WO2023190837A1 - Solid-state imaging device and method for manufacturing same - Google Patents

Abstract

A solid-state imaging device (10) comprises a base member (11), a frame, a frame-like light-blocking member (13), and a transparent substrate (14) in this order. The base member (11) includes a semiconductor substrate (15) in which a pixel area (15a) is provided, and a mounting substrate (16) on which the semiconductor substrate (15) is mounted. The frame is disposed so as to surround the pixel area (15a). When the light-blocking member (13) and the pixel area (15a) are viewed from the transparent substrate (14) side, the minimum spacing (Smin) between the light-blocking member (13) and the pixel area (15a) is more than 100 μm. When the light-blocking member (13) and the pixel area (15a) are viewed from the transparent substrate (14) side, the maximum spacing (Smax) between the light-blocking member (13) and the pixel area (15a) is less than or equal to 1600 μm.

Description

Solid-state imaging device and its manufacturing method

The present invention relates to a solid-state imaging device and a manufacturing method thereof.

Solid-state imaging devices that make up image sensors such as CMOS sensors and CCD sensors are used in digital cameras and smartphones, and in recent years, with the spread of surveillance cameras in automobiles and factories, their usage has increased and they have also become smaller.・Higher definition is increasingly required.

A solid-state imaging device has, for example, a hollow structure in which a semiconductor substrate having a pixel area and a glass substrate are bonded together with an adhesive. When strong light enters a solid-state imaging device, optical noise (specifically, flare, ghost, etc.) may occur in the captured image due to the generated stray light. In order to suppress the generation of optical noise, a method has been taken to suppress the intrusion of light into areas other than the imaging area of a solid-state imaging device by forming a light shielding material on a glass substrate (for example, Patent Document 1 reference).

US Patent No. 10312276

However, using only the technique described in Patent Document 1, it is difficult to suppress the reflection of the light shielding material while suppressing the generation of optical noise.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a solid-state imaging device and a method for manufacturing the same that can suppress reflections in a light-shielding material while suppressing the generation of optical noise. .

<Aspects of the present invention>
The present invention includes the following aspects.

[1] A solid-state imaging device comprising a base material, a frame, a frame-shaped light shielding material, and a transparent substrate in this order,
The base material includes a semiconductor substrate provided with a pixel area,
The frame is arranged to surround the pixel area,
When the light shielding material and the pixel area are viewed from the transparent substrate side, the minimum distance between the light shielding material and the pixel area is more than 100 μm, and the maximum distance between the light shielding material and the pixel area is 1600 μm or less. A solid-state imaging device.

[2] The base material further includes a mounting board on which the semiconductor substrate is mounted,
The frame is a frame-like member,
The frame member is arranged to surround the semiconductor substrate,
The solid-state imaging device according to [1], wherein the frame member and the light shielding material are bonded to each other with an adhesive.

[3] The frame is made of a cured adhesive,
The solid-state imaging device according to [1], wherein the base material and the light shielding material are bonded to each other via the frame.

[4] The solid-state imaging according to any one of [1] to [3] above, wherein the angle between the base-side surface of the transparent substrate and the outer wall surface of the light shielding material is less than 90°. Device.

[5] The solid-state imaging device according to any one of [1] to [4], wherein the light shielding material has a transmittance of 5% or less for light at a wavelength of 800 nm.

[6] The solid-state imaging device according to any one of [1] to [5], wherein the light shielding material contains a black pigment or a black dye.

[7] The solid-state imaging device according to any one of [1] to [6], wherein the variation in thickness of the light shielding material is within 10% of the average thickness of the light shielding material.

[8] The solid-state imaging device according to any one of [1] to [7], wherein the line width variation of the light shielding material is within 20 μm.

[9] The solid-state imaging device according to any one of [1] to [8], wherein the shape of the inner peripheral side of the corner of the light shielding material is a curved shape.

[10] The solid-state imaging device according to any one of [1] to [9], wherein the light shielding material is made of a cured product of a photosensitive composition.

[11] A method for manufacturing a solid-state imaging device according to [10], comprising:
A method for manufacturing a solid-state imaging device, comprising forming the light shielding material on one main surface of the transparent substrate by photolithography.

According to the present invention, it is possible to provide a solid-state imaging device and a method for manufacturing the same that can suppress reflection of a light shielding material while suppressing the generation of optical noise.

1 is a plan view showing an example of a solid-state imaging device according to the present invention. 2 is a sectional view taken along line II-II in FIG. 1. FIG. 3 is a partially enlarged sectional view of the solid-state imaging device shown in FIG. 2. FIG. FIG. 7 is a partially enlarged sectional view showing another example of the solid-state imaging device according to the present invention. FIG. 3 is a cross-sectional view showing another example of the solid-state imaging device according to the present invention. FIG. 3 is a cross-sectional view showing another example of the solid-state imaging device according to the present invention. FIG. 2 is a partially enlarged plan view showing an example of a photomask.

Hereinafter, preferred embodiments of the present invention will be described in detail, but the present invention is not limited thereto. In addition, all academic literature and patent literature described in this specification are incorporated herein by reference.

First, the terms used in this specification will be explained. A "polysiloxane compound" is a compound having a polysiloxane structure having siloxane units (Si--O--Si) as constituent elements. Examples of the polysiloxane structure include a chain polysiloxane structure (specifically, a linear polysiloxane structure, a branched polysiloxane structure, etc.) and a cyclic polysiloxane structure. "Alicyclic epoxy group" refers to a functional group formed by bonding one oxygen atom to two adjacent carbon atoms among the carbon atoms constituting an alicyclic structure, for example, 3 , 4-epoxycyclohexyl group, etc. The term "alkali-soluble group" refers to a functional group that increases solubility in an alkaline solution by interacting with or reacting with an alkali. The "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).

If the value of the "thickness" of each layer constituting the solid-state imaging device is not specified, 10 measurement points were randomly selected from an electron microscope image of a cross-section of the solid-state imaging device cut in the thickness direction. It is an arithmetic mean value of 10 measured values obtained by measuring the thickness at 10 measurement points.

The "principal surface" of a layered object (more specifically, a transparent substrate, etc.) refers to a surface perpendicular to the thickness direction of the layered object.

Hereinafter, the compound and its derivatives may be collectively referred to by adding "system" after the compound name. Furthermore, when a polymer name is expressed by adding "system" after the compound name, it means that the repeating unit of the polymer is derived from the compound or its derivative. Furthermore, acrylic and methacrylic may be collectively referred to as "(meth)acrylic". Furthermore, acryloyl and methacryloyl may be collectively referred to as "(meth)acryloyl." The components, functional groups, etc. illustrated in this specification may be used alone, or two or more types may be used in combination, unless otherwise specified.

The drawings referred to in the following explanation mainly schematically show each component for ease of understanding. The above may differ from the actual one. Further, for convenience of explanation, in the drawings to be explained later, the same components as those in the drawings explained earlier may be denoted by the same reference numerals, and the explanation thereof may be omitted.

