JP2013256634A - Packing material for semiconductor device three-dimensional mounting - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a member for a semiconductor manufacture process useful for manufacture of a thin three-dimensional semiconductor device apparatus in COW process, and to provide a curing composition capable of forming the member.SOLUTION: A packing material for semiconductor device three-dimensional mounting fills gaps between semiconductor devices adjacent in the lateral direction when a plurality of semiconductor devices are stacked and integrated to manufacture a three-dimensional semiconductor device apparatus. The packing material is a member polished and/or ground and then flattened from the back surface side with the semiconductor devices in a state where the gaps between semiconductor devices are filled.

Description

  The present invention relates to a semiconductor element three-dimensional mounting filler used in a method of manufacturing a three-dimensional semiconductor element device by stacking and laminating a plurality of semiconductor elements, and a raw material for the semiconductor element three-dimensional mounting filler. The present invention relates to a curable composition useful as:

  In recent years, semiconductor devices have been highly integrated, and a semiconductor integrated circuit device having a three-dimensional stacked structure has been demanded from a planar layout. As a method of manufacturing a three-dimensional semiconductor integrated circuit device, there is known a method (a COW process; a chip-on-wafer process process) in which a second semiconductor wafer is made into a chip state by dicing and then stacked on the first semiconductor wafer. (Patent Document 1 etc.). In the case of a COW process in which a through hole (TSV) is formed in a chip, it is manufactured by performing an etching process using a photoresist.

JP 2006-19429 A

  However, when chips cut out from the second semiconductor wafer by dicing are stacked on the first semiconductor wafer, a gap is generated between the chips adjacent in the lateral direction. If there is such a gap, the photoresist cannot be applied to the entire surface of the laminate composed of the first semiconductor wafer and the chip with a uniform thickness, so that it is necessary to fill the gap generated between the chips adjacent in the lateral direction. However, unevenness remains only by filling the gap by applying resin or the like. Further, the resin remains on the chip surface, which causes an increase in thickness. Therefore, when filling the gap between adjacent chips in the lateral direction, grooves can be easily formed by coating, cracking and bubbles due to curing do not occur, and processing without cracking or peeling in the flattening or thinning process There has been a demand for a filler having excellent properties.

  Accordingly, an object of the present invention is to provide a member for a semiconductor manufacturing process useful for manufacturing a thin and low-profile three-dimensional semiconductor element device in a COW process, and a curable composition capable of forming the member. There is.

  As a result of intensive studies to achieve the above object, the present inventors have found that gaps between adjacent chips in the lateral direction are reduced in a method of manufacturing a three-dimensional semiconductor element device (such as a three-dimensional semiconductor integrated circuit device) by a COW process. It is found that if the chip and the filler are polished or ground together on the back side of the chip with the filler filled with the gap between the chips, the chip back side is flattened and the chip can be easily thinned. The present invention has been completed.

  That is, the present invention is a filler that fills a gap between adjacent semiconductor elements in a lateral direction when a plurality of semiconductor elements are stacked and integrated to manufacture a three-dimensional semiconductor element device, Provided is a filler for three-dimensional mounting of semiconductor elements, which is a member that is polished and / or ground together with elements from the back side of the semiconductor elements in a state where gaps between the semiconductor elements are filled, and is planarized.

  The filler is preferably a cured product of a curable composition containing at least an epoxy compound having a bisphenol skeleton and a cationic polymerization initiator.

  The present invention is also a curable composition used for forming the filler for semiconductor element three-dimensional mounting, which contains at least an epoxy compound having a bisphenol skeleton and a cationic polymerization initiator and is liquid at 25 ° C. A curable composition for three-dimensional mounting of a semiconductor element is provided.

  The curable composition for three-dimensional mounting of a semiconductor element may further contain an alicyclic epoxy compound.

  The curable composition for three-dimensional mounting of a semiconductor element may further contain an inorganic filler having an average particle diameter of 0.05 to 1 μm.

  The curable composition for three-dimensional mounting of a semiconductor element may further contain a silane coupling agent.

  According to the present invention, the chip and the filler are polished together from the back side of the semiconductor element in a state where the gap between the semiconductor elements adjacent in the lateral direction is filled with the filler, so that the chip back side is flattened and thinned. Thus, a thin and low-profile three-dimensional semiconductor element device can be manufactured with a high yield.

It is a schematic process drawing which shows an example of the manufacturing method of the three-dimensional semiconductor element device using the filler for semiconductor element three-dimensional mounting of this invention. It is a schematic process drawing (continuation of Drawing 1) showing an example of a manufacturing method of a three-dimensional semiconductor element device using a filler for semiconductor element three-dimensional mounting of the present invention.

[Filler for 3D mounting of semiconductor elements]
The filler for semiconductor element three-dimensional mounting according to the present invention (hereinafter sometimes simply referred to as “filler”) is used in the lateral direction when a plurality of semiconductor elements are stacked and integrated to manufacture a three-dimensional semiconductor element device. It is a filler (gap filling material) that fills a gap between adjacent semiconductor elements. This filler is a member that is polished or ground together with the chip from the back surface side of the semiconductor element in a state in which a gap between the semiconductor elements is filled, and is planarized.

