Curable resin composition and method for producing substrate laminate

Abstract

To provide a curable resin composition capable of forming an organic insulating layer having high bonding stability and excellent moisture resistance and durability in a substrate laminate using hybrid bonding and a method for producing a substrate laminate using the curable resin composition.SOLUTION: There is provided a curable resin composition used for forming a substrate laminate in a substrate laminate using hybrid bonding, wherein the curable resin composition comprises a thermosetting resin and an inorganic filler and the inorganic filler has a volume average particle diameter of 150 nm or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition and a method for producing a substrate laminate using the curable resin composition. [Background technology]

[0002] As semiconductor devices become more sophisticated, they are increasingly being made three-dimensional by stacking multiple semiconductor chips. In such substrate stacks where multiple semiconductor chips are stacked, electrodes on the substrates have traditionally been joined via solder, but in recent years hybrid bonding has been considered as a method for joining electrodes.

[0003] Figure 1 shows a schematic diagram illustrating the manufacturing process of a substrate laminate using hybrid bonding. In hybrid bonding, first, an electrode 3 and an insulating layer 4 are formed on one side of a first substrate 1 and a second substrate 2. Next, the surfaces on which the electrode 3 and insulating layer 4 are formed are polished and flattened, and then the electrodes 3 and insulating layers 4 of the first substrate 1 and the second substrate 2 are simultaneously bonded by high-temperature treatment to obtain a substrate laminate. A substrate laminate produced by hybrid bonding has excellent properties, such as shorter wiring distances and improved electrical properties and packaging density, because it does not use solder.

[0004] In hybrid bonding, inorganic materials such as SiO2 have been considered for the insulating layer, but the use of inorganic insulating layers has the problem of prone to bonding failure when foreign matter or voids get trapped between the substrates. Therefore, it has been proposed to use a resin material such as a thermosetting resin for the insulating layer (for example, Patent Documents 1 and 2). By using a resin material for the insulating layer, even if foreign matter or voids get trapped, they can be embedded in the insulating layer, thereby preventing bonding failure. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2021-197430 [Patent Document 2] Japanese Patent Publication No. 2023-039804 Summary of the Invention [Problem to be solved by the invention]

[0006] However, insulating layers using resin materials such as those described in Patent Documents 1 and 2 have problems with reliability, such as poor moisture resistance (peeling due to moisture) and durability against temperature changes (peeling due to temperature cycles). Therefore, the use of inorganic fillers to improve the reliability of insulating layers has been considered, but the use of inorganic fillers in insulating layers has the problem of easily causing scratches when the insulating layer and electrodes are polished and flattened. Scratches on the bonding surfaces of the substrates reduce bonding stability and moisture resistance, so there is a need for insulating layers that use resin materials but have excellent bonding stability, moisture resistance, and durability.

[0007] The present invention aims to provide a curable resin composition capable of forming an organic insulating layer having high bonding stability and excellent moisture resistance and durability in a substrate laminate using hybrid bonding, and a method for manufacturing a substrate laminate using the curable resin composition. [Means for solving the problem]

[0008] The present invention is comprised of the following Disclosures 1 to 8. The present invention will be described in detail below. [Disclosure 1] A curable resin composition used to form an organic insulating layer in a substrate laminate using hybrid bonding, The composition includes a thermosetting resin and an inorganic filler, The curable resin composition, wherein the inorganic filler has a volume average particle size of 150 nm or less. [Disclosure 2] The curable resin composition according to Disclosure 1, wherein the content of the inorganic filler in 100% by weight of the curable resin composition is 30% by weight or more. [Disclosure 3] The curable resin composition according to claim 1 or 2, wherein the inorganic filler is silica. [Disclosure 4] The curable resin composition according to any one of Disclosures 1 to 3, wherein the thermosetting resin contains at least one selected from the group consisting of a phenoxy resin, a polyimide resin, a polyimide precursor, a polyamide resin, a maleimide resin, and an epoxy resin. [Disclosure 5] 5. The curable resin composition according to any one of Aspects 1 to 4, wherein the inorganic filler has a volume average particle size of 90 nm or less. [Disclosure 6] 5. The curable resin composition according to claim 4, wherein the thermosetting resin contains a polyfunctional maleimide resin. [Disclosure 7] 7. The curable resin composition according to any one of Disclosures 1 to 6, wherein the cured product obtained by heat treatment at 140°C for 30 minutes has a storage modulus at 25°C of 2 GPa or more. [Disclosure 8] forming a film of the curable resin composition according to Disclosure 1 or 2 on an electrode surface of a first substrate having an electrode; a step of curing the formed curable resin composition to form an organic insulating layer; polishing the organic insulating layer of the first substrate; forming an insulating layer on an electrode surface of a second substrate having an electrode; polishing the insulating layer of the second substrate; activating the electrode surface of at least one of the polished first substrate or the polished second substrate; and joining an electrode of the first substrate to an electrode of the second substrate.

