Semiconductor structure and method for manufacturing the same

Abstract

This semiconductor structure comprises an organic bonding layer that includes an organic insulating layer and metal pads, a plurality of silicon dies that are arranged in a two-dimensional manner on the organic bonding layer and hybrid-bonded thereto, and a resin mold layer that is filled between the silicon dies on the organic bonding layer.

Description

[Technical Field]

[0001] This disclosure relates to semiconductor structures and methods for manufacturing the same. [Background technology]

[0002] In recent years, in the field of semiconductor devices, techniques for bonding semiconductor chips (e.g., silicon dies) onto redistribution layers have been investigated (see, for example, Non-Patent Document 1).

[0003] Non-Patent Literature 1: Shinko Electric Industries, Ltd. Homepage, Product Information, Semiconductor Packages, Substrates for Semiconductor Packages, Substrates for 2.3D Packages ~i-THOP(registered trademark)~ (Under Development), [online], Shinko Electric Industries, Ltd., [Retrieved January 27, 2023], Internet<URL: https: / / www.shinko.co.jp / product / package / substrate / i-thop.php> [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] The bonding of semiconductor chips (e.g., silicon dies) to redistribution layers is typically done using solder and epoxy adhesives. However, in this case, there is room for improvement in terms of narrowing the spacing between wires.

[0005] This disclosure was made in light of the above-mentioned issues. One object of this disclosure is to provide a semiconductor structure and a method for manufacturing the same that enable narrowing of the wiring pitch. [Means for solving the problem]

[0006] Specific means for solving the aforementioned problems include the following embodiments. <1> An organic bonding layer including an organic insulating layer and a metal pad, Multiple silicon dies are arranged in a two-dimensional manner and hybrid-bonded on the aforementioned organic bonding layer, A resin mold layer filled between the plurality of silicon dies on the organic bonding layer, A semiconductor structure comprising. <2> Further, the semiconductor structure according to <1>, comprising a rewiring layer disposed on a side opposite to the side on which the plurality of silicon dies are disposed when viewed from the organic bonding layer. <3> Further, the semiconductor structure according to <1>, comprising a build-up substrate disposed on a side opposite to the side on which the plurality of silicon dies are disposed when viewed from the organic bonding layer. The semiconductor structure according to <1>. <4> Further, A high-density wiring layer disposed on a side opposite to the side on which the plurality of silicon dies are disposed when viewed from the organic bonding layer, A build-up substrate disposed on a side opposite to the side on which the organic bonding layer is disposed when viewed from the high-density wiring layer, The semiconductor structure according to <1>, comprising. <5> The organic insulating layer contains a cured product of the following Composition A or a cured product of the following Composition B, The Composition A is A compound (A) having a cationic functional group containing at least one selected from a primary nitrogen atom and a secondary nitrogen atom and a Si-O bond, [[ID=2"3]] A compound (B) having three or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and among the three or more -C(=O)OX groups, one or more to six are -C(=O)OH groups, A compound (C) having a ring structure and one or more primary nitrogen atoms directly bonded to the ring structure, and is a composition in which the ratio of the primary nitrogen atoms and secondary nitrogen atoms contained in the compound (A) to the total of the primary nitrogen atoms contained in the compound (A) and the primary nitrogen atoms contained in the compound (C) is 3 mol% to 95 mol%, The Composition (B) is a composition containing at least one of a compound (X1) having a structure represented by the following general formula (1) and a molecular weight of 400 to 5000, and a compound (X2) having a structure represented by the following general formula (2) and a molecular weight of 400 to 5000. ​The semiconductor structure according to any one of <1> to <4>.

[0007]

Chemical formula

[0008] In general formula (1), R1 and R3 are each independently an organic group having 6 or fewer carbon atoms, R2 is a methylene group, an ethylene group, a propylene group or a phenylene group, a is 2 or 3, b is the number of 3 - a, and X1 is a structure derived from a carboxylic dianhydride. In general formula (2), R1 and R3 are each independently an organic group having 6 or fewer carbon atoms, R2 is a methylene group, an ethylene group, a propylene group or a phenylene group, a is 2 or 3, b is the number of 3 - a, X1 is a structure derived from a carboxylic dianhydride, X2 is a structure derived from an amine compound, and n is a positive number.

[0009] <6> Each of the plurality of silicon dies includes a silicon die body and a silicon die bonding layer in contact with the organic bonding layer. The silicon die bonding layer includes an organic insulating layer, a SiO2 layer, a SiCN layer, or a SiN layer and a metal pad. The semiconductor structure according to any one of <1> to <5>. <7> The semiconductor structure according to any one of <1> to <6>, wherein the resin mold layer covers the upper surfaces of the plurality of silicon dies. <8> Further, It is disposed on the side opposite to the side where the organic bonding layer is disposed when viewed from the plurality of silicon dies, and includes a second organic bonding layer including an organic insulating layer and a metal pad. The semiconductor structure according to any one of <1> to <7>. <9> Further, On the second organic bonding layer, a plurality of second silicon dies are two-dimensionally arranged and hybrid-bonded. The semiconductor structure according to <8>. <10> Each of the plurality of second silicon dies includes a silicon die body and a silicon die bonding layer in contact with the second organic bonding layer. The silicon die bonding layer includes an organic insulating layer, an SiO2 layer, a SiCN layer, or a SiN layer, and a metal pad. <9> The semiconductor structure described above. <11> Furthermore, The device comprises a second redistribution layer disposed between the second organic bonding layer and the plurality of silicon dies, <8> ~ <10> A semiconductor structure described in any one of the following. <12> Furthermore, A temporary fixing substrate or build-up substrate is located on the side opposite to the side where the multiple silicon dies are arranged, as viewed from the organic bonding layer. Equipped with, <8> ~ <11> A semiconductor structure described in any one of the following. <13> The process of forming a redistribution layer on a temporary fixed substrate and The process involves forming an organic bonding layer including an organic insulating layer and a metal pad on the rewiring layer that is temporarily fixed on the temporary fixing substrate, A step of hybrid bonding by arranging a plurality of silicon dies in a two-dimensional manner on the organic bonding layer formed on the redistribution layer, A step of forming a resin mold layer which is filled between the plurality of silicon dies on the organic bonding layer and covers the upper surface of the plurality of silicon dies, The step of removing the temporary fixed substrate, A method for manufacturing a semiconductor structure, including [the specified element]. <14> A step of forming a redistribution layer on a temporary fixed substrate, The process involves forming an organic bonding layer including an organic insulating layer and a metal pad on the rewiring layer that is temporarily fixed on the temporary fixing substrate, A step of hybrid bonding by arranging a plurality of silicon dies in a two-dimensional manner on the organic bonding layer formed on the redistribution layer, A step of forming a resin mold layer which is filled between the plurality of silicon dies on the organic bonding layer and covers the upper surface of the plurality of silicon dies, The step of removing the temporary fixed substrate, The steps include forming electrodes on the side of the rewiring layer from which the temporary fixing substrate has been removed, A step of joining the redistribution layer and the build-up substrate via the electrodes, A method for manufacturing a semiconductor structure, including [the specified element]. <15> A step of forming an organic bonding layer including an organic insulating layer and a metal pad on a temporary fixing substrate, A step of hybrid bonding by arranging a plurality of silicon dies in a two-dimensional manner on the organic bonding layer formed on the redistribution layer, A step of forming a resin mold layer which is filled between the plurality of silicon dies on the organic bonding layer and covers the upper surface of the plurality of silicon dies, The step of removing the temporary fixed substrate, A method for manufacturing a semiconductor structure, including [the specified element]. <16> A step of forming an organic bonding layer including an organic insulating layer and a metal pad on a temporary fixing substrate, A step of hybrid bonding by arranging multiple silicon dies in a two-dimensional manner on the organic bonding layer formed on the temporary fixing substrate, A step of forming a resin mold layer which is filled between the plurality of silicon dies on the organic bonding layer and covers the upper surface of the plurality of silicon dies, The step of removing the temporary fixed substrate, A step of forming an electrode on the side of the organic bonding layer from which the temporary fixing substrate has been removed, A step of joining the organic bonding layer and the build-up substrate via the electrode, A method for manufacturing a semiconductor structure, including [the specified element]. <17> A process of forming a high-density wiring layer on a build-up substrate, The process of forming an organic bonding layer including an organic insulating layer and a metal pad on the high-density wiring layer, A step of hybrid bonding by arranging a plurality of silicon dies in a two-dimensional manner on the organic bonding layer formed on the high-density wiring layer, A step of forming a resin mold layer which is filled between the plurality of silicon dies on the organic bonding layer and covers the upper surface of the plurality of silicon dies, A method for manufacturing a semiconductor structure, including [the specified element]. <18> Furthermore, A step of removing the portion of the resin mold layer that covers the upper surfaces of the plurality of silicon dies, thereby exposing the upper surfaces of the plurality of silicon dies, A step of forming a second organic bonding layer including an organic insulating layer and a metal pad on the plurality of silicon dies and the resin mold layer whose upper surfaces are exposed, including, <13> ~ <17> A method for manufacturing a semiconductor structure as described in any one of the following. <19> Furthermore, The process includes a step of hybrid bonding by arranging a plurality of second silicon dies in a two-dimensional manner on the second organic bonding layer, <18> A method for manufacturing the semiconductor structure described above. <20> Furthermore, A step of removing the portion of the resin mold layer that covers the upper surfaces of the plurality of silicon dies, thereby exposing the upper surfaces of the plurality of silicon dies, A step of forming a second redistribution layer on the plurality of silicon dies and the resin mold layer whose upper surfaces are exposed, A step of forming a second organic bonding layer including an organic insulating layer and a metal pad on the second redistribution layer, including, <13> ~ <17> A method for manufacturing a semiconductor structure as described in any one of the following. <21> Furthermore, The process includes a step of hybrid bonding by arranging a plurality of second silicon dies in a two-dimensional manner on the second organic bonding layer, <20> A method for manufacturing the semiconductor structure described above. <22> The step of forming the organic bonding layer includes curing composition A or composition B to form the organic insulating layer, The aforementioned composition A is A compound (A) having a cationic functional group containing at least one selected from primary and secondary nitrogen atoms and a Si-O bond, Compound (B) having three or more -C(=O)OX groups (where X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and of the three or more -C(=O)OX groups, one to six are -C(=O)OH groups, A compound (C) having a ring structure and one or more primary nitrogen atoms directly bonded to the ring structure, The composition is such that the proportion of primary and secondary nitrogen atoms contained in compound (A) to the total of primary nitrogen atoms contained in compound (C) is 3 mol% to 95 mol%, The composition (B) is a composition comprising at least one of a compound (X1) having a structure represented by the following general formula (1) and a molecular weight of 400 to 5000, and a compound (X2) having a structure represented by the following general formula (2) and a molecular weight of 400 to 5000. <13> ~ <21> A method for manufacturing a semiconductor structure as described in any one of the following.

[0010] [ka]

[0011] In general formula (1), R1 and R3 are each independently organic groups having 6 or fewer carbon atoms, R2 is a methylene group, an ethylene group, a propylene group, or a phenylene group, a is 2 or 3, b is the number of 3-a, and X1 is a structure derived from a carboxylic acid dianhydride. In general formula (2), R1 and R3 are each independently organic groups having 6 or fewer carbon atoms, R2 is a methylene group, an ethylene group, a propylene group, or a phenylene group, a is 2 or 3, b is the number of 3-a, X1 is a structure derived from a carboxylic acid dianhydride, X2 is a structure derived from an amine compound, and n is a positive number. [Effects of the Invention]

[0012] According to one aspect of this disclosure, a semiconductor structure capable of narrowing the wiring pitch and a method for manufacturing the same are provided. [Brief explanation of the drawing]

[0013] [Figure 1] This is a schematic cross-sectional view of a first specific example of a semiconductor structure in this disclosure. [Figure 2]This is a schematic cross-sectional view showing an example of an electronic device using a first specific example of the semiconductor structure of this disclosure. [Figure 3A] This is a schematic flowchart illustrating the process for manufacturing another example of an electronic device using the first specific example of the semiconductor structure of this disclosure. [Figure 3B] This is a schematic flowchart illustrating the process for manufacturing another example of an electronic device using the first specific example of the semiconductor structure of this disclosure. [Figure 3C] This is a schematic flowchart illustrating the process for manufacturing another example of an electronic device using the first specific example of the semiconductor structure of this disclosure. [Figure 4] This is a schematic cross-sectional view of a second specific example of the semiconductor structure of this disclosure. [Figure 5A] This is a schematic flowchart illustrating the process for manufacturing an example of an electronic device using a second specific example of the semiconductor structure of this disclosure. [Figure 5B] This is a schematic flowchart illustrating the process for manufacturing an example of an electronic device using a second specific example of the semiconductor structure of this disclosure. [Figure 6] This is a schematic cross-sectional view of a third specific example of the semiconductor structure of this disclosure. [Figure 7A] This is a schematic flowchart showing the process for manufacturing a first specific example of the semiconductor structure disclosed herein. [Figure 7B] This is a schematic flowchart showing the process for manufacturing a first specific example of the semiconductor structure disclosed herein. [Figure 7C] This is a schematic flowchart showing the process for manufacturing a first specific example of the semiconductor structure disclosed herein. [Figure 7D] This is a schematic flowchart showing the process for manufacturing a first specific example of the semiconductor structure disclosed herein. [Figure 7E] This is a schematic flowchart showing the process for manufacturing a first specific example of the semiconductor structure disclosed herein. [Figure 8A] This is a schematic flowchart showing the process for manufacturing a second specific example of the semiconductor structure of this disclosure. [Figure 8B] This is a schematic flowchart showing the process for manufacturing a second specific example of the semiconductor structure of this disclosure. [Figure 8C]This is a schematic flowchart showing the process for manufacturing a second specific example of the semiconductor structure of this disclosure. [Figure 8D] This is a schematic flowchart showing the process for manufacturing a second specific example of the semiconductor structure of this disclosure. [Figure 9A] This is a schematic flowchart showing the process for manufacturing a third specific example of the semiconductor structure disclosed herein. [Figure 9B] This is a schematic flowchart showing the process for manufacturing a third specific example of the semiconductor structure disclosed herein. [Figure 9C] This is a schematic flowchart showing the process for manufacturing a third specific example of the semiconductor structure disclosed herein. [Figure 9D] This is a schematic flowchart showing the process for manufacturing a third specific example of the semiconductor structure disclosed herein. [Figure 10A] This is a schematic flowchart showing the process for manufacturing a fourth specific example of the semiconductor structure of this disclosure. [Figure 10B] This is a schematic flowchart showing the process for manufacturing a fourth specific example of the semiconductor structure of this disclosure. [Figure 10C] This is a schematic flowchart showing the process for manufacturing a fourth specific example of the semiconductor structure of this disclosure. [Figure 10D] This is a schematic flowchart showing the process for manufacturing a fourth specific example of the semiconductor structure of this disclosure. [Figure 11A] This is a schematic flowchart showing the process for manufacturing a fifth specific example of the semiconductor structure disclosed herein. [Figure 11B] This is a schematic flowchart showing the process for manufacturing a fifth specific example of the semiconductor structure disclosed herein. [Figure 11C] This is a schematic flowchart showing the process for manufacturing a fifth specific example of the semiconductor structure disclosed herein. [Figure 11D] This is a schematic flowchart showing the process for manufacturing a fifth specific example of the semiconductor structure disclosed herein. [Modes for carrying out the invention]

[0014] In this disclosure, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In numerical ranges described in stages within this disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described within this disclosure, the upper or lower limit of that range may be replaced with the values ​​shown in the examples.

