Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/30—Die-attach connectors
  • H10W72/351—Materials of die-attach connectors
  • H10W72/352—Materials of die-attach connectors comprising metals or metalloids, e.g. solders
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P95/00—Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/30—Die-attach connectors
  • H10W72/331—Shapes of die-attach connectors
  • H10W72/334—Cross-sectional shape, i.e. in side view
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W80/00—Direct bonding of chips, wafers or substrates
  • H10W80/211—Direct bonding of chips, wafers or substrates using auxiliary members, e.g. aids for protecting the bonding area
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W90/00—Package configurations

Definitions

• This disclosure relates to a substrate laminate.
• 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.
• Patent document 1 JP 2012-174937 A
• substrate laminate formed by bonding substrates together there are cases where it is required to further improve the bonding strength between the substrates.
• substrate bonded together means that the substrates are bonded together directly or via another layer.
• An object of one embodiment of the present disclosure is to provide a substrate laminate having excellent bonding strength between substrates.
• a first substrate A resin layer containing a resin; A second substrate; A substrate laminate including, in this order, The first substrate and the second substrate are both thicker than the resin layer,
• the resin contains Si atoms
• a Si ratio which is a 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, is 1.5 or more.
• Substrate stack 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 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, is 1.5 or more.
• the resin further contains an O atom
• an O ratio which is a 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, is 1.3 or more.
• the resin contains O atoms
• an O ratio which is a 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, is 1.3 or more.
• ⁇ 4> The substrate laminate according to any one of ⁇ 1> to ⁇ 3>, wherein, when a composition analysis is performed by energy dispersive X-ray spectroscopy on a cross section of the substrate laminate, a change in the abundance ratio of O atoms in the resin layer in a thickness direction of the resin layer is continuous.
• ⁇ 5> The substrate laminate according to any one of ⁇ 1> to ⁇ 4>, wherein, when a composition analysis is performed by energy dispersive X-ray spectroscopy on a cross section of the substrate laminate, a change in the abundance ratio of Si atoms in the resin layer in a thickness direction of the resin layer is continuous.
• a substrate laminate that has excellent bonding strength between the substrates.
• FIG. 1 is a schematic cross-sectional view conceptually illustrating an example of a substrate laminate according to the present disclosure.
• a numerical range expressed using “to” means a range that includes the numerical values before and after "to” as the lower and upper limits.
• 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.
• the upper or lower limit value of the numerical range may be replaced with a value shown in the examples.
• the substrate laminate of the present disclosure (the substrate laminate of the first embodiment and the substrate assembly of the second embodiment) will be described below.
• the substrate laminate according to the first embodiment of the present disclosure includes: A first substrate; A resin layer containing a resin; A second substrate; A substrate laminate including, in this order, The first substrate and the second substrate are both thicker than the resin layer,
• the resin contains Si atoms
• a Si ratio which is a value obtained by dividing the maximum value of the abundance ratio of Si atoms in the resin layer (hereinafter also referred to as "Si ratio") by the minimum value of the abundance ratio of Si atoms in the resin layer (i.e., Si ratio) (i.e., maximum value of Si ratio/minimum value of Si ratio), is 1.5 or more.
• Si ratio which is a value obtained by dividing the maximum value of the abundance ratio of Si atoms in the resin layer (hereinafter also referred to as "Si ratio") by the minimum value of the abundance ratio of Si atoms in the resin layer (i.e., Si ratio) (i.e., maximum value of Si ratio/minimum value of Si ratio)
• Si ratio
• the substrate laminate of the first embodiment has a Si ratio of 1.5 or more, which results in excellent bonding strength between the substrates (more specifically, the bonding strength between the first substrate and the second substrate bonded via the resin layer).
• the substrate laminate of the first embodiment has excellent bonding strength between the substrates (hereinafter also referred to simply as “bonding strength at low temperatures") even when the substrates are bonded at low temperatures (e.g., 140°C or lower) during the manufacturing process.
• the substrate laminate according to the second embodiment of the present disclosure includes: A first substrate; A resin layer containing a resin; A second substrate; A substrate laminate including, in this order, The first substrate and the second substrate are both thicker than the resin layer,
• the resin contains O atoms
• O ratio which is the maximum value of the abundance ratio of O atoms in the resin layer (hereinafter also referred to as "O ratio") divided by the minimum value of the abundance ratio of O atoms in the resin layer (i.e., O ratio) (i.e., maximum value of O ratio/minimum value of O ratio)
• O ratio the maximum value of the abundance ratio of O atoms in the resin layer
• 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, the bonding strength between the first substrate and the second substrate bonded via the resin layer).
• the substrate laminate of the second embodiment has excellent bonding strength between the substrates (hereinafter also referred to simply as “bonding strength at low temperatures”) even when the substrates are bonded to each other at low temperatures (e.g., 140°C or lower) during the manufacturing process.
• the first and second embodiments may have an overlapping portion. 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 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)
• 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.
• the substrate laminate of the first embodiment includes a first substrate, a resin layer having a thickness of 20 ⁇ m 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.
• the substrate stack of the first embodiment includes a first substrate.
• the first substrate is a substrate having a thickness greater than the thickness of the resin layer.
• the material of the first substrate is not particularly limited, and may be any material that is commonly used.
• 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.
• the material of the first substrate include: Semiconductors such as Si, InP, InAs, GaN, GaP, GaAs, InGaAs, InGaAlAs, SiGe, and SiC; Oxides , carbides or nitrides such as borosilicate glass (Pyrex), quartz glass ( SiO2 ) , sapphire ( Al2O3 ) , ZrO2, Si3N4 , AlN, MgAl2O4 ; Piezoelectric or dielectric materials such as BaTiO3 , LiNbO3 , SrTiO3 , LiTaO3 , gadolinium gallium garnet ( Gd3Ga5O12 ), etc.; diamond; Metals such as Al, Ti, Fe, Cu, Ag, Au, Pt, Pd, Ta, Nb; carbon; Resins such as polydimethylsiloxane (PDMS), epoxy resins, phenolic resins, polyimides, benzocycl
• the main applications of the first substrate including each material include the following.
• Si is used in semiconductor memories, LSIs, CMOS image sensors, MEMS, optical devices, LEDs, etc.
• SiO2 is used in MEMS sealing, microchannels, interposers for 2.5D mounting, displays, etc.
• BaTiO3 , LiNbO3 , SrTiO3 , LiTaO3 , and Gd3Ga5O12 are used in surface acoustic wave devices and the like.
• PDMS is used for microchannels and the like.
• InGaAlAs, InGaAs, and InP are used in optical devices and the like.
• InGaAlAs, GaAs, and GaN are used in LEDs and the like.
