JPH07239489A - Nonlinear optical material - Google Patents

Abstract

PURPOSE:To obtain a nonlinear optical element having large nonlinear sensitivity by dispersing metallic particulates into a matrix which has an optically isotropic refractive index in a specific range and is transparent. CONSTITUTION:This nonlinear optical material has a structure formed by dispersing the metallic particulates having radio of 1 to 100nm into the transparent glass and/or crystal which has the optically isotropic refractive index of >=1.9 to <=4 and is transparent. The large nonlinear sensitivity (¦x<(3)>¦) is exhibited in the metallic particulates sufficiently smaller than the wavelength of the light in the matrix by the effect of the local electric fields by the dielectric confinement of the matrix. Further, large ¦x<(3)>¦/alpha is obtd. by the effect of the refractive index and the effect of the dependency of the virtual part of the dielectric constant of the metallic particulates on wavelengths by increasing the refractive index of the matrix. Then, this nonlinear optical material has the performance of the ¦x<(3)>¦/alpha larger by >=2 times the performance of the conventional materials dispersed with the metallic particulates. The nonlinear optical element which can operate at light intensity of a semiconductor laser is produced by using such nonlinear optical material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-linear optical material, a manufacturing method thereof and a non-linear optical element using the non-linear optical material.

[0002]

2. Description of the Related Art Third-order nonlinear characteristics of glass in which fine metal particles sufficiently smaller than the wavelength of light are dispersed in a matrix glass have been measured and reported to exhibit relatively large nonlinear characteristics (Opt. Lett., 10,511 (19
85), Appl. Phys. , A47,347 (19
88)), and metal fine particle-dispersed glass have attracted attention as a nonlinear optoelectronic material for optical switches and optical computers.

In such a method for producing a metal fine particle-dispersed glass, as described in JP-A-5-270861, a silicate glass or a borosilicate glass (n) is generally used as a matrix glass.
_d = 1.5 to 1.6), phosphate glass, etc. borate glass (n _d = 1.5~1.8) is used and the phosphate glass and borate glass matrix As the metal fine particle-dispersed glass, the glass containing P ₂ O ₅ and / or B ₂ O ₃ , MgO, CaO, SrO, BaO, ZnO and CdO, and SnO as essential constituent components is added with copper and / or silver. A non-linear optical material in which fine particles are dispersed is disclosed. Then, the metal fine particle-dispersed glass having these glasses as a matrix is prepared by heating and melting a mixture containing a starting material for these glasses and a starting material for the metal fine particles to form a glass melt. To obtain a uniform glass in which the metal element is dissolved in the matrix in the form of ions or atoms in the matrix, and then this glass is heated from room temperature to a predetermined temperature and heat-treated at this predetermined temperature to precipitate fine metal particles. It is manufactured by a method (generally called a melting / thermal precipitation method).

The non-linear characteristic is the absorption coefficient α = 4 in the material in which the concentration of metal fine particles is increased by using phosphate glass.
Nonlinear susceptibility at 000 cm ⁻¹ | χ ⁽³⁾ | = 1.2 × 10
^-7 esu (| χ ⁽³⁾ | /α=3.0×10 ^-11 esu · cm).

[0005]

However, in the case of a metal fine particle dispersed material using a material having a relatively low refractive index such as silicate glass, borosilicate glass and phosphate glass as a matrix, a third-order nonlinear characteristic nonlinear susceptibility representing the magnitude | χ ⁽³⁾ | were normalized by metal particle concentration ^{(α) | χ (3)} | / value of alpha is proportional to the fourth power of the refractive index of the matrix, at most 10 ^{- 11} esu ・ c
Small on the order of m.

Therefore, when a non-linear optical element such as an optical switch or an optical computer is manufactured by using the conventional metal fine particle-dispersed glass, it is difficult to operate with the light intensity of the semiconductor laser.

The present invention has been made to solve the above-mentioned drawbacks in the conventional metal fine particle-dispersed glass as a non-linear optical material. The first object of the present invention is to provide a non-linear optical material having a large non-linear susceptibility. To provide. A second object of the present invention is to provide a method for manufacturing the above-mentioned nonlinear optical material. A third object of the present invention is to provide a non-linear optical element using the non-linear optical material.

[0008]

The present invention has been made to achieve the above object, and the nonlinear optical material of the present invention is an optically isotropic material having a refractive index of 1.9 or more and 4 or less. In addition, it is characterized in that fine metal particles are dispersed in a transparent matrix.

The manufacturing method of the nonlinear optical material of the present invention is
The method is characterized by using a melting / thermal deposition method, an ion implantation method, an ion exchange method or a sputtering method.

Further, the non-linear optical element of the present invention uses the above-mentioned non-linear optical material in which fine metal particles are dispersed in an optically isotropic and transparent matrix having a refractive index of 1.9 or more and 4 or less. It is characterized by becoming.

The present invention will be described in detail below.

In the nonlinear optical material of the present invention, optically isotropic and transparent glass and / or crystal having a refractive index of 1.9 or more and 4 or less is used as a matrix, and metal fine particles are dispersed in the matrix. By doing so, a nonlinear optical material having a large value of | χ ⁽³⁾ | / α can be obtained.

First, the matrix used in the nonlinear optical material of the present invention will be described in detail.

The reason for using a material having a refractive index of 1.9 or more and 4 or less is | χ ⁽³⁾ | /
As a result of studying the effect of the refractive index of the matrix on α, the value of | χ ⁽³⁾ | / α increases with the refractive index of the matrix, and a matrix with a large refractive index is used to obtain high nonlinearity. This is because it has been found to be preferable. The reason why the refractive index is limited to 1.9 or more is that by using a matrix having a refractive index of 1.9 or more, the phosphate glass and / or borate glass having the highest refractive index among conventional materials can be obtained. metal particle-dispersed material used for the matrix | χ ⁽³⁾ | / 2 times or larger α | χ ⁽³⁾ | is because / alpha performance is obtained. Further, the reason why the refractive index is 4 or less is that when the refractive index exceeds 4, the optical loss due to reflection increases and it is difficult to prevent reflection. The refractive index is preferably 2.0 or more and 3.5 or less.

The reason why an optically isotropic matrix is used is that if the matrix has optical anisotropy, the optical characteristics such as refraction, absorption, and reflection differ depending on the direction, which causes the nonlinear characteristics to also differ depending on the direction. Is caused, which causes a problem in use.

The reason why the transparent matrix is used is that the metal fine particle dispersion material is used in the wavelength region near the surface plasmon resonance absorption peak of the metal fine particles where the non-linearity increases, but when the absorption of the matrix exists near this absorption peak. This is because the incident light is lost by this absorption, the light absorption coefficient (α) is increased, and the | χ ⁽³⁾ | / α is decreased, which is not preferable. Regarding the transparency of the matrix, it is preferable that the light absorption coefficient α is 10 cm ⁻¹ or less in the surface plasmon resonance absorption peak wavelength region of the metal fine particles.

Regarding the type of glass used for the matrix, the first glass (oxide glass) is composed of B ₂ O ₃ and PbO as essential components, and the amount of B ₂ O ₃ is 15 to 5.
A glass is 0 mol% and the amount of PbO is 50 to 85 mol%. The reasons for limiting the amounts of B ₂ O ₃ and PbO as described above are as follows. That B is lower than the amount of ₂ O ₃ is 15 mol% is difficult vitrification, it is not preferable because crystallization becomes opaque and B ₂
This is because if the amount of O ₃ exceeds 50 mol%, the refractive index is lowered and a refractive index of 1.9 or more cannot be obtained. Therefore, B
The amount of ₂ O ₃ is limited to 15-50 mol%. The amount of B ₂ O ₃ is preferably 15-40 mol%. Also, PbO
If the amount is less than 50 mol%, the refractive index decreases, and the refractive index is 1.
No more than 9 can be obtained. Also, the amount of PbO is 85 mol
If it exceeds%, vitrification is difficult, and crystallization becomes opaque, which is not preferable. Therefore, the amount of PbO is 50-
Limited to 85 mol%. The amount of PbO is 55-85 mol
% Is preferred.

In this glass, SiO ₂ , GeO ₂ , Al ₂ O ₃ , In ₂ O ₃ ZrO are added as additional components.
₂ Y ₂ O ₃ , SnO, Sb ₂ O ₃ or their corresponding fluorides can be contained in a proportion of 10 mol% or less, if necessary.

As the second glass (oxide glass),
The essential constituents are Ga ₂ O ₃ , Bi ₂ O ₃ , PbO and / or CdO, and the amount of Ga ₂ O ₃ is 10 to 35 mol.
%, The amount of Bi ₂ O ₃ is 10 to 70 mol%, P
A glass having a total content of bO and CdO of 20 to 80 mol% can be mentioned. If the amount of Ga ₂ O ₃ is less than 10 mol%, vitrification is difficult and crystallization becomes opaque, which is not preferable. Further, when the amount of Ga ₂ O ₃ exceeds 35 mol%, the refractive index is lowered and the refractive index of 1.9 or more cannot be obtained. Therefore, the amount of Ga ₂ O ₃ is limited to 10 to 35 mol%. Ga ₂
The amount of O ₃ is preferably 10 to 30 mol%. Bi ₂
When the amount of O ₃ is less than 10 mol%, the refractive index is lowered and the refractive index of 1.9 or more cannot be obtained. Moreover, the amount of Bi ₂ O ₃ is 7
When it exceeds 0 mol%, vitrification is difficult, and it is crystallized and becomes opaque, which is not preferable. Therefore, the amount of Bi ₂ O ₃ is 1
It is limited to 0 to 70 mol%. The amount of Bi ₂ O ₃ is 20 to 7
It is preferably 0 mol%. If the total amount of PbO and CdO is less than 20 mol% or more than 80 mol%, vitrification is difficult and crystallization becomes opaque, which is not preferable. Therefore, the total amount of PbO and CdO is 20-80 mol.
Limited to%. The total amount of PbO and CdO is 20-70 m
It is preferably ol%.

