Semiconductor structure and method for manufacturing the same

Abstract

A semiconductor structure has a semiconductor substrate including a semiconductor substrate bonding layer including an insulating layer and an electrode, a composite substrate including a plurality of silicon dies in a two-dimensional configuration and an organic gap filling material filled between the plurality of silicon dies, and an intermediate bonding layer disposed between the plurality of silicon dies. And an intermediate bonding layer interposed between the semiconductor substrate bonding layer in the semiconductor substrate and the composite substrate, the intermediate bonding layer including an insulating layer and an electrode, the semiconductor substrate bonding layer in the semiconductor substrate being hybrid-bonded to the intermediate bonding layer.

Description

Technical Field

[0001] The present disclosure relates to semiconductor structures and methods of manufacturing the same. Background Art

[0002] In recent years, from the viewpoint of high integration of semiconductor devices, a technique of stacking a semiconductor substrate and a semiconductor chip (eg, a silicon bare die) in a thickness direction has been studied.

[0003] For example, Patent Document 1 discloses a semiconductor structure including: a die group provided on a wiring layer; and an inorganic gap-filling material containing silicon provided on the wiring layer and surrounding the die group.

[0004] Patent Document 1: U.S. Patent Publication No. 2022 / 0013504 Summary of the Invention

[0005] Problems to be solved by the invention

[0006] However, in the technology of stacking a semiconductor substrate and a silicon bare die in the thickness direction, hybrid bonding is being developed as a technology for performing bonding at a high density in order to improve data transmission per unit area.

[0007] In the present disclosure, hybrid bonding refers to bonding in which electrodes are bonded to each other and insulating films are bonded to each other by bringing two surfaces of the electrode and the insulating material exposed into contact with each other.

[0008] In a semiconductor structure having a semiconductor substrate, a plurality of silicon dies, and a gap-filling material bonded by hybrid bonding, when the inorganic gap-filling material described in Patent Document 1 is used as the gap-filling material, warping of the semiconductor structure may occur due to film stress of the inorganic gap-filling material.

[0009] The present disclosure has been made in view of the above-mentioned problems.

[0010] The subject of one embodiment of the present disclosure is to provide a semiconductor structure with suppressed warping and a method for manufacturing the same. The semiconductor structure comprises a semiconductor substrate, a composite substrate and an intermediate bonding layer. The semiconductor substrate includes a semiconductor substrate bonding layer. The composite substrate includes a plurality of two-dimensionally arranged silicon dies and a gap-filling material filled between the plurality of silicon dies. The intermediate bonding layer is interposed between the composite substrate and the semiconductor substrate bonding layer in the semiconductor substrate, and the semiconductor substrate bonding layer and the intermediate bonding layer are hybrid-bonded.

[0011] Means for solving problems

[0012] Specific means for solving the above-mentioned problems include the following aspects.

[0013] <1> A semiconductor structure comprising:

[0014] A semiconductor substrate comprising a semiconductor substrate bonding layer, wherein the semiconductor substrate bonding layer comprises an insulating layer and an electrode,

[0015] A composite substrate comprising a plurality of two-dimensionally arranged silicon dies and an organic gap-filling material filled between the plurality of silicon dies, and

[0016] an intermediate bonding layer comprising an insulating layer and an electrode, and disposed between the semiconductor substrate and the composite substrate;

[0017] The semiconductor substrate bonding layer and the intermediate bonding layer in the semiconductor substrate are mixed and bonded.

[0018] <2> according to <1> In the semiconductor structure, the intermediate bonding layer is arranged across at least two of the plurality of silicon dies.

[0019] <3> according to <1> or <2> The semiconductor structure further comprises a redistribution layer including an insulating layer and wirings between the composite substrate and the intermediate bonding layer.

[0020] <4> according to <3> In the semiconductor structure, at least two of the plurality of silicon bare chips are electrically connected via the redistribution layer.

[0021] <5> according to <3> or <4> In the semiconductor structure, the insulating layer in the redistribution layer includes at least one selected from the group consisting of a SiO 2 layer, a SiCN layer, a SiN layer, and a resin layer containing a siloxane bond.

[0022] <6> according to <1> ~ <5> In any one of the semiconductor structures, the insulating layer in the semiconductor substrate bonding layer and the insulating layer in the intermediate bonding layer each contain at least one selected from the group consisting of a SiO2 layer, a SiCN layer, a SiN layer and a resin layer containing a siloxane bond.

[0023] <7> according to <1> ~ <6> In any one of the semiconductor structures, the organic gap-filling material comprises at least one selected from the group consisting of polyimide, polyamide, polyamideimide, maleimide resin, parylene, polyarylene ether polyimide, polybenzoxazole, benzocyclobutene resin, epoxy resin and resin having a siloxane bond.

[0024] <8> A method for manufacturing a semiconductor structure, comprising: <1> ~ <7> The method of any one of the semiconductor structures, comprising:

[0025] a step of two-dimensionally arranging and temporarily fixing a plurality of silicon bare chips on a first temporary fixing substrate, and then filling the organic gap filling material between the plurality of silicon bare chips to form the composite substrate on the first temporary fixing substrate;

[0026] A step of temporarily fixing a second temporary fixing substrate on the side opposite to the side where the first temporary fixing substrate is arranged when viewed from the composite substrate to obtain a laminated body X1;

[0027] a step of removing the first temporary fixing substrate from the stacked body X1 to obtain a stacked body X2 in which the plurality of silicon bare dies are exposed;

[0028] A step of preparing the semiconductor substrate including the semiconductor substrate bonding layer, wherein the semiconductor substrate bonding layer includes the insulating layer and the electrode;

[0029] forming an intermediate bonding layer including an insulating layer and electrodes on the exposed surfaces of the plurality of silicon bare chips in the stacked body X2;

[0030] a step of hybridly bonding the intermediate bonding layer in the stacked body X2 having the intermediate bonding layer formed thereon and the semiconductor substrate bonding layer in the semiconductor substrate to obtain a stacked body X3; and

[0031] A step of removing the second temporary fixing substrate from the stacked body X3 to obtain the semiconductor structure.

[0032] <9> according to <8> The method for manufacturing the semiconductor structure, wherein the step of forming the intermediate bonding layer comprises:

[0033] forming a redistribution layer including an insulating layer and wiring on the exposed surface side of the plurality of silicon bare chips in the stacked body X2; and

[0034] An intermediate bonding layer is formed on the redistribution layer.

[0035] Effects of the Invention

[0036] The subject of one embodiment of the present disclosure is to provide a semiconductor structure with suppressed warping and a method for manufacturing the same. The semiconductor structure comprises a semiconductor substrate, a composite substrate and an intermediate bonding layer. The semiconductor substrate includes a semiconductor substrate bonding layer. The composite substrate includes a plurality of two-dimensionally arranged silicon dies and a gap-filling material filled between the plurality of silicon dies. The intermediate bonding layer is interposed between the composite substrate and the semiconductor substrate bonding layer in the semiconductor substrate, and the semiconductor substrate bonding layer and the intermediate bonding layer are hybrid-bonded. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] [ Figure 1] is a schematic cross-sectional view showing an example of the semiconductor structure disclosed herein.

[0038] [ Figure 2 ] is a schematic cross-sectional view showing another example of the semiconductor structure disclosed herein.

[0039] [ Figure 3A ] is a schematic process diagram showing an example of a method for manufacturing the semiconductor structure disclosed in the present invention.

[0040] [ Figure 3B ] is a schematic process diagram showing an example of a method for manufacturing the semiconductor structure disclosed in the present invention.

[0041] [ Figure 3C ] is a schematic process diagram showing an example of a method for manufacturing the semiconductor structure disclosed in the present invention.

[0042] [ Figure 3D ] is a schematic process diagram showing an example of a method for manufacturing the semiconductor structure disclosed in the present invention.

[0043] [ Figure 3E ] is a schematic process diagram showing an example of a method for manufacturing the semiconductor structure disclosed in the present invention.

[0044] [ Figure 3F ] is a schematic process diagram showing an example of a method for manufacturing the semiconductor structure disclosed in the present invention.

[0045] [ Figure 3G ] is a schematic process diagram showing an example of a method for manufacturing the semiconductor structure disclosed in the present invention.

[0046] [ Figure 3H ] is a schematic process diagram showing an example of a method for manufacturing the semiconductor structure disclosed in the present invention. DETAILED DESCRIPTION

[0047] In the present disclosure, a numerical range expressed using “to” means a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit.

[0048] In the numerical range of recording in stages in this disclosure, the upper limit or lower limit recorded in one numerical range can also be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical range of recording in this disclosure, the upper limit or lower limit of the numerical range can also be replaced by the value shown in the embodiments.

