Semiconductor device manufacturing method, hybrid bonding insulating film forming material, and semiconductor device

Abstract

This method for manufacturing a semiconductor device involves: preparing a first semiconductor substrate having a first semiconductor substrate body, and a first electrode and a first organic insulating film which are provided on one surface of the first semiconductor substrate body, the first organic insulating film having a surface roughness Ra of 2.0 nm or less; preparing a second semiconductor substrate having a second semiconductor substrate body, and a second electrode and a second organic insulating film which are provided on one surface of the second semiconductor substrate body, the second organic insulating film having a surface roughness Ra of 2.0 nm or less; and performing adhesion of the first organic insulating film and the second organic insulating film at 70C or lower and performing bonding of the first electrode and the second electrode.

Description

[Technical Field]

[0001] The present disclosure relates to a method for manufacturing a semiconductor device, a hybrid bonding insulating film forming material, and a semiconductor device. [Background technology]

[0002] In recent years, three-dimensional packaging of semiconductor chips has been studied to improve the integration degree of LSIs (Large Scale Integrated Circuits). Non-Patent Document 1 discloses an example of three-dimensional packaging of semiconductor chips.

[0003] When three-dimensionally mounting semiconductor chips using C2W (Chip-to-Wafer) bonding, the use of hybrid bonding technology used in W2W (Wafer-to-Wafer) bonding is being considered to achieve fine bonding of the wiring between devices.

[0004] In C2W hybrid bonding, heating during bonding can cause misalignment due to thermal expansion of the substrate, chip, etc. To address this issue, Patent Document 1 discloses an example of technology that can lower the bonding temperature by using a cyclic olefin resin. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2019-204818 [Non-patent literature]

[0006] [Non-Patent Document 1] FC Chen et al., “System on Integrated Chips(SoIC TM) for 3D Heterogeneous Integration”, 2019 IEEE 69th Electronic Components and Technology Conference (ECTC), p.594-599(2019) Summary of the Invention [Problem to be solved by the invention]

[0007] A method of C2W bonding using an organic insulating film and hybrid bonding technology is still in the investigation stage and has not yet been put to practical use. When the cyclic olefin resin described in Patent Document 1 is used, the heat resistance of the resulting organic insulating film is insufficient, and there is a risk of bonding failure occurring at the interface between the substrate and the organic insulating film due to exposure to high temperatures during C2W bonding. On the other hand, as mentioned above, a low bonding temperature is required for the method of C2W bonding using an insulating film and hybrid bonding technology. The present disclosure has been made in consideration of the above-described conventional circumstances, and aims to provide a method for manufacturing a semiconductor device that enables bonding between insulating films under low-temperature conditions, a hybrid bonding insulating film forming material used in this semiconductor device manufacturing method, and a semiconductor device that reduces electrode bonding defects. [Means for solving the problem]

[0008] Specific means for achieving the above object are as follows. <1> a first semiconductor substrate including a first semiconductor substrate body, a first electrode provided on one surface of the first semiconductor substrate body, and a first organic insulating film having a surface roughness Ra of 2.0 nm or less; a second semiconductor substrate including a second semiconductor substrate body, a second electrode provided on one surface of the second semiconductor substrate body, and a second organic insulating film having a surface roughness Ra of 2.0 nm or less; The first organic insulating film and the second organic insulating film are bonded together at a temperature of 70° C. or less; A method for manufacturing a semiconductor device in which the first electrode and the second electrode are bonded together. <2> The thermal expansion coefficients of the first and second organic insulating films are 50 ppm / K or less. <1> 10. A method for manufacturing a semiconductor device according to claim 9. <3> The first organic insulating film and the second organic insulating film are a polyimide film, a polybenzoxazole film, a benzocyclobutene film, a polyamideimide film, an epoxy resin film, an acrylic resin film, or a methacrylic resin film. <1> or <2> 10. A method for manufacturing a semiconductor device according to claim 9. <4> The first semiconductor substrate is a semiconductor wafer, and the second semiconductor substrate is a semiconductor wafer. <1> ~ <3> 10. The method for manufacturing a semiconductor device according to claim 9, wherein the semiconductor device is a semiconductor device. <5> The first semiconductor substrate is a semiconductor wafer, and the second semiconductor substrate is a semiconductor chip. <1> ~ <3> 10. The method for manufacturing a semiconductor device according to claim 9, wherein the semiconductor device is a semiconductor device. <6> The first semiconductor substrate is a semiconductor chip, and the second semiconductor substrate is a semiconductor chip. <1> ~ <3> 10. The method for manufacturing a semiconductor device according to claim 9, wherein the semiconductor device is a semiconductor device. <7> In the manufactured semiconductor device, the total thickness of the organic insulating film formed by bonding the first organic insulating film and the second organic insulating film is 0.1 μm or more. <1> ~ <6> 10. The method for manufacturing a semiconductor device according to claim 9, wherein the semiconductor device is a semiconductor device. <8> Before the first organic insulating film and the second organic insulating film are bonded to each other, at least one of the first surface of the first semiconductor substrate and the second surface of the second semiconductor substrate is polished. <1> ~ <7> 10. The method for manufacturing a semiconductor device according to claim 9, wherein the semiconductor device is a semiconductor device. <9> The polishing comprises chemical mechanical polishing. <8> 10. A method for manufacturing a semiconductor device according to claim 9. <10> The polishing further comprises mechanical polishing. <9> 10. A method for manufacturing a semiconductor device according to claim 9. <11> The height of the first organic insulating film is equal to or greater than the height of the first electrode, and the height of the second organic insulating film is equal to or greater than the height of the second electrode. <1> ~ <10> 10. The method for manufacturing a semiconductor device according to claim 9, wherein the semiconductor device is a semiconductor device. <12> The height of the first organic insulating film is greater than the height of the first electrode by 0.1 nm or more, and the height of the second organic insulating film is greater than the height of the second electrode by 0.1 nm or more. <11> 10. A method for manufacturing a semiconductor device according to claim 9. <13> A hybrid bonding insulating film forming material containing a thermosetting polyamide and a solvent, which has a thermal expansion coefficient of 50 ppm / K or less when cured. <14> The thermosetting polyamide comprises a polybenzoxazole precursor or a polyimide precursor. <13> 2. The hybrid bonding insulating film forming material according to claim 1. <15> The thermosetting polyamide contains a polyimide precursor and further contains a polyimide resin. <13> 2. The hybrid bonding insulating film forming material according to claim 1. <16> a first semiconductor substrate having a first semiconductor substrate body, and a first organic insulating film and a first electrode provided on one surface of the first semiconductor substrate body; a second semiconductor substrate having a second semiconductor substrate body, and a second organic insulating film and a second electrode provided on one surface of the second semiconductor substrate body; the first organic insulating film and the second organic insulating film are bonded together, and the first electrode and the second electrode are bonded together; The semiconductor device has a thermal expansion coefficient of the first organic insulating film and the second organic insulating film of 50 ppm / K or less. [Effects of the Invention]

[0009] According to the present disclosure, it is possible to provide a method for manufacturing a semiconductor device that enables bonding between insulating films under low-temperature conditions, a hybrid bonding insulating film forming material used in this method for manufacturing a semiconductor device, and a semiconductor device that reduces electrode bonding defects. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a cross-sectional view schematically illustrating an example of a semiconductor device manufactured by a method for manufacturing a semiconductor device according to an embodiment. [Figure 2] 2A to 2C are diagrams sequentially showing a method for manufacturing the semiconductor device shown in FIG. [Figure 3] FIG. 3 is a diagram showing in more detail the bonding method in the method for manufacturing the semiconductor device shown in FIG. [Figure 4] 4A to 4C are diagrams showing a method for manufacturing the semiconductor device shown in FIG. 1, sequentially illustrating steps subsequent to the step shown in FIG. [Figure 5] FIG. 5 is a diagram showing an example in which the method for manufacturing a semiconductor device according to an embodiment is applied to Chip-to-Wafer (C2W). DETAILED DESCRIPTION OF THE INVENTION

[0011] The present disclosure will be described in detail below. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0012] In the present disclosure, the term "process" includes not only a process that is independent of other processes, but also a process that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved. In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this 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 the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple substances corresponding to the component. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, the terms "layer" and "film" include cases where the layer or film is formed over the entire area when the area in which the layer or film is present is observed, as well as cases where the layer or film is formed over only a portion of the area. In the present disclosure, "(meth)acrylic" means at least one of acrylic and methacrylic. In the present disclosure, the thickness of a layer or film is determined by measuring the thickness of the layer or film at five points and calculating the arithmetic mean value. The thickness of a layer or film can be measured using a micrometer or the like. In the present disclosure, when the thickness of a layer or film can be measured directly, it is measured using a micrometer. On the other hand, when measuring the thickness of a single layer or the total thickness of multiple layers, it may be measured by observing the cross section of the object to be measured using an electron microscope. In the present disclosure, the thermal expansion coefficient is the rate at which the length of a measurement sample expands due to a rise in temperature, expressed per unit of temperature. The thermal expansion coefficient is a value calculated by measuring the change in length of a measurement sample at temperatures between 30°C and 100°C using a thermomechanical analyzer or the like.

[0013] <Method of manufacturing a semiconductor device and a semiconductor device> The method for manufacturing a semiconductor device disclosed herein includes preparing a first semiconductor substrate having a first semiconductor substrate body, a first electrode provided on one surface of the first semiconductor substrate body, and a first organic insulating film having a surface roughness Ra of 2.0 nm or less; preparing a second semiconductor substrate having a second semiconductor substrate body, a second electrode provided on one surface of the second semiconductor substrate body, and a second organic insulating film having a surface roughness Ra of 2.0 nm or less; bonding the first organic insulating film and the second organic insulating film together at 70°C or less; and joining the first electrode and the second electrode. The method for manufacturing a semiconductor device according to the present disclosure enables bonding of insulating films at low temperatures. Although the reason for this is not clear, it is presumed that the contact area between the insulating films is increased by setting the surface roughness Ra of both the first and second organic insulating films to 2.0 nm or less, thereby increasing the intermolecular force and electrostatic force acting between the insulating films. The semiconductor device of the present disclosure comprises: a first semiconductor substrate having a first semiconductor substrate body, a first organic insulating film and a first electrode provided on one surface of the first semiconductor substrate body; and a second semiconductor substrate having a second organic insulating film and a second electrode provided on one surface of the second semiconductor substrate body, wherein the first organic insulating film and the second organic insulating film are bonded together, the first electrode and the second electrode are bonded together, and the thermal expansion coefficients of the first organic insulating film and the second organic insulating film are 50 ppm / K or less. The semiconductor device according to the present disclosure reduces electrode bonding defects. Although the reason for this is not clear, it is presumed that when the thermal expansion coefficients of the first and second organic insulating films are 50 ppm / K or less, the thermal expansion coefficients of these insulating films generally approach the thermal expansion coefficients of the members disposed around the insulating films, such as the semiconductor substrate and electrodes, thereby reducing the difference in thermal expansion coefficient between the insulating films and these members, making electrode bonding defects due to thermal expansion less likely to occur.

[0014] Hereinafter, an embodiment of a method for manufacturing a semiconductor device according to the present disclosure and an embodiment of a semiconductor device according to the present disclosure will be described in detail with reference to the drawings. In the following description, the same or equivalent parts will be denoted by the same reference numerals, and duplicated explanations will be omitted. Furthermore, unless otherwise specified, positional relationships such as up, down, left, and right will be based on the positional relationships shown in the drawings. Furthermore, the dimensional ratios of the drawings are not limited to those shown. In the following embodiment, a case will be described in which both the first semiconductor substrate and the second semiconductor substrate are semiconductor chips, but the present embodiment is not limited to this.

[0015] (An example of a semiconductor device) 1 is a cross-sectional view schematically illustrating an example of a semiconductor device according to the present disclosure. As shown in FIG. 1, the semiconductor device 1 is, for example, an example of a semiconductor package, and includes a first semiconductor chip 10 (first semiconductor substrate), a second semiconductor chip 20 (second semiconductor substrate), a pillar portion 30, a redistribution layer 40, a substrate 50, and a circuit board 60.