[0015] [Semiconductor Structures] The semiconductor structure disclosed herein is An organic bonding layer including an organic insulating layer and a metal pad, Multiple silicon dies are arranged in a two-dimensional manner and hybrid-bonded on the aforementioned organic bonding layer, A resin mold layer filled between the plurality of silicon dies on the organic bonding layer, It is equipped with. The semiconductor structure of this disclosure may comprise other elements (e.g., other layers and / or other components).

[0016] In the semiconductor structure of this disclosure, since a silicon die is hybrid-bonded on an organic junction layer, it is possible to narrow the wiring pitch compared to cases where a semiconductor chip (e.g., a silicon die) is bonded to a redistribution layer or junction layer using solder and epoxy resin.

[0017] Furthermore, the organic junction layer in the semiconductor structure of this disclosure includes an organic insulating layer that can be formed by a wet process such as a coating method. Therefore, compared to the case in which an inorganic junction layer including an inorganic insulating layer such as SiO2 is formed by a dry process, the semiconductor structure of this disclosure has a simpler junction layer formation process and can be adapted to semiconductor structures of various sizes.

[0018] The semiconductor structure of this disclosure may include a redistribution layer located on the side opposite to the side where the plurality of silicon dies are arranged, with respect to the organic junction layer. An example of an embodiment that includes a redistribution layer is the first specific example described later. An example of an embodiment that does not include a rewiring layer is the second specific example described later.

[0019] The semiconductor structure of this disclosure may include a build-up substrate disposed on the side opposite to the side on which the plurality of silicon dies are arranged, with respect to the organic junction layer. Embodiments comprising a build-up substrate also include electronic devices in which a build-up substrate is bonded to a semiconductor structure according to the first and second specific examples (details of these will also be described later).

[0020] The semiconductor structure of this disclosure may include a high-density wiring layer disposed on the side opposite to the side on which the plurality of silicon dies are arranged when viewed from the organic junction layer, and a build-up substrate disposed on the side opposite to the side on which the organic junction layer is arranged when viewed from the high-density wiring layer. An example of an embodiment comprising this high-density wiring layer and build-up substrate is the third specific example described later.

[0021] In the semiconductor structure of this disclosure, the organic insulating layer may include a cured product of composition A or a cured product of composition B. Composition A is, A compound (A) having a cationic functional group containing at least one selected from primary and secondary nitrogen atoms and a Si-O bond, Compound (B) having three or more -C(=O)OX groups (where X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and of the three or more -C(=O)OX groups, one to six are -C(=O)OH groups, A compound (C) having a ring structure and one or more primary nitrogen atoms directly bonded to the ring structure, The composition is such that the proportion of primary and secondary nitrogen atoms contained in compound (A) to the total of primary nitrogen atoms contained in compound (C) is 3 mol% to 95 mol%, Composition (B) is The composition comprises at least one of a compound (X1) having a structure represented by the following general formula (1) and a molecular weight of 400 to 5000, and a compound (X2) having a structure represented by the following general formula (2) and a molecular weight of 400 to 5000.

[0022] [ka]

[0023] In general formula (1), R1 and R3 are each independently organic groups having 6 or fewer carbon atoms, R2 is a methylene group, an ethylene group, a propylene group, or a phenylene group, a is 2 or 3, b is the number of 3-a, and X1 is a structure derived from a carboxylic acid dianhydride. In general formula (2), R1 and R3 are each independently organic groups having 6 or fewer carbon atoms, R2 is a methylene group, an ethylene group, a propylene group, or a phenylene group, a is 2 or 3, b is the number of 3-a, X1 is a structure derived from a carboxylic acid dianhydride, X2 is a structure derived from an amine compound, and n is a positive number.

[0024] Details of composition A and composition B will be described later.

[0025] In the semiconductor structure of this disclosure, each of the plurality of silicon dies may include a silicon die body and a silicon die junction layer in contact with the organic junction layer. The silicon die bonding layer may include an organic insulating layer, an SiO2 layer, a SiCN layer, or a SiN layer, and a metal pad.

[0026] In the semiconductor structure of this disclosure, the resin mold layer may cover the upper surfaces of multiple silicon dies (for example, the first and second specific examples described below).

[0027] The semiconductor structure disclosed herein further comprises, A second organic bonding layer may be provided, which is located on the side opposite to the side where the organic bonding layer is located when viewed from multiple silicon dies, and which includes an organic insulating layer and a metal pad (for example, the fourth and fifth specific examples described below).

[0028] The semiconductor structure of this disclosure, when comprising a second organic junction layer, Furthermore, The second organic bonding layer may comprise a plurality of second silicon dies arranged in a two-dimensional manner and hybrid-bonded (for example, the fourth and fifth specific examples described later).

[0029] Each of the multiple second silicon dies may include a silicon die body and a silicon die bonding layer in contact with the second organic bonding layer. The silicon die bonding layer may include an organic insulating layer, an SiO2 layer, a SiCN layer, or a SiN layer, and a metal pad.

[0030] The semiconductor structure of this disclosure, when comprising a second organic junction layer, Furthermore, The system may also include a second redistribution layer positioned between the second organic bonding layer and the plurality of silicon dies (for example, the fourth and fifth specific examples described below).

[0031] The semiconductor structure of this disclosure, when comprising a second organic junction layer, Furthermore, A temporary fixing substrate or build-up substrate is located on the side opposite to the side where the multiple silicon dies are arranged, as viewed from the organic bonding layer. It may also include (for example, the fourth and fifth specific examples described below).

[0032] Specific examples of the semiconductor structures described herein will be explained below, with reference to the drawings as appropriate. However, the semiconductor structures described herein are not limited to the following specific examples. In the following explanation, substantially identical elements (e.g., parts or components) will be given the same reference numeral, and redundant explanations may be omitted.

[0033] <First example> Figure 1 is a schematic cross-sectional view of a semiconductor structure 100, which is a first specific example of the semiconductor structure of this disclosure. As shown in Figure 1, the semiconductor structure 100 is An organic bonding layer 10 including an organic insulating layer (not shown) and a metal pad (not shown), Multiple silicon dies 20 are arranged in a two-dimensional manner and hybrid-bonded on an organic bonding layer 10, A resin mold layer 30 is filled between multiple silicon dies 20 on the organic bonding layer 10 and covers the upper surface of the multiple silicon dies 20, A redistribution layer 40 is located on the opposite side from the side where multiple silicon dies 20 are arranged, as viewed from the organic bonding layer 10, It is equipped with.

[0034] Each of the multiple silicon dies 20 in the semiconductor structure 100 may include a silicon die body 22 and a silicon die junction layer 24 in contact with the organic junction layer 10. The silicon die bonding layer 24, although not shown in the figure, includes an organic insulating layer or an SiO2 layer and a metal pad.

[0035] In the semiconductor structure 100, the silicon die 20 is hybrid-bonded to the organic bonding layer 10, which allows for a narrower wiring pitch compared to cases where semiconductor chips (e.g., silicon dies) are bonded to the redistribution layer or bonding layer using solder and epoxy resin.

[0036] Next, preferred embodiments of each element of the semiconductor structure of this disclosure will be described.

[0037] (Rewiring layer) In this disclosure, a known redistribution layer (RDL) consisting of a resin insulating material such as polyimide and Cu wiring can be used as the redistribution layer (e.g., redistribution layer 40). For example, a method for forming a redistribution layer is: The damascene method involves dry etching a resin insulating material to form Cu wiring, followed by planarization using methods such as CMP. Cu wiring formation by semi-additive method and method using photosensitive resin; These are some examples.

[0038] Furthermore, the configuration of the high-density wiring layer (for example, the high-density wiring layer 42 in the third specific example described later) is the same as that of the redistribution layer.

[0039] (Organic bonding layer) The organic bonding layer in this disclosure (for example, the organic bonding layer 10) includes an organic insulating layer and a metal pad.

[0040] An example of an organic insulating layer in an organic bonding layer is an insulating resin layer formed by a coating method. Examples of materials for the organic insulating layer include polyimide, benzocyclobutene resin (BCB), polymaleimide, siloxaneimide, epoxy-modified siloxane, polybenzoxazole, and sol-gel silica. In particular, insulating materials containing siloxane are preferred because they can be bonded at room temperature. As mentioned above, the organic insulating layer preferably contains a cured product of composition A or a cured product of composition B. The organic insulating layer preferably has a curing reaction rate of 70% or more.

[0041] The metal pad in the organic bonding layer is a pad containing metals such as Cu, gold, or tin. Methods for forming the metal pad include, for example; A method for forming a metal pad using the damascene method after forming an organic insulating layer; A method for forming an organic insulating layer, creating holes using a laser drilling method, and then forming a gold pad using plating or sputtering; A method for forming a metal pad using a semi-additive process, followed by the formation of an organic insulating layer, and then the formation of an organic bonding layer by CMP or diamond bit cutting; These are some examples.

[0042] In the bonding surface of the organic bonding layer, the metal pad may be recessed or convex relative to the organic insulating layer.

[0043] (Silicon Die) In this disclosure, the silicon die (e.g., the silicon die 20) includes a silicon die body (e.g., the silicon die body 22) and a silicon die bonding layer (e.g., the silicon die bonding layer 24) provided on the surface of the silicon die body. The silicon die itself is a silicon substrate that includes device layers such as memory and logic. The silicon die bonding layer may include an organic insulating layer, an SiO2 layer, a SiCN layer, or a SiN layer, and a metal pad. A preferred embodiment of the organic insulating layer in the silicon die bonding layer is the same as the preferred embodiment of the organic insulating layer in the organic bonding layer described above. The SiO2 layer, SiCN layer, or SiN layer in the silicon die bonding layer can be formed by known vapor phase methods. The preferred embodiment of the metal pad in the silicon die bonding layer is the same as the preferred embodiment of the metal pad in the organic bonding layer described above.

[0044] (Hybrid bonding) In the semiconductor structure described herein, a silicon die (e.g., the silicon die 20) is hybrid-bonded to an organic junction layer (e.g., the organic junction layer 10). The above hybrid bonding can be performed in a configuration in which the organic bonding layer and the silicon die bonding layer in the silicon die are in contact.

[0045] In this disclosure, hybrid bonding means a type of bonding in which electrodes are joined together and insulating films are joined together by bringing two surfaces in which electrodes and insulating materials are exposed into contact with each other.

[0046] Hybrid bonding between an organic bonding layer and a silicon die is, for example; Thermal compression bonding; A method for joining metal pads together by heating or gang bonding after bonding insulating layers together at room temperature; These are some examples. Here, from the viewpoint of increasing bonding strength, it is preferable to perform surface activation treatment (such as ozone treatment, plasma treatment, or high-speed atomic beam treatment) on the bonding surface in the silicon die and the bonding surface in the organic bonding layer before bonding. Furthermore, from the viewpoint of promoting the bonding of metal pads, it is preferable to remove the metal oxide film by acid cleaning the bonding surface with citric acid or the like before bonding.

[0047] (Resin mold layer) Examples of materials for the resin mold layer (e.g., resin mold layer 30) in this disclosure include epoxy resin.

[0048] (Example of usage of the semiconductor structure 100 in the first specific example) Next, we will describe an example of how the semiconductor structure 100 relating to the first specific example can be used. The semiconductor structure 100 is used by being connected to a build-up substrate directly or via other components.

[0049] Figure 2 is a schematic cross-sectional view showing an example of an electronic device (electronic device 101) using the semiconductor structure 100, which is a first specific example of the semiconductor structure of this disclosure. As shown in Figure 2, the electronic device 101 is obtained by connecting solder balls 110 to the semiconductor structure 100 on the side opposite to the side where the organic junction layer 10 exists, as viewed from the redistribution layer 40. An example of using the electronic device 101 is to electrically connect the semiconductor structure 100 and a build-up substrate (not shown) via the solder balls 110 in the electronic device 101.