  1 and 2 are schematic process diagrams showing an example of a manufacturing method of a three-dimensional semiconductor element device (three-dimensional semiconductor integrated circuit device) using the semiconductor element three-dimensional mounting filler of the present invention. In this process, a three-dimensional semiconductor element device is manufactured as follows.

(A) A first base wafer 30 in which a semiconductor element 20 is stacked on a silicon wafer 1 including a circuit formation region is prepared.
(B) A gap between adjacent semiconductor elements 20 is filled with the semiconductor element three-dimensional mounting filler 2 of the present invention (a curable composition for semiconductor element three-dimensional mounting described later is poured into the gap). Harden)
(C) The back surface of the semiconductor element 20 and the surface of the filler 2 are polished and / or ground together to flatten and thin the surface.
(D) to (e) The through hole 3 is formed in the semiconductor element 20 or in the semiconductor element three-dimensional mounting filler 2, the through electrode 4 is formed, and the semiconductor wafer 40 is manufactured.

  (F) to (j) Then, the semiconductor element 20 ′ is laminated on the surface of the semiconductor wafer 40 having the two wiring layers obtained as described above, and the above steps are repeated, so that three wiring layers are formed. A semiconductor wafer 50 having the following is obtained.

  By repeating such an operation a desired number of times and dicing at a desired position, a three-dimensional semiconductor element device (three-dimensional semiconductor integrated circuit device) can be obtained.

  In the step (c), the thickness of the semiconductor element 20 can be set to, for example, 10 to 20 μm by polishing and / or grinding.

  As described above, the backside of the element is flattened and thinned because the element and the filler are polished or ground together from the backside of the element with the gap between the elements adjacent in the lateral direction filled with the filler. Is done. Therefore, the element itself can be made thin and a low-profile three-dimensional semiconductor element device (three-dimensional semiconductor integrated circuit device) can be efficiently manufactured. At that time, neither cracks nor bubbles are generated.

  The semiconductor element 20 is an element using a semiconductor, and may be, for example, a MEMS or an image sensor. The stacked semiconductor element 20 ′ may be the same size as the semiconductor element 20 or may have different sizes (vertical, horizontal, height).

  The silicon wafer 1 including the circuit formation region may be a MEMS or an image sensor.

  The filler 2 is preferably a cured product of a curable composition containing at least an epoxy compound having a bisphenol skeleton and a cationic polymerization initiator.

[Curable composition for three-dimensional mounting of semiconductor element]
The curable composition for three-dimensional mounting of a semiconductor element of the present invention (hereinafter sometimes referred to as “the curable composition of the present invention”) contains at least an epoxy compound having a bisphenol skeleton and a cationic polymerization initiator, It is liquid at 25 ° C. The curable composition of this invention can be used for formation of the said filler for semiconductor element three-dimensional mounting. That is, the filler is formed by being injected into a gap between adjacent elements in the lateral direction and cured.

  When an epoxy compound having a bisphenol skeleton is used as the curable compound, cracks do not occur at the time of curing, and cracking and chipping do not occur even when polished together with the element after curing, and clogging of the polishing disk does not occur. In addition, when the conventional element laminating adhesive is diverted to the above-mentioned gap filling agent, cracks are generated at the time of curing. Cause clogging. Moreover, when only an alicyclic epoxy compound is used as the curable compound, the cured resin is too hard or the shrinkage occurs, and the cured product is likely to crack.

  Examples of the epoxy compound having a bisphenol skeleton include an epoxy compound having a bisphenol A skeleton (bisphenol A type epoxy resin), an epoxy compound having a bisphenol F skeleton (bisphenol F type epoxy resin), and an epoxy compound having a bisphenol AD skeleton ( Bisphenol AD type epoxy resin), epoxy compounds having a bisphenol S skeleton (bisphenol S type epoxy resin), and the like. These epoxy compounds may have structural units other than the structural units derived from bisphenol and epichlorohydrin in the molecule.

  Representative examples of the epoxy compound having a bisphenol skeleton include compounds represented by the following formulas (1), (2), and (3).

  In said formula, r shows the number of 0-8. As r, the range of 0.01-3 is preferable, and the range of 1-2 is more preferable.

  The epoxy equivalent of the epoxy compound having a bisphenol skeleton is, for example, 155 to 800 g / eq, preferably 155 to 500 g / eq, and more preferably 160 to 180 g / eq. The epoxy compound having a bisphenol skeleton is preferably in a liquid state at room temperature (25 ° C.). However, even if it is a solid, another liquid (25 ° C.) compound that dissolves the epoxy compound having a bisphenol skeleton (others By using in combination with an epoxy compound or the like, the entire curable composition may be liquid (25 ° C.).

  The curable composition of the present invention may contain an epoxy compound other than an epoxy compound having a bisphenol skeleton. As such an epoxy compound, an epoxy compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring (= alicyclic epoxy compound) in the molecule; Examples include an epoxy compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond; a glycidyl ether type epoxy compound having an alicyclic ring and a glycidyl ether group; and other epoxy compounds.

