CN110741288A - Solid-state imaging device - Google Patents

Abstract

The solid-state imaging device includes a first near-infrared cut filter and a solid-state imaging element, and the first near-infrared cut filter includes a glass substrate and a dielectric multilayer film provided on at least one of the glass substrates. The solid-state imaging element includes: a semiconductor substrate; a first light-receiving element provided on the semiconductor substrate; and an optical filter provided on the first light-receiving element. The optical filter has: a color filter layer provided on the first light receiving element; and a second near-infrared cut filter provided on the color filter layer. The first near-infrared cut filter is provided at a position opposite to the second near-infrared cut filter. The number of layers of the dielectric multilayer film is set to be 10 or more and less than 40 layers.

Description

Solid-state imaging device

technical field

The present invention relates to a solid-state imaging device.

Background technique

An imaging device such as a digital camera is equipped with a semiconductor solid-state imaging element such as a Charge Coupled Device (CCD) image sensor or a Complementary Metal Oxide Semiconductor (CMOS) image sensor. The sensitivity of these solid-state imaging elements extends from the visible region to the infrared region. Therefore, in the imaging device, an infrared cut filter for blocking infrared rays is provided between the imaging lens and the solid-state imaging element. With the infrared cut filter, the sensitivity of the solid-state imaging element can be corrected so as to be close to the visual acuity of humans.

For example, Patent Document 1 discloses an infrared cut filter formed by providing a dielectric multilayer film on a glass substrate. In addition, a structure in which a coating layer is provided on a glass substrate and a dielectric multilayer film is provided on the coating layer is disclosed.

prior art literature

Patent Literature

Patent Document 1: International Publication No. 2014/030628

SUMMARY OF THE INVENTION

The problem to be solved by the invention

In the solid-state imaging device described in Patent Document 1, a dielectric multilayer film of a near-infrared cut filter is alternately laminated with a high-refractive-index dielectric film and a low-refractive-index dielectric film. However, when the number of layers of the film used for the near-infrared cut filter increases, the warpage generated in the entire near-infrared cut filter increases. In addition, the number of manufacturing steps is increased, so that the manufacturing cost is increased, and the yield rate is decreased.

Therefore, one of the objectives of the present invention is to provide a high-quality solid-state imaging device with good yield.

technical solutions to problems

A solid-state imaging device according to an embodiment of the present invention includes a first near-infrared cut filter and a solid-state imaging element, and the first near-infrared cut filter includes a glass substrate and a dielectric multilayer film on at least one of the glass substrate. The solid-state imaging element has a semiconductor substrate, a first light-receiving element provided on the semiconductor substrate, and an optical filter provided on the first light-receiving element, and the optical filter has a color filter layer provided on the first light-receiving element , and a second near-infrared cut-off filter arranged on the color filter, the first near-infrared cut-off filter is arranged at a position opposite to the second near-infrared cut-off filter, and the number of layers of the dielectric multilayer film is 10 Set the level above and below 40 levels.

In the above configuration, the glass substrate is a CuO-containing fluorophosphate glass or a CuO-containing phosphate glass.

In the said structure, an optical filter further has a 1st cured film on a 2nd near-infrared cut filter.

In the said structure, an optical filter further has a 2nd cured film between a color filter layer and a 2nd near-infrared cut filter.

In the above configuration, the second light-receiving element provided on the semiconductor substrate and a pass filter layer overlapping the second light-receiving element are further provided.

In the above configuration, the number of layers of the dielectric multilayer films is set to be 20 or more and 30 or less.

In the above configuration, the second near-infrared cut filter includes a cesium tungsten oxide compound, and a compound selected from the group consisting of diiminium-based compounds, squaraine-based compounds, cyanine-based compounds, phthalocyanine-based compounds, and naphthalene-based compounds. At least one organic dye among organic dye-based compounds of cyanine-based compounds, quaterrylene-based compounds, ammonium-based compounds, imine-based compounds, pyrrolopyrrole-based compounds, and ketonium-based compounds.

A solid-state imaging device according to an embodiment of the present invention includes a first near-infrared cut filter and a solid-state imaging element. The first near-infrared cut filter includes a base material and a first dielectric multilayer provided on a first surface of the base material. a film, a resin layer provided on the second surface of the base material, and a second dielectric multilayer film provided on the second surface of the base material via the resin layer, the solid-state imaging device has a semiconductor substrate, a first dielectric layer provided on the semiconductor substrate A light-receiving element, and an optical filter provided on the first light-receiving element, the optical filter having a color filter layer provided on the first light-receiving element, and a second near infrared ray provided on the color filter layer Cut filter, the resin layer of the first near-infrared cut filter is provided at a position opposite to the second near-infrared cut filter, and the number of layers of the first dielectric multilayer film is 10 or more and less than 40 layers. set up.

In the said structure, an optical filter further has a 1st cured film on a 1st near-infrared cut filter.

In the said structure, the optical filter further has a 2nd cured film between the color filter layer and the 1st near-infrared cut filter.

In the above configuration, the second light-receiving element provided on the semiconductor substrate and the filter layer overlapping the second light-receiving element are further provided.

In the above configuration, the number of layers of the first dielectric multilayer films is set to be 20 or more and 30 or less.

In the above configuration, the second near-infrared cut filter includes a cesium tungsten oxide compound, and a compound selected from the group consisting of a diimine-based compound, a squaraine-based compound, a cyanine-based compound, a phthalocyanine-based compound, and a naphthalocyanine-based compound. , at least one organic dye among organic dye-based compounds of quartane-based compounds, ammonium-based compounds, imine-based compounds, pyrrolopyrrole-based compounds, and ketonium-based compounds.

A solid-state imaging device according to an embodiment of the present invention includes a first near-infrared cut filter and a solid-state imaging element, wherein the first near-infrared cut filter includes a resin substrate containing a near-infrared absorber, and at least one of the resin substrate The dielectric multilayer film on the solid-state imaging element has a semiconductor substrate, a first light-receiving element provided on the semiconductor substrate, and an optical filter provided on the first light-receiving element, and the optical filter has a first light-receiving element provided on the first light-receiving element. The color filter layer on the receiving element and the second near-infrared cut-off filter arranged on the color filter layer, the first near-infrared cut-off filter is arranged at a position opposite to the second near-infrared cut-off filter, the dielectric The number of laminations of the laminated film is set to be 10 or more and less than 40 layers. By using together with the second near-infrared cut filter, the incident angle dependence can be reduced.

In the said structure, an optical filter further has a 1st cured film on a 1st near-infrared cut filter.

In the said structure, the optical filter further has a 2nd cured film between the color filter layer and the 1st near-infrared cut filter.

In the above configuration, the second light-receiving element provided on the semiconductor substrate and the filter layer overlapping the second light-receiving element are further provided.

In the above configuration, the number of layers of the dielectric multilayer films is set to be 20 or more and 30 or less.

In the above configuration, the second near-infrared cut filter includes a cesium tungsten oxide compound, and a compound selected from the group consisting of a diimine-based compound, a squaraine-based compound, a cyanine-based compound, a phthalocyanine-based compound, and a naphthalocyanine-based compound. , at least one organic dye among organic dye-based compounds of quartane-based compounds, ammonium-based compounds, imine-based compounds, pyrrolopyrrole-based compounds, and ketonium-based compounds.

effect of invention

According to the present invention, the incident angle dependence can be reduced, and a high-quality solid-state imaging device can be provided with good yield.

Description of drawings

FIG. 1 is a schematic configuration of an example of a solid-state imaging device to which each embodiment of the present invention is applied.

2 is a schematic configuration of an example of a solid-state imaging device to which each embodiment of the present invention is applied.

3 is a schematic configuration of an example of a solid-state imaging device to which each embodiment of the present invention is applied.

FIG. 4A is a diagram showing the configuration of a sample of an example of the present invention.

FIG. 4B is a diagram showing the structure of a sample of an example of the present invention.

FIG. 4C is a diagram showing the configuration of a sample of an example of the present invention.

FIG. 5 is a graph showing the result of measuring the transmittance of a sample according to an example of the present invention.

Detailed ways

(first embodiment)

A cross-sectional view of the solid-state imaging device of the present embodiment is shown in FIG. 1 . As shown in FIG. 1 , the solid-state imaging device 210 includes a solid-state imaging element 110 and a near-infrared cut filter 130 .

[Configuration of solid-state imaging element]

First, the configuration of the solid-state imaging element 110 will be described. The solid-state imaging element 110 includes a semiconductor substrate 111 including a light receiving portion that photoelectrically converts incident light, and an optical filter layer 114 provided on the semiconductor substrate 111 .

The pixel portion 101 is provided on the semiconductor substrate 111 . In the pixel portion 101, a plurality of pixels are arranged in the row direction and the column direction. FIG. 1 shows a cross-sectional view of a plurality of pixels in the row direction.

As shown in FIG. 1 , the pixel unit 101 includes a visible light detection pixel 102 and an infrared light detection pixel 103 . The visible light detection pixel 102 includes first pixels 104 a to 104 c , and the infrared light detection pixel 103 includes a second pixel 105 . In the pixel portion 101 , a semiconductor layer 112 , a wiring layer 113 , an optical filter layer 114 , and a microlens array 115 are stacked on a semiconductor substrate 111 .

As the semiconductor substrate 111 , for example, a silicon substrate or a substrate in which a silicon layer is provided on an insulating layer (a silicon-on-insulator (SOI) substrate) or the like can be used. Furthermore, the semiconductor layer 112 is provided in the semiconductor region of the semiconductor substrate 111 . For example, when the semiconductor substrate 111 is a silicon substrate, the semiconductor layer 112 is included on the upper part of the silicon substrate. In the semiconductor layer 112, photodiodes 106a to 106d are provided corresponding to the respective pixels.