<First embodiment: solid-state imaging device>
The solid-state imaging device according to the first embodiment of the present invention includes a base material, a frame, a frame-shaped light shielding material, and a transparent substrate in this order. The base material includes a semiconductor substrate provided with a pixel area. The frames are arranged to surround the pixel area. In the first embodiment, when the light shielding material and the pixel area are viewed from the transparent substrate side, the minimum distance between the light shielding material and the pixel area is more than 100 μm. Further, in the first embodiment, when the light shielding material and the pixel area are viewed from the transparent substrate side, the maximum distance between the light shielding material and the pixel area is 1600 μm or less.

The above-mentioned "minimum interval" means the minimum interval between the inner circumference of the light shielding material and the outer circumference of the pixel area when the light shielding material and the pixel area are viewed from the transparent substrate side. The above-mentioned "maximum interval" means the maximum interval between the inner circumference of the light shielding material and the outer circumference of the pixel area when the light shielding material and the pixel area are viewed from the transparent substrate side.

Hereinafter, the minimum distance between the light shielding material and the pixel area when the light shielding material and the pixel area are viewed from the transparent substrate side may be referred to as "minimum distance S _min " or "S _min ." Further, the maximum distance between the light shielding material and the pixel area when the light shielding material and the pixel area are viewed from the transparent substrate side may be described as "maximum distance S _max " or "S _max ".

The solid-state imaging device according to the first embodiment can suppress reflections in the light shielding material while suppressing the generation of optical noise. The reason is assumed to be as follows.

Since the solid-state imaging device according to the first embodiment has S _max of 1600 μm or less, the light shielding material effectively suppresses light from entering into areas other than the imaging area. This suppresses stray light from entering the pixel area, so the solid-state imaging device according to the first embodiment can suppress the generation of optical noise.

Further, in the solid-state imaging device according to the first embodiment, since S _min is more than 100 μm, when the light shielding material and the pixel area are viewed from the transparent substrate side, a sufficient distance is provided between the light shielding material and the pixel area. ing. Therefore, according to the solid-state imaging device according to the first embodiment, it is possible to suppress reflection of the light shielding material in the image.

In the first embodiment, in order to improve the productivity of the solid-state imaging device, S _min is preferably 101 μm or more, more preferably 120 μm or more, even more preferably 150 μm or more, and even more preferably 200 μm or more. It is even more preferable that it is, and it is particularly preferable that it is 300 μm or more.

In the first embodiment, in order to further suppress the occurrence of optical noise, S _max is preferably 1550 μm or less, more preferably 1500 μm or less, even more preferably 1450 μm or less, and 1400 μm or less. It is even more preferable that the diameter is 1300 μm or less, 1200 μm or less, 1100 μm or less, 1000 μm or less, 900 μm or less, 800 μm or less, 700 μm or less, or 600 μm or less.

Note that in the first embodiment, S _min and S _max may be different values or the same value.

[Solid-state imaging device configuration]
Hereinafter, a configuration example of the solid-state imaging device according to the first embodiment will be described with reference to the drawings as appropriate. FIG. 1 to be referred to is a plan view (specifically, a plan view of the light shielding material and the pixel area viewed from the transparent substrate side) showing an example of the solid-state imaging device according to the first embodiment. 2 is a sectional view taken along the line II-II in FIG. 1. 3 is a partially enlarged sectional view of the solid-state imaging device shown in FIG. 2. Referring to FIG.

As shown in FIG. 2, the solid-state imaging device 10 is a laminate including a base material 11, a frame member 12 (frame), a frame-shaped light shielding material 13, and a transparent substrate 14 in this order. The base material 11 includes a semiconductor substrate 15 provided with a pixel area 15a, and a mounting substrate 16 on which the semiconductor substrate 15 is mounted. The frame member 12 is arranged to surround the pixel area 15a and the semiconductor substrate 15. The semiconductor substrate 15 and the mounting substrate 16 are electrically connected via metal wires 18. Solder balls 19 (external connection terminals) are formed on the surface of the mounting board 16 opposite to the semiconductor substrate 15 side.

As shown in FIG. 1, in the solid-state imaging device 10, when the light shielding material 13 and the pixel area 15a are viewed from the transparent substrate 14 side, the minimum distance S _min between the light shielding material 13 and the pixel area 15a is more than 100 μm. Further, in the solid-state imaging device 10, when the light shielding material 13 and the pixel area 15a are viewed from the transparent substrate 14 side, the maximum distance S _max between the light shielding material 13 and the pixel area 15a is 1600 μm or less.

As shown in FIG. 2, the frame member 12 and the light shielding material 13 are bonded together via an adhesive layer 17 (adhesive). The adhesive layer 17 is arranged to cover the outer wall surface of the light shielding material 13 and a part of the end surface of the light shielding material 13 on the base material 11 side, and to surround the light shielding material 13.

The internal space Z surrounded by the base material 11, the frame member 12, the adhesive layer 17, and the transparent substrate 14 may be a sealed space. In this case, the frame member 12 and the adhesive layer 17 function as a partition wall that prevents moisture and dust from entering the effective pixel area.

The shape and dimensions of the pixel area 15a are not particularly limited. As shown in FIG. 1, when the pixel area 15a has a rectangular shape, the length of one side of the pixel area 15a is, for example, 1 mm or more and 100 mm or less, preferably 2 mm or more and 80 mm or less, and more preferably 3 mm or more and 50 mm or less. It is as follows.

The shape of the light shielding material 13 is not particularly limited as long as it is frame-shaped. In FIGS. 1 and 2, the light shielding material 13 having a square cylindrical structure is shown as an example of a frame shape. The light shielding material may have a polygonal cylindrical structure.

When the light shielding material 13 has a polygonal cylindrical structure, in order to obtain a solid-state imaging device with excellent reliability evaluated in a thermal shock test, the shape of the inner peripheral side of the corner 13a (see FIG. 1) of the light shielding material 13 must be adjusted. However, it is preferable that the shape is curved. When the shape of the inner peripheral side of the corner portion 13a of the light shielding material 13 is a curved shape, stress concentration on the corner portion 13a is alleviated during the thermal shock test, and peeling and cracking of the light shielding material 13 can be reduced. In order to obtain a solid-state imaging device with better reliability evaluated in a thermal shock test, it is preferable that the radius of curvature of the inner peripheral side of the corner 13a of the light shielding material 13 is 0.1 mm or more and 1.0 mm or less, It is more preferably 0.2 mm or more and 1.0 mm or less, and even more preferably 0.3 mm or more and 1.0 mm or less.

In order to obtain a solid-state imaging device with even better reliability as evaluated by a thermal shock test, it is preferable that both the inner and outer circumferential sides of the corner portion 13a of the light shielding material 13 have a curved shape. In this case, the radius of curvature on the inner and outer circumferential sides of the corner portion 13a may be the same value or may be different values. The preferred range of the radius of curvature on the outer peripheral side of the corner portion 13a is the same as the preferred range of the radius of curvature on the inner peripheral side of the corner portion 13a.

In order to further suppress the occurrence of optical noise, the height H from the pixel area 15a to the transparent substrate 14 (see FIG. 2) is preferably 5000 μm or less, more preferably 4000 μm or less. Note that the height H from the pixel area 15a to the transparent substrate 14 is the distance between the surface 14a of the transparent substrate 14 on the base material 11 side and the surface of the pixel area 15a. Hereinafter, the height from the pixel area to the transparent substrate may be simply referred to as "height H". In order to suppress contact between the transparent substrate 14 and the wire 18, the height H is preferably 2000 μm or more, more preferably 3000 μm or more.

