WO2021106670A1 - 固体撮像素子 - Google Patents
固体撮像素子 Download PDFInfo
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- WO2021106670A1 WO2021106670A1 PCT/JP2020/042704 JP2020042704W WO2021106670A1 WO 2021106670 A1 WO2021106670 A1 WO 2021106670A1 JP 2020042704 W JP2020042704 W JP 2020042704W WO 2021106670 A1 WO2021106670 A1 WO 2021106670A1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14683—Processes or apparatus peculiar to the manufacture or treatment of these devices or parts thereof
- H01L27/14685—Process for coatings or optical elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14601—Structural or functional details thereof
- H01L27/1462—Coatings
- H01L27/14621—Colour filter arrangements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14601—Structural or functional details thereof
- H01L27/14625—Optical elements or arrangements associated with the device
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14601—Structural or functional details thereof
- H01L27/1463—Pixel isolation structures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14643—Photodiode arrays; MOS imagers
- H01L27/14645—Colour imagers
Definitions
- the present invention relates to a solid-state image sensor provided with an optical filter.
- CCD charge-coupled device
- a solid-state image sensor having an optical filter such as a color filter having two or more types of pixels arranged in a pattern and a partition wall arranged between the pixels is known. ..
- Patent Document 1 includes an imaging optical system including a lens group and an aperture aperture, and a solid-state imaging device that captures an image formed on an imaging surface of the imaging optical system.
- an image sensor having a plurality of pixels on a substrate, and separates a photoelectric conversion layer made of an organic material, a color filter of two or more colors arranged above the photoelectric conversion layer, and a color filter of each color.
- a color filter layer composed of a transparent separation wall is provided, the thickness of the photoelectric conversion layer is 0.1 ⁇ m to 1 ⁇ m, the refractive index of each color filter is 1.5 to 1.8, and the separation wall is provided.
- An invention relating to an image sensor having a width of 0.05 ⁇ m to 0.2 ⁇ m and a refractive index of 1.22 to 1.34 of a separation wall is described.
- the angle of light incident on the pixels located in the central portion of the photoelectric conversion unit may differ from the angle of light incident on the pixels in the peripheral portion of the photoelectric conversion unit.
- light is likely to be incident on the pixels located in the central portion of the photoelectric conversion unit from a substantially vertical direction, but light is likely to be incident on the pixels in the peripheral portion of the photoelectric conversion unit from an oblique direction.
- an object of the present invention is to provide a solid-state image sensor in which the difference between the sensitivity to vertically incident light and the sensitivity to obliquely incident light is reduced and the variation in sensitivity characteristics is suppressed.
- a support having a photoelectric conversion unit and It has an optical filter provided on the light incident side to the photoelectric conversion unit.
- the optical filter has two or more kinds of pixels arranged in a pattern and a partition wall arranged between each pixel.
- the refractive index of the partition wall with respect to light having a wavelength of 533 nm is 1.10 to 1.30.
- the width of the partition wall is 80 to 150 nm.
- the refractive index of the pixel with respect to light having a wavelength of 1000 nm is 1.60 to 1.90.
- the difference between the thickness of the partition wall and the thickness of the pixel adjacent to the partition wall is 200 nm or less.
- the difference between the refractive index of the partition wall with respect to light having a wavelength of 533 nm and the refractive index of the pixel adjacent to the partition wall with respect to light having a wavelength of 1000 nm is 0.30 to 0.80.
- Solid-state image sensor. ⁇ 2> The solid-state image sensor according to ⁇ 1>, wherein the partition wall has a thickness of 300 to 650 nm.
- ⁇ 3> The solid-state image sensor according to ⁇ 1> or ⁇ 2>, wherein the pixel thickness is 300 to 600 nm.
- ⁇ 4> The solid-state image sensor according to any one of ⁇ 1> to ⁇ 3>, wherein the width of the pixel is 300 to 1100 nm.
- ⁇ 5> The solid-state image sensor according to any one of ⁇ 1> to ⁇ 4>, wherein the pixel pitch of the optical filter is 400 to 1200 nm.
- ⁇ 6> The solid-state image sensor according to any one of ⁇ 1> to ⁇ 5>, wherein the difference between the thickness of the partition wall and the thickness of the pixel adjacent to the partition wall is 1 nm or more.
- ⁇ 7> The solid-state image sensor according to any one of ⁇ 1> to ⁇ 6>, wherein the partition wall has a thickness larger than that of the pixel.
- the partition wall is any one of ⁇ 1> to ⁇ 8>, which comprises at least one selected from silica particles having a shape in which a plurality of spherical silicas are connected in a bead shape and silica particles having a hollow structure.
- ⁇ 11> The solid-state image sensor according to any one of ⁇ 1> to ⁇ 10>, wherein the surface roughness Ra value of the pixel is 0.1 to 5.0 nm.
- the optical filter includes at least one pixel selected from yellow pixels, cyan pixels, and magenta pixels.
- FIG. 5 is a plan view seen from directly above the optical filter used in the solid-state image sensor of FIG. 1.
- the numerical range represented by the symbol "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
- the notation that does not describe substitution or non-substitution means to include those having a substituent as well as those having no substituent.
- alkyl group when simply described as "alkyl group", this includes both an alkyl group having no substituent (unsubstituted alkyl group) and an alkyl group having a substituent (substituted alkyl group). Means.
- (meth) acrylate means both “acrylate” and “methacrylate”, or either
- (meth) acrylic means both “acrylic” and “methacrylic", or , Either
- (meth) acryloyl means both “acryloyl” and “methacrylic”, or either.
- the concentration of the solid content in the composition is expressed by the mass percentage of the other components excluding the solvent with respect to the total mass of the composition.
- weight average molecular weight (Mw) and the number average molecular weight (Mn) are shown as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
- the solid-state image sensor of the present invention A support having a photoelectric conversion part and It has an optical filter provided on the light incident side to the photoelectric conversion unit.
- the optical filter has two or more kinds of pixels arranged in a pattern and a partition wall arranged between each pixel.
- the refractive index of the partition wall with respect to light having a wavelength of 533 nm is 1.10 to 1.30.
- the width of the partition is 80-150 nm
- the refractive index of the pixel with respect to light having a wavelength of 1000 nm is 1.60 to 1.90.
- the difference between the thickness of the partition wall and the thickness of the pixel adjacent to the partition wall is 200 nm or less.
- the difference between the refractive index of the partition wall with respect to light having a wavelength of 533 nm and the refractive index of the pixel adjacent to the partition wall with respect to light having a wavelength of 1000 nm is 0.30 to 0.80.
- the solid-state image sensor of the present invention has the above-mentioned optical filter, even if light is incident on the pixels of the optical filter from an oblique direction, the light can be efficiently incident on the photoelectric conversion unit, and the sensitivity to vertically incident light can be obtained. And the difference in sensitivity to obliquely incident light can be reduced. Therefore, it is possible to suppress the variation in the incident amount of light between the central portion and the peripheral portion of the photoelectric conversion unit, and it is possible to obtain a solid-state image sensor in which the variation in the sensitivity characteristics is suppressed.
- the thickness of the partition wall means the length of the partition wall in the vertical direction
- the width of the partition wall means the length of the partition wall in the horizontal direction. The same applies to the pixel thickness and pixel width.
- FIG. 1 is a side sectional view showing an embodiment of the solid-state image sensor
- FIG. 2 is a plan view seen from directly above the optical filter used in the solid-state image sensor 100 shown in FIG.
- the solid-state image sensor 100 shown in FIG. 1 is irradiated with light from the upper side in the figure.
- reference numeral 1 is a support.
- the material of the support 1 is not particularly limited.
- a silicon substrate, an InGaAs substrate, and the like can be mentioned.
- a base layer may be formed on the surface of the support 1 in order to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the surface of the substrate.
- the support 1 of the solid-state image sensor 100 shown in FIG. 1 is provided with a photoelectric conversion unit 10.
- the photoelectric conversion unit 10 include a silicon photodiode, an InGaAs photodiode, an organic photoelectric conversion film, and quantum dots. Further, a gap may be formed between the photoelectric conversion portions 10 adjacent to each other of the support 1.
- An optical filter 20 is provided on the light incident side of the support 1 to the photoelectric conversion unit 10.
- the optical filter 20 has pixels 21, 22, and 23 arranged in a pattern, and a partition wall 25 arranged between the pixels.
- FIG. 2 has three types of pixels 21, 22, and 23, the optical filter 20 may have two types of pixels or four or more types of pixels. The number of types of pixels and the arrangement of pixels can be appropriately selected according to the application and purpose.
- the types of pixels included in the optical filter 20 include colored pixels such as red pixels, green pixels, blue pixels, yellow pixels, cyan pixels, and magenta pixels; white pixels; pixels for near-infrared cut filters; and near-infrared transmission filters. Examples include pixels for use.
- the optical filter preferably has colored pixels. It is also preferable that the optical filter includes at least one pixel selected from yellow pixels, cyan pixels and magenta pixels. According to this aspect, the effect of the present invention can be obtained more remarkably, the sensitivity becomes higher, and a clearer and brighter image can be obtained.
- the optical filter preferably includes yellow pixels, cyan pixels, and magenta pixels, respectively.
- the near-infrared cut filter pixel examples include a filter layer having a maximum absorption wavelength in the wavelength range of 700 to 1800 nm.
- the near-infrared cut filter pixel is preferably a filter layer having a maximum absorption wavelength in the wavelength range of 700 to 1300 nm, and more preferably a filter layer having a maximum absorption wavelength in the wavelength range of 700 to 1000 nm.
- the light transmittance of the near-infrared cut filter pixel in the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. preferable.
- the transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less.
- the absorbance Amax / absorbance A550 which is the ratio of the absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter pixel to the absorbance A550 at a wavelength of 550 nm, is preferably 20 to 500, and preferably 50 to 500. More preferably, it is more preferably 70 to 450, and particularly preferably 100 to 400.
- the near-infrared transmission filter pixel is a filter layer that transmits at least a part of near-infrared rays.
- the near-infrared transmission filter pixel may be a filter layer (transparent film) that transmits both visible light and near-infrared light, and is a filter that blocks at least a part of visible light and transmits at least a part of near-infrared light. It may be a layer.
- the near-infrared transmissive filter layer the maximum value of the transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the transmittance in the wavelength range of 1100 to 1300 nm.
- the near-infrared transmission filter pixel is preferably a filter layer satisfying any of the following spectral characteristics (1) to (4).
- the maximum value of the transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 800 to 1300 nm is.
- a filter layer of 70% or more (preferably 75% or more, more preferably 80% or more).
- the maximum value of the transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 900 to 1300 nm is.
- a filter layer of 70% or more preferably 75% or more, more preferably 80% or more).
- the maximum value of the transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1000 to 1300 nm is.
- a filter layer of 70% or more (preferably 75% or more, more preferably 80% or more).
- the maximum value of the transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1100 to 1300 nm is.
- a filter layer of 70% or more preferably 75% or more, more preferably 80% or more).
- the colored pixels can be formed by using a composition for forming colored pixels, which will be described later.
- the white pixels can be formed by using a composition for forming white pixels, which will be described later.
- the pixels for the near-infrared cut filter can be formed by using a pixel-forming composition for the near-infrared cut filter, which will be described later.
- the pixels for the near-infrared transmission filter can be formed by using a composition for forming pixels for the near-infrared transmission filter, which will be described later.
- the refractive index of pixels 21, 22 and 23 with respect to light having a wavelength of 1000 nm is 1.60 to 1.90.
- the lower limit of the refractive index of the pixel is preferably 1.63 or more, and more preferably 1.65 or more, from the viewpoint of condensing light incident on the pixel.
- the upper limit of the refractive index of the pixel is preferably 1.80 or less, and more preferably 1.75 or less, from the viewpoint of the light condensing property of the light incident on the pixel.
- the thickness H2 of the pixels 21, 22 and 23 is preferably 300 to 600 nm.
- the lower limit is preferably 350 nm or more, and more preferably 390 nm or more.
- the upper limit is preferably 550 nm or less, and more preferably 510 nm or less. If the thickness H2 of the pixels 21, 22, and 23 is within the above-mentioned range, crosstalk can be easily suppressed.
- the difference in thickness between the pixels is preferably 100 nm or less, more preferably 50 nm or less, and further preferably 30 nm or less.
- the thickness of each pixel is preferably the same.
- the width W2 of the pixels 21, 22 and 23 is preferably 300 to 1100 nm.
- the lower limit is preferably 400 nm or more, and more preferably 450 nm or more.
- the upper limit is preferably 1000 nm or less, and more preferably 900 nm or less. If the width W2 of the pixels 21, 22, and 23 is within the above-mentioned range, the solid-state image sensor can be miniaturized and have high resolution.