[0009] The curable resin composition of the present invention contains a thermosetting resin. By using a cured thermosetting resin as the insulating film of the substrate laminate formed by hybrid bonding, even if foreign matter or voids are trapped during bonding of the substrates, these can be filled in and bonding failure of the substrates can be prevented. Furthermore, even if warping occurs in the substrate, stress can be alleviated and the warping can be eliminated.

[0010] The thermosetting resin may be a resin containing a polymerizable compound and, if necessary, a curing agent. Since high-temperature treatment is performed during substrate bonding, the polymerizable compound preferably has excellent heat resistance when cured. Examples of such polymerizable compounds include phenoxy resin, polyimide resin, polyimide precursor, polyamide resin, maleimide resin, epoxy resin, and silicone resin. Among these, the thermosetting resin preferably contains at least one selected from the group consisting of phenoxy resin, polyimide resin, polyimide precursor, polyamide resin, maleimide resin, and epoxy resin, due to its excellent adhesive strength. Epoxy resin or maleimide resin is more preferred, and maleimide resin is even more preferred due to its particularly excellent moisture resistance.

[0011] Examples of the epoxy resin include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, biphenyl type epoxy resins, biphenyl novolac type epoxy resins, biphenol type epoxy resins, naphthalene type epoxy resins, fluorene type epoxy resins, phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, anthracene type epoxy resins, epoxy resins having an adamantane skeleton, epoxy resins having a tricyclodecane skeleton, and epoxy resins having a triazine nucleus in the skeleton.

[0012] The maleimide resin is preferably a polyfunctional maleimide resin, since it can easily increase the elastic modulus after curing. Examples of polyfunctional maleimide resins include bismaleimide and trifunctional or higher functional maleimide compounds. Examples of bismaleimide include bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, 1,4-bis(maleimido)butane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 1,2-bis(maleimido)ethane, N,N'-1,4-phenylenedimaleimide, N,N'-1,3-phenylenedimaleimide, and 4,4'-bismaleimidodiphenylmethane. Examples of trifunctional or higher functional maleimide compounds include phenylaralkyl-type maleimide compounds, tolylaralkyl-type maleimide compounds, and biphenylaralkyl-type maleimide compounds.

[0013] The content of the polymerizable compound, or the total content of the polymerizable compound and the curing agent when the curing agent is contained, is preferably 20% by weight or more, more preferably 30% by weight or more, and preferably 90% by weight or less, and more preferably 80% by weight or less, based on 100% by weight of the curable resin composition. By having the content of the polymerizable compound within the above range, the organic insulating layer formed from the curable resin composition of the present invention can be imparted with superior heat resistance and moisture resistance, and even if foreign matter or voids are trapped during bonding of substrates, these can be filled to prevent bonding failure of the substrates. In this specification, "100% by weight of the curable resin composition" refers to 100% by weight of the components (solids) of the curable resin composition excluding the solvent.

[0014] Examples of the curing agent include active ester compounds, acid anhydride compounds, phenol compounds, and amine compounds when the polymerizable compound is an epoxy resin; and examples of the curing agent include vinyl compounds, styryl compounds, allyl compounds, and (meth)acrylic compounds when the polymerizable compound is a maleimide resin.

[0015] The curable resin composition of the present invention may contain a curing accelerator. The use of the curing accelerator can shorten the curing time of the thermosetting resin. Examples of the curing accelerator include imidazole-based curing accelerators, tertiary amine-based curing accelerators, phosphine-based curing accelerators, photobase generators, sulfonium salt-based curing accelerators, organic peroxide initiators, and azo compound initiators.