In order to obtain a solid-state imaging device with excellent reliability evaluated in a thermal shock test, the thickness T (see FIG. 3) of the light shielding material 13 is preferably 100 μm or less, more preferably 80 μm or less, More preferably, it is 50 μm or less. Note that the thickness T of the light shielding material 13 is the height of the light shielding material 13 with respect to the surface 14a of the transparent substrate 14 on the base material 11 side. In order to further suppress the generation of optical noise, the thickness T of the light shielding material 13 is preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more.

In order to further suppress the occurrence of optical noise, it is preferable that the variation in the thickness T of the light shielding material 13 is within 20% of the average thickness of the light shielding material 13, and within 10% of the average thickness of the light shielding material 13. It is more preferable that there be. The lower limit of the variation in the thickness T of the light shielding material 13 is not particularly limited, and may be 0%. The method for measuring the thickness variation (thickness variation) of the light shielding material is the same method as in the examples described later or a method similar thereto.

In order to further reduce the size of the solid-state imaging device and further suppress the generation of optical noise, the line width W (see FIG. 3) of the light shielding material 13 is preferably 50 μm or more and 4000 μm or less, and 100 μm or less. More preferably, the thickness is not less than 3000 μm. In addition, in this specification, "the line width of a light-shielding material" is the line width of the base material side end surface of a light-shielding material.

In order to further suppress the occurrence of optical noise, the variation in the line width W of the light shielding material 13 is preferably within 30 μm, and more preferably within 20 μm. The lower limit of the variation in the line width W of the light shielding material 13 is not particularly limited, and may be 0 μm. Note that in this specification, "variation in line width of the light shielding material (line width variation)" is a value obtained by subtracting the minimum value of the line width of the light shielding material from the maximum value of the line width of the light shielding material. For example, the variation in line width of a light shielding material having a polygonal shape in plan view is the value obtained by subtracting the minimum value of line width from the maximum value of line width on one randomly selected side. The method for measuring the variation in line width of the light shielding material is the same method as in the examples described later or a method similar thereto.

In order to further suppress the generation of optical noise, the transmittance of light at a wavelength of 800 nm of the light shielding material 13 is preferably 5% or less, more preferably 4% or less, and 3% or less. More preferably. The lower limit of the transmittance of the light shielding material 13 for light having a wavelength of 800 nm is not particularly limited, and may be 0%. When the light shielding material 13 contains a black pigment or black dye, the transmittance of the light shielding material 13 for light having a wavelength of 800 nm tends to be low. Therefore, in order to further suppress the occurrence of optical noise, it is preferable that the light shielding material 13 contains a black pigment or a black dye.

In order to obtain a solid-state imaging device with excellent reliability evaluated in a thermal shock test, the angle TA (see FIG. 3) formed by the surface 14a of the transparent substrate 14 on the base material 11 side and the outer wall surface 13b of the light shielding material 13 must be The angle is preferably less than 90°, more preferably 85° or less. In the following description, the angle (angle TA in FIG. 3) formed by the base material side surface of the transparent substrate and the outer wall surface of the light shielding material may be referred to as a "taper angle." When the taper angle is less than 90°, when bonding the light shielding material 13 and the frame-shaped member 12 (or the base material 11) with adhesive, there is no adhesion between the outer wall surface 13b of the light shielding material 13 and the transparent substrate 14. Since it can be filled with a chemical agent, reliability is improved due to the anchor effect. In order to improve the adhesion between the transparent substrate 14 and the light shielding material 13, the taper angle is preferably 60° or more.

Note that the tapered shape of the cross section of the light shielding material 13 does not have to be a linear shape as shown in FIG. 3, but may be a curved shape as shown in FIG. 4. When the tapered shape of the cross section of the light shielding material 13 is a curved shape, a virtual plane VP (see FIG. 4) connecting both ends of the light shielding material 13 in the thickness direction on the outer peripheral side and a surface 14a of the transparent substrate 14 on the base material 11 side. Let the angle TA formed by the angle TA be the taper angle.

Although the configuration example of the solid-state imaging device according to the first embodiment has been described above, the solid-state imaging device according to the first embodiment is not limited to the above configuration example. For example, the solid-state imaging device according to the first embodiment may have a structure in which the frame member is removed from the structure shown in FIG. In this case, the adhesive layer 17 becomes the frame.

Further, the solid-state imaging device according to the first embodiment may be a chip size package type (CSP type) solid-state imaging device 50 as shown in FIG. 5, or a solid-state imaging device 100 having the structure shown in FIG. There may be.

A solid-state imaging device 50 shown in FIG. 5 does not include the frame member 12 used in the solid-state imaging device 10 described above, but includes an adhesive layer 51 made of a cured adhesive as a frame. In the solid-state imaging device 50, the base material 11 and the light shielding material 13 are bonded together with an adhesive layer 51 interposed therebetween. Furthermore, the solid-state imaging device 50 does not include the mounting board 16 used in the solid-state imaging device 10 described above. In the solid-state imaging device 50, since the semiconductor substrate 15 serves as the base material 11, the wire 18 used in the solid-state imaging device 10 described above becomes unnecessary. The solid-state imaging device 50 has a CSP type structure, which has the advantage that the device can be made smaller. Since the solid-state imaging device 50 does not have a mounting board, it is necessary to electrically connect the semiconductor substrate 15 and the solder balls 19 separately. The electrical connection method is not particularly limited, and the connection can be made by known means such as a Si through-silicon via. In order to further suppress the generation of optical noise in the solid-state imaging device 50, the height H is preferably 120 μm or less, more preferably 100 μm or less, and even more preferably 60 μm or less. Further, in the solid-state imaging device 50, in order to suppress the reflection of foreign matter attached to the transparent substrate 14, the height H is preferably 30 μm or more. Other aspects of the solid-state imaging device 50 are the same as the solid-state imaging device 10 described above.

Similar to the solid-state imaging device 50, the solid-state imaging device 100 shown in FIG. 6 does not include the frame member 12, but includes an adhesive layer 51 as a frame. Further, in the solid-state imaging device 100, the base material 11 includes a semiconductor substrate 15 and a mounting board 16, similarly to the solid-state imaging device 10. In the solid-state imaging device 100, the semiconductor substrate 15 and the light shielding material 13 are bonded to each other via an adhesive layer 51, and the area on the outer peripheral side of the adhesive layer 51 (the area including the wire 18) is sealed with a sealing resin 101. It has been stopped. The sealing resin 101 is not particularly limited, but thermosetting resins such as epoxy resins, acrylic resins, and silicone resins are preferable, and epoxy resins are particularly preferable from the viewpoint of the toughness and heat resistance of the resin. From the viewpoint of reducing optical noise, the sealing resin 101 is preferably colored black. In the solid-state imaging device 100, in order to further suppress the generation of optical noise, the height H is preferably 200 μm or less, and more preferably 150 μm or less. Further, in the solid-state imaging device 100, in order to suppress the reflection of foreign matter attached to the transparent substrate 14, the height H is preferably 15 μm or more, and more preferably 30 μm or more. Other aspects of the solid-state imaging device 100 are the same as the solid-state imaging device 10 described above.

