WO2008075546A1

WO2008075546A1 - Glass for substrate

Info

Publication number: WO2008075546A1
Application number: PCT/JP2007/073157
Authority: WO
Inventors: Seiki Ohara; Yuki Kondo; Naoki Sugimoto
Original assignee: Asahi Glass Company, Limited
Priority date: 2006-12-19
Filing date: 2007-11-30
Publication date: 2008-06-26

Abstract

Disclosed is a glass for a substrate, which shows a transmittance of light having a wavelength of 5.5 μm of 50% or more and a transmittance of light having a wavelength of 7.0 μm of 10% or less when prepared in a thickness of 1 mm. Specifically disclosed is a glass for a substrate, which comprises (by mole, in terms of oxide): 10 to 55% of Bi2O3; 20 to 85% of GeO2; 0 to 19% of Ga2O3; and 0 to 15% of Al2O3, wherein the sum total of Bi2O3 and GeO2 accounts for 50% or more and, when MgO is contained, the sum total of Ga2O3 and MgO accounts for 20% or less. In the glass, the content of Bi2O3 may be 15% or more, the content of GeO2 may be 80% or less, and the sum total of Ga2O3 and Al2O3 may account for 2 to 30%. In the glass, the sum total of GeO2 and Al2O3 may account for 60% or more. The glass may have a glass transition temperature of 400˚C or higher.

Description

Specification

Substrate glass

Technical field

[0001] The present invention is a sensor for detecting concentration of CO gas, CO gas, NO gas, etc., which transmits infrared rays.

2 X

The present invention relates to a glass for a substrate suitable for a substrate or the like.

Background art

[0002] Infrared light with a wavelength of 4 μm is used for CO gas detection and CO gas detection.

2

Infrared rays with a wavelength of 3-5 m are used for temperature detection.

In the case of CO gas or CO gas concentration detection sensors, infrared light with a wavelength of 5 μm or more

2

An infrared filter in which a multilayer film is formed on a substrate that transmits rays is used. As such a substrate, a germanium substrate or a silicon substrate is widely used. These substrates are expensive and an alternative material is required.

[0003] While such fluoride glass and chalcogenide glass as a material is known, the glass transition point of the glass (Tg) of issues force ^s that any one is low immediately thermally unstable.

Bi O -PbO-ZnO-CdF glass is a thermally stable glass that transmits infrared light.

2 3 2 glass (see Patent Document 1), Bi 2 O 3 —ZnO—R 2 O glass (R is an alkali metal. Patent Document 2

2 3 2

For example).

[0004] Patent Document 1: Japanese Patent Laid-Open No. 8-188445

Patent Document 2: JP-A-8-133779

Disclosure of the invention

Problems to be solved by the invention

[0005] The BiO-PbO-ZnO-CdF-based glass is not preferable in that it contains PbO.

2 3 2

Yes

The BiO-ZnO-R ○ glass has high light transmission up to the infrared region with a wavelength of 7.5 μm.

2 3 2

Therefore, when used for a substrate such as a gas sensor, it transmits even unnecessary infrared rays having a wavelength of 7 m or more. Therefore, it is not possible to increase the sensitivity of the gas sensor. There is a problem that light of a necessary wavelength must be blocked by forming a multilayer film on the substrate or by another filter.

An object of the present invention is to provide a glass for a substrate that can solve such problems. Means for solving the problem

[0006] In the present invention, BiO is 10 to 55%, GeO is 20 to 8 in terms of mol% based on the following oxides.

2 3 2

5%, GaO 0 ~; 19%, AlO 0 ~; 15%, BiO + GeO force ¾0% or more

2 3 2 3 2 3 2 Thus, in the case of containing MgO, a glass for a substrate having Ga O + MgO of 20% or less is provided.

twenty three

Yes

In particular, Bi O 10—55%, GeO 20—85%

2 3 2

Ga〇 0 to 18.9%, Ga〇 + A1〇 2—30%, CaO + SrO + BaO 0—25%,

2 3 2 3 2 3

ZnO 0-20%, Na〇 + K〇0-25%, Ce〇0-2%, force, etc.

2 2 2 2

Substrate glass (Aspect A glass) containing 50% or more of O + GeO and not containing MgO

3 2

provide.

For example, “contains 0-19% GaO” means that GaO is not essential, but 19%

2 3 2 3

It may be contained in the following range.

The invention's effect

[0007] A glass for substrates is obtained that has a high Tg (glass transition point), is thermally stable, has a high transmittance at a wavelength of 5.5 111, and a low transmittance at a wavelength of 7 am.

BEST MODE FOR CARRYING OUT THE INVENTION

[0008] The glass for a substrate of the present invention (hereinafter, the glass of the present invention and V) is suitable for a glass substrate of a gas analyzer, a radiation thermometer, an infrared sensor or the like.

The Tg of the glass of the present invention is preferably 400 ° C or higher. Below 400 ° C, the substrate may be deteriorated when detecting relatively high-temperature infrared rays, or the substrate may be deformed in the vapor deposition process for forming the multilayer film.