[0050] Figures 3A to 3C are schematic flowcharts showing the process for manufacturing another example of an electronic device (electronic device 102) using the semiconductor structure 100, which is the first specific example of the semiconductor structure of this disclosure. To manufacture the electronic device 102, first, as shown in Figure 3A, an organic junction layer 12 including an organic insulating layer (not shown) and a metal pad (not shown) is formed on the side of the semiconductor structure 100 opposite to the side where the organic junction layer 10 exists, as viewed from the redistribution layer 40. Next, as shown in Figure 3B, a plurality of silicon bridges 120 are connected to the organic bonding layer 12. Each of the plurality of silicon bridges 120 is connected to the organic bonding layer 12 in a configuration that spans two adjacent silicon dies 20 in a plan view. As a result, the two adjacent silicon dies 20 are electrically connected via the silicon bridges 120. Here, the silicon bridge 120 includes a silicon bridge body 122, a silicon bridge bonding layer 124 in contact with the organic bonding layer 12, and a through electrode 126 that penetrates the silicon bridge body 122. Next, as shown in Figure 3C, a resin mold 130 is formed to cover the organic bonding layer 12 and the multiple silicon bridges 120, and a through electrode 134 is formed that penetrates the resin mold 130. Furthermore, a through electrode 132 is formed in the portion of the resin mold 130 that covers the multiple silicon bridges 120. This through electrode 132 is electrically connected to the through electrode 126 in the silicon bridge 120. Next, the solder balls 110 are connected to the surface of the resin mold 130. The solder balls 110 are electrically connected to the through electrodes 132 and 134 that are exposed on the surface of the resin mold 130. As a result, the electronic device 102 is obtained. An example of using the electronic device 102 is to electrically connect the semiconductor structure 100 and a build-up substrate (not shown) via the solder balls 110 in the electronic device 102.

[0051] As described above, in the electronic device 102, the silicon bridge 120 is covered by the resin mold 130, and the solder ball 110 is connected to the portion of the resin mold 130 that covers the silicon bridge 120. However, the silicon bridge 120 does not need to be covered by the resin mold 130 and may be exposed (a modified example of the electronic device 102). For example, first, as shown in Figure 3C, the resin mold 130 may be formed to cover the organic bonding layer 12 and the silicon bridge 120, and then the resin mold 130 may be polished by CMP or the like to expose the silicon bridge 120, and then the through electrode 134 may be formed. In this case, the solder ball 110 is directly connected to the exposed silicon bridge 120.

[0052] <Second specific example> Figure 4 is a schematic cross-sectional view of a semiconductor structure 200, which is a second specific example of the semiconductor structure of this disclosure. As shown in Figure 4, the semiconductor structure 200 is An organic bonding layer 10 including an organic insulating layer (not shown) and a metal pad (not shown), Multiple silicon dies 20 are arranged in a two-dimensional manner and hybrid-bonded on an organic bonding layer 10, A resin mold layer 30 is filled between multiple silicon dies 20 on the organic bonding layer 10 and covers the upper surface of the multiple silicon dies 20, It is equipped with. The structure of the semiconductor structure 200 is the same as that of the semiconductor structure 100, except that it does not have a redistribution layer 40.

[0053] In the semiconductor structure 200, the silicon die 20 is hybrid-bonded to the organic bonding layer 10, which allows for a narrower wiring pitch compared to cases where semiconductor chips (e.g., silicon dies) are bonded to the redistribution layer or bonding layer using solder and epoxy resin.

[0054] The semiconductor structure 200 is used by being connected to a build-up substrate. The following describes examples of how the semiconductor structure 200 can be used.

[0055] Figures 5A and 5B are schematic flowcharts showing the process of manufacturing another example of an electronic device (electronic device 202) using the semiconductor structure 200, which is a second specific example of the semiconductor structure of this disclosure. To manufacture the electronic device 202, first, as shown in Figure 5A, a plurality of silicon bridges 120 are connected to the organic junction layer 10 in the semiconductor device 200. Each of the plurality of silicon bridges 120 is connected to the organic junction layer 10 in a configuration that spans two adjacent silicon dies 20 in a plan view. This electrically connects the two adjacent silicon dies 20 via the silicon bridges 120. Here, the silicon bridge 120 includes a silicon bridge body 122, a silicon bridge junction layer 124 in contact with the organic junction layer 12, and a through electrode 126 penetrating the silicon bridge body 122. Next, as shown in Figure 5B, a resin mold 130 is formed to cover the organic bonding layer 10 and the multiple silicon bridges 120, and a through electrode 134 is formed that penetrates the resin mold 130. Furthermore, a through electrode 132 is formed in the portion of the resin mold 130 that covers the multiple silicon bridges 120. This through electrode 132 is electrically connected to the through electrode 126 in the silicon bridge 120. Next, the solder balls 110 are connected to the surface of the resin mold 130. The solder balls 110 are electrically connected to the through electrodes 132 and 134 that are exposed on the surface of the resin mold 130. As a result, the electronic device 202 is obtained. An example of using the electronic device 202 is to electrically connect the semiconductor structure 200 and a build-up substrate (not shown) via the solder balls 110 in the electronic device 202.

[0056] <Third specific example> Figure 6 is a schematic cross-sectional view of a semiconductor structure 300, which is a third specific example of the semiconductor structure of this disclosure. As shown in Figure 6, the semiconductor structure 300 is An organic bonding layer 10 including an organic insulating layer (not shown) and a metal pad (not shown), Multiple silicon dies 20 are arranged in a two-dimensional manner and hybrid-bonded on an organic bonding layer 10, A resin mold layer 30 is filled between multiple silicon dies 20 on the organic bonding layer 10 and covers the upper surface of the multiple silicon dies 20, A high-density wiring layer 42 is located on the opposite side from the side where multiple silicon dies 20 are arranged, as viewed from the organic bonding layer 10, A build-up substrate 50 connected to the side opposite to the side where the organic bonding layer 10 is located, as viewed from the high-density wiring layer 42, It is equipped with.

[0057] [Method for manufacturing semiconductor structures] Embodiments of a manufacturing method for producing the semiconductor structure described above will now be explained. However, the manufacturing method is not limited to the following embodiments.

[0058] <First Embodiment> The method for manufacturing a semiconductor structure according to the first embodiment is: A step of forming a redistribution layer on a temporary fixed substrate, The process involves forming an organic bonding layer including an organic insulating layer and a metal pad on the rewiring layer that is temporarily fixed on the temporary fixing substrate, A step of hybrid bonding by arranging a plurality of silicon dies in a two-dimensional manner on the organic bonding layer formed on the redistribution layer, A step of forming a resin mold layer which is filled between the plurality of silicon dies on the organic bonding layer and covers the upper surface of the plurality of silicon dies, The step of removing the temporary fixed substrate, Includes.

[0059] The method for manufacturing a semiconductor structure according to the first embodiment is particularly suitable, for example, as a method for manufacturing the semiconductor structure 100 according to the first specific example described above.

[0060] Figures 7A to 7E are schematic flowcharts showing the process for manufacturing a semiconductor structure 100 according to a first specific example of the semiconductor structure of this disclosure.

[0061] First, as shown in Figure 7A, a redistribution layer 40 is formed on the temporary fixing substrate 60. Next, as shown in Figure 7B, an organic bonding layer 10 including an organic insulating layer and a metal pad is formed on the redistribution layer 40 that has been temporarily fixed onto the temporary fixing substrate 60. Next, as shown in Figure 7C, multiple silicon dies 20 are arranged in a two-dimensional manner on the organic bonding layer 10 formed on the redistribution layer 40 and hybrid bonded. The hybrid bond is performed in a configuration where the silicon die bonding layer 24 on the silicon die 20 and the organic bonding layer 10 are in contact. Next, as shown in Figure 7D, a resin mold layer 30 is formed which is filled between the multiple silicon dies 20 on the organic bonding layer 10 and covers the upper surfaces of the multiple silicon dies 20. Next, as shown in Figure 7E, the semiconductor structure 100 is obtained by removing the temporary fixing substrate 60.

[0062] In this disclosure, a temporary fixing substrate (e.g., temporary fixing substrate 60) can be, for example, a glass substrate, a silicon substrate, or the like. In this disclosure, the removal of the temporary fixing substrate (e.g., temporary fixing substrate 60) can be performed by methods such as laser lift-off or mechanical peeling.

[0063] The method for manufacturing the semiconductor structure according to the first embodiment further includes: A step of forming electrodes on the side where the temporary fixing substrate of the redistribution layer has been removed, A process of joining the redistribution layer and the build-up substrate via electrodes, It may include.

[0064] <Second Embodiment> The method for manufacturing a semiconductor structure according to the second embodiment is as follows: A step of forming an organic bonding layer including an organic insulating layer and a metal pad on a temporary fixing substrate, A step of hybrid bonding by arranging multiple silicon dies in a two-dimensional manner on the organic bonding layer formed on the temporary fixing substrate, A step of forming a resin mold layer which is filled between the plurality of silicon dies on the organic bonding layer and covers the upper surface of the plurality of silicon dies, The step of removing the temporary fixed substrate, Includes.

[0065] The method for manufacturing a semiconductor structure according to the second embodiment is particularly suitable, for example, as a method for manufacturing the semiconductor structure 200 according to the second specific example described above.

[0066] Figures 8A to 8D are schematic flowcharts showing the process for manufacturing a semiconductor structure 200 according to a second specific example of the semiconductor structure of this disclosure.

[0067] First, as shown in Figure 8A, an organic bonding layer 10 including an organic insulating layer and a metal pad is formed on the temporary fixing substrate 60. Next, as shown in Figure 8B, multiple silicon dies 20 are arranged in a two-dimensional manner on the organic bonding layer 10 formed on the temporary fixed substrate 60 and hybrid bonded. The hybrid bond is performed in a configuration where the silicon die bonding layer 24 on the silicon die 20 and the organic bonding layer 10 are in contact. Next, as shown in Figure 8C, a resin mold layer 30 is formed, which is filled between the multiple silicon dies 20 on the organic bonding layer 10 and covers the upper surfaces of the multiple silicon dies 20. Next, as shown in Figure 8D, the semiconductor structure 200 is obtained by removing the temporary fixing substrate 60.

[0068] The method for manufacturing a semiconductor structure according to the second embodiment further includes: A step of forming electrodes on the side from which the temporary fixing substrate of the organic bonding layer has been removed, A process of joining the redistribution layer and the build-up substrate via electrodes, It may include.

[0069] <Third Embodiment> The method for manufacturing a semiconductor structure according to the third embodiment is: A process of forming a high-density wiring layer on a build-up substrate, The process of forming an organic bonding layer including an organic insulating layer and a metal pad on the high-density wiring layer, A step of hybrid bonding by arranging a plurality of silicon dies in a two-dimensional manner on the organic bonding layer formed on the high-density wiring layer, A step of forming a resin mold layer which is filled between the plurality of silicon dies on the organic bonding layer and covers the upper surface of the plurality of silicon dies, Includes.

[0070] The method for manufacturing a semiconductor structure according to the third embodiment is particularly suitable, for example, as a method for manufacturing the semiconductor structure 300 according to the third specific example described above.

[0071] Figures 9A to 9D are schematic flowcharts showing the process for manufacturing a semiconductor structure 300 according to a third specific example of the semiconductor structure of this disclosure.

[0072] First, as shown in Figure 9A, a high-density wiring layer 42 is formed on the build-up substrate 50. Next, as shown in Figure 9B, an organic bonding layer 10 including an organic insulating layer and a metal pad is formed on the high-density wiring layer 42. Next, as shown in Figure 9C, multiple silicon dies 20 are arranged in a two-dimensional manner on the organic bonding layer 10 formed on the high-density wiring layer 42 and hybrid bonded. The hybrid bond is performed in a configuration where the silicon die bonding layer 24 on the silicon die 20 and the organic bonding layer 10 are in contact. Next, as shown in Figure 9D, a resin mold layer 30 is formed which is filled between the multiple silicon dies 20 on the organic bonding layer 10 and covers the upper surfaces of the multiple silicon dies 20. Thus, a semiconductor structure 300 is obtained.

[0073] <Formation of the second organic bonding layer> The method for manufacturing a semiconductor structure according to the first to third embodiments is as follows: Furthermore, A process of removing the portion of the resin mold layer that covers the top surface of multiple silicon dies, thereby exposing the top surfaces of multiple silicon dies, A step of forming a second organic bonding layer including an organic insulating layer and a metal pad on a plurality of silicon dies and resin mold layers with their upper surfaces exposed, It may include. A preferred embodiment of the second organic bonding layer is the same as the preferred embodiment of the organic bonding layer described above.

[0074] <Formation of the second redistribution layer> The method for manufacturing a semiconductor structure according to the first to third embodiments, which includes the step of forming the second organic bonding layer described above, may further include the step of forming a second redistribution layer on the exposed silicon dies and the resin mold layer between the step of exposing the upper surfaces of the plurality of silicon dies and the step of forming the second organic bonding layer. A preferred embodiment of the second redistribution layer is the same as the preferred embodiment of the redistribution layer described above.

[0075] <Hybrid bonding of the second silicon die> The method for manufacturing a semiconductor structure according to the first to third embodiments, which includes the step of forming the second organic junction layer described above, Furthermore, The process may include a step of hybrid bonding by arranging a plurality of second silicon dies in a two-dimensional manner on a second organic bonding layer. A second preferred embodiment of the silicon die is the same as the preferred embodiment of the silicon die described above.

