Substrate laminate

Abstract

This substrate laminate includes a first substrate, a bonding layer containing a resin, and a second substrate arranged in this order, wherein the first substrate and the second substrate are both thicker than the bonding layer, and when composition analysis is performed on a cross section of the substrate laminate by means of an energy dispersive X-ray spectroscopy, an Si ratio, which is a value obtained by dividing the maximum value of an abundance ratio of Si atoms in the bonding layer by the minimum value of the abundance ratio of Si atoms in the bonding layer, is 1.5 or more.

Description

Substrate stack

[0001] The present disclosure relates to substrate stacks.

[0002] In recent years, substrate stacks formed by bonding substrates together have been studied. For example, Patent Document 1 discloses a method for manufacturing a semiconductor device in which a first semiconductor wafer and a second semiconductor wafer are stacked as a substrate stack.

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 2012-174937

[0004] In a substrate laminate formed by bonding substrates together, there is a need to further improve the bonding strength between the substrates. Here, the concept of "substrates bonded together" means that the substrates are bonded together directly or via another layer.

[0005] The present disclosure has been made in view of the above-mentioned problems. An object of one aspect of the present disclosure is to provide a substrate stack having excellent bonding strength between substrates.

[0006] Specific means for solving the above problems include the following: <1> A substrate laminate comprising, in this order: a first substrate, a resin layer containing a resin, and a second substrate, wherein the first substrate and the second substrate are both thicker than the resin layer, and the resin contains Si atoms, and when a composition analysis is performed on a cross section of the substrate laminate by energy dispersive X-ray spectroscopy, a Si ratio, which is a value obtained by dividing the maximum abundance ratio of Si atoms in the resin layer by the minimum abundance ratio of Si atoms in the resin layer, is 1.5 or more. <2> The substrate laminate according to <1>, wherein the resin further contains O atoms, and when a composition analysis is performed on a cross section of the substrate laminate by energy dispersive X-ray spectroscopy, a O ratio, which is a value obtained by dividing the maximum abundance ratio of O atoms in the resin layer by the minimum abundance ratio of O atoms in the resin layer, is 1.3 or more. <3> A substrate laminate comprising, in this order: a first substrate, a resin layer containing a resin, and a second substrate, wherein the first substrate and the second substrate are both thicker than the resin layer, the resin contains O atoms, and when a composition analysis is performed on a cross section of the substrate laminate by energy dispersive X-ray spectroscopy, an O ratio, which is the maximum abundance ratio of O atoms in the resin layer divided by the minimum abundance ratio of O atoms in the resin layer, is 1.3 or more. <4> The substrate laminate according to any one of <1> to <3>, wherein, when a composition analysis is performed on a cross section of the substrate laminate by energy dispersive X-ray spectroscopy, the abundance ratio of O atoms in the resin layer changes continuously in the thickness direction of the resin layer. <5> The substrate laminate according to any one of <1> to <4>, wherein, when a composition analysis is performed on a cross section of the substrate laminate by energy dispersive X-ray spectroscopy, the abundance ratio of Si atoms in the resin layer changes continuously in the thickness direction of the resin layer. <6> The substrate laminate according to any one of <1> to <5>, wherein the resin layer has a composite elastic modulus of 1 GPa to 20 GPa. <7> The substrate laminate according to any one of <1> to <6>, further comprising an electrode penetrating the resin layer between the first substrate and the second substrate.<8> The substrate laminate according to any one of <1> to <7>, wherein each of the first substrate and the second substrate includes an inorganic substrate body and an inorganic layer.

[0007] According to one aspect of the present disclosure, a substrate stack having excellent bonding strength between substrates is provided.

[0008] 1 is a schematic cross-sectional view conceptually illustrating an example of a substrate laminate according to the present disclosure.

[0009] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the upper and lower limits. In numerical ranges described in stages in the present disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in numerical ranges described in the present disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in an example.

[0010] The substrate laminates (the substrate laminate of the first embodiment and the substrate assembly of the second embodiment) of the present disclosure will be described below.

[0011] A substrate laminate according to a first embodiment of the present disclosure is a substrate laminate including, in this order: a first substrate; a resin layer containing a resin; and a second substrate; wherein the first substrate and the second substrate are both thicker than the resin layer; the resin contains Si atoms; and when a composition analysis is performed on a cross section of the substrate laminate by energy dispersive X-ray spectroscopy, a Si ratio, which is the maximum abundance ratio of Si atoms in the resin layer (hereinafter also referred to as "Si ratio") divided by the minimum abundance ratio of Si atoms in the resin layer (i.e., Si ratio) (i.e., maximum Si ratio / minimum Si ratio), is 1.5 or more.

[0012] The substrate laminate of the first embodiment has an Si ratio of 1.5 or more, and therefore has excellent bonding strength between the substrates (more specifically, bonding strength between the first substrate and the second substrate bonded via a resin layer).

[0013] The substrate stack of the first embodiment has excellent bonding strength between the substrates (hereinafter simply referred to as "bonding strength at low temperatures") even when the substrates are bonded at low temperatures (for example, 140°C or below) during the manufacturing process.

[0014] A substrate laminate according to a second embodiment of the present disclosure is a substrate laminate including, in this order: a first substrate; a resin layer containing a resin; and a second substrate; wherein the first substrate and the second substrate are both thicker than the resin layer; the resin contains O atoms; and when a composition analysis is performed on a cross section of the substrate laminate by energy dispersive X-ray spectroscopy, an O ratio, which is the maximum abundance ratio of O atoms in the resin layer (hereinafter also referred to as "O ratio") divided by the minimum abundance ratio of O atoms in the resin layer (i.e., O ratio) (i.e., maximum O ratio / minimum O ratio), is 1.3 or more.

[0015] The substrate laminate of the second embodiment has an O ratio of 1.3 or more, and therefore has excellent bonding strength between the substrates (more specifically, bonding strength between the first substrate and the second substrate bonded via the resin layer).

[0016] The substrate stack of the second embodiment has excellent bonding strength between the substrates (hereinafter simply referred to as "bonding strength at low temperatures") even when the substrates are bonded at low temperatures (for example, 140°C or below) during the manufacturing process.

[0017] The first embodiment and the second embodiment may have overlapping portions. That is, the substrate laminate of the first embodiment may have the features of the substrate laminate of the second embodiment (i.e., the features related to the O atoms), and the substrate laminate of the second embodiment may have the features of the substrate laminate of the first embodiment (i.e., the features related to the Si atoms). The following description will focus on the substrate laminate of the first embodiment.

[0018] [Substrate Laminate (First Embodiment)] The substrate laminate of the first embodiment includes a first substrate, a resin layer having a thickness of 20 μm or less and containing a resin, and a second substrate, arranged in this order. The substrate laminate of the first embodiment may include layers other than the first substrate, the second substrate, and the resin layer, as necessary.

[0019] <First Substrate> The substrate laminate of the first embodiment includes a first substrate. The first substrate is a substrate having a thickness greater than that of the resin layer. The material of the first substrate is not particularly limited, and may be any material that is commonly used.

[0020] The first 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, and is preferably a semiconductor substrate containing at least one element selected from the group consisting of Si, Ga, Ge, and As.

[0021] Specific examples of the material of the first substrate include: semiconductors such as Si, InP, InAs, GaN, GaP, GaAs, InGaAs, InGaAlAs, SiGe, and SiC; boron silicate glass (Pyrex (registered trademark)), quartz glass (SiO ２ ), sapphire (Al ２ O ３ ), ZrO ２ , Si ３ N ４ , AlN, MgAl ２ O ４ Oxides, carbides, or nitrides such as BaTiO ３ , LiNbO ３ , SrTiO ３ , LiTaO ３ , gadolinium gallium garnet (Gd ３ Ga ５ O １２ Diamond; metals such as Al, Ti, Fe, Cu, Ag, Au, Pt, Pd, Ta, and Nb; carbon; resins such as polydimethylsiloxane (PDMS), epoxy resin, phenolic resin, polyimide, benzocyclobutene resin, and polybenzoxazole; and the like.

[0022] The main applications of the first substrate including each material are as follows: Si is used in semiconductor memories, LSIs, CMOS image sensors, MEMS, optical devices, LEDs, etc. SiO ２is used in MEMS sealing, microchannels, 2.5D mounting interposers, displays, etc. ３ , LiNbO ３ , SrTiO ３ , LiTaO ３ , Gd ３ Ga ５ O １２ is used in surface acoustic wave devices, etc. PDMS is used in microchannels, etc. InGaAlAs, InGaAs, and InP are used in optical devices, etc. InGaAlAs, GaAs, and GaN are used in LEDs, etc.

[0023] For the material of the first substrate, for example, reference may be made to publicly known documents such as those described in paragraphs 0097 to 0098 of International Publication No. 2022 / 54839; and information such as https: / / www.jstage.jst.go.jp / article / ejisso / 22a / 0 / 22a_0_233 / _pdf and http: / / www.musashino-eng.co.jp / setsugou / img / sabsample.pdf.

[0024] The thickness of the first substrate is not particularly limited as long as it is thicker than the thickness of the resin layer, and is, for example, 50 μm or more, preferably 50 μm to 10 mm, preferably 100 μm to 5 mm, and more preferably 200 μm to 1 mm.

[0025] The first substrate may include an inorganic substrate body and an inorganic layer. Examples of the material of the inorganic substrate body include the materials of the first substrate exemplified above (excluding resin) (i.e., semiconductors, "oxides, carbides, or nitrides," "piezoelectrics or dielectrics," metals, and carbon), preferably semiconductors, and particularly preferably Si. The inorganic layer is preferably made of SiO ２ layer, SiCN layer, or SiN layer, and particularly preferably SiO ２ It is a layer.

[0026] The inorganic layer can be formed by a vapor deposition method such as sputtering, CVD, or ALD. The inorganic layer can also be formed by a native oxide film (specifically, SiO ２It can also be formed as a layer.

[0027] The thickness of the inorganic substrate body is, for example, 50 μm or more, preferably 50 μm to 10 mm, preferably 100 μm to 5 mm, more preferably 150 μm to 2 mm. The thickness of the inorganic layer is, for example, 1 nm to 10 μm, preferably 3 nm to 5 μm, more preferably 5 nm to 1 μm.

[0028] <Second Substrate> The substrate laminate of the first embodiment includes a second substrate. The second substrate is a substrate having a thickness greater than that of the resin layer. The material of the second substrate is not particularly limited, and may be any commonly used material. Specific examples and preferred aspects of the second substrate are the same as those of the first substrate. However, the first substrate and the second substrate may be the same or different in at least one of the material, shape, size, and physical properties. For example, the coefficient of thermal expansion (CTE) of the first substrate and the coefficient of thermal expansion (CTE) of the second substrate may be the same or different.