- the surface roughness Ra value of the pixels 21, 22 and 23 is preferably 0.1 to 5.0 nm.
- the upper limit of the surface roughness Ra value is preferably 4.5 nm or less, and more preferably 4.0 nm or less.
- the surface roughness Ra value of the pixel can be measured by the dynamic force mode method with AFM5500 (manufactured by Hitachi High-Technologies Corporation).
- the surfaces of the pixels 21, 22, and 23 are flat, but may be convex.
- a partition wall 25 is arranged between each pixel of the optical filter 20.
- the refractive index of the partition wall 25 with respect to light having a wavelength of 533 nm is 1.10 to 1.30.
- the lower limit of the refractive index is preferably 1.12 or more, and more preferably 1.15 or more, from the viewpoint of the strength of the partition wall.
- the upper limit of the refractive index is preferably 1.29 or less, and more preferably 1.28 or less, from the viewpoint of light condensing property.
- the width W1 of the partition wall 25 is 80 to 150 nm.
- the lower limit of the width W1 of the partition wall 25 is preferably 90 nm or more, more preferably 100 nm or more, and further preferably 110 nm or more from the viewpoint of the strength of the partition wall.
- the upper limit of the width W1 of the partition wall 25 is preferably 140 nm or less, and more preferably 130 nm or less from the viewpoint of ensuring an effective pixel size.
- the thickness H1 of the partition wall 25 is preferably 300 to 650 nm.
- the lower limit of the thickness H1 of the partition wall 25 is preferably 350 nm or more, more preferably 400 nm or more, and further preferably 450 nm or more.
- the upper limit of the thickness H1 of the partition wall 25 is preferably 600 nm or less, more preferably 550 nm or less, and further preferably 500 nm or less.
- the difference between the thickness H1 of the partition wall 25 and the thickness H2 of the pixels 21 (22, 23) adjacent to the partition wall 25 is 200 nm or less, preferably 150 nm or less, and more preferably 100 nm or less. , 50 nm or less is more preferable.
- the difference in thickness between the two is 200 nm or less, even if light is incident on the pixel from an oblique direction, light leakage to adjacent pixels can be effectively suppressed.
- the thickness H1 of the partition wall 25 and the thickness H2 of the pixels 21 (22, 23) adjacent to the partition wall 25 are substantially the same, and the difference in thickness between the two is substantially zero.
- the difference between the thickness H1 of the partition wall 25 and the thickness H2 of the pixels 21 (22, 23) adjacent to the partition wall 25 can be 1 nm or more, or 3 nm or more.
- the thickness of the partition wall is smaller than the thickness of the pixel, that is, when the upper surface of the partition wall is located below the upper surface of the pixel, the coating property of the composition for pixel formation is good and the pixel formation is performed. It is possible to suppress uneven coating of the composition for use.
- the thickness of the partition wall is larger than the pixel, that is, when the upper surface of the partition wall is located above the upper surface of the pixel, even if light is incident on the pixel from an oblique direction, the adjacent pixel It is possible to more effectively suppress light leakage to the image.
- the difference between the refractive index of the partition wall 25 with respect to light having a wavelength of 533 nm and the refractive index of the pixels 21 (22, 23) adjacent to the partition wall 25 with respect to light having a wavelength of 1000 nm is 0.30 to 0.80.
- the lower limit of the difference in refractive index is preferably 0.40 or more, and more preferably 0.50 or more, for the reason of suppressing crosstalk.
- the upper limit of the difference in refractive index is preferably 0.75 or less, and more preferably 0.70 or less.
- the porosity of the partition wall 25 is preferably 20 to 80%.
- the lower limit of the porosity is preferably 30% or more, more preferably 40% or more.
- the upper limit of the porosity is preferably 70% or less, more preferably 60% or less.
- the material of the partition wall 25 is not particularly limited. Examples thereof include organic materials such as siloxane resin and fluororesin, and inorganic particles such as silica particles and magnesium fluoride.
- the partition wall 25 preferably contains silica particles because the strength of the partition wall can be increased.
- silica particles examples include silica particles having a shape in which a plurality of spherical silicas are connected in a bead shape (hereinafter, also referred to as beaded silica), silica particles having a hollow structure (hereinafter, also referred to as hollow silica), and the like. It is preferably silica. Further, it is also preferable that at least a part of the hydroxy groups on the surface of the silica particles of the silica particles is treated with a hydrophobizing agent that reacts with the hydroxy groups.
- the hydrophobizing agent a compound having a structure that reacts with the hydroxy group on the surface of the silica particles (preferably a structure that couples with the hydroxy group on the surface of the silica particles) and improves the hydrophobicity of the silica particles is used. ..
- the hydrophobizing agent is preferably an organic compound.
- Specific examples of the hydrophobizing agent include an organic silane compound, an organic titanium compound, an organic zirconium compound and an organic aluminum compound, and an organic silane compound is more preferable because an increase in the refractive index can be suppressed.
- "spherical" means that it may be substantially spherical and may be deformed as long as the effect of the present invention is exhibited.
- a plurality of spherical silica particles are connected in a beaded shape means a structure in which a plurality of spherical silica particles are connected in a linear and / or branched form.
- a structure in which a plurality of spherical silica particles are connected to each other at a joint having a smaller outer diameter can be mentioned.
- the structure in which "a plurality of spherical silica particles are connected in a beaded shape" is not only a structure in which the particles are connected in a ring shape but also a chain shape having an end. Structure is also included.
- the beaded silica preferably has a ratio D 1 / D 2 of the average particle size D 1 measured by the dynamic light scattering method and the average particle size D 2 obtained by the following formula (1) of 3 or more.
- D 1 / D 2 There is no particular upper limit of D 1 / D 2 , but it is preferably 1000 or less, more preferably 800 or less, and even more preferably 500 or less. By setting D 1 / D 2 in such a range, good optical characteristics can be exhibited.
- D 2 is the average particle size of the beaded silica
- the unit is nm
- S is the specific surface area of the beaded silica measured by the nitrogen adsorption method, and the unit is m 2 / g. is there.
- the average particle size D 2 of the beaded silica can be regarded as an average particle size close to the diameter of the primary particles of spherical silica.
- the average particle size D 2 is preferably 1 nm or more, more preferably 3 nm or more, further preferably 5 nm or more, and particularly preferably 7 nm or more.
- the upper limit is preferably 100 nm or less, more preferably 80 nm or less, further preferably 70 nm or less, further preferably 60 nm or less, and particularly preferably 50 nm or less.
- the average particle size D 2 can be replaced by the equivalent circle diameter (D0) in the projected image of the spherical portion measured by a transmission electron microscope (TEM). Unless otherwise specified, the average particle size based on the circle-equivalent diameter is evaluated by averaging the number of 50 or more particles.
- D0 equivalent circle diameter
- TEM transmission electron microscope
- the average particle size D 1 of the beaded silica can be regarded as the number average particle size of the secondary particles in which a plurality of spherical silicas are collected. Therefore, the relationship of D 1 > D 2 usually holds.
- the average particle size D 1 is preferably 5 nm or more, more preferably 7 nm or more, and particularly preferably 10 nm or more.
- the upper limit is preferably 100 nm or less, more preferably 70 nm or less, further preferably 50 nm or less, and particularly preferably 45 nm or less.
- the measured average particle diameter D 1 of the beaded silica unless otherwise indicated, carried out using a dynamic light scattering particle size distribution analyzer (Nikkiso Co., Ltd., Microtrac UPA-EX150).
- the procedure is as follows. The dispersion of beaded silica is divided into 20 ml sample bottles, and diluted with propylene glycol monomethyl ether so that the solid content concentration becomes 0.2% by mass. The diluted sample solution is irradiated with ultrasonic waves of 40 kHz for 1 minute, and immediately after that, it is used for the test. Data is captured 10 times using a 2 ml quartz cell for measurement at a temperature of 25 ° C., and the obtained "number average” is taken as the average particle size.
- JISZ8828 2013 "Particle size analysis-Dynamic light scattering method” as necessary. Five samples are prepared for each level and the average value is adopted.
- the beaded silica it is preferable that a plurality of spherical silicas having an average particle diameter of 1 to 80 nm are connected via a connecting material.
- the upper limit of the average particle size of the spherical silica is preferably 70 nm or less, more preferably 60 nm or less, and further preferably 50 nm or less.
- the lower limit of the average particle size of the spherical silica is preferably 3 nm or more, more preferably 5 nm or more, and further preferably 7 nm or more.
- the value of the average particle diameter of the spherical silica the value of the average particle diameter obtained from the equivalent circle diameter in the projected image of the spherical portion measured by the transmission electron microscope (TEM) is used.
- TEM transmission electron microscope
- Examples of the connecting material for connecting spherical silica to each other in prayer-shaped silica include metal oxide-containing silica.
- Examples of the metal oxide include oxides of metals selected from Ca, Mg, Sr, Ba, Zn, Sn, Pb, Ni, Co, Fe, Al, In, Y, and Ti.
- Examples of the metal oxide-containing silica include a reaction product and a mixture of these metal oxides and silica (SiO 2).
- the connecting material the description of International Publication No. 2000/015552 can be referred to, and this content is incorporated in the present specification.
- the number of connected spherical silicas in the beads of silica is preferably 3 or more, and more preferably 5 or more.
- the upper limit is preferably 1000 or less, more preferably 800 or less, and even more preferably 500 or less.
- the number of connected spherical silicas can be measured by TEM.
- particle liquids containing beaded silica include Snowtex series and organosilica sol series (methanol dispersion, isopropyl alcohol dispersion, ethylene glycol dispersion, methyl ethyl ketone dispersion, etc.) manufactured by Nissan Chemical Industry Co., Ltd. Part No. IPA -ST-UP, MEK-ST-UP, etc.). Further, as the particle liquid containing beaded silica, for example, the silica sol described in Japanese Patent No. 4328935 can be used.
- the average particle size of hollow silica is preferably 10 to 500 nm.
- the lower limit is preferably 15 nm or more, more preferably 20 nm or more, and even more preferably 25 nm or more.
- the upper limit is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less.
- the average particle size of hollow silica is a value measured by a dynamic light scattering method. Examples of commercially available particle liquids containing hollow silica include "Thruria 4110" manufactured by JGC Catalysts and Chemicals Co., Ltd.
- the partition wall 25 can be formed by using a conventionally known method.
- the partition wall can be formed as follows. First, a bulkhead material layer is formed on the support.
- the partition wall material layer can be formed, for example, by applying a composition containing inorganic particles such as silica particles (partition wall composition) onto a support and then curing the partition wall material layer. Examples of such a composition include the compositions described in paragraphs 0012 to 0077 and 093 to 0105 of International Publication No. 2019/017280, the compositions described in paragraph number 0079 of International Publication No. 2019/111748, and the like. These contents are incorporated herein by reference.
- an inorganic material such as silicon dioxide can be formed on the support by a vapor deposition method such as chemical vapor deposition (CVD) or vacuum vapor deposition, or a method such as sputtering to form a partition wall material layer.
- a resist pattern is then formed on the bulkhead material layer using a mask that has a pattern that follows the shape of the bulkhead.
- the partition wall material layer is etched to form a pattern. Examples of the etching method include a dry etching method and a wet etching method. Etching by the dry etching method can be performed under the conditions described in paragraphs 0128 to 0133 of JP-A-2016-014856. Then, the resist pattern is peeled off from the partition material layer. In this way, the partition wall can be formed.
- a base layer may be provided at the boundary 25a between the partition wall 25 and the pixels 21, 22, 23.
- the adhesion between the pixel and the partition wall can be improved. Further, it is possible to suppress the diffusion of the components in the pixel into the partition wall and increase the strength of the partition wall.
- the material of the base layer various inorganic materials and organic materials can be used.
- the organic material include acrylic resin, polystyrene resin, polyimide resin, and organic SOG (Spin On Glass) resin.
- a composition containing a compound having an ethylenically unsaturated bond-containing group can be used to form an underlayer.
- an underlayer can be formed by using an organic silane compound such as 1,1,1,3,3,3-hexamethyldisilazane.
- organic silane compound such as 1,1,1,3,3,3-hexamethyldisilazane.
- the ethylenically unsaturated bond-containing group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a styryl group and the like, and a (meth) allyl group and a (meth) acryloyl group are preferable.
- the compound having an ethylenically unsaturated bond-containing group may be a monomer or a resin such as a polymer.
- the inorganic material include silicon dioxide and aluminum oxide.
- the base layer can be formed by using a conventionally known method.
- a composition containing an organic material (composition for a base layer) can be applied and dried on a partition wall.