Examples of the alicyclic ring include monocyclic alicyclic rings such as cyclopentane ring, cyclohexane ring, cyclooctane ring, and cyclododecane ring (3 to 15 member, preferably about 5 to 6 membered cycloalkane ring); decalin ring ( Perhydronaphthalene ring), perhydroindene ring (bicyclo [4.3.0] nonane ring), perhydroanthracene ring, perhydrofluorene ring, perhydrophenanthrene ring, perhydroacenaphthene ring, perhydrophenalene ring, Norbornane ring (bicyclo [2.2.1] heptane ring), isobornane ring, adamantane ring, bicyclo [3.3.0] octane ring, tricyclo [5.2.1.0 ^2,6 ] decane ring, tricyclo [ 6.2.1.0 ^2,7 ] Polycyclic (about 2 to 4 rings) alicyclic ring (bridged carbon ring) such as undecane ring. Examples of the alicyclic epoxy group include an epoxycyclopentyl group, a 3,4-epoxycyclohexyl group, and a 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane 8- (or 9) yl. Group (epoxidized dicyclopentadienyl group) and the like. A substituent such as an alkyl group such as a methyl group may be bonded to the cyclohexane ring.

  Examples of the alicyclic epoxy compound include a compound represented by the following formula (4) (a compound in which two alicyclic epoxy groups are bonded by a single bond or via a linking group).

In the above formula, Y ¹ represents a single bond or a linking group. Examples of the linking group include a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), an ester bond (—COO—), an amide bond (—CONH—), and a carbonate bond (— OCOO-) and a group in which a plurality of these are bonded. Examples of the divalent hydrocarbon group include linear or branched alkylene groups such as methylene, ethylidene, isopropylidene, ethylene, propylene, trimethylene, and tetramethylene groups (for example, C _1-6 alkylene groups); 2-valent such as 2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, cyclohexylidene group, etc. And alicyclic hydrocarbon groups (particularly divalent cycloalkylene groups); groups in which a plurality of these are bonded.

  Representative compounds included in the compound represented by formula (4) are shown below.

  In the above formula, t is an integer of 1-30.

  In addition, as the alicyclic epoxy compound, there are two adjacent carbon atoms and oxygen having an alicyclic ring and two or more epoxy groups in the molecule, and only one of the two or more epoxy groups forms the alicyclic ring. The compound which is an epoxy group (alicyclic epoxy group) comprised with an atom is mentioned. This representative compound (limonene diepoxide) is shown below.

  Moreover, as an alicyclic epoxy compound, it has only one alicyclic epoxy group which has 3 or more alicyclic epoxy groups as shown below, and an alicyclic epoxy group, and does not have an epoxy group in others. An alicyclic epoxy compound can also be used.

  In the above formula, a, b, c, d, e, and f are integers from 0 to 30.

  Examples of the epoxy compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond include a compound represented by the following formula (5).

In the above formula, R is a group obtained by dividing q OH from a q-valent alcohol [R— (OH) _q ], p is an integer of 1 to 30, and q is an integer of 1 to 10. In the groups in q parentheses, p may be the same or different. As the q-valent alcohol [R- (OH) _q ], monovalent alcohols such as methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol; ethylene glycol, 1,2-propanediol, 1,3- Divalent alcohols such as propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polypropylene glycol; glycerin, diglycerin, erythritol , Trivalent or higher alcohols such as trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol. The alcohol may be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, or the like. As said alcohol, C1-C10 aliphatic alcohol (especially aliphatic polyhydric alcohols, such as a trimethylol propane), is preferable.

  Examples of the glycidyl ether type epoxy compound having an alicyclic ring and a glycidyl ether group include glycidyl ethers of alicyclic alcohols (particularly alicyclic polyhydric alcohols). This compound may be a compound in which the aromatic ring of the epoxy compound having the bisphenol skeleton [for example, the compound represented by the formula (1), (2), (3)] is nuclear hydrogenated.

Examples of the other epoxy compounds include glycidyl ethers of the above-mentioned q-valent alcohol [R- (OH) _q ]; acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, sebacic acid, maleic acid, itaconic acid and the like. Glycidyl esters of mono- or polyvalent carboxylic acids; epoxidized products of oils and fats having double bonds such as epoxidized linseed oil, epoxidized soybean oil, and epoxidized castor oil; polyolefins such as epoxidized polybutadiene (including polyalkadienes) An epoxidized product is exemplified.

  Among the epoxy compounds other than the epoxy compound having the bisphenol skeleton, an alicyclic epoxy compound is preferable. By using an epoxy compound having a bisphenol skeleton and an alicyclic epoxy compound in combination, the heat resistance of the cured product (filler 2) can be improved. Moreover, the change of the hardness at high temperature of hardened | cured material (filler 2) can be suppressed.

  The content of the total epoxy compound in the curable composition of the present invention is, for example, 30 to 99.99% by weight, preferably 50 to 99.9% by weight, and more preferably 60 to 99.5% by weight. . The ratio of the epoxy compound having a bisphenol skeleton in the total epoxy compound in the curable composition of the present invention is, for example, 30% by weight or more, preferably 40% by weight or more, and more preferably 50% by weight or more. Furthermore, the ratio of the total amount of the epoxy compound having a bisphenol skeleton and the alicyclic epoxy compound in the total epoxy compound in the curable composition of the present invention is, for example, 50% by weight or more, preferably 70% by weight or more, and more preferably Is 90% by weight or more.