[0029] Generally, when a first substrate and a second substrate having different CTEs are stacked, warping or stress generated during heating for stacking may cause damage to the first substrate and / or the second substrate. In this regard, the substrate stack of the present disclosure has excellent bonding strength at low temperatures, and therefore can suppress damage to the first substrate and / or the second substrate by bonding at low temperatures.

[0030] The substrate laminate of the present disclosure has excellent bonding strength at low temperatures, and therefore, the first substrate and / or the second substrate may be made of polyimide, GaAs, glass, LiNbO ３ Thermally weak substrates such as InGaAs, InGaAlAs, etc. can be used.

[0031] Furthermore, the substrate laminate of the present disclosure has excellent bonding strength at low temperatures, and is therefore applicable to optical devices, thermally sensitive devices (for example, phase change memory), and the like.

[0032] <Resin Layer> The substrate laminate of the first embodiment includes a resin layer containing a resin. The resin layer is disposed between the first substrate and the second substrate.

[0033] The resin layer may have a single layer structure or a laminated structure consisting of multiple layers. The resin layer may be formed by bonding multiple layers. In this case, the resin layer formed may have clear interfaces between the bonded multiple layers (i.e., the laminated structure may be maintained), or the interfaces between the bonded multiple layers may be fused and become unclear (for example, a single layer structure may be formed).

[0034] The thickness of the resin layer is 50 μm or less, preferably 0.01 μm to 50 μm, more preferably 0.02 μm to 35 μm, and even more preferably 0.03 μm to 20 μm.

[0035] The resin contained in the resin layer is a resin containing Si atoms. The resin contained in the resin layer may be only one type or two or more types. When the resin contained in the resin layer is two or more types of resin, at least one resin needs to contain Si atoms. The resin contained in the resin layer is, for example, at least one selected from the group consisting of polyimide, polyamide, polyamideimide, maleimide resin, parylene, polyarylene ether polyimide, polybenzoxazole, benzocyclobutene (BCB) resin, and epoxy resin. In this example, at least one resin contains Si atoms. Further, examples of the resin contained in the resin layer include a cured product of composition A described below or a cured product of composition B described below.

[0036] The resin layer can be formed by a coating method (i.e., a method of applying a coating liquid and then heating) using a coating liquid containing at least one of a resin and a resin precursor (e.g., a monomer). Examples of the coating liquid include Composition A and Composition B described below.

[0037] From the viewpoint of further improving the bonding strength between the substrates, the resin contained in the resin layer more preferably further contains an O atom, and even more preferably contains at least one of a silanol group and a siloxane bond.

[0038] The resin contained in the resin layer is preferably at least one selected from the group consisting of a siloxane bond, an amide bond, and an imide bond. This further improves the bonding strength between the substrates. A resin layer containing at least one selected from the group consisting of a siloxane bond, an amide bond, and an imide bond can be formed using, for example, Composition A described below or Composition B described below.

[0039] The resin layer may contain components other than resin. The resin layer preferably contains a resin as a main component. Here, the main component means the component having the largest content ratio on a mass basis. The content of the resin relative to the entire resin layer is preferably 50 mass% or more, more preferably 60 mass% or more, even more preferably 80 mass% or more, and even more preferably 90 mass% or more. The content of the resin relative to the entire resin layer may be 100 mass% or less.

[0040] (Si ratio) When a composition analysis is performed on a cross section of the substrate laminate of the present disclosure by energy dispersive X-ray spectroscopy (hereinafter also referred to as "EDX"), the Si ratio (i.e., the value obtained by dividing the maximum value of the abundance ratio of Si atoms in the resin layer by the minimum value of the abundance ratio of Si atoms in the resin layer; i.e., the maximum value of Si ratio / the minimum value of Si ratio) is 1.5 or more. This improves the bonding strength between the substrates. The Si ratio (i.e., the maximum value of Si ratio / the minimum value of Si ratio) is preferably 1.5 to 5.0, more preferably 1.6 to 3.0, and even more preferably 1.7 to 2.5.

[0041] In the composition analysis by EDX, the minimum value of the abundance ratio of Si atoms (i.e., Si ratio) is not particularly limited, but is, for example, 0.1 atomic % to 30 atomic %, preferably 0.5 atomic % to 20 atomic %, and more preferably 1 atomic % to 10 atomic %.

[0042] In the present disclosure, the measurement conditions for energy dispersive X-ray spectroscopy (EDX) can be found in the Examples described below.

[0043] (Surface activation treatment) A specific means for achieving a Si ratio of 1.5 or more includes performing a surface activation treatment on the bonding surface of the resin layer before bonding the first substrate and the second substrate via the resin layer during the manufacturing stage of the substrate laminate. When the surface activation treatment is performed on the bonding surface of the resin layer, the abundance ratio of Si atoms in the vicinity of the surface-activated surface (specifically, in the vicinity in the thickness direction of the resin layer) can be increased. This results in a location where the abundance ratio of Si atoms shows a maximum value and a location where it shows a minimum value, making it easy to achieve a Si ratio of 1.5 or more. For example, when the bonding surface of the resin layer is subjected to a plasma treatment described below as a surface activation treatment, the abundance ratio of carbon (C) in the vicinity of the surface-activated surface can be reduced, and as a result, the abundance ratio of Si in the vicinity can be increased.

[0044] The surface activation treatment may be performed not only on the bonding surface of the resin layer (i.e., the surface of the resin layer) but also on the surface to be bonded to the resin layer.

[0045] Examples of the bonding surface in the resin layer include: a bonding surface in the resin layer with the first substrate or second substrate (hereinafter also simply referred to as substrate) itself; a bonding surface with a resin layer or inorganic layer provided on the substrate; etc. For example, when a laminate including a first substrate and a resin layer is bonded to a second substrate in a direction in which the resin layer and the second substrate are in contact, the "bonding surface in the resin layer" is the bonding surface in the resin layer with the second substrate. Furthermore, when a laminate including a first substrate and a resin layer A is bonded to a laminate including a second substrate and a resin layer B in a direction in which the resin layer A and the resin layer B are in contact, the "bonding surface in the resin layer A" is the bonding surface in the resin layer A with the resin layer B.

[0046] Examples of surface activation treatments that can be performed on the bonding surfaces of the resin layers include treatment with a chemical solution, Si impregnation treatment, plasma treatment, fast atom beam irradiation, and ozone treatment.

[0047] Examples of the Si impregnation treatment include application of a liquid containing a silane coupling agent.

[0048] The plasma treatment is, for example, at least one selected from the group consisting of an oxygen plasma treatment and a nitrogen plasma treatment.

[0049] In at least one plasma treatment selected from the group consisting of an oxygen plasma treatment and a nitrogen plasma treatment, the gas flow rate of the oxygen gas or nitrogen gas is preferably 5 sccm to 200 sccm, more preferably 10 sccm to 100 sccm, and even more preferably 10 sccm to 60 sccm.

[0050] The treatment pressure in the plasma treatment is preferably 10 Pa to 100 Pa, more preferably 20 Pa to 80 Pa.

[0051] The RF power in the plasma treatment is preferably 10W to 200W, more preferably 20W to 150W.

[0052] The treatment time in the plasma treatment is preferably 10 to 200 seconds, more preferably 20 to 100 seconds.

[0053] In the manufacturing stage of the substrate laminate, the surface of the resin layer after the surface activation treatment may be washed with water.

[0054] (Change in abundance ratio of Si atoms) In the first embodiment, when a composition analysis is performed by XDS, it is preferable that the abundance ratio of Si atoms in the resin layer changes continuously in the thickness direction of the resin layer, thereby further improving the bonding strength between the substrates.

[0055] In the present disclosure, "the change in the abundance ratio of Si atoms in the resin layer in the thickness direction of the resin layer is continuous" means that the amount of change in the abundance ratio of Si atoms per 1 nm of the resin layer thickness is 1 atomic % or less.

[0056] As a means for achieving "a continuous change in the abundance ratio of Si atoms in the resin layer in the thickness direction of the resin layer," for example, the above-mentioned plasma treatment may be applied to the bonding surface of the resin layer.

[0057] (O ratio) When a composition analysis is performed by EDX on a cross section of the substrate laminate of the present disclosure, the O ratio (i.e., the value obtained by dividing the maximum value of the abundance ratio of O atoms in the resin layer by the minimum value of the abundance ratio of O atoms in the resin layer; i.e., maximum value / minimum value) is 1.3 or more. This further improves the bonding strength between the substrates. The O ratio (maximum value / minimum value) is preferably 1.3 to 5.0, more preferably 1.4 to 3.0, and even more preferably 1.5 to 2.0.

[0058] In the composition analysis by EDX described above, the minimum value of the abundance ratio of O atoms is not particularly limited, but is, for example, 1 atomic % to 50 atomic %, preferably 2 atomic % to 40 atomic %, and more preferably 3 atomic % to 30 atomic %.

[0059] (Change in abundance ratio of O atoms) In the first embodiment, when a composition analysis is performed by XDS, it is preferable that the abundance ratio of O atoms in the resin layer changes continuously in the thickness direction of the resin layer. This further improves the bonding strength between the substrates. The meaning of "continuous" in the change in abundance ratio of O atoms is the same as the meaning of "continuous" in the change in abundance ratio of Si atoms.

[0060] As a means for achieving "a continuous change in the abundance ratio of O atoms in the resin layer in the thickness direction of the resin layer," for example, the above-mentioned plasma treatment may be performed on the bonding surface of the resin layer.

[0061] (Abundance ratio of C atoms) The resin in the resin layer naturally contains C (carbon) atoms. In composition analysis by XDS, the C value at the position where Si shows the maximum value is preferably 20 atomic % to 55 atomic %, more preferably 30 atomic % to 55 atomic %. In composition analysis by XDS, the C value at the position where Si shows the minimum value is preferably 40 atomic % to 90 atomic %, more preferably 50 atomic % to 80 atomic %.

[0062] In the composition analysis by XDS, the C value at the position where O shows the maximum value is preferably 20 atomic % to 55 atomic %, more preferably 30 atomic % to 55 atomic %. In the composition analysis by XDS, the C value at the position where O shows the minimum value is preferably 40 atomic % to 90 atomic %, more preferably 50 atomic % to 80 atomic %.

[0063] (Complex Elastic Modulus) The composite elastic modulus of the resin layer in the substrate laminate is not particularly limited, but is, for example, 1 GPa to 20 GPa, preferably 2 GPa to 15 GPa, and more preferably 3 GPa to 10 GPa. For a method for measuring the composite elastic modulus, see the Examples described later.