In this glass, SiO ₂ , GeO ₂ , Al ₂ O ₃ , In ₂ O ₃ and Zr are added as additional components.
O ₂ Y ₂ O ₃ , SnO, Sb ₂ O ₃ or their corresponding fluorides can be contained, if desired, in a proportion of 10 mol% or less.

As the third glass (oxide glass),
The essential constituents are Bi ₂ O ₃ and / or PbO, and Zn
It is at least one selected from O, BaO, CdO and Al ₂ O ₃ , and the total amount of Bi ₂ O ₃ and PbO is 30 to 85.
Examples of the glass include mol%, and the total amount of ZnO, BaO, CdO, and Al ₂ O ₃ is 15 to 70 mol%. Bi
_{When the} total amount of ₂ O ₃ and PbO is less than 30 mol%, the refractive index is lowered and the refractive index of 1.9 or more cannot be obtained. Also Bi ₂ O ₃
If the total amount of PbO and PbO exceeds 85 mol%, vitrification is difficult and crystallization becomes opaque, which is not preferable. Therefore, the total amount of Bi ₂ O ₃ and PbO is limited to 30 to 85 mol%. The total amount of Bi ₂ O ₃ and PbO is preferably 40 to 85 mol%. In addition, ZnO, BaO, CdO, Al
_{If the} total amount of ₂ O ₃ is less than 15 mol%, vitrification is difficult and crystallization becomes opaque, which is not preferable. Also, Z
When the total amount of nO, BaO, CdO and Al ₂ O ₃ exceeds 70 mol%, the refractive index is lowered and the refractive index of 1.9 or more cannot be obtained. Therefore, the total content of ZnO, BaO, CdO and Al ₂ O ₃ is limited to 15 to 70 mol%. The total amount of ZnO, BaO, CdO and Al ₂ O ₃ is preferably 15 to 60 mol%.

In this glass, B ₂ O ₃ , SiO ₂ , GeO ₂ , In ₂ O ₃ and ZrO are added as additional components.
₂ , Y ₂ O ₃ , SnO, Sb ₂ O ₃ or their corresponding fluorides can be contained, if necessary, in a proportion of 10 mol% or less.

As the fourth glass (oxide glass),
The essential constituents are GeO ₂ and Bi ₂ O 3, T1 ₂ O and P
at least one selected from bO, the amount of GeO ₂ is 25 to 70 mol%, Bi ₂ O ₃ , T1 ₂ O and Pb
A glass in which the total amount of O is 30 to 75 mol% is mentioned. If the amount of GeO ₂ is less than 25 mol% or more than 70 mol%, vitrification is difficult and crystallization becomes opaque, which is not preferable. Therefore, the amount of GeO ₂ is 25 to 70 mo
Limited to l%. The amount of GeO ₂ is preferably 25 to 65 mol%. Further, when the total amount of Bi ₂ O ₃ , T1 ₂ O and PbO is less than 30 mol%, the refractive index is lowered and the refractive index is 1.
No more than 9 can be obtained. Also, Bi ₂ O ₃ and T1 ₂ O and P
If the total amount of bO exceeds 75 mol%, vitrification is difficult, and crystallization becomes opaque, which is not preferable. Therefore B
The total amount of i ₂ O ₃ , T1 ₂ O and PbO is limited to 30 to 75 mol%. The total amount of Bi ₂ O ₃ , T1 ₂ O and PbO is 35.
It is preferably ˜75 mol%.

In this glass, B ₂ O ₃ , SiO ₂ , Al ₂ O 3, In ₂ O ₃ and Zr are added as additional components.
O ₂ , Y ₂ O ₃ , SnO, Sb ₂ O ₃ or their corresponding fluorides can be contained in a proportion of 10 mol% or less, if necessary.

As the fifth glass (oxide glass),
The essential constituents are TiO ₂ and PbO, the amount of TiO ₂ is 30 to 75 mol%, and the amount of PbO is 25 to 70 m.
Examples of the glass include ol%. The amount of TiO ₂ is 30 mo
If it is less than 1% or exceeds 75 mol%, it is difficult to vitrify, and it is crystallized and becomes opaque, which is not preferable. Therefore, the amount of TiO ₂ is limited to 30 to 70 mol%. TiO ₂
The amount of is preferably 40 to 65 mol%. Also, P
If the amount of bO is less than 25 mol% or more than 70 mol%, vitrification is difficult, and crystallization becomes opaque, which is not preferable. Therefore, the amount of PbO is limited to 25 to 70 mol%. The amount of PbO is preferably 35-60 mol%.

In this glass, B ₂ O ₃ , SiO ₂ , GeO ₂ , Al ₂ O ₃ and In ₂ are added as additional components.
O ₃ , ZrO ₂ , Y ₂ O ₃ , SnO, Sb ₂ O ₃ or their corresponding fluorides can be contained in a proportion of 10 mol% or less, if necessary.

As the sixth glass (oxide glass),
The essential constituents are TeO ₂ and / or Sb ₂ O ₃ , and P
bO, and the total amount of TeO ₂ and Sb ₂ O ₃ is 20 to 95 mo.
1%, and the amount of PbO is 5 to 80 mol%. If the total content of TeO ₂ and / or Sb ₂ O ₃ is less than 20 mol% or more than 95 mol%, vitrification is difficult and crystallization becomes opaque, which is not preferable. Therefore, the total amount of TeO ₂ and Sb ₂ O ₃ is 20 to 95 mol.
Limited to%. The total amount of TeO ₂ and Sb ₂ O ₃ is 25 to 9
It is preferably 0 mol%. Also, the amount of PbO is 5 m
If it is less than ol% or exceeds 80 mol%, vitrification is difficult, and crystallization becomes opaque, which is not preferable. Therefore, the amount of PbO is limited to 5-80 mol%. PbO
The amount of is preferably 10 to 75 mol%.

In this glass, Li ₂ O, Na ₂ O, BaO, WO ₃ , ZrO ₂ or their corresponding fluorides are added as an additional component in an amount of 10 mol% if necessary.
It can be contained in the following proportions.

As the seventh glass (oxide glass),
The essential constituents are TeO ₂ and / or Sb ₂ O ₃ , and B
at least one selected from aO, BeO, MgO, SrO, ZnO and CdO, and TeO ₂ and Sb ₂ O ₃
The total content of BaO, BeO and M is 60 to 98 mol%.
The total amount of gO, SrO, ZnO, and CdO is 2 to 40 mol%
The glass that is If the total amount of TeO ₂ and Sb ₂ O ₃ is less than 60 mol%, the refractive index is lowered and the refractive index of 1.9 or more cannot be obtained. _{On the} other hand, if the total amount of TeO ₂ and Sb ₂ O ₃ exceeds 98 mol%, vitrification is difficult and crystallization becomes opaque, which is not preferable. Therefore, TeO ₂ and S
The total amount of b ₂ O ₃ is limited to 60 to 98 mol%. TeO
_The total amount of ₂ and Sb ₂ O ₃ is preferably 65 to 98 mol%. In addition, BaO, BeO, MgO, SrO, ZnO
If the total amount of CdO and CdO is less than 2 mol%, vitrification is difficult and crystallization becomes opaque, which is not preferable. Also, B
If the total amount of aO, BeO, MgO, SrO, ZnO, and CdO exceeds 40 mol%, the refractive index decreases, and the refractive index is 1.9.
The above cannot be obtained. Therefore, BaO, BeO and Mg
The total amount of O, SrO, ZnO and CdO is limited to 2 to 40 mol%. BaO, BeO, MgO, SrO, ZnO
The total amount of CdO and CdO is preferably 2-35 mol%.

In this glass, B ₂ O ₃ , SiO ₂ , GeO ₂ , Al ₂ O ₃ and In ₂ are added as additional components.
O ₃ , ZrO ₂ , Y ₂ O ₃ , SnO or their corresponding fluorides can be contained in a proportion of 10 mol% or less, if necessary.

As the eighth glass (oxide glass),
The essential constituents are Bi ₂ O ₃ and CdO and / or Zn
O and at least one selected from B ₂ O ₃ , SiO ₂ and P ₂ O ₅ , and the amount of Bi ₂ O ₃ is 10 to 90 mol.
%, The total amount of CdO and ZnO is 5 to 85 mol%, and the total amount of B ₂ O ₃ , SiO ₂ and P ₂ O ₅ is 1 to 30 mol%.
The glass that is The amount of Bi ₂ O ₃ is 90 mol%
If it exceeds, vitrification is difficult and crystallization becomes opaque, which is not preferable. Also, the amount of Bi ₂ O ₃ is 10 mol%
If it is less than 1, the refractive index is lowered, and a refractive index of 1.9 or more cannot be obtained. Therefore, the amount of Bi ₂ O ₃ is limited to 10 to 90 mol%. The amount of Bi ₂ O ₃ is preferably 20-80 mol%. Further, when the total amount of CdO and ZnO exceeds 85 mol%, the refractive index is lowered and the refractive index of 1.9 or more cannot be obtained. Further, if the total amount of CdO and ZnO is less than 5 mol%, vitrification is difficult, and crystallization becomes opaque, which is not preferable. Therefore, the total amount of CdO and ZnO is 5-85 m
Limited to ol%. The total amount of CdO and ZnO is 10-80
It is preferably mol%. On the other hand, if the total amount of B ₂ O ₃ , SiO ₂ and P ₂ O ₅ is less than 1 mol% or more than 30 mol%, vitrification is difficult and crystallization becomes opaque, which is not preferable. Therefore, the total amount of B ₂ O ₃ , SiO ₂ and P ₂ O 5 is limited to 1 to 30 mol%. B ₂ O ₃ and SiO ₂ and P ₂ O
The total amount of ₅ is preferably 2 to 25 mol%.