• the material of the first substrate is, for example: Publicly known literature such as the descriptions in paragraphs 0097 to 0098 of WO 2022/54839; 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; You may also refer to:
• the thickness of the first substrate is not particularly limited as long as it is thicker than the thickness of the resin layer.
• the thickness of the first substrate is, for example, 50 ⁇ m or more, preferably 50 ⁇ m to 10 mm, preferably 100 ⁇ m to 5 mm, and more preferably 200 ⁇ m to 1 mm.
• the first substrate may include an inorganic substrate body and an inorganic layer.
• 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 a SiO2 layer, a SiCN layer, or a SiN layer, and particularly preferably a SiO2 layer.
• the inorganic layer can be formed by a vapor deposition method such as sputtering, CVD, or ALD.
• the inorganic layer may also be formed as a native oxide film (specifically, a SiO2 layer).
• the thickness of the inorganic substrate body is, for example, 50 ⁇ m or more, preferably 50 ⁇ m to 10 mm, preferably 100 ⁇ m to 5 mm, and more preferably 150 ⁇ m to 2 mm.
• the thickness of the inorganic layer is, for example, 1 nm to 10 ⁇ m, preferably 3 nm to 5 ⁇ m, and more preferably 5 nm to 1 ⁇ m.
• the substrate stack of the first embodiment includes a second substrate.
• the second substrate is a substrate having a thickness greater than the thickness of the resin layer.
• the material of the second substrate is not particularly limited, and may be any material that is commonly used. Specific examples and preferred aspects of the second substrate are the same as those of the first substrate.
• the first and second substrates 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.
• the substrate laminate of the present disclosure has excellent bonding strength at low temperatures, and therefore, damage to the first substrate and/or the second substrate can be suppressed by bonding at low temperatures.
• thermally weak substrates such as polyimide, GaAs, glass, LiNbO 3 , InGaAs, and InGaAlAs can be used as the first substrate and/or the second substrate.
• the substrate laminate disclosed herein has excellent bonding strength at low temperatures, making it applicable to optical devices and thermally sensitive devices (e.g., phase change memory).
• the substrate laminate of the first embodiment includes a resin layer that contains a resin.
• the resin layer is disposed between the first substrate and the second substrate.
• the resin layer may have a single-layer structure or a laminate structure made up of a plurality of layers.
• the resin layer may be a layer formed by bonding a plurality of layers.
• the interfaces between the bonded layers may remain clear (i.e., the laminated structure may be maintained), or the interfaces between the bonded layers may be fused and become unclear (for example, a single layer structure may be formed).
• the resin layer has a thickness of 50 ⁇ m or less.
• the thickness of the resin layer is preferably 0.01 ⁇ m to 50 ⁇ m, more preferably 0.02 ⁇ m to 35 ⁇ m, and further preferably 0.03 ⁇ m to 20 ⁇ m.
• the resin contained in the resin layer is a resin containing Si atoms.
• the resin layer may contain only one type of resin, or two or more types of resins. When the resin layer contains two or more kinds of resins, at least one of the resins should contain Si atoms.
• the resin contained in the resin layer is 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.
• the at least one resin contains Si atoms.
• examples of the resin contained in the resin layer include a cured product of composition A described below and a cured product of composition B described below.
• the resin layer can be formed by a coating method (that is, a method in which a coating liquid is applied and then heated) using a coating liquid containing at least one of a resin and a resin precursor (for example, a monomer).
• a coating liquid containing at least one of a resin and a resin precursor (for example, a monomer).
• the coating liquid include composition A and composition B described below.
• the resin contained in the resin layer further contains O atoms, and even more preferable that it contains at least one of a silanol group and a siloxane bond.
• 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.
• the resin layer having at least one bond selected from the group consisting of a siloxane bond, an amide bond, and an imide bond can be formed, for example, using composition A described below or composition B described below.
• the resin layer may contain components other than the resin.
• the resin layer preferably contains a resin as a main component.
• the main component means the component that has the largest content ratio on a mass basis.
• the content of the resin in the entire resin layer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, and still more preferably 90% by mass or more.
• the content of the resin in the entire resin layer may be 100% by mass or less than 100% by mass.
• 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., maximum value of Si ratio/minimum value of Si ratio) is 1.5 or more. This improves the bonding strength between the substrates.
• the Si ratio ie, maximum Si ratio/minimum Si ratio
• the Si ratio is preferably 1.5 to 5.0, more preferably 1.6 to 3.0, and further preferably 1.7 to 2.5.
• the minimum value of the abundance ratio of Si atoms 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 %.
• EDX energy dispersive X-ray spectroscopy
• a specific means for making the Si ratio 1.5 or more is to perform a surface activation treatment on the bonding surface of the resin layer before bonding the first substrate and the second substrate together via the resin layer during the manufacturing stage of the substrate laminate.
• the surface activation treatment is applied to the bonding surface of the resin layer, the abundance ratio of Si atoms in the vicinity of the surface activation treatment (specifically, the vicinity in the thickness direction of the resin layer) can be increased. This makes it possible to obtain a location where the abundance ratio of Si atoms shows a maximum value and a location where the abundance ratio shows a minimum value, and as a result, it is easy to achieve a Si ratio of 1.5 or more.
• the abundance ratio of carbon (C) in the vicinity of the surface that has been subjected to the surface activation treatment can be reduced, and as a result, the abundance ratio of Si in the above vicinity can be increased.
• 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 that is attached to the resin layer.
• the bonding surface of the resin layer examples include: A surface of the resin layer that is bonded to the first substrate or the second substrate (hereinafter, also simply referred to as the substrate); a surface to be bonded to a resin layer or an inorganic layer provided on a substrate; etc.
• the "bonding surface of the resin layer” is the bonding surface of the resin layer that is bonded to the second substrate.
• the "bonding surface of the resin layer A" is the bonding surface of the resin layer A with the resin layer B.
• Surface activation treatments applied to the bonding surfaces of the resin layers include treatment with chemical solutions, silicon impregnation, plasma treatment, fast atom beam irradiation, and ozone treatment.
• Examples of silicon impregnation treatment include applying a liquid containing a silane coupling agent.
• the plasma treatment is, for example, at least one selected from the group consisting of oxygen plasma treatment and nitrogen plasma treatment.
• the gas flow rate of 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.
• the treatment pressure in the plasma treatment is preferably 10 Pa to 100 Pa, and more preferably 20 Pa to 80 Pa.
• the RF power in the plasma treatment is preferably 10W to 200W, more preferably 20W to 150W.
• the treatment time for plasma treatment is preferably 10 to 200 seconds, and more preferably 20 to 100 seconds.
• the surface of the resin layer after the surface activation treatment may be washed with water.
• the content 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.
• 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 nm of the resin layer thickness is 1 atomic % or less.
