JP2019195051A - Photoelectric conversion device and equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoelectric conversion device and equipment having excellent optical characteristics. A photoelectric conversion device, a photoelectric conversion substrate having a plurality of photoelectric conversion units, and a microlens array arranged on the plurality of photoelectric conversion units, and a translucent plate covering the microlens array, A film disposed between the microlens array and the translucent plate has a refractive index of 1.05 to 1.15 and an average light transmittance of 98. It is 5% or more, and the film thickness is 500 nm to 5000 nm. [Selection diagram] Figure 1

Description

  The present disclosure relates to a photoelectric conversion device and an apparatus.

In recent years, a semiconductor mounting technique called a wafer level chip size package (WL-CSP) has attracted attention. In the WL-CSP, all processes such as wiring, electrode formation, sealing, and dicing are performed on the wafer as it is, and the size of the finally cut chip becomes the package size.
The structure of the photoelectric conversion device manufactured by WL-CSP includes a cavity structure in which the space between the microlens array and the light transmitting plate is hollow, and a solid having a refractive index relatively lower than that of the microlens between the microlens array and the light transmitting plate. There is a cavityless structure in which is arranged.
Conventional photoelectric conversion devices generally have a cavity structure. However, the cavity structure tends to have low strength due to its hollow structure. Further, since it is necessary to form a frame-like adhesive layer around the cavity in order to support the light-transmitting plate, the photoelectric conversion device tends to become larger and costs increase.
On the other hand, the cavityless structure is excellent in strength because a solid is arranged between the microlens array and the light transmitting plate so as to cover the microlens, and a frame-like adhesive layer formed around the cavity is unnecessary. become. Therefore, the photoelectric conversion device can be reduced in size and cost can be reduced.
Further, the light condensing property of the microlens depends on the refractive index of the microlens and the refractive index of the solid covering the microlens, and the light condensing property increases as the difference between the refractive indexes increases.
In the case of the cavity structure, since it is air with a refractive index of 1.0 that is arranged to cover the microlens, even if the material of the microlens is a resin with a refractive index of 1.5 to 1.6. Sufficient light collecting property can be obtained.
However, in the cavityless structure, since the refractive index of the solid covering the microlens is larger than that of air, the light condensing performance is lowered when the microlens having the same refractive index as that of the cavity structure is used. .

In the cavityless structure disclosed in Patent Document 1, since the microlens is made of acrylic resin having a refractive index of 1.5 to 1.6, fluorine having a refractive index of about 1.3 as a solid covering the microlens. Low refractive index material such as polymer is used.
In Patent Document 2, since a resin material having a refractive index of 1.5 is used as a solid covering the microlens, a microlens having a high refractive index of 1.7 to 2.1 is used.

As a typical low refractive index light-transmitting film, there is a porous film using hollow particles.
Patent Document 3 discloses a light transmissive material in which hollow particles and voids coexist in a light transmissive matrix.
Patent Document 4 discloses a low-refractive index film in which strength is increased by applying a binder containing SiO ₂ as a main component to a close-packed hollow particle layer.

On the other hand, in Patent Document 5, the refractive index is low, and furthermore, the low refractive index that can form a pattern that exhibits excellent performance in weather resistance due to excellent adhesion to the substrate, small change in refractive index under high temperature and high humidity. A rate membrane is disclosed.
Patent Document 6 discloses a material having sufficient antireflection performance with only a single-layer antireflection film.
Further, Patent Document 7 discloses a technique for improving the coupling between the light transmitting plate and the photoelectric conversion substrate.

JP 2010-040621 A JP-A-2005-026314 JP 2014-228614 A Japanese Patent Laying-Open No. 2015-4753 JP 2012-032673 A JP 2003-266606 A JP 2018-032792 A

The cavityless structure disclosed in Patent Document 1 uses a low-refractive index microlens coating layer in order to increase the refractive index difference between the microlens and the microlens coating layer. However, since the difference in refractive index is still small, there is a possibility that the light condensing property of the microlens is lowered.
The cavityless structure disclosed in Patent Document 2 uses a high-refractive index microlens to increase the difference in refractive index between the microlens and the microlens coating layer. However, the process of forming the microlens with a material having a high refractive index such as silicon nitride is technically advanced and expensive.
The light transmissive material disclosed in Patent Document 3 may have a high refractive index because the void ratio of voids relative to the total volume of the light transmissive material is small. Moreover, since the void size is not controlled, the transmittance may be reduced.
In the low refractive index film disclosed in Patent Document 4, the hollow particles are closely packed, that is, the volume of voids formed between the hollow particles is minimized, and a binder is added to the voids. Since it is filled, high transmittance can be obtained, but low refractive index is insufficient. Therefore, it is not suitable for a translucent film used in an optical device.
In addition, the translucent film members disclosed in Patent Document 5 and Patent Document 6 do not have sufficient film strength required for practical use in device processing.
Furthermore, a photoelectric conversion device superior to the photoelectric conversion device described in Patent Document 7 is required.
That is, the present disclosure provides a photoelectric conversion device and a device excellent in optical characteristics.

This disclosure
A photoelectric conversion device,
A plurality of photoelectric conversion units, and a photoelectric conversion substrate having a microlens array disposed on the plurality of photoelectric conversion units;
A translucent plate covering the microlens array;
A film disposed between the microlens array and the translucent plate,
The membrane is
Refractive index is 1.05-1.15,
The average transmittance of light in the wavelength region of 400 nm to 700 nm is 98.5% or more,
The photoelectric conversion device is characterized in that the film thickness is 500 nm to 5000 nm.

In addition, this disclosure
The photoelectric conversion device;
An optical system for forming an optical image on the photoelectric conversion device, a control device for controlling the photoelectric conversion device, a processing device for processing a signal output from the photoelectric conversion device, a moving device for moving the photoelectric conversion device, And at least one selected from the group consisting of display devices that display information based on signals output from the photoelectric conversion device,
It is the apparatus characterized by providing.

Furthermore, the present disclosure
A photoelectric conversion device,
A plurality of photoelectric conversion units, and a photoelectric conversion substrate having a microlens array disposed on the plurality of photoelectric conversion units;
A translucent plate covering the microlens array;
A film disposed between the microlens array and the translucent plate,
The membrane contains a plurality of hollow particles,
The ratio of the total volume of the voids in the plurality of hollow particles to the unit volume of the membrane is defined as the porosity X (%), and the ratio of the total volume of the voids between the hollow particles to the unit volume of the membrane is defined as the porosity Y ( %), The relationship X <Y is satisfied.
This is a photoelectric conversion device.

  According to the present disclosure, it is possible to provide a photoelectric conversion device and a device excellent in optical characteristics.

An example of a cross-sectional view showing the structure of a photoelectric conversion device Block diagram showing schematic configuration of imaging system The figure which shows the structure of an imaging system and a moving body The figure which shows the structure of an imaging system and a moving body Diagram showing the structure of the membrane An example of a cross-sectional view showing the structure of a photoelectric conversion device An example of a cross-sectional view showing the structure of a photoelectric conversion device Diagram showing the structure of the membrane Diagram showing the structure of the membrane The figure explaining the relationship between the refractive index n of a film | membrane, and X, Y, and X + Y Diagram showing the structure of the membrane The figure explaining the aggregation state of a hollow particle Diagram showing the structure of the membrane The figure explaining the aggregation state of a hollow particle Diagram showing the structure of the membrane The figure explaining the aggregation state of a hollow particle Diagram showing the structure of the membrane SEM image of the film formed in Example III-1. SEM image of the film formed in Example III-2 SEM image of the film formed in Example III-3 SEM image of the film formed in Example III-4 SEM image of the film formed in Example III-5

In the present disclosure, the description of “XX or more and YY or less” or “XX to YY” representing a numerical range means a numerical range including a lower limit and an upper limit as end points unless otherwise specified. In addition, the description “A and / or B” is a concept including any of A, B, and both A and B.

  Embodiments of the present disclosure will be described with reference to the accompanying drawings. In the following description and drawings, common reference numerals are given to common configurations over a plurality of drawings. Therefore, a common configuration is described with reference to a plurality of drawings, and a description of a configuration with a common reference numeral is omitted as appropriate. Each embodiment can be appropriately changed and combined. In the accompanying drawings, the scale of each element may be different from that of an actual device to facilitate understanding of the elements described.

A photoelectric conversion device,
A plurality of photoelectric conversion units, and a photoelectric conversion substrate having a microlens array disposed on the plurality of photoelectric conversion units;
A translucent plate covering the microlens array;
A film disposed between the microlens array and the translucent plate,
The membrane is
Refractive index is 1.05-1.15,
The average transmittance of light in the wavelength region of 400 nm to 700 nm is 98.5% or more,
The film thickness is 500 nm to 5000 nm.

FIG. 1 is an example of a cross-sectional view illustrating a configuration of the photoelectric conversion device 100.
The photoelectric conversion device 100 includes a photoelectric conversion substrate 3 having a photoelectric conversion unit 1 and a microlens array 2, a translucent plate 4, and a functional film 5. The functional film 5 can be a multi-functional film having various optical and / or mechanical functions as described later. From the viewpoint that the functional film 5 is particularly excellent in optical characteristics, the functional film 5 can be referred to as an optical film. Hereinafter, unless otherwise specified, the term “film” refers to this functional film 5.
In FIG. 1, the functional film 5 is disposed between the microlens array 2 and the translucent plate 4, and has a surface along the unevenness of the microlens array 2 and a surface along the translucent plate 4. The mylo lens array 2 includes a plurality of microlenses arranged two-dimensionally. Each microlens has a width of 0.5 μm to 10 μm, for example, and each microlens has a height of 0.3 μm to 3 μm, for example. Therefore, the height difference of the unevenness of the microlens array 2 is, for example, 0.3 μm to 3 μm.
The photoelectric conversion device 100 has a cavityless structure in which the functional film 5 is disposed between the photoelectric conversion substrate 3 and the translucent plate 4, so that the space between the photoelectric conversion substrate 3 and the translucent plate 4 is hollow. Excellent mechanical strength than cavity structure. From the viewpoint that the functional film 5 fills the space between the photoelectric conversion substrate 3 and the translucent plate 4, the functional film 5 can also be referred to as a filling film.

FIG. 5 is another example of a cross-sectional view illustrating a configuration of the photoelectric conversion device 100.
The coupling member 12 is disposed between the functional film 5 and the translucent plate 4 and couples the functional film 5 and the translucent plate 4 to each other. Further, an antireflection layer 13 may be disposed between the functional film 5 and the coupling member 12 as necessary. Furthermore, an antireflection layer 11 may be disposed between the functional film 5 and the microlens array 2 as necessary.
The upper and lower surfaces of the antireflection layer 11 have irregularities corresponding to the irregularities of the microlens array 2. The antireflection layers 11 and 13 may be thinner than the functional film 5, and the thickness of the antireflection layers 11 and 13 may be ¼ or less of the thickness of the functional film 5.

FIG. 6 is another example of a cross-sectional view illustrating a configuration of the photoelectric conversion device 100.
With reference to FIG. 6, another cross-sectional structure of the photoelectric conversion device 100 will be described. FIG. 6 shows a cross section through the electrode 714. In the cross-sectional view of FIG. 6, attention is paid from a part of the pixel region 716 to the outside of the photoelectric conversion device 100 beyond the side surface 713 of the photoelectric conversion device 100. In FIG. 6, one side surface 713 of the photoelectric conversion device 100 is described, but the photoelectric conversion device 100 may have a similar cross-sectional structure also on the other side surface.
As shown in FIG. 6, a through hole 718 is formed in the semiconductor layer 700 and the insulating layer 702. One end of the through hole 718 reaches a part 717 of the wiring layer 703. The photoelectric conversion device 100 further includes an electrode 714 that passes through the through hole 718. A part of the electrode 714 is in contact with and coupled to a part 717 of the wiring layer 703, and the other part 714 a of the electrode 714 is a lower surface of the semiconductor layer 700 (that is, a surface opposite to the light transmitting plate 4). ) Extending in parallel. A solder bump 719 for soldering the photoelectric conversion device 100 to a mounting substrate is provided on a part 714a of the electrode 714.
The functional film 5 is disposed between the microlens array 2 and the translucent plate 4. In addition, the coupling member 12 is disposed between, for example, the photoelectric conversion substrate constituted by the semiconductor layer 700 to the microlens array 2 and the translucent plate 4, and the photoelectric conversion substrate and the translucent plate 4 May be combined with each other. An antireflection layer (not shown) may be disposed between the functional film 5 and the coupling member 12 as necessary. Further, an antireflection layer 11 may be disposed between the functional film 5 and the microlens array 2 as necessary. Further, in FIG. 6, 1 represents a photoelectric conversion portion, 704 represents a passivation member, 705 represents a planarization layer, for example, a resin layer formed of resin, 706 represents a color filter layer, and 707 is planarization. A layer, for example, a resin layer formed of resin, 712 represents a moisture-resistant ring, and 715 represents a peripheral region.

