Thermosetting resin composition for hybrid bonding and method for producing circuit connection body

Abstract

The present disclosure relates to a novel thermosetting resin composition used for forming an insulating film applied to hybrid bonding.SOLUTION: A thermosetting resin composition for hybrid bonding, comprising a maleimide compound having a maleimide group represented by formula (I): and a reactive component other than the maleimide compound. The reactive component includes an allyl compound having an allyl group.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The present disclosure relates to a thermosetting resin composition for hybrid bonding and a method for producing a circuit connection body by hybrid bonding. [Background technology]

[0002] In the three-dimensional packaging of semiconductor chips, hybrid bonding, which bonds insulating films together with electrodes, is being considered for miniaturizing wiring. It has also been proposed to form the insulating film for hybrid bonding using a resin material such as polyimide (Patent Document 1).

[0003] On the other hand, it is known that compositions containing maleimide compounds and allyl compounds are thermally cured by addition reactions including ene reactions and Diels-Alder reactions or radical polymerization (Non-Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2020 / 085183 [Non-patent literature]

[0005] [Non-Patent Document 1] Handbook of Thermoset Plastics, Third Edition, 2014, p. 459-510 Summary of the Invention [Problem to be solved by the invention]

[0006] The present disclosure relates to a novel thermosetting resin composition used to form an insulating film applied to hybrid bonding. [Means for solving the problem]

[0007] The present disclosure includes the following: [1] Formula (I): [ka] a maleimide compound having a maleimide group represented by the formula: a reactive component other than the maleimide compound; Including, the reactive component comprises an allyl compound having an allyl group; Thermosetting resin composition for hybrid bonding. [2] The thermosetting resin composition for hybrid bonding according to [1], further comprising a silane coupling agent. [3] The thermosetting resin composition for hybrid bonding according to claim [2], wherein the silane coupling agent comprises at least one selected from the group consisting of tris[3-(trimethoxysilyl)propyl]isocyanurate, 3-aminopropyltriethoxysilane, triethoxy(3-glycidyloxypropyl)silane, trimethoxy(4-vinylphenyl)silane, and 1-[3-(trimethoxysilyl)propyl]urea. [4] The thermosetting resin composition for hybrid bonding according to [2], wherein the silane coupling agent comprises tris[3-(trimethoxysilyl)propyl]isocyanurate, 3-aminopropyltriethoxysilane, or a combination thereof. [5] The thermosetting resin composition for hybrid bonding according to any one of [1] to [4], further comprising an azole compound. [6] The thermosetting resin composition for hybrid bonding according to any one of [1] to [5], further comprising a solvent, the content of the solvent being 10% by mass or more and 90% by mass or less, based on the mass of the thermosetting resin composition. [7] 1. A method for manufacturing a circuit connector comprising a first circuit member having a first electrode and a second circuit member having a second electrode, the method comprising: The method comprises: heating the first resin film including the portion provided around the first electrode, thereby forming a first insulating film; joining the first circuit member and the second circuit member, which has the second electrode and a second insulating film including a portion provided around the second electrode, by hybrid bonding so that the first electrode and the second electrode are electrically connected; A method in which the first resin film comprises the thermosetting resin composition for hybrid bonding according to any one of claims [1] to [5]. [8] 1. A method for manufacturing a circuit connector comprising a first circuit member having a first electrode and a second circuit member having a second electrode, the method comprising: The method comprises: heating the first resin film including the portion provided around the first electrode, thereby forming a first insulating film; heating the second resin film including the portion provided around the second electrode, thereby forming a second insulating film; and joining the first circuit member and the second circuit member by hybrid bonding so that the first electrode and the second electrode are electrically connected, The method, wherein the first resin film and the second resin film contain the thermosetting resin composition for hybrid bonding according to any one of [1] to [5]. [Effects of the Invention]

[0008] A novel thermosetting resin composition is provided that is used to form an insulating film that is applied to hybrid bonding. [Brief explanation of the drawings]

[0009] [Figure 1] 1A to 1C are process diagrams showing an example of a method for manufacturing a semiconductor device. [Figure 2]1A to 1C are process diagrams showing an example of a method for manufacturing a semiconductor device. [Figure 3] 1A to 1C are process diagrams showing an example of a method for manufacturing a semiconductor device. [Figure 4] FIG. 1 is a schematic diagram showing a method of a shear test. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention is not limited to the following examples.