[0049] [Semiconductor structure]

[0050] The semiconductor structure disclosed herein comprises:

[0051] A semiconductor substrate comprising a semiconductor substrate bonding layer, wherein the semiconductor substrate bonding layer comprises an insulating layer and an electrode;

[0052] A composite substrate comprising a plurality of silicon dies arranged in a two-dimensional manner and an organic gap-filling material filled between the plurality of silicon dies; and

[0053] The intermediate bonding layer is located between the composite substrate and the semiconductor substrate bonding layer in the semiconductor substrate and includes an insulating layer and an electrode.

[0054] The semiconductor substrate bonding layer and the intermediate bonding layer in the semiconductor substrate are hybrid-bonded.

[0055] Regarding the semiconductor structure disclosed herein, the technology described in Patent Document 1 (US Patent Publication No. 2022 / 0013504) uses an inorganic gap-filling material as the gap-filling material. This poses a problem of warping of the semiconductor structure due to film stress of the gap-filling material.

[0056] In contrast, the semiconductor structure disclosed herein utilizes an organic gapfill material to suppress warping of the semiconductor structure due to film stress of the inorganic gapfill material. This can prevent poor bonding and / or misalignment between the semiconductor substrate and the composite substrate caused by warping of the semiconductor structure.

[0057] In addition, the semiconductor structure disclosed in the present invention uses an organic gap filling material as the gap filling material. Compared with the case where an inorganic gap filling material is formed by a vapor growth method (i.e., a dry process) such as CVD (Chemical Vapor Deposition), it also has the advantage of being able to form the gap filling material in a short time and simply through wet processes such as spin coating, slit coating, spraying, screen printing, scraping, and inkjet printing.

[0058] <An Example of a Semiconductor Structure>

[0059] Hereinafter, an example of the semiconductor structure (semiconductor structure 100 ) of the present disclosure will be described with reference to the drawings.

[0060] However, the semiconductor structure disclosed herein is not limited to the following example.

[0061] In the following description, substantially the same elements (for example, members or parts) are denoted by the same reference numerals, and overlapping descriptions may be omitted.

[0062] Figure 1 1 is a schematic cross-sectional view showing a semiconductor structure 100 as an example of the semiconductor structure of the present disclosure.

[0063] like Figure 1As shown, the semiconductor structure 100 includes a semiconductor substrate 10 , a composite substrate 31 , and an intermediate bonding layer 32 interposed between the semiconductor substrate 10 and the composite substrate 31 .

[0064] The semiconductor substrate 10 includes a substrate body 12 , a semiconductor substrate bonding layer 14 provided on one surface of the substrate body 12 , and a through electrode 16 electrically connected to the semiconductor substrate bonding layer 14 and penetrating the substrate body 12 .

[0065] The substrate body 12 in the semiconductor substrate 10 is not particularly limited as long as it is a commonly used substrate body, and a silicon substrate can be given as an example. A specific example of the substrate body 12 will be described later.

[0066] An integrated circuit (not shown) is formed inside the substrate body 12 of the semiconductor substrate 10 .

[0067] The semiconductor substrate bonding layer 14 in the semiconductor substrate 10 includes an insulating layer and electrodes (not shown).

[0068] The semiconductor substrate bonding layer 14 preferably includes an insulating layer and an electrode penetrating the insulating layer.

[0069] The electrodes in the semiconductor substrate bonding layer 14 are electrically connected to the integrated circuit in the substrate body 12. These structures are common structures and therefore are not shown in the figure.

[0070] In the present disclosure, the term "electrode penetrating the insulating layer" in preferred embodiments of the semiconductor substrate bonding layer and the intermediate bonding layer refers to an electrode disposed within the insulating layer and exposed from both sides of the insulating layer. The electrode may penetrate the insulating layer in a straight line or in a curved (e.g., serpentine) manner. Furthermore, the electrode may be a single component (e.g., a metal component) or a composite component composed of multiple components (e.g., metal components).

[0071] In addition, the through-electrode 16 in the semiconductor substrate 10 may be omitted.

[0072] The composite substrate 31 includes a plurality of two-dimensionally arranged silicon dies 20 and an organic gap-filling material 30 filled between the plurality of silicon dies 20 .

[0073] An integrated circuit (not shown) is formed inside the silicon die 20 .

[0074] The internal structure of the silicon bare chip 20 is a common structure, and therefore is not shown in the figure.

[0075] The semiconductor structure 100 includes an intermediate bonding layer 32 interposed between the semiconductor substrate 10 and the composite substrate 31 .

[0076] The intermediate bonding layer 32 includes an insulating layer and electrodes (not shown).

[0077] The intermediate bonding layer 32 preferably includes an insulating layer and an electrode penetrating the insulating layer.

[0078] In the semiconductor structure 100 , the semiconductor substrate bonding layer 14 and the intermediate bonding layer 32 in the semiconductor substrate 10 are hybrid-bonded.

[0079] Through this hybrid bonding, the integrated circuits in the substrate body 12 of the semiconductor substrate 10 and the integrated circuits in the plurality of silicon bare dies 20 are electrically connected via the electrodes in the semiconductor substrate bonding layer 14 and the electrodes in the intermediate bonding layer 32 of the semiconductor substrate 10 .

[0080] As described above, the composite substrate 31 in the semiconductor structure 100 includes the organic gap-filling material 30 as the gap-filling material filled between the plurality of silicon dies 20 .

[0081] Therefore, in the semiconductor structure 100, compared to a case where the gap filler is an inorganic gap filler (e.g., as described in Patent Document 1 (U.S. Patent Publication No. 2022 / 0013504)), the film stress of the gap filler is reduced, thereby suppressing warping of the entire semiconductor structure. This can suppress bonding defects and / or positional misalignment between the semiconductor substrate and the composite substrate caused by warping of the semiconductor structure.

[0082] Furthermore, as described above, in the semiconductor structure 100 , the gap-filling material can be formed easily and in a short time.

[0083] The intermediate bonding layer 32 is arranged across at least two of the plurality of silicon dies 20 (see Figure 1 ).

[0084] <Another Example of Semiconductor Structure>

[0085] Figure 2 2 is a schematic cross-sectional view showing a semiconductor structure 200 as another example of the semiconductor structure of the present disclosure.

[0086] The semiconductor structure 200 is a modified example of the semiconductor structure 100 .

[0087] The semiconductor structure 200 differs from the aforementioned semiconductor structure 100 in the following respects. The semiconductor structure 200 is the same as the aforementioned semiconductor structure 100 except for the following respects.

[0088] like Figure 2 As shown, the semiconductor structure 200 includes a redistribution layer 34 between the composite substrate 31 and the intermediate bonding layer 32 .

[0089] The redistribution layer 34 includes an insulating layer and wiring (not shown) formed in the insulating layer.

[0090] In the semiconductor structure 200 , the semiconductor substrate bonding layer 14 and the intermediate bonding layer 32 in the semiconductor substrate 10 are also mixed and bonded.

[0091] It is preferable that at least two of the plurality of silicon bare dies 20 are electrically connected via the redistribution layer 34 (more specifically, the wiring in the redistribution layer 34 ).

[0092] <One Embodiment of the Method for Manufacturing a Semiconductor Structure (Manufacturing Method X)>

[0093] The method of manufacturing the semiconductor structure of the present disclosure is not particularly limited.

[0094] As one embodiment of a method for producing the semiconductor structure of the present disclosure, the following “Production Method X” can be cited.

[0095] Preparation method X includes:

[0096] A process of two-dimensionally arranging and temporarily fixing a plurality of silicon bare chips on a first temporary fixing substrate, and then filling an organic gap-filling material between the plurality of silicon bare chips to form a composite substrate on the first temporary fixing substrate;

[0097] A step of temporarily fixing a second temporary fixing substrate on the side opposite to the side where the first temporary fixing substrate is arranged when viewed from the composite substrate to obtain a laminated body X1;

[0098] a step of removing the first temporary fixing substrate from the stacked body X1 to obtain a stacked body X2 in which the plurality of silicon bare dies are exposed;

[0099] A step of preparing a semiconductor substrate including a semiconductor substrate bonding layer including an insulating layer and an electrode;

[0100] A step of forming an intermediate bonding layer including an insulating layer and electrodes on the exposed surfaces of the plurality of silicon bare chips in the stack X2;

[0101] a step of hybridly bonding the intermediate bonding layer in the stacked body X2 having the intermediate bonding layer formed thereon and the semiconductor substrate bonding layer in the semiconductor substrate to obtain a stacked body X3; and

[0102] A step of removing the second temporary fixing substrate from the stacked body X3 to obtain a semiconductor structure.

[0103] Preparation method X may include other steps as needed.

[0104] <An Example of Production Method X (Production Method X1)>

[0105] Figures 3A to 3HThis is a schematic process diagram showing an example of Production Method X (hereinafter also referred to as "Production Method X1").

[0106] (Steps for forming a composite substrate: Figure 3A to Figure 3C )

[0107] Figure 3A to Figure 3C The step of forming a composite substrate in manufacturing method X1 is shown.

[0108] like Figure 3A to Figure 3C As shown, in the process of forming a composite substrate in manufacturing method X1, a plurality of silicon bare chips 20 are two-dimensionally arranged and temporarily fixed on a first temporary fixed substrate 40, and then an organic gap filling material 30 is filled between the plurality of silicon bare chips 20, thereby forming a composite substrate 31 on the first temporary fixed substrate 40.

