JP2005350322A - Yb-CONTAINING GLASS - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material for an adhesive which is suitable for joining a single crystal as a heat sink to laser glass. <P>SOLUTION: The glass composition contains each component of SiO<SB>2</SB>, B<SB>2</SB>O<SB>3</SB>, ZnO, La<SB>2</SB>O<SB>3</SB>and Yb<SB>2</SB>O<SB>3</SB>, wherein the content of the Yb<SB>2</SB>O<SB>3</SB>component is >10.0 to 30.0 mass%, the ratio (SiO<SB>2</SB>+B<SB>2</SB>O<SB>3</SB>+MgO+CaO)/Yb<SB>2</SB>O<SB>3</SB>by mass is 0.65-5.5 and the refractive index (nd) is 1.70-1.90 and the average linear expansion coefficient (α) at 100-300°C is 50-85×10<SP>-7</SP>/°C. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to an optical glass, particularly a laser glass, and more particularly to a Yb-containing glass suitable as a laser medium for a high peak output, ultrashort pulse laser.

In recent years, high output, short pulse, and high repetition rate of solid-state lasers have been advanced. These high-power solid-state lasers use a single crystal doped with an optically active component as a laser medium and a single crystal that does not contain an optically active component as a heat sink in order to prevent damage due to thermal stress and thermal fatigue resulting from the heat generation. Techniques have been developed for bonding and solid-state laser elements.

For example, in Non-Patent Document 1, a YAG single crystal doped with Yb is used as a medium, and a sapphire single crystal is used as a heat sink. Since both of these laser media and the heat radiating plate are single crystals, their thermal expansion coefficients are close to each other, and even when both are bonded, there is no problem such as poor bonding due to the difference in thermal expansion coefficient.

However, there is a growing demand for higher output of solid state lasers. Since single crystals have a low degree of freedom in composition, even if an attempt is made to increase the content of optically active components in the single crystal in order to achieve further increase in laser output, the crystal structure may change, There was a problem that it could not be obtained.

  Further, if an optically active component typified by Er or Nd is contained in a large amount in order to obtain a laser output, the laser output is reduced due to concentration quenching, and a higher output than a certain level cannot be expected.

On the other hand, it is known that Yb ³⁺ ions have a simple energy structure, so that concentration quenching and excited state absorption do not occur. Also, because of high efficiency, low heat generation and a wide oscillation wavelength range make ultra short pulse operation possible. It is suitable as an optically active component of a high-power solid-state laser medium, for example, because it has a long fluorescence lifetime and can store high energy. If this Yb component can be contained in the laser medium in a large amount as an optically active component, further higher output and higher efficiency of the solid-state laser can be expected. However, as described above, it is difficult to obtain a single crystal laser medium containing a large amount of Yb due to the low degree of freedom of composition, and there has been a limit to further increasing the output of a solid-state laser.
University of Fukui, Department of Electrical and Electronic Engineering, Graduate School of Engineering, Fiber Amenity Engineering, Optoelectronics Laboratory, Development of Yb: YAG Laser, 2) Characteristics of Crystals Used in this Study, [online], [Search May 11, 2004] , Internet <http: // fuee. fukui-u. ac. jp / ~ optele / JP / solid / slab. html>

  An object of the present invention is to provide a novel material that can be used as a solid-state laser medium that can expect a higher output.

In general, glass has a high degree of freedom in composition with respect to a single crystal. If a large amount of Yb can be contained in the glass, further increase in the output of the solid-state laser should be expected. Glass is useful as a laser medium because it is excellent in processability and formability and can be easily enlarged.
However, glass generally has lower thermal conductivity and lower heat resistance than single crystal. Therefore, the necessity of a heat sink for preventing damage due to thermal stress or thermal fatigue resulting from the heat generation of the laser medium is higher in a glass laser medium (laser glass) than in a single crystal laser medium. The heat sink is preferably a single crystal with high thermal conductivity, but at this time, if the thermal expansion coefficients of the laser glass and the single crystal that is the heat sink are greatly different, it is impossible to join the two, Even if it can be temporarily joined, it may be damaged due to thermal fatigue or thermal stress, resulting in joint failure. In addition, when the laser medium and the heat sink are joined in the laser beam output direction and the laser medium is transmitted through the heat sink to output the laser light, if the refractive index of the laser medium and the heat sink is greatly different, the joint interface As a result, the reflection of the laser beam is increased, causing loss. Therefore, it is necessary to approximate the average linear expansion coefficient (α) and refractive index (nd) of the laser glass to the average linear expansion coefficient and refractive index of a single crystal that is a heat sink (this is referred to as matching in this specification). Become.