[0011] Manufacturing method of circuit connection body (semiconductor device) 1, 2, and 3 are process diagrams illustrating an example of a method for manufacturing a circuit connection body. The method illustrated in FIGS. 1 to 3 includes preparing a first circuit member 10 having a first substrate 11, a first electrode 12, and a first insulating film 13; preparing a second circuit member 20 having a second substrate 21, a second electrode 22, and a second insulating film 23; and joining the first circuit member 10 and the second circuit member 20 by hybrid bonding so that the first electrode and the second electrode are electrically connected. In hybrid bonding, the first circuit member 10 and the second circuit member 20 are heated and pressurized, thereby joining the first circuit member 10 and the second circuit member 20 so that the first insulating film 13 and the second insulating film 23 are joined and the first electrode 12 and the second electrode 22 are joined. At least one of the first substrate 11 and the second substrate 21 can be a semiconductor substrate having a circuit surface. Typically, an integrated circuit is provided on the circuit surface of the semiconductor substrate. This method forms a circuit connection body 1, which is a joint between the first circuit member 10 and the second circuit member 20. For example, the first substrate 11 may be a semiconductor wafer, and the second substrate 21 may be a semiconductor chip. A plurality of second circuit members 20 each having a semiconductor chip may be bonded to a single first circuit member 10 having a semiconductor wafer. In this case, the semiconductor wafer (first substrate 11) of the resulting bonded body may be diced into a plurality of semiconductor chips. The semiconductor substrate may be, for example, a silicon substrate. When the first circuit member 10 or the second circuit member 20 is not a semiconductor substrate, they may be various types of wiring substrates (for example, interposers).

[0012] In the first circuit member 10 before bonding, a first electrode 12 and a first insulating film 13 are provided on the first substrate 11. When the first substrate 11 is a semiconductor substrate having a circuit surface, the first electrode 12 and the first insulating film 13 are provided on the circuit surface. The first insulating film 13 has a plurality of openings 13a formed therein, which are through holes through which the first substrate 11 is exposed, and the first electrodes 12 are provided in the openings 13a.

[0013] In the second circuit member 20 before bonding, a second electrode 22 and a second insulating film 23 are provided on the second substrate 21. When the second substrate 21 is a semiconductor substrate, the second electrode 22 and the second insulating film 23 are provided on the circuit surface. The second insulating film 23 has a plurality of openings 23a formed therein, which are through holes through which the second substrate 21 is exposed, and the second electrode 22 is provided in the openings 23a.

[0014] The shapes of the first electrode 12 and the second electrode 22 are not particularly limited, but some or all of these electrodes are arranged so that the first electrode 12 and the second electrode 22 face each other and are joined. The widths of the first electrode 12 and the second electrode 22 may be, for example, 1 μm or more or 100 μm or more, and 300 μm or less or 30 μm or less. Here, the width refers to the maximum width of each electrode in a direction parallel to the main surface (circuit surface) of the first substrate 11 or the second substrate 21. The spacing between adjacent first electrodes 12 and adjacent second electrodes 22 may be, for example, 1 μm or more or 100 μm or more, and 300 μm or less or 30 μm or less. The heights of the first electrodes 12 and the second electrodes 22 may be, for example, 1 μm or more or 10 μm or more, and 100 μm or less or 10 μm or less. The height of the first electrode 12 may be the same as or different from the thickness of the first insulating film 13. The height of the second electrode 22 may be the same as or different from the thickness of the second insulating film 23.

[0015] At least one of the first insulating film 13 and the second insulating film 23 can be an organic insulating film containing a cured product of a maleimide compound having a maleimide group and a reactive component thermosetting resin composition (hereinafter also referred to as a "thermosetting maleimide resin composition") that is a compound other than the maleimide compound. The reactive component may contain an allyl compound having an allyl group. An organic insulating film containing a cured product of the thermosetting maleimide resin composition can be well bonded to other insulating films by heating and pressurization. The surface of an organic insulating film containing a cured product of the thermosetting maleimide resin composition may contain many maleimide groups, allyl groups, or functional groups derived therefrom. Therefore, the organic insulating film can exhibit good bonding properties without necessarily requiring an activation treatment such as plasma treatment. In addition, the polishing rate of the organic insulating film may be adjustable based on the crosslink density of the cured product. More detailed examples of thermosetting maleimide resin compositions will be described later.

[0016] Particularly good bonding properties are likely to be exhibited when both the first insulating film 13 and the second insulating film 23 are organic insulating films containing a cured product of a thermosetting maleimide resin composition. However, one of the first insulating film 13 or the second insulating film 23 may be an organic insulating film other than one containing a cured product of a thermosetting maleimide resin composition, or may be an inorganic insulating film.

[0017] When the first insulating film 13 is an organic insulating film containing a cured product of a thermosetting maleimide resin composition, the first circuit member 10 can be prepared by a method including: providing a plurality of columnar first electrodes 12 on one main surface 11S of the first substrate 11, as shown in FIGS. 1 and 2 ; forming a first resin film 13A containing a thermosetting resin composition (thermosetting maleimide resin composition) and covering the first electrode 12 on the main surface 11S of the first substrate 11 facing the first electrode 12; curing or semi-curing the first resin film 13A to form the first insulating film 13, which is an organic insulating film; and polishing the first insulating film 13 from the side opposite to the first substrate 11 to form an opening 13a in the first insulating film 13 that exposes the first electrode 12.