[0009] The glass of the present invention has a light transmittance (T) of 50% or more at a wavelength of 5.5 m at a thickness of lmm.

5.5

In addition, the transmittance (T) of light having a wavelength of 7. O ^ m at a thickness of lmm is preferably 10% or less.

7. 0

Masle. If the T force is less than ¾0%, the necessary amount of light may not be obtained. T

5.5. If 7.5 exceeds 10%, a multilayer film such as an oxide film or metal film is used to block light of unnecessary wavelengths. There is a risk that a process for vapor deposition lamination may be required. This preferred! / Substrate made of glass can be used as an alternative to sapphire substrates (T = 73%, T = 5%)

5. 5 7. 0

Become.

[0010] A substrate made of the glass of the present invention, a concentration detection sensor substrate such as NO gas, a high temperature sensor

X

When used on a single substrate, it is preferred that the transmittance (T) of the light of a wavelength of 6.5 m at a thickness lmm of the glass of the present invention is 4% or less! /. If it exceeds 4%, light of unnecessary wavelength is blocked.

6.5

Therefore, there is a possibility that a multilayer film must be deposited on the glass substrate.

Next, the components and contents of the glass of the present invention will be described. "Mole%" is simply displayed as "%"

BiO is an essential component. If its content is less than 10%, the melting temperature becomes high, and

twenty three

Becomes easier to separate. It is preferably 13% or more, more preferably 15% or more, particularly preferably 18% or more, and typically 20% or more. If it exceeds 55%, vitrification becomes difficult. Preferably it is 50% or less, typically 45% or less.

[0012] GeO is a network former and a component that lowers T and is essential

2 7. 0

. If the content is less than 20%, T becomes high or devitrification tends to occur. More preferable

7. 0

Is over 25%. If it exceeds 85%, it tends to be devitrified. More preferably, it is 80% or less, and typically 75% or less.

T may decrease if the total content of BiO and GeO is less than 50%.

2 3 2 5.5

. Typically 55% or more.

[0013] Neither Ga 2 O nor Al 2 O is a component that suppresses devitrification, although it is not essential.

2 3 2 3

For such purposes, it may be contained in a range of 19% or less and 15% or less, respectively. Ga

2

If O exceeds 19% or Al O exceeds 15%, the glass tends to devitrify. Typical

3 2 3

GaO is 16% or less, and AlO is 12% or less.

2 3 2 3

[0014] In that case, it is preferable to contain at least one of Ga 2 O and Al 2 O

2 3 2 3

The total content of GaO and AlO is preferably 2 to 30%.

2 3 2 3 2 3 2 3

That's right. If less than Ga O + A1 O force, the devitrification suppressing effect of the glass may be insufficient.

2 3 2 3

There is. More preferably, it is 4% or more. If it exceeds 30%, the glass tends to be devitrified. More preferably, it is 25% or less, particularly preferably 22% or less. Typically, the BiO content is 15% or more, the GeO content is 80% or less, and GaO +

2 3 2 2 3

A1 0 force ¾ to 30%.

twenty three

[0015] GeO + A10 is preferably 60% or more. T less than 60%, for example 4

2 2 3 6. 5

It may be difficult to make it below%.

[0016] The glass of the present invention does not impair the object of the present invention, and BiO, GeO, GaO and

Components other than 2 3 2 2 3 and Al 2 O may be contained. In the following, such components are illustratively described.

twenty three

The total content of BiO, GeO, GaO and AlO is preferably 70% or more, T

2 3 2 2 3 2 3

In an embodiment that is less than force, it is typically 90% or more.

6.5

[0017] None of MgO, CaO, SrO and BaO is essential, but may be contained in a total content of 25% or less in order to suppress devitrification. If it exceeds 25%, the glass tends to be easily devitrified. Preferably it is 20% or less. MgO + CaO + SrO is typically 0-8%.

When MgO, CaO, SrO and BaO are contained, their content is preferably 10% or less, 15% or less, 15% or less, and 20% or less, respectively, typically 7% or less, % Or less, 7% or less, 18% or less.

When MgO is contained, Ga 2 O + MgO must be 20% or less. 20%

twenty three

If it is too high, the glass tends to devitrify.

[0018] ZnO is not essential, but may be contained up to 20% in order to suppress devitrification. If it exceeds 20%, devitrification tends to occur. Typically less than 15%.

[0019] Both Na 2 O and K 2 O are not essential, but in order to suppress devitrification, these components

twenty two

V, which may contain up to 25% of total content. If it exceeds 25%, chemical durability may be reduced. Preferably it is 20% or less, typically 15% or less.

[0020] CeO is not essential, but Bi O precipitates as metallic bismuth in the glass melt

2 2 3

In order to prevent this, it may be contained up to 2%. If it exceeds 2%, the glass tends to be devitrified. Preferably it is 1% or less, More preferably, it is 0.5% or less. When containing CeO

2

The content is preferably 0.05% or more, more preferably 0.1% or more.

[0021] One or more kinds selected from the group consisting of TiO, ZrO, InO, LaO, YO and NbO forces

2 2 2 3 2 3 2 3 2 3

In some cases, the oxide may be contained. In this case, the total content of these components is 10% The following is preferable. If it exceeds 10%, devitrification tends to occur. Typically less than 5%.

