JP3089888B2 - Fine particle dispersed glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to CuCl and CuBr.
And the like. This CuCl and C
Particle-dispersed glass such as uBr is used as a nonlinear optoelectronic material or an ultraviolet absorbing filter glass.

[0002]

2. Description of the Related Art Glass in which fine particles such as CuCl and CuBr are dispersed in a matrix glass exhibits relatively large third-order nonlinear characteristics due to quantization of translational motion of excitons due to confinement of excitons. For example, Solid State Commun, Vol. 56, pp. 921 (So
lid State Commun, 56, P921
(1985)), CuCl and CuBr
Fine particle-dispersed glass has attracted attention as a nonlinear optoelectronic material for optical switches and optical computers. Glass containing fine particles such as CuCl and CuBr is a material that has been well known as one of the ultraviolet absorbing glasses.

[0003] In the production of such a glass in which fine particles such as CuCl and CuBr are dispersed, as described in Glass Engineering Handbook, page 760 (Asakura Shoten, 1963), silicate glass or glass is used as a matrix glass. Borosilicate glass is used. And CuCl or C with glass as matrix
The fine particle-dispersed glass such as uBr is obtained by heating and melting a mixture containing the starting materials of these glasses and the starting material of fine particles such as CuCl and CuBr to form a glass melt, and then cooling the glass melt to room temperature. A method in which a glass in which constituent elements of fine particles are dissolved as ions in a matrix is obtained, and then the glass is heated from room temperature to a predetermined temperature, and heat-treated (held) at the predetermined temperature to precipitate fine particles. (Generally called a melting method).

[0004]

However, in the case of producing fine particle-dispersed glass such as CuCl or CuBr using silicate glass or borosilicate glass as a matrix glass, the starting material is heated and melted so that the constituent elements of the fine particles are contained in the matrix. In the process of obtaining a molten homogeneous glass, the elements constituting the fine particles such as CuCl and CuBr have low solubility in the matrix, so that they do not dissolve in the glass but are separated and CuCl or CuBr is contained in the raw material.
However, even if a large amount of starting materials such as fine particles are added, the concentration of fine particle constituent elements dissolved in glass cannot be increased, and as a result, the concentration of fine particles precipitated by heat treatment becomes low. is there.

The value of the nonlinear susceptibility (| χ ⁽³⁾ |), which represents the magnitude of the third-order nonlinear characteristic, is proportional to the volume ratio of the fine particles in the fine particle-dispersed glass. When a nonlinear optoelectronic device such as an optical switch or an optical computer is manufactured using CuCl or CuBr fine particle-dispersed glass, for example, International Conference on Science and Technology of New Glass, p. 394 (Internati)
onal Conference on Science
e and Technology of New G
As described in J. Lases, P394 (1991), the volume fraction of CuCl fine particles in the borosilicate glass dispersed with CuCl fine particles is about 10 ⁻³ (CuCl concentration, about 0.5 mol%), and | χ ^{( 3)} | is 1
On the order of 0 ^-6 esu, it was insufficient to operate at the light intensity of the semiconductor laser.

Further, when a thin CuCl fine particle-dispersed glass is produced, the rising of the light absorption curve is broad and has a gentle slope, and it is difficult to reduce the thickness while maintaining the optical filter (sharp cut filter) characteristics. Met. The present invention has been made to solve the above-mentioned disadvantages in the conventional fine particle-dispersed glass such as CuCl and CuBr as a nonlinear optoelectronic material and an optical filter material, and an object of the present invention is to provide a high-concentration CuCl or CuBr such as An object of the present invention is to provide a fine particle-dispersed glass containing fine particles.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made to achieve the above object, and the CuCl or CuBr fine particle-dispersed glass of the present invention comprises P ₂ O ₅ and B ₂ O _3.
At least one selected from the group consisting of MgO, CaO, and Sr
At least one selected from O, BaO, ZnO and CdO, SnO, and at least one selected from CuCl and CuBr compounds are essential components, and P ₂
The total amount of O ₅ and B ₂ O ₃ is 30 to 60 mol%,
The total amount of MgO, CaO, SrO, BaO, ZnO, and CdO is 20 to 60 mol%, and the amount of SnO is
0 mol%, and the total amount of CuCl and CuBr is 2 to 2.
20 mol%, CuCl, CuBr and Cu
At least one selected from (Cl _X Br _{1 -X} ) (where 0 <X <1) is precipitated as fine particles in glass.

