JP2001318222A - Glass-ceramics for optical filter and the optical filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass-ceramics for an optical filter and the optical filter, having mechanical characteristics with durability taken in consideration and having thermal expansion characteristics to avoid changes in the refractive index with the temperature for use of the filter member having a single layer or multilayered film, so as to match with higher accuracy of a band-pass filter (by selecting a substrate material having a high coefficient of thermal expansion and adding compressive stress on the film by the substrate so as to improve the temperature stability of the refractive index of the film). SOLUTION: A glass-ceramics for an optical filter has 95×10-7 to 140×10-7/ deg.C range for the coefficient of thermal expansion in the temperature range from -20 to +70 deg.C and >=85 GPa for Young's modulus and contains (a) lithium disilicate and (b) at least one kind selected from α-quartz, α-quartz solid solution, α-cristobalite and α-cristobalite solid solution as the main crystal phase. The optical filter is produced by forming a film of a dielectric material on the glass-ceramics.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a glass ceramic for an optical filter and an optical filter using the glass ceramic.

[0002]

2. Description of the Related Art Optical filters include those that cut or transmit a specific wavelength, and those that reduce light intensity regardless of wavelength. The former optical filters include band-pass filters that transmit only specific wavelengths, notch-pass filters that cut only specific wavelengths, high-pass filters that transmit only shorter and longer wavelengths than specific wavelengths, and low-pass filters. , The latter optical filter has ND
There is a filter.

[0003] Optical filters include an absorption type and an interference type. Typical absorption type optical filters are N
There is a D filter and the like, and a typical example of the interference type optical filter is a band pass filter. Plastic is used as a substrate for absorption type optical filters such as those for photography, but the substrate of optical filters using strong lasers is required to have durability and heat resistance. I have.

A band-pass filter is formed, for example, on a substrate material such as glass by a dielectric thin film (H layer) having a high refractive index.
And a dielectric multilayer film having a structure in which dielectric thin films (L layers) having a low refractive index are alternately laminated.

[0005] WDM (Wavelength Div)
In a band-pass filter used in an optical communication system, when the bandwidth of a passing wavelength is set to be narrow and the application to a higher-density wavelength is attempted, the temperature stability of the center wavelength of the band is reduced. It is a problem. In other words, since it is a sensitive element whose center wavelength of the band fluctuates even with a slight temperature change, temperature compensation should be performed with a temperature controller in its use, but due to space issues when using it, Virtually no temperature controller can be turned on. The temperature stability of the center wavelength increases its importance because the bandwidth must be narrowed as the amount of optical information increases.

Conventionally, amorphous glass is used as a substrate material of a band-pass filter. However, since the thermal expansion characteristics are not sufficiently high and the mechanical strength is low, the film is sufficiently compressed in terms of compressive stress and durability. It was not something.
Furthermore, amorphous glass has a low surface hardness, and it is necessary to contain a large amount of an alkali component in order to obtain high expansion characteristics, which has problems such as alkali elution at the time of film formation and alkali elution over time. It cannot sufficiently cope with the requirements as a substrate material for an optical filter, particularly a substrate material for a bandpass filter.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the prior art and to increase the operating temperature of a filter member having a single-layer or multi-layer film in accordance with the improvement in the precision of a band-pass filter. A machine that takes into account the thermal expansion characteristics and durability for avoiding fluctuations in the refractive index in (the substrate material is set to have a high thermal expansion coefficient, thereby applying compressive stress to the film and improving the refractive index temperature stability of the film). It is an object of the present invention to provide a glass ceramic for an optical filter and an optical filter, which also have specific characteristics.

[0008]

As a result of intensive studies and studies, the present inventor has found that glass ceramics having a specific range of thermal expansion coefficient, mechanical strength, and light transmittance are suitable for solving the above-mentioned problems. And reached the present invention.

