Optical semiconductor device and method for manufacturing the same, solid-state imaging device, and electronic apparatus

Abstract

A light semiconductor device (10) includes a semiconductor substrate (12), a transparent substrate (13), and an adhesive layer (14). The semiconductor substrate (12) has a light receiving element (11) provided thereon. The transparent substrate (13) is disposed so as to oppose the semiconductor substrate (12) in which the light receiving element (11) is provided. The adhesive layer (14) is a layer that adheres the semiconductor substrate (12) and the transparent substrate (13), and is provided so as to surround the light receiving element (11). The refractive index of the adhesive layer (14) is 1.60 or less.

Description

Technical Field

[0001] This invention relates to optical semiconductor devices and methods for manufacturing them, solid-state imaging devices, and electronic devices. Background Technology

[0002] Optical semiconductor devices that make up image sensors such as CMOS sensors and CCD sensors are used in digital cameras, smartphones, etc. In recent years, their usage has increased with the popularization of surveillance cameras in automobiles and factories, and there is a growing demand for miniaturization and high precision.

[0003] Optical semiconductor devices, for example, have a hollow structure in which a semiconductor substrate with a light-receiving element is bonded to a glass substrate with an adhesive. An optical semiconductor device with a hollow structure is obtained by coating the periphery of a semiconductor substrate with a liquid adhesive such as epoxy resin or acrylic resin, setting a glass substrate as a sealing substrate, and then heating it to cure the liquid adhesive (see, for example, Non-Patent Literature 1).

[0004] Existing technical documents

[0005] Non-patent literature

[0006] Non-patent literature 1: 21st Electronics Packaging Technology Conference, 2019, pp. 560-565 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] However, with the increasing demand for miniaturization and high precision in optical semiconductor devices in recent years, existing optical semiconductor devices, as described in Non-Patent Document 1, sometimes affect the imaging characteristics. In particular, when strong incident light is present, optical noise (specifically stray light, ghosting, etc.) is generated in the captured image, indicating that the original imaging characteristics cannot be fully utilized.

[0009] The present invention was made in view of the above-mentioned problems, and its object is to provide: an optical semiconductor device capable of suppressing the generation of optical noise and a method for manufacturing the same, as well as a solid-state imaging device and an electronic device having the optical semiconductor device.

[0010] Solution for solving the problem

[0011] The optical semiconductor device of the present invention includes: a semiconductor substrate having a light-receiving element disposed thereon; a transparent substrate facing the semiconductor substrate having the light-receiving element disposed thereon; and an adhesive layer for bonding the semiconductor substrate and the transparent substrate. The adhesive layer is disposed such that it surrounds the light-receiving element. The refractive index of the adhesive layer is 1.60 or less.

[0012] In one embodiment of the optical semiconductor device of the present invention, the angle between the surface of the aforementioned transparent substrate on the semiconductor substrate side and the inner wall surface of the aforementioned adhesive layer is 90° or more and 130° or less.

[0013] In one embodiment of the optical semiconductor device of the present invention, the height of the aforementioned adhesive layer is 15 μm or more and 300 μm or less.

[0014] An embodiment of the optical semiconductor device of the present invention further includes a wiring substrate disposed on the side opposite to the transparent substrate side of the aforementioned semiconductor substrate.

[0015] In one embodiment of the optical semiconductor device of the present invention, an electrode pad is provided on the aforementioned semiconductor substrate, and the aforementioned adhesive layer is disposed between the aforementioned electrode pad and the aforementioned light receiving element.

[0016] One embodiment of the optical semiconductor device of the present invention is a chip-scale package.

[0017] In one embodiment of the optical semiconductor device of the present invention, the aforementioned adhesive layer comprises a cured layer composed of a cured product of a photosensitive composition.

[0018] In one embodiment of the photo-semiconductor device of the present invention, the aforementioned photosensitizing composition contains a polysiloxane compound and a photopolymerization initiator, wherein the aforementioned polysiloxane compound has a cationic polymerizable group and an alkali-soluble group in one molecule.

[0019] In one embodiment of the optical semiconductor device of the present invention, the aforementioned cationic polymerizable group is one or more selected from the group consisting of glycidyl group, alicyclic epoxy group and oxetyl group.

[0020] In one embodiment of the optical semiconductor device of the present invention, the aforementioned alkali-soluble group is one or more selected from the group consisting of a monovalent organic group represented by the following chemical formula (X1) and a divalent organic group represented by the following chemical formula (X2).

[0021]

[0022] In one embodiment of the photo-semiconductor device of the present invention, the aforementioned photosensitive composition further comprises a compound having a free radical polymerizable group, and contains a photoradical polymerization initiator as the aforementioned photopolymerization initiator.

[0023] The solid-state imaging device of the present invention has the optical semiconductor device of the present invention.

[0024] The electronic device of the present invention has the solid-state imaging device of the present invention.

[0025] The method for manufacturing an optical semiconductor device of the present invention includes an adhesive layer forming step, a lamination step, and a curing step. In the adhesive layer forming step, a patterned adhesive layer is formed on a transparent substrate. In the lamination step, the transparent substrate on which the adhesive layer is formed and a semiconductor substrate having a light-receiving element are disposed thereon are laminated such that the surface of the transparent substrate on which the adhesive layer is formed faces the surface of the semiconductor substrate having the light-receiving element. In the curing step, the adhesive layer is cured, bonding the transparent substrate and the semiconductor substrate. In the method for manufacturing an optical semiconductor device of the present invention, in the lamination step, the adhesive layer is disposed around the light-receiving element. The refractive index of the cured adhesive layer is 1.60 or less.

[0026] In a method for manufacturing an optical semiconductor device according to an embodiment of the present invention, in the aforementioned adhesive layer formation step, a film composed of a photosensitive composition is patterned in a semi-cured state by photolithography.

[0027] In a method for manufacturing an optical semiconductor device according to an embodiment of the present invention, in the aforementioned adhesive layer forming step, the aforementioned film composed of the aforementioned photosensitive composition is exposed through soda-lime glass, and then the exposed aforementioned film is developed.

[0028] In a method for manufacturing a photo-semiconductor device according to an embodiment of the present invention, the aforementioned photosensitive composition contains: a polysiloxane compound, a photoradical polymerization initiator, and a compound having radical polymerizable groups, wherein the aforementioned polysiloxane compound has cationic polymerizable groups and alkali-soluble groups in one molecule.

[0029] The effects of the invention

[0030] According to the present invention, a light semiconductor device capable of suppressing the generation of optical noise and a method thereof can be provided, as well as a solid-state imaging device and an electronic device having the light semiconductor device. Attached Figure Description

[0031] Figure 1 This is a cross-sectional view illustrating an example of the optical semiconductor device of the present invention.

[0032] Figure 2 A partially enlarged cross-sectional view illustrating another example of the optical semiconductor device of the present invention.

[0033] Figure 3 A cross-sectional view illustrating another example of the optical semiconductor device of the present invention.

[0034] Figure 4 A partially enlarged cross-sectional view illustrating another example of the optical semiconductor device of the present invention.

[0035] Figure 5A partially enlarged cross-sectional view showing another example of the optical semiconductor device of the present invention.

[0036] Figure 6 A cross-sectional view illustrating another example of the optical semiconductor device of the present invention.

[0037] Figure 7 A top view of a transparent substrate after the adhesive layer has been formed, illustrating an example of manufacturing the optical semiconductor device of the present invention.

[0038] Figure 8 A top view of a monolithically mounted transparent substrate used to illustrate an example of manufacturing the optical semiconductor device of the present invention.

[0039] Figure 9 A, B, and C are process-independent cross-sectional views illustrating an example of the adhesive layer formation process in manufacturing the optical semiconductor device of the present invention.

[0040] Figure 10 A, B, and C are process-independent cross-sectional views illustrating an example of the lamination and curing processes in manufacturing the optical semiconductor device of the present invention.

[0041] Figure 11 A top view of a semiconductor substrate after the light-receiving element has been formed, illustrating an example of manufacturing the optical semiconductor device of the present invention.

[0042] Figure 12 A and B are process-independent cross-sectional views illustrating another example of the stacking process in manufacturing the optical semiconductor device of the present invention.

[0043] Figure 13 This is a top view showing an example of a printing mask used when forming an adhesive layer by screen printing. Detailed Implementation

[0044] Hereinafter, suitable embodiments of the present invention will be described in detail, but the present invention is not limited thereto. Furthermore, all academic and patent documents described in this specification are incorporated herein by reference.

[0045] First, the terms used in this specification will be explained. "Refractive index" refers to the refractive index of light with a wavelength of 404 nm in an atmosphere at 23°C. The method for determining the refractive index can be the same as or based on the methods described in the examples below.

[0046] "Polysiloxane compounds" refer to compounds having a polysiloxane structure with siloxane units (Si-O-Si) as constituent elements. Examples of polysiloxane structures include chain polysiloxane structures (specifically, linear polysiloxane structures, branched polysiloxane structures, etc.) and cyclic polysiloxane structures. "Photopolymerization initiators" refer to compounds that generate active substances (specifically, free radicals, cations, anions, etc.) by irradiation with active energy rays. "Photoradical polymerization initiators" refer to compounds that generate free radicals as active substances by irradiation with active energy rays. "Photocationic polymerization initiators" refer to compounds that generate cations (acids) as active substances by irradiation with active energy rays. Examples of active energy rays include visible light, ultraviolet light, infrared light, electron beams, X-rays, alpha rays, beta rays, and gamma rays.

[0047] "Catonic polymerizable group" refers to a functional group that undergoes chain polymerization in the presence of a cation. "Base-soluble group" refers to a functional group that increases the solubility in alkaline solutions by interacting with or reacting with a base. "Alicyclic epoxy group" refers to a functional group formed by bonding one oxygen atom to two adjacent carbon atoms in an alicyclic structure; examples include 3,4-epoxycyclohexyl. "Free radical polymerizable group" refers to a functional group possessing unsaturated bonds capable of free radical polymerization. "Solids component" refers to the non-volatile components in the composition; "total solids component" refers to the total amount of solvent removed from the composition's constituent components.

[0048] Hereinafter, the use of "system" after the compound name sometimes includes the general term for the compound and its derivatives. Additionally, when "system" is used after the compound name to indicate a polymer, it means that the repeating unit of the polymer originates from the compound or its derivatives. Furthermore, acrylic acid and methacrylic acid are sometimes collectively referred to as "(meth)acrylic acid". Additionally, acrylates and methacrylates are sometimes collectively referred to as "(meth)acrylate". Furthermore, acryloyl groups and methacryloyl groups are sometimes collectively referred to as "(meth)acryloyl". Finally, the cured adhesive layer is sometimes abbreviated as "adhesive layer".

[0049] The ingredients and functional groups exemplified in this instruction manual may be used alone or in combination with two or more unless otherwise specified.

[0050] The accompanying drawings referenced in the following description schematically illustrate the constituent elements for ease of understanding. The size, number, and shape of the constituent elements in the drawings may differ from the actual figures for the convenience of creating the drawings. Furthermore, for ease of explanation, the same symbols are used for the same constituent parts as in the preceding drawings in the following descriptions, and sometimes their descriptions are omitted.

[0051] <First Embodiment: Optical Semiconductor Device>

[0052] The optical semiconductor device according to the first embodiment of the present invention includes: a semiconductor substrate having a light-receiving element, a transparent substrate facing the semiconductor substrate having the light-receiving element, and an adhesive layer for bonding the semiconductor substrate and the transparent substrate. The adhesive layer is provided in a manner that surrounds the light-receiving element. The refractive index of the adhesive layer is 1.60 or less.

[0053] The optical semiconductor device of the first embodiment can suppress the generation of optical noise. The reason for this is as follows.

[0054] In the optical semiconductor device of the first embodiment, the refractive index of the adhesive layer is 1.60 or less, therefore, the reflectivity of light at the surface of the adhesive layer (specifically, the inner wall surface of the adhesive layer) is low. Consequently, in the optical semiconductor device of the first embodiment, the amount of reflected light incident on the light receiving element (specifically, reflected light from the inner wall surface of the adhesive layer) is reduced, resulting in less optical noise originating from the reflected light. Thus, the optical semiconductor device of the first embodiment can suppress the generation of optical noise.

[0055] Hereinafter, as a specific example of the optical semiconductor device of the first embodiment, an optical semiconductor device further comprising a wiring substrate will be described. Figure 1 The optical semiconductor device 10 shown and the chip-size package type optical semiconductor device ( Figure 3 The optical semiconductor device 100 shown will be described with reference to the accompanying drawings.

[0056] [Optical Semiconductor Device 10]

[0057] Figure 1 A cross-sectional view of a light semiconductor device 10, which is a specific example of a light semiconductor device according to the first embodiment, is shown. Figure 1The optical semiconductor device 10 shown includes a semiconductor substrate 12, a transparent substrate 13, and an adhesive layer 14. A light-receiving element 11 is provided on a first surface 12a of the semiconductor substrate 12. Additionally, the optical semiconductor device 10 also includes a wiring substrate 17 (intermediate layer) bonded to a second surface 12b of the semiconductor substrate 12 (the side of the semiconductor substrate 12 opposite to the transparent substrate 13 side) by means of a chip bonding material 18. It should be noted that "the first surface 12a of the semiconductor substrate 12" refers to one of the two surfaces orthogonal to the thickness direction of the semiconductor substrate 12. Similarly, "the second surface 12b of the semiconductor substrate 12" refers to the other of the two surfaces orthogonal to the thickness direction of the semiconductor substrate 12. The transparent substrate 13 is arranged opposite to the first surface 12a of the semiconductor substrate 12. The adhesive layer 14 is a layer that bonds the semiconductor substrate 12 and the transparent substrate 13, and is provided to surround the light-receiving element 11. The adhesive layer 14, for example, has a rectangular cylindrical structure (see reference). Figure 8 ).

[0058] Semiconductor substrate 12 and wiring substrate 17 are respectively provided with semiconductor substrate electrode pads 15 and wiring substrate electrode pads 16. Semiconductor substrate electrode pads 15 and wiring substrate electrode pads 16 assist in the electrical connection of metal lines 19. An adhesive layer 14 is disposed between semiconductor substrate electrode pads 15 and light receiving element 11, and the periphery of adhesive layer 14 (including the area containing lines 19) is sealed with sealing resin 20. In addition, solder balls 21 (external connection terminals) are formed on the side of wiring substrate 17 opposite to the chip bonding material 18 side.

[0059] The internal space Z enclosed by the semiconductor substrate 12, the transparent substrate 13, and the adhesive layer 14 can be a sealed space. In this case, the adhesive layer 14 functions as a partition to prevent moisture and dust from entering the effective pixel area. When vent holes are formed in the adhesive layer 14, the intrusion of foreign objects into the internal space Z can be prevented by forming the adhesive layer 14 in a labyrinthine manner.