  The curable composition of the present invention contains a cationic polymerization initiator (curing catalyst). The cationic polymerization initiator is an initiator that releases a substance that initiates cationic polymerization by light or heating.

  Among the cationic polymerization initiators, a known photocationic polymerization initiator can be used as a cationic polymerization initiator that generates a cationic species by ultraviolet irradiation. For example, hexafluoroantimonate salt, pentafluorohydroxyantimonate salt, hexafluorophosphate salt, hexafluoroarsenate salt, etc. can be mentioned, and trade name “CPI-100P”, trade name “CPI-101A”, trade name “LW-S1” (above, manufactured by San Apro Co., Ltd.), trade names “CD-1010”, “CD-1011”, “CD-1012” (above, manufactured by Sartomer, USA), trade name “Irgacure 264” (BASF) And commercial products such as “CIT-1682” (manufactured by Nippon Soda Co., Ltd.) can be preferably used.

  Among the cationic polymerization initiators, a known thermal cationic polymerization initiator can be used as a cationic polymerization initiator that generates cationic species by heating. For example, aryldiazonium salts, aryliodonium salts, arylsulfonium salts, allene-ion complexes, and the like can be mentioned. PP-33, CP-66, CP-77 (manufactured by ADEKA Corporation), FC-509 (manufactured by 3M) ), UVE1014 (manufactured by GE), Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L, Sun-Aid SI-110L (Sanshin Chemical Industry Co., Ltd.), CG-24-61 (BASF) ) And the like can be preferably used. Furthermore, a chelate compound of a metal such as aluminum or titanium and a acetoacetate or diketone compound and a silanol such as triphenylsilanol, or a chelate compound of a metal such as aluminum or titanium and acetoacetate or diketone and bisphenol S The compound with phenols, such as these, may be sufficient.

  By using a cationic polymerization initiator, the curable composition of the present invention is cationically cured by heat or light to obtain the filler.

  Although the compounding quantity of a cationic polymerization initiator is not specifically limited, 0.01-15 weight part is preferable with respect to 100 weight part of total epoxy compounds in the said curable composition, More preferably, it is 0.05-10 weight. Parts, more preferably 0.1 to 8 parts by weight. By mix | blending in the said range, favorable hardened | cured material (filler), such as heat resistance, transparency, a weather resistance, can be obtained.

[Additive]
The curable composition of the present invention may contain an inorganic filler. By containing an inorganic filler, the thermal expansion of the cured product (filler 2) can be suppressed. Moreover, the heat resistance of hardened | cured material (filler 2) can be improved.

  Examples of the inorganic filler include silica, alumina, magnesia, titanium oxide, antimony oxide, talc, clay, montmorillonite, hydrotalcite, synthetic mica, calcium carbonate, aluminum hydroxide, magnesium hydroxide and the like. Among these, silica (especially spherical silica) and alumina are preferable.

  The average particle diameter of the inorganic filler is, for example, 0.05 to 1 μm, preferably 0.1 to 0.8 μm.

  The amount of the inorganic filler is, for example, 0 to 70% by weight (for example, 0.1 to 70% by weight), preferably 0 to 50% by weight, based on 100 parts by weight of the total epoxy compound in the curable composition of the present invention. (For example, 1 to 50% by weight), more preferably 0 to 40% by weight (for example, 5 to 40% by weight).

  The curable composition of the present invention may contain a silane coupling agent. By containing the silane coupling agent, the adhesion of the cured product (filler 2) to the silicon wafer can be improved.

  As the silane coupling agent, various known silane coupling agents can be used. Representative examples of silane coupling agents include 3-trimethoxysilylpropyl (meth) acrylate, 3-triethoxysilylpropyl (meth) acrylate, 3-dimethoxymethylsilylpropyl (meth) acrylate, 3-diethoxymethylsilyl And propyl (meth) acrylate. When using a silane coupling agent whose functional group is a (meth) acryloyloxy group, a small amount of a radical polymerization initiator may be added. In addition, the silane coupling agent whose functional group is an epoxy group [2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.] can also be used, and such coupling agents belong to the other epoxy compounds.

  The compounding quantity of a silane coupling agent is 0-10 weight% (for example, 0.1-10 weight%) with respect to 100 weight part of all the epoxy compounds in the curable composition of this invention, Preferably it is 0-5. % By weight (for example, 0.2 to 5% by weight), more preferably 0 to 3% by weight (for example, 0.3 to 3% by weight).

  In the curable composition of the present invention, if necessary, the viscosity of the curable composition and the properties of the cured product are not impaired, and silicone-based or fluorine-based antifoaming agent, leveling agent, surfactant, organic Rubber particles, flame retardants, colorants, plasticizers, antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers, ion adsorbents, pigments, dyes, phosphors, and the like can also be added. The compounding quantity of these various additives is 5 weight% or less with respect to the whole curable composition, for example. The curable composition of the present invention may contain a solvent, but if the amount of the solvent is too large, bubbles may be formed in the cured resin, preferably 10% by weight or less based on the entire curable composition, In particular, it is 1% by weight or less.

