Method for manufacturing substrate laminate

Abstract

A method for manufacturing a substrate laminate includes: a step for preparing a first laminate (10) and a second laminate (20); a step for providing a surface protection layer (27) on a second surface layer (22) of the second laminate; a step in which a dicing tape (42) is attached to the surface protection layer side of the second laminate provided with the surface protection layer and a dicing process is performed; peeling off the chip (28A) with the surface protection layer from the dicing tape, and laminating the chip with the surface protection layer on the first laminated body; a step of removing the surface protection layer; and a step for heating the first laminate and the chip (20A) of the second laminate from which the surface protective layer has been removed, thereby obtaining a substrate laminate (100) in which the chip of the second laminate is bonded to the first laminate.

Description

Technical Field

[0001] The present disclosure relates to a method for manufacturing a substrate laminate. Background Art

[0002] As electronic devices become smaller, lighter, and more powerful, there's a growing demand for higher integration of semiconductor chips and other devices. However, as circuits become increasingly miniaturized, it becomes increasingly difficult to fully meet this demand. In recent years, a method has been proposed for achieving higher integration by stacking multiple semiconductor substrates (wafers) and semiconductor chips vertically (in the thickness direction) to create a multilayered, three-dimensional structure.

[0003] One method for stacking and joining semiconductor substrates (wafers), semiconductor chips, etc. (hereinafter sometimes referred to as "semiconductor substrates, etc.") involves joining electrodes on the stacked semiconductor substrates, etc., via solder. However, as circuits become increasingly miniaturized, problems arise, such as the melting of adjacent solders, cracking due to alloying, and device malfunction caused by heat generated by the solder.

[0004] On the other hand, there have been proposed methods such as a direct bonding method for directly bonding electrodes of stacked semiconductor substrates or the like without soldering, and a method using an adhesive (for example, Patent Documents 1 to 3).

[0005] Furthermore, methods for producing a laminated body in which substrates such as semiconductor substrates are bonded to each other with high bonding strength via a resin layer having a low thermal expansion coefficient have been proposed (for example, Patent Documents 4 and 5).

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 4-132258

[0007] Patent Document 2: Japanese Patent Application Laid-Open No. 2010-226060

[0008] Patent Document 3: Japanese Patent Application Laid-Open No. 2016-47895

[0009] Patent Document 4: Japanese Patent Application Laid-Open No. 2021-182621

[0010] Patent Document 5: International Publication No. 2022 / 054839 Summary of the Invention

[0011] Problems to be solved by the invention

[0012] For example, when a substrate stack is manufactured by stacking semiconductor chips obtained by cutting processing on a semiconductor substrate, etc., it is easy to generate contamination of the semiconductor chips due to contact with the cutting tape, damage to the semiconductor chips when peeling the semiconductor chips from the cutting tape, contamination of the semiconductor chips due to contact with the device when handling the semiconductor chips, and voids caused by foreign matter such as particles mixed in when stacking the semiconductor chips.

[0013] One aspect of the present disclosure is completed in view of the above-mentioned problems, and its subject is to provide a method for manufacturing a substrate stack in which damage, contamination and foreign matter mixing of the chip can be suppressed when a chip including a substrate obtained by cutting is stacked on another substrate to manufacture a substrate stack.

[0014] Methods for solving problems

[0015] The specific means for solving the above-mentioned problems are as follows.

[0016] <1> A method for manufacturing a substrate laminate, comprising:

[0017] a laminate preparation step of preparing a first laminate having a first surface layer, a first substrate, and a first back layer laminated in sequence, and a second laminate having a second surface layer, a second substrate, and a second back layer laminated in sequence;

[0018] a surface protection step of providing a surface protection layer on the second surface layer of the second laminate;

[0019] a dicing step of attaching a dicing tape to the surface protective layer side of the second laminate provided with the surface protective layer and dicing the laminate into individual chips with the surface protective layer, each including the divided second laminate and the surface protective layer;

[0020] a lamination step of peeling the chip with the surface protection layer from the dicing tape and laminating the chip with the surface protection layer on the first laminate in such a manner that the first surface layer is in contact with the second back surface layer;

[0021] a cleaning and removing step of cleaning the stacked first stack and the chip with the surface protection layer and removing the surface protection layer; and

[0022] The bonding step comprises heating the first stack and the chips of the second stack from which the surface protective layer has been removed, thereby obtaining a substrate stack in which the chips of the second stack are bonded to the first stack.

[0023] <2> The method for producing a substrate laminate according to <1>,

[0024] The first laminate includes a first electrode exposed from the first surface layer and the first back surface layer.

[0025] The second laminate includes a second electrode exposed from the second surface layer and the second back surface layer.

[0026] In the lamination step, the chip with the surface protection layer is laminated on the first laminate so that the first electrode exposed from the first surface layer is in contact with the second electrode exposed from the second back surface layer.

[0027] <3> The method for producing a substrate laminate according to <1> or <2>,

[0028] The first surface layer is an inorganic material layer formed of an inorganic material.

[0029] The second back surface layer is a resin layer formed of resin.

[0030] The lamination step includes a temporary fixing step of temporarily fixing the laminated first stack and the chip with the surface protection layer at a first temperature.

[0031] The bonding step is a step of heating the temporarily fixed chips of the first stack and the second stack at a second temperature higher than the first temperature.

[0032] <4> According to the manufacturing method of the substrate stack described in <3>, the chip of the second stack after the above-mentioned temporary fixing process and before the above-mentioned joining process is regarded as the above-mentioned first stack in the above-mentioned stack preparation process, and before the above-mentioned joining process, the process from the above-mentioned stack preparation process to the above-mentioned temporary fixing process is repeated more than once, thereby the chip of the second stack is stacked in more than two layers and becomes temporarily fixed, and the above-mentioned joining process is performed after the last above-mentioned temporary fixing process.

[0033] <5> The method for producing a substrate laminate according to <3>, wherein the resin layer has at least one functional group selected from the group consisting of a silanol group, an amino group, an epoxy group, a hydroxyl group, and a functional group having an unsaturated bond on its surface.

[0034] <6> The method for producing a substrate laminate according to <3>, wherein the resin layer includes a siloxane bond and at least one selected from the group consisting of an ester bond, an ether bond, an amide bond, and an imide bond.

[0035] Effects of the Invention

[0036] According to one embodiment of the present disclosure, a method for manufacturing a substrate stack can be provided in which damage, contamination, and incorporation of foreign matter into the chips are suppressed when manufacturing the substrate stack by stacking chips including a substrate obtained by dicing on another substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1It is a schematic structural diagram showing an example of each of a first stack and a second stack that can be used in the method for producing a substrate stack of the present disclosure.

[0038] Figure 2 This is a schematic diagram showing a part of the steps included in an example of the method for producing the substrate laminate of the present disclosure.

[0039] Figure 3 This is a schematic diagram showing a part of the steps included in an example of the method for producing the substrate laminate of the present disclosure.

[0040] Figure 4 This is a schematic diagram showing a part of the steps included in an example of the method for producing the substrate laminate of the present disclosure.

[0041] Figure 5 This is a schematic diagram showing a part of the steps included in an example of the method for producing the substrate laminate of the present disclosure.

[0042] Figure 6 This is a schematic diagram showing a part of the steps included in an example of the method for producing the substrate laminate of the present disclosure.

[0043] Figure 7 This is a schematic configuration diagram showing an example of a substrate laminate produced by the method for producing a substrate laminate of the present disclosure. DETAILED DESCRIPTION

[0044] In the present disclosure, a numerical range expressed using “to” means a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit.

[0045] In the numerical ranges described in stages in this disclosure, the upper limit value described in one numerical range may be replaced by the upper limit value of the numerical range described in another stage, and the lower limit value may be replaced by the lower limit value of the numerical range described in another stage. In addition, in the numerical ranges described in this disclosure, the upper limit value or the lower limit value of the numerical range may be replaced by the value shown in the Examples.

[0046] In the present disclosure, a "substrate laminate" refers to a laminate having a structure in which two substrates, i.e., a first substrate and a second substrate, are laminated or bonded via a first surface layer and a second back layer. It should be noted that the substrate laminate may also have three or more substrates, or may have a structure in which two of the three or more substrates are laminated or bonded via a first surface layer and a second back layer.

[0047] In the present disclosure, “substrate” refers to “at least one of the first substrate and the second substrate.” In addition, in the present disclosure, “at least one of the first stacked body and the second stacked body” may be simply referred to as “stacked body.”

[0048] [Method for Manufacturing Substrate Laminate]

[0049] The method for manufacturing a substrate laminate disclosed herein includes:

[0050] a laminate preparation step of preparing a first laminate having a first surface layer, a first substrate, and a first back layer laminated in sequence, and a second laminate having a second surface layer, a second substrate, and a second back layer laminated in sequence;

[0051] a surface protection step of providing a surface protection layer on the second surface layer of the second laminate;

[0052] a dicing step of attaching a dicing tape to the surface protective layer side of the second laminate provided with the surface protective layer and dicing the laminate into individual chips with the surface protective layer, each including the divided second laminate and the surface protective layer;

[0053] a lamination step of peeling the chip with the surface protection layer from the dicing tape and laminating the chip with the surface protection layer on the first laminate in such a manner that the first surface layer is in contact with the second back surface layer;

[0054] a cleaning and removing step of cleaning the stacked first stack and the chip with the surface protection layer and removing the surface protection layer; and

[0055] The bonding step comprises heating the first stack and the chips of the second stack from which the surface protective layer has been removed, thereby obtaining a substrate stack in which the chips of the second stack are bonded to the first stack.

[0056] In the disclosed method for manufacturing a substrate laminate, a surface protective layer is provided on a second laminate, followed by dicing. The chipped second laminate is then stacked on the first laminate without removing the surface protective layer. This prevents contamination from the dicing tape, damage to the second surface layer during dicing tape removal, contamination of the semiconductor chips from contact with equipment during semiconductor chip handling, and the introduction of foreign matter such as particles when stacking the chips of the second laminate on the first laminate after dicing.

[0057] The first and second stacks used in the method for manufacturing a substrate stack of the present disclosure may also include other elements such as electrodes. For example, the first stack may include a first electrode exposed from the first surface layer and the first back layer, and the second stack may include a second electrode exposed from the second surface layer and the second back layer. During the stacking process, a chip with a surface protective layer may be stacked on the first stack such that the first electrode exposed from the first surface layer contacts the second electrode exposed from the second back layer.

[0058] In addition, the method for manufacturing a substrate laminate of the present disclosure may also include other steps, such as a cleaning step and a temporary fixing step before the bonding step. For example, the first surface layer may be an inorganic material layer formed of an inorganic material, the second back layer may be a resin layer formed of a resin, the lamination step may include a temporary fixing step of temporarily fixing the laminated first laminate and the chip with the surface protective layer at a first temperature, and the bonding step may include a step of heating the temporarily fixed first laminate and the chip of the second laminate at a second temperature higher than the first temperature.

[0059] In the disclosed method for manufacturing a substrate stack, the second stack (chip), formed into chips by dicing, is stacked on the first stack while still having a surface protective layer. This prevents foreign matter from adhering to or entering the stack during chip handling during the stacking process. Furthermore, after temporarily securing the second stack (chip) stacked on the first stack, the surface protective layer is removed through a cleaning and removal process. This prevents positional displacement between the first and second stacks (chips) during the cleaning and removal process.

[0060] In addition, in the manufacturing method of the substrate stack disclosed in the present invention, the chip of the second stack after the temporary fixing process and before the bonding process can be regarded as the first stack in the stack preparation process. Before the bonding process, the stack preparation process to the temporary fixing process are repeated more than once, thereby the chip of the second stack is stacked in more than two layers and becomes temporarily fixed. After the last temporary fixing process, the bonding process is performed.

[0061] By applying the method of manufacturing a substrate stack of the present disclosure when manufacturing a substrate stack by stacking two or more chips of the second stack, it is possible to suppress the intrusion of foreign matter such as particles between the stacked chips of the second stack.

[0062] The resin layer can be set, for example, as: a resin layer having at least one functional group selected from the group consisting of a silanol group, an amino group, an epoxy group, a hydroxyl group and a functional group having an unsaturated bond on the surface of the resin layer, or a resin layer containing a siloxane bond and at least any one bond selected from the group consisting of an ester bond, an ether bond, an amide bond and an imide bond (hereinafter, these resin layers are sometimes collectively referred to as "specific resin layers").

