Ribbed substrates and optoelectronic devices

Abstract

A ribbed substrate (10) is provided with a transparent substrate (11) and a rib material (12) provided on one major surface of the transparent substrate (11). The rib material (12) is formed in the shape of a frame. The rib material (12) has an inner peripheral surface (12a) with an arithmetic mean roughness Ra of 50 nm to 3000 nm inclusive. The rib material (12) has an inner peripheral surface (12a) with a skewness Ssk of preferably a negative value. Preferably, the arithmetic mean roughness Ra of the inner peripheral surface (12a) of the rib material (12) is 200 nm to 900 nm inclusive.

Description

[Technical Field]

[0001] This invention relates to a ribbed substrate and an optoelectronic device. [Background technology]

[0002] Optoelectronic devices such as CMOS sensors and CCD sensors are used in digital cameras and smartphones, and in recent years, their use has increased with the proliferation of surveillance cameras in automobiles and factories, while there is an increasing demand for miniaturization and higher resolution.

[0003] An optoelectronic device has, for example, a hollow structure in which a semiconductor substrate on which a photodetector is provided and a glass substrate are bonded together with an adhesive. An optoelectronic device having a hollow structure can be obtained, for example, by applying a liquid adhesive such as epoxy resin or acrylic resin to the periphery of the semiconductor substrate, placing a glass substrate which will serve as a sealing substrate, and then heating to cure the liquid adhesive. In addition, a method using a photosensitive composition instead of a liquid adhesive has been investigated for the purpose of improving pattern accuracy (see, for example, Patent Document 1).

[0004] An example of a method for manufacturing an optoelectronic device using a photosensitive composition is shown below. First, a photosensitive composition is applied to one side of a transparent substrate (e.g., a glass substrate) to form a coating film on the transparent substrate. Next, light is irradiated onto the coating film through a photomask to form exposed areas and unexposed areas in the coating film, which are composed of a semi-cured photosensitive composition. Then, the unexposed areas are removed from the transparent substrate with a developer to form a patterned semi-cured coating film (rib material) on the transparent substrate, obtaining a ribbed substrate (a substrate having a transparent substrate and rib material). Next, the ribbed substrate and the semiconductor substrate are laminated so that the side of the ribbed substrate with the rib material is facing the semiconductor substrate, and then the rib material is cured to bond the transparent substrate and the semiconductor substrate. Through these steps, an optoelectronic device having a hollow structure is obtained. [Prior art documents] [Patent Documents]

[0005] Patent Document 1 Japanese Patent Application Laid-Open No. 2004-296453 Summary of the Invention Problems to be Solved by the Invention

[0006] However, with the recent demand for further miniaturization and higher definition of optical semiconductor devices, the conventional optical semiconductor devices may affect the imaging characteristics. In particular, when strong light is incident, optical noise (specifically, flare, ghost, etc.) occurs in the captured image, and it has been found that there is a problem that the original imaging characteristics cannot be fully exhibited.

[0007] The present invention has been made in view of the above problems, and an object thereof is to provide a ribbed substrate and an optical semiconductor device capable of suppressing the generation of optical noise. Means for Solving the Problems

[0008] <Aspects of the Present Invention> The present invention includes the following aspects.

[0009] [1] A ribbed substrate including a transparent substrate and a rib material provided on one main surface of the transparent substrate, wherein the rib material is formed in a frame shape, [[ID=3 and]] the arithmetic mean roughness Ra of the inner peripheral surface of the rib material is 50 nm or more and 3000 nm or less.

[0010] [2] The ribbed substrate according to [1], wherein the skewness Ssk of the inner peripheral surface of the rib material is a negative value.

[0011] [3] The ribbed substrate according to [1] or [2], wherein the arithmetic mean roughness Ra of the inner peripheral surface of the rib material is 200 nm or more and 900 nm or less.

[0012] [4] The content rate of the filler in the rib material is 30% by weight or less with respect to the total amount of the rib material, the ribbed substrate according to any one of [1] to [3] above.

[0013] [5] The arithmetic mean roughness Ra of the end face of the rib material on the side opposite to the transparent substrate side is 50 nm or more and 3000 nm or less, the ribbed substrate according to any one of [1] to [4] above.

[0014] [6] The transparent substrate is a glass substrate, the ribbed substrate according to any one of [1] to [5] above.

[0015] [7] The rib material is composed of a cured product of a photosensitive composition, The photosensitive composition contains a curable compound having a polymerizable group and a photoinitiator, and is alkali-soluble, the ribbed substrate according to any one of [1] to [6] above.

[0016] [8] The photosensitive composition has a linear structure and a cyclic structure, the ribbed substrate according to [7] above.

[0017] [9] The photosensitive composition contains a polysiloxane compound having the linear structure, the ribbed substrate according to [8] above. [[ID=​​​​​​​​​​​

[12] The photosensitive composition contains a compound having one or more alkali-soluble groups selected from the group consisting of a monovalent organic group represented by the following chemical formula (X1), a divalent organic group represented by the following chemical formula (X2), a phenolic hydroxyl group, and a carboxyl group, as described in any one of [7] to

[11] above, the ribbed substrate described in any one of [7] to

[11] .

[0021] [ka]

[0022]

[13] comprising a ribbed substrate as described in any one of [1] to

[12] above, and a semiconductor substrate on which a light-receiving element is provided, The transparent substrate of the ribbed substrate and the semiconductor substrate are laminated together via the rib material of the ribbed substrate. The rib material is provided so as to surround the light-receiving element in the optoelectronic device.

[0023]

[14] The optical semiconductor device according to

[13] , further comprising an adhesive layer for bonding the rib material and the semiconductor substrate. [Effects of the Invention]

[0024] According to the present invention, it is possible to provide a ribbed substrate and an optoelectronic device that can suppress the generation of optical noise. [Brief explanation of the drawing]

[0025] [Figure 1] This is a plan view showing an example of a ribbed substrate according to the present invention. [Figure 2] This is a cross-sectional view along line II-II in Figure 1. [Figure 3] This is a cross-sectional view showing an example of a photoelectronic device according to the present invention. [Figure 4] This is a partially enlarged cross-sectional view showing another example of an optoelectronic device according to the present invention. [Figure 5] This is a cross-sectional view showing another example of an optoelectronic device according to the present invention. [Figure 6]This is a partially enlarged cross-sectional view showing another example of an optoelectronic device according to the present invention. [Figure 7] This is a partially enlarged cross-sectional view showing another example of an optoelectronic device according to the present invention. [Figure 8] This is a cross-sectional view showing another example of an optoelectronic device according to the present invention. [Figure 9] This is a cross-sectional view showing another example of an optoelectronic device according to the present invention. [Figure 10] This is a plan view showing a transparent substrate after rib material formation, when manufacturing an example of an optical semiconductor device according to the present invention. [Figure 11] A, B, and C are cross-sectional views showing the process steps involved in manufacturing an example of an optoelectronic device according to the present invention. [Figure 12] A, B, and C are cross-sectional views showing the process steps involved in manufacturing an example of an optoelectronic device according to the present invention. [Figure 13] This is a plan view showing a semiconductor substrate after a photodetector has been formed, when manufacturing another example of an optical semiconductor device according to the present invention. [Figure 14] A and B are cross-sectional views illustrating a process for manufacturing another example of an optoelectronic device according to the present invention. [Figure 15] This is a plan view showing an example of a photomask. [Figure 16] This is a plan view showing another example of a photomask. [Modes for carrying out the invention]

[0026] Preferred embodiments of the present invention will be described in detail below, but the present invention is not limited thereto. Furthermore, all academic and patent documents cited herein are incorporated herein by reference.

[0027] First, let's explain the terminology used in this specification. The "main surface" of a layered material (more specifically, a transparent substrate, a semiconductor substrate, etc.) refers to the surface perpendicular to the thickness direction of the layered material. The "arithmetic mean roughness Ra" is measured by the method described in JIS B0601:2013. The "skewness Ssk" is measured by the method described in JIS B0681-2:2018.

[0028] A "polymerizable group" refers to a functional group that enables polymerization reactions. A "photopolymerization initiator" refers to a compound that generates active species (specifically, radicals, cations, anions, etc.) when irradiated with active energy rays. A "photocationic polymerization initiator" refers to a compound that generates cations (acids) as active species when irradiated with active energy rays. A "photoradical polymerization initiator" refers to a compound that generates radicals as active species when irradiated with active energy rays. Examples of active energy rays include visible light, ultraviolet rays, infrared rays, electron beams, X-rays, alpha rays, beta rays, and gamma rays.

[0029] An "alkali-soluble group" refers to a functional group that enhances solubility in alkaline solutions by interacting with or reacting with alkali. "A photosensitive composition is alkali-soluble" means that the photosensitive composition contains a compound having an alkali-soluble group.

[0030] A "polysiloxane compound" is a compound having a polysiloxane structure composed of siloxane units (Si-O-Si). Examples of polysiloxane structures include linear polysiloxane structures (specifically, linear polysiloxane structures, branched polysiloxane structures, etc.) and cyclic polysiloxane structures.

[0031] A "cationic polymerizable group" refers to a functional group that undergoes a chain polymerization reaction in the presence of a cation. An "alicyclic epoxy group" refers to a functional group formed when one oxygen atom is bonded to two adjacent carbon atoms in an alicyclic structure, such as the 3,4-epoxycyclohexyl group. A "radical polymerizable group" refers to a functional group that has an unsaturated bond that allows for radical polymerization.

[0032] An "epoxy adhesive" refers to an adhesive that contains a compound with epoxy groups (for example, a compound containing at least two epoxy groups in one molecule) as its main component. A "semi-cured state" refers to a state in which the degree of curing can be further increased by a subsequent process (for example, a heating process).

[0033] The "thickness" of each layer constituting the optoelectronic device is the arithmetic mean of 10 measurements obtained by randomly selecting 10 measurement points from an electron microscope image of a cross-section obtained by cutting the optoelectronic device in the thickness direction, and measuring the thickness of the 10 selected measurement points.

[0034] The "main component" of a material, unless otherwise specified, refers to the component present in the greatest quantity by weight. "Solid content" refers to the non-volatile components in a composition, and "total solid content" refers to the total amount of components of the composition excluding the solvent.

[0035] In the following, the compound name may be followed by "system" to refer to the compound and its derivatives collectively. When "system" is followed by a compound name to represent a polymer name, it indicates that the repeating units of the polymer originate from the compound or its derivative. Additionally, acrylic and methacrylic may be collectively referred to as "(meth)acrylic." Similarly, acrylate and methacrylate may be collectively referred to as "(meth)acrylate." Furthermore, acryloyl and methacryloyl may be collectively referred to as "(meth)acryloyl."

[0036] Unless otherwise specified, the components and functional groups exemplified herein may be used individually or in combination of two or more.

[0037] The diagrams referenced in the following explanation are schematic representations of each component for ease of understanding, and the size, number, shape, etc., of each component shown may differ from the actual dimensions due to the limitations of drawing creation. Furthermore, for the sake of explanation, components identical to those described earlier may be denoted by the same reference numerals in later diagrams, and their explanations may be omitted.

[0038] <First Embodiment: Ribbed Substrate> A ribbed substrate according to the first embodiment of the present invention comprises a transparent substrate and a rib material provided on one main surface of the transparent substrate. The rib material is formed in a frame shape. The arithmetic mean roughness Ra of the inner surface of the rib material is 50 nm or more and 3000 nm or less.

[0039] The ribbed substrate according to the first embodiment can suppress the generation of optical noise. The reason for this is presumed to be as follows.

[0040] Generally, when strong light is incident on an optoelectronic device, stray light is generated in the space inside the rib material (internal space). This stray light is then reflected from the inner surface of the rib material and incident on the photodetector, generating optical noise. In contrast, the ribbed substrate according to the first embodiment has an arithmetic mean roughness Ra of 50 nm to 3000 nm on the inner surface of the rib material. Therefore, in an optoelectronic device manufactured using the ribbed substrate according to the first embodiment, the generated stray light is diffusely reflected when it is reflected from the inner surface of the rib material. Even if the diffusely reflected stray light is incident on the photodetector, it does not have enough intensity to generate optical noise. Therefore, the ribbed substrate according to the first embodiment can suppress the generation of optical noise.

[0041] In the first embodiment, in order to further suppress the generation of optical noise, the arithmetic mean roughness Ra of the inner surface of the rib material is preferably 100 nm or more, more preferably 150 nm or more, even more preferably 200 nm or more, and may be 250 nm or more, 300 nm or more, or 350 nm or more.

[0042] In the first embodiment, in order to further suppress the generation of optical noise, the arithmetic mean roughness Ra of the inner surface of the rib material is preferably 2000 nm or less, more preferably 1500 nm or less, even more preferably 1000 nm or less, even more preferably 900 nm or less, and particularly preferably 850 nm or less.

[0043] In the first embodiment, in order to further suppress the generation of optical noise, the arithmetic mean roughness Ra of the inner surface of the rib material is preferably 200 nm or more and 900 nm or less, more preferably 250 nm or more and 900 nm or less, even more preferably 300 nm or more and 900 nm or less, even more preferably 350 nm or more and 900 nm or less, and particularly preferably 350 nm or more and 850 nm or less.

[0044] In the first embodiment, in order to further suppress the generation of optical noise, the skewness Ssk of the inner circumferential surface of the rib material is preferably a negative value, more preferably -0.80 or more and -0.10 or less, even more preferably -0.70 or more and -0.10 or less, and even more preferably -0.70 or more and -0.20 or less. The skewness Ssk indicates the symmetry of the height distribution with respect to the average plane of the uneven surface. When the skewness Ssk is 0, the height distribution is a normal distribution (symmetrical vertically). On the other hand, when the skewness Ssk is a negative value, the surface has many fine valleys, and when the skewness Ssk is a positive value, the surface has many fine peaks.

[0045] [Configuration of ribbed substrate] The following describes an example of the configuration of a ribbed substrate according to the first embodiment, with reference to the drawings as appropriate. Figure 1 is a plan view showing an example of a ribbed substrate according to the first embodiment. Figure 2 is a cross-sectional view taken along line II-II in Figure 1.

[0046] As shown in Figures 1 and 2, the ribbed substrate 10 comprises a transparent substrate 11 and a rib material 12 provided on one main surface of the transparent substrate 11. The rib material 12 is formed in a frame shape. The arithmetic mean roughness Ra of the inner circumferential surface 12a of the rib material 12 is 50 nm to 3000 nm.

