KR20200054911A - Infrared absorbing glass plate and manufacturing method thereof, and solid-state imaging element device - Google Patents

Abstract

An infrared absorbing glass plate that enables miniaturization of a solid-state imaging element device is provided. An infrared absorbing glass plate (1) having first and second main surfaces (1a, 1b) facing each other and side surfaces (1c) connecting the first and second main surfaces (1a, 1b), in% cation. , P ⁵⁺ 10 to 70%, Al ^{3+ 7 to} 50%, Cu ²⁺ 0.1 to 15%, and anionic%, containing F ^- 10 to 90% and O ^{2 to} 10 to 90% An infrared absorbing glass plate 1 made of glass, having a thickness of 0.2 mm or less, and having no micro-cracks on the side surfaces 1c.

Description

Infrared absorbing glass plate and manufacturing method thereof, and solid-state imaging element device

The present invention relates to an infrared absorbing glass plate, a method for manufacturing the same, and a solid-state imaging element device using the infrared absorbing glass plate.

In digital cameras and smartphone cameras, solid-state imaging devices such as CCDs and CMOSs are used. Since these solid-state imaging element devices have a wide range of light-receiving sensitivities, it is necessary to remove the infrared light in order to meet human vision. In the following patent document 1, an infrared absorbing glass plate made of a fluorine phosphate-based glass is disclosed as a near-infrared cut filter for removing light in the infrared region. In Patent Document 1, the thickness of the glass plate is reduced by physical polishing.

Japanese Patent Publication 2007-99604

In recent years, further reduction in size is required in the solid-state imaging element device. Therefore, further reduction in thickness is also required in the infrared absorbing glass plate constituting the solid-state imaging element device. However, in the method of thinning by physical polishing as in Patent Document 1, when the thickness of the glass plate is made too thin, cracks may occur in the glass plate. Therefore, there are cases in which the glass plate cannot be sufficiently thinned, so that the solid-state imaging element device cannot be sufficiently downsized.

An object of the present invention is to provide an infrared absorbing glass plate, a method for manufacturing the infrared absorbing glass plate, and a solid-state imaging element device, which makes it possible to achieve miniaturization of the solid-state imaging element device.

The infrared absorbing glass plate according to the present invention is an infrared absorbing glass plate having first and second main surfaces facing each other and side surfaces connecting the first and second main surfaces, in% cation, P ⁵⁺ 10-70 %, Al ³⁺ 7~50%, with Cu ²⁺ 0.1~15%, and anionic%, F ^- 10-90%, O ^2-, and is composed of a fluorine-phosphate-based glass containing 10-90%, It has a thickness of 0.2 mm or less, and is characterized in that no micro-cracks are present on the side surfaces.

In the conventional method of thinning the thickness of the infrared absorbing glass plate by physical polishing, when the thickness of the carrier is made thin to reduce the thickness of the glass plate to 0.2 mm or less, cracks may occur in the carrier. In addition, even when the thickness of the glass plate could be reduced, cracks were formed in the glass plate when taken out from the carrier. In addition, even when a glass plate having a large area was produced, cracks were formed at the time of cutting.

On the other hand, the present inventors have found that a glass plate having a thickness of 0.2 mm or less and hardly cracking is obtained when the glass base material of a fluorine phosphate-based glass base material which has been thinned to some extent by physical polishing is immersed in an alkali detergent. About this reason, it thinks as follows.

Although fluorine phosphate-based glass generally has high alkali resistance, the fluorine phosphate-based glass in the present invention has low alkali resistance because it contains at least 7 c% of Al ³⁺ which lowers alkali resistance. For this reason, it is considered that the microcracks of the glass base material are melted in the etching step with an alkaline detergent, and that no microcracks exist on the side surfaces of the obtained infrared absorbing glass plate. It is considered that the disappearance of the cracks in the infrared absorbing glass plate is eliminated by the disappearance of the micro-cracks, so that the strength of the infrared absorbing glass plate is increased, so that it is difficult to break even if the thickness is thin.