[0063] For example, in the case of bonding the inorganic material layer of the first stack to the resin layer of the second stack, if a cleaning and removal process for removing the surface protective layer is performed after the lamination process, the positions of the first stack and the second stack (chip) are easily offset. On the other hand, the above-mentioned specific resin layer is easy to be temporarily fixed even at room temperature (e.g., 23°C) when stacked on the inorganic material layer. Therefore, after the second stack (chip) having a specific resin layer is stacked on the first stack and temporarily fixed, the surface protective layer is removed by a cleaning and removal process, thereby suppressing the positional offset of the first stack and the second stack (chip) generated during the cleaning and removal process.

[0064] Hereinafter, before describing the details of each step in the method for manufacturing a substrate laminate of the present disclosure, an example of the method for manufacturing a substrate laminate of the present disclosure will be described with reference to the accompanying drawings. It should be noted that the present disclosure is not limited to the configuration shown in the accompanying drawings. In addition, the size, shape, and other configurations of the components in the various figures are conceptual, and the relative relationships between the components are not limited thereto. In addition, in the various drawings, components having substantially the same function are marked with the same reference numerals in all drawings, and the reference numerals and descriptions of duplicate components are sometimes omitted.

[0065] Figure 1 An example of each structure of the first stacked body 10 and the second stacked body 20 that can be used in the method for manufacturing a substrate stacked body according to the present disclosure is shown.

[0066] In the first stack 10, a first surface inorganic material layer 12 composed of an inorganic material is disposed on one surface of a silicon substrate 11 serving as a first substrate, and a first back surface inorganic material layer 13 is disposed on the other surface, serving as a first back surface layer. Furthermore, a first surface electrode 14 surrounded by the first surface inorganic material layer 12 is disposed on one surface of the silicon substrate 11, and a first back surface electrode 15 surrounded by the first back surface inorganic material layer 13 is disposed on the other surface. Furthermore, a first through electrode 16 is provided that penetrates the silicon substrate 11 in the thickness direction and electrically connects the first surface electrode 14 to the first back surface electrode 15.

[0067] In the second laminate 20, a second surface inorganic material layer 22 composed of an inorganic material is disposed on one surface of a silicon substrate 21 serving as a second substrate, and a second back-surface resin layer 23 composed of a resin is disposed on the other surface, serving as a second back-surface layer. Furthermore, a second front surface electrode 24 surrounded by the second surface inorganic material layer 22 is disposed on one surface of the silicon substrate 21, and a second back-surface electrode 25 surrounded by the second back-surface resin layer 23 is disposed on the other surface. Furthermore, a second through electrode 26 is provided that penetrates the silicon substrate 21 in the thickness direction and electrically connects the second front surface electrode 24 to the second back-surface electrode 25.

[0068] Figures 2 to 6 The schematic diagram shows the use of Figure 1 The first stack 10 and the second stack 20 shown are one example of a method for manufacturing a substrate stack according to the present disclosure.

[0069] (1) On the side of the silicon substrate 21 on which the internal electrode serving as the second through electrode 26 and the second back electrode 25 connected to the internal electrode are formed, a resin composition is spin-coated and cured to form a second back resin layer 23. The resin layer is then highly flattened by CMP (chemical mechanical polishing) to expose the back electrode 25 ( Figure 2 (1)).

[0070] (2) The second back surface resin layer 23 side of the silicon substrate 21 is temporarily supported on a temporary support 31 via a temporary support layer 32. For example, an adhesive layer is used as the temporary support layer 32, and a glass substrate, a silicon substrate, a ceramic substrate, etc. is used as the temporary support 31 ( Figure 2 (2)).

[0071] (3) The surface (surface) of the silicon substrate 21 temporarily supported on the temporary support 31 opposite to the second back surface resin layer 23 is highly flattened by CMP (chemical mechanical polishing), and the internal electrode is exposed as the second through electrode 26 ( Figure 2 (3)).

[0072] (4) The second surface electrode 24 connected to the second through-electrode 26 exposed from the surface of the silicon substrate 21 is formed. Figure 3 (4)).

[0073] (5) After forming the second surface inorganic material layer 22 as the second surface layer on the surface side of the silicon substrate 21, it is highly flattened by CMP and the surface electrode 24 is exposed ( Figure 3 (5)). Thus, the second stacked body 20 is obtained.

[0074] (6) A surface protection layer 27 is provided on the second surface inorganic material layer 22 and the back electrode 24 of the second stack 20 ( Figure 3 (6)).

[0075] (7) A dicing tape 42 is attached to the surface protection layer 27 side of the second laminate 20 provided with the surface protection layer 27, and the second laminate 20 is peeled off from the temporary support layer 32. After lamination, cleaning is performed ( Figure 4 (7)).

[0076] (8) Cutting is performed from the second back surface resin layer 23 side of the second laminate 20 to cut the surface protection layer 27 together with the second laminate 20, and the surface protection layer 27 is chipped (single-chipped) into a chip 28A with a surface protection layer (a chip 20A of the second laminate 20 with the surface protection layer 27A on the cut second surface inorganic material layer 22A) ( Figure 4 (8)).

[0077] (9) After cutting, clean and remove foreign matter such as particles. Figure 4 (9)).

[0078] (10) The chip 28A with the surface protection layer is peeled off from the dicing tape 42 by pushing it up with the needle 51 from the back side of the dicing tape 42. Figure 5 (10)).

[0079] (11) The surface protection layer 27A side of the chip 28A with the surface protection layer is adsorbed by the head 52 of the processing device and stacked on the first stack 10. At this time, the stacking is performed in such a manner that the first surface inorganic material layer 12 of the first stack 10 contacts the second back surface resin layer 23A of the chip 28A with the surface protection layer, and the first surface electrode 14 of the first stack 10 contacts the second back surface electrode 25 of the second stack 20 (chip 28A with the surface protection layer). Figure 5 (11)).

[0080] After stacking the first stack 10 and the chip 28A with the surface protective layer, the first stack 10 and the second stack 20 are temporarily fixed at a first temperature, such as room temperature. In this case, temporary fixing is achieved by stacking the chip 28A with the surface protective layer on the first stack 10, without heating. It should be noted that temporary fixing can also be achieved by heating at a temperature below 100°C as needed.

[0081] (12) The temporarily fixed first stacked body 10 and the chip 28A with the surface protection layer are cleaned, and the surface protection layer 24 is removed. Figure 6 (12)).

[0082] The chip 20A of the second laminate 20 (sometimes referred to as the "second laminate chip 20A" in this disclosure) and the first laminate 10, which have been temporarily fixed and have had their surface protective layer 24 removed, are heated at a second temperature higher than the first temperature, for example, 100° C. or higher. This results in a substrate laminate 100 in which the chip 20A of the second laminate 20 is bonded to the first laminate 10.

[0083] above Figures 1 to 6 The steps shown are examples of the method for manufacturing a substrate laminate according to the present disclosure and are not limited to these. Below, each step of the method for manufacturing a substrate laminate according to the present disclosure is described in detail. It should be noted that in the following description, reference is sometimes made to the accompanying drawings, but the accompanying drawings are omitted as appropriate.

[0084] [Laminate preparation step]

[0085] The method for manufacturing a substrate laminate of the present disclosure includes a laminate preparation step ( Figure 1 ). The first laminate is stacked in the order of a first surface layer, a first substrate, and a first back layer in the thickness direction. The first surface layer is arranged on one side, and the first back layer is arranged on the other side (the side on the opposite side). Similarly, the second laminate is stacked in the order of a second surface layer, a second substrate, and a second back layer in the thickness direction. The second surface layer is arranged on one side, and the second back layer is arranged on the other side (the side on the opposite side).

[0086] (First Substrate and Second Substrate)

[0087] The material of the substrate is not particularly limited as long as it is a commonly used material. The materials of the first substrate and the second substrate may be the same or different.

[0088] The substrate preferably contains at least one element selected from the group consisting of Si, Al, Ti, Zr, Hf, Fe, Ni, Cu, Ag, Au, Ga, Ge, Sn, Pd, As, Pt, Mg, In, Ta, and Nb. Examples of the substrate material include semiconductors such as Si, InP, GaN, GaAs, InGaAs, InGaAlAs, and SiC; oxides, carbides, and nitrides such as borosilicate glass (Pyrex (registered trademark)), quartz glass (SiO2), sapphire, ZrO2, Si3N4, and AlN; piezoelectrics and dielectrics such as BaTiO3, LiNbO3, and SrTiO3; and diamond; and metals such as Al, Ti, Fe, Cu, Ag, Au, Pt, Pd, Ta, and Nb.

[0089] The substrate may be made of resins such as polydimethylsiloxane (PDMS), epoxy resin, phenolic resin, polyimide, benzocyclobutene resin, and polybenzoxazole.

[0090] The substrate may also have a multilayer structure. Examples include structures in which an inorganic layer such as silicon oxide, silicon nitride, or SiCN (silicon carbonitride) is formed on the surface of a silicon substrate; structures in which an organic layer such as an organic-inorganic composite low-k layer such as polyimide resin, polybenzoxazole resin, epoxy resin, CYCLOTENE (Dow Chemical), imide-crosslinked siloxane resin, epoxy-modified siloxane, porous silica, organo-crosslinked siloxane, or Black Diamond (Applied Materials) is formed on the surface of a silicon substrate; and structures in which a composite of inorganic and organic materials is formed on a silicon substrate.

[0091] As main applications, each material can be used for the following applications.

[0092] Si is used in semiconductor memory, LSI stacking, CMOS image sensors, MEMS sealing, optical devices, LEDs, etc.

[0093] SiO2 is used in semiconductor memory, LSI stacking, MEMS sealing, micro-flow path, CMOS image sensor, optical devices, LED, etc.

[0094] PDMS is used for microfluidics;

[0095] InGaAlAs, InGaAs, and InP are used in optical devices;

[0096] InGaAlAs, GaAs, and GaN are used in LEDs, etc.

[0097] The thickness of the substrate is not particularly limited, but is independently preferably 0.5 μm to 1 mm, more preferably 1 μm to 900 μm, and even more preferably 2 μm to 900 μm.

[0098] The shape of the substrate is not particularly limited. For example, if the substrate is a silicon substrate, it can be a silicon substrate formed with an interlayer insulating layer (Low-k film), and further, fine grooves (recesses), fine through holes, etc. can be formed on the silicon substrate.

[0099] In the method for manufacturing a substrate laminate disclosed herein, the surface of the substrate in contact with the resin layer may be surface treated from the perspective of bonding strength. The surface treatment may be performed to form at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, a carboxyl group, an amino group, and a mercapto group.

[0100] Examples of the surface treatment include plasma treatment, chemical treatment, and ozone treatment such as ultraviolet (UV) ozone treatment.

[0101] The hydroxyl groups can be provided on the surfaces of the substrates by subjecting the surfaces to surface treatment such as plasma treatment, chemical treatment, or ozone treatment such as UV ozone treatment.

[0102] The hydroxyl group is preferably present in a state bonded to at least one element selected from the group consisting of Si, Al, Ti, Zr, Hf, Fe, Ni, Cu, Ag, Au, Ga, Ge, Sn, Pd, As, Pt, Mg, In, Ta, and Nb contained in the substrate. The surface of the substrate that contacts the resin layer preferably has a silanol group containing a hydroxyl group.

[0103] The epoxy groups can be provided on the surfaces of the substrates by subjecting the surfaces to surface treatment such as silane coupling using epoxysilane.

[0104] The carboxyl groups can be provided on the surfaces of the substrates by subjecting the surfaces of the substrates to surface treatment such as silane coupling using carboxylsilane.

[0105] The amino groups can be provided on the surfaces of the substrates by subjecting the surfaces of the substrates to surface treatment such as silane coupling using aminosilane.

[0106] Mercapto groups can be provided on the surfaces of the substrates by subjecting the surfaces of the substrates to surface treatment such as silane coupling using mercaptosilane.

[0107] In addition, from the viewpoint of improving the bonding strength, a primer such as a silane coupling agent may be formed into a film on the surface of the substrate on which the resin material is applied.