[0018] The first electrode 12 is made of a conductive material containing a metal such as copper, etc. The first electrode 12 containing a metal can be formed by a common method such as plating.

[0019] After the first electrode 12 is formed, a first resin film 13A containing a thermosetting resin composition is formed on the main surface 11S of the first substrate 11 facing the first electrode 12. The first resin film 13A is formed, for example, by applying a thermosetting resin composition having flowability. The thermosetting resin composition having flowability may contain a solvent. When a thermosetting resin composition containing a solvent is used, the first resin film 13A can be formed by heating the applied thermosetting resin composition to remove the solvent. The heating temperature for removing the solvent may be, for example, 60°C or higher and 150°C or lower. The first resin film 13A may be formed to cover the entire first electrode 12, including a portion that fills the gaps between the multiple first electrodes 12 around the first electrode 12.

[0020] The formed first resin film 13A is cured or semi-cured by heating. The curing or semi-curing of the first resin film 13A forms a first insulating film 13 (organic insulating film), which is a cured product of the thermosetting resin composition. Heating promotes an ene reaction between the maleimide group and the allyl group, a Diels-Alder reaction involving the addition of the maleimide group, and radical polymerization, resulting in the formation of a cured product. Because curing proceeds primarily through an addition reaction, volatile matter resulting from elimination of components is unlikely to be generated. Furthermore, because curing proceeds at a relatively low temperature, thermal damage to a semiconductor substrate or the like can be reduced. The heating temperature for curing or semi-curing the first resin film 13A may be, for example, 170°C or higher and 260°C or lower. The heating time for curing or semi-curing the first resin film 13A may be, for example, 15 minutes or higher and 180 minutes or lower.

[0021] When the formed first insulating film 13 covers the first electrode 12, the first insulating film 13 is polished from the side opposite the first substrate 11. A conventional polishing method, such as chemical mechanical polishing (CMP), can be used. This polishing removes a portion of the first insulating film 13, forming an opening 13a in the first insulating film 13 that exposes the first electrode 12. For CMP, for example, an abrasive containing silica particles or alumina particles can be used. The thickness of the first insulating film 13 after polishing may be, for example, 1 μm to 100 μm. Typically, a portion of the first electrode 12 is also removed by polishing, thereby planarizing the tip surface of the first electrode 12 (the surface opposite the first substrate 11). Depending on the polishing rate, the height of the first electrode 12 may be greater than the thickness of the first insulating film 13 in the polished first circuit member 10. The difference between the height of the first electrode 12 and the thickness of the first insulating film 13 may be adjusted taking into account differences in the linear thermal expansion coefficients of the first electrode 12 and the first insulating film 13, etc. The difference between the height of the first electrode 12 and the thickness of the first insulating film 13 may be, for example, 20 nm or more and 0.5 μm or less.

[0022] From the viewpoint of bonding between electrodes, the surface of the tip of first electrode 12 may have a surface roughness Ra of 1 nm or less. The surface of the tip of second electrode 22 may also have a similar surface roughness Ra. The surface roughness Ra here is the arithmetic mean roughness (Ra) defined in JIS B 0601-2001.

[0023] The second circuit member 20 can also be prepared by forming a second resin film and heating it in a similar manner as above. The configurations (including height, thickness, and surface roughness Ra) of the second electrode 22 and the second insulating film 23 may be similar to those of the first electrode 12 and the first insulating film 13.

[0024] 2(e), the prepared first circuit member 10 and second circuit member 20 are aligned so that the first electrode 12 and second electrode 22 to be joined face to face. Then, as shown in FIG. 3, the first circuit member 10 and second circuit member 20 are heated and pressurized to bond the first electrode 12 and second electrode 22 together and to bond the first insulating film 13 and second insulating film 23 together.

[0025] The bonding of the first electrode 12 and the second electrode 22 and the bonding of the first insulating film 13 and the second insulating film 23 may proceed simultaneously or sequentially. For example, after heating and pressurizing mainly for bonding the first insulating film 13 and the second insulating film 23, the first circuit member 10 and the second circuit member 20 may be further heated and pressurized to bond the first electrode 12 and the second electrode 22. The first insulating film 13 and / or the second insulating film 23 may be further cured during the heating and pressurizing for bonding the first circuit member 10 and the second circuit member 20. The first insulating film 13 and / or the second insulating film 23 may be further cured by heating after bonding.