In the photoelectric conversion device 100, light incident from the outside passes through the light transmitting plate 4 and the functional film 5, is collected by the microlens, enters the photoelectric conversion unit 1, and is converted into an electric signal.
The refractive index of the functional film 5 needs to be lower than the refractive index of the microlens constituting the microlens array 2. In this respect, the functional film 5 can be referred to as a low refractive index film.
The functional film 5 suitable as a low refractive index film has a refractive index of 1.05 to 1.15.
The refractive index of the functional film 5 is preferably 1.05 to 1.14, more preferably 1.05 to 1.13, and still more preferably 1.05 to 1.12. 1.05 to 1.11 is particularly preferable, and 1.05 to 1.10.
Since the refractive index of air is 1.00, it is impossible to make the refractive index less than 1.00. In order to improve the light condensing property of the microlens, it is preferable to increase the refractive index difference between the functional film 5 and the microlens.
When the refractive index of the functional film 5 exceeds 1.15, for example, when a microlens having a refractive index of 1.50 to 1.60 is used, the difference in refractive index between the functional film 5 and the microlens is small. The light condensing performance of the lens decreases.

From the viewpoint of transmitting light through the functional film 5, if the average transmittance of light in the wavelength region of 400 nm to 700 nm (hereinafter also referred to as transmittance) is 90.0% or more, the functional film 5 is referred to as a translucent film. Can be called. In the photoelectric conversion device, the average transmittance of light in the wavelength region of 400 nm to 700 nm of the functional film 5 suitable as a light transmissive film is 98.5% or more.
Further, the transmittance is preferably 99.0% or more, more preferably 99.2% or more, and further preferably 99.4% or more. On the other hand, the transmittance is preferably 100.0% or less, and more preferably 99.9% or less.
In addition, the said numerical range can be combined arbitrarily.
Unless otherwise specified, the transmittance means the transmittance of parallel transmitted light, and does not include the transmittance of diffuse transmitted light.
When the transmittance of the functional film 5 is 98.5% or more, the performance of the photoelectric conversion device is improved.

The film thickness of the functional film 5 is 500 nm to 5000 nm.
The thickness of the functional film 5 is preferably 800 nm to 5000 nm, more preferably 1000 nm to 5000 nm, still more preferably 1200 nm to 5000 nm, and particularly preferably 1500 nm to 5000 nm. Further, the film thickness of the functional film 5 may be 2000 nm or less. The film thickness of the functional film 5 may be, for example, 500 nm to 2000 nm, 800 nm to 2000 nm, 1000 nm to 2000 nm, 1200 nm to 2000 nm, 1500 nm to 2000 nm, and the like.
The functional film 5 is disposed so as to completely cover the microlens array. However, when the thickness of the functional film 5 is less than 500 nm, it is difficult to completely cover the microlens, and the apex of the microlens is the functional film 5. May be exposed.
On the other hand, when the film thickness of the functional film 5 exceeds 5000 nm, cracks are likely to occur when the functional film 5 is formed, and the transmittance may decrease.
Here, when the functional film 5 is arranged so as to completely cover the microlens array, the film thickness of the functional film 5 is from the top of the microlens to the upper surface of the functional film 5 (in FIG. 1, a translucent plate). 4 and the contact surface of the functional film 5).

It is preferable that the surface of the film on the light transmitting plate side is flatter than the surface of the film on the microlens array side. That is, the surface of the functional film 5 on the light transmitting plate 4 side is preferably flatter than the surface of the functional film 5 on the microlens array 2 side (hereinafter also simply referred to as “lower surface”).
Here, the lower surface of the functional film 5 refers to an uneven surface of the functional film 5 having unevenness corresponding to the unevenness of the microlens array 2. That is, preferably, the unevenness of the upper surface along the light transmitting plate 4 of the functional film 5 is flatter than the unevenness of the lower surface of the functional film 5. From this viewpoint, the functional film 5 can be referred to as a flattening film that flattens the unevenness of the microlens array 2.
When the functional film 5 is used as a planarizing film as described above, the film thickness of the functional film 5 is preferably at least twice the height difference of the unevenness of the microlens array 2, and more preferably at least three times. The film thickness of the functional film 5 may be 5 times or less the height difference of the unevenness of the microlens array 2.
The upper surface of the functional film 5 is preferably flat. When the upper surface of the functional film 5 is flat, light scattering due to the unevenness is suppressed, and the transmittance of the functional film 5 is further improved. In addition, a space is formed at the interface between the translucent plate 4 and the functional film 5, moisture enters the functional film 5 through this space, and the refractive index or transmittance of the functional film 5 changes, so that the performance of the photoelectric conversion device is improved. Can be reduced.
Here, the term “flat” refers to the thickness from the upper surface of the photoelectric conversion unit 1 to the upper surface of the functional film 5 (in FIG. 1, from the contact surface between the substrate provided with the photoelectric conversion unit 1 and the microlens array 2 It means that the difference between the maximum value and the minimum value (thickness to the contact surface between the plate 4 and the functional film 5) is 100 nm or less. That is, it means that the height difference of the upper surface of the functional film 5 is 100 nm or less.

The refractive index of the microlens array 2 is, for example, 1.40 to 2.10, preferably 1.45 to 1.80, and more preferably 1.50 to 1.75.
When the refractive index of the microlens array 2 is in the above range, the refractive index difference between the functional film 5 and the microlens array 2 becomes appropriate, and the light condensing property of the microlens array is further improved.

The material of the microlens array is preferably a transparent material, and more preferably a colorless and transparent material.
As a material for the microlens array, inorganic substances such as silicon oxide, titanium oxide, niobium oxide, zirconium oxide, tantalum oxide, silicon nitride, and silicon oxynitride can be used.
However, in order to form a uniform microlens array with an inorganic material with good reproducibility, a high level of technology is required, which may increase the cost.
Therefore, the microlens array preferably contains a resin material.
Specific examples of the resin material include resin materials such as acrylic resin, epoxy resin, polyimide resin, and styrene resin.
The resin material may contain fine particles having a high refractive index.

The functional film 5 preferably contains a solid material having a refractive index of 1.10 to 1.65, and may contain a solid material of 1.20 to 1.65 and 1.20 to 1.60. .25 to 1.65, 1.25 to 1.60 solid substances may be contained, 1.30 to 1.65, 1.30 to 1.60 solid substances may be contained, and 1 .35 to 1.60 solid material may be included.
There is almost no solid substance having a single refractive index of less than 1.10.
Further, when a solid material having a refractive index of 1.65 or less is used as a skeleton, the porosity can be appropriately set for reducing the refractive index, and the strength of the functional film 5 can be improved.

The solid material may be crystalline or amorphous. The solid material may be a particle. The particles are not particularly limited, and are spherical particles, irregularly shaped particles, particles in which the spherical or irregularly shaped particles are connected in a beaded or branched manner, hollow particles having cavities therein, and hollow particles are beaded or separated. Examples include particles connected in a chain.
The following can be illustrated as a material of this solid substance.
Resins such as fluoropolymers and acrylic resins, fluorides such as magnesium fluoride and calcium fluoride, carbonates such as calcium carbonate and potassium carbonate, sulfates such as barium sulfate, silicon dioxide (hereinafter also referred to as silica) And oxides such as aluminum oxide.
Examples of the solid material having a low refractive index include fluorine-based polymers for organic materials and magnesium fluoride and silicon dioxide for inorganic materials.
However, the refractive index of the fluoropolymer is low, about 1.30, the refractive indexes of magnesium fluoride and silicon dioxide (quartz) are 1.38 and 1.46, respectively, and the refractive index of a single substance is 1.30. The material far below is mainly a gas such as nitrogen or oxygen.
Of the solid materials, silicon dioxide is preferable from the viewpoints of refractive index, cost, and chemical stability.
That is, the main component of the solid substance is preferably silicon dioxide. Here, “the main component of the solid substance is silicon dioxide” means that silicon dioxide is 50% by mass or more in the solid substance. Typically, silicon dioxide in the solid material is 90% by weight or more.
Specific examples of the silicon dioxide particles include Snowtex series manufactured by Nissan Chemical Co., Ltd., organosilica sol, through rear series manufactured by JGC Catalysts & Chemicals Co., Ltd., Aerosil series manufactured by EVONIK Co., Ltd. sold by Nippon Aerosil Co., Ltd., and the like.

In general, the refractive index nc of _a composite material C composed of _a material A having a refractive index _{na and} a material B having a refractive index _nb is approximately expressed by the following equation (1).
n _c = _{[n a} × _{v a} / 100] + _{[n b} × _{v b} / 100] (1)
Here, v _a and v _b are volume fractions of the substance A and the substance B constituting the composite substance, respectively (v _a + v _b = 100).
According to the formula (1), the refractive index of the original solid substance can be reduced by using a composite substance of a solid substance and air, that is, a porous film having a solid substance as a skeleton as the functional film 5. At this time, the refractive index of the functional film 5 decreases as the refractive index of the solid substance serving as the skeleton decreases and as the porosity of the functional film 5 increases. In order to increase the porosity of the functional film 5, the functional film 5 may have a porous structure. From this viewpoint, the functional film 5 can be referred to as a porous film.
In the above formula (1), when the substance A is air and the substance B is silicon dioxide, the refractive index of air n _a = 1.00, the refractive index of silicon dioxide n _b = 1.46, the volume of silicon dioxide a fraction _v b = _{100-v a.} That, _{v a} is a function of the refractive index _{n c} of the functional film 5, it is possible to determine the _{v a.} The _{v a} is the porosity.

The porosity of the functional film 5 is preferably 60.0% to 95.0%, and more preferably 65.0% to 90.0%.
For example, according to the formula (1), when the porosity of the functional film 5 having a skeleton of silicon dioxide (refractive index 1.46) is less than 60.0%, the refractive index may exceed 1.15.
On the other hand, when the porosity exceeds 95.0%, the refractive index of the functional film 5 is less than 1.05 and the refractive index is excessively low, and the strength may be reduced because the skeleton constituting the functional film 5 is small. There is sex.

The case where the functional membrane 5 contains hollow particles will be further described, but is not limited thereto. The hollow particles are particles in which the outer shell is formed of a solid material and has a cavity inside the outer shell.
The functional membrane 5 preferably includes a plurality of hollow particles. Each of the plurality of hollow particles is a particle having an outer shell made of a solid substance, and the outer shell surrounding a void. The functional membrane 5 including a plurality of hollow particles may include solid particles or a binder in addition to the hollow particles.
FIG. 8 shows an example of the structure of the functional film 5 in the case where hollow particles are included as primary particles composed of a solid substance.
The functional membrane 5 contains a plurality of hollow particles 301, and voids 302 between the hollow particles exist between the plurality of hollow particles 301. There are also voids 304 inside the hollow particles. In FIG. 8, reference numeral 303 denotes an outer shell, and reference numeral 305 denotes a base material.

The ratio of the total volume of the voids in the plurality of hollow particles to the unit volume of the functional membrane 5 is the porosity X (%), and the ratio of the total volume of the voids between the hollow particles to the unit volume of the functional membrane 5 is the porosity Y ( %), It is preferable to satisfy the relationship of X <Y.
Here, (X + Y) means the porosity of the functional film 5.
The refractive index n of the functional film 5 is expressed by the following formula (2).
n = _{[n a × (X + Y)} / 100 ] + _{[n s × (100-X-} Y) / 100 ] (2)
Here, n _a is the refractive index of air (n _a = 1), and n _s is the refractive index of the outer shell of the hollow particles (n _s > 1). According to equation (2), as X + Y is greater and the higher _{n s} is low, n represents lower.
Further, the refractive index n of the functional film 5 is also expressed by the following formula (3).
n = _{[n a} × Y / 100] + _{[n p × (100-Y)} / 100 ] (3)
Here, n _p is the refractive index of one hollow particle (n _p > 1). The refractive index n _p is an apparent refractive index calculated from the ratio of the volume and refractive index of the outer shell and the volume and refractive index of the voids in one hollow particle. That is, in equation _(1), and _{n a = 1, n b =} n s, v void volume of _a hollow particle, if the _{v b} as the volume of the outer _shell, and _n c = n _p.
According to the equation (3), the larger Y is, and the lower _np is, the lower n is.
Incidentally, determine the refractive index n of the functional film 5 by an optical measurement, the formula (2), (3) By substituting the known _{n a,} n s, _{n p,} it is also possible to estimate the X and Y.