[0047] The rib material 12 may be in a semi-cured state or in a cured state (a state in which the semi-cured material has been further cured). The semi-cured rib material 12 has adhesive properties.

[0048] The inner circumferential surface 12a of the rib material 12 does not necessarily have to be formed with an uneven surface (an uneven surface with an arithmetic mean roughness Ra of 50 nm to 3000 nm). In the following, an uneven surface with an arithmetic mean roughness Ra of 50 nm to 3000 nm may simply be referred to as "uneven surface."

[0049] To further suppress the generation of optical noise, the proportion of the area formed in an uneven shape on the inner circumferential surface 12a of the rib material 12 is preferably 50% or more, more preferably 80% or more, even more preferably 90% or more, and particularly preferably 100% (the entire surface is formed in an uneven shape), when the total area of ​​the inner circumferential surface 12a of the rib material 12 is taken as 100%.

[0050] To obtain an optical semiconductor device with excellent reliability as evaluated by thermal shock tests, the thickness T (height) of the rib material 12 is preferably 500 μm or less, more preferably 400 μm or less, even more preferably 300 μm or less, even more preferably 150 μm or less, and may also be 140 μm or less, 130 μm or less, 120 μm or less, 110 μm or less, or 100 μm or less. Furthermore, to further suppress the generation of optical noise, the thickness T (height) of the rib material 12 is preferably 10 μm or more, more preferably 12 μm or more, even more preferably 15 μm or more, even more preferably 20 μm or more, and particularly preferably 25 μm or more.

[0051] To obtain a photographic image with reduced distortion, it is preferable that there is little variation in the thickness T of the rib material 12. Specifically, the variation in the thickness T of the rib material 12 is preferably within 20% of the average value of the thickness T of the rib material 12 (for example, the average value of 10 randomly selected measurement points), and more preferably within 10%.

[0052] In order to further miniaturize the optoelectronic device while improving the adhesion between the transparent substrate 11 and the rib material 12, the width of the rib material 12 is preferably 10 μm or more and 300 μm or less, and more preferably 20 μm or more and 250 μm or less.

[0053] The outer surface 12b of the rib material 12 may or may not have an uneven surface (an uneven surface with an arithmetic mean roughness Ra of 50 nm to 3000 nm). If an uneven surface is formed on the outer surface 12b of the rib material 12, the contact area between the outer surface 12b and the sealing resin 20 (see Figure 3), which will be described later, increases, thereby improving the adhesion between the outer surface 12b and the sealing resin 20.

[0054] To further improve the adhesion between the outer peripheral surface 12b and the sealing resin 20, the arithmetic mean roughness Ra of the outer peripheral surface 12b is preferably 100 nm or more and 2000 nm or less, more preferably 150 nm or more and 1500 nm or less, even more preferably 200 nm or more and 1000 nm or less, even more preferably 200 nm or more and 900 nm or less, and may also be 250 nm or more and 900 nm or less, 300 nm or more and 900 nm or less, 350 nm or more and 900 nm or less, or 350 nm or more and 850 nm or less.

[0055] The end face 12c of the rib material 12 opposite to the transparent substrate 11 may or may not have an uneven surface (an uneven surface with an arithmetic mean roughness Ra of 50 nm to 3000 nm). Hereinafter, the end face of the rib material opposite to the transparent substrate may simply be referred to as the "end face of the rib material". When the rib material 12 and the semiconductor substrate 14 (see Figure 3) are bonded via an adhesive layer 301 (see Figure 8), which will be described later, if an uneven surface is formed on the end face 12c of the rib material 12, the contact area between the end face 12c and the adhesive layer 301 increases, thereby improving the adhesion between the end face 12c and the adhesive layer 301.

[0056] To further improve the adhesion between the end face 12c and the adhesive layer 301, the arithmetic mean roughness Ra of the end face 12c of the rib material 12 is preferably 100 nm to 2000 nm, more preferably 150 nm to 1500 nm, even more preferably 200 nm to 1000 nm, even more preferably 200 nm to 900 nm, and may also be 250 nm to 900 nm, 300 nm to 900 nm, 350 nm to 900 nm, or 350 nm to 850 nm.

[0057] The shape of the rib material 12 is not particularly limited, as long as it is frame-shaped. In Figures 1 and 2, a rib material 12 having a rectangular tubular structure is shown as an example of a frame shape, but it may also be a rib material having a cylindrical structure, or a rib material having a polygonal tubular structure other than a rectangular tubular shape.

[0058] When the rib material 12 has a rectangular tubular structure, it is preferable that the four corners of the rib material 12 are curved. When the four corners of the rib material 12 are curved, stress concentration at the four corners is mitigated during solder reflow and thermal shock testing, which can reduce delamination and cracking of the rib material 12. To further reduce delamination and cracking of the rib material 12 during solder reflow and thermal shock testing, it is preferable that the radius of curvature on both the outer and inner sides of the four corners of the rib material 12 be between 0.01 mm and 1.0 mm.

[0059] The uneven surface shape of the inner circumferential surface 12a of the rib material 12 may be regular or irregular, as long as the arithmetic mean roughness Ra is between 50 nm and 3000 nm. To further reduce optical noise, it is preferable that the uneven surface shape of the inner circumferential surface 12a is irregular. When the uneven surface shape of the inner circumferential surface 12a is irregular, the reflected light from the inner circumferential surface 12a can be diffusely reflected more effectively.

[0060] In the ribbed substrate 10, when the direction perpendicular to the thickness direction of the transparent substrate 11 is defined as the X direction, and the direction parallel to the thickness direction of the transparent substrate 11 is defined as the Y direction, the inner circumferential surface 12a of the rib material 12 may have a bumpy shape formed only in the X direction, or only in the Y direction, or in both the X and Y directions. Here, "a bumpy shape formed only in the X direction (or Y direction)" means that the bumpy shape is observed only when scanned in the X direction (or Y direction), and is not observed when scanned in a direction perpendicular to that direction. To further reduce optical noise, it is preferable that the inner circumferential surface 12a of the rib material 12 has a bumpy shape formed in both the X and Y directions.

[0061] Hereinafter, the arithmetic mean roughness Ra of the surface irregularities observed when scanning in a direction perpendicular to the thickness direction of the transparent substrate (X direction) may be referred to as "arithmetic mean roughness Ra in the direction perpendicular to the thickness direction of the transparent substrate." Similarly, the arithmetic mean roughness Ra of the surface irregularities observed when scanning in a direction parallel to the thickness direction of the transparent substrate (Y direction) may be referred to as "arithmetic mean roughness Ra in the direction parallel to the thickness direction of the transparent substrate." Furthermore, unless otherwise specified in this specification, the numerical value of the arithmetic mean roughness Ra of the inner surface of the rib material is the larger of the arithmetic mean roughness Ra in the direction perpendicular to the thickness direction of the transparent substrate and the arithmetic mean roughness Ra in the direction parallel to the thickness direction of the transparent substrate.

[0062] The method for forming the uneven shape on the inner circumferential surface 12a, outer circumferential surface 12b, and end surface 12c of the rib material 12 is not particularly limited, and examples include a method of forming the rib material 12 from a material containing a filler, a method of forming the unevenness using a mold, a method of using a photomask with unevenness formed on it when patterning a photosensitive composition by photolithography, and a method of forming the rib material 12 by photolithography from a photosensitive composition having a linear structure and a non-linear structure.

[0063] Among these, the method of forming the rib material 12 by photolithography from a photosensitive composition having a linear structure and a non-linear structure is preferred because it can form fine irregularities, reduce the number of steps, and easily form a highly accurate pattern shape. When the rib material 12 is formed by photolithography from a photosensitive composition having a linear structure and a non-linear structure, an irregular shape can be formed on the inner circumferential surface 12a, the outer circumferential surface 12b, and the end surface 12c of the rib material 12. The reason for this is presumed to be that when a photosensitive composition having a linear structure and a non-linear structure is used, a phase separation structure is formed in the photosensitive composition before the photolithography development process, and as a result, irregularities originating from the phase separation structure are formed on the inner circumferential surface 12a, the outer circumferential surface 12b, and the end surface 12c of the rib material 12 after the development process.

[0064] The above-mentioned "structures other than linear structures" include branched structures, network structures, and cyclic structures. To easily adjust the arithmetic mean roughness Ra to a range of 50 nm to 3000 nm, a cyclic structure is preferred as the structure other than linear. The "photosensitive composition having linear structures and non-linear structures" may contain compounds having linear structures and compounds having non-linear structures, or it may contain compounds having both linear and non-linear structures. Examples of compounds having linear structures include polysiloxane compounds having both linear and non-linear structures, linear polysiloxane compounds, linear polyacrylates, linear polyethers, linear polyesters, linear polyimides, and linear polyolefins. From the viewpoint of heat resistance, polysiloxane compounds having both linear and non-linear structures, or linear polysiloxane compounds, are preferred.

[0065] Furthermore, when a rib material 12 is formed by photolithography from a photosensitive composition having a linear structure and a non-linear structure, the skewness Ssk of the inner circumferential surface 12a, outer circumferential surface 12b, and end face 12c of the rib material 12 tends to be negative. On the other hand, when a rib material 12 is formed from a material containing a filler, the skewness Ssk of the inner circumferential surface 12a, outer circumferential surface 12b, and end face 12c of the rib material 12 tends to be positive. Details of the above photosensitive composition will be described later.

[0066] When forming the rib material 12 from a material containing a filler, it is preferable that the filler content in the obtained rib material 12 be 30% by weight or less of the total amount of the rib material 12. When the filler content in the rib material 12 is 30% by weight or less, it is possible to suppress the retention of foreign matter caused by the filler between patterns when patterning by photolithography. In order to easily form an uneven shape on the surface of the rib material 12 while suppressing the retention of foreign matter between patterns, it is preferable that the filler content in the rib material 12 be 0.5% by weight or more and 30% by weight or less, more preferably 0.5% by weight or more and 20% by weight or less, and even more preferably 0.5% by weight or more and 10% by weight or less, based on the total amount of the rib material 12.

[0067] [Elements of a ribbed substrate] Next, the elements of the ribbed substrate according to the first embodiment will be described.

[0068] (Transparent substrate 11) As the transparent substrate 11, for example, a glass substrate, a transparent plastic substrate (more specifically, an acrylic resin substrate, a polycarbonate substrate, etc.) can be used, and a glass substrate is preferred from the viewpoint of reliability. The type of glass is not particularly limited, but examples include quartz glass, borosilicate glass, and alkali-free glass. The thickness of the transparent substrate 11 is, for example, 50 μm or more and 2000 μm or less.

[0069] If necessary, a coating film having functions such as an infrared reflective film (or infrared cut filter), an anti-reflective film (AR coating), a non-reflective film, a protective film, a strengthening film, a shielding film, a conductive film, an anti-static film, a low-pass filter, a high-pass filter, or a band-pass filter may be formed on the surface of the transparent substrate 11. In particular, an anti-reflective film or an infrared reflective film (or infrared cut filter) is preferred because it further reduces optical noise in the captured image.

[0070] In particular, when using an anti-reflective coating, it is preferable to use a multilayer anti-reflective coating containing one or more inorganic materials selected from the group consisting of TiO2, Nb2O5, Ta2O5, CaF2, SiO2, Al2O3, MgS2, ZrO2, NiO, and MgF2.

[0071] These coatings can be applied to one or both main surfaces of the transparent substrate 11. If applied to both main surfaces, the coatings may be of the same type or different types. It is also possible to laminate different types of coatings with the same function on one main surface. Furthermore, it is possible to laminate different types of coatings with different functions on one main surface. The number of layers is not particularly limited and can range from several layers to several tens of layers.

[0072] (Rib material 12) The material of the rib material 12 is not particularly limited as long as it is a material that can adjust the arithmetic mean roughness Ra of the inner circumferential surface 12a of the rib material 12 to 50 nm or more and 3000 nm or less. Examples include cured products of photosensitive compositions and cured products of thermosetting resins, and from the viewpoint of ease of patterning, cured products of photosensitive compositions are preferred. In other words, from the viewpoint of ease of patterning, it is preferable that the rib material 12 is made of a cured product of a photosensitive composition.

[0073] [Photosensitive composition] Next, a photosensitive composition that can be used as a material for the rib material 12 will be described. Examples of photosensitive compositions that can be used as a material for the rib material 12 include a photosensitive composition that contains a curable compound having a polymerizable group and a photopolymerization initiator, and is alkali soluble. Examples of polymerizable groups include cationic polymerizable groups such as epoxy groups, oxetanyl groups, vinyl ether groups, and alkoxysilyl groups, and radical polymerizable groups having an unsaturated bond that can be radically polymerized. From the viewpoint of storage stability of the photosensitive composition, it is preferable that the cationic polymerizable group be one or more selected from the group consisting of glycidyl groups, alicyclic epoxy groups, and oxetanyl groups, and more preferably one or more selected from the group consisting of glycidyl groups and alicyclic epoxy groups. Specific examples of radical polymerizable groups include (meth)acryloyl groups and vinyl groups. A curable compound having a polymerizable group may have both a cationic polymerizable group and a radical polymerizable group in one molecule, or it may have only one of them. Furthermore, a compound having a cationic polymerizable group and a compound having a radical polymerizable group may be used in combination.

[0074] Furthermore, the photosensitive composition contains a compound having an alkali-soluble group. The alkali-soluble group is preferably one or more selected from the group consisting of 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, and a carboxyl group. Note that the X1 group is a monovalent organic group derived from N-monosubstituted isocyanuric acid. The X2 group is a divalent organic group derived from N,N'-disubstituted isocyanuric acid.

[0075] [ka]

[0076] In order to form a rib material 12 with excellent heat resistance, it is preferable to use one or more alkali-soluble groups selected from the group consisting of X1 groups and X2 groups.

[0077] In order to form a rib material 12 with excellent heat resistance, it is preferable that the photosensitive composition contains a polysiloxane compound. Below, preferred examples of photosensitive compositions containing a polysiloxane compound will be described.

[0078] A preferred photosensitive composition (hereinafter sometimes referred to as "specific photosensitive composition") as a material for the rib material 12 contains a polysiloxane compound having a cationic polymerizable group and an alkali-soluble group in one molecule (hereinafter sometimes referred to as "component (A)") and a photopolymerization initiator (hereinafter sometimes referred to as "component (B)"). Component (A) is an example of a curable compound having a polymerizable group.