[0064] (Bonding Strength) In the substrate laminate of the first embodiment, the bonding strength between the first substrate and the second substrate, expressed in terms of surface energy, is preferably 0.2 J / m ２ More preferably, 1.0 J / m ２ More preferably, 2.0 J / m ２ The surface energy can be determined by the blade insertion test described later.

[0065] (Voids) It is preferable that voids are unlikely to occur at the bonding surface between the resin layer and the substrate in the substrate laminate of the first embodiment, even when heated to 400°C. The ratio of the total area of ​​voids (void area ratio) when heated to 400°C is preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less. The void area ratio is a value calculated by dividing the total area of ​​voids by the total area where transmitted light was observable in infrared light transmission observation and multiplying the result by 100. When infrared light transmission observation is difficult, the void area ratio can be determined by a similar method using reflected waves from an ultrasonic microscope, transmitted waves from an ultrasonic microscope, or reflected infrared light, preferably using reflected waves from an ultrasonic microscope.

[0066] <Electrode> The substrate laminate of the first embodiment may further include an electrode penetrating the resin layer between the first substrate and the second substrate. This electrode can electrically connect the first substrate and the second substrate. Examples of the electrode include an electrode containing at least one metal selected from the group consisting of Cu, gold, and tin.

[0067] 1 is a schematic cross-sectional view conceptually illustrating an example of a substrate laminate including an electrode. As shown in FIG. 1, the substrate laminate 100 according to this example includes a first substrate 11, a resin layer 31, and a second substrate 21 arranged in this order, and further includes an electrode 32 penetrating the resin layer 31 between the first substrate 11 and the second substrate 21.

[0068] In the substrate stack 100, the first substrate 11 and the second substrate 21 each include a substrate body (e.g., a Si substrate body) and an inorganic layer (e.g., SiO ２ In this case, an inorganic layer may be disposed at least on either side of the substrate body and the resin layer 31.

[0069] Furthermore, in the substrate laminate 100, the resin layer 31 and the electrode 32 may each be formed by stacking multiple layers. In this case, the structure of the resin layer 31 and the electrode 32 may each be a laminate structure in which multiple layers are stacked, or a single-layer structure formed by stacking multiple layers and then fusing them together. A substrate laminate in which the resin layer 31 and the electrode 32 are each formed by stacking multiple layers may be manufactured by hybrid bonding. Here, hybrid bonding refers to a bonding form in which the electrodes and insulating layers are joined by contacting the two exposed surfaces of the electrode and insulating layer. Hybrid bonding is advantageous in terms of narrowing the wiring pitch.

[0070] [Substrate Laminate (Second Embodiment)] The substrate laminate of the second embodiment has the feature of the first embodiment, that is, the O ratio of 1.3 or more, and may or may not have the feature of the first embodiment, that is, the Si ratio of 1.5 or more, but is similar to the substrate laminate of the first embodiment, and the preferred aspects are also similar.

[0071] [Specific examples of compositions for forming resin layer] Hereinafter, compositions A and B, which are specific examples of compositions (e.g., coating liquids) for forming a resin layer in the present disclosure, will be described. For compositions for forming a resin layer, for example, WO 2018 / 199117, WO 2022 / 054839, JP 2021-182621 A and other known documents may be referenced.

[0072] <Composition A> Composition A is a composition comprising: a compound (A) having a weight-average molecular weight of 130 or more and 10,000 or less, which has a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom, a siloxane bond (Si—O bond), and an amino group; and a compound (B) having three or more —C(═O)OX groups (X is a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms) in the molecule, wherein one to six of the three or more —C(═O)OX groups are —C(═O)OH groups, and having a weight-average molecular weight of 200 or more and 600 or less.

[0073] By containing compound (A) and compound (B), the composition A can form a resin layer of uniform thickness (i.e., the resin layer in the present disclosure; the same applies hereinafter) and also has excellent bonding strength between substrates. Furthermore, since the bonding strength between substrates is excellent even when the resin layer is thin, it is advantageous when forming a multilayer three-dimensional structure while achieving miniaturization. In addition, since the thickness of the resin layer can be thinned, the solvent can be easily volatilized when producing a substrate laminate, and the occurrence of voids is suppressed. Furthermore, since the occurrence of voids is suppressed, the adhesive area is less likely to be reduced, and unintended peeling of the substrates can be suppressed.

[0074] (Compound (A)) Compound (A) is a compound having a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom, a siloxane bond (Si—O bond), and an amino group, and having a weight average molecular weight of 130 to 10,000. The cationic functional group is not particularly limited as long as it is a functional group that can bear a positive charge and contains at least one of a primary nitrogen atom and a secondary nitrogen atom.

[0075] Furthermore, the compound (A) may contain a tertiary nitrogen atom in addition to the primary and secondary nitrogen atoms.

[0076] As used herein, the term "primary nitrogen atom" refers to a nitrogen atom that is bonded to only two hydrogen atoms and one atom other than a hydrogen atom (e.g., a primary amino group (-NH ２ A "secondary nitrogen atom" refers to a nitrogen atom bonded to only one hydrogen atom and two atoms other than hydrogen atoms (i.e., a nitrogen atom contained in a functional group represented by formula (a) below), or a nitrogen atom (cation) bonded to only two hydrogen atoms and two atoms other than hydrogen atoms. A "tertiary nitrogen atom" refers to a nitrogen atom bonded to only three atoms other than hydrogen atoms (i.e., a nitrogen atom that is a functional group represented by formula (b) below), or a nitrogen atom (cation) bonded to only one hydrogen atom and three atoms other than hydrogen atoms.

[0077]

[0078] In formula (a) and formula (b), * indicates the bonding position with an atom other than a hydrogen atom. Here, the functional group represented by formula (a) is a secondary amino group (-NHR ａ group; where R ａ The functional group represented by the formula (b) (i.e., a tertiary nitrogen atom) may be a functional group constituting a part of a tertiary amino group (-NR ｂ R ｃ group; where R ｂ and R ｃeach independently represents an alkyl group), or may be a trivalent linking group contained in the skeleton of the polymer.

[0079] The weight average molecular weight of the compound (A) is 130 or more and 10,000 or less, more preferably 130 or more and 5,000 or less, and even more preferably 130 or more and 2,000 or less.

[0080] In this specification, the weight-average molecular weight refers to a polyethylene glycol-equivalent weight-average molecular weight measured by Gel Permeation Chromatography (GPC). Specifically, the weight-average molecular weight is calculated using an aqueous solution of sodium nitrate with a concentration of 0.1 mol / L as a developing solvent, a Shodex DET RI-101 analyzer, and two analytical columns (TSKgel G6000PWXL-CP and TSKgel G3000PWXL-CP, manufactured by Tosoh Corporation) at a flow rate of 1.0 mL / min to detect the refractive index, and polyethylene glycol / polyethylene oxide as standards using analytical software (Empower3, manufactured by Waters Corporation).

[0081] Furthermore, compound (A) may further have an anionic functional group, a nonionic functional group, or the like, as necessary. The nonionic functional group may be a hydrogen bond acceptor group or a hydrogen bond donor group. Examples of the nonionic functional group include a hydroxy group, a carbonyl group, an ether group (—O—), and the like. The anionic functional group is not particularly limited as long as it is a functional group that can bear a negative charge. Examples of the anionic functional group include a carboxylic acid group, a sulfonic acid group, and a sulfate group.

[0082] Examples of the compound (A) include siloxane diamine, a silane coupling agent having an amino group, a siloxane polymer of a silane coupling agent having an amino group, etc. Examples of the silane coupling agent having an amino group include a compound represented by the following formula (A-3):

[0083]

[0084] In formula (A-3), R １ represents an alkyl group having 1 to 4 carbon atoms which may be substituted. ２ and R ３ R each independently represents an alkylene group having 1 to 12 carbon atoms, an ether group, or a carbonyl group which may be substituted (the skeleton may contain a carbonyl group, an ether group, etc.). ４ and R ５ each independently represents an optionally substituted alkylene group having 1 to 4 carbon atoms or a single bond. Ar represents a divalent or trivalent aromatic ring. X １ represents hydrogen or an alkyl group having 1 to 5 carbon atoms which may be substituted. X 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 (which may contain a carbonyl group, an ether group, etc. in the skeleton). １ , R ２ , R ３ , R ４ , R ５ , X １ may be the same or different. １ , R ２ , R ３ , R ４ , R ５ , X １ , X ２ In X, the substituents of the alkyl group and alkylene group each independently include an amino group, a hydroxy group, an alkoxy group, a cyano group, a carboxylic acid group, a sulfonic acid group, a halogen atom, etc. The divalent or trivalent aromatic ring in Ar includes, for example, a divalent or trivalent benzene ring. ２ Examples of the aryl group in the formula (I) include a phenyl group, a methylbenzyl group, and a vinylbenzyl group.

[0085] 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, (aminoethylaminoethyl)phenyltriethoxysilane,

[0033] Examples of suitable silanes include (2-(2-aminoethyl)-3-aminopropyl)phenylaminoethyl)phenethyltrimethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, N-[2-[3-(trimethoxysilyl)propylamino]ethyl]ethylenediamine, 3-aminopropyldiethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldimethylmethoxysilane, trimethoxy[2-(2-aminoethyl)-3-aminopropyl]silane, diaminomethylmethyldiethoxysilane, methylaminomethylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, N-methylaminopropyltriethoxysilane, N-methylaminopropylmethyldiethoxysilane, (phenylaminomethyl)methyldiethoxysilane, acetamidopropyltrimethoxysilane, and hydrolysates thereof.

[0086] 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 hydrolysates thereof.

[0087] The silane coupling agent having the amino group may be used alone or in combination of two or more kinds.In addition, the silane coupling agent having the amino group may be used in combination with the silane coupling agent not having the amino group.For example, the silane coupling agent having the mercapto group may be used to improve adhesion with metal.

[0088] Alternatively, polymers (siloxane polymers) formed from these silane coupling agents via siloxane bonds (Si—O—Si) may be used. For example, a hydrolyzate of 3-aminopropyltrimethoxysilane can produce a polymer having a linear siloxane structure, a polymer having a branched siloxane structure, a polymer having a cyclic siloxane structure, or a polymer having a cage siloxane structure. The cage siloxane structure is represented, for example, by the following formula (A-1):

[0089]

[0090] Examples of siloxane diamines 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.

[0091]

[0092] Examples of siloxane diamines 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).