In the infrared absorbing glass plate according to the present invention, there are preferably no polishing marks on the first and second main surfaces.

In the infrared absorbing glass plate according to the present invention, preferably, the areas of the first and second main surfaces are 100 mm2 or more and 25000 mm2 or less.

The infrared absorbing glass plate according to the present invention preferably has a three-point bending strength of 35 N / mm 2 or more at a point-to-point distance of 2.5 mm.

In the infrared absorbing glass plate according to the present invention, preferably, the areas of the first and second main surfaces are 1 mm2 or more and less than 1000 mm2.

The infrared absorbing glass plate according to the present invention is preferably used for a solid-state imaging element device.

The array of infrared absorbing glass plates according to the present invention includes a support and a plurality of infrared absorbing glass plates of the present invention arranged in a matrix shape on the support.

The method for producing an infrared absorbing glass plate according to the present invention is, as a cation%, P ⁵⁺ 10-70%, Al ³⁺ 7-50%, Cu ²⁺ 0.1-15%, and anion%, F ^- 10- 90%, O ^2- 10~90 polishing physical polishing fluorine phosphate-based base material of the plate-like which is composed of a glass containing a% step of etching for etching by dipping the physical grinding the glass base material in an alkaline detergent Provide a process.

The method for manufacturing an infrared absorbing glass plate according to the present invention preferably has a thickness of the glass base material of more than 0.2 mm and 0.3 mm or less by the physical polishing in the polishing step.

The method for producing an infrared absorbing glass plate according to the present invention is preferably etched by immersing the physically polished glass base material in an alkaline detergent having a pH of 7.1 or higher in the etching step.

It is preferable that the said alkali detergent contains the alkali salt of amino polycarboxylic acid.

The solid-state imaging element device according to the present invention includes an infrared absorbing glass plate constructed in accordance with the present invention.

ADVANTAGE OF THE INVENTION According to this invention, the infrared absorption glass plate which can attain size reduction of a solid-state imaging element device can be provided.

1 is a schematic perspective view showing an infrared absorbing glass plate of the present invention.
2 is a schematic cross-sectional view showing a modification of the infrared absorbing glass plate of the present invention.
3 is a schematic cross-sectional view showing a solid-state imaging element device using the infrared absorbing glass plate of the present invention.
4 is a schematic cross-sectional view for explaining the manufacturing process of the array of infrared absorbing glass plates of the present invention.
5 is a schematic plan view for explaining the manufacturing process of the array of infrared absorbing glass plates of the present invention.
6 is a schematic plan view showing an array of infrared absorbing glass plates of the present invention.

Hereinafter, a preferred embodiment is described. However, the following embodiments are merely examples, and the present invention is not limited to the following embodiments. In addition, in each figure, the member which has substantially the same function may be referred with the same code | symbol.

(Infrared absorption glass plate)

1 is a schematic perspective view showing an infrared absorbing glass plate of the present invention. As shown in Fig. 1, the infrared absorbing glass plate 1 has a rectangular planar shape. The corner portion of the infrared absorbing glass plate 1 may be chamfered.

The infrared absorbing glass plate 1 has first and second main surfaces 1a, 1b and side surfaces 1c. The first and second main surfaces 1a and 1b face each other. In the infrared absorbing glass plate 1, both the first and second main surfaces 1a and 1b are optical surfaces. The side surfaces 1c connect the first and second main surfaces 1a and 1b.

The infrared absorbing glass plate 1 is made of fluorine phosphate-based glass containing CuO. Therefore, the infrared absorption glass plate 1 is excellent in infrared absorption function.