[0079] {Component (A)} Component (A) is not particularly limited as long as it is a polysiloxane compound having both cationic polymerizable groups and alkali-soluble groups in one molecule. By having both cationic polymerizable groups and alkali-soluble groups in one molecule of component (A), a specific photosensitive composition with excellent developability and curability can be obtained. It is preferable that component (A) has multiple cationic polymerizable groups in one molecule. When component (A) has multiple cationic polymerizable groups in one molecule, a rib material 12 with a high crosslink density can be obtained, and as a result, the heat resistance of the rib material 12 tends to be further improved. The multiple cationic polymerizable groups may be of the same type or two or more different functional groups. It is also preferable that component (A) has multiple alkali-soluble groups in one molecule. When component (A) has multiple alkali-soluble groups in one molecule, the removal of unexposed areas during development is improved, and thus the developability tends to be further improved. The multiple alkali-soluble groups may be of the same type or two or more different functional groups.

[0080] Component (A) may have a linear polysiloxane structure or a cyclic polysiloxane structure. To form a rib material 12 with superior heat resistance, it is preferable that component (A) has a cyclic polysiloxane structure. Furthermore, when component (A) has a cyclic polysiloxane structure, the film-forming and developability of the specific photosensitive composition tend to be improved.

[0081] Component (A) may have a polysiloxane structure in its main chain or in its side chains. To form a rib material 12 with superior heat resistance, it is preferable that component (A) has a polysiloxane structure in its main chain. To form a rib material 12 with even superior heat resistance, it is preferable that component (A) has a cyclic polysiloxane structure in its main chain.

[0082] The cyclic polysiloxane structure may be monocyclic or polycyclic. The polycyclic structure may also be polyhedral. Among the siloxane units that make up the ring, the T unit (XSiO 3 / 2 ) or Q unit (SiO 4 / 2The higher the content of (X3SiO), the harder and more heat-resistant the resulting rib material 12 tends to be. 1 / 2 ) or D unit (X2SiO 2 / 2 The higher the content of ), the more flexible the resulting rib material 12 tends to be, and the more residual stress can be reduced.

[0083] When component (A) is a polymer having a polysiloxane structure in its main chain, the weight-average molecular weight of the polymer is preferably 10,000 to 50,000, more preferably 10,000 to 40,000, even more preferably 10,000 to 35,000, even more preferably 10,000 to 30,000, and may also be 10,000 to 25,000 or 15,000 to 25,000. When the weight-average molecular weight is 10,000 or more, the heat resistance of the resulting rib material 12 tends to be improved. On the other hand, when the weight-average molecular weight is 50,000 or less, the developability tends to be improved.

[0084] Examples of cationic polymerizable groups in component (A) include epoxy groups, vinyl ether groups, oxetanyl groups, and alkoxysilyl groups. From the viewpoint of storage stability of the specific photosensitive composition, one or more cationic polymerizable groups selected from the group consisting of glycidyl groups, alicyclic epoxy groups, and oxetanyl groups are preferred, and one or more groups selected from the group consisting of glycidyl groups and alicyclic epoxy groups are more preferred. Among these, alicyclic epoxy groups are particularly preferred because they have excellent photocationic polymerizability.

[0085] Examples of alkali-soluble groups in component (A) include X1 groups, X2 groups, phenolic hydroxyl groups, and carboxyl groups. In order to form a rib material 12 with excellent heat resistance, it is preferable that the alkali-soluble groups in component (A) be one or more selected from the group consisting of X1 groups and X2 groups.

[0086] While there are no particular limitations on the method for introducing cationic polymerizable groups into a polysiloxane compound, a method using a hydrosilylation reaction is preferred because it allows for the introduction of cationic polymerizable groups into the polysiloxane compound via chemically stable silicon-carbon bonds (Si-C bonds). In other words, component (A) is preferably a polysiloxane compound that has been organically modified by a hydrosilylation reaction and into which cationic polymerizable groups have been introduced via silicon-carbon bonds. It is also preferable that alkali-soluble groups are introduced into the polysiloxane compound via a hydrosilylation reaction and silicon-carbon bonds.

[0087] Component (A) can be obtained, for example, by a hydrosilylation reaction using the following compounds (α), (β), and (γ) as starting materials. • Compound (α): A polysiloxane compound having at least two SiH groups (hydrosilyl groups) in one molecule. • Compound (β): A compound having a carbon-carbon double bond that is reactive with a SiH group and a cationic polymerizable group in one molecule. • Compound (γ): A compound having a carbon-carbon double bond that is reactive with a SiH group and an alkali-soluble group in one molecule.

[0088] (Compound (α)) Compound (α) is a polysiloxane compound having at least two SiH groups in one molecule. For example, a compound described in International Publication No. 96 / 15194, which has at least two SiH groups in one molecule, can be used. Specific examples of compound (α) include hydrosilyl group-containing polysiloxanes with a linear structure, polysiloxanes with hydrosilyl groups at the molecular ends, and cyclic polysiloxanes with hydrosilyl groups (hereinafter sometimes simply referred to as "cyclic polysiloxanes"). Cyclic polysiloxanes may have a polycyclic structure, and the polycyclic structure may be a polyhedral structure. To form a rib material 12 with high heat resistance and mechanical strength, it is preferable to use a cyclic polysiloxane having at least two SiH groups in one molecule 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 group present on the Si atom is either a hydrogen atom or a methyl group.

[0089] Examples of hydrosilyl group-containing polysiloxanes having a linear structure include copolymers of dimethylsiloxane units, methylhydrogensiloxane units, and terminal trimethylsiloxy units; copolymers of diphenylsiloxane units, methylhydrogensiloxane units, and terminal trimethylsiloxy units; copolymers of methylphenylsiloxane units, methylhydrogensiloxane units, and terminal trimethylsiloxy units; and polysiloxanes whose ends are sealed by dimethylhydrogensilyl groups.

[0090] Polysiloxanes having hydrosilyl groups at the molecular ends include polysiloxanes whose ends are sealed by dimethylhydrogensilyl groups, and dimethylhydrogensiloxane units (H(CH3)2SiO 1 / 2 (units), and SiO2 units, SiO 3 / 2 Examples include polysiloxanes, which consist of one or more siloxane units selected from the group consisting of units and SiO units.

[0091] The cyclic polysiloxane is represented by, for example, the following general formula (I).

[0092] [Chemical formula]

[0093] In the general formula (I), R 1 , R 2 and R 3 each independently represents a monovalent organic group having 1 to 20 carbon atoms, m represents an integer of 2 or more and 10 or less, and n represents an integer of 0 or more and 10 or less. In order to easily carry out the hydrosilylation reaction, it is preferable that m is 3 or more. In order to easily carry out the hydrosilylation reaction, it is preferable that m + n is 3 or more and 12 or less. In order to more easily carry out the hydrosilylation reaction, it is preferable that n is 0.

[0094] R 1 , R 2 and R 3 is preferably an organic group composed of elements selected from the group consisting of C, H, and O. Examples of R 1 , R 2 and R 3 include an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an oxyalkyl group, an aryl group, etc. Among them, a chain alkyl group such as a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group; a cyclic alkyl group such as a cyclohexyl group, a norbornyl group; or a phenyl group is preferable. From the viewpoint of the availability of the cyclic polysiloxane, R 1 , R 2 and R 3 is preferably a chain alkyl group having 1 to 6 carbon atoms or a phenyl group. In order to easily carry out the hydrosilylation reaction, R 1 , R 2 and R 3 is preferably a chain alkyl group, more preferably a chain alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group.

[0095] Examples of cyclic polysiloxanes represented by general formula (I) include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-1,3,5-trimethylcyclotrisiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclopentasiloxane, and 1,3,5,7,9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane. In particular, from the viewpoint of availability and the reactivity of the SiH group, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (in general formula (I), m=4, n=0, R 1 Compounds in which the group is a methyl group are preferred.

[0096] Compound (α) can be obtained by known synthesis methods. For example, a cyclic polysiloxane represented by general formula (I) can be synthesized by the method described in International Publication No. 96 / 15194, etc. Cyclic polysiloxanes having a polyhedral skeleton can be synthesized by the method described in, for example, Japanese Patent Publication No. 2004-359933, Japanese Patent Publication No. 2004-143449, Japanese Patent Publication No. 2006-269402, etc. Alternatively, a commercially available polysiloxane compound may be used as compound (α).

[0097] In order to form a rib material 12 that has superior heat resistance while improving the developability of the specific photosensitive composition, the content of structural units derived from compound (α) in component (A) is preferably 10% by weight or more and 50% by weight or less, and more preferably 15% by weight or more and 45% by weight or less, based on 100% by weight of component (A).

[0098] (Compound (β)) Compound (β) is a compound having a carbon-carbon double bond that reacts with a SiH group (hydrosilyl group) and a cationic polymerizable group in one molecule, and is a compound for introducing a cationic polymerizable group into a polysiloxane compound. The cationic polymerizable group in compound (β) is the same as the cationic polymerizable group in component (A) described above, and the preferred embodiment is also the same. That is, compound (β) preferably has one or more cationic polymerizable groups selected from the group consisting of a glycidyl group, an alicyclic epoxy group, and an oxetanyl group, more preferably one or more selected from the group consisting of a glycidyl group and an alicyclic epoxy group, and even more preferably an alicyclic epoxy group.

[0099] Groups containing a carbon-carbon double bond that are reactive with the SiH group (hereinafter sometimes simply referred to as "alkenyl group") include, for example, vinyl group, allyl group, methallyl group, allyloxy group (-O-CH2-CH=CH2), 2-allylphenyl group, 3-allylphenyl group, 4-allylphenyl group, 2-(allyloxy)phenyl group, 3-(allyloxy)phenyl group, 4-(allyloxy)phenyl group, 2-(allyloxy)ethyl group, 2,2-bis(allyloxymethyl)butyl group, 3-allyloxy-2,2-bis(allyloxymethyl)propyl group, vinyl ether group, etc. From the viewpoint of reactivity with the SiH group, compound (β) preferably has one or more alkenyl groups selected from the group consisting of vinyl group, allyl group, and allyloxy group, and more preferably has one or more alkenyl groups selected from the group consisting of vinyl group and allyl group.

[0100] Specific examples of compound (β) include 1-vinyl-3,4-epoxycyclohexane, allyl glycidyl ether, allyl oxetanyl 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 a compound having an alicyclic epoxy group is more preferred. To further enhance the reactivity in cationic polymerization, compound (β) is preferably one or more compounds selected from the group consisting of diallyl monoglycidyl isocyanurate and 1-vinyl-3,4-epoxycyclohexane, and 1-vinyl-3,4-epoxycyclohexane is more preferred.

[0101] In order to form a rib material 12 that has superior heat resistance while improving the developability of the specific photosensitive composition, the content of structural units derived from compound (β) in component (A) is preferably 10% to 50% by weight, and more preferably 12% to 45% by weight, based on 100% by weight of component (A).

[0102] (Compound (γ)) Compound (γ) is a compound having a carbon-carbon double bond that reacts with a SiH group and an alkali-soluble group in one molecule, and is a compound for introducing an alkali-soluble group to a polysiloxane compound. The alkali-soluble group in compound (γ) is the same as the alkali-soluble group in component (A) described above, and the preferred embodiment is also the same. That is, it is preferable that compound (γ) has one or more alkali-soluble groups selected from the group consisting of X1 and X2 groups.

[0103] Compound (γ) has a group (alkenyl group) containing a carbon-carbon double bond that is reactive with a SiH group. Examples of the alkenyl group of compound (γ) include the same alkenyl group as exemplified for compound (β) above, and the preferred embodiments are also the same. That is, compound (γ) preferably has one or more alkenyl groups selected from the group consisting of vinyl groups, allyl groups, and allyloxy groups, and more preferably has one or more alkenyl groups selected from the group consisting of vinyl groups and allyl groups.

[0104] Compound (γ) may have two or more alkenyl groups in one molecule. When compound (γ) contains multiple alkenyl groups in one molecule, multiple compounds (α) can be crosslinked by the hydrosilylation reaction, which tends to increase the crosslinking density of the resulting cured product and improve its heat resistance.

[0105] Specific examples of compound (γ) include diallyl isocyanurate, monoallyl isocyanurate, 2,2'-diallylbisphenol A, vinylphenol, allylphenol, butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid, and undecylenic acid.

[0106] To obtain a specific photosensitive composition with superior developability, compound (γ) is preferably one or more selected from the group consisting of diallyl isocyanurate, monoallyl isocyanurate, and 2,2'-diallylbisphenol A, and more preferably one or more selected from the group consisting of diallyl isocyanurate and monoallyl isocyanurate. When monoallyl isocyanurate is used as compound (γ), component (A) having an X1 group as an alkali-soluble group is obtained. When diallyl isocyanurate is used as compound (γ), component (A) having an X2 group as an alkali-soluble group is obtained.

[0107] To obtain a specific photosensitive composition with superior developability, the content of structural units derived from compound (γ) in component (A) is preferably 5% to 50% by weight, and more preferably 10% to 30% by weight, based on 100% by weight of component (A).

[0108] (Other starting materials) In the hydrosilylation reaction, other starting materials may be used in addition to the above-mentioned compounds (α), (β), and (γ). For example, other starting materials may include alkenyl group-containing compounds different from those described above as compounds (β) and (γ) (hereinafter sometimes referred to as "other alkenyl group-containing compounds").

[0109] In order to introduce a radical polymerizable group into component (A), it is preferable to use a compound having both an alkenyl group and a (meth)acryloyl group in one molecule (hereinafter sometimes referred to as "compound (δ)") as another alkenyl group-containing compound. By using compound (δ), a (meth)acryloyl group is introduced into component (A), making it possible to photo-radical polymerize component (A).

[0110] Specific examples of compound (δ) include vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl methacrylate, 2-butenyl acrylate, and 2-butenyl methacrylate.

[0111] To enhance the reactivity of photoradical polymerization, the content of structural units derived from compound (δ) in component (A) is preferably 5% to 30% by weight, and more preferably 8% to 20% by weight, based on 100% by weight of component (A).

[0112] To obtain a rib material 12 with superior heat resistance, it is preferable to use a compound having two or more alkenyl groups in one molecule (hereinafter sometimes referred to as "compound (ε)") as the other alkenyl group-containing compound. When compound (ε) is used, the number of crosslinking sites increases during the hydrosilylation reaction, which tends to further improve the heat resistance of the resulting rib material 12.

[0113] Specific examples of compound (ε) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, 1,1,2,2-tetraallyloxyethane, 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(vinyloxy)adamantane, 1,3,5-tris(allyloxy)adamantane, 1,3,5-tris(vinyloxy)adamantane, dicyclopentadiene, vinylcyclohexene, 1,5-hexadiene, 1,9-decadien, diallyl ether, and their oligomers.