  As a result of intensive research to solve the above problems, the present inventor has paid attention to the fact that sapphire that is transparent and has high thermal conductivity is suitable as a single crystal as a heat sink, and makes the glass composition specific. By doing so, it was found that a glass having good matching with sapphire and capable of containing a large amount of Yb was obtained, and the present invention was made.

The first configuration of the present invention for achieving the above object includes each component of SiO ₂ , B ₂ O ₃ , ZnO, La ₂ O ₃ and Yb ₂ O ₃ , and the content of the Yb ₂ O ₃ component The value of (SiO ₂ + B ₂ O ₃ + MgO + CaO) / Yb ₂ O ₃ is 0.65 to 5.5 at a mass% ratio of more than 10.0% to 30.0% in each component. The glass composition has a refractive index (nd) of 1.70 to 1.90 and an average linear expansion coefficient (α) at 100 to 300 ° C. of 50 to 85 × 10 ⁻⁷ / ° C.

The second configuration of the present invention contains each component of SiO ₂ , B ₂ O ₃ , ZnO, La ₂ O ₃ and Yb ₂ O ₃ , and the content of the Yb ₂ O ₃ component is 3.0% in terms of mol%. The value of (SiO ₂ + B ₂ O ₃ + MgO + CaO) / Yb ₂ O ₃ is ₂ to 38 and the refractive index (nd) is 1.70 to 1.90. The glass composition whose average linear expansion coefficient ((alpha)) in 100-300 degreeC is 50-85 * 10 < ^-7 > / degreeC.

The third configuration of the present invention is mass%,
SiO ₂ less than 3.0 to 10.0%, and _B 2 _O 3 15.0 to 30.0%, and _Yb 2 _O 3 10.0% to more than 30.0%, and ZnO from 5.0 to 40 less than 2.0%, and _La 2 _O 3 from 5.0 to 30.0%, and _Al 2 _O 3 0 to 5.0%, and / or _TiO 2 0 to 5.0%, and / or _Nb 2 _{O 5} 0 to 15.0%, and / or _Ta 2 _O 5 0 to 15.0%, and / or _Bi 2 _O 3 0 to 10.0% and / or _WO 3 0 to 10.0% and / or ZrO _{2 0 to} 10.0%, and / or MgO 0 to 10.0%, and / or CaO 0 to 10.0%, and / or BaO 0 to 10.0%, and / or Li ₂ O 0 less than 2.0%, and / or _Na 2 O 0 to 3.0% and / Other _K 2 O _0~3.0%, and / or _Sb 2 _O 3 _0~1.0%
It is the glass composition of the said 1st structure containing each component of these.

The fourth configuration of the present invention is mol%,
SiO ₂ from 6.0 to 25.0%, and _B 2 _O 3 _25.0~60.0%, and _Yb 2 _O 3 _3.0~20.0%, and ZnO from 10.0 to 65.0%, and _La 2 _O 3 _1.0~12.0%, and _Al 2 _O 3 _0~7.0%, and / or _TiO 2 from 0 to 9.0%, and / or _Nb 2 _O 5 _0~8.0 % And / or Ta ₂ O ₅ 0-5.0% and / or Bi ₂ O ₃ 0-5.0% and / or WO ₃ 0-6.0% and / or ZrO ₂ 0-11 .0%, and / or MgO from 0 to 35.0%, and / or CaO from 0 to 25.0%, and / or BaO 0 to 9.0%, and / or _Li 2 O 0 to 9.0%, and / or _Na 2 O _0~5.0%, and / or _K 2 O _0~4.0%, Contact Beauty / or _Sb 2 _O 3 _0~1.0%
It is a glass composition of the said 2nd structure containing each component of these.

The fifth configuration of the present invention is mass%,
TiO ₂ + Nb ₂ O ₅ + Ta ₂ O ₅ + Bi ₂ O ₃ + WO ₃ + ZrO ₂ + La ₂ O ₃
20.0% to 50.0%, and / or MgO + CaO 10.0% or less, and / or _{Li 2 O + Na 2 O +} K 2 O0% ~3.0%
It is the glass composition of the said 1st or 3rd structure which is.

The sixth configuration of the present invention is mol%,
TiO ₂ + Nb ₂ O ₅ + Ta ₂ O ₅ + Bi ₂ O ₃ + WO ₃ + ZrO ₂ + La ₂ O ₃
9.0% to 30.0%, and / or MgO + CaO 25.0% or less, and / or _{Li 2 O + Na 2 O +} K 2 O0% ~4.5%
It is the glass composition of the said 2nd or 4th structure which is.