• One way to achieve "continuous change in the ratio of Si atoms present in the resin layer in the thickness direction of the resin layer" is to subject the bonding surfaces of the resin layers to the aforementioned plasma treatment.
• 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
• the O ratio (maximum value/minimum value) is preferably 1.3 to 5.0, more preferably 1.4 to 3.0, and further preferably 1.5 to 2.0.
• 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 %.
• 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 "continuously” in the change in the abundance ratio of O atoms is the same as the meaning of "continuously” in the change in the abundance ratio of Si atoms.
• One way to achieve "continuous change in the ratio of O atoms in the resin layer in the thickness direction of the resin layer" is to subject the bonding surfaces of the resin layers to the aforementioned plasma treatment.
• the resin in the resin layer naturally contains C (carbon) atoms.
• the C value at the position where Si shows a maximum value is preferably 20 atomic % to 55 atomic %, and more preferably 30 atomic % to 55 atomic %.
• the C value at the position where the Si content is at a minimum is preferably 40 atomic % to 90 atomic %, and more preferably 50 atomic % to 80 atomic %.
• the C value at the position where O shows a maximum value is preferably 20 atomic % to 55 atomic %, and more preferably 30 atomic % to 55 atomic %.
• the C value at the position where O shows a minimum value is preferably 40 atomic % to 90 atomic %, and more preferably 50 atomic % to 80 atomic %.
• 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.
• the method for measuring the composite elastic modulus can be seen in the Examples described later.
• the bonding strength between the first substrate and the second substrate expressed in terms of surface energy, is preferably 0.2 J/ m2 or more, more preferably 1.0 J/ m2 or more, and even more preferably 2.0 J/ m2 or more.
• the surface energy can be determined by the blade insertion test described below.
• voids are unlikely to occur at the bonding surface between the resin layer and the substrate 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 was 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.
• the measurement can be performed in a similar manner 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.
• the substrate laminate of the first embodiment may further include an electrode penetrating the resin layer between the first substrate and the second substrate.
• the first substrate and the second substrate can be electrically connected by this electrode.
• the electrode may be an electrode containing at least one metal selected from the group consisting of Cu, gold, and tin.
• FIG. 1 is a schematic cross-sectional view conceptually showing an example of a substrate laminate including an electrode.
• the substrate laminate 100 of 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 that penetrates the resin layer 31 between the first substrate 11 and the second substrate 21.
• the first substrate 11 and the second substrate 21 may each include a substrate body (e.g., a Si substrate body) and an inorganic layer (e.g., a SiO2 layer).
• a substrate body e.g., a Si substrate body
• an inorganic layer e.g., a SiO2 layer
• an inorganic layer may be disposed at least on one side between the substrate body and the resin layer 31.
• the resin layer 31 and the electrode 32 may each be formed by laminating a plurality of layers.
• the structure of the resin layer 31 and the electrode 32 may each be a laminated 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 a plurality of layers can be manufactured by hybrid bonding.
• hybrid bonding refers to a type of bonding in which the electrodes are bonded to each other and the insulating layers are bonded to each other by bringing the two exposed surfaces of the electrodes and the insulating layers into contact with each other.
• Hybrid junctions are advantageous in that they allow for narrower wiring pitches.
• the substrate laminate of the second embodiment has the characteristic of an O ratio of 1.3 or more in the first embodiment, and may or may not have the characteristic of a Si ratio of 1.5 or more in the first embodiment, but is similar to the substrate laminate of the first embodiment and has the same preferred aspects.
• composition A and composition B which are specific examples of compositions (e.g., coating liquids) for forming a resin layer in the present disclosure, will be described below.
• compositions for forming the resin layer for example, known documents such as International Publication No. 2018/199117, International Publication No. 2022/054839, and JP-A-2021-182621 may be referred to.
• X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
• composition A contains compound (A) and compound (B), and thus can form a resin layer (i.e., the resin layer in this disclosure; the same applies below) of uniform thickness, and also has excellent bonding strength between substrates. Furthermore, since the bonding strength between substrates is excellent even when the resin layer is thin, this is advantageous when forming a multi-layer three-dimensional structure while achieving miniaturization.
• the resin layer can be thin, the solvent can be easily volatilized when manufacturing the substrate laminate, and the occurrence of voids is suppressed. Furthermore, since the occurrence of voids is suppressed, the adhesion area is less likely to become small, and unintended peeling of the substrates can be suppressed.
• 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 or more and 10,000 or less.
• 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.
• compound (A) may contain a tertiary nitrogen atom in addition to the primary and secondary nitrogen atoms.
• a "primary nitrogen atom” refers to a nitrogen atom bonded to only two hydrogen atoms and one atom other than a hydrogen atom (for example, a nitrogen atom contained in a primary amino group ( -NH2 group)), or a nitrogen atom bonded to only three hydrogen atoms and one atom other than a hydrogen atom (cation).
• the term “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 the following formula (a)), or a nitrogen atom (cation) bonded to only two hydrogen atoms and two atoms other than hydrogen atoms.
• 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 the following formula (b)), or a nitrogen atom (cation) bonded to one hydrogen atom and only three atoms other than hydrogen atoms.
• the functional group represented by the formula (a) may be a functional group constituting a part of a secondary amino group (-NHR a group; here, R a represents an alkyl group), or may be a divalent linking group contained in the skeleton of a polymer.
• the functional group represented by formula (b) may be a functional group constituting a part of a tertiary amino group (-NR b R c group; here, R b and R c each independently represent an alkyl group), or may be a trivalent linking group contained in the skeleton of a polymer.
• the weight average molecular weight of 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.
• the weight average molecular weight refers to a weight average molecular weight calculated as polyethylene glycol, measured by GPC (Gel Permeation Chromatography). Specifically, the weight average molecular weight is calculated by detecting the refractive index at a flow rate of 1.0 mL/min using an aqueous solution of sodium nitrate having a concentration of 0.1 mol/L as a developing solvent, a Shodex DET RI-101 analyzer, and two types of analytical columns (TSKgel G6000PWXL-CP and TSKgel G3000PWXL-CP, manufactured by Tosoh Corporation), and using polyethylene glycol/polyethylene oxide as standards with analytical software (Empower3, manufactured by Waters Corporation).
• GPC Gel Permeation Chromatography
• the 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 accepting group or a hydrogen bond donating group.
• Examples of the nonionic functional group include a hydroxyl group, a carbonyl group, and an ether group (-O-).
• 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.
• Examples of the compound (A) include siloxane diamines, silane coupling agents having an amino group, and siloxane polymers of silane coupling agents having an amino group.
• An example of the silane coupling agent having an amino group is a compound represented by the following formula (A-3).
• R 1 represents an alkyl group having 1 to 4 carbon atoms which may be substituted.