[0114] To further improve the heat resistance of the resulting rib material 12, one or more compounds selected from the group consisting of triallyl isocyanurate and diallyl monomethyl isocyanurate are preferred as compound (ε), with diallyl monomethyl isocyanurate being more preferred.

[0115] In order to further improve the heat resistance of the resulting rib material 12 while enhancing its alkali developability, the content of structural units derived from compound (ε) in component (A) is preferably 1% by weight or more and 30% by weight or less, and more preferably 3% by weight or more and 20% by weight or less, based on 100% by weight of component (A).

[0116] In order to adjust the skewness Ssk of the inner circumferential surface 12a of the rib material 12 to a negative value by forming irregularities derived from the phase separation structure on the inner circumferential surface 12a, it is preferable to use a linear polysiloxane compound having alkenyl groups at both ends (hereinafter sometimes referred to as "compound (ζ)") as another alkenyl group-containing compound, and to use a cyclic polysiloxane as compound (α). When the skewness Ssk of the inner circumferential surface 12a of the rib material 12 is a negative value, the generation of optical noise tends to be further suppressed. When compound (ζ) is used, a polysiloxane compound having a linear structure is obtained as component (A). Furthermore, when a cyclic polysiloxane is used as compound (α) and compound (ζ) is used, a specific photosensitive composition having both a linear structure and a cyclic structure is obtained. In other words, when a cyclic polysiloxane is used as compound (α) and compound (ζ) is used, a linear structure (a linear structure derived from compound (ζ)) and a cyclic structure (a cyclic structure derived from the cyclic polysiloxane) are introduced into component (A). A specific example of compound (ζ) is the compound represented by the following general formula (Y) (hereinafter sometimes referred to as "compound (Y)").

[0117] [ka]

[0118] In general formula (Y), the ratio of r, s, and t (r:s:t) represents the molar ratio of each structural unit. For example, r+s+t=100. Furthermore, in general formula (Y), the arrangement of structural units is not particularly limited.

[0119] To further suppress the generation of optical noise, the weight-average molecular weight of compound (ζ) is preferably between 1,000 and 30,000, and more preferably between 2,000 and 29,000.

[0120] To further suppress the generation of optical noise, the content of structural units derived from compound (ζ) in component (A) is preferably 1.0% by weight or more and 10.0% by weight or less, and more preferably 1.2% by weight or more and 5.0% by weight or less, based on 100% by weight of component (A).

[0121] Compound (ζ) may be incorporated into the specific photosensitive composition. In other words, compound (ζ) may be used not as a starting material for component (A), but as a component other than components (A) and (B) (other components described later). Even when compound (ζ) is used as another component of the specific photosensitive composition and compound (α) is a cyclic polysiloxane, the skewness Ssk of the inner circumferential surface 12a can be adjusted to a negative value. Furthermore, since compound (ζ) is a polysiloxane compound having a linear structure, even when compound (α) is a cyclic polysiloxane and compound (ζ) is used as another component of the specific photosensitive composition, a specific photosensitive composition having both a linear and a cyclic structure can be obtained. When a specific photosensitive composition containing compound (ζ) as another component is used, the irregularities on the inner circumferential surface 12a of the rib material 12 tend to be larger than when a specific photosensitive composition containing component (A) obtained with compound (ζ) as one of the starting materials is used.

[0122] In order to increase the unevenness of the inner circumferential surface 12a of the rib material 12, it is preferable that the specific photosensitive composition contains both component (A) having a linear structure derived from compound (ζ) and compound (ζ) as another component.

[0123] When the specific photosensitive composition contains compound (ζ) as another component, in order to further suppress the generation of optical noise, it is preferable that the content of compound (ζ) in the specific photosensitive composition be 1% by weight or more and 5% by weight or less, relative to the total amount of solids in the specific photosensitive composition. Furthermore, when the specific photosensitive composition contains compound (ζ) as another component, compound (ζ) functions, for example, as a crosslinking agent that crosslinks components (A) together during the curing of the rib material 12.

[0124] The arithmetic mean roughness Ra of the inner circumferential surface 12a, outer circumferential surface 12b, and end surface 12c of the rib material 12, and the skewness Ssk of the inner circumferential surface 12a of the rib material 12 can be adjusted, for example, by changing at least one of the following: the content of structural units derived from compound (ζ) in component (A), the weight-average molecular weight of compound (ζ), and the content of compound (ζ) as another component in the specific photosensitive composition.

[0125] (Hydrosilylation reaction) The sequence and method of the hydrosilylation reaction to obtain component (A) are not particularly limited. For example, component (A) can be obtained by a hydrosilylation reaction using the above-mentioned compound (α), compound (β), compound (γ), and other optional starting materials in accordance with the method described in International Publication No. 2009 / 075233. Component (A) obtained using the above-mentioned compound (α), compound (β), compound (γ), and other optional starting materials is, for example, a polymer having multiple cationic polymerizable groups and multiple alkali-soluble groups in one molecule, and having a polysiloxane structure in the main chain.

[0126] The proportions of each compound in the hydrosilylation reaction are not particularly limited, but it is preferable that the total amount of alkenyl groups A and the total amount of SiH groups B of the starting material satisfy 1 ≤ B / A ≤ 30, and more preferably 1 ≤ B / A ≤ 10.

[0127] Hydrosilylation catalysts such as chloroplatinic acid, platinum-olefin complexes, and platinum-vinylsiloxane complexes may be used in the hydrosilylation reaction. A hydrosilylation catalyst and a co-catalyst may also be used in combination. The amount (substance) of hydrosilylation catalyst added is not particularly limited, but preferably 10 times the total amount of alkenyl groups contained in the starting material. -8 more than 10 times -1 More than double, more convenient 10 -6 more than 10 times -2 It is less than double.

[0128] The reaction temperature for hydrosilylation can be set appropriately, preferably between 30°C and 200°C, and more preferably between 50°C and 150°C. The oxygen concentration in the gas phase during the hydrosilylation reaction is preferably 3% by volume or less. From the viewpoint of promoting the hydrosilylation reaction, the gas phase may contain 0.1% to 3% by volume of oxygen.

[0129] A solvent may be used in the hydrosilylation reaction. The solvent can be a single solvent or a mixed solvent of two or more solvents. 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 halogenated solvents such as chloroform, methylene chloride, and 1,2-dichloroethane. Toluene, xylene, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, or chloroform are preferred because they are easily removed after the reaction. A gelation inhibitor may be used in the hydrosilylation reaction as needed.

[0130] To further suppress the generation of optical noise, it is preferable that the content of component (A) in the specific photosensitive composition be 20% by weight or more and 97% by weight or less, relative to the total solid content of the specific photosensitive composition.

[0131] {Component (B)} Component (B) is preferably one or more selected from the group consisting of photocationic polymerization initiators and photoradical polymerization initiators. Since the specific photosensitive composition contains component (A) having a cationic polymerizable group, if the specific photosensitive composition contains a photocationic polymerization initiator as component (B), component (A) can be crosslinked by photocationic polymerization. Furthermore, if a component (A) with a (meth)acryloyl group introduced is used, or if component (C) described later is used, if the specific photosensitive composition contains a photoradical polymerization initiator as component (B), component (A) or component (C) can be crosslinked by photoradical polymerization. The specific photosensitive composition may contain both a photocationic polymerization initiator and a photoradical polymerization initiator as component (B).

[0132] (Photocationic polymerization initiator) As the photocationic polymerization initiator, for example, known photocationic polymerization initiators can be used. For example, various compounds that are preferred as photocationic polymerization initiators in Japanese Patent Publication No. 2000-1648, Japanese Patent Publication No. 2001-515533, International Publication No. 2002 / 83764, etc., can be cited, but are not particularly limited. As the photocationic polymerization initiator, sulfonate ester compounds, carboxylic acid ester compounds, or onium salt compounds are preferred, onium salt compounds are more preferred, and sulfonium salt compounds are even more preferred.

[0133] Various sulfonic acid derivatives can be used as sulfonate ester compounds, including, for example, disulfone compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, sulfonylbenzoylmethane compounds, imidosulfonate compounds, benzoin sulfonate compounds, pyrogalloltrisulfonate compounds, and benzylsulfonate compounds. These can be used individually or in combination of two or more. In the present invention, carboxylic acid ester compounds can also be used as photocationic polymerization initiators.

[0134] Examples of onium salt compounds include sulfonium salt compounds and iodonium salt compounds.

[0135] If we arrange the photocationic polymerization initiators in order from the strongest acid produced, we get SbF6. - A compound containing B(C6F5)4 as an anion. - A compound containing PF6 as an anion. - Compounds containing as anions, such as CF3SO3 - A compound containing HSO4 as an anion. - This results in a compound containing as an anion. When a photocationic polymerization initiator with a strong acid strength is used, the residual film rate tends to be high. The pKa of the acid generated from the photocationic polymerization initiator is preferably less than 3, more preferably less than 1.

[0136] Examples of cations found in sulfonium salt compounds include the cation represented by the following chemical formula (II).

[0137] [ka]

[0138] Examples of commercially available sulfonium salt compounds (sulfonium salt photocationic polymerization initiators) include a photocationic polymerization initiator containing a fluoroalkyl fluorophosphate (anion) and a cation represented by chemical formula (II) (SunApro's "CPI-210S").

[0139] There are no particular restrictions on the content of the photocationic polymerization initiator in the specific photosensitive composition. From the viewpoint of curing speed and balance of physical properties of the cured product, the content of the photocationic polymerization initiator is preferably 0.1% by weight or more and 10% by weight or less, and more preferably 1% by weight or more and 5% by weight or less, based on the total solid content of the specific photosensitive composition.

[0140] If necessary, a thermal cationic polymerization initiator (a compound that generates cations when heated) can be added to the specific photosensitive composition. Examples of thermal cationic polymerization initiators include sulfonium salt compounds, iodonium salt compounds, benzothiazonium salt compounds, ammonium salt compounds, and phosphonium salt compounds, among which sulfonium salt compounds and benzothiazonium salt compounds are preferred.

[0141] (Photoradical polymerization initiator) Examples of photoradical polymerization initiators include acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, α-diketone compounds, biimidazole compounds, polynuclear quinone compounds, triazine compounds, oxime ester compounds, titanocene compounds, xanthone compounds, thioxanthone compounds, ketal compounds, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, and fluoroamine compounds. From the viewpoint of ease of patterning, one or more selected from the group consisting of acetophenone compounds, benzophenone compounds, and oxime ester compounds are preferred as photoradical polymerization initiators, with benzophenone compounds being more preferred.

[0142] Examples of benzophenone compounds include benzyldimethyl ketone, benzophenone, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone.

[0143] There are no particular restrictions on the content of the photoradical polymerization initiator in the specific photosensitive composition. From the viewpoint of the curing speed and the balance of physical properties of the cured product, the content of the photoradical polymerization initiator is preferably 0.1% by weight or more and 5% by weight or less, and more preferably 0.5% by weight or more and 1% by weight or less, based on the total solid content of the specific photosensitive composition.

[0144] If necessary, a thermal radical polymerization initiator (a compound that generates radicals when heated) may be incorporated into the specific photosensitive composition. Specific examples of thermal radical polymerization initiators include acetyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, t-butyl peroxyacetate, t-butyl peroxypivalate, azobisisobutyronitrile, azobisisovaleronitrile, ammonium persulfate, sodium persulfate, potassium persulfate, and the like. These thermal radical polymerization initiators may be used alone or in combination of two or more.

[0145] {solvent} The specific photosensitive composition may contain a solvent. For example, the specific photosensitive composition can be obtained by dissolving or dispersing the above-mentioned component (A), component (B), and other components used as needed (described later) in a solvent.

[0146] 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-acetate, 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, methylene chloride, and 1,2-dichloroethane. From the viewpoint of the coatability (film-forming stability) of the specific photosensitive composition, glycol solvents are preferred as solvents, and propylene glycol 1-monomethyl ether 2-acetate is more preferred.

[0147] From the viewpoint of the coatability (film-forming stability) of the specific photosensitive composition, the amount of solvent is preferably 0.5 parts by weight or more and 100 parts by weight or less, and more preferably 1 part by weight or more and 50 parts by weight or less, per 100 parts by weight of component (A).

[0148] {other components} The specific photosensitive composition may contain components other than the above-mentioned components (A) and (B) as solid content (components other than the solvent) to the extent that it does not impair the objectives and effects of the present invention. However, in order to further suppress the generation of optical noise and form a rib material 12 with excellent heat resistance, the total content of components (A) and (B) 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, based on the total amount of solid content of the specific photosensitive composition.

[0149] Other components include compounds (ζ), compounds having radical polymerizable groups, reactive diluents, sensitizers, polymer dispersants, thermoplastic resins, fillers, crosslinking agents, basic compounds, adhesion modifiers, coupling agents (silane coupling agents, etc.), antioxidants, radical scavengers, colorants, mold release agents, flame retardants, flame retardant aids, surfactants, defoamers, emulsifiers, leveling agents, anti-repellent agents, ion trapping agents (antimony-bismuth, etc.), thixotropic agents, tackifiers, storage stability modifiers, ozone degradation inhibitors, light stabilizers, thickeners, plasticizers, thermal stabilizers, conductivity modifiers, antistatic agents, radiation shielding agents, nucleating agents, phosphorus-based peroxide decomposing agents, lubricants, metal deactivators, thermal conductivity modifiers, and property modifiers.

[0150] (Compounds having radical polymerizable groups) The specific photosensitive composition may also contain a compound having a radical polymerizable group (hereinafter sometimes referred to as "component (C)") as another component. Since component (C) is another component (a component other than components (A) and (B)), it is a compound that has a radical polymerizable group and does not have siloxane units. The specific photosensitive composition containing component (C) tends to have excellent deep curing properties (the property of being able to be photocrosslinked to a deep extent) when patterning. Furthermore, when the rib material 12 described above is formed by photolithography using the specific photosensitive composition containing component (C), the taper angle described later can be easily adjusted to a range greater than 90°.

[0151] Component (C) may include compounds having radically polymerizable unsaturated bonds (such as ethylenically unsaturated bonds). Examples of ethylenically unsaturated bonds include (meth)acryloyl groups and vinyl groups.