In this glass, GeO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZrO ₂ and Y ₂ are added as additional components.
O ₃ , SnO, Sb ₂ O ₃ or their corresponding fluorides can be contained, if necessary, in a proportion of 10 mol% or less.

In addition, using the above-mentioned first to eighth glasses,
When the nonlinear optical material is produced by the melting / heat treatment method, SnO and / or Sb ₂ O ₃ (thermal reducing agent) can be contained as an additional component in a proportion of 10 mol% or less, if necessary. In addition, when a nonlinear optical material is manufactured by the ion exchange method, an alkali metal oxide (Li
2O, Na ₂ O, K ₂ O: ions to be exchanged) can be contained in a proportion of 10 mol% or less, if necessary.

9th glass (chalcogenide glass)
The essential constituents are at least one selected from As, Ge and Sb and at least one selected from S, Se and Te, and the total amount of As, Ge and Sb is 1
0 to 60 at% and the total amount of S, Se and Te is 90 to 4
The glass is 0 at%. If the total amount of As, Ge and Sb is less than 10 at% or more than 60 at%, vitrification becomes difficult and crystallization becomes opaque, which is not preferable. Therefore, the total amount of As, Ge, and Sb is 10 to 60 at%
Limited to The total amount of As, Ge and Sb is 15 to 55 at
% Is preferred. The total amount of S, Se and Te is 40 at%
If less than or more than 90 at%, vitrification becomes difficult,
It is not preferable because it crystallizes and becomes opaque. Therefore S and S
The total amount of e and Te is limited to 90 to 40 at%. S and S
The total amount of e and Te is preferably 85 to 45 at%.

The glass used for the matrix has been described above. Next, the crystal used for the matrix will be described. As crystals used for the matrix, ZnS, ZnS
e, ZnTe, CuCl, CuBr, CuI, TlI,
CsPbCl ₃ , AgGaSe ₂ , As ₂ S ₃ , Tl ₃ Ta
S ₄ , Tl ₃ TaSe ₄ , Tl ₃ VS ₄ , CdS, CdS
e, PbS, GaSe, GaP, diamond, Y
₂ O ₃ , La ₂ O ₂ S, SrTiO ₃ , K (Ta, Nb)
O ₃ , Tl ₃ TaSe ₄ , Bi ₂ WO ₆ , Bi ₄ Ti ₃ O ₁₂ ,
_{Bi 4 Ge 3 O 12, Bi} 4 Si 3 O 12, Y 3 Ga 5 O 12, Gd
₃ Ga ₅ O ₁₂ , (Ga, Al) As, Ga (As, P),
Bi ₁₂ GeO ₂₀ , Bi ₁₂ SiO ₂₀ , CoFe ₂ O ₄ , Pb
GeO ₃ , Pb (Mg _1/3 , Nb _2/3 ) O ₃ , Pb (Mg
_1/3 , Ta _2/3 ) O ₃ , Pb (Zn _1/3 , Nb _2/3 ) O ₃ ,
At least one selected from (Pb, La) (Zr, Ti) O ₂ and ZnWO 4 is used. The reason for using these crystals is that these crystals have a refractive index of 1.9 or more and 4 or less, and are optically isotropic, and in the vicinity of the surface plasmon resonance absorption peak of the metal fine particles dispersed in these crystals. This is because the light absorption has transparency of α = 10 cm ⁻¹ or less. As the crystal used for the matrix, ZnS,
ZnSe, CuCl, CuBr, GaP, _{diamond, Y2O 3, K (Ta,} Nb) O 3, Bi 2 WO 6, Bi 4
_{Ti 3 O 12, Bi 4 Ge} 3 O 12, Bi 4 Si 3 O 12, Y 3 G
_{a 5 O 12, Gd 3 Ga} 5 O 12 ,, Bi 12 GeO 20, Bi 1 2
At least one selected from SiO ₂₀ , PbGeO ₃ and ZnWO ₄ is particularly preferable. Next, the dispersed metal fine particles in the nonlinear optical material of the present invention will be described in detail.

The increase in nonlinearity in the nonlinear optical material of the present invention is caused by the concentration effect of the local electric field due to the dielectric confinement of the matrix, resulting in a large nonlinear susceptibility (| χ
⁽³⁾ |) is expressed.

First, the dispersed metal fine particles are copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium,
Iridium, iron, ruthenium, osmium, manganese,
Molybdenum, tungsten, niobium, tantalum, titanium, bismuth, antimony, lead, or alloys thereof,
Alternatively, at least one selected from alloys containing 80 mol% or more of these is used. The reason for limiting to these metals is 300 to 20 used as a non-linear optical element.
This is because it has a light absorption peak due to surface plasmon resonance of the metal fine particles in the wavelength range of 00 nm. As the metal used for the dispersed fine particles, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten or an alloy thereof, or 80 mol% thereof It is more preferable to use at least one selected from the alloys described above. As the metal used for the dispersed fine particles, it is particularly preferable to use at least one selected from copper, silver, gold, platinum, palladium, nickel, tin or alloys thereof, or alloys containing 80 mol% or more of these.

The fine metal particles cause surface plasmon resonance absorption at a frequency (wavelength) satisfying the condition of the equation (1).

Ε _m ′ (ω) = − ² ε _d (ε _d = n ² ) (1) ε _m ′ (ω): Real part of dielectric constant of fine metal particles at a certain frequency ε _d : Dielectric constant of matrix: of matrix Refractive index

From the equation (1), it can be seen that ε _d is increased by increasing n. Then, resonance absorption occurs at a frequency at which the relation of the expression (1) is established between the ε _d and the ε _m ′ (ω). In general, in metals, ε _m ′ (ω) increases negatively with increasing wavelength, so increasing the refractive index n of the matrix and increasing ε _d causes the surface plasmon resonance absorption position by the metal fine particles to shift to the long wavelength side. To do. In the case of copper, silver, gold, tin, manganese, etc., a conventional matrix (refractive index: 1.5 to 1.
Although resonance absorption exists in the visible light region even when 8) is used,
By using a matrix of 1.9 or more and 4 or less, it is possible to shift to the long wavelength side of several tens to several hundreds of nm, and it is possible to use at longer wavelengths. On the other hand, when platinum, palladium, nickel, cobalt, rhodium, iridium, etc. are used in the conventional matrix, the resonance absorption exists in the ultraviolet region of a wavelength shorter than the absorption edge of the matrix, and it is impossible to use it as a nonlinear optical material. . However, by using a matrix of 1.9 or more and 4 or less, absorption shifts to the visible light region even in these metals, and it becomes possible to use it as a nonlinear optical material.

Regarding the non-linear characteristic, in the present invention,
χ ⁽³⁾ | / α is expressed as in equation (2).

| Χ ⁽³⁾ | / α = nc / ω (9n ⁴ / | ε _m ″ | ³ ) | χ _m ⁽³⁾ | (2) χ ⁽³⁾ : third-order nonlinear susceptibility α: optical absorption Coefficient c: Speed of light ω: Frequency ε _m ″: Imaginary part of dielectric constant of fine metal particles χ _m ⁽³⁾ : Third-order nonlinear susceptibility of fine metal particles themselves

As can be seen from the equation (2), when the refractive index of the matrix is increased, | χ ⁽³⁾ | / α increases. In addition to this, there is ε _m ″ as a factor for increasing | χ ⁽³⁾ | / α. Resonance absorption shifts to a longer wavelength by increasing the refractive index, and due to the wavelength dependence of ε _m ″, The smaller ε _m ″, the larger | χ ⁽³⁾ | / α. Copper and gold can be cited as the metals applicable to this.
Therefore, in addition to the effect of increasing the refractive index of copper and gold, the effect due to the wavelength dependence of ε _m ″ is added, and | χ ⁽³⁾ | / α is greatly increased.

Further, the radius of the dispersed metal particles is 1 to 10
The reason why 0 nm is preferable is as follows. ｜ χ ⁽³⁾
The value of | / α is inversely proportional to the cube of the imaginary part of the dielectric constant of the metal fine particles, as can be seen from the equation (2). Further, the imaginary part of the dielectric constant of the metal fine particles increases as the size of the metal fine particles becomes smaller.
Therefore, in order to obtain a nonlinear optical material having a large value of | χ ⁽³⁾ | / α, it is preferable that the metal fine particles are large. However, when the radius of the dispersed metal fine particles is 100 nm or more, | χ ⁽³⁾ | / α decreases due to light scattering or the like, which is not preferable. Also, when the radius of the dispersed metal fine particles becomes less than 1 nm, the imaginary part of the dielectric constant of the metal fine particles increases, so that | χ ⁽³⁾ | / α
Is extremely reduced, and the difference from the conventional metal fine particle dispersed material using phosphate glass is insufficient, which is not preferable. Therefore, the radius of the dispersed metal fine particles is limited to 1 to 100 nm. The radius of the dispersed metal fine particles is preferably 3 to 50 nm.

Next, the method for producing the nonlinear optical material of the present invention will be described in detail.

For producing the nonlinear optical material of the present invention, melting
A thermal deposition method, an ion implantation method, an ion exchange method or a sputtering method is used.

In the case of the melting / thermal deposition method, when the starting material for the glass and the starting material for the metal fine particles and the metal fine particles are deposited, they have a thermal reducing action, so that the metal fine particles can be deposited accurately. And / or Sb ₂ O ₃ which is a component of
After heating and melting a mixture containing and to form a glass melt, the glass melt is cooled to room temperature to obtain a uniform glass in which the metal element is dissolved in the matrix in the form of ions or atoms, and then this glass Can be heated from room temperature to a predetermined temperature and heat-treated at this predetermined temperature to precipitate fine metal particles in the matrix glass.