[0016] From the viewpoint of further promoting curing, the content of the curing accelerator is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and is preferably 10% by weight or less, more preferably 5% by weight or less, based on 100% by weight of the curable resin composition.

[0017] The curable resin composition of the present invention may contain a film-forming agent. By using a film-forming agent, film-forming properties can be further improved. Examples of the film-forming agent include phenoxy resin, acrylic resin, polyimide resin, polyamide resin, polyamideimide resin, and silicone resin.

[0018] From the viewpoint of further enhancing film-forming properties, the content of the film-forming agent is preferably 0.1% by weight or more, more preferably 1% by weight or more, and is preferably 50% by weight or less, more preferably 40% by weight or less, based on 100% by weight of the curable resin composition.

[0019] Examples of additives other than the curing accelerator and film-forming agent include adhesion promoters, dispersants, surfactants, pigments, dyes, and the like.

[0020] The curable resin composition of the present invention contains an inorganic filler. By using an inorganic filler in the curable resin composition, it is possible to reduce the linear expansion coefficient and to impart excellent moisture resistance to the cured organic insulating layer. Examples of materials for the inorganic filler include silica, talc, asbestos, gypsum, diatomaceous earth, smectite, glass beads, alumina, zinc oxide, magnesium oxide, etc. Among these, silica is preferred as the inorganic filler because it further enhances the heat resistance and moisture resistance of the organic insulating layer.

[0021] The inorganic filler has a volume average particle size of 150 nm or less. In conventional substrate laminates using hybrid bonding, it was thought that the use of fillers in the organic insulating layer should be avoided because they could cause pinching. Furthermore, even when fillers are used, the larger the particle size, the higher the packing density. Therefore, it was thought that a larger particle size of filler would be preferable from the perspective of significantly improving the linear expansion coefficient and moisture absorption. On the other hand, in the present invention, by intentionally reducing the volume average particle size of the inorganic filler, it is possible to reduce the likelihood of filler detachment and scratches caused by detached filler during the process of planarizing (polishing) the bonding surfaces of the substrates. As a result, the flatness of the bonding surfaces after polishing is improved, and detached filler is less likely to become embedded as foreign matter, thereby improving the bonding stability of the substrates. Furthermore, improved substrate bonding stability suppresses the intrusion of moisture through gaps caused by foreign matter or scratches, thereby improving the moisture resistance and durability (long-term reliability against temperature changes) of the substrate laminate. The reason why the durability of the substrate laminate is improved by setting the volume average particle size of the inorganic filler within the above range is unclear, but the following reasons are thought to be involved.

[0022] When substrates are bonded, there are areas on the bonding surface where the organic insulating layers contact each other, where the organic insulating layer and the inorganic filler contact each other, and where the inorganic fillers contact each other. However, the areas where the inorganic fillers contact each other have a lower adhesive strength than the areas where the organic insulating layers contact each other, resulting in weaker bonding. The area where the inorganic fillers contact each other is proportional to the area of ​​the inorganic filler exposed on the bonding surface of each substrate. When the volume average particle diameter of the inorganic filler is small, the number of inorganic fillers exposed on the bonding surface of the substrate increases, but the cross-sectional area decreases. As a result, when the volume average particle diameter of the inorganic filler is within the above range, the area of ​​exposed inorganic filler on the entire bonding surface is small, and the area where the inorganic fillers contact each other is also small, which is thought to improve durability.

[0023] The volume average particle diameter of the inorganic filler is preferably 90 nm or less, more preferably 80 nm or less, and even more preferably 70 nm or less, in order to further improve the moisture resistance and durability of the substrate laminate. The lower limit of the volume average particle diameter of the inorganic filler is not particularly limited, but is preferably 5 nm or more, more preferably 10 nm or more, in order to further improve the coatability of the curable resin composition. The volume average particle diameter can be measured by dynamic light scattering or the like. Specifically, a dispersion of the inorganic filler in methanol is prepared so that the concentration is 0.05 mg / L, and the volume average particle diameter can be measured using a nanoparticle analyzer (nanoPartica SZ-100V2, manufactured by Horiba, Ltd., or an equivalent).