[0152] Specific examples of component (C) include allyl (meth)acrylate, vinyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, (meth)acrylate-modified allyl glycidyl ether (Denacol® Acrylate DA111 manufactured by Nagase ChemteX), urethane (meth)acrylate compounds, epoxy (meth)acrylate compounds, trimethylolpropane tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate. Examples include ditrimethylolpropanetetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, butanediol di(meth)acrylate, nonanediol di(meth)acrylate, polypropylene glycol (meth)acrylate, bisphenol A di(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, caprolactone-modified tris-(2-acryloxyethyl) isocyanurate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., "A-9300-1CL"), etc.

[0153] In order to obtain an optical semiconductor device with superior reliability while further suppressing the generation of optical noise, the content of component (C) in the specific photosensitive composition is preferably 1% to 50% by weight, more preferably 5% to 40% by weight, and even more preferably 10% to 30% by weight, based on the total amount of solids in the specific photosensitive composition.

[0154] Furthermore, if the photosensitive composition used as the material for the rib material 12 contains a curable compound having a cationic polymerizable group (preferably one or more cationic polymerizable groups selected from the group consisting of glycidyl groups and alicyclic epoxy groups) (hereinafter sometimes referred to as "cationic polymerizable compound"), component (C), and a photoradical polymerization initiator, the semi-cured state of the rib material 12 can be stably maintained. The reason for this is presumed to be as follows.

[0155] When patterning by photolithography using a photosensitive composition containing a cationic polymerizable compound, component (C), and a photoradical polymerization initiator (hereinafter sometimes referred to as "cation-radical combined photosensitive composition"), only radicals are generated as active species by irradiation with active energy rays, and component (C) in the exposed area undergoes radical polymerization, thereby forming a semi-cured rib material 12 without generating cations. Therefore, with the cationic-radical combined photosensitive composition, even if the ribbed substrate 10 with the semi-cured rib material 12 is stored for a long time before being laminated with the semiconductor substrate 14, further hardening of the rib material 12 due to residual cations can be suppressed. Thus, when the rib material 12 is formed using the cationic-radical combined photosensitive composition, the semi-cured state of the rib material 12 can be stably maintained. When bonding the ribbed substrate 10 and the semiconductor substrate 14, the semiconductor substrate 14 and the transparent substrate 11 (the transparent substrate 11 provided by the ribbed substrate 10) are laminated via the rib material 12, which is maintained in a semi-cured state. By heating the laminated product, the cationic polymerizable compound in the rib material 12 is cationically polymerized, thereby bonding the semiconductor substrate 14 and the transparent substrate 11.

[0156] (filling material) The specific photosensitive composition may contain a filler. When the specific photosensitive composition contains a filler, the arithmetic mean roughness Ra of the inner circumferential surface 12a of the rib material 12 can be easily adjusted. The filler is not particularly limited, but for example, silica-based fillers (quartz, fumed silica, settling silica, anhydrous silicic acid, fused silica, crystalline silica, ultrafine amorphous silica, etc.), silicon nitride, silver powder, alumina, aluminum hydroxide, titanium oxide, glass fiber, carbon fiber, mica, carbon black, graphite, diatomaceous earth, white clay, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate, inorganic balloons, and other inorganic fillers can be used, as well as organic fillers such as epoxy-based fillers. Among these, silica-based fillers (silica particles) are preferred from the viewpoint of availability.

[0157] Furthermore, in order to improve the patternability of the specific photosensitive composition while also improving the adhesion between the transparent substrate 11 and the semiconductor substrate 14, it is preferable that the specific photosensitive composition does not contain a filler.

[0158] (Radical scavenger) The specific photosensitive composition may contain a radical scavenger. When the specific photosensitive composition contains a radical scavenger, the diffusion of active radicals generated by irradiation with active energy rays into the unexposed areas during patterning is suppressed. As a result, hardening of the unexposed areas is suppressed, and the generation of residue after development (for example, unexposed areas that remain without being removed by development) can be suppressed.

[0159] Examples of radical scavengers include 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-cyano-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-benzoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxyl, and bis-(2,2,6,6-tetramethylpiperidine-1-oxyl)-sebacate. To further suppress the generation of residue after development, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl is preferred as the radical scavenger.

[0160] There are no particular restrictions on the content of the radical scavenger in the specific photosensitive composition, but from the viewpoint of balance between curability and the physical properties of the cured product, it is preferable that the content is 0.01 parts by weight or more and 10 parts by weight or less, and more preferably 0.05 parts by weight or more and 1 part by weight or less, per 100 parts by weight of component (A).

[0161] In addition to the specified photosensitive composition described above, a photosensitive composition containing cationic polymerizable compounds other than component (A) can also be used as the photosensitive composition material for the rib material 12. Furthermore, a specified photosensitive composition containing component (A) and cationic polymerizable compounds other than component (A) can also be used. Cationic polymerizable compounds other than component (A) include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolacphenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 2,2'-bis(4-glycidyloxycyclohexyl)propane, vinylcyclohexene dioxide, 2-(3,4-epoxycyclohexyl)-5,5-spiro-(3,4-epoxycyclohexane)-1,3-dioxane, bis(3,4-epoxycyclohexyl)adipane Examples include bisglycidyl ester of 1,2-cyclopropanedicarboxylic acid, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, 3-ethyl-3-(phenoxymethyl)oxetane, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Daicel Corporation's "Celoxide® 2021P"), and ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Daicel Corporation's "Celoxide® 2081"), etc.

[0162] When component (A) and a cationic polymerizable compound (curable compound) other than component (A) are used in combination, in order to form a rib material 12 with excellent heat resistance while improving the storage stability of the specific photosensitive composition, the amount of the cationic polymerizable compound other than component (A) is preferably 1 part by weight or more and 10 parts by weight or less, and more preferably 3 parts by weight or more and 8 parts by weight or less, per 100 parts by weight of component (A).

[0163] [Preferred embodiment of a ribbed substrate] In order to obtain an optical semiconductor device that can further suppress the generation of optical noise, the ribbed substrate according to 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. Condition 1: The arithmetic mean roughness Ra of the inner surface of the rib material is between 200 nm and 900 nm, and the skewness Ssk of the inner surface of the rib material is a negative value. Condition 2: The above condition 1 is met, and the skewness Ssk of the inner surface of the rib material is between -0.80 and -0.10. Condition 3: The above condition 2 is met, and the rib material is made of a cured product of a photosensitive composition having a linear structure and an annular structure. Condition 4: The above condition 3 is met, and the photosensitive composition that is the material for the rib material contains a polysiloxane compound having a linear structure.

[0164] <Second Embodiment: Optical Semiconductor Device> Next, an optoelectronic semiconductor device according to a second embodiment of the present invention will be described with reference to the drawings as appropriate. The optoelectronic semiconductor device according to the second embodiment is an optoelectronic semiconductor device (for example, a solid-state imaging device, etc.) equipped with a ribbed substrate according to the first embodiment described above. In the following description, explanations of content that overlaps with the first embodiment may be omitted.

[0165] The optoelectronic device according to the second embodiment comprises a ribbed substrate according to the first embodiment and a semiconductor substrate on which a photodetector is provided. The transparent substrate of the ribbed substrate and the semiconductor substrate are laminated together via the rib material of the ribbed substrate. The rib material is provided so as to surround the photodetector.

[0166] The optoelectronic device according to the second embodiment includes the ribbed substrate according to the first embodiment described above, and therefore can suppress the generation of optical noise.

[0167] Hereinafter, as specific examples of the optoelectronic semiconductor device according to the second embodiment, an optoelectronic semiconductor device further comprising a wiring board (optoelectronic semiconductor device 50) and a chip-size package type optoelectronic semiconductor device (optoelectronic semiconductor device 100) will be described with reference to the drawings.

[0168] [Optical semiconductor device 50] Figure 3 is a cross-sectional view showing an optoelectronic device 50, which is a specific example of an optoelectronic device according to the second embodiment. The optoelectronic device 50 comprises a ribbed substrate 10 and a semiconductor substrate 14. As described above, the ribbed substrate 10 comprises a transparent substrate 11 and rib material 12. A light-receiving element 13 is provided on the first surface 14a of the semiconductor substrate 14. The optoelectronic device 50 further comprises a wiring board 17 (interposer) bonded to the second surface 14b of the semiconductor substrate 14 (the side of the semiconductor substrate 14 opposite to the transparent substrate 11 side) via a die bond material 18. Note that "first surface 14a of the semiconductor substrate 14" means one of the two main surfaces perpendicular to the thickness direction of the semiconductor substrate 14. Also, "second surface 14b of the semiconductor substrate 14" means the other main surface of the two main surfaces perpendicular to the thickness direction of the semiconductor substrate 14. The transparent substrate 11 is arranged to face the first surface 14a of the semiconductor substrate 14. The transparent substrate 11 and the semiconductor substrate 14 are laminated together via rib material 12. The rib material 12 is provided so as to surround the light-receiving element 13.

[0169] The semiconductor substrate 14 and the wiring board 17 are provided with electrode pads 15 for the semiconductor substrate and electrode pads 16 for the wiring board, respectively. The electrode pads 15 and 16 are electrically connected via metal wires 19. The rib material 12 is positioned between the electrode pads 15 and the light-receiving element 13, and the periphery of the rib material 12 (the area including the wires 19) is sealed with sealing resin 20. In addition, solder balls 21 (external connection terminals) are formed on the side of the wiring board 17 opposite to the die bond material 18 side.

[0170] The internal space Z, enclosed by the semiconductor substrate 14, the transparent substrate 11, and the rib material 12, may be a sealed space. In this case, the rib material 12 functions as a partition to prevent moisture and dust from entering the effective pixel area. If ventilation holes are formed in the rib material 12, foreign matter can be prevented from entering the internal space Z by forming the rib material 12 in a labyrinthine pattern.

[0171] The ribbed substrate 10 has an arithmetic mean roughness Ra of the inner circumferential surface 12a of the rib material 12 of 50 nm to 3000 nm. Therefore, in the optoelectronic device 50 manufactured using the ribbed substrate 10, stray light is diffusely reflected when it is reflected off the inner circumferential surface 12a of the rib material 12. Even when the diffusely reflected stray light is incident on the photodetector 13, it does not have enough intensity to generate optical noise, so the optoelectronic device 50 can suppress the generation of optical noise.

[0172] Examples of semiconductor substrates 14 include image sensor substrates. The thickness of the semiconductor substrate 14 is, for example, 50 μm to 800 μm.

[0173] The die bond material 18 is not particularly limited, but thermosetting resins such as epoxy resins and silicone resins that do not degrade easily during reflow at temperatures of around 260°C are preferred.

[0174] The wiring board 17 is a multilayer wiring board 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 side of the wiring board 17 on which the semiconductor substrate 14 is installed, a wiring board electrode pad 16 is provided for connecting to the semiconductor substrate electrode pad 15 on the semiconductor substrate 14 with a wire 19. On the side of the wiring board 17 opposite to the semiconductor substrate 14, a solder ball 21, which is an external connection terminal, is formed. The wiring board 17 also functions as a support substrate to suppress deformation of the semiconductor substrate 14.

[0175] The encapsulating resin 20 is not particularly limited, but thermosetting resins such as epoxy resins, acrylic resins, and silicone resins are preferred, with epoxy resins being preferred from the viewpoint of toughness and heat resistance. From the viewpoint of reducing optical noise such as flare, the encapsulating resin 20 is preferably colored black. Furthermore, from the viewpoint of handling, the encapsulating resin 20 is preferably thixotropic, containing a filler such as silica before curing.

[0176] In Figure 3, the rib material 12 has a rectangular cross-sectional shape, but the cross-sectional shape of the rib material 12 is not limited to this. For example, as shown in Figure 4, the angle TA formed by the main surface 11a of the transparent substrate 11 on the semiconductor substrate 14 side and the inner circumferential surface 12a of the rib material 12 may exceed 90°. In the following description, the angle formed by the main surface of the transparent substrate on the semiconductor substrate side and the inner circumferential surface of the rib material (angle TA in Figure 4) may be referred to as the "taper angle".

[0177] In order to obtain an optoelectronic device that can further suppress the generation of optical noise by suppressing the reflection of light incident on the rib material 12 to the photodetector 13, the taper angle is preferably 90° or more, more preferably greater than 90°, even more preferably 95° or more, even more preferably 100° or more, and may also be 110° or more. Furthermore, in order to obtain an optoelectronic device with excellent reliability by ensuring a sufficient bonding area between the rib material 12 and the semiconductor substrate 14, the taper angle is preferably 130° or less, more preferably 125° or less, and even more preferably 120° or less.

[0178] [Optical semiconductor device 100] Next, as another specific example of the optoelectronic semiconductor device according to the second embodiment, a chip-size package type (CSP type) optoelectronic semiconductor device 100 will be described with reference to the drawings. In the following description, explanations that overlap with those of the optoelectronic semiconductor device 50 may be omitted.

[0179] Figure 5 is a cross-sectional view showing the optoelectronic device 100. The optoelectronic device 100 is the same as the optoelectronic device 50 described above in that it comprises a ribbed substrate 10 and a semiconductor substrate 14 on which a light-receiving element 13 is provided on the first surface 14a. Furthermore, the optoelectronic device 100 is the same as the optoelectronic device 50 described above in that the transparent substrate 11 and the semiconductor substrate 14 are laminated with rib material 12 in between, and the rib material 12 is provided so as to surround the light-receiving element 13.

[0180] Since the optoelectronic device 100 is of the CSP type, the width of the optoelectronic device 100 and the width of the semiconductor substrate 14 are approximately equal. Furthermore, since the optoelectronic device 100 does not have a wiring board, electrode pads for the wiring board, and wires that the optoelectronic device 50 has, sealing with sealing resin is unnecessary. In the optoelectronic device 100, solder balls 21, which are external connection terminals, are provided on the second surface 14b of the semiconductor substrate 14. The advantage of the optoelectronic device 100 is that the device can be miniaturized by adopting a CSP type structure. Since the optoelectronic device 100 does not have a wiring board, it is necessary to electrically connect the semiconductor substrate 14 and the solder balls 21 separately. The following describes examples of methods for electrically connecting the semiconductor substrate 14 and the solder balls 21, but these are not the only methods.

[0181] As an example of the method of electrical connection described above, one method is to provide through-silicon vias 200, as shown in Figure 6. In the configuration of Figure 6, an insulating layer 201, a redistribution layer 203, and a solder resist 202 are provided in this order on the side of the semiconductor substrate 14 opposite to the rib material 12 side. Solder balls 21 are formed in the openings of the solder resist 202 and are electrically connected to electrode pads 204 formed on the side of the semiconductor substrate 14 facing the rib material 12 via the redistribution layer 203.