Each metal and a compound of each metal can be used as a starting material for the metal fine particles. As the copper compound, C
u ₂ O, oxides such as CuO, CuF, CuCl, CuB
Halides such as r and CuI, and carbonates such as CuCO ₃ can be used. Further, as the silver compound, Ag
₂ O, oxides such as AgO, AgF, AgCl, AgB
R, halides such as AgI, carbonates such as AgCO _{3 and the} like can be used. As the gold compound, Au
₂ O _{3 and} other oxides, AuBr ₃ , AuCl ₃ , AuHCl ₄
And the like can be used. In addition, organometallic compounds of copper and silver can be used. Also,
Also in compounds of other metals, compounds similar to the above-mentioned copper, silver and gold can be used. Further, it is possible to contain the above metal compound in a ratio of 0.1 to 10 mol% when converted to a simple metal.

SnO and / or Sb ₂ O ₃ can be used as a component that has a thermal reducing action when the metal fine particles are deposited and is used for appropriately depositing the metal fine particles. The amount is preferably 0.1 to 10 mol%.

The deposition of the metal fine particles is carried out in a temperature range in which the metal fine particles are deposited, for example, Sn ions (derived from SnO) and / or metal ions derived from the metal and the metal compound added at 200 to 1000 ° C. and having a reducing action. Sb
It is based on the fact that a metal atom is generated by reacting with an ion (derived from Sb ₂ O ₃ ), and then the metal atom aggregates to form a crystal nucleus, and the crystal grows.

In the ion implantation method, an ordinary ion implantation apparatus is used to implant metal ions into the glass and / or crystal matrix at a high speed so that the glass and / or crystal matrix contains a metal component. According to the above, heat treatment may be performed to generate and disperse the metal fine particles in the glass and / or crystal matrix.

In the ion exchange method, the material containing the exchanged ions (eg, alkali ions) contained in the glass matrix is used to exchange the exchanged ions with the metal ions by a dry method or a wet method. By so doing, it is possible to cause the glass matrix to contain a metal component and, if necessary, perform heat treatment to generate and disperse the metal fine particles in the glass matrix.

In the sputtering method, the glass and / or crystal matrix and the metal are alternately or simultaneously vapor-deposited on a substrate (for example, quartz glass) using an ordinary sputtering apparatus to deposit a material containing a metal component. It is possible to produce and disperse the metal fine particles in the glass and / or crystal matrix by preparing and performing heat treatment as necessary.

Next, the non-linear optical element of the present invention can be manufactured in various forms (for example, by using the above-mentioned non-linear optical material).
Fabry-Perot resonator type, waveguide type, optical Kerr shutter type) optical switch element. By using the above-mentioned non-linear optical material, it is possible to provide a non-linear optical element which maintains high optical quality and has extremely fast response performance and good non-linear optical performance.

[0055]

The nonlinear optical material of the present invention having the above structure has a radius of 1 to 100 n in an optically isotropic and transparent glass and / or crystal having a refractive index of 1.9 or more and 4 or less.
m has a structure in which fine metal particles are dispersed, and such fine metal particles that are sufficiently smaller than the wavelength of light in the matrix have a large nonlinear susceptibility (due to the effect of the local electric field due to the dielectric confinement of the matrix ( ｜ χ ⁽³⁾ ｜)
Is expressed. Furthermore, by increasing the refractive index of the matrix, a large | χ ⁽³⁾ | due to the effect of the refractive index and the wavelength dependence of the imaginary part of the dielectric constant of the metal fine particles
/ Α is obtained. Due to the above action, the material of the present invention has a performance of | χ ⁽³⁾ | / α that is at least twice as large as that of the conventional metal fine particle dispersed material, and by using the nonlinear optical material of the present invention, It becomes possible to fabricate a non-linear optical element that can operate at the light intensity of a semiconductor laser.

[0056]

EXAMPLES Examples of the present invention will be described below.

Example 1 (1 described above as a matrix
The second glass is used) As a raw material for the glass to be the matrix, a composition comprising 29 mol% B ₂ O ₃ and 71 mol% PbO is used,
To 100 mol% of this composition, 2 mol% of SnO was mixed as a thermal reducing component, and 1 mol% of Cu ₂ O ( ₂ mol% as Cu) was mixed as a raw material of copper fine particles. After heating at 1,000 ° C. for 15 minutes to form a uniform glass melt, it was cast on an iron plate to obtain colorless and transparent glass.

Next, the obtained glass is preliminarily subjected to 37
When the glass was placed in an electric furnace kept at 0 ° C. and heat-treated at this temperature for 1 hour, the glass was colored blue.

When the refractive index of this matrix glass was measured, it was n _d = 2.07. When the glass thus obtained was measured by the X-ray diffraction method,
A copper metal crystal peak was observed, and it was confirmed that a glass containing copper particles dispersed therein was obtained. Furthermore, when the size of the copper fine particles contained in the copper fine particle-dispersed glass was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius of the copper fine particles was 29.8 nm.

Further, the obtained copper fine particle-dispersed glass was used for 15
When the optical absorption spectrum was measured by optical polishing to a thickness of μm, a sharp absorption peak of surface plasmon resonance of copper was confirmed as shown by the solid line 1 in FIG. In addition, the light absorption peak position is 608 nm, which is 35 in comparison with the light absorption peak position 573 nm of the conventional copper fine particle dispersed glass (Comparative Example 1) using the phosphate glass shown in FIG.
The wavelength was shifted to the longer wavelength side by about nm, and the effect of increasing the refractive index of the matrix material was observed. The nonlinear susceptibility was measured at room temperature by the degenerate four-wave mixing method at a wavelength near the optical absorption peak, and the value of | χ ⁽³⁾ | / α was 1.2 × 10 ^-10 esu · cm (| χ ⁽³⁾ | = 2.4 × 10 ^-7 es
u, α = 2000 cm ⁻¹ ), and the value of | χ ⁽³⁾ | / α of the conventional copper fine particle-dispersed glass (Comparative Example 1, fine particle radius 29.0 nm) using phosphate glass as a matrix. The value was more than 4 times 8 × 10 ^-11 esu.

Example 2 (The above 2 was used as a matrix.
The second glass is used.) As a raw material for the glass to be the matrix, a composition consisting of 18 mol% Ga ₂ O ₃ , 25 mol% Bi ₂ O ₃ and 57 mol% PbO was used. 2 mol% Sb ₂ O ₃ as a thermal reducing component,
A mixture of ol% Cu ₂ O (2 mol% as Cu) as a raw material for fine copper particles was heated to 1,050 ° C in a refractory crucible.
After heating for 15 minutes to obtain a uniform glass melt,
A colorless and transparent glass was obtained by casting on an iron plate. Then, when this glass was heat-treated at 430 ° C. for 1 hour, the glass was colored.

The refractive index of this matrix glass was measured and found to be n _d = 2.27. When the glass thus obtained was measured by the X-ray diffraction method,
A copper metal crystal peak was observed, and it was confirmed that a glass containing copper particles dispersed therein was obtained. Furthermore, when the size of the copper fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 15.0 nm. Furthermore, the light absorption characteristics of this copper fine particle-dispersed glass are shown in Example 1.
The light absorption peak position was 62 when measured in the same manner as
It was 0 nm. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 3.2.
× 10 ^-10 esu · cm (| χ ⁽³⁾ ｜ = 4.0 × 10 ^-7 esu, α
= 1250 cm ⁻¹ ), which is 11 times or more of | χ ⁽³⁾ | / α (Comparative Example 1) of copper fine particle-dispersed glass using phosphate glass as a matrix.

Example 3 (The above 2 was used as a matrix.
The second glass is used) Same as in Example 2 except that a composition of 13 mol% Ga ₂ O ₃ , 61 mol% Bi ₂ O ₃ and 26 mol% CdO is used as a raw material for the glass serving as the matrix. To obtain glass. Then, when this glass was heat-treated at 430 ° C. for 1 hour, the glass was colored.

When the refractive index of this matrix glass was measured, it was found that n _d = 2.21. When the glass thus obtained was measured by the X-ray diffraction method,
A copper metal crystal peak was observed, and it was confirmed that a glass containing copper particles dispersed therein was obtained. Furthermore, when the size of the copper fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 15.3 nm. Furthermore, the light absorption characteristics of this copper fine particle-dispersed glass are shown in Example 1.
The light absorption peak position was 61 when measured in the same manner as
It was 6 nm. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 2.8.
× 10 ^-10 esu ・ cm (| χ ⁽³⁾ ｜ = 3.4 × 10 ^-7 esu, α
= 1210 cm ^-1 ), which is 10 times or more of | χ ⁽³⁾ | / α (Comparative Example 1) of the copper fine particle-dispersed glass using phosphate glass as a matrix.

Example 4 (The above 2 was used as a matrix.
The second glass was used.) As a raw material for the glass to be the matrix, a composition consisting of 13 mol% Ga ₂ O ₃ , 25 mol% Bi ₂ O ₃ , 57 mol% PbO and 5 mol% B ₂ O ₃ was used. A glass was obtained in the same manner as in Example 3 except for the above. Then, when this glass was heat-treated at 440 ° C. for 1 hour, the glass was colored.

When the refractive index of this matrix glass was measured, it was found that n _d = 2.24. When the glass thus obtained was measured by the X-ray diffraction method,
A copper metal crystal peak was observed, and it was confirmed that a glass containing copper particles dispersed therein was obtained. Furthermore, when the size of the copper fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 14.8 nm. Furthermore, the light absorption characteristics of this copper fine particle-dispersed glass are shown in Example 1.
The light absorption peak position was 61 when measured in the same manner as
It was 9 nm. Further, when the non-linear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 3.0.
× 10 ^-10 esu ・ cm (| χ ⁽³⁾ ｜ = 5.6 × 10 ^-7 esu, α
= 1860 cm ⁻¹ ), which is 10 times or more of | χ ⁽³⁾ | / α (Comparative Example 1) of the copper fine particle-dispersed glass using phosphate glass as a matrix.