[0108] (first surface layer and second surface layer)

[0109] The first surface layer is a layer disposed on one surface of the first substrate, and is a layer that comes into contact with the second back surface layer of the second laminate in the lamination step.

[0110] The second surface layer is a layer disposed on the other surface of the second substrate, and is a layer on which the surface protection layer is provided in the surface protection step.

[0111] The first surface layer and the second surface layer may be composed of an inorganic material or a resin.

[0112] From the viewpoint of resistance to removal by washing in the washing and removal step, etc., each of the first surface layer and the second surface layer is preferably an inorganic material layer composed of an inorganic material.

[0113] (First back layer and second back layer)

[0114] The first back layer is disposed on the other side of the first substrate, that is, on the side opposite to the first surface layer. The second back layer is disposed on the other side of the second substrate, that is, on the side opposite to the second surface layer.

[0115] The first back surface layer and the second back surface layer may be made of an inorganic material or a resin.

[0116] From the viewpoint of cleaning resistance and the like, the first back surface layer located at the bottom of the substrate stack produced by the method for producing a substrate stack of the present disclosure is preferably an inorganic material layer.

[0117] On the other hand, from the viewpoint of suppressing the generation of voids during temporary fixing of the first and second stacks in the temporary fixing step and during joining of the first and second stacks in the joining step, the second back surface layer is preferably a resin layer made of resin.

[0118] Below, inorganic material layer and the resin layer that can constitute the first surface layer, the first back layer, the second surface layer and / or the second surface layer are described respectively.It should be noted that in the present disclosure, for example, the first surface layer and the second surface layer that are constituted by inorganic material are sometimes referred to as the first surface inorganic material layer and the second surface inorganic material layer respectively.In addition, the second back layer that is constituted by resin is sometimes referred to as the second back side resin layer.

[0119] (Inorganic material layer)

[0120] The material of the inorganic material layer is not particularly limited. For example, any material of the inorganic material used when bonding inorganic materials to each other in a semiconductor substrate is sufficient. Specifically, the inorganic material layer may include at least one element selected from the group consisting of Si, Al, Ti, Zr, Hf, Fe, Ni, Cu, Ag, Au, Ga, Ge, Sn, Pd, As, Pt, Mg, In, Ta, and Nb, preferably at least one element selected from the group consisting of Si, Ga, Ge, and As. The inorganic material layer may also include oxides, carbides, nitrides, etc. of the above elements.

[0121] The materials of the inorganic material layers may be the same or different.

[0122] The method for forming the inorganic material layer on at least one surface of the substrate is not particularly limited, and conventionally known methods for forming an inorganic material layer may be used, such as CVD, sputtering, AGD (aerosol vapor deposition), sol-gel method, anodization, thermal decomposition, and the like.

[0123] (Resin layer)

[0124] The resin layer is formed by applying a resin composition containing a resin material to one surface of a substrate and curing the formed resin composition layer.

[0125] The resin material contained in the resin composition is not particularly limited, and examples thereof include materials that form bonds or structures such as polyimide, polyamide, polyamideimide, polyparaxylene (Parylene), polyarylene ether, tetralin, octahydroanthracene, etc. through cross-linking; materials that form nitrogen-containing ring structures such as polybenzoxazole and polybenzoxazine; materials that form bonds or structures such as Si—O through cross-linking; and organic materials such as siloxane-modified compounds.

[0126] The resin materials used to form the respective resin layers may be the same or different.

[0127] Examples of the structure having a Si—O bond (siloxane bond) include structures represented by the following formulae (1) to (3).

[0128] [Chemistry 1]

[0129]

[0130] In the structure having Si-O bond (siloxane bond), the group bonded to Si may be substituted by (alkylene, phenylene, etc., for example, it may be (-O-) x (R1) y Si-(R2)-Si(R1) y (-O-) x etc. (R1 represents a methyl group, etc., R2 represents an alkylene group, a phenylene group, etc., x and y are each independently an integer greater than 0, and x+y is 3).

[0131] Examples of materials that form Si-O bonds by crosslinking include compounds represented by the following formulae (4) and (5). Furthermore, structures represented by formulae (1) and (2) can be generated by, for example, heating the compounds represented by formulae (4) and (5) to react.

[0132] [Chemistry 2]

[0133]

[0134] For example, in the case where the resin material contains a material that forms a bond or structure of polyimide, polyamide, polyamideimide, etc. by cross-linking, it preferably contains: a compound (A) having a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom, and a weight-average molecular weight of 900,000 to 400,000; and a cross-linking agent (B) having 3 or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, 1 or more and 6 or less of the 3 or more -C(=O)OX groups are -C(=O)OH groups, and the weight-average molecular weight is 200 to 2000.

[0135] (Compound (A))

[0136] Compound (A) is a compound having a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom and having a weight average molecular weight of 90 to 400,000. The cationic functional group is not particularly limited as long as it is a functional group capable of carrying a positive charge and containing at least one of a primary nitrogen atom and a secondary nitrogen atom.

[0137] Furthermore, the compound (A) may contain a tertiary nitrogen atom in addition to the primary and secondary nitrogen atoms.

[0138] In the present disclosure, "primary nitrogen atom" refers to a nitrogen atom that is bonded only to two hydrogen atoms and one atom other than a hydrogen atom (for example, a nitrogen atom contained in a primary amino group (-NH2 group)), or a nitrogen atom (cation) that is bonded only to three hydrogen atoms and one atom other than a hydrogen atom.

[0139] In addition, a "secondary nitrogen atom" refers to a nitrogen atom bonded only to one hydrogen atom and two atoms other than hydrogen atoms (i.e., a nitrogen atom contained in the functional group represented by the following formula (a)), or a nitrogen atom bonded only to two hydrogen atoms and two atoms other than hydrogen atoms (cation).

[0140] Furthermore, a "tertiary nitrogen atom" refers to a nitrogen atom bonded only to three atoms other than hydrogen atoms (i.e., a nitrogen atom serving as a functional group represented by the following formula (b)), or a nitrogen atom bonded only to one hydrogen atom and three atoms other than hydrogen atoms (cation).

[0141] [Chemistry 3]

[0142]

[0143] In formula (a) and formula (b), * represents a bonding position to an atom other than a hydrogen atom.

[0144] Here, the functional group represented by the above formula (a) may be a secondary amino group (-NHR a Here, R aThe functional group representing a part of the group (representing an alkyl group) may be a divalent linking group contained in the polymer skeleton.

[0145] In addition, the functional group (ie, tertiary nitrogen atom) represented by the above formula (b) may be a tertiary amino group (-NR b R c Here, R b and R c The functional groups each independently represent a part of an alkyl group may be trivalent linking groups contained in the polymer skeleton.

[0146] The weight average molecular weight of compound (A) is 90 to 400,000. As compound (A), for example, aliphatic amines, compounds having a siloxane bond (Si-O bond) and an amino group, amine compounds having a ring structure without a Si-O bond in the molecule, etc. can be cited. In the case where compound (A) is an aliphatic amine, the weight average molecular weight is preferably 10,000 to 200,000. In the case where compound (A) is a compound having a siloxane bond (Si-O bond) and an amino group, the weight average molecular weight is preferably 130 to 10,000, more preferably 130 to 5,000, and further preferably 130 to 2,000. In the case where compound (A) is an amine compound having a ring structure without a Si-O bond in the molecule, the weight average molecular weight is preferably 90 to 600.

[0147] In addition, in this disclosure, the weight average molecular weight means the weight average molecular weight in terms of polyethylene glycol measured by GPC (Gel Permeation Chromatography) method for substances other than monomers.

[0148] Specifically, the weight-average molecular weight was calculated as follows: using an aqueous solution with a sodium nitrate concentration of 0.1 mol / L as the elution solvent, the refractive index was detected at a flow rate of 1.0 mL / min using an analytical apparatus Shodex DET RI-101 and two analytical columns (TSKgel G6000 PWXL-CP and TSKgel G3000 PWXL-CP manufactured by Tosoh), and polyethylene glycol / polyethylene oxide as the standard, and the weight-average molecular weight was calculated using analytical software (Empower3 manufactured by Waters).

[0149] Furthermore, the compound (A) may further have an anionic functional group, a nonionic functional group, or the like, as necessary.

[0150] The nonionic functional group may be a hydrogen bond acceptor group or a hydrogen bond donor group. Examples of the nonionic functional group include a hydroxyl group, a carbonyl group, and an ether group (-O-).

[0151] The anionic functional group is not particularly limited as long as it is a functional group capable of being negatively charged. Examples of the anionic functional group include a carboxylic acid group, a sulfonic acid group, and a sulfate group.

[0152] Examples of the compound (A) include aliphatic amines, and more specifically, polymers of alkyleneimines such as ethyleneimine, propyleneimine, butyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, octyleneimine, trimethyleneimine, tetramethyleneimine, pentamethyleneimine, hexamethyleneimine, and octamethyleneimine, i.e., polyalkyleneimines; polyallylamine; and polyacrylamide.

[0153] Polyethyleneimine (PEI) can be produced by the known methods described in Japanese Patent Publication No. 43-8828, Japanese Patent Publication No. 49-33120, Japanese Patent Application Laid-Open No. 2001-213958, International Publication No. 2010 / 137711, etc. Polyalkyleneimines other than polyethyleneimine can also be produced by the same method as polyethyleneimine.

[0154] Compound (A) is also preferably a derivative of the above-mentioned polyalkyleneimine (a polyalkyleneimine derivative; particularly preferably a polyethyleneimine derivative). The polyalkyleneimine derivative is not particularly limited as long as it is a compound that can be produced using the above-mentioned polyalkyleneimine. Specifically, examples include polyalkyleneimine derivatives in which an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) or an aryl group is introduced into the polyalkyleneimine, and polyalkyleneimine derivatives in which a crosslinking group such as a hydroxyl group is introduced into the polyalkyleneimine.

[0155] These polyalkyleneimine derivatives can be produced by a conventional method using the above-mentioned polyalkyleneimine, and specifically, can be produced according to the method described in, for example, Japanese Patent Application Laid-Open No. 6-016809.

[0156] Furthermore, the polyalkyleneimine derivative is preferably a highly branched polyalkyleneimine obtained by reacting a cationic functional group-containing monomer with polyalkyleneimine to increase the branching degree of the polyalkyleneimine.

[0157] Examples of methods for obtaining highly branched polyalkyleneimines include: a method in which a monomer containing a cationic functional group is reacted with a polyalkyleneimines having a plurality of secondary nitrogen atoms in its backbone, and at least one of the plurality of secondary nitrogen atoms is replaced with a monomer containing a cationic functional group; a method in which a monomer containing a cationic functional group is reacted with a polyalkyleneimines having a plurality of primary nitrogen atoms at its terminals, and at least one of the plurality of primary nitrogen atoms is replaced with a monomer containing a cationic functional group; and the like.

[0158] Examples of the cationic functional group introduced to increase the degree of branching include aminoethyl, aminopropyl, diaminopropyl, aminobutyl, diaminobutyl, and triaminobutyl. From the perspective of reducing the cationic functional group equivalent and increasing the cationic functional group density, the aminoethyl group is preferred.

[0159] The polyethyleneimine and its derivatives may be commercially available products. For example, polyethyleneimine and its derivatives sold by Nippon Shokubai Co., Ltd., BASF, MP Biomedicals, etc. may be appropriately selected and used.

[0160] Examples of compound (A) include, in addition to the aforementioned aliphatic amines, compounds having a Si—O bond and an amino group. Examples of compounds having a Si—O bond and an amino group include siloxane diamines, silane coupling agents having an amino group, and siloxane polymers of silane coupling agents having an amino group.

[0161] As a silane coupling agent which has an amino group, the compound represented by following formula (A-3) is mentioned, for example.