[0026] The heating and pressurizing conditions for bonding are adjusted so that the insulating film and the electrode are properly bonded. For example, the heating temperature for bonding may be 100°C or higher and 300°C or lower, and the pressure for bonding may be 1.0 MPa or higher and 10.0 MPa or lower. The heating and pressurizing time may be, for example, 10 seconds or higher and 1 hour or lower.

[0027] thermosetting resin composition The thermosetting resin composition used to form the organic insulating film (first insulating film 13 and / or second insulating film 23) in the above-described production method can be a thermosetting maleimide resin composition containing a maleimide compound having a maleimide group and an allyl compound having an allyl group.

[0028] The maleimide compound is a compound having one or more maleimide groups. The maleimide group may be a monovalent group represented by the following formula (I). From the viewpoints of improving the heat resistance and reducing the thermal expansion coefficient of the cured product, the thermosetting maleimide resin composition may contain a maleimide compound having two or more maleimide groups. [ka]

[0029] The maleimide compound may have an imide group containing a nitrogen atom directly bonded to a cyclic group (e.g., an aromatic group). For example, the maleimide compound in the thermosetting maleimide resin composition may include a compound represented by the following formula (Ia), (Ib), or (1c): [ka]

[0030] In formula (Ia), Q 1 and Q 2 each independently represents a cyclic group which may have a substituent; L 1 represents a divalent organic group or a single bond. 1 and Q 2 may each independently be an aromatic group (e.g., a phenylene group). 1 L may be a group containing one or more cyclic groups (excluding a maleimide group) selected from a monocyclic ring, a fused ring, a non-fused bridged ring, and a spiro ring, which may have a substituent, a linear alkylene group (e.g., a methylene group or a propane-1,3-diyl group) which may have a substituent, a propane-2,2-diyl group which may have a substituent, or a single bond. 1 L may have two or more cyclic groups and a single bond or a divalent organic group (for example, an optionally substituted methylene group, an optionally substituted propane-2,2-diyl group) connecting the two or more cyclic groups. 1 However, the cyclic group and Q 1 or Q 2 and L may further have a methylene group connecting them. 1However, L may have a cyclic group formed by removing one or more hydrogen atoms from benzene, 2,3-dihydro-1H-indene, or succinimide. Examples of the maleimide compound represented by formula (Ia) include compounds represented by formula (11) below. 1 is L in formula (Ia) 1 It is defined similarly to R 31 is an alkyl group having 1 to 3 carbon atoms, and p and q are each independently an integer of 0 to 4. 31 may be the same or different. [ka]

[0031] In formula (Ib), Q 3 represents a cyclic group which may have a substituent. 3 may be an aromatic group (e.g., a phenylene group). 3 The cyclic group therein may be substituted, for example, with a methyl group or a maleimide group.

[0032] In formula (Ic), Q 4 , Q 5 and Q 6 are each independently a cyclic group which may have a substituent, and L 2 and L 3 are each independently a divalent organic group or a single bond, and n is an integer of 1 or greater. 4 , Q 5 and Q 6 An example of this is Q 1 and Q 2 This is similar to the example in L 2 and L 3 An example of L 1 Examples of the maleimide compound represented by formula (Ic) include compounds represented by the following formula (12): 2 and L 3 represents L in formula (Ia). 1 and L 7 where n is an integer equal to or greater than 1. [ka]

[0033] Specific examples of the maleimide compound include compounds represented by the following formulas 101, 102, 103, 104, and 105. In these formulas, n represents an integer of 1 or more. [ka] [ka] [ka] [ka] [ka]

[0034] Examples of commercially available maleimide compounds include NE-X-9470S (trade name, DIC), MIR-3000-70MT (trade name, Nippon Kayaku), BMI-2300 (trade name, Yamato Chemical Industries), BMI-5100 (trade name, Yamato Chemical Industries), BMI-80 (trade name, Yamato Chemical Industries), BMI (trade name, Yamato Chemical Industries), and SFR-2300MR-T (trade name, Resonac).

[0035] The maleimide group of the maleimide compound may be blocked with a blocking agent that dissociates upon heating. In other words, the curable resin composition may contain a block maleimide compound having a blocked maleimide group. When the curable resin composition contains a block maleimide compound, the term "maleimide compound" in the following description can be read as "block maleimide compound."

[0036] The allyl compound is a compound having one or more allyl groups (2-propenyl groups, -CHCH=CH). From the viewpoints of improving the heat resistance and reducing the thermal expansion coefficient of the cured product, the thermosetting maleimide resin composition may contain an allyl compound having two or more allyl groups.