[0024] The inorganic filler is preferably surface-treated with a silane coupling agent. By surface treating the inorganic filler with a silane coupling agent, aggregation of the inorganic filler can be suppressed even when a large amount of the inorganic filler is blended. Furthermore, adhesion at the interface with the thermosetting resin can be improved, and moisture resistance can be improved. Examples of the silane coupling agent include aminosilane, methacrylsilane, mercaptosilane, epoxysilane, isocyanatesilane, alkylsilane, and phenylsilane.

[0025] The content of the inorganic filler in the curable resin composition is preferably 30% by weight or more based on 100% by weight of the curable resin composition. By setting the content of the inorganic filler within the above range, it is possible to make the surface less susceptible to scratches during the process of planarizing (polishing) the bonding surfaces of the substrates, and to further improve the bonding stability, moisture resistance, and durability of the substrates. The content of the inorganic filler is more preferably 35% by weight or more, and even more preferably 40% by weight or more, and is preferably 90% by weight or less, and more preferably 80% by weight or less, based on 100% by weight of the curable resin composition.

[0026] The curable resin composition of the present invention preferably has a storage modulus at 25°C of 2 GPa or more after heat treatment at 140°C for 30 minutes. When the storage modulus at 25°C of the cured product is within the above range, surface scratches due to polishing can be more unlikely to occur. The storage modulus at 25°C of the cured product is more preferably 2.5 GPa or more, and even more preferably 3.0 GPa or more. There is no particular upper limit to the storage modulus at 25°C of the cured product, but from the viewpoint of obtaining a certain level of processing speed during polishing, it is preferably 15 GPa or less. The storage modulus of the cured product at 25°C can be increased, for example, by increasing the degree of crosslinking of the cured product or by increasing the content of inorganic filler. The storage modulus can be obtained by measuring dynamic viscoelasticity under the conditions described in the Examples.

[0027] The curable resin composition of the present invention is used to form an organic insulating layer in a substrate laminate by hybrid bonding. By using the curable resin composition of the present invention to form an organic insulating layer in the production of a substrate laminate by hybrid bonding, the bonding stability of the substrates can be improved and the obtained substrate laminate can be imparted with excellent moisture resistance and durability. The present invention also provides a method for manufacturing a substrate laminate, comprising the steps of: forming a film of the curable resin composition according to claim 1 or 2 on an electrode surface of a first substrate having such electrodes; curing the formed film of the curable resin composition to form an organic insulating layer; polishing the organic insulating layer of the first substrate; forming an insulating layer on an electrode surface of a second substrate having electrodes; polishing the insulating layer of the second substrate; activating the polished electrode surface of at least one of the first substrate or the second substrate; and bonding the electrode of the first substrate to the electrode of the second substrate.

[0028] The method for producing a substrate laminate of the present invention first involves a step of forming a film of the curable resin composition of the present invention on the electrode surface of a first substrate having an electrode. Examples of methods for forming a film from the curable resin composition of the present invention include spin coating, slit coating, curtain coating, etc. Alternatively, a film may be formed in advance on a release-treated substrate film by solvent casting, and then the film may be supplied to the surface of a substrate by lamination, followed by peeling off the release-treated substrate.

[0029] The first substrate is not particularly limited, and may be a circuit element having elements and wiring formed thereon, such as a sensor circuit element provided with a pixel section (pixel region), a circuit element having a peripheral circuit section such as a logic circuit that performs various signal processing related to the operation of the solid-state imaging device, or a circuit element having a peripheral circuit such as a memory circuit.

[0030] The material of the electrodes is not particularly limited, and conventionally known electrode materials such as gold, copper, aluminum, and nickel can be used.

[0031] The thickness of the electrodes is not particularly limited, but from the viewpoint of shortening the wiring distance while ensuring the reliability of electrical connection and from the viewpoint of reducing the thickness of the resulting substrate laminate, it is preferable that the thickness after the polishing step described below is 0.1 μm or more and 20 μm or less.