FIG. 9 shows an example of the relationship between the refractive index n, the porosity X (hereinafter also simply referred to as X), and the porosity Y (hereinafter also simply referred to as Y) of the functional film 5 containing hollow particles.
In FIG. 9, N <b> 1 represents the void ratio between the solid particles of the functional film 5 and the refractive index n of the functional film 5 when the functional film 5 is composed of only solid particles and / or voids with a refractive index of 1.25. It can be considered that this relationship is shown. Here, when the hollow shell has an outer shell with a refractive index n _s = 1.46 and the voids in the hollow particle have a predetermined volume, the hollow particle whose refractive index n _p is 1.25 Is assumed to exist. Then, N1 has an outer shell with a refractive index n _s = 1.46, and only a hollow particle with a refractive index n _p = 1.25 of one hollow particle and / or a void between the hollow particles is a functional film. 5 shows the relationship between the void ratio between the hollow particles of the functional film 5 and the refractive index n. Further, N2 is a refractive index of 1.46 when the functional film 5 is composed of only a solid substance (for example, solid particles) having a refractive index of 1.46 and / or voids. The relationship with the rate n is shown. Note that this configuration is an example for explaining the relationship among n, X, and Y, and does not limit the present disclosure.
The relationship N1 in FIG. 9 indicates that when a functional film having a refractive index of 1.20 is obtained using solid particles having a refractive index of 1.25, the porosity between the solid particles is y2. . In addition, the relationship N1 indicates that when a solid film having a refractive index of 1.25 is used to obtain a functional film having a refractive index of 1.15, the porosity between the solid particles is y1. FIG. 9 shows that when a functional film having a refractive index of 1.20 is obtained using a solid substance (for example, solid particles) having a refractive index of 1.46, the porosity is x2 + y2. In addition, when a functional film having a refractive index of 1.20 is obtained using a solid material (for example, solid particles) having a refractive index of 1.46, the porosity is x1 + y1.
Here, a solid particle having a refractive index of 1.25 is replaced with a hollow particle having a refractive index n _p = 1.25 of one particle, which can be regarded as equivalent to this, to obtain a functional film having a refractive index of 1.20. Then, the total volume of the voids in the hollow particles can be estimated as (x2 + y2) −y2 = x2. Similarly, a solid particle having a refractive index of 1.25 is replaced with a hollow particle having a refractive index n _p = 1.25 of one particle, which can be regarded as equivalent to this, to obtain a functional film having a refractive index of 1.15. Then, the total volume of the voids in the hollow particles can be estimated as (x1 + y1) −y1 = x1.
In FIG. 9, when the refractive index of the functional film including the hollow particles having a refractive index n _p = 1.25 of one hollow particle is 1.20, x2> y2. On the other hand, in FIG. 9, when the refractive index of the functional film including the hollow particles having a refractive index n _p = 1.25 of one hollow particle is 1.15, x1 <y1. Thus, it will be understood that the refractive index of the functional film is lower when x1 <y1 (X <Y) than when x2> y2 (X> Y).
According to FIG. 9, for example, when the refractive index n of the functional film 5 is 1.20, a porosity of y2 (%) is sufficient for the functional film 5 composed only of the hollow particles. In the case of the functional film 5 composed only of particles, a porosity of y2 + x2 (%) is required. That is, in this case, the difference x2 between y2 + x2 (%) and y2 (%) is the porosity X, and the y2 is the porosity Y.
Further, according to FIG. 9, it can be seen that as X increases, Y decreases, and as a result, the value of X + Y decreases and n increases. This means that when the hollow particles are densely arranged, the volume fraction of voids existing between the hollow particles decreases, and the volume fraction of the outer shell, which is a component having a higher refractive index than air, increases. Therefore, this means that the refractive index of the functional film 5 is increased.
On the other hand, as is apparent from the comparison of y2 + x2 and y1 + x1 in FIG. 9, it can be seen that when X is decreased, Y increases, and as a result, the value of X + Y increases and n decreases. This is because when the hollow particles are sparsely arranged, the volume fraction of the voids existing between the hollow particles increases and the volume fraction of the outer shell decreases, so that the refractive index of the functional film 5 decreases. It means that.
That is, in order to lower the refractive index of the functional film 5, Y / X should be increased.
Specifically, it is preferable to satisfy the relationship of Y / X> 1, that is, X <Y.
Moreover, it is preferable that X and Y satisfy the relationship of X <(100−X−Y) <Y.
The functional film 5 may contain particles composed of a solid substance and a binder that binds the particles for high strength.
When a binder is used, the solid contained in the functional membrane 5 is an outer shell and a binder of hollow particles, and the volume fraction of the solid with respect to the unit volume of the functional membrane 5 is (100−XY) (%). expressed.
When the relationship of X <(100−XY) is satisfied, the strength of the functional film 5 is further improved. On the other hand, when the relationship of (100−X−Y) <Y is satisfied, the refractive index of the functional film 5 becomes lower.

  The total value of X and Y (X + Y) is preferably 60.0% to 95.0%, and more preferably 65.0% to 90.0%. By setting (X + Y) within the above range, the strength of the functional film 5 and the refractive index of the functional film 5 can be easily adjusted to a desired range.

In the functional film 5, X is preferably 8.0% to 32.0%, more preferably 10.0% to 28.0%, and further preferably 12.0% to 24.0%. is there.
On the other hand, Y is preferably 30.0% to 80.0%, more preferably 35.0% to 75.0%, and further preferably 40.0% to 70.0%.
By setting X and Y in the above ranges, it becomes easy to adjust the strength of the functional film 5 and the refractive index of the functional film 5 to a desired range.

In the illustration of FIG. 8, the shape of the hollow particles is substantially spherical, but is not limited thereto. The hollow particles have an outer shell 303 and voids 304 surrounded by the outer shell and formed inside the hollow particles. In this case, the hollow particles can be regarded as a kind of core / shell particles whose core is air.
The refractive index n _{p of} one hollow particle is represented by the formula (4).
n _p = [n _s × (100−V _a ) / 100] + [n _a × V _a / 100] (4)
Here, V _a is the volume fraction of internal voids to the total volume of the hollow particles. That is, the refractive index n _p of one hollow particle is determined by the refractive index n _s of the outer shell material and the porosity V _{a of} one hollow particle.
The porosity n _{p of} one hollow particle is preferably 30.0% to 70.0%, and more preferably 35.0% to 65.0%.
When the porosity n _p is in the above range, the refractive index of the functional film 5 can be easily lowered, and the strength of the hollow shell and the strength of the functional film 5 can be stabilized.

The refractive index of shell _{n s} of the hollow particles is similar to the refractive index of the solid material, 1.10 or more, 1.20 or more, 1.25 or more, it 1.30 or more, 1.35 or more Preferably, it is 1.65 or less and 1.60 or less. The numerical ranges can be arbitrarily combined.
If the refractive index n _s of the outer shell of the hollow particles is within the above range, the ease of manufacture of the functional film 5, the strength of the hollow particles, is excellent in the strength of the functional film 5 and lower adjusting the refractive index of the functional film 5 can do.

As the material of the outer shell of the hollow particle, the same material as the above solid substance can be used.
Moreover, the outer shell of the hollow particles may have micro pores. If micropores are formed in the outer shell, the refractive index of the outer shell can be further reduced.
The number average particle size of primary particles of the hollow particles is preferably 1 nm to 200 nm, more preferably 5 nm to 100 nm, further preferably 10 nm to 100 nm, and particularly preferably 20 nm to 100 nm. preferable.
When the number average particle diameter is in the above range, hollow particles can be easily produced, light scattering can be easily suppressed, and the transmittance of the functional film 5 can be further improved.

  The functional film 5 is composed of secondary particles in which primary particles composed of solid substances form a three-dimensional structure, chain-shaped secondary particles in which primary particles composed of solid substances are linked in a chain, and solid substances It is preferable that the primary particles contain at least one particle selected from the group consisting of branched secondary particles connected in a branched manner. Here, when the particle | grains comprised with the solid substance form the aggregate, this aggregate is also contained in the secondary particle which the primary particle | grains comprised with the solid substance formed the three-dimensional structure.

  Secondary particles in which the primary particles composed of the solid material form a three-dimensional structure, chain-shaped secondary particles in which the primary particles composed of the solid material are connected in a chain, and primary particles composed of the solid material The chain-like secondary particles connected in a chain form can reduce the volume fraction of the solid substance contained in the functional film 5 and can increase the volume fraction of the voids. That is, the refractive index of the functional film 5 can be lowered.

The number average particle diameter of the primary particles composed of the solid substance is preferably 1 nm to 200 nm, more preferably 5 nm to 100 nm, still more preferably 10 nm to 100 nm, and more preferably 20 nm to 100 nm. It is particularly preferred.
When the number average particle diameter of the primary particles is in the above range, the aggregation of the particles can be appropriately controlled, and the dispersibility in the coating liquid can be improved. Moreover, it can suppress that this primary particle becomes a light scatterer in the wavelength range of 400 nm-700 nm, and can improve the transmittance | permeability of the functional film 5 more.

Here, an example using fumed silica particles will be described as an example of secondary particles in which primary particles composed of a solid substance form a three-dimensional structure, but the present invention is not limited to this.
Fumed silica particles can be produced by high temperature hydrolysis of silicon tetrachloride in oxygen and hydrogen flames.
In the fumed silica particles produced by the above-described production method, primary particles of several tens of nanometers are fused to form secondary particles having a three-dimensional structure. In addition, the secondary particles may have a complicated higher order structure by agglomeration.
The fumed silica particles, because of its characteristic structure, the specific gravity of the apparent is very bulky particles is ^{0.01g / cm 3 ~0.1g / cm 3} . Therefore, the functional film 5 containing the fumed silica particles has a high porosity and can significantly reduce the refractive index.

The number average particle diameter of the secondary particles is preferably 10 nm to 1000 nm, and more preferably 50 nm to 500 nm.
When the number average particle diameter of the secondary particles is in the above range, for example, the secondary particles have a simple structure in which the primary particles of silicon dioxide form a three-dimensional structure and several primary particles are aggregated. Must not.
When the secondary particles have the above structure, the porosity of the functional film 5 can be easily controlled within the above range, and the refractive index of the functional film 5 can be easily controlled within the above range. Moreover, it is difficult to form a huge gap that can be a light scatterer in the wavelength range of 400 nm to 700 nm in the gap between the secondary particles, and the light transmittance of the functional film 5 can be easily controlled within the above range.
The number average particle diameter of primary particles and secondary particles can be measured using a transmission electron microscope (TEM) (both are calculated from the arithmetic average value of the maximum diameter). The number average particle size of the primary particles and secondary particles can be controlled by adjusting the conditions for hydrolyzing silicon tetrachloride in an oxygen and hydrogen flame as described above, for example. .

Silicon dioxide preferably has at least one of an organic group and a hydroxyl group on its surface.
Since silicon dioxide with exposed hydroxyl groups has high hydrophilicity, the functional film 5 having high hydrophilicity can be formed by using such silicon dioxide particles as a skeleton.
Further, for example, the functionality of the functional film 5 can be imparted by modifying the surface of the silicon dioxide with a silane coupling agent. When a hydroxyl group is exposed on the surface of silicon dioxide, a dehydration condensation reaction between the hydroxyl group and a hydrolysis product of the silane coupling agent can be used.

Examples of the organic group include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group; a hydrocarbon group having a polymerizable site such as a vinyl group, an acrylic group, and a methacryl group; a phenyl group An aromatic hydrocarbon group such as However, it is not necessarily limited to these.
When an organic group is present on the surface of the silicon dioxide, various functions such as water repellency, oil repellency, biocompatibility, electron transport property, and polymerizability can be imparted to the functional film 5.
Further, it is not necessary that all the functional groups exposed on the surface of silicon dioxide are substituted with organic groups, and both the organic groups and the hydroxyl groups may be exposed at an arbitrary ratio.