The present invention will be described in detail. Hereinafter, the description of the content of each component is expressed in mass% unless otherwise specified.
In the present invention, when the lower limit of the refractive index (nd) of the glass is 1.70, reflection of laser light at the bonding interface with sapphire is difficult to occur, and the solid laser becomes efficient. The lower limit of the refractive index is more preferably 1.73, and most preferably 1.76. Further, similarly to the case where the upper limit of the refractive index is 1.90, the reflection of the laser light hardly occurs. The upper limit of the refractive index is more preferably 1.85, and most preferably 1.82. When the refractive index of the glass is in the above-described range, it becomes efficient as a solid laser when bonded to sapphire.

Moreover, the difference of the average linear expansion coefficient with sapphire becomes it small that the average linear expansion coefficient ((alpha)) in 100-300 degreeC of glass is 50x10 < ^-7 > / degreeC or more, and joining becomes favorable. The lower limit of the average linear expansion coefficient is more preferably 60 × 10 ⁻⁷ / ° C., and most preferably 62 × 10 ⁻⁷ / ° C. Moreover, joining becomes favorable similarly that an average linear expansion coefficient is 85 * 10 < ^-7 > / degrees C or less. The upper limit of the average linear expansion coefficient is more preferably 83 × 10 ⁻⁷ / ° C., and most preferably 80 × 10 ⁻⁷ / ° C.
By making the refractive index of glass and the average linear expansion coefficient within the above-mentioned ranges, it becomes difficult for laser light to be reflected at the bonding interface in the bonding of glass and sapphire, and the bonding of both is easy. It is difficult to cause poor bonding due to thermal fatigue or breakage due to thermal stress, and better bonding can be obtained.

The reason why the composition range of each component is limited in one of the constitutions of the present invention is as follows.
That is, the SiO ₂ component is an important component as a glass-forming oxide, and is preferably 3.0%, more preferably 3.1%, and most preferably 3.2 in order to obtain a stable glass without devitrification. % Is contained as a lower limit. However, since it is also a component that lowers the refractive index, the upper limit is preferably less than 10.0%, more preferably 9.0%, and more preferably 8.5% for good matching with sapphire. Most preferably.

The B ₂ O ₃ component is an important component as a glass-forming oxide, and is preferably 15.0%, more preferably 16.0%, and most preferably 17.0 in order to obtain a stable glass without devitrification. % Is contained as the lower limit, preferably 30.0%, more preferably 25.0%, and most preferably 23.0%.

The Yb ₂ O ₃ component is an optically active component and an essential component. In order to obtain a sufficiently high laser output, the content is preferably more than 10.0%, more preferably 12.0%, and most preferably 13.0%. However, since it is a component that deteriorates devitrification resistance, in order to maintain good devitrification resistance, the upper limit is preferably 30.0%, more preferably 25.0%, and most preferably 23.0%. Contained as.

Here, it is preferable to set the lower limit of the value of the mass% of each component of the glass (SiO ₂ + B ₂ O ₃ + MgO + CaO) / Yb ₂ O ₃ to 0.65 and the upper limit to 5.5. As described above, it is preferable that the Yb ₂ O ₃ component is contained in the glass as much as possible in terms of laser output, but excessive inclusion deteriorates the devitrification resistance. Conversely, each component of SiO ₂ , B ₂ O ₃ , MgO, and CaO is a component that is effective in suppressing devitrification. The present inventor has found an optimum range in which as much Yb ₂ O ₃ component as possible can be contained while suppressing the devitrification of the glass by adjusting the value of the ratio by earnest research. The lower limit of the ratio value is more preferably 0.7, and most preferably 1.0. The upper limit is more preferably 5.0, and most preferably 3.0.

  The ZnO component is effective for lowering the average linear expansion coefficient of the glass, and is preferably 5.0%, more preferably 7.0%, and most preferably 8.5% for the good matching with sapphire. Contained as. In order to maintain good devitrification resistance, the upper limit is preferably less than 40.0%, more preferably 30.0%, and most preferably 25.0%.

The La ₂ O ₃ component is an effective component for increasing the refractive index, and is preferably 5.0%, more preferably 10.0%, and most preferably 15.0% for good matching with sapphire. Is contained as a lower limit. In order to maintain good devitrification resistance, the upper limit is preferably 30.0%, more preferably 29.0%, and most preferably 28.5%.

The Al ₂ O ₃ component is effective in improving the chemical durability of the glass. However, in order to maintain good devitrification resistance, the upper limit is preferably 5.0%, more preferably 2.0%, and most preferably 1.5%.