[0060] When the internal space Z is filled with air, the reflectivity R of light at the surface of the adhesive layer 14 is calculated as R = (1 - n1), assuming the refractive index of air is 1 and the refractive index of the adhesive layer 14 is n1. 2 / (1+n1) 2Therefore, the lower the refractive index of the adhesive layer 14, the lower the light reflectivity at the surface of the adhesive layer 14, and the better the stray light. Specifically, the refractive index of the adhesive layer 14 is preferably 1.60 or less, more preferably 1.55 or less, and even more preferably 1.53 or less. There is no particular limitation on the lower limit of the refractive index of the adhesive layer 14; for example, it is 1.30. The refractive index of the adhesive layer 14 can be adjusted by changing the constituent material of the adhesive layer 14. For example, as described later, if a polysiloxane compound is used as the constituent material of the adhesive layer 14, the refractive index of the adhesive layer 14 can be easily adjusted to 1.60 or less. Furthermore, by using the filler material described later as the constituent material of the adhesive layer 14, the refractive index of the adhesive layer 14 can be adjusted.

[0061] The constituent material of the adhesive layer 14 is not particularly limited as long as it can be adjusted to a refractive index of 1.60 or less. Examples include cured products of photosensitive compositions and cured products of thermosetting resins. From the viewpoint of ease of patterning, cured products of photosensitive compositions are preferred. That is, from the viewpoint of ease of patterning, the adhesive layer 14 is preferably a cured layer composed of a cured product of a photosensitive composition. Among the photosensitive compositions, photosensitive compositions such as cationic curable epoxy resin compositions and free radical curable acrylic resin compositions can be used. From the viewpoint of adhesion, photosensitive compositions containing cationic curable compounds are particularly preferred. Details of the photosensitive composition will be described later.

[0062] To obtain an optical semiconductor device that exhibits excellent reliability (hereinafter sometimes abbreviated as "reliability") as evaluated in thermal shock tests and can further suppress the generation of optical noise, the height H of the adhesive layer 14 is preferably 500 μm or less, more preferably 400 μm or less, even more preferably 300 μm or less, and even more preferably 150 μm or less, and can be 140 μm or less, 130 μm or less, 120 μm or less, 110 μm or less, or 100 μm or less. Furthermore, to obtain an optical semiconductor device that can suppress the ingress of foreign matter attached to the transparent substrate 13, the height H of the adhesive layer 14 is preferably 10 μm or more, more preferably 12 μm or more, even more preferably 15 μm or more, and even more preferably 20 μm or more, and can be 25 μm or more or 30 μm or more.

[0063] In order to obtain an optical semiconductor device with excellent reliability and further suppression of optical noise generation and foreign object ingress, the height H of the adhesive layer 14 is preferably 15 μm or more and 300 μm or less, more preferably 20 μm or more and 150 μm or less, even more preferably 30 μm or more and 150 μm or less, even more preferably 30 μm or more and 120 μm or less, and particularly preferably 30 μm or more and 100 μm or less.

[0064] In order to obtain images with reduced distortion, it is preferable that the height H of the adhesive layer 14 has minimal fluctuation. Specifically, the fluctuation of the height H of the adhesive layer 14 relative to the average height H of the adhesive layer 14 (e.g., the average value of measurement sites at 10 randomly selected locations) is preferably within 20%, more preferably within 10%.

[0065] Adhesive layer 14 has a square cylindrical structure (see reference). Figure 8 In the case of [missing information], the shape of the four corners of the adhesive layer 14 is preferably curved. If the shape of the four corners of the adhesive layer 14 is curved, the stress concentration at the four corners during reflow soldering and thermal shock testing is mitigated, which can reduce peeling and cracking of the adhesive layer 14. During reflow soldering and thermal shock testing, in order to further reduce peeling and cracking of the adhesive layer 14, the radius of curvature of the outer and inner circumferences of the four corners of the adhesive layer 14 is preferably 0.01 mm or more and 1.0 mm or less.

[0066] On the surface of adhesive layer 14, there can be a height difference in both the horizontal and vertical directions, such as in a wave shape. This shape helps to alleviate stress during reflow soldering and thermal shock testing, thus improving the reliability of adhesive layer 14.

[0067] The width of the adhesive layer 14 is, for example, 10 μm or more and 200 μm or less, preferably 20 μm or more and 150 μm or less.

[0068] Examples of semiconductor substrates 12 include image sensor substrates. The thickness of the semiconductor substrate 12 is, for example, 50 μm or more and 800 μm or less.

[0069] As the transparent substrate 13, for example, a glass substrate or a transparent plastic substrate (more specifically, an acrylic resin substrate, a polycarbonate substrate, etc.) can be used. From a reliability point of view, a glass substrate is preferred. The type of glass is not particularly limited, and examples include quartz glass, borosilicate glass, and alkali-free glass. The thickness of the transparent substrate 13 is, for example, 50 μm or more and 2000 μm or less.

[0070] Depending on the requirements, functional cover films such as infrared reflective films (or infrared cut-off filters), anti-reflective films (AR coatings), non-reflective films, protective films, reinforcing films, shielding films, conductive films, antistatic films, low-pass filters, high-pass filters, and band-pass filters can be formed on the surface of the transparent substrate 13. Anti-reflective films and infrared reflective films (or infrared cut-off filters) reduce optical noise in the captured images, and are therefore particularly preferred.

[0071] Specific examples of the aforementioned covering film include: silicon dioxide (SiO2), titanium dioxide (TiO2), aluminum oxide (Al2O3), zirconium oxide (ZrO2), tantalum oxide (Ta2O5), niobium oxide (Nb2O5), lanthanum oxide (La2O3), yttrium oxide (Y2O3), magnesium oxide (MgO), hafnium oxide (HfO2), chromium oxide (Cr2O3), magnesium fluoride (MgF2), molybdenum oxide (MoO3), tungsten oxide (WO3), cerium oxide (CeO2), vanadium oxide (VO2), zirconium titanium oxide (ZrTiO4), zinc sulfide (ZnS), cryolite (Na3AlF6), and cone cryolite (Na5Al3F6). 14 Single-layer films formed from yttrium fluoride (YF3), calcium fluoride (CaF2), aluminum fluoride (AlF3), barium fluoride (BaF2), lithium fluoride (LiF), lanthanum fluoride (LaF3), gadolinium fluoride (GdF3), dysprosium fluoride (DyF3), lead fluoride (PbF3), strontium fluoride (SrF2), antimony-containing tin oxide (ATO), indium tin oxide (ITO), etc.; multilayer films such as SiO2 and Al2O3, SiOx-TiOx series multilayer films, SiO2-Ta2O5 series multilayer films, SiOx-LaOx-TiOx series multilayer films, etc.; solid solution films such as In2O3-Y2O3 solid solution films, alumina solid solution films, etc.; metal films; colloidal particle dispersion films; resin films such as polymethyl methacrylate (PMMA) films, polycarbonate (PC) films, polystyrene films, methyl methacrylate-styrene copolymer films, polyacrylate films, etc.

[0072] When using an antireflective film as a cover film, it is particularly preferred to use a multilayer film containing one or more inorganic materials selected from the group consisting of TiO2, Nb2O5, Ta2O5, CaF2, SiO2, Al2O3, MgS2, ZrO2, NiO and MgF2.

[0073] These cover films can be applied to both sides or one side of the transparent substrate 13. When applied to both sides, the types of cover films can be the same or different. Different types of cover films with the same function can also be stacked on one side. In addition, different types of cover films with different functions can also be stacked on one side. There is no particular limitation on the number of layers, and it can be set to a multilayer structure of several to dozens of layers.

[0074] Multiple photodiodes (not shown) are formed on the light receiving element 11. A color filter layer (not shown) and a microlens (not shown) are formed on the photodiodes. The color filters are divided in a manner corresponding to each photodiode and are colored with any of the three primary colors of light. The microlenses are hemispherical in shape, which focuses the incident light onto each photodiode.

[0075] The chip bonding material 18 is not particularly limited, but preferably a thermosetting resin such as epoxy resin or silicone resin that deteriorates less under reflow at a temperature of around 260°C.

[0076] The wiring substrate 17 is a multilayer wiring substrate having a glass epoxy resin substrate or the like and metal wiring, with wiring and interlayer connection vias formed on its surface and interior. On the surface of the wiring substrate 17 where the semiconductor substrate 12 is located, wiring substrate electrode pads 16 are provided for connecting the semiconductor substrate electrode pads 15 on the semiconductor substrate 12 to the lines 19. On the surface of the wiring substrate 17 opposite to the semiconductor substrate 12 side, solder balls 21 serving as external connection terminals are formed. The wiring substrate 17 also functions as a support substrate to suppress deformation of the semiconductor substrate 12.

[0077] The sealing resin 20 is not particularly limited, but thermosetting resins such as epoxy resin, acrylic resin, and silicone resin are preferred. From the viewpoint of resin toughness and heat resistance, epoxy resin is preferred. From the viewpoint of reducing optical noise such as stray light, the sealing resin 20 is preferably colored black. In addition, from the viewpoint of operability, the sealing resin 20 preferably contains fillers such as silica and has thixotropic properties before curing.

[0078] Figure 1 In this structure, adhesive layer 14 has a rectangular cross-section, but the cross-sectional shape of adhesive layer 14 is not limited to this. For example, as... Figure 2 As shown, the angle TA formed by the semiconductor substrate 12 side surface 13a of the transparent substrate 13 and the inner wall surface 14a of the adhesive layer 14 can exceed 90°. It should be noted that, in the following description, the angle (TA) formed by the semiconductor substrate side surface of the transparent substrate and the inner wall surface of the adhesive layer... Figure 2 The angle of the middle angle (TA) is sometimes written as "cone angle".

[0079] In order to obtain an optical semiconductor device that can further suppress the generation of optical noise by suppressing the reflection of light incident on the adhesive layer 14 to the light receiving element 11, the cone angle is preferably 90° or more, more preferably more than 90°, even more preferably 95° or more, even more preferably 100° or more, and can be 110° or more. In addition, in order to obtain an optical semiconductor device with excellent reliability by sufficiently ensuring the bonding area between the adhesive layer 14 and the semiconductor substrate 12, the cone angle is preferably 130° or less, more preferably 125° or less, and even more preferably 120° or less.

[0080] In order to obtain an optical semiconductor device that further suppresses the generation of optical noise and has excellent reliability, the cone angle is preferably 90° or more and 130° or less, more preferably 90° or more and 125° or less, even more preferably 95° or more and 125° or less, even more preferably 100° or more and 125° or less, and can be 100° or more and 120° or 110° or more and 120° or less.

[0081] [Optical Semiconductor Device 100]

[0082] Next, as another specific example of the optical semiconductor device of the first embodiment, a chip-scale package (CSP) type optical semiconductor device 100 will be described with reference to the accompanying drawings. In the following description, content that is repeated in the description of the optical semiconductor device 10 will sometimes be omitted.

[0083] Figure 3 This is a cross-sectional view of the optical semiconductor device 100. The optical semiconductor device 100 is the same as the optical semiconductor device 10 described above in that it includes a semiconductor substrate 12 on its first surface 12a where a light-receiving element 11 is provided, a transparent substrate 13, and an adhesive layer 14 that bonds the semiconductor substrate 12 and the transparent substrate 13. Furthermore, the optical semiconductor device 100 is also the same as the optical semiconductor device 10 in that the transparent substrate 13 is arranged opposite to the first surface 12a of the semiconductor substrate 12, and the adhesive layer 14 is provided to surround the light-receiving element 11.

[0084] The optical semiconductor device 100 is a CSP type; therefore, the width of the optical semiconductor device 100 is substantially equal to the width of the semiconductor substrate 12. Furthermore, the optical semiconductor device 100 lacks the wiring board, wiring board electrode pads, and lines present in the optical semiconductor device 10, thus eliminating the need for encapsulation based on encapsulating resin. In the optical semiconductor device 100, solder balls 21 serving as external connection terminals are provided on the second surface 12b of the semiconductor substrate 12. By adopting a CSP type structure, the optical semiconductor device 100 offers the advantage of miniaturization. Since the optical semiconductor device 100 lacks a wiring board, the semiconductor substrate 12 and solder balls 21 must be electrically connected separately. Examples of methods for electrically connecting the semiconductor substrate 12 and solder balls 21 will be described below, but are not limited to these examples.

[0085] As a method of the above-mentioned electrical connection, for example, Figure 4 As shown, a method for setting a through-silicon via 200 can be given. Figure 4In this configuration, an insulating layer 201, a redistribution layer 203, and a solder resist layer 202 are sequentially disposed on the side of the semiconductor substrate 12 opposite to the side of the adhesive layer 14. Solder balls 21 are formed in the opening of the solder resist layer 202 and are electrically connected to the electrode pads 204 formed on the side of the adhesive layer 14 of the semiconductor substrate 12 via the redistribution layer 203.

[0086] As for the insulating layer 201, there are no particular limitations as long as it is a material with high insulating properties, and examples include silicon oxide film (SiO2 film), silicon nitride film (SiN film), silicon oxynitride film (SiON film), SiOC film, HSQ (Hydrogen Silsesquioxane) film, MSQ (Methyl Silsesquioxane) film, etc. Furthermore, as for the formation method of the insulating layer 201, examples include CVD method, coating method, etc.

[0087] As for the solder resist layer 202, there are no particular limitations as long as it is a material with heat resistance and insulation properties during installation. Examples include epoxy resin and acrylic resin. Among these, epoxy resin is preferred from the viewpoint of high heat resistance and insulation. In addition, as for the formation method of the solder resist layer 202, examples include photolithography and screen printing.

[0088] The material used for the redistribution layer 203 is not particularly limited as long as it is a conductive material, and examples include copper (Cu), aluminum (Al), tungsten (W), gold (Au), titanium (Ti), and nickel (Ni). Furthermore, methods for forming the redistribution layer 203 include wet etching, dry etching, and stripping.

[0089] In addition, as another example of the above-mentioned electrical connection method, the following can be cited: Figure 5 As shown, a redistribution layer 203 is formed along the outer periphery of a semiconductor substrate 12, and solder balls 21 are electrically connected to electrode pads 204 by means of the redistribution layer 203.

[0090] Other aspects of the optical semiconductor device 100 are the same as those described in the above-mentioned [optical semiconductor device 10].

[0091] The configuration of the optical semiconductor device of the first embodiment has been described above with reference to the accompanying drawings, but the present invention is not limited to the above examples. For example, the adhesive layer of the optical semiconductor device of the present invention can be a stacked structure of two or more layers.

[0092] Examples of optical semiconductor devices with a stacked structure of two or more adhesive layers include: Figure 6The optical semiconductor device 300 is shown. In the optical semiconductor device 300, the adhesive layer 14 has a first adhesive layer 141 and a second adhesive layer 142 sequentially from the transparent substrate 13 side. The first adhesive layer 141 is, for example, a cured layer composed of a cured product of a specific photosensitive composition described later. The second adhesive layer 142 is, for example, a cured layer composed of a cured product of a liquid adhesive (more specifically, a cured layer formed by curing the liquid adhesive without patterning).

