# US 10,310,150 B2 · Near-infrared cut filter and solid-state imaging device

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- Number: US 10,310,150 B2
- Document ID: US10310150B2
- Status: Granted
- Kind: B2
- Application number: 15/279,688
- Filed: 2016-09-29
- Published: 2017-01-19
- Granted: 2019-06-04
- Earliest claimed: 2015-01-14
- Assignees: AGC Inc.
- Applicants: AGC Inc.
- Inventors: Takashi Sugiyama; Katsumasa Hosoi; Atsushi Komori; Yoshiharu Ooi; Makoto Hasegawa
- Web page: https://patentgrep.com/patent/US10310150B2

## CPC

- G02B 5/208: {for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation}
- G02B 5/223: {containing organic substances, e.g. dyes, inks or pigments}
- G02B 5/226: {Glass filters}
- G02B 5/26: Reflecting filters (G02B5/28 takes precedence)
- G02B 5/281: {designed for the infrared light}
- H10F 39/804: {Containers or encapsulations}
- H10F 39/806: {Optical elements or arrangements associated with the image sensors}
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- H10F: INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION

## Abstract

There are provided a near-infrared cut filter having a sufficient near-infrared blocking property and being capable of reducing or preventing, in a solid-state imaging device using the near-infrared cut filter, occurrence of a phenomenon that an object which did not exist on the original subject appears in a taken image, and also a highly sensitive solid-state imaging device having the near-infrared cut filter. A near-infrared cut filter includes a stack having a near-infrared absorbing glass substrate and a near-infrared absorbing layer containing a near-infrared absorbing dye and a transparent resin on at least one main surface of the near-infrared absorbing glass substrate, and a dielectric multilayer film formed on at least one main surface of the stack, wherein maximum transmittance at an incident angle of 31 to 60 degrees with respect to light with a wavelength of from 775 to 900 nm is 50% or less.

## Claims

### Claim 1

A near-infrared cut filter comprising:
a stack comprising:
a near-infrared absorbing glass substrate; and
a near-infrared absorbing layer provided on at least one main surface of the near-infrared absorbing glass substrate and comprising a near-infrared absorbing dye and a transparent resin; and
a dielectric multilayer film provided on at least one main surface of the stack, wherein
the near-infrared absorbing glass substrate has a maximum absorption wavelength λGmax in a wavelength of from 775 to 900 nm in an absorption spectrum of a wavelength of from 400 to 1100 nm at an incident angle of 0 degree,
the near-infrared absorbing dye has a maximum absorption wavelength λmax at a wavelength of from 650 to 750 nm,
the dielectric multilayer film has a near-infrared reflective property,
transmittance λ(λmax) in λmax of the near-infrared absorbing layer is lower than transmittance T(λGmax) in λGmax of the near-infrared absorbing glass,
transmittance T(λmax) of the near-infrared absorbing layer is 5% or less,
transmittance T(λGmax) of the near-infrared absorbing glass substrate is 50% or less,
the dielectric multilayer film has a near-infrared reflecting band in which average transmittance of light with a wavelength of from 430 to 660 nm is 90% or more, and in which transmittance is 20% or less in a wavelength of from 700 to 1200 nm,
an average value of the near-infrared cut filter of transmittance of light with a wavelength of 450 to 550 nm is 80% or more, and
maximum transmittance of the near-infrared cut filter at an incident angle of 31 to 60 degrees with respect to light with a wavelength of from 775 to 900 nm is 50% or less.

### Claim 2 (depends on 1)

The near-infrared cut filter according to claim 1, wherein the near-infrared absorbing glass substrate has absorptance at an incident angle of 0 degree with respect to light with a wavelength of from 775 to 900 nm of 75% or more.

### Claim 3 (depends on 1)

The near-infrared cut filter according to claim 1, wherein the dielectric multilayer film comprises a dielectric multilayer film with a near-infrared reflective property, the film having maximum transmittance of 1% or less at an incident angle of 0 degree with respect to light with a wavelength of from 800 to 900 nm, and maximum transmittance of 3% or more at an incident angle of 31 to 60 degrees with respect to light with a wavelength of from 775 to 900 nm.