  In the curable composition of the present invention, the total content of the epoxy compound, the cationic polymerization initiator, the inorganic filler, and the silane coupling agent is, for example, 80% by weight or more, preferably 90% with respect to the entire curable composition. % Or more, more preferably 95% by weight or more.

  The viscosity (25 degreeC) of the curable composition of this invention is 10-100,000 mPa * s, for example, Preferably it is 100-10000 mPa * s, More preferably, it is 500-3000 mPa * s. The curable composition of the present invention is preferably in the form of a paste having fluidity at room temperature. When this viscosity is too large, it is difficult for bubbles to escape, and workability, handleability, and the like are likely to deteriorate.

  The curable composition of the present invention may be either a two-component type or a one-component type.

  The curable composition of the present invention is obtained by stirring and mixing an epoxy compound having a bisphenol skeleton and a cationic polymerization initiator, and if necessary, an alicyclic epoxy compound, an inorganic filler, a silane coupling agent, and other components. Can be prepared. For the stirring and mixing, a general-purpose mixer or kneader can be used.

  The curable composition for three-dimensional mounting of a semiconductor element thus prepared is injected into a gap between adjacent semiconductor elements in the lateral direction when manufacturing a three-dimensional semiconductor element device, and is cured (photocured or heated) under predetermined conditions. Cured) and functions as the filler 2.

When the curable composition of the present invention is photocured (photocationic curing), the active energy ray (light) to be irradiated is not particularly limited, and examples thereof include ultraviolet rays and electron beams. Among them, ultraviolet rays are preferably used. it can. The wavelength of the ultraviolet light can be appropriately selected according to the type of the cationic polymerization initiator. The irradiation conditions of the active energy rays can be appropriately selected according to the type and thickness of the compounded epoxy compound, the type and amount of the cationic polymerization initiator, and are not particularly limited. For example, ultraviolet rays are used. in this case, the irradiation amount (dose) is preferably 10~10,000mJ / cm ^2, more preferably 50~5,000mJ / cm ^2. Examples of the ultraviolet irradiation source include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, and an LED lamp.

  Moreover, although the curing temperature at the time of carrying out heat curing (thermal cation curing) of the curable composition of this invention is not specifically limited, 45-200 degreeC is preferable. The curing time is preferably 1 to 60 minutes, for example. Curing can also be performed in multiple stages.

  As described above, after the composition of the present invention is irradiated with active energy rays and photocured, it may be further heated as necessary. By performing such heating, effects such as reduction of unreacted substances in the cured resin, improvement of the degree of curing of the cured resin, relaxation of distortion, and the like can be obtained. In addition, the effect of improving the hardness and adhesion of the cured resin may be obtained. The said heating can be normally performed on the conditions for 1 to 300 minutes at the atmospheric temperature of 100-200 degreeC.

  In the case of heat curing, when the curable composition is injected into the gap between the adjacent semiconductor elements, the fluidity of the curable composition is increased by heat and gathers in the center (the wettability with the silicon wafer is increased). Since the in-plane film thickness distribution may not be constant, photocuring is preferable to heat curing.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
100 parts by weight of a bisphenol F type epoxy resin (product name “RE-303” manufactured by Nippon Kayaku Co., Ltd.) and 2 parts by weight of a cationic polymerization initiator (product name “CPI-100P” manufactured by San Apro Co., Ltd.) The product was stirred and mixed under the trade name “Awatori Nertaro” to obtain a curable composition for a filler.

Example 2
70 parts by weight of a bisphenol F type epoxy resin (made by Nippon Kayaku Co., Ltd., trade name “RE-303”), an alicyclic epoxy compound (made by Daicel Corporation, trade name “Celoxide 2021P”, 3,4-epoxycyclohexylmethyl ( 3,4-epoxy) cyclohexanecarboxylate) 30 parts by weight and cationic polymerization initiator (trade name “CPI-100P”, manufactured by San Apro Co., Ltd.) 2 parts by weight are stirred by Shinky Co., Ltd., under the trade name “Awatori Netaro” It mixed and the curable composition for fillers was obtained.

Example 3
70 parts by weight of a bisphenol F type epoxy resin (made by Nippon Kayaku Co., Ltd., trade name “RE-303”), an alicyclic epoxy compound (made by Daicel Corporation, trade name “Celoxide 2021P”, 3,4-epoxycyclohexylmethyl ( 3,4-epoxy) cyclohexanecarboxylate) 30 parts by weight and cationic polymerization initiator (trade name “CPI-101A” manufactured by San Apro Co., Ltd.) 2 parts by weight are stirred by Shinky Co. It mixed and the curable composition for fillers was obtained.

Example 4
70 parts by weight of a bisphenol F type epoxy resin (made by Nippon Kayaku Co., Ltd., trade name “RE-303”), an alicyclic epoxy compound (made by Daicel Corporation, trade name “Celoxide 2021P”, 3,4-epoxycyclohexylmethyl ( 3,4-epoxy) cyclohexanecarboxylate) 30 parts by weight and cationic polymerization initiator (trade name “LW-S1” manufactured by San Apro Co., Ltd.) 2 parts by weight are stirred with Shinky Co., Ltd., trade name “Awatori Netaro” It mixed and the curable composition for fillers was obtained.