[0016] The first semiconductor chip 10 is a semiconductor chip such as an LSI (Large Scale Integrated Circuit) chip or a CMOS (Complementary Metal Oxide Semiconductor) sensor, and has a three-dimensional mounting structure in which the second semiconductor chip 20 is mounted downward. The second semiconductor chip 20 is a semiconductor chip such as an LSI or memory, and is a chip component having a smaller area in a plan view than the first semiconductor chip 10. The second semiconductor chip 20 is bonded to the back surface of the first semiconductor chip 10 by chip-to-chip (C2C) bonding. The first semiconductor chip 10 and the second semiconductor chip 20 are firmly and finely bonded to each other by hybrid bonding, the details of which will be described later, at their respective terminal electrodes and the insulating films surrounding them.

[0017] The pillar portion 30 is a connection portion in which multiple pillars 31 made of a metal such as copper (Cu) are sealed with resin 32. The multiple pillars 31 are conductive members extending from the upper surface of the pillar portion 30 to the lower surface. The multiple pillars 31 may have a cylindrical shape with a diameter of, for example, 3 μm to 20 μm (for example, a diameter of 5 μm) and may be arranged so that the center-to-center distance between each pillar 31 is 15 μm or less. The multiple pillars 31 flip-chip connect the lower terminal electrodes of the first semiconductor chip 10 to the upper terminal electrodes of the rewiring layer 40. By using the pillar portion 30, the semiconductor device 1 can form connection electrodes without using a technique called TMV (Through Mold Via), which involves drilling holes in a mold and soldering the connections. The pillar portion 30 has, for example, a thickness approximately the same as that of the second semiconductor chip 20 and is arranged on the lateral side of the second semiconductor chip 20 in the horizontal direction. In addition, multiple solder balls may be arranged instead of the pillar portion 30, and the solder balls may electrically connect the lower terminal electrode of the first semiconductor chip 10 and the upper terminal electrode of the rewiring layer 40.

[0018] The rewiring layer 40 is a wiring layer having a terminal pitch conversion function, which is a function of the package substrate, and is a layer in which a rewiring pattern is formed using polyimide, copper wiring, etc. on the insulating film below the second semiconductor chip 20 and on the lower surface of the pillar portion 30. The rewiring layer 40 is formed in a state in which the first semiconductor chip 10, the second semiconductor chip 20, etc. are turned upside down (see FIG. 4(d)).

[0019] The redistribution layer 40 electrically connects the terminal electrodes on the underside of the second semiconductor chip 20 and the terminal electrodes of the first semiconductor chip 10 via the pillar portions 30 to the terminal electrodes of the substrate 50. The terminal pitch of the substrate 50 is wider than the terminal pitch of the pillars 31 and the terminal pitch of the second semiconductor chip 20. Various electronic components 51 may be mounted on the substrate 50. Furthermore, if there is a large difference in the terminal pitch between the redistribution layer 40 and the substrate 50, an inorganic interposer or the like may be used between the redistribution layer 40 and the substrate 50 to establish electrical connection between the redistribution layer 40 and the substrate 50.

[0020] The circuit board 60 is a substrate having the first semiconductor chip 10 and the second semiconductor chip 20 mounted thereon, and having a plurality of through electrodes therein electrically connected to the substrate 50 connected to the first semiconductor chip 10, the second semiconductor chip 20, and electronic components 51, etc. In the circuit board 60, the plurality of through electrodes electrically connect the terminal electrodes of the first semiconductor chip 10 and the second semiconductor chip 20 to terminal electrodes 61 provided on the back surface of the circuit board 60.

[0021] (An example of a manufacturing method for a semiconductor device) Next, an example of a method for manufacturing the semiconductor device 1 will be described with reference to Fig. 2 to Fig. 4. Fig. 2 is a diagram sequentially showing a method for manufacturing the semiconductor device shown in Fig. 1. Fig. 3 is a diagram showing in more detail a bonding method (hybrid bonding) in the method for manufacturing the semiconductor device shown in Fig. 2. Fig. 4 is a diagram sequentially showing steps subsequent to the steps shown in Fig. 2 in the method for manufacturing the semiconductor device shown in Fig. 1.

[0022] The semiconductor device 1 can be manufactured, for example, through the following steps (a) to (n). (a) A step of preparing a first silicon substrate 100 corresponding to a first semiconductor chip 10. (b) A step of preparing a second silicon substrate 200 corresponding to the second semiconductor chip 20. (c) A step of polishing the first silicon substrate 100. (d) A step of polishing the second silicon substrate 200. (e) A step of dividing the second silicon substrate 200 into individual pieces to obtain a plurality of semiconductor chips 205. (f) A step of aligning the terminal electrodes 203 of each of the plurality of semiconductor chips 205 with the terminal electrodes 103 of the first silicon substrate 100. (g) A step of bonding the insulating film 102 of the first silicon substrate 100 and each insulating film portion 202b of the plurality of semiconductor chips 205 together (see FIG. 3(b)). (h) A step of bonding the terminal electrodes 103 of the first silicon substrate 100 to the terminal electrodes 203 of each of the plurality of semiconductor chips 205 (see FIG. 3(c)). (i) A step of forming a plurality of pillars 300 (corresponding to pillars 31) on the connection surface of the first silicon substrate 100 and between the plurality of semiconductor chips 205. (j) A step of molding a resin 301 onto the connection surface of the first silicon substrate 100 so as to cover the semiconductor chip 205 and the pillar 300, thereby obtaining a semi-finished product M1. (k) A step of grinding and thinning the resin 301 side of the semi-finished product M1 molded in the step (j) to obtain a semi-finished product M2. (l) A step of forming a wiring layer 400 corresponding to the rewiring layer 40 on the semi-finished product M2 thinned in the step (k). (m) A step of cutting the semi-finished product M3 on which the wiring layer 400 has been formed in the step (l) along the cutting lines A into individual semiconductor devices 1. (n) A step of inverting the semiconductor device 1a separated in step (m) and placing it on the substrate 50 and the circuit board 60 (see FIG. 1).

[0023] [Step (a) and Step (b)] Step (a) is a step of preparing a first silicon substrate 100 (first semiconductor substrate), which is a silicon substrate on which integrated circuits made of semiconductor elements and wiring connecting them are formed, corresponding to a plurality of first semiconductor chips 10. In step (a), as shown in FIG. 2(a), a plurality of terminal electrodes 103 (first electrodes) made of copper, aluminum, or the like are provided at predetermined intervals on one surface 101a of a first silicon substrate body 101 (first semiconductor substrate body) made of silicon or the like, and an insulating film 102 (first organic insulating film) is provided in the spaced apart portions. The insulating film 102 may be provided on the one surface 101a of the first silicon substrate body 101 before the plurality of terminal electrodes 103 are provided, or the insulating film 102 may be provided after the plurality of terminal electrodes 103 are provided on the one surface 101a of the first silicon substrate body 101. In addition, a predetermined gap is provided between the multiple terminal electrodes 103 in order to form pillars 300 in a process described below, and another terminal electrode (not shown) connected to the pillars 300 is formed between them.

[0024] Step (b) is a step of preparing a second silicon substrate 200 (second semiconductor substrate), which is a silicon substrate on which integrated circuits including semiconductor elements and wiring connecting the semiconductor elements are formed, corresponding to the plurality of second semiconductor chips 20. In step (b), as shown in FIG. 2(a), a plurality of terminal electrodes 203 (a plurality of second electrodes) made of copper, aluminum, or the like are continuously provided on one surface 201a of a second silicon substrate body 201 (second semiconductor substrate body) made of silicon, or the like, and an insulating film 202 (second organic insulating film, organic insulating region) is also provided. The insulating film 202 may be provided on the one surface 201a of the second silicon substrate body 201 before the plurality of terminal electrodes 203 are provided, or the insulating film 202 may be provided after the plurality of terminal electrodes 203 are provided on the one surface 201a of the second silicon substrate body 201.

[0025] The insulating films 102 and 202 used in steps (a) and (b) both have a surface roughness Ra of 2.0 nm or less, preferably 1.5 nm or less, and more preferably 1.0 nm or less. The insulating films 102 and 202 are preferably a polyimide film, a polybenzoxazole film, a benzocyclobutene film, a polyamideimide film, an epoxy resin film, an acrylic resin film, or a methacrylic resin film, and from the viewpoint of heat resistance, a polyimide film or a polybenzoxazole film is more preferable, and a polyimide film is even more preferable. The tensile modulus of the insulating films 102 and 202 at 25°C is preferably 7.0 GPa or less, more preferably 5.0 GPa or less, even more preferably 3.0 GPa or less, and particularly preferably 2.5 GPa or less. The tensile modulus of the insulating films 102 and 202 at 25°C may be 2.0 MPa or more.

[0026] The thermal expansion coefficient of the insulating films 102 and 202 is preferably 50 ppm / K or less, more preferably 40 ppm / K or less, and even more preferably 30 ppm / K or less. The thermal expansion coefficient of the insulating films 102 and 202 may be 3 ppm / K or more. By setting the thermal expansion coefficient of the insulating films 102 and 202 to 50 ppm / K or less, the expansion of the insulating films relative to the expansion of the terminal electrodes in the step (h) described below is prevented, and the contact area between the terminal electrodes after bonding can be kept wide, making it possible to keep the electrical resistance low, and further reducing bonding defects between the terminal electrodes.

[0027] The thickness of the insulating films 102 and 202 is preferably 0.1 μm to 50 μm, more preferably 1 μm to 15 μm, which ensures uniformity in the thickness of the insulating films and shortens the processing time in the subsequent polishing step.

[0028] From the viewpoint of facilitating the operations in steps (c) and (d) and simplifying these steps, it is preferable that the polishing rate of the insulating film 102 is 0.1 to 5 times the polishing rate of the terminal electrode 103, and / or the polishing rate of the insulating film 202 is 0.1 to 5 times the polishing rate of the terminal electrode 203 (preferably both of these are satisfied). As an example, when the terminal electrode 103 or 203 is made of copper and the polishing rate of copper is 500 nm / min, the polishing rate of the insulating film 102 or 202 is preferably 1500 nm / min or less (three times or less the polishing rate of copper), more preferably 1000 nm / min or less (twice or less the polishing rate of copper), and even more preferably 500 nm / min or less (equal to or less than the polishing rate of copper).

[0029] Next, a method for producing an insulating film will be described. An insulating film can be obtained by curing an insulating film-forming material. Examples of the above-mentioned insulating film production method include (α) a method including a step of applying an insulating film-forming material to a substrate and drying it to form a resin film, and a step of heat-treating the resin film, and (β) a method including a step of forming a film of a certain thickness using an insulating film-forming material on a film that has been subjected to a release treatment, transferring the resin film to a substrate by a lamination method, and a step of heat-treating the resin film formed on the substrate after transfer. From the viewpoint of flatness, the method (α) is preferred. When the method (α) is used, the hybrid bonding insulating film-forming material of the present disclosure, which will be described later, may be used.

[0030] Examples of methods for applying the insulating film forming material include spin coating, ink jet coating, and slit coating.

[0031] In the spin coating method, the insulating film forming material may be spin coated under conditions such as a rotation speed of 300 rpm (revolutions per minute) to 3,500 rpm, preferably 500 rpm to 1,500 rpm, an acceleration of 500 rpm / sec to 15,000 rpm / sec, and a rotation time of 30 seconds to 300 seconds.

[0032] A drying step may be included after applying the insulating film-forming material to a support, film, or the like. Drying may be performed using a hot plate, oven, or the like. The drying temperature is preferably 75°C to 130°C, and more preferably 90°C to 120°C from the viewpoint of improving the flatness of the insulating film. The drying time is preferably 30 seconds to 5 minutes. Drying may be carried out two or more times, thereby obtaining a resin film in which the insulating film-forming material is formed into a film shape.