[0162] [Chemistry 4]

[0163]

[0164] In formula (A-3), R 1 represents an alkyl group having 1 to 4 carbon atoms which may be substituted. 2 and R 3 Each independently represents an alkylene group having 1 to 12 carbon atoms, an ether group or a carbonyl group which may be substituted (a carbonyl group, an ether group or the like may be contained in the skeleton). 4 and R 5 Each independently represents an alkylene group having 1 to 4 carbon atoms which may be substituted or a single bond. Ar represents a divalent or trivalent aromatic ring. 1 represents hydrogen or an optionally substituted alkyl group having 1 to 5 carbon atoms. 2 represents hydrogen, a cycloalkyl group, a heterocyclic group, an aryl group, or an alkyl group having 1 to 5 carbon atoms which may be substituted (a carbonyl group, an ether group, etc. may be included in the skeleton). 1 、R 2 、R 3 、R 4 、R 5 、X 1 Can be the same or different.

[0165] As R 1 、R 2 、R 3 、R 4 、R 5 、X 1 、X 2The substituents of the alkyl group and the alkylene group in the group are each independently amino, hydroxy, alkoxy, cyano, carboxylic acid, sulfonic acid, halogen and the like.

[0166] Examples of the divalent or trivalent aromatic ring in Ar include a divalent or trivalent benzene ring. 2 Examples of the aryl group in include phenyl, methylbenzyl, and vinylbenzyl.

[0167] Specific examples of the silane coupling agent represented by formula (A-3) include 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, alkyl, (aminoethylaminoethyl)phenethyltrimethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, N-[2-[3-(trimethoxysilyl)propylamino]ethyl]ethylenediamine, 3-aminopropyldiethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldimethylmethoxysilane, trimethoxy[2-(2-aminoethyl)-3-aminopropyl]silane, diaminomethylmethyldiethoxysilane, methylaminomethylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, N-methylaminopropyltriethoxysilane, N-methylaminopropylmethyldiethoxysilane, (phenylaminomethyl)methyldiethoxysilane, acetamidopropyltrimethoxysilane, and hydrolyzates thereof.

[0168] Examples of silane coupling agents containing an amino group other than those represented by formula (A-3) include N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, bis[(3-triethoxysilyl)propyl]amine, piperazinylpropylmethyldimethoxysilane, bis[3-(triethoxysilyl)propyl]urea, bis(methyldiethoxysilylpropyl)amine, 2,2-dimethoxy-1,6-diaza-2-silacyclooctane, 3,5-diamino-N-(4-(methoxydimethylsilyl)phenyl)benzamide, 3,5-diamino-N-(4-(triethoxysilyl)phenyl)benzamide, 5-(ethoxydimethylsilyl)benzene-1,3-diamine, and hydrolyzates thereof.

[0169] The above-mentioned silane coupling agent with amino group can be used alone or in combination of two or more. In addition, a silane coupling agent with amino group and a silane coupling agent without amino group can be used in combination. For example, a silane coupling agent with mercapto group can be used to improve adhesion to metal.

[0170] In addition, polymers (siloxane polymers) formed from these silane coupling agents via siloxane bonds (Si-O-Si) can also be used. For example, polymers having a linear siloxane structure, a branched siloxane structure, a cyclic siloxane structure, and a cage siloxane structure can be obtained from the hydrolyzate of 3-aminopropyltrimethoxysilane. The cage siloxane structure is represented by the following formula (A-1), for example.

[0171] [Chemistry 5]

[0172]

[0173] Examples of the siloxane diamine include compounds represented by the following formula (A-2): In formula (A-2), i is an integer of 0 to 4, j is an integer of 1 to 3, and Me is a methyl group.

[0174] [Chemistry 6]

[0175]

[0176] Examples of the siloxane diamine include 1,3-bis(3-aminopropyl)tetramethyldisiloxane (in formula (A-2), i=0, j=1) and 1,3-bis(2-aminoethylamino)propyltetramethyldisiloxane (in formula (A-2), i=1, j=1).

[0177] As compound (A), in addition to the above-mentioned aliphatic amines and compounds having Si-O bonds and amino groups, amine compounds having a ring structure but not having a Si-O bond in the molecule can also be mentioned. Among them, preferably, an amine compound having a weight average molecular weight of 90 or more and 600 or less that does not have a Si-O bond in the molecule but has a ring structure. As amine compounds having a weight average molecular weight of 90 or more and 600 or less that do not have a Si-O bond in the molecule but have a ring structure, alicyclic amines, aromatic ring amines, heterocyclic amines, etc. can be mentioned. There can be multiple ring structures in the molecule, and the multiple ring structures can be the same or different. As the amine compound having a ring structure, a compound having an aromatic ring is more preferred because it is easy to obtain a compound that is more stable to heat.

[0178] In addition, as an amine compound having a weight-average molecular weight of 90 to 600, which does not have an Si-O bond in the molecule but has a ring structure, a compound having a primary amino group is preferred because it can easily form a thermally crosslinked structure such as an amide, amideimide, or imide with the crosslinking agent (B), thereby improving heat resistance. Furthermore, as the above-mentioned amine compound, a diamine compound having two primary amino groups, a triamine compound having three primary amino groups, etc. are preferred because it can easily increase the number of thermally crosslinked structures such as an amide, amideimide, or imide with the crosslinking agent (B), thereby further improving heat resistance.

[0179] Examples of the alicyclic amine include cyclohexylamine and dimethylaminocyclohexane.

[0180] Examples of the aromatic cyclic amine include diaminodiphenyl ether, xylenediamine (preferably p-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, 2,7-diaminofluorene, 1,9-diaminofluorene, and dibenzylamine.

[0181] Examples of the heterocyclic ring of the heterocyclic amine include a heterocyclic ring containing a sulfur atom as a heteroatom (e.g., a thiophene ring), or a heterocyclic ring containing a nitrogen atom as a heteroatom (e.g., a 5-membered ring such as a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, and a triazole ring; a 6-membered ring such as an isocyanurate ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, and a triazine ring; and a condensed ring such as an indole ring, an indoline ring, a quinoline ring, an acridine ring, a naphthyridine ring, a quinazoline ring, a purine ring, and a quinoxaline ring).

[0182] For example, examples of the heterocyclic amine having a nitrogen-containing heterocyclic ring include melamine, ammeline, melam, melem, and tris(4-aminophenyl)amine.

[0183] Furthermore, examples of the amine compound having both a heterocyclic ring and an aromatic ring include N2,N4,N6-tris(4-aminophenyl)-1,3,5-triazine-2,4,6-triamine.

[0184] Compound (A) has a primary or secondary amino group, and therefore can firmly bond the substrates to each other through electrostatic interaction with functional groups such as hydroxyl, epoxy, carboxyl, amino, and mercapto groups that may be present on the surfaces of the first and second substrates, or by tightly forming covalent bonds with the above-mentioned functional groups.

[0185] In addition, compound (A) has a primary or secondary amino group and is therefore easily soluble in the polar solvent (D) described below. By using a compound (A) that is easily soluble in a polar solvent (D), the affinity for the hydrophilic surface of a substrate such as a silicon substrate is increased, thereby easily forming a smooth film and enabling the thickness of the resin layer to be reduced.

[0186] The compound (A) is preferably an aliphatic amine or a compound having a Si—O bond and an amino group from the viewpoint of forming a smooth thin film, and more preferably a compound having a Si—O bond and an amino group from the viewpoint of heat resistance.

[0187] When compound (A) contains a compound having a Si-O bond and an amino group, from the perspective of forming a smooth thin film, the ratio of the total number of primary nitrogen atoms and secondary nitrogen atoms in compound (A) to the number of silicon atoms (total number of primary nitrogen atoms and secondary nitrogen atoms / number of silicon atoms) is preferably greater than 0.2 and less than 5.

[0188] When compound (A) includes a compound having a Si—O bond and an amino group, from the perspective of adhesion between substrates, the non-crosslinking groups such as methyl groups bonded to Si in the compound having a Si—O bond and an amino group preferably satisfy the relationship (non-crosslinking group) / Si<2 in terms of molar ratio. It is speculated that satisfying this relationship increases the crosslink density (crosslinks between Si—O—Si bonds and amide bonds, imide bonds, etc.) of the formed film, resulting in sufficient adhesion between substrates and suppressing delamination of the substrates.

[0189] As described above, compound (A) has a cationic functional group comprising at least one of a primary nitrogen atom and a secondary nitrogen atom. Here, when compound (A) contains a primary nitrogen atom, the proportion of primary nitrogen atoms in compound (A) to all nitrogen atoms is preferably 20 mol% or more, more preferably 25 mol% or more, and even more preferably 30 mol% or more. Alternatively, compound (A) may have a cationic functional group comprising a primary nitrogen atom and excluding nitrogen atoms other than primary nitrogen atoms (e.g., secondary nitrogen atoms or tertiary nitrogen atoms).

[0190] When compound (A) contains secondary nitrogen atoms, the proportion of secondary nitrogen atoms in compound (A) to all nitrogen atoms is preferably 5 mol% to 50 mol%, more preferably 10 mol% to 45 mol%.

[0191] In addition, compound (A) may contain tertiary nitrogen atoms in addition to primary nitrogen atoms and secondary nitrogen atoms. When compound (A) contains tertiary nitrogen atoms, the proportion of tertiary nitrogen atoms in compound (A) to all nitrogen atoms is preferably from 20 mol% to 50 mol%, and more preferably from 25 mol% to 45 mol%.

[0192] In the present disclosure, the content of the component derived from compound (A) in the resin layer is not particularly limited. For example, it can be set to 1 mass % to 82 mass % relative to the entire resin layer, preferably 5 mass % to 82 mass %, and more preferably 13 mass % to 82 mass %.

[0193] (Crosslinking agent (B))

[0194] The crosslinking agent (B) is a compound having three or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, one or more but no more than six of the three or more -C(=O)OX groups (hereinafter also referred to as "COOX") are -C(=O)OH groups (hereinafter also referred to as "COOH"), and a weight-average molecular weight of 200 to 2000.

[0195] The crosslinking agent (B) is a compound having three or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, preferably a compound having three or more -C(=O)OX groups in the molecule, and more preferably a compound having three or four -C(=O)OX groups in the molecule.

[0196] In the crosslinking agent (B), X in the -C(=O)OX group may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, with a hydrogen atom, a methyl group, an ethyl group, and a propyl group being preferred. It should be noted that X in the -C(=O)OX group may be the same or different.

[0197] The crosslinking agent (B) is a compound having one or more -C(=O)OH groups in which X is a hydrogen atom in the molecule, preferably a compound having one or more -C(=O)OH groups in which X is a hydrogen atom in the molecule, more preferably a compound having two or more -C(=O)OH groups in which X is a hydrogen atom, and further preferably a compound having two or three -C(=O)OH groups in the molecule.

[0198] The crosslinking agent (B) is a compound having a weight average molecular weight of 200 to 2000. The weight average molecular weight of the crosslinking agent (B) is preferably 200 to 1000, more preferably 200 to 600, and even more preferably 200 to 400.

[0199] The crosslinking agent (B) preferably has a ring structure in the molecule. Examples of the ring structure include alicyclic structures and aromatic ring structures. In addition, the crosslinking agent (B) may have multiple ring structures in the molecule, and the multiple ring structures may be the same or different.

[0200] Examples of the alicyclic structure include alicyclic structures having 3 to 8 carbon atoms, preferably alicyclic structures having 4 to 6 carbon atoms. The ring structure may be saturated or unsaturated. More specifically, examples of the alicyclic structure include saturated alicyclic structures such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring; and unsaturated alicyclic structures such as a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, and a cyclooctene ring.

[0201] The aromatic ring structure is not particularly limited as long as it is a ring structure showing aromaticity. Examples thereof include benzene-based aromatic rings such as benzene ring, naphthalene ring, anthracene ring, and perylene ring; aromatic heterocycles such as pyridine ring and thiophene ring; and non-benzene-based aromatic rings such as indene ring and azulene ring.

[0202] The ring structure possessed by the crosslinking agent (B) in the molecule is preferably at least one selected from the group consisting of a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a benzene ring and a naphthalene ring. From the perspective of further improving the heat resistance of the resin layer, at least one of a benzene ring and a naphthalene ring is more preferred.

[0203] As described above, the crosslinking agent (B) may have a plurality of ring structures in the molecule. When the ring structure is benzene, the crosslinking agent (B) may have a biphenyl structure, a benzophenone structure, a diphenyl ether structure, or the like.