The thickness of the infrared absorbing glass plate 1 is 0.2 mm or less. It is preferably 0.19 mm or less, and more preferably 0.16 mm or less. Since the infrared absorbing glass plate 1 has a thickness of 0.2 mm or less, it is possible to reduce the size of the solid-state imaging element device when used in the solid-state imaging element device. Moreover, since a thickness may become easy to generate | occur | produce when the infrared absorption glass plate 1 is lifted in a conveyance process when thickness is too thin, it is preferable that thickness is 0.05 mm or more, and it is more preferable that it is 0.08 mm or more.

In this way, the infrared absorbing glass plate 1 is excellent in infrared absorption function, and can be used in a solid-state imaging element device as it is possible to reduce the size of the solid-state imaging element device.

In general, the fluorine phosphate-based glass has low strength and is easy to crack when thinned, but in the present invention, since microcracks are not present on the side surface 1c of the infrared absorbing glass plate 1, even if the thickness is 0.2 mm or less, It is difficult to crack. Micro crack refers to a crack having a length of 1 to 15 μm. The microcracks sometimes become the starting point of cracks when the infrared absorbing glass plate 1 is bent. In particular, when microcracks are present on the side surfaces 1c, it is likely to be a starting point for cracks. Therefore, when there is no micro-cracks on the side surfaces 1c, it is possible to make it difficult to generate cracks in the infrared absorbing glass plate 1. In addition, the presence or absence of microcracks can be confirmed by an optical microscope.

In addition, there may be cases where microcracks are present in the first and second main surfaces 1a and 1b as well as the side surfaces 1c. Therefore, from the viewpoint of making it difficult to further generate cracks in the infrared absorbing glass plate 1, it is more preferable that microcracks are not present in the first and second main surfaces 1a and 1b in addition to the side surfaces 1c. desirable.

Further, it is preferable that no polishing marks at the time of manufacturing are present on the first and second main surfaces 1a and 1b of the infrared absorbing glass plate 1. In that case, it is possible to make it more difficult for the infrared absorption glass plate 1 to crack more. From the viewpoint of making it difficult to further generate cracks in the infrared absorbing glass plate 1, it is more preferable that no polishing marks exist on the side surfaces 1c in addition to the first and second main surfaces 1a and 1b. . In addition, the polishing marks can be confirmed by an atomic force microscope.

The three-point bending strength of the infrared absorbing glass plate 1 at a point-to-point distance of 2.5 mm is preferably 35 N / mm 2 or more, and more preferably 50 N / mm 2 or more. When the three-point bending strength is more than the lower limit, cracks in the infrared absorbing glass plate 1 can be made more difficult. Moreover, although the upper limit of the three-point bending strength of the infrared absorbing glass plate 1 is not specifically limited, it is about 450 N / mm2 in the nature of the material.

Hereinafter, the material constituting the infrared absorbing glass plate 1 will be described in more detail.

Material details;

The infrared absorbing glass 1 is a cation%, and contains P ⁵⁺ 10 to 70%, Al ^{3+ 7 to} 50%, and Cu ²⁺ 0.1 to 15%. The reason for limiting the glass composition as described above will be explained below.

P ⁵⁺ is a component for forming a glass skeleton. The content of P ⁵⁺ is 10 to 70%, preferably 18 to 63%, particularly 25 to 55%. When the content of P ⁵⁺ is too small, vitrification tends to become unstable. On the other hand, when the content of P ⁵⁺ is too large, devitrification resistance tends to decrease.

Al ³⁺ is a component that lowers alkali resistance. The content of Al ³⁺ is 7 to 50%, preferably 7 to 31%, particularly 7 to 16%. When the content of Al ³⁺ is too small, the alkali resistance becomes high and it is difficult to be etched by an alkaline detergent, making it difficult to thin the infrared absorbing glass plate. In addition, since the microcracks on the side surfaces are less likely to disappear, the strength of the infrared absorbing glass plate is weakened, and cracks are likely to occur. On the other hand, when the content of Al ³⁺ is too large, the ^meltability decreases and the melting temperature tends to rise. Moreover, when the melting temperature rises, Cu ions are reduced and shift from Cu ²⁺ to Cu ⁺ becomes easy, so that it is difficult to obtain desired optical properties. Specifically, the light transmittance in the near-ultraviolet-visible region decreases, or the near-infrared absorption property tends to decrease.