In this specification and the like, the photodiodes 106a to 106c are also referred to as first light receiving elements, and the photodiodes 106d are also referred to as second light receiving elements. Furthermore, the first light-receiving element and the second light-receiving element are not limited to photodiodes, and other elements may be substituted as long as they have the function of generating current or voltage by the photovoltaic effect. Note that, in the semiconductor layer 112, a circuit for acquiring a detection signal from each of the plurality of photodiodes 106a to 106d is formed using active elements such as transistors.

The wiring layer 113 is a layer including wiring such as address lines and signal lines provided in the pixel portion 101 . A plurality of wirings in the wiring layer 113 are separated by an interlayer insulating film, and may be multi-layered. For example, the address lines and the signal lines extend and intersect in the row direction and the column direction, so they can be provided as different layers sandwiching the insulating layer.

The optical filter layer 114 is composed of a plurality of layers having different optical properties. In the present embodiment, color filter layers 107 a to 107 c having transmission bands in the visible light wavelength region are provided on the wiring layer 113 in regions overlapping with the photodiodes 106 a to 106 c . The region overlapping with the photodiode 106d is provided with the infrared filter layer 108 .

A near-infrared cut filter 122 that blocks light in the near-infrared wavelength region and transmits light in the visible ray wavelength region is provided in a region overlapping the color filter layers 107a to 107c. In other words, the near-infrared cut filter 122 is provided on the color filter layer 107 a to the color filter layer 107 c , not on the infrared pass filter layer 108 . That is, the near-infrared cut filter 122 has an opening in the region where the photodiode 106d is provided.

As shown in FIG. 1 , a cured film 121 is provided between the color filter layers 107 a to 107 c , the infrared pass filter layer 108 , and the near-infrared cut filter 122 . By providing the cured film 121, the surface unevenness of the color filter layer 107a - the color filter layer 107c and the infrared pass filter layer 108 can be alleviated, and the near-infrared cut filter 122 can be provided on the flat surface. Thereby, thinning of the near-infrared cut filter 122 can be achieved.

A cured film 123 is further provided on the upper surface of the near-infrared cut filter 122 . The near-infrared cut filter 122 is provided on the light-receiving surfaces of the photodiodes 106a to 106c, not on the light-receiving surfaces of the photodiodes 106d. Therefore, a level difference portion caused by the near-infrared cut filter 122 is formed. However, by providing the cured film 123, the step portion can be filled, and the base surface of the microlens array 115 can be made flat.

The microlens array 115 is provided on the upper surface of the optical filter layer 114 . The position of each microlens of the microlens array 115 corresponds to the position of each pixel, and incident light collected by each microlens is received by each corresponding pixel (specifically, each photodiode). The microlens array 115 can be formed using a resin material, and thus can be formed in an on-chip form. For example, the resin material applied on the cured film 123 can be processed to form the microlens array 115 .

[Near infrared cut filter]

Next, the configuration of the near-infrared cut filter 130 will be described. The near-infrared cut filter 130 has a base material 131 , a dielectric multilayer film 132 , and a dielectric multilayer film 133 . The near-infrared cut filter 130 is provided at a position facing the near-infrared cut filter 122 .

"Substrate"

As the base material 131, a glass base material or a resin base material can be used. As the glass substrate, for example, a quartz glass substrate, a borosilicate glass substrate, a soda glass substrate, or the like can be used. In addition, near-infrared absorbing glass containing CuO-containing fluorophosphate glass or CuO-containing phosphate glass can be used. Using glass containing CuO as the base material 131 is preferable because it has high transmittance to visible light and also has high shielding properties to near-infrared rays.

The thickness of the glass substrate is preferably 30 μm or more and 1000 μm or less, more preferably 50 μm or more and 750 μm or less, and particularly preferably 50 μm or more and 700 μm or less. When the thickness of a glass base material is thinner than 30 micrometers, since a glass base material itself is easily broken, handling may become extremely difficult. Moreover, when a glass base material is thicker than 1000 micrometers, the objective of thinning a near-infrared cut filter may not be achieved.

When the thickness of the glass substrate is within the above range, the near-infrared cut filter can be reduced in size and weight, and can be suitably used for various applications such as solid-state imaging devices. In particular, when used for a lens unit such as a camera module, the lens unit can be reduced in size.

"Dielectric Multilayer Films"

The dielectric multilayer film is a film having a function of reflecting near infrared rays. The dielectric multilayer film may be provided on one side of the substrate 131 or may be provided on both sides. When provided on one side, the manufacturing cost and manufacturing easiness are excellent, and when provided on both sides, a near-infrared cut filter that has high strength and is less likely to be warped can be obtained.

In FIG. 1, the case where the dielectric multilayer film 132 and the dielectric multilayer film 133 are provided on both surfaces of the base material 131 will be described. In addition, the side of the base material 131 facing the light-receiving surface of the solid-state imaging element 110 will be described as the first surface, and the side opposite to the first surface will be described as the second surface.

As the dielectric multilayer film, for example, ceramics can be used. In order to form a near-infrared cut filter utilizing the interference effect of light, it is preferable to use two or more kinds of ceramics having different refractive indices.

In addition, it is preferable to use a noble metal film having absorption in the near-infrared region in consideration of the thickness and the number of layers so as not to affect the transmittance of the near-infrared cut filter. The dielectric multilayer film preferably has a structure in which high-refractive-index material layers and low-refractive-index material layers are alternately laminated.

As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index in the range of 1.7 to 2.5 can be selected. Examples of the material include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, or indium oxide as a main component, and a small amount of titanium oxide is included. , tin oxide and/or cerium oxide, etc.

As the material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index in the range of 1.2 to 1.6 can be selected. Examples of the material include silica, alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

As a method of forming the dielectric multilayer film on the base material 131, for example, a high-refractive-index material layer and a low-refractive-index material layer are alternately laminated by a CVD method, a sputtering method, a vacuum deposition method, or the like. A method of attaching the dielectric multilayer film made of the dielectric layer to the base material 131 using an adhesive, or directly forming the high-refractive index material layer on the base material 131 by a CVD method, a sputtering method, a vacuum evaporation method, etc. A method of a dielectric multilayer film in which low-refractive-index material layers are alternately laminated.

The thickness of each layer of the high-refractive-index material layer and the low-refractive-index material layer is a thickness of 0.1λ to 0.5λ of the near-infrared wavelength λ (nm) to be blocked. If the thickness is outside the above-mentioned range, the product (n×d) of the refractive index (n) and the film thickness (d) is very different from the optical film thickness calculated by λ/4. As a result, the relationship between the optical properties of reflection and refraction tends to collapse, making it difficult to control blocking and transmission of specific wavelengths.

The number of stacks of the dielectric multilayer films 133 provided on the first surface side of the base material 131 is preferably smaller than the number of stacks of the dielectric multilayer films 132 provided on the second surface side. In addition, the number of laminates of the dielectric multilayer films 133 provided on the first surface side of the base material 131 is 10 or less, preferably 7 or less. The number of layers of the dielectric multilayer films 132 provided on the second surface side of the base material 131 is preferably 10 or more and less than 40 layers, more preferably 20 or more and less than 40 layers, and particularly preferably 20 or more layers and below 30 floors.

When the substrate 131 is warped when the dielectric multilayer film 132 or the dielectric multilayer film 133 is vapor-deposited, in order to eliminate such a situation, more dielectric materials may be vapor-deposited on both sides of the substrate 131 . The layered film may be irradiated with radiation such as ultraviolet rays on the surface of the substrate 131 on which the dielectric multilayer film is deposited. In addition, in the case of irradiating radiation, the irradiation may be performed while vapor deposition of the dielectric multilayer film 132 or the dielectric multilayer film 133 is performed, or may be irradiated separately after vapor deposition.

In FIG. 1 , the number of dielectric multilayer films 133 provided on the first surface side of the base material 131 is preferably seven or less layers, for example. In addition, it is preferable that the dielectric multilayer film 132 provided on the second surface side of the base material 131 is, for example, not less than 20 layers and not more than 30 layers. By setting the near-infrared cut filter 130 to such a configuration, the warpage of the near-infrared cut filter 130 as a whole can be reduced. When a resin base material is used as the base material 131, the warpage of the resin base material can be reduced, which is preferable. In addition, the number of layers of the dielectric multilayer film 132 and the number of layers of the dielectric multilayer film 133 can be reduced, thereby reducing the number of manufacturing steps and improving the yield.

1, the case where the dielectric multilayer film 132 and the dielectric multilayer film 133 are provided on both surfaces of the base material 131 has been described, but the embodiment of the present invention is not limited to this. When the base material 131 has sufficient rigidity, the dielectric multilayer film 133 may not be provided on the first surface of the base material 131 and the dielectric multilayer film 132 may be provided on the second surface. By setting the near-infrared cut filter 130 as a configuration in which the dielectric multilayer film 133 is provided only on one side of the base material 131, the number of layers of the entire dielectric multilayer film can be reduced, thus further reducing the number of manufacturing steps and improving Yield.

[Operation of solid-state imaging device]

In the solid-state imaging device 210 shown in FIG. 1 , light is incident through the near-infrared cut filter 130 , whereby near-infrared rays are cut. Next, the light incident through the microlens array 115 passes through the near-infrared cut filter 122 to further cut near-infrared rays, and the visible light enters the color filter layers 107a to 107c. On the other hand, in the infrared light detection pixel 103 , the infrared filter layer 108 is directly incident.