[0037] The allyl compound may include a compound having a cyclic group and an allyl group or an allyloxy group directly bonded to the cyclic group. For example, the allyl compound in the thermosetting maleimide resin composition may be represented by the following formula (IIa), (IIb), (IIc), or (IId): [ka] The compound may contain a compound represented by the following formula:

[0038] In formulas (IIa) and (IIb), Q 4 and Q 5 each independently represents a cyclic group which may have a substituent; L 4 represents a divalent organic group or a single bond. 4 and Q 5 may each independently be a group in which one or more hydrogen atoms have been removed from benzene, isocyanuric acid, or nadimide. 4 L may be a group containing one or more cyclic groups (excluding a maleimide group) selected from a monocyclic ring, a fused ring, a non-fused bridged ring, and a spiro ring, which may have a substituent, a linear alkylene group (e.g., a methylene group or a propane-1,3-diyl group) which may have a substituent, a propane-2,2-diyl group which may have a substituent, or a single bond. 4 L may have two or more cyclic groups and a single bond or a divalent organic group (for example, an optionally substituted methylene group, an optionally substituted propane-2,2-diyl group) connecting the two or more cyclic groups. 4 However, the cyclic group and Q 4 or Q 5 and L may further have a methylene group connecting them. 4 The cyclic group in L may be substituted with a substituent selected from, for example, a methyl group, a hydroxy group, and an allyl group. 2may have a phenylene group which may have a substituent.

[0039] In formulas (IIc) and (IId), Q 6 represents a cyclic group which may have a substituent. 6 However, it may be an aromatic group (e.g., a phenylene group) or a group in which one or more hydrogen atoms have been removed from isocyanuric acid. 3 The cyclic groups therein may be substituted, for example, with methyl or allyl groups.

[0040] Specific examples of the allyl compound include compounds represented by the following formulas 21, 22, 23, 24, 25, 26, 27, 28, 29, and 30. In these formulas, n represents an integer of 1 or more. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0041] Examples of commercially available allyl compounds include DABPA (trade name, Kanto Chemical), DA-BPF (trade name, Yokkaichi Chemical), LVA01 (trade name, Gun-ei Chemical Industry), BPA-AE (trade name, Konishi Chemical Industry), BANI-X (trade name, Maruzen Petrochemical), BANI-M (trade name, Maruzen Petrochemical), FATC-809 (trade name, Gun-ei Chemical Industry), FATC-809AP (trade name, Gun-ei Chemical Industry), DAIC (trade name, Shikoku Chemical Industry), and DD-1 (trade name, Shikoku Chemical Industry).

[0042] The content of the allyl compound may be 10% by mass or more and 70% by mass or less, based on the total amount of the maleimide compound and the allyl compound. The content of the allyl compound may be 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more, based on the total amount of the maleimide compound and the allyl compound, and may be 65% by mass or less, 60% by mass or less, or 55% by mass or less.

[0043] The thermosetting maleimide resin composition may further include a component that initiates or accelerates the reaction of the maleimide compound and the allyl compound.

[0044] The thermosetting maleimide resin composition may further contain a component that reduces the dielectric tangent of the cured product (hereinafter referred to as a "dielectric tangent adjuster"). The dielectric tangent adjuster may be, for example, a compound represented by the following formula (IIIa), (IIIb), or (IIIc): [ka] The aromatic compounds include those represented by the formula:

[0045] In formula (IIIa), R 11 , R 14 and R 15 each independently represents a hydrogen atom, a methyl group, or a t-butyl group; R 12 and R 13each independently represents a hydrogen atom, a hydroxy group, or an organic group having 1 to 30 carbon atoms; Z 1 represents an organic group having 7 to 80 carbon atoms and containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen, or an organic group having 2 to 15 carbon atoms and containing a carbonyl group.

[0046] In formula (IIIb), R 16 , R 19 , R 20 , R 21 , R 22 and R 25 each independently represents a hydrogen atom, a methyl group, or a t-butyl group; R 17 , R 18 , R 23 and R 24 each independently represents a hydrogen atom, a hydroxy group, or an organic group having 1 to 30 carbon atoms; Z 2 represents a divalent organic group having 1 to 50 carbon atoms or a divalent organic group having 1 to 75 carbon atoms, which contains at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen.

[0047] In formula (IIIc), R 26 , R 29 , R 30 , R 31 , R 34 , R 35 , R 36 , R 37 and R 40 each independently represents a hydrogen atom, a methyl group, or a t-butyl group; R 27 , R 28 , R 32 , R 33 , R 38 and R 39 each independently represents a hydrogen atom, a hydroxy group, or an organic group having 1 to 30 carbon atoms; Z 3 represents a trivalent organic group having 1 to 50 carbon atoms containing at least one heteroatom selected from the group consisting of sulfur, phosphorus, oxygen, and nitrogen, or a trivalent organic group having 1 to 50 carbon atoms.