- a vapor deposition method such as chemical vapor deposition (CVD) or vacuum vapor deposition, or a method such as sputtering. Can be formed.
- the pixel pitch P1 in the optical filter 20 is preferably 400 to 1200 nm.
- the lower limit of the pixel pitch P1 is preferably 450 nm or more, and more preferably 500 nm or more.
- the upper limit of the pixel pitch P1 is preferably 1000 nm or less, more preferably 900 nm or less, and further preferably 800 nm or less.
- the pixel pitch is the total value of the width of the partition wall and the width of the pixels located on one side surface side of the partition wall. Further, when the base layer exists between the partition wall and the pixel, it is a value including the width of the base layer.
- the solid-state image sensor of the present invention can obtain a particularly remarkable effect when the optical filter 20 having a narrow pixel pitch is used.
- the solid-state image sensor shown in FIG. 1 is provided with a microlens 30 on the surface of the optical filter 20 on the light incident side. Although not shown, a flattening layer may be provided between the microlens 30 and the optical filter 20.
- the shape of the microlens 30 shown in FIG. 1 is a semicircular lens shape, but this shape is not particularly limited and is described in a trapezoidal lens or JP-A-2014-029524. Shaped lenses can also be used.
- the refractive index of the microlens 30 with respect to light having a wavelength of 550 nm is preferably 1.50 to 1.80.
- the upper limit of the refractive index is preferably 1.75 or less, and more preferably 1.70 or less.
- the lower limit of the refractive index is preferably 1.55 or more, and more preferably 1.58 or more.
- the minimum transmittance of the microlens 30 with respect to light having a wavelength of 400 to 700 nm is preferably 90% or more, and more preferably 95% or more.
- the microlens may contain a near-infrared absorber. Examples of the near-infrared absorber include those described later.
- the microlens 30 is provided on the surface of the optical filter 20, but in the solid-state image sensor of the present invention, the microlens 30 can be omitted.
- the image pickup device provided with the solid-state image sensor of the present invention can be used not only for digital cameras and electronic devices having an image pickup function (mobile phones, etc.), but also for in-vehicle cameras and surveillance cameras.
- composition for forming colored pixels which is preferably used for forming colored pixels of an optical filter, will be described.
- the composition for forming colored pixels preferably contains a chromatic colorant.
- the chromatic colorant include chromatic colorants such as a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant.
- the chromatic colorant may be a pigment or a dye. Pigments and dyes may be used in combination. Examples of the pigment include those shown below.
- a halogenated zinc phthalocyanine having an average of 10 to 14 halogen atoms in one molecule, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms. Pigments can also be used. Specific examples include the compounds described in WO 2015/118720. Further, as a green colorant, a compound described in Chinese Patent Application No. 106909027, a phthalocyanine compound having a phosphate ester described in International Publication No. 2012/10395 as a ligand, and Japanese Patent Application Laid-Open No. 2019-008014. , The phthalocyanine compound described in JP-A-2018-180023, the compound described in JP-A-2019-038958, and the like can also be used.
- an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP2012-247591A and paragraph numbers 0047 of JP2011-157478A.
- Methine dyes described in JP-A-2019-073695, methine dyes described in JP-A-2019-073696, methine dyes described in JP-A-2019-073697, methine dyes described in JP-A-2019-073698, etc. Can also be used. Further, a multimerized version of these compounds is also preferably used from the viewpoint of improving the color value. Further, as the yellow colorant, C.I. I. Pigment Yellow129 and C.I. I. It is also preferable to use Pigment Yellow 215.
- a pigment multimer can be used as the chromatic colorant.
- the dye multimer is preferably a dye that is used by dissolving it in a solvent. Further, the dye multimer may form particles. When the dye multimer is a particle, it is usually used in a state of being dispersed in a solvent.
- the pigment multimer in the particle state can be obtained by, for example, emulsion polymerization, and specific examples thereof include the compounds and production methods described in JP-A-2015-214682.
- the dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less.
- the plurality of dye structures contained in one molecule may have the same dye structure or different dye structures.
- the weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50,000.
- the lower limit is more preferably 3000 or more, and even more preferably 6000 or more.
- the upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
- Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, International Publication No. 2016/031442, and the like. Compounds can also be used.
- the content of the chromatic colorant is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and 40% by mass or more in the total solid content of the composition for forming colored pixels. Is particularly preferable.
- the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less.
- the composition for forming colored pixels can further contain a pigment derivative.
- the pigment derivative include compounds having a structure in which a part of the chromophore is replaced with an acid group, a basic group or a phthalimide methyl group.
- the chromogens constituting the pigment derivative include quinoline skeleton, benzoimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthracinone skeleton, quinacridone skeleton, dioxazine skeleton, perinone skeleton, perylene skeleton, thioindigo skeleton, and iso.
- the azo skeleton and the benzoimidazolone skeleton are more preferred.
- the acid group contained in the pigment derivative a sulfo group and a carboxyl group are preferable, and a sulfo group is more preferable.
- the basic group contained in the pigment derivative an amino group is preferable, and a tertiary amino group is more preferable.
- a pigment derivative having excellent visible transparency hereinafter, also referred to as a transparent pigment derivative
- the maximum value of the molar extinction coefficient in the wavelength region of 400 ⁇ 700 nm of the transparent pigment derivative (.epsilon.max) is that it is preferable, 1000L ⁇ mol -1 ⁇ cm -1 or less is not more than 3000L ⁇ mol -1 ⁇ cm -1 Is more preferable, and 100 L ⁇ mol -1 ⁇ cm -1 or less is further preferable.
- the lower limit of ⁇ max is, for example, 1 L ⁇ mol -1 ⁇ cm -1 or more, and may be 10 L ⁇ mol -1 ⁇ cm -1 or more.
- pigment derivative examples include the compounds described in Examples described later, JP-A-56-118462, JP-A-63-246674, JP-A-01-217777, and JP-A-03-009961.
- Japanese Patent Application Laid-Open No. 03-026767 Japanese Patent Application Laid-Open No. 03-153780
- Japanese Patent Application Laid-Open No. 03-045662 Japanese Patent Application Laid-Open No. 04-285669
- Japanese Patent Application Laid-Open No. 06-145546 Japanese Patent Application Laid-Open No. 06-120888
- Japanese Patent Application Laid-Open No. 06-240158 Japanese Patent Application Laid-Open No. 10-030063
- the content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the pigment. Only one kind of pigment derivative may be used, or two or more kinds may be used in combination.
- the composition for forming colored pixels can contain a polymerizable compound.
- the polymerizable compound is preferably, for example, a compound having an ethylenically unsaturated bond-containing group.
- examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
- the polymerizable compound is preferably a radically polymerizable compound.
- the polymerizable compound may be in any chemical form such as a monomer, a prepolymer, or an oligomer, but a monomer is preferable.
- the molecular weight of the polymerizable compound is preferably 100 to 3000.
- the upper limit is more preferably 2000 or less, and even more preferably 1500 or less.
- the lower limit is more preferably 150 or more, and even more preferably 250 or more.
- the polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond-containing groups, and an ethylenically unsaturated bond. It is more preferable that the compound contains 3 to 6 containing groups.
- the radically polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities.
- radically polymerizable compound examples include paragraph numbers 0905 to 0108 of JP2009-288705A, paragraph 0227 of JP2013-209760A, and paragraphs 0254 to 0257 of JP2008-292970.
- Examples include the compounds described in the publication, the contents of which are incorporated herein by reference.
- radically polymerizable compound examples include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku (commercially available)).
- the content of the polymerizable compound in the total solid content of the composition for forming colored pixels is preferably 0.1 to 50% by mass.
- the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
- the upper limit is more preferably 45% by mass or less, further preferably 40% by mass or less.
- the polymerizable compound may be used alone or in combination of two or more.
- the composition for forming colored pixels can contain a photopolymerization initiator.
- the photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet region to the visible region is preferable.
- the photopolymerization initiator is preferably a photoradical polymerization initiator.
- photopolymerization initiator examples include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, and thio compounds. , Ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds and the like.
- the photopolymerization initiator is a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triarylimidazole.
- It is preferably a dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxaziazole compound and a 3-aryl substituted coumarin compound, and an oxime compound and an ⁇ -hydroxyketone compound.
- ⁇ -Aminoketone compound, and an acylphosphine compound are more preferable, and an oxime compound is further preferable.
- the photopolymerization initiator the compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173 and JP-A-6301489, MATERIAL STAGE 37-60p, vol.
- ⁇ -hydroxyketone compounds Commercially available products of the ⁇ -hydroxyketone compound include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins BV), Irgacare 184, Irgacare 1173, Irgacare 1173, Irgacure29. (Manufactured by the company) and the like.
- Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, IGM Resins BV), Irgacare 907, Irgacare 369, Irgacure 369, Irgacure 369, Irgar (Made) and so on.
- acylphosphine compounds examples include Omnirad 819, Omnirad TPO (above, manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (above, manufactured by BASF).
- Examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, and the compounds described in JP-A-2006-342166.
- oxime compound examples include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminovtan-2-one, 2-acetoxyimiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy Examples thereof include imino-1-phenylpropane-1-one.
- an oxime compound having a fluorine atom can also be used as the photopolymerization initiator.
- Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471. Compound (C-3) and the like.
- the content of the photopolymerization initiator in the total solid content of the composition for forming colored pixels is preferably 0.1 to 30% by mass.
- the lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more.
- the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less. Only one type of photopolymerization initiator may be used, or two or more types may be used.
- the composition for forming colored pixels can contain a resin.
- the resin is blended, for example, for the purpose of dispersing particles such as pigments in a composition for forming colored pixels and for the purpose of a binder.
- a resin mainly used for dispersing particles such as pigments is also referred to as a dispersant.
- the weight average molecular weight (Mw) of the resin is preferably 3000 to 2000000.
- the upper limit is more preferably 1,000,000 or less, still more preferably 500,000 or less.
- the lower limit is more preferably 4000 or more, further preferably 5000 or more.
- the resin examples include (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, and polyamideimide resin. , Polyolefin resin, cyclic olefin resin, polyester resin, styrene resin and the like. One of these resins may be used alone, or two or more thereof may be mixed and used.
- the resin described in JP-A-2017-032685, the resin described in JP-A-2017-075248, and the resin described in JP-A-2017-066240 can also be used.
- the resin it is preferable to use a resin having an acid group.
- the developability of the composition for forming colored pixels can be improved.
- the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and a carboxyl group is preferable.
- the resin having an acid group can be used as, for example, an alkali-soluble resin.
- the resin having an acid group preferably contains a repeating unit having an acid group in the side chain, and more preferably contains 5 to 70 mol% of the repeating unit having an acid group in the side chain in all the repeating units of the resin.
- the upper limit of the content of the repeating unit having an acid group in the side chain is more preferably 50 mol% or less, and particularly preferably 30 mol% or less.
- the lower limit of the content of the repeating unit having an acid group in the side chain is more preferably 10 mol% or more, and particularly preferably 20 mol% or more.
- the composition for forming colored pixels may also contain a resin as a dispersant.
- the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
- the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups.
- the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, and is substantially an acid. A resin consisting only of groups is more preferable.
- the acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group.
- the acid value of the acidic dispersant is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and even more preferably 60 to 105 mgKOH / g.
- the basic dispersant represents a resin in which the amount of basic groups is larger than the amount of acid groups.
- the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%.
- the basic group contained in the basic dispersant is preferably an amino group.
- the resin used as the dispersant is preferably a graft resin.
- the graft resin examples include the resins described in paragraphs 0025 to 0094 of JP2012-255128A, the contents of which are incorporated in the present specification.
- the resin used as the dispersant is preferably a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain.
- the polyimine-based dispersant has a main chain having a partial structure having a functional group of pKa14 or less, a side chain having 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and the side chain.
- the resin to have is preferable.
- the basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity.
- the polyimine-based dispersant examples include the resins described in paragraphs 0102 to 0166 of JP2012-255128A, the contents of which are incorporated in the present specification.
- the resin used as the dispersant is preferably a resin having a structure in which a plurality of polymer chains are bonded to the core portion.
- examples of such a resin include dendrimers (including star-shaped polymers).
- Specific examples of the dendrimer include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962.
- the resin used as the dispersant is preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in the side chain.
- the content of the repeating unit having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and 20 to 70 in all the repeating units of the resin. It is more preferably mol%.
- Dispersants are also available as commercial products, and specific examples thereof include DISPERBYK series manufactured by BYK Chemie (for example, DISPERBYK-111, 161 etc.) and Solsparse series manufactured by Nippon Lubrizol Co., Ltd. (for example, DISPERBYK-111, 161 etc.). For example, Solsparse 76500) and the like.