[0033] In the slit coating method, the insulating film forming material may be slit coated under conditions such as a chemical solution discharge speed of 10 μL / sec to 400 μL / sec, a chemical solution discharge part height of 0.1 μm to 1.0 μm, a stage speed (or a chemical solution discharge part speed) of 1.0 mm / sec to 50.0 mm / sec, a stage acceleration of 10 mm / sec to 1000 mm / sec, an ultimate vacuum during reduced pressure drying of 10 Pa to 100 Pa, a reduced pressure drying time of 30 seconds to 600 seconds, a drying temperature of 60°C to 150°C, and a drying time of 30 to 300 seconds.

[0034] The formed resin film may be subjected to a heat treatment. The heating temperature is preferably 150° C. to 450° C., more preferably 150° C. to 350° C. By keeping the heating temperature within the above range, damage to the substrate, device, etc. can be suppressed, and an insulating film can be suitably produced while realizing energy saving in the process.

[0035] The heating time is preferably 5 hours or less, and more preferably 30 minutes to 3 hours. By keeping the heating time within the above range, the crosslinking reaction or dehydration ring-closing reaction can be allowed to proceed sufficiently. The heat treatment may be carried out in air or in an inert atmosphere such as nitrogen, but is preferably carried out in a nitrogen atmosphere in order to prevent oxidation of the resin film.

[0036] Examples of equipment used for the heat treatment include a quartz tube furnace, a hot plate, a rapid thermal annealer, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace.

[0037] When a negative-type photosensitive insulating film forming material or a positive-type photosensitive insulating film forming material is used, when forming the insulating film 202 on one surface 201a of the second silicon substrate body 201 and then providing the plurality of terminal electrodes 203, a method including, for example, a step of applying the insulating film forming material onto the substrate, a step of drying to form a resin film, a step of pattern-exposing the resin film and developing it with a developer to obtain a patterned resin film, and a step of heat-treating the patterned resin film may be used, whereby a hardened patterned insulating film can be obtained.

[0038] The pattern exposure is carried out by exposing a predetermined pattern through a photomask, for example. Examples of actinic rays to be irradiated include i-rays, broadband ultraviolet rays, visible light, and radioactive rays, and i-rays are preferred. Examples of exposure devices that can be used include parallel exposure devices, projection exposure devices, steppers, and scanner exposure devices.

[0039] By developing after exposure, a patterned resin film can be obtained, which is a resin film having a pattern formed therein. When the insulating film forming material is a negative photosensitive insulating film forming material, the unexposed areas are removed with a developer. The organic solvent used as the negative developer may be a good solvent for the photosensitive resin film, either alone or in combination with a poor solvent. Examples of good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, cyclopentanone, cyclohexanone, and cycloheptanone. Examples of poor solvents include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

[0040] When the insulating film forming material is a positive photosensitive insulating film forming material, the exposed portion is removed with a developer. Examples of solutions used as positive developers include tetramethylammonium hydroxide (TMAH) solutions and sodium carbonate solutions.

[0041] At least one of the negative developer and the positive developer may contain a surfactant. The content of the surfactant is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the developer.

[0042] The development time can be set to, for example, twice the time required for a photosensitive resin film to be immersed in a developer and for the resin film to be completely dissolved. The development time may be adjusted depending on the thermosetting polyamide contained in the insulating film-forming material, and is, for example, preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and from the viewpoint of productivity, even more preferably 20 seconds to 5 minutes.

[0043] After development, the patterned resin film may be washed with a rinse solution. As the rinse liquid, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. may be used alone or in appropriate mixtures, or these may be used in stepwise combinations.

[0044] The organic material constituting the insulating films 102 and 202 may be a thermosetting non-conductive film (NCF) or the like. This organic material may be an underfill material. The organic material constituting the insulating films 102 and 202 may also be a heat-resistant resin.

[0045] [Step (c) and step (d)] Step (c) is a step of polishing the first silicon substrate 100. In step (c), as shown in FIG. 3A, the first surface 101a of the first silicon substrate 100 is polished using chemical mechanical polishing (CMP) so that the surface 102a of the insulating film 102 is at the same level as or slightly higher (protruding) than the surfaces 103a of the terminal electrodes 103. This makes the thickness of the insulating film 102 the same as or thicker than the thickness of the terminal electrodes 103. In other words, the height of the insulating film 102 is the same as or thicker than the height of the terminal electrodes 103. In step (c), the first silicon substrate 100 can also be polished by CMP under conditions that selectively and deeply polish the terminal electrodes 103 made of copper or the like. In step (c), the surfaces 103a of the terminal electrodes 103 may be polished by CMP so that they are flush with the surface 102a of the insulating film 102. The polishing method is not limited to CMP, and back grinding or the like may also be used. Prior to polishing by the CMP method, mechanical polishing may be carried out using a polishing device such as a surface planer. When the surface 102a of the insulating film 102 is at the same level or slightly higher than each surface 103a of the terminal electrode 103, the difference in height between each surface 103a and the surface 102a (i.e., the difference between the thickness of the insulating film 102 and the thickness of the terminal electrode 103) is preferably 0 nm or more, more preferably 0.1 nm or more, even more preferably 0.1 nm to 30 nm, and particularly preferably 2 nm to 15 nm. In this disclosure, the height difference between the organic insulating film (such as the surface 102a) and the electrode (such as the surface 103a) refers to the arithmetic mean when five points on a measurement object such as a wafer are measured with an atomic force microscope (AFM).

[0046] Step (d) is a step of polishing the second silicon substrate 200. In step (d), as shown in FIG. 3A, the first surface 201a of the second silicon substrate 200 is polished using the CMP method so that the surface 202a of the insulating film 202 is at the same level as or slightly higher (protruding) than the surfaces 203a of the terminal electrodes 203. As a result, the thickness of the insulating film 202 becomes equal to or thicker than the thickness of the terminal electrodes 203. In other words, the height of the insulating film 202 becomes equal to or thicker than the height of the terminal electrodes 203. In step (d), the second silicon substrate 200 is polished by the CMP method under conditions that selectively and deeply polish the terminal electrodes 203 made of copper or the like. In step (d), the CMP method may be used to polish the surfaces 203a of the terminal electrodes 203 so that they are flush with the surface 202a of the insulating film 202. The polishing method is not limited to the CMP method, and back grinding or the like may also be used. When the surface 202a of the insulating film 202 is at the same level or slightly higher than each surface 203a of the terminal electrode 203, the difference in height between each surface 203a and the surface 202a (i.e., the difference in thickness between the insulating film 202 and the terminal electrode 203) is preferably 0 nm or more, more preferably 0.1 nm or more, even more preferably 0.1 nm to 30 nm, and particularly preferably 2 nm to 15 nm.

[0047] In steps (c) and (d), the insulating film 102 and the insulating film 202 may be polished to have the same thickness. Alternatively, for example, the insulating film 202 may be polished to have a thickness greater than the thickness of the insulating film 102. On the other hand, the insulating film 202 may be polished to have a thickness smaller than the thickness of the insulating film 102. When the insulating film 202 is thicker than the insulating film 102, the insulating film 202 can contain most of the foreign matter that adheres to the bonding interface when the second silicon substrate 200 is diced or when chips are mounted, thereby further reducing bonding defects. On the other hand, when the insulating film 202 is thicker than the insulating film 102, the height of the mounted semiconductor chip 205, i.e., the semiconductor device 1, can be reduced. At least one of the steps (c) and (d) may be performed, and it is preferable to perform both the steps (c) and (d).

[0048] [Step (e)] Step (e) is a step of singulating the second silicon substrate 200 to obtain a plurality of semiconductor chips 205. In step (e), as shown in FIG. 2(b), the second silicon substrate 200 is singulated into a plurality of semiconductor chips 205 by cutting means such as dicing. When dicing the second silicon substrate 200, the insulating film 202 may be covered with a protective material or the like before being singulated. In step (e), the insulating film 202 of the second silicon substrate 200 is divided into insulating film portions 202b corresponding to each semiconductor chip 205. Examples of dicing methods for singulating the second silicon substrate 200 include plasma dicing, stealth dicing, and laser dicing. As a surface protective material for the second silicon substrate 200 during dicing, for example, an organic film removable with water, TMAH, or the like, or a thin film such as a carbon film removable with plasma or the like may be provided. In this embodiment, the large-area second silicon substrate 200 is prepared and then diced into individual pieces to obtain the plurality of semiconductor chips 205, but the method for preparing the semiconductor chips 205 is not limited to this.

[0049] [Process (f)] Step (f) is a step of aligning the terminal electrodes 203 of each of the plurality of semiconductor chips 205 with the terminal electrodes 103 of the first silicon substrate 100. In step (f), as shown in (c) of Fig. 2, each semiconductor chip 205 is aligned so that the terminal electrodes 203 of each semiconductor chip 205 face the corresponding plurality of terminal electrodes 103 of the first silicon substrate 100. For this alignment, an alignment mark or the like may be provided on the first silicon substrate 100.

[0050] [Process (g)] Step (g) is a step of bonding the insulating film 102 of the first silicon substrate 100 and each insulating film portion 202b of each of the multiple semiconductor chips 205 to each other. In step (g), after removing organic substances, metal oxides, and the like adhering to the surface of each semiconductor chip 205, the semiconductor chip 205 is aligned with the first silicon substrate 100 as shown in FIG. 2(c), and then the insulating film portion 202b of each of the multiple semiconductor chips 205 is bonded to the insulating film 102 of the first silicon substrate 100 at 70°C or less by hybrid bonding (see FIG. 3(b)). In the present disclosure, "bonding the insulating film at 70°C or less" means bonding the insulating film at a temperature of 70°C or less. The bonding temperature is more preferably 60°C or less, and even more preferably 50°C or less. The pressure when bonding the insulating films is preferably 7 MPa or less and 0.1 MPa or more, more preferably 5 MPa or less and 0.3 MPa or more, and even more preferably 2 MPa or less and 0.5 MPa or more. By setting the pressure within this range, it is possible to prevent damage to the semiconductor elements to be bonded and maintain a certain level or higher yield of the bonded substrates. The time required for the process of bonding the insulating films is preferably 30 seconds or less and 0.5 seconds or more, and more preferably 20 seconds or less and 1 second or more, which allows the yield of bonded substrates to be maintained at a certain level or higher without reducing production efficiency. At this attachment stage, the terminal electrodes 103 of the first silicon substrate 100 and the terminal electrodes 203 of the semiconductor chip 205 are spaced apart from each other and are not connected (however, they are aligned within the range including the tolerance of the device).

[0051] [Process (h)] Step (h) is a step of bonding the terminal electrodes 103 of the first silicon substrate 100 to the terminal electrodes 203 of each of the multiple semiconductor chips 205. In step (h), as shown in FIG. 2(d), after the bonding in step (g) is completed, heat H and, if necessary, pressure are applied to bond the terminal electrodes 103 of the first silicon substrate 100 to each of the terminal electrodes 203 of the multiple semiconductor chips 205 by hybrid bonding (see FIG. 3(c)). When the terminal electrodes 103 and 203 are made of copper, the annealing temperature in step (g) is preferably 150°C or higher and 400°C or lower, and more preferably 200°C or higher and 300°C or lower. This bonding process forms an electrode bonding portion S2 where the terminal electrode 103 and the corresponding terminal electrode 203 are bonded, and the terminal electrodes 103 and 203 are firmly bonded mechanically and electrically. Furthermore, the laminated insulating film 102 and insulating film portion 202b are bonded together to form an insulating bonded portion S1. Application of heat H causes the insulating film 102, the insulating film portion 202b, the terminal electrode 103, and the terminal electrode 203 to expand. In step (c), the first silicon substrate 100 may be polished so that the height of the insulating film 102 becomes approximately equal to or greater than the height of the terminal electrode 103 due to thermal expansion caused by heating, and in step (d), the second silicon substrate 200 may be polished so that the height of the insulating film portion 202b becomes approximately equal to or greater than the height of the terminal electrode 203. When polishing the first silicon substrate 100 in step (c), the polishing amount may be adjusted taking into account the thermal expansion coefficients of the insulating film 102 and the terminal electrode 103. Furthermore, when polishing the second silicon substrate 200 in step (d), the polishing amount may be adjusted taking into account the thermal expansion coefficients of the insulating film 202 and the terminal electrode 203.