In the first pixel 104a to the first pixel 104c, regarding the light in the visible light wavelength region incident on the color filter layer 107a to the color filter layer 107c, the visible light transmitted according to the respective optical characteristics is incident on the photodiode 106a to photodiode 106c. Thereby, visible light rays can be detected with high accuracy without being affected by noise caused by near infrared rays. In the second pixel 105, the infrared filter layer 108 blocks the light in the visible light wavelength region, and the light in the infrared wavelength region (especially the near-infrared wavelength region) enters the photodiode 106d. Thereby, near-infrared rays can be detected with high accuracy without being affected by noise or the like caused by visible light.

In the solid-state imaging device 210 of the present embodiment, a near-infrared cut filter 122 is provided on the solid-state imaging element 110 , and a near-infrared cut filter 130 is further provided on the near-infrared cut filter 122 . Near-infrared rays can be cut off even by a near-infrared cut filter provided on the solid-state imaging element 110 . Thereby, the number of layers of the dielectric multilayer film 132 and the dielectric multilayer film 133 can be reduced. The warpage of the near-infrared cut filter 130 can be reduced by reducing the number of layers of the dielectric multilayer film 132 and the dielectric multilayer film 133 . In addition, the number of layers of the dielectric multilayer film 132 and the dielectric multilayer film 133 can be reduced, so that the manufacturing steps can be reduced and the yield can be improved.

Next, each layer provided in the optical filter layer 114 will be described in detail.

"Color Filter Layer"

The color filter layer 107a to the color filter layer 107c are filters that transmit visible rays of different wavelength ranges, respectively. For example, the color filter layer 107a may be formed by a filter that transmits light in the wavelength range of red light (approximately wavelengths of 610 nm to 780 nm), and the color filter layer 107b may be configured by transmitting green light (approximately wavelengths of 500 nm to 570 nm). The color filter layer 107c can be configured by a filter that transmits light in the wavelength range of blue light (approximately wavelengths of 430 nm to 460 nm). The transmitted light from the color filter layer 107a to the color filter layer 107c is incident on each of the plurality of photodiodes.

The color filter layer 107a - the color filter layer 107c can be formed by the composition which contains the pigment (pigment or dye) which has absorption in a specific wavelength range in resin materials, such as a binder resin and a hardening|curing agent. Such dyes may be used alone or in combination of two or more.

When the photodiode is a silicon photodiode, it has sensitivity over a wide range from the visible light wavelength region to the infrared wavelength region. Therefore, by providing the color filter layers 107a to 107c corresponding to the photodiodes, the color filter layers 107a to 107c can be provided in a plurality of pixels corresponding to various colors.

"Infrared filter layer"

The infrared filter layer 108 is a filter that transmits at least light in the near-infrared wavelength region. The infrared filter layer 108 can be formed by adding a pigment (pigment or dye) having absorption at a wavelength in the visible light wavelength region to a binder resin, a polymerizable compound, or the like. The infrared filter layer 108 has the following spectral transmission characteristics: it absorbs (cuts off) light with a wavelength of approximately less than 700 nm, preferably less than 750 nm, more preferably less than 800 nm, and transmits light with a wavelength of 700 nm or more, preferably 750 nm or more, More preferably, it is light of 800 nm or more.

The infrared filter layer 108 blocks light of a predetermined wavelength (for example, a wavelength of less than 750 nm) as described above, and transmits near-infrared rays in a predetermined wavelength region (for example, 750 nm to 950 nm), and the near-infrared rays can be incident on the photoelectric Diode 106d. Thereby, the photodiode 106d can detect near-infrared rays with high accuracy without being affected by noise or the like caused by visible light. In this way, by providing the infrared filter layer 108, the second pixel 105 can be used as the pixel 103 for infrared light detection. The infrared filter layer 108 can be formed using, for example, the photosensitive composition described in Japanese Patent Laid-Open No. 2014-130332.

"Near Infrared Cut Filter"

The near-infrared cut filter 122 is a filter that transmits light in the visible ray wavelength region and blocks light in the near-infrared wavelength region. The near-infrared cut filter 122 preferably contains a compound (hereinafter, also referred to as an "infrared absorber") having a maximum absorption wavelength within a wavelength range of 600 nm to 2000 nm. For example, an infrared absorber and a binder selected from An infrared absorbing composition of at least one of a resin and a polymerizable compound is formed.

＜Infrared absorber＞

As the infrared absorber, for example, a diimine-based compound, a squaraine-based compound, a cyanine-based compound, a phthalocyanine-based compound, a naphthalocyanine-based compound, a quartane-based compound, and an ammonium-based compound can be used. , imine-based compounds, azo-based compounds, anthraquinone-based compounds, porphyrin-based compounds, pyrrolopyrrole-based compounds, oxocyanine-based compounds, ketonium-based compounds, hexavalent porphyrin-based compounds, metal dithiols At least one compound in the group consisting of a series compound, a copper compound, a tungsten compound, and a metal boride. These can be used alone or in combination of two or more.

Compounds that can be used as infrared absorbers are exemplified below.

Specific examples of the diimine (diimine)-based compound include, for example, International Publication No. 2007/148595, Japanese Patent Laid-Open No. 2011-038007, Paragraph [0118] of International Publication No. 2011/118171, and the like. Compounds described, etc. Examples of commercially available products include EPOLIGHT series such as EPOLIGHT 1178 (manufactured by Epolin), CIR-108X series such as CIR-1085, and CIR-96X series (Japan Carlit (Carlit) Co., Ltd.), IRG022, IRG023, PDC-220 (Nippon Kayaku Co., Ltd.) and the like.

Specific examples of the squaraine ylide-based compound include compounds described in paragraph [0178] of Japanese Patent Laid-Open No. 1-228960 and Japanese Patent Laid-Open No. 2012-215806, for example.

Specific examples of cyanine-based compounds include those described in paragraph [0160] of JP 2012-215806 A, paragraphs [0047] to [0049] in JP 2013-155353 A, and the like. compound. As commercially available products, for example, Daito chmix 1371F (manufactured by Daito Chemix), NK series such as NK-3212 and NK-5060 (Hashihara Institute of Biochemistry) can be mentioned. manufacture) etc.

Specific examples of the phthalocyanine-based compound include, for example, Japanese Patent Laid-Open No. 2004-18561, Japanese Patent Laid-Open No. 2005-220060, Japanese Patent Laid-Open No. 2007-169343, and Japanese Patent Laid-Open No. 2013-195480 Compounds and the like described in paragraphs [0026] to [0027] of Gazette No. Examples of commercially available products include FB series such as FB-22 and 24 (manufactured by Yamada Chemical Industry Co., Ltd.), Excolor series, Excolor TX-EX720, Excolor (Excolor) Excolor) 708K (manufactured by Nippon Catalyst), Lumogen IR788 (manufactured by BASF), ABS643, ABS654, ABS667, ABS670T, IRA693N, IRA735 (manufactured by Exciton), etc.

Specific examples of the naphthalocyanine-based compound include compounds described in paragraphs [0046] to [0049] of Japanese Patent Laid-Open No. 2009-215542, for example.

The copper compound is preferably a copper complex, and specific examples thereof include compounds described in Japanese Patent Laid-Open No. 2014-139616, Japanese Patent Laid-Open No. 2014-139617, and the like.

The tungsten compound is preferably a tungsten oxide compound, more preferably cesium tungsten oxide or rubidium tungsten oxide, and still more preferably cesium tungsten oxide. As a composition formula of tungsten cesium oxide, Cs _0.33 WO ₃ etc. are mentioned, and as a composition formula of tungsten rubidium oxide, Rb _0.33 WO ₃ etc. are mentioned. The tungsten oxide-based compound can also be obtained as a dispersion of tungsten fine particles such as YMF-02A manufactured by Sumitomo Metal Mining Co., Ltd., for example.

Specific examples of metal borides include compounds described in paragraph [0049] of Japanese Patent Laid-Open No. 2012-068418 and the like. Among them, lanthanum boride is preferable.

Furthermore, when the infrared absorber is soluble in an organic solvent disclosed later, it can be laked and used as an infrared absorber that is insoluble in an organic solvent. A known method can be adopted as a method of lake formation, and for example, Japanese Patent Laid-Open No. 2007-271745 and the like can be referred to.

Among such infrared absorbers, those selected from the group consisting of diimine-based compounds, squaraine-based compounds, cyanine-based compounds, phthalocyanine-based compounds, naphthalocyanine-based compounds, quartane-based compounds, At least one of the group consisting of organic dye-based compounds such as ammonium-based compounds, imine-based compounds, pyrrolopyrrole-based compounds, ketonium-based compounds, metal dithiol-based compounds, and inorganic compounds such as copper compounds and tungsten compounds kind. Among these, in particular, the combination of a cesium tungsten oxide compound and a compound selected from the group consisting of diimine-based compounds, squaraine-based compounds, cyanine-based compounds, phthalocyanine-based compounds, naphthalocyanine-based compounds, and quartane-based compounds At least one organic dye among the organic dye-based compounds of ammonium-based compounds, imine-based compounds, pyrrolopyrrole-based compounds, and ketonium-based compounds exhibits high blocking properties in the infrared absorption region, so It is preferable for the above-mentioned aspects.

By such an embodiment, the infrared rays incident on the light receiving element can be blocked more efficiently.

In addition, if the kind and content ratio of the infrared absorber in the near-infrared cut filter 122 are constant, the more the film thickness is increased, the more the infrared absorption characteristics can be improved. Thereby, the solid-state imaging device can obtain a higher S/N ratio, and can perform high-sensitivity imaging. However, if the film thickness of the near-infrared cut filter 122 is increased, there is a problem that the thinning of the solid-state imaging device 230 cannot be achieved. If the near-infrared cut filter 122 is thinned in order to reduce the thickness of the solid-state imaging device, there is a problem that the infrared blocking capability is lowered and the visible light detection pixels are easily affected by noise caused by infrared rays.