- the pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can also be used, and the contents thereof are incorporated in the present specification.
- the resin described as the dispersant can also be used for purposes other than the dispersant. For example, it can also be used as a binder.
- the content of the resin in the total solid content of the colored pixel forming composition is preferably 5 to 50% by mass.
- the lower limit is more preferably 10% by mass or more, further preferably 15% by mass or more.
- the upper limit is more preferably 40% by mass or less, further preferably 35% by mass or less, and particularly preferably 30% by mass or less.
- the composition for forming colored pixels can contain a compound having a cyclic ether group.
- the cyclic ether group include an epoxy group and an oxetanyl group.
- the compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter, also referred to as an epoxy compound).
- the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferable.
- the epoxy compound preferably has 1 to 100 epoxy groups in one molecule.
- the upper limit of the number of epoxy groups may be, for example, 10 or less, or 5 or less.
- the lower limit of the number of epoxy groups is preferably two or more.
- Examples of the epoxy compound are described in paragraphs 0034 to 0036 of JP2013-011869A, paragraph numbers 0147 to 0156 of JP2014-043556, and paragraph numbers 0085 to 0092 of JP2014-089408.
- Compounds, compounds described in JP-A-2017-179172 can also be used. These contents are incorporated herein by reference.
- Commercially available products of compounds having a cyclic ether group include, for example, EHPE3150 (manufactured by Daicel Co., Ltd.), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G.
- the content of the compound having a cyclic ether group in the total solid content of the colored pixel-forming composition is preferably 0.1 to 20% by mass. ..
- the lower limit is, for example, more preferably 0.5% by mass or more, further preferably 1% by mass or more.
- the upper limit is, for example, more preferably 15% by mass or less, further preferably 10% by mass or less.
- the compound having a cyclic ether group may be only one kind or two or more kinds.
- the composition for forming colored pixels can contain a silane coupling agent.
- the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
- the hydrolyzable group refers to a substituent that is directly linked to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction.
- Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and the like, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
- Examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group and an isocyanate group.
- a phenyl group and the like preferably an amino group, a (meth) acryloyl group and an epoxy group.
- Specific examples of the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP2009-288703A and the compounds described in paragraphs 0056 to 0066 of JP2009-242604A.
- the contents of are incorporated herein by reference.
- the content of the silane coupling agent in the total solid content of the composition for forming colored pixels is preferably 0.1 to 5% by mass.
- the upper limit is preferably 3% by mass or less, and more preferably 2% by mass or less.
- the lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more.
- the silane coupling agent may be only one kind or two or more kinds.
- the composition for forming colored pixels can contain a surfactant.
- a surfactant various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used.
- the surfactant the surfactant described in paragraph Nos. 0238 to 0245 of International Publication No. 2015/166779 is mentioned, and the content thereof is incorporated in the present specification.
- the surfactant is preferably a fluorine-based surfactant. Examples of the fluorine-based surfactant include the surfactants described in paragraphs 0060 to 0064 of Japanese Patent Application Laid-Open No.
- the surfactants described in paragraphs 0117 to 0132 of JP 132503 are mentioned and their contents are incorporated herein by reference. Further, the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorine-based surfactants used in the present invention.
- the weight average molecular weight of the above compounds is preferably 3000-50000, for example 14000.
- % indicating the ratio of the repeating unit is mol%.
- the content of the surfactant in the total solid content of the composition for forming colored pixels is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005 to 3.0% by mass.
- the surfactant may be only one kind or two or more kinds.
- the composition for forming colored pixels can contain an ultraviolet absorber.
- an ultraviolet absorber a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound and the like can be used. Examples of such compounds include paragraph numbers 0038 to 0052 of JP2009-217221A, paragraph numbers 0052 to 0072 of JP2012-208374A, and paragraph numbers 0317 to 0334 of JP2013-068814. Examples include the compounds described in paragraphs 0061 to 0080 of JP 2016-162946, the contents of which are incorporated herein.
- Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.).
- Examples of the benzotriazole compound include the MYUA series made by Miyoshi Oil & Fat Co., Ltd. (The Chemical Daily, February 1, 2016).
- the ultraviolet absorber the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used.
- the content of the ultraviolet absorber in the total solid content of the composition for forming colored pixels is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. In the present invention, only one type of ultraviolet absorber may be used, or two or more types may be used.
- the composition for forming colored pixels preferably contains an organic solvent.
- the organic solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition for forming colored pixels.
- the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents and the like. More details thereof include the solvents described in paragraph No. 0223 of WO 2015/166779, the contents of which are incorporated herein by reference. Further, an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used.
- organic solvent examples include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -Heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N , N-Dimethylpropanamide and the like.
- aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may need to be reduced for environmental reasons (for example, 50 mass ppm (parts) with respect to the total amount of organic solvent. Per million) or less, 10 mass ppm or less, or 1 mass ppm or less).
- the content of the organic solvent in the composition for forming colored pixels is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.
- Colored pixel-forming compositions include sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliaries (eg, conductive particles, fillers, defoamers, etc.) It may contain a flame retardant, a leveling agent, a peeling accelerator, a fragrance, a surface tension modifier, a chain transfer agent, etc.). By appropriately containing these components, properties such as film physical characteristics can be adjusted. These components are described in, for example, paragraph No. 0183 and subsequent paragraphs of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraphs of JP-A-2008-250074. The descriptions of Nos.
- the composition for forming colored pixels may contain a latent antioxidant, if necessary.
- the latent antioxidant is a compound whose site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst.
- Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
- Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation) and the like.
- the composition for forming white pixels preferably contains a white pigment.
- the white pigment includes not only pure white but also a light gray (for example, grayish white, light gray, etc.) pigment close to white.
- White pigments include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow. Examples include resin particles and zinc sulfide.
- the white pigment is preferably particles having a titanium atom, and more preferably titanium oxide.
- titanium oxide described in "Titanium Oxide Physical Properties and Applied Technology, Manabu Kiyono, pp. 13-45, published on June 25, 1991, published by Gihodo" can also be used.
- the white pigment not only those composed of a single inorganic substance but also particles compounded with other materials may be used. For example, particles having pores or other materials inside, particles in which a large number of inorganic particles are attached to core particles, core particles composed of core particles composed of polymer particles, and core and shell composite particles composed of a shell layer composed of inorganic nanoparticles are used. Is preferable.
- Hollow inorganic particles can also be used as the white pigment.
- Hollow inorganic particles are inorganic particles having a structure having cavities inside, and refer to inorganic particles having cavities surrounded by an outer shell. Examples of the hollow inorganic particles include the hollow inorganic particles described in JP-A-2011-075786, International Publication No. 2013/061621, JP-A-2015-164881, and the like, and the contents thereof are incorporated in the present specification. Is done.
- the content of the white pigment is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and particularly preferably 30% by mass or more, based on the total solid content of the white pixel forming composition.
- the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 65% by mass or less, and particularly preferably 60% by mass or less.
- the composition for forming white pixels can further contain a polymerizable compound, a photopolymerization initiator, a resin, a compound having a cyclic ether group, a silane coupling agent, a surfactant, an ultraviolet absorber, an organic solvent and the like. ..
- the preferable range of these materials and contents is the same as the materials and contents described in the above-mentioned section of the composition for forming colored pixels.
- the composition for forming pixels for a near-infrared cut filter preferably contains a near-infrared absorber.
- the near-infrared absorber is preferably a compound having a maximum absorption wavelength on the longer wavelength side than the wavelength of 700 nm.
- the near-infrared absorber is preferably a compound having a maximum absorption wavelength in the range of more than 700 nm and 1800 nm or less.
- near infrared absorber that the ratio A 1 / A 2 between the absorbance A 2 in the absorbance A 1 and the maximum absorption wavelength in the wavelength 500nm is preferably 0.08 or less, 0.04 or less More preferred.
- Near-infrared absorbers include pyrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonor compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyromethene compounds, Examples thereof include azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, and metal borides.
- Examples of the pyrrolopyrrole compound include the compounds described in paragraphs 0016 to 0058 of JP2009-263614, the compounds described in paragraphs 0037 to 0052 of JP2011-066731, and International Publication No. 2015/166783. Examples thereof include the compounds described in paragraphs 0010 to 0033.
- Examples of the squarylium compound include the compounds described in paragraphs 0044 to 0049 of JP2011-208101A, the compounds described in paragraphs 0060 to 0061 of Patent No. 6065169, and paragraph numbers 0040 of International Publication No. 2016/181987. , The compound described in JP-A-2015-176046, the compound described in paragraph number 0072 of International Publication No.
- JP2012-077153 the oxytitanium phthalocyanine described in JP2006-343631, and paragraphs 0013 to 0029 of JP2013-195480.
- vanadium phthalocyanine compound described in Japanese Patent No. 6081771.
- examples of the naphthalocyanine compound include the compounds described in paragraph No. 0093 of JP2012-077153.
- Examples of the dithiolene metal complex include the compounds described in Japanese Patent No. 5733804.
- the metal oxide include indium tin oxide, antimonthine oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, and tungsten oxide.
- tungsten oxide paragraph number 0080 of JP-A-2016-006476 can be referred to, and the contents thereof are incorporated in the present specification.
- the metal boride include lanthanum hexaboride. Examples of commercially available lanthanum boride, LaB 6 -F (manufactured by Japan New Metals Co., Ltd.), and the like. Further, as the metal boride, the compound described in International Publication No. 2017/119394 can also be used. Examples of commercially available indium tin oxide products include F-ITO (manufactured by DOWA Hi-Tech Co., Ltd.).
- Examples of the near-infrared absorber include a squarylium compound described in JP-A-2017-197437, a squarylium compound described in JP-A-2017-025311, a squarylium compound described in International Publication No. 2016/154782, and Patent No. Squalylium compounds described in 5884953, squalylium compounds described in Japanese Patent No. 6036689, squalylium compounds described in Japanese Patent No. 5810604, squalylium compounds described in paragraph numbers 0090 to 0107 of International Publication No.
- An amide-linked squalylium compound a compound having a pyrrolbis-type squalylium skeleton or a croconium skeleton described in JP-A-2017-141215, a dihydrocarbazolebis-type squalylium compound described in JP-A-2017-082029, JP-A-2017-
- the content of the near-infrared absorber is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, based on the total solid content of the pixel-forming composition for the near-infrared cut filter.
- the lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more.
- the composition for forming pixels for a near-infrared cut filter further contains a polymerizable compound, a photopolymerization initiator, a resin, a compound having a cyclic ether group, a silane coupling agent, a surfactant, an ultraviolet absorber, an organic solvent and the like. can do.
- the preferable range of these materials and contents is the same as the materials and contents described in the above-mentioned section of the composition for forming colored pixels.
- composition for forming pixels for a near-infrared transmissive filter which is preferably used for forming pixels for a near-infrared transmissive filter of an optical filter.
- the composition for forming pixels for a near-infrared ray transmitting filter may also contain a color material that transmits near-infrared rays and blocks visible light (hereinafter, also referred to as a color material that blocks visible light).
- the color material that blocks visible light is preferably a color material that absorbs light in the wavelength region of purple to red.
- the color material that blocks visible light is preferably a color material that blocks light in the wavelength region of 450 to 650 nm. Further, the color material that blocks visible light is preferably a color material that transmits light having a wavelength of 900 to 1300 nm.
- the coloring material that blocks visible light preferably satisfies at least one of the following requirements (A) and (B).
- B Contains an organic black colorant.
- Examples of the chromatic colorant include those described above.
- Examples of the organic black colorant include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, and bisbenzofuranone compounds and perylene compounds are preferable.
- Examples of the bisbenzofuranone compound include the compounds described in JP-A-2010-534726, JP-A-2012-515233, and JP-A-2012-515234.
- Examples of the perylene compound include the compounds described in paragraphs 0016 to 0020 of JP-A-2017-226821, C.I. I. Pigment Black 31, 32 and the like can be mentioned.
- Examples of the azomethine compound include compounds described in JP-A-01-170601 and JP-A-02-0346664, and are available as, for example, "Chromofine Black A1103" manufactured by Dainichiseika.
- Examples of the combination of chromatic colorants when black is formed by the combination of two or more kinds of chromatic colorants include the following. (1) An embodiment containing a yellow colorant, a blue colorant, a purple colorant, and a red colorant. (2) An embodiment containing a yellow colorant, a blue colorant, and a red colorant. (3) An embodiment containing a yellow colorant, a purple colorant, and a red colorant. (4) An embodiment containing a yellow colorant and a purple colorant. (5) An embodiment containing a green colorant, a blue colorant, a purple colorant, and a red colorant. (6) An embodiment containing a purple colorant and an orange colorant. (7) An embodiment containing a green colorant, a purple colorant, and a red colorant. (8) An embodiment containing a green colorant and a red colorant.