[0052] The thickness of the organic insulating film, which is the insulating junction where the insulating film 102 and the insulating film portion 202b are joined (the total thickness of the organic insulating film formed by bonding the first organic insulating film and the second organic insulating film), is not particularly limited and may be, for example, 0.1 μm or more, or from the viewpoint of suppressing the influence of foreign matter and from the viewpoint of device design, may be 1 μm to 20 μm, and preferably 1 μm to 5 μm.

[0053] As a result of the above, multiple semiconductor chips 205 are electrically and mechanically mounted at predetermined positions with high precision on the first silicon substrate 100. For example, a reliability test (connection test, etc.) of the product may be performed at the stage of the semi-finished product shown in Figure 2(d), and only non-defective products may be used in the subsequent processes. Next, an example of a method for manufacturing a semiconductor device using such a semi-finished product will be described with reference to Figure 4.

[0054] [Step (i)] Step (i) is a step of forming a plurality of pillars 300 on the connection surface 100a of the first silicon substrate 100 and between a plurality of semiconductor chips 205. In step (i), as shown in FIG. 4A, a large number of pillars 300 made of, for example, copper are formed between the plurality of semiconductor chips 205. The pillars 300 can be formed from copper plating, conductive paste, copper pins, or the like. One end of each pillar 300 is formed to be connected to one of the terminal electrodes of the first silicon substrate 100 that is not connected to the terminal electrode 203 of the semiconductor chip 205, and the other end extends upward. The pillars 300 have a diameter of, for example, 10 μm to 100 μm and a height of, for example, 10 μm to 1000 μm. Note that, for example, 1 to 10,000 pillars 300 may be provided between a pair of semiconductor chips 205.

[0055] [Process (j)] Step (j) is a step of molding resin 301 onto the connection surface 100a of the first silicon substrate 100 so as to cover the plurality of semiconductor chips 205 and the plurality of pillars 300. In step (j), as shown in FIG. 4(b), epoxy resin or the like is molded to entirely cover the plurality of semiconductor chips 205 and the plurality of pillars 300. Examples of molding methods include compression molding, transfer molding, and laminating a film-like epoxy film. This resin molding fills the resin 301 between the plurality of pillars 300 and between the pillars 300 and the semiconductor chips 205. This forms a semi-finished product M1 filled with resin. A curing process may be performed after molding the epoxy resin or the like. Furthermore, when steps (i) and (j) are performed substantially simultaneously, i.e., when the pillars 300 are formed at the same time as the resin molding, the pillars may be formed using imprinting, which is a fine transfer technique, and a conductive paste or electrolytic plating.

[0056] [Process (k)] In step (k), the semi-finished product M1, which is made up of the resin 301, the plurality of pillars 300, and the plurality of semiconductor chips 205 molded in step (j), is ground from the resin 301 side to thin it, thereby obtaining a semi-finished product M2. In step (k), as shown in FIG. 4(c), the upper side of the semi-finished product M1 is polished with a grinder or the like to thin the resin-molded first silicon substrate 100 and the like, thereby obtaining a semi-finished product M2. By polishing in step (k), the thicknesses of the semiconductor chips 205, the pillars 300, and the resin 301 are thinned to, for example, about several tens of μm, and the semiconductor chips 205 have a shape corresponding to the second semiconductor chip 20, and the pillars 300 and the resin 301 have shapes corresponding to the pillar portions 30.

[0057] [Process (l)] Step (l) is a step of forming a wiring layer 400 corresponding to the rewiring layer 40 on the semi-finished product M2 thinned in step (k). In step (l), as shown in FIG. 4(d), a rewiring pattern is formed using polyimide, copper wiring, or the like on the second semiconductor chip 20 and pillar portion 30 of the ground semi-finished product M2. This forms a semi-finished product M3 having a wiring structure in which the terminal pitch of the second semiconductor chip 20 and pillar portion 30 is widened.

[0058] [Process (m) and process (n)] In step (m), the semi-finished product M3 on which the wiring layer 400 has been formed in step (l) is cut along the cutting line A to obtain the individual semiconductor devices 1. In step (m), as shown in (d) of FIG. 4, the semiconductor device substrate is cut along the cutting line A by dicing or the like to obtain the individual semiconductor devices 1. Thereafter, in step (n), the semiconductor devices 1a separated in step (m) are inverted and placed on the substrate 50 and the circuit board 60 to obtain the multiple semiconductor devices 1 shown in FIG.

[0059] Although one embodiment of the semiconductor device manufacturing method according to the present disclosure has been described in detail above, the present disclosure is not limited to the above embodiment. For example, in the above embodiment, after the step (i) of forming the pillars 300 in the process shown in FIG. 4 , the step (j) of molding the resin 301 and the step (k) of grinding and thinning the resin 301 and the like are performed in that order. However, the step (j) of molding the resin 301 onto the connection surface of the first silicon substrate 100 may be performed first, followed by the step (k) of grinding and thinning the resin 301 to a predetermined thickness, and then the step (i) of forming the pillars 300. In this case, the work of grinding the pillars 300 can be reduced, and since the portions of the pillars 300 that need to be ground are no longer necessary, material costs can be reduced.

[0060] Although the above embodiment describes an example of C2C bonding, the present disclosure may also be applied to chip-to-wafer (C2W) bonding shown in FIG. 5. In C2W, a semiconductor wafer 410 (first semiconductor substrate) is prepared, which includes a substrate body 411 (first semiconductor substrate body), an insulating film 412 (first insulating film) provided on one surface of the substrate body 411, and a plurality of terminal electrodes 413 (first electrodes). A semiconductor substrate is also prepared, which includes a substrate body 421, an insulating film portion 422 (second insulating film) provided on one surface of the substrate body 421, and a plurality of terminal electrodes 423 (second electrodes), before being singulated into a plurality of semiconductor chips 420 (second semiconductor substrate). Then, one surface of the semiconductor wafer 410 and one surface of the semiconductor substrate before being singulated into the semiconductor chips 420 are polished by CMP or the like, similar to the above steps (c) and (d). Thereafter, the semiconductor substrate before being singulated is subjected to a singulation process similar to that in step (e) to obtain a plurality of semiconductor chips 420.

[0061] Next, as shown in FIG. 5(a), the terminal electrodes 423 of the semiconductor chip 420 are aligned with the terminal electrodes 413 of the semiconductor wafer 410 (step (f)). Then, the insulating film 412 of the semiconductor wafer 410 and the insulating film portion 422 of the semiconductor chip 420 are attached to each other (step (g)), and the terminal electrodes 413 of the semiconductor wafer 410 and the terminal electrodes 423 of the semiconductor chip 420 are bonded to each other (step (h)), thereby obtaining the semi-finished product shown in FIG. 5(b). As a result, the insulating film 412 and the insulating film portion 422 are bonded to form an insulating bonding portion S3, and the semiconductor chip 420 is attached to the semiconductor wafer 410 mechanically firmly and with high precision. Furthermore, the terminal electrodes 413 and the corresponding terminal electrodes 423 are bonded to form an electrode bonding portion S4, and the terminal electrodes 413 and 423 are bonded to each other mechanically and electrically firmly.

[0062] 5(c) and 5(d), a plurality of semiconductor chips 420 are bonded to a semiconductor wafer 410 in a similar manner to obtain a semiconductor device 401. Note that the plurality of semiconductor chips 420 may be bonded to the semiconductor wafer 410 one by one by hybrid bonding, or may be bonded to the semiconductor wafer 410 collectively by hybrid bonding.

[0063] The method for manufacturing a semiconductor device according to the present disclosure is also applicable to a W2W manufacturing method in which the first semiconductor substrate is a semiconductor wafer and the second semiconductor substrate is a semiconductor wafer.

[0064] Furthermore, in the above-described method for manufacturing a semiconductor device, the insulating film 102 of the semiconductor substrate 100, the insulating film 202 of the semiconductor chip 205, etc. may contain an inorganic material as long as the effects of the present disclosure are achieved.

[0065] <Hybrid bonding insulating film forming material> The hybrid bonding insulating film forming material of the present disclosure (hereinafter, the hybrid bonding insulating film forming material may be simply referred to as the "insulating film forming material") contains a thermosetting polyamide and a solvent, and has a thermal expansion coefficient of 50 ppm / K or less when cured. The thermal expansion coefficient of the cured product is preferably 40 ppm / K or less, and more preferably 30 ppm / K or less. The thermal expansion coefficient of the cured product may be 3 ppm / K or more. In the method for manufacturing a semiconductor device according to the present disclosure, the first organic insulating film and the second organic insulating film may be a cured product of the insulating film-forming material according to the present disclosure. Furthermore, the insulating film forming material of the present disclosure may use a thermosetting or photosetting resin such as an epoxy resin, an acrylic resin, or a methacrylic resin instead of a thermosetting polyamide. Furthermore, the insulating film-forming material of the present disclosure may contain a thermosetting or photocurable resin such as an epoxy resin, an acrylic resin, or a methacrylic resin in combination with the thermosetting polyamide. In this case, the content of the thermosetting polyamide in the entire resin contained in the insulating film-forming material of the present disclosure is preferably 50% by mass or more and less than 100% by mass, more preferably 70% by mass or more and less than 100% by mass, even more preferably 90% by mass or more and less than 100% by mass, and particularly preferably 95% by mass or more and less than 100% by mass. Examples of the thermosetting polyamide used in the present disclosure include polybenzoxazole precursors and polyimide precursors (such as polyamic acids). Among these, polyimide precursors are preferred from the viewpoints of heat resistance, adhesion to electrodes, and the like. Hereinafter, the insulating film-forming material of the present disclosure will be described in detail, mainly taking as an example a case where the thermosetting polyamide contains a polyimide precursor.

[0066] The (A) polyimide precursor is preferably at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide. The polyamic acid ester and polyamic acid amide are compounds in which the hydrogen atoms of at least some of the carboxy groups in a polyamic acid are substituted with monovalent organic groups, and the polyamic acid salt is a compound in which at least some of the carboxy groups in a polyamic acid form a salt structure with a basic compound having a pH of 7 or higher.

[0067] The (A) polyimide precursor preferably contains a compound having a structural unit represented by the following general formula (1): This tends to provide a semiconductor device having an insulating film that exhibits high reliability.

[0068] [ka]

[0069] In general formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group. 6 and R 7each independently represents a hydrogen atom or a monovalent organic group; R 6 and R 7 At least one of them may have a polymerizable unsaturated bond. The polyimide precursor may have a plurality of structural units represented by the general formula (1), and X, Y, and R in the plurality of structural units may be 6 and R 7 may be the same or different. In addition, R 6 and R 7 are each independently a hydrogen atom or a monovalent organic group, the combination of which is not particularly limited. For example, R 6 and R 7 At least one of R may be a hydrogen atom and the rest may be a monovalent organic group described later, or they may be the same or different monovalent organic groups. 6 and R 7 The combinations may be the same or different.

[0070] In general formula (1), the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 5 to 13 carbon atoms, and even more preferably 6 to 12 carbon atoms. The tetravalent organic group represented by X may contain an aromatic ring or an alicyclic ring. Examples of the aromatic ring include aromatic hydrocarbon groups (for example, aromatic rings having 6 to 20 carbon atoms) and aromatic heterocyclic groups (for example, heterocyclic rings having 5 to 20 atoms). Examples of the alicyclic ring include cycloalkane structures having 3 to 8 carbon atoms and spiro ring structures having 5 to 25 carbon atoms. From the viewpoint of heat resistance, the tetravalent organic group represented by X is preferably an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, and a phenanthrene ring. When the tetravalent organic group represented by X contains an aromatic ring, each aromatic ring may have a substituent or may be unsubstituted. Examples of the substituent on the aromatic ring include an alkyl group, a fluorine atom, a halogenated alkyl group, a hydroxyl group, and an amino group. When the tetravalent organic group represented by X contains a benzene ring, the tetravalent organic group represented by X preferably contains one to four benzene rings, more preferably contains one to three benzene rings, and even more preferably contains one or two benzene rings. When the tetravalent organic group represented by X contains two or more benzene rings, the benzene rings may be connected by a single bond, or may be connected by an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a silylene bond (-Si(R A )2-; Two R A each independently represents a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (—O—(Si(R B )2-O-) n ;Two R's B each independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or greater.) or a composite linking group comprising at least two of these linking groups. Furthermore, two benzene rings may be linked at two positions by at least one of a single bond and a linking group to form a 5- or 6-membered ring containing a linking group between the two benzene rings.