That is, the invention according to claim 1 provides -2
The coefficient of thermal expansion at 0 to + 70 ° C. is 95 × 10^-7/ ℃ ~
140 × 10^-7/ ° C, Young's modulus is 85 GPa or more
And (a) lithium disilicate and (b) as main crystal phases.
α-quartz, α-quartz solid solution, α-cristobala
And α-cristobalite solid solution
Optical film characterized by containing at least one kind
3. The invention according to claim 2, which is a glass ceramic for a heater.
Represents SiO 2 in the composition of the glass ceramics.₂7
2. The composition according to claim 1, wherein the content is 0 to 77% by mass.
4. A glass ceramic for an optical filter according to claim 3, wherein
The described invention relates to the composition of glass ceramics,
i₂O is contained in an amount of 8 to 12% by mass.
Item 3. Glass ceramic for optical filter according to item 1 or 2
The invention according to claim 4 is a glass ceramics
In composition, Li₂Contains 8.5 to 9.9% by mass of O
3. An optical filter according to claim 1, wherein
Glass ceramics. Further, according to claim 5
The invention relates to a composition of glass ceramics,₂O
₃Is contained in an amount of 3 to 9% by mass.
4. The glass ceramic for an optical filter according to any one of 4.
The invention according to claim 6 is a glass ceramic
In the composition of₂O₃4.0 to 7.0% by mass.
The method according to any one of claims 1 to 4, wherein
8. A glass ceramic for an optical filter according to claim 7, wherein
The described invention relates to the composition of glass ceramics,
rO₂Is contained in an amount of 2 to 9% by mass.
A glass ceramic for an optical filter according to any one of claims 1 to 6.
The invention according to claim 8 is a glass ceramic.
In the composition of the mixture, P₂O₅1.5-3% by mass
The method according to any one of claims 1 to 7, wherein
It is a glass ceramic for optical filters. Also, billing
Item 9 relates to the composition of glass ceramics.
The total amount of the MgO, ZnO, SrO, and BaO components is 1
9. The composition according to claim 1, wherein the content is from 5 to 5% by mass.
The glass ceramics for optical filters described in any of
The invention according to claim 10 is a glass ceramic set.
In the formation₂Containing 0.5 to 3% by mass of O
The optical filter according to any one of claims 1 to 9, wherein:
The invention according to claim 11, which is a glass-ceramic for use in manufacturing.
Means that in the composition of glass ceramics, K₂O to 0.
The composition according to claim 1, wherein the content is 6 to 2.0% by mass.
9. The glass ceramic for an optical filter according to any one of 9.
The invention according to claim 12 is a glass ceramic
In the composition of₂Substantial O and / or PbO
12. The method according to claim 1, wherein the component is not included.
A glass ceramic for an optical filter described in Crab,
The invention according to claim 13 has a bending strength of 10 kg / mm.²
The method according to any one of claims 1 to 12, wherein
2. The glass ceramic for an optical filter described in 1. above. Ma
The invention according to claim 14 provides the glass cell according to claim 2.
An optical filter formed by depositing a dielectric on Lamix.
The invention according to claim 15 provides the glass cell according to claim 3.
An optical filter formed by depositing a dielectric on Lamix.
The invention according to claim 16 provides the glass cell according to claim 5.
An optical filter formed by depositing a dielectric on Lamix.
The invention according to claim 17 is a glass cell according to claim 7.
An optical filter formed by depositing a dielectric on Lamix.
The invention according to claim 18 provides the glass cell according to claim 8.
An optical filter formed by depositing a dielectric on Lamix.
The invention of claim 19 provides the glass cell of claim 9.
An optical filter formed by depositing a dielectric on Lamix.
The invention according to claim 20 is the glass according to claim 10
An optical filter formed by depositing a dielectric on ceramics
The invention according to claim 21 is the invention according to claim 12,
Optical filter formed by depositing a dielectric on ceramics
The invention according to claim 22 is the gas monitor according to claim 13.
Optical filter with dielectric film formed on glass ceramics
It is. The invention according to claim 23 is the invention according to claims 1 to
13. A dielectric on a glass ceramic according to any one of
3. A band pass filter formed by forming a film.
The invention described in Item 4 is the invention according to any one of Items 14 to 22.
Bandpass filter characterized by using an optical filter
Luther.

The thermal expansion characteristics, Young's modulus, bending strength, light transmittance, composition, and main crystal phase of the glass ceramic used in the optical filter of the present invention are described below.
The composition is expressed in terms of% by mass on the basis of oxide, as in the case of the raw glass.