[0093] It should be noted that in the case of an optical semiconductor device with a stacked structure of two or more adhesive layers, the height of the adhesive layer in this specification refers to the total height of all layers constituting the adhesive layer. Furthermore, in the case of an optical semiconductor device with a stacked structure of two or more adhesive layers, it is preferable that the refractive index of each layer constituting the adhesive layer is 1.60 or less.

[0094] [Photosensitive Composition]

[0095] Next, a photosensitive composition that can be used as an adhesive layer material in the photo-semiconductor device of the first embodiment will be described. As a photosensitive composition that can be used as an adhesive layer material, there is no particular limitation as long as it is a photosensitive composition in which the photosensitive groups are crosslinked and cured by a cationic or free radical generated by a photopolymerization initiator when irradiated with active energy rays. Examples of photosensitive groups include cationic polymeric groups such as epoxy, oxetyl, vinyl ether, and alkoxysilyl groups, and free radical polymeric groups having unsaturated bonds capable of free radical polymerization. Specific examples of free radical polymeric groups include (meth)acryloyl and vinyl groups. The photosensitive compound contained in the photosensitive composition may have both cationic and free radical polymeric groups in one molecule, or only one of them. Furthermore, compounds having cationic polymeric groups and compounds having free radical polymeric groups may be used together.

[0096] In order to form an adhesive layer with excellent heat resistance that further suppresses optical noise by reducing the refractive index of the adhesive layer, the photosensitive composition preferably contains a polysiloxane compound. Hereinafter, preferred examples of photosensitive compositions containing polysiloxane compounds will be described.

[0097] The preferred photosensitive composition (hereinafter, sometimes referred to as "specific photosensitive composition") as the material of the adhesive layer contains a polysiloxane compound having cationic polymerizable groups and alkali-soluble groups in one molecule (hereinafter, sometimes referred to as "component (A)") and a photopolymerization initiator (hereinafter, sometimes referred to as "component (B)").

[0098] {ingredient(A)}

[0099] As for component (A), there is no particular limitation as long as it is a polysiloxane compound having both cationic polymeric groups and alkali-soluble groups in one molecule. Component (A) having both cationic polymeric groups and alkali-soluble groups in one molecule results in a specific photosensitive composition with excellent developability and curability. Component (A) preferably has multiple cationic polymeric groups in one molecule. When component (A) has multiple cationic polymeric groups in one molecule, an adhesive layer with high crosslinking density is obtained, resulting in a tendency for further improvement in the heat resistance of the adhesive layer. The multiple cationic polymeric groups can be of the same type or can be two or more different functional groups. Furthermore, component (A) preferably has multiple alkali-soluble groups in one molecule. When component (A) has multiple alkali-soluble groups in one molecule, the removal of non-exposed areas during development becomes higher, thus tending to further improve developability. The multiple alkali-soluble groups can be of the same type or can be two or more different functional groups.

[0100] Component (A) can have a chain-like polysiloxane structure or a cyclic polysiloxane structure. To form an adhesive layer with superior heat resistance, component (A) preferably has a cyclic polysiloxane structure. Furthermore, if component (A) has a cyclic polysiloxane structure, there is a tendency for improved film-forming properties and developability of certain photosensitive compositions.

[0101] Component (A) may have a polysiloxane structure in its main chain or in its side chains. For forming an adhesive layer with superior heat resistance, it is preferred that component (A) has a polysiloxane structure in its main chain. For forming an adhesive layer with even superior heat resistance, it is preferred that component (A) has a cyclic polysiloxane structure in its main chain.

[0102] Cyclic polysiloxane structures can be monocyclic or polycyclic. Polycyclic structures can be polyhedral. Among the siloxane units constituting the rings, the T unit (XSiO)... 3 / 2 ) or Q unit (SiO) 4 / 2 The higher the content of M unit (X3SiO), the higher the hardness of the resulting adhesive layer, and the better its heat resistance tends to be. On the other hand, M unit (X3SiO) 1 / 2 ) or D unit (X2SiO) 2 / 2 The higher the content of ), the softer the resulting adhesive layer tends to be and the more it can reduce residual stress.

[0103] When component (A) is a polymer having a polysiloxane structure on its main chain, the weight-average molecular weight of the polymer is preferably 10,000 or more and 50,000 or less, more preferably 20,000 or more and 40,000 or less. When the weight-average molecular weight is 10,000 or more, the heat resistance of the resulting adhesive layer tends to be further improved. On the other hand, when the weight-average molecular weight is 50,000 or less, the reproducibility tends to be further improved.

[0104] Examples of cationic polymerizable groups in component (A) include epoxy groups, vinyl ether groups, oxetyl groups, and alkoxysilyl groups. From the viewpoint of the storage stability of a specific photosensitive composition, at least one cationic polymerizable group is preferably selected from the group consisting of glycidyl groups, alicyclic epoxy groups, and oxetyl groups, and more preferably from the group consisting of glycidyl groups and alicyclic epoxy groups. Among these, alicyclic epoxy groups have excellent photocationic polymerizability and are therefore particularly preferred.

[0105] Examples of alkali-soluble groups present in component (A) include, for example, a monovalent organic group represented by the following chemical formula (X1) (hereinafter sometimes referred to as "X1 group"), a divalent organic group represented by the following chemical formula (X2) (hereinafter sometimes referred to as "X2 group"), a phenolic hydroxyl group, a carboxyl group, etc. It should be noted that the X1 group is a monovalent organic group derived from N-monosubstituted isocyanuric acid. Furthermore, the X2 group is a divalent organic group derived from N,N'-disubstituted isocyanuric acid.

[0106]

[0107] In order to form an adhesive layer with better heat resistance, the alkali-soluble groups contained in component (A) are preferably selected from one or more groups consisting of X1 groups and X2 groups.

[0108] There are no particular limitations on the method for introducing cationic polymeric groups into polysiloxane compounds. However, from the perspective that cationic polymeric groups can be introduced into polysiloxane compounds via chemically stable silicon-carbon bonds (Si-C bonds), the hydrosilylation reaction method is preferred. In other words, component (A) is preferably an organically modified polysiloxane compound in which cationic polymeric groups are introduced via silicon-carbon bonds through a hydrosilylation reaction. Alkali-soluble groups are also preferably introduced into the polysiloxane compound via silicon-carbon bonds through a hydrosilylation reaction.

[0109] Component (A) is obtained, for example, by a hydrosilylation reaction using the following compounds (α), (β) and (γ) as starting materials.

[0110] • Compound (α): A polysiloxane compound having at least two SiH groups (hydrosilyl groups) in one molecule.

[0111] • Compound (β): A compound that contains a carbon-carbon double bond that is reactive with the SiH group and a cationic polymerizable group in one molecule.

[0112] • Compound (γ): A compound that contains a carbon-carbon double bond that is reactive with the SiH group and a base-soluble group in one molecule.

[0113] (Compound (α))

[0114] Compound (α) is a polysiloxane compound having at least two SiH groups in one molecule. For example, compounds described in International Publication No. 96 / 15194 that have at least two SiH groups in one molecule can be used. Specific examples of compound (α) include hydrosilyl-containing polysiloxanes with a linear structure, polysiloxanes with hydrosilyl groups at the molecule's end, and cyclic polysiloxanes with hydrosilyl groups (hereinafter sometimes abbreviated as "cyclic polysiloxanes"). Cyclic polysiloxanes can have a polycyclic structure, which can be a polyhedral structure. To form an adhesive layer with high heat resistance and mechanical strength, cyclic polysiloxanes having at least two SiH groups in one molecule are preferred as compound (α). Compound (α) is preferably a cyclic polysiloxane having three or more SiH groups in one molecule. From the viewpoint of heat resistance and light resistance, it is preferable that the groups present on the Si atoms are either hydrogen atoms or methyl groups.

[0115] Examples of hydrogen-containing silyl polysiloxanes having a linear structure include copolymers of dimethylsiloxane units with methylhydrosiloxane units and terminal trimethylsiloxy units, copolymers of diphenylsiloxane units with methylhydrosiloxane units and terminal trimethylsiloxy units, copolymers of methylphenylsiloxane units with methylhydrosiloxane units and terminal trimethylsiloxy units, and polysiloxanes obtained by end-capping with dimethylhydrosilyl groups.

[0116] Examples of polysiloxanes having a dimethylhydrosilyl group at the molecule's end include polysiloxanes obtained by end-capping with a dimethylhydrosilyl group, and dimethylhydrosiloxane units (H(CH3)2SiO2). 1 / 2 (unit) and selected from SiO2 unit, SiO 3 / 2 Polysiloxanes formed from one or more siloxane units in a group consisting of SiO and SiO units.

[0117] Cyclic polysiloxanes are represented, for example, by the following general formula (I).

[0118]

[0119] In general formula (I), R 1 R 2and R 3 Each group independently represents a monovalent organic group with 1 or more and 20 or less carbon atoms, where m represents an integer of 2 or more and 10 or more, and n represents an integer of 0 or more and 10 or less. For ease of hydrosilylation, m is preferably 3 or more. For ease of hydrosilylation, m+n is preferably 3 or more and 12 or less. For easier hydrosilylation, n is preferably 0.

[0120] As R 1 R 2 and R 3 Preferably, it consists of an organic group composed of elements selected from the group consisting of C, H, and O. As R 1 R 2 and R 3 Examples include alkyl, hydroxyalkyl, alkoxyalkyl, oxyalkyl, and aryl groups. Among these, preferred are chain alkyl groups such as methyl, ethyl, propyl, hexyl, octyl, decyl, and dodecyl; cyclic alkyl groups such as cyclohexyl and norbornyl; or phenyl groups. From the viewpoint of the ease of obtaining cyclic polysiloxanes, as R... 1 R 2 and R 3 Preferably, it is a chain alkyl group or phenyl group with 1 or more but less than 6 carbon atoms. To facilitate the hydrosilylation reaction, R is used as... 1 R 2 and R 3 Preferably, it is a chain alkyl group, more preferably a chain alkyl group with 1 or more but less than 6 carbon atoms, and even more preferably methyl.

[0121] Examples of cyclic polysiloxanes represented by general formula (I) include 1,3,5,7-tetrahydro-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydro-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydro-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydro-1,3,5-trimethylcyclotrisiloxane, 1,3,5,7,9-pentahydro-1,3,5,7,9-pentamethylcyclopentasiloxane, and 1,3,5,7,9,11-hexahydro-1,3,5,7,9,11-hexamethylcyclohexasiloxane, etc. From the viewpoints of ease of acquisition and reactivity of the SiH group, 1,3,5,7-tetrahydro-1,3,5,7-tetramethylcyclotetrasiloxane (in general formula (I), m=4, n=0, R) is preferred. 1 (A compound containing methyl groups).

[0122] Compound (α) is obtained by known synthetic methods. For example, the cyclic polysiloxane represented by general formula (I) can be synthesized by the methods described in International Patent Publication No. 96 / 15194, etc. Cyclic polysiloxanes having a polyhedral framework can be synthesized, for example, by the methods described in Japanese Patent Application Publication Nos. 2004-359933, 2004-143449, and 2006-269402, etc. Alternatively, commercially available polysiloxane compounds can also be used as compound (α).

[0123] In order to improve the developability of a particular photosensitive composition and form an adhesive layer with better heat resistance, the content of structural units derived from compound (α) in component (A) is preferably 10% or more and 50% or less, more preferably 15% or more and 45% or less, relative to 100% by weight of component (A).

[0124] (Compound (β))

[0125] Compound (β) is a compound having a carbon-carbon double bond and a cationic polymerizable group that are reactive with a SiH group (hydrosilyl group) in one molecule, and is used to introduce cationic polymerizable groups into polysiloxane compounds. The cationic polymerizable group in compound (β) is the same as that in the aforementioned component (A), and preferably in the same manner. That is, compound (β) preferably has one or more of the following groups selected from glycidyl groups, alicyclic epoxy groups, and oxetyl groups, more preferably one or more of the following groups selected from glycidyl groups and alicyclic epoxy groups, and even more preferably has an alicyclic epoxy group as a cationic polymerizable group.

[0126] Examples of groups comprising a carbon-carbon double bond that is reactive with the SiH group (hereinafter sometimes abbreviated as "alkenyl") include vinyl, allyl, methyl allyl, allyloxy (-O-CH2-CH=CH2), 2-allylphenyl, 3-allylphenyl, 4-allylphenyl, 2-(allyloxy)phenyl, 3-(allyloxy)phenyl, 4-(allyloxy)phenyl, 2-(allyloxy)ethyl, 2,2-bis(allyloxymethyl)butyl, 3-allyloxy-2,2-bis(allyloxymethyl)propyl, vinyl ether, etc. From the viewpoint of reactivity with the SiH group, the compound (β) preferably has one or more alkenyl groups selected from the group consisting of vinyl, allyl, and allyloxy groups, and more preferably has one or more alkenyl groups selected from the group consisting of vinyl and allyl groups.

[0127] Specific examples of compound (β) include 1-vinyl-3,4-epoxycyclohexane, allyl glycidyl ether, allyl oxetane ether, diallyl monoglycidyl isocyanurate, and monoallyl diglycidyl isocyanurate. From the viewpoint of reactivity in cationic polymerization, compound (β) is preferably a compound having one or more functional groups selected from the group consisting of alicyclic epoxy groups and glycidyl groups, and more preferably a compound having alicyclic epoxy groups. To further improve reactivity in cationic polymerization, compound (β) is preferably a compound selected from the group consisting of diallyl monoglycidyl isocyanurate and 1-vinyl-3,4-epoxycyclohexane, and more preferably 1-vinyl-3,4-epoxycyclohexane.

[0128] In order to improve the developability of a particular photosensitive composition and form an adhesive layer with better heat resistance, the content of structural units derived from compound (β) in component (A) is preferably 20% or more and 50% or less, more preferably 22% or more and 45% or less, relative to 100% by weight of component (A).

[0129] (Compound (γ))

[0130] Compound (γ) is a compound having a carbon-carbon double bond reactive with a SiH group and an alkali-soluble group in one molecule, and is used to introduce alkali-soluble groups into polysiloxane compounds. The alkali-soluble groups in compound (γ) are the same as those in the aforementioned component (A), and preferably in the same manner. That is, compound (γ) preferably has one or more alkali-soluble groups selected from the group consisting of X1 and X2 groups.

[0131] Compound (γ) has a group (alkenyl) comprising a carbon-carbon double bond that is reactive with the SiH group. Examples of alkenyl groups in compound (γ) can be the same as those in the aforementioned compound (β), and are preferably in the same manner. That is, compound (γ) preferably has one or more alkenyl groups selected from the group consisting of vinyl, allyl, and allyloxy groups, and more preferably has one or more alkenyl groups selected from the group consisting of vinyl and allyl groups.

[0132] Compound (γ) can have more than two alkenyl groups in one molecule. When compound (γ) contains multiple alkenyl groups in one molecule, multiple compounds (α) can be crosslinked by hydrosilylation reaction. Therefore, there is a tendency for the crosslinking density of the obtained cured product to increase and the heat resistance of the cured product to improve.