The TiO ₂ component is an effective component for increasing the refractive index, but is preferably 5.0%, more preferably 4.8%, most preferably 4.5% in order to maintain good devitrification resistance. Is contained as the upper limit.

The Nb ₂ O ₅ component is an effective component for increasing the refractive index. Although it is optionally contained, the lower limit of the content is more preferably 1.0% for matching with sapphire, and most preferably 3.0%. However, in order to maintain good devitrification resistance, the upper limit is preferably 15.0%, more preferably 14.0%, and most preferably 12.0%.

The Ta ₂ O ₅ component is an effective component for increasing the refractive index, but is preferably contained at an upper limit of 15.0%, more preferably 10.0% for maintaining good devitrification resistance, Most preferably, it is not substantially contained.

The Bi ₂ O ₃ component is an effective component for increasing the refractive index, but is preferably 10.0%, more preferably 8.0%, and most preferably 7.7 in order to maintain good devitrification resistance. It is contained up to 0%.

The WO ₃ component is an effective component for increasing the refractive index, but is preferably 10.0%, more preferably 8.0%, and most preferably 6.0% in order to maintain good devitrification resistance. Is contained as the upper limit.

The ZrO ₂ component is an effective component for increasing the refractive index, but is preferably 10.0%, more preferably 8.0%, and most preferably 6.0% in order to maintain good devitrification resistance. Is contained as the upper limit.

Also, the sum of TiO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , Bi ₂ O ₃ , WO ₃ , ZrO ₂ and La ₂ O ₃ is the lower limit of 20.0% for good matching with sapphire. The lower limit is more preferably 25.0%, and the lower limit is most preferably 30.0%. However, in order to maintain good devitrification resistance, the upper limit of the sum of the components is preferably 50.0%, more preferably 48.0%, and more preferably 45.0%. Most preferred.

  The BaO component is an effective component for increasing the refractive index. However, since it is a component that increases the average linear expansion coefficient of glass, it is preferably 10.0%, more preferably 5.0%, and most preferably 4.0% as the upper limit for good matching with sapphire. Is done.

  The MgO component is effective in suppressing devitrification of the glass, but is a component that lowers the refractive index. Therefore, for good matching with sapphire, the upper limit is preferably 10.0%, more preferably 5.0%. Most preferably, it is contained but not substantially contained.

  The CaO component is effective in suppressing devitrification of the glass, but is a component that lowers the refractive index. Therefore, for good matching with sapphire, the upper limit is preferably 10.0%, more preferably 5.0%. Most preferably, it is contained but not substantially contained.

  Moreover, in order to maintain a refractive index and to make good matching with sapphire, the sum of both MgO and CaO components is preferably 10.0% or less, more preferably 5.0% or less, and most preferably 3.0% or less.

The Li ₂ O component is a component that improves the solubility of the glass, but it greatly increases the average coefficient of linear expansion of the glass, so it is preferably less than 2.0%, more preferably for good matching with sapphire. The upper limit is 1.5%, and most preferably 1.0%.

The Na ₂ O component is a component that improves the solubility of the glass. However, since the average linear expansion coefficient of the glass is extremely increased, it is preferably 3.0%, more preferably 1 for good matching with sapphire. It is most preferable that it is contained up to 0.0% and is not substantially contained.

The K ₂ O component is a component that improves the solubility of the glass. However, since the average linear expansion coefficient of the glass is very large, it is preferably 3.0%, more preferably 1 for good matching with sapphire. It is most preferable that it is contained up to 0.0% and is not substantially contained.

For each of the Li ₂ O, Na ₂ O, and K ₂ O components, the lower limit of the sum of the components is more preferably 0.05% from the viewpoint of improving the solubility of the glass, and is 0.1%. Most preferred. However, the upper limit of the sum of the components is preferably 3.0%, more preferably 2.8%, and most preferably 2.5% from the viewpoint of the average linear expansion coefficient.

The Sb ₂ O ₃ component is effective as a glass fining agent and is optionally contained, but the lower limit of the content is more preferably 0.005%, and most preferably 0.01%. However, the upper limit of the content is preferably 1.0%, more preferably 0.095%, so as not to affect the desired physical properties obtained in the balance of the composition of other components. % Is most preferable.

In addition, components other than the above such as Rb ₂ O, Cs ₂ O, SnO, etc. may be added to the glass of the present invention up to about 5% as necessary.