First, regarding the thermal expansion characteristic, as described above, the temperature stability of the center wavelength of the band is very important, and a material having a larger thermal expansion coefficient than the film constituting material is required. As a result of the present inventor's testing and research, if the coefficient of thermal expansion at -20 ° C to + 70 ° C is 95 × 10 ^-7 / ° C or higher, the temperature range used as a bandpass filter is as follows:
It has been found that sufficient compressive stress can be applied to the film. However, on the other hand, when it exceeds 140 × 10 ^-7 / ° C,
The difference in thermal expansion coefficient between the film and the film becomes too large, and problems such as peeling of the film are likely to occur. A more preferred range is 110 × 1
0 ^{-7 to} 130 × 10 ^-7 / ° C, more preferably 120
The range is ± 5 × 10 ⁻⁷ / ° C.

The temperature stability of the center wavelength in the band-pass filter naturally depends on the temperature coefficient of the refractive index of the dielectric material constituting the thin film, but is more greatly affected by the coefficient of thermal expansion of the substrate material. This is because the refractive index is also determined by the filling rate of the thin film. That is, the higher the filling rate of the thin film, the smaller the change of the center wavelength with temperature.
The filling rate of the thin film is greatly affected by the coefficient of thermal expansion of the optical filter substrate material on which the thin film is formed.
In other words, the substrate material at the time of film formation is about 200 ° C., but the substrate material itself is greatly expanded by the heat, and the thin film is attached to the expanded substrate material, and then as the substrate material is cooled, The thin film receives a compressive stress due to the difference in thermal expansion coefficient of the thin film. As a result, the filling rate of the thin film increases and the refractive index increases. As the coefficient of thermal expansion of the substrate material increases, the compressive stress applied to the formed dielectric thin film increases, and the rate of change of the refractive index at the operating temperature with temperature decreases. For this reason, it is desirable to set the thermal expansion coefficient of the glass ceramic larger than the thermal expansion coefficient of the dielectric thin film.

In addition, in consideration of severe use conditions, in addition to the characteristics other than the above, strength against mechanical deformation and the like,
That is, the bending strength and Young's modulus cannot be ignored.

Next, with respect to the Young's modulus, these substrate materials are formed into fine chips (less than 2 mm × 2 m) after film formation.
m or less x 2 mm or less), high Young's modulus and high strength are required. Considering the subsequent processing steps as described above, the Young's modulus is 85 GPa or more, and the bending strength is 10 kg.
/ Mm ² or more.

Next, regarding the light transmittance, if the light transmittance is low, it is naturally inconvenient for signal extraction (S / N).
The ratio is preferably large, and the light transmittance must be at least 60% or more. Further, the operating wavelength of the bandpass filter is 950 nm.
１1600 nm, and the light transmittance at this wavelength in a 10 mm-thick material needs to be 60% or more.
The light transmittance at the above-mentioned wavelength is preferably 75% or more, more preferably 80% or more.

Next, regarding the precipitated crystal phase, glass ceramics used for the optical filter of the present invention are as follows.
“(A) lithium disilicate” and “(b) α-quartz, α-quartz solid solution, α-cristobalite, α-quartz
At least one selected from cristobalite solid solutions. " By precipitating these crystal phases, the bending strength and Young's modulus can be significantly increased, and the temperature range is -20 ° C to + 70 ° C.
The coefficient of thermal expansion at 95 ° C. is 95 × 10 ^{−7 to} 140 × 10 ^−7.
/ ° C. Furthermore, the light transmittance (%) of a 10 mm-thick material can be 60% or more with respect to the wavelength used for the band filter, 950 nm to 1600 nm.

Next, the reasons for limiting the composition range of the raw glass will be described below. The SiO ₂ component contains lithium disilicate, α, which is precipitated as a main crystal phase by heat treatment of the raw glass.
-Quartz, α-quartz solid solution, α-cristobalite, and a very important component for producing α-cristobalite solid solution. When the amount is less than 70%, precipitated crystals of the obtained glass ceramic are unstable and the structure is coarse. If it exceeds 77%, the melting and forming properties of the raw glass become difficult.