[0109] In this example, the organic gap-fill material 30 between the plurality of silicon dies 20 is formed as follows.

[0110] First, an organic gap filling material 30A is formed on one side of the first temporary fixing substrate 40 where the plurality of silicon dies 20 are temporarily fixed, a portion of the organic gap filling material 30A is filled between the plurality of silicon dies 20, and a portion of the remaining portion of the organic gap filling material 30A is used to cover the upper surfaces of the plurality of silicon dies 20 ( Figure 3B ).

[0111] Next, the organic gap filling material 30A on the upper surfaces of the plurality of silicon bare chips 20 is removed to expose the upper surfaces of the plurality of silicon bare chips 20. As a result, the organic gap filling material 30A filled between the plurality of silicon bare chips 20 remains. The remaining organic gap filling material 30A becomes Figure 3C The organic gap filling material 30 is used.

[0112] The method of forming the organic gap-filling material 30 is not limited to the above-mentioned example of forming the organic gap-filling material 30A. The organic gap-filling material 30 may also be directly formed between the plurality of silicon dies 20 .

[0113] As the first temporary fixing substrate 40 , for example, a silicon substrate, a glass substrate, a resin substrate, or the like can be used.

[0114] The temporary fixing of the plurality of silicon dies 20 on the first temporary fixing substrate 40 can be performed, for example, by the following method:

[0115] Methods using adhesives such as acrylic and epoxy polymers;

[0116] Methods using heat-resistant resins such as polyimide, polyamide-imide, polymaleimide, and silicone polymers;

[0117] Direct bonding of SiO2, etc.

[0118] The first temporary fixing substrate 40 is removed (ie, peeled off) during the manufacturing method X1. Therefore, the surface of the first fixing substrate 40 facing the plurality of silicon bare dies 20 may be subjected to a surface treatment for facilitating peeling from the plurality of silicon bare dies 20.

[0119] The organic gap-filling material 30A can be formed on the first temporary fixing substrate 40 by a wet process such as spray coating, spin coating, screen printing, doctor blade coating, or inkjet printing.

[0120] The organic gap-filling material 30A on the upper surfaces of the plurality of silicon dies 20 can be removed by, for example, polishing.

[0121] Polishing can be performed by conventional methods such as mechanical polishing, chemical polishing, and chemical mechanical polishing.

[0122] (Step of obtaining the laminate X1; Figure 3D )

[0123] Figure 3D The steps of obtaining the laminate X1 in the production method X1 are shown.

[0124] like Figure 3D As shown, in the main step of the manufacturing method X1, the second temporary fixing substrate 42 is temporarily fixed on the side opposite to the side where the first temporary fixing substrate 40 is arranged when viewed from the composite substrate 31, thereby obtaining a stacked body X101 as the stacked body X1.

[0125] The second temporary fixing substrate 42 can be temporarily fixed using, for example, an adhesive.

[0126] The second temporary fixing substrate 42 is removed (i.e., peeled off) during the manufacturing process X1. Therefore, the surface of the second fixing substrate 42 facing the plurality of silicon bare dies 20 and the organic gap-filling material 30 may be subjected to a surface treatment to facilitate peeling from the plurality of silicon bare dies 20 and the organic gap-filling material 30.

[0127] (Step of obtaining laminate X2; Figure 3E )

[0128] Figure 3E The steps of obtaining the laminate X2 in the production method X1 are shown.

[0129] like Figure 3E As shown, in the main step of the manufacturing method X1, the first temporary fixing substrate 40 is removed from the stacked body X101 as the stacked body X1, thereby obtaining a stacked body X102 as the stacked body X2 in which the plurality of silicon bare dies 20 are exposed.

[0130] The first temporary fixing substrate 40 can be removed by, for example, the following method.

[0131] When the first temporary fixing substrate 40 is temporarily fixed by an acrylic adhesive or an epoxy adhesive, the first temporary fixing substrate 40 can be removed by, for example, thermal foaming, mechanical peeling, thermal sliding, laser peeling, or the like.

[0132] When the first temporary fixing substrate 40 is temporarily fixed using a heat-resistant resin such as polyimide, polyamideimide, polymaleimide, or siloxane polymer, the first temporary fixing substrate 40 can be removed by, for example, laser peeling, mechanical peeling, or thermal sliding.

[0133] When the first temporary fixing substrate 40 is temporarily fixed by direct bonding of SiO 2 particles, the first temporary fixing substrate 40 can be removed by laser lift-off using infrared rays or the like, for example.

[0134] In the main process, the exposed surfaces of the plurality of silicon bare dies 20 exposed by removing the first temporary fixing substrate 40 may be cleaned.

[0135] The cleaning method is not particularly limited, and examples thereof include plasma cleaning, cleaning with a cleaning liquid, and polishing.

[0136] (Step of Preparing a Semiconductor Substrate)

[0137] In the step of preparing a semiconductor substrate in the manufacturing method X1, a semiconductor substrate 10 including a semiconductor substrate bonding layer 14 is prepared (see the following). Figure 3G ), the semiconductor substrate bonding layer 14 includes an insulating layer and an electrode.

[0138] (Step of forming an intermediate bonding layer; Figure 3F )

[0139] Figure 3F One embodiment of the step of forming the intermediate bonding layer in the manufacturing method X1 is shown.

[0140] like Figure 3F As shown, in this embodiment, an intermediate bonding layer 32 including an insulating layer and electrodes is formed on the exposed surface side of the plurality of silicon bare chips 20 in the stacked body X102.

[0141] (Step of obtaining laminate X3; Figure 3G )

[0142] Figure 3G The steps of obtaining the laminate X3 in the production method X1 are shown.

[0143] like Figure 3GAs shown, in the main process, the intermediate bonding layer 32 in the stacked body X102 formed with the intermediate bonding layer 32 and the semiconductor substrate bonding layer 14 in the semiconductor substrate 10 are mixed and bonded to obtain the stacked body X102 as the stacked body X3.

[0144] (Step of obtaining a semiconductor structure; Figure 3H )

[0145] Figure 3H The steps of obtaining a semiconductor structure in Production Method X1 are shown.

[0146] like Figure 3H As shown, in the formal process, Figure 3G The second temporary fixing substrate 42 is removed from the laminate X103 to obtain the semiconductor structure 100.

[0147] The second temporary fixing substrate 42 can be removed by the same method as that of removing the first temporary fixing substrate.

[0148] Although not shown in the figure, the semiconductor structure (for example, Figure 2 1 and 2. The semiconductor structure 200 shown has a redistribution layer 34.

[0149] In the manufacturing method X in this case, the step of forming the intermediate bonding layer (for example Figure 3F The process shown) includes:

[0150] forming a redistribution layer (eg, redistribution layer 34 ) including an insulating layer and wiring on the exposed surfaces of a plurality of silicon dies (eg, silicon dies 20 ) in the stack X2 (eg, stack X102 ); and

[0151] An intermediate bonding layer (eg, intermediate bonding layer 32 ) is formed on the redistribution layer (eg, redistribution layer 34 ).

[0152] Hereinafter, preferred embodiments of the semiconductor structure disclosed herein will be described.

[0153] <Semiconductor Substrate>

[0154] The semiconductor structure of the present disclosure (eg, semiconductor structure 100 ) includes a semiconductor substrate (eg, semiconductor substrate 10 ).

[0155] The semiconductor substrate may include a substrate body and a semiconductor substrate bonding layer provided on one surface side of the substrate body. The semiconductor substrate bonding layer may also be provided on both surfaces of the substrate body.

[0156] (Board main body)

[0157] The material of the substrate body is not particularly limited as long as it is a material commonly used as a semiconductor substrate.

[0158] The substrate body preferably contains at least one element selected from the group consisting of Si, Al, Ti, Zr, Hf, Fe, Ni, Cu, Ag, Au, Ga, Ge, Sn, Pd, As, Pt, Mg, In, Ta and Nb.

[0159] More specifically, as the material of the substrate body, for example, there are:

[0160] Semiconductors (e.g. Si, InP, GaN, GaAs, InGaAs, InGaAlAs, SiC, etc.);

[0161] Oxides, carbides, or nitrides (e.g., borosilicate glass (Pyrex (registered trademark)), quartz glass (SiO2), sapphire, ZrO2, Si3N4, AlN, etc.);

[0162] Piezoelectrics or dielectrics (e.g. BaTiO3, LiNbO3, SrTiO3, diamond, etc.);

[0163] Metals (e.g. Al, Ti, Fe, Cu, Ag, Au, Pt, Pd, Ta, Nb, etc.);

[0164] Resins (such as polydimethylsiloxane (PDMS), epoxy resin, phenolic resin, polyimide, benzocyclobutene resin, polybenzoxazole, etc.); etc.

[0165] The substrate body may include only one of these materials, or may include two or more of them.