- the content of the coloring material that blocks visible light is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, based on the total solid content of the pixel-forming composition for the near-infrared transmission filter. 20% by mass or less is even more preferable, and 15% by mass or less is particularly preferable.
- the lower limit can be, for example, 0.01% by mass or more, or 0.5% by mass or more.
- composition for forming pixels for a near-infrared transmission filter can further contain a near-infrared absorber.
- the preferable range of these materials and contents is the same as the materials and contents described in the section of the pixel forming composition for the near infrared transmission filter described above.
- the composition for forming pixels for a near-infrared transmission filter further contains a polymerizable compound, a photopolymerization initiator, a resin, a compound having a cyclic ether group, a silane coupling agent, a surfactant, an ultraviolet absorber, an organic solvent and the like. can do.
- the preferable range of these materials and contents is the same as the materials and contents described in the above-mentioned section of the composition for forming colored pixels.
- composition for base layer ⁇ Manufacturing of composition for base layer> The following raw materials were mixed to produce a composition for an underlayer.
- Resin A 0.7 parts by mass
- Surfactant A 0.8 parts by mass
- compositions for partition walls 1-3, 6 Each component is mixed so as to have the composition shown in the table below (the numerical value of the blending amount is a part by mass), and filtration is performed using DFA4201NIEY (0.45 ⁇ m nylon filter) manufactured by Nippon Pole to perform partition wall compositions 1 to 3 and 6 were manufactured.
- silica particle solution A propylene glycol monomethyl ether solution (silica particle concentration 20 mass) of silica particles (beaded silica) in which a plurality of spherical silicas having an average particle diameter of 15 nm are connected in a bead shape by a metal oxide-containing silica (connecting material). %) To 100.0 g of a silica particle solution prepared by adding 3.0 g of trimethylmethoxysilane as a hydrophobizing agent and reacting at 20 ° C. for 6 hours.
- the average particle diameter of spherical silica was obtained by calculating the number average of the equivalent circle diameters in the projected images of the spherical portions of 50 spherical silica measured by a transmission electron microscope (TEM). .. Further, in the silica particle liquid P1, it was examined by the method of TEM observation whether or not a plurality of spherical silicas contained silica particles having a shape in which a plurality of spherical silicas were connected in a bead shape.
- TEM transmission electron microscope
- P2 Through rear 4110 (manufactured by JGC Catalysts and Chemicals Co., Ltd., a solution of silica particles (silica particles having a hollow structure) having an average particle diameter of 60 nm. Solid content concentration 20% by mass in terms of SiO 2)
- P3 Silica particle solution P3 prepared by the following method A reaction mother liquor was prepared by mixing 100 g of a silica sol having an average particle size of 5 nm and a SiO 2 concentration of 20% by mass and 1900 g of pure water, and heated to 80 ° C.
- the pH of this reaction mother liquor was 10.5, and 9000 g of a 1.17 mass% sodium silicate aqueous solution as SiO 2 and 9000 g of a 0.83 mass% sodium aluminate aqueous solution as Al2O3 were simultaneously added to the mother liquor. During that time, the temperature of the reaction solution was maintained at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition of sodium silicate and sodium aluminate, and remained almost unchanged thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO 2 ⁇ Al 2 O 3 primary particle dispersion having a solid content concentration of 20% by mass.
- aqueous dispersion of the silica-based fine particles (1) 500 g of pure water, 1750 g of ethanol, and 626 g of 28% aqueous ammonia are added, and the obtained mixed solution is heated to 35 ° C. and then ethyl silicate (SiO). 2 28 wt%) 104 g was added. Then, while adding 5 L of pure water, the mixture was washed with an ultrafiltration membrane to prepare a dispersion liquid of silica-based fine particles (2) having a solid content concentration of 20% by mass. Then, the dispersion of the silica-based fine particles (2) was hydroheat-treated at 200 ° C.
- This organosol is an organosol in which hollow silica fine particles having an average particle diameter of 23 nm are dispersed (hereinafter, referred to as “hollow silica sol A”).
- organosols 100 g (water content of SiO 2 minutes 20 wt% to SiO 2 minutes 0.5% by mass) was prepared.
- a 28% aqueous ammonia solution was added to 100 g of the organosol so as to be 100 mass ppm as ammonia, and the mixture was sufficiently mixed.
- reaction solution was heated to 50 ° C. and heated at 50 ° C. for 15 hours with stirring. After completion of heating, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a silica particle solution P3 composed of coated hollow fine particles having a SiO2 concentration of 20% by mass.
- F-2 Compound with the following structure
- Silane coupling agent 1 Compound with the following structure
- composition for partition wall 4 To 1000 g of an aqueous solution containing 40% by mass of tetrapropylammonium hydroxide (TPAOH, manufactured by Lion Co., Ltd.), 300 g of cation exchange resin powder (WK-40, manufactured by Mitsubishi Chemical Co., Ltd.) was added, and under room temperature conditions. After stirring at a rate of 100 rpm for 1 hour, the added cation exchange resin powder was filtered off. Next, 2100 g of anion exchange resin powder (SAT-10, manufactured by Mitsubishi Chemical Corporation) was added, and the mixture was stirred at a speed of 100 rpm for 1 hour under room temperature conditions, and then the added anion exchange resin powder was filtered. Removed.
- TPAOH tetrapropylammonium hydroxide
- Ultrapure water is added to the obtained aqueous solution of tetrapropylammonium hydroxide (TPAOH) to adjust the concentration to 10% by mass, and the alkali metal elements of sodium (Na) and potassium (K) contained as impurities in the aqueous solution.
- Atomic absorption method AAS method, polarized Zeeman atomic absorption spectrophotometer Z-5710 manufactured by Hitachi, Ltd.
- ion chromatography method respectively, for the amounts of the compounds of bromine (Br) and halogen group elements of chlorine (Cl). (2020i manufactured by DIONEX) was measured.
- ultrapure water is added to an aqueous solution (commercially available) of tetrapropylammonium hydroxide before the above ion exchange treatment to adjust the concentration to 10% by mass, and then the impurities contained therein are also contained therein. The amount was measured.
- the amount of impurities contained in the aqueous solution before the ion exchange treatment was 50 mass ppm of sodium, 2500 mass ppm of potassium, 2250 mass ppm of bromine and 13 mass ppm of chlorine on an elemental basis, whereas the ion exchange treatment
- the content of impurities contained in the subsequent aqueous solution was sodium 10 mass ppb or less (detection limit), potassium 10 mass ppb (detection limit), bromine 1 mass ppm or less, and chlorine 1 mass ppm or less on an elemental basis.
- tetraethyl orthosilicate (TEOS, manufactured by Tama Chemical Industry Co., Ltd.), methyltrimethoxysilane (MTMS, manufactured by Shin-Etsu Chemical Co., Ltd.) and ethanol (ETOH, manufactured by Wako Pure Chemical Industries, Ltd.) at a concentration of 99.5% by mass. ) was mixed, and the mixed solution was kept at a temperature of 20 ° C. and stirred at a rate of 150 rpm for 30 minutes.
- a highly purified aqueous solution of tetrapropylammonium hydroxide (containing 10% by mass of TPAOH) was added dropwise to these mixed solutions over 10 minutes, and the mixture was further stirred at a temperature of 20 ° C.
- the mixture was heated to a temperature of 50 ° C., and the silica-based film-forming components (TEOS and MTMS) were hydrolyzed for 20 hours while stirring at a speed of 200 rpm under these temperature conditions.
- ethanol in the mixed solution containing the hydrolyzate of the silica-based film-forming component was subjected to a step of solvent-substituting with propylene glycol monopropyl ether using a rotary evaporator, and then tetraethyl orthosilicate (TEOS) and methyltrimethoxy.
- the concentration of the silicon compound composed of the hydrolyzate of silane (MTMS) was adjusted to obtain a liquid composition containing 12% by mass of this compound on the basis of SiO 2 conversion. This liquid composition was designated as the partition wall composition 4.
- composition for partition wall 5 0.05 g (0.4 mmol) of methyltrimethoxysilane (KBM-13: manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and trifluoropropyltrimethoxysilane (KBM-7103: Shin-Etsu Chemical Industry Co., Ltd.) in a 500 ml three-mouth flask.
- an aqueous phosphoric acid solution prepared by dissolving 0.088 g of phosphoric acid in 4.09 g of water was added over 3 minutes. Then, the flask was immersed in an oil bath at 40 ° C. and stirred for 60 minutes, and then the temperature of the oil bath was raised to 115 ° C. over 30 minutes. One hour after the start of the temperature rise, the internal temperature of the solution reached 100 ° C., and the mixture was heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain the partition wall composition 4.
- the solid content concentration of the obtained partition wall composition 4 was 24.3% by mass, and the contents of the polysiloxane and silica particles in the solid content were 15% by mass and 85% by mass, respectively.
- Pigment derivative 1 Compound with the following structure
- Pigment derivative 2 A compound having the following structure
- Pigment derivative 3 A compound having the following structure
- Pigment derivative 4 A compound having the following structure
- Dispersant 1 Resin having the following structure (the numerical value added to the main chain is the molar ratio of the repeating unit, and the numerical value added to the side chain is the number of repeating units).
- Dispersant 3 Resin having the following structure (the numerical value added to the main chain is wt%, and the numerical value added to the side chain is the number of repeating units. Mw: 13000, acid value: 65 mgKOH / g)
- composition for pixel formation After stirring the mixed solution containing the following raw materials, the mixture is filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 ⁇ m to form a pixel-forming composition (green coloring composition G1 to 7, red coloring composition).
- a product R1, a blue coloring composition B1, a yellow coloring composition Y1, a magenta coloring composition M1 and a cyan coloring composition C1) were obtained, respectively.
- the values shown in the table below are parts by mass.
- Resin 1 A 40% by mass PGMEA solution of a resin having the following structure (the numerical value attached to the main chain represents the molar ratio of the repeating unit).
- Resin 2 A 40% by mass PGMEA solution of a resin having the following structure (the numerical value added to the main chain represents the molar ratio of the repeating unit. Mw: 18000).
- Polymerizable compound 1 A compound having the following structure
- Polymerizable compound 2 A compound having the following structure
- Polymerizable compound 3 A mixture of the following structural compounds (molar ratio of compound on the left side to compound on the right side 7: 3)
- Photopolymerization initiator 1 Compound with the following structure
- Photopolymerization Initiator 2 Compound with the following structure
- Photopolymerization Initiator 3 Compound with the following structure
- Photopolymerization Initiator 4 Compound with the following structure
- UV absorber 1 Compound with the following structure
- UV absorber 2 Compound with the following structure
- Silane coupling agent 1 Compound with the following structure
- Silane coupling agent 2 A compound having the following structure
- Epoxy compound 1 EHPE3150 (manufactured by Daicel Corporation, 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2'-bis (hydroxymethyl) -1-butanol)
- Lens Material Composition 1 The following raw materials were mixed to produce a lens material composition 1.
- -Raw material of lens material composition 1- Resin with the following structure (Mw: 19000, the numerical value attached to the main chain is the molar ratio of the repeating unit) ... 10 parts by mass Surfactant (Futergent DFX-18, manufactured by Neos Co., Ltd.) ⁇ ⁇ ⁇ 0.01 parts by mass PGMEA ⁇ ⁇ ⁇ 51.4 parts by mass Propylene glycol monomethyl ether (PGME) ⁇ ⁇ ⁇ 22.0 parts by mass
- lens material composition 2 The following raw materials were mixed to produce a lens material composition 2.
- Examples 1 to 27 As a support, a silicon wafer having a diameter of 8 inches (20.32 cm) on which a silicon photodiode was formed was used.
- the composition for partition walls described in the table below is post-baked on the surface of the silicon wafer on the side where the silicon photodiode is formed, and then applied by a spin coating method to the film thickness shown in the table below, and then hot.
- a film was formed by heating at 100 ° C. for 120 seconds and at 200 ° C. for 300 seconds using a plate. When the partition wall composition 5 was used, it was further heated at 300 ° C. for 10 minutes to form a film.
- a base layer having a film thickness of 10 nm was formed on the surfaces of the silicon wafer and the partition wall.
- the composition for forming pixels of the first color described in the following table is applied to the surface of the silicon wafer on which the partition wall is formed by a spin coating method, and then heated at 100 ° C. for 2 minutes using a hot plate. A first color composition layer was formed.