Cu ²⁺ is a component for absorbing near infrared rays. The content of Cu ²⁺ is 0.1 to 15%, preferably 2 to 13%, particularly 4 to 10%. When the content of Cu ²⁺ is too small, the above effect is difficult to obtain. On the other hand, when the content of Cu ²⁺ is too large, the light transmittance between ultraviolet and visible regions tends to decrease. Moreover, devitrification resistance tends to decrease.

In addition to the above components, various components shown below can be included.

Li ⁺ is a component that lowers the melting temperature. The content of Li ⁺ is preferably 0 to 30%, particularly 0.1 to 25%. When the content of Li ⁺ is too large, devitrification resistance tends to decrease.

Na ⁺ , like Li ⁺ , is a component that lowers the melting temperature. The content of Na ⁺ is preferably 0 to 30%, particularly 0.1 to 20%. When the content of Na ⁺ is too large, devitrification resistance tends to decrease.

K ⁺ is a component that lowers the melting temperature as well as Li ⁺ . The content of K ⁺ is preferably 0 to 30%, particularly 0.1 to 20%. When the content of K ⁺ is too large, devitrification resistance tends to decrease.

Mg ²⁺ is a component that improves devitrification resistance. The content of Mg ²⁺ is preferably 0 to 20%, particularly 0.1 to 11%. When the content of Mg ²⁺ is too large, stability of vitrification tends to decrease.

Ca ²⁺ is a component that improves devitrification resistance like Mg ²⁺ . The content of Ca ²⁺ is preferably 0 to 12%, particularly 0.1 to 10%. When the content of Ca ²⁺ is too large, stability of vitrification tends to decrease.

Sr ²⁺ , like Mg ²⁺ , is a component that improves devitrification resistance. The content of Sr ²⁺ is preferably 0 to 20%, particularly 0.1 to 10%. When the content of Sr ²⁺ is too large, stability of vitrification tends to decrease.

Ba ²⁺ is a component that improves devitrification resistance similarly to Mg ²⁺ . The content of Ba ²⁺ is preferably 0 to 13%, particularly 0.1 to 11%. When the content of Ba ²⁺ is too large, stability of vitrification tends to decrease.

Zn ²⁺ , like Mg ²⁺ , is a component that improves devitrification resistance. The content of Zn ²⁺ is preferably 0 to 10%, particularly 0.1 to 5%. When the content of Zn ²⁺ is too large, stability of vitrification tends to decrease.

In addition, as the cation component in the optical glass of the present invention, Bi ³⁺ , La ³⁺ , Y ³⁺ , Gd ³⁺ , Te ⁴⁺ , Si ⁴⁺ , Ta ⁵⁺ , Nb ⁵⁺ , Ti ⁴⁺ , Zr ⁴⁺ or Sb ³⁺ or the like may be contained within a range that does not impair the effects of the present invention. Specifically, the content of these components is preferably 0 to 3%, and more preferably 0 to 1%.

Since the Pb component (Pb ^2+, etc.) and the As component (As ^3+, etc.) are environmental load substances, it is preferable not to contain substantially in the present invention. Here, "substantially free" means that these components are not intentionally added to the glass, and does not mean that even inevitable impurities are completely excluded. More objectively, it means that the content of these components containing impurities is less than 0.1%.

The composition of the anion component contains F ^- 10 to 90%, and O ^{2 to} 10 to 90%, particularly preferably F ^- 10 to 70% and O ^{2 to} 30 to 90%. When the content of F ^- is too small (if the content of O ² is too large), devitrification resistance tends to decrease. On the other hand, if the content of F ^- is too large (the content of O ² is too small), stability of vitrification tends to decrease.