[0071] In the general formula (1), -COOR 6 The -COOR group and the -CONH- group are preferably in the ortho position relative to each other. 7 The group and the -CO- group are preferably in the ortho position relative to each other.

[0072] Specific examples of the tetravalent organic group represented by X include groups represented by the following formulae (A) to (F). Among them, from the viewpoint of obtaining an insulating film that is excellent in flexibility and in which the generation of voids at the bonding interface is further suppressed, a group represented by the following formula (E) is preferred, and in the group represented by the following formula (E), C is more preferably a group containing an ether bond, and even more preferably an ether bond. It should be noted that the present disclosure is not limited to the following specific examples.

[0073] [ka]

[0074] In formula (D), A and B are each independently a single bond or a divalent group that is not conjugated with a benzene ring. However, A and B cannot both be single bonds. Examples of divalent groups that are not conjugated with a benzene ring include a methylene group, a halogenated methylene group, a halogenated methylmethylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a silylene bond (-Si(R A )2-; Two R A each independently represents a hydrogen atom, an alkyl group, or a phenyl group.) Among these, A and B each independently preferably represent a methylene group, a bis(trifluoromethyl)methylene group, a difluoromethylene group, an ether bond, a sulfide bond, or the like, and more preferably an ether bond.

[0075] In formula (E), C represents an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-OC(=O)-), a silylene bond (-Si(R A )2-; Two R A each independently represents a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (—O—(Si(R B )2-O-) n ;Two R's Beach independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or greater than 2. C preferably contains an ether bond, and is preferably an ether bond. Furthermore, C may be a structure represented by the following formula (C1).

[0076] [ka]

[0077] The alkylene group represented by C in formula (E) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms. Specific examples of the alkylene group represented by C in formula (E) include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; methylmethylene, methylethylene, ethylmethylene, dimethylmethylene, 1,1-dimethylethylene, 1-methyltrimethylene, 2-methyltrimethylene, ethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1-ethyltrimethylene, 2-ethyltrimethylene, 1,1-dimethylethylene; branched alkylene groups such as 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-methylpentamethylene, 2-methylpentamethylene, 3-methylpentamethylene, 1-ethyltetramethylene, 2-ethyltetramethylene, 1,1-dimethyltetramethylene, 1,2-dimethyltetramethylene, 2,2-dimethyltetramethylene, 1,3-dimethyltetramethylene, 2,3-dimethyltetramethylene, and 1,4-dimethyltetramethylene; and the like. Among these, a methylene group is preferred.

[0078] The halogenated alkylene group represented by C in formula (E) is preferably a halogenated alkylene group having 1 to 10 carbon atoms, more preferably a halogenated alkylene group having 1 to 5 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 3 carbon atoms. Specific examples of the halogenated alkylene group represented by C in formula (E) include alkylene groups in which at least one hydrogen atom contained in the alkylene group represented by C in formula (E) has been substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, a fluoromethylene group, a difluoromethylene group, a hexafluorodimethylmethylene group, etc. are preferred.

[0079] R contained in the silylene bond or siloxane bond A or R B The alkyl group represented by R is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. A or R B Specific examples of the alkyl group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.

[0080] Specific examples of the tetravalent organic group represented by X may be groups represented by the following formulae (J) to (O).

[0081] [ka]

[0082] The tetravalent organic group represented by X may contain an alicyclic ring from the viewpoint of adjusting the thermal expansion coefficient of the cured product. When the tetravalent organic group represented by X contains an alicyclic ring, examples of the alicyclic ring include a ring structure containing no unsaturated bond, such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a decahydronaphthalene ring, a norbornane ring, an adamantane ring, and a bicyclo[2.2.2]octane ring, and a ring structure containing an unsaturated bond, such as a cyclohexene ring. Examples of spirocyclic ring structures containing these ring structures also include the alicyclic ring. The alicyclic ring may have a substituent, such as an oxo group (=O), an alkyl group, a fluorine atom, a halogenated alkyl group, a hydroxyl group, or an amino group, or may be unsubstituted. Specific examples of the tetravalent organic group represented by X having a spiro ring structure include the following formula (P).

[0083] [ka]

[0084] In general formula (1), the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 12 to 18 carbon atoms. The skeleton of the divalent organic group represented by Y may be the same as the skeleton of the tetravalent organic group represented by X, and a preferred skeleton of the divalent organic group represented by Y may be the same as the preferred skeleton of the tetravalent organic group represented by X. The skeleton of the divalent organic group represented by Y may have a structure in which two bonding positions of the tetravalent organic group represented by X are substituted with atoms (e.g., hydrogen atoms) or functional groups (e.g., alkyl groups). The divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, the divalent organic group represented by Y is preferably a divalent aromatic group. Examples of the divalent aromatic group include a divalent aromatic hydrocarbon group (for example, an aromatic ring having 6 to 20 carbon atoms) and a divalent aromatic heterocyclic group (for example, a heterocyclic ring having 5 to 20 atoms), and the like, with a divalent aromatic hydrocarbon group being preferred.

[0085] Specific examples of the divalent aromatic group represented by Y include groups represented by the following formulae (G) to (H). Among them, from the viewpoint of obtaining an insulating film that is excellent in flexibility and in which the generation of voids at the bonding interface is further suppressed, the group represented by the following formula (H) is preferred, and in the group represented by the following formula (H), D is more preferably a group containing a single bond or an ether bond, and even more preferably a single bond or an ether bond.

[0086] [ka]

[0087] In formulae (G) to (H), each R independently represents an alkyl group, an alkoxy group, a hydroxyl group, a halogenated alkyl group, a phenyl group, or a halogen atom; each n independently represents an integer of 0 to 4. In formula (H), D is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-OC(=O)-), a silylene bond (-Si(R A )2-; Two R A each independently represents a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (—O—(Si(R B )2-O-) n ;Two R's B each independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more. ) or a divalent group formed by combining at least two of them. D may also be a structure represented by the above formula (C1). Specific examples of D in formula (H) are a single bond or the same as the specific examples of C in formula (E). In formula (H), each D is preferably independently a single bond, an ether bond, a group containing an ether bond and a phenylene group, a group containing an ether bond, a phenylene group and an alkylene group, or the like.

[0088] The alkyl group represented by R in formulas (G) to (H) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. Specific examples of the alkyl group represented by R in formulae (G) to (H) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.

[0089] The alkoxy group represented by R in formulas (G) to (H) is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably an alkoxy group having 1 or 2 carbon atoms. Specific examples of the alkoxy group represented by R in Formulas (G) to (H) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, an s-butoxy group, and a t-butoxy group.

[0090] The halogenated alkyl group represented by R in formulas (G) to (H) is preferably a halogenated alkyl group having 1 to 5 carbon atoms, more preferably a halogenated alkyl group having 1 to 3 carbon atoms, and even more preferably a halogenated alkyl group having 1 or 2 carbon atoms. Specific examples of the halogenated alkyl group represented by R in Formulas (G) to (H) include alkyl groups in which at least one hydrogen atom contained in the alkyl group represented by R in Formulas (G) to (H) is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, etc. are preferred.

[0091] In formulae (G) to (H), n is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0092] Specific examples of the divalent aliphatic group represented by Y include a linear or branched alkylene group, a cycloalkylene group, and a divalent group having a polyalkylene oxide structure.

[0093] The linear or branched alkylene group represented by Y is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms. Specific examples of the alkylene group represented by Y include a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a 2-methylpentamethylene group, a 2-methylhexamethylene group, a 2-methylheptamethylene group, a 2-methyloctamethylene group, a 2-methylnonamethylene group, and a 2-methyldecamethylene group.

[0094] The cycloalkylene group represented by Y is preferably a cycloalkylene group having 3 to 10 carbon atoms, and more preferably a cycloalkylene group having 3 to 6 carbon atoms. Specific examples of the cycloalkylene group represented by Y include a cyclopropylene group and a cyclohexylene group.

[0095] The unit structure contained in the divalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, and even more preferably an alkylene oxide structure having 1 to 4 carbon atoms. Of these, the polyalkylene oxide structure is preferably a polyethylene oxide structure or a polypropylene oxide structure. The alkylene group in the alkylene oxide structure may be linear or branched. The unit structure in the polyalkylene oxide structure may be one type or two or more types.

[0096] The divalent organic group represented by Y may be a divalent group having a polysiloxane structure. Examples of the divalent group having a polysiloxane structure represented by Y include divalent groups having a polysiloxane structure in which a silicon atom in the polysiloxane structure is bonded to a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms bonded to a silicon atom in the polysiloxane structure include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-octyl group, a 2-ethylhexyl group, an n-dodecyl group, etc. Among these, a methyl group is preferred. The aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted. Specific examples of the substituent when the aryl group has a substituent include a halogen atom, an alkoxy group, and a hydroxy group. Specific examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, and a benzyl group. Of these, a phenyl group is preferred. The alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be of one type or of two or more types. The silicon atom constituting the divalent group having a polysiloxane structure represented by Y may be bonded to the NH group in general formula (1) via an alkylene group such as a methylene group or an ethylene group, or an arylene group such as a phenylene group.

[0097] The group represented by formula (G) is preferably a group represented by the following formula (G'), and the group represented by formula (H) is preferably a group represented by the following formula (H'), formula (H'') or formula (H''').

[0098] [ka]

[0099] In formula (H'''), each R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom. R is preferably an alkyl group, and more preferably a methyl group.

[0100] In general formula (1), the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y is not particularly limited. From the viewpoint of achieving a thermal expansion coefficient of 50 ppm / K or less when cured, the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y includes a combination in which X is a group represented by formula (F) or a group represented by formula (P) and Y is a group represented by formula (G), and a combination in which X is a combination of a group represented by formula (P) and a group represented by formula (F) and Y is a group represented by formula (G). When X is a combination of a group represented by formula (P) and a group represented by formula (F), the molar ratio of the group represented by formula (P) to the group represented by formula (F) (group represented by formula (P):group represented by formula (F), ratio (P:F)) is preferably 50:50 to 20:80, more preferably 30:70 to 20:80.

[0101] R 6 and R 7 R each independently represents a hydrogen atom or a monovalent organic group. 6 and R 7 When is a monovalent organic group, the monovalent organic group may have a polymerizable unsaturated bond. The monovalent organic group is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an organic group having an unsaturated double bond, more preferably a group represented by the following general formula (2), an ethyl group, an isobutyl group, or a t-butyl group, and even more preferably contains an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2). When the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), the i-ray transmittance is high, and a good cured product tends to be formed even when cured at a low temperature of 400° C. or less. Furthermore, when the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), at least a portion of the unsaturated double bond moiety is eliminated by the (C) compound.

[0102] Specific examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group, and among these, an ethyl group, an isobutyl group, and a t-butyl group are preferred.

[0103] [ka]

[0104] In general formula (2), R 8 ~R 10 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R x represents a divalent linking group.

[0105] R in general formula (2) 8 ~R 10 The aliphatic hydrocarbon group represented by R has 1 to 3 carbon atoms, preferably 1 or 2. 8 ~R 10 Specific examples of the aliphatic hydrocarbon group represented by the formula include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc., with a methyl group being preferred.

[0106] R in general formula (2) 8 ~R 10 As a combination of 8 and R 9 is a hydrogen atom, and R 10 is preferably a hydrogen atom or a methyl group.

[0107] R in general formula (2) xis a divalent linking group, and is preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms include linear or branched alkylene groups. R x The number of carbon atoms in is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.