- the composition layer was exposed with an exposure amount of 150 mJ / cm 2 using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) through a mask having a Bayer pattern.
- the composition layer was paddle-developed at 23 ° C. for 60 seconds. After that, rinsing with a spin shower and washing with pure water were carried out, and further, the pixels were heated at 220 ° C. for 5 minutes using a hot plate, and the pixels of the first color were contained in the region partitioned by the partition wall on the silicon wafer.
- TMAH tetramethylammonium hydroxide
- Pixels of the second color and pixels of the third color were sequentially formed inside to form an optical filter.
- the pixel height and refractive index values are shown in the table below.
- the pixel pitch is also described in the table below.
- the pixel pitch is the total size of the pixel width and the partition wall width (the total size of the partition wall opening size (width) and the partition wall width).
- the lens material composition described in the table below is applied onto this optical filter by a spin coating method, then heated at 100 ° C. for 2 minutes using a hot plate, and then at 200 ° C. using a hot plate.
- the lens material composition layer having a film thickness of 1.2 ⁇ m was formed by heating for 5 minutes.
- the lens material composition layer is processed so that the height from the lens top to the lens bottom is 400 nm to form a microlens for solid-state imaging. Manufactured the element.
- the refractive index of the partition wall was measured by the following method. That is, the composition for partition walls is applied onto a quartz glass substrate using a spin coater (manufactured by Mikasa Co., Ltd.) to form a coating film, and then heated at 100 ° C. for 120 seconds using a hot plate (pre-baking). ), Then, using a hot plate, heating (post-baking) at 200 ° C. for 300 seconds was performed to form a film having a thickness of 0.3 ⁇ m. The refractive index of the obtained film with respect to light having a wavelength of 533 nm was measured using ellipsometry VUV-VASE (manufactured by JA Woolam Japan).
- the refractive index of the pixel was measured by the following method. That is, the coloring composition is applied onto a quartz glass substrate using a spin coater (manufactured by Mikasa Co., Ltd.) to form a coating film, and then heated (prebaked) at 100 ° C. for 120 seconds using a hot plate. Then, heating (post-baking) at 200 ° C. for 300 seconds was performed using a hot plate to form a film having a thickness of 0.3 ⁇ m.
- the refractive index of the obtained film with respect to light having a wavelength of 1000 nm was measured using ellipsometry VUV-VASE (manufactured by JA Woolam Japan).
- a silicon wafer having a diameter of 8 inches (20.32 cm) on which a silicon photodiode was formed was used.
- the composition for the base layer prepared above is applied on the surface of the silicon wafer on the side where the silicon photodiode is formed by the spin coating method, and is used at 100 ° C. for 2 minutes and then at 230 ° C. for 2 minutes using a hot plate.
- a base layer having a film thickness of 10 nm was formed by heating.
- the first color coloring composition described in the following table is applied to the surface of the base layer by a spin coating method, and then heated at 100 ° C. for 2 minutes using a hot plate to heat the first color composition layer.
- the colored composition layer was exposed with an exposure amount of 150 mJ / cm 2 using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) through a mask having a Bayer pattern. Then, using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), the green composition layer was paddle-developed at 23 ° C. for 60 seconds. Then, rinsing with a spin shower and washing with pure water were carried out, and further, the first color pixels were formed by heating at 220 ° C. for 5 minutes using a hot plate.
- TMAH tetramethylammonium hydroxide
- the second color composition and the third color composition are also developed and exposed in the same manner as the first color composition, and the second color pixel and the third color pixel are formed in the missing portion of the first color pixel.
- the pixel height and refractive index values are shown in the table below.
- the pixel pitch is also described in the table below. In Comparative Example 1, the pixel pitch is the width of the pixels.
- the lens material composition shown in the table below is applied onto an optical filter by a spin coating method, then heated at 100 ° C. for 2 minutes using a hot plate, and then heated at 200 ° C. using a hot plate 5
- the lens material composition layer having a film thickness of 1.2 ⁇ m was formed by heating for 1 minute.
- the lens material composition layer is processed so that the height from the lens top to the lens bottom is 400 nm to form a microlens for solid-state imaging. Manufactured the element.
- the sensitivity (QE30) of the silicon photodiode at the portion corresponding to each pixel with respect to the light emitted from the angular direction was measured, and the sensitivity ratio (QE0 / QE30) was calculated. The results are shown in the table below. The closer the sensitivity ratio is to 1, the better the sensitivity to light in the oblique direction.
- the sensitivity was measured by measuring the charge obtained from the silicon photodiode.
- the example had a sensitivity ratio closer to 1 than the comparative example, and was superior in sensitivity to light in the oblique direction. Further, in the solid-state image sensor of the example, the variation in the sensitivity characteristics between the central portion and the peripheral portion of the silicon photodiode is smaller than that of the solid-state image sensor of the comparative example, and a clearer image can be obtained. Further, the same effect was obtained even if the green coloring composition G1 was changed to G2 to G7.
- Support 10 Photoelectric conversion unit 20: Optical filter 21-23: Pixel 25: Partition 30: Microlens 100: Solid-state image sensor
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Abstract
Description
<1> 光電変換部を有する支持体と、
上記光電変換部への光入射側に設けられた光学フィルタと、を有し、
上記光学フィルタは、パターン状に配置された2種以上の画素と、各画素間に配置された隔壁とを有し、
上記隔壁の波長533nmの光に対する屈折率が1.10~1.30であり、
上記隔壁の幅が80~150nmであり、
上記画素の波長1000nmの光に対する屈折率が1.60~1.90であり、
上記隔壁の厚さと、上記隔壁と隣接する画素の厚さとの差が200nm以下であり、
上記隔壁の波長533nmの光に対する屈折率と、上記隔壁と隣接する画素の波長1000nmの光に対する屈折率との差が0.30~0.80である、
固体撮像素子。
<2> 上記隔壁の厚さが300~650nmである、<1>に記載の固体撮像素子。
<3> 上記画素の厚さが300~600nmである、<1>または<2>に記載の固体撮像素子。
<4> 上記画素の幅が300~1100nmである、<1>~<3>のいずれか1つに記載の固体撮像素子。
<5> 上記光学フィルタの画素ピッチが400~1200nmである、<1>~<4>のいずれか1つに記載の固体撮像素子。
<6> 上記隔壁の厚さと、上記隔壁と隣接する画素の厚さとの差が1nm以上である、<1>~<5>のいずれか1つに記載の固体撮像素子。
<7> 上記隔壁は、上記画素よりも厚さが大きい、<1>~<6>のいずれか1つに記載の固体撮像素子。
<8> 上記隔壁の空隙率が20~80%である、<1>~<7>のいずれか1つに記載の固体撮像素子。
<9> 上記隔壁は、複数個の球状シリカが数珠状に連結した形状のシリカ粒子、および、中空構造のシリカ粒子から選ばれる少なくとも1種を含む、<1>~<8>のいずれか1つに記載の固体撮像素子。
<10> 上記隔壁と上記画素側との間に下地層を有する、<1>~<9>のいずれか1つに記載の固体撮像素子。
<11> 上記画素の表面粗さRa値が0.1~5.0nmである、<1>~<10>のいずれか1つに記載の固体撮像素子。
<12> 上記光学フィルタは、黄色画素、シアン色画素およびマゼンタ色画素から選ばれる少なくとも1種の画素を含む、<1>~<11>のいずれか1つに記載の固体撮像素子。