Hereinafter, the present invention will be described in detail. According to the present invention, at least one selected from P ₂ O ₅ and B ₂ O _{3 is used} as a component constituting the matrix of the fine particle dispersed glass, and MgO, CaO, SrO, BaO, ZnO
And at least one selected from CdO and SnO. By limiting these composition ranges as described above, the solubility of CuCl and CuBr in the glass melt can be increased, and by performing the heat treatment, at least one type of fine particles selected from CuCl and CuBr becomes high. A fine particle-dispersed glass precipitated at a concentration is obtained.

The precipitated fine particles are CuCl, Cu
Br alone or both of them may be used.
u (Cl _X Br _1-X ) (where 0 <X <1,). Next, the reason for limiting the composition ratio of the glass composition serving as the matrix of the fine particle-dispersed glass of the present invention as described above will be described.

The total amount of P ₂ O ₅ and B ₂ O ₃ is 30 mol
%, The thermal stability of the glass becomes insufficient and CuC
In a heat treatment step of precipitating fine particles such as l and CuBr, the glass itself is easily crystallized, which is not preferable.
On the other hand, when the total amount of P ₂ O ₅ and B ₂ O ₃ exceeds 60 mol%, the chemical durability of the glass becomes insufficient, which causes a problem in use. Therefore, the total amount of P ₂ O ₅ and B ₂ O ₃ is 3
It is limited to 0 to 60 mol%. The total amount of P ₂ O ₅ to B ₂ O ₃ is particularly preferably from 30~55mol%.

[0011] MgO, CaO, SrO, BaO and ZnO
If the combined amount of CdO and CdO exceeds 60 mol%, the thermal stability of the glass becomes insufficient, and the glass itself tends to crystallize in the heat treatment step, which is not preferable. On the other hand, if the total amount is less than 20 mol%, the chemical durability of the glass becomes insufficient, which is not preferable. Therefore, MgO and Ca
The total amount of O, SrO, BaO, ZnO, and CdO is 20 to
Limited to 60 mol%. The total amount of MgO, CaO, SrO, BaO, ZnO and CdO is 20 to 55 mol%
Is particularly preferred.

SnO is made of CuCl, CuB
has a thermal reduction effect when depositing fine particles such as
Although it is a component for accurately depositing fine particles such as uCl and CuBr, if its amount exceeds 20 mol%, it is not preferable because it becomes undissolved and precipitates in the matrix. On the other hand, if the amount of SnO is less than 1 mol%, it is not preferable because fine particles such as CuCl and CuBr cannot be accurately deposited by heat treatment. Therefore, the amount of SnO is limited to 1 to 20 mol%. The amount of SnO is 1 to 1
Particularly preferred is 5 mol%. The components having thermal reduction include Sb ₂ O ₃ , As, as well as SnO.
₂ 0 _3, PbO, can be used Bi ₂ 0 _3, etc., these components are weak thermally reducing action compared with SnO,
Not practical.

By limiting the composition ratio of the glass composition serving as the matrix of the fine particle-dispersed glass of the present invention as described above, CuCl, CuBr, etc.
２２22 mol% contained in the glass component, and the glass is heat-treated to have a high concentration of Cu.
At least one type of fine particles selected from Cl, CuBr and Cu (Cl _x Br _1-x ) (where 0 <X <1) can be precipitated.