Example 5 (The above 2 was used as a matrix.
The second glass was used) A glass having the same composition was obtained in the same manner as in Example 3. However, C
₂ mol% Ag ₂ O instead of u ₂ O (4 mol as Ag
%) Was used. Then, when this glass was heat-treated at 420 ° C. for 1 hour, the glass was colored.

When the glass thus obtained was measured by the X-ray diffraction method, a silver metal crystal peak was observed, and it was confirmed that a silver fine particle dispersed glass was obtained.
Furthermore, when the size of the silver fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 14.3 nm. Further, the light absorption characteristics of this silver fine particle-dispersed glass were measured in the same manner as in Example 1. The light absorption peak position was 516 nm and the conventional silver fine particle-dispersed glass using phosphate glass as a matrix (Comparative Example 2). Compared with the light absorption peak position of 430 nm, the wavelength was shifted to the longer wavelength side by about 86 nm, and the effect of increasing the refractive index of the matrix material was observed. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 6.1 × 10 ⁻¹¹ esu · cm (| χ ⁽³⁾ | = 9.2 ×. 10
^-8 esu, α = 1510 cm ⁻¹ ), and the value of | χ ⁽³⁾ | / α of the conventional silver fine particle-dispersed glass (Comparative Example 2, fine particle radius 15.3 nm) using phosphate glass as the matrix. It has a value more than twice as large as 2.7 × 10 ⁻¹¹ esu.

Example 6 (The above 2 was used as a matrix.
The second glass was used) A glass having the same composition was obtained in the same manner as in Example 3. However, C
1 mol% AuCl ₃ instead of u ₂ O (1 mol as Au
%) Was used. Then, when this glass was heat-treated at 470 ° C. for 1 hour, the glass was colored.

When the glass thus obtained was measured by the X-ray diffraction method, a gold metal crystal peak was observed, and it was confirmed that a glass containing fine gold particles was obtained.
Furthermore, when the size of the fine gold particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 15.1 nm. Further, the obtained gold fine particle-dispersed glass was optically polished to a thickness of 200 μm, and its light absorption spectrum was measured. As a result, the light absorption peak position was 591.
nm of a conventional fine gold particle-dispersed glass (comparative example 3) using a nanometer and a phosphate glass as a matrix, the light absorption peak position 545.
It is shifted to the long wavelength side by about 46 nm compared to nm,
The effect of increasing the refractive index of the matrix material was observed. Further, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 2.6 × 10 ⁻¹¹ esu · cm (|
χ ⁽³⁾ | = 3.9 × 10 ⁻⁹ esu, α = 150 cm ⁻¹ ), and a conventional gold fine particle dispersed glass using a phosphate glass as a matrix (Comparative Example 3, fine particle radius 14.9 nm).
The value of | χ ⁽³⁾ | / α of 5.0 × 10 ⁻¹² esu or more.

Example 7 (3 described above as a matrix
The second glass is used) As a raw material for the glass to be the matrix, 38 mol% Bi ₂ O ₃ , 34 mol% PbO, 14 mol% ZnO and 1
Using a composition consisting of 4 mol% of BaO, 100 mol% of this composition, 5 mol% of SnO as a thermal reducing component, and 6 mol% of Cu as a raw material of copper fine particles were mixed to obtain fire resistance. After heating in a crucible at 1,100 ° C. for 15 minutes to form a uniform glass melt, it was cast on an iron plate to obtain colorless and transparent glass. Then, when this glass was heat-treated at 420 ° C. for 16 hours, the glass was colored.

The refractive index of this matrix glass was measured and found to be n _d = 2.50. When the glass thus obtained was measured by the X-ray diffraction method,
A copper metal crystal peak was observed, and it was confirmed that a glass containing copper particles dispersed therein was obtained. Furthermore, when the size of the copper fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 35.2 nm. Furthermore, the light absorption characteristics of this copper fine particle-dispersed glass are shown in Example 1.
The light absorption peak position was 65 when measured in the same manner as
It was 0 nm. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 8.1.
× 10 ^-10 esu ・ cm (| χ ⁽³⁾ ｜ = 2.5 × 10 ^-6 esu, α
= 3100 cm ^-1 ), which is 28 times or more of | χ ⁽³⁾ | / α (Comparative Example 1) of the copper fine particle-dispersed glass using a phosphate glass as a matrix.

Example 8 (The above 3 was used as a matrix.
The second glass is used) As a raw material for the glass to be the matrix, 26 mol% Bi ₂ O ₃ , 39 mol% PbO, 23 mol% CdO and 1
Example 7 using a composition consisting of 1 mol% Al ₂ O _3.
A glass was obtained in the same manner as in. However, 1 mol% AuCl ₃ (1 mol% as Au) was used instead of Cu ₂ O, and 2 mol% Sb ₂ O ₃ was used instead of SnO. Then, when this glass was heat-treated at 450 ° C. for 3 hours, the glass was colored.

When the refractive index of this matrix glass was measured, it was n _d = 2.42. When the glass thus obtained was measured by the X-ray diffraction method,
A gold metal crystal peak was observed, and it was confirmed that a glass containing fine gold particles was obtained. Furthermore, when the size of the fine gold particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 16.1 nm. Furthermore, the light absorption characteristics of this gold fine particle-dispersed glass are shown in Example 6.
The light absorption peak position was 62 when measured in the same manner as
It was 8 nm. Further, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 5.2.
× 10 ^-11 esu · cm (| χ ⁽³⁾ ｜ = 9.7 × 10 ^-9 esu, α
= 187 cm ⁻¹ ), which is 10 times or more of | χ ⁽³⁾ | / α (Comparative Example 3) of the gold fine particle-dispersed glass using a phosphate glass as a matrix.

Example 9 (4 above as matrix
The second glass is used.) As a raw material for the glass to be the matrix, a composition comprising 46 mol% GeO ₂ , 23 mol% Bi ₂ O ₃ and 31 mol% Tl ₂ O was used, and the composition was based on 100 mol% of the composition. 3 mol% SnO as a thermal reducing component, 3 mol%
% Cu ₂ O (6 mol% as Cu) was mixed as a raw material for the copper fine particles, and the mixture was heated in a refractory crucible at 1,000 ° C. for 15 minutes to form a uniform glass melt, which was then cast on an iron plate. Then, colorless and transparent glass was obtained. Then, when this glass was heat-treated at 320 ° C. for 2 hours, the glass was colored.

The refractive index of this matrix glass was measured and found to be n _d = 2.29. When the glass thus obtained was measured by the X-ray diffraction method,
A copper metal crystal peak was observed, and it was confirmed that a glass containing copper particles dispersed therein was obtained. Furthermore, when the size of the copper fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 10.8 nm. Furthermore, the light absorption characteristics of this copper fine particle-dispersed glass are shown in Example 1.
The light absorption peak position was 62 when measured in the same manner as
It was 1 nm. Further, when the non-linear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 2.7.
× 10 ^-10 esu ・ cm (| χ ⁽³⁾ ｜ = 5.7 × 10 ^-7 esu, α
= 2110 cm ⁻¹ ), which is 9 times or more of | χ ⁽³⁾ | / α (Comparative Example 1) of the copper fine particle-dispersed glass using phosphate glass as a matrix.

Example 10 (using the above-mentioned fourth glass as a matrix) As a raw material for a glass to be a matrix, 48 mol% of GeO ₂ , 8 mol% of Bi ₂ O ₃ and 28 mol% of Tl ₂ O were mixed with 1
A glass was obtained in the same manner as in Example 9 using a composition containing 6 mol% PbO. However, 6m instead of Cu ₂ O
ol% CuCl (6 mol% as Cu) was used. Then, when this glass was heat-treated at 300 ° C. for 5 hours, the glass was colored.

When the refractive index of this matrix glass was measured, it was found that n _d = 2.20. When the glass thus obtained was measured by the X-ray diffraction method,
A copper metal crystal peak was observed, and it was confirmed that a glass containing copper particles dispersed therein was obtained. Furthermore, when the size of the copper fine particles was measured by an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 12.2 nm. Furthermore, the light absorption characteristics of this copper fine particle-dispersed glass are shown in Example 1.
The light absorption peak position was 61 when measured in the same manner as
It was 3 nm. Further, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 2.4.
× 10 ^-10 esu · cm (| χ ⁽³⁾ ｜ = 4.7 × 10 ^-7 esu, α
= 1960 cm ⁻¹ ), which is 8 times or more of | χ ⁽³⁾ | / α (Comparative Example 1) of the copper fine particle-dispersed glass using a phosphate glass as a matrix.

Example 11 (Use of the Fourth Glass as the Matrix) As a raw material for the glass to be the matrix, a composition consisting of 51 mol% GeO ₂ , 24 mol% Tl ₂ O and 25 mol% PbO was used. A glass was obtained in the same manner as in Example 9. However, instead of Cu ₂ O, 2 mol% of Ag ₂ O (Ag
4 mol%) instead of SnO and 4 mol% of Sb ₂ O ₃
Was used. Then, when this glass was heat-treated at 310 ° C. for 2 hours, the glass was colored.

When the refractive index of this matrix glass was measured, it was found that n _d = 2.11. When the glass thus obtained was measured by the X-ray diffraction method,
A silver metal crystal peak was observed, and it was confirmed that a glass in which silver particles were dispersed was obtained. Furthermore, when the size of the silver fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 18.8 nm. Furthermore, the light absorption characteristics of this silver fine particle-dispersed glass are shown in Example 1.
When measured in the same manner as above, the light absorption peak position is 50
It was 3 nm. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 6.8.
× 10 ^-11 esu · cm (| χ ⁽³⁾ ｜ = 9.0 × 10 ^-8 esu, α
= 1330 cm ^-1 ), which is more than twice the value of | χ ⁽³⁾ | / α (Comparative Example 2) of silver fine particle-dispersed glass using phosphate glass as a matrix.