By having the above composition, it becomes possible to achieve both higher light transmittance in the visible region and more excellent light absorption characteristics in the infrared region. Specifically, the light transmittance at a wavelength of 500 nm is preferably 75% or more, and more preferably 77% or more. On the other hand, the light transmittance at a wavelength of 700 nm is preferably 27% or less, more preferably 25% or less, and the light transmittance at a wavelength of 1200 nm is preferably 38% or less, more preferably 36 % Or less

Modification;

2 is a schematic cross-sectional view showing a modification of the infrared absorbing glass plate of the present invention.

In the modified example shown in FIG. 2, the antireflection film 2 is formed on the first main surface 1a of the infrared absorbing glass plate 1. Further, an infrared reflecting film 3 is formed on the second main surface 1b of the infrared absorbing glass plate 1.

The antireflection film 2 is a film having a function of reducing reflectance. The antireflection film 2 may be a film having a lower reflectance when the antireflection film 2 is formed than when the antireflection film 2 is not formed, and is not necessarily a film having a zero reflectance. Above all, in the present invention, it is not necessary to form the antireflection film 2.

The antireflection film 2 can be formed of, for example, a low-refractive-index film having a relatively low refractive index and a dielectric multilayer film in which a high-refractive-index film having a relatively high refractive index is alternately stacked. The number of layers of the dielectric multilayer film is not particularly limited, but is usually about 3 to 5 layers. Further, the antireflection film 2 may be formed of a low refractive index film having a lower refractive index than the infrared absorbing glass plate 1.

The infrared reflecting film 3 is a film having a function of reflecting infrared rays. The infrared reflecting film 3 can be formed of, for example, SiO ₂ , Nb ₂ O ₅ or TiO ₂ .

In this modified example, if the infrared absorbing glass plate 1 is provided on a solid-state imaging element device or the like so as to be an antireflection film 2 on the light incident side and an infrared reflecting film 3 on the light output side, the visible light can be sufficiently transmitted. In addition, infrared rays can be efficiently blocked. Moreover, since the thickness of the infrared absorbing glass plate 1 is thin, the size of the solid-state imaging element device can be reduced when used for the solid-state imaging element device.

(Method for manufacturing infrared absorbing glass plate)

Hereinafter, the manufacturing method of the infrared absorbing glass plate of this invention is demonstrated.

First, a glass base material is obtained by melting a raw material powder batch of a fluorine phosphate-based glass prepared to have a desired composition and molding it into a plate shape.

The melting temperature is preferably 700 to 900 ° C, and more preferably 700 to 850 ° C. If the melting temperature is too low, homogeneous glass may be difficult to obtain. On the other hand, when the melting temperature is too high, Cu ions are reduced, and shifting from Cu ²⁺ to Cu ⁺ may be easy, and desired optical properties may be difficult to obtain.

Moreover, although it does not specifically limit as a shaping | molding method, For example, the shaping | molding method, such as a casting method, a rollout method, a down draw method, or a lead draw method, can be used.

Subsequently, the plate-shaped glass base material prepared as described above is polished by physical polishing (polishing step). In a polishing process, it is preferable to make the thickness of a glass base material into more than 0.2 mm and 0.3 mm or less by physical polishing. When the thickness of the glass base material is too thin by physical polishing, the glass base material may crack. In addition, if the thickness of the glass base material is too thick, it may not be possible to sufficiently reduce the thickness of the glass plate in the etching process described later.

In the polishing step, a physically polished glass base material is obtained by polishing a glass base material to a thickness of about 0.3 mm by, for example, wrap polishing, and subsequently polishing to a thickness of more than 0.2 mm and 0.3 mm or less by optical polishing. Can be.

Subsequently, the physically polished glass base material is etched by immersing it in an alkaline detergent in a vertically standing state (etching step). Thereby, the infrared absorbing glass plate of this invention whose thickness is 0.2 mm or less can be obtained.