The Li ₂ O component is a very important component for producing lithium disilicate precipitated as a main crystal phase by heat treatment of the raw glass, but if its amount is less than 8%,
At the same time, precipitation of the above crystals becomes difficult, and melting of the raw glass becomes difficult. On the other hand, if it exceeds 12%, the obtained crystals are unstable, the structure is likely to be coarse, and the chemical durability is deteriorated.

The K ₂ O component improves the melting property of the glass and at the same time prevents the precipitation crystals from becoming coarse. And the amount is preferably 0.5% or more. However, if it is contained excessively, the precipitated crystals become coarse, the crystal phase changes, and the chemical durability deteriorates. Therefore, the amount is preferably 3% or less.

The MgO, ZnO, SrO and BaO components are
It is a component that improves the melting property of glass while preventing coarsening of precipitated crystals, and by adjusting the refractive index of the glass phase as a matrix, it is possible to adjust the light transmittance. If the total amount is less than 1%, these effects cannot be obtained, and if it exceeds 5%, the obtained crystals are unstable and the structure tends to be coarse.

In the present invention, the P ₂ O ₅ component is indispensable as a nucleating agent for precipitated crystals, but is preferably 1.5% or more in order to obtain its effect. Further, the content is preferably 3% or less in order to prevent devitrification of the raw glass and maintain mass production stability.

Like the P ₂ O ₅ component, the ZrO ₂ component not only functions as a nucleating agent for precipitated crystals, but is also remarkable for improving the crystal size of the precipitated crystals, improving the mechanical strength of the material, and improving the chemical durability. It is a very important ingredient that has been found to have an effect. In order to obtain these effects, ZrO ₂ is preferably 2% or more. However, if it is added excessively, it becomes difficult to melt the raw glass and, at the same time, undissolved ZrSiO ₄ or the like is generated. Therefore, the content is preferably 9% or less.

Al_TwoO_ThreeThe components are glass ceramics
To improve the mechanical durability and mechanical strength, especially the bending strength
Component in order to achieve the object of the present invention.
Must be at least 3% and at least 4%
Is more preferable. Al _TwoO_ThreeIf the ingredients are in excess,
Meltability and devitrification resistance deteriorate, and β-
Spodumene, to precipitate β-cristobalite
Become. β-spodumene, β-cristoba
Light is a crystalline phase with a very low coefficient of thermal expansion.
The precipitation of crystals is related to the thermal expansion of the obtained glass ceramic.
Significantly reduce the number. Therefore, Al_TwoO_ThreeThe component is 9
%, Preferably 8% or less.
Is more preferable.

The Sb ₂ O ₃ and As ₂ O ₃ components can be added as a fining agent when the glass is melted, but the sum of these components is sufficient to be 2% or less, more preferably 1% or less.

[0025] Then Na ₂ O, in the formation of preferred multilayer film that is substantially free of PbO, Na in the material ₂
O is a problematic component. This is because Na ions are eluted into the multilayer film to cause deterioration of the film characteristics. PbO is an environmentally unfavorable component and should be avoided as much as possible.

Next, with respect to the production of the glass ceramic used for the optical filter according to the present invention, the glass having the above composition is melted, hot-formed and / or cold-worked, and then 500-600 ° C. Heat treatment for 1 to 7 hours at a temperature in the range of
Heat treatment is performed at a temperature in the range of ８０780 ° C. for 1 to 7 hours to perform crystallization.

The main crystal phase of the glass ceramic crystallized by the heat treatment is “(a) lithium disilicate”
And "(b) α-quartz, α-quartz solid solution,
α-cristobalite, at least one selected from α-cristobalite solid solutions ”.

The heat-crystallized glass ceramic is wrapped by a conventional method and then polished to obtain a surface roughness Ra (arithmetic mean roughness) of 1.0 ° or more.
A glass-ceramic substrate for an optical filter in the range of 5.0 ° or less is obtained. These glass ceramics
It is suitable for an interference type optical filter in which a dielectric multilayer film is formed on the surface of the substrate. In particular, as the dielectric multilayer film, a dielectric thin film (H layer) having a high refractive index and a dielectric thin film having a low refractive index It is suitable for a band-pass filter having a structure in which thin films (L layers) are alternately laminated.

