5) Synthesis of Second Silicone Resin In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 62 g of trimethylmethoxysilane, 78 g of vinylmethyldimethoxysilane, 66 g of methyltrimethoxysilane and phenyltrimethoxysilane 81 g was added and stirred at 50 ° C. A solution obtained by dissolving 0.8 g of potassium hydroxide in 114 g of water was slowly dropped therein, and after the dropwise addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, 0.9 g of acetic acid was added to the reaction solution, the pressure was reduced to remove volatile components, and potassium acetate was removed by filtration to obtain a polymer (E).

The number average molecular weight (Mn) of the obtained polymer (E) was 1800. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (E) had the following average composition formula (E1).

(Me ₃ SiO _1/2 ) _0.30 (ViMeSiO _2/2 ) _0.30 (MeSiO _3/2 ) _0.20 (PhSiO _3/2 ) _0.20 ... Formula (E1)

  In the above formula (E1), Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group.

  The phenyl group content ratio (aryl group content ratio) of the obtained polymer (E) was 8.6 mol%.

Synthesis Example 6 Synthesis of Resin Similar to First Silicone Resin Into a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 40 g of 1,1,3,3-tetramethyldisiloxane, phenylmethyldimethoxy 75 g of silane, 66 g of methyltrimethoxysilane and 120 g of phenyltrimethoxysilane were added and stirred at 50 ° C. Into this, a solution of 1.2 g of hydrochloric acid and 83 g of water was slowly added dropwise. After the addition, the solution was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by removing the volatile component under reduced pressure. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (F) was obtained.

The number average molecular weight (Mn) of the obtained polymer (F) was 2500. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (F) had the following average composition formula (F1).

(HMe ₂ SiO _1/2 ) _0.20 (PhMeSiO _2/2 ) _0.30 (MeSiO _3/2 ) _0.20 (PhSiO _3/2 ) _0.30 ... Formula (F1)

  In the formula (F1), Me represents a methyl group, and Ph represents a phenyl group.

  The polymer group (F) had a phenyl group content (aryl group content) of 18.7 mol%.

(Synthesis Example 7) Synthesis of Resin Similar to First Silicone Resin Into a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 40 g of 1,1,3,3-tetramethyldisiloxane and dimethyldimethoxysilane 48 g, 99 g of methyltrimethoxysilane and 120 g of phenyltrimethoxysilane were added and stirred at 50 ° C. Into this, a solution of 1.2 g of hydrochloric acid and 83 g of water was slowly added dropwise. After the addition, the solution was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by removing the volatile component under reduced pressure. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer (G) was obtained.

The number average molecular weight (Mn) of the obtained polymer (G) was 2300. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (G) had the following average composition formula (G1).

(HMe ₂ SiO _1/2 ) _0.20 (Me ₂ SiO _2/2 ) _0.20 (MeSiO _3/2 ) _0.30 (PhSiO _3/2 ) _0.30 ... Formula (G1)

  In the above formula (G1), Me represents a methyl group, and Ph represents a phenyl group.

  The phenyl group content ratio (aryl group content ratio) of the obtained polymer (G) was 10.1 mol%.

Synthesis Example 8 Synthesis of Resin Similar to Second Silicone Resin In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 41 g of trimethylmethoxysilane, 156 g of vinylmethyldimethoxysilane, 33 g of methyltrimethoxysilane, And 40 g of phenyltrimethoxysilane were added and stirred at 50 ° C. A solution obtained by dissolving 0.8 g of potassium hydroxide in 114 g of water was slowly dropped therein, and after the dropwise addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, 0.9 g of acetic acid was added to the reaction solution, the pressure was reduced to remove volatile components, and potassium acetate was removed by filtration to obtain a polymer (H).

The number average molecular weight (Mn) of the obtained polymer (H) was 1800. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (H) had the following average composition formula (H1).

(Me ₃ SiO _1/2 ) _0.20 (ViMeSiO _2/2 ) _0.60 (MeSiO _3/2 ) _0.10 (PhSiO _3/2 ) _0.10 Formula (H1)

  In the above formula (H1), Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group.