On the other hand, when the content ratio of the infrared absorber is increased, for example, the ratio of the polymerizable compound, which is one of the other components forming the near-infrared cut filter, decreases, and the hardness of the near-infrared cut filter 122 decreases. In this way, the optical filter layer 114 becomes brittle, and the layer in contact with the near-infrared cut filter 122 is peeled off, or cracks are generated. For example, there exists a problem that the adhesiveness of the cured film 121 and the cured film 123 in contact with the near-infrared cut filter 122 falls and peels easily.

In the near-infrared cut filter 122, the ratio of the infrared absorber selected from the above is preferably 0.1 to 80% by mass, more preferably 1 to 70% by mass, and still more preferably 3% by mass -60 mass % is suitable.

Furthermore, in the case of producing a near-infrared cut filter using an infrared-absorbing composition, the preferable content ratio of the infrared absorber with respect to the total solid mass of the infrared-absorbing composition is the same as that of the near-infrared cut filter 122. The proportion of infrared absorber in the same is the same. The solid content in this case is a component other than the solvent which comprises an infrared absorbing composition.

Hereinafter, other components constituting the infrared-absorbing composition that can be preferably used for producing the near-infrared cut filter 122 of the present invention will be described.

＜Binder resin＞

The infrared absorbing composition preferably contains a binder resin. The binder resin is not particularly limited, but is preferably at least one selected from the group consisting of acrylic resins, polyimide resins, polyamide resins, polyurethane resins, epoxy resins, and polysiloxanes. A sort of.

First, the acrylic resin will be described. Among acrylic resins, acrylic resins having acidic functional groups such as a carboxyl group and a phenolic hydroxyl group are preferable. By using an acrylic resin having an acidic functional group, when exposing the near-infrared cut filter obtained from the infrared-absorbing composition into a predetermined pattern, it is possible to more reliably remove unexposed light with an alkaline developing solution part, and can form a more excellent pattern by alkali development. The acrylic resin having an acidic functional group is preferably a polymer having a carboxyl group. By using a polymer having a carboxyl group, an infrared absorbing composition excellent in alkali developability and coating film formation can be obtained.

Specific examples of polymers having such a carboxyl group include copolymers disclosed in Japanese Patent Laid-Open No. 11-258415, Japanese Patent Laid-Open No. 2000-56118, and Japanese Patent Laid-Open No. 2004-101728, for example. thing.

In addition, as disclosed in, for example, Japanese Patent Laid-Open No. 11-140144, Japanese Patent Laid-Open No. 2008-181095, etc., a polymer containing a polymerizable unsaturated group such as a (meth)acryloyl group in a side chain may be added. A polymer of carboxyl groups is used as a binder resin. Thereby, the near-infrared cut filter 122 excellent in the adhesiveness with a cured film can be formed.

As a carboxyl group-containing polymer which has a polymerizable unsaturated group in a side chain, the polymer of following (a)-(d) is mentioned, for example.

(a) a polymer obtained by reacting an unsaturated isocyanate compound with a copolymer of a monomer comprising an unsaturated monomer (1) and a polymerizable unsaturated compound having a hydroxyl group,

(b) a (co)polymer obtained by reacting a polymerizable unsaturated compound having an oxetanyl group with a (co)polymer of a monomer containing the unsaturated monomer (1),

(c) a polymer obtained by reacting an unsaturated monomer (1) with a copolymer of a monomer comprising a polymerizable unsaturated compound having an oxanyl group and an unsaturated monomer (1),

(d) (co)polymerization obtained by reacting an unsaturated monomer (1) with a (co)polymer of a monomer containing a polymerizable unsaturated compound having an oxetanyl group, and further reacting a polybasic acid anhydride body.

In addition, the "(co)polymer" in this specification is a term including a polymer and a copolymer.

The weight average molecular weight (Mw) of the acrylic resin in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as "GPC (Gel Permeation Chromatography)") is usually 1,000 to 100,000, preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. Moreover, the ratio (Mw/Mn) of Mw and a number average molecular weight (Mn) is 1.0-5.0 normally, Preferably it is 1.0-3.0. By setting it as such an embodiment, the near-infrared cut filter excellent in sclerosis|hardenability and adhesiveness can be formed. In addition, Mw and Mn mentioned here mean the weight average molecular weight and number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran).

From the viewpoint of the adhesiveness with the cured film, the acid value of the acrylic resin having an acidic functional group is preferably 10 mgKOH/g to 300 mgKOH/g, more preferably 30 mgKOH/g to 250 mgKOH/g, and still more preferably 50 mgKOH/g to 50 mgKOH/g. 200 mgKOH/g. According to such an embodiment, since a near-infrared cut filter with a low contact angle and excellent wettability can be formed, the adhesiveness with the cured film can be improved. Here, the term "acid value" in this specification is the number of mg of KOH required to neutralize 1 g of the acrylic resin having an acidic functional group.

The acrylic resin can be produced by a known method, but can also be produced by a method disclosed in, for example, Japanese Patent Laid-Open No. 2003-222717, Japanese Patent Laid-Open No. 2006-259680, International Publication No. 2007/029871 Pamphlet, and the like to control its structure or Mw, Mw/Mn.

Specific examples of polyamide resins and polyimide-based resins include compounds described in paragraphs [0118] to [0120] of Japanese Patent Laid-Open No. 2012-189632.

The polyurethane resin is not particularly limited as long as it has a urethane bond as a repeating unit, and can be produced by the reaction of a diisocyanate compound and a diol compound. As a diisocyanate compound, the compound described in the paragraph [0043] of Unexamined-Japanese-Patent No. 2014-189746 is mentioned. As a diol compound, the compound described in the paragraph [0022] of Unexamined-Japanese-Patent No. 2014-189746 is mentioned, for example.

The epoxy resins include bisphenol-type epoxy resins, hydrogenated bisphenol-type epoxy resins, and novolak-type epoxy resins, and among them, bisphenol-type epoxy resins and novolak-type epoxy resins are preferable.

Such an epoxy resin can be obtained as a commercial item, for example, the commercial item described in the paragraph [0121] of the specification of Japanese Patent No. 5213944 is mentioned.

The polysiloxane is preferably a hydrolysis condensate of a hydrolyzable silane compound. As the hydrolyzable silane compound, a hydrolyzable silane compound having an oxetanyl group, an oxetanyl group, an episulfide group, a vinyl group, an allyl group, a (meth)acryloyl group, a carboxyl group, or the like can be preferably used.

Specific examples of such hydrolyzable silane compounds include compounds described in paragraphs [0047] to [0051] and [0060] to [0069] of JP-A-2010-055066.

Polysiloxanes can be synthesized by known methods. Mw by GPC is usually 500 to 20,000, preferably 1,000 to 10,000, more preferably 1,500 to 7,000, and still more preferably 2,000 to 5,000. In addition, Mw/Mn is preferably 1.0 to 4.0, and more preferably 1.0 to 3.0. By setting it as such an embodiment, it is excellent in coatability, and sufficient adhesiveness can be expressed.

In one Embodiment of this invention, a binder resin can be used individually or in mixture of 2 or more types. Among them, the binder resin constituting the infrared absorbing composition is preferably an acrylic resin, a polyimide resin, a polyamide resin, an epoxy resin, from the viewpoint of forming a near-infrared cut filter excellent in adhesion to the cured film. The resin and polysiloxane are more preferably acrylic resin, polyimide resin, polyamide resin, and epoxy resin, and still more preferably acrylic resin.

In one embodiment of the present invention, the content of the binder resin is usually 5 parts by mass to 1,000 parts by mass, preferably 10 parts by mass to 500 parts by mass, and more preferably 20 parts by mass to 100 parts by mass of the infrared absorber. 150 parts by mass. By setting it as such an embodiment, the infrared absorbing composition excellent in coatability and storage stability can be obtained, and when alkali developability is imparted, an infrared absorbing composition excellent in alkali developability can be obtained.

<Polymerizable compound>

The infrared absorbing composition preferably contains a polymerizable compound (except for the binder resin). The term "polymerizable compound" in this specification refers to a compound having two or more groups capable of being polymerized. The molecular weight of the polymerizable compound is 4,000 or less, more preferably 2,500 or less, and still more preferably 1,500 or less. Examples of the polymerizable group include ethylenically unsaturated groups, oxetanyl groups, oxetanyl groups, N-hydroxymethylamino groups, N-alkoxymethylamino groups, and the like. In the present invention, the polymerizable compound is preferably a compound having two or more (meth)acryloyl groups, or a compound having two or more N-alkoxymethylamino groups.

Among these polymerizable compounds, compounds having two or more (meth)acryloyl groups and compounds having two or more N-alkoxymethylamino groups are preferable, and trivalent or higher aliphatic polyhydroxy groups are more preferable. Polyfunctional (meth)acrylates obtained by reacting compounds with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, and alkylene oxide-modified polyfunctional (meth)acrylic acids Esters, polyfunctional (meth)acrylic urethanes, polyfunctional (meth)acrylates with carboxyl groups, N,N,N',N',N",N"-hexa(alkoxymethyl) Melamine, N,N,N',N'-tetra(alkoxymethyl)benzoguanamine (N,N,N',N'-tetra(alkoxymethyl)benzoguanamine), more preferably trivalent or higher Polyfunctional (meth)acrylates obtained by reacting aliphatic polyhydroxy compounds with (meth)acrylic acid, polyfunctional (meth)acrylates modified with alkylene oxide, polyfunctional (meth)acrylic urethanes Esters, polyfunctional (meth)acrylates having carboxyl groups. The near-infrared cut filter is excellent in strength and surface smoothness, and when alkali developability is imparted to the infrared-absorbing composition, it is difficult to generate scum, film residue, etc. on the substrate of the unexposed portion. Among polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate are particularly preferred Among acrylates, dipentaerythritol hexaacrylate, and alkylene oxide-modified polyfunctional (meth)acrylates, triglycerides modified with at least one selected from ethylene oxide and propylene oxide are particularly preferred. Methylol propane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate modified by at least one selected from ethylene oxide and propylene oxide, by selected from ethylene oxide and cyclic Dipentaerythritol penta(meth)acrylate modified with at least one of oxypropylene, dipentaerythritol hexa(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide Among the polyfunctional (meth)acrylates having a carboxyl group, compounds obtained by reacting pentaerythritol triacrylate and succinic anhydride, and compounds obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride are particularly preferred. In one Embodiment of this invention, a polymerizable compound can be used individually or in mixture of 2 or more types.