Example 5
70 parts by weight of a bisphenol F type epoxy resin (made by Nippon Kayaku Co., Ltd., trade name “RE-303”), an alicyclic epoxy compound (made by Daicel Corporation, trade name “Celoxide 2021P”, 3,4-epoxycyclohexylmethyl ( 3,4-epoxy) cyclohexanecarboxylate) 30 parts by weight, cationic polymerization initiator (manufactured by Sun Apro, trade name “CPI-100P”), silica (manufactured by Admatechs, trade name “SC4050-SEJ”, average 30 parts by weight of particles having a particle diameter of 1 μm were mixed by stirring under the trade name “Awatori Netaro” manufactured by Shinky Corporation to obtain a curable composition for a filler.

Example 6
70 parts by weight of a bisphenol F type epoxy resin (made by Nippon Kayaku Co., Ltd., trade name “RE-303”), an alicyclic epoxy compound (made by Daicel Corporation, trade name “Celoxide 2021P”, 3,4-epoxycyclohexylmethyl ( 3,4-epoxy) cyclohexanecarboxylate) 30 parts by weight, cationic polymerization initiator (manufactured by Sun Apro, trade name “CPI-100P”), silica (manufactured by Admatechs, trade name “SC4050-SEJ”, average 30 parts by weight of particle diameter (1 μm) and 1 part by weight of silane coupling agent (3-trimethoxysilylpropyl acrylate) are stirred and mixed under the trade name “Awatori Netaro” manufactured by Shinky Corporation, and a curable composition for a filler. I got a thing.

Example 7
70 parts by weight of a bisphenol F type epoxy resin (made by Nippon Kayaku Co., Ltd., trade name “RE-303”), 30 parts by weight of an alicyclic epoxy compound (3,4,3 ′, 4′-diepoxybicyclohexyl), a cation 2 parts by weight of a polymerization initiator (trade name “CPI-100P” manufactured by San Apro Co., Ltd.) was stirred and mixed using a trade name “Awatori Nertaro” manufactured by Shinky Co., Ltd. to obtain a curable composition for a filler.

Example 8
70 parts by weight of a bisphenol F type epoxy resin (made by Nippon Kayaku Co., Ltd., trade name “RE-303”), 30 parts by weight of an alicyclic epoxy compound (3,4,3 ′, 4′-diepoxybicyclohexyl), a cation 2 parts by weight of a polymerization initiator (trade name “CPI-101A” manufactured by San Apro Co., Ltd.) was stirred and mixed using a trade name “Awatori Netaro” manufactured by Shinky Co., Ltd. to obtain a curable composition for a filler.

Example 9
70 parts by weight of a bisphenol F type epoxy resin (made by Nippon Kayaku Co., Ltd., trade name “RE-303”), 30 parts by weight of an alicyclic epoxy compound (3,4,3 ′, 4′-diepoxybicyclohexyl), a cation 2 parts by weight of a polymerization initiator (trade name “LW-S1” manufactured by San Apro Co., Ltd.) was stirred and mixed using a trade name “Awatori Nertaro” manufactured by Shinky Corp. to obtain a curable composition for a filler.

Example 10
70 parts by weight of a bisphenol F type epoxy resin (made by Nippon Kayaku Co., Ltd., trade name “RE-303”), 30 parts by weight of an alicyclic epoxy compound (3,4,3 ′, 4′-diepoxybicyclohexyl), a cation 2 parts by weight of a polymerization initiator (manufactured by San Apro, trade name “CPI-100P”), 30 parts by weight of silica (manufactured by Admatechs, trade name “SC4050-SEJ, average particle diameter 1 μm), manufactured by Shinky Corporation, trade name The mixture was stirred and mixed with “Awatori Netaro” to obtain a curable composition for a filler.

Example 11
70 parts by weight of a bisphenol F type epoxy resin (made by Nippon Kayaku Co., Ltd., trade name “RE-303”), 30 parts by weight of an alicyclic epoxy compound (3,4,3 ′, 4′-diepoxybicyclohexyl), a cation 2 parts by weight of a polymerization initiator (manufactured by San Apro, trade name “CPI-100P”), 30 parts by weight of silica (manufactured by Admatechs, trade name “SC4050-SEJ, average particle diameter 1 μm), silane coupling agent (3- 1 part by weight of trimethoxysilylpropyl acrylate) was stirred and mixed under the trade name “Awatori Netaro” manufactured by Shinky Corporation to obtain a curable composition for a filler.

Example 12
100 parts by weight of bisphenol A type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name “RE-303”), 2 parts by weight of a cationic polymerization initiator (trade name “CPI-100P” by San Apro Co., Ltd.) The product was stirred and mixed under the trade name “Awatori Nertaro” to obtain a curable composition for a filler.

Example 13
70 parts by weight of a bisphenol A type epoxy resin (product name “RE-303” manufactured by Nippon Kayaku Co., Ltd.), an alicyclic epoxy compound (product name “Celoxide 2021P” manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl ( 3,4-epoxy) cyclohexanecarboxylate) 30 parts by weight and cationic polymerization initiator (trade name “CPI-100P”, manufactured by San Apro Co., Ltd.) 2 parts by weight are stirred by Shinky Co., Ltd., under the trade name “Awatori Netaro” It mixed and the curable composition for fillers was obtained.