[0166] The substrate body is preferably a silicon substrate, a GaAs substrate, a SiC substrate, a diamond substrate, a glass substrate, or a resin substrate, and is typically a silicon substrate.

[0167] The substrate body may have a multi-layer structure.

[0168] (Semiconductor substrate bonding layer)

[0169] The semiconductor substrate bonding layer includes an insulating layer and an electrode.

[0170] The semiconductor substrate bonding layer preferably includes an insulating layer and an electrode (eg, a Cu electrode) penetrating the insulating layer.

[0171] The electrodes penetrating the insulating layer are as described above.

[0172] Examples of the material of the electrode in the semiconductor substrate bonding layer include Cu, Sn, Au, Ag, Al, and solder.

[0173] The electrode in the semiconductor substrate bonding layer preferably contains Cu.

[0174] The electrodes in the semiconductor substrate bonding layer can be formed by a known manufacturing method such as a damascene process or a semi-additive process.

[0175] The insulating layer in the semiconductor substrate bonding layer preferably includes at least one selected from the group consisting of a SiO 2 layer, a SiCN layer, a SiN layer, and a resin layer containing a siloxane bond.

[0176] The SiO 2 layer, SiCN layer, and SiN layer serving as insulating layers can be formed by vapor phase growth methods such as sputtering, chemical vapor deposition (CVD), and atomic layer deposition (ALD).

[0177] Examples of the material of the siloxane bond-containing resin layer of the insulating layer include the same materials as the “siloxane bond-containing resin” as the “organic gap-filling material” described later.

[0178] Regarding the method for forming the resin layer containing siloxane bonds as the insulating layer, the example of the method for forming the “organic gap-filling material” described later may be appropriately referred to.

[0179] (Through electrode)

[0180] The semiconductor substrate may include a through-electrode penetrating the substrate body.

[0181] The through-electrode is not particularly limited, and a known through-electrode can be applied.

[0182] The through-electrodes enable electrical connection between the integrated circuit in the semiconductor substrate and electronic devices and the like disposed outside the semiconductor structure.

[0183] <Composite substrate>

[0184] The semiconductor structure of the present disclosure (eg, semiconductor structure 100 ) includes a composite substrate (eg, composite substrate 31 ).

[0185] The composite substrate includes a plurality of silicon dies (eg, silicon dies 20 ) and an organic gap-filling material (eg, organic gap-filling material 30 ) filled between the plurality of silicon dies.

[0186] (Silicon die)

[0187] The composite substrate (eg, composite substrate 31 ) includes a plurality of silicon dies (eg, silicon die 20 ) arranged in a two-dimensional manner.

[0188] As the silicon bare chip, a general silicon bare chip obtained by forming an integrated circuit on a silicon substrate (for example, a silicon wafer) and then cutting it into a chip shape can be used.

[0189] The interval between the plurality of silicon dies (ie, the distance between the side surface of a silicon die and the side surface of an adjacent silicon die) is preferably 0.1 μm to 100,000 μm, more preferably 1 μm to 10,000 μm, and even more preferably 50 μm to 1,000 μm.

[0190] The thickness of the silicon bare chip is preferably 5 μm to 700 μm, more preferably 10 μm to 300 μm, and even more preferably 15 μm to 100 μm.

[0191] (Organic gap filling material)

[0192] The composite substrate (eg, composite substrate 31 ) includes an organic gap-filling material (eg, organic gap-filling material 30 ) filled between a plurality of two-dimensionally arranged silicon dies (eg, silicon dies 20 ).

[0193] The organic gap-filling material includes at least one organic material (preferably a resin, more preferably a heat-resistant resin).

[0194] The glass transition temperature of the organic material in the organic gap-filling material is preferably 110° C. or higher and 400° C. or lower, more preferably 120° C. or higher and 350° C. or lower, and preferably 150° C. or higher and 300° C. or lower.

[0195] The glass transition temperature can be measured by the following method.

[0196] That is, a test piece of organic material with a width of 4 mm and a length of 20 mm was prepared. A thermal analyzer (TMA-50) manufactured by Shimadzu Corporation was used to analyze the sample in the temperature range of 25 to 350°C at a heating rate of 5°C / min and a load of 14 g / mm. 2 The glass transition temperature (Tg) of the test piece can be determined by TMA measurement under the measurement conditions of the temperature-test piece elongation curve obtained.

[0197] Examples of the resin in the organic gap-filling material include polyimide, polyamide, polyamideimide, maleimide resin, polyparaxylylene, polyarylene ether, polybenzoxazole, benzocyclobutene resin, epoxy resin, and resin containing a siloxane bond.

[0198] Examples of the resin containing a siloxane bond include polybenzoxazole, divinylsiloxane benzocyclobutene polymer, siloxane imide polymer, and epoxy-modified siloxane polymer.

[0199] The resin containing a siloxane bond may contain structures represented by the following formulae (1) to (3).

[0200] [Chemistry 1]

[0201]

[0202] In the structure having Si-O bond (siloxane bond), the group bonded to Si may be substituted by an alkylene group, a phenylene group, or the like. For example, a group having (-O-) x (R1) y Si-(R2)-Si(R1) y (-O-) x etc. (R1 represents a methyl group, etc., R2 represents an alkylene group, a phenylene group, etc. x and y are each independently an integer greater than 0, and x+y is 3.).

[0203] Examples of materials for forming Si—O bonds include compounds represented by the following formulas (4) and (5).

[0204] Furthermore, the structures represented by formula (1) and formula (2) can be produced by, for example, heating the compounds represented by formula (4) and formula (5) to cause them to react.

[0205] [Chemistry 2]

[0206]

[0207] The organic gap-filling material including a resin can be formed by, for example, spin coating, slit coating, spray coating, screen printing, doctor blade coating, inkjet printing, or the like.

[0208] (An example of a solution for forming an organic gap-filling material)

[0209] The organic gap-filling material can be formed using, for example, an organic gap-filling material forming solution.

[0210] Examples of the solution for forming an organic gap-filling material include a solution containing a resin material.

[0211] The solution comprising the resin material preferably comprises:

[0212] Compound (A) has a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom, and has a weight average molecular weight of 90 to 400,000;

[0213] A crosslinking agent (B) having three or more -C(═O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, one or more and six or less of the three or more -C(═O)OX groups being -C(═O)OH groups, and having a weight-average molecular weight of 200 to 600; and

[0214] Polar solvent (D).

[0215] -Compound (A)-

[0216] Compound (A) is a compound having a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom and having a weight average molecular weight of 90 to 400,000. The cationic functional group is not particularly limited as long as it is a functional group capable of carrying a positive charge and containing at least one of a primary nitrogen atom and a secondary nitrogen atom.

[0217] Furthermore, compound (A) may contain a tertiary nitrogen atom in addition to the primary and secondary nitrogen atoms.

[0218] In the present disclosure, "primary nitrogen atom" refers to a nitrogen atom bonded only to two hydrogen atoms and one atom other than a hydrogen atom (for example, a nitrogen atom contained in a primary amino group (-NH2 group)), or a nitrogen atom bonded only to three hydrogen atoms and one atom other than a hydrogen atom (cation).

[0219] In addition, a "secondary nitrogen atom" refers to a nitrogen atom bonded only to one hydrogen atom and two atoms other than hydrogen atoms (i.e., a nitrogen atom contained in a functional group represented by the following formula (a)), or a nitrogen atom bonded only to two hydrogen atoms and two atoms other than hydrogen atoms (cation).

[0220] Furthermore, a "tertiary nitrogen atom" refers to a nitrogen atom bonded only to three atoms other than hydrogen atoms (i.e., a nitrogen atom serving as a functional group represented by the following formula (b)), or a nitrogen atom bonded only to one hydrogen atom and three atoms other than hydrogen atoms (cation).

[0221] [Chemistry 3]

[0222]

[0223] In formula (a) and formula (b), * represents a bonding position to an atom other than a hydrogen atom.

[0224] Here, the functional group represented by the above formula (a) may be a secondary amino group (-NHR a Here, R a The functional group representing a part of an alkyl group may be a divalent linking group contained in the polymer skeleton.

[0225] In addition, the functional group represented by the above formula (b) (ie, the tertiary nitrogen atom) may be a tertiary amino group (-NR b R c Base; here, R b and R cThe functional groups each independently represent a part of an alkyl group may be trivalent linking groups contained in the polymer skeleton.

[0226] The weight average molecular weight of compound (A) is 90 or more and 400,000 or less. As compound (A), for example, aliphatic amines, compounds having a siloxane bond (Si-O bond) and an amino group, amine compounds having a ring structure but not having a Si-O bond in the molecule, etc. can be cited. When compound (A) is an aliphatic amine, the weight average molecular weight is preferably 10,000 or more and 200,000 or less. When compound (A) is a compound having a siloxane bond (Si-O bond) and an amino group, the weight average molecular weight is preferably 130 or more and 10,000 or less, more preferably 130 or more and 5,000 or less, and further preferably 130 or more and 2,000 or less. When compound (A) is an amine compound having a ring structure but not having a Si-O bond in the molecule, the weight average molecular weight is preferably 90 or more and 600 or less.