[0093] Since the compound (A) has a primary or secondary amino group, it can strongly bond the substrates together by electrostatic interaction with functional groups such as hydroxyl groups, epoxy groups, carboxy groups, amino groups, and mercapto groups that may be present on the surfaces of the first and second substrates, or by forming a close covalent bond with the functional groups. Furthermore, since the compound (A) has a primary or secondary amino group, it is easily soluble in the polar solvent (D) described below. By using the compound (A) that is easily soluble in the polar solvent (D), it has a high affinity with the hydrophilic surface of a substrate such as a silicon substrate, making it easier to form a smooth film and allowing the thickness of the resin layer to be reduced.

[0094] As the compound (A), a compound having an Si—O bond and a primary amino group is preferred from the viewpoint of forming a thermally crosslinked structure such as an amide, amide-imide, or imide and further improving heat resistance.

[0095] It is preferable from the viewpoint of forming a smooth thin film that the ratio of the total number of primary nitrogen atoms and secondary nitrogen atoms to the number of silicon atoms in compound (A) (total number of primary nitrogen atoms and secondary nitrogen atoms / number of silicon atoms) is 0.2 or more and 5 or less.

[0096] In terms of adhesiveness between substrates, it is preferable that the molar ratio of Si element to non-crosslinkable group such as methyl group bonded to Si element in compound (A) satisfies the relationship (non-crosslinkable group) / Si<2. By satisfying this relationship, it is presumed that the density of crosslinks (crosslinks between Si-O-Si bonds and amide bonds, imide bonds, etc.) in the formed film is improved, the substrates have sufficient adhesive strength, and peeling of the substrates can be suppressed.

[0097] As described above, compound (A) has a cationic functional group containing 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 the total nitrogen atoms in compound (A) is preferably 20 mol% or more, more preferably 25 mol% or more, and even more preferably 30 mol% or more. In addition, compound (A) may have a cationic functional group that contains a primary nitrogen atom and does not contain any nitrogen atoms other than the primary nitrogen atom (for example, a secondary nitrogen atom or a tertiary nitrogen atom).

[0098] Furthermore, when compound (A) contains a secondary nitrogen atom, the proportion of the secondary nitrogen atoms in all nitrogen atoms in compound (A) is preferably 5 mol % or more and 50 mol % or less, and more preferably 10 mol % or more and 45 mol % or less.

[0099] Furthermore, compound (A) may contain a tertiary nitrogen atom in addition to a primary nitrogen atom and a secondary nitrogen atom. When compound (A) contains a tertiary nitrogen atom, the proportion of tertiary nitrogen atoms in all nitrogen atoms in compound (A) is preferably 20 mol % or more and 50 mol % or less, and more preferably 25 mol % or more and 45 mol % or less.

[0100] In the present embodiment, the content of the component derived from compound (A) in the resin layer is not particularly limited, and can be, for example, 1% by mass or more and 82% by mass or less, preferably 5% by mass or more and 82% by mass or less, and more preferably 13% by mass or more and 82% by mass or less, based on the entire resin layer.

[0101] (Compound (B)) Compound (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, of which one to 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 having a weight average molecular weight of 200 to 600.

[0102] Compound (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 to six -C(=O)OX groups in the molecule, and more preferably a compound having three or four -C(=O)OX groups in the molecule.

[0103] In compound (B), X in the -C(=O)OX group may be a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms, and among these, a hydrogen atom, a methyl group, an ethyl group, or a propyl group is preferred. Note that X in the -C(=O)OX group may be the same or different.

[0104] Compound (B) is a compound having one to six -C(=O)OH groups in which X is a hydrogen atom in the molecule, preferably a compound having one to four -C(=O)OH groups in the molecule, more preferably a compound having two to four -C(=O)OH groups in the molecule, and even more preferably a compound having two or three -C(=O)OH groups in the molecule.

[0105] The compound (B) has a weight average molecular weight of 200 or more and 600 or less, preferably 200 or more and 400 or less.

[0106] Compound (B) preferably has a ring structure in the molecule. Examples of the ring structure include an alicyclic structure and an aromatic ring structure. Compound (B) may also have multiple ring structures in the molecule, and the multiple ring structures may be the same or different.

[0107] Examples of the alicyclic structure include an alicyclic structure having from 3 to 8 carbon atoms, preferably from 4 to 6 carbon atoms, and the ring structure may be saturated or unsaturated. More specific 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.

[0108] The aromatic ring structure is not particularly limited as long as it is a ring structure exhibiting aromaticity, and examples thereof include benzene-based aromatic rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a perylene ring; aromatic heterocycles such as a pyridine ring and a thiophene ring; and non-benzene-based aromatic rings such as an indene ring and an azulene ring.

[0109] The ring structure that compound (B) has in its 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, and from the viewpoint of further increasing the heat resistance of the resin layer, at least one of a benzene ring and a naphthalene ring is more preferred.

[0110] As described above, the compound (B) may have a plurality of ring structures in the molecule, and when the ring structure is benzene, it may have a biphenyl structure, a benzophenone structure, a diphenyl ether structure, or the like.

[0111] The ring structure that compound (B) has in the molecule is preferably a ring structure having two or more —C(═O)OX groups.

[0112] Compound (B) preferably has a fluorine atom in the molecule, more preferably has 1 to 6 fluorine atoms in the molecule, and further preferably has 3 to 6 fluorine atoms in the molecule. For example, compound (B) may have a fluoroalkyl group in the molecule, specifically, a trifluoroalkyl group or a hexafluoroisopropyl group.

[0113] Further examples of compound (B) include carboxylic acid compounds such as alicyclic carboxylic acids, benzenecarboxylic acids, naphthalenecarboxylic acids, diphthalic acids, and fluorinated aromatic ring carboxylic acids; and carboxylic acid ester compounds such as alicyclic carboxylic acid esters, benzenecarboxylic acid esters, naphthalenecarboxylic acid esters, diphthalic acid esters, and fluorinated aromatic ring carboxylic acid esters. The carboxylic acid ester compound is a compound having a carboxy group (-C(=O)OH group) in the molecule, and having three or more -C(=O)OX groups, where at least one X is an alkyl group having 1 to 6 carbon atoms (i.e., having an ester bond). In this embodiment, when compound (B) is a carboxylic acid ester compound, aggregation due to association between compound (A) and compound (B) is suppressed, resulting in fewer aggregates and pits, and facilitating adjustment of film thickness.

[0114] 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.

[0115] The carboxylic acid ester compound is preferably a compound containing three or less carboxy groups (—C(═O)OH groups) and three or less ester bonds in the molecule, and more preferably a compound containing two or less carboxy groups and two or less ester bonds in the molecule.

[0116] Furthermore, in the carboxylic acid ester compound, when X is an alkyl group having from 1 to 6 carbon atoms in three or more —C(═O)OX groups, X is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or the like, and is preferably an ethyl group or a propyl group from the viewpoint of further suppressing aggregation due to association between compound (A) and compound (B).

[0117] Specific examples of the carboxylic acid compound 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; benzenecarboxylic acids such as 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, benzenepentacarboxylic acid, and mellitic acid; 1,4,5,8-naphthalenetetracarboxylic acid; naphthalene carboxylic acids such as 2,3,6,7-naphthalenetetracarboxylic acid; 3,3',5,5'-tetracarboxydiphenylmethane, biphenyl-3,3',5,5'-tetracarboxylic acid, biphenyl-3,4',5-tricarboxylic acid, biphenyl-3,3',4,4'-tetracarboxylic acid, benzophenone-3,3',4,4'-tetracarboxylic acid, 4,4'-oxydiphthalic acid, 3,4'-oxydiphthalic acid, 1,3-bis(phthalic acid)tetramethyldisiloxane, 4,4'-(ethyn-1,2-diyl)diphthalic acid diphthalic acids such as 4,4'-(1,4-phenylenebis(oxy))diphthalic acid, 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))diphthalic acid, and 4,4'-((oxybis(4,1-phenylene))bis(oxy))diphthalic acid; perylene carboxylic acids such as perylene-3,4,9,10-tetracarboxylic acid; anthracene carboxylic acids such as anthracene-2,3,6,7-tetracarboxylic acid;Examples of fluorinated aromatic carboxylic acids include 4,4'-(hexafluoroisopropylidene)diphthalic acid, 9,9-bis(trifluoromethyl)-9H-xanthene-2,3,6,7-tetracarboxylic acid, and 1,4-ditrifluoromethylpyromellitic acid;

[0118] Specific examples of the carboxylic acid ester compound include compounds in which at least one carboxy group in the specific examples of the carboxylic acid compound described above is substituted with an ester group, such as half-esterified compounds represented by the following general formulas (B-1) to (B-6).

[0119]

[0120] In general formulas (B-1) to (B-6), R each independently represents an alkyl group having 1 to 6 carbon atoms. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are preferred, and an ethyl group and a propyl group are more preferred.

[0121] The half-esterified compound can be produced, for example, by mixing a carboxylic acid anhydride, which is an anhydride of the above-mentioned carboxylic acid compound, with an alcohol solvent and ring-opening the carboxylic acid anhydride.

[0122] In the present embodiment, the content of the component derived from compound (B) in the resin layer is not particularly limited, and for example, the ratio ((-(C=O)-Y) / N) of the number of carbonyl groups (-(C=O)-Y) in the substance derived from compound (B) to the total number of nitrogen atoms in the substance derived from compound (A) is preferably 0.1 or more and 3.0 or less, more preferably 0.3 or more and 2.5 or less, and even more preferably 0.4 or more and 2.2 or less. Here, in -(C=O)-Y, Y represents an imide-crosslinked or amide-crosslinked nitrogen atom, OH, or an ester group. By having (-(C=O)-Y) / N be 0.1 or more and 3.0 or less, the resin layer suitably has a thermally crosslinked structure such as amide, amideimide, or imide, and has better heat resistance.

[0123] Since compound (A) has an uncrosslinked cationic functional group, it is thought that when compound (A) is contained as a component of the resin layer without compound (B), the crosslink density is low and heat resistance is insufficient. On the other hand, in the resin layer, the cationic functional group of compound (A) reacts with the carboxy group of compound (B) to form a covalent bond, thereby increasing the crosslink density and providing high heat resistance.

[0124] (Compound (C)) Composition A may further contain the following compound (C). Compound (C) is a compound having a ring structure and one or more primary nitrogen atoms directly bonded to the ring structure. Compound (C) reacts with compound (A) and compound (B) to form a cured product. Compound (C) has a ring structure and one or more primary nitrogen atoms directly bonded to the ring structure. It is believed that the introduction of this structure into the cured product increases the rigidity of the cured product and reduces the thermal expansion coefficient. One type of compound (C) may be used alone, or two or more types may be used in combination.