  The phenyl group content ratio (aryl group content ratio) of the obtained polymer (H) was 4.3 mol%.

(Synthesis Example 9) A synthetic thermometer of a resin similar to the second silicone resin, a 1000 mL separable flask equipped with a dropping device and a stirrer, 41 g of trimethylmethoxysilane, 24 g of dimethyldimethoxysilane, 78 g of vinylmethyldimethoxysilane, methyl 66 g of trimethoxysilane and 80 g of phenyltrimethoxysilane were added and stirred at 50 ° C. A solution obtained by dissolving 0.8 g of potassium hydroxide in 114 g of water was slowly dropped therein, and after the dropwise addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, 0.9 g of acetic acid was added to the reaction solution, the pressure was reduced to remove volatile components, and potassium acetate was removed by filtration to obtain polymer (I).

The number average molecular weight (Mn) of the obtained polymer (I) was 1900. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer (I) had the following average composition formula (I1).

(Me ₃ SiO _1/2 ) _0.20 (Me ₂ SiO _2/2 ) _0.10 (ViMeSiO _2/2 ) _0.30 (MeSiO _3/2 ) _0.20 (PhSiO _3/2 ) _0.20 ... Formula (I1)

  In the above formula (I1), Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group.

  The polymer (I) had a phenyl group content (aryl group content) of 8.2 mol%.

Example 1
Polymer A 5 parts by weight, polymer D 5 parts by weight, platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex 0.02 part by weight, and silicon oxide fine particles (AEROSIL RY200, polydimethylsiloxane group) 2.2 parts by weight of silicon oxide particles surface-treated with an organosilicon compound having a specific surface area of 120 m ² / g, manufactured by Nippon Aerosil Co., Ltd. were mixed and defoamed to obtain a die bond material for an optical semiconductor element.

(Examples 2-5 and Comparative Examples 1-4)
A die bond material for an optical semiconductor device was obtained in the same manner as in Example 1 except that the type and blending amount of the materials used were changed as shown in Table 1 below.

(Evaluation)
(1) Viscosity measurement at 25 ° C. Silicone resin (first and second silicone resins) used for an optical semiconductor device die bond material using an E-type viscometer (TV-22 type, manufactured by Toki Sangyo Co., Ltd.) The viscosity (mPa · s) at 10 rpm at 25 ° C. was measured.

(2) Wire bondability at the time of wire bonding Using a die bonder ("BESTEM-D01R" manufactured by Canon Machinery Co., Ltd.), a die bond material for an optical semiconductor device obtained on a silver-plated copper substrate has a thickness of 5 m. It apply | coated so that it might become the magnitude | size of the optical semiconductor element laminated | stacked on a die-bonding material, and the die-bonding layer was formed. Next, an optical semiconductor element was stacked on the die bond layer to obtain a stacked body.

  The obtained laminate was heated at 150 ° C. for 3 hours to cure the die bond layer. Next, wire bonding was performed on the electrode pad provided on the optical semiconductor element on the die bond layer. The wire bondability at this time was determined according to the following criteria.

[Criteria for wire bondability]
○○: No wire bond NG (defective) in 1000 samples ○: Wire bond NG1 sample in 1000 samples Δ: Wire bond NG2 sample in 1000 samples ×: Wire bond NG3 sample in 1000 samples or more

(3) Heat-resistant crack characteristics A die-bonding material for an optical semiconductor device was applied on an Ag-plated Cu substrate so that the adhesion area was 3 mm × 3 mm, and a 3 mm square Si chip was placed thereon. Then, it heated at 150 degreeC for 3 hours, the die-bonding material was hardened, and the joined body (test sample) by which the said board | substrate and the said Si chip were joined by hardened | cured material was obtained. 1000 pieces of the obtained joined bodies were put in an oven and heated at 270 ° C. for 5 minutes.