[0032] The method for producing a substrate laminate of the present invention then carries out a step of curing the formed curable resin composition to form an organic insulating layer. The curable resin composition is heated to cure the thermosetting resin, thereby forming an organic insulating layer disposed between the first substrate and the second substrate. The temperature at which the curable resin composition is cured is determined depending on the thermosetting resin constituting the curable resin composition, and may be, for example, 80°C to 200°C.

[0033] The method for producing a substrate laminate of the present invention then carries out a step of polishing the organic insulating layer of the first substrate. By polishing the surface on which the organic insulating layer is formed, the organic insulating layer formed on the electrode can be removed and the surface can be planarized to improve bonding stability. In the method for producing a substrate laminate of the present invention, the volume average particle diameter of the inorganic filler in the curable resin composition that is the material for the organic insulating layer is set to a certain value or less, so that the inorganic filler is less likely to fall off or be damaged on the surface even when polished. As a result, the bonding stability of the obtained substrate laminate can be improved, and the moisture resistance and durability can be enhanced. The polishing is carried out until the electrode is completely exposed. Examples of the polishing method include CMP (Chemical Mechanical Polishing) and flycut processing.

[0034] The method for producing a substrate laminate of the present invention includes a step of forming an insulating layer on the electrode surface of a second substrate having an electrode. The second substrate is a substrate laminated on the first substrate, and the same substrate type and electrodes as those of the first substrate can be used. The insulating layer may be an organic insulating layer formed by the same method as that for the first substrate, or an insulating layer made of an inorganic material may be formed.

[0035] Examples of the inorganic material include SiO2, SiCN, SiON, etc. The insulating layer made of the inorganic material can be formed by, for example, PECVD (plasma enhanced chemical vapor deposition).

[0036] The method for producing a substrate laminate of the present invention then carries out a step of activating the electrode surface of at least one of the polished first substrate or second substrate. By activating the electrode surface of at least one of the first substrate or the second substrate after the polishing step, foreign matter on the surface can be removed and the adhesive strength can be improved, thereby improving bonding stability and durability. Examples of the activation method include a method in which plasma treatment is performed followed by surface treatment with an NaOH solution.

[0037] The method for manufacturing a substrate laminate of the present invention then carries out a step of bonding the electrodes of the first substrate and the electrodes of the second substrate. The electrodes of the first substrate and the electrodes of the second substrate are stacked and thermocompression bonded so that they are connected to each other, and the electrodes and insulating layers (organic insulating layer and inorganic insulating layer) of the two substrates are bonded to each other to obtain a substrate laminate. Examples of thermocompression bonding conditions for bonding the first substrate and the second substrate include 300°C, 10 minutes, and 10 MPa. [Effects of the Invention]

[0038] According to the present invention, it is possible to provide a curable resin composition capable of forming an organic insulating layer having high bonding stability and excellent moisture resistance and durability in a substrate laminate using hybrid bonding, and a method for manufacturing a substrate laminate using the curable resin composition. [Brief explanation of the drawings]

[0039] [Figure 1] 1A to 1C are schematic diagrams illustrating the manufacturing process of a substrate laminate by hybrid bonding. DETAILED DESCRIPTION OF THE INVENTION

[0040] The following examples will further illustrate the present invention, but the present invention is not limited to these examples.

[0041] (1) Production of a composition of maleimide-based thermosetting resin and additives A composition of maleimide-based thermosetting resin and additives (referred to as "maleimide" in the table) was obtained by adding 30 parts by weight of MIR-3000-70T (biphenylaralkyl-type maleimide compound, manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, 30 parts by weight of BMI689 (bismaleimide, manufactured by Design Molecules), 40 parts by weight of OPE-2St (manufactured by SABIC) as a film-forming agent and curing agent, and 5 parts by weight of 2E4MZ (imidazole, manufactured by Shikoku Kasei Co., Ltd.) as a curing accelerator to cyclohexanone and kneading them together.

[0042] (2) Manufacturing of epoxy thermosetting resin and additive compositions A composition of epoxy thermosetting resin and additives (referred to as "epoxy" in the table) was obtained by adding 40 parts by weight of NC3000 (biphenylaralkyl epoxy resin, manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, 40 parts by weight of YL980 (bisphenol A epoxy resin, manufactured by Mitsubishi Chemical Corporation), 5 parts by weight of 2E4MZ (imidazole, manufactured by Shikoku Chemical Industry Co., Ltd.) as a curing accelerator, 20 parts by weight of YX6954BH30 (manufactured by Mitsubishi Chemical Corporation) as a film-forming agent, and 80 parts by weight of HPC-8000-65T (active ester, manufactured by DIC Corporation) as a curing agent to cyclohexanone and kneading them.