The glass composition of the present invention cannot be expressed directly in the description of mol% because the composition is expressed by mass%, but the glass satisfying various properties required in the present invention depends on mol%. It contains each component with the following values.
SiO ₂ from 6.0 to 25.0%, and _B 2 _O 3 _25.0~60.0%, and _Yb 2 _O 3 _3.0~20.0%, and ZnO from 10.0 to 65.0%, and _La 2 _O 3 _1.0~12.0%, and _Al 2 _O 3 _0~7.0%, and / or _TiO 2 from 0 to 9.0%, and / or _Nb 2 _O 5 _0~8.0 % And / or Ta ₂ O ₅ 0-5.0% and / or Bi ₂ O ₃ 0-5.0% and / or WO ₃ 0-6.0% and / or ZrO ₂ 0-11 .0%, and / or MgO from 0 to 35.0%, and / or CaO from 0 to 25.0%, and / or BaO 0 to 9.0%, and / or _Li 2 O 0 to 9.0%, and / or _Na 2 O _0~5.0%, and / or _K 2 O _0~4.0%, Contact Beauty / or _Sb 2 _O 3 _0~1.0%

In one of the configurations of the present invention, in order to achieve the effects of each component described above, each component is contained in the range described below according to mol%.
That is, the SiO ₂ component is preferably contained at a lower limit of preferably about 6.0 mol%, more preferably about 6.5 mol%, and most preferably about 6.8 mol%. The upper limit is preferably about 25.0 mol%, more preferably about 23.0 mol%, and most preferably about 20.0 mol%.

The B ₂ O ₃ component is preferably approximately 25.0 mol%, more preferably approximately 28.0 mol%, most preferably approximately 30.0 mol%, and preferably approximately 60.0 mol%, more preferably approximately The upper limit is 55.0 mol%, and most preferably 50.0 mol%.

The Yb ₂ O ₃ component is preferably contained at about 3.0 mol%, more preferably about 4.0 mol%, most preferably about 4.5 mol%, and preferably about 20.0 mol%, more preferably about It is contained at an upper limit of 15.0 mol%, most preferably approximately 10.0 mol%.

The lower limit of the ratio of mol% of each component of glass (SiO ₂ + B ₂ O ₃ + MgO + CaO) / Yb ₂ O ₃ is preferably about 2.0, more preferably about 5.4, Most preferred is 5.8. The upper limit is preferably about 38.0, more preferably less than about 14.0, and most preferably less than about 12.0.

  The ZnO component is preferably contained at a lower limit of approximately 10.0 mol%, more preferably approximately 12.0 mol%, and most preferably approximately 14.0 mol%. Further, the upper limit is preferably about 65.0 mol%, more preferably about 55.0 mol%, and most preferably about 40.0 mol%.

The La ₂ O ₃ component is preferably about 1.0 mol%, more preferably about 3.0 mol%, most preferably about 4.0 mol%, and preferably about 12.0 mol%, more preferably about It is contained at an upper limit of 12.5 mol%, most preferably approximately 11.5 mol%.

The Al ₂ O ₃ component is preferably contained at an upper limit of approximately 7.0 mol%, more preferably approximately 6.0 mol%, and most preferably approximately 4.5 mol%.

The TiO ₂ component is preferably contained at an upper limit of approximately 9.0 mol%, more preferably approximately 8.0 mol%, and most preferably approximately 7.0 mol%.

The Nb ₂ O ₅ component is optionally contained, but is more preferably about 1.0 mol%, most preferably about 2.0 mol%, and preferably about 8.0 mol%, more preferably about 7 mol. It is contained at an upper limit of 0.0 mol%, most preferably approximately 6.0 mol%.

The Ta ₂ O ₅ component is preferably contained at an upper limit of preferably about 5.0 mol%, more preferably about 3.0 mol%, and most preferably not substantially contained.

The Bi ₂ O ₃ component is preferably contained at an upper limit of approximately 5.0 mol%, more preferably approximately 4.0 mol%, and most preferably approximately 3.0 mol%.

The WO ₃ component is preferably contained at an upper limit of approximately 6.0 mol%, more preferably approximately 4.0 mol%, and most preferably approximately 3.5 mol%.

The ZrO ₂ component is preferably contained at an upper limit of approximately 11.0 mol%, more preferably approximately 8.0 mol%, and most preferably approximately 6.0 mol%.

The sum of the components of TiO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , Bi ₂ O ₃ , WO ₃ , ZrO ₂ and La ₂ O ₃ is preferably about 9.0 mol%, More preferably, the lower limit is 11.0 mol%, and most preferably the lower limit is approximately 13.0%. The sum of the components is preferably about 30.0 mol% as an upper limit, more preferably about 27.0 mol%, more preferably about 25.0 mol%, and most preferably about 25.0 mol%.