CuCl or C contained in the glass composition
As a raw material of uBr, CuCl, CuBr and Cu
Oxides such as ₂ O and CuO, carbonates such as CuCO ₃ , Cu
A nitrate such as NO ₃ can be used. Further, as chlorides, MgCl ₂ , CaCl ₂ , SrCl ₂ , B
aCl ₂ , ZnCl ₂ , CdCl ₂ , LiCl, NaC
1, KCl and the like can be used. Furthermore, as the _{bromide, MgBr 2, CaBr 2, SrBr} 2, BaB
r ₂ , ZnBr ₂ , CdBr ₂ , LiBr, NaBr,
KBr or the like can be used.

In the glass composition of the present invention, which serves as a matrix of the fine particle-dispersed glass, SiO ₂ , Al ₂ O ₃ , Ga ₂ O ₃ , In ₂ O ₃ , Zr
O ₂ and Y ₂ O ₃ can be contained at a ratio of 10 mol% or less. As a method of precipitating at least one kind of fine particles selected from CuCl and CuBr by heat treatment, the following method is exemplified.

(1) The glass melt is cooled to a temperature at which fine particles such as CuCl and CuBr precipitate, for example, 380 to 600 ° C., and the glass is held in this temperature range to hold fine particles such as CuCl and CuBr. Is precipitated.

(2) The glass melt is heated to a temperature lower than the temperature at which fine particles of CuCl, CuBr, etc. precipitate, for example, 380.
Once cooled to a temperature lower than ℃, CuCl, Cu
Temperature at which fine particles such as Br precipitate, for example, 380 to 600
° C and the glass is kept in this temperature range
l, to precipitate fine particles such as CuBr.

(3) The glass melt is once cooled to room temperature to obtain a solid glass, which is raised to a temperature at which CuCl, CuBr, etc. precipitates, for example, 380 to 600 ° C., and the glass is held in this temperature range. To precipitate fine particles such as CuCl and CuBr.

[0019]

The precipitation of fine particles such as CuCl and CuBr is
CuCl, CuBr in the above temperature range (380-600 ° C)
Reacts with Sn ions (derived from SnO) having a reducing action to form copper monovalent ions, and then the copper monovalent ions diffuse into chloride ions, bromide ions, etc. , Agglomerates to form a crystal nucleus, and the crystal grows.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.
As a raw material for obtaining the glasses of Examples 1 to 18, P
₂ O ₅ , B ₂ O ₃ , Mg (PO ₃ ) ₂ , Ca (PO ₃ )
₂ , Sr (PO ₃ ) ₂ , Ba (PO ₃ ) ₂ , MgC
O ₃ , CaCO ₃ , SrCO ₃ , BaCO ₃ , ZnO,
CdO, SnO, CuCl, CuBr and the like were used.

(Example 1) Materials necessary for obtaining glass are appropriately selected from the above-mentioned materials, and the composition of the obtained glass is 44 mol% of P ₂ O ₅ , 44 mol% of BaO,
A total of 25 g was mixed so as to be 6 mol% of SnO and 6 mol% of CuCl. The obtained mixture was heated at 1200 ° C. for 15 minutes in a refractory crucible to form a uniform glass melt, and then cast on an iron plate to obtain a colorless and transparent glass.

Next, the obtained glass was previously
The glass was gradually cooled to room temperature after it was placed in an electric furnace maintained at ℃ and maintained at this temperature for 3 hours. When the glass thus obtained was measured using a powder X-ray diffractometer, a CuCl crystal peak was observed, and it was confirmed that CuCl fine particle dispersed glass was obtained. Further, C
The size of the copper crystal fine particles contained in the uCl fine particle dispersed glass was measured using a powder X-ray diffractometer and a transmission electron microscope (TE).
M), the average particle size (diameter) of the CuCl crystal particles was 40 °.