[0125] In the present disclosure, the term "primary nitrogen atom directly bonded to a ring structure" refers to a primary nitrogen atom (-NH) bonded to a ring structure via a single bond (i.e., not via a carbon atom, etc.). ２ ) means

[0126] The number of primary nitrogen atoms directly bonded to the ring structure in the molecule of compound (C) is not particularly limited as long as it is at least 1. From the viewpoint of increasing the crosslink density, it is preferably at least 2, and a diamine compound having two primary amino groups or a triamine compound having three primary amino groups is more preferred.

[0127] Compound (C) may have one ring structure or multiple ring structures in the molecule. When compound (C) has multiple ring structures in the molecule, it may have a cationic functional group containing a primary nitrogen atom directly bonded to each ring structure, or may have a cationic functional group containing a primary nitrogen atom directly bonded to only one of the ring structures.

[0128] When compound (C) has multiple ring structures in the molecule, the multiple ring structures may be the same or different, or may form a fused ring, or the multiple ring structures may be bonded by a single bond or via a linking group such as an ether group, a carbonyl group, a sulfonyl group, or a methylene group.

[0129] Examples of the ring structure contained in compound (C) include an alicyclic structure, an aromatic ring (including a heterocyclic ring), and a condensed ring structure thereof. Examples of the alicyclic structure include an alicyclic structure having 3 to 8 carbon atoms, preferably 4 to 6 carbon atoms. The ring structure may be saturated or unsaturated. More specifically, examples include saturated alicyclic structures such as 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.

[0130] Examples of aromatic ring structures include aromatic ring structures having from 6 to 20 carbon atoms, preferably from 6 to 10 carbon atoms. Specific examples include benzene-based aromatic ring structures such as a benzene ring, a naphthalene ring, an anthracene ring, and a perylene ring, and non-benzene-based aromatic ring structures such as a pyridine ring, a thiophene ring, an indene ring, and an azulene ring.

[0131] The heterocyclic structure may be a 3- to 10-membered ring, preferably a 5- or 6-membered ring.Heteroatoms contained in the heterocycle include sulfur atoms, nitrogen atoms, and oxygen atoms, and may be one or more of these.Specific examples of the heterocyclic structure include an oxazole ring, a thiophene ring, a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, a triazole ring, an isocyanuric ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a triazine ring, 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.

[0132] The ring structure contained in the molecule of compound (C) is more preferably a benzene ring, a cyclohexane ring, or a benzoxazole ring.

[0133] The ring structure contained in the molecule of compound (C) may have a substituent other than a primary nitrogen atom, such as an alkyl group having from 1 to 6 carbon atoms or an alkyl group substituted with a halogen atom.

[0134] The weight average molecular weight of the compound (C) is not particularly limited and may be, for example, 80 to 600, 90 to 500, or 100 to 450.

[0135] Examples of the compound (C) include alicyclic amines, aromatic amines, heterocyclic amines having a nitrogen-containing heterocycle, and amine compounds having both a heterocycle and an aromatic ring. Specific examples of the alicyclic amines include cyclohexylamine and dimethylaminocyclohexane. Specific examples of the aromatic amines include diaminodiphenyl ether, xylylenediamine (preferably paraxylylenediamine), 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, and tris(4-aminophenyl)amine. Specific examples of heterocyclic amines having a nitrogen-containing heterocycle include melamine, ammeline, melam, melem, tris(4-aminophenyl)amine, etc. Specific examples of amine compounds having both a heterocycle and an aromatic ring include N2,N4,N6-tris(4-aminophenyl)-1,3,5-triazine-2,4,6-triamine, 2-(4-aminophenyl)benzoxazole-5-amine, etc.

[0136] The content of compound (C) in composition A is not particularly limited, as long as the proportion of primary nitrogen atoms contained in compound (A) to the total of primary and secondary nitrogen atoms contained in compound (A) and primary nitrogen atoms contained in compound (C) is 3 mol % to 95 mol %. From the viewpoint of the balance between the thermal expansion coefficient and the bonding strength, the proportion is preferably 5 mol % to 75 mol %, more preferably 10 mol % to 50 mol %, and even more preferably 10 mol % to 30 mol %.

[0137] (Polar solvent) Composition A may contain a polar solvent. In the present disclosure, "polar solvent" refers to a solvent having a relative dielectric constant of 5 or more at room temperature (25°C). When composition A contains a polar solvent, the solubility of each component in composition A is improved. The polar solvent may be used alone or in combination of two or more.

[0138] Specific examples of polar solvents include protic solvents such as water and heavy water; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, benzyl alcohol, diethylene glycol, triethylene glycol, and glycerin; ethers such as tetrahydrofuran and dimethoxyethane; aldehydes and ketones such as furfural, acetone, ethyl methyl ketone, and cyclohexanone; acid derivatives such as acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, formaldehyde, N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and hexamethylphosphoric acid amide; nitriles such as acetonitrile and propionitrile; and nitro compounds such as nitromethane and nitrobenzene; and sulfur compounds such as dimethyl sulfoxide. The polar solvent preferably contains a protic solvent, more preferably contains water, and further preferably contains ultrapure water.

[0139] When composition A contains a polar solvent, the content thereof is not particularly limited, and may be, for example, 1.0 mass% or more and 99.99896 mass% or less, or 40 mass% or more and 99.99896 mass% or less, relative to the entire composition A.

[0140] (Additives) Composition A may contain additives as needed. Examples of additives include an acid having a carboxy group and a weight average molecular weight of 46 to 195, and a base having a nitrogen atom and no ring structure and a weight average molecular weight of 17 to 120.

[0141] It is presumed that, by including an acid having a carboxy group and a weight-average molecular weight of 46 to 195 inclusive in composition A, the primary or secondary nitrogen atoms of compounds (A) and (C) form ionic bonds with the carboxy groups in the acid, thereby suppressing aggregation due to association of compounds (A) and (C) with compound (B). More specifically, it is presumed that the interaction (e.g., electrostatic interaction) between the ammonium ions derived from compounds (A) and (C) and the carboxylate ions derived from the carboxy groups in the acid is stronger than the interaction between the ammonium ions derived from compounds (A) and (C) and the carboxylate ions derived from the carboxy groups in compound (B), thereby suppressing aggregation. However, the present invention is not limited by this presumption in any way.

[0142] The type of acid having a carboxy group and a weight-average molecular weight of 46 to 195 is not particularly limited, and examples thereof include monocarboxylic acid compounds, dicarboxylic acid compounds, oxydicarboxylic acid compounds, etc. More specific examples thereof include formic acid, acetic acid, malonic acid, oxalic acid, benzoic acid, lactic acid, glycolic acid, glyceric acid, butyric acid, methoxyacetic acid, ethoxyacetic acid, phthalic acid, terephthalic acid, picolinic acid, salicylic acid, 3,4,5-trihydroxybenzoic acid, etc. (However, those corresponding to compound (B) are excluded.)

[0143] When composition A contains an acid having a weight-average molecular weight of 46 or more and 195 or less, its content is not particularly limited, but, for example, an amount such that the ratio (COOH / N) of the number of carboxy groups in the acid to the total number of primary and secondary nitrogen atoms in compound (A) and compound (C) is 0.01 or more and 10 or less, more preferably 0.02 or more and 6 or less, and even more preferably 0.5 or more and 3 or less.

[0144] It is presumed that when composition A contains a base having a nitrogen atom and a weight-average molecular weight of 17 to 120, the carboxy group of compound (B) forms an ionic bond with the amino group of the base, thereby suppressing aggregation due to association of compound (A) and compound (C) with compound (B). More specifically, it is presumed that aggregation is suppressed because the interaction between the carboxylate ion derived from the carboxy group in compound (B) and the ammonium ion derived from the amino group in the base is stronger than the interaction between the ammonium ion derived from compound (A) and compound (C) and the carboxylate ion derived from the carboxy group in compound (B). However, the present invention is in no way limited by this presumption.

[0145] The type of the compound having a nitrogen atom and a weight average molecular weight of 17 to 120 is not particularly limited, and examples thereof include monoamine compounds and diamine compounds (excluding those corresponding to compound (A) and compound (C)). More specific examples thereof include ammonia, ethylamine, ethanolamine, diethylamine, triethylamine, ethylenediamine, N-acetylethylenediamine, N-(2-aminoethyl)ethanolamine, and N-(2-aminoethyl)glycine.

[0146] When composition A contains a base having a weight-average molecular weight of 17 to 120, the content thereof is not particularly limited, but, for example, the ratio of the number of nitrogen atoms in the base to the number of carboxy groups in compound (B) (N / COOH) is preferably 0.5 to 5, and more preferably 0.9 to 3.

[0147] (Other Components) When selectivity in plasma etching resistance is required for composition A (for example, when used as a gap fill material or a buried insulating film), composition A may contain a metal alkoxide represented by the following general formula (I): ｎ M (OR2) ｍ－ｎ ...(I) (In the formula, R1 is a non-hydrolyzable group, R2 is an alkyl group having 1 to 6 carbon atoms, M is at least one metal atom selected from the group consisting of Ti, Al, Zr, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La, Nd, and In, m is the valence of the metal atom M and is 3 or 4, n is an integer of 0 to 2 when m is 4, and is 0 or 1 when m is 3, when there are multiple R1s, each R1 may be the same as or different from another, and when there are multiple OR2s, each OR2 may be the same as or different from another.)

[0148] In cases where insulating properties are required for a film produced from composition A (for example, for use as an insulating film for a through-silicon via or as a buried insulating film), a silane compound (excluding those corresponding to compound (A)) may be contained in the film to improve the insulating properties or mechanical strength. Specific examples of the silane compound include tetraethoxysilane, tetramethoxysilane, bistriethoxysilylethane, bistriethoxysilylmethane, bis(methyldiethoxysilyl)ethane, 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahydroxylcyclosiloxane, 1,1,4,4-tetramethyl-1,4-diethoxydisilethylene, 1,3,5-trimethyl-1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane, and silane coupling agents having a functional group other than an amino group (such as an epoxy group or a mercapto group).

[0149] Composition A may contain a solvent other than the polar solvent. Examples of the solvent other than the polar solvent include normal hexane.

[0150] Composition A may contain benzotriazole or a derivative thereof, for example to inhibit copper corrosion.

[0151] The pH of composition A is not particularly limited, but is preferably 2.0 or more and 12.0 or less. When the pH of composition A is 2.0 or more and 12.0 or less, damage to the substrate by composition A is suppressed. The sodium and potassium contents of composition A are preferably 10 mass ppb or less on an elemental basis, respectively. When the sodium or potassium contents are 10 mass ppb or less on an elemental basis, it is possible to suppress the occurrence of problems in the electrical characteristics of the semiconductor device, such as transistor malfunction.