本発明の固体撮像素子は、
光電変換部を有する支持体と、
光電変換部への光入射側に設けられた光学フィルタと、を有し、
光学フィルタは、パターン状に配置された2種以上の画素と、各画素間に配置された隔壁とを有し、
隔壁の波長533nmの光に対する屈折率が1.10~1.30であり、
隔壁の幅が80~150nmであり、
画素の波長1000nmの光に対する屈折率が1.60~1.90であり、
隔壁の厚さと、隔壁と隣接する画素の厚さとの差が200nm以下であり、
隔壁の波長533nmの光に対する屈折率と、隔壁と隣接する画素の波長1000nmの光に対する屈折率との差が0.30~0.80である、ことを特徴とする。
(2):波長400~750nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長900~1300nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ層。
(3):波長400~830nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長1000~1300nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ層。
(4):波長400~950nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長1100~1300nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ層。
隔壁の厚さと画素と厚さとが同じ場合、すなわち、隔壁の上面と画素上面がそろっている場合は、上部に形成されるマイクロレンズの形成性を高めることができる。
隔壁の厚さが画素の厚さよりも小さい場合、すなわち、隔壁の上面が画素の上面よりも下方に位置している場合には、画素形成用の組成物の塗布性が良好であり、画素形成用の組成物の塗布ムラを抑制できる。
隔壁の厚さが画素よりも厚さが大きい場合、すなわち、隔壁の上面が画素の上面よりも上方に位置している場合には、画素に斜め方向から光が入射しても、隣接する画素への光漏れなどをより効果的に抑制できる。
D2=2720/S ・・・(1)
式中、D2は数珠状シリカの平均粒子径であって、単位はnmであり、Sは、窒素吸着法により測定された数珠状シリカの比表面積であって、単位はm2/gである。
次に、光学フィルタの着色画素の形成に好ましく用いられる着色画素形成用組成物について説明する。着色画素形成用組成物は有彩色着色剤を含有することが好ましい。有彩色着色剤としては、赤色着色剤、緑色着色剤、青色着色剤、黄色着色剤、紫色着色剤、オレンジ色着色剤などの有彩色着色剤が挙げられる。有彩色着色剤は、顔料であってもよく、染料であってもよい。顔料と染料とを併用してもよい。顔料としては以下に示すものが挙げられる。
C.I.Pigment Orange 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73等(以上、オレンジ色顔料)、
C.I.Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,291,294(キサンテン系、Organo Ultramarine、Bluish Red),295(モノアゾ系),296(ジアゾ系),297(アミノケトン系)等(以上、赤色顔料)、
C.I.Pigment Green 7,10,36,37,58,59,62,63,64(フタロシアニン系),65(フタロシアニン系),66(フタロシアニン系)等(以上、緑色顔料)、
C.I.Pigment Violet 1,19,23,27,32,37,42,60(トリアリールメタン系),61(キサンテン系)等(以上、紫色顔料)、
C.I.Pigment Blue 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,29,60,64,66,79,80,87(モノアゾ系),88(メチン系)等(以上、青色顔料)。
次に、光学フィルタの白色画素の形成に好ましく用いられる白色画素形成用組成物について説明する。白色画素形成用組成物は、白色顔料を含有することが好ましい。本発明において、白色顔料は純白色のみならず、白に近い明るい灰色(例えば灰白色、薄灰色など)の顔料などを含む。白色顔料としては、酸化チタン、チタン酸ストロンチウム、チタン酸バリウム、酸化亜鉛、酸化マグネシウム、酸化ジルコニウム、酸化アルミニウム、硫酸バリウム、シリカ、タルク、マイカ、水酸化アルミニウム、ケイ酸カルシウム、ケイ酸アルミニウム、中空樹脂粒子、硫化亜鉛などが挙げられる。白色顔料は、チタン原子を有する粒子が好ましく、酸化チタンがより好ましい。また、白色顔料は「酸化チタン 物性と応用技術 清野学著 13~45ページ 1991年6月25日発行、技報堂出版発行」に記載の酸化チタンを用いることもできる。白色顔料は、単一の無機物からなるものだけでなく、他の素材と複合させた粒子を用いてもよい。例えば、内部に空孔や他の素材を有する粒子、コア粒子に無機粒子を多数付着させた粒子、ポリマー粒子からなるコア粒子と無機ナノ微粒子からなるシェル層とからなるコアおよびシェル複合粒子を用いることが好ましい。上記ポリマー粒子からなるコア粒子と無機ナノ微粒子からなるシェル層とからなるコアおよびシェル複合粒子としては、例えば、特開2015-047520号公報の段落番号0012~0042の記載を参酌することができ、この内容は本明細書に組み込まれる。白色顔料は、中空無機粒子を用いることもできる。中空無機粒子とは、内部に空洞を有する構造の無機粒子であり、外殻に包囲された空洞を有する無機粒子のことを言う。中空無機粒子としては、特開2011-075786号公報、国際公開第2013/061621号、特開2015-164881号公報などに記載された中空無機粒子が挙げられ、これらの内容は本明細書に組み込まれる。
次に、光学フィルタの近赤外線カットフィルタ用画素の形成に好ましく用いられる近赤外線カットフィルタ用画素形成用組成物について説明する。近赤外線カットフィルタ用画素形成用組成物は、近赤外線吸収剤を含有することが好ましい。近赤外線吸収剤は、極大吸収波長を波長700nmよりも長波長側に有する化合物であることが好ましい。近赤外線吸収剤は波長700nmを超え1800nm以下の範囲に極大吸収波長を有する化合物であることが好ましい。また、近赤外線吸収剤は、波長500nmにおける吸光度A1と極大吸収波長における吸光度A2との比率A1/A2が、0.08以下であることが好ましく、0.04以下であることがより好ましい。
次に、光学フィルタの近赤外線透過フィルタ用画素の形成に好ましく用いられる近赤外線透過フィルタ用画素形成用組成物について説明する。近赤外線透過フィルタ用画素形成用組成物は、近赤外線を透過させて可視光を遮光する色材(以下、可視光を遮光する色材ともいう)を含有することもできる。本発明において、可視光を遮光する色材は、紫色から赤色の波長領域の光を吸収する色材であることが好ましい。また、本発明において、可視光を遮光する色材は、波長450~650nmの波長領域の光を遮光する色材であることが好ましい。また、可視光を遮光する色材は、波長900~1300nmの光を透過する色材であることが好ましい。本発明において、可視光を遮光する色材は、以下の(A)および(B)の少なくとも一方の要件を満たすことが好ましい。
(A):2種類以上の有彩色着色剤を含み、2種以上の有彩色着色剤の組み合わせで黒色を形成している。
(B):有機系黒色着色剤を含む。
(1)黄色着色剤、青色着色剤、紫色着色剤および赤色着色剤を含有する態様。
(2)黄色着色剤、青色着色剤および赤色着色剤を含有する態様。
(3)黄色着色剤、紫色着色剤および赤色着色剤を含有する態様。
(4)黄色着色剤および紫色着色剤を含有する態様。
(5)緑色着色剤、青色着色剤、紫色着色剤および赤色着色剤を含有する態様。
(6)紫色着色剤およびオレンジ色着色剤を含有する態様。
(7)緑色着色剤、紫色着色剤および赤色着色剤を含有する態様。
(8)緑色着色剤および赤色着色剤を含有する態様。
下記原料を混合して下地層用組成物を製造した。
樹脂A ・・・0.7質量部
界面活性剤A ・・・0.8質量部
プロピレングリコールモノメチルエーテルアセテート(PGMEA) ・・・98.5質量部
・樹脂A:サイクロマーP(ACA)230AA ((株)ダイセル製、酸価=30mgKOH/g、Mw=15000、54質量%PGME溶液)
・界面活性剤A:下記構造の化合物(Mw=14000、繰り返し単位の割合を示す%の数値はモル%である、フッ素系界面活性剤)の0.2質量%PGMEA溶液
(隔壁用組成物1~3、6)
以下の表の組成(配合量の数値は質量部である)となるように各成分を混合し、日本ポール製DFA4201NIEY(0.45μmナイロンフィルター)を用いてろ過を行って隔壁用組成物1~3、6を製造した。
[シリカ粒子液]
P1:平均粒子径15nmの球状シリカの複数個が金属酸化物含有シリカ(連結材)によって数珠状に連結された形状のシリカ粒子(数珠状シリカ)のプロピレングリコールモノメチルエーテル溶液(シリカ粒子濃度20質量%)の100.0gに疎水化処理剤としてトリメチルメトキシシランの3.0gを添加し、20℃で6時間反応させて調製したシリカ粒子液である。なお、シリカ粒子液P1において、球状シリカの平均粒子径は、透過型電子顕微鏡(TEM)によって測定した50個の球状シリカの球状部分の投影像における円相当直径の数平均を算出して求めた。また、シリカ粒子液P1において、TEM観察の方法で、複数個の球状シリカが数珠状に連結された形状のシリカ粒子を含むものであるかどうか調べた。
P2:スルーリア4110(日揮触媒化成(株)製、平均粒子径60nmのシリカ粒子(中空構造のシリカ粒子)の溶液である。SiO2換算の固形分濃度20質量%)
P3:以下の方法で調製したシリカ粒子液P3
平均粒径5nm、SiO2濃度20質量%のシリカゾル100gと純水1900gとを混合して反応母液を調製し、80℃に加温した。この反応母液のpHは10.5であり、同母液にSiO2として1.17質量%の珪酸ナトリウム水溶液9000gと、Al2O3として0.83質量%のアルミン酸ナトリウム水溶液9000gとを同時に添加した。その間、反応液の温度を80℃に保持した。反応液のpHは、珪酸ナトリウムおよびアルミン酸ナトリウムの添加直後、12.5に上昇し、その後、ほとんど変化しなかった。添加終了後、反応液を室温まで冷却し、限外濾過膜で洗浄して固形分濃度20質量%のSiO2・Al2O3一次粒子分散液を調製した。ついで、このSiO2・Al2O3一次粒子分散液500gを採取し、純水1700gを加えて98℃に加温し、この温度を保持しながら、濃度0.5質量%の硫酸ナトリウム50400gを添加し、ついでSiO2として濃度1.17質量%の珪酸ナトリウム水溶液3000gとAl2O3としての濃度0.5質量%のアルミン酸ナトリウム水溶液9000gを添加して複合酸化物微粒子分散液を得た。そして、これを限外濾過膜で洗浄して固形分濃度13質量%の複合酸化物微粒子分散液とした。この複合酸化物微粒子分散液500gに純水1125gを加え、さらに濃塩酸(35.5%)を滴下してpH1.0とし、脱アルミニウム処理を行った。次いで、pH3の塩酸水溶液10Lと純水5Lを加えながら限外濾過膜で溶解したアルミニウム塩を分離し、洗浄して固形分濃度20質量%のシリカ系微粒子(1)の分散液を得た。このシリカ系微粒子(1)の水分散液1500gに、純水500gと、エタノール1750gと、28%アンモニア水626gとを加え、得られた混合液を35℃に加温した後、エチルシリケート(SiO228質量%)104gを添加した。ついで、純水5Lを加えながら、限外濾過膜で洗浄して固形分濃度20質量%のシリカ系微粒子(2)の分散液を調製した。ついで、再びシリカ系微粒子(2)の分散液を200℃にて11時間水熱処理した後、純水5Lを加えながら限外濾過膜で洗浄して固形分濃度20質量%に調整した。そして、限外濾過膜を用いて、この分散液の分散媒をプロピレングリコールモノメチルエーテルに置換し、固形分濃度20質量%のオルガノゾルを調製した。このオルガノゾルは、平均粒子径が23nmの中空シリカ微粒子が分散したオルガノゾル(以下、「中空シリカゾルA」と称する。)である。中空シリカゾルA(シリカ固形分濃度20質量%)200gを用意し、限外濾過膜にて、メタノールへの溶媒置換を行い、SiO2分が20質量%のオルガノゾル100g(水分量はSiO2分に対して0.5質量%)を調製した。そこへ28%アンモニア水溶液をオルガノゾル100gに対してアンモニアとして100質量ppmとなるように加え、充分に混合し、次に、メタクリルシラン(信越化学株式会社製KBM503)4g(SiO2分100質量部に対して20質量部相当)を添加し、反応液(水分量はSiO2分に対して0.6質量%)とした。これを50℃に加温し、攪拌しながら50℃で15時間加熱を行なった。加熱終了後、反応液を常温まで冷却し、限外濾過膜で洗浄して、SiO2濃度20質量%の被覆中空微粒子からなるシリカ粒子液P3を調製した。
S-1:1,4-ブタンジオールジアセテート(沸点232℃、粘度3.1mPa・s、分子量174)
S-2:プロピレングリコールモノメチルエーテルアセテート(沸点146℃、粘度1.1mPa・s、分子量132)
S-4:メタノール(沸点=64℃、粘度=0.6mPa・s)
S-5:エタノール(沸点=78℃、粘度=1.2mPa・s)
S-6:水(沸点100℃、粘度0.9mPa・s)
S-7:下記構造の化合物(以下の構造式中n=6)
テトラプロピルアンモニウムハイドロオキサイドを40質量%含む水溶液1000g(TPAOH、ライオン(株)製)に、陽イオン交換樹脂の粉末300g(WK-40、三菱化学(株)製)を添加し、室温条件下、100rpmの速度で1時間撹拌した後、添加した陽イオン交換樹脂粉末を濾過して取り除いた。次に、陰イオン交換樹脂の粉末2100g(SAT-10、三菱化学(株)製)を添加し、室温条件下、100rpmの速度で1時間攪拌した後、添加した陰イオン交換樹脂粉末を濾過して取り除いた。得られたテトラプロピルアンモニウムハイドロオキサイド(TPAOH)の水溶液に超純水を加えて、10質量%の濃度に調整し、水溶液中に不純物として含まれるナトリウム(Na)およびカリウム(K)のアルカリ金属元素の化合物、並びに臭素(Br)および塩素(Cl)のハロゲン族元素の化合物の量をそれぞれ原子吸光法(AAS法、(株)日立製作所製偏光ゼーマン原子吸光光度計Z-5710)およびイオンクロマト法(DIONEX製2020i)で測定した。さらに、上記のイオン交換処理を行う前のテトラプロピルアンモニウムハイドロオキサイドの水溶液(市販品)に超純水を加えて、10質量%の濃度に調整した後、同様にその中に含まれる不純物の含有量を測定した。その結果、イオン交換処理前の水溶液中に含まれていた不純物量が元素基準でナトリウム50質量ppm、カリウム2500質量ppm、臭素2250質量ppmおよび塩素13質量ppmであったのに対し、イオン交換処理後の水溶液中に含む不純物の含有量は、元素基準でナトリウム10質量ppb以下(検出限界)、カリウム10質量ppb(検出限界)、臭素1質量ppm以下および塩素1質量ppm以下であった。次に、テトラエチルオルソシリケート(TEOS、多摩化学工業(株)製)、メチルトリメトキシシラン(MTMS、信越化学工業(株)製)および99.5質量%濃度のエタノール(ETOH、和光純薬(株)製)を混合し、この混合溶液を20℃の温度に保持し、150rpmの速度で30分間撹拌した。これらの混合溶液に、高純度化されたテトラプロピルアンモニウムハイドロオキサイド水溶液(10質量%のTPAOHを含む)を10分かけて滴下し、さらに20℃の温度で200rpmの速度で1時間撹拌した。その後、50℃の温度に加熱し、この温度条件下にて200rpmの速度で攪拌しながら20時間、シリカ系被膜形成成分(TEOSおよびMTMS)の加水分解を行った。次いで、シリカ系被膜形成成分の加水分解物を含む混合溶液中のエタノールを、ロータリーエバポレーターを用いてプロピレングリコールモノプロピルエーテルと溶媒置換する工程に供した後、テトラエチルオルソシリケート(TEOS)とメチルトリメトキシシラン(MTMS)の加水分解物からなるケイ素化合物の濃度を調整して、この化合物をSiO2換算基準で12質量%含む液状組成物を得た。この液状組成物を隔壁用組成物4とした。