The content of the polymerizable compound in one embodiment of the present invention is preferably 10 parts by mass to 1,000 parts by mass, more preferably 15 parts by mass to 500 parts by mass, and preferably 20 parts by mass to 150 parts by mass with respect to 100 parts by mass of the infrared absorber share. By setting it as such an embodiment, sclerosis|hardenability and adhesiveness can be improved further.

＜Solvent＞

The infrared absorbing composition is usually prepared as a liquid composition by mixing a vehicle. The solvent can be appropriately selected and used as long as it disperses or dissolves the components constituting the infrared absorbing composition, and does not react with these components and has moderate volatility.

Among these solvents, from the viewpoint of solubility, coatability, etc., (poly)alkanediol monoalkyl ethers, lactic acid alkyl esters, (poly)alkanediol monoalkyl ether acetates, Other ethers, ketones, diacetates, alkoxycarboxylates, and other esters, particularly preferably propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, etc.

In one Embodiment of this invention, a solvent can be used individually or in mixture of 2 or more types.

The content of the solvent is not particularly limited, but the total concentration of the components other than the solvent in the infrared absorbing composition is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. By setting it as such an embodiment, the infrared absorbing composition with favorable coatability can be obtained.

＜Sensitizer＞

A photosensitizer may be contained in the infrared-absorbing composition of the present invention. Here, the term "sensitizer" in the present specification refers to a compound having a property of changing the solubility of the infrared absorbing composition in a solvent by light irradiation. As such a compound, a photoinitiator, an acid generator, etc. are mentioned, for example. The photosensitizers may be used alone or in combination of two or more.

The photopolymerization initiator is not particularly limited as long as it can generate an acid or a radical by light, and examples thereof include thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, and triazine-based compounds. Compounds, O-acyl oxime-based compounds, onium salt-based compounds, benzoin-based compounds, benzophenone-based compounds, α-diketone-based compounds, polynuclear quinone-based compounds, bisazo-based compounds, imide sulfonate-based compounds compounds, etc. The photopolymerization initiators may be used alone or in combination of two or more.

The acid generator is not particularly limited as long as it is a compound that generates an acid by heat or light, and examples thereof include onium salts such as sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts, and N-hydroxyimides. Sulfonate compounds, oxime sulfonates, o-nitrobenzyl sulfonates, quinonediazide compounds, and the like. The acid generator may be used alone or in combination of two or more. Specific examples of the oxime sulfonate include compounds described in paragraphs [0122] to [0131] of JP-A No. 2014-115438. Specific examples of the quinonediazide compound include compounds described in paragraphs [0040] to [0048] of JP 2008-156393 A, and paragraph [0172] in JP 2014-174406 A. ] to the compound described in paragraph [0186].

In the solid content of the infrared absorbing composition, the content of the sensitizer is preferably 0.03% by mass to 10% by mass, more preferably 0.1% by mass to 8% by mass, and still more preferably 0.5% by mass to 6% by mass. By setting it as such an embodiment, sclerosis|hardenability and adhesiveness can be made more favorable.

＜Dispersant＞

A dispersant may be contained in the infrared absorbing composition. Examples of dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyalkylene alkyl ether-based dispersants, polyoxyalkylene alkylphenyl ether-based dispersants, Poly(alkylene glycol) diester-based dispersants, sorbitan fatty acid ester-based dispersants, polyester-based dispersants, (meth)acrylic-based dispersants, and the like.

Among these, in the case of imparting alkali developability to the infrared-absorbing composition, a dispersant containing a repeating unit having an alkylene oxide structure is preferable from the viewpoint of forming the near-infrared cut filter 122 with less development residue.

A dispersing agent can be used individually or in mixture of 2 or more types. The content of the dispersant is preferably 5 parts by mass to 200 parts by mass, more preferably 10 parts by mass to 100 parts by mass, and still more preferably 20 parts by mass to 70 parts by mass with respect to 100 parts by mass of the total solid content of the infrared absorbing composition. .

＜Additives＞

The infrared absorbing composition may contain various additives as needed. Examples of additives include fillers such as glass and alumina, polymer compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate), and surfactants such as fluorine-based surfactants and silicon-based surfactants. Accelerators, Antioxidants, etc.

"hardened film"

The cured film 144 may be provided between the color filter layers 107 a to 107 c and the microlens array 115 . The cured film 144 preferably has light transmittance in both the visible light wavelength region and the infrared wavelength region. The light incident through the microlens array 115 passes through the near-infrared cut filter 122 , the infrared pass filter layer 108 , the color filter layer 107 a to the color filter layer 107 c , and light in a specific wavelength range enters the photodiodes 106 a to 107 c In the photodiode 106d, it is preferable that in the optical path of the incident light, the light is not attenuated as much as possible in the regions other than the various filter layers.

In addition, it is preferable that the cured film 144 has insulating properties, for example, in order not to generate parasitic capacitance with the wiring layer 113 . Since the cured film 144 is provided on the substantially front surface of the optical filter layer 114 , if the cured film 144 has conductivity, an inadvertent parasitic capacitance will be generated between the cured film 144 and the wiring layer 113 . If the parasitic capacitance is generated, the detection operation of the photodiodes 106a to 106d will be hindered, so the cured film 144 preferably has insulating properties.

Moreover, it is expected that the cured film 144 has excellent adhesiveness with the layer in contact with the cured film 144 . For example, when the adhesiveness between the cured film 144 and the near-infrared cut filter 122 is poor, peeling occurs and the optical filter layer 114 is damaged.

Furthermore, the cured film 144 is embedded in the near-infrared cut filter 122, the infrared filter layer 108, the color filter layers 107a to 107c, and the like, and the microlens array 115 is provided thereon. flattened. That is, it is preferable that the cured film 144 also functions as a planarization film.

It is preferable to use an organic film as the cured film 144 from a viewpoint of obtaining the cured film which has translucent and insulating properties with respect to the characteristic requested|required in this way. The organic film is further preferably a planarized film obtained by using the curable composition for planarizing film formation. That is, even if it contains unevenness|corrugation in a base surface, the planarization film (cured film) which has a flat surface can be obtained by the leveling effect|action after apply|coating the curable composition for planarizing film formation.

The composition for producing the cured film 144 is preferably a curable composition containing a curable compound and a solvent, and particularly preferably a curable composition for planarizing film formation containing a curable compound and a solvent. As the solvent in the curable composition, the same solvent as that described as the solvent in the infrared absorbing composition can be used, and preferred embodiments are also the same as described above.

Hereinafter, the curable compound constituting the curable composition will be described.

＜Curable compound＞

The curable compound constituting the curable composition may be any compound that can be cured by light or heat, and examples thereof include resins having oxygen-containing saturated heterocyclic groups and resins having polymerizable unsaturated groups in side chains. , polysiloxane, polyimide resin, polyamide resin, polymeric compounds, etc.

Examples of the oxygen-containing saturated heterocyclic group in the resin having an oxygen-containing saturated heterocyclic group include the same ones as described above, and among them, oxetanyl and oxetanyl are preferred, and oxetane is more preferred. base.

The resin having an oxygen-containing saturated heterocyclic group is preferably an acrylic resin having an oxygen-containing saturated heterocyclic group, and specific examples thereof include (co)polymers of (meth)acrylates having an oxygen-containing saturated heterocyclic group. As such a (co)polymer, the same (co)polymer as described in the infrared absorbing composition can be exemplified.

Examples of the polyimide resin, polyamide resin, and polymerizable compound include the same polyimide resin, polyamide resin, and polymerizable compound as described in the infrared absorbing composition.

Among the polymerizable compounds constituting such a curable composition, from the viewpoint of forming a cured film having excellent adhesiveness with a near-infrared cut filter, it is preferable that it is a resin having an oxygen-containing saturated heterocyclic group, and having an oxygen-containing saturated heterocyclic group in a side chain. Polymerizable unsaturated group resins, polysiloxanes, polyimide resins, polyamide resins, more preferably resins having oxygen-containing saturated heterocyclic groups, resins having polymerizable unsaturated groups in side chains, polysilicon oxane.

＜Sensitizer＞

A photosensitizer may be further contained in the curable composition. Examples of the photosensitizer include the same ones as described above, and the specific compounds and embodiments are the same as those described above.

＜Additives＞

Additives may be further contained in the curable composition. As an additive, the thing similar to the above is mentioned. Among them, an adhesion promoter and a blocked isocyanate compound are preferable.

In the curable composition for planarizing film formation demonstrated above, from a viewpoint of forming the cured film excellent in the adhesiveness with a near-infrared cut filter, it is preferable that it is any one of the following.