Example 12 (Use of the above-mentioned fifth glass as a matrix) As a raw material of a glass to be a matrix, a composition consisting of 40 mol% TiO ₂ and 60 mol% PbO was used,
0.5 mol% SnO based on 100 mol% of this composition
As a thermal reducing component, and 1 mol% CuCO ₃ (Cu
(1 mol%) as a raw material for copper fine particles is heated in a refractory crucible at 1,400 ° C. for 15 minutes to form a uniform glass melt, which is then cast on an iron plate to give a colorless, transparent glass. Got Then, this glass 5
When heat-treated at 20 ° C. for 3 hours, the glass was colored.

When the refractive index of this matrix glass was measured, it was n _d = 2.50. When the glass thus obtained was measured by the X-ray diffraction method,
A copper metal crystal peak was observed, and it was confirmed that a glass containing copper particles dispersed therein was obtained. Furthermore, when the size of the copper fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 21.0 nm. Furthermore, the light absorption characteristics of this copper fine particle-dispersed glass are shown in Example 1.
When measured in the same manner as above, the light absorption peak position was 64.
It was 1 nm. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 7.3.
× 10 ^-10 esu ・ cm (| χ ⁽³⁾ ｜ = 5.5 × 10 ^-7 esu, α
= 753 cm ⁻¹ ), which is 26 times or more of | χ ⁽³⁾ | / α (Comparative Example 1) of copper fine particle-dispersed glass using phosphate glass as a matrix.

Example 13 (Use of the sixth glass as the matrix) As a raw material for the glass to be the matrix, a composition comprising 83 mol% TeO ₂ and 17 mol% PbO was used.
A mixture of 100 mol% of this composition with 1 mol% of SnO as a thermal reducing component and 2 mol% of CuO (2 mol% as Cu) as a raw material of copper fine particles was mixed in a refractory crucible for 1,000 times. After heating at 0 ° C for 15 minutes to form a uniform glass melt, it was cast on an iron plate to obtain colorless and transparent glass. Then 380 this glass
The glass was colored when heat-treated at a temperature of 3 hours for 3 hours.

When the refractive index of this matrix glass was measured, it was n _d = 2.25. When the glass thus obtained was measured by the X-ray diffraction method,
A copper metal crystal peak was observed, and it was confirmed that a glass containing copper particles dispersed therein was obtained. Furthermore, when the size of the copper fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 7.2 nm. Furthermore, when the light absorption characteristics of this copper fine particle-dispersed glass were measured in the same manner as in Example 1, the light absorption peak position was 610.
was nm. Further, when the non-linear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 1.7 ×
10 ^-10 esu · cm (| χ ⁽³⁾ | = 1.6 × 10 ^-7 esu, α =
942 cm ⁻¹ ), which is 6 times or more of | χ ⁽³⁾ | / α (Comparative Example 1) of copper fine particle-dispersed glass using phosphate glass as a matrix.

Example 14 (Use of the 7th Glass as the Matrix) As a raw material for the matrix glass, a composition comprising 80 mol% TeO ₂ and 20 mol% BaO was used.
To 100 mol% of this composition, 2 mol% of SnO was mixed as a thermal reducing component, and 2 mol% of Cu ₂ O (4 mol% as Cu) was mixed as a raw material of copper fine particles. After heating at 200 ° C. for 15 minutes to form a uniform glass melt, it was cast on an iron plate to obtain colorless and transparent glass. Then 400 this glass
The glass was colored when heat-treated at a temperature of 3 hours for 3 hours.

When the refractive index of this matrix glass was measured, it was found that n _d = 2.15. When the glass thus obtained was measured by the X-ray diffraction method,
A copper metal crystal peak was observed, and it was confirmed that a glass containing copper particles dispersed therein was obtained. Furthermore, when the size of the copper fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 25.7 nm. Furthermore, the light absorption characteristics of this copper fine particle-dispersed glass are shown in Example 1.
The light absorption peak position was 62 when measured in the same manner as
It was 3 nm. Further, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 2.9.
× 10 ^-10 esu · cm (| χ ⁽³⁾ ｜ = 5.1 × 10 ^-7 esu, α
= 1760 cm ⁻¹ ), which is 10 times or more of | χ ⁽³⁾ | / α (Comparative Example 1) of copper fine particle dispersed glass using phosphate glass as a matrix.

Example 15 (Use of the 8th Glass As Matrix) As a raw material for the glass to be a matrix, a composition of 70 mol% Bi ₂ O ₃ , 20 mol% CdO and 10 mol% B ₂ O _3. 2 mol% of Sb ₂ O ₃ as a thermal reducing component with respect to 100 mol% of this composition.
Mixing ol% Cu ₂ O (4 mol% as Cu) as a raw material for copper fine particles in a refractory crucible at 1,100 ° C
After heating for 10 minutes to obtain a uniform glass melt,
A colorless and transparent glass was obtained by casting on an iron plate. Then, when this glass was heat-treated at 450 ° C. for 1 hour, the glass was colored.

When the refractive index of this matrix glass was measured, it was n _d = 2.32. When the glass thus obtained was measured by the X-ray diffraction method,
A copper metal crystal peak was observed, and it was confirmed that a glass containing copper particles dispersed therein was obtained. Furthermore, when the size of the copper fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 14.2 nm. Furthermore, the light absorption characteristics of this copper fine particle-dispersed glass are shown in Example 1.
The light absorption peak position was 62 when measured in the same manner as
It was 3 nm. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 3.3.
× 10 ^-10 esu · cm (| χ ⁽³⁾ ｜ = 6.8 × 10 ^-7 esu, α
= 2070 cm ⁻¹ ), which is 11 times or more of | χ ⁽³⁾ | / α (Comparative Example 1) of the copper fine particle dispersed glass using phosphate glass as a matrix.

Example 16 (Use of Crystal as Matrix) ZnSe crystal (n _d = 2.61) was used as a matrix, and copper ion (Cu ⁺ ) was added at 160 ke with an ion implantation apparatus.
A V dose of 1 × 10 ¹⁷ ions / cm ² was implanted. When the crystal thus obtained was measured by an X-ray diffraction method, a copper metal crystal peak was observed together with a ZnSe crystal peak, and it was confirmed that copper fine particles were dispersed in the ZnSe crystal. Furthermore, when the size of the copper fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 6.5 nm. Furthermore, when the light absorption characteristics of this copper fine particle-dispersed ZnSe crystal were measured, the light absorption peak position was 643 nm. further,
When the nonlinear susceptibility was measured in the same manner as in Example 1,
The value of | χ ⁽³⁾ | / α is 3.6 × 10 ^-10 esu · cm (| χ ^{(3 )}
| = 2.5 × 10 ⁻⁵ esu, α = 70000 cm ⁻¹ ), which is 12 times as high as | χ ⁽³⁾ | / α (Comparative Example 1) of copper fine particle dispersed glass using phosphate glass as a matrix. It has the above value.

Example 17 (using the above-mentioned third glass as a matrix) 38 mol% Bi ₂ O ₃ and 34 mol% Pb were used as a matrix.
O and 11 mol% ZnO and 11 mol% BaO and 6 mol%
A glass having a composition consisting of Na ₂ O (n _d = 2.45) was used. This glass was melted at 300 ℃ (AgNO ₃ -KNO ₃ -NaN
It was immersed in O ₃ ) for 100 hours and the silver component was contained in the matrix glass by the ion exchange method. Then, this glass was heat-treated at 420 ° C. for 1 hour.

When the glass thus obtained was measured by the X-ray diffraction method, a silver metal crystal peak was observed, and it was confirmed that a silver fine particle dispersed glass was obtained.
Furthermore, when the size of the silver fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 15.7 nm. Furthermore, when the light absorption characteristics of this silver fine particle-dispersed glass were measured, the light absorption peak position was 633 nm. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 6.5 × 10 ⁻¹¹ esu · cm (| χ ⁽³⁾ | = 5.0 × 10 ^-8 es
u, α = 77 cm ⁻¹ ) and | χ ⁽³⁾ | / α of silver fine particle dispersed glass using phosphate glass as a matrix
It has a value twice or more that of (Comparative Example 2).

Example 18 (Crystal is used as matrix) K (Ta, Nb) O ₃ crystal (n _d = 2.2) is used as a matrix.
9) was used. K (Ta, Nb) O ₃ and copper were simultaneously sputtered on a quartz substrate in an argon-hydrogen atmosphere with a sputtering device to form a K (Ta, Nb) O ₃ film containing a copper component. Next, the obtained film was heat-treated at 800 ° C. for 1 hour.

When the film thus obtained was measured by the X-ray diffraction method, a copper metal crystal peak was observed together with a K (Ta, Nb) O ₃ crystal peak, and K (Ta, N
b) It was confirmed that fine copper particles were dispersed in the O ₃ crystal film. Furthermore, when the size of the copper fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 9.8 nm. Furthermore, when the light absorption characteristics of this K (Ta, Nb) O ₃ crystal film with dispersed copper particles were measured, the light absorption peak position was 620 nm. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 2.6 × 10 ⁻¹⁰ esu · cm (| χ
⁽³⁾ | = 3.5 × 10 ⁻⁶ esu, α = 13500 cm ⁻¹ ) and | χ ⁽³⁾ | / α of the copper fine particle-dispersed glass using phosphate glass as a matrix (Comparative Example 1) 9 times or more.

Example 19 (Use of Crystal as Matrix) Bi ₁₂ Ti ₃ O ₁₂ crystal (n _d = 2.70) as matrix
Was used. Bi ₁₂ Ti ₃ O ₁₂ and copper were alternately sputtered on a quartz substrate in an argon-hydrogen atmosphere with a sputtering apparatus to form a Bi ₁₂ Ti ₃ O ₁₂ film containing a copper component. next,
The obtained film was heat-treated at 800 ° C. for 16 hours.