[0076] <Process for manufacturing the fourth specific example> Figures 10A to 10D are schematic flowcharts showing the process for manufacturing a semiconductor structure 400 according to a fourth specific example of the semiconductor structure of this disclosure. The semiconductor structure 400 according to the fourth specific example is provided with the aforementioned second organic junction layer, the aforementioned second redistribution layer, and the aforementioned second silicon die.

[0077] First, as shown in Figure 10A, an organic bonding layer 10 including an organic insulating layer and a metal pad is formed on the redistribution layer 40 that has been temporarily fixed on the temporary fixing substrate 60, similar to the process shown in Figure 7B described above. Next, perform the operation shown in Figure 10B. In detail, as shown in Figure 10B, multiple silicon dies 20 are arranged in a two-dimensional manner on an organic bonding layer 10 formed on a redistribution layer 40 to perform hybrid bonding. Next, a resin mold layer 30 is formed, which is filled between the multiple silicon dies 20 on the organic bonding layer 10 and covers the upper surface of the multiple silicon dies 20. Next, the portion of the resin mold layer 30 that covers the upper surfaces of the multiple silicon dies is removed to expose the upper surfaces of the multiple silicon dies 20, and then through electrodes 34 that penetrate the resin mold layer 30 and through electrodes 32 that penetrate the silicon die body in the silicon die 20 are formed. Next, a second redistribution layer 40A is formed on the multiple silicon dies 20 and resin mold layer 30 with their upper surfaces exposed (see Figure 10B for details). Next, as shown in Figure 10C, a second organic bonding layer 10A, including an organic insulating layer and a metal pad, is formed on the second redistribution layer 40A. Next, as shown in Figure 10D, multiple second silicon dies 20A are arranged in a two-dimensional manner on the second organic bonding layer 10A to perform hybrid bonding. This results in the production of a semiconductor structure 400 including a second organic junction layer 10A, a second redistribution layer 40A, and a second silicon die 20A. In the fourth specific example, the second redistribution layer is an optional element and may be omitted. Furthermore, the temporary fixing substrate 60 may be removed from the semiconductor structure 400 according to the fourth specific example.

[0078] <Process for manufacturing the fifth specific example> Figures 11A to 11D are schematic flowcharts showing the process for manufacturing a semiconductor structure 500 according to a fifth specific example of the semiconductor structure of this disclosure. The semiconductor structure 500 according to the fifth specific example is also provided with the aforementioned second organic junction layer, the aforementioned second redistribution layer, and the aforementioned second silicon die, similar to the semiconductor structure 400 according to the fourth specific example.

[0079] First, as shown in Figure 11A, an organic bonding layer 10 including an organic insulating layer and a metal pad is formed on the high-density wiring layer 42 formed on the build-up substrate 50, similar to the process shown in Figure 9B described above. Next, perform the operation shown in Figure 11B. In detail, as shown in Figure 11B, multiple silicon dies 20 are arranged in a two-dimensional manner on an organic bonding layer 10 formed on a high-density wiring layer 42 to perform hybrid bonding. Next, a resin mold layer 30 is formed, which is filled between the multiple silicon dies 20 on the organic bonding layer 10 and covers the upper surface of the multiple silicon dies 20. Next, the portion of the resin mold layer 30 that covers the upper surfaces of the multiple silicon dies is removed to expose the upper surfaces of the multiple silicon dies 20, and then through electrodes 34 that penetrate the resin mold layer 30 and through electrodes 32 that penetrate the silicon die body in the silicon die 20 are formed. Next, a second redistribution layer 40A is formed on the multiple silicon dies 20 and resin mold layer 30 with their upper surfaces exposed (see Figure 11B for details). Next, as shown in Figure 11C, a second organic bonding layer 10A, including an organic insulating layer and a metal pad, is formed on the second redistribution layer 40A. Next, as shown in Figure 11D, multiple second silicon dies 20A are arranged in a two-dimensional manner on the second organic bonding layer 10A to perform hybrid bonding. This results in the production of a semiconductor structure 500 including a second organic junction layer 10A, a second redistribution layer 40A, and a second silicon die 20A. In the fifth specific example, the second redistribution layer is an optional element and may be omitted.

[0080] <Preferred embodiment of the process for forming an organic bonding layer> In the method for manufacturing a semiconductor structure according to the first to third embodiments described above, the step of forming an organic junction layer preferably includes curing composition A or composition B, which will be described later, to form an organic insulating layer. This results in the formation of an organic insulating layer containing a cured product of composition A or a cured product of composition B. The same applies to the process of forming the second organic bonding layer in the process of manufacturing the fourth and fifth specific examples described above.

[0081] [Composition for forming an organic insulating layer] The following describes specific examples of compositions for forming the organic insulating layer in this disclosure: Composition A and Composition B. Composition A below is the composition described in International Publication No. 2022 / 054839, and Composition B is the composition described in Japanese Patent Publication No. 2021-182621.

[0082] <Composition A> Composition A comprises a compound (A) having a cationic functional group containing at least one selected from primary and secondary nitrogen atoms and a Si-O bond, a compound (B) having three or more -C(=O)OX groups (where X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and one to six of the three or more -C(=O)OX groups being -C(=O)OH groups, and a compound (C) having a ring structure and one or more primary nitrogen atoms directly bonded to the ring structure, wherein the proportion of primary and secondary nitrogen atoms contained in compound (A) to the total of primary nitrogen atoms contained in compound (C) is 3 mol% to 95 mol%.

[0083] Composition A contains two components, compound (A) and compound (C), which react with compound (B). Our investigations have shown that the cured product obtained using composition A has a lower coefficient of thermal expansion compared to the cured product obtained using only compound (A) as the component reacting with compound (B). Therefore, the laminate obtained using composition A is less prone to strain at the bonding surface between the layer made of composition A and the substrate, and is considered to have excellent reliability. The layer obtained using the above composition A also exhibits excellent bonding strength with the substrate.

[0084] (Compound (A)) Compound (A) has a cationic functional group containing at least one primary nitrogen atom and a secondary nitrogen atom, and a Si-O bond. The cationic functional group is not particularly limited as long as it can carry a positive charge and contains at least one primary nitrogen atom and a secondary nitrogen atom.

[0085] The cationic functional group in compound (A), which contains at least one primary nitrogen atom and one secondary nitrogen atom, reacts with the carboxyl group of compound (B) to form a cured product. The Si-O bond in compound (A) contributes to improving the bonding strength with the substrate. Compound (A) may be used alone or in combination of two or more types.

[0086] Compound (A) may contain tertiary nitrogen atoms in addition to primary and secondary nitrogen atoms.

[0087] In this disclosure, "primary nitrogen atom" refers to a nitrogen atom bonded to only two hydrogen atoms and one non-hydrogen atom (for example, a nitrogen atom contained in a primary amino group (-NH2 group)), or a nitrogen atom (cation) bonded to only three hydrogen atoms and one non-hydrogen atom. A "secondary nitrogen atom" refers to a nitrogen atom bonded to only one hydrogen atom and two other atoms (i.e., a nitrogen atom contained in a functional group represented by formula (a) below), or a nitrogen atom (cation) bonded to only two hydrogen atoms and two other atoms. A "tertiary nitrogen atom" refers to a nitrogen atom bonded to only three atoms other than hydrogen (i.e., a nitrogen atom that is a functional group represented by formula (b) below), or a nitrogen atom (cation) bonded to only one hydrogen atom and three atoms other than hydrogen.

[0088] [ka]

[0089] In formulas (a) and (b), * indicates a bonding position with an atom other than a hydrogen atom. The functional group represented by formula (a) above is a secondary amino group (-NHR a Base; here, R a The functional group may be part of an alkyl group, or it may be a divalent linking group included in the polymer backbone. The functional group represented by formula (b) above (i.e., the tertiary nitrogen atom) is a tertiary amino group (-NR b R c Base; here, R b and R c Each of these may independently be a functional group that constitutes part of an alkyl group, or it may be a trivalent linking group included in the polymer backbone.

[0090] From the viewpoint of reducing the water absorption rate of the cured product and minimizing the amount of outgassing, compound (A) preferably has two alkyl groups bonded to the oxygen atoms constituting the Si-O bond, and more preferably has alkyl groups bonded to two oxygen atoms bonded to one silicon atom constituting the Si-O bond. The number of carbon atoms of each of the two alkyl groups is preferably 1 to 5, more preferably 1 or 2, and even more preferably 2.

[0091] The weight-average molecular weight of compound (A) is not particularly limited. For example, it may be between 130 and 10,000, between 130 and 5,000, or between 130 and 2,000.

[0092] In this disclosure, the weight-average molecular weight of a compound refers to the weight-average molecular weight in terms of polyethylene glycol, measured by the GPC (Gel Permeation Chromatography) method. Specifically, the weight-average molecular weight is calculated using an aqueous solution with 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 Shodex DET RI-101 as the analyzer and two types of analytical columns (TSKgel G6000PWXL-CP and TSKgel G3000PWXL-CP manufactured by Tosoh Corporation), and analyzed with polyethylene glycol / polyethylene oxide as the standard product using analysis software (Empower3 manufactured by Waters).

[0093] Compound (A) may further have an anionic functional group, a nonionic functional group, etc. as necessary. 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 hydroxy group, a carbonyl group, an ether group (-O-), etc. The anionic functional group is not particularly limited as long as it can carry a negative charge. Examples of the anionic functional group include a carboxylic acid group, a sulfonic acid group, a sulfuric acid group, etc.

[0094] Specific examples of compound (A) include compounds having a Si-O bond and an amino group. Examples of compounds having a Si-O bond and an amino group include siloxanediamine, a silane coupling agent having an amino group, a siloxane polymer of a silane coupling agent having an amino group, etc. Examples of the silane coupling agent having an amino group include compounds represented by the following formula (A-3).

[0095]

Chemical formula

[0096] <000​​​​​​Each of these independently represents an alkylene group, ether group, or carbonyl group having 1 to 12 carbon atoms, which may be substituted (the skeleton may contain carbonyl groups, ether groups, etc.). 4 and R 5 Each of these independently represents an alkylene group or single bond having 1 to 4 carbon atoms, which may be substituted. Ar represents a divalent or trivalent aromatic ring. X 1 X represents hydrogen or an alkyl group having 1 to 5 carbon atoms, which may be substituted. 2 R represents hydrogen, a cycloalkyl group, a heterocyclic group, an aryl group, or a C1-C5 alkyl group which may be substituted (may contain a carbonyl group, ether group, etc. in its skeleton). 1 , R 2 , R 3 , R 4 , R 5 , X 1 They may be the same or different. R 1 , R 2 , R 3 , R 4 , R 5 , X 1 , X 2 Examples of substituents on the alkyl group and alkylene group in the compound include, independently, amino groups, hydroxyl groups, alkoxy groups, cyano groups, carboxylic acid groups, sulfonic acid groups, halogens, and the like. Examples of divalent or trivalent aromatic rings in Ar include divalent or trivalent benzene rings. 2 Examples of aryl groups in this context include phenyl groups, methylbenzyl groups, and vinylbenzyl groups.

[0097] Specific examples of silane coupling agents represented by 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)phenyltriethoxysilane, Examples include (Tylaminoethyl)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 hydrolysates thereof.

[0098] Examples of silane coupling agents containing amino groups other than 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 their hydrolysates.

[0099] The aforementioned silane coupling agents having an amino group may be used individually or in combination of two or more.

[0100] Alternatively, polymers formed via siloxane bonds (Si-O-Si) from these silane coupling agents (siloxane polymers) may be used. For example, from the hydrolysis product of 3-aminopropyltrimethoxysilane, polymers having a linear siloxane structure, a branched siloxane structure, a cyclic siloxane structure, a cage-like siloxane structure, and the like can be obtained. The cage-like siloxane structure can be represented, for example, by the following formula (A-1).

[0101] [ka]

[0102] Examples of siloxanediamines include compounds represented by the following formula (A-2). In formula (A-2), i is an integer from 0 to 4, j is an integer from 1 to 3, and Me is a methyl group.

[0103] [ka]

[0104] Examples of siloxanediamines 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).

[0105] Compound (A) has a cationic functional group containing at least one primary nitrogen atom and a secondary nitrogen atom, and can therefore strongly bond substrates together through electrostatic interactions with functional groups such as hydroxyl groups, epoxy groups, carboxyl groups, amino groups, and mercapto groups that may be present on the substrate surface, or by forming dense covalent bonds with the functional groups. Furthermore, compound (A) has a cationic functional group containing at least one primary nitrogen atom and one secondary nitrogen atom, and therefore exhibits excellent solubility in polar solvents. For this reason, it has a high affinity for substrates with hydrophilic surfaces, such as silicon, and can form smooth films.

[0106] As for compound (A), a compound having an amino group as a cationic functional group is preferred from the viewpoint of heat resistance. Furthermore, from the viewpoint of further improving heat resistance by forming thermal crosslinking structures such as amides, amide-imides, and imides, a compound having a primary amino group is preferred.

[0107] The ratio of the total number of primary and secondary nitrogen atoms in compound (A) to the number of silicon atoms (total number of primary and secondary nitrogen atoms / number of silicon atoms) is not particularly limited, but a ratio of 0.2 to 5 is preferable from the viewpoint of forming a smooth thin film.

[0108] It is preferable that compound (A) has a molar ratio (non-crosslinking group / Si element) of less than 2 between the Si element in the molecule and non-crosslinking groups such as methyl groups bonded to the Si element (satisfying the relationship non-crosslinking group / Si element < 2). By satisfying this condition, the crosslinking density of the formed film (crosslinking between Si-O-Si bonds and amide bonds, imide bonds, etc.) is improved, and excellent bonding strength can be obtained.