  The number of bonded bodies in which cracks had occurred was counted in 1000 bonded bodies after heating, and the heat-resistant crack characteristics were determined according to the following criteria.

[Criteria for heat-resistant crack characteristics]
○○: No cracked sample in 1000 samples (defect) in cured samples ○: Cracked in cured samples in 2 samples in 1000 samples Δ: Cracked in cured products in 2 samples in 1000 samples ×: Cracks occurred in the cured product in 3 or more samples out of 1000 samples

(4) Cooling and heat cycle characteristics A die-bonding material for an optical semiconductor device was applied on an Ag-plated Cu substrate so that the adhesion area was 3 mm × 3 mm, and a 3 mm square Si chip was placed thereon. Then, it heated at 150 degreeC for 3 hours, the die-bonding material was hardened, and the joined body (test sample) by which the said board | substrate and the said Si chip were joined by hardened | cured material was obtained. Using 1000 test samples obtained and using a liquid thermal shock tester (“TSB-51”, manufactured by ESPEC), the sample was held at −50 ° C. for 5 minutes, and then heated to 135 ° C. Then, a thermal cycle test was performed in which the process of holding at 135 ° C. for 5 minutes and then lowering the temperature to −50 ° C. was one cycle. After 1000 cycles, the number of bonded bodies in which cracks occurred in 1000 bonded bodies was counted, and the cold-heat cycle characteristics were determined according to the following criteria.

[Criteria for cold cycle resistance characteristics]
○○: No cracked sample in 1000 samples (defect) in cured sample ○: Cracked in cured sample in 1 sample in 1000 sample Δ: Cracked in cured product in 2 samples in 1000 sample X: The results of cracks occurring in the cured product in three or more samples out of 1000 samples are shown in Table 1 below.

(5) Adhesiveness (die shear strength)
A die-bonding material for an optical semiconductor device was applied on an Ag-plated Cu substrate so that the adhesion area was 3 mm × 3 mm, and a 3 mm square Si chip was placed thereon to obtain a test sample.

  The obtained test sample was heated at 150 ° C. for 3 hours to cure the die bond material. Next, the die shear strength at 185 ° C. was evaluated at a speed of 300 μ / sec using a die shear tester (manufactured by Arctech, model number: DAGE 4000).

[Die shear strength criteria]
○○: Die shear strength is 1800 g or more ○: Die shear strength is 1000 g or more and less than 1800 g ×: Die shear strength is less than 1000 g

(6) Bleeding Light that is obtained by stacking a die bond material for an optical semiconductor device obtained on a silver-plated copper substrate using a die bonder (“BESTEM-D01R” manufactured by Canon Machinery Co., Ltd.) with a thickness of 5 μm on the die bond material. It apply | coated so that it might become the magnitude | size of a semiconductor element, and the coating material by which the die-bonding material was apply | coated on the board | substrate was obtained.

  The obtained coated material was viewed in plan and the coated area of the die bond material for optical semiconductor devices was evaluated. Bleeding was determined according to the following criteria.

[Judgment criteria for bleeding]
○○: Less than 1% of the projected area of the optically bonded semiconductor device to be bonded to the die-bonding material is less than 1%. ○: To the area of the optically-semiconductor device stacked on the die-bonding material. The application area of the protruding die bond material for an optical semiconductor device is 1% or more and less than 3%. X: The application area of the protruding die bond material for an optical semiconductor device with respect to the area of the optical semiconductor element laminated on the die bond material. 3% or more

  The results are shown in Table 1 below.

DESCRIPTION OF SYMBOLS 1 ... Optical semiconductor device 2 ... Housing 2a ... Inner surface 3 ... Optical semiconductor element 4 ... Lead electrode 5 ... Die-bonding material 6 ... Bonding wire 7 ... Sealing agent

Claims (6)

A first silicone resin represented by the following formula (1) and having a hydrogen atom bonded to an aryl group and a silicon atom;
A second silicone resin represented by the following formula (51) and having no hydrogen atom bonded to a silicon atom and having an aryl group and an alkenyl group;
A catalyst for hydrosilylation reaction;
A die bond material for an optical semiconductor device, comprising: silicon oxide particles, wherein the first silicone resin does not have a dimethylsiloxane skeleton, and the second silicone resin does not have a dimethylsiloxane skeleton.