[0204] The crosslinking agent (B) preferably has a fluorine atom in the molecule, more preferably has 1 or more and 6 or less fluorine atoms in the molecule, and even more preferably has 3 or more and 6 or less fluorine atoms in the molecule. For example, the crosslinking agent (B) may have a fluoroalkyl group in the molecule, specifically a trifluoroalkyl group or a hexafluoroisopropyl group.

[0205] Furthermore, examples of the crosslinking agent (B) include carboxylic acid compounds such as alicyclic carboxylic acids, benzene carboxylic acids, naphthalene carboxylic acids, diphthalic acids, and fluorinated aromatic ring carboxylic acids; and carboxylate compounds such as alicyclic carboxylic acid esters, benzene carboxylic acid esters, naphthalene carboxylic acid esters, diphthalic acid esters, and fluorinated aromatic ring carboxylic acid esters. It should be noted that the carboxylate compound is a compound having a carboxyl group (-C(=O)OH group) in the molecule, and at least one X among three or more -C(=O)OX groups is an alkyl group having 1 to 6 carbon atoms (i.e., having an ester bond). In the present disclosure, since the crosslinking agent (B) is a carboxylate compound, the aggregation caused by the association of the compound (A) and the crosslinking agent (B) is suppressed, the number of aggregates and pits is reduced, and the adjustment of the film thickness becomes easy.

[0206] The carboxylic acid compound is preferably a tetravalent or less carboxylic acid compound containing four or less -C(=O)OH groups, and more preferably a trivalent or tetravalent carboxylic acid compound containing three or four -C(=O)OH groups.

[0207] The carboxylate compound preferably contains three or less carboxyl groups (—C(═O)OH groups) and three or less ester bonds in the molecule, and more preferably contains two or less carboxyl groups and two or less ester bonds in the molecule.

[0208] In the case of the carboxylate compound, when X in three or more -C(=O)OX groups is an alkyl group having 1 to 6 carbon atoms, X is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or the like. From the perspective of further suppressing aggregation caused by the association of the compound (A) and the crosslinking agent (B), an ethyl group or a propyl group is preferred.

[0209] Specific examples of the carboxylic acid compounds include, but are not limited to, alicyclic carboxylic acids such as 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and 1,2,3,4,5,6-cyclohexanehexacarboxylic acid; 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, and 3,4'-biphenyldicarboxylic acid; acid), p-phenylenebis(trimellitic acid), benzene pentacarboxylic acid, mellitic acid and other phenylcarboxylic acids; 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid and other naphthalenecarboxylic acids; 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'-oxybis(phthalic acid) Acid, 3,4'-oxydiphthalic acid, 1,3-bis(phthalic acid)tetramethyldisiloxane, 4,4'-(ethynyl-1,2-diyl)diphthalic acid, 4,4'-(1,4-phenylenebis(oxy))diphthalic acid diphthalic acid, such as 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))diphthalic acid and 4,4'-((oxybis(4,1-phenylene))bis(oxy))diphthalic acid; perylene carboxylic acids such as perylene-3,4,9,10-tetracarboxylic acid; anthracene carboxylic acids such as anthracene-2,3,6,7-tetracarboxylic acid; and fluorinated aromatic ring carboxylic acids such as 4,4'-(hexafluoroisopropylidene)diphthalic acid, 9,9-bis(trifluoromethyl)-9H-xanthene-2,3,6,7-tetracarboxylic acid and 1,4-bis(trifluoromethyl)pyromellitic acid.

[0210] Specific examples of the carboxylic acid ester compounds include compounds in which at least one carboxyl group in the specific examples of the carboxylic acid compounds is substituted with an ester group. Examples of the carboxylic acid ester compounds include half-esterified compounds represented by the following general formulas (B-1) to (B-5).

[0211] [Chemistry 7]

[0212]

[0213] R in general formulae (B-1) to (B-5) is independently an alkyl group having 1 to 6 carbon atoms, preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably an ethyl group or a propyl group.

[0214] Y in the general formula (B-2) is a single bond, O, C=O or C(CF3)2.

[0215] The half-esterified compound can be produced by, for example, mixing carboxylic anhydride, which is an anhydride of the above-mentioned carboxylic acid compound, with an alcohol solvent and ring-opening the carboxylic anhydride.

[0216] In the present disclosure, the content of the component derived from the crosslinking agent (B) in the resin layer is not particularly limited. For example, the ratio of the number of carbonyl groups (-(C=O)-Y) in the substance derived from the crosslinking agent (B) to the number of all nitrogen atoms in the substance derived from the compound (A) ((-(C=O)-Y) / N) is preferably 0.1 to 3.0, more preferably 0.3 to 2.5, and further preferably 0.4 to 2.2. Here, in -(C=O)-Y, Y represents a nitrogen atom, OH or ester group crosslinked by imide or amide. By making (-(C=OY) / N 0.1 to 3.0, the resin layer appropriately has a crosslinked structure such as amide, amideimide, and imide, and the heat resistance is more excellent.

[0217] (Polar solvent (D))

[0218] The laminate preparation step may include applying a resin composition containing a resin material to at least one surface of the substrate. In this case, the resin composition containing the resin material preferably includes a polar solvent (D) along with the resin material such as the compound (A) and the crosslinking agent (B). Here, the polar solvent (D) refers to a solvent having a relative dielectric constant of 5 or greater at room temperature. Specific examples of the polar solvent (D) include protic inorganic compounds such as water and heavy water; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, isopentanol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, benzyl alcohol, diethylene glycol, triethylene glycol, and glycerol; ethers such as tetrahydrofuran and dimethoxyethane; aldehydes and ketones such as furfural, acetone, methyl ethyl ketone, and cyclohexane; acid derivatives such as acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, formaldehyde, N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and hexamethylphosphoramide; nitriles such as acetonitrile and propionitrile; nitro compounds such as nitromethane and nitrobenzene; and sulfur compounds such as dimethyl sulfoxide. As the polar solvent (D), a protic solvent is preferably contained, water is more preferably contained, and ultrapure water is further preferably contained.

[0219] The content of the polar solvent (D) in the resin composition is not particularly limited, and is, for example, 1.0% by mass to 99.99896% by mass, and preferably 40% by mass to 99.99896% by mass, based on the entire resin composition.

[0220] The boiling point of the polar solvent (D) is preferably 150° C. or lower, more preferably 120° C. or lower, from the viewpoint of volatilizing the polar solvent (D) by heating during resin layer formation and reducing the amount of residual solvent in the resin layer.

[0221] (Additive (C))

[0222] The resin composition containing the resin material may further contain an additive (C) in addition to the above-mentioned compound (A), a crosslinking agent (B) and other resin materials, a polar solvent (D), etc. Examples of the additive (C) include an acid (C-1) having a carboxyl group and a weight-average molecular weight of 46 to 195, and a base (C-2) having a nitrogen atom and a weight-average molecular weight of 17 to 120 without a ring structure. Although the additive (C) may volatilize due to heating during the formation of the resin layer, the resin layer in the substrate laminate of the present disclosure may also contain the additive (C).

[0223] Acid (C-1) is an acid having a weight-average molecular weight of 46 or more and 195 or less having a carboxyl group. It can be speculated that by including acid (C-1) as additive (C), the amino group in compound (A) and the carboxyl group in acid (C-1) form an ionic bond, thereby suppressing the aggregation caused by the association of compound (A) and cross-linking agent (B). In more detail, it can be speculated that the interaction (for example, electrostatic interaction) between the ammonium ion from the amino group in compound (A) and the carboxyl group from the carboxyl group in acid (C-1) is stronger than the interaction between the ammonium ion from the amino group in compound (A) and the carboxyl group from the cross-linking agent (B). Therefore, aggregation can be suppressed. It should be noted that the present disclosure is not limited by the above speculation.

[0224] The acid (C-1) is not particularly limited as long as it is a compound having a carboxyl group and a weight-average molecular weight of 46 to 195, and examples thereof include monocarboxylic acid compounds, dicarboxylic acid compounds, and oxydicarboxylic acid compounds. More specifically, examples of the acid (C-1) include formic acid, acetic acid, malonic acid, oxalic acid, citric acid, benzoic acid, lactic acid, glycolic acid, glyceric acid, butyric acid, methoxyacetic acid, ethoxyacetic acid, phthalic acid, terephthalic acid, picolinic acid, salicylic acid, and 3,4,5-trihydroxybenzoic acid.

[0225] In the present disclosure, the content of the acid (C-1) in the resin composition containing the resin material is not particularly limited. For example, the ratio of the number of carboxyl groups in the acid (C-1) to the total number of nitrogen atoms in the compound (A) (COOH / N) is preferably 0.01 to 10, more preferably 0.02 to 6, and even more preferably 0.5 to 3.

[0226] Base (C-2) is a base having a weight average molecular weight of 17 or more and 120 or less having nitrogen atoms. It can be speculated that the resin composition containing the resin material contains the base (C-2) as the additive (C), so that the carboxyl group in the cross-linking agent (B) and the amino group in the base (C-2) form an ionic bond, thereby suppressing the aggregation caused by the association of the compound (A) and the cross-linking agent (B). In more detail, it can be speculated that the interaction between the carboxyl group of the cross-linking agent (B) and the ammonium ion from the amino group in the base (C-2) is stronger than the interaction between the ammonium ion from the amino group in the compound (A) and the carboxyl group of the cross-linking agent (B). Therefore, aggregation can be suppressed. It should be noted that the present disclosure is not limited by the above speculation.

[0227] The base (C-2) is not particularly limited as long as it is a compound having a nitrogen atom and a weight-average molecular weight of 17 to 120, and does not have a ring structure. Examples thereof include monoamine compounds and diamine compounds. More specifically, the base (C-2) includes ammonia, ethylamine, ethanolamine, diethylamine, triethylamine, ethylenediamine, N-acetylethylenediamine, N-(2-aminoethyl)ethanolamine, and N-(2-aminoethyl)glycine.

[0228] In the present disclosure, the content of the base (C-2) in the resin composition containing the resin material is not particularly limited. For example, the ratio of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the cross-linking agent (B) (N / COOH) is preferably 0.5 to 5, more preferably 0.9 to 3.

[0229] When the resin layer of the substrate laminate of the present disclosure is required to have insulating properties, tetraethoxysilane, tetramethoxysilane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)methane, bis(methyldiethoxysilyl)ethane, 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahydroxycyclosiloxane, 1,1,4,4-tetramethyl-1,4-diethoxydisilazane, 1,3,5-trimethyl-1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane may be mixed to improve the insulating properties or mechanical strength. Furthermore, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, etc. may be mixed to improve the hydrophobicity of the insulating resin layer. These compounds may also be mixed to control the etching selectivity.

[0230] The resin composition containing the resin material may contain a solvent other than the polar solvent (D), and examples thereof include n-hexane.

[0231] Furthermore, in order to improve, for example, electrical characteristics, the resin composition containing the resin material may contain phthalic acid, benzoic acid, or the like, or derivatives thereof.

[0232] In addition, in order to suppress corrosion of copper, for example, the resin composition including the resin material may contain benzotriazole or a derivative thereof.

[0233] The pH of the resin composition containing the resin material is not particularly limited, but is preferably 2.0 or more and 12.0 or less.

[0234] When an acid (C-1) is used as the additive (C), it is preferred to mix a mixture of the acid (C-1) and the compound (A) with the crosslinking agent (B). Specifically, it is preferred to mix the compound (A) and the acid (C-1) before mixing them. This allows for the resin composition containing the resin material to be appropriately suppressed from becoming cloudy or gelling when the compound (A) and the crosslinking agent (B) are mixed (gelling may take time for the resin composition to become transparent, which is not preferred).

[0235] When a base (C-2) is used as the additive (C), it is preferred to mix a mixture of the base (C-2) and the crosslinking agent (B) with the compound (A). Specifically, it is preferred to mix the crosslinking agent (B) and the base (C-2) before mixing the compound (A) and the crosslinking agent (B). This can appropriately suppress cloudiness and gelation of the resin composition containing the resin material when the compound (A) and the crosslinking agent (B) are mixed (gelation may take time for the resin composition to become transparent, which is not preferred).