[0182] The insulating layer 201 is not particularly limited as long as it is a highly insulating material, but 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. Methods for forming the insulating layer 201 include CVD (Chemical Vapor Deposition) and coating methods.

[0183] The material for the solder resist 202 is not particularly limited as long as it has heat resistance and insulating properties during mounting, but examples include epoxy resin and acrylic resin, with epoxy resin being preferred from the viewpoint of high heat resistance and insulating properties. Methods for forming the solder resist 202 include photolithography and screen printing.

[0184] The material for the redistribution layer 203 is not particularly limited as long as it is conductive, but examples include copper (Cu), aluminum (Al), tungsten (W), gold (Au), titanium (Ti), and nickel (Ni). Methods for forming the redistribution layer 203 include wet etching, dry etching, and lift-off methods.

[0185] Another example of the electrical connection method described above is to form a redistribution layer 203 along the outer periphery of the semiconductor substrate 14, as shown in Figure 7, and to electrically connect the solder ball 21 and the electrode pad 204 via this redistribution layer 203.

[0186] Other aspects of the optoelectronic device 100 are the same as those described in the section on [Optoelectronic device 50] above.

[0187] The configuration of the optical semiconductor device according to the second embodiment has been described above with reference to the drawings, but the present invention is not limited to the examples described above. For example, the optical semiconductor device according to the present invention may further have an adhesive layer for bonding the rib material and the semiconductor substrate. If the optical semiconductor device further has an adhesive layer for bonding the rib material and the semiconductor substrate, the adhesion between the rib material and the semiconductor substrate will be improved.

[0188] Examples of optoelectronic devices having an adhesive layer include the optoelectronic device 300 shown in Figure 8 and the optoelectronic device 350 shown in Figure 9. The optoelectronic device 300 is the same as the optoelectronic device 50 described above, except that the rib material 12 and the semiconductor substrate 14 are bonded together by an adhesive layer 301. Similarly, the optoelectronic device 350 is the same as the optoelectronic device 100 described above, except that the rib material 12 and the semiconductor substrate 14 are bonded together by an adhesive layer 301.

[0189] The adhesive layer 301 is composed of cured adhesive. Examples of adhesives used as materials for the adhesive layer 301 include thermosetting adhesives (more specifically, epoxy adhesives, etc.) and ultraviolet curing adhesives (more specifically, acrylic adhesives, etc.). Note that "acrylic adhesive" refers to an adhesive whose main component is (meth)acrylic acid or its derivatives (more specifically, (meth)acrylic acid esters, etc.), or polymers of (meth)acrylic acid or its derivatives.

[0190] To obtain an optoelectronic device with superior adhesion between substrates, an epoxy adhesive is preferred as the adhesive material for the adhesive layer 301. When using an epoxy adhesive as the adhesive material for the adhesive layer 301, in order to obtain an optoelectronic device with superior adhesion between substrates, an aromatic epoxy compound having two or more epoxy groups is preferred as the main component of the epoxy adhesive, a bisphenol-based diglycidyl ether (more specifically, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, etc.) is more preferred, and bisphenol A diglycidyl ether is even more preferred.

[0191] When using an epoxy adhesive as the adhesive material for the adhesive layer 301, an imidazole-based curing agent is preferred as the curing agent for the epoxy adhesive in order to obtain an optoelectronic device with superior adhesion between substrates.

[0192] To obtain an optoelectronic device with even better adhesion between substrates, the adhesive material for the adhesive layer 301 is preferably an epoxy adhesive containing bisphenol-based diglycidyl ether as the main component and an imidazole-based curing agent as the curing agent, and more preferably an epoxy adhesive containing bisphenol A diglycidyl ether as the main component and an imidazole-based curing agent as the curing agent. In this case, the weight ratio of the main component to the curing agent in the epoxy adhesive (main component / curing agent) is, for example, 100 / 10 or more and 100 / 1 or less.

[0193] To obtain an optoelectronic device that exhibits excellent adhesion between substrates and superior reliability as evaluated by thermal shock tests, the thickness (height) of the adhesive layer 301 is preferably 0.01 μm to 200 μm, more preferably 0.1 μm to 100 μm, and even more preferably 1 μm to 50 μm. The width of the adhesive layer 301 can be appropriately changed according to the width of the rib material 12, but for example, it is 10 μm to 500 μm, preferably 10 μm to 300 μm, and more preferably 20 μm to 250 μm. To obtain an optoelectronic device with superior reliability as evaluated by thermal shock tests, the width of the adhesive layer 301 when the width of the rib material 12 is taken as 100% is preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, and may be 100% or more, 110% or more, or 120% or more.

[0194] [Manufacturing method for optoelectronic devices] Next, a preferred manufacturing method for the optical semiconductor device according to the second embodiment of the present invention will be described with reference to the drawings as appropriate.

[0195] Hereinafter, as preferred manufacturing methods for the optical semiconductor device according to the second embodiment, an example of a manufacturing method for the optical semiconductor device 50 shown in Figure 3 (hereinafter sometimes referred to as "manufacturing method M1") and an example of a manufacturing method for the optical semiconductor device 100 shown in Figure 5 (hereinafter sometimes referred to as "manufacturing method M2") will be described with reference to the drawings.

[0196] (Manufacturing method M1) First, manufacturing method M1 will be explained with reference to Figures 10 to 12. Figure 10 is a plan view showing a transparent substrate (large transparent substrate) after rib material formation when manufacturing an optical semiconductor device using manufacturing method M1. Figures 11A to C and 12A to C are cross-sectional views of each process when manufacturing an optical semiconductor device using manufacturing method M1.

[0197] In manufacturing method M1, first, a large transparent substrate 11 is made by forming a large number of semi-cured rib material 12 in a rectangular tubular pattern (Figure 10). Hereinafter, the semi-cured rib material may be referred to as "semi-cured rib material". After forming the semi-cured rib material 12 on the transparent substrate 11, the transparent substrate 11 on which the semi-cured rib material 12 is formed is divided into individual pieces by dicing along the dividing line 400 in Figure 10. When dicing, for example, the large transparent substrate 11 is attached and fixed to a dicing tape (not shown), and cut with a dicing blade (not shown). At this time, the side of the transparent substrate 11 opposite to the side on which the semi-cured rib material 12 is formed may be attached to the dicing tape, or the side on which the semi-cured rib material 12 is formed may be attached.

[0198] In the process of forming semi-cured rib material 12 on a large transparent substrate 11, for example, a film made of a photosensitive composition (more specifically, a coating film made of a photosensitive composition after heating) is patterned in a semi-cured state using photolithography. Photolithography allows for the formation of a large number of semi-cured rib material 12 with excellent dimensional accuracy.

[0199] A method for forming a semi-cured rib material 12 by photolithography will be described with reference to Figures 11A to C. First, a photosensitive composition is applied to a large transparent substrate 11 to form a film (coating) composed of the photosensitive composition. The application method is not particularly limited, and general application methods such as spin coating and slit coating can be used. Next, the coating is heated to remove the solvent in the coating and form a thin film 401 (coating after heating) on ​​the transparent substrate 11 (Figure 11A). The heating temperature of the coating can be set as appropriate, but is preferably 60°C to 200°C.

[0200] Next, a photomask 402 with a light-transmitting region 402a formed in a predetermined position is placed on the thin film 401, and the thin film 401 is irradiated with an active energy ray E (Figure 11B). As a result, only the thin film 401 located below the light-transmitting region 402a (exposed portion 401a) is exposed, and the photocuring reaction proceeds. The cumulative exposure amount during exposure is not particularly limited, but preferably 1 mJ / cm². 2 More than 20000mJ / cm 2 The following is more preferable: 10 mJ / cm² 2 More than 10000mJ / cm 2 The following applies: The time for irradiating the thin film 401 with the active energy ray E is preferably 1 second or more and 600 seconds or less, and more preferably 1 second or more and 150 seconds or less.

[0201] After exposure, the thin film 401 can be baked at a predetermined temperature as needed to maintain a semi-cured state while the curing reaction progresses.

[0202] Next, the exposed thin film 401 is developed. The method of developing the thin film 401 is not particularly limited. For example, by contacting the thin film 401 with an alkaline developer by immersion or spraying, the unexposed areas 401b are dissolved and removed, thereby forming a patterned semi-cured rib material 12 on the transparent substrate 11 (Figure 11C). Any commonly used alkaline developer can be used without particular limitation. Specific examples of alkaline developers include organic alkaline aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solution and choline aqueous solution; and inorganic alkaline aqueous solutions such as potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution, and lithium carbonate aqueous solution. From the viewpoint of increasing the contrast between the exposed areas 401a and the unexposed areas 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. Alcohol or surfactants may be added to the alkaline developer for purposes such as adjusting the dissolution rate. Alternatively, the thin film 401 may be washed with water after contacting it with the alkaline developer. When washing the thin film 401 with water, it is preferable to remove the moisture from the surface of the thin film 401 with compressed air after washing.

[0203] Furthermore, an organic solvent developer may be used instead of an alkaline developer as the developer for the thin film 401. Any organic solvent developer may be used as long as it can remove the unexposed areas 401b from the transparent substrate 11 and leave the patterned exposed areas 401a on the transparent substrate 11. Examples of organic solvent developers include acetone, ethyl acetate, alkoxyethanol having an alkoxy group with 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1,1,1-trichloroethane, N-methyl-2-pyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone, triethylene glycol dimethyl ether, and propylene glycol 1-monomethyl ether 2-acetate. Small amounts of surfactants, defoamers, etc., may be added to the organic solvent developer, and water may be added in a range of 1% to 30% by volume for the purpose of preventing ignition. The method for removing the unexposed areas 401b from the transparent substrate 11 using an organic solvent developer is not particularly limited. For example, a method may be used in which the organic solvent developer is brought into contact with the thin film 401 by immersion, spraying, or paddle methods to dissolve and remove the unexposed areas 401b.

[0204] When a thin film 401 composed of a photo-radical polymerizable photosensitive composition is exposed, in the region of the exposed area 401a relatively close to the photomask 402, radical polymerization of the unexposed area 401b adjacent to the exposed area 401a is easily suppressed due to oxygen inhibition. On the other hand, when a thin film 401 composed of a photo-radical polymerizable photosensitive composition is exposed, in the region of the exposed area 401a relatively far from the photomask 402, the effects of oxygen inhibition are less pronounced, and therefore radical polymerization of the unexposed area 401b adjacent to the exposed area 401a is less easily suppressed. For this reason, when a thin film 401 composed of a photo-radical polymerizable photosensitive composition is patterned by photolithography, the width of the semi-cured rib material 12 on the transparent substrate 11 side tends to be larger than the width on the opposite side (surface layer) of the transparent substrate 11. Therefore, when a thin film 401 composed of a photo-radical polymerizable photosensitive composition is patterned by photolithography, the above-mentioned taper angle can be made larger than 90°. The taper angle can be adjusted, for example, by changing at least one of the following: the gap G between the thin film 401 and the photomask 402 (see Figure 11B) and the cumulative exposure. The gap G is, for example, 50 μm to 2000 μm.

[0205] In order to easily adjust the taper angle to a range greater than 90°, it is preferable that the photosensitive composition applied to the transparent substrate 11 is a photosensitive composition containing component (A), component (B), and component (C), and that component (B) contains a photoradical polymerization initiator.

[0206] Next, the process of laminating the semi-cured rib material 12 and the individualized rib-attached substrate 10 with the semiconductor substrate 14 (lamination process) will be described. First, the semiconductor substrate laminate is prepared. As shown in Figure 12A, a semiconductor substrate 14 on which a light-receiving element 13 is provided and a wiring substrate 17 are bonded together via a die bond material 18, and the electrode pads 15 for the semiconductor substrate and the electrode pads 16 for the wiring substrate are electrically connected via wires 19 can be used as the semiconductor substrate laminate.

[0207] Then, as shown in Figure 12A, the transparent substrate 11 on which the semi-cured rib material 12 is formed and the semiconductor substrate laminate are arranged so that the main surface of the transparent substrate 11 on which the semi-cured rib material 12 is formed faces the main surface of the semiconductor substrate 14 on which the light-receiving element 13 is provided, and then they are laminated (Figure 12B). In the lamination process, the semi-cured rib material 12 is placed around the light-receiving element 13.

[0208] Next, the curing process for the semi-cured rib material 12 (curing process) will be described. First, the laminate obtained in the lamination process is heated, for example, while applying a load, to thermocompression-bond the transparent substrate 11 and the semiconductor substrate laminate. The heating temperature at this time is, for example, 80°C to 200°C. Then, the laminate after thermocompression-bonding is heated, for example, at a temperature of 100°C to 300°C. Through the above curing process, the semi-cured rib material 12 hardens, and the transparent substrate 11 and the semiconductor substrate 14 are bonded together via the rib material 12. Next, as shown in Figure 12C, the peripheral part of the rib material 12 (the area including the wire 19) is sealed with sealing resin 20, and solder balls 21 are formed on the side of the wiring board 17 opposite to the semiconductor substrate 14 side, thereby obtaining the optoelectronic device 50.

[0209] In manufacturing method M1, the semi-cured rib material 12 was formed on the transparent substrate 11, but the semi-cured rib material 12 may also be formed on the semiconductor substrate 14, and the lamination and curing processes may be carried out in the same procedure as described above.

[0210] (Manufacturing method M2) Next, manufacturing method M2 will be explained with reference to Figures 13 and 14. Figure 13 is a plan view showing a semiconductor substrate after the formation of a photodetector element when manufacturing an optoelectronic device using manufacturing method M2. Figures 14A and 14B are cross-sectional views showing the lamination process of manufacturing method M2.

[0211] In manufacturing method M2, first, the semi-cured rib material 12 is formed using the same method as in manufacturing method M1. Specifically, the semi-cured rib material 12 is formed on a large transparent substrate 11 in a pattern of numerous rectangular tubes using the same method as in manufacturing method M1 (see Figure 10). In addition, a large semiconductor substrate 14 (see Figure 13) on which multiple light-receiving elements 13 are provided is prepared separately.

[0212] Next, the lamination process will be described. As shown in Figure 14A, a large transparent substrate 11 on which semi-cured rib material 12 is formed and a large semiconductor substrate 14 on which multiple light-receiving elements 13 are provided are placed so that the main surface of the transparent substrate 11 on which the semi-cured rib material 12 is formed and the main surface of the semiconductor substrate 14 on which the light-receiving elements 13 are provided face each other, and then they are laminated (Figure 14B). In the lamination process, the semi-cured rib material 12 is placed around the light-receiving elements 13.