[0152] When composition A contains components other than compound (A), compound (B), and compound (C), the total mass of compound (A), compound (B), and compound (C) is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 80 mass% or more of the total mass of non-volatile components in composition A. In the present disclosure, "non-volatile components" refers to components other than components (such as solvents) that are removed when composition A becomes a cured product.

[0153] <Composition B> Composition B contains at least one of a compound (X1) having a structure represented by the following general formula (1) and a molecular weight of 400 to 5000, and a compound (X2) having a structure represented by the following general formula (2) and a molecular weight of 400 to 5000:

[0154]

[0155] In general formula (1), R １ and R ３ are each independently an organic group having 6 or less carbon atoms, and R ２ is a methylene group, an ethylene group, a propylene group, or a phenylene group, a is 2 or 3, b is the number 3-a, and X １ is a structure derived from a carboxylic acid dianhydride.

[0156]

[0157] In general formula (2), R １ and R ３ are each independently an organic group having 6 or less carbon atoms, and R ２is a methylene group, an ethylene group, a propylene group, or a phenylene group, a is 2 or 3, b is the number 3-a, and X １ is a structure derived from a carboxylic acid dianhydride, X2 is a structure derived from an amine compound, and n is a positive number.

[0158] Composition B allows the formation of a resin layer with less residual stress than composition B containing unreacted precursors of compound (X1) or compound (X2), such as a silane coupling agent, a carboxylic acid dianhydride, or an amine compound. The reason for this is not necessarily clear, but it is thought that, for example, by having the precursor of compound (X1) or compound (X2) in a reacted state before composition B is applied to the substrate, cure shrinkage of the resin layer associated with the reaction is suppressed, and the residual stress of the resin layer is reduced, compared to when a resin layer is formed by reacting these precursors on a substrate.

[0159] In general formula (1), X １ is a structure derived from a carboxylic acid dianhydride, and preferably contains a ring structure. １ The amide group and carboxyl group bonded to the polymer react on the substrate to form an imide bond, and the resulting resin layer exhibits excellent heat resistance.

[0160] In general formula (1), a is preferably 2. In general formula (1), R １ and R ３ The organic group having 6 or less carbon atoms represented by the formula (I) includes an alkyl group having 6 or less carbon atoms, preferably 3 or less carbon atoms, and more preferably 2 or less carbon atoms.

[0161] In general formula (2), X １ and X ２ are structures derived from a carboxylic acid dianhydride and an amine compound, respectively, and preferably contain a ring structure. １ The amide group and carboxyl group bonded to the polymer react on the substrate to form an imide bond, and the resulting resin layer exhibits excellent heat resistance.

[0162] In the general formula (2), a is preferably 2. In the general formula (2), R １ and R ３Examples of the organic group having 6 or less carbon atoms, represented by the formula (2), include an alkyl group having 6 or less carbon atoms, preferably 3 or less carbon atoms, and more preferably 2 or less carbon atoms. n in general formula (2) is not particularly limited as long as it is a positive number, and may be, for example, within the range of 1 to 6. Compound (X2) represented by general formula (2) may be in a state in which a structure derived from a carboxylic acid dianhydride and a structure derived from an amine compound are arranged alternately (polyamic acid).

[0163] The compound (X1) contained in the composition B may be a compound having a structure obtained by reacting a silane coupling agent (A) with a carboxylic acid dianhydride (B) having a ring structure and a molecular weight of 200 to 600. The compound (X2) contained in the composition B may be a compound having a structure obtained by reacting a silane coupling agent (A) with a carboxylic acid dianhydride (B) having a ring structure and a molecular weight of 200 to 600, and a structure obtained by reacting an amine compound (C) having a ring structure, having a molecular weight of 90 to 600, and no Si—O bond, with a carboxylic acid dianhydride (B) having a ring structure and a molecular weight of 200 to 600.

[0164] In the present disclosure, the carboxylic acid dianhydride (B) having a molecular weight of 200 to 600 and a ring structure, and the amine compound (C) having a molecular weight of 90 to 600 and a ring structure without an Si—O bond may be simply referred to as the carboxylic acid dianhydride (B) and the amine compound (C), respectively.

[0165] (Silane Coupling Agent (A)) The silane coupling agent (A) is a compound having one or more Si—O bonds in the molecule, and reacting with a carboxylic acid dianhydride to produce compound (X1) or compound (X2). The Si—O bonds in the silane coupling agent (A) contribute to improving the bonding strength between the resin layer formed using composition B and the substrate.

[0166] The silane coupling agent (A) is not particularly limited as long as it has a functional group capable of reacting with the anhydride group of the carboxylic acid dianhydride (B). Specific examples of the functional group include an amino group, an epoxy group, and an isocyanate group. From the viewpoint of the thermal expansion coefficient and bonding strength of the resin layer, the silane coupling agent (A) preferably has an amino group, and from the viewpoint of forming an imide structure in the resin layer to improve heat resistance, a compound having a primary amino group (—NH2) is more preferred.

[0167] The silane coupling agent (A) may be used alone or in combination of two or more.

[0168] The molecular weight of the silane coupling agent (A) is not particularly limited and may be, for example, 130 or more and 10,000 or less, 130 or more and 5,000 or less, or 130 or more and 2,000 or less.

[0169] Examples of the silane coupling agent (A) having an amino group include compounds represented by the following formula (A-3).

[0170]

[0171] In formula (A-3), R １ represents an alkyl group having 1 to 4 carbon atoms which may be substituted. ２ and R ３ R each independently represents an alkylene group having 1 to 12 carbon atoms, an ether group, or a carbonyl group which may be substituted (the skeleton may contain a carbonyl group, an ether group, etc.). 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. X1 represents hydrogen or an alkyl group having 1 to 5 carbon atoms which may be substituted. X2 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 (which may contain a carbonyl group, an ether group, etc. in the skeleton). Multiple R １ , R ２ , R ３ , R ４ , R ５ , X １may be the same or different. １ , R ２ , R ３ , R ４ , R ５ , X １ , X ２ In X, the substituents of the alkyl group and alkylene group each independently include an amino group, a hydroxy group, an alkoxy group, a cyano group, a carboxylic acid group, a sulfonic acid group, a halogen atom, etc. The divalent or trivalent aromatic ring in Ar includes, for example, a divalent or trivalent benzene ring. ２ Examples of the aryl group in the formula (I) include a phenyl group, a methylbenzyl group, and a vinylbenzyl group.

[0172] 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, (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 the like.

[0173] 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, and 5-(ethoxydimethylsilyl)benzene-1,3-diamine.

[0174] The silane coupling agent (A) having an amino group may be used alone or in combination of two or more kinds.

[0175] (Carboxylic Acid Dianhydride (B)) The carboxylic acid dianhydride (B) is a compound having one or more ring structures and two anhydride groups in the molecule and having a molecular weight of 200 or more and 600 or less. The molecular weight of the carboxylic acid dianhydride (B) may be 200 or more and 400 or less. One type of carboxylic acid dianhydride (B) may be used alone, or two or more types may be used in combination.

[0176] Examples of the ring structure that the carboxylic acid dianhydride (B) has in its molecule include an alicyclic structure, an aromatic ring (including a heterocyclic ring), etc. The carboxylic acid dianhydride (B) may have one ring structure or multiple ring structures in its molecule.

[0177] Examples of the alicyclic structure include an alicyclic structure having from 3 to 8 carbon atoms, preferably from 4 to 6 carbon atoms, and the ring structure may be saturated or unsaturated. More specific 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.

[0178] The aromatic ring structure is not particularly limited as long as it is a ring structure exhibiting aromaticity, and examples thereof include benzene-based aromatic rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a perylene ring; aromatic heterocycles such as a pyridine ring and a thiophene ring; and non-benzene-based aromatic rings such as an indene ring and an azulene ring.

[0179] The ring structure contained in the molecule of the carboxylic acid dianhydride (B) is preferably at least one selected from the group consisting of a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a benzene ring, and a naphthalene ring, and from the viewpoint of further improving the heat resistance of the resin layer, at least one of a benzene ring and a naphthalene ring is more preferred. Furthermore, from the viewpoint of suppressing the generation of voids in the resin layer when a resin layer is formed between multiple substrates using the composition B, it is preferable that the carboxylic acid dianhydride (B) contains two or more benzene rings.

[0180] When the carboxylic acid dianhydride (B) has multiple ring structures in the molecule, the multiple ring structures may be the same or different, or may form a condensed ring, or the multiple ring structures may be bonded by a single bond or via a linking group such as an ether group, a carbonyl group, a sulfonyl group, or a methylene group.

[0181] The carboxylic acid dianhydride (B) may have a fluorine atom in the molecule. For example, it may have 1 to 6 fluorine atoms in the molecule, or may have 3 to 6 fluorine atoms in the molecule. For example, the carboxylic acid dianhydride (B) may have a fluoroalkyl group in the molecule, specifically, a trifluoroalkyl group or a hexafluoroisopropyl group.

[0182] Examples of the carboxylic acid dianhydride (B) include dianhydrides of compounds having a ring structure and four carboxy groups capable of forming an anhydride group in the molecule. For example, anhydrides of alicyclic tetracarboxylic acids such as 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and 1,2,3,4,5,6-cyclohexanehexacarboxylic acid; dianhydrides of benzenetetracarboxylic acids such as pyromellitic acid; dianhydrides of naphthalenetetracarboxylic acids such as 1,4,5,8-naphthalenetetracarboxylic acid and 2,3,6,7-naphthalenetetracarboxylic acid; dianhydrides of biphenyltetracarboxylic acids such as 3,3',4,4'-biphenyltetracarboxylic acid; dianhydrides of benzophenonetetracarboxylic acids such as benzophenone-3,3',4,4'-tetracarboxylic acid; Diphthalic acid dianhydrides such as 4,4'-oxydiphthalic acid (ODPA), 3,4'-oxydiphthalic acid, 1,3-bis(phthalic acid)tetramethyldisiloxane, 4,4'-(ethyne-1,2-diyl)diphthalic acid, 4,4'-(1,4-phenylenebis(oxy))diphthalic acid, 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))diphthalic acid, and 4,4'-((oxybis(4,1-phenylene))bis(oxy))diphthalic acid; perylenecarboxylic acid dianhydrides such as perylene-3,4,9,10-tetracarboxylic acid; anthracenecarboxylic acid dianhydrides such as anthracene-2,3,6,7-tetracarboxylic acid; Examples of the dianhydride include fluorinated aromatic carboxylic acids such as 4,4'-(hexafluoroisopropylidene)diphthalic acid, 9,9-bis(trifluoromethyl)-9H-xanthene-2,3,6,7-tetracarboxylic acid, and 1,4-ditrifluoromethylpyromellitic acid; bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)1,4-phenylene dianhydride; 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic acid (IPBDA); and bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)1,4-phenylene dianhydride (TAHQ).