  The BaO component is preferably contained at an upper limit of approximately 9.0 mol%, more preferably approximately 7.0 mol%, and most preferably approximately 5.0 mol%.

  The MgO component is preferably contained in an amount of approximately 35.0 mol%, more preferably less than 10.0 mol%, and most preferably not substantially contained.

  The CaO component is preferably contained in an amount of approximately 25.0 mol%, more preferably approximately 15.0 mol%, and most preferably not substantially contained.

  The sum of both MgO and CaO components is preferably about 25.0 mol% or less, more preferably about 15.0 mol% or less, and most preferably about 10.0 mol% or less.

The Li ₂ O component is preferably contained at an upper limit of approximately 9.0 mol%, more preferably approximately less than 7.0 mol%, and most preferably approximately 5.5 mol%.

The Na ₂ O component is preferably contained in an amount of approximately 5.0 mol%, more preferably approximately 3.0 mol%, and most preferably not substantially contained.

The K ₂ O component is preferably contained in an amount of approximately 4.0 mol%, more preferably approximately 3.0 mol%, and most preferably not substantially contained.

In addition, each component of Li ₂ O, NaO, and K ₂ O is an optionally contained component, but it is more preferable that the lower limit of the sum of the components is approximately 0.3 mol%, and approximately 0.5 mol%. Most preferred. However, the upper limit of the sum of the components is preferably about 4.5 mol%, more preferably about 4.2 mol%, and most preferably about 3.8 mol%.

The upper limit of the content of the Sb ₂ O ₃ component is preferably approximately 1.0 mol%, more preferably approximately 0.5 mol%, and most preferably approximately 0.1 mol%.

It should be noted that components other than the above, such as Rb ₂ O, Cs ₂ O, SnO, etc. may be added to the glass of the present invention up to about 5 mol% in total if necessary.

Next, the components preferably not substantially contained in the glass of the present invention will be described.
The glass of the present invention preferably contains substantially no environmentally harmful PbO or As ₂ O ₃ component.

Lu ₂ O ₃ is generally used less frequently as a glass component than other components. Moreover, since it is a substance with a rare value compared with a general glass raw material, it is expensive as a glass raw material, and it is a component which it does not want to use from an economical viewpoint. Since the glass of the present invention has the above characteristics and stability as a glass, it is preferable that the glass does not substantially contain a Lu ₂ O ₃ component.

  The F component is a component that lowers the refractive index, and is preferably not substantially contained from the viewpoint of matching with sapphire.

Components such as HfO ₂ , Gd ₂ O ₃ , Tb ₂ O ₃ , and MnO ₂ are preferably not substantially contained since the stability, acid resistance, meltability, and the like of the glass are lowered.

It is preferable that coloring components such as V, Cr, Fe, Co, Ni, Cu, and Mo are not substantially contained.

  In addition, in this specification, it does not contain substantially means not to contain it artificially except when mixed as an impurity.

According to the present invention, Yb which is an optically active component can be contained in a large amount, and the average linear expansion coefficient approximated to sapphire (50 to 85 × 10 ⁻⁷ / ° C. at 100 to 300 ° C.) and refraction. It has a high rate (1.70 to 1.90), has good bonding with a sapphire single crystal as a heat sink, and has very little reflection of laser light at the bonding interface, and can be expected to have high output as a laser medium. New materials can be obtained.

Next, examples of the glass composition according to the present invention (unit: mass%) are shown in Tables 1 to 3 together with the refractive index (nd) and the average linear expansion coefficient (α) of 100 to 300 ° C. However, the present invention is not limited to these examples.
In these tables, the refractive index (nd) is obtained by casting molten glass, holding it at a temperature in the vicinity of Tg for 3 hours, then lowering the temperature at a rate of 25 ° C./hour for 10 hours, and then reaching room temperature in the annealing furnace. The glass obtained by natural temperature reduction was measured using a differential automatic refractometer. The average linear expansion coefficient (α) was obtained by processing the glass of each example into a rod-shaped sample having a length of 20.0 (+0.0, −1.0) mm and a diameter of 4.7 (± 0.1) mm. Using a TAS200-TMA vertical thermal dilatometer manufactured by Rigaku Corporation, a force of 98 mN was applied to the sample, and the sample was heated so as to rise at 4 ° C. per minute, and measured in a temperature range of 100 to 300 ° C.

All the glasses of the examples of the present invention are weighed and mixed using raw materials of nitrate, carbonate and oxide, and dissolved and defoamed at about 1100 to 1500 ° C. for about 2 to 5 hours using a platinum crucible. After stirring and homogenizing, it was obtained by casting into a mold and slow cooling.