[0213] Next, the curing process will be described. First, the laminate obtained in the lamination process is heated, for example, while applying a load, to thermally bond the transparent substrate 11 and the semiconductor substrate 14. The heating temperature at this time is, for example, between 80°C and 200°C. Then, the laminate after thermal bonding is heated, for example, at a temperature between 100°C and 300°C. Through the above curing process, the semi-cured rib material 12 hardens, and the transparent substrate 11 and the semiconductor substrate 14 are bonded together via the rib material 12.

[0214] Next, after dicing along the dividing line 500 in Figure 14B, solder balls 21 are formed on the side of the semiconductor substrate 14 opposite to the transparent substrate 11 side, thereby obtaining the optoelectronic device 100 shown in Figure 5.

[0215] In manufacturing method M2, the semi-cured rib material 12 was formed on the transparent substrate 11, but the semi-cured rib material 12 may be formed on the semiconductor substrate 14, and the lamination and curing processes may be carried out in the same procedure as described above. Alternatively, the lamination and curing processes may be carried out in the same procedure as described above using the individual semiconductor substrate 14 and the individual transparent substrate 11.

[0216] Although a preferred method for manufacturing the optical semiconductor device according to the second embodiment has been described above, the method for manufacturing the optical semiconductor device according to the second embodiment is not limited to the method described above. For example, in the manufacturing methods M1 and M2 described above, a large transparent substrate 11 on which the semi-cured rib material 12 is formed is laminated with a semiconductor substrate 14, and then the semi-cured rib material 12 is cured. However, the semi-cured rib material 12 may be cured before the lamination process, and the cured rib material 12 and the semiconductor substrate 14 may be bonded together via an adhesive. According to this method, for example, the optical semiconductor device 300 shown in Figure 8 or the optical semiconductor device 350 shown in Figure 9 can be obtained. The heating temperature when curing the semi-cured rib material 12 before the lamination process is preferably 80°C to 350°C, and more preferably 150°C to 250°C. After curing the semi-cured rib material 12, the reaction rate of the curable compound in the rib material 12 before bonding the cured rib material 12 and the semiconductor substrate 14 is preferably 90% or more. The method for measuring the above reaction rate is the same as or similar to the method described in the examples later. After curing the semi-cured rib material 12, the alkali content in the rib material 12 before bonding the cured rib material 12 to the semiconductor substrate 14 is preferably 1000 ppm or less, and more preferably 100 ppm or less. [Examples]

[0217] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0218] <Synthesis of curable compounds> The synthesis methods for curable compounds P1 to P6 are described below. The weight-average molecular weights of curable compounds P1 and P2, and linear polysiloxane compounds LP1 to LP4 were calculated from chromatograms obtained using Tosoh Corporation's "HLC-8420GPC" (columns: Shodex GPC KD-806M (2) and TSKgel SuperAWM-H (2)) with N,N-dimethylformamide as the solvent at a flow rate of 1.0 mL / min, and converted to standard polystyrene equivalents.

[0219] [Synthesis of curable compound P1] Solution S1 was obtained by adding 95.5 μL of a xylene solution of a platinum-vinylsiloxane complex (Pt-VTSC-3X, manufactured by Yumicore Precious Metals Japan, containing 3% by weight of platinum) to a mixture of 40 g of diallyl isocyanurate, 4.8 g of diallyl monomethyl isocyanurate, 2.2 g of linear polysiloxane compound LP1, and 240 g of 1,4-dioxane. The linear polysiloxane compound LP1 was polydimethylsiloxane (DMS-V31, manufactured by Gelest, with vinyl groups at both ends, weight-average molecular weight 28000). Separately, solution S2 was obtained by dissolving 58.8 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane in 117.6 g of toluene.

[0220] Then, under a nitrogen atmosphere containing 3 volume% oxygen, solution S2 was heated to a temperature of 105°C, and solution S1 was added dropwise to solution S2 over 3 hours. After the dropwise addition was complete, the mixture was stirred for 30 minutes while maintaining the temperature at 105°C to obtain solution S3. The reaction rate of the alkenyl groups of the compounds contained in the obtained solution S3 was then determined. 1 When measured by 1H-NMR, the reaction rate was found to be over 95%.

[0221] In addition, 41.17 g of 1-vinyl-3,4-epoxycyclohexane was dissolved in 41.17 g of toluene to obtain solution S4.

[0222] Then, under a nitrogen atmosphere containing 3% by volume of oxygen, solution S3 was heated to 105°C, and solution S4 was added dropwise to solution S3 over 1 hour. After the dropwise addition was complete, the mixture was stirred for 30 minutes while maintaining the temperature at 105°C to obtain solution S5. The reaction rate of the alkenyl groups of the compounds contained in the obtained solution S5 was then determined. 1 When measured by 1H-NMR, the reaction rate was found to be over 95%.

[0223] Next, after cooling solution S5, the solvents (toluene, xylene, and 1,4-dioxane) were removed from solution S5 under reduced pressure to obtain a solid. Then, propylene glycol 1-monomethyl ether 2-acetate (hereinafter referred to as "PGMEA") was added to the obtained solid to obtain solution SP1 containing curable compound P1 (concentration of curable compound P1: 70% by weight). Curable compound P1 was a polysiloxane compound with a weight-average molecular weight of 18200. Furthermore, curable compound P1 had multiple cationic polymerizable groups (specifically alicyclic epoxy groups), multiple alkali-soluble groups (specifically X2 groups), and a linear structural portion (a linear structural portion derived from the linear polysiloxane compound LP1) in one molecule, and had a cyclic polysiloxane structure in the main chain.

[0224] [Synthesis of curable compound P2] Solution SP2 (concentration of curable compound P2: 70 wt%) containing curable compound P2 (a polysiloxane compound with a weight-average molecular weight of 16950) was obtained using the same synthesis method as for curable compound P1, except that 2.2 g of linear polysiloxane compound LP2 was used instead of 2.2 g of linear polysiloxane compound LP1. Linear polysiloxane compound LP2 was a compound represented by the following general formula (Y). Furthermore, linear polysiloxane compound LP2 had a molar ratio of each structural unit (r, s, and t ratio) of r:s:t = 30:0:70 and a weight-average molecular weight of 26000.

[0225] [ka]

[0226] The curable compound P2 had multiple cationic polymerizable groups (specifically alicyclic epoxy groups), multiple alkali-soluble groups (specifically X2 groups), and a linear structural portion (a linear structural portion derived from the linear polysiloxane compound LP2) in one molecule, and the main chain had a cyclic polysiloxane structure.

[0227] [Synthesis of curable compound P3] Solution SP3 containing curable compound P3 (concentration of curable compound P3: 70 wt%) was obtained using the same synthesis method as for curable compound P1, except that 2.2 g of linear polysiloxane compound LP3 was used instead of 2.2 g of linear polysiloxane compound LP1. Linear polysiloxane compound LP3 was a compound represented by general formula (Y). Furthermore, linear polysiloxane compound LP3 had a molar ratio of each structural unit (r, s, and t ratio) of r:s:t = 0:100:0 and a weight-average molecular weight of 2300.

[0228] The curable compound P3 had multiple cationic polymerizable groups (specifically alicyclic epoxy groups), multiple alkali-soluble groups (specifically X2 groups), and a linear structural portion (a linear structural portion derived from the linear polysiloxane compound LP3) in one molecule, and the main chain had a cyclic polysiloxane structure.

[0229] [Synthesis of curable compound P4] Solution SP4 containing curable compound P4 (concentration of curable compound P4: 70 wt%) was obtained using the same synthesis method as for curable compound P1, except that 2.2 g of linear polysiloxane compound LP4 was used instead of 2.2 g of linear polysiloxane compound LP1. Linear polysiloxane compound LP4 was a compound represented by general formula (Y). Furthermore, linear polysiloxane compound LP4 had a molar ratio of each structural unit (r, s, and t ratio) of r:s:t = 0:100:0 and a weight-average molecular weight of 10000.

[0230] The curable compound P4 had multiple cationic polymerizable groups (specifically alicyclic epoxy groups), multiple alkali-soluble groups (specifically X2 groups), and a linear structural portion (a linear structural portion derived from the linear polysiloxane compound LP4) in one molecule, and the main chain had a cyclic polysiloxane structure.

[0231] [Synthesis of curable compound P5] Solution SP5 containing curable compound P5 (concentration of curable compound P5: 70 wt%) was obtained using the same synthesis method as for curable compound P1, except that 2.2 g of linear polysiloxane compound LP1 was not used. Curable compound P5 had multiple cationic polymerizable groups (specifically alicyclic epoxy groups) and multiple alkali-soluble groups (specifically X2 groups) in one molecule, and had a cyclic polysiloxane structure in its main chain.

[0232] [Synthesis of curable compound P6] Solution SP6 (concentration of curable compound P6: 70 wt%) containing curable compound P6 was obtained by the same synthesis method as curable compound P1, except that solution S4 was prepared by dissolving 20.6 g of 1-vinyl-3,4-epoxycyclohexane and 18.6 g of allyl acrylate in 39.2 g of toluene. Curable compound P6 had multiple cationic polymerizable groups (specifically alicyclic epoxy groups), multiple alkali-soluble groups (specifically X2 groups), a linear structural portion (a linear structural portion derived from the linear polysiloxane compound LP1), and multiple radical polymerizable groups (specifically acryloyl groups) in one molecule, and had a cyclic polysiloxane structure in its main chain.

[0233] <Preparing other materials> In addition to solutions SP1 to SP6 and PGMEA, the following materials were prepared as materials for the photosensitive composition. • Linear polysiloxane compound LP1 (Gelest "DMS-V31", weight-average molecular weight 28,000, hereinafter referred to as "LP1") • 3',4'-Epoxycyclohexylmethyl 3,4-Epoxycyclohexanecarboxylate as a curable compound (Daicel Corporation's "Celoxide® 2021P," hereinafter referred to as "2021P") • Ditrimethylolpropanetetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "AD-TMP," a compound having four acryloyl groups in one molecule; hereinafter referred to as "AD-TMP") • Caprolactone-modified tris-(2-acryloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "A-9300-1CL", a compound having three acryloyl groups in one molecule, hereinafter referred to as "A-9300") • Silica particles as a filler (Ryumori Co., Ltd. "KYKLOS(registered trademark) MSR-04", average particle size: 4.1 μm) • Aromatic sulfonium salt compounds as photocationic polymerization initiators (SunApro's "CPI-210S," hereinafter referred to as "CPI-210S") • Benzophenone compounds as photoradical polymerization initiators (Omnirad® 651, manufactured by IGM Resins, hereinafter referred to as "651") • 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Evonik, hereinafter referred to as "H-TEMPO") as a radical scavenger.

[0234] <Preparation of photosensitive composition> The materials listed in Tables 1 and 2 were blended in the amounts specified in Tables 1 and 2 to obtain photosensitive compositions PS1 to PS13 for use in the examples and comparative examples, respectively. When curable compounds P1 to P6 were blended, they were blended as solutions SP1 to SP6, respectively. In Tables 1 and 2, the blending amount of PGMEA also includes the amount of PGMEA in solutions SP1, SP2, SP3, SP4, SP5, or SP6. In Tables 1 and 2, "P1" to "P6" refer to curable compounds P1 to P6, respectively. In Tables 1 and 2, "-" means that the material was not blended.

[0235] [Table 1]

[0236] [Table 2]

[0237] <Fabrication of ribbed substrates and optoelectronic devices> Hereinafter, the manufacturing methods of the ribbed substrates of Examples 1 to 15 and Comparative Examples 1 to 3, and the manufacturing methods of the optical semiconductor devices of Examples 1 to 15 and Comparative Examples 1 to 3 will be described.

[0238] [Example 1] On a glass substrate as a transparent substrate, a photosensitive composition PS1 was applied by a spin coater to obtain a first laminate in which a coating film composed of the photosensitive composition PS1 was formed on the glass substrate. Next, the first laminate was heated on a hot plate heated to 120°C for 10 minutes. Then, using a manual exposure machine ("MA-1300" manufactured by Dainippon Scientific Co., Ltd., lamp: high-pressure mercury lamp), through the photomask 601 shown in FIG. 15 (photomask 601 having a light-transmitting region 601a with a width of 200 μm), under the condition of an integrated exposure amount of 2000 mJ / cm 2 , the coating film of the first laminate after heating was irradiated with light to expose the coating film (specifically, soft contact exposure).

[0239] Then, the first laminate after exposure was left standing in an atmosphere at a temperature of 25°C for 1 minute, and then immersed in an aqueous TMAH solution as an alkaline developer (concentration of TMAH: 2.38% by weight) for 60 seconds. Next, the first laminate immersed in the alkaline developer was washed with water for 30 seconds, and then the surface moisture was removed with compressed air. As a result, the coating film on the glass substrate was patterned in a semi-cured state, and a glass substrate provided with a plurality of rib members having a square tubular structure was obtained. The thickness of the rib member was 50 μm. Hereinafter, the glass substrate provided with a plurality of rib members having the above square tubular structure will be referred to as "Sample 1".

[0240] Next, Sample 1 was cut together with the rib members with a dicing blade to obtain the ribbed substrate of Example 1 (fragmented Sample 1).

[0241] Next, the obtained ribbed substrate and the semiconductor substrate laminate were stacked to form a second laminate. In this case, the main surface of the semiconductor substrate on which the photodetector element is provided and the main surface of the ribbed substrate on which the rib material is provided were stacked facing each other. The semiconductor substrate laminate used was one in which the semiconductor substrate on which the photodetector element is provided and the wiring substrate are bonded together via a die bond material, and the electrode pads on the semiconductor substrate and the electrode pads on the wiring substrate are electrically connected via metal wires. Next, the semiconductor substrate and the glass substrate were thermocompressed onto the second laminate by applying a load of 500g on a hot plate at a temperature of 120°C for 30 seconds, via the rib material. Then, the thermally compressed laminate was heated in an oven at a temperature of 200°C for 2 hours to cure the rib material. Next, the peripheral part of the rib material (the area including the wire) was sealed with sealing resin, and solder balls were formed on the side of the wiring substrate opposite to the semiconductor substrate side to obtain the optoelectronic device of Example 1. The optical semiconductor device of Example 1 had the structure shown in Figure 3. Furthermore, the thickness of the rib material in the optical semiconductor device of Example 1 was 50 μm.