[0183] The content of the carboxylic acid dianhydride (B) in the composition B is, for example, an amount such that the ratio (A / B) of the functional group equivalent number A of the silane coupling agent (A) capable of reacting with the anhydride group of the carboxylic acid dianhydride (B) to the anhydride group equivalent number B of the carboxylic acid dianhydride (B) is preferably 0.9 or more and 1.1 or less, more preferably 0.95 or more and 1.05 or less, and even more preferably 0.98 or more and 1.02 or less.

[0184] When the composition B further contains a compound capable of reacting with an anhydride group of the carboxylic acid dianhydride (B), such as the compound (C) described below, the amount of the compound (C) is such that the ratio (A' / B') of the functional group equivalent number A' of all the compounds capable of reacting with an anhydride group of the carboxylic acid dianhydride (B) to the anhydride group equivalent number B' of the carboxylic acid dianhydride (B) is preferably 0.9 or more and 1.1 or less, more preferably 0.95 or more and 1.05 or less, and even more preferably 0.98 or more and 1.02 or less.

[0185] (Amine Compound (C)) The amine compound (C) is a compound having one or more ring structures and one or more amino groups in the molecule, a molecular weight of 90 to 600, and no Si—O bond. One type of amine compound (C) may be used alone, or two or more types may be used in combination.

[0186] The number of amino groups that the amine compound (C) has in the molecule may be one or more, but from the viewpoint of reducing the thermal expansion coefficient of the resin layer, it is preferable that the number be more than one, and more preferably two (diamine) or three (triamine). From the viewpoint of forming an imide structure in the resin layer and improving heat resistance, it is preferable that the number be a primary amino group (-NH ２ ) is more preferred.

[0187] From the viewpoint of reducing the thermal expansion coefficient of the resin layer, it is preferable that the amine compound (C) has one or more amino groups directly bonded to the ring structure. When the molecular structure of the compound (X2) contains a structure derived from an amino group directly bonded to the ring structure, it is thought that the rigidity of the molecular structure increases, thereby further reducing the thermal expansion coefficient.

[0188] In the present disclosure, an "amino group directly bonded to a ring structure" refers to an amino group bonded to a ring structure via a single bond (i.e., not via a carbon atom, etc.).

[0189] The amine compound (C) may have one ring structure or multiple ring structures in the molecule. When the amine compound (C) has multiple ring structures in the molecule, the multiple ring structures may be the same or different, or may form a condensed ring. Alternatively, the multiple ring structures may be bonded by a single bond, or may be bonded via a linking group such as an ether group, a carbonyl group, a sulfonyl group, or a methylene group.

[0190] Examples of the ring structure contained in the amine compound (C) include an alicyclic structure, an aromatic ring (including a heterocyclic ring), and a condensed ring structure thereof. Examples of the alicyclic structure include an alicyclic structure having from 3 to 8 carbon atoms, preferably from 4 to 6 carbon atoms. The ring structure may be saturated or unsaturated. More specific examples 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.

[0191] Examples of aromatic ring structures include aromatic ring structures having from 6 to 20 carbon atoms, preferably from 6 to 10 carbon atoms. Specific examples include benzene-based aromatic ring structures such as a benzene ring, a naphthalene ring, an anthracene ring, and a perylene ring, and non-benzene-based aromatic ring structures such as a pyridine ring, a thiophene ring, an indene ring, and an azulene ring.

[0192] The heterocyclic structure may be a 3- to 10-membered ring, preferably a 5- or 6-membered ring.Heteroatoms contained in the heterocycle include sulfur atoms, nitrogen atoms, and oxygen atoms, and may be one or more of these.Specific examples of the heterocyclic structure include an oxazole ring, a thiophene ring, a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, a triazole ring, an isocyanuric ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a triazine ring, 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.

[0193] The ring structure contained in the molecule of the amine compound (C) is more preferably a benzene ring, a cyclohexane ring, or a benzoxazole ring.

[0194] The ring structure contained in the molecule of the amine compound (C) may have a substituent other than an amino group, such as an alkyl group having from 1 to 6 carbon atoms or an alkyl group substituted with a halogen atom.

[0195] Specific examples of the amine compound (C) include the following compounds. Examples of alicyclic amines include cyclohexylamine and dimethylaminocyclohexane. Examples of aromatic amines include diaminodiphenyl ether, xylylenediamine (preferably paraxylylenediamine), diaminobenzene, diaminotoluene, methylenedianiline, dimethyldiaminobiphenyl, bis(trifluoromethyl)diaminobiphenyl (TFDB), diaminobenzophenone, diaminobenzanilide, bis(aminophenyl)fluorene, bis(aminophenoxy)benzene, bis(aminophenoxy)biphenyl, dicarboxydiaminodiphenylmethane, diaminoresorcinol, dihydroxybenzidine, diaminobenzidine, 1,3,5-triaminophenoxybenzene, 2,2'-dimethylbenzidine, and tris(4-aminophenyl)amine. Examples of heterocyclic amines having a nitrogen-containing heterocycle include melamine, ammeline, melam, melem, and tris(4-aminophenyl)amine. Furthermore, examples of amine compounds having both a heterocycle and an aromatic ring include N2,N4,N6-tris(4-aminophenyl)-1,3,5-triazine-2,4,6-triamine and 2-(4-aminophenyl)benzoxazol-5-amine (AAPD).

[0196] (Method for Obtaining Compound (X1)) Examples of a method for obtaining compound (X1) by reacting silane coupling agent (A) with carboxylic dianhydride (B) include a method in which carboxylic dianhydride (B) is added to a solvent and stirred, while gradually adding silane coupling agent (A) dropwise to obtain compound (X1).

[0197] (Method for Obtaining Compound (X2)) Examples of a method for obtaining compound (X2) by reacting silane coupling agent (A), carboxylic acid dianhydride (B), and amine compound (C) include a method in which a solvent is added to amine compound (C) and the mixture is stirred while adding carboxylic acid dianhydride (B), stirring is continued until the viscosity of the obtained reaction product (polymer) becomes constant, and then silane coupling agent (A) is gradually added dropwise to obtain compound (X2).

[0198] (Precursor of Resin (D)) Composition B may further contain a compound other than Compound (X1) and Compound (X2). For example, it may further contain a precursor of Resin (D) having a CTE of 90 ppm / K or less between 50°C and 150°C. When Composition B contains a precursor of Resin (D), the thermal expansion coefficient of the resulting resin layer tends to be further reduced.

[0199] Specific examples of the resin (D) having a CTE of 90 ppm / K or less between 50° C. and 150° C. include at least one selected from the group consisting of polyimide and polybenzoxazole. The CTE of the resin (D) can be measured in the same manner as the CTE of the resin layer.

[0200] When composition B contains resin (D), the proportion of resin (D) contained in composition B is preferably 99% by mass to 30% by mass of the total non-volatile content of composition B, from the viewpoint of the balance between the thermal expansion coefficient and bonding strength of the resulting resin layer. In the present disclosure, the term "non-volatile content" refers to components other than components (such as solvents) that are removed when composition B becomes a cured product.

[0201] (Organic Solvent) Composition B may contain an organic solvent. The organic solvent is not particularly limited as long as it can dissolve compound (X). Examples thereof include aprotic solvents, phenol-based solvents, ether-based solvents, and glycol-based solvents. The organic solvent may be used alone or in combination of two or more.

[0202] Specific examples of the aprotic solvent include amide solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, 1,3-dimethylimidazolidinone, and tetramethylurea; lactone solvents such as γ-butyrolactone and γ-valerolactone; phosphorus-containing amide solvents such as hexamethylphosphoric amide and hexamethylphosphine triamide; sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide, and sulfolane; ketone solvents such as cyclohexanone and methylcyclohexanone; tertiary amine solvents such as picoline and pyridine; and ester solvents such as 2-methoxy-1-methylethyl acetate. Specific examples of phenol-based solvents include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, etc. Specific examples of ether-based solvents and glycol-based solvents include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, 1,4-dioxane, etc.

[0203] The boiling point of the organic solvent at normal pressure is preferably 60°C to 300°C, more preferably 140°C to 280°C, and even more preferably 170°C to 270°C. If the boiling point of the solvent is 300°C or lower, the organic solvent can be easily volatilized and removed in the resin layer formation step. If the boiling point of the solvent is 60°C or higher, a resin layer with a uniform surface condition can be obtained.

[0204] When composition B contains an organic solvent, the content thereof is not particularly limited, and may be, for example, 1.0% by mass or more and 99.99896% by mass or less, or 40% by mass or more and 99.99896% by mass or less, relative to the entire composition B.

[0205] (Other Components) Composition B may contain components other than those described above, as necessary. For example, when selectivity in plasma etching resistance is required for Composition B (for example, when used as a gap fill material or a buried insulating film), it may contain a metal alkoxide represented by the following general formula (I): R1nM(OR2)m-n... (I) (In the formula, R1 is a non-hydrolyzable group; R2 is an alkyl group having 1 to 6 carbon atoms; M is at least one metal atom selected from the group consisting of Ti, Al, Zr, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La, Nd, and In; m is the valence of metal atom M and is 3 or 4; n is an integer from 0 to 2 when m is 4, and 0 or 1 when m is 3; when there are multiple R1s, each R1 may be the same as or different from another; and when there are multiple OR2s, each OR2 may be the same as or different from another.)

[0206] In cases where insulating properties are required for the film produced from composition B (for example, for use as an insulating film for a through-silicon via or as a buried insulating film), a silane compound (excluding those corresponding to the silane coupling agent (A)) may be contained to improve insulating properties or mechanical strength. Specific examples of the silane compound include tetraethoxysilane, tetramethoxysilane, bistriethoxysilylethane, bistriethoxysilylmethane, bis(methyldiethoxysilyl)ethane, 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahydroxylcyclosiloxane, 1,1,4,4-tetramethyl-1,4-diethoxydisilethylene, and 1,3,5-trimethyl-1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane.

[0207] Composition B may contain benzotriazole or a derivative thereof, for example to inhibit copper corrosion.