500mlの三口フラスコに、メチルトリメトキシシラン(KBM-13:信越化学工業(株)製)を0.05g(0.4mmol)、トリフルオロプロピルトリメトキシシラン(KBM-7103:信越化学工業(株)製)を0.66g(3.0mmol)、トリメトキシシリルプロピルコハク酸無水物(KBM-967:信越化学工業(株)製)を0.10g(0.4mmol)、γ-アクリロキシプロピルトリメトキシシラン(KBM-5103:信越化学工業(株)製)を7.97g(34mmol)、15.6質量%のシリカ粒子のイソプロピルアルコール分散液(IPA-ST-UP:日産化学工業(株)製)を224.37g混合し、エチレングリコールモノ-t-ブチルエーテル163.93gを加えた。室温で撹拌しながら、水4.09gにリン酸0.088gを溶かしたリン酸水溶液を3分間かけて添加した。その後、フラスコを40℃のオイルバスに浸けて60分間撹拌した後、オイルバスを30分間かけて115℃まで昇温した。昇温開始1時間後に溶液の内温が100℃に到達し、そこから2時間加熱撹拌し(内温は100~110℃)、隔壁用組成物4を得た。得られた隔壁用組成物4の固形分濃度は24.3質量%、固形分中のポリシロキサンとシリカ粒子の含有量はそれぞれ15質量%、85質量%であった。
(分散液の製造)
下記表に記載の原料を混合した混合液を、ビーズミル(ジルコニアビーズ0.1mm径)を用いて3時間混合および分散した。次いで、減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製)を用いて圧力2000kg/cm3および流量500g/minの条件の下、分散処理を行なった。この分散処理を全10回繰り返して、各分散液を得た。下記表に記載の数値は質量部である。
[着色剤]
・PG7 :C.I.Pigment Green 7
・PG58 :C.I.Pigment Green 58
・PG36 :C.I.Pigment Green 36
・PY129 :C.I.Pigment Yellow 129
・PY139 :C.I.Pigment Yellow 139
・PY150 :C.I.Pigment Yellow 150
・PY185 :C.I.Pigment Yellow 185
・PR122 :C.I.Pigment Red 122
・PR254 :C.I.Pigment Red 254
・PB15:6 :C.I.Pigment Blue 15:6
・PV23 :C.I.Pigment Violet 23
分散剤1:下記構造の樹脂(主鎖に付記された数値は繰り返し単位のモル比であり、側鎖に付記された数値は繰り返し単位の数である。)
溶剤1:PGMEA
下記原料を混合した混合液を撹拌した後、孔径0.45μmのナイロン製フィルタ(日本ポール(株)製)でろ過して、画素形成用組成物(緑色着色組成物G1~7、赤色着色組成物R1、青色着色組成物B1、黄色着色組成物Y1、マゼンタ色着色組成物M1およびシアン色着色組成物C1)をそれぞれ得た。下記表に記載の数値は質量部である。
分散液G1~5、分散液R1、分散液B1、分散液Y1、分散液M1、分散液C1:上述した分散液G1~5、分散液R1、分散液B1、分散液Y1、分散液M1、分散液C1
樹脂1:下記構造の樹脂(主鎖に付記された数値は繰り返し単位のモル比を表す。)の40質量%PGMEA溶液
界面活性剤1:下記構造の化合物(Mw=14000、繰り返し単位の割合を示す%の数値はモル%である、フッ素系界面活性剤)の1質量%PGMEA溶液
エポキシ化合物1:EHPE3150((株)ダイセル製、2,2’-ビス(ヒドロキシメチル)-1-ブタノールの1,2-エポキシ-4-(2-オキシラニル)シクロヘキサン付加物)
溶剤1:PGMEA
溶剤2:エチル3-エトキシプロピオネート(EEP)
(レンズ材組成物1)
下記原料を混合してレンズ材組成物1を製造した。
-レンズ材組成物1の原料-
下記構造の樹脂(Mw:19000、主鎖に付記された数値は繰り返し単位のモル比である) ・・・10質量部
PGMEA ・・・51.4質量部
プロピレングリコールモノメチルエーテル(PGME) ・・・22.0質量部
[分散液IR-1の製造]
下記原料を混合して分散液IR-1を製造した。
-分散液IR-1の原料-
近赤外線吸収色素(下記構造の化合物) ・・・6.1質量部
下記原料を混合してレンズ材組成物2を製造した。
-レンズ材組成物2の原料-
分散液IR-1 ・・・12.0質量部
重合性化合物(下記構造の化合物) ・・・6.9質量部
重合禁止剤(p-メトキシフェノール) ・・・0.0195質量部
界面活性剤(下記構造の化合物(Mw=14000、繰り返し単位の割合を示す%の数値はモル%である、フッ素系界面活性剤) ・・・0.00025質量部
PGME ・・・42.8質量部
(実施例1~27)
支持体として、シリコンフォトダイオードが形成された直径8インチ(20.32cm)のシリコンウエハを用いた。シリコンウエハのシリコンフォトダイオードが形成された側の表面上に、下記表に記載の隔壁用組成物をポストベーク後、下記表に記載の膜厚になるようにスピンコート法で塗布した後、ホットプレートを用いて100℃で120秒、200℃で300秒加熱して膜を形成した。なお、隔壁用組成物5を用いた場合は更に追加で300℃10分加熱して膜を形成した。これらの膜を特開2016-014856号公報の段落番号0128~0133に記載された条件にてドライエッチング法でパターニングして隔壁を表に記載のピッチで格子状に形成した。隔壁の幅、高さ、屈折率、シリコンウエハ上の隔壁の開口の寸法(シリコンウエハ上の隔壁で区画された領域)をそれぞれ下記表に示す。
次に、これらの隔壁を形成したシリコンウエハ及び隔壁の表面に、上記で作製した下地層用組成物をスピンコート法で塗布し、ホットプレートを用いて100℃で2分間、さらに230℃で2分間、加熱して、膜厚10nmの下地層をシリコンウエハ及び隔壁の表面に形成した。
次に、隔壁を形成したシリコンウエハの表面に、下記表に記載の1色目の画素形成用組成物をスピンコート法で塗布し、次いで、ホットプレートを用いて100℃で2分間加熱して、1色目の組成物層を形成した。次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を用い、ベイヤーパターンを有するマスクを介して、150mJ/cm2の露光量で上記組成物層を露光した。次いで、水酸化テトラメチルアンモニウム(TMAH)0.3質量%水溶液を用い、組成物層に対し23℃で60秒間パドル現像を行った。その後、スピンシャワーによるリンス、純水を用いた水洗を実施し、さらに、ホットプレートを用いて220℃で5分間を加熱して、シリコンウエハ上の隔壁で区画された領域内に1色目の画素を形成した。2色目の画素形成用組成物、3色目の画素形成用組成物についても、1色目の画素形成用組成物と同様の方法にて現像および露光を行い、シリコンウエハ上の隔壁で区画された領域内に2色目の画素、3色目の画素を順次形成して光学フィルタを形成した。画素の高さおよび屈折率の値をそれぞれ下記表に示す。また、画素ピッチについても併せて下記表に記す。画素ピッチは、画素の幅と隔壁の幅との合計サイズ(隔壁の開口部の寸法(幅)と隔壁の幅との合計サイズ)のことである。
次いで、この光学フィルタ上に、下記表に記載のレンズ材組成物をスピンコート法で塗布し、次いで、ホットプレートを用いて100℃で2分間加熱し、次いで、ホットプレートを用いて200℃で5分間加熱して膜厚1.2μmのレンズ材組成物層を形成した。その後、公知の技術であるエッチバックによる転写方法を用いて、レンズトップからレンズボトムまでの高さが400nmになるようにレンズ材組成物層を加工することにより、マイクロレンズを形成して固体撮像素子を製造した。
支持体として、シリコンフォトダイオードが形成された直径8インチ(20.32cm)のシリコンウエハを用いた。シリコンウエハのシリコンフォトダイオードが形成された側の表面上に、上記で作製した下地層用組成物をスピンコート法で塗布し、ホットプレートを用いて100℃で2分間、さらに230℃で2分間、加熱して、膜厚10nmの下地層を形成した。
次に、下地層表面に、下記表に記載の1色目の着色組成物をスピンコート法で塗布し、次いで、ホットプレートを用いて100℃で2分間加熱して、1色目の着色組成物層を形成した。次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を用い、ベイヤーパターンを有するマスクを介して、150mJ/cm2の露光量で上記着色組成物層を露光した。次いで、水酸化テトラメチルアンモニウム(TMAH)0.3質量%水溶液を用い、緑色組成物層に対し23℃で60秒間パドル現像を行った。その後、スピンシャワーによるリンス、純水を用いた水洗を実施し、さらに、ホットプレートを用いて220℃で5分間を加熱して、1色目の画素を形成した。2色目の着色組成物、3色目の着色組成物についても、1色目の着色組成物と同様の方法にて現像および露光を行い1色目の画素の抜け部に2色目の画素、3色目の画素を順次形成して光学フィルタを形成した。画素の高さおよび屈折率の値をそれぞれ下記表に示す。また、画素ピッチについても併せて下記表に記す。なお、比較例1においては画素ピッチは、画素の幅のことである。
次いで、光学フィルタ上に、下記表に記載のレンズ材組成物をスピンコート法で塗布し、次いで、ホットプレートを用いて100℃で2分間加熱し、次いで、ホットプレートを用いて200℃で5分間加熱して膜厚1.2μmのレンズ材組成物層を形成した。その後、公知の技術であるエッチバックによる転写方法を用いて、レンズトップからレンズボトムまでの高さが400nmになるようにレンズ材組成物層を加工することにより、マイクロレンズを形成して固体撮像素子を製造した。
実施例および比較例の固体撮像素子について、シリコンフォトダイオードに対して垂直方向から照射した光に対する各画素に対応する部位のシリコンフォトダイオードの感度(QE0)と、シリコンフォトダイオードに対して30度の角度方向から照射した光に対する各画素に対応する部位のシリコンフォトダイオードの感度(QE30)とをそれぞれ測定し、感度比(QE0/QE30)を算出した。結果を下記表に示す。なお、感度比が1に近いほど斜め方向の光に対する感度が優れることを意味する。また、感度はシリコンフォトダイオードから得られた電荷を測定した。
10:光電変換部
20:光学フィルタ
21~23:画素
25:隔壁
30:マイクロレンズ
100:固体撮像素子
Claims (12)
- 光電変換部を有する支持体と、
前記光電変換部への光入射側に設けられた光学フィルタと、を有し、
前記光学フィルタは、パターン状に配置された2種以上の画素と、各画素間に配置された隔壁とを有し、
前記隔壁の波長533nmの光に対する屈折率が1.10~1.30であり、
前記隔壁の幅が80~150nmであり、
前記画素の波長1000nmの光に対する屈折率が1.60~1.90であり、
前記隔壁の厚さと、前記隔壁と隣接する画素の厚さとの差が200nm以下であり、
前記隔壁の波長533nmの光に対する屈折率と、前記隔壁と隣接する画素の波長1000nmの光に対する屈折率との差が0.30~0.80である、
固体撮像素子。 - 前記隔壁の厚さが300~650nmである、請求項1に記載の固体撮像素子。
- 前記画素の厚さが300~600nmである、請求項1または2に記載の固体撮像素子。
- 前記画素の幅が300~1100nmである、請求項1~3のいずれか1項に記載の固体撮像素子。
- 前記光学フィルタの画素ピッチが400~1200nmである、請求項1~4のいずれか1項に記載の固体撮像素子。
- 前記隔壁の厚さと、前記隔壁と隣接する画素の厚さとの差が1nm以上である、請求項1~5のいずれか1項に記載の固体撮像素子。
- 前記隔壁は、前記画素よりも厚さが大きい、請求項1~6のいずれか1項に記載の固体撮像素子。
- 前記隔壁の空隙率が20~80%である、請求項1~7のいずれか1項に記載の固体撮像素子。
- 前記隔壁は、複数個の球状シリカが数珠状に連結した形状のシリカ粒子、および、中空構造のシリカ粒子から選ばれる少なくとも1種を含む、請求項1~8のいずれか1項に記載の固体撮像素子。
- 前記隔壁と前記画素側との間に下地層を有する、請求項1~9のいずれか1項に記載の固体撮像素子。
- 前記画素の表面粗さRa値が0.1~5.0nmである、請求項1~10のいずれか1項に記載の固体撮像素子。
- 前記光学フィルタは、黄色画素、シアン色画素およびマゼンタ色画素から選ばれる少なくとも1種の画素を含む、請求項1~11のいずれか1項に記載の固体撮像素子。
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KR102468312B1 (ko) * | 2017-04-18 | 2022-11-17 | 도판 인사츠 가부시키가이샤 | 고체 촬상 소자 및 고체 촬상 소자의 제조 방법 |
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2020
- 2020-11-17 WO PCT/JP2020/042704 patent/WO2021106670A1/ja active Application Filing
- 2020-11-17 JP JP2021561324A patent/JP7454592B2/ja active Active
- 2020-11-17 KR KR1020227016637A patent/KR20220086620A/ko active IP Right Grant
- 2020-11-20 TW TW109140869A patent/TW202136829A/zh unknown
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2022
- 2022-05-09 US US17/739,281 patent/US20220271078A1/en active Pending
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WO2018174147A1 (ja) * | 2017-03-24 | 2018-09-27 | 富士フイルム株式会社 | 構造体、近赤外線透過フィルタ層形成用組成物および光センサ |
WO2019039172A1 (ja) * | 2017-08-22 | 2019-02-28 | 富士フイルム株式会社 | 構造体、構造体の製造方法、吸収層形成用組成物、固体撮像素子および画像表示装置 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2023056460A (ja) * | 2021-10-07 | 2023-04-19 | 采▲ぎょく▼科技股▲ふん▼有限公司 | 固体撮像素子 |
JP7465298B2 (ja) | 2021-10-07 | 2024-04-10 | 采▲ぎょく▼科技股▲ふん▼有限公司 | 固体撮像素子 |
US12046609B2 (en) | 2021-10-07 | 2024-07-23 | Visera Technologies Company Limited | Solid-state image sensor |
Also Published As
Publication number | Publication date |
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JPWO2021106670A1 (ja) | 2021-06-03 |
JP7454592B2 (ja) | 2024-03-22 |
US20220271078A1 (en) | 2022-08-25 |
KR20220086620A (ko) | 2022-06-23 |
TW202136829A (zh) | 2021-10-01 |
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