If any of these components contain one or more types and ZnO, TiO + ZrO + In O + La

2 2 2 3

O + Y O + Nb O + ZnO is preferably 15% or less. More than 15% is devitrified

2 3 2 3 2 3

May be easier. Typically less than 10%.

[0022] When SiO is contained, its content is preferably 1% or less. Over 1%

2

May decrease T. Typically no SiO.

5. 5 2

When B 2 O is contained, the content is preferably 1% or less. Over 1%

twenty three

May decrease T. Typically no B 2 O is contained.

5. 5 2 3

P o is typically not included.

twenty five

[0023] The glass of the aspect A is essentially composed of Bi O and GeO, which are essential components, and any one component.

2 3 2

Quasi-essential components that must contain GaO, AlO and optional components CaO, Sr

2 3 2 3

〇, Ba〇, Zn〇, Na〇, K〇, CeO

2 2 2

And may contain other components. In this case, the total content of such components is preferably 15% or less, more preferably 10% or less, typically 5% or less. Examples of such components include TiO, ZrO, InO, LaO, YO, and the like described above as examples.

2 2 2 3 2 3 2 3

NbO is typical, and the above explanation regarding SiO, B 2 O, and P 2 O applies as well.

2 3 2 2 3 2 5

It is.

In aspect A, typically, Bi 0 force 0 to 55%, GeO force 0 to 75%, Ga 0

2 3 2 2 3

+ A1 0 force -25%, Ca 0 0-15%, Sr 0 0-15%, Ba 0 0-20%, Zn 0

twenty three

0—15%, Na 2 O + K 0 is 0-20%.

twenty two

[0024] The method for producing the glass of the present invention is not particularly limited. For example, raw materials are prepared and mixed, and then placed in a gold crucible, platinum crucible, alumina crucible, or quartz crucible, and 800 to; air at 1300 ° C. Can be manufactured by dissolving in the melt (melting method) In addition, the sol-gel method may be manufactured by a method other than the melting method such as a vapor deposition method.

Example

[0025] Table; Examples of! ~ 6; Except for Example 47 of! ~ 53, the Bi O force, etc.

2 3 2

A glass having a composition indicated by% is produced by a melting method. Examples;! -47 are examples, examples 48-5 3 is a comparative example.

Examples 1 to 46 Tg (unit: ° C), T (unit:%), T (unit:%), Τ (unit:%)

5. 5 6. 5 7. 0

) Was measured. Those marked with * are those estimated from the composition without measurement. For the glass having the composition of Example 47, Tg, T, Τ, and Τ were estimated by calculation from the force not produced by the melting method, that is, from the composition.

5. 5 6. 5 7. 0

Since the glasses of Examples 48 to 53 were devitrified, Tg and the like were not measured.

[table 1]

[Table 2]

賺 / υ / O-ε 卜 02τ1 ϋ800ίAV

0030

Industrial applicability

The substrate glass of the present invention is a concentration detection sensor for CO gas, CO gas, NO gas, etc.

2 X

Used for any gas sensor substrate. The specification, claim scope, drawings and abstract of Japanese Patent Application 2006-340941 filed on December 19, 2006 and Japanese Patent Application 2007-174262 filed on July 2, 2007 The entire contents of this document are hereby incorporated herein by reference as the disclosure of the specification of the present invention.

Claims

The scope of the claims

[1] in a molar ^_0/0 based on the following oxides, Bi O 10 to 55%, the GeO 20 to 85%, Ga O

2 3 2 2 0 ~; 19%, AlO 0 ~; 15%, BiO + GeO force 50% or more, MgO

3 2 3 2 3 2

When it contains, Glass for substrates characterized by GaO + MgO being 20% or less.

twenty three

[2] The substrate according to claim 1, containing at least one of Ga 2 O and Al 2 O

2 3 2 3

Glass.

[3] BiO content is 15% or more, GeO content is 80% or less, GaO + A1O force ¾-30%

The glass for a substrate according to claim 1, which is 2 3 2 2 3 2 3.

[4] The glass for a substrate according to claim 1, 2 or 3, wherein the GeO + A1 O force is 60% or more.

2 2 3

[5] The glass for a substrate according to any one of [1] to [4], containing 0 to 2% or less of CeO.

2

[6] A claim that does not contain SiO or contains 1% or less of SiO;

twenty two

The glass for a board | substrate of description.

[7] The composition according to any one of claims 1 to 6, which does not contain B 2 O or contains 1% or less.

twenty three

Glass for substrates.

8. The glass for a substrate according to any one of claims 1 to 7, wherein the glass transition point is 400 ° C or higher.

[9] The transmittance of light having a wavelength of 5.5 μm at a thickness of lmm is 50% or more, and the transmittance of light having a wavelength of 7.0 μm is 10% or less. Glass for substrates.

10. The glass for a substrate according to claim 9, wherein the transmittance of light having a wavelength of 6.5 m at a thickness of 1 mm is 4% or less.