• R 2 and R 3 each independently represent 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.).
• R 4 and R 5 each independently represent 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.
• 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 (the skeleton may contain a carbonyl group, an ether group, etc.).
• a plurality of R 1 , R 2 , R 3 , R 4 , R 5 , and X 1 may be the same or different.
• Substituents of the alkyl and alkylene groups in R1 , R2 , R3 , R4 , R5 , X1 and X2 each independently include an amino group, a hydroxy group, an alkoxy group, a cyano group, a carboxylic acid group, a sulfonic acid group and halogens.
• Examples of the divalent or trivalent aromatic ring in Ar include a divalent or trivalent benzene ring.
• Examples of the aryl group in X2 include a phenyl group, a methylbenzyl group, and a vinylbenzyl group.
• silane coupling agents represented by formula (A-3) include, for example, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminoisobutyldimethylmethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, N-(2-aminoethyl)-11-aminoundecyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, (aminoethylaminoethyl)phenyltriethoxysilane, methylbenzylaminoethyla
• 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-methyl-2-phenylpropanedi ...
• silane coupling agents having an amino group may be used alone or in combination of two or more.
• a silane coupling agent having an amino group may also be used in combination with a silane coupling agent not having an amino group.
• a silane coupling agent having a mercapto group may be used to improve adhesion to metals.
• polymers (siloxane polymers) formed from these silane coupling agents via siloxane bonds may be used.
• siloxane polymers formed from these silane coupling agents via siloxane bonds
• Si-O-Si siloxane bonds
• a polymer having a linear siloxane structure a polymer having a branched siloxane structure, a polymer having a cyclic siloxane structure, a polymer having a cage siloxane structure, etc.
• the cage siloxane structure is represented, for example, by the following formula (A-1).
• siloxane diamines examples include compounds represented by the following formula (A-2).
• i is an integer from 0 to 4
• j is an integer from 1 to 3
• Me is a methyl group.
• compound (A) Since compound (A) has a primary or secondary amino group, it can strongly bond the substrates to each other 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 substrate and the second substrate, or by forming a close covalent bond with the functional groups.
• the compound (A) since the compound (A) has a primary or secondary amino group, it is easily dissolved in the polar solvent (D) described below.
• the affinity with the hydrophilic surface of a substrate such as a silicon substrate is increased, so that a smooth film can be easily formed and the thickness of the resin layer can be reduced.
• compound (A) a compound having a 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 to further improve heat resistance.
• the ratio of the total number of primary and secondary nitrogen atoms to the number of silicon atoms in compound (A) is 0.2 or more and 5 or less.
• compound (A) has a molar ratio of Si element to non-crosslinkable group such as methyl group bonded to Si element that satisfies the relationship (non-crosslinkable group)/Si ⁇ 2.
• compound (A) has a cationic functional group containing at least one of a primary nitrogen atom and a secondary 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.
• Compound (A) may also have a cationic functional group that contains a primary nitrogen atom and does not contain any nitrogen atoms other than the primary nitrogen atom (e.g., a secondary nitrogen atom, a tertiary nitrogen atom).
• the ratio of secondary nitrogen atoms to the total 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.
• compound (A) may contain a tertiary nitrogen atom in addition to a primary nitrogen atom and a secondary nitrogen atom.
• the ratio of the tertiary nitrogen atoms to the total 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.
• 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 with respect to the entire resin layer, 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.
• X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
• Compound (B) is a compound having a weight average molecular weight of 200 or more and 600 or less. Preferably, it is a compound having a weight average molecular weight of 200 or more and 400 or less.
• Compound (B) preferably has a ring structure in the molecule.
• 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.
• Examples of the alicyclic structure include alicyclic structures having 3 to 8 carbon atoms, preferably alicyclic structures having 4 to 6 carbon atoms, and the ring structure may be saturated or unsaturated. More specifically, examples of 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.
• saturated alicyclic structures such as a cyclopropane ring, a cyclobutane ring
• the aromatic ring structure is not particularly limited as long as it is a ring structure that exhibits 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.
• 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
• non-benzene-based aromatic rings such as an indene ring and an azulene ring.
• the ring structure that compound (B) has in the molecule is, for example, 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 preferable.
• compound (B) may have multiple 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, etc.
• Compound (B) preferably has a fluorine atom in the molecule, more preferably has 1 to 6 fluorine atoms in the molecule, and even more preferably has 3 to 6 fluorine atoms in the molecule.
• compound (B) may have a fluoroalkyl group in the molecule, and specifically, may have a trifluoroalkyl group or a hexafluoroisopropyl group.
• examples of compound (B) include carboxylic acid compounds such as alicyclic carboxylic acid, benzene carboxylic acid, naphthalene carboxylic acid, diphthalic acid, and fluorinated aromatic ring carboxylic acid; and carboxylic acid ester compounds such as alicyclic carboxylic acid ester, benzene carboxylic acid ester, naphthalene carboxylic acid ester, diphthalic acid ester, and fluorinated aromatic ring carboxylic acid ester.
• carboxylic acid compounds such as alicyclic carboxylic acid, benzene carboxylic acid, naphthalene carboxylic acid, diphthalic acid ester, and fluorinated aromatic ring carboxylic acid ester.
• compound (B) is a carboxylic acid ester compound, aggregation due to association between compound (A) and compound (B) is suppressed, aggregates and pits are reduced, and adjustment of the film thickness is made easier.
• X is preferably a methyl group, an ethyl group, a propyl group, a butyl group, etc., but 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).
• carboxylic acid compound examples include, but are not limited to, alicyclic carboxylic acids such as 1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentane tetracarboxylic acid, 1,3,5-cyclohexane tricarboxylic acid, 1,2,4-cyclohexane tricarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid, and 1,2,3,4,5,6-cyclohexane hexacarboxylic acid; benzene carboxylic acids such as 1,2,4-benzene tricarboxylic acid, 1,3,5-benzene tricarboxylic acid, pyromellitic acid, benzene pentacarboxylic acid, and mellitic acid; and 1,4,5,8-naphthalene tetracarboxylic acid.
• alicyclic carboxylic acids such as 1,2,3,4-cyclobutan
• naphthalene carboxylic acids such as 2,3,6,7-naphthalene tetracarboxylic 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 acid), 4,4'-(1,4-phenylenebis(oxy))diphthalic acid, 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy
• carboxylic acid ester compound examples include compounds in which at least one carboxy group in the specific examples of the carboxylic acid compound described above has been replaced with an ester group.
• carboxylic acid ester compound examples include half-esterified compounds represented by the following general formulas (B-1) to (B-6).
• R is each independently an alkyl group having 1 to 6 carbon atoms, of which methyl, ethyl, propyl, and butyl are preferred, and ethyl and propyl are more preferred.