In the formula (1), a, b and c are a / (a + b + c) = 0.05 to 0.50, b / (a + b + c) = 0 to 0.20 and c / (a + b + c) = 0.30. 0.90 is satisfied, R1 to R6 each represents at least one aryl group, at least one represents a hydrogen atom, and R1 to R6 other than the aryl group and the hydrogen atom are hydrocarbon groups having 1 to 8 carbon atoms. Represents. However, in the formula (1), in the structural unit represented by (R4R5SiO2 _{/ 2} ), both R4 and R5 are not methyl groups and are not dimethylsiloxane structural units.

In the formula (51), p, q and r are p / (p + q + r) = 0.05 to 0.50, q / (p + q + r) = 0.05 to 0.50 and r / (p + q + r) = 0. R51 to R56, at least one represents an aryl group, at least one represents an alkenyl group, and R51 to R56 other than the aryl group and the alkenyl group are carbon atoms having 1 to 8 carbon atoms. Represents a hydrogen group. However, in the formula (51), in the structural unit represented by (R54R55SiO _2/2 ), both R54 and R55 are not methyl groups and are not dimethylsiloxane structural units. The die-bonding material for optical semiconductor devices according to claim 1, wherein the first silicone resin represented by the formula (1) is a first silicone resin represented by the following formula (1A).

In the formula (1A), a, b, c1 and c2 are a / (a + b + c1 + c2) = 0.05 to 0.50, b / (a + b + c1 + c2) = 0 to 0.20, (c1 + c2) / (a + b + c1 + c2) = 0.30-0.90, satisfying c1 / (a + b + c1 + c2) = 0.30-0.90 and c2 / (a + b + c1 + c2) = 0-0.20, R1 to R6 each represents at least one aryl group, At least one represents a hydrogen atom, and R1 to R6 other than the aryl group and the hydrogen atom represent a hydrocarbon group having 1 to 8 carbon atoms. However, in the formula (1A), the structural unit represented by (R4R5SiO2 _{/ 2} ) is not a methyl group in R4 and R5, and is not a dimethylsiloxane structural unit. The die-bonding material for optical semiconductor devices according to claim 1 or 2, wherein the second silicone resin represented by the formula (51) is a second silicone resin represented by the following formula (51A).

In the formula (51A), p, q, r1 and r2 are p / (p + q + r1 + r2) = 0.05 to 0.50, q / (p + q + r1 + r2) = 0.05 to 0.50, (r1 + r2) / (p + q + r1 + r2) ) = 0.05 to 0.50, r1 / (p + q + r1 + r2) = 0.05 to 0.40 and r2 / (p + q + r1 + r2) = 0 to 0.50, R51 to R56 are at least one aryl group And at least one represents an alkenyl group, and R51 to R56 other than an aryl group and an alkenyl group represent a hydrocarbon group having 1 to 8 carbon atoms. However, in the formula (51A), in the structural unit represented by (R54R55SiO _2/2 ), both R54 and R55 are not methyl groups and are not dimethylsiloxane structural units.   2. The viscosity at 25 ° C. and 10 rpm measured using an E-type viscometer of each of the first silicone resin and the second silicone resin is 1200 mPa · s or more and 6000 mPa · s or less. The die-bonding material for optical semiconductor devices of any one of -3.   5. The optical semiconductor device according to claim 1, wherein the first silicone resin is a first silicone resin having an aryl group, a hydrogen atom bonded to a silicon atom, and an alkenyl group. Die bond material. The die-bonding material for optical semiconductor devices according to any one of claims 1 to 5,
A connection target member;
An optical semiconductor device comprising: an optical semiconductor element connected to the connection target member using the die bond material for an optical semiconductor device.

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