The film strength of the functional film 5 is measured using the SAICAS method (surface interface physical property evaluation apparatus), indicates the value of horizontal force when the cutting depth is 0.5 μm, and the unit is N / m. The horizontal force means a horizontal load applied to the cutting edge when a diamond cutting edge is used to obliquely cut from the sample surface to the interface between the film and the substrate.
The strength of the functional film 5 is preferably 3.0 N / m to 100.0 N / m.
The strength of the functional film 5 is preferably 5.0 N / m or more, more preferably 10.0 N / m or more. The strength of the functional film 5 is preferably 50.0 N / m or less, more preferably 30.0 N / m or less, still more preferably 25.0 N / m or less, and particularly preferably 21.0 N / m. It is as follows. The numerical ranges can be arbitrarily combined. The strength of the functional film 5 may be, for example, 3.0 N / m to 25.0 N / m.
When the strength of the functional film 5 is higher than 30.0 N / m, the transmittance of the functional film 5 becomes considerably low. For example, the transmittance is less than 90.0%, and the function as a light-transmitting film is desired. Becomes difficult.

The photoelectric conversion device can be manufactured using existing technology.
For example, a microlens array is disposed on the photoelectric conversion unit. The microlens array may be formed by applying an organic material or an inorganic material on the photoelectric conversion portion and then performing a photolithography process or an etchback process. Thereafter, the functional film 5 may be formed on the microlens array.

As an example of the manufacturing method of the functional film 5,
Preparing a liquid mixture (mixture) containing a solid substance and a solvent;
A step of applying a dispersion treatment to the mixed solution (mixture) to obtain a coating solution; and
It includes a step of forming a film by drying the coating solution and obtaining a film.

A method for preparing a coating solution for forming the functional film 5 will be described.
An example in which fumed silica particles in which the primary particles of silicon dioxide form a three-dimensional structure is described, but is not limited thereto.
Disperse the fumed silica particles in a solvent. As the solvent for dispersing the fumed silica particles, a solvent having high affinity with the fumed silica particles is preferable, and one type of solvent or a mixture of two or more types is used depending on the type of functional group on the surface of the fumed silica particles. May be.
The solvent is preferably an organic solvent, an alcohol solvent such as methanol, ethanol, propanol or isopropanol, a glycol solvent such as ethylene glycol or propylene glycol, dimethyl ether, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Use ether solvents such as propylene glycol monomethyl ether and propylene glycol monoethyl ether, acetate solvents such as ethyl acetate, propyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, and ketone solvents such as acetone and methyl ethyl ketone. be able to.
Although water can be used as the solvent, since water has a large surface tension, a large capillary force is generated during drying, and the voids between the fumed silica particles may shrink. For this reason, the porosity of the functional film 5 tends to decrease, and the refractive index may increase.

As the particles composed of the solid substance, one kind may be used alone, or two or more kinds may be used in combination.
The content of particles composed of a solid substance in the coating liquid is preferably 1.00% by mass or more, more preferably 2.00% by mass or more, further preferably 3.00% by mass or more, and 7.00. A mass% or more is particularly preferred. The content of silica particles in the coating solution is preferably 50.00% by mass or less, more preferably 30.00% by mass or less, and further preferably 20.00% by mass or less. The numerical ranges can be arbitrarily combined.
For example, the concentration (solid content concentration) of fumed silica particles in the coating liquid is preferably 1.00% by mass to 30.00% by mass, and is 2.00% by mass to 20.00% by mass. It is more preferable.
When the content of particles composed of a solid substance in the coating liquid, for example, the content (concentration) of the fumed silica particles is within the above range, the film thickness of the functional film 5 is adjusted to 500 nm or more. Becomes easy. Moreover, the uniform dispersibility of the fumed silica particles in the solvent can be improved, and the transmittance of the obtained functional film 5 can be easily adjusted to the above range.

After the fumed silica particles are added to the solvent, a dispersion treatment is performed.
When forming a coating liquid in which fumed silica particles are dispersed in a solution while maintaining a complex higher order structure, the fumed silica particles and the voids between the fumed silica particles have a size that scatters visible light. For this reason, the transmittance of the functional film 5 may decrease.
When the fumed silica particles are subjected to a dispersion treatment, the transparency of the coating liquid increases with the dispersion treatment time.
When forming a coating liquid with moderately dispersed fumed silica particles, the skeleton of the fumed silica particles and the gaps between the fumed silica particles have a size that does not become a visible light scatterer. A film 5 is formed.
When the dispersion treatment is further performed, the bulky higher order structure of the fumed silica particles is easily broken down to the primary particles, the porosity may be lowered, and the refractive index of the obtained functional film 5 tends to be increased.
If the dispersion treatment is excessive, the so-called over-dispersion state occurs, and the fumed silica particles are likely to re-aggregate, and the transmittance of the functional film 5 after film formation may be reduced.
Therefore, it is preferable to set it to an appropriate dispersion state. For the dispersion treatment, a stirrer, an ultrasonic wave, a rotation and revolution mixer, a ball mill, a bead mill, a homogenizer, or the like can be used.

An example in which hollow particles whose outer shell is silicon dioxide is used as the solid substance will be described, but the present invention is not limited to this.
A dispersion of hollow particles can be used. The hollow particle dispersion is not particularly limited as long as it is a hollow particle dispersion satisfying the void ratio of the hollow particles, the refractive index of the outer shell of the hollow particles, the number average particle diameter of the primary particles of the hollow particles, and the like.
For example, JGC Catalysts and Chemicals through rear series, which is an isopropanol (hereinafter also referred to as IPA) dispersion of hollow particles (hereinafter also referred to as hollow silica particles) whose outer shell is silicon dioxide, is preferably used. In addition to commercially available products such as the Thruria series, hollow silica particles may be used in which hollow particles are dispersed in a solvent in the same manner as the solvent dispersion of the fumed silica particles.
The hollow particle concentration in the solvent may be in the same range as the fumed silica particle concentration (solid content concentration) in the coating liquid.

Since the surface of the hollow silica particles is hydrophilic with hydroxyl groups exposed, a highly hydrophobic solvent is not suitable. Specifically, the following solvents having an octanol / water partition coefficient _logPow of 2 or less are preferable.
Organic solvents such as alcohol solvents such as methanol, ethanol, propanol and isopropanol, glycol solvents such as ethylene glycol and propylene glycol, dimethyl ether, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, Ether solvents such as propylene glycol monoethyl ether, acetate solvents such as ethyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ketone solvents such as acetone and methyl ethyl ketone.

The relationship between the aggregation state of the hollow particles and the structure of the membrane will be described with reference to FIGS. 11A to 11F.
When a non-aggregated and well-dispersed dispersion of hollow silica particles 310 (FIG. 11A) is applied onto a substrate, the hollow silica particles 310 are arranged relatively densely (FIG. 11B), and Y and X + Y are Get smaller. However, since the hollow silica particles composed of the silica outer shell of the low refractive index material and the voids surrounded by the outer shell itself have a low refractive index, even if the functional film 5 has a densely arranged structure. A low refractive index can be maintained. However, in the photoelectric conversion device, in order to improve the light collection rate of the microlens, it is required to further reduce the refractive index of the film.
As described above, in order to reduce the refractive index of the film, it is necessary to increase Y and X + Y. One method is to randomly arrange the hollow silica particles.

Here, a method for randomly arranging the hollow silica particles will be described.
By forming loose aggregates 311 of hollow silica particles in the dispersion (FIG. 11C), the hollow silica particles can be randomly arranged (FIG. 11D).
The aggregates are also included in the secondary particles in which the primary particles composed of a solid substance form a three-dimensional structure.
One method of agglomerating the hollow silica particles that are well dispersed in the dispersion includes a method of adding a solvent (hereinafter referred to as an aggregating agent) having a relatively large log _Pow than the dispersion medium. The method is not limited to this method, and a method capable of controlling the aggregation state of the hollow silica particles is preferable.
Since the hollow silica particles have a hydrophilic surface with exposed hydroxyl groups, the log _Pow is larger than that of the dispersion medium, that is, if a relatively hydrophobic flocculant is added to the dispersion medium, the hollow silica particles are aggregated. Is caused.
The _logPow and addition amount in the flocculant for aggregating the hollow silica particles that are well dispersed in the dispersion will be described.
If the difference in log _Pow between the dispersion medium and the flocculant is too small, the hollow silica particles do not aggregate. If the difference is too large, the hollow silica particles agglomerate violently even if the addition amount of the flocculant is small (FIG. 11E). . When hollow silica particles form large aggregates 312, the aggregates themselves may become light scatterers.
On the other hand, since the huge gap 313 formed between the large aggregates 312 of hollow silica particles is also likely to be a light scatterer, the functional film 5 after application may become cloudy and the transmittance may be reduced.
Moreover, when intense aggregation is caused, the storage stability of the coating liquid tends to be lowered. Therefore, in order to form the functional film 5 having a low refractive index and a high transmittance, the aggregation state of the hollow silica particles may be controlled by the type and addition amount of the flocculant. By utilizing such properties, the refractive index of the functional film 5 may be controlled by controlling the aggregation state of the hollow silica particles by the type and addition amount of the flocculant.
In addition, when the voids between the hollow silica particles are filled with some substance, Y and X + Y may be reduced, and the refractive index of the functional film 5 may be increased. Therefore, the flocculant can be removed in a later step. It is preferable to volatilize by heating.
Examples of the flocculant include silicone oil such as X-22-164 (manufactured by Shin-Etsu Chemical Co., Ltd.), tetraethoxysilane (TEOS), triethoxyvinylsilane (TEVS), and the like, but are not limited thereto.

Hereinafter, a method for forming the functional film 5 will be described.
A film is formed by depositing the coating solution. As a film forming method, a bar coating method, a doctor blade method, a squeegee method, a spray method, a spin coating method, a dip coating method, a screen printing method, or the like can be used. Among these, the spin coating method is preferable from the viewpoint of making the thickness of the functional film 5 uniform.
Further, the transmittance and the film thickness of the functional film 5 are in a reciprocal relationship. When the transmittance per unit film thickness is constant, the transmittance is low when the film thickness is thick, and the transmittance is high when the film thickness is thin. .
Therefore, in order to obtain a film having a desired transmittance and film thickness and a flat top surface, for example, the number of rotations in the spin coating method may be appropriately adjusted.
The film formed by the above method is preferably dried at 20 to 100 ° C.
The obtained film may be further subjected to heat treatment.
The heat treatment is preferably 100 to 300 ° C, more preferably 120 to 240 ° C.
When the heating temperature is 100 ° C. or higher, for example, the possibility that the solvent remains in the voids inside the hollow particles can be reduced. On the other hand, when the heating temperature is 240 ° C. or less, even when the microlens array is made of resin, the microlens array is difficult to soften, and the possibility that the performance of the microlens array is lowered can be reduced.
Moreover, when a film | membrane contains a binder and a polymerization initiator, it is preferable to include the process of thermosetting or photocuring. In the case of thermosetting, the binder can be thermally cured simultaneously with the evaporation of the solvent in the drying or heating step.
In general, a film formed of fine particles maintains its film shape by intermolecular force. In addition, when the surface of the fine particles is hydrophobic, hydrophobic interaction acts. When the surface of the fine particles is hydrophilic, liquid crosslinking also acts, both of which are physical interactions. When the membrane is heat-treated, for example, the hydroxyl groups present on the surface of the fumed silica particles are chemically bonded to each other by a dehydration reaction, so that an improvement in the strength of the membrane can be expected.

For the purpose of lowering the refractive index, when forming a film containing particles composed of the above solid substance, the structure and film shape are changed by intermolecular forces such as van der Waals force acting between the particles and liquid crosslinking. Is maintained.
As one of the methods for improving the strength of the film having the structure, a binder for binding particles may be used.
From the viewpoint of improving the strength of the film, the functional film 5 may further contain a binder.
Moreover, it is preferable that the functional film 5 contains the conjugate | bonded_body with which the solid substance couple | bonded with the binder. Specifically, the functional film 5 preferably contains a combined body in which particles made of a solid substance are combined with a binder. The binding of the solid material by the binder may be any combination of primary particles composed of the solid material, secondary particles formed by the primary particles composed of the solid material, and between the primary particles and the secondary particles. Is a concept that also includes The bond may be a chemical bond such as an ionic bond or a covalent bond, or may be a bond such as mechanical adhesion.
As the binder, resins such as acrylic resin, fluorine resin, styrene resin, imide resin, urethane resin, and phenol resin can be used.
Moreover, the organosilicon compound obtained by polymerizing the silicone oil which has a polymeric group, hydrolyzing a silicon alkoxide, and making it polycondensate can be used.
It is not limited to these as long as it has a low refractive index, is colorless and transparent, and can bind particles.