• a half-esterified compound can be produced, for example, by mixing a carboxylic acid anhydride, which is the anhydride of the aforementioned carboxylic acid compound, with an alcohol solvent and opening the ring of the carboxylic acid anhydride.
• Y represents an imide-bridged or amide-bridged nitrogen atom, OH, or an ester group.
• the resin layer preferably has a thermally crosslinked structure such as amide, amide-imide, or imide, and has excellent heat resistance.
• compound (A) has an uncrosslinked cationic functional group
• the resin layer contains compound (A) but not compound (B)
• the crosslink density is likely to be low and the heat resistance insufficient.
• the cationic functional group of compound (A) reacts with the carboxyl group of compound (B) to form a covalent bond, resulting in a high crosslink density and high heat resistance.
• 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.
• the compound (C) reacts with the compound (A) and the 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 a cured product increases the rigidity of the cured product and reduces the thermal expansion coefficient.
• the compound (C) may be used alone or in combination of two or more kinds.
• a "primary nitrogen atom directly bonded to a ring structure” refers to a primary nitrogen atom (-NH 2 ) that is bonded to a ring structure via a single bond (ie, not via a carbon atom or the like).
• 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 one or more. From the viewpoint of increasing the crosslink density, it is preferable that there are two or more, and a diamine compound having two primary amino groups or a triamine compound having three primary amino groups is more preferable.
• 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.
• the multiple ring structures may be the same or different and may form a condensed ring.
• 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.
• Examples of the ring structure contained in the compound (C) include an alicyclic structure, an aromatic ring (including a heterocyclic ring) structure, and a condensed ring structure thereof.
• the alicyclic structure may be an alicyclic structure having 3 to 8 carbon atoms, preferably 4 to 6 carbon atoms.
• the ring structure may be saturated or unsaturated.
• it may be a saturated alicyclic structure such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, or a cyclooctane ring; or an unsaturated alicyclic structure such as a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, or a cyclooctene ring.
• a saturated alicyclic structure such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, or a cyclooctane ring
• aromatic ring structures include aromatic ring structures having 6 to 20 carbon atoms, preferably 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.
• the heterocyclic structure may be a 3- to 10-membered, preferably a 5- or 6-membered heterocyclic structure.
• heteroatoms contained in the heterocyclic ring include a sulfur atom, a nitrogen atom, and an oxygen atom, and may contain only one or more of these.
• heterocyclic structure examples 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.
• the ring structure that compound (C) has in the molecule is preferably a benzene ring, a cyclohexane ring, or a benzoxazole ring.
• the ring structure in the molecule of compound (C) may have a substituent other than a primary nitrogen atom.
• it may have an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom, etc.
• the weight average molecular weight of compound (C) is not particularly limited. For example, it may be 80 or more and 600 or less, 90 or more and 500 or less, or 100 or more and 450 or less.
• Examples of the compound (C) include alicyclic amines, aromatic ring amines, heterocyclic amines having a nitrogen-containing heterocycle, and amine compounds having both a heterocycle and an aromatic ring.
• Specific examples of the alicyclic amine include cyclohexylamine and dimethylaminocyclohexane.
• aromatic ring 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, diaminoresorcin, dihydroxybenzidine, diaminobenzidine, 1,3,5-triaminophenoxybenzene, 2,2'-dimethylbenzidine, and tris(4-aminophenyl)amine.
• diaminodiphenyl ether xylylenediamine (preferably paraxylylenediamine),
• heterocyclic amines having a nitrogen-containing heterocycle include melamine, ammeline, melam, melem, and tris(4-aminophenyl)amine.
• Specific examples of the amine compound 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)benzoxazole-5-amine.
• the content of compound (C) in composition A is not particularly limited, so long as the proportion of the primary nitrogen atoms contained in compound (A) to the total of the primary nitrogen atoms and secondary nitrogen atoms contained in compound (A) and the primary nitrogen atoms contained in compound (C) is 3 mol % to 95 mol %. From the viewpoint of the balance between the thermal expansion coefficient and the bonding strength, the above ratio is preferably 5 mol % to 75 mol %, more preferably 10 mol % to 50 mol %, and even more preferably 10 mol % to 30 mol %.
• composition A may contain a polar solvent.
• polar solvent refers to a solvent having a relative dielectric constant of 5 or more at room temperature (25° C.).
• the polar solvent may be used alone or in combination of two or more kinds.
• 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-
• composition A contains a polar solvent
• its content 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 total amount of composition A.
• Composition A may contain additives as necessary.
• the 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.
• the type of acid having a carboxy group and a weight average molecular weight of 46 to 195 is not particularly limited, and examples include monocarboxylic acid compounds, dicarboxylic acid compounds, and oxydicarboxylic acid compounds. More specifically, examples include formic acid, acetic acid, malonic acid, oxalic acid, benzoic acid, lactic acid, glycolic acid, glyceric acid, butyric acid, methoxyacetic acid, ethoxyacetic acid, phthalic acid, terephthalic acid, picolinic acid, salicylic acid, and 3,4,5-trihydroxybenzoic acid (excluding those that fall under compound (B)).
• 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, the content is preferably such that the ratio (COOH/N) of the number of carboxy groups of the acid to the total number of primary and secondary nitrogen atoms of 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.
• a nitrogen atom-containing base having a weight-average molecular weight of 17 to 120 causes the carboxy group of compound (B) to form 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 speculated 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).
• the present invention is in no way limited by the above speculation.
• the type of compound having a nitrogen atom and a weight average molecular weight of 17 to 120 is not particularly limited, and examples include monoamine compounds and diamine compounds (excluding compounds (A) and (C)). More specifically, examples include ammonia, ethylamine, ethanolamine, diethylamine, triethylamine, ethylenediamine, N-acetylethylenediamine, N-(2-aminoethyl)ethanolamine, and N-(2-aminoethyl)glycine.
• composition A contains a base having a weight average molecular weight of 17 to 120
• the content 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.
• composition A may contain a metal alkoxide represented by the following general formula (I).
• R1 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 each other, and when there are multiple OR2s, each OR2 may
• a silane compound (excluding those corresponding to compound (A)) may be contained in order to improve the insulating properties or mechanical strength.
• silane compound examples 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).
• silane coupling agents having a functional group other than an amino group (such as an epoxy group or a mercapto group).
• Composition A may contain a solvent other than a polar solvent.
• solvent other than a polar solvent include normal hexane.
• Composition A may contain benzotriazole or a derivative thereof, for example to inhibit copper corrosion.
• the pH of composition A is not particularly limited, but is preferably from 2.0 to 12.0. When the pH of composition A is 2.0 or more and 12.0 or less, damage to the substrate caused by composition A is suppressed.