[0227] In addition, in this disclosure, the weight average molecular weight means the weight average molecular weight in terms of polyethylene glycol measured by gel permeation chromatography (GPC) method for components other than monomers.

[0228] Specifically, the weight-average molecular weight was determined by using an aqueous solution having a sodium nitrate concentration of 0.1 mol / L as the developing solvent, and detecting the refractive index at a flow rate of 1.0 mL / min using an analytical apparatus Shodex DET RI-101 and two analytical columns (TSKgel G6000PWXL-CP and TSKgel G3000PWXL-CP manufactured by Tosoh). The weight-average molecular weight was calculated using analytical software (Empower 3 manufactured by Waters) using polyethylene glycol / polyethylene oxide as the standard.

[0229] Furthermore, the compound (A) may further have an anionic functional group, a nonionic functional group, or the like, as necessary.

[0230] The nonionic functional group may be a hydrogen bond acceptor group or a hydrogen bond donor group. Examples of the nonionic functional group include a hydroxyl group, a carbonyl group, and an ether group (—O—).

[0231] The anionic functional group is not particularly limited as long as it is a functional group capable of carrying a negative charge. Examples of the anionic functional group include a carboxylic acid group, a sulfonic acid group, and a sulfate group.

[0232] Examples of the compound (A) include aliphatic amines, and more specifically, polymers of alkyleneimines such as ethyleneimine, propyleneimine, butyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, octyleneimine, trimethyleneimine, tetramethyleneimine, pentamethyleneimine, hexamethyleneimine, and octamethyleneimine, i.e., polyalkyleneimines; polyallylamine; and polyacrylamide.

[0233] Polyethyleneimine (PEI) can be produced by the known methods described in Japanese Patent Publication No. 43-8828, Japanese Patent Publication No. 49-33120, Japanese Patent Application Laid-Open No. 2001-213958, International Publication No. 2010 / 137711, etc. Polyalkyleneimines other than polyethyleneimine can also be produced by the same method as polyethyleneimine.

[0234] Compound (A) is also preferably a derivative of the above-mentioned polyalkyleneimine (a polyalkyleneimine derivative; particularly preferably a polyethyleneimine derivative). The polyalkyleneimine derivative is not particularly limited as long as it is a compound that can be produced using the above-mentioned polyalkyleneimine. Specifically, examples include polyalkyleneimine derivatives in which an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) or an aryl group is introduced into the polyalkyleneimine, and polyalkyleneimine derivatives in which a crosslinking group such as a hydroxyl group is introduced into the polyalkyleneimine.

[0235] These polyalkyleneimine derivatives can be produced by a commonly used method using the above-mentioned polyalkyleneimine, and specifically, can be produced according to the method described in, for example, Japanese Patent Application Laid-Open No. 6-016809.

[0236] Furthermore, as the polyalkyleneimine derivative, highly branched polyalkyleneimine obtained by reacting a cationic functional group-containing monomer with a polyalkyleneimine to increase the branching degree of the polyalkyleneimine is also preferred.

[0237] Examples of methods for obtaining highly branched polyalkyleneimines include: a method in which a cationic functional group-containing monomer is reacted with a polyalkyleneimines having a plurality of secondary nitrogen atoms in its backbone, and at least one of the plurality of secondary nitrogen atoms is substituted with the cationic functional group-containing monomer; a method in which a cationic functional group-containing monomer is reacted with a polyalkyleneimines having a plurality of primary nitrogen atoms at its terminals, and at least one of the plurality of primary nitrogen atoms is substituted with the cationic functional group-containing monomer; and the like.

[0238] Examples of the cationic functional group introduced to increase the degree of branching include aminoethyl, aminopropyl, diaminopropyl, aminobutyl, diaminobutyl, and triaminobutyl. From the perspective of reducing the cationic functional group equivalent and increasing the cationic functional group density, the aminoethyl group is preferred.

[0239] The polyethyleneimine and its derivatives may be commercially available products. For example, polyethyleneimine and its derivatives commercially available from Nippon Shokubai Co., Ltd., BASF Corporation, MP-Biomedicals Corporation, etc. may be appropriately selected and used.

[0240] Examples of the compound (A) include compounds having a Si—O bond and an amino group in addition to the aforementioned aliphatic amines.

[0241] A compound having a Si—O bond and an amino group as the compound (A) is suitable as a material for the siloxane bond-containing resin.

[0242] Examples of the compound having a Si—O bond and an amino group include siloxane diamine, a silane coupling agent having an amino group, and a siloxane polymer of a silane coupling agent having an amino group.

[0243] As a silane coupling agent which has an amino group, the compound represented by following formula (A-3) is mentioned, for example.

[0244] [Chemistry 4]

[0245]

[0246] p1=0-2, q1=1-3, n1=1-3, r1=0-1, s1=0-1, t1=0-1, u1=0-1, v1=0-1, w1=0-1, p1+q1=3

[0247] In formula (A-3), R 1 represents an alkyl group having 1 to 4 carbon atoms which may be substituted. 2 and R 3 Each independently represents an alkylene group having 1 to 12 carbon atoms, an ether group or a carbonyl group which may be substituted (a carbonyl group, an ether group or the like may be contained in the skeleton). 4 and R 5 Each independently represents an optionally substituted alkylene group having 1 to 4 carbon atoms or a single bond. Ar represents a divalent or trivalent aromatic ring. 1 represents hydrogen or an optionally substituted alkyl group having 1 to 5 carbon atoms. 2 represents hydrogen, a cycloalkyl group, a heterocyclic group, an aryl group, or an alkyl group having 1 to 5 carbon atoms which may be substituted (the skeleton may contain a carbonyl group, an ether group, etc.). 1 、R 2 、R 3 、R 4 、R 5 、X 1 Can be the same or different.

[0248] As R 1 、R 2 、R3 、 R 4 、 R 5 、 X 1 、 X 2 Examples of the substituents of the alkyl and alkylene groups in, can be independently cited as amino, hydroxy, alkoxy, cyano, carboxy, sulfo, halogen, etc.

[0249] As the divalent or trivalent aromatic ring in Ar, for example, a divalent or trivalent benzene ring can be cited. As X 2 Examples of the aryl group in, can be cited as phenyl, methylbenzyl, vinylbenzyl, etc.

[0250] Specific examples of the silane coupling agent represented by the formula (A-3) include, for example, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminoisobutyldimethylmethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, N-(2-aminoethyl)-11-aminoundecyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, (aminoethylaminoethyl)phenyltriethoxysilane, methylbenzylaminoethylaminopropyltrimethoxysilane, benzylaminoethylaminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, (aminoethylaminoethyl)phenethyltrimethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, N-[2-[3-(trimethoxysilyl)propylamino]ethyl]ethylenediamine, 3-aminopropyldiethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldimethylmethoxysilane, trimethoxy[2-(2-aminoethyl)-3-aminopropyl]silane, diaminomethylmethyldiethoxysilane, methylaminomethylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, N-methylaminopropyltriethoxysilane, N-methylaminopropylmethyldiethoxysilane, (phenylaminomethyl)methyldiethoxysilane, acetamidopropyltrimethoxysilane and their hydrolyzates.

[0251] Examples of amino group-containing silane coupling agents other than those represented by formula (A-3) include N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N′-bis[3-(trimethoxysilyl)propyl]ethylenediamine, bis[(3-triethoxysilyl)propyl]amine, piperazinylpropylmethyldimethoxysilane, bis[3-(triethoxysilyl)propyl]urea, bis(methyldiethoxysilylpropyl)amine, 2,2-dimethoxy-1,6-diaza-2-silacyclooctane, 3,5-diamino-N-(4-(methoxydimethylsilyl)phenyl)benzamide, 3,5-diamino-N-(4-(triethoxysilyl)phenyl)benzamide, 5-(ethoxydimethylsilyl)benzene-1,3-diamine, and hydrolyzates thereof.

[0252] The aforementioned silane coupling agent having an amino group may be used alone or in combination of two or more. In addition, a silane coupling agent having an amino group and a silane coupling agent not having an amino group may also be used in combination. For example, a silane coupling agent having a mercapto group may be used to improve adhesion to metals.

[0253] In addition, polymers (siloxane polymers) formed from these silane coupling agents via siloxane bonds (Si-O-Si) can also be used. For example, polymers having a linear siloxane structure, a branched siloxane structure, a cyclic siloxane structure, and a cage siloxane structure can be obtained from the hydrolyzate of 3-aminopropyltrimethoxysilane. The cage siloxane structure is represented by the following formula (A-1), for example.

[0254] [Chemistry 5]

[0255]

[0256] Examples of the siloxane diamine include compounds represented by the following formula (A-2): In formula (A-2), i is an integer of 0 to 4, j is an integer of 1 to 3, and Me is a methyl group.