As an example of a method for producing a film containing a binder,
Preparing a mixed liquid (mixture) containing a solid substance, a solvent, and a binder;
A step of applying a dispersion treatment to the mixed solution (mixture) to obtain a coating solution; and
Examples include a step of forming a film by forming the coating liquid, drying it, and heating or irradiating it with high energy rays as necessary.

The binder preferably contains siloxane, and more preferably contains silsesquioxane.
Silsesquioxane has a composition formula [R ¹ (SiO _1.5 ) _n ] (R ¹ is a reactive functional group, such as a polymerizable group, a hydroxyl group, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, and It represents a compound having a T3 unit structure represented by the formula (1) and is a hybrid material of silicon oxide and an organic substance.
Silsesquioxane (hereinafter sometimes abbreviated as SQ) is a siloxane-based compound whose main chain skeleton is composed of Si—O bonds, and is represented by a composition formula of [R ¹ (SiO _1.5 ) _n ]. The R ¹ is preferably at least one polymerizable group selected from the group consisting of an acryloyl group, a methacryloyl group, an oxetanyl group and an epoxy group.
When silsesquioxane plays a role of bonding particles composed of a large number of solid substances, it is possible to achieve better film strength while maintaining a high porosity.
Silsesquioxane is not particularly limited as the form of the polymer, and examples thereof include known linear polysiloxanes, cage-type polysiloxanes, and ladder-type polysiloxanes. The silsesquioxane structure is a structure in which each silicon atom is bonded to three oxygen atoms and each oxygen atom is bonded to two silicon atoms (the number of oxygen atoms is 1.5 with respect to the number of silicon atoms). is there. From the viewpoint of cost, linear polysiloxane, cage-type polysiloxane, and ladder-type polysiloxane may be mixed.

Silsesquioxane is preferably a compound having a polymerizable group (R ¹ in the above formula) in the molecule and cured by radical polymerization or cationic polymerization.
Examples of the silsesquioxane that is cured by radical polymerization include an acryloyl group and a methacryloyl group as the R. On the other hand, in the type cured by cationic polymerization, examples of R include an oxetanyl group and an epoxy group.
Specific examples include Silsesquioxane derivative SQ series (AC-SQ, MAC-SQ, OX-SQ) manufactured by Toa Gosei Co., Ltd.
Since silsesquioxane is a highly viscous liquid, it may be added to the coating solution. A polymerization initiator may be added as necessary.
The content of the binder in the functional film is preferably 3.0 parts by mass to 60.0 parts by mass with respect to 100 parts by mass of particles composed of a solid substance, and 7.0 parts by mass to 30.0 parts by mass. Is more preferably 7.0 parts by weight to 25.0 parts by weight, and particularly preferably 10.0 parts by weight to 25.0 parts by weight.
Silsesquioxane can be hardened by applying this coating liquid on a substrate and heating or irradiating it with light.
By this operation, a film containing a conjugate in which particles made of a solid substance are bonded with silsesquioxane is formed. By curing the silsesquioxane, the strength of the film can be increased.

  Examples of the polymerization initiator include a radical photopolymerization initiator, a cationic photopolymerization initiator, a thermal radical polymerization initiator, and a thermal cationic polymerization initiator. These polymerization initiators may be composed of one kind of polymerization initiator or may be composed of a plurality of kinds of polymerization initiators.

The following are mentioned as radical photopolymerization initiators.
For example, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) 2,4,5-triaryl which may have a substituent such as -4,5-diphenylimidazole dimer, 2- (o- or p-methoxyphenyl) -4,5-diphenylimidazole dimer Imidazole dimer; benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylamino Benzophenone derivatives such as benzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone Conductor; 2-benzyl-2-dimethylamino-1
Α-amino aromatic ketone derivatives such as-(4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one; 2-ethyl Anthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methyl Quinones such as anthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone; benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc. Benzoin Ether derivatives; benzoin derivatives such as benzoin, methylbenzoin, ethylbenzoin, propylbenzoin; benzyl derivatives such as benzyldimethyl ketal; acridine derivatives such as 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane; N-phenylglycine derivatives such as N-phenylglycine; acetophenone derivatives such as acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone; thioxanthone, diethylthioxanthone, Thioxanthone derivatives such as 2-isopropylthioxanthone and 2-chlorothioxanthone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide Acylphosphine oxide derivatives such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; Octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- , 1- (O-acetyloxime), etc .; xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1 -One, 2-hydroxy-2-methyl-1-phenyl Although propan-1-one etc. are mentioned, it is not limited to these.
Commercially available radical photopolymerization initiators include Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 1173, Lucirin TPO, LR8893, LR8970 (above Manufactured by BASF, “Darocur” and “Lucirin” are registered trademarks), Ubekrill P36 (manufactured by UCB), and the like, but are not limited thereto.

As the cationic photopolymerization initiator, onium salts, aromatic onium salts, arylsulfonium salts, and aryliodonium salts are preferable. Specific examples of the anion include tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, perchlorate ion, trifluoromethanesulfonate ion, fluorosulfonate ion and the like.
Examples of commercially available photocationic polymerization initiators include CPI-210S (manufactured by San Apro), UVI-6950 (manufactured by Union Carbide), Adekaoptomer SP-150 (manufactured by ADEKA), and the like.

  As for content of the polymerization initiator in a coating liquid, 0.01 mass part-1.5 mass parts are preferable with respect to 100 mass parts of silsesquioxane solid content, More preferably, 0.03 mass part-1 .. 0 parts by mass.

A coating liquid may be prepared by mixing particles composed of a solid substance, a solvent and a binder, and, if necessary, a polymerization initiator. As the solvent, an organic solvent is preferable. The organic solvent is not particularly limited, but alcohol, carboxylic acid, aliphatic or alicyclic hydrocarbons, aromatic hydrocarbons, esters, ketones, ethers, or a mixture of two or more of these. A solvent can be used.
Examples of the alcohol include methanol, ethanol, 2-propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, Examples include 4-methyl-2-pentanol, 2-ethylbutanol, 3-methoxy-3-methylbutanol, ethylene glycol, diethylene glycol, and glycerin.
Specific examples of the carboxylic acid include n-butyric acid, α-methylbutyric acid, i-valeric acid, 2-ethylbutyric acid, 2,2-dimethylbutyric acid, 3,3-dimethylbutyric acid, 2,3-dimethylbutyric acid, 3-methylpentanoic acid, 4-methylpentanoic acid, 2-ethylpentanoic acid, 3-ethylpentanoic acid, 2,2-dimethylpentanoic acid, 3,3-dimethylpentanoic acid, 2,3-dimethylpentanoic acid, 2- Examples include ethylhexanoic acid and 3-ethylhexanoic acid.
Specific examples of the aliphatic or alicyclic hydrocarbons include n-hexane, n-octane, cyclohexane, cyclopentane, and cyclooctane.
As the aromatic hydrocarbon, toluene, xylene, ethylbenzene and the like are preferable.
Examples of the esters include ethyl formate, ethyl acetate, n-butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, and γ-butyrolactone.
Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
Examples of ethers include dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether and the like.
In preparing the coating liquid, it is preferable to use alcohol among the various solvents described above from the viewpoint of the stability of the solution.

  The coating liquid can be prepared by adding a predetermined amount of a binder and, if necessary, a polymerization initiator to a liquid in which particles previously composed of a solid substance are dispersed in a solvent. The liquid in which the particles are dispersed in an organic solvent may be prepared by dispersing the particle powder in a solvent using a method similar to the above-described dispersion treatment (for example, a ball mill). Also good.

When forming a film using the coating liquid, it is preferable that the atmosphere for the application is an inert gas atmosphere such as dry air or dry nitrogen. The relative humidity in the dry atmosphere is preferably 30% or less.
Furthermore, as a solution coating method for forming a film, known coating means such as a dipping method, a spin coating method, a spray method, a printing method, a flow coating method, and a combination thereof can be appropriately employed. The film thickness can be controlled by changing the pulling speed in the dipping method, the substrate rotation speed in the spin coating method, and the like, and changing the concentration of the coating liquid.

Curing of the obtained film may be performed by irradiation with high energy rays such as light irradiation or radiation irradiation, or may be performed by heating. Curing may be performed using both high energy ray irradiation and heating.
In the case of curing by irradiation with high energy rays, examples of the high energy rays include electron beams, X-rays, and ultraviolet rays, and are not particularly limited. When ultraviolet rays are used as the high-energy radiation, the irradiation wavelength region is preferably 160Nm～400nm, the output is preferably ^{0.1mW / cm 2 ~2000mW / cm 2} . From the viewpoint of preventing the oxidation of silsesquioxane, the curing atmosphere is preferably an inert atmosphere such as nitrogen. In the case of curing by heating, it may be carried out at a temperature of 50 ° C. to 250 ° C., more preferably at a temperature of 80 ° C. to 200 ° C. for 1 minute to 20 minutes.

<Membrane structure>
A structure of a film containing a binder containing a binder and particles formed of a solid substance bonded with a binder will be described with reference to FIG.
Primary particles 26 made of a solid material (for example, silica particles) form a three-dimensional structure, and secondary particles 27 made of a solid material (for example, silica particles) are formed. In the secondary particles 27, there are a large number of voids 29 of about several nm to several tens of nm. Further, the binder 20 and the secondary particles 27 are present in the film so as to form a combined body.

  Further, the contact point between the primary particles 26 is a complicated mixture of the part where the primary particles 26 are completely fused and the part where the interface exists. Such a structure is formed as a film on the substrate 28. A large amount of voids 21 are also formed in the gaps between the secondary particles 27. Thus, since the voids 29 inside the secondary particles and the voids 21 between the secondary particles are contained, the above refractive index is realized. In addition, the strength of the film is improved.

Another structure of a film containing a binder containing a binder and containing a binder in which particles composed of a solid substance are bonded with the binder will be described with reference to FIG.
FIG. 10 shows a schematic diagram of a film containing particles (for example, hollow particles) made of a solid substance and a binder. When the binder 308 is introduced into a film including the hollow particles 309 having a small surface area and few contacts between the hollow particles, and the binder 308 and the hollow particles 309 form a combined body, the binder 308 positioned at the contact between the hollow particles is obtained. Since it contributes to the binding between the hollow particles 309, the strength of the membrane is improved.
On the other hand, if the binder content is excessive, the binder (indicated by 307 in FIG. 10) that does not contribute to the binding of the hollow particles 309 increases. Such a binder 307 does not contribute to the improvement of the strength of the functional film 5, but can cause the refractive index n of the functional film 5 to increase. Therefore, it is preferable that the content of the binder in the functional film 5 is not excessive, and as described above, it is preferable to satisfy the relationship of (100−X−Y) <Y.

  After the functional film is formed on the microlens array, a separately prepared translucent plate is bonded using a curable bonding member (such as an adhesive), and the bonding member is cured, whereby the photoelectric conversion device is can get.

The device of the present disclosure is
The photoelectric conversion device;
An optical system for forming an optical image on the photoelectric conversion device, a control device for controlling the photoelectric conversion device, a processing device for processing a signal output from the photoelectric conversion device, a moving device for moving the photoelectric conversion device, And at least one selected from the group consisting of display devices that display information based on signals output from the photoelectric conversion device;
It is characterized by providing.
An example of the device of the present disclosure is an imaging system. Therefore, the imaging system will be described with reference to FIG.
FIG. 2 is a block diagram illustrating a schematic configuration of the imaging system.
The photoelectric conversion device can be applied to various imaging systems. Applicable imaging systems are not particularly limited. For example, digital still cameras, digital camcorders, surveillance cameras, copying machines, fax machines, scanners, mobile phones, in-vehicle cameras, observation satellites, medical cameras, etc. Various types of devices are listed. Examples of devices equipped with an imaging system are electronic devices such as various cameras, office devices such as copiers, and information devices such as personal computers and smartphones. Examples of equipment equipped with an imaging system include transportation equipment such as vehicles, ships, and aircraft, medical equipment for endoscopes and radiation diagnosis, analytical equipment such as an electron microscope, and industrial equipment such as robots.
A camera module including an optical system such as a lens and a photoelectric conversion device is also included in the imaging system. FIG. 2 illustrates a block diagram of a digital still camera as an example of these.
As shown in FIG. 2, the imaging system 500 includes a photoelectric conversion device 100, an imaging optical system 502, a CPU 510, a lens control unit 512, an imaging device control unit 514, an image processing unit 516, an aperture shutter control unit 518, a display unit 520, An operation switch 522 and a recording medium 524 are provided.
The imaging optical system 502 is an optical system for forming an optical image of a subject, and includes a lens group, a diaphragm 504, and the like. The diaphragm 504 has a function of adjusting the amount of light at the time of shooting by adjusting the aperture diameter, and also has a function as a shutter for adjusting the exposure time at the time of still image shooting. The lens group and the diaphragm 504 are held so as to be able to advance and retreat along the optical axis direction, and realize a zooming function (zoom function) and a focus adjustment function by their interlocking operations. The imaging optical system 502 may be integrated with the imaging system or may be an imaging lens that can be attached to the imaging system.