• the sodium and potassium contents of Composition A are preferably 10 ppb by mass or less on an elemental basis, respectively. If the sodium or potassium contents are 10 ppb by mass or less on an elemental basis, respectively, the occurrence of problems in the electrical characteristics of the semiconductor device, such as transistor malfunctions, can be suppressed.
• non-volatile components refers to components other than components (solvent, etc.) that are removed when composition A becomes a cured product.
• 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 5,000, and a compound (X2) having a structure represented by the following general formula (2) and a molecular weight of 400 to 5,000:
• R1 and R3 each independently represent an organic group having 6 or less carbon atoms
• R2 represents a methylene group, an ethylene group, a propylene group, or a phenylene group
• a represents 2 or 3
• b represents the number 3-a
• X1 represents a structure derived from a carboxylic acid dianhydride.
• R1 and R3 each independently represent an organic group having 6 or less carbon atoms
• R2 represents a methylene group, an ethylene group, a propylene group, or a phenylene group
• a represents 2 or 3
• b represents the number 3-a
• X1 represents a structure derived from a carboxylic acid dianhydride
• X2 represents a structure derived from an amine compound
• n represents a positive number.
• composition B described above can form a resin layer with less residual stress than the 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.
• precursors of compound (X1) or compound (X2) such as a silane coupling agent, a carboxylic acid dianhydride, or an amine compound.
• X1 is a structure derived from a carboxylic dianhydride, and preferably contains a ring structure.
• the amide group and the carboxy group bonded to X1 react with each other on the substrate to form an imide bond. Therefore, the resulting resin layer exhibits excellent heat resistance.
• a is preferably 2.
• the organic group having 6 or less carbon atoms represented by R1 and R3 includes an alkyl group having 6 or less carbon atoms, preferably 3 or less carbon atoms, more preferably 2 or less carbon atoms.
• X1 and X2 are structures derived from a carboxylic dianhydride and an amine compound, respectively, and preferably contain a ring structure.
• the amide group and the carboxyl group bonded to X1 react with each other on the substrate to form an imide bond. Therefore, the resulting resin layer exhibits excellent heat resistance.
• a is preferably 2.
• examples of the organic group having 6 or less carbon atoms represented by R1 and R3 include alkyl groups having 6 or less carbon atoms, preferably 3 or less carbon atoms, and more preferably 2 or less carbon atoms.
• n is not particularly limited as long as it is a positive number, and may be, for example, within the range of 1 or more and 6 or less.
• the compound (X2) represented by the 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).
• 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 molecular weight of 200 to 600 and a ring structure.
• the compound (X2) contained in the above composition B may be a compound having a structure obtained by reacting a silane coupling agent (A) with a carboxylic acid dianhydride (B) having a molecular weight of 200 to 600 and a ring structure, and a structure obtained by reacting an amine compound (C) having a ring structure, having a molecular weight of 90 to 600, no Si—O bond, and with a carboxylic acid dianhydride (B) having a ring structure and a molecular weight of 200 to 600.
• 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 a Si-O bond may be referred to simply as the carboxylic acid dianhydride (B) and the amine compound (C), respectively.
• the silane coupling agent (A) is a compound having one or more Si—O bonds in the molecule and reacting with a carboxylic dianhydride to produce the compound (X1) or the compound (X2).
• the Si—O bonds in the silane coupling agent (A) contribute to improving the bonding strength between the resin layer formed by using the composition B and the substrate.
• 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).
• functional groups include amino groups, epoxy groups, and isocyanate groups.
• the silane coupling agent (A) it is preferable for the silane coupling agent (A) to have an amino group, and from the viewpoint of forming an imide structure in the resin layer to improve heat resistance, a compound having a primary amino group (-NH2) is more preferable.
• the silane coupling agent (A) may be used alone or in combination of two or more.
• the molecular weight of the silane coupling agent (A) is not particularly limited. For example, it may be 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.
• silane coupling agent (A) having an amino group is a compound represented by the following formula (A-3).
• R 1 represents an alkyl group having 1 to 4 carbon atoms which may be substituted.
• R 2 and R 3 each independently represent 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.).
• R 4 and R 5 each independently represent 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 (the skeleton may contain a carbonyl group, an ether group, etc.).
• Multiple R 1 , R 2 , R 3 , R 4 , R 5 , and X 1 may be the same or different.
• Substituents of the alkyl and alkylene groups in R1 , R2 , R3 , R4 , R5 , X1 and X2 each independently include an amino group, a hydroxy group, an alkoxy group, a cyano group, a carboxylic acid group, a sulfonic acid group and halogens.
• Examples of the divalent or trivalent aromatic ring in Ar include a divalent or trivalent benzene ring.
• Examples of the aryl group in X2 include a phenyl group, a methylbenzyl group, and a vinylbenzyl group.
• silane coupling agents represented by formula (A-3) include, for example, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminoisobutyldimethylmethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, N-(2-aminoethyl)-11-aminoundecyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, (aminoethylaminoethyl)phenyltriethoxysilane, methylbenzylaminoethyla
• 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-methyl-2-phenylpropanedi ...
• the silane coupling agent (A) having an amino group may be used alone or in combination of two or more.
• 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.
• the carboxylic acid dianhydride (B) may be used alone or in combination of two or more kinds.
• the ring structure that the carboxylic acid dianhydride (B) has in the molecule may be an alicyclic structure, an aromatic ring (including a heterocyclic ring), or the like.
• the carboxylic acid dianhydride (B) may have one ring structure or multiple ring structures in the molecule.
• Examples of the alicyclic structure include alicyclic structures having 3 to 8 carbon atoms, preferably alicyclic structures having 4 to 6 carbon atoms, and the ring structure may be saturated or unsaturated. More specifically, examples of 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.
• saturated alicyclic structures such as a cyclopropane ring, a cyclobutane ring
• the aromatic ring structure is not particularly limited as long as it is a ring structure that exhibits 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.
• 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
• non-benzene-based aromatic rings such as an indene ring and an azulene ring.
• the ring structure that the carboxylic acid dianhydride (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 preferable. Furthermore, from the viewpoint of suppressing the occurrence of voids in the resin layer when a resin layer is formed between multiple substrates using composition B, it is preferable that the resin layer contains two or more benzene rings.
• the multiple ring structures may be the same or different and may form a condensed ring.
• 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.
• 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 it may have 3 to 6 fluorine atoms in the molecule.
• carboxylic acid dianhydride (B) may have a fluoroalkyl group in the molecule, specifically, it may have a trifluoroalkyl group or a hexafluoroisopropyl group.
• Examples of the carboxylic acid dianhydride (B) include dianhydrides of compounds having a ring structure in the molecule and four carboxy groups capable of forming an anhydride group.