[0048] The content of the dielectric loss tangent adjuster may be 1% by mass or more and 50% by mass or less, based on the total amount of the maleimide compound and the allyl compound. The content of the dielectric loss tangent adjuster may be 2% by mass or more or 5% by mass or more, based on the total amount of the maleimide compound and the allyl compound, and may be 50% by mass or less or 40% by mass or less.

[0049] The thermosetting maleimide resin composition may further contain a solvent that dissolves or disperses the maleimide compound and the allyl compound. Examples of the solvent include γ-butyrolactone, cyclohexanone, cyclopentanone, mesitylene, N,N-dimethylformamide, propylene glycol monomethyl ether acetate, and ethyl lactate. The content of the solvent may be 10% by mass or more and 90% by mass or less, based on the mass of the thermosetting maleimide resin composition. The content of the solvent may be 20% by mass or more, or 30% by mass or more, and 80% by mass or less, or 70% by mass or less, based on the mass of the thermosetting maleimide resin composition.

[0050] The thermosetting maleimide resin composition may further include an adhesion promoter, such as a silane coupling agent, an aluminum-based adhesion promoter, or a combination thereof.

[0051] Examples of silane coupling agents include tris[3-(trimethoxysilyl)propyl] isocyanurate, 3-aminopropyltriethoxysilane, triethoxy(3-glycidyloxypropyl)silane, trimethoxy(4-vinylphenyl)silane, and 1-[3-(trimethoxysilyl)propyl]urea, γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, Examples include 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, and N-phenylaminopropyltrimethoxysilane. The silane coupling agent may include at least one selected from the group consisting of tris[3-(trimethoxysilyl)propyl]isocyanurate, 3-aminopropyltriethoxysilane, triethoxy(3-glycidyloxypropyl)silane, trimethoxy(4-vinylphenyl)silane, and 1-[3-(trimethoxysilyl)propyl]urea. The silane coupling agent may include tris[3-(trimethoxysilyl)propyl]isocyanurate, 3-aminopropyltriethoxysilane, or a combination thereof.

[0052] Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0053] The content of the adhesion promoter may be, for example, 0.5% by mass or more and 25% by mass or less, based on the total amount of the maleimide compound and the allyl compound. The content of the silane coupling agent may be 0.5% by mass or more and 25% by mass or less, based on the total amount of the maleimide compound and the allyl compound. The content of the silane coupling agent may be 1.0% by mass or more, 1.5% by mass or more, 2.0% by mass or more, 2.5% by mass or more, 3.0% by mass or more, 3.5% by mass or more, 4.0% by mass or more, 4.5% by mass or more, 5.0% by mass or more, or 20% by mass or less, 15% by mass or less, 10% by mass or less, or 8.0% by mass or less, based on the total amount of the maleimide compound and the allyl compound.

[0054] The thermosetting maleimide resin composition may further contain a polymerization inhibitor, examples of which include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, 4-methoxyphenol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0055] The content of the polymerization inhibitor may be 0.005% by mass or more and 12% by mass or less based on the total amount of the maleimide compound and the allyl compound.

[0056] The thermosetting maleimide resin composition may further contain an azole compound. The azole compound is a compound having a five-membered heterocyclic ring containing a nitrogen atom and can function as a rust inhibitor. The azole compound may be a compound having a triazole ring or a tetrazole ring. Examples of azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, triazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole.

[0057] The content of the azole compound may be 0.1% by mass or more and 20% by mass or less, or 0.5% by mass or more and 5% by mass or less, based on the total amount of the maleimide compound and the allyl compound.

[0058] The thermosetting maleimide resin composition may contain a hindered phenol compound. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), and 4,4'-butylidene-bis(3-methyl-6-t-butylphenol). ol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2 '-Methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5 H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3 ,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5 -Tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)- Examples include 1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0059] The content of the hindered phenol compound may be 0.1% by mass or more and 20% by mass or less, or 0.5% by mass or more and 10% by mass or less, based on the total amount of the maleimide compound and the allyl compound.

[0060] The thermosetting maleimide resin composition may contain an organotitanium compound, such as a titanium chelate compound having two or more alkoxy groups, a tetraalkoxytitanium compound, a titanocene compound, a monoalkoxytitanium compound, a titanium oxide compound, a titanium tetraacetylacetonate compound, a titanate coupling agent, or a combination thereof.

[0061] Examples of titanium chelate compounds having two or more alkoxy groups include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate).

[0062] Examples of tetraalkoxytitanium compounds include titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, and titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}].

[0063] Examples of titanocene compounds include pentamethylcyclopentadienyltitanium trimethoxide, bis(η-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and bis(η-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.

[0064] Examples of monoalkoxytitanium compounds include titanium tris(dioctylphosphate) isopropoxide and titanium tris(dodecylbenzenesulfonate) isopropoxide.