[0257] [Chemistry 6]

[0258]

[0259] Examples of the siloxane diamine include 1,3-bis(3-aminopropyl)tetramethyldisiloxane (in formula (A-2), i=0, j=1) and 1,3-bis(2-aminoethylamino)propyltetramethyldisiloxane (in formula (A-2), i=1, j=1).

[0260] Examples of the compound (A) include amine compounds having a ring structure.

[0261] Among them, an amine compound having a ring structure and a weight average molecular weight of 90 to 600 is preferred. Examples of the amine compound having a ring structure and a weight average molecular weight of 90 to 600 include alicyclic amines, aromatic ring amines, and heterocyclic ring amines. The molecule may have multiple ring structures, which may be the same or different. As the amine compound having a ring structure, a compound having an aromatic ring is more preferred in order to easily obtain a compound that is more stable to heat.

[0262] In addition, as the amine compound having a ring structure and a weight-average molecular weight of 90 to 600, compounds having primary amino groups are preferred from the perspective of easily forming a thermally crosslinked structure such as an amide, amideimide, or imide with the crosslinking agent (B), thereby improving heat resistance. Furthermore, as the amine compound, diamine compounds having two primary amino groups and triamine compounds having three primary amino groups are preferred from the perspective of easily increasing the number of thermally crosslinked structures such as an amide, amideimide, or imide with the crosslinking agent (B), thereby further improving heat resistance.

[0263] Examples of the alicyclic amine include cyclohexylamine and dimethylaminocyclohexane.

[0264] Examples of the aromatic cyclic amine include diaminodiphenyl ether, xylylenediamine (preferably p-xylylenediamine), diaminobenzene, diaminotoluene, methylenedianiline, dimethyldiaminobiphenyl, bis(trifluoromethyl)diaminobiphenyl, diaminobenzophenone, diaminobenzanilide, bis(aminophenyl)fluorene, bis(aminophenoxy)benzene, bis(aminophenoxy)biphenyl, dicarboxydiaminodiphenylmethane, diaminoresorcinol, dihydroxybenzidine, diaminobenzidine, 1,3,5-triaminophenoxybenzene, 2,2'-dimethylbenzidine, tris(4-aminophenyl)amine, 2,7-diaminofluorene, 1,9-diaminofluorene, and dibenzylamine.

[0265] Examples of the heterocyclic ring of the heterocyclic amine include a heterocyclic ring containing a sulfur atom as a heteroatom (e.g., a thiophene ring), or a heterocyclic ring containing a nitrogen atom as a heteroatom (e.g., a 5-membered ring such as a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, and a triazole ring; a 6-membered ring such as an isocyanurate ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, and a triazine ring; and a condensed ring such as an indole ring, an indoline ring, a quinoline ring, an acridine ring, a naphthyridine ring, a quinazoline ring, a purine ring, and a quinoxaline ring).

[0266] For example, examples of the heterocyclic amine having a nitrogen-containing heterocyclic ring include melamine, ammeline, melam, melem, and tris(4-aminophenyl)amine.

[0267] Furthermore, examples of the amine compound having both a heterocyclic ring and an aromatic ring include N2,N4,N6-tris(4-aminophenyl)-1,3,5-triazine-2,4,6-triamine.

[0268] Compound (A) has a primary or secondary amino group, and therefore can firmly bond the substrates to each other through electrostatic interaction with functional groups such as hydroxyl, epoxy, carboxyl, amino, and mercapto groups that may be present on the surfaces of the first and second substrates, or by tightly forming covalent bonds with the above-mentioned functional groups.

[0269] In addition, compound (A) has primary or secondary amino groups and is therefore easily soluble in the polar solvent (D) described below. By using a compound (A) that is easily soluble in a polar solvent (D), affinity for the hydrophilic surface of a substrate such as a silicon substrate is increased, thereby facilitating formation of a smooth film and enabling the thickness of the hybrid bonded portion to be reduced.

[0270] As described above, compound (A) has a cationic functional group comprising at least one of a primary nitrogen atom and a secondary nitrogen atom. Here, when compound (A) contains a primary nitrogen atom, the proportion of primary nitrogen atoms in all nitrogen atoms in compound (A) is preferably 20 mol% or more, more preferably 25 mol% or more, and even more preferably 30 mol% or more. Alternatively, compound (A) may have a cationic functional group comprising a primary nitrogen atom and excluding nitrogen atoms other than primary nitrogen atoms (e.g., secondary nitrogen atoms or tertiary nitrogen atoms).

[0271] When compound (A) contains secondary nitrogen atoms, the proportion of secondary nitrogen atoms in all nitrogen atoms in compound (A) is preferably 5 mol% to 50 mol%, more preferably 10 mol% to 45 mol%.

[0272] In addition, compound (A) may contain tertiary nitrogen atoms in addition to primary nitrogen atoms and secondary nitrogen atoms. When compound (A) contains tertiary nitrogen atoms, the proportion of tertiary nitrogen atoms in all nitrogen atoms in compound (A) is preferably greater than 20 mol% and less than 50 mol%, and more preferably greater than 25 mol% and less than 45 mol%.

[0273] In the present disclosure, the content of the component derived from compound (A) in the joint is not particularly limited. For example, it can be set to 1 mass % or more and 82 mass % or less, preferably 5 mass % or more and 82 mass % or less, and more preferably 13 mass % or more and 82 mass % or less, relative to the entire joint.

[0274] - Cross-linking agent (B) -

[0275] The crosslinking agent (B) is a compound having three or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, one or more and six or less of the three or more -C(=O)OX groups (hereinafter also referred to as "COOX") are -C(=O)OH groups (hereinafter also referred to as "COOH"), and having a weight-average molecular weight of 200 to 600.

[0276] The crosslinking agent (B) is a compound having three or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, preferably a compound having three or more to 6 -C(=O)OX groups in the molecule, and more preferably a compound having three or four -C(=O)OX groups in the molecule.

[0277] In the crosslinking agent (B), X in the -C(=O)OX group may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, with a hydrogen atom, a methyl group, an ethyl group, and a propyl group being preferred. It should be noted that X in the -C(=O)OX group may be the same or different.

[0278] The crosslinking agent (B) is a compound having one or more and six or less -C(=O)OH groups in which X is a hydrogen atom in the molecule, preferably a compound having one or more and four or less -C(=O)OH groups in the molecule, more preferably a compound having two or more and four or less -C(=O)OH groups in the molecule, and even more preferably a compound having two or three -C(=O)OH groups in the molecule.

[0279] The crosslinking agent (B) is a compound having a weight average molecular weight of 200 or more and 600 or less, preferably a compound having a weight average molecular weight of 200 or more and 400 or less.

[0280] The crosslinking agent (B) preferably has a ring structure in the molecule. Examples of the ring structure include alicyclic structures and aromatic ring structures. In addition, the crosslinking agent (B) may have multiple ring structures in the molecule, and the multiple ring structures may be the same or different.

[0281] Examples of the alicyclic structure include an alicyclic structure having 3 to 8 carbon atoms, preferably an alicyclic structure having 4 to 6 carbon atoms. The ring structure may be saturated or unsaturated. More specifically, examples of the alicyclic structure include saturated alicyclic structures such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring; and unsaturated alicyclic structures such as a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, and a cyclooctene ring.

[0282] The aromatic ring structure is not particularly limited as long as it is a ring structure showing aromaticity. Examples thereof include benzene-based aromatic rings such as benzene ring, naphthalene ring, anthracene ring, and perylene ring; aromatic heterocycles such as pyridine ring and thiophene ring; and non-benzene-based aromatic rings such as indene ring and azulene ring.

[0283] The ring structure possessed by the crosslinking agent (B) in the molecule is preferably at least one selected from the group consisting of a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a benzene ring, and a naphthalene ring. From the perspective of further improving the heat resistance of the bonded portion, at least one of a benzene ring and a naphthalene ring is more preferred.

[0284] As described above, the crosslinking agent (B) may have a plurality of ring structures in the molecule. When the ring structure is benzene, the crosslinking agent (B) may have a biphenyl structure, a benzophenone structure, a diphenyl ether structure, or the like.

[0285] The crosslinking agent (B) preferably has a fluorine atom in the molecule, more preferably has 1 or more and 6 or less fluorine atoms in the molecule, and even more preferably has 3 or more and 6 or less fluorine atoms in the molecule. For example, the crosslinking agent (B) may have a fluoroalkyl group in the molecule, specifically a trifluoroalkyl group or a hexafluoroisopropyl group.

[0286] Furthermore, examples of the crosslinking agent (B) include carboxylic acid compounds such as alicyclic carboxylic acids, benzene carboxylic acids, naphthalene carboxylic acids, diphthalic acids, and fluorinated aromatic ring carboxylic acids; and carboxylate compounds such as alicyclic carboxylic acid esters, benzene carboxylic acid esters, naphthalene carboxylic acid esters, diphthalic acid esters, and fluorinated aromatic ring carboxylic acid esters. It should be noted that the carboxylate compound is a compound having a carboxyl group (-C(=O)OH group) in the molecule, and at least one X among three or more -C(=O)OX groups is an alkyl group having 1 or more and 6 or less carbon atoms (i.e., having an ester bond). In the present disclosure, since the crosslinking agent (B) is a carboxylate compound, the aggregation caused by the association of the compound (A) and the crosslinking agent (B) is suppressed, the number of aggregates and pits is reduced, and the adjustment of the film thickness becomes easy.