The photoelectric conversion device 100 is arranged in the image space of the imaging optical system 502 so that the imaging surface is located. The photoelectric conversion device 100 is the above-described photoelectric conversion device, and includes a CMOS sensor (pixel portion) and its peripheral circuit (peripheral circuit region). In the photoelectric conversion device 100, pixels having a plurality of photoelectric conversion units are two-dimensionally arranged, and a color filter is arranged for these pixels to constitute a two-dimensional single-plate color sensor. The photoelectric conversion device 100 photoelectrically converts the subject image formed by the imaging optical system 502 and outputs it as an image signal or a focus detection signal.
The lens control unit 512 is for performing zooming operation and focus adjustment by controlling the forward / backward drive of the lens group of the imaging optical system 502, and is configured by a circuit or a processing device configured to realize the function. Has been. The aperture shutter control unit 518 is for adjusting the photographing light quantity by changing the aperture diameter of the aperture 504 (with the aperture value being variable), and is configured by a circuit or a processing device configured to realize the function. Is done.
The CPU 510 is a control device in the camera that controls various controls of the camera body, and includes a calculation unit, a ROM, a RAM, an A / D converter, a D / A converter, a communication interface circuit, and the like. The CPU 510 controls the operation of each part in the camera in accordance with a computer program stored in a ROM or the like, and performs a series of photographing such as AF, imaging, image processing, and recording including detection of the focus state (focus detection) of the imaging optical system 502. Perform the action. The CPU 510 is also a signal processing unit.

The imaging device control unit 514 controls the operation of the photoelectric conversion device 100, A / D-converts the signal output from the photoelectric conversion device 100, and transmits the signal to the CPU 510 so as to realize these functions. It is comprised by the circuit and control apparatus comprised by these. The photoelectric conversion device 100 may have the A / D conversion function. The image processing unit 516 is a processing device that generates an image signal by performing image processing such as γ conversion and color interpolation on the A / D converted signal, and includes a circuit configured to realize the function, Consists of a control device. The display unit 520 is a display device such as a liquid crystal display (LCD), and displays information on the shooting mode of the camera, a preview image before shooting, a confirmation image after shooting, a focus state at the time of focus detection, and the like. The operation switch 522 includes a power switch, a release (shooting trigger) switch, a zoom operation switch, a shooting mode selection switch, and the like. The recording medium 524 is for recording a photographed image or the like, and may be a built-in image pickup system or a removable one such as a memory card.
In this manner, by configuring the imaging system 500 to which the photoelectric conversion device 100 is applied, a high-performance imaging system can be realized.

Another example of the device of the present disclosure is a moving body (transport device).
The mobile body is a mobile body, and controls the mobile device based on the photoelectric conversion device, the mobile device, a processing device that acquires information from a signal output from the photoelectric conversion device, and the information. And a control device.
Hereinafter, the imaging system and the moving body will be described with reference to FIGS. 3A and 3B. 3A and 3B are diagrams illustrating configurations of the imaging system and the moving body.
FIG. 3A shows an example of an imaging system 400 relating to an in-vehicle camera.
The imaging system 400 includes the photoelectric conversion device 100. The photoelectric conversion device 100 is the photoelectric conversion device. The imaging system 400 has a parallax (parallax) from a plurality of image data acquired by the photoelectric conversion device 100 and an image processing unit 412 that is a processing device that performs image processing, and a plurality of image data acquired by the photoelectric conversion device 100. It has a parallax acquisition unit 414 that is a processing device that calculates (phase difference of an image). In addition, the imaging system 400 determines whether or not there is a possibility of a collision based on the calculated distance, and a distance acquisition unit 416 that is a processing device that calculates the distance to the object based on the calculated parallax. A collision determination unit 418 that is a processing device. Here, the parallax acquisition unit 414 and the distance acquisition unit 416 are an example of an information acquisition unit that acquires information such as distance information to the object. That is, the distance information is information related to the parallax, the defocus amount, the distance to the object, and the like. The collision determination unit 418 may determine the possibility of collision using any of these distance information. The above-described processing device may be realized by hardware designed exclusively, or may be realized by general-purpose hardware that performs an operation based on a software module. The processing device is an FPGA (Field
It may be realized by Programmable Gate Array (ASIC), Application Specific Integrated Circuit (ASIC), or a combination thereof.

The imaging system 400 is connected to a vehicle information acquisition device 420, and can acquire vehicle information such as a vehicle speed, a yaw rate, and a steering angle. In addition, the imaging system 400 is connected to a control ECU 430 that is a control device that outputs a control signal for generating a braking force for the vehicle based on a determination result in the collision determination unit 418. That is, the control ECU 430 is an example of a moving body control unit that controls the moving body based on the distance information. The imaging system 400 is also connected to an alarm device 440 that issues an alarm to the driver based on the determination result in the collision determination unit 418. For example, when the possibility of a collision is high as a determination result of the collision determination unit 418, the control ECU 430 performs vehicle control that avoids a collision and reduces damage by applying a brake, returning an accelerator, and suppressing engine output. The alarm device 440 warns the user by sounding an alarm such as a sound, displaying alarm information on a screen of a car navigation system, or applying vibration to the seat belt or the steering.
In this embodiment, the imaging system 400 images the periphery of the vehicle, for example, the front or rear. FIG. 3B shows an imaging system 400 when imaging the front of the vehicle (imaging range 450). The vehicle information acquisition apparatus 420 sends an instruction to operate the imaging system 400 to execute imaging. By using the above-described photoelectric conversion device as the photoelectric conversion device 100, the imaging system 400 of this embodiment can further improve the accuracy of distance measurement.

  In the above description, an example of controlling so as not to collide with another vehicle has been described. is there. Furthermore, the imaging system is not limited to a vehicle such as an automobile, but can be applied to a moving body (transport equipment) such as a ship, an aircraft, or an industrial robot. A moving device in a moving body (transport equipment) is various drive sources such as an engine, a motor, wheels, and a propeller. In a transport device equipped with a photoelectric conversion device, the moving device can move the photoelectric conversion device. In addition, the present invention can be applied not only to mobile objects but also to devices that widely use object recognition, such as intelligent road traffic systems (ITS).

The photoelectric conversion device may have a structure (chip stacked structure) in which a first semiconductor chip provided with pixels and a second semiconductor chip provided with a readout circuit are stacked. Each readout circuit in the second semiconductor chip can be a column circuit corresponding to the pixel column of the first semiconductor chip. In addition, the readout circuits in the second semiconductor chip are respectively the first
A matrix circuit corresponding to a pixel or pixel block of a semiconductor chip can also be used. For connection between the first semiconductor chip and the second semiconductor chip, inter-chip wiring by direct bonding of metals such as through electrodes (TSV) and copper (Cu), connection by micro bumps between chips, and the like can be employed.

  Hereinafter, the present disclosure will be specifically described by way of examples. However, the present disclosure is not limited to these examples. “Parts” described in the examples all indicate parts by mass. The “film” described below is a film that can be used as the functional film 5 in the above-described photoelectric conversion device. The “film” described below is a film that can be used in various optical devices.

<Evaluation method of membrane>
The average transmittance of the film (hereinafter referred to as T. The unit is%) is determined using haze (hereinafter referred to as H. The unit is%), ignoring the loss of transmittance due to reflection on the front and back surfaces of the substrate. (5) can be calculated.
T = 100−H (5)
Haze was measured using a haze meter (HZ-V3; Suga Test Instruments; International Illumination Commission (CIE) standard light source D65).

The refractive index of the film (hereinafter referred to as n) was calculated from the following formula (6) using the reflectance (hereinafter referred to as R. The unit is%).
R / 100 = {(n−n _a × n _sub ) / (n + n _a × n _sub )} ² (6)
Here, the reflectance was set to the minimum value of the nearest reflectance of 550 nm.
n _a is the refractive index of air, and n _sub is the refractive index of the substrate.
The reflectance was measured in the range of 380 nm to 800 nm using a reflectance measuring machine (USPM-RU III; manufactured by Olympus Corporation).
When the haze is high, the reflectance loss is large, that is, the reflectance is smaller than the actual one, and the reliability of the refractive index obtained from the equation (6) is low.
Therefore, here, when the haze exceeds 10%, the refractive index cannot be measured.
In addition, when there are regions having different porosity at the interface between the film and the substrate or air, the maximum value of the reflectance of the film becomes larger or smaller than the reflectance of the substrate. Even in such a case, since the reliability of the refractive index obtained from the equation (6) is low, the refractive index of the film is not measurable.

The film thickness (hereinafter referred to as t. The unit is nm) was calculated from the following formula (7).
t = 1 / 4n | λ ₁ · λ ₂ / (λ ₁ −λ ₂ ) | (7)
Here, n is the refractive index of the film calculated from equation (6), λ ₁ nm is the wavelength that gives the minimum value of the nearest reflectance of 550 nm used in equation (6), and λ ₂ nm is λ ₁ It is a wavelength that gives the maximum value of the adjacent reflectance.

<Preparation of coating liquid for film formation and film formation>
Fumed silica particles (manufactured by Nippon Aerosil Co., Ltd.) were used as the skeleton forming the film. The fumed silica particles and the solvent were weighed into a glass container capable of being sealed so as to obtain a desired solid content concentration. A zirconia (ZrO ₂ ) ball having a diameter of 0.5 mm was added to the solvent containing the fumed silica particles, and the glass container was sealed. The glass container was rotated on a ball mill rotary table at a rotation speed of 30 rpm to disperse the fumed silica particles.
A dispersion obtained by the dispersion treatment using the ball mill was used as a coating solution.
This coating liquid was formed into a film on a synthetic quartz glass substrate (diameter 30 mm, thickness 1 mm, refractive index 1.46) previously washed by spin coating, and dried at room temperature to obtain a film.
In addition, you may heat in drying. Although this heating should just be higher than room temperature, it can be performed at about 100 to 200 degreeC, for example, 180 degreeC. When heating is performed during film formation, the film strength can be improved.
<Membrane structure>
The structure of the obtained film will be described with reference to FIG.
The primary particles 6 of the fumed silica particles form a three-dimensional structure, and the secondary particles 7 of the fumed silica particles are formed. A large amount of voids 9 of about several nm to several tens of nm exist in the secondary particles 7. Further, the contact point between the primary particles 6 is complicated and mixed with a part where the primary particles 6 are completely fused and a part where the interface exists. Such a structure is formed as a film on the substrate 8. A large amount of voids 10 are also formed in the gaps between the secondary particles 7. Thus, since the void 9 inside the secondary particle and the void 10 between the secondary particles are contained, the above refractive index is realized.

<Examples 01-1, 01-2, 31-1, and 31-2>
In preparation of the coating liquid for film formation and film formation,
As a skeleton for forming a film, AEROSIL 200 (manufactured by Nippon Aerosil Co., Ltd.), which is a fumed silica particle with a hydroxyl group exposed on the surface, was used.
Further, it was dispersed in propylene glycol monomethyl ether (PGME) so that the solid content concentration of AEROSIL 200 was 6.88% by mass. The dispersion time is as shown in Tables 1-1 and 1-5.
A film was formed from the obtained coating solution under the conditions shown in Tables 1-1 and 1-5. The physical properties of the obtained film are shown in Tables 1-1 and 1-5.

<Examples 02-1, 02-2, and 32-1 to 32-4>
In Example 01-1, the same procedure was followed except that the solid content concentration, dispersion time, and spin coating conditions of AEROSIL 200 were changed to those described in 1-1 and 1-5.

<Examples 03-1, 03-2, and 33-1>
In Example 01-1, the same procedure was followed except that the solid content concentration, dispersion time, and spin coating conditions of AEROSIL 200 were changed to those described in Tables 1-1 and 1-5.

<Examples 04-1, 04-2, 34-1 and 34-2>
In Example 01-1, the same procedure was followed except that the solid content concentration, dispersion time, and spin coating conditions of AEROSIL 200 were changed to those described in Tables 1-1 and 1-5.

