JP2019195051A5 - - Google Patents

Description

FIG. 1 is an example of a cross-sectional view showing the configuration of the photoelectric conversion device 100.
The photoelectric conversion device 100 is composed of a photoelectric conversion substrate 3 having a photoelectric conversion unit 1, a microlens array 2, a translucent plate 4, and a functional film 5. The functional film 5 can be a multifunctional film having various optical and / or mechanical functions as described later. The functional film 5 can be referred to as an optical film from the viewpoint that the functional film 5 is particularly excellent in optical characteristics. Hereinafter, unless otherwise specified, the term "membrane" refers to this functional membrane 5.
In FIG. 1, the functional film 5 is arranged 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. In the microlens array 2, a plurality of microlenses are arranged two-dimensionally, the width of each microlens is, for example, 0.5 μm to 10 μm, and the height of each microlens is, for example, 0.3 μm to 3 μm. be. Therefore, the height difference of the unevenness of the microlens array 2 is, for example, 0.3 μm to 3 μm.
Since the photoelectric conversion device 100 has a cavityless structure in which the functional film 5 is arranged between the photoelectric conversion substrate 3 and the translucent plate 4, the space between the photoelectric conversion substrate 3 and the translucent plate 4 is hollow. It has better mechanical strength than the cavity structure. The functional film 5 can also be referred to as a filling film from the viewpoint that the functional film 5 fills the space between the photoelectric conversion substrate 3 and the translucent plate 4.

FIG. 9 shows an example of the relationship between the refractive index n of the functional film 5 containing hollow particles, the porosity X (hereinafter, also simply referred to as X), and the porosity Y (hereinafter, also simply referred to as Y).
In FIG. 9, N1 is 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 the solid particles having a refractive index of 1.25 and / or the voids. Can be thought of as showing the relationship between. Here, when the hollow particles have an outer shell having a refractive index n _s = 1.46 and the voids in the hollow particles have a predetermined volume, the refractive index n _p of the hollow particles is 1.25. Suppose that exists. Then, N1 has an outer shell having a refractive index n _s = 1.46, and is a functional film consisting only of voids between hollow particles and / or hollow particles having a refractive index n _p = 1.25 of one hollow particle. It also shows the relationship between the void ratio between the hollow particles of the functional film 5 and the refractive index n when 5 is configured. Further, N2 is the void ratio between the solid particles of the functional film 5 and the refraction of the functional film 5 when the functional film 5 is composed of only a solid substance having a refractive index of 1.46 (for example, solid particles) and / or voids. The relationship with the rate n is shown. It should be noted that the configuration is an example for explaining the relationship between n, X and Y, and does not limit the present disclosure at all.
The relationship N1 in FIG. 9 shows that when a functional film having a refractive index of 1.20 is to be obtained using solid particles having a refractive index of 1.25, the porosity between the solid particles is y2. .. Further, the relation N1 indicates that the porosity between the solid particles is y1 when a functional film having a refractive index of 1.15 is to be obtained by using the solid particles having a refractive index of 1.25. Further, FIG. 9 shows that when a solid substance having a refractive index of 1.46 (for example, solid particles) is used to obtain a functional film having a refractive index of 1.20, the porosity is x2 + y2. Further, using a solid substance having a refractive index of 1.46 (for example, solid particles), the refractive index is 1. When trying to obtain 15 functional films, it is shown that the porosity is x1 + y1.
Here, let's replace the solid particles with a refractive index of 1.25 with hollow particles having a refractive index of n _p = 1.25 for 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, let's replace the solid particles with a refractive index of 1.25 with hollow particles having a refractive index of n _p = 1.25 for 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 containing the hollow particles having the 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 containing the hollow particles having the refractive index n _p = 1.25 of one hollow particle is 1.15, x1 <y1. As described above, it can be understood that the refractive index of the functional film is lower when x1 <y1 (X <Y) is set 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, the porosity of y2 (%) is sufficient for the functional film 5 composed of only the hollow particles. In the case of the functional film 5 composed of only 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 y2 is the porosity Y.
Further, according to FIG. 9, it can be seen that as X becomes larger, Y becomes smaller, and as a result, the value of X + Y becomes smaller and n becomes higher. This means that when the hollow particles are densely arranged, the volume fraction of the 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, it means that the refractive index of the functional film 5 becomes high.
On the other hand, as is clear when comparing y2 + x2 and y1 + x1 in FIG. 9, when X is made small, Y becomes large, and as a result, the value of X + Y becomes large and n becomes low. 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, it is preferable to increase Y / X.
Specifically, it is preferable that Y / X> 1, that is, the relationship of X <Y is satisfied.
Further, it is preferable that the X and the Y satisfy the relationship of X <(100-XY) <Y.
The functional film 5 may contain particles made of a solid substance and a binder for binding the particles in order to increase the strength.
When a binder is used, the solids contained in the functional film 5 are the outer shell of hollow particles and the binder, and the volume fraction of the solid with respect to the unit volume of the functional film 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-XY) <Y is satisfied, the refractive index of the functional film 5 becomes lower.