[0133] Specific examples of compounds (γ) include diallyl isocyanurate, monoallyl isocyanurate, 2,2'-diallylbisphenol A, vinylphenol, allylphenol, butenoic acid, pentenoic acid, hexenoic acid, heptenic acid, undecenoic acid, etc.

[0134] To obtain a specific photosensitive composition with superior developability, the compound (γ) is preferably selected from the group consisting of diallyl isocyanurate, monoallyl isocyanurate, and 2,2'-diallylbisphenol A, and more preferably from the group consisting of diallyl isocyanurate and monoallyl isocyanurate. If monoallyl isocyanurate is used as compound (γ), a component (A) having an X1 group as an alkali-soluble group is obtained. Alternatively, if diallyl isocyanurate is used as compound (γ), a component (A) having an X2 group as an alkali-soluble group is obtained.

[0135] In order to obtain a specific photosensitive composition with better developability, the content of structural units derived from compound (γ) in component (A) is preferably 5% or more and 50% or less, more preferably 10% or more and 30% or less, relative to 100% by weight of component (A).

[0136] (Other starting materials)

[0137] In the hydrosilylation reaction, other starting materials besides the compounds (α), (β), and (γ) mentioned above can be used. For example, alkenyl-containing compounds (hereinafter sometimes referred to as "other alkenyl-containing compounds") different from the compounds (β) and (γ) mentioned above can be used as other starting materials.

[0138] To introduce free radical polymerizable groups into component (A), it is preferable to use a compound having an alkenyl group and a (meth)acryloyl group in one molecule (hereinafter, sometimes referred to as "compound (δ)"). If compound (δ) is used, a (meth)acryloyl group is introduced into component (A), thus enabling component (A) to undergo photoradical polymerization.

[0139] Specific examples of compounds (δ) include vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl methacrylate, 2-butenyl acrylate, and 2-butenyl methacrylate.

[0140] To obtain an adhesive layer with superior heat resistance, it is preferable to use compounds having two or more alkenyl groups in one molecule (hereinafter sometimes referred to as "compound (ε)"). If compound (ε) is used, the number of crosslinking sites increases during the hydrosilylation reaction, thus tending to further improve the heat resistance of the resulting adhesive layer.

[0141] Specific examples of compounds (ε) include diallyl phthalate, triallyl trimellitate, diethylene glycol dielyl carbonate, 1,1,2,2-tetraallylpropoxyethane, triallyl cyanurate, triallyl isocyanurate, diallyl monobenzyl isocyanurate, diallyl monomethyl isocyanurate, 1,2,4-trivinylcyclohexane, triethylene glycol divinyl ether, divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-bis(allyloxy)adamantane, 1,3-bis(ethyleneoxy)adamantane, 1,3,5-tri(allyloxy)adamantane, 1,3,5-tri(ethyleneoxy)adamantane, dicyclopentadiene, vinylcyclohexene, 1,5-hexadiene, 1,9-decadiene, diallyl ether, and their oligomers.

[0142] To further improve the heat resistance of the obtained adhesive layer, the compound (ε) is preferably selected from one or more of the group consisting of triallyl isocyanurate and diallyl monomethyl isocyanurate, and more preferably diallyl monomethyl isocyanurate.

[0143] In order to further improve the heat resistance of the obtained adhesive layer and improve the alkaline developability, the content of structural units derived from compound (ε) in component (A) is preferably 5% or more and 30% or less, more preferably 8% or more and 20% or less, relative to 100% by weight of component (A).

[0144] (Hydrosilaneization reaction)

[0145] The order and method of the hydrosilylation reaction used to obtain component (A) are not particularly limited. For example, component (A) can be obtained by hydrosilylation reaction according to the method described in International Publication No. 2009 / 075233, using the above-described compounds (α), (β), (γ), and other starting materials as optional components. Component (A) obtained using the above-described compounds (α), (β), (γ), and other starting materials as optional components is, for example, a polymer having a plurality of cationic polymeric groups and a plurality of alkali-soluble groups in one molecule, and having a polysiloxane structure on the main chain.

[0146] The proportions of the compounds in the hydrosilylation reaction are not particularly limited. Preferably, the total mass A of alkenyl groups and the total mass B of SiH groups of the starting material satisfy 1 ≤ B / A ≤ 30, and more preferably, 1 ≤ B / A ≤ 10.

[0147] Hydrosilylation reactions can utilize catalysts such as chloroplatinic acid, platinum-olefin complexes, and platinum-vinylsiloxane complexes. Hydrosilylation catalysts and co-catalysts can also be used in combination. The amount (mass) of hydrosilylation catalyst added is not particularly limited, but preferably 10% relative to the total mass of alkenes contained in the starting material. -8 More than 10 times -1 less than twice, more preferably 10 times -6 More than 10 times -2 Less than twice.

[0148] The reaction temperature for hydrosilylation can be set appropriately, preferably 30°C or higher and 200°C or lower, more preferably 50°C or higher and 150°C or lower. The oxygen concentration in the gas phase of the hydrosilylation reaction is preferably 3% by volume or lower. From the viewpoint of promoting the hydrosilylation reaction, the gas phase may contain 0.1% by volume or higher and 3% by volume or lower oxygen.

[0149] Solvents can be used in the hydrosilylation reaction. A single solvent or a mixture of two or more solvents can be used. Suitable solvents include hydrocarbon solvents such as benzene, toluene, xylene, hexane, and heptane; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, and diethyl ether; ketone solvents such as acetone and methyl ethyl ketone; and halogen solvents such as chloroform, dichloromethane, and 1,2-dichloroethane. For ease of post-reaction distillation removal, toluene, xylene, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, or chloroform are preferred. Gelation inhibitors may also be used in the hydrosilylation reaction as needed.

[0150] In order to form an adhesive layer with excellent heat resistance that can further suppress the generation of optical noise by reducing the refractive index of the adhesive layer, the content of component (A) in the specific photosensitive composition is preferably 20% by weight or more and 95% by weight or less relative to the total amount of solid components in the specific photosensitive composition.

[0151] {Component (B)}

[0152] As component (B), it is preferable to select one or more from the group consisting of cationic photopolymerization initiators and photoradical photopolymerization initiators. Since the specific photosensitizing composition contains component (A) having cationic polymerizable groups, if the specific photosensitizing composition contains a cationic photopolymerization initiator as component (B), component (A) can be crosslinked by cationic photopolymerization. Furthermore, when using component (A) with (meth)acryloyl groups or component (C) described later, if the specific photosensitizing composition contains a photoradical photopolymerization initiator as component (B), components (A) and (C) can be crosslinked by photoradical photopolymerization. The specific photosensitizing composition may also contain both a cationic photopolymerization initiator and a photoradical photopolymerization initiator as component (B).

[0153] (Photocationic polymerization initiator)

[0154] As a photocationic polymerization initiator, known photocationic polymerization initiators can be used, for example. Various suitable compounds can be cited as examples from Japanese Patent Application Publication No. 2000-1648, Japanese Patent Application Publication No. 2001-515533, and International Publication No. 2002 / 83764, but there are no particular limitations. Sulfonate ester compounds, carboxylic acid ester compounds, or onium salt compounds are preferred as photocationic polymerization initiators, onium salt compounds are more preferred, and sulfonate salt compounds are even more preferred.

[0155] As sulfonate compounds, various sulfonic acid derivatives can be used, such as disulfone compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, sulfonylbenzoylmethane compounds, imide sulfonate compounds, benzoin sulfonate compounds, pyrogallol trisulfonate compounds, and benzoyl sulfonate compounds.

[0156] Specific examples of sulfonate compounds include diphenyl disulfone, xylenesulfonyl disulfone, bis(phenylsulfonyl)diazomethane, bis(chlorophenylsulfonyl)diazomethane, bis(xylylsulfonyl)diazomethane, phenylsulfonylbenzoyldiazomethane, bis(cyclohexylsulfonyl)methane, 1,8-naphthalenedicarboxylic acid imide methanesulfonate, 1,8-naphthalenedicarboxylic acid imide toluenesulfonyl sulfonate, 1,8-naphthalenedicarboxylic acid imide trifluoromethyl sulfonate, 1,8-naphthalenedicarboxylic acid imide camphor sulfonate, succinic acid imide phenyl sulfonate, and succinic acid imide. Toluenesulfonyl sulfonate, succinic imide trifluoromethyl sulfonate, succinic imide camphor sulfonate, phthalic acid imide trifluoromethyl sulfonate, cis-5-norbornene-intra-2,3-dicarboxylic acid imide trifluoromethyl sulfonate, benzoin toluene sulfonate, 1,2-diphenyl-2-hydroxypropyl toluene sulfonate, 1,2-di(4-methylmercaptophenyl)-2-hydroxypropyl toluene sulfonate, pyrogallol methyl sulfonate, pyrogallol ethyl sulfonate, 2,6-dinitrophenylmethyl toluene sulfonate, o-nitrophenylmethyl toluene sulfonate, and p-nitrophenyl toluene sulfonate, etc.

[0157] They can be used alone or in combination of two or more. Similarly, carboxylic acid ester compounds can also be used as photocationic polymerization initiators in this invention.

[0158] Examples of ononium salt compounds include sulfonium salt compounds and iodonium salt compounds. Examples of anions found in sulfonium salt compounds and iodonium salt compounds include tetrafluoroborate (BF4). - ), hexafluorophosphate (PF6) - ), hexafluoroantimonate (SbF6) - ), hexafluoroarsenate (AsF6) - ), hexachloroantimonate (SbCl6) - Tetraphenylborate, tetra(trifluoromethylphenyl)borate, tetra(pentafluoromethylphenyl)borate, fluoroalkyl fluorophosphate, perchlorate ion (ClO4) - ), trifluoromethanesulfonate ion (CF3SO3) - ), fluorosulfonate ions (FSO3) - ), toluenesulfonate ions, etc.

[0159] If the photocationic polymerization initiators are arranged in order of increasing acid strength, starting with the strongest acid produced, then the resulting initiator includes SbF6. - Compounds containing B(C6F5)4 as anions - Compounds containing PF6 as anions - Compounds containing CF3SO3 as anions - Compounds containing HSO4 as anions- Compounds that are anions. If a photocationic polymerization initiator with a strong acid strength is used, there is a tendency for a higher residual film yield. The pKa of the acid produced by the photocationic polymerization initiator is preferably lower than 3, more preferably lower than 1.

[0160] There is no particular limitation on the content of the photocationic polymerization initiator in a specific photosensitive composition. From the viewpoint of curing speed and the balance of physical properties of the cured product, the content of the photocationic polymerization initiator relative to 100 parts by weight is preferably 0.1 parts by weight or more and 20 parts by weight or less, more preferably 0.5 parts by weight or more and 10 parts by weight or less.

[0161] As needed, a thermo-cationic polymerization initiator (a compound that generates cations by heat) can also be mixed into a specific photosensitive composition. Examples of thermo-cationic polymerization initiators include sulfonium salt compounds, iodonium salt compounds, benzothiazolium salt compounds, ammonium salt compounds, phosphonium salt compounds, etc., among which sulfonium salt compounds and benzothiazolium salt compounds are preferred.

[0162] (Photoradical polymerization initiator)

[0163] Examples of photoradical polymerization initiators include acetophenone compounds, phosphine oxide compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, biimidazole compounds, polyquinone compounds, triazine compounds, oxime ester compounds, dicerocene compounds, xanthone compounds, thioxanone compounds, ketal compounds, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, and fluoroamine compounds. From the viewpoint of patternability, one or more compounds selected from the group consisting of acetophenone compounds, benzophenone compounds, and oxime ester compounds are preferred as photoradical polymerization initiators, with acetophenone compounds being more preferred.

[0164] Examples of acetophenone compounds include 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-(4'-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2'-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)one, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1-(4'-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4'-morpholinophenyl)butane-1-one, and 1-hydroxycyclohexylphenyl ketone.

[0165] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0166] Examples of oxime ester compounds include 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyl oxime)] and acetone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime).

[0167] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0168] Examples of benzophenone compounds include benzyl dimethyl ketone, benzophenone, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone.

[0169] Examples of α-diketone compounds include methyl benzoyl carbamate.

[0170] Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5 5'-Tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4,6-tribromophenyl) 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5 5'-Tetraphenyl-1,2'-Biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc.

[0171] Examples of polynuclear quinone compounds include anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1,4-naphthoquinone.

[0172] Examples of xanthonone compounds include xanthonone, thioxanone, and 2-chlorothioxanone.

[0173] Examples of triazine compounds include 1,3,5-tris(trichloromethyl)-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-triazine, 1,3-bis(trichloromethyl)-5-(4'-chlorophenyl)-triazine, 1,3-bis(trichloromethyl)-5-(2'-methoxyphenyl)-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-triazine, and 2-(2'-furanylethidene)-4,6-bis(trichloromethyl)-triazine. 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-triazine, 2-(2'-bromo-4'-methylphenyl)-4,6-bis(trichloromethyl)-triazine, 2-(2'-thiophenylethoxy)-4,6-bis(trichloromethyl)-triazine, etc.

[0174] There is no particular limitation on the content of the photoradical polymerization initiator in a specific photosensitive composition. From the viewpoint of curing speed and the balance of physical properties of the cured product, the content of the photoradical polymerization initiator relative to 100 parts by weight of the specific photosensitive composition is preferably 0.1 parts by weight or more and 20 parts by weight or less, more preferably 0.5 parts by weight or more and 10 parts by weight or less.

[0175] Thermal free radical polymerization initiators (compounds that generate free radicals through heat) can also be mixed into specific photosensitive compositions as needed. Specific examples of thermal free radical polymerization initiators include acetyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, hydrogen peroxide, tert-butyl hydrogen peroxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxypentanoate, azobisisobutyronitrile, azobisisovalerate, ammonium persulfate, sodium persulfate, and potassium persulfate. These thermal free radical polymerization initiators can be used alone or in combination of two or more.

[0176] {solvent}

[0177] A particular photosensitive composition may also contain a solvent. For example, a particular photosensitive composition is obtained by dissolving or dispersing the above-described components (A), (B), and other components described below as needed in a solvent.

[0178] Specific examples of solvents include hydrocarbon solvents such as benzene, toluene, hexane, and heptane; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, and diethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; glycol solvents such as propylene glycol 1-monomethyl ether 2-acetic acid ester, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and ethylene glycol diethyl ether; ester solvents such as isobutyl isobutyrate; and halogen solvents such as chloroform, dichloromethane, and 1,2-dichloroethane. From the viewpoint of the coatability (film stability) of a specific photosensitive composition, ester solvents are preferred, and isobutyl isobutyrate is more preferred.

[0179] From the viewpoint of the coatability (film stability) of a particular photosensitive composition, the amount of solvent relative to 100 parts by weight of component (A) is preferably 0.5 parts by weight or more and 100 parts by weight or less, more preferably 1 part by weight or more and 50 parts by weight or less.