As can be seen from Tables 1 to 3, the glasses of the examples of the present invention all have an average linear expansion coefficient in the range of 50 to 85 × 10 ⁻⁷ / ° C. at 100 to 300 ° C., and the refractive index (nd). Was in the range of 1.70 to 1.90. And these glass had favorable joining with sapphire.

As described above, the novel material obtained in the present invention can contain a large amount of Yb, which is an optically active component, has an average linear expansion coefficient and a refractive index that are similar to sapphire, and a single sapphire as a heat sink. It is a glass that can be expected to have high output as a laser medium that has good bonding with crystals and does not have a problem of reflection of laser light at the bonding interface. Therefore, it is suitable as a high-power solid-state laser that requires high output, short pulse, and high repetition rate.

  Although it is possible to use the glass of the present invention alone as a solid laser medium, since the glass of the present invention is matched with sapphire, the conventional technique of joining a single crystal as a heat sink to a single crystal laser medium. Thus, it can use as a solid laser which has favorable heat resistance by joining the sapphire single crystal to the glass of this invention as a heat sink.

Moreover, it is not limited to a single crystal of sapphire, it is matched with the glass of the present invention, and if the thermal conductivity is at least better than that of the glass of the present invention, it is joined to the glass of the present invention as a heat sink and used as a solid laser. Can be used.

The glass and the heat sink of the present invention may be joined by direct joining such as an optical contact, or by using some bonding material matched with sapphire.

As the adhesive material, it is preferable to use a material that is transparent and has an average linear expansion coefficient and a refractive index similar to those of sapphire. For example, the refractive index (nd) exceeds 1.70 to 1.82, the thermal expansion coefficient (α) at 100 to 300 ° C. is 50 to 80 × 10 ⁻⁷ / ° C., and the glass transition point (Tg) is 600 ° C. or less. Glass is suitable as an adhesive material.

An example of the composition of the bonding glass having the physical properties is shown below.
% By mass
SiO ₂ > 5.0% to 15.0%, and B ₂ O ₃ 10.0% to> 30.0%, and Al ₂ O ₃ 4.0% to> 10.0%, and less than 40.0% than the ZnO 10.0, and _TiO 2 0 to 5.0%, and / or _Nb 2 _O 5 _0~20.0%, and / or _Ta 2 _O 5 0 to 8.0% And / or Bi ₂ O _{3 0 to} 10.0%, and / or WO _{3 0 to} 10.0%, and / or ZrO ₂ 0 to less than 3.0%, and / or La ₂ O ₃ 5 less than 30.0%, and / or MgO less than 0 to 5.0%, and / or CaO less than 0 to 5.0%, and / or BaO less than 0 to 5.0%, and / or _Li 2 O 0 to less than 3.5%, and / or _Na less than 2 O 0 to 3.5% Oyo / Or _K less than 2 O 0 to 3.5%, and / or _Sb 2 _O 3 _0~1.0%
It is the glass containing each component of.

Similarly, when expressed in mol%,
SiO ₂ from 8.0 to 30.0%, and _B 2 _O 3 _15.0~50.0%, and _Al 2 _O 3 1.0% less than 10.0, and ZnO 13.0 to 50.0% , and _TiO 2 0 to 7.0%, and / or _Nb 2 _O 5 _0~8.0%, and / or _Ta 2 _O 5 _0~3.0%, and / or _Bi 2 _O 3 _0~3. 0%, and / or _WO 3 0 to 5.0% and / or _ZrO 2 0 to 3.0% and / or _La 2 _O 3 1.5 to 10.0% and / or MgO 0 to 5 .0%, and / or CaO 0 to 5.0%, and / or BaO 0 to 5.0%, and / or _Li 2 O 0 to 12.0%, and / or _Na 2 O 0-6.0 % And / or K ₂ O 0-4.0% and / or Sb ₂ O ₃ 0-1 .0%
It is the glass containing each component of.

When glass is used as the bonding material, the glass is made into a thin plate, pulverized and dispersed in a solvent, or other suitable state for bonding, and interposed between the glass of the present invention and sapphire and heat-treated. The solid laser with excellent heat resistance can be produced with little loss due to light reflection at the glass / sapphire interface of the present invention.

Tables 4 to 6 show composition examples of the adhesive material. The refractive index (nd) and the average linear expansion coefficient (α) in Tables 4 to 6 were the same as the methods for measuring the refractive index and the average linear expansion coefficient in the examples of Tables 1 to 3.
Further, the glass transition point (Tg) was measured using the same sample, apparatus, and temperature raising conditions as those for the method for measuring the average linear expansion coefficient.