<Examples 05-1, 05-2, and 35-1>
In Example 01-1, the same procedure was followed except that the solid content concentration, dispersion time, and spin coating conditions of AEROSIL 200 were changed to those described in Tables 1-1 and 1-5.

<Examples 06-1 and 36-1>
In Example 01-1, AEROSIL R812 (manufactured by Nippon Aerosil Co., Ltd.), which is a fumed silica particle having a methyl group on the surface, was used as a skeleton to form a film. Is the same except that is changed to the description in Tables 1-1 and 1-5.

<Examples 07-1 and 07-2>
In Example 01-1, AEROSIL R711 (manufactured by Nippon Aerosil Co., Ltd.), which is a fumed silica particle having a methacryl group on the surface, was used as a skeleton for forming a film, and the solid content concentration, dispersion time, and spin coating conditions of the AEROSIL R711 were used. Is the same except that is changed to the description in Tables 1-1 and 1-5.
<Examples 08-1 and 08-2>
In Example 01-1, AEROSIL R976 (manufactured by Nippon Aerosil Co., Ltd.), which is a fumed silica particle having a methyl group on the surface, was used as a skeleton for forming a film.
The same procedure was followed except that the solid content concentration, dispersion time, and spin coating conditions of IL R976 were changed to those described in Tables 1-1 and 1-5.
<Examples 12-1 to 28-8 and 41-1 to 58-1>
In Example 01-1, the same procedure was followed except that the conditions for the coating solution and the spin coating conditions were changed to those described in Tables 1-1 to 1-8.

In the refractive index in the table, “−” means a non-uniform film in which the refractive index cannot be measured.
Moreover, the refractive index of AEROSIL 200, R812, R711, R976 is 1.46.

  According to Example 01-1 and Example 31-1, Example 02-1 and Example 32-1, Example 06-1 and Example 36-1, in the case of short-time dispersion processing, the refractive index cannot be measured. And a low permeability film. On the other hand, in the case of long-time dispersion treatment, a film having a desired refractive index, transmittance, and film thickness was formed.

  According to Example 01-1 and Example 32-3, Example 02-2 and Example 33-1, under the same dispersion treatment conditions, a low concentration coating solution of fumed silica particles was formed. A high film was formed. On the other hand, when a coating solution having a high concentration was formed, the transmittance of the film was lowered due to insufficient dispersion.

  According to Example 05-1 and Example 35-2, when the dispersion treatment was for a short time, a film having a high porosity and a low refractive index was formed, but when the dispersion treatment was for a long time, the tertiary of fumed silica particles Since the original structure was destroyed, the porosity of the film decreased relatively and the refractive index increased.

  According to Example 05-2 and Example 35-1, in the case of the same concentration and the same dispersion treatment condition, the film thickness was 500 nm or more when the rotation speed by the spin coating method was low. When it was high, it was less than 500 nm.

<(Example II-1) Preparation of coating liquid 1>
Silsesquioxane (Toa) was added to fumed silica particles (AEROSIL 200, manufactured by Nippon Aerosil Co., Ltd.) dispersion A-1 (solid content concentration 9% by mass) dispersed in 1-methoxy-2-propanol (PGME) solvent. A liquid B (solid content concentration 50 mass%) in which OX-SQ SI-20 manufactured by Synthetic Co., Ltd. was dissolved in PGME was added, and a photocationic polymerization initiator (triarylsulfonium / special phosphorus anion salt, sunapro) Manufactured, CPI-210S) in PGME was added to prepare a coating solution 1.
Fumed silica particle dispersion A-1 was obtained by ball milling fumed silica particles AEROSIL 200 manufactured by Nippon Aerosil Co., Ltd. in PGME. The solid content mass ratio between the fumed silica particles and the silsesquioxane was 10: 1.5. The addition amount of the photopolymerization initiator was 0.4 parts with respect to 100 parts of silsesquioxane solid content.

<(Example II-2) Preparation of coating liquid 2>
The coating liquid was prepared in the same manner as in Example II-1, except that the solid content mass ratio between the fumed silica particles and the silsesquioxane was 10: 3.
<(Example II-3) Preparation of coating solution 3>
The coating liquid was prepared in the same manner as in Example II-1, except that the solid mass ratio of fumed silica particles and silsesquioxane was 10: 4.
<(Example II-4) Preparation of coating solution 4>
The coating liquid was prepared in the same manner as in Example II-1, except that the solid mass ratio of fumed silica particles and silsesquioxane was 10: 5.
<(Example II-5) Preparation of coating solution 5>
The coating liquid was prepared in the same manner as in Example II-1, except that the solid mass ratio of fumed silica particles and silsesquioxane was 10: 6.

<(Example II-6) Preparation of coating solution 6>
Fumed silica particles dispersed in 1-methoxy-2-propanol (PGME) solvent (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) dispersion A-1 (solid content concentration 9% by mass) and chains dispersed in PGME solvent B (solid content) in which silsesquioxane (manufactured by Toa Gosei Co., Ltd., OX-SQ SI-20) was dissolved in PGME in a mixed solution of the silica gel dispersion A-2 (solid content concentration 10% by mass) A liquid obtained by dissolving a photocationic polymerization initiator (triarylsulfonium / special phosphorus anion salt, manufactured by San Apro, CPI-210S) in PGME was added to prepare a coating liquid 6. .
The chain silica particle dispersion A-2 was obtained by replacing the 2-propanol dispersion of chain silica particles (manufactured by Nissan Chemical Co., Ltd., IPA-ST-UP) with PGME. The solid content mass ratio between the fumed silica particles and the chain silica particles was 9.5: 0.5. The total mass ratio of the two kinds of particles and the silsesquioxane was 10: 1.5. The addition amount of the photopolymerization initiator was 0.4 parts with respect to 100 parts of silsesquioxane solid content.

<(Example II-7) Preparation of coating solution 7>
The coating liquid was prepared in the same manner as in Example II-6, except that the solid mass ratio of the fumed silica particles and the chain silica particles was 9.0: 1.0.
<(Example II-8) Preparation of coating solution 8>
The coating liquid was prepared in the same manner as in Example II-6, except that the solid mass ratio between the fumed silica particles and the chain silica particles was 8.5: 1.5.
<(Example II-9) Preparation of coating liquid 9>
The solid content mass ratio of the fumed silica particles and the chain silica particles is 9.75: 0.25, except that the total amount of the two kinds of particles and the silsesquioxane is 10: 2.25. The preparation method of the coating solution was performed in the same manner as in Example II-6.
<(Example II-10) Preparation of coating solution 10>
The coating liquid was prepared in the same manner as in Example II-6, except that the total mass ratio of the two kinds of particles and the silsesquioxane was 10: 2.25.
<(Example 11) Preparation of coating solution 11>
The coating liquid was prepared in the same manner as in Example II-1, except that the fumed silica particles in Example II-1 were changed to chain silica particles.

<(Example II-12) Preparation of coating liquid 12>
Fumed silica particles dispersed in 1-methoxy-2-propanol (PGME) solvent (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) dispersion A-1 (solid content concentration 9 mass%) and hollow dispersed in PGME solvent Liquid B (solid content concentration) in which silsesquioxane (manufactured by Toa Gosei Co., Ltd., OX-SQ SI-20) is dissolved in PGME in a mixed solution of silica particle dispersion A-3 (solid content concentration 10% by mass) 50 mass%) was added, and a solution obtained by dissolving a photocationic polymerization initiator (triarylsulfonium / special phosphorus anion salt, manufactured by San Apro, CPI-210S) in PGME was added to prepare a coating solution 12.
The hollow silica particle dispersion A-3 was obtained by subjecting a 2-propanol dispersion of hollow silica particles (manufactured by JGC Catalysts and Chemicals Co., Ltd., Surria 4110) to PGME as a solvent. The solid mass ratio of the fumed silica particles and the hollow silica particles was 9.0: 1.0. The total mass ratio of the two kinds of particles and the silsesquioxane was 10: 1.5. The addition amount of the photopolymerization initiator was 0.4 parts with respect to 100 parts of silsesquioxane solid content.

<(Example II-13) Preparation of coating solution 13>
The solid content mass ratio of the fumed silica particles and the hollow silica particles was 9.5: 0.5, the solid content mass ratio of the total amount of the two kinds of particles and the silsesquioxane was 10: 3. The liquid was prepared in the same manner as in Example II-6.
<(Example II-14) Preparation of coating solution 14>
The solid content mass ratio between the fumed silica particles and the hollow silica particles was 9.0: 1.0, and the solid content mass ratio between the two kinds of particles and the silsesquioxane was 10: 3. The liquid was prepared in the same manner as in Example II-6.
<(Example II-15) Preparation of coating solution 15>
The coating liquid was prepared in the same manner as in Example II-1, except that the fumed silica particles in Example II-1 were changed to hollow silica particles.

<(Example II-16) Preparation of coating solution 16>
Using the fumed silica particles of Example II-1, a coating solution was prepared without adding silsesquioxane and a photocationic polymerization initiator. The method for preparing the coating solution was the same as in Example II-1.
<(Example II-17) Preparation of coating liquid 17>
The coating liquid was prepared in the same manner as in Example II-1, except that the solid mass ratio of fumed silica particles and silsesquioxane was 10:12.

[Membrane preparation]
A film was formed on the substrate by spin coating using the coating solutions prepared in Examples II-1 to II-17. An S-LAH66 substrate (manufactured by OHARA) as a substrate for evaluating optical characteristics (refractive index and transmittance), and a silicon substrate (product name: flatness dummy wafer, manufacturer: E & M Co., Ltd.) as a substrate for evaluating film strength. Was used. The formed film was cured using an ultrahigh pressure mercury lamp apparatus (manufactured by HOYA, EX250). The irradiation intensity was 25 mW / cm ² and the irradiation time was 3 minutes.

Evaluation of the refractive index of the film was performed by calculating the refractive index using the same method as described above, that is, using a reflectance measuring machine (USPM-RU III, manufactured by Olympus Corporation).
The average transmittance of the membrane was calculated by the method described above.

<Calculation method of membrane porosity>
Calculation of porosity X (%) and porosity Y (%) in the film was performed as follows.
First, a film formed on a substrate is coated with a carbon film using a Model 681 ion beam coater IBC (manufactured by Gatan), and then in a focused ion beam processing apparatus (FIB-SEM, manufactured by FEI, Nova 600). After performing the cross-section processing (30 kV-0.1 nA) by SEM, an SEM image was acquired at an acceleration voltage of 2 kV with a scanning electron microscope (hereinafter referred to as SEM).
The observation magnification of the SEM image covers the entire film at least in the thickness direction, and, for example,
The magnification was such that the shape of each hollow particle could be identified. Specifically, it was about 50,000 to 200,000 times.
The unit volume of the film was 1000 nm × 1000 nm × (thickness direction) 100 nm.
For calculating the porosity in the acquired cross-sectional SEM image, the area of each region was calculated by classifying the hollow particles and the voids between the hollow particles by binarizing the gray scale image. For image processing, image analysis software Image J (available from NIH Image, https://imagej.nih.gov/ij/) was used.
More specifically, the area of the hollow particles obtained A (%), multiplied by the volume fraction V _a of the hollow space to the total volume of the hollow particles, a void ratio X (%), X = A × was _{V a.} The multi-porosity Y (%) was set to Y = 100-A.

Evaluation of film strength is performed by obliquely cutting from the surface of the sample to the interface between the film and the substrate using a diamond cutting blade with a surface interface property evaluation apparatus (SAICAS-NN5, manufactured by Daipura Wintes Co., Ltd.). The horizontal force was measured to determine the shear strength. The measurement conditions are as follows.
The measuring device was SAICAS-NN5, the cutting edge was 1 mm wide, the squeeze angle was 20 °, the dent angle was 10 °, and the cutting mode was a constant speed mode. As the evaluation value of the film strength, a horizontal force value at a cutting depth of 0.5 μm was used.

  The obtained optical characteristics and evaluation values of film strength are shown in Table 2-1. In Table 2-1, FS represents fumed silica particles, CS represents chain silica particles, HS represents hollow silica particles, and SQ represents silsesquioxane.