Examples of the photoradical polymerization initiator include the following.
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, etc. Imidazole dimer; benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michlerketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylamino Benzophenone derivatives such as benzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Α-Amino aromatic ketone derivatives such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one; 2-ethylanthraquinone, phenanthrenquinone, 2-t-butylanthraquinone, octa Methylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-fe Kinones such as nantaraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone; benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether; benzoin, methyl benzoin, ethyl benzoin, propyl Benzoin derivatives such as benzoin; benzyl derivatives such as benzyldimethylketal; aclysine derivatives such as 9-phenylaclydin, 1,7-bis (9,9'-acrydinyl) heptane; N-phenylglycine derivatives such as N-phenylglycine; Acetphenone derivatives such as acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-2-phenylacetophenone; thioxanthone such as thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone. Derivatives; 2,4,6- Acylphosphine such as trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphinoxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide Oxide derivatives; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- Oxime ester derivatives such as carbazole-3-yl]-, 1- (O-acetyloxime); xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 1- (4-isopropylphenyl) -2-hydroxy -2-Methylpropane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one and the like can be mentioned, but the present invention is not limited thereto.
Commercially available photo-radical polymerization initiators include Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 1173, Lucirin TPO, LR8883, LR8970 (and above). , BASF, "Darocur" and "Lucirin" are registered trademarks), Evecryl P36 (UCB) and the like, but are not limited thereto.

Other structures of the membrane containing the binder and the conjugate of the particles composed of the solid substance bound by the binder will be described with reference to FIG.
FIG. 10 shows a schematic diagram of a film containing particles (for example, hollow particles) composed of a solid substance and a binder. When the binder 308 is introduced into a film containing 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 bond, the binder 308 located at the contact points between the hollow particles is formed. Since it contributes to the binding of the hollow particles 309 to each other, the strength of the film is improved.
On the other hand, if the binder content is excessive, the number of binders that do not contribute to the binding of the hollow particles 309 increases. Such a binder does not contribute to the improvement of the strength of the functional film 5, but may be a factor of increasing the refractive index n of the functional film 5. Therefore, it is preferable that the content of the binder in the functional film 5 is not too large, and it is preferable that the relationship of (100-XY) <Y is satisfied as described above.

<Examples 02-1, 02-2, and 32-1 to 32-4>
In Example 01-1, the solid content concentration, dispersion time, and spin coating conditions of AEROSIL 200 were changed to those shown in Tables 1-1 and 1-5.

<(Example II-7) Preparation of coating liquid 7>
The method for preparing the coating liquid was the same as in Example II-6, except that the solid content mass ratio of the fused silica particles and the chain silica particles was 9.0: 1.0.
<(Example II-8) Preparation of coating liquid 8>
The method for preparing the coating liquid was the same as in Example II-6, except that the solid content mass ratio of the fused 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 fused silica particles and the chain silica particles was 9.75: 0.25, except that the total mass ratio of the two types of particles and the solid content mass ratio of silsesquioxane were 10: 2.25. The method for preparing the coating liquid was the same as in Example II-6.
<(Example II-10) Preparation of coating liquid 10>
The method for preparing the coating liquid was the same as in Example II-6, except that the total amount of the two types of particles and the solid content mass ratio of silsesquioxane were 10: 2.25.
<(Example II -11) Preparation of coating liquid 11>
The method for preparing the coating liquid was the same as that for Example II-1, except that the fumed silica particles of Example II-1 were changed to chain silica particles.

<Calculation method of film porosity>
The porosity X (%) and the porosity Y (%) in the membrane were calculated as follows.
First, the film formed on the substrate is coated with a carbon film using a Model 681 ion beam coater IBC (manufactured by Gaan), and then the ion beam is applied in a focused ion beam processing device (FIB-SM, manufactured by FEI, Nova600). After performing the cross-sectioning process (30 kV-1 nA), an SEM image was acquired with an acceleration voltage of 2 kV by a scanning electron microscope (hereinafter referred to as SEM).
The observation magnification of the SEM image was set to a magnification that covers the entire film at least in the thickness direction and that, for example, the shape of each empty particle can be discriminated. Specifically, it was set to about 50,000 to 200,000 times.
The unit volume of the film was 1000 nm × 1000 nm × (thickness direction) 100 nm.
In the calculation of the porosity in the acquired cross-sectional SEM image, the hollow particles and the voids between the hollow particles were separated by binarization of the gray scale image, and the area of each region was calculated. For image processing, image analysis software ImageJ (available from NIH Image, https: //imagej.nih.gov/ij/) was used.
Specifically, the porosity X (%) is obtained by multiplying the obtained area A (%) of the hollow particles by the volume fraction _Va of the internal voids with respect to the total volume of the hollow particles, and X = A. It was set to × _Va . Also ,
The porosity Y (%) was Y = 100-A.