[0065] Examples of titanium oxide compounds include titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), and phthalocyanine titanium oxide.

[0066] An example of a titanium tetraacetylacetonate compound is titanium tetraacetylacetonate.

[0067] An example of a titanate coupling agent is isopropyl tridodecylbenzenesulfonyl titanate.

[0068] The content of the organotitanium compound may be 0.05% by mass or more and 10% by mass or less, or 0.1% by mass or more and 2% by mass or less, based on the total amount of the maleimide compound and the allyl compound.

[0069] [Example] raw material The following maleimide compounds and allyl compounds were prepared. Maleimide compounds Phenylmethanemaleimide (compound of formula 104, BMI-2300, Daiwa Chemical Industry Co., Ltd.) 4,4'-Diphenylmethanebismaleimide (compound of formula 101, BMI, Daiwa Chemical Industry Co., Ltd.) Allyl compounds Arylphenol resin (compound of formula 23, LVA01, Gun-ei Chemical Industry Co., Ltd.) 2,2'-Diallylbisphenol A (Compound of Formula 21, DABPA, Kanto Chemical Co., Ltd.) Compound of formula 25 (BATE, synthesized according to conventional methods) Bisallylnadiimide (compound of formula 29, BANI-M, Maruzen Petrochemical Co., Ltd.)

[0070] Examples 1 to 4 (1) Thermal property evaluation of organic insulating films A thermosetting resin composition was prepared by mixing a maleimide compound and an allyl compound in the compounding ratio (parts by mass) shown in Table 1 while melting them by heating. The thermosetting resin composition was applied to a substrate using a bar coater to form a resin film. The resin film was heated at 175°C for 1 hour, at 200°C for 30 minutes, and at 250°C for 1 hour, in that order. The resin film was cured by this heating. An organic insulating film with a thickness of 100 μm was formed by curing the resin film.

[0071] (2) Glass transition temperature (Tg) The Tg of the organic insulating film was measured by dynamic mechanical analysis (DMA) under the following conditions: The temperature at which Tan δ showed a maximum value was recorded as Tg. Frequency: 10Hz Heating rate: 5℃ / min

[0072] (3) Coefficient of linear thermal expansion (CTE) The coefficient of linear thermal expansion (CTE) of the organic insulating film was measured by the TMA method. The CTE was determined in the temperature range of 50° C. to 100° C. The measurement results are shown in Table 1.

[0073] [Table 1]

[0074] (4) Bonding test The thermosetting resin composition of Example 2 was applied to a silicon wafer (diameter: 8 inches) using a spin coater. The coating was heated at 175°C for 1 hour, 200°C for 30 minutes, and 250°C for 1 hour, in that order. This heating cured the resin film. A 10 μm-thick organic insulating film was formed by the curing of the resin film. The silicon wafer was diced into individual pieces together with the organic insulating film using a blade dicing to obtain a lower test piece having a size of 8 mm × 8 mm and an upper test piece having a size of 4 mm × 4 mm. The upper test piece was overlapped on the center of the organic insulating film of the lower test piece, with the organic insulating films facing each other. In this state, the laminate of the lower test piece and the upper test piece was heated to 250°C and pressurized at a pressure of 2.6 MPa for 1 hour. This heating and pressurization formed a bonded structure in which the organic insulating film of the lower test piece and the organic insulating film of the upper test piece were bonded together. The shear strength at 60°C was measured by a peel test in which a load was applied to the upper test piece of the bonded structure along the bonding surface of the organic insulating film. In the peel test, peeling occurred in a mode that caused the silicon wafer to break, and the shear strength was 16.3 MPa. This result confirmed that organic insulating films formed from thermosetting resin compositions containing a maleimide compound and an allyl compound can be bonded together.

[0075] (Examples 5 to 8) A resin composition was prepared by mixing a maleimide compound and an allyl compound in the compounding ratio (parts by mass) shown in Table 2 while melting them by heating. The resin composition was applied to a substrate using a bar coater to form a resin film. The resin film was heated at 175°C for 1 hour, at 200°C for 30 minutes, and at 250°C for 1 hour, in that order. The resin film was cured by this heating. An organic insulating film with a thickness of 100 μm was formed by curing the resin film. The Tg of the organic insulating film was measured in the same manner as in Examples 1 to 4.