The obtained CuCl fine particle dispersed glass was
Optical polishing was performed to a thickness of μm, and the light absorption spectrum was measured. As a result, a sharp absorption peak of CuCl was confirmed as shown by a solid line 1 in FIG. Also, from FIG.
The rising of the light absorption curve of the Cl particle dispersed glass was sharp, and it was also confirmed that the glass had excellent spectral characteristics. Further, the light absorption curve (solid line 1 in FIG. 1) of the CuCl fine particles dispersed glass obtained in this example is the same as that of the conventional CuC using the borosilicate glass of Comparative Example 1 described later as a matrix.
l Fine particle dispersed glass (52.5 mol% B ₂ O ₃ , 3
0.0 mol% of SiO ₂ , 0.5 mol% of SnO,
6.5 mol% Al ₂ O ₃ , 10.0 mol% Na
Light absorption curve of ₂ O, 0.5 mol% CuCl) (FIG. 1)
The light absorption amount is increased by 10 times or more compared to the broken line 2) of
It can be seen that the concentration of the CuCl fine particles in the CuCl fine particle-dispersed glass of the present example was extremely high, at least 10 times the concentration of the CuCl fine particles in the CuCl fine particle-dispersed glass of Comparative Example 1.

Further, a degenerate four-wave mixing method (Degener
added FourWave Mixing Meth
od), the wavelength near the light absorption peak (380 nm)
When | 値⁽³⁾ | value was measured at 77K,
^-5 The order of esu. Therefore, in the present embodiment, Cu
The glass in which the Cl fine particles are dispersed is 10 times or more the optical non-linear susceptibility (| χ) of the glass in which the CuCl fine particles are dispersed in Comparative Example 1.
^{(3) It} can be seen that |) is satisfied.

Further, the value of the non-linear susceptibility (| χ ⁽³⁾ |) representing the magnitude of the third-order non-linear characteristic is proportional to the volume ratio of the fine particles in the fine particle-dispersed glass.
Comparative Example 1 also shows that the fine particle-dispersed glass has a non-linear susceptibility value.
It can be seen that the glass has a CuCl fine particle concentration 10 times or more that of the CuCl fine particle-dispersed glass. Glass composition of Example 1, heat treatment temperature and time for precipitating fine particles,
Further, a conventional CuCl fine particle-dispersed glass (52.5 m
ol% of B ₂ O ₃ , 30.0 mol% of SiO ₂ , 1
0.0 mol% Na ₂ O, 6.5 mol% Al ₂ O
₃ , 0.5 mol% SnO, 0.5 mol% CuC
Table 1 shows the relative concentration when the concentration of the CuCl fine particles of 1) was set to 1.

(Examples 2 to 15) After obtaining the glasses shown in Tables 1 to 3 in the same manner as in Example 1, CuCl fine particle dispersed glass was obtained under the heat treatment conditions shown in Tables 1 to 3. However, in Example 5, C was used as a raw material instead of CuCl.
uNO ₃ and CaCl ₂ were used. Examples 2-1 obtained
When the glass of Example 5 was measured using a powder X-ray diffractometer, the glasses of Examples 2 to 15 showed Cu as in Example 1.
A Cl crystal peak was observed, and it was confirmed that CuCl fine particle dispersed glass was obtained.

The light absorption characteristics of these CuCl fine particle dispersed glasses were measured in the same manner as in Example 1.
Any of the CuCl fine particle-dispersed glass has a sharp CuCl fine particle like the CuCl fine particle-dispersed glass obtained in Example 1.
The absorption peak of was confirmed. Furthermore, it was also confirmed that the light absorption curve had a sharp rise and had excellent spectral characteristics. From these light absorption characteristics, each CuCl
When the concentration of CuCl fine particles in the fine particle-dispersed glass was determined, as shown in Tables 1 to 3, the concentration was 5 times or more that of the conventional CuCl fine particle-dispersed glass having the borosilicate glass of Comparative Example 1 as a matrix. It can be seen that the optical nonlinear susceptibility (χ ⁽³⁾ ) is twice or more. Tables 1 to 3 show the CuCl fine particle concentrations of these examples.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

[Table 3]