[0242] [Examples 2-11, Example 15, and Comparative Example 1] Except for using the types of photosensitive compositions shown in Tables 3 to 5 described later, the ribbed substrates of Examples 2 to 11, Example 15, and Comparative Example 1, as well as the photosemiconductor devices of Examples 2 to 11, Example 15, and Comparative Example 1, were obtained using the same method as in Example 1.

[0243] [Example 12] After obtaining sample 1 using the same method as in Example 1, sample 1 was heated on a hot plate heated to 230°C for 30 minutes to cure the rib material. Next, sample 1, after the rib material had been cured, was cut into individual rib pieces with a dicing blade to obtain the ribbed substrate of Example 12 (individually separated sample 1). Then, the ribbed substrate and the semiconductor substrate laminate were laminated together using an epoxy adhesive to obtain a third laminate. The semiconductor substrate laminate used was one in which a semiconductor substrate on which a photodetector is provided and a wiring substrate are bonded together via a die bond material, and electrode pads on the semiconductor substrate and electrode pads on the wiring substrate are electrically connected via metal wires. Furthermore, during lamination, the epoxy adhesive was interposed between the rib material and the semiconductor substrate laminate. The epoxy adhesive used was a thermosetting adhesive containing bisphenol A diglycidyl ether as the main component and an imidazole-based curing agent as the curing agent, with a weight ratio of main component to curing agent (main component / curing agent) of 100 / 3.

[0244] Next, the third laminate was heated in an oven at 200°C for 2 hours, then the peripheral portion of the rib material (the area including the wires) was sealed with sealing resin, and solder balls were formed on the side of the wiring board opposite to the semiconductor substrate side to obtain the optical semiconductor device of Example 12. The optical semiconductor device of Example 12 had the structure shown in Figure 8. In addition, the thickness of the rib material in the optical semiconductor device of Example 12 was 50 μm, and the thickness of the adhesive layer was 10 μm.

[0245] [Example 13] The ribbed substrate of Example 13 and the optoelectronic device of Example 13 were obtained in the same manner as in Example 12, except that photosensitive composition PS2 was used instead of photosensitive composition PS1.

[0246] [Example 14] The ribbed substrate of Example 14 and the optoelectronic device of Example 14 were obtained in the same manner as in Example 12, except that photosensitive composition PS5 was used instead of photosensitive composition PS1.

[0247] [Comparative Example 2] The ribbed substrate of Comparative Example 2 and the optoelectronic device of Comparative Example 2 were obtained in the same manner as in Example 12, except that photosensitive composition PS12 was used instead of photosensitive composition PS1.

[0248] [Comparative Example 3] The ribbed substrate of Comparative Example 3 and the optical semiconductor device of Comparative Example 3 were obtained in the same manner as in Example 1, except that photosensitive composition PS12 was used instead of photosensitive composition PS1, and photomask 602 shown in Figure 16 was used instead of photomask 601 shown in Figure 15. The photomask 602 shown in Figure 16 had a light-transmitting region 602a with a width of 200 μm. Furthermore, an uneven surface 602b with an arithmetic mean roughness Ra of 5000 nm was formed on the inner surface 602b of the light-transmitting region 602a, and this uneven surface was formed only in a direction perpendicular to the thickness direction of the photomask 602.

[0249] <Methods for measuring and evaluating physical properties> Next, we will explain the methods for measuring and evaluating various physical properties.

[0250] [Patternability] The pattern shape of the rib material of sample 1 was observed using a 3D measuring laser microscope (Olympus "LEXT® OLS4000") and a stylus-type surface profile analyzer (Veeco "Dektak® 150"), and evaluated according to the following criteria. A: No residue or peeling occurred between the patterns. B: Either residue or peeling occurred between the patterns.

[0251] [Surface shape] Using a 3D measuring laser microscope (Olympus "LEXT® OLS5100"), the arithmetic mean roughness Ra (evaluation length: 20 μm) of the inner and end surfaces of the rib material of a ribbed substrate, and the skewness Ssk of the inner surface of the rib material were measured. For the arithmetic mean roughness Ra of the inner surface of the rib material, the arithmetic mean roughness Ra in the direction perpendicular to the thickness direction of the glass substrate and the arithmetic mean roughness Ra in the direction parallel to the thickness direction of the glass substrate were measured. For the measurement of skewness Ssk, 10 measurement locations (20 μm × 20 μm square areas) were randomly selected on the inner surface of the rib material, and the skewness Ssk of the selected measurement locations was measured. The arithmetic mean of the obtained 10 measurements was taken as the evaluation value (skewness Ssk shown in Tables 3 to 5 below).

[0252] [Response rate] First, the solid content of the photosensitive compositions PS1 to PS13 was analyzed according to the following analytical conditions. 13 A 1C-NMR chart was obtained. The area of ​​the peak attributed to the "cationic polymerizable group of the curable compound" in the obtained NMR chart was then determined, and this obtained peak area was defined as the "first peak area." Next, the solid rib material of the ribbed substrate (rib material of the same mass as the sample for which the first peak area was measured) was analyzed according to the following analytical conditions. 13 A 1C-NMR chart was obtained. The area of ​​the peak attributed to the "cationic polymerizable group of the curable compound" in the obtained NMR chart was determined, and this obtained peak area was designated as the "second peak area." The reaction rate (in %) was then calculated according to the formula "Reaction rate = (1 - second peak area / first peak area) × 100." The reaction rate obtained here represents the reaction rate of the curable compound in the rib material before bonding the semiconductor substrate and the glass substrate.

[0253] (solid 13 (Analysis conditions for 1C-NMR) • Measurement equipment: Nuclear magnetic resonance spectrometer (Agilent Technologies "VNMRS600") ·Resonance frequency: 150.85MHz • Measurement mode: DP / MAS method (Direct Polarization method) · Rotation speed of the measurement sample: 20 kHz · Measurement temperature: 25 °C · Number of integrations: 4096 times · Relaxation waiting time: 15.000 s · FID acquisition time: 0.015 s · Flip angle: 90°

[0254] [Die shear strength] Using a die shear tester (Nordson DAGE's "SERIES4000"), a shearing force (specifically, a shearing force on the glass substrate and the semiconductor substrate) was applied to the optical semiconductor device, and the load when the semiconductor substrate peeled off from the optical semiconductor device was measured. Then, the maximum value of the load was taken as the die shear strength. The die shear strength was measured in accordance with MIL STD 883 under the conditions of a shear height of 50 μm and a shear speed of 80 μm / s.

[0255] [Ghost index] First, for the optical semiconductor device to be evaluated, using a ghost flare evaluation system ("GCS-2T" manufactured by Kamban Electric Co., Ltd.), the number of pixels exceeding a predetermined threshold value (one hundred millionth of the brightness of the light source) (hereinafter referred to as "the number of abnormal pixels") was obtained, and then the value obtained by dividing the number of abnormal pixels by the total number of pixels (number of abnormal pixels / total number of pixels) was calculated. Hereinafter, the value obtained by dividing the number of abnormal pixels by the total number of pixels (number of abnormal pixels / total number of pixels) may be referred to as the abnormal pixel ratio.

[0256] Then, taking the abnormal pixel ratio of Comparative Example 1 as 100, the abnormal pixel ratios of Examples 1 to 15, Comparative Example 2, and Comparative Example 3 were normalized, and the normalized value (hereinafter referred to as the "ghost index") was used as an index of the performance of suppressing ghost generation. When the ghost index was 80 or less, it was evaluated that the generation of ghosts was suppressed. On the other hand, when the ghost index exceeded 80, it was evaluated that the generation of ghosts was not suppressed. <000098​​​​First, the surface modulus of the rib material at the end face of the rib substrate to be evaluated (rib substrate before storage in the constant temperature chamber) was measured using the method shown in (Method for measuring surface modulus) below. Hereafter, the surface modulus measured here may be referred to as the "initial surface modulus". Next, the rib substrate was stored in a constant temperature chamber set to 40°C for 30 days, and then the surface modulus of the rib material at the end face of the rib substrate after storage was measured using the method shown in (Method for measuring surface modulus) below. Hereafter, the surface modulus measured here may be referred to as the "surface modulus after storage". Then, the rate of change of surface modulus (unit: %) was calculated according to the formula "Rate of change of surface modulus = 100 × Surface modulus after storage / Initial surface modulus". If the rate of change of surface modulus was 100% or less, it was evaluated as A (the semi-hardened state of the rib material is stably maintained). On the other hand, if the rate of change of surface modulus exceeded 100%, it was evaluated as B (the semi-hardened state of the rib material is not stably maintained).

[0258] (Method for measuring surface modulus) The ribbed substrate was placed on the measuring platform of the measuring device with the ribs facing upwards. Next, a load was gradually applied to the ribs from above using an indenter, and the displacement for each load (the depth to which the ribs were pressed in by the indenter) was measured to obtain a load-displacement curve. Then, the Young's modulus was calculated from the obtained load-displacement curve, and the calculated Young's modulus was defined as the surface modulus. The detailed measurement conditions are as follows. Measurement device: Nanoindentation tester (ENT-NEXUS®, manufactured by Elionix Corporation) Temperature of the ribbed substrate during measurement (ambient temperature): 100°C Indenter approach speed: 100 nm / second Maximum load: 1mN Load application acceleration: 0.6mN / sec Maximum load holding time: 5 seconds Unloading speed: 0.6mN / sec Stiffness calculation: When 10% load is removed from the maximum load. Drift measurement: When 90% of the load is removed from the maximum load.

[0259] <Result> Tables 3 to 5 show the type of photosensitive composition used, the type of photomask used, the evaluation results of patternability, the measurement results of surface shape, the presence or absence of an adhesive layer, the reaction rate, die shear strength, ghost index, and the evaluation results of the stability of the semi-cured state for Examples 1 to 15 and Comparative Examples 1 to 3, respectively. In Tables 3 to 5, "601" refers to photomask 601 (see Figure 15). In Table 5, "602" refers to photomask 602 (see Figure 16). In Tables 3 to 5, "Orthogonal Direction Ra" refers to the arithmetic mean roughness Ra of the inner surface of the rib material in the direction perpendicular to the thickness direction of the glass substrate. In Tables 3 to 5, "Parallel Direction Ra" refers to the arithmetic mean roughness Ra of the inner surface of the rib material in the direction parallel to the thickness direction of the glass substrate. In Tables 3 to 5, "End Face Ra" refers to the arithmetic mean roughness Ra of the end face of the rib material. Furthermore, in Tables 4 and 5, "-" indicates that the item was not evaluated.

[0260] [Table 3]

[0261] [Table 4]

[0262] [Table 5]

[0263] As shown in Tables 3 to 5, in Examples 1 to 15, the arithmetic mean roughness Ra of the inner surface of the rib material was between 50 nm and 3000 nm in both the direction perpendicular to the thickness direction of the glass substrate and the direction parallel to the thickness direction of the glass substrate. As shown in Tables 3 to 5, the ghost index was 80 or less in Examples 1 to 15. Therefore, the optoelectronic devices in Examples 1 to 15 were able to suppress the generation of ghosts.

[0264] As shown in Table 5, in Comparative Examples 1 to 3, the arithmetic mean roughness Ra of the inner surface of the rib material was less than 50 nm or greater than 3000 nm in both the direction perpendicular to the thickness direction of the glass substrate and the direction parallel to the thickness direction of the glass substrate. As shown in Table 5, the ghost index exceeded 80 in Comparative Examples 1 to 3. Therefore, the optoelectronic devices in Comparative Examples 1 to 3 were unable to suppress the occurrence of ghosting.

[0265] The results above demonstrate that the present invention provides an optical semiconductor device that can suppress the generation of optical noise. [Explanation of Symbols]

[0266] 10 Ribbed circuit boards 11 Transparent substrate 12 Rib material 13. Photodetector 14 Semiconductor substrates 50, 100, 300, 350 Optoelectronic devices 301 Adhesive layer

Claims

1. A ribbed substrate comprising a transparent substrate and a rib material provided on one main surface of the transparent substrate, The aforementioned rib material is formed in a frame shape, The arithmetic mean roughness Ra of the inner circumferential surface of the rib material is 50 nm or more and 3000 nm or less. A ribbed substrate in which the skewness Ssk of the inner circumferential surface of the rib material is a negative value.

2. The ribbed substrate according to claim 1, wherein the arithmetic mean roughness Ra of the inner surface of the rib material is 200 nm or more and 900 nm or less.

3. The ribbed substrate according to claim 1, wherein the content of the filler in the rib material is 30% by weight or less relative to the total amount of the rib material.

4. The ribbed substrate according to claim 1, wherein the arithmetic mean roughness Ra of the end face of the rib material opposite to the transparent substrate side is 50 nm or more and 3000 nm or less.

5. The ribbed substrate according to claim 1, wherein the transparent substrate is a glass substrate.

6. The rib material is composed of a cured product of a photosensitive composition, The photosensitive composition contains a curable compound having polymerizable groups and a photopolymerization initiator, and is alkali soluble, as described in claim 1, for the ribbed substrate.

7. The photosensitive composition has a linear structure and an annular structure, as described in claim 6, for the ribbed substrate.

8. The photosensitive composition comprises the polysiloxane compound having the linear structure, as described in claim 7, for the ribbed substrate.

9. The ribbed substrate according to claim 6, wherein the photosensitive composition contains, as the curable compound, one or more compounds having cationic polymerizable groups selected from the group consisting of glycidyl groups and alicyclic epoxy groups.

10. The photosensitive composition contains, as the curable compound, a compound having one or more cationic polymerizable groups selected from the group consisting of glycidyl groups and alicyclic epoxy groups, and a compound having radical polymerizable groups. The ribbed substrate according to claim 6, wherein the photopolymerization initiator is a photoradical polymerization initiator.

11. The ribbed substrate according to claim 6, wherein the photosensitive composition contains a compound having one or more alkali-soluble groups selected from the group consisting of a monovalent organic group represented by the following chemical formula (X1), a divalent organic group represented by the following chemical formula (X2), a phenolic hydroxyl group, and a carboxyl group. 【Chemistry 1】

12. The invention comprises a ribbed substrate as described in claim 1 and a semiconductor substrate on which a light-receiving element is provided, The transparent substrate of the ribbed substrate and the semiconductor substrate are laminated together via the rib material of the ribbed substrate. The rib material is provided so as to surround the light-receiving element in the optoelectronic device.

13. The optical semiconductor device according to claim 12, further comprising an adhesive layer for bonding the rib material and the semiconductor substrate.

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