[0208] The pH of Composition B is not particularly limited, but is preferably 2.0 or more and 12.0 or less. The sodium and potassium contents of Composition B are preferably 10 mass ppb or less on an elemental basis. When the sodium or potassium contents are 10 mass ppb or less on an elemental basis, the occurrence of problems in the electrical characteristics of the semiconductor device, such as transistor malfunctions, can be suppressed.

[0209] In composition B, the content of inorganic or resin fillers having a maximum diameter of 0.3 μm or more is preferably 30% by mass or less, more preferably 10% by mass or less, and even more preferably 0% by mass, of the total non-volatile content. When the content of the filler contained in composition B is within the above range, poor bonding of the laminate can be suppressed even when the thickness of the resin layer formed using composition B is reduced. Furthermore, when a first substrate on which a resin layer has been formed is laminated on a second substrate, alignment marks formed on each substrate may be recognized by a machine to perform alignment. When the content of the filler is within the above range, the transparency of the resin film is improved, enabling more accurate alignment.

[0210] The present disclosure will be specifically described below using examples, but the present disclosure is not limited to the following examples. In the following, ultrapure water (Milli-Q water manufactured by Millipore, resistivity 18 MΩ cm (25°C) or less) was used as "water."

[0211] Example 1 Preparation of Solution Containing Resin Layer-Forming Material A solution containing a resin layer-forming material was prepared. Details are as follows. As the resin layer-forming material, 50% by mass of 3-aminopropyldiethoxymethylsilane (3APDES) and 50% by mass of water were blended to obtain Solution A containing a hydrolyzate of 3APDES. Solution B was obtained to obtain 70% by mass of oxydiphthalic acid half ester (Y in formula (B-2) is O and R is an ethyl group) and 30% by mass of ethanol. 24 g of Solution A, 18 g of Solution B, 20 g of 1-propanol, and 38 g of water were blended to prepare a solution containing a resin layer-forming material.

[0212] <Preparation of First Laminate> A silicon wafer serving as a first substrate was placed on a spin coater. 2.0 mL of the solution containing the resin layer-forming material was dripped onto the silicon wafer at a constant speed for 10 seconds. After holding the wafer for 23 seconds, the wafer was rotated at 2000 rpm (rpm: rotations per minute) for 1 second, 600 rpm for 30 seconds, and then 2000 rpm for 10 seconds to dry the wafer. This applied the resin layer-forming material to the first substrate. The first substrate to which the resin layer-forming material had been applied was heated at 200°C for 1 hour under a nitrogen atmosphere. This resulted in a resin layer (1 μm thick) containing siloxane bonds and imide bonds being formed on the first substrate, yielding a first laminate. Here, the resin layer contained the following structure containing siloxane bonds and imide bonds:

[0213]

[0214] <Preparation of Second Substrate> The second substrate is a substrate body that is a silicon wafer and an SiO 2 layer having a thickness of 0.1 nm to 10 nm as an inorganic layer formed on the substrate body. ２ A second substrate was provided, comprising a layer.

[0215] <Surface Activation Treatment of Resin Layer in First Laminate> The resin layer in the first laminate obtained above was subjected to O 2 as a surface activation treatment using a plasma treatment device (PL12 manufactured by SUSS). ２ The plasma treatment was carried out. Specifically, the first laminate was fixed to a metal holder and set in a load lock chamber of a plasma treatment apparatus. The load lock chamber was evacuated to a vacuum level of 1.0×10 －３ The first laminate was transferred from the load lock chamber into the plasma processing chamber. The plasma processing chamber was evacuated to a vacuum of 2.0×10 －４ Oxygen gas was introduced into the plasma treatment chamber to adjust the pressure in the plasma treatment chamber. Next, RF power was applied to irradiate the surface of the resin layer of the first laminate with oxygen gas plasma (i.e., O ２ plasma) as a surface activation treatment. ２The plasma treatment chamber was then evacuated, and the plasma-treated first laminate was transferred to a load lock chamber. The load lock chamber was vented with oxygen gas and opened to the atmosphere, and the plasma-treated first laminate was removed from the load lock chamber.

[0216] - Processing conditions for surface activation treatment - Material gas: O ２ Gas flow rate: 35 sccm Processing pressure: 46.7 Pa RF power: 100 W (reverse sputtering mode: applied to the sample holder) Processing time: 60 seconds

[0217] <SiO in the second substrate ２ Surface activation treatment for the SiO layer on the second substrate ２ The layer was subjected to a surface activation treatment under the same conditions as those for the resin layer in the first laminate.

[0218] <Production of Substrate Laminate (Bonding of First Laminate and Second Substrate)> After the surface activation treatment, the resin layer of the first laminate was washed with water at 25° C. for 30 seconds. Next, the first laminate and the second substrate (i.e., the aforementioned SiO ２ a silicon wafer with a resin layer in the first laminate and a silicon wafer with a SiO ２ The layers were bonded together at room temperature (25° C.) with the layers facing each other to obtain a substrate laminate. The bonding conditions were that the layers were pressed at 0.2 MPa for 1 second in the atmosphere at room temperature.

[0219] <Measurements and Evaluations> The substrate laminate was subjected to the following measurements and evaluations.

[0220] (EDX composition analysis) Using a focused ion beam (FIB), a thin film sample for cross-sectional observation of the resin layer was cut out from the substrate laminate. EDX composition analysis was performed on the cross section of the resin layer in the cut-out thin film sample using a FIB / TEM (Talos F200X manufactured by FEI) at a magnification of 8600 times and an acceleration voltage of 200 kV.

[0221] The EDX composition analysis was used to determine the ratios (atomic %) shown in Table 1. The position where the Si ratio was maximum and the position where the O ratio was maximum were the same. The position where the Si ratio was minimum and the position where the O ratio was minimum were the same.

[0222] In Example 1, the change in the abundance ratio of Si atoms in the thickness direction of the resin layer and the change in the abundance ratio of O atoms in the thickness direction of the resin layer were both continuous changes.

[0223] (Composite Elastic Modulus of Resin Layer) For the resin layer in the substrate laminate, 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 under the condition of a test depth of 20 nm, and the composite elastic modulus at 23°C was calculated from the maximum load and maximum displacement according to the calculation method in a reference document (Handbook of Micro / nano Tribology (second edition), edited by Bharat Bhushan, CRC Press). Here, the composite elastic modulus is defined by the following formula (1): In formula (1), Er represents the composite elastic modulus, Ei represents the Young's modulus of the indenter, which is 1140 GPa, νi represents the Poisson's ratio of the indenter, which is 0.07, and Es and νs represent the Young's modulus and Poisson's ratio of the resin layer, respectively.

[0224]

[0225] (Bonding Strength at Room Temperature) For the substrate laminate obtained above, the bonding strength between the first substrate and the second substrate was determined at room temperature (25°C). The bonding strength at room temperature (25°C) is an example of the bonding strength at low temperature in the present disclosure. The results are shown in Table 1. Here, the bonding strength at room temperature was determined by a blade insertion test according to the method of M.P. Maszara, G. Goetz, A. Cavigila, and J.B.M. McKitterick, Journal of Applied Physics, 64 (1988) 4943-4950. Specifically, the bonding strength at the bonding interface between the first laminate and the second substrate in the substrate laminate (i.e., the interface between the resin layer in the first laminate and the SiO ２ A blade having a thickness of 0.1 mm to 0.3 mm was inserted into the bonded interface between the first laminate and the second substrate at room temperature (25°C), and the distance from the blade tip to the position where the first laminate and the second substrate peeled off was measured using an infrared light source and an infrared camera. Based on the obtained distance, the surface energy was calculated according to the following formula. The obtained surface energy was taken as the bond strength. γ=3×10 ９ ×t ｂ ２ ×E ２ ×t ６ / (32 x L ４ ×E×t ３ ) where γ is the surface energy (J / m ２ ), t ｂ is the blade thickness (m), E is the Young's modulus (GPa) of the silicon substrate included in the first laminate and the second substrate, t is the thickness (m) of the first laminate and the second substrate, and L is the distance from the blade tip to the position where the first laminate and the second substrate are peeled off.

[0226] Comparative Example 1 The same procedure as in Example 1 was carried out except that the surface activation treatment was not carried out. The results are shown in Table 1.

[0227]

[0228] As shown in Table 1, Example 1, in which the Si ratio was 1.5 or more, was superior in bonding strength between the substrates compared to Comparative Example 1, in which the Si ratio was less than 1.5.

[0229] The disclosure of Japanese Patent Application No. 2023-106422, filed on June 28, 2023, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A substrate laminate comprising, in this order: a first substrate; a resin layer containing a resin; and a second substrate, wherein the first substrate and the second substrate are both thicker than the resin layer, the resin contains Si atoms, and when a composition analysis is performed on a cross section of the substrate laminate by energy dispersive X-ray spectroscopy, a Si ratio, which is the maximum value of the abundance ratio of Si atoms in the resin layer divided by the minimum value of the abundance ratio of Si atoms in the resin layer, is 1.5 or more.

2. The substrate laminate according to claim 1, wherein the resin further contains O atoms, and when a composition analysis is performed on a cross section of the substrate laminate by energy dispersive X-ray spectroscopy, an O ratio obtained by dividing the maximum value of the abundance ratio of O atoms in the resin layer by the minimum value of the abundance ratio of O atoms in the resin layer is 1.3 or more.

3. A substrate laminate comprising a first substrate, a resin layer containing a resin, and a second substrate, in this order, wherein the first substrate and the second substrate are both thicker than the resin layer, the resin contains O atoms, and when a composition analysis is performed on a cross section of the substrate laminate by energy dispersive X-ray spectroscopy, an O ratio, which is the maximum abundance ratio of O atoms in the resin layer divided by the minimum abundance ratio of O atoms in the resin layer, is 1.3 or more.

4. The substrate laminate according to claim 2 or 3, wherein, when a composition analysis is performed by energy dispersive X-ray spectroscopy on a cross section of the substrate laminate, the change in the abundance ratio of O atoms in the resin layer in the thickness direction of the resin layer is continuous.

5. A substrate laminate as described in claim 1 or claim 2, wherein, when a composition analysis is performed on a cross section of the substrate laminate by energy dispersive X-ray spectroscopy, the change in the abundance ratio of Si atoms in the resin layer in the thickness direction of the resin layer is continuous.

6. The substrate laminate according to claim 1 or 3, wherein the composite elastic modulus of the resin layer is 1 GPa to 20 GPa.

7. The substrate laminate according to claim 1 or 3, further comprising an electrode penetrating the resin layer between the first substrate and the second substrate.

8. The substrate laminate according to claim 1 or claim 3, wherein each of the first substrate and the second substrate comprises an inorganic substrate body and an inorganic layer.