[Elements of solid-state imaging device]
Next, elements of the solid-state imaging device according to the first embodiment will be explained.

(Transparent substrate 14)
As the transparent substrate 14, 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 preferable 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 14 is, for example, 50 μm or more and 2000 μm or less.

If necessary, an infrared reflective film (or infrared cut filter), an antireflective film (AR coat), a nonreflective film, a protective film, a reinforced film, a shielding film, a conductive film, an antistatic film, and a low-pass film are applied to the surface of the transparent substrate 14. A coating film having a function of a filter, high-pass filter, band-pass filter, etc. may be formed. In particular, antireflection films and infrared reflective films (or infrared cut filters) are preferable because they further reduce optical noise in captured images.

In particular, when using an antireflection film as a coating film, TiO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , CaF ₂ , SiO ₂ , Al ₂ O ₃ , MgS ₂ , ZrO ₂ , NiO and MgF ₂ It is preferable to use a multilayer antireflection film containing one or more inorganic materials selected from the group consisting of:

These coating films can be provided on one main surface or both main surfaces of the transparent substrate 14. When provided on both main surfaces, the types of coating films may be the same or different. It is also possible to laminate different types of coating films having the same function on one main surface. It is also possible to laminate different types of coatings having different functions on one main surface. The number of laminated layers is not particularly limited either, and can be multilayered from several layers to several tens of layers.

(Light shielding material 13)
Examples of the material of the light shielding material 13 include metals such as chromium and black resin. A black resin is preferable because it can be formed at low cost, and as the black resin, a photosensitive resin (specifically, a black photosensitive resin) whose line width and thickness can be easily controlled by patterning by photolithography is preferable. In other words, the light shielding material 13 is preferably composed of a cured product of a photosensitive composition from the viewpoint of patternability, and from the viewpoint of optical noise reduction and patternability, the light-shielding material 13 is preferably composed of a photosensitive composition containing a black colorant. More preferably, it is made of a cured product.

Next, a photosensitive composition that can be used as a material for the light shielding material 13 will be described. Examples of the photosensitive composition that can be used as a material for the light shielding material 13 include a photosensitive composition that contains a curable compound having a polymerizable group and a photopolymerization initiator and is alkali-soluble. Examples of the polymerizable group include cationic polymerizable groups such as an epoxy group, oxetanyl group, vinyl ether group, and alkoxysilyl group, and radically polymerizable groups having an unsaturated bond capable of radical polymerization. From the viewpoint of storage stability of the photosensitive composition, the cationically polymerizable group is preferably one or more selected from the group consisting of a glycidyl group, an alicyclic epoxy group, and an oxetanyl group; One or more types selected from the group consisting of groups are more preferable. Specific examples of the radically polymerizable group include (meth)acryloyl group, vinyl group, and the like. The curable compound having a polymerizable group may have both a cationically polymerizable group and a radically polymerizable group, or only one of them, in one molecule. Further, a compound having a cationically polymerizable group and a compound having a radically polymerizable group may be used together.

Additionally, the photosensitive composition contains a compound having an alkali-soluble group. Examples of the alkali-soluble group include 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 carboxy group is preferred. Note that the X1 group is a monovalent organic group derived from N-monosubstituted isocyanuric acid. Furthermore, the X2 group is a divalent organic group derived from N,N'-disubstituted isocyanuric acid.

In order to form the light shielding material 13 with excellent heat resistance, the alkali-soluble group is preferably one or more selected from the group consisting of X1 group and X2 group.

In order to form the light shielding material 13 having excellent heat resistance, the photosensitive composition preferably contains a polysiloxane compound as a curable compound, and the photosensitive composition has a cyclic polysiloxane structure as the curable compound. It is more preferable to contain a polysiloxane compound. Examples of photosensitive compositions containing polysiloxane compounds include polysiloxane compounds (specifically, polysiloxanes having a polymerizable group and an alkali-soluble group in one molecule) described in International Publication No. 2023/008534. a second developable composition containing a compound) and a colorant. From the viewpoint of further suppressing the generation of optical noise, the colorant contained in the photosensitive composition for forming the light shielding material 13 is preferably a black pigment or a black dye, more preferably a black pigment, and even more preferably carbon black. preferable.

In order to further suppress the generation of optical noise, the amount of colorant in the photosensitive composition is preferably 3 parts by weight or more, and 4 parts by weight or more based on 100 parts by weight of the curable compound. It is more preferable that the amount is at least 5 parts by weight, and even more preferably 5 parts by weight or more. In order to improve patterning properties by photolithography, the amount of colorant in the photosensitive composition is preferably 10 parts by weight or less based on 100 parts by weight of the curable compound.

(Semiconductor substrate 15)
As a material for the semiconductor substrate 15, for example, a silicon wafer is used. A large number of photodiodes are formed on the semiconductor substrate 15 as light receiving elements, and a color filter layer and a microlens are formed on the photodiodes. The area where the light receiving element is formed is the pixel area 15a. The thickness of the semiconductor substrate 15 is, for example, 50 μm or more and 800 μm or less.

(Mounting board 16)
Examples of the mounting board 16 include organic materials such as polyimide, polyester, epoxy resin, bismaleimide triazine resin, and phenol resin; structures obtained by impregnating paper, glass fiber nonwoven fabric, etc. with the above organic materials and curing them by heating; alumina, nitride, etc. Examples include substrates made of ceramics such as aluminum, beryllium oxide, and silicon nitride, and among these, glass epoxy substrates and ceramic substrates are preferred. On the surface and inside of the mounting board 16, a circuit having a metal wiring pattern and metal bumps is formed.

(Frame-shaped member 12)
As the material of the frame member 12, thermosetting resin (for example, epoxy resin, etc.), ceramic, or the like can be used. The frame member 12 may be bonded to the mounting board 16 with an adhesive in advance, or may be formed on the mounting board 16 by molding or the like.

(Adhesive layer 17 and adhesive layer 51)
The adhesive layer 17 and the adhesive layer 51 are composed of cured adhesives. Examples of adhesives that can be used as materials for the adhesive layer 17 and the adhesive layer 51 include thermosetting adhesives (more specifically, epoxy adhesives, etc.), ultraviolet curable adhesives (more specifically, acrylic adhesives, etc.) agents, etc.). Note that the term "epoxy adhesive" refers to an adhesive containing a compound having an epoxy group (for example, a compound containing at least two epoxy groups in one molecule) as a main ingredient. In addition, "acrylic adhesive" refers to (meth)acrylic acid or its derivatives (more specifically, (meth)acrylic acid ester, etc.), or a polymer of (meth)acrylic acid or its derivatives as the main component. means an adhesive that is

In order to improve the adhesiveness between the light shielding material 13 and the frame member 12 (or the base material 11), an epoxy adhesive is preferably used as the material for the adhesive layer 17 and the adhesive layer 51. In order to further improve the adhesiveness between the light shielding material 13 and the frame member 12 (or the base material 11), the main agent of the epoxy adhesive is preferably an aromatic epoxy compound having two or more epoxy groups, and 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. In order to further improve the adhesion between the light shielding material 13 and the frame-shaped member 12 (or the base material 11), an imidazole-based curing agent is preferable as the curing agent for the epoxy adhesive.