[0236] As a method for imparting a resin material to at least one surface of a substrate, for example, vapor deposition polymerization, CVD (chemical vapor deposition) method, ALD (atomic layer deposition) method and other vapor phase film forming methods, dipping method, spraying method, spin coating method, rod coating method and other coating methods can be cited. In the case of imparting a resin material by a coating method, it is preferred to impart a resin composition containing the above-mentioned resin material. For example, in the case of forming a film with a film thickness of micrometer size, it is preferred to use a rod coating method, and in the case of forming a film with a film thickness of nanometer size (several nm to hundreds of nm), it is preferred to use a spin coating method. It should be noted that the film thickness of the resin material can be appropriately adjusted according to the expected thickness of the resin layer.

[0237] For example, the method of applying the resin material by spin coating is not particularly limited. For example, the following method can be used: while rotating the substrate with a spin coater, a resin composition containing the resin material is dripped onto the surface of the first substrate, and then the rotation speed of the substrate is increased to dry it.

[0238] In the method of applying the resin material by spin coating, there are no particular restrictions on the conditions such as the rotation speed of the substrate, the amount and time of dripping the resin composition containing the resin material, and the rotation speed of the substrate during drying. They can be appropriately adjusted while considering the thickness of the formed resin material.

[0239] The substrate coated with the resin material may be cleaned to remove excess resin material. Examples of the cleaning method include wet cleaning using a rinse solution such as a polar solvent, and plasma cleaning.

[0240] In the method for manufacturing a substrate laminate of the present disclosure, the laminate preparation step may include a step of curing a resin material applied to one surface of the substrate to form a resin layer. For example, the resin layer may be formed by curing the resin material by heating or the like. In this case, if the resin material comprises a thermosetting compound, curing is achieved by heating the resin material at a temperature above its curing temperature.

[0241] The resin material applied to one surface of the substrate is preferably heated at 100° C. to 450° C. to be cured.

[0242] In addition, the said temperature refers to the temperature of the surface of the resin material applied to the said surface.

[0243] By heating the resin material, the solvent in the resin composition containing the resin material is removed. In addition, the components in the resin material react to obtain a cured product, and a resin layer containing the cured product is formed.

[0244] From the viewpoint of suppressing thermal damage to devices such as semiconductor memories, the temperature is preferably 150°C to 450°C, more preferably 180°C to 400°C, further preferably 180°C to 250°C, and particularly preferably 180°C to 200°C.

[0245] The pressure when heating the resin material applied to the surface is not particularly limited, but is preferably an absolute pressure greater than 17 Pa and equal to or less than atmospheric pressure.

[0246] The absolute pressure is more preferably 1000 Pa or more and below atmospheric pressure, further preferably 5000 Pa or more and below atmospheric pressure, and particularly preferably 10000 Pa or more and below atmospheric pressure.

[0247] The resin material applied to the surface can be heated by a conventional method using a furnace or a hot plate. Examples of furnaces that can be used include SPX-1120 manufactured by APPEX and VF-1000LP manufactured by Koyo Thermo Systems.

[0248] The heating of the resin material applied to the surface may be performed in air atmosphere or in an inert gas (nitrogen, argon, helium, etc.) atmosphere.

[0249] The heating time of the resin material applied to the surface is not particularly limited, and is, for example, 3 hours or less, preferably 1 hour or less. The lower limit of the heating time is not particularly limited, and can be, for example, 5 minutes.

[0250] In order to shorten the curing time of the resin material applied to the above-mentioned surface, the resin material applied to the above-mentioned surface can be subjected to ultraviolet (UV) irradiation. As ultraviolet rays, ultraviolet light with a wavelength of 170nm to 230nm, excimer light with a wavelength of 222nm, excimer light with a wavelength of 172nm, etc. are preferably used. In addition, ultraviolet irradiation is preferably carried out under an inert gas atmosphere.

[0251] Whether the resin material has been cured can be confirmed by measuring the peak intensity of specific bonds and structures using FT-IR (Fourier Transform Infrared Spectroscopy). Examples of specific bonds and structures include those generated by a crosslinking reaction.

[0252] For example, when an amide bond, imide bond, siloxane bond, tetralin structure, oxazole ring structure, etc. are formed, it can be determined that the resin material has been cured. This can be confirmed by measuring the peak intensity derived from these bonds and structures using FT-IR.

[0253] The amide bond can be detected by the -1 and about 1520cm -1The presence of the vibration peak is confirmed.

[0254] The imide bond can be detected by the -1 and about 1720cm -1 The presence of the vibration peak is confirmed.

[0255] Siloxane bonds can pass through 1000cm -1 ~1080cm -1 The presence of the vibration peak between them is confirmed.

[0256] The structure of tetralin can be seen at 1500 cm -1 The presence of the vibration peak between them is confirmed.

[0257] The oxazole ring structure can be detected by the -1 and about 1460cm -1 The presence of the vibration peak is confirmed.

[0258] The resin layer formed by curing the resin material preferably has a siloxane bond and at least one bond selected from the group consisting of an ester bond, an ether bond, an amide bond, and an imide bond, and more preferably has a siloxane bond and an imide bond.

[0259] The resin layer formed by curing the resin material preferably contains sodium and potassium at a content of 10 ppb by mass or less, respectively, on an elemental basis. When the sodium or potassium content is 10 ppb by mass or less, respectively, on an elemental basis, it is possible to suppress the occurrence of poor electrical properties of the semiconductor device, such as transistor malfunction.

[0260] The amount of silicon on the surface of each resin layer is independently preferably 20 atomic % or less, more preferably 15 atomic % or less, and further preferably 10 atomic % or less.

[0261] The amount of silicon on the surface of the resin layer can be evaluated by atomic ratio measurement using an X-ray photoelectron spectroscopy (XPS). Specifically, the atomic ratio can be measured using the AXIS-NOVA XPS (manufactured by Kratos) instrument, based on the peak intensity of the narrow spectrum when the total amount of each element detected in the broad spectrum is set to 100%.

[0262] The thickness of the resin layer is preferably 0.001 μm to 8.0 μm, more preferably 0.01 μm to 6.0 μm, and even more preferably 0.03 μm to 5.0 μm. By setting the thickness of the resin layer to 0.001 μm or greater, the bonding strength with the inorganic material layer and other layers can be improved. By setting the thickness of the resin layer to 8.0 μm or less, it is possible to suppress thickness variations in the resin layer when the resin layer is formed on a large substrate.

[0263] When an electrode is provided on a portion of the surface of the resin layer, from the viewpoint of improving the bonding strength with the inorganic material layer, other layers, etc. and suppressing the thickness deviation of the resin layer, the thickness of the resin layer is preferably 0.01 μm to 8.0 μm, more preferably 0.03 μm to 6.0 μm, and further preferably 0.05 μm to 5.0 μm.

[0264] When no electrode is provided on the surface of the resin layer, from the viewpoint of improving the bonding strength with the inorganic material layer, other layers, etc. and suppressing the thickness deviation of the resin layer, the thickness of the resin layer is preferably greater than 0.001 μm and less than 1.0 μm, more preferably 0.01 μm to 0.8 μm, and further preferably 0.03 μm to 0.6 μm.

[0265] From the viewpoint of the bonding strength of the first stack and the second stack in improving the substrate laminate, resin layer preferably has the functional group that can form chemical bond on the surface of resin layer, more preferably there is at least one functional group selected from the group consisting of silanol group (Si-OH group), amino, epoxy group(ing), hydroxyl and the functional group with unsaturated bond, from the aspect of thermotolerance, further preferably there is silanol group.These functional groups can be formed by surface treatment after resin layer is formed, also can be formed by silane coupling agent processing etc..Or, also can mix the compound comprising these functional groups in resin combination.

[0266] Examples of the functional group having an unsaturated bond include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, and a styryl group.

[0267] Whether the surface of the resin layer has Si-OH groups can be evaluated by analyzing the surface of the resin layer using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Specifically, the presence of a peak with a mass-to-charge ratio (m / z) of 45 can be used as a TOF-SIMS analyzer such as PH Inano TOFII (ULVAC-PHI Co., Ltd.).

[0268] After forming the resin layer, the resin layer may be planarized. Examples of planarization methods include fly cutting and chemical mechanical polishing (CMP). One planarization method may be used alone or in combination of two or more methods.

[0269] After forming the resin layer, the resin layer may be cleaned. Examples of cleaning methods include wet cleaning using a rinse solution and dry cleaning using plasma or the like. Examples of wet cleaning methods include ultrasonic cleaning using pure water and spin cleaning using a solvent such as NMP.

[0270] (electrode)

[0271] The first and second stacks may each include an electrode exposed from a portion of one or both surfaces. In the stacking step, the electrodes are preferably arranged so that the electrode provided on the first surface layer side of the first stack contacts the electrode provided on the second back layer side of the second stack.

[0272] A through hole may be provided that extends from the surface of the first surface layer side of the first stack to the surface of the first back layer side, and an electrode that extends through the first stack may be provided in the through hole. Similarly, a through hole may be provided that extends from the surface of the second surface layer side of the second stack to the surface of the second back layer side, and an electrode that extends through the second stack may be provided in the through hole.

[0273] The material of the electrode is not particularly limited, and examples thereof include conventionally known electrode materials, etc. Specific examples thereof include copper, solder, tin, gold, silver, aluminum, indium, cobalt, and tungsten.

[0274] The method of providing electrodes on the laminate is not particularly limited, and a conventionally known method can be employed.

[0275] For example, the electrodes may be formed on the surface on which the resin material is applied before forming the resin layer of the laminate, or the electrodes may be formed on the surface on which the resin layer is formed after forming the resin layer.

[0276] Alternatively, the electrode may be formed on the surface where the inorganic material layer is to be formed before forming the inorganic material layer of the laminate, or may be formed on the surface where the inorganic material layer is to be formed after forming the inorganic material layer.

[0277] The electrodes may be formed in a protruding shape on the surface of the substrate, may be formed in a state of penetrating the substrate, or may be formed in a state of being embedded in the substrate.

[0278] Furthermore, when a resin layer is formed on one surface of a substrate and an inorganic material layer is formed on the other surface, the order in which the resin layer and the inorganic material layer are formed is not particularly limited. For example, the resin layer may be formed on one surface of the substrate before the inorganic material layer is formed on the other surface of the substrate, or vice versa.

[0279] In the case where an electrode is formed before forming the resin layer or before forming the inorganic material layer, after forming the resin layer or the inorganic material layer, the resin layer or the inorganic material layer on the electrode is removed, thereby forming a structure in which a portion of the surface of the resin layer or the inorganic material layer has an electrode. As a method for removing the resin layer or the inorganic material layer on the electrode, fly cutting, chemical mechanical polishing (CMP), plasma dry etching, etc. can be cited. The removal method can use one method alone or two or more methods in combination. For example, in the fly cutting method, a surface planer (DFS8910 (manufactured by DISCO Co., Ltd.)) can be used. When using CMP, as a slurry, for example, a slurry containing silicon dioxide or aluminum oxide commonly used for resin polishing, a slurry containing hydrogen peroxide and silicon dioxide used for metal polishing, etc. can be used. When using plasma dry etching, fluorocarbon plasma, oxygen plasma, etc. can also be used.

[0280] When the resin layer or inorganic material layer on the electrode is removed to expose the electrode, a reduction treatment can be performed on the oxide on the electrode surface as needed. Examples of reduction treatment methods include heating the substrate at 100°C to 300°C in an acid atmosphere such as formic acid or heating the substrate in a hydrogen atmosphere. These treatments can also be performed simultaneously with the bonding step described below.

[0281] When the electrodes are formed after forming the resin layer or the inorganic material layer, for example, holes for forming the electrodes can be formed on the surface of the substrate on which the resin layer is formed or the surface of the substrate on which the inorganic material layer is formed by a known method, and the electrodes can be formed in the formed holes. Examples of methods for forming the holes include dry etching using a gas and laser ablation.

[0282] Examples of the method for forming the electrode include electroplating, chemical plating, sputtering, and inkjet methods.

[0283] If the resin material is photosensitive, holes for forming electrodes can be formed in the resin material applied to at least one surface of the substrate by photolithography. Alternatively, the electrodes can be formed in the holes after the resin material is cured to form a resin layer.

[0284] [Surface protection process]

[0285] The manufacturing method of the substrate laminate of the present disclosure includes a surface protection step ( Figure 3 (6)).