[0180] {Other ingredients}

[0181] Within the scope of not impairing the purpose and effect of the present invention, a specific photosensitive composition may contain components other than components (A) and (B) (other components) as solid components (components other than solvents). Specifically, in order to form an adhesive layer with excellent heat resistance that further suppresses optical noise by reducing the refractive index of the adhesive layer, the total content of components (A) and (B) relative to the total amount of solid components in the specific photosensitive composition is preferably 50% by weight or more, more preferably 60% by weight or more, and even more preferably 70% by weight or more and 100% by weight or less.

[0182] Other components include compounds with free radical polymerizable groups, reactive diluents, sensitizers, polymeric dispersants, thermoplastic resins, fillers, basic compounds, adhesion modifiers, coupling agents (silane coupling agents, etc.), antioxidants, free radical inhibitors, release agents, flame retardants, flame retardant additives, surfactants, defoamers, emulsifiers, leveling agents, anti-repulsion agents, ion scavengers (antimony-bismuth, etc.), thixotropic agents, tackifiers, storage stability modifiers, ozone deterioration inhibitors, light stabilizers, thickeners, plasticizers, heat stabilizers, conductivity modifiers, antistatic agents, radiation shielding agents, nucleating agents, phosphorus peroxide decomposers, lubricants, metal deactivators, thermal conductivity modifiers, and property modifiers.

[0183] (Compounds with free radical polymerizable groups)

[0184] Specific photosensitive compositions may contain compounds having free radical polymerizable groups (hereinafter, sometimes referred to as "component (C)") as other components. Component (C) is another component (component other than component (A) and component (B), and therefore, is a compound having free radical polymerizable groups and not having siloxane units. Specific photosensitive compositions containing component (C) tend to have excellent deep curing properties during patterning (the characteristic of being able to perform photocrosslinking up to the deep layers). In addition, if the above-mentioned adhesive layer is formed by photolithography using a specific photosensitive composition containing component (C), the cone angle can be easily adjusted to a range exceeding 90°. It should be noted that even when using a specific photosensitive composition containing component (A) with introduced free radical polymerizable groups to form the above-mentioned adhesive layer by photolithography, the cone angle can be adjusted to a range exceeding 90°. When forming the adhesive layer using a photosensitive composition via photolithography, in order to easily adjust the cone angle to 95° or more, the photosensitive composition used is preferably a photosensitive composition containing components (A), (B), and (C), and containing a photoradical polymerization initiator as component (B).

[0185] As component (C), examples include compounds having unsaturated bonds (such as olefinic unsaturated bonds) capable of undergoing free radical polymerization. Examples of olefinic unsaturated bonds include (meth)acryloyl groups and vinyl groups.

[0186] Specific examples of ingredient (C) include allyl methacrylate, vinyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenoxyethyl methacrylate, modified allyl glycidyl ether (Denacol acrylate DA111 manufactured by Nagase ChemteX Corporation), urethane compounds, epoxy methacrylate compounds, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, di(trimethylolpropane tetramethacrylate), dipentaerythritol hexamethacrylate, butanediol dimethacrylate, nonanediol dimethacrylate, polypropylene glycol methacrylate, bisphenol A dimethacrylate, and tri(2-(meth)acryloyloxyethyl) isocyanurate, etc.

[0187] It should be noted that component (C) has high curability, and therefore, it is also a suitable material for photosensitive compositions when patterning by methods other than photolithography (such as screen printing, 3D printing, etc.).

[0188] In order to obtain a photonic semiconductor device that further suppresses the generation of optical noise and has excellent reliability, the content of component (C) in the specific photosensitive composition is preferably 1% or more and 50% or less, more preferably 5% or more and 40% or less, and even more preferably 10% or more and 30% or less, relative to the total amount of solid components in the specific photosensitive composition.

[0189] (Reactive diluent)

[0190] Certain photosensitive compositions may also contain reactive diluents. Reactive diluents are components that reduce the viscosity of a particular photosensitive composition and participate in the curing reaction. By containing reactive diluents, certain photosensitive compositions enable reduced curing shrinkage of the adhesive layer and control over the mechanical strength of the adhesive layer.

[0191] As a reactive diluent, a compound having two or more cationic polymerizable groups per molecule is used, for example. Examples of cationic polymerizable groups in a reactive diluent include those present in the aforementioned component (A). The cationic polymerizable group of the reactive diluent may be the same type as that of component (A), or it may be a different type. From the viewpoint of improving cationic polymerization reactivity, the reactive diluent preferably has an alicyclic epoxy group as a cationic polymerizable group. A particularly preferred embodiment is that component (A) contains an alicyclic epoxy group as a cationic polymerizable group, and the reactive diluent has two or more alicyclic epoxy groups per molecule.

[0192] Examples of compounds having two or more alicyclic epoxy groups in one molecule include 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (Daicel Corporation's "CELLOXIDE (registered trademark) 2021P"), ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (Daicel Corporation's "CELLOXIDE (registered trademark) 2081"), bis(3,4-epoxycyclohexylmethyl) adipate, epoxy-modified chain siloxane compound shown in the following chemical formula (S1) (Shin-Etsu Chemical Industry Co., Ltd.'s "X-40-2669"), and epoxy-modified cyclic siloxane compound shown in the following chemical formula (S2) (Shin-Etsu Chemical Industry Co., Ltd.'s "KR-470"), etc.

[0193]

[0194] Regarding the content of reactive diluent, from the viewpoint of balancing the improvement of curing speed of the specific photosensitive composition and the physical property balance of the cured product, it is preferably 2% by weight or more and 50% by weight or less, more preferably 3% by weight or more and 40% by weight or less, relative to the total amount of solid components of the specific photosensitive composition.

[0195] (Sensitizer)

[0196] Certain photosensitizing compositions may also contain sensitizers. By using sensitizers, exposure sensitivity during patterning is improved. Anthracene compounds are preferred as sensitizers. Specific examples of anthracene compounds include anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 2,6-ditert-butylanthracene, and 9,10-diphenyl-2,6-ditert-butylanthracene. Among these, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-diethoxyanthracene are preferred from the viewpoint of compatibility with the specific photosensitizing composition.

[0197] There is no particular limitation on the content of sensitizer in a specific photosensitizing composition. From the viewpoint of curing properties and the balance of physical properties of the cured product, it is preferable to be 0.01 parts by weight or more and 20 parts by weight or less, more preferably 0.1 parts by weight or more and 15 parts by weight or less, relative to 100 parts by weight of component (A).

[0198] (Polymer dispersant)

[0199] Certain photosensitive compositions may also contain a polymeric dispersant. As a polymeric dispersant, compounds having acidic functional groups are preferred. Examples of acidic functional groups include carboxyl, sulfonyl, and phosphate groups, with carboxyl groups being preferred. The acid value of the polymeric dispersant is preferably 10 mg KOH / g or more and 100 mg KOH / g or less. Examples of polymeric dispersants include urethane compounds, polyimide compounds, alkyd compounds, epoxy compounds, polyester compounds, melamine compounds, phenolic compounds, acrylic compounds, vinyl chloride compounds, vinyl chloride-vinyl acetate copolymer compounds, polyamide compounds, and polycarbonate compounds. Preferably, one or more compounds are selected from the group consisting of acrylic compounds and polyester compounds.

[0200] (Thermoplastic resin)

[0201] Certain photosensitive compositions may also contain thermoplastic resins. Examples of thermoplastic resins include acrylic resins, polycarbonate resins, cycloolefin resins, olefin-maleimide resins, polyester resins, polyethersulfone resins, polyarylate resins, polyvinyl alcohol acetal resins, polyethylene resins, polypropylene resins, polystyrene resins, polyamide resins, silicone resins, fluoropolymers, and rubbery resins. Thermoplastic resins may also have crosslinking groups such as epoxy groups, amino groups, free radical polymerizable unsaturated groups, carboxyl groups, isocyanate groups, hydroxyl groups, and alkoxysilyl groups.

[0202] (Filling material)

[0203] Certain photosensitive compositions may also contain filler materials. Especially when the adhesive layer is formed using screen printing or 3D printing, adding filler materials to exhibit thixotropic properties is preferred. There are no particular limitations on the filler material; examples include inorganic fillers such as silica-based fillers (quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine amorphous silica, etc.), silicon nitride, silver powder, alumina, aluminum hydroxide, titanium dioxide, glass fiber, carbon fiber, mica, carbon black, graphite, diatomaceous earth, kaolin, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate, and inorganic microspheres; organic fillers such as epoxy-based fillers can also be used. Among these, fumed silica is preferred from the perspective that thixotropic properties can be exhibited with a small amount of addition. For example, various grades of fumed silica manufactured by Aerosil Corporation of Japan can be used.

[0204] (Alkaline compound)

[0205] Certain photosensitive compositions may also contain alkaline compounds. These alkaline compounds act as quenchers. That is, by incorporating an appropriate amount of an alkaline compound into a particular photosensitive composition, the photocuring reaction can be prevented from spreading to the unexposed areas. As a result, the contrast between the exposed and unexposed areas becomes clearer, and consequently, the resolution is improved.

[0206] The amount of the alkaline compound mixed relative to 100 parts by weight of component (A) is preferably 0.001 parts by weight or more and 2.0 parts by weight or less, more preferably 0.01 parts by weight or more and 1.0 parts by weight or less. If the amount of the alkaline compound mixed is 0.001 parts by weight or more, its function as a quencher can be fully utilized. If the amount of the alkaline compound mixed is 2.0 parts by weight or less, sensitivity can be improved.

[0207] The weight ratio of the basic compound to the photocationic polymerization initiator (basic compound / photocationic polymerization initiator) is, for example, 0.001 or more and 0.2 or less, preferably 0.01 or more and 0.15 or less. If this weight ratio is 0.001 or more, the function as a quencher can be fully utilized. If this weight ratio is 0.2 or less, crosslinking can be sufficiently achieved.

[0208] There are no particular limitations on basic compounds; examples include primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, amide derivatives, and imide derivatives. Among these, aromatic amines and heterocyclic amines are suitable for use as basic compounds.

[0209] Examples of the aforementioned aromatic amine compounds and heterocyclic amine compounds include aniline, pyrrole, oxazole, thiazole, imidazole, pyrazole, furazon, pyrrolidone, pyrrolidine, imidazoline, imidazoline, pyridine, pyridazine, pyrimidine, pyrazine, pyrazine, pyrazoline, pyrazolidine, piperidine, piperazine, morpholine, indole, isoindole, 1H-indazole, indomethacin, quinoline, porphyrin, quinazoline, quinoxaline, phthalazine, purine, pteridine, carbazole, phenanthridine, acridine, phenazine, 1,10-phenanthridine, adenine, adenosine, guanine, guanosine, uracil and uridine, and their derivatives (e.g., bis(2-morpholinoethyl) ether, etc.). Additionally, 2,6-dimethylpyridine can also be cited as an example of the aforementioned heterocyclic amine compounds.

[0210] As a basic compound, one type can be used, or two or more types can be used in combination.

[0211] In addition, among basic compounds, hindered amines having the structure shown in the following general formula (II) are also used as antioxidants, and thus the heat resistance and light resistance of the adhesive layer can be improved by adding them.

[0212]

[0213] In general formula (II), X represents a hydrogen atom; an alkyl group having 1 or more but less than 20 carbon atoms; a cycloalkyl group having 3 or more but less than 20 carbon atoms; or an acyl group having 2 or more but less than 20 carbon atoms. Additionally, * in general formula (II) indicates a bonding site with other structures. From the viewpoint of solubility and performance as a quencher and antioxidant, alkyl groups having 1 or more but less than 20 carbon atoms are preferred as X, and methyl groups are more preferred.

[0214] Specific examples of compounds in which X is an alkyl group having 1 or more carbon atoms and 20 or fewer, a cycloalkyl group having 3 or more carbon atoms and 20 or fewer, or an acyl group having 2 or more carbon atoms and 20 or fewer include mixtures of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidinyl sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, and bis(1,2,2,6,6-pentamethyl-4-piperidinyl) malonate. -4-piperidinyl)2-n-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl) ester, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)4-methoxybenzyl ester, tetra(1,2,2,6,6-pentamethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylate, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, etc.

[0215] Specific examples of compounds where X is a hydrogen atom include bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 2,2,6,6-tetramethyl-4-piperidinyl benzoate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, a mixed ester of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-hydroxypiperidine and 1-tetranol, an ester compound formed by dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, and a polymer of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine with 1,2-dibromoethane, etc.

[0216] (Adhesion modifier)

[0217] Certain photosensitive compositions may also contain adhesive modifiers. Examples of adhesive modifiers include various coupling agents, epoxy compounds, oxetane compounds, phenolic resins, coumarone-indene resins, rosin ester resins, terpene-phenolic resins, α-methylstyrene-vinyltoluene copolymers, polyethyl methylstyrene, and aromatic polyisocyanates.

[0218] Examples of coupling agents include silane coupling agents. As a silane coupling agent, there is no particular limitation as long as it is a compound having at least one reactive functional group and one hydrolyzable silicon-containing group in its molecule. As a reactive functional group, from an operational viewpoint, one or more functional groups selected from the group consisting of epoxy, (meth)acryloyl, isocyanate, isocyanurate, vinyl, and urethane groups are preferred; from a curing and adhesion viewpoint, epoxy, methacryloyl, or acryloyl groups are particularly preferred. As a hydrolyzable silicon-containing group, from an operational viewpoint, alkoxysilane is preferred; from a reactive viewpoint, methoxysilane or ethoxysilane is particularly preferred.

[0219] Examples of preferred silane coupling agents include alkoxysilane compounds with epoxy groups such as 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; alkoxysilane compounds with (meth)acryloyl groups such as 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltriethoxysilane, acryloyloxymethyltrimethoxysilane, and acryloyloxymethyltriethoxysilane; tris[3-(trimethoxysilylpropyl)]isocyanurate; and γ-isocyanate propyltrimethoxysilane. These silane coupling agents can be used in one or more combinations.

[0220] The amount of silane coupling agent added can be appropriately set, preferably 0.1 parts by weight or more and 20 parts by weight or less, more preferably 0.3 parts by weight or more and 10 parts by weight or less, and even more preferably 0.5 parts by weight or more and 5 parts by weight or less, relative to 100 parts by weight of the compound having cationic polymerizable groups.

[0221] (Antioxidants)

[0222] Certain photosensitizing compositions may also contain antioxidants. In addition to commonly used antioxidants such as hindered phenolic antioxidants, examples of antioxidants include citric acid, phosphoric acid, and sulfur-based antioxidants. As the aforementioned hindered phenolic antioxidants, various products, such as IRGANOX (registered trademark) 1010, available from BASF Corporation, can be used. As the aforementioned sulfur-based antioxidants, examples include thiol compounds, salts of thiol compounds, thioether compounds (thioether carboxylic acid ester compounds, etc.), polysulfide compounds, dithiocarboxylate compounds, thiourea compounds, thiophosphate compounds, sulfonium compounds, thioaldehyde compounds, thionol compounds, methaqualols, methaquinones, monothioic acid compounds, polythioic acid compounds, thioamide compounds, and sulfoxide compounds. Furthermore, one or more of these antioxidants may be used.