[0108] In general formula (1), R 6 and R 7 At least one of R is preferably a group represented by the general formula (2). 6 and R 7 It is more preferable that both of the above are groups represented by the general formula (2).

[0109] (A) When the polyimide precursor contains a compound having a structural unit represented by the above-mentioned general formula (1), R of all structural units contained in the compound 6 and R 7 R is a group represented by general formula (2) relative to the total 6 and R 7 The proportion is preferably 60 mol % or more, more preferably 70 mol % or more, and even more preferably 80 mol % or more. There is no particular upper limit, and it may be 100 mol %. The above ratio may be 0 mol % or more and less than 60 mol %.

[0110] The group represented by general formula (2) is preferably a group represented by the following general formula (2').

[0111] [ka]

[0112] In general formula (2'), R 8 ~R 10 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; and q represents an integer of 1 to 10.

[0113] In general formula (2′), q is an integer of 1 to 10, preferably an integer of 2 to 5, and more preferably 2 or 3.

[0114] The content of the structural unit represented by general formula (1) contained in the compound having the structural unit represented by general formula (1) is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more, based on the total structural units. The upper limit of the content is not particularly limited, and may be 100 mol%.

[0115] The polyimide precursor (A) may be synthesized using a tetracarboxylic dianhydride and a diamine compound. In this case, in general formula (1), X corresponds to a residue derived from the tetracarboxylic dianhydride, and Y corresponds to a residue derived from the diamine compound. The polyimide precursor (A) may be synthesized using a tetracarboxylic acid instead of the tetracarboxylic dianhydride.

[0116] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic dianhydride. carboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride phenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-( 3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, octahydro-3H,3''H-dispiro[[4,7]methanoisobenzofuran-5,1'-cyclopentane-3',5''-[4,7]methanoisobenzofuran]-1,1'',2',3,3''(4H,4''H)-pentane (CpODA), and the like. The tetracarboxylic dianhydrides may be used alone or in combination of two or more.

[0117] Specific examples of the diamine compound include 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4 ... ,2'-Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,4'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 2,4'-diaminodiphenyl sulfide, 2,2'-diaminodiphenyl sulfide, o-tolidine, o-tolidine sulfone, 4,4'-methylenebis(2,6- diethylaniline), 4,4'-methylenebis(2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenonediamine, bis-{4-(4'-aminophenoxy)phenyl}sulfone, 2,2-bis{4-(4'-aminophenoxy)phenyl}propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis{4-(3'-aminophenoxy)phenyl}sulfone, 2,2-bis(4-amino (aminophenyl)propane, 9,9-bis(4-aminophenyl)fluorene, 1,3-bis(3-aminophenoxy)benzene, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2-methyl-1,Examples of suitable diamine compounds include 9-diaminononane, 2-methyl-1,10-diaminodecane, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and diaminopolysiloxane. Preferred diamine compounds include 2,2'-dimethylbiphenyl-4,4'-diamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, and 1,3-bis(3-aminophenoxy)benzene. The diamine compounds may be used alone or in combination of two or more.

[0118] Having a structural unit represented by general formula (1), and R 6 and R 7 A compound in which at least one of the above is a monovalent organic group can be obtained, for example, by the following method (a) or (b). (a) A tetracarboxylic dianhydride (preferably a tetracarboxylic dianhydride represented by the following general formula (8)) is reacted with a compound represented by R—OH in an organic solvent to form a diester derivative, and then the diester derivative is subjected to a condensation reaction with a diamine compound represented by H2N-Y-NH2. (b) A tetracarboxylic dianhydride and a diamine compound represented by H2N-Y-NH2 are reacted in an organic solvent to obtain a polyamic acid solution, and a compound represented by R-OH is added to the polyamic acid solution and reacted in an organic solvent to introduce an ester group. Here, Y in the diamine compound represented by H2N-Y-NH2 is the same as Y in general formula (1), and specific examples and preferred examples are also the same. Furthermore, R in the compound represented by R-OH represents a monovalent organic group, and specific examples and preferred examples are the same as R in general formula (1). 6 and R 7 This is the same as in the case of The tetracarboxylic dianhydride represented by general formula (8), the diamine compound represented by H2N-Y-NH2, and the compound represented by R-OH may each be used alone or in combination of two or more. Examples of the organic solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, dimethoxyimidazolidinone, and 3-methoxy-N,N-dimethylpropionamide, and among these, 3-methoxy-N,N-dimethylpropionamide is preferred. A polyimide precursor may be synthesized by reacting a polyamic acid solution with a dehydration condensation agent together with the compound represented by R-OH. The dehydration condensation agent preferably includes at least one selected from the group consisting of trifluoroacetic anhydride, N,N'-dicyclohexylcarbodiimide (DCC), and 1,3-diisopropylcarbodiimide (DIC).

[0119] The above-described compound contained in (A) polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R—OH to form a diester derivative, then converting this into an acid chloride by reacting it with a chlorinating agent such as thionyl chloride, and then reacting the acid chloride with a diamine compound represented by HN-Y-NH. The above-mentioned compound contained in (A) polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R—OH to form a diester derivative, and then reacting the diamine compound represented by H2N-Y-NH2 with the diester derivative in the presence of a carbodiimide compound. The aforementioned compound contained in (A) polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a diamine compound represented by H2N-Y-NH2 to form a polyamic acid, then isoimidizing the polyamic acid in the presence of a dehydration condensation agent such as trifluoroacetic anhydride, and then reacting it with a compound represented by R-OH. Alternatively, a part of the tetracarboxylic dianhydride may be reacted in advance with a compound represented by R-OH, and the partially esterified tetracarboxylic dianhydride may be reacted with the diamine compound represented by H2N-Y-NH2.

[0120] [ka]

[0121] In the general formula (8), X is the same as X in the general formula (1), and specific examples and preferred examples are also the same.

[0122] (A) The compound represented by R—OH used in the synthesis of the above-mentioned compound contained in the polyimide precursor is R of the group represented by general formula (2). x The compound may be a compound having a hydroxy group bonded to the terminal methylene group of a group represented by general formula (2'), or a compound having a hydroxy group bonded to the terminal methylene group of a group represented by general formula (2'). Specific examples of the compound represented by R-OH include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate, and among these, 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are preferred.

[0123] Having a structural unit represented by general formula (1), and R 6 and R 7 The compound in which both are hydrogen atoms can be produced by a conventional method.

[0124] There are no particular restrictions on the molecular weight of (A) the polyimide precursor, and for example, the weight average molecular weight is preferably 10,000 to 200,000, and more preferably 10,000 to 100,000. The weight average molecular weight can be measured, for example, by gel permeation chromatography, and can be calculated using a standard polystyrene calibration curve.

[0125] The insulating film-forming material may further contain a dicarboxylic acid, and the (A) polyimide precursor contained in the insulating film-forming material may have a structure formed by reaction of some of the amino groups in the (A) polyimide precursor with carboxy groups in the dicarboxylic acid. For example, when synthesizing the polyimide precursor, some of the amino groups of a diamine compound may be reacted with carboxy groups in the dicarboxylic acid. The dicarboxylic acid may be a dicarboxylic acid having a (meth)acrylic group, for example, a dicarboxylic acid represented by the following formula: In this case, when synthesizing the polyimide precursor (A), a methacrylic group derived from the dicarboxylic acid can be introduced into the polyimide precursor (A) by reacting some of the amino groups of the diamine compound with the carboxyl groups of the dicarboxylic acid.

[0126] [ka]

[0127] The insulating film-forming material may contain a polyimide resin in addition to the (A) polyimide precursor. By combining the polyimide precursor and the polyimide resin, it is possible to suppress the generation of volatiles due to dehydration cyclization during imide ring formation, which tends to suppress the generation of voids. The polyimide resin referred to here refers to a resin having an imide skeleton in all or part of the resin skeleton. It is preferable that the polyimide resin is soluble in a solvent in the insulating film-forming material using the polyimide precursor.

[0128] The polyimide resin is not particularly limited as long as it is a polymer compound having a plurality of structural units containing imide bonds, and preferably contains, for example, a compound having a structural unit represented by the following general formula (X): This tends to provide a semiconductor device having an insulating film that exhibits high reliability.

[0129] [ka]

[0130] In general formula (X), X represents a tetravalent organic group, and Y represents a divalent organic group. Preferred examples of the substituents X and Y in general formula (X) are the same as the preferred examples of the substituents X and Y in general formula (1) described above.

[0131] When the insulating film-forming material contains a polyimide resin, the proportion of the polyimide resin relative to the total of the polyimide precursor and the polyimide resin may be 15% by mass to 50% by mass, or 10% by mass to 20% by mass.

[0132] The insulating film-forming material may contain other resins in addition to the (A) polyimide precursor and polyimide resin. Examples of the other resins include, from the viewpoint of heat resistance, novolac resins, acrylic resins, polyethernitrile resins, polyethersulfone resins, epoxy resins, polyethylene terephthalate resins, polyethylene naphthalate resins, and polyvinyl chloride resins. The other resins may be used singly or in combination of two or more.

[0133] In the insulating film-forming material, the content of the (A) polyimide precursor relative to the total amount of resin components is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.

[0134] ((B) Solvent) The insulating film-forming material contains a (B) solvent (hereinafter also referred to as "component (B)"). The component (B) preferably contains at least one compound selected from the group consisting of compounds represented by the following formulas (3) to (7):

[0135] [ka]

[0136] In formulas (3) to (7), R 1 , R 2 , R 8 and R 10 are each independently an alkyl group having 1 to 4 carbon atoms, and R3 ~R 7 and R 9 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. s is an integer of 0 to 8, t is an integer of 0 to 4, r is an integer of 0 to 4, and u is an integer of 0 to 3.

[0137] In formula (3), s is preferably 0. In equation (4), R 2 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. t is preferably 0, 1 or 2, and more preferably 1. In equation (5), R 3 The alkyl group having 1 to 4 carbon atoms in R is preferably a methyl group, an ethyl group, a propyl group, or a butyl group. 4 and R 5 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. In equation (6), R 6 ~R 8 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. r is preferably 0 or 1, and more preferably 0. In equation (7), R 9 and R 10 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. u is preferably 0 or 1, and more preferably 0.

[0138] The component (B) may be, for example, at least one of the compounds represented by formulas (4), (5), (6), and (7), or may be a compound represented by formula (5) or a compound represented by formula (7).

[0139] Specific examples of the component (B) include the following compounds:

[0140] [ka]

[0141] The component (B) contained in the insulating film-forming material is not limited to the above-mentioned compounds and may be other solvents, such as ester solvents, ether solvents, ketone solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, and sulfoxide solvents.

[0142] Examples of ester solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates such as methyl alkoxyacetate, ethyl alkoxyacetate, and butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate), and alkyl 3-alkoxypropionates such as methyl 3-alkoxypropionate and ethyl 3-alkoxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate). 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate; methyl 2-alkoxy-2-methylpropionates such as methyl 2-methoxy-2-methylpropionate; ethyl 2-alkoxy-2-methylpropionates such as ethyl 2-ethoxy-2-methylpropionate; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, and ethyl 2-oxobutanoate.

[0143] Examples of ether solvents include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. Examples of ketone solvents include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone (NMP). Examples of hydrocarbon solvents include limonene. Examples of aromatic hydrocarbon solvents include toluene, xylene, and anisole. Examples of the solvent for sulfoxides include dimethyl sulfoxide.

[0144] Preferred examples of the solvent for component (B) include γ-butyrolactone, cyclopentanone, and ethyl lactate.

[0145] In the insulating film-forming material, from the viewpoint of reducing toxicity such as reproductive toxicity and reducing the environmental load, the content of NMP may be 1 mass % or less based on the total amount of the insulating film-forming material, or may be 3 mass % or less based on the total amount of the (A) polyimide precursor.

[0146] In the insulating film-forming material, the content of the component (B) is preferably 1 to 10,000 parts by mass, and more preferably 50 to 10,000 parts by mass, per 100 parts by mass of the polyimide precursor (A).