[0286] By providing the surface protection layer on the second surface layer before the dicing process, it is possible to prevent the second surface layer from being contaminated by the dicing tape and from being damaged when the chips of the second stack are peeled off from the dicing tape after the dicing process.

[0287] As the surface protection layer, as long as it can protect the second surface layer, the resin layer or inorganic material layer constituting the first stack and the second stack is not dissolved in the cleaning and removal process and the surface protection layer is selectively peeled off, then there is no particular limitation. For example, a water-soluble resin or a developer containing TMAH (tetramethylammonium hydroxide), a photoresist that can be cleaned with an organic solvent such as NMP (N-methyl-2-pyrrolidone), etc. can be cited. As the water-soluble resin, for example, Hogomax from Disco can be used.

[0288] The method for forming the surface protection layer 27 is not particularly limited. For example, a method of spin-coating a composition for forming the surface protection layer 27 on the second surface layer 22 and then curing the composition by drying, heating, or the like can be mentioned.

[0289] The thickness of the surface protection layer 27 is, for example, in the range of 0.1 μm to 1 mm.

[0290] Examples of the layers of the laminate, the surface protective layer, and the means for cleaning and removing the surface protective layer include the following combinations.

[0291] Inorganic material layer: SiO2

[0292] Resin layer: Resin layer containing imide bonds

[0293] Surface protective layer: Sumitomo Chemical Co., Ltd. positive photoresist Sumiresist PFI-58A7MS

[0294] Cleaning and removal method: TMAH

[0295] (Formation of Surface Protective Layer)

[0296] After spin coating a positive photoresist on the substrate surface, the entire surface is exposed to UV light to form a surface protection layer with a thickness of 1 μm.

[0297] (Cleaning and removal of surface protective layer)

[0298] A positive photoresist developer (Tokuyama Co., Ltd. SD-1) was dropped onto the surface protective layer on the substrate surface for 65 seconds, and then washed with pure water to remove the surface protective layer.

[0299] [Cutting process]

[0300] The method for manufacturing a substrate laminate of the present disclosure includes the following dicing process: a dicing tape 42 is attached to the surface protection layer side of the second laminate 20 provided with the surface protection layer 27, and the dicing process is performed to separate the second laminate 20A and the surface protection layer 27A into chips 28A with surface protection layers ( Figure 4 (7), (8)).

[0301] After the surface protection layer 27 is provided on the first surface layer 22, the second laminate 20 is peeled off from the temporary support 31. Figure 4 As shown in (7), the surface protection layer side is attached to the cutting tape 42 and cleaned as needed. Figure 4 As shown in (8), the second laminate 20 is cut from the back surface layer 23 side to separate the second laminate 20 including the surface protection layer 27 into chips 28A (chip formation).

[0302] As the dicing tape 42 , for example, a resin film having an adhesive layer provided on one surface thereof whose adhesive strength is reduced by irradiation with ultraviolet rays (UV) can be used.

[0303] By cutting, the second back surface resin layer 23 , silicon substrate 21 , second surface inorganic material layer 22 , and surface protection layer 27 are respectively divided into a second back surface resin layer 23A, silicon substrate 21A, second surface inorganic material layer 22A, and surface protection layer 27A.

[0304] For the cutting process, for example, a dicing machine (DAD6340 (manufactured by DISCO Corporation)) can be used. Alternatively, the cutting process can be performed by stealth cutting or plasma cutting.

[0305] The method for producing a substrate laminate of the present disclosure may include a step of washing the cut second laminate after the cutting step and before the lamination step in order to remove particles.

[0306] Alternatively, the first surface layer in the first laminate may be cleaned, and in particular, the first surface layer may be cleaned before the first surface layer is brought into contact with other layers (eg, resin layer) in the lamination step.

[0307] The cleaning method is not particularly limited, and examples include wet cleaning using solvents such as alkaline cleaning solutions, acidic cleaning solutions, cleaning solutions containing hydrofluoric acid, and solutions containing permanganate (desmear solutions), wet cleaning using pure water, etc., and dry cleaning using UV ozone, plasma, etc.

[0308] [Lamination process]

[0309] The method for manufacturing a substrate laminate of the present disclosure includes the following lamination step: peeling the chip 28A with a surface protective layer including the chipped second laminate and the surface protective layer from the dicing tape 42, laminating the chip 28A with a surface protective layer on the first laminate 10 in such a manner that the first surface layer 12 and the second back surface layer 23A are in contact with each other ( Figure 5 (10), (11)).

[0310] The lamination process is a process for bringing the first surface layer and the second back layer into contact before joining the first and second stacks via the first surface layer and the second back layer (e.g., the first surface inorganic material layer and the second back resin layer) in the joining process described later. For example, after the adhesion of the dicing tape 42 is reduced by ultraviolet irradiation, the chip 28A with the surface protective layer is lifted from the back side by a needle 51 to peel it from the dicing tape 42. The chip 28A with the surface protective layer is stacked on the first stack 10 in a manner that forms the desired positional relationship when the first stack 10 and the second stack chip 28A are joined.

[0311] For example, when the first and second stacks are provided with the above-mentioned electrodes, the chip 28A with the surface protection layer is stacked on the first stack 10 so that the electrode 14 provided on the first surface layer side contacts the electrode 25 provided on the second back surface layer side.

[0312] When the inorganic material layer and the resin layer are brought into contact during the lamination process, the curing rate of the resin layer before contact is preferably 70% or more and 100% or less. This tends to ensure that the first stack and the second stack chips are firmly bonded in the temporary fixing process and the bonding process described later, and that positional misalignment (alignment misalignment) of the bond is less likely to occur.

[0313] The curing rate of the resin layer is more preferably 80% or more, further preferably 85% or more, particularly preferably 90% or more, and further preferably 93% or more. In addition, the curing rate of the resin layer may be 100%, 99% or less, 95% or less, or 90% or less.

[0314] The curing rate of the resin layer may be the curing rate before the resin layer comes into contact with other layers (eg, other inorganic material layers).

[0315] The curing rate of a resin layer containing at least one selected from the group consisting of an amide bond, an imide bond, a siloxane bond, a tetralin structure, an oxazole ring structure, an ester bond, and an ether bond is more preferably 80% or higher, further preferably 85% or higher, particularly preferably 90% or higher, and even more preferably 93% or higher. The curing rate of a resin layer containing at least one selected from the group consisting of a siloxane bond and an ester bond, an ether bond, an amide bond, and an imide bond is more preferably 80% or higher, further preferably 85% or higher, particularly preferably 90% or higher, and even more preferably 93% or higher.

[0316] The cure rate of a resin layer formed by curing a resin material can be confirmed by, for example, measuring the peak intensity of specific bonds and structures (the sum of the peak intensities in the case of multiple peaks, such as those of imides and amides) using FT-IR (Fourier transform infrared spectroscopy) in the resin material before being applied to the substrate, in the resin layer before contacting the resin layer with the inorganic material layer in the lamination process, and in the resin layer after the bonding process, and calculating the rate of increase or decrease in the peak intensity. It should be noted that in the case of band-like peaks that are difficult to separate, such as siloxane bonds, the maximum peak intensity can be used.

[0317] Specifically, when a specific bond and structure are generated by the curing reaction, the increase rate of the peak intensity can be calculated by the following formula, and the calculated value can be used as the curing rate of the resin layer.

[0318] Peak intensity increase rate (curing rate of resin layer) = [(peak intensity of specific bonds and structures of the resin layer before the resin layer and the inorganic material layer are brought into contact in the lamination process) / (peak intensity of specific bonds and structures of the resin layer after heating at 300°C for 1 hour in the bonding process)] × 100

[0319] It should be noted that background signal removal can be performed by a conventional method. In addition, FT-IR measurement can be performed by a transmission method or a reflection method as needed.

[0320] Regarding the increase rate of the peak intensity, when there are a plurality of bonds or structures causing an increase in peak intensity, the peak intensity may be replaced with the total intensity of the plurality of peak intensities.

[0321] Before the resin layer and the inorganic material layer are brought into contact in the lamination process, the complex elastic modulus of the resin layer at 23°C is preferably from 0.1 GPa to 20 GPa, and more preferably from 0.1 GPa to 10 GPa. Thus, voids formed when the resin layer and the inorganic material layer are brought into contact in the lamination process tend to be absorbed by the resin layer during the bonding process, thereby suppressing the generation of voids.

[0322] From the perspective of appropriately suppressing the generation of voids, the composite elastic modulus of the resin layer at 23°C is preferably 8 GPa or less, more preferably 6 GPa or less. Furthermore, from the perspective of appropriately suppressing misalignment, the composite elastic modulus of the resin layer at 23°C is preferably 0.1 GPa or more, more preferably 1 GPa or more.

[0323] The preferred range of the complex elastic modulus of the resin layer at 23° C. is the same as the preferred range of the complex elastic modulus of the resin layer at 23° C. The complex elastic modulus of the resin layer at 23° C. may be the complex elastic modulus of the resin layer at 23° C. before contact with other layers (e.g., other inorganic material layers).

[0324] The complex elastic modulus of the resin layer at 23° C. can be measured by the method described below.

[0325] A resin composition containing a resin material was prepared, spin-coated on a silicon substrate, and then heated at 400°C for 10 minutes to prepare a measurement sample. For the prepared measurement sample, a nanoindenter (trade name TI-950 Tribo Indenter, manufactured by Hysitron, Berkovich-type indenter) was used to measure the unloading-displacement curve at 23°C at a test depth of 20 nm. The complex elastic modulus at 23°C was calculated from the maximum load and maximum displacement according to the calculation method of the reference document (Handbook of Micro / nano Tribology (2nd Edition), edited by Bharat Bhushan, CRC Press).

[0326] It should be noted that the complex elastic modulus is defined by the following formula (1). In formula (1), E r Represents the composite elastic modulus, E i The Young's modulus of the indenter is 1140 GPa, ν i The Poisson's ratio of the pressure head is 0.07, E s and ν s represent the Young's modulus and Poisson's ratio of the sample, respectively.

[0327] [Number 1]

[0328]

[0329] Before the first surface layer is brought into contact with the second back layer in the lamination process, the surface roughness (Ra) of the first surface layer is preferably 0.01 nm or more and 1.2 nm or less, more preferably 0.1 nm or more and 1.0 nm or less. Thus, it is easy to temporarily fix the first surface layer and the second back layer described later at low temperatures.

[0330] The preferred range of the surface roughness (Ra) of the second back surface layer is the same as the preferred range of the surface roughness (Ra) of the first surface layer.

[0331] The surface roughness (Ra) of each layer may be the surface roughness (Ra) before contacting each other.

[0332] The surface roughness of each layer can be evaluated by morphological observation using a scanning probe microscope (SPM). Specifically, the surface roughness is determined by measuring a 3 μm x 3 μm square area using a SPA400 SPM (manufactured by Hitachi High-Technologies Corporation) in dynamic force microscopy mode.

[0333] The method for producing a substrate laminate of the present disclosure may include the following various steps before the above-mentioned lamination step. The following various steps are preferably performed after the laminate preparation step and before the lamination step.

[0334] The manufacturing method of the substrate laminate disclosed herein may include a step of performing a surface activation treatment on the second back layer before the lamination step. By performing the surface activation treatment, the bonding strength between the first surface layer and the second back layer can be improved. In particular, when electrodes are provided at the bonding surfaces of the first laminate and the second laminate and the electrodes are bonded to each other, it is preferred to perform the surface activation treatment from the perspective of promoting the diffusion of metals such as copper contained in the electrodes and improving the bonding strength between the electrodes, and from the perspective of reducing the heating temperature during metal diffusion.

[0335] Furthermore, the first surface layer of the first substrate may be subjected to a surface activation treatment, particularly before the first surface layer comes into contact with other layers (eg, other resin layers).

[0336] Specific examples of the surface activation treatment include plasma treatment and FAB (Fast Atom Bombardment) treatment.

[0337] [Temporary fixing process]

[0338] The method for manufacturing the substrate laminate of the present disclosure may include: temporarily fixing the laminated first laminate 10 and the chip 28A with the surface protection layer at a first temperature ( Figure 5 (11)). It should be noted that the resin layer 23A can be temporarily fixed to the inorganic material layer 12 even at room temperature, so the temporary fixing process is part of the lamination process and can also be considered to be included in the lamination process.