• 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
• the content of carboxylic dianhydride (B) in 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 dianhydride (B) to the anhydride group equivalent number B of the carboxylic dianhydride (B) is 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.
• composition B further contains a compound capable of reacting with the anhydride group of the carboxylic dianhydride (B), such as compound (C) described below
• the ratio (A'/B') of the functional group equivalent number A' of all compounds capable of reacting with the anhydride group of the carboxylic dianhydride (B) to the anhydride group equivalent number B' of the carboxylic dianhydride (B) is preferably an amount that is 0.9 or more and 1.1 or less, more preferably an amount that is 0.95 or more and 1.05 or less, and even more preferably an amount that is 0.98 or more and 1.02 or less.
• 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.
• the amine compound (C) may be used alone or in combination of two or more kinds.
• the number of amino groups in the molecule of the amine compound (C) 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 is more than one, and more preferably two (diamine) or three (triamine). From the viewpoint of forming an imide structure in the resin layer to improve heat resistance, it is more preferable that the amine compound (C) has a primary amino group (-NH 2 ).
• the amine compound (C) has one or more amino groups directly bonded to the ring structure. If the molecular structure of the compound (X2) contains a structure derived from an amino group directly bonded to the ring structure, it is believed that the rigidity of the molecular structure increases, further reducing the thermal expansion coefficient.
• an amino group directly bonded to a ring structure means an amino group that is bonded to a ring structure via a single bond (i.e., not via a carbon atom, etc.).
• the amine compound (C) may have one ring structure or multiple ring structures in the molecule.
• the multiple ring structures may be the same or different and may form a condensed ring.
• 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.
• Examples of the ring structure contained in the amine compound (C) include an alicyclic structure, an aromatic ring (including a heterocyclic ring) structure, and a condensed ring structure thereof.
• the alicyclic structure may be an alicyclic structure having 3 to 8 carbon atoms, preferably 4 to 6 carbon atoms.
• the ring structure may be saturated or unsaturated.
• it may be a saturated alicyclic structure such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, or a cyclooctane ring; or an unsaturated alicyclic structure such as a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, or a cyclooctene ring.
• a saturated alicyclic structure such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, or a cyclooctane ring
• aromatic ring structures include aromatic ring structures having 6 to 20 carbon atoms, preferably 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.
• the heterocyclic structure may be a 3- to 10-membered, preferably a 5- or 6-membered heterocyclic structure.
• heteroatoms contained in the heterocyclic ring include a sulfur atom, a nitrogen atom, and an oxygen atom, and may contain only one or more of these.
• heterocyclic structure examples 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.
• the ring structure that the amine compound (C) has in its molecule is preferably a benzene ring, a cyclohexane ring, or a benzoxazole ring.
• the ring structure that the amine compound (C) has in its molecule may have a substituent other than an amino group.
• it may have an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen atom, etc.
• amine compound (C) examples include the following compounds.
• alicyclic amine examples include cyclohexylamine and dimethylaminocyclohexane.
• aromatic ring amines include diaminodiphenyl ether, xylylene diamine (preferably paraxylylene diamine), diaminobenzene, diaminotoluene, methylene dianiline, dimethyldiaminobiphenyl, bis(trifluoromethyl)diaminobiphenyl (TFDB), diaminobenzophenone, diaminobenzanilide, bis(aminophenyl)fluorene, bis(aminophenoxy)benzene, bis(aminophenoxy)biphenyl, dicarboxydiaminodiphenylmethane, diaminoresorcin, dihydroxybenzidine, diaminobenzidine, 1,3,5-triaminophenoxybenzene, 2,2'-dimethyl
• heterocyclic amines having a nitrogen-containing heterocycle include melamine, ammeline, melam, melem, and tris(4-aminophenyl)amine.
• 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).
• Method for obtaining compound (X1) As a method for obtaining the compound (X1) by reacting the silane coupling agent (A) with the carboxylic dianhydride (B), for example, a method in which the silane coupling agent (A) is gradually added dropwise to the carboxylic dianhydride (B) while adding and stirring the carboxylic dianhydride (B) in a solvent to obtain the compound (X1) can be mentioned.
• Method for obtaining compound (X2) As a method for obtaining the compound (X2) by reacting the silane coupling agent (A), the carboxylic dianhydride (B) and the amine compound (C), for example, a method can be mentioned in which a solvent is added to the amine compound (C) and the mixture is stirred while the carboxylic dianhydride (B) is added, the mixture is stirred until the viscosity of the obtained reaction product (polymer) becomes constant, and then the silane coupling agent (A) is gradually added dropwise to obtain the compound (X2).
• composition B may further contain a compound other than compound (X1) and compound (X2).
• a precursor of resin (D) having a CTE of 90 ppm/K or less between 50° C. and 150° C.
• composition B contains a precursor of resin (D)
• the thermal expansion coefficient of the resulting resin layer tends to be further reduced.
• 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.
• composition B contains resin (D)
• the proportion of resin (D) contained in composition B is preferably 99% 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.
• non-volatile content refers to components other than components (solvent, etc.) that are removed when composition B becomes a cured product.
• 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 of the organic solvent 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 kinds.
• aprotic solvents include amide-based solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, 1,3-dimethylimidazolidinone, and tetramethylurea; lactone-based solvents such as ⁇ -butyrolactone and ⁇ -valerolactone; phosphorus-containing amide-based solvents such as hexamethylphosphoric amide and hexamethylphosphine triamide; sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide, and sulfolane; ketone-based solvents such as cyclohexanone and methylcyclohexanone; tertiary amine-based solvents such as picoline and pyridine; and ester-based solvents such as 2-methoxy-1-methylethyl acetate.
• phenol-based solvent examples include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol.
• 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, and 1,4-dioxane.
• 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 process. If the boiling point of the solvent is 60°C or higher, a resin layer with a uniform surface condition can be obtained.
• composition B contains an organic solvent
• its content 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, based on the total amount of composition B.
• composition B may contain components other than those described above, if necessary.
• the composition B 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 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.)
• a silane compound (excluding those corresponding to the silane coupling agent (A)) may be contained in order to improve the insulation properties or mechanical strength.
• silane compound examples 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.
• Composition B may contain benzotriazole or a derivative thereof, for example to inhibit copper corrosion.
• composition B is not particularly limited, but is preferably from 2.0 to 12.0.
• the sodium and potassium contents of Composition B are preferably 10 ppb by mass or less on an elemental basis, respectively. If the sodium or potassium contents are 10 ppb by mass or less on an elemental basis, respectively, the occurrence of problems in the electrical characteristics of the semiconductor device, such as transistor malfunctions, can be suppressed.