[0147] Component (B) preferably contains at least one of solvent (1), which is at least one selected from the group consisting of compounds represented by formulas (3) to (6), and solvent (2), which is at least one selected from the group consisting of ester solvents, ether solvents, ketone solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, and sulfoxide solvents. The content of the solvent (1) may be 5% by mass to 100% by mass, or 5% by mass to 50% by mass, based on the total of the solvent (1) and the solvent (2). The content of the solvent (1) may be 10 parts by mass to 1000 parts by mass, 10 parts by mass to 100 parts by mass, or 10 parts by mass to 50 parts by mass relative to 100 parts by mass of the polyimide precursor (A).

[0148] ((C) compound) The second insulating film-forming material may contain a compound (C), which acts on the polymerizable unsaturated bond sites of the polyimide precursor (A) and promotes the elimination of the polymerizable unsaturated bond sites. The compound (C) may be, for example, a nitrogen-containing compound. The nitrogen-containing compound may be a thermal base generator. The thermal base generator generates a base upon heating, and this base promotes elimination of the unsaturated bond site of the polyimide precursor (A).

[0149] Specific examples of the nitrogen-containing compound include aniline diacetic acid, 2-(methylphenylamino)ethanol, 2-(ethylanilino)ethanol, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, 4-aminobenzamide, 2-aminobenzamide, nicotinamide, 4-amino-N-methylbenzamide, 4-aminoacetanilide, 4-aminoacetophenone, diazabicycloundecene, and salts thereof. Among these, aniline diacetic acid, 4-aminobenzamide, nicotinamide, diazabicycloundecene, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, and salts thereof are preferred. The nitrogen-containing compounds may be used alone or in combination of two or more.

[0150] The content of the (C) compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) polyimide precursor, and from the viewpoint of storage stability, is more preferably 0.3 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass.

[0151] The insulating film-forming material contains (A) a polyimide precursor and (B) a solvent, and optionally contains (C) a compound, (D) a photopolymerization initiator, (E) a polymerizable monomer, (F) a thermal polymerization initiator, (G) a polymerization inhibitor, an antioxidant, a coupling agent, a surfactant, a leveling agent, a rust inhibitor, etc., and may contain other components and inevitable impurities within a range that does not impair the effects of the present disclosure. The insulating film-forming material preferably further contains component (D) and component (E). Hereinafter, the (C) compound will also be referred to as the (C) component, the (D) photopolymerization initiator as the (D) component, the (E) polymerizable monomer as the (E) component, the (F) thermal polymerization initiator as the (F) component, and the (G) polymerization inhibitor as the (G) component.

[0152] In one embodiment, for example, 80 mass % or more, 90 mass % or more, 95 mass % or more, 98 mass % or more, or 100 mass % of the insulating film-forming material is (A) Polyimide precursor to (B) component, (A) polyimide precursor to component (B) and components (D) to (E), (A) polyimide precursor to component (B) and components (D) to (F), (A) polyimide precursor to component (B) and components (D) to (G), The composition may comprise at least one selected from the group consisting of (A) a polyimide precursor to (B) components and (D) to (G) components, and (C) component, an antioxidant, a coupling agent, a surfactant, a leveling agent, and a rust inhibitor. In other embodiments, for example, 80 mass % or more, 90 mass % or more, 95 mass % or more, 98 mass % or more, or 100 mass % of the insulating film-forming material is (A) polyimide precursor to component (B) and components (E) to (F), (A) polyimide precursor to component (B) and components (E) to (G), The composition may comprise at least one selected from the group consisting of (A) a polyimide precursor to (B) components and (E) to (G) components, and (C) component, an antioxidant, a coupling agent, a surfactant, a leveling agent, and a rust inhibitor. As the (D) photopolymerization initiator, (E) polymerizable monomer, (F) thermal polymerization initiator, (G) polymerization inhibitor, antioxidant, coupling agent, surfactant, leveling agent, rust inhibitor, and the like, conventionally known components may be used as appropriate. [Example]

[0153] The present disclosure will be described in more detail below based on examples and comparative examples, but the present disclosure is not limited to the following examples.

[0154] (Synthesis of Polyimide Precursor A1) 6.71 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 2.09 g of p-phenylenediamine (PPD) were dissolved in 30 g of 3-methoxy-N,N-dimethylpropanamide. The resulting solution was stirred at 30°C for 2 hours to obtain polyimide precursor A1 (hereinafter referred to as polymer A1). The resulting polymer A1 was added dropwise to dehydrated ethanol, and the precipitate was collected by filtration and dried under reduced pressure to obtain polymer A1 powder. The weight-average molecular weight of polymer A1 was determined using gel permeation chromatography (GPC) in terms of standard polystyrene. The weight-average molecular weight of polymer A1 was 20,000.

[0155] (Synthesis of Polyimide Precursor A2) 7.07 g of 3,3',4,4'-biphenylethertetracarboxylic dianhydride (ODPA) and 4.12 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) were dissolved in 30 g of 3-methoxy-N,N-dimethylpropanamide. The resulting solution was stirred at 30°C for 4 hours to obtain polyamic acid. 9.45 g of trifluoroacetic anhydride was added to the solution at room temperature (25°C), followed by 7.08 g of 2-hydroxyethyl methacrylate (HEMA), and the mixture was stirred at 45°C for 10 hours. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyimide precursor A2 (hereafter referred to as polymer A2). The weight-average molecular weight of polymer A2, as determined by GPC using standard polystyrene standards, was 20,000.

[0156] (Synthesis of Polyimide Precursor A3) The same procedure was followed to synthesize Polyimide Precursor A2, except that DMAP was replaced with 3.6 g of 4,4'-diaminodiphenyl ether (ODA) and 0.2 g of m-phenylenediamine (MPD), to obtain Polyimide Precursor A3 (hereinafter referred to as Polymer A3). The weight-average molecular weight of Polymer A3, calculated using GPC as a standard polystyrene standard, was 25,000.

[0157] (Synthesis of Polyimide Precursor A4) 8.76 g of octahydro-3H,3'H-dispiro[[4,7]methanoisobenzofuran-5,1'-cyclopentane-3',5'-[4,7]methanoisobenzofuran]-1,1',2',3,3'(4H,4'H)-pentaone (CpODA) and 2.09 g of PPD were dissolved in 30 g of 3-methoxy-N,N-dimethylpropanamide. The resulting solution was stirred at 30 °C for 2 hours to obtain polyimide precursor A4 (hereafter referred to as polymer A4). The resulting polymer A4 was added dropwise to dehydrated ethanol, and the precipitate was collected by filtration and dried under reduced pressure to obtain polymer A4 powder. The weight-average molecular weight of polymer A4 was determined using gel permeation chromatography (GPC) in terms of standard polystyrene. The weight-average molecular weight of polymer A4 was 20,000.

[0158] (Synthesis of Polyimide Precursor A5) In a reaction vessel, 15.5 g of ODPA and 13.1 g of HEMA were dissolved in 50 mL of γ-butyrolactone and stirred at 25°C, and 8 g of pyridine was added with stirring to obtain a reaction mixture. After the heat generated by the reaction had ceased, the reaction mixture was allowed to cool to 25°C and left to stand for 15 hours. Next, under ice cooling, a solution prepared by suspending 20 g of dicyclohexylcarbodiimide (DCC) in 180 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Next, a suspension prepared by suspending 9.3 g of 4,4'-diaminodiphenyl ether in 35 mL of γ-butyrolactone was added to the reaction mixture over 60 minutes with stirring. The reaction mixture was further stirred at 25°C for 2 hours, after which 30 mL of ethyl alcohol was added and stirred for 1 hour. Next, 40 mL of γ-butyrolactone was added to the reaction mixture. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution. The resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The resulting crude polymer was filtered and dissolved in 1 liter of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to water to precipitate the polymer, and the resulting precipitate was filtered and then vacuum dried to obtain a powdery polymer, Polyimide Precursor A5 (hereinafter referred to as Polymer A5). The weight-average molecular weight of Polymer A5, determined by GPC using standard polystyrene standards, was 35,000.

[0159] (Synthesis of Polyimide Precursor A6) Polyimide precursor A6 (hereinafter referred to as polymer A6) was obtained by the same procedure as in the synthesis of polyimide precursor A5, except that 15.5 g of ODPA was replaced with 14.7 g of BPDA. The weight average molecular weight of polymer A6, calculated by GPC using standard polystyrene, was 28,000.

[0160] The weight-average molecular weights of polymers A1 to A6 were determined by gel permeation chromatography (GPC) in terms of standard polystyrene. Specifically, 0.5 mg of polyimide precursor was dissolved in 1 mL of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)] under the following conditions:

[0161] (Measurement conditions) Measuring device: Shimadzu Corporation SPD-M20A Pump: Shimadzu Corporation LC-20AD Column oven: Shimadzu Corporation: CTO-20A Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 Eluent: THF / DMF=1 / 1 (volume ratio) LiBr(0.03mol / L), H3PO4(0.06mol / L) Flow rate: 1.0 mL / min, detector: UV 270 nm, column temperature: 40°C Standard polystyrene: Tosoh TSKgel standard polystyrene Type F-1, F-4, F-20, F-80, A-2500 to create a calibration curve

[0162] [Examples 1 to 6, Comparative Example 1] (Preparation of insulating film forming material) The insulating film-forming materials of Examples 1 to 6 and Comparative Example 1 were prepared as follows using the components and blending amounts shown in Table 1. The blending amount of each component in Table 1 is in parts by mass. A blank cell in Table 1 indicates that the corresponding component was not blended. In each Example and Comparative Example, a mixture of the components was kneaded overnight at room temperature (25°C) in a general solvent-resistant container, and then pressure filtered using a filter with 0.2 μm pores. The insulating film-forming materials obtained were used to carry out the following evaluations.

[0163] The components in Table 1 are as follows: Polyimide precursor The above-mentioned polymers A1 to A6 ·solvent B1: 3-Methoxy-N,N-dimethylpropanamide B2: γ-butyrolactone B3: Dimethyl sulfoxide Polymerizable monomers C1: Tetraethylene glycol dimethacrylate (TEGDMA) C2: Tricyclodecane dimethanol diacrylate (A-DCP) Rust inhibitor D1: Benzotriazole (BT) Polymerization initiator E1: 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime (PDO) E2: 4,4'-bis(diethylamino)benzophenone (EMK) E3: Bis(1-phenyl-1-methylethyl) peroxide (Percumyl D) Antioxidants F1: N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide] (HP300) Adhesion aid G1: 3-Ureidopropyltriethoxysilane (UCT-801)

[0164] (Measurement of thermal expansion coefficient of cured film) Cured films were formed as follows using the insulating film-forming materials of Examples 1 to 6 and Comparative Example 1, and then the thermal expansion coefficients were measured. The insulating film-forming materials were spin-coated onto a Si substrate, and dried by heating on a hot plate at 95°C for 120 seconds, and then at 105°C for 120 seconds, to form a resin film with a thickness of approximately 10 μm after curing.

[0165] For Examples 1 and 4, the resulting resin film was cured in a vertical diffusion furnace μ-TF under a nitrogen atmosphere at the curing temperature and for the curing time listed in Table 1 to obtain a cured product with a film thickness of 10 μm. The resulting cured product was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid and peeled from the Si substrate. The resulting cured product was shaped to a width of 10 mm using a razor to obtain a patterned cured product with a width of 10 mm. In Examples 2, 3, 5, and 6 and Comparative Example 1, the obtained resin film was exposed to light at a dose of 600 mJ / cm using a mask aligner MA-8 (manufactured by SUSS MicroTec). 2 After broadband (BB) exposure, the film was cured in a vertical diffusion furnace μ-TF under a nitrogen atmosphere at the curing temperature and for the curing time listed in Table 1 to obtain a cured product with a film thickness of 10 μm. The cured product was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid and peeled off from the Si substrate. The obtained cured product was shaped into a 10 mm width using a razor to obtain a 10 mm wide patterned cured product. Using a TMA tester (TMA2940 manufactured by DuPont), the linear thermal expansion coefficient of the patterned cured material (measured sample) in the in-plane direction was measured from 30°C to 100°C under the conditions of an initial sample length of 10 mm, a load of 10 g, and a heating rate of 5°C / min. The results obtained are shown in Table 1 as thermal expansion coefficients.