Examples 16 and 17 Glasses shown in Table 3 were obtained in the same manner as in Example 1 except that CuBr was used instead of CuCl. After heat-treating this glass under the conditions shown in Table 3, the glass was gradually cooled to room temperature. Examples 16 and 17
Was measured using a powder X-ray diffractometer,
A CuBr crystal peak was observed, and it was confirmed that CuBr fine particle dispersed glass was obtained. Furthermore, these C
When the light absorption characteristics of the uBr fine particle-dispersed glass were measured in the same manner as in Example 1, any of the CuBr fine particle-dispersed glasses showed a sharp absorption peak of CuBr similarly to the CuCl fine particle-dispersed glass obtained in Example 1. Was done. It was also confirmed that the light absorption curve had a sharp rise and had excellent spectral characteristics. CuB of these examples
Table 3 shows the concentration of the r fine particles.

Example 18 Glasses shown in Table 3 were obtained in the same manner as in Example 1 except that a mixture of CuCl and CuBr was used. After heat-treating this glass under the conditions shown in Table 3, the glass was gradually cooled to room temperature. When the glass of Example 18 was measured using a powder X-ray diffractometer, a mixed crystal peak of CuCl and CuBr was observed, and CuCl and CuB were observed.
It was confirmed that r mixed crystal fine particle dispersed glass was obtained. Further, when the light absorption characteristics of these fine particle-dispersed glasses were measured in the same manner as in Example 1, a sharp absorption peak of a mixed crystal of CuCl and CuBr was confirmed. It was also confirmed that the light absorption curve had a sharp rise and had excellent spectral characteristics. Table 3 shows the concentration of fine particles of a mixed crystal of CuCl and CuBr in this example.

Comparative Examples P ₂ O ₅ , B ₂ O ₃ , and Ba (PO ₃ ) were used as raw materials for obtaining the glasses of Comparative Examples 1 to ₅ .
₂ , BaCO ₃ , SnO, CuCl, SiO ₂ , Na ₂
CO ₃ , Al ₂ O ₃ or the like was used.

(Comparative Example 1) In order to obtain the glass of Comparative Example 1, necessary raw materials were appropriately selected from these raw materials, and the composition of the obtained glass was 52.5 mol% of B ₂ O ₃ , 30 mo.
1% SiO ₂ , 10 mol% Na ₂ O, 6.5mo
1% Al ₂ O ₃ , 0.5 mol% SnO, 0.5 m
The solution was mixed in a total amount of 25 g so as to obtain ol% of CuCl.
A glass was obtained in the same manner as in Example 1 except that the obtained mixture was heated at 1,400 ° C. for 2 hours to obtain a uniform glass melt. Next, the obtained glass was placed in an electric furnace maintained at 535 ° C., and maintained at this temperature for 10 minutes, and then the glass was gradually cooled to room temperature.

When the glass thus obtained was measured using a powder X-ray diffractometer, a CuCl crystal peak was observed, and it was confirmed that CuCl fine particle dispersed glass was obtained. When the light absorption spectrum of the obtained CuCl fine particle dispersed glass was measured, as shown by the broken line 2 in FIG. 1, the CuCl fine particle dispersed glass of Comparative Example 1 had a broad light absorption curve with a gentle slope. Was. Table 4 shows the CuCl fine particle concentration of this comparative example as 1.0.

[0036]

[Table 4]

(Comparative Example 2) The composition of the obtained glass was 4
6.5 mol% of P ₂ O ₅ and 46.5 mol% of BaO
And 0.5 mol% of SnO and 6.5 mol% of CuCl
Glass was obtained in the same manner as in Example 1 except that the raw materials were mixed so that Thereafter, this glass was heat-treated at 500 ° C. for 3 hours as shown in Table 4. The light absorption characteristic of the obtained CuCl fine particle-dispersed glass was determined assuming that the CuCl fine particle concentration of Comparative Example 1 was 1, and it was as low as 0.5 times. Table 4 shows the CuCl fine particle concentration of this comparative example.