[0043] Example 1 <Production of Curable Resin Composition> To the obtained composition of maleimide-based thermosetting resin and additives, YA010C-SP3 (silica filler, manufactured by Admatechs Co., Ltd., volume average particle size: 10 nm, phenylsilane treatment) was added as an inorganic filler so that the content relative to the solid content was 30 wt %, and the mixture was kneaded to obtain a curable resin composition.

[0044] <Production of substrate laminate> An 8-inch silicon wafer with electrodes was prepared as the first substrate. A curable resin composition obtained by spin coating was applied to the electrode side of the 8-inch silicon wafer. The solvent was then dried in a circulating oven at 100°C for 2 minutes to form a 5 μm-thick organic film. The resulting film was then heated in a circulating oven at 140°C for 30 minutes to form an organic insulating layer consisting of the cured organic film. The organic insulating layer was then polished using a CMP system (ARW-8C1MS, manufactured by MAT) with a polyurethane polishing pad (IC1000, manufactured by Nitta DuPont) and a silica-blended slurry (COMPOL80, manufactured by Fujimi Incorporated), followed by finish polishing using a suede-type finish polishing pad. The wafer was then subjected to CMP by cleaning with a cleaning solution (CMP-B01, manufactured by Kanto Chemical Co., Ltd.) using a cleaning system (ZAB-8S1M, manufactured by MAT) to remove the organic insulating layer on the electrodes and flatten the surface. On the other hand, a second substrate was prepared, consisting of a 500 nm thick SiO2 insulating layer laminated on the electrode-bearing surface of the same substrate as the first substrate. The SiO2 insulating layer of the second substrate was subjected to CMP in the same manner as the first substrate to flatten the surface. Next, the SiO2 insulating layer of the second substrate was subjected to O2 plasma treatment using a plasma treatment device (OP-300, manufactured by SAMCO Corporation), and the surface was activated by surface treatment with a 0.5 N NaOH aqueous solution. The electrodes of the first substrate and the second substrate were then stacked facing each other, and the wafer was heated from room temperature to 200°C using a wafer bonding device (EVG510, manufactured by EVG Corporation), followed by thermocompression bonding at 1 MPa for 60 minutes to obtain a substrate laminate.

[0045] <Measurement of storage modulus after curing> A measurement sample consisting of only a 20 μm-thick organic insulating layer was prepared in the same manner as in the production of the substrate laminate, except that the curable resin composition was applied to a release-treated PET film instead of a silicon wafer. The obtained measurement sample was measured using a dynamic viscoelasticity measuring device (DMA7100, manufactured by Hitachi High-Tech Corporation) under conditions of a frequency of 10 Hz, a heating rate of 5°C / min, and a measurement range of 0 to 40°C, to measure the storage modulus at 25°C.

[0046] (Examples 2 to 7, Comparative Example 2) Curable resin compositions and substrate laminates were obtained in the same manner as in Example 1, except that the types and contents of the thermosetting resin and additive compositions, and the types and contents of the inorganic fillers were as shown in Table 1, and the storage modulus after curing was measured. The details of the inorganic filler (silica filler) having each volume average particle size are as follows: 50 nm: Sciqas 0.05 μm, phenylsilane treated, Sakai Chemical Industry Co., Ltd. 100 nm: Sciqas 0.1 μm, phenylsilane treated, Sakai Chemical Industry Co., Ltd. 110 nm: QSG-100, phenylsilane treated, manufactured by Shin-Etsu Silicone Co., Ltd. 250 nm: SC2050, phenylsilane treatment, manufactured by Admatechs Co., Ltd.

[0047] (Comparative Example 1) A curable resin composition and a substrate laminate were obtained in the same manner as in Example 1, except that no inorganic filler was added and the organic insulating layer was polished using only a suede-type finish polishing pad, and the storage modulus after curing was measured.