[0109] As described above, compound (A) has a cationic functional group containing at least one primary nitrogen atom and a secondary nitrogen atom. Here, if compound (A) contains a primary nitrogen atom, it is preferable that the proportion of primary nitrogen atoms to the total nitrogen atoms in compound (A) is 20 mol% or more, more preferably 25 mol% or more, and even more preferably 30 mol% or more. Furthermore, compound (A) may have a cationic functional group that contains a primary nitrogen atom but does not contain nitrogen atoms other than primary nitrogen atoms (e.g., secondary nitrogen atoms, tertiary nitrogen atoms). If the proportion of primary nitrogen atoms in compound (A) is 20 mol% or more, bonds with functional groups that may be present on the substrate surface are formed more densely, allowing for stronger adhesion between substrates.

[0110] If compound (A) contains secondary nitrogen atoms, it is preferable that the proportion of secondary nitrogen atoms to the total nitrogen atoms in compound (A) be 5 mol% or more and 50 mol% or less, and more preferably 5 mol% or more and 30 mol% or less.

[0111] Compound (A) may contain tertiary nitrogen atoms in addition to primary and secondary nitrogen atoms. If compound (A) contains tertiary nitrogen atoms, the proportion of tertiary nitrogen atoms to the total nitrogen atoms in compound (A) is preferably 20 mol% to 50 mol%, and more preferably 25 mol% to 45 mol%.

[0112] The amount of compound (A) in composition A is not particularly limited, as long as the proportion of primary and secondary nitrogen atoms contained in compound (A) to the total of primary nitrogen atoms contained in compound (C) is between 3 mol% and 95 mol%. From the viewpoint of balancing thermal expansion coefficient and bonding strength, the above ratio is preferably 5 mol% to 75 mol%, and more preferably 10 mol% to 50 mol%.

[0113] (Compound (B)) Compound (B) is a compound having three or more -C(=O)OX groups (where X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in its molecule, and of the three or more -C(=O)OX groups (hereinafter also referred to as "COOX"), one to six are -C(=O)OH groups (hereinafter also referred to as "COOH"). If compound (B) has a -C(=O)OX group (where X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in its molecule, its solubility in composition A is improved. Compound (B) may be used alone or in combination of two or more types.

[0114] Compound (B) is a compound having three or more -C(=O)OX groups (where X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in its molecule, preferably a compound having three to six -C(=O)OX groups in its molecule, and more preferably a compound having three or four -C(=O)OX groups in its molecule. Compound (B) can react efficiently with compound (A) if it has three or four -C(=O)OX groups in its molecule.

[0115] In compound (B), X in the -C(=O)OX group can be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, with hydrogen atoms, methyl groups, ethyl groups, and propyl groups being preferred. The X in the -C(=O)OX group may be the same or different from each other.

[0116] Compound (B) is a compound having one to six -C(=O)OH groups in its molecule where X is a hydrogen atom, preferably a compound having one to four -C(=O)OH groups in its molecule, more preferably a compound having two to four -C(=O)OH groups in its molecule, and even more preferably a compound having two or three -C(=O)OH groups in its molecule. If compound (B) has one to four -C(=O)OH groups in its molecule, its solubility in composition A improves.

[0117] The weight-average molecular weight of compound (B) is not particularly limited. For example, the weight-average molecular weight of compound (B) may be between 200 and 600, between 200 and 500, between 200 and 450, or between 200 and 400. When the weight-average molecular weight of compound (B) is within the above range, its solubility in composition A improves.

[0118] Compound (B) preferably has a ring structure within its molecule. Examples of ring structures include alicyclic structures and aromatic ring structures. Compound (B) may also have multiple ring structures within its molecule, and these multiple ring structures may be the same or different. If compound (B) has a ring structure within its molecule, the heat resistance of the cured product is improved.

[0119] Examples of alicyclic structures include alicyclic structures having 3 to 8 carbon atoms, preferably alicyclic structures having 4 to 6 carbon atoms, and the ring structure may be saturated or unsaturated. More specifically, examples of alicyclic structures include saturated alicyclic structures such as cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, and cyclooctane rings; and unsaturated alicyclic structures such as cyclopropene rings, cyclobutene rings, cyclopentene rings, cyclohexene rings, cycloheptene rings, and cyclooctene rings.

[0120] The aromatic ring structure is not particularly limited as long as it is an aromatic ring structure, and examples include benzene-based aromatic rings such as benzene rings, naphthalene rings, anthracene rings, and perylene rings; aromatic heterocycles such as pyridine rings and thiophene rings; and non-benzene-based aromatic rings such as indene rings and azulene rings.

[0121] The ring structure of compound (B) 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, and at least one of the benzene ring and the naphthalene ring is more preferred from the viewpoint of further improving the heat resistance of the cured product.

[0122] As mentioned above, compound (B) may have multiple ring structures within its molecule, and if the ring structure is benzene, it may have a biphenyl structure, a benzophenone structure, a diphenyl ether structure, etc.

[0123] Compound (B) may have fluorine atoms in its molecule. For example, it may have one to six fluorine atoms in its molecule, or three to six fluorine atoms in its molecule. For example, compound (B) may have a fluoroalkyl group in its molecule, specifically a trifluoroalkyl group or a hexafluoroisopropyl group. If compound (B) contains a fluorine atom in its molecule, the water absorption of the cured product decreases.

[0124] Furthermore, compound (B) can be a carboxylic acid compound such as alicyclic carboxylic acid, benzenecarboxylic acid, naphthalenecarboxylic acid, diphthalic acid, or fluorinated aromatic carboxylic acid; or a carboxylic acid ester compound such as alicyclic carboxylic acid ester, benzenecarboxylic acid ester, naphthalenecarboxylic acid ester, diphthalic acid ester, or fluorinated aromatic carboxylic acid ester. Note that a carboxylic acid ester compound is a compound that has a carboxyl group (-C(=O)OH group) in its molecule, and in three or more -C(=O)OX groups, at least one X is an alkyl group having 1 to 6 carbon atoms (i.e., having an ester bond). In composition A, because compound (B) is a carboxylic acid ester compound, aggregation due to association between compound (A) and compound (B) is suppressed, resulting in fewer aggregates and pits, and making it easier to adjust the film thickness.

[0125] The carboxylic acid compound is preferably a tetravalent or less carboxylic acid compound containing four or fewer -C(=O)OH groups, and more preferably a trivalent or tetravalent carboxylic acid compound containing three or four -C(=O)OH groups.

[0126] The carboxylic acid ester compound is preferably a compound that contains three or fewer carboxyl groups (-C(=O)OH groups) and three or fewer ester bonds in its molecule, and more preferably a compound that contains two or fewer carboxyl groups and two or fewer ester bonds in its molecule.

[0127] Furthermore, in the carboxylic acid ester compound, if X is an alkyl group having 1 to 6 carbon atoms in three or more -C(=O)OX groups, X is preferably a methyl group, ethyl group, propyl group, butyl group, etc., but it is preferable that X be an ethyl group or a propyl group in order to further suppress aggregation due to association between compound (A) and compound (B).

[0128] Specific examples of the carboxylic acid compounds mentioned above are not limited to these, but include 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; benzenecarboxylic acids such as 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, benzenepentacarboxylic acid, and mellitic acid; and 1,4,5,8-naphthalenetetracarboxylic acid. Naphthalene carboxylic acids such as naphthalene acid, 2,3,6,7-naphthalenetetracarboxylic 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'-(ethyne-1,2-diinyl)diphthalic acid Diphthalic acids such as perylene-3,4,9,10-tetracarboxylic acid; anthracenecarboxylic acids such as anthracene-2,3,6,7-tetracarboxylic acid;Examples include 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-ditrifluoromethylpyromellitic acid.

[0129] Specific examples of the carboxylic acid ester compounds include compounds in which at least one carboxyl group in the above-mentioned specific examples of carboxylic acid compounds is substituted with an ester group. Examples of carboxylic acid ester compounds include half-esterified compounds represented by the following general formulas (B-1) to (B-6).

[0130] [ka]

[0131] In general formulas (B-1) to (B-6), R is independently an alkyl group having 1 to 6 carbon atoms, with methyl, ethyl, propyl, and butyl groups being preferred, and ethyl and propyl groups being more preferred.

[0132] Half-esterified compounds can be produced, for example, by mixing a carboxylic acid anhydride (the anhydride of the aforementioned carboxylic acid compound) with an alcohol solvent and opening the ring of the carboxylic acid anhydride.

[0133] The content of compound (B) in composition A is preferably such that the ratio of the number of carboxyl group equivalents (COOH) of compound (B) to the total number of amine equivalents (N) of compounds (A) and (C) (COOH / N) is 0.1 or more and 3.0 or less, more preferably 0.3 or more and 2.5 or less, and even more preferably 0.4 or more and 2.2 or less. When COOH / N is 0.1 or more and 3.0 or less, a sufficiently cross-linked structure is formed by the reaction of compounds (A), (B), and (C), and a cured product with excellent heat resistance and insulating properties tends to be obtained.

[0134] (Compound (C)) Compound (C) is a compound having a ring structure and one or more primary nitrogen atoms directly bonded to the ring structure. Compound (C) reacts with compound (B) together with compound (A) to form a hardened product. Compound (C) has a ring structure and one or more primary nitrogen atoms directly bonded to the ring structure. It is believed that the introduction of this structure into the cured product increases the rigidity of the cured product and reduces its coefficient of thermal expansion. Compound (C) may be used alone or in combination of two or more types.

[0135] In this disclosure, "primary nitrogen atom directly bonded to a ring structure" means a primary nitrogen atom (-NH2) that is bonded to a ring structure by a single bond (i.e., without the intermediary of carbon atoms, etc.).

[0136] The number of primary nitrogen atoms directly bonded to the ring structure of compound (C) within the molecule is not particularly limited, as long as there is one or more. From the viewpoint of increasing the crosslinking density, it is preferable that there be two or more, and more preferably a diamine compound having two primary amino groups or a triamine compound having three primary amino groups.

[0137] Compound (C) may have one ring structure or multiple ring structures within its molecule. If compound (C) has multiple ring structures within its molecule, it may have a cationic functional group containing a primary nitrogen atom directly bonded to each ring structure, or it may have a cationic functional group containing a primary nitrogen atom directly bonded to only one of the ring structures.

[0138] If compound (C) has multiple ring structures within its molecule, these ring structures may be the same or different, and may form a fused ring. Alternatively, the multiple ring structures may be linked by single bonds, or they may be linked via linking groups such as ether groups, carbonyl groups, sulfonyl groups, or methylene groups.

[0139] Examples of ring structures included in compound (C) include alicyclic structures, aromatic rings (including heterocyclic structures), and fused ring structures of these. Examples of alicyclic structures include those having 3 to 8 carbon atoms, preferably 4 to 6 carbon atoms. The ring structure may be saturated or unsaturated. More specifically, examples include saturated alicyclic structures such as cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, and cyclooctane rings; and unsaturated alicyclic structures such as cyclopropene rings, cyclobutene rings, cyclopentene rings, cyclohexene rings, cycloheptene rings, and cyclooctene rings.

[0140] Examples of aromatic ring structures include those with 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. Specifically, examples include benzene-based aromatic ring structures such as benzene rings, naphthalene rings, anthracene rings, and perylene rings, and non-benzene-based aromatic ring structures such as pyridine rings, thiophene rings, indene rings, and azulene rings.

[0141] Examples of heterocyclic structures include three-membered to ten-membered rings, preferably five-membered or six-membered rings. Examples of heteroatoms included in the heterocyclic ring include sulfur atoms, nitrogen atoms, and oxygen atoms, and one or more of these may be present. Examples of heterocyclic structures include oxazole rings, thiophene rings, pyrrole rings, pyrrolidine rings, pyrazole rings, imidazole rings, triazole rings, isocyanuric rings, pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, piperidine rings, piperazine rings, triazine rings, indole rings, indoline rings, quinoline rings, acridine rings, naphthyridine rings, quinazoline rings, purine rings, and quinoxaline rings.

[0142] The ring structure that compound (C) has within the molecule is more preferably a benzene ring, a cyclohexane ring, or a benzoxazole ring.

[0143] The ring structure of compound (C) within the molecule may have substituents other than a primary nitrogen atom. For example, it may have an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom, and so on.

[0144] The weight average molecular weight of compound (C) is not particularly limited. For example, it may be 80 or more and 600 or less, may be 90 or more and 500 or less, or may be 100 or more and 450 or less.

[0145] Examples of compound (C) include alicyclic amines, aromatic amines, heterocyclic amines having a nitrogen-containing heterocycle, and amine compounds having both a heterocycle and an aromatic ring. Specific examples of alicyclic amines include cyclohexylamine, dimethylaminocyclohexane, and the like. Specific examples of aromatic amines include diaminodiphenyl ether, xylenediamine (preferably para-xylenediamine), 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, and the like. Specific examples of heterocyclic amines having a nitrogen-containing heterocycle include melamine, ammeline, melam, melem, tris(4-aminophenyl)amine, and the like. Specific examples of amine compounds having both a heterocycle and an aromatic ring include N2,N4,N6-tris(4-aminophenyl)-1,3,5-triazine-2,4,6-triamine, 2-(4-aminophenyl)benzoxazole-5-amine, and the like.