Copper fine particle dispersion Bi thus obtained
_When the size of the copper fine particles contained in the ₁₂ Ti ₃ O ₁₂ crystal film was measured using a transmission electron microscope (TEM), the average radius was 47.9 nm. Furthermore, when the light absorption characteristics of the Bi ₁₂ Ti ₃ O ₁₂ crystal film having the copper particles dispersed therein were measured, the light absorption peak position was 705 nm. Further, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 2.0 × 10 ⁻⁹ esu · cm (| χ
⁽³⁾ | = 2.1 × 10 ⁻⁵ esu, α = 10500 cm ⁻¹ ) and | χ ⁽³⁾ | / α of the copper fine particle dispersed glass using phosphate glass as a matrix (Comparative Example 1) 71 times or more.

Example 20 (Using Crystal as Matrix) PbGeO ₃ crystal (n _d = 2.02) was used as a matrix.
A PbGeO ₃ film containing a platinum component was prepared in the same manner as in Example 19 except that platinum was used as the metal, and the obtained film was heat-treated at 900 ° C. for 1 hour.

Platinum fine particle dispersion P thus obtained
When the size of the platinum fine particles contained in the bGeO ₃ crystal film was measured by using a transmission electron microscope (TEM), the average radius was 12.5 nm. Further, the light absorption characteristics of this platinum fine particle-dispersed PbGeO ₃ crystal film were measured, and the light absorption peak position was 503 nm. further,
When the nonlinear susceptibility was measured in the same manner as in Example 1,
The value of │χ ⁽³⁾ ｜ / α is 1.3 × 10 ^-11 esu ・ cm (｜ χ ⁽³⁾
| = 4.8 × 10 ⁻⁸ esu, α = 3700 cm ⁻¹ ).

Example 21 (using crystals as a matrix) Bi ₁₂ SiO ₂₀ crystals (n _d = 2.54) as a matrix
A Bi ₁₂ SiO ₂₀ crystal film containing a palladium component was prepared in the same manner as in Example 19 except that palladium was used as the metal, and the obtained film was heat-treated at 800 ° C. for 1 hour.

The size of the palladium fine particles contained in the thus obtained palladium fine particle-dispersed Bi ₁₂ SiO ₂₀ crystal film was measured by using a transmission electron microscope (TEM), and the average radius was 8.3 nm. there were. further,
When the light absorption characteristics of this Bi ₁₂ SiO ₂₀ crystal film with dispersed palladium particles were measured, the light absorption peak position was 572n.
It was m. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 9.8 × 1.
0 ^-12 esu ・ cm (| χ ⁽³⁾ ｜ = 4.5 × 10 ^-8 esu, α = 4
It was 600 cm ^-1 ).

Example 22 (Use of Crystal as Matrix) The procedure of Example 19 was repeated except that ZnWO ₄ crystal (n _d = 2.14) was used as the matrix and nickel was used as the metal,
A ZnWO ₄ crystal film containing a nickel component was produced, and the obtained film was heat-treated at 800 ° C. for 3 hours.

The size of the nickel fine particles contained in the thus obtained nickel fine particle-dispersed ZnWO ₄ crystal film was measured by using a transmission electron microscope (TEM), and the average radius was 16.1 nm. . Further, when the light absorption characteristics of this nickel fine particle-dispersed ZnWO ₄ crystal film were measured, the light absorption peak position was 545 nm.
Further, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 1.1 × 10 ⁻¹² esu · cm.
(| Χ ⁽³⁾ | = 3.1 × 10 ⁻⁸ esu, α = 2800c
m ⁻¹ ).

Example 23 (Use of Crystal as Matrix) ZnWO ₄ containing an iridium component was prepared in the same manner as in Example 19 except that ZnWO ₄ crystal (n _d = 2.14) was used as a matrix and iridium was used as a metal. _{A four-} crystal film was prepared, and the obtained film was heat-treated at 700 ° C. for 8 hours.

The size of the iridium fine particles contained in the thus obtained iridium fine particle-dispersed ZnWO ₄ crystal film was measured with a transmission electron microscope (TEM), and the average radius was 43.2 nm. .. Furthermore, when the light absorption characteristics of this iridium fine particle-dispersed ZnWO ₄ crystal film were measured, the light absorption peak position was 428 nm. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ^{(3 )} | / α was 5.6 × 10 ^-12 es.
u · cm (| χ ⁽³⁾ | = 1.8 × 10 ⁻⁸ esu, α = 3200c
m ⁻¹ ).

[0104] Example 24 Y ₂ O ₃ crystals in the matrix (the use crystal as the matrix) (n _d = 1.92), except for using the iron metal in the same manner as in Example 19, the fine iron particles dispersed Y _{A 2} O ₃ crystal film was prepared.

Iron fine particle dispersion Y ₂ thus obtained
When the size of the iron fine particles contained in the O ₃ crystal film was measured using a transmission electron microscope (TEM), the average radius was 7.9 nm. Further, this iron fine particle dispersed Y ₂ O ₃
When the light absorption characteristics of the crystal film were measured, the light absorption peak position was 1060 nm. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 2.6 × 10 ⁻¹² esu · cm (| χ ⁽³⁾ | = 6.8 ×. 10
^-9 esu, α = 2600 cm ^-1 ) and | χ ⁽³⁾ | of iron fine particle dispersed glass using silica glass as a matrix
/ Α (Comparative Example 13) is twice or more.

Example 25 (Use of Crystal as Matrix) Y ₃ Ga ₅ O ₁₂ crystal (n _d = 1.93) was used as a matrix.
An osmium fine particle-dispersed Y ₃ Ga ₅ O ₁₂ crystal film was prepared in the same manner as in Example 19 except that osmium was used as the metal.

The size of the osmium fine particles contained in the osmium fine particle-dispersed Y ₃ Ga ₅ O ₁₂ crystal film thus obtained was measured with a transmission electron microscope (TEM), and the average radius was 6. It was 2 nm. Further, the light absorption characteristics of the Y ₃ Ga ₅ O ₁₂ crystal film having the osmium particles dispersed therein were measured, and the light absorption peak position was 1078 nm.
Met. Furthermore, when the non-linear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 1.8 × 10 5.
^-12 esu ・ cm (| χ ⁽³⁾ ｜ = 2.7 × 10 ^-9 esu, α = 15
00 cm ⁻¹ ), which is more than twice the | χ ⁽³⁾ | / α (Comparative Example 14) of osmium fine particle-dispersed glass using silica glass as a matrix.

Example 26 (Use of Crystal as Matrix) K (Ta, Nb) O ₃ crystal (n _d = 2.2) was used as a matrix.
9), K (Ta, Nb) O ₃ containing gold and silver components was prepared in the same manner as in Example 19 except that a gold-silver alloy (Au: Ag = 19: 1; molar ratio) was used as the metal. A crystal film was prepared, and the obtained film was heat-treated at 700 ° C. for 8 hours.

When the film thus obtained was measured by X-ray diffractometry, an Au ₁₉ Ag alloy crystal peak was observed together with a K (Ta, Nb) O ₃ crystal peak.
It was confirmed that Au—Ag alloy fine particles were dispersed in the (Ta, Nb) O ₃ crystal film. Furthermore, when the size of the Au—Ag alloy fine particles was measured using a transmission electron microscope (TEM), the average radius was 15.6 nm.
Further, this Au-Ag alloy fine particle dispersion K (Ta, N
b) When the light absorption characteristics of the O ₃ crystal film were measured,
The peak position was 582 nm. Further, when the nonlinear susceptibility was measured in the same manner as in Example 1, it was found that | χ ⁽³⁾ |
The value of / α is 2.8 × 10 ⁻¹¹ esu · cm (| χ ^{(3 )} | = 1.
2 × 10 ⁻⁷ esu, α = 4300 cm ⁻¹ ), which is 5 times or more than | χ ⁽³⁾ | / α (Comparative Example 3) of gold fine particle dispersed glass using phosphate glass as a matrix. Have.

Example 27 (Use of Crystal as Matrix) K (Ta, Nb) O ₃ crystal (n _d = 2.2) was used as a matrix.
In 9), K (Ta, Nb) O ₃ containing gold and copper components was prepared in the same manner as in Example 19 except that gold-copper alloy (Au: Cu = 7: 3; molar ratio) was used as the metal. A crystal film was prepared, and the obtained film was heat-treated at 700 ° C. for 8 hours.

When the film thus obtained was measured by the X-ray diffraction method, an Au ₇ Cu ₃ alloy crystal peak was observed together with a K (Ta, Nb) O ₃ crystal peak, and K
It was confirmed that Au—Cu alloy fine particles were dispersed in the (Ta, Nb) O ₃ crystal film. Furthermore, when the size of the Au—Cu alloy fine particles was measured using a transmission electron microscope (TEM), the average radius was 14.8 nm.
Furthermore, this Au-Cu alloy fine particle dispersion K (Ta, N
b) When the light absorption characteristics of the O ₃ crystal film were measured,
The peak position was 599 nm. Further, when the nonlinear susceptibility was measured in the same manner as in Example 1, it was found that | χ ⁽³⁾ |
The value of / α is 1.1 × 10 ⁻¹⁰ esu · cm (| χ ^{(3 )} | = 4.
2 × 10 ⁻⁷ esu, α = 3800 cm ⁻¹ ), which is 22 times or more than | χ ⁽³⁾ | / α (Comparative Example 3) of gold fine particle-dispersed glass using phosphate glass as a matrix. Have.

Example 28 (Use of Crystal as Matrix) K (Ta, Nb) O ₃ crystal (n _d = 2.2) was used as a matrix.
9) as a metal, platinum-palladium-rhodium-ruthenium alloy (Pt: Pd: Rh: Ru = 43: 5: 1: 1;
A K (Ta, Nb) O ₃ crystal film containing platinum, palladium, rhodium and ruthenium components was prepared in the same manner as in Example 19 except that the molar ratio was used. It heat-processed on condition of time.