[Preferred embodiment of solid-state imaging device]
In order to obtain a solid-state imaging device that can suppress the generation of optical noise, suppress reflection on the light-shielding material, and has excellent reliability evaluated in a thermal shock test, the solid-state imaging device plate according to the first embodiment is required. preferably satisfies Condition 1 below, more preferably satisfies Condition 2 below, still more preferably satisfies Condition 3 below, and even more preferably satisfies Condition 4 below.
Condition 1: The taper angle is less than 90°, and the shape of the inner peripheral side of the corner of the light shielding material is curved.
Condition 2: Condition 1 above is satisfied, and the transmittance of the light shielding material for light at a wavelength of 800 nm is 5% or less.
Condition 3: Condition 2 above is satisfied, and the variation in the thickness of the light shielding material is within 10% of the average thickness of the light shielding material.
Condition 4: Condition 3 above is satisfied, and the variation in line width of the light shielding material is within 20 μm.

<Second embodiment: Method for manufacturing solid-state imaging device>
Next, a method for manufacturing a solid-state imaging device according to a second embodiment of the present invention will be described. The method for manufacturing the solid-state imaging device according to the second embodiment is a preferred method for manufacturing the solid-state imaging device according to the first embodiment described above. In the following description, the description of content that overlaps with the first embodiment may be omitted.

In the method for manufacturing a solid-state imaging device according to the second embodiment, a light-shielding material is formed on one main surface of a transparent substrate by photolithography using a photosensitive composition. The method of patterning the photosensitive composition on one main surface of the transparent substrate using photolithography is not particularly limited, and for example, the method described in International Publication No. 2023/008534, or the method described in International Publication No. 2022/2022/ The method described in No. 210797 can be adopted. Note that the light shielding material of the solid-state imaging device according to the first embodiment may be formed using a coating means such as a screen printer or a dispenser.

Hereinafter, each process included in an example of the method for manufacturing a solid-state imaging device according to the second embodiment will be described.

[Coating film formation process]
First, a photosensitive composition is applied onto a transparent substrate to form a film (coating film) made of the photosensitive composition. The coating method at this time is not particularly limited, and for example, general coating methods such as spin coating and slit coating can be used. Next, the coating film is heated to remove the solvent in the coating film. The heating temperature of the coating film can be set appropriately, but is preferably 60°C or higher and 200°C or lower.

[Exposure process]
Next, a photomask in which a plurality of transparent areas are formed at predetermined positions is placed on the coating film, and the coating film is irradiated with light. As a result, only the coating film located below the light-transmitting area is exposed to light, and the photocuring reaction proceeds. By changing the width of the thin line in the transparent region, the above-mentioned S _min and S _max can be adjusted. The cumulative exposure amount during exposure is not particularly limited, but is preferably 1 mJ/cm ² or more and 20,000 mJ/cm 2 or less, more preferably 1,000 mJ/cm ^{2 or} more and 15,000 mJ/cm ² or less.

After exposure, baking may be performed at a predetermined temperature if necessary to advance the curing reaction while maintaining the semi-cured state of the coating film.

[Development process]
Next, the exposed coating film is developed. The method of developing the coating film is not particularly limited. For example, by bringing an alkaline developer into contact with the coating film by dipping or spraying, and dissolving and removing the non-exposed areas, the coating film on the transparent substrate is patterned in a semi-cured state, and the semi-cured light-shielding A transparent substrate (hereinafter sometimes referred to as "sample 1") on which a plurality of materials are provided is obtained. As the alkaline developer, commonly used alkaline developers can be used without particular limitation. Specific examples of alkaline developers include organic alkali aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solution and choline aqueous solution; potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution, lithium carbonate aqueous solution, etc. Examples include inorganic alkali aqueous solutions. From the viewpoint of increasing the contrast between exposed areas and non-exposed areas, 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 a surfactant may be added to the alkaline developer for the purpose of adjusting the dissolution rate or the like. Further, after the coating film is brought into contact with the alkaline developer, the coating film may be washed with water. When washing the coating film with water, it is preferable to remove water on the surface of the coating film with compressed air after washing with water. The above-mentioned taper angle can be adjusted by changing the development time of the coating film (for example, the time of immersion in a developer).

[Transparent substrate formation process with light shielding material]
Next, the light shielding material is cured by heating the sample 1 at a temperature of, for example, 150° C. or more and 250° C. or less. Thereby, a transparent substrate (hereinafter sometimes referred to as "sample 2") provided with a plurality of light shielding materials made of a cured product of the photosensitive composition is obtained. Next, by cutting the sample 2 into each light-shielding material using a dicing blade, a laminate having a transparent substrate and a light-shielding material (one light-shielding material) formed on one main surface of this transparent substrate is obtained. (hereinafter sometimes referred to as "transparent substrate with light shielding material") is obtained.

By carrying out the steps from the above-mentioned [coating film formation step] to the above-mentioned [light-shielding material-equipped transparent substrate formation step] under the above-mentioned preferable conditions, variations in the thickness of the light-shielding material and variations in the line width of the light-shielding material can be reduced to the above-mentioned preferable conditions. It can be adjusted within the range.

[Solid-state imaging device formation process]
Next, the obtained transparent substrate with a light-shielding material and a base material (or frame-shaped member) are laminated with an adhesive interposed therebetween, and then the adhesive is cured. In the case of the above lamination, the layers are laminated so that an adhesive is interposed between at least a portion of the base material side end surface of the light shielding material and the base material (or the frame-shaped member). Next, solder balls are formed on the surface of the base material opposite to the transparent substrate side, thereby obtaining the solid-state imaging device according to the first embodiment.

Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

<Synthesis of curable compound P1>
A xylene solution of platinum-vinylsiloxane complex (Pt-VTSC-3X manufactured by Umicore Precious Metals Japan Co., Ltd. 143 μL of a solution containing 3% by weight of platinum was added to obtain a solution S1. Separately, 88 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane was dissolved in 176 g of toluene to obtain a solution S2.

Then, in a nitrogen atmosphere containing 3% by volume of oxygen, solution S2 was heated to a temperature of 105°C, and solution S1 was dropped into solution S2 over 3 hours. After stirring for a minute, solution S3 was obtained. Note that when the reaction rate of alkenyl groups of the compound contained in the obtained solution S3 was measured by ¹ H-NMR, the reaction rate was 95% or more.

Separately, 62 g of 1-vinyl-3,4-epoxycyclohexane was dissolved in 62 g of toluene to obtain solution S4.

Then, in a nitrogen atmosphere containing 3% by volume of oxygen, solution S4 was dropped into solution S3 over 1 hour while heating solution S3 to a temperature of 105°C, and after the dropwise addition was completed, the temperature was maintained at 105°C. After stirring for 30 minutes, solution S5 was obtained. Note that when the reaction rate of alkenyl groups of the compound contained in the obtained solution S5 was measured by ¹ H-NMR, the reaction rate was 95% or more.