[0146] The content of compound (C) in composition A is not particularly limited as long as the ratio of the primary nitrogen atoms contained in compound (A) to the total of the primary nitrogen atoms and secondary nitrogen atoms contained in compound (A) and the primary nitrogen atoms contained in compound (C) is 3 mol% to 95 mol%. From the perspective of the balance between the thermal expansion coefficient and the bonding strength, the above ratio is preferably 5 mol% to 75 mol%, more preferably 10 mol% to 50 mol%, and even more preferably 10 mol% to 30 mol%.

[0147] (Polar solvent) Composition A may contain a polar solvent. In the present disclosure, the "polar solvent" refers to a solvent having a relative permittivity of 5 or more at room temperature (25 °C). When Composition A contains a polar solvent, the solubility of each component in Composition A is improved. Only one kind of polar solvent may be used alone, or two or more kinds may be combined.

[0148] Specific examples of the polar solvent include protic solvents such as water and heavy water; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, benzyl alcohol, diethylene glycol, triethylene glycol, and glycerin; ethers such as tetrahydrofuran and dimethoxyethane; aldehyde-ketones such as furfural, acetone, ethyl methyl ketone, and cyclohexanone; 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 hexamethylphosphoric triamide; nitriles such as acetonitrile and propionitrile; and nitro compounds such as nitromethane and nitrobenzene; and sulfur compounds such as dimethyl sulfoxide. The polar solvent preferably contains a protic solvent, more preferably contains water, and even more preferably contains ultrapure water.

[0149] If composition A contains a polar solvent, its content is not particularly limited. For example, it may be 1.0% by mass or more and 99.99896% by mass or 40% by mass or more and 99.99896% by mass relative to the entire composition A.

[0150] (Additives) Composition A may contain additives as needed. Examples of additives include acids having a carboxyl group with a weight-average molecular weight of 46 to 195, and bases having a nitrogen atom and a weight-average molecular weight of 17 to 120, which do not have a ring structure.

[0151] It is presumed that because composition A contains an acid with a weight-average molecular weight of 46 to 195 that has a carboxyl group, the primary or secondary nitrogen atoms of compounds (A) and (C) form ionic bonds with the carboxyl group in the acid, thereby suppressing aggregation due to association between compounds (A) and (C) and compound (B). More specifically, it is presumed that aggregation is suppressed because the interaction (e.g., electrostatic interaction) between the ammonium ions derived from compounds (A) and (C) and the carboxylate ions derived from the carboxyl group in the acid is stronger than the interaction between the ammonium ions derived from compounds (A) and (C) and the carboxylate ions derived from the carboxyl group in compound (B). However, the present invention is not limited in any way by the above presumption.

[0152] The types of acids with a carboxyl group and a weight-average molecular weight of 46 to 195 are not particularly limited, and include monocarboxylic acid compounds, dicarboxylic acid compounds, and oxydicarboxylic acid compounds. More specifically, examples include formic acid, acetic acid, malonic acid, oxalic 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 (excluding those that fall under compound (B)).

[0153] When composition A contains an acid with a weight-average molecular weight of 46 to 195, the amount is not particularly limited, but for example, it is preferable that the ratio of the number of carboxyl groups of the acid to the total number of primary and secondary nitrogen atoms of compound (A) and compound (C) (COOH / N) is 0.01 to 10, more preferably 0.02 to 6, and even more preferably 0.5 to 3.

[0154] It is presumed that the aggregation of compounds (A) and (C) with compound (B) is suppressed because composition A contains a base with a weight-average molecular weight of 17 to 120 having a nitrogen atom, causing an ionic bond to form between the carboxyl group of compound (B) and the amino group of the base. More specifically, it is presumed that aggregation is suppressed because the interaction between the carboxylate ion derived from the carboxyl group in compound (B) and the ammonium ion derived from the amino group in the base is stronger than the interaction between the ammonium ions derived from compounds (A) and (C) and the carboxylate ion derived from the carboxyl group in compound (B). However, the present invention is not limited in any way by the above presumption.

[0155] The types of compounds containing a nitrogen atom and having a weight-average molecular weight of 17 to 120 are not particularly limited, and include monoamine compounds, diamine compounds, etc. (except for those falling under compound (A) and compound (C)). More specifically, examples include ammonia, ethylamine, ethanolamine, diethylamine, triethylamine, ethylenediamine, N-acetylethylenediamine, N-(2-aminoethyl)ethanolamine, N-(2-aminoethyl)glycine, etc.

[0156] When composition A contains a base with a weight-average molecular weight of 17 or more and 120 or less, the amount is not particularly limited, but for example, the ratio of the number of nitrogen atoms in the base to the number of carboxyl groups in compound (B) (N / COOH) is preferably 0.5 or more and 5 or less, and more preferably 0.9 or more and 3 or less.

[0157] (Other ingredients) When selectivity for plasma etching resistance is required for composition A (for example, when used as a gap fill material or embedded insulating film), it may contain a metal alkoxide represented by the following general formula (I). R1 n M(OR2) m-n ...(I) (wherein R1 is a non-hydrolyzable group, R2 is an alkyl group having 1 to 6 carbon atoms, M represents at least one metal atom selected from the group of metal atoms Ti, Al, Zr, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La, Nd, and In, m is the valence of the metal atom M, which is 3 or 4, n is an integer from 0 to 2 if m is 4, and 0 or 1 if m is 3, if there are multiple R1s, each R1 may be the same or different from each other, and if there are multiple OR2s, each OR2 may be the same or different from each other.)

[0158] When the film produced from composition A is required to have insulating properties (for example, for use as an insulating film for silicon through-vias or for use as an embedded insulating film), a silane compound (excluding those corresponding to compound (A)) may be included to improve insulating properties or mechanical strength. Specific examples of silane compounds include tetraethoxysilane, tetramethoxysilane, bistriethoxysilylethane, bistriethoxysilylmethane, bis(methyldiethoxysilyl)ethane, 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahydroxylcyclosiloxane, 1,1,4,4-tetramethyl-1,4-diethoxydisylethylene, 1,3,5-trimethyl-1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane, and silane coupling agents having functional groups other than amino groups (epoxy groups, mercapto groups, etc.).

[0159] Composition A may contain solvents other than polar solvents. Examples of solvents other than polar solvents include n-hexane.

[0160] Composition A may contain benzotriazole or its derivative, for example, to suppress the corrosion of copper.

[0161] The pH of Composition A is not particularly limited, but it is preferably 2.0 or more and 12.0 or less. When the pH of Composition A is 2.0 or more and 12.0 or less, damage to the substrate by Composition A is suppressed. Composition A preferably has a sodium content and a potassium content of 10 mass ppb or less each on an elemental basis. If the sodium or potassium content is 10 mass ppb or less each on an elemental basis, it is possible to suppress the occurrence of disadvantages in the electrical characteristics of semiconductor devices such as malfunction of transistors.

[0162] When Composition A contains components other than Compound (A), Compound (B), and Compound (C), the total mass of Compound (A), Compound (B), and Compound (C) is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 80 mass% or more of the total mass of the non-volatile components in Composition A. In the present disclosure, "non-volatile components" refers to components other than components (such as solvents) that are removed when Composition A becomes a cured product.

[0163] <Composition B> Composition B contains at least one of Compound (X1) having a structure represented by the following general formula (1) and a molecular weight of 400 to 5000, and Compound (X2) having a structure represented by general formula (2) and a molecular weight of 400 to 5000.

[0164]

Chemical formula

[0165] In general formula (1), R1 and R3 are each independently an organic group having 6 or less carbon atoms, R2 is a methylene group, an ethylene group, a propylene group, or a phenylene group, a is 2 or 3, b is the number of 3 - a, and X1 is a structure derived from a carboxylic dianhydride.

[0166] [ka]

[0167] In general formula (2), R1 and R3 are each independently organic groups having 6 or fewer carbon atoms, R2 is a methylene group, an ethylene group, a propylene group, or a phenylene group, a is 2 or 3, b is the number of 3-a, X1 is a structure derived from a carboxylic acid dianhydride, X2 is a structure derived from an amine compound, and n is a positive number.

[0168] According to composition B, a resin layer with less residual stress can be formed compared to composition B in which the precursors of compound (X1) or compound (X2), such as a silane coupling agent, a carboxylic acid dianhydride, or an amine compound, are present in an unreacted state. The reason for this is not entirely clear, but for example, it is thought that because the precursors of compound (X1) or compound (X2) are reacted before composition B is applied to the substrate, the curing shrinkage of the resin layer associated with the reaction is suppressed, and the residual stress of the resin layer is reduced, compared to when these precursors are reacted on the substrate to form the resin layer.

[0169] In general formula (1), X1 is a structure derived from a carboxylic acid dianhydride, and preferably includes a ring structure. Furthermore, the amide group and carboxyl group bonded to X1 react on the substrate to form an imide bond. As a result, the resulting resin layer exhibits excellent heat resistance.

[0170] In general formula (1), it is preferable that a is 2. In general formula (1), R1 and R3 represent organic groups having 6 or fewer carbon atoms, and preferably alkyl groups having 6 or fewer carbon atoms, more preferably 3 or fewer carbon atoms.

[0171] In general formula (2), X1 and X2 are structures derived from a carboxylic acid dianhydride and an amine compound, respectively, and preferably include a ring structure. Furthermore, the amide group and carboxyl group bonded to X1 react on the substrate to form an imide bond. As a result, the resulting resin layer exhibits excellent heat resistance.

[0172] In general formula (2), it is preferable that a is 2. In general formula (2), R1 and R3 represent an organic group having 6 or fewer carbon atoms, and preferably an alkyl group having 6 or fewer carbon atoms, more preferably 3 or fewer carbon atoms. In general formula (2), n is not particularly restricted as long as it is a positive number, but for example, it may be within the range of 1 to 6. The compound (X2) represented by general formula (2) may be a polyamic acid in which structures derived from carboxylic acid dianhydrides and structures derived from amine compounds are arranged alternately.

[0173] The compound (X1) contained in the above composition B may be a compound having a structure obtained by reacting a silane coupling agent (A) with a carboxylic acid dianhydride (B) having a molecular weight of 200 to 600 and a cyclic structure. The compound (X2) contained in the above composition B may have a structure obtained by reacting a silane coupling agent (A) with a carboxylic acid dianhydride (B) having a molecular weight of 200 to 600 and a cyclic structure, and a structure obtained by reacting an amine compound (C) having a molecular weight of 90 to 600, lacking Si-O bonds and having a cyclic structure, with a carboxylic acid dianhydride (B) having a molecular weight of 200 to 600 and a cyclic structure.

[0174] In this disclosure, carboxylic acid dianhydrides (B) having a molecular weight of 200 to 600 and a cyclic structure, and amine compounds (C) having a molecular weight of 90 to 600, a cyclic structure, and lacking Si-O bonds, may be simply referred to as carboxylic acid dianhydrides (B) and amine compounds (C), respectively.

[0175] (Silane coupling agent (A)) Silane coupling agent (A) is a compound having one or more Si-O bonds in its molecule and reacting with a carboxylic acid dianhydride to produce compound (X1) or compound (X2). The Si-O bonds in silane coupling agent (A) contribute to improving the bonding strength between the resin layer formed using composition B and the substrate.

[0176] The silane coupling agent (A) is not particularly limited as long as it has a functional group that can react with the anhydride group of the carboxylic acid dianhydride (B). Specific examples of functional groups include amino groups, epoxy groups, and isocyanate groups. From the viewpoint of the thermal expansion coefficient of the resin layer and bonding strength, the silane coupling agent (A) preferably has an amino group, and from the viewpoint of forming an imide structure in the resin layer to improve heat resistance, a compound having a primary amino group (-NH2) is more preferable.

[0177] The silane coupling agent (A) may be used alone or in combination of two or more types.

[0178] The molecular weight of the silane coupling agent (A) is not particularly limited. For example, it may be between 130 and 10,000, between 130 and 5,000, or between 130 and 2,000.

[0179] Examples of silane coupling agents (A) having an amino group include compounds represented by the following formula (A-3).

[0180] [ka]

[0181] In formula (A-3), R 1 R represents an alkyl group having 1 to 4 carbon atoms, which may be substituted. 2 and R 3 Each of these independently represents an alkylene group, ether group, or carbonyl group having 1 to 12 carbon atoms, which may be substituted (the skeleton may contain carbonyl groups, ether groups, etc.). 4 and R5 Each independently represents an optionally substituted C1-C4 alkylene group or single bond. Ar represents a divalent or trivalent aromatic ring. X1 represents hydrogen or an optionally substituted C1-C5 alkyl group. X2 represents hydrogen, a cycloalkyl group, a heterocyclic group, an aryl group, or an optionally substituted (may contain carbonyl groups, ether groups, etc.) C1-C5 alkyl group. Multiple R 1 , R 2 , R 3 , R 4 , R 5 , X 1 They may be the same or different. R 1 , R 2 , R 3 , R 4 , R 5 , X 1 , X 2 Examples of substituents on the alkyl group and alkylene group in the compound include, independently, amino groups, hydroxyl groups, alkoxy groups, cyano groups, carboxylic acid groups, sulfonic acid groups, halogens, and the like. Examples of divalent or trivalent aromatic rings in Ar include divalent or trivalent benzene rings. 2 Examples of aryl groups in this context include phenyl groups, methylbenzyl groups, and vinylbenzyl groups.

[0182] Specific examples of silane coupling agents represented by 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, Examples include (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, and acetamidopropyltrimethoxysilane.

[0183] Examples of silane coupling agents containing amino groups other than 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, and 5-(ethoxydimethylsilyl)benzene-1,3-diamine.

[0184] The silane coupling agent (A) having an amino group may be used alone or in combination of two or more types.