[0287] The carboxylic acid compound is preferably a tetravalent or less carboxylic acid compound containing four or less -C(=O)OH groups, and more preferably a trivalent or tetravalent carboxylic acid compound containing three or four -C(=O)OH groups.

[0288] The carboxylate compound preferably contains three or less carboxyl groups (—C(═O)OH groups) and three or less ester bonds in the molecule, and more preferably contains two or less carboxyl groups and two or less ester bonds in the molecule.

[0289] In the carboxylate compound, when X in three or more -C(=O)OX groups is an alkyl group having 1 to 6 carbon atoms, X is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or the like. From the perspective of further suppressing aggregation caused by the association of the compound (A) and the crosslinking agent (B), an ethyl group or a propyl group is preferred.

[0290] Specific examples of the carboxylic acid compounds include, but are not limited to, alicyclic carboxylic acids such as 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and 1,2,3,4,5,6-cyclohexanehexacarboxylic acid; phenylcarboxylic acids such as 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, benzenepentacarboxylic acid, and mellitic acid; naphthylcarboxylic acids such as 1,4,5,8-naphthalenetetracarboxylic acid and 2,3,6,7-naphthalenetetracarboxylic acid. Acid; 3,3',5,5'-tetracarboxydiphenylmethane, biphenyl-3,3',5,5'-tetracarboxylic acid, biphenyl-3,4',5-tricarboxylic acid, biphenyl-3,3',4,4'-tetracarboxylic acid, benzophenone-3,3',4,4'-tetracarboxylic acid, 4,4'-oxydiphthalic acid, 3,4'-oxydiphthalic acid, 1,3-bis(phthalic acid)tetramethyldisiloxane, 4,4'-(ethynyl-2-diyl)diphthalic acid (4,4'-(Ethyne-1,2-diyl)diphthalic acid acid), (4,4'-(1,4-phenylenebis(oxy))diphthalic acid), (4,4'-(1,4-phenylenebis(oxy))diphthalic acid), (4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))diphthalic acid), (4,4'-((oxybis(4,1-phenylene))bis(oxy))diphthalic acid perylenecarboxylic acids such as perylene-3,4,9,10-tetracarboxylic acid; anthracenecarboxylic acids such as anthracene-2,3,6,7-tetracarboxylic acid; fluorinated aromatic ring carboxylic acids such as 4,4'-(hexafluoroisopropylidene)diphthalic acid, 9,9-bis(trifluoromethyl)-9H-xanthene-2,3,6,7-tetracarboxylic acid, and 1,4-bis(trifluoromethyl)pyromellitic acid.

[0291] Specific examples of the carboxylic acid ester compounds include compounds in which at least one carboxyl group in the aforementioned specific examples of carboxylic acid compounds is substituted with an ester group. Examples of the carboxylic acid ester compounds include half-esterified compounds represented by the following general formulas (B-1) to (B-5).

[0292] [Chemistry 7]

[0293]

[0294] R in general formulae (B-1) to (B-5) is independently an alkyl group having 1 to 6 carbon atoms, preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably an ethyl group or a propyl group.

[0295] Y in the general formula (B-2) is a single bond, O, C=O, or C(CF 3 ) 2 , and is preferably O.

[0296] The half-esterified compound can be produced by, for example, mixing carboxylic acid anhydride, which is the anhydride of the aforementioned carboxylic acid compound, with an alcohol solvent and ring-opening the carboxylic acid anhydride.

[0297] The content of the component from the cross-linking agent (B) in the organic gap filling material is not particularly limited. For example, the ratio of the number of carbonyl groups (-(C=O)-Y) in the substance from the cross-linking agent (B) to the number of all nitrogen atoms in the substance from the compound (A) ((-(C=O)-Y) / N) is preferably 0.1 or more and 3.0 or less, more preferably 0.3 or more and 2.5 or less, and further preferably 0.4 or more and 2.2 or less. Here, in -(C=O)-Y, Y represents a nitrogen atom, OH or ester group cross-linked by imide or amide. By making (-(C=O)-Y) / N 0.1 or more and 3.0 or less, the joint portion suitably has a cross-linked structure such as amide, amideimide, or imide, and the heat resistance is more excellent.

[0298] It is believed that because compound (A) has uncrosslinked cationic functional groups, when compound (A) is included as a component of the bonding portion and crosslinking agent (B) is not included, the crosslinking density is low and the heat resistance is insufficient. On the other hand, in organic gap-filling materials, the cationic functional groups of compound (A) react with the carboxyl groups of crosslinking agent (B) to form covalent bonds, thereby increasing the crosslinking density and providing high heat resistance.

[0299] -Polar solvent (D)-

[0300] Specific examples of the polar solvent (D) include:

[0301] Protic inorganic compounds such as water and heavy water;

[0302] Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, isopentanol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, benzyl alcohol, diethylene glycol, triethylene glycol, glycerol and other alcohols;

[0303] Ethers such as tetrahydrofuran and dimethoxyethane;

[0304] Furfural, acetone, methyl ethyl ketone, cyclohexane and other aldehydes / ketones;

[0305] Acid derivatives such as acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, formaldehyde, N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and hexamethylphosphoramide;

[0306] Nitriles such as acetonitrile and propionitrile; nitro compounds such as nitromethane and nitrobenzene;

[0307] Sulfur compounds such as dimethyl sulfoxide.

[0308] As the polar solvent (D), a protic solvent is preferably contained, water is more preferably contained, and ultrapure water is further preferably contained.

[0309] The content of the polar solvent (D) in the solution is not particularly limited, and is, for example, 1.0% by mass to 99.99896% by mass, and preferably 40% by mass to 99.99896% by mass, based on the entire solution.

[0310] From the viewpoint of volatilizing the polar solvent (D) by heating during formation of the organic gap-filling material and reducing the amount of residual solvent in the organic gap-filling material, the boiling point of the polar solvent (D) is preferably 150° C. or lower, more preferably 120° C. or lower.

[0311] -Additive (C)-

[0312] The solution containing the resin material may contain an additive (C).

[0313] Examples of the additive (C) include an acid (C-1) having a carboxyl group and a weight average molecular weight of 46 to 195, and a base (C-2) having a nitrogen atom and a weight average molecular weight of 17 to 120 without a ring structure.

[0314] Acid (C-1) is an acid having a weight average molecular weight of 46 or more and 195 or less and having a carboxyl group. It is speculated that by including acid (C-1) as additive (C), the amino group in compound (A) and the carboxyl group in acid (C-1) form an ionic bond, thereby suppressing the aggregation caused by the association of compound (A) and crosslinking agent (B). More specifically, it is speculated that the interaction (e.g., electrostatic interaction) between the ammonium ion from the amino group in compound (A) and the carboxyl ion from the carboxyl group in acid (C-1) is stronger than the interaction between the ammonium ion from the amino group in compound (A) and the carboxyl ion from the carboxyl group in crosslinking agent (B), thereby suppressing aggregation. In addition, the present invention is not limited by the above speculation.

[0315] The acid (C-1) is not particularly limited as long as it is a compound having a carboxyl group and a weight-average molecular weight of 46 to 195, and examples thereof include monocarboxylic acid compounds, dicarboxylic acid compounds, and oxydicarboxylic acid compounds. More specifically, examples of the acid (C-1) include formic acid, acetic acid, malonic acid, oxalic acid, citric acid, benzoic acid, lactic acid, glycolic acid, glyceric acid, butyric acid, methoxyacetic acid, ethoxyacetic acid, phthalic acid, terephthalic acid, picolinic acid, salicylic acid, and 3,4,5-trihydroxybenzoic acid.

[0316] In the present disclosure, the content of the acid (C-1) in the solution containing the resin material is not particularly limited. For example, the ratio of the number of carboxyl groups in the acid (C-1) to the number of all nitrogen atoms in the compound (A) (COOH / N) is preferably 0.01 or more and 10 or less, more preferably 0.02 or more and 6 or less, and even more preferably 0.5 or more and 3 or less.

[0317] Base (C-2) is a base having a weight average molecular weight of 17 or more and 120 or less and containing nitrogen atoms. It is speculated that the solution containing the resin material contains base (C-2) as an additive (C), so that the carboxyl group in the crosslinker (B) and the amino group in the base (C-2) form an ionic bond, thereby suppressing the aggregation caused by the association of compound (A) and crosslinker (B). More specifically, it is speculated that the interaction between the carboxyl group-derived carboxyl group in the crosslinker (B) and the ammonium ion derived from the amino group in the base (C-2) is stronger than the interaction between the ammonium ion derived from the amino group in the compound (A) and the carboxyl group-derived carboxyl group in the crosslinker (B), and thus aggregation is suppressed. In addition, the present invention is not limited by the above speculation.