As described above, in the method for producing an infrared absorbing glass plate according to the present invention, an infrared absorbing glass plate having a thickness of 0.2 mm or less, which has been difficult to obtain conventionally, can be easily produced.

Although it does not specifically limit as an alkali detergent, For example, alkali components, such as alkali components, such as Na and K, surfactants, such as triethanolamine, benzyl alcohol, or glycol, and water or alcohol, can be used.

It is preferable that alkali salts of chelating agents, such as aminopolycarboxylic acid, are contained as an alkali component contained in an alkali detergent. Examples of the alkali salt of the aminopolycarboxylic acid include sodium and potassium salts such as diethylenetriamine 5acetic acid, ethylenediamine tetraacetic acid, triethylenetetraamine 6acetic acid, and nitro triacetic acid. Among these, diethylenetriamine pentaacetate 5 sodium, ethylenediamine tetraacetate 4 sodium, triethylenetetraamine hexaacetate 6 sodium, and nitro triacetate 3 sodium are preferably used, especially diethylenetriamine pentaacetate 5 sodium. Is used.

The immersion temperature in the alkali detergent is not particularly limited, but can be, for example, 20 to 40 ° C.

The immersion time in the alkali detergent is not particularly limited, but can be, for example, 1 to 30 hours. Moreover, it is preferable that the physically polished glass base material is immersed in an alkaline detergent for 1 to 30 hours in an upright state, and then upside down and immersed for the same time. In that case, an infrared absorbing glass plate with a more uniform thickness distribution can be obtained.

From the viewpoint of making it more difficult for microcracks to be present and making it difficult to generate cracks in the resulting infrared absorbing glass plate, the pH of the alkali detergent is preferably 7.1 or more, more preferably 8.0 or more.

In addition, since the infrared absorbing glass plate obtained by the above method is hardly cracked, it is possible to increase the areas of the first and second main surfaces. For example, the area of the first and second main surfaces can be 100 mm 2 or more and 25000 mm 2 or less. The more preferable range of the area of the first and second major surfaces is 400 mm2 or more, 25000 mm2 or less, more preferably 1000 mm2 or more, 25000 mm2 or less, more preferably 2500 mm2 or more, 25000 mm2 or less, particularly preferably Is 5000 kPa or more and 25000 kPa or less. Even in the infrared absorbing glass plate having a large area of the first and second main surfaces, cracks are unlikely to occur, and thus, it can be cut to a desired size and used. In this case, the infrared absorbing glass plate can be manufactured more efficiently. Moreover, the area of the 1st and 2nd main surfaces after cutting is preferably 1 mm2 or more and less than 1000 mm2.

(Solid imaging device device)

3 is a schematic cross-sectional view showing a solid-state imaging element device using the infrared absorbing glass plate of the present invention. As shown in Fig. 3, the solid-state imaging element device 10 includes an infrared absorbing glass plate 1, a solid-state imaging element 11, a package 12, and an adhesive layer 13.

The package 12 is made of ceramic. The solid-state imaging element 11 is housed in the package 12. In addition, an infrared absorbing glass plate 1 is provided in the opening of the package 12. Moreover, the package 12 and the infrared absorbing glass plate 1 are joined by the adhesive layer 13. The adhesive layer 13 can be formed of a suitable ultraviolet curable resin or a thermosetting resin.

Since the solid-state imaging element device 10 is provided with an infrared absorbing glass plate 1 on the light incident side of the solid-state imaging element 11, it sufficiently absorbs light in the infrared region and enters the light into the solid-state imaging element 11 I can do it. In addition, since the infrared absorbing glass plate 1 constituting the solid-state imaging element device 10 is as thin as 0.2 mm or less as described above, the solid-state imaging element device 10 can be miniaturized. Moreover, as the infrared absorbing glass plate 1, the infrared absorbing glass plate which formed the antireflection film and infrared reflecting film shown in FIG. 2 can also be employ | adopted.