[0185] (Carboxylic acid dianhydride (B)) Carboxylic acid dianhydrides (B) are compounds that have one or more ring structures and two anhydride groups in their molecule, and have a molecular weight of 200 to 600. The molecular weight of the carboxylic acid dianhydride (B) may be between 200 and 400. Carboxylic acid dianhydride (B) may be used alone or in combination of two or more types.

[0186] Examples of ring structures that carboxylic acid dianhydride (B) may have within its molecule include alicyclic structures and aromatic rings (including heterocyclic structures). Carboxylic acid dianhydride (B) may have one ring structure or multiple ring structures within its molecule.

[0187] Examples of alicyclic structures include alicyclic structures having 3 to 8 carbon atoms, preferably alicyclic structures having 4 to 6 carbon atoms, and the ring structure may be saturated or unsaturated. More specifically, examples of alicyclic structures include saturated alicyclic structures such as cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, and cyclooctane rings; and unsaturated alicyclic structures such as cyclopropene rings, cyclobutene rings, cyclopentene rings, cyclohexene rings, cycloheptene rings, and cyclooctene rings.

[0188] The aromatic ring structure is not particularly limited as long as it is an aromatic ring structure, and examples include benzene-based aromatic rings such as benzene rings, naphthalene rings, anthracene rings, and perylene rings; aromatic heterocycles such as pyridine rings and thiophene rings; and non-benzene-based aromatic rings such as indene rings and azulene rings.

[0189] The ring structure of the carboxylic acid dianhydride (B) 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, and at least one of a benzene ring and a naphthalene ring is more preferred from the viewpoint of further improving the heat resistance of the resin layer. Furthermore, when forming a resin layer using composition B between multiple substrates, it is preferable to include two or more benzene rings from the viewpoint of suppressing the generation of voids in the resin layer.

[0190] If the carboxylic acid dianhydride (B) has multiple ring structures within the molecule, these ring structures may be the same or different, and may form a fused ring. Alternatively, the multiple ring structures may be linked by single bonds, or they may be linked via linking groups such as ether groups, carbonyl groups, sulfonyl groups, or methylene groups.

[0191] The carboxylic acid dianhydride (B) may contain fluorine atoms in its molecule. For example, it may contain one to six fluorine atoms, or three to six fluorine atoms. For example, the carboxylic acid dianhydride (B) may contain a fluoroalkyl group in its molecule, specifically a trifluoroalkyl group or a hexafluoroisopropyl group.

[0192] Examples of carboxylic acid dianhydrides (B) include dianhydrides of compounds having a ring structure and four carboxyl groups capable of forming anhydride groups within the molecule. For example, anhydrides of alicyclic tetracarboxylic acids such as 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and 1,2,3,4,5,6-cyclohexanehexacarboxylic acid; Dianhydrides of benzenetetracarboxylic acids such as pyromellitic acid; Dianhydrides of naphthalenetetracarboxylic acids, such as 1,4,5,8-naphthalenetetracarboxylic acid and 2,3,6,7-naphthalenetetracarboxylic acid; Dianhydrides of biphenyltetracarboxylic acids, such as 3,3',4,4'-biphenyltetracarboxylic acid; Benzophenone-tetracarboxylic dianhydrides such as benzophenone-3,3',4,4'-tetracarboxylic acid Dianhydrides of diphthalic acids such as 4,4'-oxydiphthalic acid (ODPA), 3,4'-oxydiphthalic acid, 1,3-bis(phthalic acid)tetramethyldisiloxane, 4,4'-(ethyn-1,2-diyl)diphthalic acid, 4,4'-(1,4-phenylenebis(oxy))diphthalic acid, 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))diphthalic acid, and 4,4'-((oxybis(4,1-phenylene))bis(oxy))diphthalic acid; Dianhydrides of perylenecarboxylic acids, such as perylene-3,4,9,10-tetracarboxylic acid; Anthracene carboxylic acid dianhydrides such as anthracene-2,3,6,7-tetracarboxylic acid; Dianhydrides of 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-ditrifluoromethylpyromellitic acid; The dianhydride of bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)1,4-phenylene; 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic acid (IPBDA) dianhydride; Examples include the dianhydride of bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)1,4-phenylene (TAHQ).

[0193] The amount of carboxylic acid dianhydride (B) in composition B is preferably such that the ratio (A / B) of the number of functional group equivalents A of the silane coupling agent (A) that can react with the anhydride group of carboxylic acid dianhydride (B) to the number of anhydride group equivalents B of carboxylic acid dianhydride (B) is 0.9 to 1.1, more preferably 0.95 to 1.05, and even more preferably 0.98 to 1.02.

[0194] If composition B further contains compounds that can react with the anhydride group of carboxylic acid dianhydride (B), such as compound (C) described later, the ratio (A' / B') of the total functional group equivalent number A' of all compounds that can react with the anhydride group of carboxylic acid dianhydride (B) to the anhydride group equivalent number B' of carboxylic acid dianhydride (B) is preferably 0.9 to 1.1, more preferably 0.95 to 1.05, and even more preferably 0.98 to 1.02.

[0195] (Amine compound (C)) Amine compounds (C) are compounds that have one or more ring structures and one or more amino groups in their molecule, have a molecular weight of 90 to 600, and do not contain Si-O bonds. The amine compound (C) may be used alone or in combination of two or more types.

[0196] The amine compound (C) may have one or more amino groups in its molecule, but from the viewpoint of reducing the thermal expansion coefficient of the resin layer, it is preferable to have more than one amino group, and more preferably two (diamine) or three (triamine) amino groups. From the viewpoint of forming an imide structure in the resin layer to improve heat resistance, it is more preferable to have a primary amino group (-NH2).

[0197] From the viewpoint of reducing the thermal expansion coefficient of the resin layer, it is preferable that the amine compound (C) has one or more amino groups directly bonded to the ring structure. It is thought that if the molecular structure of compound (X2) includes a structure derived from amino groups directly bonded to the ring structure, the rigidity of the molecular structure increases and the thermal expansion coefficient decreases further.

[0198] In this disclosure, "amino group directly bonded to a ring structure" means an amino group bonded to a ring structure by a single bond (i.e., without the intervening of carbon atoms, etc.).

[0199] The amine compound (C) may have one ring structure or multiple ring structures within its molecule. If the amine compound (C) has multiple ring structures within its molecule, the multiple ring structures may be the same or different, and may form a fused ring. Alternatively, the multiple ring structures may be linked by single bonds, or they may be linked via linking groups such as ether groups, carbonyl groups, sulfonyl groups, or methylene groups.

[0200] Examples of ring structures included in amine compounds (C) include alicyclic structures, aromatic rings (including heterocyclic structures), and fused ring structures of these. Examples of alicyclic structures include those having 3 to 8 carbon atoms, preferably 4 to 6 carbon atoms. The ring structure may be saturated or unsaturated. More specifically, examples include saturated alicyclic structures such as cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, and cyclooctane rings; and unsaturated alicyclic structures such as cyclopropene rings, cyclobutene rings, cyclopentene rings, cyclohexene rings, cycloheptene rings, and cyclooctene rings.

[0201] Examples of aromatic ring structures include those with 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. Specifically, examples include benzene-based aromatic ring structures such as benzene rings, naphthalene rings, anthracene rings, and perylene rings, and non-benzene-based aromatic ring structures such as pyridine rings, thiophene rings, indene rings, and azulene rings.

[0202] Examples of heterocyclic structures include three-membered to ten-membered rings, preferably five-membered or six-membered rings. Examples of heteroatoms included in the heterocyclic ring include sulfur atoms, nitrogen atoms, and oxygen atoms, and one or more of these may be present. Examples of heterocyclic structures include oxazole rings, thiophene rings, pyrrole rings, pyrrolidine rings, pyrazole rings, imidazole rings, triazole rings, isocyanuric rings, pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, piperidine rings, piperazine rings, triazine rings, indole rings, indoline rings, quinoline rings, acridine rings, naphthyridine rings, quinazoline rings, purine rings, and quinoxaline rings.

[0203] The amine compound (C) is more likely to have a benzene ring, a cyclohexane ring, or a benzoxazole ring as its intramolecular ring structure.

[0204] The ring structure of the amine compound (C) may have substituents other than an amino group. For example, alkyl groups having 1 to 6 carbon atoms, alkyl groups substituted with halogen atoms, etc. It may have.

[0205] Specific examples of amine compounds (C) include the following compounds: Examples of alicyclic amines include cyclohexylamine and dimethylaminocyclohexane. Examples of aromatic ring amines include diaminodiphenyl ether, xylenediamine (preferably paraxylenediamine), diaminobenzene, diaminotoluene, methylenedianiline, dimethyldiaminobiphenyl, bis(trifluoromethyl)diaminobiphenyl (TFDB), diaminobenzophenone, diaminobenzanilide, bis(aminophenyl)fluorene, bis(aminophenoxy)benzene, bis(aminophenoxy)biphenyl, dicarboxydiaminodiphenylmethane, diaminoresorcinol, dihydroxybenzidine, diaminobenzidine, 1,3,5-triaminophenoxybenzene, 2,2'-dimethylbenzidine, and tris(4-aminophenyl)amine. For example, heterocyclic amines having a nitrogen-containing heterocycle include melamine, ammeline, melam, melem, and tris(4-aminophenyl)amine. Furthermore, examples of amine compounds that have both heterocyclic and aromatic rings include N2,N4,N6-tris(4-aminophenyl)-1,3,5-triazine-2,4,6-triamine and 2-(4-aminophenyl)benzoxazole-5-amine (AAPD).

[0206] (Method for obtaining compound (X1)) One method for obtaining compound (X1) by reacting a silane coupling agent (A) with a carboxylic acid dianhydride (B) is to gradually add the silane coupling agent (A) dropwise to the carboxylic acid dianhydride (B) while stirring with a solvent.

[0207] (Method for obtaining compound (X2)) One method for obtaining compound (X2) by reacting a silane coupling agent (A), a carboxylic acid dianhydride (B), and an amine compound (C) is to add a solvent to the amine compound (C) and stir, then add the carboxylic acid dianhydride (B), stir until the viscosity of the resulting reactant (polymer) becomes constant, and then gradually add the silane coupling agent (A) dropwise to obtain compound (X2).

[0208] (Precursor of resin (D)) Composition B may further contain compounds other than compounds (X1) and (X2). For example, it may further contain a precursor of resin (D) having a CTE of 90 ppm / K or less between 50°C and 150°C. When composition B contains a precursor of resin (D), the coefficient of thermal expansion of the resulting resin layer tends to be further reduced.

[0209] Specifically, resins (D) having a CTE of 90 ppm / K or less between 50°C and 150°C include at least one selected from the group consisting of polyimides and polybenzoxazoles. The CTE of resin (D) can be measured in the same manner as the CTE of the resin layer.

[0210] If composition B contains resin (D), the proportion of resin (D) in composition B is preferably 99% to 30% by mass of the total nonvolatile content of composition B, from the viewpoint of balancing the thermal expansion coefficient and bonding strength of the resulting resin layer. In this disclosure, "nonvolatile content" refers to components other than those removed when composition B becomes a cured product (solvent, etc.).

[0211] (organic solvent) Composition B may contain an organic solvent. The organic solvent is not particularly limited as long as it can dissolve compound (X). Examples include aprotic solvents, phenolic solvents, etheric solvents, and glycolic solvents. Organic solvents may be used individually or in combination of two or more.

[0212] Examples of aprotic solvents include amide solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, 1,3-dimethylimidazolidinone, and tetramethylurea; lactone solvents such as γ-butyrolactone and γ-valerolactone; phosphorus-containing amide solvents such as hexamethylphosphoricamide and hexamethylphosphinetriamide; sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide, and sulfolane; ketone solvents such as cyclohexanone and methylcyclohexanone; tertiary amine solvents such as picoline and pyridine; and ester solvents such as acetic acid (2-methoxy-1-methylethyl). Examples of phenolic solvents include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol. Examples of ether-based and glyco-based solvents include 1,2-dimethoxyethane, bis(2-methoxyethyl) ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl] ether, tetrahydrofuran, and 1,4-dioxane.

[0213] The organic solvent preferably has a boiling point of 60°C to 300°C at atmospheric pressure, more preferably 140°C to 280°C, and even more preferably 170°C to 270°C. If the boiling point of the solvent is 300°C or lower, the organic solvent is easily volatilized and removed during the resin layer formation process. If the boiling point of the solvent is 60°C or higher, a resin layer with a uniform surface condition can be obtained.

[0214] If composition B contains an organic solvent, its content is not particularly limited. For example, it may be 1.0% by mass or more and 99.99896% by mass or 40% by mass or more and 99.99896% by mass relative to the entire composition B.

[0215] (Other ingredients) Composition B may contain components other than those described above, if necessary. For example, if selectivity for plasma etching resistance is required for composition B (for example, when used as a gap fill material or embedded insulating film), it may contain a metal alkoxide represented by the following general formula (I). R1nM(OR2)mn···(I) (wherein R1 is a non-hydrolyzable group, R2 is an alkyl group having 1 to 6 carbon atoms, M represents at least one metal atom selected from the group of metal atoms Ti, Al, Zr, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La, Nd, and In, m is the valence of the metal atom M, which is 3 or 4, n is an integer from 0 to 2 if m is 4, and 0 or 1 if m is 3, if there are multiple R1s, each R1 may be the same or different from each other, and if there are multiple OR2s, each OR2 may be the same or different from each other.)