Example 14
70 parts by weight of a bisphenol A type epoxy resin (product name “RE-303” manufactured by Nippon Kayaku Co., Ltd.), an alicyclic epoxy compound (product name “Celoxide 2021P” manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl ( 3,4-epoxy) cyclohexanecarboxylate) 30 parts by weight and cationic polymerization initiator (trade name “CPI-101A” manufactured by San Apro Co., Ltd.) 2 parts by weight are stirred by Shinky Co. It mixed and the curable composition for fillers was obtained.

Example 15
70 parts by weight of a bisphenol A type epoxy resin (product name “RE-303” manufactured by Nippon Kayaku Co., Ltd.), an alicyclic epoxy compound (product name “Celoxide 2021P” manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl ( 3,4-epoxy) cyclohexanecarboxylate) 30 parts by weight and cationic polymerization initiator (trade name “LW-S1” manufactured by San Apro Co., Ltd.) 2 parts by weight are stirred with Shinky Co., Ltd., trade name “Awatori Netaro” It mixed and the curable composition for fillers was obtained.

Example 16
70 parts by weight of a bisphenol A type epoxy resin (product name “RE-303” manufactured by Nippon Kayaku Co., Ltd.), an alicyclic epoxy compound (product name “Celoxide 2021P” manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl ( 3,4-epoxy) cyclohexanecarboxylate) 30 parts by weight, cationic polymerization initiator (manufactured by Sun Apro, trade name “CPI-100P”), silica (manufactured by Admatechs, trade name “SC4050-SEJ”, average 30 parts by weight of particles having a particle diameter of 1 μm were mixed by stirring under the trade name “Awatori Netaro” manufactured by Shinky Corporation to obtain a curable composition for a filler.

Example 17
70 parts by weight of a bisphenol A type epoxy resin (product name “RE-303” manufactured by Nippon Kayaku Co., Ltd.), an alicyclic epoxy compound (product name “Celoxide 2021P” manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl ( 3,4-epoxy) cyclohexanecarboxylate) 30 parts by weight, cationic polymerization initiator (manufactured by Sun Apro, trade name “CPI-100P”), silica (manufactured by Admatechs, trade name “SC4050-SEJ”, average 30 parts by weight of particle diameter (1 μm) and 1 part by weight of silane coupling agent (3-trimethoxysilylpropyl acrylate) are stirred and mixed under the trade name “Awatori Netaro” manufactured by Shinky Corporation, and a curable composition for a filler. I got a thing.

Example 18
70 parts by weight of a bisphenol A type epoxy resin (trade name “RE-303” manufactured by Nippon Kayaku Co., Ltd.), 30 parts by weight of an alicyclic epoxy compound (3,4,3 ′, 4′-diepoxybicyclohexyl), a cation 2 parts by weight of a polymerization initiator (trade name “CPI-100P” manufactured by San Apro Co., Ltd.) was stirred and mixed using a trade name “Awatori Nertaro” manufactured by Shinky Co., Ltd. to obtain a curable composition for a filler.

Example 19
70 parts by weight of a bisphenol A type epoxy resin (trade name “RE-303” manufactured by Nippon Kayaku Co., Ltd.), 30 parts by weight of an alicyclic epoxy compound (3,4,3 ′, 4′-diepoxybicyclohexyl), a cation 2 parts by weight of a polymerization initiator (trade name “CPI-101A” manufactured by San Apro Co., Ltd.) was stirred and mixed using a trade name “Awatori Netaro” manufactured by Shinky Co., Ltd. to obtain a curable composition for a filler.

Example 20
70 parts by weight of a bisphenol A type epoxy resin (trade name “RE-303” manufactured by Nippon Kayaku Co., Ltd.), 30 parts by weight of an alicyclic epoxy compound (3,4,3 ′, 4′-diepoxybicyclohexyl), a cation 2 parts by weight of a polymerization initiator (trade name “LW-S1” manufactured by San Apro Co., Ltd.) was stirred and mixed using a trade name “Awatori Nertaro” manufactured by Shinky Corp. to obtain a curable composition for a filler.

Example 21
70 parts by weight of a bisphenol A type epoxy resin (trade name “RE-303” manufactured by Nippon Kayaku Co., Ltd.), 30 parts by weight of an alicyclic epoxy compound (3,4,3 ′, 4′-diepoxybicyclohexyl), a cation 2 parts by weight of a polymerization initiator (manufactured by San Apro, trade name “CPI-100P”), 30 parts by weight of silica (manufactured by Admatechs, trade name “SC4050-SEJ, average particle diameter 1 μm), manufactured by Shinky Corporation, trade name The mixture was stirred and mixed with “Awatori Netaro” to obtain a curable composition for a filler.

Example 22
70 parts by weight of a bisphenol A type epoxy resin (trade name “RE-303” manufactured by Nippon Kayaku Co., Ltd.), 30 parts by weight of an alicyclic epoxy compound (3,4,3 ′, 4′-diepoxybicyclohexyl), a cation 2 parts by weight of a polymerization initiator (manufactured by San Apro, trade name “CPI-100P”), 30 parts by weight of silica (manufactured by Admatechs, trade name “SC4050-SEJ, average particle diameter 1 μm), silane coupling agent (3- 1 part by weight of trimethoxysilylpropyl acrylate) was stirred and mixed under the trade name “Awatori Netaro” manufactured by Shinky Corporation to obtain a curable composition for a filler.