[0076] [Table 2]

[0077] Examples 9 to 14 Thermosetting resin compositions were prepared by mixing while melting by heating maleimide compounds and allyl compounds in the compounding ratios (parts by mass) shown in Table 2. Silane coupling agents A to E are the following compounds. silane coupling agent A: Triethoxy(3-glycidyloxypropyl)silane B: 1-[3-(trimethoxysilyl)propyl]urea C: Tris[3-(trimethoxysilyl)propyl] isocyanurate D: Trimethoxy(4-vinylphenyl)silane E: 3-aminopropyltriethoxysilane

[0078] Adhesives for shear testing A Cu film was formed on a silicon wafer by sputtering. Each thermosetting resin composition of Examples 9 to 14 was applied onto the Cu film by spin coating, and the coating was dried to form a resin film (10 μm thick) containing the thermosetting resin composition. The resin film was semi-cured by heating at 175°C for 1 hour in a nitrogen atmosphere. The semi-cured organic insulating film was then diced together with the silicon wafer and Cu film to obtain a lower chip component (8.0 mm wide). Each thermosetting resin composition of Examples 9 to 14 was applied directly onto a silicon wafer by spin coating without forming a Cu film, and the coating was dried to form a resin film (10 μm thick) containing the thermosetting resin composition. The resin film was semi-cured by heating at 175°C for 1 hour in a nitrogen atmosphere. The semi-cured organic insulating film was then diced together with the silicon wafer to obtain an upper chip component (4.0 mm wide). Using a flip-chip bonder, the upper chip component was placed on the lower chip component with the resin films facing each other, and the two components were pre-bonded at 150°C, 0.5 MPa, and 10 seconds, followed by 250°C, 2.0 MPa, and 5 minutes, to obtain a bonded assembly for shear testing.

[0079] Shear Test FIG. 4 is a schematic diagram illustrating the shear test method. The bonded structure 15 used for the shear test included a lower chip member 30 having a chip 31, a Cu film 32, and an organic insulating film 33, and an upper chip member 50 having a chip 41 and an organic insulating film 43. The shear strength of the bonded structure was measured using a shear tester. While the bonded structure 15 was heated on a stage at 60°C, a load was applied to the upper chip member 40 from the side of the upper chip member 40 using a head 55 moving at a speed of 20 μm / s. The shear strength was calculated from the load at the time the upper chip member 40 peeled off. The upper chip member 40, along with the organic insulating film 33 of the lower chip member 30, peeled off due to interfacial peeling between the organic insulating film 33 and the Cu film 32. The measurement results are shown in Table 3. [Table 3] [Explanation of symbols]

[0080] 1...circuit connector, 10...first circuit member, 11...first substrate, 12...first electrode, 13...first insulating film, 13a, 23a...opening, 13A...first resin film, 20...second circuit member, 21...second substrate, 22...second electrode, 23...second insulating film.

Claims

1. Formula (I): 【Chemistry 1】 a maleimide compound having a maleimide group represented by the formula: a reactive component other than the maleimide compound; Including, the reactive component comprises an allyl compound having an allyl group; Thermosetting resin composition for hybrid bonding.

2. The thermosetting resin composition for hybrid bonding according to claim 1 , further comprising a silane coupling agent.

3. The thermosetting resin composition for hybrid bonding according to claim 2, wherein the silane coupling agent comprises at least one selected from the group consisting of tris[3-(trimethoxysilyl)propyl]isocyanurate, 3-aminopropyltriethoxysilane, triethoxy(3-glycidyloxypropyl)silane, trimethoxy(4-vinylphenyl)silane, and 1-[3-(trimethoxysilyl)propyl]urea.

4. 3. The thermosetting resin composition for hybrid bonding according to claim 2, wherein the silane coupling agent comprises tris[3-(trimethoxysilyl)propyl]isocyanurate, 3-aminopropyltriethoxysilane, or a combination thereof.

5. The thermosetting resin composition for hybrid bonding according to claim 1 , further comprising an azole compound.

6. 2. The thermosetting resin composition for hybrid bonding according to claim 1, further comprising a solvent, the content of the solvent being 10% by mass or more and 90% by mass or less, based on the mass of the thermosetting resin composition.

7. 1. A method for manufacturing a circuit connector comprising a first circuit member having a first electrode and a second circuit member having a second electrode, the method comprising: The method comprises: heating the first resin film including the portion provided around the first electrode, thereby forming a first insulating film; joining the first circuit member and the second circuit member, which has the second electrode and a second insulating film including a portion provided around the second electrode, by hybrid bonding so that the first electrode and the second electrode are electrically connected; The method, wherein the first resin film comprises the thermosetting resin composition for hybrid bonding according to any one of claims 1 to 5.

8. 1. A method for manufacturing a circuit connector comprising a first circuit member having a first electrode and a second circuit member having a second electrode, the method comprising: The method comprises: heating the first resin film including the portion provided around the first electrode, thereby forming a first insulating film; heating the second resin film including the portion provided around the second electrode, thereby forming a second insulating film; and joining the first circuit member and the second circuit member by hybrid bonding so that the first electrode and the second electrode are electrically connected, The method, wherein the first resin film and the second resin film comprise the thermosetting resin composition for hybrid bonding according to any one of claims 1 to 5.

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