(Array of infrared absorbing glass plates)

4 is a schematic cross-sectional view for explaining the manufacturing process of the array of infrared absorbing glass plates of the present invention. 5 is a schematic plan view for explaining the manufacturing process of the array of infrared absorbing glass plates of the present invention. Infrared absorbing glass plates used in smartphone cameras and the like are generally of a small size. Therefore, a mother glass plate made of infrared absorbing glass having a size capable of collecting a plurality of glass plates is produced, and this is divided by dicing or the like to prepare an array of individualized infrared absorbing glass plates, and withdrawing individual infrared absorbing glass plates from the array. You may use it. Hereinafter, a method of manufacturing an array of infrared absorbing glass plates will be described.

First, a mother glass plate 21 made of an infrared absorbing glass that has been alkali-cleaned as a glass base material is prepared. On the first main surface 21a and the second main surface 21b of the mother glass plate 21, optical films 22 and 23, such as an antireflection film or an infrared reflecting film, may be provided as necessary.

The mother glass plate 21 on which the optical films 22 and 23 are formed is adhered to the support 30. As the support 30, it is possible to use, for example, a UV tape whose adhesive strength is lowered by ultraviolet irradiation.

Subsequently, along the cutting line A, the mother glass plate 21 on the support 30 is cut with a dicing saw or the like and divided into a plurality of infrared absorbing glass plates 31 arranged in a matrix shape.

Next, the plurality of individual infrared absorbing glass plates 31 adhered to the support 30 are immersed in the alkali detergent together with the support 30 to etch the side surfaces of the infrared absorbing glass plate 31. Thereby, microcracks or the like formed on the side surfaces by dicing can be removed. For this reason, it can be set as the infrared-absorption glass plate 31 in which cracks are hardly generated.

Further, the mother glass plate 21 may be cut by laser irradiation. In the case of cutting by laser irradiation, it is difficult to generate microcracks or the like on the cut surface, so the etching step may be omitted.

Fig. 6 is a schematic plan view showing an array of infrared absorbing glass plates of the present invention produced as described above. The array 40 of infrared absorbing glass plates of this embodiment includes a support 30 and a plurality of infrared absorbing glass plates 31 arranged in a matrix shape on the support 30. In addition, when a UV tape is used as the support 30, the adhesive strength can be lowered by irradiating ultraviolet rays so that the infrared absorbing glass plate 31 can be easily separated from the support 30.

(Example)

Hereinafter, the present invention will be described based on examples. In addition, the present invention is not limited to the following examples.

Table 1 shows examples (samples No. 1 to 10) and comparative examples (samples No. 11) of the present invention.

The raw material powder batch prepared to have the glass composition shown in Table 1 was melted at a temperature of 700 to 850 ° C, and was formed into a plate shape by a roll-out method to obtain a plate-shaped glass base material.

The obtained glass base material was cut to a size of 125.1 mm x 125.1 mm using a dicer, and the cut glass base material was placed in the hole of a carrier set on the bottom plate of a double-sided grinder, and the top plate was lowered to apply pressure. Both surfaces were polished while the polishing liquid containing Al ₂ O ₃ was flowed while rotating the top plate, the bottom plate, and the carrier to make the thickness of the glass base material 0.3 mm. Subsequently, the glass base material was further polished with CeO ₂ to make the thickness of the glass base material 0.25 mm.

Subsequently, the polished glass base material was immersed in an alkaline detergent having a composition of mass%, alkali salt of aminopolycarboxylic acid 37%, triethanolamine 20%, and water 43%, at a temperature of 30 ° C for 14 hours. An infrared absorbing glass plate (30 sheets each) having a size of 125 mm x 125 mm and a thickness shown in Table 1 was obtained.

The alkali detergent contains diethylenetriamine pentaacetate 5 sodium as an alkali salt of aminopolycarboxylic acid.