Next, after cooling the solution S5, the solvent (toluene, xylene, and 1,4-dioxane) was distilled off from the solution S5 under reduced pressure to obtain a solid content. Next, propylene glycol 1-monomethyl ether 2-acetate was added to the obtained solid content to obtain a solution SP1 containing the curable compound P1 (concentration of the curable compound P1: 70% by weight). The curable compound P1 has a plurality of cationic polymerizable groups (specifically, alicyclic epoxy groups) and a plurality of alkali-soluble groups (specifically, the X2 group) in one molecule, and It was a polysiloxane compound with a cyclic polysiloxane structure in its chain.

<Preparation of photosensitive composition>
100 g of solution SP1 (solution SP1 prepared by the above procedure), 15 g of 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate ("Celoxide (registered trademark) 2021P" manufactured by Daicel), and 21 g After mixing a photocationic polymerization initiator ("SP-606" manufactured by ADEKA Corporation), 1.5 g of 9,10-dipropoxyanthracene, and 4 g of carbon black ("MA100" manufactured by Mitsubishi Chemical Corporation), The viscosity was adjusted to be suitable for coating using propylene glycol 1-monomethyl ether 2-acetate to obtain a photosensitive composition PS1.

<Production of transparent substrate with light shielding material and solid-state imaging device>
Hereinafter, methods for manufacturing transparent substrates with light shielding materials in Examples 1 to 28, Comparative Examples 1 and 2, and methods for manufacturing solid-state imaging devices in Examples 1 to 28, Comparative Examples 1 and 2 will be described.

[Example 2]
(Coating film formation process)
The photosensitive composition PS1 was applied onto a glass substrate (thickness: 0.7 mm) as a transparent substrate using a spin coater, and a coating film composed of the photosensitive composition PS1 was formed on the glass substrate. A laminate was obtained. Next, the first laminate was heated for 10 minutes on a hot plate heated to a temperature of 125°C.

(Exposure process)
Next, using a manual exposure machine (“MA-1300” manufactured by Dainippon Kaken Co., Ltd., lamp: high-pressure mercury lamp), the cumulative exposure amount is The coating film was exposed (specifically, soft contact exposure) by irradiating the coating film of the heated first laminate with light under the condition of 10000 mJ/cm ² . The photomask 200 used had a plurality of transparent regions 201 arranged in a grid pattern. Regarding the dimensions of the light-transmitting area 201, the length _L1 in the longitudinal direction (horizontal direction in FIG. 7) was 15.6 mm, and the length _L2 in the transverse direction (vertical direction in FIG. 7) was 11 mm. . Regarding the line width of the light-transmitting area 201, the line width W ₁ (hereinafter simply referred to as "line width W ₁ ") of the thin line extending in the transverse direction is 2450 μm, and the line width of the thin line extending in the longitudinal direction is 2450 μm. W ₂ (hereinafter simply referred to as "line width W ₂ ") was 2150 μm. Further, the radius of curvature of the inner peripheral side of the four corners of the light-transmitting region 201 (hereinafter referred to as "radius of curvature of the photomask") was 0.3 mm.

(Developing process)
Next, the first laminate after exposure was heated for 10 minutes on a hot plate heated to a temperature of 95°C, and then left for 60 seconds in an atmosphere at a temperature of 25°C, and then a TMAH aqueous solution as an alkaline developer was applied. (TMAH concentration: 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 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 (Sample 1) on which a plurality of semi-cured light shielding materials were provided was obtained. The thickness of the light shielding material of Sample 1 was 15 μm.

(Transparent substrate formation process with light shielding material)
Next, Sample 1 was heated in an oven at a temperature of 200°C for 2 hours to cure the light shielding material, thereby producing a glass substrate (Sample 2) provided with a plurality of light shielding materials made of a cured product of the photosensitive composition. ) was obtained. Next, a dicing film was temporarily attached to the surface of the glass substrate of Sample 2 on which the light shielding material was not provided. Next, using a dicing blade, sample 2 was cut into a size of 22 mm x 18 mm for each light shielding material, and then the dicing film was peeled off and the transparent substrate with light shielding material of Example 2 (sample 2 in pieces) was cut. Obtained.

(Solid-state imaging device formation process)
Next, a second laminate was obtained by laminating the obtained transparent substrate with a light shielding material and a base material via an epoxy adhesive. Note that during lamination, the epoxy adhesive was interposed between a part of the base material side end surface of the light shielding material and the base material. Further, the amount of the epoxy adhesive used was adjusted so that the height H (see FIG. 2) after curing the epoxy adhesive was 3000 μm. As the base material, a semiconductor substrate (size: 14 mm x 9 mm) provided with a pixel area (size: 10 mm x 6 mm) consisting of a light receiving element and a mounting board (size: 22 mm x 18 mm) are laminated via a die bonding material. A base material was used in which the electrode pads on the semiconductor substrate and the electrode pads on the mounting substrate were electrically connected via metal wires. In addition, the epoxy adhesive used contains bisphenol A diglycidyl ether as a base agent, an imidazole hardener as a hardening agent, and the weight ratio of the base agent and hardener (main agent/hardener) is 100/3. It was a thermosetting adhesive.

Next, after heating the second laminate in an oven at a temperature of 200° C. for 2 hours, solder balls were formed on the surface of the mounting board opposite to the semiconductor substrate side to obtain the solid-state imaging device of Example 2. Ta. The solid-state imaging device of Example 2 had a structure in which the frame member was removed from the solid-state imaging device shown in FIG.

[Example 1, Examples 3 to 5, Comparative Example 1 and Comparative Example 2]
Examples 1 and 3 to 5 were prepared in the same manner as in Example 2, except that the line width W ₁ and line width W ₂ of the photomask used in the exposure process were as shown in Table 1 below. , transparent substrates with light shielding materials of Comparative Examples 1 and 2, and solid-state imaging devices of Example 1, Examples 3 to 5, Comparative Examples 1 and 2 were obtained, respectively.

[Examples 6 and 8 to 10]
In the development process, the time (development time) for immersing the first laminate in the TMAH aqueous solution was 45 seconds for Example 6, 50 seconds for Example 8, 75 seconds for Example 9, and 75 seconds for Example 10. Transparent substrates with light-shielding materials in Examples 6 and 8 to 10 and solid-state imaging devices in Examples 6 and 8 to 10 were obtained in the same manner as in Example 2, except that the time was changed to 90 seconds.

[Example 7]
A transparent substrate with a light-shielding material of Example 7 and a solid-state imaging device of Example 7 were obtained in the same manner as in Example 2, except that the steps from the coating film formation step to the development step were performed as described below.

(From the coating film forming step to the developing step of Example 7)
One set of operations from the coating film forming step to the developing step was performed in the same manner as in Example 2, except that the coating amount of photosensitive composition PS1 was adjusted so that the thickness of the light shielding material after the developing step was 5 μm. This operation was repeated for 3 sets. As a result, Sample 1 having a light shielding material with a thickness of 15 μm was obtained.

[Examples 11 to 14]
Same as Example 2 except that the radius of curvature of the photomask used in the exposure process was changed to 0.2 mm for Example 12, 0.5 mm for Example 13, and 1.0 mm for Example 14. Transparent substrates with light shielding materials of Examples 12 to 14 and solid-state imaging devices of Examples 12 to 14 were obtained by the method. In addition, in the exposure process, the transparent material with light shielding material of Example 11 was prepared in the same manner as in Example 2, except that a photomask in which the angles of the inner periphery of the four corners of the light-transmitting area 201 were right angles was used. A substrate and a solid-state imaging device were obtained.