### Claim 4 (depends on 3)

The near-infrared cut filter according to claim 3, wherein the near-infrared absorbing layer is provided on one main surface of the near-infrared absorbing glass substrate, and the dielectric multilayer film with a near-infrared reflective property is provided on another main surface of the near-infrared absorbing glass substrate.

### Claim 5 (depends on 1)

The near-infrared cut filter according to claim 1, wherein
λSh(D_T20%)≤λSh(R30_Ts50%)≤λSh(R0_T50%)≤λLo(D_T20%) Formula (1)
is satisfied,
provided that a wavelength with which transmittance of light at an incident angle of 0 degree becomes 50% on a short wavelength side of the near-infrared reflecting band of the dielectric multilayer film is λSh(R0_T50%), a wavelength with which transmittance of s polarization component becomes 50% in light at an incident angle of 30 degrees is λSh(R30_Ts50%), a wavelength with which transmittance becomes 20% on a short wavelength side of the λmax of the near-infrared absorbing layer is λSh(D_T20%), and a wavelength with which transmittance becomes 20% on a long wavelength side of the λmax is λLo(D_T20%).

### Claim 6 (depends on 1)

The near-infrared cut filter according to claim 1, wherein wavelength λ(T85%), wavelength λ(T45%), and wavelength λ(T5%) with which transmittance of light at an incident angle of 0 degree in a wavelength of from 550 to 720 nm becomes 85%, 45%, and 5%, respectively, satisfy
{λ(T45%)−λ(T85%)}≥{λ(T5%)−λ(T45%)} Formula (2).

### Claim 7 (depends on 1)

The near-infrared cut filter according to claim 1, wherein on the at least one main surface of the near-infrared absorbing glass substrate, reflectance at an incident angle of 5 degree with respect to light with a wavelength of from 430 to 600 nm is 2% or less, which is measured excluding reflection on an interface and a surface opposite to the at least one main surface of the near-infrared absorbing glass substrate.

### Claim 8 (depends on 1)

The near-infrared cut filter according to claim 1, wherein the dielectric multilayer film is provided on the near-infrared absorbing layer, and has dielectric film in contact with the near-infrared absorbing layer, and a refractive index of the dielectric film is 1.4 or more and 1.7 or less.

### Claim 9 (depends on 1)

The near-infrared cut filter according to claim 1, having a wavelength λ0(NIR) with which transmittance at an incident angle of 0 degree becomes 50% and a wavelength λ30(NIR) with which transmittance at an incident angle of 30 degrees becomes 50% in a region of a wavelength longer than 600 nm, wherein an absolute value of a difference between the wavelengths |λ0(NIR)−λ30(NIR)| is 5 nm or less.

### Claim 10 (depends on 1)

The near-infrared cut filter according to claim 1, wherein an average of an absolute value of a difference between transmittance at an incident angle of 0 degree and transmittance at an incident angle of 30 degrees is 3% or less in light with a wavelength of from 600 to 750 nm.

### Claim 11 (depends on 1)

The near-infrared cut filter according to claim 1, wherein the near-infrared absorbing dye comprises at least one selected from the group consisting of a cyanine-based compound, a phthalocyanine-based compound, a naphthalocyanine-based compound, a dithiol metal complex-based compound, a diimonium-based compound, a polymethine-based compound, a phthalide compound, a naphthoquinone-based compound, an anthraquinone-based compound, an indophenol-based compound and a squarylium-based compound.

### Claim 12 (depends on 1)

The near-infrared cut filter according to claim 1, further comprising an ultraviolet absorbing layer comprising an ultraviolet absorber and a transparent resin, wherein an average value of transmittance of the near-infrared cut filter at an incident angle of 0 degree is 70% or more in a wavelength of from 430 to 450 nm, and an average value of transmittance of the near-infrared cut filter at an incident angle of 0 degree is 5% or less in a wavelength of from 350 to 390 nm.

### Claim 13 (depends on 1)

A solid-state imaging device comprising the near-infrared cut filter according to claim 1 and an optical member comprising a solid-state image sensing device, wherein the near-infrared cut filter and the solid-state image sensing device are disposed in order from a side of object of shooting or a side through which light from a light source enters.