[0339] The first stack and the chip with the surface protection layer are temporarily fixed at a first temperature, for example, a low temperature of room temperature (eg, 23°C) or higher and less than 100°C. Preferably, it is performed at a low temperature of room temperature or higher and 50°C or lower, more preferably at room temperature.

[0340] When the first substrate and the second substrate are silicon substrates, the surface energy of the bonding interface between the first and second stacked bodies in the state of being temporarily fixed is preferably 0.05 J / m2 from the perspectives of ease of handling during the bonding process, suppression of misalignment (bonding position deviation), and suppression of foreign matter intrusion. 2 More than 0.1 J / m 2 More than, more preferably 0.15 J / m 2 above.

[0341] The surface energy (bonding strength) of the above-mentioned bonding interface can be obtained by a blade insertion test according to the method of the non-patent document "MP Maszara, G. Goetz, A. Cavigila and JB Mckitterick, Journal of Applied Physics, 64 (1988) 4943-4950." A blade with a thickness of 0.1mm to 0.3mm is inserted into the bonding interface of the temporarily fixed laminate. Using an infrared light source and an infrared camera, the distance the laminate is peeled from the blade tip is measured. Then, the surface energy can be obtained based on the following formula.

[0342] γ=3×10 9 ×t b 2 ×E 2 ×t 6 / (32×L 4 ×E×t 3 )

[0343] Where γ represents the surface energy (J / m 2 ), t b represents the thickness of the blade (m), E represents the Young's modulus of the silicon substrate contained in the first substrate and the second substrate (GPa), t represents the thickness of the first substrate and the second substrate (m), and L represents the distance (m) that the laminate is peeled off from the blade tip.

[0344] [Cleaning and Removal Process]

[0345] In the method for manufacturing a substrate laminate of the present disclosure, after the lamination step, or when a temporary fixing step is performed after the lamination step (including when the temporary fixing step is performed as part of the lamination step), a cleaning and removing step ( Figure 6 (12)).

[0346] As a cleaning and removal method for removing the surface protective layer, the following cleaning and removal means is used: the surface protective layer can be removed without causing positional displacement between the first stacked body 10 and the chip 28A with the surface protective layer after stacking, and the stacking (temporary fixation) of the first stacked body and the second stacked body chip can be maintained, for example, without dissolving the second back resin layer.

[0347] Such a cleaning and removing means may be selected according to the materials of the surface protection layer, the first surface layer, the second back surface layer, etc. Specific examples include a developer containing TMAH, an organic solvent such as NMP (N-methyl-2-pyrrolidone), and the like.

[0348] [Joining process]

[0349] The method for manufacturing a substrate stack disclosed herein includes a step of heating a first stack 10 and a second stack chip 20A from which a surface protective layer 27A has been removed to obtain a substrate stack 100 in which the second stack chip 20A is bonded to the first stack 10. In the bonding step, heating is performed at a second temperature, for example, 100°C or higher, which is higher than the first temperature in the temporary fixing step. The bonding step yields a substrate stack 100 in which the first stack and the second stack chip are bonded via a first surface layer and a second back surface layer.

[0350] The pressure when the first stack and the second stack are bonded together is not particularly limited, but the absolute pressure is preferably greater than 10 -4 Pa and below atmospheric pressure.

[0351] The above absolute pressure is more preferably 10 -3 It is preferably 100 Pa or more and atmospheric pressure or less, more preferably 100 Pa or more and atmospheric pressure or less, and particularly preferably 1000 Pa or more and atmospheric pressure or less.

[0352] The chip bonding of the first stack and the second stack may be performed in air atmosphere or in an inert gas (nitrogen, argon, helium, etc.) atmosphere.

[0353] In the bonding step, the temporarily fixed first laminate and second laminate chip are preferably heated at 100° C. to 450° C. in a state where the first surface inorganic material layer and the second back surface resin layer are in contact with each other.

[0354] It should be noted that the above-mentioned heating temperature refers to the temperature of the surface of the second surface layer.

[0355] The heating temperature is preferably 100°C to 400°C, more preferably 130°C to 350°C, further preferably 150°C to 300°C, further preferably 150 to 250°C, particularly preferably 150 to 200°C.

[0356] When the electrodes are arranged so that the first surface electrode provided on the first surface layer side contacts the second back electrode provided on the second back layer side during the lamination process, the temperature is preferably 130° C. or higher, more preferably 150° C. or higher, and even more preferably 200° C. or higher. As a result, components (e.g., copper) contained in the first surface electrode provided on the first surface layer side and the second back electrode provided on the second back layer side diffuse, and there is a tendency for the bonding strength between the electrodes to increase.

[0357] Heating in the bonding step can be performed by a common method using a furnace or a hot plate.

[0358] In addition, heating in the bonding step may be performed in air atmosphere or in an inert gas (nitrogen, argon, helium, etc.) atmosphere.

[0359] The heating time in the bonding step is not particularly limited, and is, for example, 3 hours or less, preferably 1 hour or less. The lower limit of the heating time is not particularly limited, and can be, for example, 5 minutes.

[0360] In the bonding step, the first and second stacked chips may be pressed with the first surface layer and the second back surface layer in contact with each other to improve the bonding strength between the first and second stacked chips. Pressing may be performed simultaneously with heating.

[0361] The pressure for pressing the temporarily fixed first and second stacked chips is not particularly limited, but is preferably 0.1 MPa to 10 MPa, more preferably 0.1 MPa to 5 MPa. For example, a pressurizing device such as TEST MINIPRESS manufactured by Toyo Seiki Co., Ltd. can be used.

[0362] The method for manufacturing a substrate stack disclosed herein may also include, after the bonding step, the step of providing through-holes in the thickness direction of the first and second stacks, and forming electrodes in the through-holes that penetrate the first and second stacks. If the substrate stack obtained in the bonding step does not have electrodes formed therein, it is preferred to perform the step of forming such electrodes to form electrodes in the through-holes that penetrate the first and second stacks.

[0363] For example, a through hole penetrating the first and second stacks may be formed by a known method, and an electrode may be formed in the formed hole. Examples of hole formation methods include dry etching using a gas and laser ablation.

[0364] Examples of a method for forming the electrode that penetrates the first stack and the second stack include electroplating, chemical plating, sputtering, and an inkjet method.

[0365] The material of the electrode penetrating the first stack and the second stack is not particularly limited, and examples thereof include conventionally known electrode materials, etc. Specific examples include copper, solder, tin, gold, silver, aluminum, indium, cobalt, and tungsten.

[0366] In the manufacturing method of the substrate stack disclosed in the present invention, the second stack chip after the temporary fixing process and before the bonding process can be regarded as the first stack in the stack preparation process, and the stack preparation process to the temporary fixing process are repeated more than once before the bonding process, thereby the chip of the second stack is stacked in more than two layers and becomes temporarily fixed, and the bonding process is performed after the last temporary fixing process.

[0367] For example, after the stacking process to the temporary fixing process are repeated three times, the joining process is performed, so that Figure 7 As shown, a substrate stack 200 can be manufactured in which three layers of second stack chips 20A, 20B, and 20C are stacked on a first stack 10. This method allows the manufacture of a substrate stack 200 in which multiple layers of second stack chips 20A, 20B, and 20C are bonded together in a single bonding step. This prevents damage to the individual stacks caused by heating, and reduces manufacturing costs associated with the bonding step.

[0368] It should be noted that the second laminated chips 20A, 20B, and 20C bonded to each other in layers may have the same configuration or different configurations. The number of layers of the stacked second laminated chips is not particularly limited and may be set as needed.

[0369] In the method for producing a substrate stack of the present disclosure, the surface of the substrate stack may be subjected to thinning processing (back grinding or back grinding) as needed after the bonding step.

[0370] (Example of the laminated structure of substrate laminate)

[0371] Examples of the laminate structure of substrate laminates in various applications are shown below. Note that the bonding layer refers to a layer in a bonded state consisting of an inorganic material layer and a resin layer.

[0372] MEMS packaging applications: Si / bonding layer / Si, SiO2 / bonding layer / Si, SiO2 / bonding layer / SiO2, Cu / bonding layer / Cu,

[0373] Microfluidic applications: PDMS / bonding layer / PDMS, PDMS / bonding layer / SiO2,

[0374] CMOS image sensor applications: SiO2 / bonding layer / SiO2, Si / bonding layer / Si, SiO2 / bonding layer / Si,

[0375] Through Silicon Via (TSV) Application: SiO2 (with Cu electrode) / bonding layer / SiO2 (with Cu electrode), Si (with Cu electrode) / bonding layer / Si (with Cu electrode),

[0376] Optical device applications: (InGaAlAs, InGaAs, InP, GaAs) / bonding layer / Si,

[0377] LED applications: (InGaAlAs, GaAs, GaN) / junction layer / Si, (InGaAlAs, GaAs, GaN) / junction layer / SiO2, (InGaAlAs, GaAs, GaN) / junction layer / (Au, Ag, Al), (InGaAlAs, GaAs, GaN) / junction layer / sapphire.

[0378] The disclosure of Japanese Patent Application No. 2023-024730 filed on February 20, 2023 is incorporated herein by reference in its entirety.

[0379] All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference.

[0380] Description of Reference Numerals

[0381] 10 First stack

[0382] 11 first substrate

[0383] 12 First surface layer

[0384] 13 First back layer

[0385] 20 Second stack

[0386] 21 Second substrate

[0387] 22 Second surface layer

[0388] 23 Second back layer

[0389] 42 cutting belt

[0390] 100 substrate laminate

[0391] 200 substrate laminate.

Claims

1. A method for manufacturing a substrate laminate, comprising: a laminate preparation step of preparing a first laminate having a first surface layer, a first substrate, and a first back layer laminated in sequence, and a second laminate having a second surface layer, a second substrate, and a second back layer laminated in sequence; a surface protection step of providing a surface protection layer on the second surface layer of the second laminate; a dicing step of attaching a dicing tape to the surface protection layer side of the second laminate provided with the surface protection layer and dicing the laminate into individual chips with the surface protection layer, each including the divided second laminate and the surface protection layer; a lamination step of peeling the chip with the surface protection layer from the dicing tape and laminating the chip with the surface protection layer on the first laminate in such a manner that the first surface layer is in contact with the second back surface layer; a cleaning and removing step of cleaning the stacked first stack and the chip with the surface protection layer and removing the surface protection layer; as well as In the bonding step, the first stack and the chips of the second stack from which the surface protection layer has been removed are heated to obtain a substrate stack in which the chips of the second stack are bonded to the first stack.

2. The method for manufacturing a substrate laminate according to claim 1, The first stack includes a first electrode exposed from the first surface layer and the first back surface layer. The second laminate includes a second electrode exposed from the second surface layer and the second back surface layer. In the lamination step, the chip with the surface protection layer is laminated on the first laminate so that the first electrode exposed from the first surface layer is in contact with the second electrode exposed from the second back surface layer.

3. The method for producing a substrate laminate according to claim 1 or 2, The first surface layer is an inorganic material layer formed of an inorganic material, The second back surface layer is a resin layer formed of resin, The lamination step includes temporarily fixing the laminated first stack and the chip with the surface protection layer at a first temperature. The bonding step is a step of heating the temporarily fixed chips of the first stack and the second stack at a second temperature higher than the first temperature.

4. The manufacturing method of the substrate stack according to claim 3, wherein the chip of the second stack after the temporary fixing process and before the bonding process is regarded as the first stack in the stack preparation process, and before the bonding process, the stack preparation process to the temporary fixing process are repeated more than once, thereby the chip of the second stack is stacked in more than two layers and becomes temporarily fixed, and the bonding process is performed after the last temporary fixing process. 5 . The method for producing a substrate laminate according to claim 3 , wherein the surface of the resin layer has at least one functional group selected from the group consisting of a silanol group, an amino group, an epoxy group, a hydroxyl group, and a functional group having an unsaturated bond. 6 . The method for producing a substrate laminate according to claim 3 , wherein the resin layer comprises a siloxane bond and at least one selected from the group consisting of an ester bond, an ether bond, an amide bond, and an imide bond.

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