[0216] When the film produced from composition B is required to have insulating properties (for example, for use as an insulating film for silicon through-vias or for use as an embedded insulating film), a silane compound (excluding those corresponding to silane coupling agent (A)) may be included to improve insulating properties or mechanical strength. Specific examples of silane compounds include tetraethoxysilane, tetramethoxysilane, bistriethoxysilylethane, bistriethoxysilylmethane, bis(methyldiethoxysilyl)ethane, 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahydroxylcyclosiloxane, 1,1,4,4-tetramethyl-1,4-diethoxydisylethylene, and 1,3,5-trimethyl-1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane.

[0217] Composition B may contain, for example, benzotriazole or a derivative thereof to suppress copper corrosion.

[0218] The pH of composition B is not particularly limited, but it is preferably between 2.0 and 12.0. It is preferable that composition B contains 10 ppb by mass or less of sodium and potassium on an elemental basis. If the sodium or potassium content is 10 ppb by mass or less on an elemental basis, it is possible to suppress the occurrence of problems in the electrical characteristics of the semiconductor device, such as malfunctions of transistors.

[0219] Composition B preferably contains inorganic or resin fillers with a maximum diameter of 0.3 μm or more, which is 30% by mass or less of the total nonvolatile content, more preferably 10% by mass or less, and even more preferably 0% by mass. When the filler content in composition B is within the above range, bonding defects in the laminate can be suppressed even when the thickness of the resin layer formed using composition B is reduced. Furthermore, when laminating a first substrate with a resin layer formed on it onto a second substrate, alignment marks formed on each substrate may be recognized by a machine to perform positioning. When the filler content is within the above range, the transparency of the resin film is improved, enabling more accurate positioning.

[0220] The disclosure of Japanese Patent Application No. 2023-015651, filed on 3 February 2023, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. An organic bonding layer comprising an organic insulating layer and a metal pad, Multiple silicon dies are arranged in a two-dimensional manner and hybrid-bonded on the aforementioned organic bonding layer, A resin mold layer filled between the plurality of silicon dies on the organic bonding layer, A semiconductor structure comprising, The aforementioned organic insulating layer comprises a cured product of composition A or a cured product of composition B below. The aforementioned composition A is A compound (A) having a cationic functional group containing at least one selected from primary and secondary nitrogen atoms and an Si-O bond, Compound (B) having three or more -C(=O)OX groups (where X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and of the three or more -C(=O)OX groups, one to six are -C(=O)OH groups, A compound (C) having a ring structure and one or more primary nitrogen atoms directly bonded to the ring structure, The composition is such that the proportion of primary and secondary nitrogen atoms contained in compound (A) to the total of primary nitrogen atoms contained in compound (C) is 3 mol% to 95 mol%, The aforementioned composition B is A composition comprising at least one of a compound (X1) having a structure represented by the following general formula (1) and a molecular weight of 400 to 5000, and a compound (X2) having a structure represented by the following general formula (2) and a molecular weight of 400 to 5000. Semiconductor structure. 【Chemistry 1】 [In general formula (1), R １ and R ３ Each of these is an organic group with 6 or fewer carbon atoms, and R ２ is a methylene group, an ethylene group, a propylene group, or a phenylene group, a is 2 or 3, b is the number of 3 minus a, X １ This structure is derived from a carboxylic acid dianhydride. In the general formula (2), R １ and R ３ are each independently an organic group having 6 or less carbon atoms, R ２ is a methylene group, an ethylene group, a propylene group or a phenylene group, a is 2 or 3, b is the number of 3 - a, X １ is a structure derived from a dicarboxylic acid dianhydride, X ２ is a structure derived from an amine compound, and n is a positive number. ]]

2. An organic bonding layer comprising an organic insulating layer and a metal pad, Multiple silicon dies are arranged in a two-dimensional manner and hybrid-bonded on the aforementioned organic bonding layer, A resin mold layer filled between the plurality of silicon dies on the organic bonding layer, A second organic bonding layer, which includes an organic insulating layer and a metal pad, is located on the opposite side from the side where the organic bonding layer is located, as viewed from the plurality of silicon dies. A semiconductor structure comprising the following features.

3. An organic bonding layer comprising an organic insulating layer and a metal pad, Multiple silicon dies are arranged in a two-dimensional manner and hybrid-bonded on the aforementioned organic bonding layer, A resin mold layer filled between the plurality of silicon dies on the organic bonding layer, A second organic bonding layer, which includes an organic insulating layer and a metal pad, is located on the opposite side from the side where the organic bonding layer is located, as viewed from the plurality of silicon dies. Multiple second silicon dies are arranged in a two-dimensional manner and hybrid-bonded on the aforementioned second organic bonding layer, A semiconductor structure comprising the following features.

4. An organic bonding layer comprising an organic insulating layer and a metal pad, Multiple silicon dies are arranged in a two-dimensional manner and hybrid-bonded on the aforementioned organic bonding layer, A resin mold layer filled between the plurality of silicon dies on the organic bonding layer, A second organic bonding layer, which includes an organic insulating layer and a metal pad, is located on the opposite side from the side where the organic bonding layer is located, as viewed from the plurality of silicon dies. Multiple second silicon dies are arranged in a two-dimensional manner and hybrid-bonded on the aforementioned second organic bonding layer, A semiconductor structure comprising, Each of the plurality of second silicon dies includes a silicon die body and a silicon die bonding layer in contact with the second organic bonding layer. The silicon die junction layer is a semiconductor structure comprising an organic insulating layer, an SiO2 layer, a SiCN layer, or a SiN layer, and a metal pad.

5. An organic bonding layer comprising an organic insulating layer and a metal pad, Multiple silicon dies are arranged in a two-dimensional manner and hybrid-bonded on the aforementioned organic bonding layer, A resin mold layer filled between the plurality of silicon dies on the organic bonding layer, A second organic bonding layer, which includes an organic insulating layer and a metal pad, is located on the opposite side from the side where the organic bonding layer is located, as viewed from the plurality of silicon dies. A redistribution layer disposed between the second organic bonding layer and the plurality of silicon dies, A semiconductor structure comprising the following features.

6. An organic bonding layer comprising an organic insulating layer and a metal pad, Multiple silicon dies are arranged in a two-dimensional manner and hybrid-bonded on the aforementioned organic bonding layer, A resin mold layer filled between the plurality of silicon dies on the organic bonding layer, A second organic bonding layer, which includes an organic insulating layer and a metal pad, is located on the opposite side from the side where the organic bonding layer is located, as viewed from the plurality of silicon dies. A temporary fixing substrate or build-up substrate is positioned on the side opposite to the side where the plurality of silicon dies are arranged, with respect to the organic bonding layer, A semiconductor structure comprising the following features.

7. The semiconductor structure according to any one of claims 1 to 6, further comprising a redistribution layer located on the opposite side from the side on which the plurality of silicon dies are arranged when viewed from the organic junction layer.

8. The semiconductor structure according to any one of claims 1 to 6, further comprising a build-up substrate disposed on the opposite side from the side on which the plurality of silicon dies are arranged when viewed from the organic junction layer.

9. Furthermore, A high-density wiring layer is located on the side opposite to the side where the plurality of silicon dies are arranged, with respect to the organic bonding layer. A build-up substrate is positioned on the side opposite to the side where the organic bonding layer is located, with respect to the high-density wiring layer, A semiconductor structure according to any one of claims 1 to 6, comprising:

10. Each of the plurality of silicon dies includes a silicon die body and a silicon die bonding layer in contact with the organic bonding layer, The silicon die bonding layer includes an organic insulating layer, an SiO2 layer, a SiCN layer, or a SiN layer, and a metal pad. A semiconductor structure according to any one of claims 1 to 6.

11. The semiconductor structure according to any one of claims 1 to 6, wherein the resin mold layer covers the upper surfaces of the plurality of silicon dies.

12. A step of forming a redistribution layer on a temporary fixed substrate, The process involves forming an organic bonding layer including an organic insulating layer and a metal pad on the rewiring layer that is temporarily fixed on the temporary fixing substrate, A step of hybrid bonding by arranging a plurality of silicon dies in a two-dimensional manner on the organic bonding layer formed on the redistribution layer, A step of forming a resin mold layer which is filled between the plurality of silicon dies on the organic bonding layer and covers the upper surface of the plurality of silicon dies, The step of removing the temporary fixed substrate, A step of removing the portion of the resin mold layer that covers the upper surfaces of the plurality of silicon dies, thereby exposing the upper surfaces of the plurality of silicon dies, A step of forming a second organic bonding layer including an organic insulating layer and a metal pad on the plurality of silicon dies and the resin mold layer whose upper surfaces are exposed, A method for manufacturing a semiconductor structure, including [the specified element].

13. A step of forming a redistribution layer on a temporary fixed substrate, The process involves forming an organic bonding layer including an organic insulating layer and a metal pad on the rewiring layer that is temporarily fixed on the temporary fixing substrate, A step of hybrid bonding by arranging a plurality of silicon dies in a two-dimensional manner on the organic bonding layer formed on the redistribution layer, A step of forming a resin mold layer which is filled between the plurality of silicon dies on the organic bonding layer and covers the upper surface of the plurality of silicon dies, The step of removing the temporary fixed substrate, A step of removing the portion of the resin mold layer that covers the upper surfaces of the plurality of silicon dies, thereby exposing the upper surfaces of the plurality of silicon dies, A step of forming a second organic bonding layer including an organic insulating layer and a metal pad on the plurality of silicon dies and the resin mold layer whose upper surfaces are exposed, A step of hybrid bonding by arranging a plurality of second silicon dies in a two-dimensional manner on the second organic bonding layer, A method for manufacturing a semiconductor structure, including [the specified element].

14. A step of forming a redistribution layer on a temporary fixed substrate, The process involves forming an organic bonding layer including an organic insulating layer and a metal pad on the rewiring layer that is temporarily fixed on the temporary fixing substrate, A step of hybrid bonding by arranging a plurality of silicon dies in a two-dimensional manner on the organic bonding layer formed on the redistribution layer, A step of forming a resin mold layer which is filled between the plurality of silicon dies on the organic bonding layer and covers the upper surface of the plurality of silicon dies, The step of removing the temporary fixed substrate, A step of removing the portion of the resin mold layer that covers the upper surfaces of the plurality of silicon dies, thereby exposing the upper surfaces of the plurality of silicon dies, A step of forming a second redistribution layer on the plurality of silicon dies and the resin mold layer whose upper surfaces are exposed, The process involves forming a second organic bonding layer, which includes an organic insulating layer and a metal pad, on the second redistribution layer. A method for manufacturing a semiconductor structure, including [the specified element].

15. A step of forming a redistribution layer on a temporary fixed substrate, The process involves forming an organic bonding layer including an organic insulating layer and a metal pad on the rewiring layer that is temporarily fixed on the temporary fixing substrate, A step of hybrid bonding by arranging a plurality of silicon dies in a two-dimensional manner on the organic bonding layer formed on the redistribution layer, A step of forming a resin mold layer which is filled between the plurality of silicon dies on the organic bonding layer and covers the upper surface of the plurality of silicon dies, The step of removing the temporary fixed substrate, A step of removing the portion of the resin mold layer that covers the upper surfaces of the plurality of silicon dies, thereby exposing the upper surfaces of the plurality of silicon dies, A step of forming a second redistribution layer on the plurality of silicon dies and the resin mold layer whose upper surfaces are exposed, The process involves forming a second organic bonding layer, which includes an organic insulating layer and a metal pad, on the second redistribution layer. A step of hybrid bonding by arranging a plurality of second silicon dies in a two-dimensional manner on the second organic bonding layer, A method for manufacturing a semiconductor structure, including [the specified element].

16. A step of forming a redistribution layer on a temporary fixed substrate, The process involves forming an organic bonding layer including an organic insulating layer and a metal pad on the rewiring layer that is temporarily fixed on the temporary fixing substrate, A step of hybrid bonding by arranging a plurality of silicon dies in a two-dimensional manner on the organic bonding layer formed on the redistribution layer, A step of forming a resin mold layer which is filled between the plurality of silicon dies on the organic bonding layer and covers the upper surface of the plurality of silicon dies, The step of removing the temporary fixed substrate, A method for manufacturing a semiconductor structure, including, The step of forming the organic bonding layer includes curing composition A or composition B to form the organic insulating layer, The aforementioned composition A is A compound (A) having a cationic functional group containing at least one selected from primary and secondary nitrogen atoms and an Si-O bond, Compound (B) having three or more -C(=O)OX groups (where X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and of the three or more -C(=O)OX groups, one to six are -C(=O)OH groups, A compound (C) having a ring structure and one or more primary nitrogen atoms directly bonded to the ring structure, The composition is such that the proportion of primary and secondary nitrogen atoms contained in compound (A) to the total of primary nitrogen atoms contained in compound (C) is 3 mol% to 95 mol%, The aforementioned composition B is A composition comprising at least one of a compound (X1) having a structure represented by the following general formula (1) and a molecular weight of 400 to 5000, and a compound (X2) having a structure represented by the following general formula (2) and a molecular weight of 400 to 5000. A method for manufacturing semiconductor structures. 【Chemistry 2】 [In general formula (1), R1 and R3 are each independently organic groups having 6 or fewer carbon atoms, R2 is a methylene group, an ethylene group, a propylene group, or a phenylene group, a is 2 or 3, b is the number of 3-a, and X1 is a structure derived from a carboxylic acid dianhydride. In general formula (2), R1 and R3 are each independently organic groups having 6 or fewer carbon atoms, R2 is a methylene group, an ethylene group, a propylene group, or a phenylene group, a is 2 or 3, b is the number of 3 minus a, X1 is a structure derived from a carboxylic acid dianhydride, X2 is a structure derived from an amine compound, and n is a positive number.

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