[0048] <Evaluation> The curable resin compositions obtained in the examples and comparative examples were evaluated as follows, and the results are shown in Table 1.

[0049] (Evaluation of scratches after CMP) The polished surface of the first substrate after CMP was visually observed, and if scratches were observed on the surface, it was marked with "X." If no scratches were observed visually but filler loss was observed when the surface was observed with an electron microscope (SEM), or if the surface was observed with a stylus profiler (P15, manufactured by KLA Tencor) and the surface roughness Ra was greater than 80 nm, it was marked with "△." If no scratches or filler loss were observed visually or with an electron microscope and the surface roughness Ra was 80 nm or less, it was marked with "○." Scratches after CMP were evaluated as follows.

[0050] (Reliability assessment) (1) Reflow resistance test (moisture resistance) evaluation The obtained substrate laminate was evaluated for reflow resistance reliability in accordance with IPC / JEDEC J-STD-020C MSL Level 2a or Level 3. Specifically, the substrate laminate was allowed to absorb moisture at 60°C and 60% RH for 120 hours (Level 2a) or 40 hours (Level 3), and then heated three times at a peak temperature of 260°C. After that, the presence or absence of delamination of the substrate laminate was measured using an ultrasonic inspection device (D9600, manufactured by Sonoscan), and the moisture resistance was evaluated according to the following criteria. ○: No peeling was observed even under Level 2a conditions △: No peeling was observed under Level 3 conditions, but peeling was observed under Level 2a conditions. ×: Peeling was observed under Level 3 conditions

[0051] (2) Temperature cycle test (durability) evaluation The obtained substrate laminate was subjected to the above-mentioned reflow resistance test under Level 3 conditions. Next, a temperature cycle test was conducted in which the temperature was changed between -40°C and 125°C for 1,000 or 2,000 cycles. The holding time on both the high and low temperature sides was 30 minutes. For the substrate laminate after the temperature cycle test, durability was evaluated as follows: "Good" if peeling did not progress after the reflow resistance test; "Fair" if peeling did not occur across the entire surface but progressed after the reflow resistance test; and "Poor" if peeling occurred across the entire surface.

[0052] [Table 1] [Industrial Applicability]

[0053] According to the present invention, it is possible to provide a curable resin composition capable of forming an organic insulating layer having high bonding stability and excellent moisture resistance and durability in a substrate laminate using hybrid bonding, and a method for manufacturing a substrate laminate using the curable resin composition. [Explanation of symbols]

[0054] 1 First board 2 Second board 3 electrodes 4. Insulation layer

Claims

1. A curable resin composition used to form an organic insulating layer in a substrate laminate using hybrid bonding, The composition includes a thermosetting resin and an inorganic filler, The curable resin composition, wherein the inorganic filler has a volume average particle size of 150 nm or less.

2. 2. The curable resin composition according to claim 1, wherein the content of the inorganic filler in 100% by weight of the curable resin composition is 30% by weight or more.

3. The curable resin composition according to claim 1 or 2, wherein the inorganic filler is silica.

4. 3. The curable resin composition according to claim 1, wherein the thermosetting resin comprises at least one selected from the group consisting of a phenoxy resin, a polyimide resin, a polyimide precursor, a polyamide resin, a maleimide resin, and an epoxy resin.

5. The curable resin composition according to claim 1 or 2, wherein the inorganic filler has a volume average particle size of 90 nm or less.

6. The curable resin composition according to claim 4 , wherein the thermosetting resin contains a polyfunctional maleimide resin.

7. 3. The curable resin composition according to claim 1, wherein the cured product obtained by heat treatment at 140°C for 30 minutes has a storage modulus at 25°C of 2 GPa or more.

8. forming a film of the curable resin composition according to claim 1 or 2 on an electrode surface of a first substrate having an electrode; a step of curing the formed curable resin composition to form an organic insulating layer; polishing the organic insulating layer of the first substrate; forming an insulating layer on an electrode surface of a second substrate having an electrode; polishing the insulating layer of the second substrate; activating the electrode surface of at least one of the polished first substrate or the polished second substrate; and joining the electrodes of the first substrate and the electrodes of the second substrate.

Images