The presence or absence of microcracks was judged by observing the side surface of the obtained infrared absorbing glass plate (30 sheets) with an optical microscope.

Further, the obtained infrared absorbing glass plate (30 sheets) was measured for a three-point bending strength at a point-to-point distance of 2.5 mm, and an average value was calculated.

As can be seen clearly from Table 1, samples No. 1 to 10, which are examples of the present invention, had a thickness of 0.16 mm or less and were etched with an alkaline detergent. In addition, there was no micro-cracks on the side surface, and despite the thin thickness, the 3-point bending strength was as high as 121 N / mm 2 or more.

On the other hand, the sample of Comparative Example No. 11 had a thickness of 0.25 mm as before etching, and was not etched with an alkali detergent. In addition, microcracks of about 1 to 10 µm were present on the side surfaces, and the three-point bending strength was low at 25 N / mm 2.

1: Infrared absorbing glass plate
1a, 1b: first and second main surfaces
1c: side
2: Anti-reflection film
3: Infrared reflective film
10: solid-state imaging element device
11: solid-state imaging element
12: Package
13: adhesive layer
21: mother glass plate
21a, 21b: first and second main surfaces
22, 23: optical film
30: support
31: infrared absorption glass plate
40: array of infrared absorbing glass plates

Claims (12)

An infrared absorbing glass plate having first and second main surfaces facing each other and side surfaces connecting the first and second main surfaces, in% cation, P ⁵⁺ 10 to 70%, Al ^{3+ 7 to} 50 %, with Cu ²⁺ 0.1~15%, and anionic%, F ^- 10-90%, O ^2-, and is composed of a fluorine-phosphate-based glass containing 10-90%, a thickness of less than 0.2㎜, the An infrared absorbing glass plate characterized in that there are no micro-cracks on the side. According to claim 1,
An infrared absorbing glass plate characterized in that no polishing marks exist on the first and second main surfaces. The method of claim 1 or 2,
The infrared absorption glass plate, characterized in that the area of the first and second main surfaces is 100 mm 2 or more and 25000 mm 2 or less. The method according to any one of claims 1 to 3,
An infrared absorbing glass plate, characterized in that the three-point bending strength at a point-to-point distance of 2.5 mm is 35 N / mm 2 or more. The method of claim 1 or 2,
The infrared absorption glass plate characterized in that the area of the first and second main surfaces is 1 mm 2 or more and less than 1000 mm 2. The method according to any one of claims 1 to 5,
An infrared absorbing glass plate, which is used in a solid-state imaging element device. An array of infrared absorbing glass plates comprising a support and a plurality of infrared absorbing glass plates according to any one of claims 1 to 6 arranged in a matrix shape on the support. A method for producing the infrared absorbing glass plate according to any one of claims 1 to 6, wherein the cationic% is P ⁵⁺ 10-70%, Al ³⁺ 7-50%, Cu ²⁺ 0.1-15%, and as ^{anionic%, F - 10~90%, O} 2- 10~90 polishing physical grinding a glass base material of the plate-like which is composed of a fluorine-phosphate type glass containing a% step, and the physical grinding the glass base material And an etching step of etching by immersing in an alkaline detergent. The method of claim 8,
In the polishing step, the method of manufacturing an infrared absorbing glass plate characterized in that the thickness of the glass base material is greater than 0.2 mm and 0.3 mm or less by the physical polishing. The method of claim 8 or 9,
In the etching step, a method for producing an infrared absorbing glass plate, wherein the physically polished glass base material is etched by immersing in an alkaline detergent having a pH of 7.1 or higher. The method according to any one of claims 8 to 10,
Method for producing an infrared absorbing glass plate, characterized in that the alkali detergent contains an alkali salt of an aminopolycarboxylic acid. A solid-state imaging element device comprising the infrared absorbing glass plate according to any one of claims 1 to 6.

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