[0318] The base (C-2) is not particularly limited as long as it is a compound having a nitrogen atom, a weight average molecular weight of 17 or more and 120 or less, and does not have a ring structure, and examples thereof include monoamine compounds and diamine compounds. More specifically, examples of the base (C-2) include ammonia, ethylamine, ethanolamine, diethylamine, triethylamine, ethylenediamine, N-acetylethylenediamine, N-(2-aminoethyl)ethanolamine, and N-(2-aminoethyl)glycine.

[0319] In the present disclosure, the content of the base (C-2) in the solution containing the resin material is not particularly limited. For example, the ratio of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the cross-linking agent (B) (N / COOH) is preferably 0.5 or more and 5 or less, and more preferably 0.9 or more and 3 or less.

[0320] In the solution containing the resin material, in order to improve insulation or mechanical strength, tetraethoxysilane, tetramethoxysilane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)methane, bis(methyldiethoxysilyl)ethane, 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahydroxycyclosiloxane, 1,1,4,4-tetramethyl-1,4-diethoxydimethylsilylethylene, and 1,3,5-trimethyl-1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane may be mixed.

[0321] Furthermore, in order to improve the hydrophobicity of the organic gap filling material, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, etc. may be mixed in order to control the etching selectivity.

[0322] The solution containing the resin material may contain a solvent other than the polar solvent (D), and examples thereof include n-hexane.

[0323] Furthermore, for example, in order to improve electrical characteristics, the solution containing the resin material may contain phthalic acid, benzoic acid, or the like, or derivatives thereof.

[0324] In addition, in order to suppress corrosion of, for example, copper, the solution containing the resin material may contain benzotriazole or a derivative thereof.

[0325] The pH of the solution containing the resin material is not particularly limited, but is preferably 2.0 or more and 12.0 or less.

[0326] When an acid (C-1) is used as the additive (C), it is preferred to mix the mixture of the acid (C-1) and the compound (A) with the crosslinking agent (B). Specifically, it is preferred to mix the compound (A) and the acid (C-1) before mixing them. This can appropriately suppress cloudiness and gelation of the solution containing the resin layer-forming material when the compound (A) and the crosslinking agent (B) are mixed (gelation may take time to clear the composition, which is not preferred).

[0327] When a base (C-2) is used as the additive (C), it is preferred to mix a mixture of the base (C-2) and the crosslinking agent (B) with the compound (A). Specifically, it is preferred to mix the crosslinking agent (B) and the base (C-2) before mixing the compound (A) and the crosslinking agent (B). This can appropriately suppress turbidity and gelation of the solution containing the resin layer-forming material when the compound (A) and the crosslinking agent (B) are mixed (gelation may take time to clear the composition, which is not preferred).

[0328] <Intermediate Bonding Layer>

[0329] The semiconductor structure disclosed herein (e.g., semiconductor structure 100) includes an intermediate bonding layer (e.g., intermediate bonding layer 32) between a semiconductor substrate bonding layer (e.g., semiconductor substrate bonding layer 14) in a semiconductor substrate (e.g., semiconductor substrate 10) and a composite substrate (e.g., composite substrate 31).

[0330] In the semiconductor structure of the present disclosure, the semiconductor substrate bonding layer and the intermediate bonding layer in the semiconductor substrate are hybrid-bonded.

[0331] As the hybrid bonding, known hybrid bonding can be applied.

[0332] The intermediate bonding layer includes an insulating layer and an electrode.

[0333] The intermediate bonding layer preferably includes an insulating layer and an electrode penetrating the insulating layer.

[0334] The electrodes penetrating the insulating layer are as described above.

[0335] Preferred aspects of the intermediate bonding layer (eg, preferred aspects of the insulating layer, the electrode, and the formation method) are the same as those of the aforementioned semiconductor substrate bonding layer.

[0336] <Rewiring Layer>

[0337] The semiconductor structure of the present disclosure (eg, semiconductor structure 200 ) may further include a redistribution layer (eg, redistribution layer 34 ) between the composite substrate (eg, composite substrate 31 ) and the intermediate bonding layer (eg, intermediate bonding layer 32 ).

[0338] In the semiconductor structure of this embodiment, the semiconductor substrate bonding layer and the intermediate bonding layer in the semiconductor substrate are hybrid-bonded.

[0339] The redistribution layer includes an insulating layer and wiring.

[0340] Preferred aspects of the insulating layer in the redistribution layer are the same as those of the insulating layer in the semiconductor substrate bonding layer.

[0341] The wiring in the rewiring layer is a metal member formed in the insulating layer in the rewiring layer and extending in the plane direction of the rewiring layer (ie, in a direction orthogonal to the thickness direction of the rewiring layer).

[0342] Examples of the material of the wiring include Cu, Sn, Au, Ag, Al, and solder.

[0343] The wiring in the semiconductor substrate bonding layer preferably contains Cu.

[0344] The wiring in the semiconductor substrate bonding layer can be formed by a known manufacturing method such as a damascene process or a semi-additive process.

[0345] In the semiconductor structure of the present disclosure (eg, semiconductor structure 200 ), at least two of the plurality of silicon dies (eg, silicon die 20 ) are preferably electrically connected via a redistribution layer (specifically, wiring in the redistribution layer).

[0346] The disclosed contents of Japanese Patent Application No. 2023-027807 filed on February 24, 2023 are incorporated into this specification by reference in their entirety.

[0347] All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference.

Claims

1. A semiconductor structure comprising: A semiconductor substrate comprising a semiconductor substrate bonding layer, wherein the semiconductor substrate bonding layer comprises an insulating layer and an electrode, A composite substrate comprising a plurality of two-dimensionally arranged silicon dies and an organic gap-filling material filled between the plurality of silicon dies, and an intermediate bonding layer, which is interposed between the semiconductor substrate bonding layer in the semiconductor substrate and the composite substrate and comprises an insulating layer and an electrode; The semiconductor substrate bonding layer and the intermediate bonding layer in the semiconductor substrate are hybrid-bonded.

2. The semiconductor structure according to claim 1, wherein The intermediate bonding layer is disposed across at least two of the plurality of silicon dies.

3. The semiconductor structure according to claim 1, wherein A redistribution layer including an insulating layer and wiring is further provided between the composite substrate and the intermediate bonding layer.

4. The semiconductor structure according to claim 3, wherein: At least two of the plurality of silicon dies are electrically connected via the redistribution layer. The semiconductor structure according to claim 3 , wherein: The insulating layer in the redistribution layer includes at least one selected from the group consisting of a SiO 2 layer, a SiCN layer, a SiN layer, and a resin layer containing a siloxane bond. The semiconductor structure according to claim 1 , wherein: The insulating layer in the semiconductor substrate bonding layer and the insulating layer in the intermediate bonding layer each include at least one selected from the group consisting of a SiO 2 layer, a SiCN layer, a SiN layer, and a resin layer containing a siloxane bond.

7. The semiconductor structure according to any one of claims 1 to 6, wherein The organic gap-filling material includes at least one selected from the group consisting of polyimide, polyamide, polyamideimide, maleimide resin, parylene, polyarylene ether polyimide, polybenzoxazole, benzocyclobutene resin, epoxy resin, and resin having a siloxane bond.

8. A method for manufacturing a semiconductor structure, which is a method for manufacturing the semiconductor structure according to claim 1 or 2, comprising: a step of two-dimensionally arranging and temporarily fixing a plurality of silicon bare chips on a first temporary fixing substrate, and then filling the organic gap filling material between the plurality of silicon bare chips to form the composite substrate on the first temporary fixing substrate; a step of temporarily fixing a second temporary fixing substrate on the side opposite to the side where the first temporary fixing substrate is arranged when viewed from the composite substrate to obtain a laminated body X1; a step of removing the first temporary fixing substrate from the stacked body X1 to obtain a stacked body X2 in which the plurality of silicon bare dies are exposed; a step of preparing the semiconductor substrate including the semiconductor substrate bonding layer, wherein the semiconductor substrate bonding layer includes the insulating layer and the electrode; forming an intermediate bonding layer including an insulating layer and electrodes on the exposed surfaces of the plurality of silicon bare chips in the stacked body X2; a step of hybridly bonding the intermediate bonding layer in the stacked body X2 having the intermediate bonding layer formed thereon and the semiconductor substrate bonding layer in the semiconductor substrate to obtain a stacked body X3; and A step of removing the second temporary fixing substrate from the stacked body X3 to obtain the semiconductor structure.

9. The method for manufacturing a semiconductor structure according to claim 8, wherein: The process of forming the intermediate bonding layer includes: forming a redistribution layer including an insulating layer and wiring on the exposed surface side of the plurality of silicon bare chips in the stacked body X2; and An intermediate bonding layer is formed on the redistribution layer.

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