[0223] (Free radical inhibitors)

[0224] Certain photosensitizing compositions may also contain free radical inhibitors. Examples of free radical inhibitors include phenolic free radical inhibitors such as 2,6-di-tert-butyl-3-methylphenol (BHT), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), and tetra(methylene-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)methane; and amine-based free radical inhibitors such as phenyl-β-naphthylamine, α-naphthylamine, N,N'-sec-butyl-p-phenylenediamine, phenothiazine, and N,N'-diphenyl-p-phenylenediamine. Furthermore, one or more of these free radical inhibitors may be used in combination.

[0225] It should be noted that, in addition to the specific photosensitive compositions described above, photosensitive compositions containing cationic polymeric compounds other than component (A) can also be used as the adhesive layer material. Examples of cationic polymeric compounds other than component (A) include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenolic varnish phenolic type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 2,2'-bis(4-glycidoxycyclohexyl)propane, vinylcyclohexene dioxide, 2-(3,4-epoxycyclohexyl)-5,5-spiro-( 3,4-Epoxycyclohexane)-1,3-dioxacyclohexane, bis(3,4-epoxycyclohexyl) adipic acid ester, 1,2-cyclopropane dicarboxylic acid diglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, 3-ethyl-3-(phenoxymethyl)oxetane, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (Daicel) The following are listed: "CELLOXIDE (registered trademark) 2021P" manufactured by Daicel Corporation; ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate ("CELLOXIDE (registered trademark) 2081" manufactured by Daicel Corporation); epoxy-modified chain siloxane compound shown in the above chemical formula (S1) ("X-40-2669" manufactured by Shin-Etsu Chemical Industry Co., Ltd.); and epoxy-modified cyclic siloxane compound shown in the above chemical formula (S2) ("KR-470" manufactured by Shin-Etsu Chemical Industry Co., Ltd.).

[0226] Alternatively, when forming the adhesive layer using methods such as dispensing, screen printing, or 3D printing, a photosensitive composition containing a polysiloxane compound that does not have alkali-soluble groups can be used as the adhesive layer material. Examples of polysiloxane compounds that do not have alkali-soluble groups include compounds with the same structure as component (A) described above, except that they do not have alkali-soluble groups.

[0227] In addition, thermosetting resins can also be used as adhesive layer materials. Especially when the adhesive layer is formed by methods such as dispensing, screen printing, or 3D printing, thermosetting resins are preferred as adhesive layer materials.

[0228] Thermosetting resins used as adhesive layers are not particularly limited as long as they are resins that undergo a curing reaction by any heating method. Specific examples of the aforementioned thermosetting resins include silicone resins, epoxy resins, alkyd resins, polyimide resins, acrylic resins, polyamide resins, polyaramid resins, and phenolic resins, which can be used alone or in combination of two or more. Among these, silicone resins, epoxy resins, and polyimide resins are preferred from the viewpoint of heat resistance and light resistance of the cured product obtained by heat curing the thermosetting resin, and silicone resins are more preferred from the viewpoint of particularly high light resistance.

[0229] To reduce curing shrinkage, addition-type silicone resins, which are preferably made of organic compounds having two or more alkenyl groups, hydrogenated silanization catalysts, and compounds having two or more SiH groups in one molecule, are preferred as thermosetting resins.

[0230] The above-mentioned photosensitive composition can be mixed into the thermosetting resin. Furthermore, adhesive modifiers, fillers, antioxidants, and other components can be mixed as needed. When forming an adhesive layer using screen printing or 3D printing with the thermosetting resin, it is preferable to add a filler to the thermosetting resin to exhibit thixotropy. The filler can be any of the above-mentioned materials, with fumed silica being preferred. For example, various grades of fumed silica manufactured by Aerosil Corporation of Japan can be used.

[0231] [Preferred method for optical semiconductor devices]

[0232] In order to obtain an optical semiconductor device that can suppress the generation of optical noise and has excellent reliability, and can suppress the ingress of foreign objects, the optical semiconductor device of the first embodiment preferably satisfies the following condition 1, more preferably satisfies the following condition 2, even more preferably satisfies the following condition 3, and even more preferably satisfies the following condition 4.

[0233] Condition 1: The height of the adhesive layer is 15μm or more and 300μm or less, and the cone angle is 90° or more and 130° or less.

[0234] Condition 2: The height of the adhesive layer is 15μm or more and 300μm or less, and the cone angle is 95° or more and 125° or less.

[0235] Condition 3: The height of the adhesive layer is 30μm or more and 150μm or less, and the cone angle is 95° or more and 125° or less.

[0236] Condition 4: The height of the adhesive layer is 30μm or more and 150μm or less, and the cone angle is 100° or more and 125° or less.

[0237] In addition, in order to obtain an optical semiconductor device having an adhesive layer with excellent heat resistance that can further suppress the generation of optical noise, the optical semiconductor device of the first embodiment preferably satisfies the following condition i, more preferably satisfies the following condition ii, even more preferably satisfies the following condition iii, and even more preferably satisfies the following condition iv.

[0238] Condition i: The adhesive layer is a cured layer composed of a cured product of a photosensitive composition, and the photosensitive composition contains component (A), a photoradical polymerization initiator as component (B), and component (C).

[0239] Condition ii: The above condition i is satisfied, and the photosensitive composition further contains a photocationic polymerization initiator as component (B).

[0240] Condition iii: The above condition ii is satisfied, and component (C) is a compound having a (meth)acryloyl group.

[0241] Condition iv: The above condition iii is satisfied, and the photosensitive composition further comprises a reactive diluent.

[0242] In addition, in order to obtain an optical semiconductor device having an adhesive layer with excellent heat resistance while further suppressing the generation of optical noise and foreign matter ingress and having excellent reliability, the optical semiconductor device of the first embodiment preferably satisfies the above conditions 1 and i, more preferably satisfies the above conditions 2 and ii, even more preferably satisfies the above conditions 3 and iii, and even more preferably satisfies the above conditions 4 and iv.

[0243] Applications of optical semiconductor devices

[0244] Examples of applications of the optical semiconductor device in the first embodiment include solid-state imaging devices, LEDs, laser diodes, photodiodes, and phototransistors.

[0245] The aforementioned solid-state imaging device (a solid-state imaging device having the photonic semiconductor device of the first embodiment) can be used, for example, to sense light such as visible light, infrared light, ultraviolet light, and X-rays. Examples of application areas include appreciation, transportation, home appliances, medical, security, manufacturing, and sports. However, it is not limited to these areas.

[0246] For example, in the field of appreciation, the aforementioned solid-state imaging device can be applied to electronic devices used to capture images for appreciation (more specifically, digital cameras, cameras attached to smartphones, etc.).

[0247] For example, in the field of transportation, the above-mentioned solid-state camera devices can be used in electronic devices (more specifically, vehicle-mounted sensors, etc.) that are installed in advanced driver support systems, autonomous driving systems, etc., to photograph the surroundings and interior of the car, electronic devices (more specifically, surveillance cameras, etc.) that monitor moving vehicles and roads, and electronic devices that measure the distance between vehicles (more specifically, distance measuring sensors, etc.).

[0248] For example, in the field of home appliances, such as television monitors, refrigerators, and air conditioners, the aforementioned solid-state camera devices can be used in electronic devices that capture people's movements and positions for equipment operation and parameter control based on their movements and positions.

[0249] For example, in the medical field, the aforementioned solid-state imaging device can be applied to electronic devices that perform vascular imaging through endoscopes and infrared light reception.

[0250] For example, in the field of security, the aforementioned solid-state camera devices can be applied to surveillance cameras for crime prevention purposes, cameras for facial recognition, iris recognition, and other personal identification purposes.

[0251] For example, in the manufacturing field, such as IC chip, automobile, food, and pharmaceutical manufacturing production lines, the aforementioned solid-state camera device can be applied to electronic devices used for serial number reading, shape anomaly inspection, and filling quantity inspection.

[0252] For example, in the field of sports, the aforementioned solid-state camera devices can be applied to action cameras, wearable cameras, and other devices designed for sports applications.

[0253] <Second Embodiment: Method for Manufacturing an Optical Semiconductor Device>

[0254] Next, a method for manufacturing an optical semiconductor device according to a second embodiment of the present invention will be described with reference to the accompanying drawings. The method for manufacturing the optical semiconductor device according to the second embodiment is a suitable method for manufacturing the optical semiconductor device according to the first embodiment described above. In the following description, content that is repeated in the first embodiment will sometimes be omitted.

[0255] The manufacturing method of the optical semiconductor device according to the second embodiment includes an adhesive layer forming step, a lamination step, and a curing step. In the adhesive layer forming step, a patterned adhesive layer is formed on a transparent substrate. In the lamination step, a transparent substrate with the adhesive layer formed and a semiconductor substrate having a light-receiving element are laminated such that the surface of the transparent substrate with the adhesive layer formed faces the surface of the semiconductor substrate having the light-receiving element. In the lamination step, the transparent substrate and the semiconductor substrate are laminated using the adhesive layer. In the curing step, the adhesive layer is cured, bonding the transparent substrate and the semiconductor substrate. In the manufacturing method of the optical semiconductor device according to the second embodiment, the adhesive layer is disposed around the light-receiving element in the lamination step. The refractive index of the cured adhesive layer is 1.60 or less. According to the manufacturing method of the optical semiconductor device according to the second embodiment, the optical semiconductor device of the first embodiment described above can be easily manufactured.

[0256] The following is a specific example of the manufacturing method of the optical semiconductor device according to the second embodiment. Figure 1 An example of a method for manufacturing the optical semiconductor device 10 shown (hereinafter, sometimes referred to as "manufacturing method M1"), and Figure 3 An example of a method for manufacturing the optical semiconductor device 100 shown (hereinafter, sometimes referred to as "manufacturing method M2") will be described with reference to the accompanying drawings.

[0257] [Manufacturing Method M1]

[0258] First, for manufacturing method M1, refer to Figures 7-10 The explanation will be provided later. Figure 7 This is a top view of a transparent substrate (wide transparent substrate) after the adhesive layer has been formed when manufacturing an optical semiconductor device according to manufacturing method M1. Figure 8 A top view of a monolithic transparent substrate during the manufacture of an optical semiconductor device according to manufacturing method M1. Figure 9 A to C are process-independent cross-sectional views showing the adhesive layer formation process in manufacturing method M1. Figure 10 A to C are process-independent sectional views showing the lamination and curing processes of manufacturing method M1.

[0259] In manufacturing method M1, firstly, a semi-cured adhesive layer 14 is formed on a wide transparent substrate 13 in a large number of patterned square cylindrical shapes. Figure 7 Hereinafter, the semi-cured adhesive layer will sometimes be referred to as a "semi-cured adhesive layer". It should be noted that "semi-cured state" refers to a state where, in the subsequent curing process, there is room for further curing of the adhesive layer. After forming the semi-cured adhesive layer 14 on the transparent substrate 13, along... Figure 7 The substrate 13 with the semi-cured adhesive layer 14 is cut along the dividing line 400 to monolithize it. Figure 8 During cutting, for example, a wide transparent substrate 13 is adhered to and fixed on a cutting strip (not shown), and then cut using a cutting plate (not shown). At this time, the side opposite to the side of the transparent substrate 13 where the semi-cured adhesive layer 14 is formed can be attached to the cutting strip, or the side where the semi-cured adhesive layer 14 is formed can be attached to the cutting strip.

[0260] In the process of forming a semi-cured adhesive layer 14 on a wide transparent substrate 13 (adhesive layer formation process), for example, a film composed of a photosensitive composition (more specifically, a coating film composed of a heated photosensitive composition) is patterned in a semi-cured state by photolithography. According to photolithography, semi-cured adhesive layers 14 with excellent dimensional accuracy can be formed in large quantities.

[0261] For the method of forming the semi-cured adhesive layer 14 by photolithography, refer to... Figure 9 The process will be explained from sides A to C. First, a photosensitive composition is coated onto the transparent substrate 13 to form a film (coating) composed of the photosensitive composition. The coating method is not particularly limited at this stage; for example, general coating methods such as spin coating or slot coating can be used. Next, the coating is heated to remove the solvent from the coating, forming a thin film 401 (the heated coating) on ​​the transparent substrate 13. Figure 9 A). The heating temperature of the coating can be set appropriately, preferably above 60°C and below 200°C.

[0262] Next, a photomask 402 with an opening 402a at a specified position is placed on the thin film 401, and the thin film 401 is irradiated with active energy rays E. Figure 9 B). Thus, only the thin film 401 (exposure portion 401a) located at the lower part of the opening 402a is exposed, and the photocuring reaction proceeds. There is no particular limitation on the cumulative exposure amount during exposure, but 1 mJ / cm² is preferred. 2 Above 8000mJ / cm 2 Below, more preferably 3mJ / cm 2 Above 3000mJ / cm 2 the following.

[0263] When exposing the thin film 401, it is preferable to expose it through soda-lime glass. Exposing the thin film 401 through soda-lime glass blocks short-wavelength light that is highly reactive with photopolymerization initiators, allowing reactive groups to remain on the surface of the thin film 401 and softening it. This facilitates the formation of a film with properties similar to the semiconductor substrate 12 (see reference 12). Figure 10A) A semi-cured adhesive layer 14 with good adhesion. As a method for exposing the thin film 401 through soda-lime glass, examples include: using a photomask 402 made of soda-lime glass, and irradiating the thin film 401 with active energy rays E in a state where the photomask 402 and soda-lime glass are overlapped.

[0264] After exposure, baking at a specified temperature as needed can maintain the semi-cured state of film 401 and promote the curing reaction.

[0265] Next, the exposed thin film 401 is developed. The development method for the thin film 401 is not particularly limited. For example, by immersion or spraying, the thin film 401 is brought into contact with an alkaline developer to dissolve and remove the non-exposed portion 401b, thereby forming a patterned semi-cured adhesive layer 14 on the transparent substrate 13. Figure 9 C). The alkaline developer can be used by general users without particular limitation. Specific examples of alkaline developers include aqueous solutions of organic bases such as tetramethylammonium hydroxide (TMAH) and choline; and aqueous solutions of inorganic bases such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, and lithium carbonate. From the viewpoint of improving the contrast between the exposed portion 401a and the unexposed portion 401b, the alkali concentration is preferably 25% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less. For purposes such as adjusting the dissolution rate, alcohol mixtures and surfactants may also be added to the alkaline developer. In addition, after the film 401 is contacted with the alkaline developer, the film 401 may be washed with water and dried.