[0166] (Possibility of bonding between insulating films) The insulating film forming materials of Examples 1 to 6 and Comparative Example 1 were spin-coated onto an 8-inch Si wafer using a spin coater coating device, and then heated and dried at 95°C for 120 seconds, and then heated and dried at 105°C for 120 seconds to form a resin film. In Examples 2, 3, 5, and 6 and Comparative Example 1, the obtained resin film was irradiated with light of 365 nm wavelength at 600 mJ / cm. 2 An exposed resin film was obtained by irradiating the resin with an exposure dose. The obtained exposed resin film and the resin films of Examples 1 and 4 were cured in a vertical diffusion furnace μ-TF under a nitrogen atmosphere at the curing temperature and for the curing time shown in Table 1 to obtain cured films.

[0167] Of the obtained cured films, the cured films of Examples 1 to 6 were polished by CMP to obtain polished cured films. Of the obtained cured films, the cured film of Comparative Example 1 was not polished. The cured films were scrubbed using a general cleaning solution, and then a portion of the cleaned cured film was cut into 5 mm square pieces using a blade dicer (DISCO DFD-6362) to obtain resin-attached chips. The obtained resin-attached chips were pressed onto the remaining cured film that had not been cut into pieces using a flip chip bonder (Toray Engineering Co., Ltd. MD4000) for 15 seconds at a predetermined pressure and at the bonding temperature shown in Table 1 to produce chip-attached cured films. For each insulating film-forming material, five chips pressed onto the cured film were evaluated as described below. The obtained cured film was measured using an AFM (atomic force microscope) and found to have a thickness of 10 μm 2 The surface roughness Ra within the sample was measured. Surface roughness Ra of 2.0 nm or less was evaluated as A, and surface roughness Ra of more than 2.0 nm was evaluated as B. The results are shown in Table 1.

[0168] (evaluation) The resulting chip-attached cured film was examined for adhesive failure at the resin interface using SAT (Scanning Acoustic Tomography). The evaluation criteria for adhesive failure were as follows. The results are shown in Table 1. - Evaluation criteria for bonding defects - A: Among 50 chips, 10 or fewer chips were found to have bonding defects. B: Among 50 chips, more than 10 chips were found to have bonding defects.

[0169] (Bonding between copper electrodes) A pair of 12-inch wafers, one on top and one on bottom, was prepared, each with Cu wiring for junction continuity testing on a Si wafer with a 500nm thick SiO2 layer formed by thermal oxidation treatment from the surface. This was used to create the 12-inch Cu patterned wafer. The 12-inch Cu patterned wafer has 2μm-high wiring and, at the junction above it, Cu pillars for bonding, with a diameter of approximately 10μm and a height of 5μm. The insulating film forming materials of Examples 1 to 6 and Comparative Example 1 were spin-coated onto a 12-inch Cu-patterned wafer using a spin coater so that the resin film would have a thickness of approximately 11 μm after curing, and the resulting film was dried by heating at 95°C for 120 seconds, and then at 105°C for 120 seconds, to form a Cu-patterned resin film. For Examples 2, 3, 5, and 6 and Comparative Example 1, the resulting resin film was irradiated with light of 365 nm wavelength at 600 mJ / cm. 2 Exposure amount irradiated. The obtained resin film with a Cu pattern was cured in a nitrogen atmosphere using a vertical diffusion furnace μ-TF at the curing temperature and for the curing time shown in Table 1 to obtain a cured film with a Cu pattern. Of the obtained cured films with a Cu pattern, those in Examples 1 to 6 were polished by CMP until the Cu pillars were exposed, to obtain a polished cured film with a Cu pattern. The obtained polished cured film with a Cu pattern was measured using an AFM (atomic force microscope) to find a polished surface roughness of 10 μm. 2 The surface roughness Ra of the resin and the Cu electrode was measured and confirmed to be 2.0 nm or less. Furthermore, the height of the cured film (organic insulating film) in the polished cured film with the Cu pattern was 5 nm higher than the combined height of the electrode including the wiring and the Cu pillar. The difference between the height of the cured film (organic insulating film) and the height of the electrode including the wiring and Cu pillars was the arithmetic average value measured at five points on the polished cured film with the Cu pattern using an atomic force microscope (AFM). The polished Cu-patterned cured film was scrubbed using a standard cleaning solution, and then a portion of the cleaned cured film was cut into 5 mm square pieces using a blade dicer (DISCO DFD-6362) to obtain Cu-patterned resin chips. The remaining Cu-patterned cured film and the Cu-patterned resin chips were immersed in a specified organic acid for 30 seconds to remove the oxide layer on the copper surface, and then dried on a hot plate at 85°C for 3 minutes. After drying, the Cu-patterned resin chip was pressed against the Cu-patterned cured film for 15 seconds at the specified pressure and bonding temperature shown in Table 1 to produce a Cu-patterned wafer with chips. The Cu-patterned wafer with chips was then heated for 30 minutes at 230°C in a nitrogen atmosphere.

[0170] The electrical resistance of the fabricated chip-attached Cu pattern wafer was measured using a standard probe tester. The electrical resistance was measured using a wiring pattern that passed through 20 pairs of bonding sections. For Comparative Example 1, poor bonding between the insulating films occurred, preventing bonding between the copper electrodes, so the feasibility of bonding between the copper electrodes was not evaluated. - Evaluation criteria for bonding between copper electrodes - A: Electrical resistance is 2000Ω or less B: Electrical resistance is greater than 2000 Ω

[0171] [Table 1]

[0172] As shown in Table 1, in Examples 1 to 6, bonding between the insulating films was possible at 25°C, whereas in Comparative Example 1, bonding between the insulating films occurred even when the bonding was performed at 250°C.

[0173] The disclosure of Japanese Patent Application No. 2022-063656, filed on April 6, 2022, is incorporated herein by reference in its entirety. All publications, patent applications, and technical standards mentioned in this specification are incorporated by reference into this specification to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference. [Explanation of symbols]

[0174] 1, 1a, 401...semiconductor device, 10...first semiconductor chip, 20...second semiconductor chip, 30...pillar portion, 40...rewiring layer, 50...substrate, 60...circuit board, 61...terminal electrode, 100...first silicon substrate, 101...first silicon substrate main body, 101a...one surface, 102...insulating film (first insulating film), 103...terminal electrode (first electrode), 103a...surface, 200...second silicon substrate, 201...second silicon substrate main body, 201a...one surface, 202...insulating film (second insulating film), 203...terminal electrode (second electrode), 203 a...surface, 205...semiconductor chip, 300...pillar, 301...resin, 410...semiconductor wafer (first semiconductor substrate), 411...substrate body (first semiconductor substrate body), 412...insulating film (first insulating film), 413...terminal electrode (first electrode), 420...semiconductor chip (second semiconductor substrate), 421...substrate body, 422...insulating film portion (second insulating film), 423...terminal electrode (second electrode), A...cutting line, H...heat, M1 to M3...semi-finished product, S1...insulating joint portion, S2...electrode joint portion, S3...insulating joint portion, S4...electrode joint portion

Claims

1. a first semiconductor substrate including a first semiconductor substrate body, a first electrode provided on one surface of the first semiconductor substrate body, and a first organic insulating film having a surface roughness Ra of 2.0 nm or less; a second semiconductor substrate including a second semiconductor substrate body, a second electrode provided on one surface of the second semiconductor substrate body, and a second organic insulating film having a surface roughness Ra of 2.0 nm or less; The first organic insulating film and the second organic insulating film are bonded together at a temperature of 70° C. or less; A method for manufacturing a semiconductor device in which the first electrode and the second electrode are bonded, comprising the steps of: The method for manufacturing a semiconductor device, wherein the first organic insulating film and the second organic insulating film contain a cured product of a polyimide precursor having a structural unit represented by the following general formula (1): 【Chemistry 1】 In general formula (1), X is a group represented by the following formula (F) or a group represented by the following formula (P), Y is a combination of groups represented by the following formula (G), or X is a combined use of a group represented by the following formula (P) and a group represented by the following formula (F), Y is a combination of groups represented by the following formula (G), and R 6 and R 7 each independently represent a hydrogen atom or a monovalent organic group. 【Chemistry 2】 In formula (G), R represents an alkyl group, an alkoxy group, a hydroxyl group, a halogenated alkyl group, a phenyl group, or a halogen atom; and n represents an integer of 0 to 4.

2. 2. The method for manufacturing a semiconductor device according to claim 1, wherein the first organic insulating film and the second organic insulating film have a thermal expansion coefficient of 50 ppm / K or less.

3. 2. The method for manufacturing a semiconductor device according to claim 1, wherein the first semiconductor substrate is a semiconductor wafer, and the second semiconductor substrate is a semiconductor wafer.

4. 2. The method for manufacturing a semiconductor device according to claim 1, wherein the first semiconductor substrate is a semiconductor wafer, and the second semiconductor substrate is a semiconductor chip.

5. 2. The method for manufacturing a semiconductor device according to claim 1, wherein the first semiconductor substrate is a semiconductor chip, and the second semiconductor substrate is a semiconductor chip.

6. 2. The method for manufacturing a semiconductor device according to claim 1, wherein in the manufactured semiconductor device, the total thickness of the organic insulating film formed by bonding the first organic insulating film and the second organic insulating film is 0.1 [mu]m or more.

7. 2. The method for manufacturing a semiconductor device according to claim 1, wherein at least one of the first surface of the first semiconductor substrate and the second surface of the second semiconductor substrate is polished before the first organic insulating film and the second organic insulating film are bonded together.

8. The method for manufacturing a semiconductor device according to claim 7 , wherein the polishing comprises chemical mechanical polishing.

9. The method for manufacturing a semiconductor device according to claim 8 , wherein the polishing further comprises mechanical polishing.

10. 2. The method for manufacturing a semiconductor device according to claim 1, wherein the height of the first organic insulating film is equal to or greater than the height of the first electrode, and the height of the second organic insulating film is equal to or greater than the height of the second electrode.

11. 11. The method for manufacturing a semiconductor device according to claim 10, wherein the height of the first organic insulating film is at least 0.1 nm higher than the height of the first electrode, and the height of the second organic insulating film is at least 0.1 nm higher than the height of the second electrode.

12. A first semiconductor substrate is provided having a first semiconductor substrate body, a first electrode provided on one surface of the first semiconductor substrate body, and a first organic insulating film having a surface roughness Ra of 2.0 nm or less; a second semiconductor substrate including a second semiconductor substrate body, a second electrode provided on one surface of the second semiconductor substrate body, and a second organic insulating film having a surface roughness Ra of 2.0 nm or less; The first organic insulating film and the second organic insulating film are bonded together at a temperature of 70° C. or less; A hybrid bonding insulating film forming material used in manufacturing the first organic insulating film and the second organic insulating film in a manufacturing method of a semiconductor device in which the first electrode and the second electrode are bonded, containing a thermosetting polyamide and a solvent, and having a coefficient of thermal expansion of 50 ppm / K or less when cured; The hybrid bonding insulating film forming material, wherein the thermosetting polyamide contains a polyimide precursor having a structural unit represented by the following general formula (1): 【Transformation 3】 In general formula (1), X is a group represented by the following formula (F) or a group represented by the following formula (P), Y is a combination of groups represented by the following formula (G), or X is a combined use of a group represented by the following formula (P) and a group represented by the following formula (F), Y is a combination of groups represented by the following formula (G), and R 6 and R 7 each independently represent a hydrogen atom or a monovalent organic group. 【Chemistry 4】 In formula (G), R represents an alkyl group, an alkoxy group, a hydroxyl group, a halogenated alkyl group, a phenyl group, or a halogen atom; and n represents an integer of 0 to 4.

13. A hybrid bonding insulating film forming material as described in claim 12, further containing a polyimide resin.

Images