[Example 15]
A transparent glass substrate (thickness: 0.7 mm) was vacuum-adsorbed on the stage of a screen printing machine, and then photosensitive composition PS1 was applied onto a printing mask with a mesh count of 250 lines/inch. The shape and dimensions of the mesh region of the printing mask used were the same as the shape and dimensions of the transparent region of the photomask used in Example 2. Next, the printing mask was installed above the glass substrate with a printing height (clearance) of 30 μm, and the photosensitive composition PS1 was screen printed on the glass substrate at a printing speed of 30 mm/sec. A third laminate on which a printed layer was formed was obtained. Next, the third laminate was heated for 10 minutes on a hot plate heated to 125°C, and then integrated using a manual exposure machine (“MA-1300” manufactured by Dainihon Kaken Co., Ltd., lamp: high-pressure mercury lamp). The printed layer was exposed to light at an exposure amount of 6000 mJ/cm ² . Next, the exposed third laminate was heated for 10 minutes on a hot plate heated to a temperature of 95° C. to obtain a glass substrate (sample 1) provided with a plurality of semi-cured light shielding materials. Thereafter, in the same manner as in Example 2, a transparent substrate with a light shielding material and a solid-state imaging device of Example 15 were obtained.

[Example 16]
By combining an air pulse dispenser ("ML-808GX" manufactured by Musashi Engineering Co., Ltd.) and a tabletop coating robot ("IMAGE MASTER 350PC SMART" manufactured by Musashi Engineering Co., Ltd.), it is possible to coat a transparent glass substrate (thickness: 0.7 mm). The photosensitive composition PS1 was applied to the glass substrate to obtain a fourth laminate in which a coating layer was formed on the glass substrate. When applying the photosensitive composition PS1, a program was used that was set to form the same pattern as the light shielding material of Example 2. Further, the coating conditions were that the discharge amount was 0.00001 mL/sec, the discharge time was 0.1 second, and the discharge pressure was 0.3 MPa. Next, the fourth laminate was heated for 10 minutes on a hot plate heated to 125°C, and then integrated using a manual exposure machine (“MA-1300” manufactured by Dainihon Kaken Co., Ltd., lamp: high-pressure mercury lamp). The coating layer was exposed to light at an exposure amount of 3000 mJ/cm ² . Next, the exposed fourth laminate was heated for 10 minutes on a hot plate heated to 95° C. to obtain a glass substrate (sample 1) provided with a plurality of semi-cured light shielding materials. Thereafter, in the same manner as in Example 2, a transparent substrate with a light shielding material and a solid-state imaging device of Example 16 were obtained.

[Example 17]
A transparent substrate with a light-shielding material and a solid-state imaging device of Example 17 were obtained in the same manner as in Example 16 except that the discharge rate when applying photosensitive composition PS1 with a dispenser was changed to 0.00002 L/sec. .

[Example 18]
First, a photosensitive composition PS2 was obtained in the same manner as the preparation method of the photosensitive composition PS1, except that the amount of carbon black ("MA100" manufactured by Mitsubishi Chemical Corporation) was changed to 6 g. Next, a transparent substrate with a light shielding material and a solid-state imaging device of Example 18 were obtained in the same manner as in Example 2 except that photosensitive composition PS2 was used instead of photosensitive composition PS1.

[Example 19]
First, a photosensitive composition PS3 was obtained in the same manner as the method for preparing the photosensitive composition PS1, except that the amount of carbon black ("MA100" manufactured by Mitsubishi Chemical Corporation) was changed to 3 g. Next, a transparent substrate with a light shielding material and a solid-state imaging device of Example 19 were obtained in the same manner as in Example 2 except that photosensitive composition PS3 was used instead of photosensitive composition PS1.

[Examples 20 and 21]
The line width W ₁ and the line width W ₂ of the photomask used in the exposure process were as described in Table 2 below, and the height after curing the epoxy adhesive in the solid-state imaging device forming process. The same procedure as in Example 2 was followed except that the amount of epoxy adhesive used was adjusted so that H (see Figure 2) was at the height listed in Table 2 below. A substrate and a solid-state imaging device, and a transparent substrate with a light-shielding material and a solid-state imaging device of Example 21 were obtained, respectively.

[Example 23]
The dimensions of the transparent area of the photomask used in the exposure process were set as shown below, the size when cutting sample 2 using a dicing blade was changed to 20 mm x 17 mm, and the size used in the solid-state imaging device formation process was changed. The base material was changed as shown below, and the height H after curing the epoxy adhesive in the solid-state imaging device forming process (see Figure 5) was adjusted to the height listed in Table 2 below. A transparent substrate with a light-shielding material and a solid-state imaging device of Example 23 were obtained in the same manner as in Example 2, except that the amount of epoxy adhesive used was adjusted. Note that the solid-state imaging device of Example 23 had the structure shown in FIG.

(Photomask and base material used in Example 23)
Regarding the dimensions of the light-transmitting region of the photomask used in Example 23, the length in the longitudinal direction (length L 1 in FIG. 7) is 16.2 mm, and the length in the transverse direction (length L ₁ in FIG. 7) is 16.2 mm. L ₂ ) was 11.2 mm. Regarding the line widths of the light-transmitting regions of the photomask used in Example 23, the line width _W1 was 1900 μm, and the line width _W2 was 1400 μm. Further, the radius of curvature of the photomask used in Example 23 was 0.3 mm. In Example 23, a semiconductor substrate (size: 15 mm x 10 mm) provided with a pixel area (size: 12 mm x 8 mm) consisting of a light receiving element was used as the base material. The semiconductor substrate was a substrate having Si through-silicon vias.

[Examples 22, 24 and 25]
The light shielding of Examples 22, 24, and 25 was performed in the same manner as in Example 23, except that the line width W ₁ and the line width W ₂ of the photomask used in the exposure process were as shown in Table 2 described below. A transparent substrate with material and solid-state imaging devices of Examples 22, 24, and 25 were obtained, respectively.

[Examples 26 to 28]
Other than adjusting the amount of epoxy adhesive used in the solid-state imaging device forming process so that the height H (see FIG. 5) after curing the epoxy adhesive becomes the height listed in Table 2 described later. By the same procedure as in Example 23, transparent substrates with light shielding materials of Examples 26 to 28 and solid-state imaging devices of Examples 26 to 28 were obtained, respectively.

<Measurement method and evaluation method>
Next, the measurement method and evaluation method will be explained.

[S _min , S _max , and the radius of curvature of the inner circumferential side of the corner of the light shielding material]
Using a 3D measurement laser microscope ("LEXT (registered trademark) OLS5100" manufactured by Olympus Corporation), S _min , S _max , and the radius of curvature of the inner peripheral side of the corner of the light shielding material ( Hereinafter, the radius of curvature of the light shielding material was measured.

[Taper angle]
The taper angle was measured from an electron microscope image of a cross section (number of samples: 5) obtained by cutting each solid-state imaging device in the thickness direction. The taper angle shown in Tables 1 and 2, which will be described later, is the arithmetic mean value of the five measured values obtained.