(Comparative Example 3) The composition of the obtained glass was 25.
mol% P ₂ O ₅ and 63 mol% BaO and 6 mol
% Glass was obtained in the same manner as in Example 1, except that the raw materials were mixed so as to be SnO of 6% and CuCl of 6 mol%. Thereafter, this glass was heat-treated at 480 ° C. for 5 hours as shown in Table 4. When the obtained glass was measured using a powder X-ray diffractometer, precipitation of CuCl crystal fine particles could not be confirmed, and instead, crystallization of the glass was recognized.

Comparative Example 4 The composition of the obtained glass was as shown in Table 4.
A glass was obtained in the same manner as in Example 1 except that the raw materials were mixed so that 65 mol% of P ₂ O ₅ , 23 mol% of BaO, 6 mol% of SnO, and 6 mol% of CuCl as shown in FIG. Thereafter, the glass was heat-treated at 530 ° C. for 5 hours as shown in Table 4. The obtained glass is powder X
As a result of measurement using a line diffraction apparatus and a light absorption spectrum apparatus, no precipitation of CuCl crystal fine particles could be confirmed. Further, when left in the air for one day, the glass deteriorated, and the chemical durability was poor.

(Comparative Example 5) A glass was produced in the same manner as in Comparative Example 1 except that CuBr was used instead of CuCl in Comparative Example 1. As a result, a CuBr crystal diffraction peak was observed, and a glass obtained by dispersing CuBr fine particles was obtained. Was confirmed. However, when the light absorption spectrum of the obtained CuBr fine particle-dispersed glass was measured, the rise of the light absorption curve was broad and had a gentle slope. Also,
The concentration of the CuBr fine particles in the CuBr fine particle-dispersed glass was about the same as the CuCl fine particle concentration of Comparative Example 1 of 1.2. Table 4 shows the concentration of the CuBr fine particles of this comparative example.

[0041]

As described above, according to the present invention,
A fine particle-dispersed glass in which fine particles such as CuCl and CuBr are dispersed at a high concentration can be produced, and the resulting Cu
Fine-particle-dispersed glass such as Cl and CuBr has excellent nonlinear characteristics as a nonlinear optical material and also has excellent spectral characteristics as a filter material.

[Brief description of the drawings]

FIG. 1 is a graph showing light absorption curves of CuCl fine particle dispersed glass of Example 1 and CuCl fine particle dispersed glass of Comparative Example 1.

Claims (2)

(57) [Claims] 1. A method according to claim 1, wherein at least one selected from P ₂ O ₅ and B ₂ O ₃ is combined with MgO, CaO, SrO, BaO, Z
at least one selected from nO and CdO, and Sn
O and at least one selected from CuCl and CuBr as essential components, and the total amount of P ₂ O ₅ and B ₂ O ₃ is 30 to 60 mol%, and MgO, CaO and Sr
The total amount of O, BaO, ZnO and CdO is 20 to 60 mo
1%, the amount of SnO is 1 to 20 mol%,
the total amount of uCl and CuBr is 2 to 20 mol%,
A fine particle-dispersed glass characterized in that at least one selected from CuCl, CuBr and Cu (Cl _x Br _1-x ) (where 0 <X <1) is precipitated as fine particles in the glass. 2. At least one selected from P ₂ O ₅ and B ₂ O ₃ , and MgO, CaO, SrO, BaO, Z
at least one selected from nO and CdO, and Sn
O and at least one selected from CuCl and CuBr as essential components, and the total amount of P ₂ O ₅ and B ₂ O ₃ is 30 to 55 mol%, and MgO, CaO and Sr
The total amount of O, BaO, ZnO and CdO is 20 to 55 mo
1%, the amount of SnO is 1 to 15 mol%,
the total amount of uCl and CuBr is 2 to 20 mol%,
A fine particle-dispersed glass characterized in that at least one selected from CuCl, CuBr and Cu (Cl _x Br _1-x ) (where 0 <X <1) is precipitated as fine particles in the glass.