### Claim 14

A near-infrared cut filter comprising:
a stack comprising:
a near-infrared absorbing glass substrate;
a near-infrared absorbing layer provided on at least one main surface of the near-infrared absorbing glass substrate and comprising a near-infrared absorbing dye and a transparent resin; and
a dielectric layer with a thickness of 5 nm or more provided between the near-infrared absorbing glass substrate and the near-infrared absorbing layer; and
a dielectric multilayer film provided on at least one main surface of the stack, wherein
the dielectric layer comprises an alkali barrier film comprising at least one material selected from SiO2, SiOx (where 0.8≤x<2) and Al2O3 and
maximum transmittance of the near-infrared cut filter at an incident angle of 31 to 60 degrees with respect to light with a wavelength of from 775 to 900 nm is 50% or less.

### Claim 15

A near-infrared cut filter comprising:
a stack comprising:
a near-infrared absorbing glass substrate;
a near-infrared absorbing layer provided on at least one main surface of the near-infrared absorbing glass substrate and comprising a near-infrared absorbing dye and a transparent resin; and
a dielectric layer with a thickness of 5 nm or more provided between the near-infrared absorbing glass substrate and the near-infrared absorbing layer; and
a dielectric multilayer film provided on at least one main surface of the stack, wherein
the dielectric layer has an adhesive film provided on the near-infrared absorbing glass substrate side and an alkali barrier film provided on the near-infrared absorbing layer side,
the adhesive film comprises Al2O3, and the alkali barrier film comprises SiO2 or SiOx (where 0.8≤x<2), and
maximum transmittance of the near-infrared cut filter at an incident angle of 31 to 60 degrees with respect to light with a wavelength of from 775 to 900 nm is 50% or less.

### Claim 16

A near-infrared cut filter comprising:
a stack comprising:
a near-infrared absorbing glass substrate; and
a near-infrared absorbing layer provided on at least one main surface of the near-infrared absorbing glass substrate and comprising a near-infrared absorbing dye, an ultraviolet absorber, and a transparent resin; and
a dielectric multilayer film provided on at least one main surface of the stack, wherein
an average value of transmittance of the near-infrared cut filter at an incident angle at 0 degree is 70% or more in a wavelength of from 430 to 450 nm,
an average value of transmittance of the near-infrared cut filter at an incident angle at 0 degree is 5% or less in a wavelength of from 350 to 390 nm, and
the ultraviolet absorber satisfies requirements (iv-1) and (iv-2):
(iv-1) the ultraviolet absorber has at least one maximum absorption wavelength in a region of a wavelength of 415 nm or less in a light absorption spectrum of a wavelength of from 350 to 800 nm measured after dissolved in dichloromethane, and a longest maximum absorption wavelength λmax(UV) having a longest wavelength among the at least one maximum absorption wavelength is in a wavelength of from 360 to 415 nm; and
(iv-2) when transmittance in the longest maximum absorption wavelength λmax(UV) is 10% in a spectral transmittance curve measured after dissolved in dichloromethane, a difference λL90−λL50 between a wavelength λL90 and a wavelength λL50 is 13 nm or less, provided that λL90 is a wavelength with which transmittance becomes 90% in a region of a wavelength longer than the longest maximum absorption wavelength λmax(UV) and λL50 is a wavelength with which transmittance becomes 50% in a region of a wavelength longer than the longest maximum absorption wavelength λmax(UV).

### Claim 17 (depends on 16)

The near-infrared cut filter according to claim 16, wherein the ultraviolet absorber comprises at least one selected from the group consisting of oxazole-based dye, merocyanine-based dye, cyanine-based dye, naphthalimide-based dye, oxadiazole-based dye, oxazine-based dye, oxazolidine-based dye, naphthalic acid-based dye, styryl-based dye, anthracene-based dye, cyclic carbonyl-based dye and triazole-based dye.

### Claim 18 (depends on 16)

The near-infrared cut filter according to claim 16, having a wavelength λ0(UV) with which transmittance of light at an incident angle of 0 degree becomes 50% and a wavelength λ30(UV) with which transmittance of light at an incident angle of 30 degrees becomes 50% in a region of a wavelength shorter than 450 nm, wherein an absolute value of a difference between the wavelengths |λ0(UV)−λ30(UV)| is 5 nm or less.

### Claim 19 (depends on 16)

The near-infrared cut filter according to claim 16, wherein an average of absolute value of the difference between transmittance of light at an incident angle of 0 degree and transmittance of light at an incident angle of 30 degrees is 8% or less in a wavelength of from 380 to 430 nm.