As the dielectric, TiO ₂ , Ta
Inorganic oxides such as ₂ O ₂ , Nb ₂ O ₅ and SiO ₂ are preferred.
Further, in a band-pass filter used for a wavelength range of 950 nm to 1600 nm, an H layer / L
As a combination of layers, TiO ₂ / SiO ₂ , Ta ₂ O ₂ / Si
O ₂ and Nb ₂ O ₅ / SiO ₂ are preferred. The optical filter of the present invention can be obtained by forming a dielectric thin film on the surface of a glass ceramic substrate. Examples of the film forming method include a vapor deposition method, an RF ion plating method, a magnetron sputtering method, and a plasma ion plating method. Among them, the vapor deposition method is preferable.

Next, a preferred embodiment of the present invention will be described. Tables 1, 2, and 3 show examples of glass ceramics used in the optical filter of the present invention (Nos. 1 to 8) and glass substrates for optical filters (comparative examples) conventionally used, in addition to compositions. Precipitated crystal phase, coefficient of thermal expansion,
It shows the Young's modulus, bending strength, and light transmittance.

BEST MODE FOR CARRYING OUT THE INVENTION

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

A method for manufacturing the glass ceramic of the above embodiment will be described. Raw materials such as oxides, carbonates, nitrates and the like are mixed, and the resulting mixture is mixed with a usual dissolution apparatus to about 1350 to 145.
After melting at a temperature of 0 ° C. and homogenizing with stirring, a glass molded body was obtained through a molding / cooling step. Then add this to 500-60
After heat treatment at 0 ° C. for 1 to 7 hours to form crystal nuclei,
Crystallization by heat treatment at 80 ° C. for 1 to 7 hours gave a desired glass ceramic. Then, add the above glass ceramics to 8
5 ~ 3 with 00 # ~ 2000 # diamond pellets
Wrap for 0 minutes, then 0.02-3 particle size (average)
Polishing and finishing were performed for 30 to 60 minutes with an abrasive oxidized cellum of μm. Surface roughness Ra of these glass ceramics
(Center line roughness) was 5 ° or less.

The precipitated crystal phase was identified by an X-ray diffraction (XRD) device and an EDS (energy dispersive analyzer).

Comparison between Examples 1 to 8 of the present invention and Comparative Example 1 shows that the conventionally used optical filter glass substrate has a thermal expansion coefficient of 93 × 10 ⁻⁷ / ° C. The value was not enough to give a compressive stress, and the Young's modulus was 75 GPa and the bending strength was 5 kg / mm ² , which was a low strength material. On the other hand, the glass ceramic used in the optical filter of the present invention has a sufficient coefficient of thermal expansion to give a compressive stress to the formed film, and has a sufficient numerical value in Young's modulus and bending strength. Therefore, it was suitable as a substrate material for an optical filter.

Further, TiO ₂ / SiO ₂ , Ta ₂ O ₂ / Si
The interference type optical filter formed by forming a multilayer film of O ₂ and Nb ₂ O ₅ / SiO ₂ has very good temperature stability at the center wavelength, and is used as a band-pass filter for optical communication. It was very good.

[0038]

As described above, according to the present invention, it is possible to provide an optical filter having excellent temperature stability at the center wavelength while eliminating the above-mentioned disadvantages of the prior art. This feature (high light transmittance, high thermal expansion characteristic, high Young's modulus, high bending strength) is suitable for an interference type optical filter, particularly for a band-pass filter, and particularly for WDM and DWDM (high-density wavelength division) in an optical communication system. Ideal for multiplexing) applications. Further, TiO ₂ / SiO ₂ , Ta ₂ O ₂
/ SiO ₂ , Nb ₂ O ₅ / SiO ₂ A band-pass filter member formed by forming a plurality of dielectric films has a temperature stability at a central wavelength, which is not included in a conventional band-pass filter member. Spa as well as terrestrial optical communication systems
There is a possibility that ce-based-satellite or the like may be used.