As can be seen from Tables 4 to 6, the glass of the composition example of the adhesive material has an average linear expansion coefficient of 100 to 300 ° C. in the range of 50 to 80 × 10 ⁻⁷ / ° C., and a refractive index (nd ) Was in the range greater than 1.70 and less than or equal to 1.82. And all these glass showed the glass transition point (Tg) of 600 degrees C or less. Further, the glass could be bonded to sapphire at a temperature at which the laser glass was not devitrified, and the bonding glass itself was not devitrified and exhibited good characteristics as the bonding glass.

Claims (6)

Each component of SiO ₂ , B ₂ O ₃ , ZnO, La ₂ O ₃ and Yb ₂ O ₃ is contained, and the content of the Yb ₂ O ₃ component exceeds 10.0% by mass to 30.0%, The value of (SiO ₂ + B ₂ O ₃ + MgO + CaO) / Yb ₂ O ₃ is 0.65 to 5.5 and the refractive index (nd) is 1.70 to 1.90, 100 in terms of mass% of each component. The glass composition whose average linear expansion coefficient ((alpha)) in -300 degreeC is 50-85 * 10 < ^-7 > / degreeC. Each component of SiO ₂ , B ₂ O ₃ , ZnO, La ₂ O ₃ and Yb ₂ O ₃ is contained, and the content of Yb ₂ O ₃ component is 3.0% to 20.0% in mol%, each component The value of (SiO ₂ + B ₂ O ₃ + MgO + CaO) / Yb ₂ O ₃ is ₂ to 38, and the refractive index (nd) is 1.70 to 1.90, an average line at 100 to 300 ° C. A glass composition having an expansion coefficient (α) of 50 to 85 × 10 ⁻⁷ / ° C. % By mass
SiO ₂ less than 3.0 to 10.0%, and _B 2 _O 3 15.0 to 30.0%, and _Yb 2 _O 3 10.0% to more than 30.0%, and ZnO from 5.0 to 40 less than 2.0%, and _La 2 _O 3 from 5.0 to 30.0%, and _Al 2 _O 3 0 to 5.0%, and / or _TiO 2 0 to 5.0%, and / or _Nb 2 _{O 5} 0 to 15.0%, and / or _Ta 2 _O 5 0 to 15.0%, and / or _Bi 2 _O 3 0 to 10.0% and / or _WO 3 0 to 10.0% and / or ZrO _{2 0 to} 10.0%, and / or MgO 0 to 10.0%, and / or CaO 0 to 10.0%, and / or BaO 0 to 10.0%, and / or Li ₂ O 0 less than 2.0%, and / or _Na 2 O 0 to 3.0% and / Other _K 2 O _0~3.0%, and / or _Sb 2 _O 3 _0~1.0%
The glass composition of Claim 1 containing each component of these. mol%,
SiO ₂ from 6.0 to 25.0%, and _B 2 _O 3 _25.0~60.0%, and _Yb 2 _O 3 _3.0~20.0%, and ZnO from 10.0 to 65.0%, and _La 2 _O 3 _1.0~12.0%, and _Al 2 _O 3 _0~7.0%, and / or _TiO 2 from 0 to 9.0%, and / or _Nb 2 _O 5 _0~8.0 % And / or Ta ₂ O ₅ 0-5.0% and / or Bi ₂ O ₃ 0-5.0% and / or WO ₃ 0-6.0% and / or ZrO ₂ 0-11 .0%, and / or MgO from 0 to 35.0%, and / or CaO from 0 to 25.0%, and / or BaO 0 to 9.0%, and / or _Li 2 O 0 to 9.0%, and / or _Na 2 O _0~5.0%, and / or _K 2 O _0~4.0%, Contact Beauty / or _Sb 2 _O 3 _0~1.0%
The glass composition of Claim 2 containing each component of these. % By mass
TiO ₂ + Nb ₂ O ₅ + Ta ₂ O ₅ + Bi ₂ O ₃ + WO ₃ + ZrO ₂ + La ₂ O ₃
20.0% to 50.0%, and / or MgO + CaO 10.0% or less, and / or _{Li 2 O + Na 2 O +} K 2 O0% ~3.0%
The glass composition according to claim 1 or 3. mol%,
TiO ₂ + Nb ₂ O ₅ + Ta ₂ O ₅ + Bi ₂ O ₃ + WO ₃ + ZrO ₂ + La ₂ O ₃
9.0% to 30.0%, and / or MgO + CaO 25.0% or less, and / or _{Li 2 O + Na 2 O +} K 2 O0% ~4.5%
The glass composition according to claim 2 or 4.