Comparative Example 1
Alicyclic epoxy compound (manufactured by Daicel Corporation, trade name “Celoxide 2021P”, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate) 100 parts by weight, cationic polymerization initiator (manufactured by San Apro, product) 2 parts by weight of “CPI-100P”) was stirred and mixed with a trade name “Awatori Netaro” manufactured by Shinky Corporation to obtain a curable composition for a filler.

Comparative Example 2
Alicyclic epoxy compound (manufactured by Daicel Corporation, trade name “Celoxide 2021P”, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate) 100 parts by weight, cationic polymerization initiator (manufactured by San Apro, product) 2 parts by weight of “CPI-101A”) was stirred and mixed under the trade name “Awatori Netaro” manufactured by Shinky Corporation to obtain a curable composition for a filler.

Comparative Example 3
100 parts by weight of an alicyclic epoxy compound (3,4,3 ′, 4′-diepoxybicyclohexyl) and 2 parts by weight of a cationic polymerization initiator (manufactured by San Apro, trade name “CPI-100P”) The mixture was stirred and mixed under the trade name “Awatori Nertaro” to obtain a curable composition for a filler.

Comparative Example 4
100 parts by weight of an alicyclic epoxy compound (3,4,3 ′, 4′-diepoxybicyclohexyl) and 2 parts by weight of a cationic polymerization initiator (manufactured by San Apro, trade name “CPI-101A”) The mixture was stirred and mixed under the trade name “Awatori Nertaro” to obtain a curable composition for a filler.

Evaluation test As an application substrate, an 8-inch silicon wafer prepared by cutting a concave-convex shape resembling a chip was prepared (simulated COW substrate: wafer thickness 725 μm, chip portion 9 mm × 9 mm × 0.2 mm thickness, groove portion 2 mm width) × 0.1 mm thickness). That is, grooves having a width of 2 mm and a depth of 0.2 mm were formed on the surface of an 8-inch silicon wafer at intervals of 10 mm in the vertical direction and the horizontal direction, respectively.
The curable composition for filler obtained in each of the above examples and comparative examples was applied to the surface of the simulated COW substrate with a squeegee (J Squeegee, manufactured by Neurong Seimitsu Kogyo Co., Ltd.).
After coating, UV light (UV-A) was irradiated at 3600 mJ / cm ² with a UV irradiation machine (trade name “UVC-02516S1AA02” manufactured by USHIO INC.). Thereafter, post-curing was performed at 120 ° C. for 10 minutes.
The state of the filler after curing was observed visually and with an optical microscope, and the presence or absence of cracks in the filler was confirmed.
Using a polishing machine (trade name “MA-200D” manufactured by Musashino Electronics Co., Ltd.) and a polishing machine (trade name “CBN DIA # 400” manufactured by Mitsui Grinding Wheel Co., Ltd.) The polishing test was performed under the conditions of 100 rpm, polishing time 10 min, and weight 500 g. In Comparative Examples 1 to 4, since the filler was cracked, no polishing test was performed.
After polishing, the presence or absence of cracks or chips in the cured filler or silicon wafer and the presence or absence of clogging of the polishing disk were confirmed visually and with a microscope. The cured filler or silicon wafer has no cracks or chips, and the polishing board is not clogged. The cured filler or silicon wafer has cracks or chips, or the polishing board is clogged. The thing was set as x.
The evaluation results are shown in Table 1.

DESCRIPTION OF SYMBOLS 1 Silicon wafer containing circuit formation area 2 Filler for three-dimensional mounting of semiconductor element 3 Through hole 4 Through electrode 20 Semiconductor element 30 First base wafer 40 Semiconductor wafer having two wiring layers 50 Having three wiring layers Semiconductor wafer

Claims (6)

  When a three-dimensional semiconductor device is manufactured by stacking and integrating a plurality of semiconductor elements, the filler is used to fill a gap between adjacent semiconductor elements in the lateral direction. A filling material for three-dimensional mounting of a semiconductor element, which is a member that is polished and / or ground together with the element from the back side of the semiconductor element in a buried state and is planarized.   The filler for semiconductor element three-dimensional mounting according to claim 1, wherein the filler is a cured product of a curable composition containing at least an epoxy compound having a bisphenol skeleton and a cationic polymerization initiator.   A curable composition used for forming a filler for three-dimensional mounting of a semiconductor element according to claim 1, comprising at least an epoxy compound having a bisphenol skeleton and a cationic polymerization initiator, and liquid at 25 ° C. A curable composition for three-dimensional mounting of semiconductor elements.   Furthermore, the curable composition for three-dimensional mounting of a semiconductor element according to claim 3, further comprising an alicyclic epoxy compound.   The curable composition for three-dimensional mounting of a semiconductor element according to claim 3 or 4, further comprising an inorganic filler having an average particle diameter of 0.05 to 1 µm.   Furthermore, the curable composition for three-dimensional mounting of a semiconductor element according to any one of claims 3 to 5, further comprising a silane coupling agent.

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