(2-1) A curable composition comprising a resin having an oxygen-containing saturated heterocyclic group and a solvent,

(2-II) A curable composition comprising a resin having a polymerizable unsaturated group in a side chain and a solvent,

(2-III) Curable composition containing polysiloxane and a solvent.

Preferred embodiments of these (2-I) to (2-III) are as described above, respectively.

Furthermore, in the solid-state imaging device 210 of the present embodiment, in addition to the above-described configuration, two bandpass filters may be provided on the microlens array 115 . That is, on the upper surfaces of the near-infrared cut filter 122 and the infrared filter layer 108, the average transmittance in the wavelength range of 430 nm to 580 nm may be 75% or more, and the average transmittance in the wavelength range of 720 nm to 750 nm may be provided. Two bandpass filters with a pass rate of 15% or less, an average transmittance within a wavelength range of 810 nm to 820 nm of 60% or more, and an average transmittance within a wavelength range of 900 nm to 2000 nm of 15% or less. By adding two bandpass filters, the filtering capability in the visible light wavelength region and the infrared wavelength region can be further improved. In addition, the light transmittance in this specification etc. means the value measured using the Hitachi spectrophotometer U-4100. Furthermore, the spectrophotometer can automatically calculate the average value of transmittance in a given wavelength range. The average transmittance is specifically the following value: in a given wavelength range, the transmittance at each wavelength is measured in units of 1 nm, and the total of the transmittances is divided by the number of the measured transmittance (wavelength). range) value.

(Second Embodiment)

The configuration of the solid-state imaging device 220 according to the present embodiment is shown in FIG. 2 . The difference from the first embodiment is that the configuration of the near-infrared cut filter 140 further includes a silicon oxide layer 134 and a resin layer 135 . The configuration of the solid-state imaging element 110 is the same as that of the first embodiment, and thus detailed description is omitted.

[Near infrared cut filter]

As shown in FIG. 2 , the near-infrared cut filter 140 has a base material 131 , a dielectric multilayer film 132 , a dielectric multilayer film 133 , a silicon oxide layer 134 , and a resin layer 135 . The dielectric multilayer film 133 is provided on one surface of the base material 131 . In addition, a silicon oxide layer 134 , a resin layer 135 , and a dielectric multilayer film 133 are provided on the other surface of the base material 131 . In addition, the resin layer 135 of the near-infrared cut filter 140 is provided at a position facing the near-infrared cut filter 122 .

As the base material 131, a glass base material or a resin base material can be used. When a glass substrate is used as the substrate 131, the glass substrate described in the first embodiment can be used.

As a specific example of such a glass base material, if it is a board|substrate containing a silicate as a main component, it will not specifically limit, A quartz glass substrate etc. which have a crystal structure are mentioned. In addition, borosilicate glass substrates, soda glass substrates, colored glass substrates, etc. can be used, but glass substrates such as alkali-free glass substrates and low-α-ray glass substrates have little influence on the solid-state imaging element, so these substrates can be used with solid-state imaging devices. It is preferable that the imaging elements are arranged close to each other.

The thickness of the glass substrate is preferably 30 μm to 1000 μm, more preferably 50 μm to 750 μm, and particularly preferably 50 μm to 700 μm. When the thickness of a glass substrate is thinner than 30 micrometers, since a glass substrate itself is easily broken, handling may become extremely difficult. Moreover, when the thickness of a glass substrate is thicker than 1000 micrometers, the original objective of thinning a near-infrared cut filter may not be achieved.

When the thickness of the glass substrate is within the above range, the near-infrared cut filter can be reduced in size and weight, and can be suitably used for various applications such as solid-state imaging devices. In particular, when it is used for a lens unit such as a camera module, it is possible to reduce the back of the lens unit, which is preferable.

Such a glass substrate is particularly preferably a CuO-containing fluorophosphate glass or a CuO-containing phosphate glass, and specifically, the glass substrates described in Japanese Patent Laid-Open No. 2006-342024 and the like can be used.

If the resin layer 135 is directly formed on the base material 131, the adhesiveness between the resin and the base material is poor, and thus peeling of the resin layer is likely to occur. By providing the silicon oxide layer 134 on the base material 131, peeling of the resin layer can be prevented. The layer formed of the oxide is not limited to silicon oxide, but is preferably silicon oxide from the viewpoint of light transmittance. In addition, from the viewpoint of improving the adhesiveness, the surface of the glass substrate may be cleaned with ultraviolet rays.

The resin layer 135 has a near-infrared absorber. The near-infrared absorber preferably has a maximum absorption wavelength (hereinafter also referred to as "λmax") between 600 nm and 800 nm, more preferably between 640 nm and 770 nm, and particularly preferably between 660 nm and 720 nm. By having λmax in the wavelength range, the wavelength range of the light incident on the light receiving element having sensitivity to near-infrared light is limited, so that the color of the image captured by the solid-state imaging element is closer to what is actually observed visually. 's color.

In addition, the resin layer 135 preferably contains a resin having heat resistance suitable for the reflow process.

The number of stacks of the dielectric multilayer films 133 provided on the first surface side of the base material 131 is preferably smaller than the number of stacks of the dielectric multilayer films 132 provided on the second surface side. In addition, the number of laminates of the dielectric multilayer films 133 provided on the first surface side of the base material 131 is 10 or less, preferably 7 or less. The number of layers of the dielectric multilayer films 132 provided on the second surface side of the base material 131 is preferably 10 or more and less than 40 layers, more preferably 20 or more and less than 40 layers, and particularly preferably 20 or more layers and below 30 floors. In addition, when the base material 131 has sufficient rigidity, the dielectric multilayer film 133 may be omitted. The configurations of the dielectric multilayer film 132 and the dielectric multilayer film 133 need only be referred to in the first embodiment, and therefore detailed descriptions are omitted.

The solid-state imaging device 220 of the present embodiment has the near-infrared cut filter 140 including the silicon oxide layer 134 and the resin layer 135 , and has heat resistance suitable for the reflow process, and is incident on a device having sensitivity to near-infrared light. Since the wavelength range of the light of the light receiving element is limited, the color of the image captured by the solid-state imaging element is closer to the color that is actually observed visually.

In the solid-state imaging device 220 of the present embodiment, a near-infrared cut filter 122 is provided on the solid-state imaging element 110 , and a near-infrared cut filter 140 is further provided on the near-infrared cut filter 122 . Infrared rays can be further cut off by the near-infrared cut filter and the resin layer 135 provided on the solid-state imaging element 110 . Thereby, the number of layers of the dielectric multilayer film 132 and the dielectric multilayer film 133 can be reduced. In addition, even if the number of layers of the dielectric multilayer film 132 and the dielectric multilayer film 133 is reduced, the warpage of the near-infrared cut filter 140 can be reduced. In addition, the number of layers of the dielectric multilayer film 132 and the dielectric multilayer film 133 can be reduced, so that the manufacturing steps can be reduced and the yield can be improved.

Next, the resin layer 135 provided in the near-infrared cut filter 140 will be described in detail.

"Resin Layer"

The resin layer 135 used in the present invention preferably contains a resin having heat resistance suitable for a reflow step and a near-infrared absorber having maximum absorption between wavelengths of 600 nm to 800 nm.

<Resin with heat resistance>

The glass transition temperature (Tg) of the resin having heat resistance is preferably 0°C to 380°C. The lower limit of Tg is more preferably 40°C or higher, still more preferably 60°C or higher, still more preferably 70°C or higher, and particularly preferably 100°C or higher. In addition, the upper limit of Tg is more preferably 370°C or lower, and still more preferably 360°C or lower. When the Tg of the transparent resin is in the range of 0° C. to 380° C., deterioration or deformation due to heat can be suppressed in the manufacturing process or use of the optical filter.

Specific examples of such resins include polyester resins, polyether resins, acrylic resins, polyolefin resins, cyclic olefin resins, polycarbonate resins, thiol-ene resins, epoxy resins resin, polyamide resin, polyimide resin, polyamideimide resin, polyurethane resin, polystyrene resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, Polyarylene ether phosphine oxide resin, etc. Among these, acrylic resin, polyester resin, polycarbonate resin, or cyclic olefin resin is preferable. The polyester resin is preferably polyethylene terephthalate resin, polyethylene naphthalate resin, or the like. In addition, in applications requiring heat resistance, polyester resins, polycarbonate resins, and polyimide resins having high Tg are preferable. The refractive index of the transparent resin can be adjusted by adjusting the molecular structure or the like of the raw material components. Specifically, the method of giving a specific structure to the main chain or side chain of the polymer of a raw material component is mentioned. The structure provided in the polymer is not particularly limited, and examples thereof include a fluorene skeleton. The transparent resin may also be a polymer alloy that combines a plurality of different resins.

Commercially available products can also be used as the resin. Commercially available products include Ogsol (registered trademark) EA-F5003 (manufactured by Osaka Gas Chemicals Co., Ltd., trade name), polymethyl methacrylate, Polyisobutyl methacrylate, BR50 (manufactured by Mitsubishi Rayon Co., Ltd., trade name), etc.

In addition, as polyester resins, OKPH4HT, OKPH4, B-OKP2, OKP-850 (all of the above are manufactured by Osaka Gas Chemical Co., Ltd., trade names), Vylon (registered trademark) 103 (Toyobo ( Co., Ltd., trade name), LeXan (registered trademark) ML9103 (manufactured by Sabic, trade name) as polycarbonate resin, EP5000 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name) ), SP3810 (made by Teijin Chemical Co., Ltd., trade name), SP1516 (made by Teijin Chemical Co., Ltd., trade name), TS2020 (made by Teijin Chemical Co., Ltd., trade name), xylex (registered trademark) ) 7507 (manufactured by Sabic, trade name) and the like.