[0266] If a thin film 401 composed of a photosensitive composition capable of photoradical polymerization is exposed, in the region of the exposed portion 401a that is relatively close to the photomask 402, free radical polymerization in the non-exposed portion 401b adjacent to the exposed portion 401a is easily suppressed due to oxygen inhibition. On the other hand, when the thin film 401 composed of a photosensitive composition capable of photoradical polymerization is exposed, in the region of the exposed portion 401a that is farther from the photomask 402, it is less susceptible to the effects of oxygen inhibition. Therefore, free radical polymerization in the non-exposed portion 401b adjacent to the exposed portion 401a is less likely to be suppressed. Therefore, if the thin film 401 composed of a photosensitive composition capable of photoradical polymerization is patterned by photolithography, the width of the semi-cured adhesive layer 14 after development tends to be greater on the side opposite to the transparent substrate 13 than on the side opposite to the transparent substrate 13 (the surface layer). Thus, if the thin film 401 composed of a photosensitive composition capable of photoradical polymerization is patterned by photolithography, the aforementioned cone angle can be greater than 90°. The cone angle can be adjusted, for example, by changing the spacing G between the thin film 401 and the photomask 402 (see reference). Figure 9 Adjustment is made based on at least one of B) and cumulative exposure. The interval G is, for example, 50 μm or more and 2000 μm or less.

[0267] As described above, in order to easily adjust the cone angle to 95° or more, the photosensitive composition coated on the transparent substrate 13 is preferably a photosensitive composition containing components (A), (B) and (C), and containing a photoradical polymerization initiator as component (B).

[0268] Next, the semi-cured adhesive layer 14 is formed and the transparent substrate 13 (refer to) is stacked and monolithically processed. Figure 8 The process (lamination process) between the semiconductor substrate 12 and the semiconductor substrate 12 will be described. First, a semiconductor substrate laminate is prepared. As a semiconductor substrate laminate, such as Figure 10 As shown in A, a laminate in which a semiconductor substrate 12 with a light receiving element 11 is bonded to a wiring substrate 17 by means of a chip bonding material 18 and an electrode pad 15 of the semiconductor substrate and an electrode pad 16 of the wiring substrate are electrically connected by means of a wire 19 can be used.

[0269] Then, as Figure 10 As shown in Figure A, a laminate of a transparent substrate 13 with a semi-cured adhesive layer 14 and a semiconductor substrate is arranged such that the surface of the transparent substrate 13 with the semi-cured adhesive layer 14 faces the surface of the semiconductor substrate 12 with the light-receiving element 11, and then they are laminated. Figure 10 B). In the lamination process, a semi-cured adhesive layer 14 is disposed around the light receiving element 11.

[0270] Next, the curing process will be described. First, the laminate obtained in the lamination process is heat-pressed onto the transparent substrate 13 and the semiconductor substrate laminate, for example, while a load is applied and the laminate is heated. The heating temperature at this time is, for example, 80°C or higher and 200°C or lower. Then, the heat-pressed laminate is heated at, for example, a temperature of 100°C or higher and 300°C or lower. Through the above curing process, the semi-cured adhesive layer 14 is cured, and the transparent substrate 13 and the semiconductor substrate 12 are bonded together by means of the adhesive layer 14. Next, as Figure 10 As shown in C, the peripheral portion (including the area containing the line 19) of the adhesive layer 14 is sealed with sealing resin 20, and solder balls 21 are formed on the surface of the wiring substrate 17 opposite to the semiconductor substrate 12 to obtain the optical semiconductor device 10.

[0271] It should be noted that in manufacturing method M1, a semi-cured adhesive layer 14 is formed on the transparent substrate 13, but a semi-cured adhesive layer 14 can also be formed on the semiconductor substrate 12, and the lamination process and curing process are performed in the same manner as described above.

[0272] [Manufacturing Method M2]

[0273] Next, for manufacturing method M2, while referring to Figure 7 , Figure 11 and Figure 12 The explanation will be provided later. Figure 11 This is a top view of a semiconductor substrate after the light-receiving element has been formed when manufacturing an optical semiconductor device according to manufacturing method M2. Figure 12 A and B are process-independent sectional views showing the stacking processes of manufacturing method M2.

[0274] In manufacturing method M2, firstly, an adhesive layer forming process is performed using the same method as in manufacturing method M1. Specifically, using the same method as in manufacturing method M1, a semi-cured adhesive layer 14 is formed on a wide transparent substrate 13 in a manner that is patterned in numerous square tubular shapes (see reference). Figure 7 In addition, a wide semiconductor substrate 12 with multiple light-receiving elements 11 is prepared separately (see reference). Figure 11 ).

[0275] Next, the lamination process will be explained. For example... Figure 12 As shown in Figure A, a wide transparent substrate 13 with a semi-cured adhesive layer 14 and a wide semiconductor substrate 12 with multiple light-receiving elements 11 are arranged such that the surface of the transparent substrate 13 with the semi-cured adhesive layer 14 faces the surface of the semiconductor substrate 12 with the light-receiving elements 11, and then they are stacked. Figure 12 B). In the lamination process, a semi-cured adhesive layer 14 is disposed around the light receiving element 11.

[0276] Next, the curing process will be described. First, the laminate obtained in the lamination process is heat-pressed onto the transparent substrate 13 and the semiconductor substrate 12, for example, while a load is applied and the material is heated. The heating temperature at this time is, for example, 80°C or higher and 200°C or lower. Then, the heat-pressed laminate is heated at, for example, 100°C or higher and 300°C or lower. Through the above curing process, the semi-cured adhesive layer 14 is cured, and the transparent substrate 13 and the semiconductor substrate 12 are bonded together by means of the adhesive layer 14.

[0277] Next, along Figure 12 After cutting along the dividing line 500 of B, solder balls 21 are formed on the side of the semiconductor substrate 12 opposite to the transparent substrate 13 side, resulting in... Figure 3 The optical semiconductor device 100 shown.

[0278] It should be noted that in manufacturing method M2, a semi-cured adhesive layer 14 is formed on the transparent substrate 13, but the semi-cured adhesive layer 14 can also be formed on the semiconductor substrate 12, and the lamination and curing processes are performed in the same manner as described above. Alternatively, a monolithized semiconductor substrate 12 and a monolithized transparent substrate 13 can be used, and the lamination and curing processes are performed in the same manner as described above.

[0279] <Other methods for forming adhesive layers>

[0280] The manufacturing method of the optical semiconductor device according to the second embodiment has been described above, but the method for manufacturing the optical semiconductor device according to the first embodiment is not limited to the manufacturing method of the second embodiment. For example, the adhesive layer can also be formed by screen printing or 3D printing.

[0281] Screen printing method

[0282] When forming the adhesive layer using screen printing, from the viewpoint of maintaining the shape after printing, the photosensitive composition used preferably has thixotropic properties. To exhibit thixotropic properties, a photosensitive composition containing microparticles or the like may also be used.

[0283] As a printing mask used in screen printing, preferably Figure 13 The printing mask 600 shown has screens in multiple openings 600a. The openings 600a are formed in a frame shape to form an adhesive layer with a square cylindrical structure. The number of screens (strips / inch) of the printing mask 600 is not particularly limited, but preferably 50 strips / inch or more and 500 strips / inch or less. The areas other than the openings 600a are fixed by an emulsion or covered by metal. Thus, the photosensitive composition can pass through only the openings 600a.

[0284] When screen printing a photosensitive composition, a printing mask is placed on a transparent substrate with a specified gap, and the photosensitive composition is printed onto the transparent substrate at a specified printing speed (squeegee speed). The gap, squeegee pressure, squeegee angle, and squeegee speed can be appropriately set to obtain the desired film thickness and shape. It should be noted that screen printing can be performed under atmospheric pressure or under vacuum.

[0285] After screen printing, the transparent substrate with the adhesive layer formed is irradiated with light at a specified cumulative exposure amount to promote curing. To ensure adhesion, it is preferable to allow the adhesive layer to remain in a semi-cured state beforehand. At this time, it is preferable to expose it through soda-lime glass.

[0286] [3D Printing Method]

[0287] 3D printing, or additive manufacturing, is a process that creates three-dimensional (3D) solid objects from digital files such as CAD documents. Specifically, the seven methods described in ASTM F2792-12a can be used. These seven methods include material jetting, material extrusion, powder bed fusion bonding, directed energy deposition, sheet lamination, binder jetting, and liquid bath photopolymerization. Among these seven methods, material jetting and material extrusion are preferred from the perspective of forming an adhesive layer directly on a transparent substrate, and material jetting is particularly preferred from the viewpoint of using photosensitive compositions for micro-processing.

[0288] The material jetting method is an inkjet method, in which a liquid photosensitive composition is repeatedly ejected from the inkjet nozzle into a transparent substrate in the form of fine droplets and then exposed to cure the photosensitive composition, forming a three-dimensional shape.

[0289] In the case of forming adhesive layers using 3D printing, for example, an inkjet nozzle moves over an area of ​​the existing adhesive layer on a transparent substrate, and a liquid photosensitive composition is ejected from the inkjet nozzle onto the transparent substrate. The ejected photosensitive composition is then exposed to allow it to cure, thus constructing one adhesive layer. This process is repeated to create multiple layers until the desired thickness is achieved, forming the adhesive layer.

[0290] When forming adhesive layers using a material spraying method, a large number of adhesive layers can be formed on a wide transparent substrate, or on a monolithically formed transparent substrate.

[0291] In the material spraying method, a support material can be used when forming adhesive layers with shapes that are difficult to manufacture in principle (such as shapes with a large degree of horizontal overflow or hangover in subsequent layering). There are no particular restrictions on the material used for the support material; it can be a photosensitive composition, a wax, or a water-soluble material. A support material can also be used when the cone angle is less than 90° or when an uneven shape is formed on the side of the adhesive layer during the adhesive layer formation process.

[0292] In addition, when forming an adhesive layer using a photosensitive composition via 3D printing, it is preferable to adjust the cumulative exposure amount, etc., to keep the photosensitive composition in a semi-cured state in order to maintain adhesion in subsequent lamination processes.

[0293] Example

[0294] The present invention will be specifically described below with reference to embodiments, but the present invention is not limited to these embodiments.

[0295] <Methods for Determining Refractive Index>

[0296] First, the method for measuring the refractive index of the adhesive layer (the cured layers composed of cured photosensitive compositions obtained in the preparation method described later) will be explained. With a cured layer thickness of 50 μm, the photosensitive composition was spin-coated onto a glass substrate (specifically, a glass substrate with a surface coated with Mo (molybdenum) by vacuum evaporation) to form a coating film on the glass substrate. Next, the coating film was heated at 80°C for 10 minutes using a hot plate, and then at 120°C for 10 minutes. Then, the heated coating film (thin film) was subjected to a cumulative exposure of 1000 mJ / cm². 2 After exposure under the specified conditions, the film was allowed to stand for 5 minutes in an atmosphere at 25°C. Then, using a hot plate, the film was heated to 120°C for 10 minutes. Next, the heated film was peeled off the glass substrate using a cutter and then heated in an oven at 200°C for 2 hours to obtain a thin-film sample (a cured layer composed of a cured photosensitive composition) for refractive index determination. For the obtained thin-film sample, the refractive index of light with a wavelength of 404 nm was measured at 23°C using a prism coupler (Metoricon "2010 / M"). It should be noted that for each thin-film sample, the refractive index was measured five times consecutively in half-mode. The arithmetic mean of the five measurements was then used as the "refractive index" listed in Table 1 below.

[0297] <Synthesis of Polymers (Polysiloxane Compounds)>

[0298] The synthesis methods of polymers P1 and P2 are described below. It should be noted that the weight-average molecular weights of polymers P1 and P2 were calculated as follows: using a Tosoh Corporation-manufactured "HLC-8420GPC" (columns: Shodex GPC KD-806M (2 columns), TSKgel SuperAWM-H (2 columns)), with N,N-dimethylformamide as the solvent, the molecular weights were determined at a flow rate of 1.0 mL / min. The molecular weights were calculated from the measured chromatograms using standard polystyrene.

[0299] [Synthesis of Polymer P1]

[0300] To a mixture of 40 g of diallyl isocyanurate, 29 g of diallyl monomethyl isocyanurate, and 264 g of 1,4-dioxane, 124 mg of a xylene solution of a platinum-vinylsiloxane complex (a solution containing 3% by weight of platinum, manufactured by Umicore Shokubai Japan Co., Ltd. as "Pt-VTSC-3X") was added to obtain solution S1. Separately, 88 g of 1,3,5,7-tetrahydro-1,3,5,7-tetramethylcyclotetrasiloxane was dissolved in 176 g of toluene to obtain solution S2.

[0301] Then, under a nitrogen atmosphere containing 3% by volume oxygen, solution S2 was heated to 105°C, and solution S1 was added dropwise to solution S2 over 3 hours. After the addition was completed, the temperature was maintained at 105°C, and the mixture was stirred for 30 minutes to obtain solution S3. It should be noted that... 1 The reaction rate of the alkenyl group of the compound contained in solution S3 was determined by H-NMR, and the result showed that the reaction rate was over 95%.

[0302] In addition, 62g of 1-vinyl-3,4-epoxycyclohexane was dissolved in 62g of toluene to obtain solution S4.

[0303] Then, under a nitrogen atmosphere containing 3% by volume oxygen, solution S3 was heated to 105°C. Solution S4 was then added dropwise to solution S3 over 1 hour. After the addition was complete, the temperature was maintained at 105°C, and the mixture was stirred for 30 minutes to obtain solution S5. It should be noted that... 1 The reaction rate of the alkenyl group of the compound contained in solution S5 was determined by H-NMR, and the result showed that the reaction rate was over 95%.

[0304] Next, after cooling solution S5, the solvent (toluene, xylene, and 1,4-dioxane) was removed from solution S5 by vacuum distillation to obtain polymer P1 (a polysiloxane compound with a weight average molecular weight of 30,000). Polymer P1 has the following characteristics: it contains multiple cationic polymerizable groups (specifically alicyclic epoxy groups) and multiple alkali-soluble groups (specifically X2 groups) in one molecule, and has a cyclic polysiloxane structure on the main chain.

[0305] [Synthesis of Polymer P2]

[0306] As solutions S1, S2 and S4, the following solutions were used respectively. In addition, polymer P2 (a polysiloxane compound with a weight average molecular weight of 1000) was obtained by the same synthesis method as polymer P1.

[0307] Solution S1: A solution obtained by adding 87 mg of a xylene solution of a platinum-vinylsiloxane complex (a solution containing 3% by weight of platinum, manufactured by Umicore Shokubai Japan Co., Ltd. as "Pt-VTSC-3X") to a mixture of 50 g diallyl monomethyl isocyanurate and 100 g toluene.

[0308] Solution S2: A solution containing 94g of 1,3,5,7-tetrahydro-1,3,5,7-tetramethylcyclotetrasiloxane dissolved in 186g of toluene.

[0309] Solution S4: A solution containing 55g of 1-vinyl-3,4-epoxycyclohexane dissolved in 55g of toluene.

[0310] Polymer P2 is as follows: it has multiple cationic polymerizable groups (specifically alicyclic epoxy groups) in one molecule, and has a cyclic polysiloxane structure on the main chain.

[0311] <Preparation of Other Materials>

[0312] In addition to the polymer mentioned above, the following materials are also prepared as materials for the photosensitive composition.

[0313] • Mitsubishi Chemical Corporation manufactures "jER (registered trademark) XY8000" (hydrogenated bisphenol A type epoxy resin, hereinafter referred to as "XY8000").