<Preparation of film forming coating solution and film formation>
As the hollow particles for forming the membrane, hollow silica particles whose outer shell is silica were selected. For the preparation of the coating liquid for film formation, the hollow silica particles 1 were manufactured as Julia Catalytic Chemical's Sululia 4110 (dispersion medium: IPA, silica solid content concentration: 20.5 mass%, number average particle diameter of one hollow particle : 60 nm, porosity of one hollow particle: 45%, refractive index of one hollow particle: 1.25) as hollow silica particles 2, Zuria Kasei Chemical Co., Ltd. through rear 1110 (dispersion medium: IPA, silica solid content) Concentration: 20.5% by mass, number average particle diameter of one hollow particle: 50 nm, porosity of one hollow particle: 35%, refractive index of one hollow particle: 1.30).
The dispersion medium of throughria 4110 was replaced with propyl alcohol-mono-methyl ether (hereinafter also referred to as PGME) from isopropyl alcohol (IPA) to obtain a hollow silica particle 1-PGME dispersion having a silica solid content concentration of 18% by mass. This hollow silica particle 1-PGME dispersion was diluted with PGME to prepare a hollow silica particle 1-PGME dispersion having a desired silica solid content concentration (hereinafter also referred to as hollow silica particle dispersion 1).
The dispersion medium of through rear 1110 was replaced with IPA to PGME to obtain a hollow silica particle 2-PGME dispersion having a silica solid content concentration of 18% by mass. This hollow silica particle 2-PGME dispersion was diluted with PGME to prepare a hollow silica particle 2-PGME dispersion having a desired silica solid content concentration (hereinafter also referred to as hollow silica particle dispersion 2).
As the binder, thermosetting silsesquioxane having an acrylic group (AC-SQ TA-100 manufactured by Toa Gosei Co., Ltd.) was used. TA-100 was dissolved in PGME so as to be 50% by mass (hereinafter referred to as a binder solution).
As the flocculant, methacryl-modified silicone oil (X-22-164 manufactured by Shin-Etsu Chemical Co., Ltd.), tetraethoxysilane (TEOS) or triethoxyvinylsilane (TEVS) was used.
A predetermined amount and a predetermined amount of a binder solution and a flocculant were added to a predetermined type and a predetermined amount of a hollow silica particle dispersion to obtain a coating liquid for film formation. This film-forming coating solution was applied onto a substrate (S-LAH66) by a spin coating method, and heated on a hot plate at 180 ° C. for 10 minutes to obtain a film. X-22-164, TEOS, and TEVS all have the effect of agglomerating the hollow silica particles, but since they volatilized at 120 ° C. to 150 ° C., they did not remain in the film.

Details of the film forming conditions for each example are shown in Table 3-1, and physical properties of the obtained film are shown in Table 3-2.
The above-described methods were used to measure the refractive index of the film, the porosity of the film, the thickness of the film, and the strength of the film.
Since the porosity is calculated by analyzing the cross-sectional SEM image, an error may occur in the porosity. Therefore, even if the values in Table 3-2 are substituted into formulas (1) to (4), the equal sign does not always hold true. However, if the refractive index is ± 0.01 and the porosity is ± 2% point, it can be said that the equations (1) to (4) are appropriate approximations.

<Example III-1>
Hollow silica particle dispersion 1 having a silica solid content concentration of 12% by mass was used as a coating solution. The coating solution was applied and heated to form a film. An SEM image of the obtained film is shown in FIG.
<Example III-2>
A coating solution was prepared by adding 0.18 g of a binder solution to a hollow silica particle dispersion 1 (3.0 g) having a silica solid content concentration of 12% by mass. The coating solution was applied and heated to form a film. An SEM image of the obtained film is shown in FIG.
<Example III-3>
To hollow silica particle dispersion 1 (3.0 g) having a silica solid content concentration of 12 mass%, 0.2 mL of a flocculant was added to prepare a coating solution. The coating solution was applied and heated to form a film. An SEM image of the obtained film is shown in FIG.
<Example III-4>
A coating liquid was prepared by adding 1.4 mL of a flocculant to a hollow silica particle dispersion 1 (3.0 g) having a solid content of silica of 12% by mass. The coating solution was applied and heated to form a film. An SEM image of the obtained film is shown in FIG.
<Example III-5>
A coating solution was prepared by adding 0.18 g of a binder solution and 1.0 mL of a flocculant to a hollow silica particle dispersion 1 (3.0 g) having a silica solid content concentration of 15% by mass. The coating solution was applied and heated to form a film. An SEM image of the obtained film is shown in FIG.
<Example III-6>
To hollow silica particle dispersion 1 (3.0 g) having a silica solid content concentration of 9% by mass, 2.0 mL of a flocculant was added to prepare a coating solution. The coating solution was applied and heated to form a film. Since the hollow silica particles aggregated vigorously in the coating solution, the resulting film was cloudy.
<Example III-7>
A coating solution was prepared by adding 0.54 g of a binder solution to hollow silica particle dispersion 1 (3.0 g) having a silica solid content concentration of 9% by mass. The coating solution was applied and heated to form a film.
<Example III-8>
A chain silica particle dispersion having a silica concentration of 9% by mass was prepared in the same manner as above except that the through rear 4110 was changed to IPA-ST-UP (IPA dispersion of chain silica particles, manufactured by Nissan Chemical Co., Ltd.). did. A coating solution was prepared in the same manner as described above except that the hollow silica particle dispersion was changed to the chain silica particle dispersion. The coating solution was applied and heated to form a film. <Example III-9 to Example III-20>
The type and amount of the hollow silica particle dispersion, the amount of the binder solution, the type and amount of the flocculant, and the spin coating conditions and heating conditions were changed as shown in Table 3-1, to prepare a coating liquid. The coating solution was applied and heated to form a film.

In Table 3-2, the value of the refractive index of the film is an actual measurement value measured based on the measurement method.
In Table 3-2, the value of the porosity of the film is a value calculated by analysis of SEM images for Examples III-1 to 8, and for Examples III-9 to 20, the formula (3 ).

Since the photoelectric conversion device of the present disclosure has a cavityless structure in which a solid is disposed between a microlens array and a light transmitting plate, the photoelectric conversion device has higher strength than the cavity structure. In addition, by using a film as a solid disposed between the microlens and the translucent plate, it is possible to use a microlens such as a resin with a medium refractive index, while maintaining the same light collecting performance as the cavity structure, It can be manufactured at low cost.
In addition, since the functional film in the present disclosure can realize a low refractive index, a high transmittance, a thick film, and a high strength, it is applied to an optical device that requires at least one of high performance, high strength, small size, and low cost. , Can be diverted. The optical device includes a base and a functional film disposed on the base. As the functional film in the optical device, a photoelectric conversion device such as an image sensor is exemplified as the optical device. However, such a functional film is formed on a substrate for realizing functions such as a lens, a filter, and a mirror in the optical device. By forming the optical device, an excellent optical device can be provided. For example, when the optical device is a lens, a functional film may be coated on the lens substrate, or a space between a plurality of lens substrates may be filled with the functional film. An optical device including such a lens (optical device) may be a lens barrel having a lens group composed of a plurality of lenses, and the lens barrel may be an interchangeable lens that can be attached to a lens interchangeable camera. Good. The interchangeable lens may have a moving device such as a motor that moves the lens.

100: photoelectric conversion device, 1: photoelectric conversion unit, 2: microlens array, 3: photoelectric conversion substrate, 4: translucent plate, 5: functional film

Claims (30)

A photoelectric conversion device,
A plurality of photoelectric conversion units, and a photoelectric conversion substrate having a microlens array disposed on the plurality of photoelectric conversion units;
A translucent plate covering the microlens array;
A film disposed between the microlens array and the translucent plate,
The membrane is
Refractive index is 1.05-1.15,
The average transmittance of light in the wavelength region of 400 nm to 700 nm is 98.5% or more,
A photoelectric conversion device having a thickness of 500 nm to 5000 nm. The porosity of the film is 65.0% to 90.0%.
The photoelectric conversion device according to claim 1. The membrane contains a solid material;
The main component of the solid material is silicon dioxide, and / or the refractive index of the solid material is 1.20 to 1.60.
The photoelectric conversion device according to claim 1. The membrane is a secondary particle in which the primary particles composed of the solid material form a three-dimensional structure, the chain-shaped secondary particles in which the primary particles composed of the solid material are linked in a chain, and the solid material Containing at least one particle selected from the group consisting of branched secondary particles in which primary particles composed of
The photoelectric conversion device according to claim 3. The number average particle size of primary particles composed of the solid material is 5 nm to 100 nm.
The photoelectric conversion device according to claim 4. The number average particle diameter of the secondary particles is 50 nm to 500 nm.
The photoelectric conversion device according to claim 4 or 5. The membrane contains a plurality of hollow particles,
The ratio of the total volume of the voids in the plurality of hollow particles to the unit volume of the membrane is defined as the porosity X (%), and the ratio of the total volume of the voids between the hollow particles to the unit volume of the membrane is defined as the porosity Y ( %), The relationship X <Y is satisfied.
The photoelectric conversion apparatus as described in any one of Claims 3-6. X and Y satisfy the relationship of X <(100−XY) <Y.
The photoelectric conversion device according to claim 7. The film contains particles composed of the solid substance, and a binder that binds the particles.
The photoelectric conversion apparatus as described in any one of Claims 3-8. The binder content in the film is 7.0 parts by mass to 30.0 parts by mass with respect to 100 parts by mass of the particles of the solid substance.
The photoelectric conversion device according to claim 9. The binder contains siloxane;
The photoelectric conversion device according to claim 9 or 10. The binder contains a substance having a T3 unit structure represented by a composition formula [R ¹ (SiO _1.5 ) _n ],
R ¹ represents at least one selected from the group consisting of a polymerizable group, a hydroxyl group, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms,
The photoelectric conversion apparatus as described in any one of Claims 9-11. R ¹ is at least one polymerizable group selected from the group consisting of an acryloyl group, a methacryloyl group, an oxetanyl group and an epoxy group.
The photoelectric conversion device according to claim 12. The silicon dioxide has at least one of an organic group and a hydroxyl group on its surface;
The photoelectric conversion apparatus as described in any one of Claims 3-13. The surface on the translucent plate side of the film is flatter than the surface on the microlens array side of the film,
The photoelectric conversion apparatus as described in any one of Claims 1-14. The microlens array contains a resin material;
The photoelectric conversion apparatus as described in any one of Claims 1-15. The strength of the film measured by the SAICAS method is 3.0 N / m to 100.0 N / m.
The photoelectric conversion apparatus as described in any one of Claims 1-16. The strength of the film measured by the SAICAS method is 3.0 N / m to 25.0 N / m.
The photoelectric conversion device according to claim 17. The photoelectric conversion device according to any one of claims 1 to 18,
An optical system for forming an optical image on the photoelectric conversion device, a control device for controlling the photoelectric conversion device, a processing device for processing a signal output from the photoelectric conversion device, a moving device for moving the photoelectric conversion device, And at least one selected from the group consisting of display devices that display information based on signals output from the photoelectric conversion device,
A device comprising: A photoelectric conversion device,
A plurality of photoelectric conversion units, and a photoelectric conversion substrate having a microlens array disposed on the plurality of photoelectric conversion units;
A translucent plate covering the microlens array;
A film disposed between the microlens array and the translucent plate,
The membrane contains a plurality of hollow particles,
The ratio of the total volume of the voids in the plurality of hollow particles to the unit volume of the membrane is defined as the porosity X (%), and the ratio of the total volume of the voids between the hollow particles to the unit volume of the membrane is defined as the porosity Y ( %), The relationship X <Y is satisfied.
A photoelectric conversion device characterized by that. X and Y satisfy the relationship of X <(100−XY) <Y.
The photoelectric conversion device according to claim 20. The sum of X and Y (X + Y) is 65.0% to 90.0%.
The photoelectric conversion device according to claim 20 or 21. The X is 8.0% to 32.0%, and the Y is 30.0% to 80.0%.
The photoelectric conversion apparatus as described in any one of Claims 20-22. The X is 12.0% to 24.0%, and the Y is 40.0% to 70.0%.
The photoelectric conversion device according to any one of claims 20 to 23. The main component of the solid substance surrounding the voids in the hollow particles is silicon dioxide.
The photoelectric conversion apparatus as described in any one of Claims 20-24. The film contains a binder that binds the plurality of particles;
The binder contains siloxane;
The photoelectric conversion device according to claim 25. The number average particle size of primary particles of the hollow particles is 20 nm to 100 nm.
The photoelectric conversion device according to any one of claims 20 to 26. The porosity n _{p of} one hollow particle is 30.0% to 70.0%.
The photoelectric conversion device according to any one of claims 20 to 27. The film thickness is 500 nm to 2000 nm.
The photoelectric conversion device according to any one of claims 20 to 28. The unit volume is 1000 nm × 1000 nm × (thickness direction) 100 nm,
The photoelectric conversion device according to any one of claims 20 to 29.