Further, as cyclic olefin resins, ARTON (registered trademark) (manufactured by JSR Co., Ltd., trade name, Tg: 165° C.), ZEONEX (registered trademark) (Zeonex (Japan) ZEON) (stock), trade name, Tg: 138°C) and the like.

＜Near infrared absorber＞

In the near-infrared absorber that can be used in the near-infrared cut filter of the present invention (iv) 5% weight loss temperature measured by thermogravimetric analysis in the atmosphere is preferably 250°C or higher, more preferably 260°C or higher, particularly preferably above 270°C. When the weight reduction temperature satisfies the above-mentioned conditions, it is not decomposed even under high temperature conditions, sufficient thermal properties for use in the reflow process can be ensured, and a near-infrared cut filter of stable quality can be provided.

In addition, the near-infrared absorber used in the present invention preferably has a maximum absorption at a wavelength of 600 nm to 800 nm, more preferably has a maximum absorption in the range of 640 (nm) to 770 (nm), and particularly preferably has a maximum absorption at 660 nm. The range from (nm) to 720 (nm) has the maximum absorption.

By using such a near-infrared absorber, a laminate and a near-infrared cut filter satisfying the above (A) to (D) and (i) can be obtained.

Examples of such near-infrared absorbers include cyanine-based dyes, phthalocyanine-based dyes, ammonium-based dyes, imine-based dyes, azo-based dyes, anthraquinone-based dyes, diimmonium-based dyes, and squaraine-based dyes. Onium salt-based dyes and porphyrin-based dyes.

The resin layer containing such a near-infrared absorber has the above-described heat resistance, and thus can be suitably used in the reflow process.

As a commercial item of the said near-infrared absorber, specifically, for example, Lumogen IR765, Lumogen IR788 (manufactured by BASF), ABS643, ABS654, ABS667, ABS670T can be mentioned. , IRA693N, IRA735 (manufactured by Exciton); SDA3598, SDA6075, SDA8030, SDA8303, SDA8470, SDA3039, SDA3040, SDA3922, SDA7257 (manufactured by H.W. Sands); TAP-15, IR- 706 (manufactured by Yamada Chemical Industry).

These near-infrared absorbers may be used alone or in combination of two or more.

In the present invention, the amount of the near-infrared absorber to be used can be appropriately selected according to the desired properties, and is usually 0.01 to 10.0 wt %, preferably 0.01 wt % relative to 100 wt % of the resin used in the present invention. % to 8.0% by weight, more preferably 0.01% to 5.0% by weight.

When the usage-amount of the near-infrared absorbing agent is within the above-mentioned range, a near-infrared cutoff filter excellent in near-infrared cutoff capability, transmittance and strength in the range of 430 nm to 580 nm can be obtained with small incident angle dependence of absorption wavelength.

When the usage-amount of the near-infrared absorbing agent is larger than the above-mentioned range, a near-infrared cut filter that exhibits the characteristics of the near-infrared absorbing agent more strongly may be obtained, but there is a transmittance in the range of 430 nm to 580 nm. There is a possibility of lowering than the desired value, or the strength of the resin layer or the near-infrared cut filter may be reduced. If the use amount of the near-infrared absorber is less than the above-mentioned range, there is also a possibility that the range of 430 nm to 580 nm can be obtained. In the case of a near-infrared cut filter with high transmittance, it is difficult to obtain a near-infrared cut filter that is difficult to express the characteristics of a near-infrared absorbing agent and has a small incident angle dependence of absorption wavelength.

<Optical Properties of Resin Layer>

The resin layer of the present invention (i) has a maximum absorption wavelength (hereinafter also referred to as "λmax") between 600 (nm) and 800 (nm), preferably between 640 (nm) and 770 (nm), and more It is preferable to have at 660 (nm) - 720 (nm). By having the λmax in the wavelength range, the wavelength range of the light incident on the light-receiving element having sensitivity to near-infrared light is limited, so that the color of the image captured by the solid-state imaging element is closer to what is actually seen visually. observed shade.

＜Other ingredients＞

Other components such as antioxidants, ultraviolet absorbers, and surfactants may be further added to the resin layer within a range that does not impair the effects of the present invention.

Examples of antioxidants include 2,6-di-tert-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-tert-butyl-5,5'-dimethylphenol Diphenylmethane and tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane.

As an ultraviolet absorber, 2, 4- dihydroxy benzophenone and 2-hydroxy- 4- methoxy benzophenone are mentioned, for example.

When a resin layer is produced by the solution casting method, the production of the resin layer can be facilitated by adding a surfactant or an antifoaming agent.

In addition, additives, such as antioxidant, an ultraviolet absorber, and surfactant, may be mixed with resin components etc. at the time of manufacture of a resin layer, and may be added at the time of synthesizing resin. In addition, the addition amount can be appropriately selected according to the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight, with respect to 100 parts by weight of the resin.

(third embodiment)

The configuration of the solid-state imaging device 230 according to the present embodiment is shown in FIG. 3 . The difference from the second embodiment is that in the configuration of the near-infrared cut filter 150, a resin base 141 containing a near-infrared absorbing agent is provided instead of the base 131, and a resin layer 135 that absorbs infrared rays is not provided . The configuration of the solid-state imaging element 110 is the same as that of the first embodiment, and thus detailed description is omitted.

[Near infrared cut filter]

As shown in FIG. 3 , the near-infrared cut filter 150 includes a resin substrate 141 containing a near-infrared absorber, a dielectric multilayer film 132 , a dielectric multilayer film 133 , and a silicon oxide layer 134 . The dielectric multilayer film 133 is provided on one surface of the resin base material 141 . In addition, the silicon oxide layer 134 and the dielectric multilayer film 133 are provided on the other surface of the resin substrate 141 . In addition, the near-infrared cut filter 150 is provided at a position facing the near-infrared cut filter 122 .

The resin base material 141 contains a resin having heat resistance suitable for a reflow step, and a near-infrared absorber having a maximum absorption wavelength (hereinafter also referred to as "λmax") between wavelengths of 600 nm to 800 nm. By having λmax in the wavelength range, the wavelength range of the light incident on the light-receiving element having sensitivity to near-infrared light is limited, so that the color of the image captured by the solid-state imaging element can be closer to what is actually observed visually. to the color.

The near-infrared absorber included in the resin substrate 141 preferably has a maximum absorption wavelength between 600 nm and 800 nm, more preferably has a maximum absorption wavelength between 640 nm and 770 nm, and particularly preferably has a maximum absorption wavelength between 660 nm and 720 nm. wavelength. By having λmax in the wavelength range, the wavelength range of the light incident on the light receiving element having sensitivity to near-infrared light is limited, so that the color of the image captured by the solid-state imaging element is closer to what is actually observed visually. 's color.

In addition, the resin base material 141 preferably contains a resin having heat resistance suitable for the reflow process.

The resin base material 141 is formed of a composition containing the infrared absorber and a heat-resistant resin. The resin base material 141 has high infrared shielding properties on the shorter wavelength side, and low infrared shielding properties on the longer wavelength side. For such a resin base material 141 , a dielectric multilayer film having low infrared shielding properties on the shorter wavelength side and high infrared shielding properties on the longer wavelength side can be preferably used as the dielectric multilayer film.

The dielectric multilayer film preferably satisfies the following formula (i).

x＜y≦z/0.95…(i)

(In the formula (i), x is the average value of the absorbance of the dielectric multilayer film in the wavelength range of 700 nm or more and 800 nm or less. y is the dielectric multilayer film in the wavelength range of 800 nm or more and 900 nm or less. Average value of absorbance. z is the average value of absorbance of the dielectric multilayer film in the wavelength range of 900 nm or more and 1200 nm or less)

The dielectric multilayer film can be produced, for example, by the method described in Japanese Patent Laid-Open No. 2016-146619 and the like.

By using such a dielectric multilayer film in combination with the resin base material 141 having infrared absorbing energy, the incident angle dependence that can occur in the dielectric multilayer film can be reduced and can be used over a wide wavelength range Play a good infrared absorption energy. The resin substrate 141 can be produced by the method described in WO2016/117596.

In addition, it is preferable that the number of stacks of the dielectric multilayer films 133 provided on the first surface side of the base material 131 is smaller than the number of stacks of the dielectric multilayer films 132 provided on the second surface side. In addition, the number of laminates of the dielectric multilayer films 133 provided on the first surface side of the base material 131 is 10 or less, preferably 7 or less. The number of layers of the dielectric multilayer films 132 provided on the second surface side of the base material 131 is preferably 10 or more and less than 40 layers, more preferably 20 or more and less than 40 layers, and particularly preferably 20 or more layers and below 30 floors. In addition, when the base material 131 has sufficient rigidity, the dielectric multilayer film 133 may be omitted. The configurations of the dielectric multilayer film 132 and the dielectric multilayer film 133 need only be referred to in the first embodiment, and therefore detailed descriptions are omitted.

The solid-state imaging device 230 of the present embodiment has the near-infrared cut filter 150 including the silicon oxide layer 134 and the resin base material 141 including the near-infrared absorbing agent, and has heat resistance suitable for the reflow process, and is incident on Since the wavelength range of the light of the light receiving element having sensitivity to near-infrared light is limited, the color of the image captured by the solid-state imaging element is closer to the color actually observed visually.

In this embodiment, the resin base material 141 has a near-infrared-absorbing dye as the near-infrared cut filter 150 . Accordingly, it is not necessary to provide the resin layer 135 described in the second embodiment. In addition, in the solid-state imaging element 110 , the near-infrared cut filter 122 is provided on the light receiving element, whereby the near-infrared cutoff effect can be obtained also on the side of the solid-state imaging element 110 . In the near-infrared cut filter 150 , it is not necessary to laminate multiple layers of dielectric multilayer films having different refractive indices, so that the occurrence of warpage in the entire near-infrared cut filter 150 can be suppressed. In addition, in the near-infrared cut filter 150 , it is not necessary to laminate multiple layers of dielectric multilayer films with different refractive indices, so that the number of manufacturing steps can be reduced, and the yield can be improved.