[Thickness variation of light shielding material]
For the light shielding material of each transparent substrate with light shielding material, five thickness measurement points were randomly selected, and the thickness of the light shielding material at the selected five locations was measured using a stylus surface profile measuring device (Bruker's "Dektak" (registered trademark)). (Trademark)"). Next, the average thickness T _av (unit: μm) was calculated, which is the average value of the three measured values excluding the maximum value and the minimum value among the obtained measured values at the five locations. Then, from the maximum value T _max (unit: μm) and minimum value T _min (unit: μm) of the above three measurement values and the above average thickness T _av , the thickness variation (unit: %) is calculated using the formula “Thickness variation =100×(T _max −T _min )/T _av ”.

[Line width variation of light shielding material]
For each thin line (randomly selected side) extending in the transverse direction of the light shielding material of each transparent substrate with light shielding material, 5 locations for measuring the line width are randomly selected, and the line widths at the selected 5 locations are measured in 3D. Measurement was performed using a laser microscope ("LEXT (registered trademark) OLS5100" manufactured by Olympus Corporation). Next, line width variation (unit: μm) is calculated from the maximum value W _max (unit: μm) and minimum value W _min (unit: μm) of the measured values at the five locations obtained using the formula “Line width variation = W _max -W _min ”.

[Transmittance of light shielding material]
Regarding the light shielding material of each transparent substrate with a light shielding material, the transmittance of light at a wavelength of 800 nm was measured using an ultraviolet-visible near-infrared spectrophotometer ("V-770" manufactured by JASCO Corporation).

[Ghost index]
For each solid-state imaging device, the number of pixels exceeding a predetermined threshold (1/100 millionth of the brightness of the light source) (hereinafter referred to as After calculating the number of abnormal pixels (hereinafter referred to as "number of abnormal pixels"), 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, and the obtained value was used as a ghost index. When the ghost index was 70 or less, it was evaluated that the occurrence of ghosts could be suppressed. On the other hand, when the ghost index exceeds 70, it was evaluated that the occurrence of ghosts could not be suppressed.

[Reflection of light shielding material]
When measuring the ghost index, the presence or absence of reflection in the image of the light shielding material was checked.

[Reliability evaluation by thermal shock test]
First, each solid-state imaging device was held in a -50°C atmosphere for 30 minutes using a heat shock test device ("Cosmopia (registered trademark) S" manufactured by Hitachi Johnson Controls Air Conditioning Co., Ltd.), and then heated to a 125°C atmosphere. 500 cycles were performed, with 1 cycle consisting of 30 minutes of holding at the lower temperature. Next, the solid-state imaging device was observed from the glass substrate side using an optical microscope, and the number of cracks in the light blocking material and the number of peeling locations in the light blocking material were counted. Then, the reliability was judged according to the following criteria.

(Reliability criteria)
A: The total number of cracks in the light blocking material and the number of peeling locations in the light blocking material is 4 or less.
B: The total number of cracks in the light shielding material and the number of peeling locations in the light shielding material is 5 or more and 10 or less.
C: The total number of cracks in the light blocking material and the number of peeling locations in the light blocking material is 11 or more.

<Results>
Regarding Examples 1 to 28, Comparative Example 1, and Comparative Example 2, the line width W ₁ and line width W ₂ of the photomask used, the height H, S _min , S _max , the radius of curvature of the light shielding material, the taper angle, and the light shielding Tables 1 and 2 show the thickness variation and line width variation of the material, the transmittance of the light shielding material, the ghost index, the presence or absence of reflection in the light shielding material, and the reliability evaluation results by the thermal shock test, respectively. In Table 1, "right angle" means that the angles on the inner peripheral side of the four corners of the light shielding material were all right angles. Moreover, in Table 2, the line width W ₁ and the line width W ₂ of Example 15 are the line widths of the fine lines in the mesh area of the printing mask used. Furthermore, in Table 2, the line width W ₁ and line width W ₂ of Examples 16 and 17 are program setting values.

As shown in Tables 1 and 2, in Examples 1 to 28, S _min was more than 100 μm and S _max was 1600 μm or less. In Examples 1 to 28, the ghost index was 70 or less. Therefore, the solid-state imaging devices of Examples 1 to 28 were able to suppress the occurrence of ghosts. In Examples 1 to 28, there was no reflection of the light shielding material on the image. Therefore, the solid-state imaging devices of Examples 1 to 28 were able to suppress reflections in the light shielding material.

As shown in Table 1, in Comparative Example 1, S _min was 100 μm or less. In Comparative Example 2, S _max exceeded 1600 μm. In Comparative Example 1, there was a reflection of the light shielding material on the image. Therefore, the solid-state imaging device of Comparative Example 1 was unable to suppress the reflection of the light shielding material. In Comparative Example 2, the ghost index was over 70. Therefore, the solid-state imaging device of Comparative Example 2 was unable to suppress the occurrence of ghosts.

From the above results, it was shown that according to the present invention, it is possible to provide a solid-state imaging device that can suppress the reflection of the light shielding material while suppressing the generation of optical noise.

10, 50, 100 Solid-state imaging device 11 Base material 12 Frame-shaped member (frame)
13 Light shielding material 14 Transparent substrate 15 Semiconductor substrate 15a Pixel area 16 Mounting board

Claims (11)

A solid-state imaging device comprising a base material, a frame, a frame-shaped light shielding material, and a transparent substrate in this order,
The base material includes a semiconductor substrate provided with a pixel area,
The frame is arranged to surround the pixel area,
When the light shielding material and the pixel area are viewed from the transparent substrate side, the minimum distance between the light shielding material and the pixel area is more than 100 μm, and the maximum distance between the light shielding material and the pixel area is 1600 μm or less. A solid-state imaging device. The base material further includes a mounting board on which the semiconductor substrate is mounted,
The frame is a frame-like member,
The frame member is arranged to surround the semiconductor substrate,
The solid-state imaging device according to claim 1, wherein the frame member and the light shielding material are bonded to each other via an adhesive. The frame is made of a cured adhesive,
The solid-state imaging device according to claim 1, wherein the base material and the light shielding material are bonded to each other via the frame. The solid-state imaging device according to claim 1, wherein the angle between the base-side surface of the transparent substrate and the outer wall surface of the light shielding material is less than 90°. The solid-state imaging device according to claim 1, wherein the light shielding material has a transmittance of 5% or less for light with a wavelength of 800 nm. The solid-state imaging device according to claim 1, wherein the light shielding material includes a black pigment or a black dye. The solid-state imaging device according to claim 1, wherein the variation in the thickness of the light shielding material is within 10% of the average thickness of the light shielding material. The solid-state imaging device according to claim 1, wherein a variation in line width of the light shielding material is within 20 μm. The solid-state imaging device according to claim 1, wherein the inner peripheral side of the corner of the light shielding material has a curved shape. The solid-state imaging device according to claim 1, wherein the light shielding material is made of a cured product of a photosensitive composition. A method for manufacturing a solid-state imaging device according to claim 10, comprising:
A method for manufacturing a solid-state imaging device, comprising forming the light shielding material on one main surface of the transparent substrate by photolithography.