• the content of inorganic or resin fillers having a maximum diameter of 0.3 ⁇ m or more is preferably 30 mass % or less of the total nonvolatile content, more preferably 10 mass % or less, and even more preferably 0 mass %.
• 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.
• alignment may be performed by mechanically recognizing alignment marks formed on each substrate, and when the content of the filler is within the above range, the transparency of the resin film is improved, enabling more accurate alignment.
• Example 1 Preparation of solution containing resin layer forming material> A solution containing a resin layer forming material was prepared. The details are as follows: As a resin layer forming material, 50% by mass of 3-aminopropyldiethoxymethylsilane (3APDES) and 50% by mass of water were mixed to obtain a solution A containing a hydrolysate of 3APDES. A solution B containing 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 was obtained. 24 g of solution A, 18 g of solution B, 20 g of 1-propanol, and 38 g of water were mixed together to prepare a solution containing a resin layer forming material.
• 3APDES 3-aminopropyldiethoxymethylsilane
• water 50% by mass of water were mixed to obtain a solution A containing a hydrolysate of 3APDES.
• a silicon wafer as a first substrate was placed on a spin coater, and 2.0 mL of the solution containing the resin layer forming material was dropped onto the silicon wafer at a constant speed for 10 seconds, and after holding for 23 seconds, the wafer was rotated at 2000 rpm (rpm is the rotation speed per minute) for 1 second, at 600 rpm for 30 seconds, and then rotated at 2000 rpm for 10 seconds to dry the wafer.
• the first substrate to which the resin layer-forming material was applied was heated in a nitrogen atmosphere at 200° C. for 1 hour.
• the resin layer contains the following structure including a siloxane bond and an imide bond.
• a second substrate including a substrate body which is a silicon wafer and a SiO 2 layer having a thickness of 0.1 nm to 10 nm formed on the substrate body as an inorganic layer was prepared.
• the resin layer in the first laminate obtained above was subjected to O2 plasma treatment as a surface activation treatment using a plasma treatment device (SUSS PL12).
• the first laminate was fixed to a metal holder and set in a load lock chamber of a plasma processing apparatus.
• the load lock chamber was evacuated to a vacuum level of 1.0 ⁇ 10 ⁇ 3 Pa or less.
• the first laminate was transferred from the load lock chamber to a plasma processing chamber.
• the plasma processing chamber was evacuated to a vacuum level of 2.0 ⁇ 10 ⁇ 4 Pa or less.
• Oxygen gas was introduced into the plasma processing chamber to adjust the pressure in the plasma processing chamber.
• RF power was applied to expose the surface of the resin layer in the first laminate to oxygen gas plasma (i.e., O2 plasma) under the following treatment conditions, thereby performing O2 plasma treatment as a surface activation treatment.
• O2 plasma oxygen gas plasma
• the plasma processing chamber was evacuated to a vacuum, and the first laminate after the plasma processing was carried out into a load lock chamber.
• the load lock chamber was vented with oxygen gas, and opened to the atmosphere, and the first laminate after the plasma processing was taken out from the load lock chamber.
• ⁇ Surface activation treatment for SiO2 layer on second substrate> The SiO2 layer in the second substrate was subjected to a surface activation treatment under the same conditions as the surface activation treatment performed on the resin layer in the first laminate.
• EDX composition analysis A thin sample for observing a cross section of the resin layer was cut out from the substrate laminate using a focused ion beam (FIB). The cross section of the resin layer in the cut-out thin sample was subjected to EDX composition analysis using a FIB/TEM (Talos F200X manufactured by FEI) at a magnification of 8600 times and an acceleration voltage of 200 kV.
• FIB/TEM Telelos F200X manufactured by FEI
• the ratios (atomic %) shown in Table 1 were determined by EDX composition analysis. The position where the Si ratio exhibits the maximum value and the position where the O ratio exhibits the maximum value were the same position. The position where the Si ratio shows the minimum value and the position where the O ratio shows the minimum value were the same position.
• 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.
• a nanoindenter product name TI-950 Tribo Indenter, manufactured by Hysitron, Berkovich type indenter
• the composite elastic modulus at 23°C was calculated from the maximum load and maximum displacement according to the calculation method in the reference literature (Handbook of Micro/nano Tribology (second Edition), edited by Bharat Bhushan, CRC Press).
• the composite elastic modulus is defined by the following formula (1):
• Er represents the composite elastic modulus
• Ei represents the Young's modulus of the indenter and is 1140 GPa
• ⁇ i represents the Poisson's ratio of the indenter and is 0.07
• Es and ⁇ s represent the Young's modulus and Poisson's ratio of the resin layer, respectively.
• the bonding strength between the first substrate and the second substrate at room temperature 25° C.
• the bonding strength at room temperature 25° C.
• the results are shown in Table 1.
• the bonding strength at room temperature was determined by a blade insertion test according to the method of MP Maszara, G. Goetz, A. Cavigila, and J. B. McKitterick, Journal of Applied Physics, 64 (1988) 4943-4950.
• a blade having a thickness of 0.1 mm to 0.3 mm was inserted at room temperature (25° C.) into the bonding interface between the first laminate and the second substrate in the substrate laminate (i.e., the bonding interface between the resin layer in the first laminate and the SiO2 layer in the second substrate), 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, and the surface energy was calculated based on the obtained distance according to the following formula. The obtained surface energy was determined as the bonding strength.
• ⁇ 3 ⁇ 109 ⁇ tb2 ⁇ E2 ⁇ t6 /(32 ⁇ L4 ⁇ E ⁇ t3 )
• ⁇ represents the surface energy (J/ m2 )
• tb represents the blade thickness (m)
• E represents the Young's modulus (GPa) of the silicon substrate contained in the first laminate and the second substrate
• t represents the thickness (m) of the first laminate and the second substrate
• L represents the distance from the blade tip to the position where the first laminate and the second substrate are peeled off.
• 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.
• Example 1 in which the Si ratio was 1.5 or more, had superior bonding strength between the substrates compared to Comparative Example 1, in which the Si ratio was less than 1.5.

Landscapes

• Laminated Bodies (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=93939079

Family Applications (1)

Country Status (5)

Citations (4)

Family Cites Families (1)

• 2024
  • 2024-06-25 JP JP2025530137A patent/JPWO2025005084A1/ja active Pending
  • 2024-06-25 CN CN202480042424.6A patent/CN121444645A/zh active Pending
  • 2024-06-25 KR KR1020257043257A patent/KR20260016540A/ko active Pending
  • 2024-06-25 WO PCT/JP2024/022999 patent/WO2025005084A1/ja not_active Ceased
  • 2024-06-27 TW TW113124086A patent/TW202501550A/zh unknown

Patent Citations (4)

Also Published As

Similar Documents

Legal Events