Claims (34)

It is a photoelectric conversion device
A photoelectric conversion board having a plurality of photoelectric conversion units and a microlens array arranged on the plurality of photoelectric conversion units.
A translucent plate covering the microlens array and
A film disposed between the microlens array and the translucent plate.
The membrane is
The refractive index is 1.05 to 1.15, and it has a refractive index of 1.05 to 1.15.
The average transmittance of light in the wavelength range of 400 nm to 700 nm is 98.5% or more.
A photoelectric conversion device having a film 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 film contains a solid substance and
The main component of the solid substance is silicon dioxide and / or the refractive index of the solid substance is 1.20 to 1.60.
The photoelectric conversion device according to claim 1 or 2. The film is a secondary particle in which primary particles composed of the solid substance form a three-dimensional structure, a chain secondary particle in which primary particles composed of the solid substance are linked in a chain, and the solid substance. Contains at least one particle selected from the group consisting of split-chain secondary particles in which the primary particles composed of are linked in a split-chain manner.
The photoelectric conversion device according to claim 3. The photoelectric conversion device according to claim 4, wherein the number average particle diameter of the primary particles composed of the solid substance is 5 nm to 100 nm. The number average particle size of the secondary particles is 50 nm to 500 nm.
The photoelectric conversion device according to claim 4 or 5. The film comprises a plurality of hollow particles and voids between the plurality of hollow particles.
The ratio of the total volume of the voids between the hollow particles to the unit volume of the film is 30.0% to 80.0%.
The photoelectric conversion device according to any one of claims 1 to 6. The ratio of the total volume of the voids between the hollow particles to the unit volume of the film is 40.0% to 70.0%.
The photoelectric conversion device according to claim 7. The film contains a plurality of hollow particles and contains a plurality of hollow particles.
The ratio of the total volume of voids in the plurality of hollow particles to the unit volume of the film is defined as porosity X (%), and the ratio of the total volume of voids between the hollow particles to the unit volume of the film is defined as porosity Y (). %), Satisfying the relationship of X <Y,
The photoelectric conversion device according to any one of claims 3 to 8 . The X and the Y satisfy the relationship of X <(100-XY) <Y.
The photoelectric conversion device according to claim 9 . The film contains particles made of the solid substance and a binder that binds the particles together.
The photoelectric conversion device according to any one of claims 3 to 10 . The content of the binder 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 11 . The binder contains siloxane,
The photoelectric conversion device according to claim 11 or 12 . The binder contains a substance having a T3 unit structure represented by the 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 device according to any one of claims 11 to 13 . 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 14 . The silicon dioxide has at least one organic group and a hydroxyl group on its surface.
The photoelectric conversion device according to any one of claims 3 to 15 . The surface of the film on the translucent plate side is flatter than the surface of the film on the microlens array side.
The photoelectric conversion device according to any one of claims 1 to 16 . The microlens array contains a resin material.
The photoelectric conversion device according to any one of claims 1 to 17 . The strength of the film measured by the SAICAS method is 3.0 N / m to 100.0 N / m.
The photoelectric conversion device according to any one of claims 1 to 18 . 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 19 . The photoelectric conversion device according to any one of claims 1 to 20 and 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 the like. And at least one selected from the group consisting of a display device that displays information based on a signal output from the photoelectric conversion device.
A device characterized by being equipped with. It is a photoelectric conversion device
A photoelectric conversion board having a plurality of photoelectric conversion units and a microlens array arranged on the plurality of photoelectric conversion units.
A translucent plate covering the microlens array and
A film disposed between the microlens array and the translucent plate.
The film contains a plurality of hollow particles and contains a plurality of hollow particles.
The ratio of the total volume of voids in the plurality of hollow particles to the unit volume of the film is defined as porosity X (%), and the ratio of the total volume of voids between the hollow particles to the unit volume of the film is defined as porosity Y (). %), Satisfying the relationship of X <Y,
A photoelectric conversion device characterized by this. The Y is 30.0% to 80.0%.
The photoelectric conversion device according to claim 22. The Y is 40.0% to 70.0%.
The photoelectric conversion device according to claim 23. The X and the Y satisfy the relationship of X <(100-XY) <Y.
The photoelectric conversion device according to any one of claims 22 to 24 . The sum (X + Y) of the X and the Y is 65.0% to 90.0%.
The photoelectric conversion device according to any one of claims 22 to 25 . The X is 8.0% to 32.0%, and the Y is 30.0% to 80.0%.
The photoelectric conversion device according to any one of claims 22 to 26 . 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 22 to 27 . The main component of the solid substance surrounding the voids in the hollow particles is silicon dioxide.
The photoelectric conversion device according to any one of claims 22 to 28 . The film contains a binder that binds the plurality of particles.
The binder contains siloxane,
The photoelectric conversion device according to claim 29 . The number average particle size of the primary particles of the hollow particles is 20 nm to 100 nm.
The photoelectric conversion device according to any one of claims 22 to 30 . The porosity _np of one hollow particle is 30.0% to 70.0%.
The photoelectric conversion device according to any one of claims 22 to 31 . The film thickness of the film is 500 nm to 2000 nm.
The photoelectric conversion device according to any one of claims 22 to 32 . The unit volume is 1000 nm × 1000 nm × (thickness direction) 100 nm.
The photoelectric conversion device according to any one of claims 22 to 33 .