Continued on the front page (72) Inventor Donald G. Pollensky Morgan Hill, California United States 635 Ardia Court 635 F-term (reference) 2H048 GA04 GA09 GA12 GA33 GA62 4G062 AA04 AA11 BB01 DA07 DB03 DC01 DD03 DE01 DE02 DE03 DF01 EA03 EA04 EB01 EC02 EC03 ED01 ED02 ED03 EE01 EF01 EF02 EF03 EG01 EG02 EG03 FA01 FB01 FC03 FD01 FE01 FF01 FG01 FH00 FJ01 FK01 FL01 GA01 GB01 GC01 GD01 GE01 HH01 HH03 HH05 HH07 KKHJ JJH17 KK QQ03

Claims (24)

[Claims] A thermal expansion coefficient at -20 to + 70 ° C. is 9
5 × 10 ⁻⁷ / ° C. to 140 × 10 ⁻⁷ / ° C. and Young's modulus of 8
5 GPa or more, and (a) lithium disilicate and (b) α-quartz, α-quartz solid solution as main crystal phases,
A glass ceramic for an optical filter comprising at least one selected from α-cristobalite and α-cristobalite solid solution. 2. The method according to claim 1, wherein the composition of the glass ceramic is Si.
Claim 1, wherein the optical filter glass ceramics of O _2, characterized in that it contains 70 to 77 wt%. 3. The method according to claim 1, wherein the composition of the glass ceramic is Li
_{3. The} glass ceramic for an optical filter according to claim 1, wherein the glass ceramic contains 8 to 12% by mass of 2O. 4. The method according to claim 1, wherein the composition of the glass ceramic is Li
_{3. The} glass ceramic for an optical filter according to claim 1, wherein 8.5 to 9.9 mass% of ₂ O is contained. 5. The glass ceramic composition according to claim 1, wherein
_The glass ceramic for an optical filter according to any one of claims 1 to 4, wherein ₃ to 9 mass% of 2O3 is contained. 6. The composition of glass ceramics, wherein
Light filter glass ceramics according to claim 1, a ₂ O _3, characterized in that it contains 4.0 to 7.0 wt%. 7. The composition of glass ceramics, wherein Zr
_{2. The} composition according to claim 1, wherein O ₂ is contained in an amount of ₂ to 9% by mass.
7. The glass ceramic for an optical filter according to any one of items 1 to 6. 8. The composition of glass ceramics, wherein P ₂
O ₅ of 1.5 to 3 wt% containing optical filter glass ceramics according to any one of claims 1 to 7, characterized in that. 9. The composition of a glass ceramic, comprising:
The glass ceramic for an optical filter according to any one of claims 1 to 8, wherein the total amount of O, ZnO, SrO, and BaO components is 1 to 5% by mass. 10. The composition of glass ceramics, wherein K
_The glass ceramic for an optical filter according to any one of claims 1 to 9, wherein ₂ O is contained in an amount of 0.5 to 3% by mass. 11. The composition of glass ceramics, wherein K
_The glass ceramic for an optical filter according to any one of claims 1 to 9, wherein ₂ O is contained in an amount of 0.6 to 2.0 mass%. 12. The composition of a glass ceramic, wherein N
_The glass ceramic for an optical filter according to any one of claims 1 to 11, wherein the glass ceramic is substantially free of ₂ O and / or PbO. 13. The glass ceramic for an optical filter according to claim 1, wherein the glass ceramic has a bending strength of 10 kg / mm ² or more. 14. An optical filter comprising a dielectric film formed on the glass ceramic according to claim 2. 15. An optical filter obtained by forming a dielectric on the glass ceramic according to claim 3. 16. An optical filter comprising a dielectric film formed on the glass ceramic according to claim 5. 17. An optical filter obtained by forming a dielectric on the glass ceramic according to claim 7. 18. An optical filter obtained by forming a dielectric on the glass ceramic according to claim 8. 19. An optical filter obtained by forming a dielectric on the glass ceramic according to claim 9. 20. An optical filter comprising a dielectric film formed on the glass ceramic according to claim 10. 21. An optical filter obtained by forming a dielectric on the glass ceramic according to claim 12. 22. An optical filter comprising a dielectric film formed on the glass ceramic according to claim 13. 23. A band pass filter comprising a dielectric film formed on the glass ceramic according to claim 1. 24. A band-pass filter using the optical filter according to any one of claims 14 to 22.