Example

In this example, in order to confirm the relationship between the number of layers of the dielectric multilayer film and the infrared cut filter layer, the results of performing the following substitution experiment (measuring the transmittance of the film) will be described.

In this example, samples A to E were produced. 4A to 4C are diagrams showing the configurations of samples A to E. FIG. 4A is a diagram showing the configuration of the sample A, FIG. 4B is a diagram showing the configuration of the samples B to D, and FIG. 4C is a diagram showing the configuration of the sample E. FIG.

As shown in FIG. 4A , the sample A has a structure in which a near-infrared cut filter 202 is provided on a glass substrate 201 . The near-infrared cut filter 202 corresponds to the near-infrared cut filter 122 described in the conventional embodiment.

As shown in FIG. 4B , Sample B has a structure in which a near-infrared cut filter 202 is provided on a glass substrate 201 , and ten layers of a dielectric multilayer film 203 are provided on the near-infrared cut filter 202 . Sample C has the same configuration as Sample B except that 20 layers of the dielectric multilayer film 203 are used. Sample D has the same configuration as Sample B except that 30-layer dielectric multilayer films 203 are used.

As shown in FIG. 4C , Sample E has a configuration in which 40 layers of dielectric multilayer films 203 are provided on a resin substrate 204 containing a near-infrared absorber. Here, the resin base material 204 corresponds to the resin base material 141 described in the conventional embodiment. For the detailed configuration of the sample E, refer to Japanese Patent No. 5499669.

Next, the transmittances of samples A to E were measured using a Hitachi spectrophotometer U-4100. The average value of transmittance in a given wavelength range can be automatically calculated using a spectrophotometer. Specifically, the average transmittance is a value obtained by measuring the transmittance at each wavelength in units of 1 nm in a given wavelength range, and dividing the total transmittance by the measured transmittance. number (wavelength range).

The results obtained by measuring the transmittances of the samples A to E, respectively, are shown in FIG. 5 . In FIG. 5 , the horizontal axis represents the wavelength (Wavelength (nm)), and the vertical axis represents the transmittance (T (%)).

As shown in FIG. 5 , the average transmittance of sample A at a wavelength of 700 nm to 1000 nm was 54.5%. In addition, the average transmittance of sample E at wavelengths of 700 nm to 1000 nm was 0.2%. On the other hand, the average transmittances of Sample B, Sample C, and Sample D at wavelengths of 700 nm to 1000 nm were 3.6%, 0.9%, and 0.2%, respectively. The samples B to D are different from the sample E, and the near-infrared cut filter 202 is used. By using the near-infrared cut filter 202, it has been shown that even if the number of layers of the dielectric laminate film is 20 to 30 layers, sufficient infrared cut-off performance can be obtained.

Industrial Availability

The solid-state imaging device of the present invention can be preferably used for digital still cameras, cameras for mobile phones, digital video cameras, cameras for personal computers, surveillance cameras, cameras for automobiles, televisions, in-vehicle devices for car navigation systems, mobile information terminals, and video games Machines, portable game machines, devices for fingerprint authentication systems, digital music players, etc.

Explanation of symbols

101: Pixel part

102: Pixels for visible light detection

103: Pixels for infrared light detection

104a: first pixel

104b: first pixel

104c: first pixel

105: Second pixel

106a: Photodiode

106b: Photodiode

106c: Photodiode

106d: Photodiode

107a: Color filter layer

107b: Color filter layer

107c: Color Filter Layer

108: Infrared filter layer

110: Solid-state imaging element

111: Semiconductor substrate

112: Semiconductor layer

113: wiring layer

114: Optical filter layer

115: Microlens Array

121: Hardened film

122: Near infrared cut filter

123: Hardened film

130: Near infrared cut filter

131: Substrate

132: Dielectric Multilayer Film

133: Dielectric multilayer film

134: Silicon oxide layer

135: Resin layer

140: Near infrared cut filter

141: Resin base

150: Near infrared cut filter

210: Solid State Cameras

220: Solid-state imaging device

230: Solid-state imaging device

Claims (19)

1. A solid-state imaging device of kinds, comprising a near infrared ray cut filter and a solid-state imaging element,

   the th near infrared ray cut filter includes:

   a glass substrate; and

   a dielectric multilayer film on at least of the glass substrates,

   the solid-state imaging element includes:

   a semiconductor substrate;

   th light-receiving element provided on the semiconductor substrate, and

   an optical filter provided on the th light receiving element,

   the optical filter has:

   a color filter layer provided on the th light-receiving element, and

   a second near infrared ray cut filter provided on the color filter layer,

   the th near infrared ray cut filter is provided at a position facing the second near infrared ray cut filter,

   the number of layers of the dielectric multilayer film is 10 or more and less than 40.
2. 2. The solid-state imaging device according to claim 1, wherein the glass substrate is a fluorophosphate glass containing CuO or a phosphate glass containing CuO.
3. 3. The solid-state imaging device according to claim 1, wherein the optical filter further has an th cured film on the second near-infrared cut filter.
4. 4. The solid-state imaging device according to claim 1, wherein the optical filter further has a second cured film between the color filter layer and the second near-infrared cut filter.
5. 5. The solid-state imaging device according to claim 1, further comprising a second light-receiving element provided on the semiconductor substrate, and a filter layer overlapping the second light-receiving element.
6. 6. The solid-state imaging device according to claim 1, wherein the number of layers of the dielectric multilayer film is 20 or more and 30 or less.
7. 7. The solid-state imaging device according to claim 1, wherein the second near-infrared cut filter contains at least kinds of organic pigments of a cesium tungsten oxide compound and an organic pigment compound selected from a diimine compound, a squarylium compound, a cyanine compound, a phthalocyanine compound, a naphthalocyanine compound, a quatrinitene compound, an ammonium compound, an imine compound, a pyrrolopyrrole compound, and a ketanium compound.
8. 8, solid-state imaging devices each having a th near infrared ray cut filter and a solid-state imaging element,

   the th near infrared ray cut filter includes:

   a substrate;

   a th dielectric multilayer film provided on the th surface of the substrate;

   a resin layer provided on the second surface of the substrate; and

   a second dielectric multilayer film provided on the second surface of the substrate via the resin layer,

   the solid-state imaging element includes:

   a semiconductor substrate;

   th light-receiving element provided on the semiconductor substrate, and

   an optical filter provided on the th light receiving element,

   the optical filter has:

   a color filter layer provided on the th light-receiving element, and

   a second near infrared ray cut filter provided on the color filter layer,

   the resin layer of the th near infrared ray cut filter is provided at a position facing the second near infrared ray cut filter,

   the number of layers of the th dielectric multilayer film is 10 or more but less than 40.
9. 9. The solid-state imaging device according to claim 8, wherein the optical filter further has a th hardened film on the th near-infrared ray cut filter.
10. 10. The solid-state imaging device according to claim 8, wherein the optical filter further has a second cured film between the color filter layer and the th near-infrared ray cut filter.
11. 11. The solid-state imaging device according to claim 8, further comprising a second light-receiving element provided on the semiconductor substrate, and a filter layer overlapping the second light-receiving element.
12. 12. The solid-state imaging device according to claim 8, wherein the number of layers of the th dielectric multilayer film is 20 or more and 30 or less.
13. 13. The solid-state imaging device according to claim 8, wherein the second near-infrared cut filter contains at least kinds of organic pigments of a cesium tungsten oxide compound and an organic pigment compound selected from a diimine compound, a squarylium compound, a cyanine compound, a phthalocyanine compound, a naphthalocyanine compound, a quatrinitene compound, an ammonium compound, an imine compound, a pyrrolopyrrole compound, and a ketanium compound.
14. 14, solid-state imaging devices each having a th near infrared ray cut filter and a solid-state imaging element,

    the th near infrared ray cut filter includes:

    a resin base material containing a near-infrared ray absorber; and

    a dielectric multilayer film on at least of the resin substrates,

    the solid-state imaging element includes:

    a semiconductor substrate;

    th light-receiving element provided on the semiconductor substrate, and

    an optical filter provided on the th light receiving element,

    the optical filter has:

    a color filter layer provided on the th light-receiving element, and

    a second near infrared ray cut filter provided on the color filter layer,

    the th near infrared ray cut filter is provided at a position facing the second near infrared ray cut filter,

    the number of layers of the dielectric laminated film is 10 or more and less than 40.
15. 15. The solid-state imaging device according to claim 14, wherein the optical filter further has a th hardened film on the th near-infrared ray cut filter.
16. 16. The solid-state imaging device according to claim 14, wherein the optical filter further has a second cured film between the color filter layer and the th near-infrared ray cut filter.
17. 17. The solid-state imaging device according to claim 14, further comprising a second light-receiving element provided on the semiconductor substrate, and a filter layer overlapping the second light-receiving element.
18. 18. The solid-state imaging device according to claim 14, wherein the number of layers of the dielectric multilayer film is 20 or more and 30 or less.
19. 19. The solid-state imaging device according to claim 14, wherein the second near-infrared cut filter contains at least kinds of organic pigments of a cesium tungsten oxide compound and an organic pigment compound selected from a diimine compound, a squarylium compound, a cyanine compound, a phthalocyanine compound, a naphthalocyanine compound, a quatrinitene compound, an ammonium compound, an imine compound, a pyrrolopyrrole compound, and a ketanium compound.

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