[0314] • Mitsubishi Chemical Corporation manufactures "jER (registered trademark) 828" (bisphenol A type epoxy resin, hereinafter referred to as "828").

[0315] • Daicel Corporation manufactures “CELLOXIDE (registered trademark) 2021P” (3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, hereinafter referred to as “2021P”).

[0316] • Pentaerythritol tetraacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as "PETA")

[0317] San-Apro Ltd. manufactures "CPI-210S" (a sulfonate-based photocationic polymerization initiator, hereinafter referred to as "CPI-210S").

[0318] ·2,2-Dimethoxy-2-phenylacetophenone (photoradical polymerization initiator manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as "DMPA")

[0319] • BASF Corporation manufactures "IRGANOX (registered trademark) 1010" (antioxidant, hereinafter referred to as "1010").

[0320] • R976 (fumed silica, hereinafter referred to as "R976") manufactured by Aerosil Corporation of Japan

[0321] • TTO-55(S) manufactured by Ishihara Sangyo Co., Ltd. (Titanium oxide microparticles, hereinafter referred to as "TTO-55(S)")

[0322] • Bis(2-morpholinoethyl) ether (a basic compound manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as "BME")

[0323] Isobutyl isobutyrate (a solvent manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as "IBIB")

[0324] <Preparation of Photosensitive Compositions>

[0325] The materials listed in Table 1 were mixed in the amounts listed in Table 1 to obtain the photosensitive compositions PS1 to PS5 used in the Examples and Comparative Examples, respectively. It should be noted that in Table 1, "-" indicates that the material was not mixed. Furthermore, the "refractive index" in Table 1 is the refractive index measured using the photosensitive composition according to the method described in the <Method for Determining Refractive Index> section above.

[0326] [Table 1]

[0327]

[0328] <Fabrication of Optical Semiconductor Devices>

[0329] The fabrication methods of the optical semiconductor devices of Examples 1 to 22 and Comparative Example 1 will be described below.

[0330] [Example 1]

[0331] A photosensitive composition PS1 was coated onto a transparent glass substrate (10cm × 10cm, 0.4mm thick) using a spin-coating method to form a coating film. Next, the coated glass substrate was heated to 80°C for 10 minutes using a hot plate, followed by heating to 120°C for 10 minutes to obtain a glass substrate with a 50μm thick film. The obtained film was then exposed using a manual exposure machine (Dai Nippon Research & Development Co., Ltd. "MA-1300", high-pressure mercury lamp) through a soda-lime glass photomask (a soda-lime glass photomask with multiple frame-shaped light-transmitting areas of 100μm linewidth) with a cumulative exposure of 1500mJ / cm². 2 Exposure is performed under the specified conditions. During exposure, the distance G between the thin film and the soda-lime glass photomask is (refer to...). Figure 9 B) Set to 100μm.

[0332] Next, the exposed film is immersed in an aqueous TMAH solution (temperature: 23°C, TMAH concentration: 2.38 wt%) as an alkaline developer for 3 minutes, and then rinsed with pure water for 1 minute. This patterning of the film on the glass substrate results in a glass substrate with multiple semi-cured adhesive layers having a quadrangular cylindrical structure. Then, a cutting film is temporarily bonded to the surface of the glass substrate without the semi-cured adhesive layer, and the film is cut along with the semi-cured adhesive layer using a cutting plate. The cutting film is then peeled off to obtain a monolithically formed glass substrate with a semi-cured adhesive layer (hereinafter referred to as "glass substrate with semi-cured adhesive layer").

[0333] Next, the obtained glass substrate with the semi-cured adhesive layer and the semiconductor substrate laminate are stacked to form a laminate. At this time, the semiconductor substrate laminate with the light-receiving element facing the glass substrate with the semi-cured adhesive layer. It should be noted that the semiconductor substrate laminate described above uses a laminate in which the semiconductor substrate with the light-receiving element is bonded to the wiring substrate using a chip bonding material, and the electrode pads on the semiconductor substrate and the electrode pads on the wiring substrate are electrically connected using metal wires.

[0334] Next, for the laminate of the glass substrate and the semiconductor substrate with the semi-cured adhesive layer, a load of 500g was applied to a hot plate at 120°C for 30 seconds to thermally bond the semiconductor substrate laminate and the glass substrate using the semi-cured adhesive layer. Then, the laminate after thermally bonding the semiconductor substrate laminate and the glass substrate was heated in an oven at 200°C for 2 hours to cure the semi-cured adhesive layer. Next, the periphery of the adhesive layer (the area containing the lines) was sealed with a sealing resin, and solder balls were formed on the side of the wiring substrate opposite to the semiconductor substrate side, resulting in the optical semiconductor device of Example 1. The optical semiconductor device of Example 1 has… Figure 1 The structure shown. Additionally, in the optical semiconductor device of Example 1, the height of the adhesive layer is 50 μm.

[0335] [Example 2]

[0336] A glass substrate (10cm x 10cm, 0.4mm thick) serving as a transparent substrate is vacuum-adsorbed onto the stage of a screen printing machine. A photosensitive composition PS2 is then coated onto a printing mask with a screen count of 250 slits / inch (used to obtain multiple adhesive layers with a tetrahedral structure). Next, ensuring a printing height (gap) of 100μm, the printing mask is positioned above the glass substrate, and the photosensitive composition PS2 is screen-printed onto the glass substrate at a printing speed of 30mm / second, forming a 100μm thick printed layer. Then, the resulting printed layer is exposed using a manual exposure machine (Dainippon Research & Development Corporation "MA-1300", lamp: high-pressure mercury lamp) through soda-lime glass at a cumulative exposure of 1500mJ / cm². 2 Exposure was performed under specific conditions to obtain a glass substrate with multiple semi-cured adhesive layers having a quadrangular cylindrical structure. Next, a diced film was temporarily bonded to the side of the glass substrate without the semi-cured adhesive layer, and the process was repeated as in Example 1, from monolithization to solder ball formation, to obtain the optical semiconductor device of Example 2. Figure 1 The structure shown.

[0337] [Example 3]

[0338] The photosensitive composition PS3 was used instead of the photosensitive composition PS2, except that the optical semiconductor device of Example 3 was obtained using the same method as in Example 2. The optical semiconductor device of Example 3 has... Figure 1 The structure shown.

[0339] [Examples 4-22]

[0340] The type of photosensitive composition, the spacing G between the thin film and the soda-lime glass photomask during exposure, and the height of the adhesive layer are set as shown in Table 2 (described later). Otherwise, the optical semiconductor devices of Examples 4 to 22 were obtained using the same method as in Example 1. The optical semiconductor devices of Examples 4 to 22 all have… Figure 1 The structure shown.

[0341] [Comparative Example 1]

[0342] The photosensitive composition PS4 was used instead of the photosensitive composition PS2, and the optical semiconductor device of Comparative Example 1 was obtained using the same method as in Example 2. The optical semiconductor device of Comparative Example 1 has… Figure 1 The structure shown.

[0343] <Evaluation of Optical Semiconductor Devices>

[0344] [Visual-based evaluation]

[0345] First, the optical semiconductor devices of Examples 1-22 and Comparative Example 1 obtained in the above steps were confirmed to operate without hindrance as optical semiconductor devices. Next, the captured images of these optical semiconductor devices were visually reviewed to evaluate their imaging performance. In Comparative Example 1, where the refractive index of the adhesive layer exceeded 1.60, ghosting and stray light were observed, but in Examples 1-22, where the refractive index of the adhesive layer was less than 1.60, no ghosting or stray light occurred.

[0346] [Evaluation based on the ghosting index]

[0347] First, for the optical semiconductor device being evaluated (any of Examples 1 and 4-22), using a ghosting and stray light evaluation system (GCS-2T manufactured by Tsubosaka Electric Co., Ltd.), the number of pixels exceeding a predetermined threshold (one hundred millionth of the brightness of the light source) is determined (hereinafter referred to as "abnormal pixel count"). Then, the value obtained by dividing the abnormal pixel count by the total number of pixels (abnormal pixel count / total pixel count) is calculated. Hereinafter, the value obtained by dividing the abnormal pixel count by the total number of pixels (abnormal pixel count / total pixel count) is sometimes referred to as the abnormal pixel count ratio.

[0348] Then, the abnormal pixel count ratio of Example 1 was set as 100, and the abnormal pixel count ratios of Examples 4 to 22 were standardized. The standardized value (hereinafter referred to as the "ghosting index") was used as an indicator of the performance in suppressing ghosting. The smaller the ghosting index, the higher the performance in suppressing ghosting.

[0349] [Reliability evaluation based on thermal shock testing]

[0350] First, using a heat shock test apparatus ("Cosmopia" manufactured by Hitachi-Johnson Controls Air Conditioning Inc., a registered trademark), the optoelectronic semiconductor device under evaluation (any of Examples 1 and 4-22) was kept at -50°C for 30 minutes, then at 125°C for 30 minutes. This operation was considered one cycle, and 500 cycles were performed. Next, the optoelectronic semiconductor device was observed from the glass substrate side using an optical microscope, and the number of cracks and peeling points in the adhesive layer were counted. Then, the reliability was determined according to the following criteria. A determination of A was evaluated as "excellent reliability." On the other hand, a determination of B was evaluated as "non-excellent reliability."

[0351] (Reliability assessment criteria)

[0352] A: The total number of cracked areas and peeling areas in the adhesive layer is less than 10.

[0353] B: The total number of cracked locations and peeling locations in the adhesive layer is more than 10.

[0354] For Examples 1 and 4-22, the types of photosensitive compositions used, the spacing between the film and the soda-lime glass photomask during exposure, the cone angle, the height of the adhesive layer, the ghosting index, and the reliability determination results are shown in Table 2. It should be noted that the cone angle and the height of the adhesive layer are the arithmetic mean values ​​obtained from electron microscope images (sample number: 5) of cross-sections cut along the thickness direction of each optical semiconductor device. Additionally, in Table 2, "spacing G" refers to the spacing between the film and the soda-lime glass photomask during exposure.

[0355] [Table 2]

[0356]

[0357] As shown in Table 2, Examples 5 to 22, with a cone angle of 90° or more and 130° or less, have a smaller ghosting index and higher performance in suppressing ghosting compared to Examples 1 and 4, with a cone angle of less than 90°.

[0358] Explanation of reference numerals in the attached figures

[0359] 10, 100, 300 Optical Semiconductor Devices

[0360] 11 Optical receiving element

[0361] 12 Semiconductor substrate

[0362] 13 Transparent substrate

[0363] 14 Adhesive Layer

[0364] 15 Electrode pads for semiconductor substrates (electrode pads)

[0365] 17 Wiring substrate

Claims

1. An optical semiconductor device comprising: A semiconductor substrate equipped with a light-receiving element; A transparent substrate facing the semiconductor substrate on which the light-receiving element is disposed; and, An adhesive layer that bonds the semiconductor substrate to the transparent substrate. The adhesive layer is arranged to surround the light-receiving element. The refractive index of the adhesive layer is below 1.

60. The angle between the semiconductor substrate side of the transparent substrate and the inner wall surface of the adhesive layer exceeds 90°.

2. The optical semiconductor device according to claim 1, wherein, The angle between the semiconductor substrate side of the transparent substrate and the inner wall surface of the adhesive layer exceeds 90° and is less than 130°.

3. The optical semiconductor device according to claim 1 or 2, wherein, The height of the adhesive layer is above 15 μm and below 300 μm.

4. The optical semiconductor device according to claim 1 or 2, further comprising a wiring substrate disposed on the side of the semiconductor substrate opposite to the transparent substrate side.

5. The optical semiconductor device according to claim 4, wherein, Electrode pads are provided on the semiconductor substrate. The adhesive layer is disposed between the electrode pad and the light receiving element.

6. The optical semiconductor device according to claim 1 or 2, wherein it is a chip-scale package.

7. The optical semiconductor device according to claim 1 or 2, wherein, The angle between the semiconductor substrate side of the transparent substrate and the inner wall surface of the adhesive layer is 95° or more and 125° or less.

8. The optical semiconductor device according to claim 1 or 2, wherein, The height of the adhesive layer is above 30 μm and below 150 μm.

9. The optical semiconductor device according to claim 1 or 2, wherein, The adhesive layer comprises a cured layer consisting of a cured product of a photosensitive composition.

10. The optical semiconductor device according to claim 9, wherein, The photosensitive composition contains a polysiloxane compound and a photopolymerization initiator. The polysiloxane compound has cationic polymerizable groups and alkali-soluble groups in one molecule.

11. The optical semiconductor device according to claim 10, wherein, The cationic polymerizable group is selected from one or more groups consisting of glycidyl groups, alicyclic epoxy groups, and oxocyclic butyl groups.

12. The optical semiconductor device according to claim 10 or 11, wherein, The alkali-soluble group is one or more selected from the group consisting of a monovalent organic group represented by the following chemical formula (X1) and a divalent organic group represented by the following chemical formula (X2). 。 13. The optical semiconductor device according to claim 10 or 11, wherein, The photosensitive composition further contains a compound having a free radical polymerizable group and a photoradical polymerization initiator as the photopolymerization initiator.

14. A solid-state imaging device comprising the optical semiconductor device according to any one of claims 1 to 13.

15. An electronic device having the solid-state camera device of claim 14.

16. A method for manufacturing an optical semiconductor device, wherein, A patterned adhesive layer is formed on a transparent substrate. The transparent substrate with the adhesive layer formed thereon and the semiconductor substrate with the light-receiving element are stacked such that the side of the transparent substrate with the adhesive layer formed thereon faces the side of the semiconductor substrate with the light-receiving element. The adhesive layer is cured to bond the transparent substrate to the semiconductor substrate. When the transparent substrate is stacked with the semiconductor substrate, the adhesive layer is disposed around the light-receiving element. The refractive index of the cured adhesive layer is below 1.

60. The angle between the semiconductor substrate side of the transparent substrate and the inner wall surface of the adhesive layer exceeds 90°.

17. The method for manufacturing an optical semiconductor device according to claim 16, wherein, When forming the patterned adhesive layer, the film composed of the photosensitive composition is patterned in a semi-cured state by photolithography.

18. The method for manufacturing an optical semiconductor device according to claim 17, wherein, When forming the patterned adhesive layer, the film composed of the photosensitive composition is exposed through soda-lime glass, and then the exposed film is developed.

19. The method of manufacturing an optical semiconductor device according to claim 17 or 18, wherein, The photosensitive composition contains: a polysiloxane compound, a photoradical polymerization initiator, and a compound having radical polymerizable groups. The polysiloxane compound has cationic polymerizable groups and alkali-soluble groups in one molecule.

20. The method of manufacturing an optical semiconductor device according to claim 17 or 18, wherein, The angle between the semiconductor substrate side of the transparent substrate and the inner wall surface of the adhesive layer is less than 130°.

21. The method of manufacturing an optical semiconductor device according to claim 17 or 18, wherein, The angle between the semiconductor substrate side of the transparent substrate and the inner wall surface of the adhesive layer is 95° or more and 125° or less.

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