When the film thus obtained was measured by an X-ray diffraction method, a Pt ₄₃ Pd ₅ RhRu alloy crystal peak was observed together with a K (Ta, Nb) O ₃ crystal peak, and K (Ta, Pt-Pd-R in nb) O ₃ crystal film
It was confirmed that the h-Ru alloy fine particles were dispersed. Furthermore, when the size of the Pt-Pd-Rh-Ru alloy fine particles was measured using a transmission electron microscope (TEM), the average radius was 13.1 nm. Furthermore, this Pt-P
When the light absorption characteristics of the d-Rh-Ru alloy fine particle dispersed K (Ta, Nb) O ₃ crystal film were measured, the light absorption peak position was 510 nm. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 1.2 × 10 ⁻¹¹ esu · cm (| χ ⁽³⁾ | = 4.7 ×. 10 ^-8 es
u, α = 3900 cm ⁻¹ ).

Example 29 (Using Crystal as Matrix) Bi ₄ Ge ₃ O ₁₂ crystal (n _d = 2.07) as matrix
The metal copper - zinc alloy; except that (Cu:: Zn = 17 3 molar ratio) was prepared in the same manner as in Example 19, producing a Bi ₄ Ge ₃ O ₁₂ crystal film containing copper and zinc components Then, the obtained film was heat-treated at 750 ° C. for 3 hours.

When the film thus obtained was measured by X-ray diffractometry, a Cu ₁₇ Zn ₃ alloy crystal peak was observed together with a Bi ₄ Ge ₃ O ₁₂ crystal peak, and Bi ₄ Ge was observed.
Cu-Zn alloy particles was confirmed to have been dispersed in ₃ O _{1 2} crystalline film. Furthermore, when the size of the Cu—Zn alloy fine particles was measured using a transmission electron microscope (TEM), the average radius was 30.2 nm. Furthermore, this C
The light absorption characteristics of the Bi ₄ Ge ₃ O ₁₂ crystal film containing u-Zn alloy fine particles dispersed therein were measured, and the light absorption peak position was 588 nm.
Met. Further, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 9.2 × 10.
^-11 esu ・ cm (| χ ⁽³⁾ ｜ = 5.7 × 10 ^-7 esu, α = 62
00 cm ⁻¹ ), which is three times or more the value of | χ ⁽³⁾ | / α (Comparative Example 1) of copper fine particle-dispersed glass using phosphate glass as a matrix.

Example 30 (Using Crystal as Matrix) Bi ₁₂ GeO ₂₀ crystal (n _d = 2.55) as matrix
To the metal copper-cadmium alloy (Cu: Cd = 99:
1; molar ratio) was used in the same manner as in Example 19,
A Bi ₁₂ GeO ₂₀ crystal film containing copper and cadmium components was produced, and the obtained film was heat-treated at 750 ° C. for 3 hours.

When the film thus obtained was measured by the X-ray diffraction method, a Cu ₉₉ Cd alloy crystal peak was observed together with a Bi ₁₂ GeO ₂₀ crystal peak, and a Bi ₄ Ge ₃ crystal was observed.
It was confirmed that Cu—Zn alloy fine particles were dispersed in the O ₁₂ crystal film. Furthermore, when the size of the Cu—Cd alloy fine particles was measured using a transmission electron microscope (TEM), the average radius was 34.8 nm. Furthermore, when the light absorption characteristics of this film were measured, the light absorption peak position was 6
It was 41 nm. Furthermore, when the nonlinear susceptibility was measured, the value of | χ ⁽³⁾ | / α was 7.1 × 10 ^-10 esu · cm (|
χ ⁽³⁾ │ = 4.2 × 10 ^-6 esu, α = 5900 cm ^-1 ), and │χ ⁽³⁾ │ / α (copper fine particle dispersed glass using phosphate glass as a matrix ⁾ (Comparative Example 1). ) 25 times or more.

Except for using; (molar ratio 1:: Al = 19 Ag) aluminum alloys - [0118] Example 31 (using the crystal as the matrix) matrix ZnWO ₄ crystal (n _d = 2.14), metallic silver In the same manner as in Example 19, a ZnWO ₄ crystal crystal film containing silver and aluminum components was produced, and the obtained film was heat-treated at 850 ° C. for 3 hours.

When the film thus obtained was measured by X-ray diffractometry, an Ag ₁₉ Al alloy crystal peak was observed together with a ZnWO ₄ crystal peak, and Ag-Al alloy fine particles were found in the ZnWO ₄ crystal film. It was confirmed that they were dispersed. Furthermore, when the size of the Ag-Al alloy fine particles was measured using a transmission electron microscope (TEM), the average radius was 19.1 nm. Furthermore, when the light absorption characteristics of this film were measured, the light absorption peak position was 485 nm. Furthermore, when the nonlinear susceptibility was measured,
⁽³⁾ | / α is 6.2 × 10 ^-11 esu · cm (| χ ⁽³⁾ ｜ ＝
4.4 × 10 ^-7 esu, α = 7100 cm ⁻¹ ), which is more than twice as high as | χ ⁽³⁾ | / α (Comparative Example 2) of silver fine particle dispersed glass using a phosphate glass as a matrix. Has a value.

Example 32 (using the above-mentioned fourth glass as matrix) 48 mol% GeO ₂ and 8 mol% Bi ₂ O were used as a matrix.
_Using glass (n _d = 2.20) having a composition of ₃ and 28 mol% of Tl ₂ O and 16 mol% of PbO, tin ion (Sn ⁺ ) is 160 keV and the dose amount is 2 ×.
10 ¹⁷ ions / cm ² was injected.

When the glass thus obtained was measured by X-ray diffractometry, a tin metal crystal peak was observed, and it was confirmed that tin fine particles were dispersed in the glass. Furthermore, when the size of the tin fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 18.3 nm. Furthermore, when the light absorption characteristics of this tin fine particle-dispersed glass were measured, the light absorption peak position was 589 nm. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 2.3 × 10 ⁻¹¹ esu · cm (| χ ⁽³⁾ | = 1.2 × 10
^-6 esu, alpha = a 52200cm ^-1), the silica glass fine particles of tin dispersion glass used in the matrix | chi ⁽³⁾
It has a value more than twice as large as | / α (Comparative Example 15).

Example 33 (Using the 9th Glass Above as the Matrix) As a raw material for the glass, 90 mol% of A was used as the matrix.
A composition consisting of s ₂ S ₃ and 10 mol% Sb ₂ S ₃ (As3
6at%, Sb 4at%, total amount of As and Sb 40at
%, S 60 at%), and then seal it in a quartz container.
Heat to 400 ° C at a heating rate of 100 ° C per hour,
After holding at 400 ° C. for 6 hours, it was heated again to 700 ° C. at a heating rate of 100 ° C. per hour, held at 700 ° C. for 12 hours, and then cooled to room temperature to obtain a glass (n
_d = 2.55), cobalt ion (Co ⁺ ) is 160 keV with an ion implanter, and the dose is 2 × 10 ¹⁷ ion.
s / cm ² was injected.

The size of the cobalt fine particles contained in the thus obtained cobalt fine particle-dispersed glass was measured with a transmission electron microscope (TEM), and the average radius was 9.5 nm. Furthermore, when the light absorption characteristics of this cobalt fine particle dispersed glass were measured, the light absorption peak position was 632 nm. Further, when the non-linear susceptibility was measured in the same manner as in Example 1, | χ ⁽³⁾ | / α
The value of is 6.4 × 10 ^-12 esu ・ cm (│χ ⁽³⁾ ｜ = 1.6 × 1
It was 0 ⁻⁷ esu, α = 25000 cm ⁻¹ ).

Example 34 (using the above-mentioned first glass as a matrix) 29 mol% B ₂ O ₃ and 71 mol% PbO were used as a matrix.
Glass having a composition of (n _d = 2.07) and 160 keV of manganese ions (Mn ⁺ ) in an ion implanter.
Then, a dose amount of 1 × 10 ¹⁷ ions / cm ² was implanted.

When the glass thus obtained was measured by the X-ray diffraction method, a manganese metal crystal peak was observed, and it was confirmed that manganese fine particles were dispersed in the glass. Furthermore, when the size of the manganese fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 13.1 nm. Furthermore, when the light absorption characteristics of this manganese fine particle-dispersed glass were measured, the light absorption peak position was 765 nm.
Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 6.8 × 10 ⁻¹² esu · cm.
(| Χ ⁽³⁾ | = 1.9 × 10 ^-7 esu, α = 28000 cm
⁻¹ ), and | χ ⁽³⁾ | / α of manganese fine particle dispersed glass using silicate glass as a matrix (Comparative Example 1)
It has a value more than 3 times that of 7).

Example 35 (Use of Crystal as Matrix) Y ₃ Ga ₅ O ₁₂ crystal (n _d = 1.93) was used as a matrix, and tungsten ions (W ⁺ ) were applied at 160 keV by an ion implanter at a dose of 1 × 10 ¹⁶ ions / cm ² was implanted.

When the size of the tungsten fine particles contained in the thus obtained tungsten fine particle-dispersed Y ₃ Ga ₅ O ₁₂ crystal was measured by using a transmission electron microscope (TEM), the average radius was 15.6 nm. Met. Furthermore, when the light absorption characteristics of this tungsten fine particle-dispersed Y ₃ Ga ₅ O ₁₂ crystal were measured, the light absorption peak position was 112.
It was 1 nm. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 2.1.
× 10 ^-12 esu ・ cm (| χ ⁽³⁾ ｜ = 2.3 × 10 ^-8 esu, α
= 11000 cm ^-1 ), and | χ ⁽³⁾ of the tungsten fine particle dispersed glass using silica glass as the matrix
It has a value of 2 times or more of | / α (Comparative Example 18).

Example 36 (Using Crystal as Matrix) GaP crystal (n _d = 3.35) was used as a matrix,
The molybdenum ion (Mo ⁺ ) is 160
A dose amount of 5 × 10 ¹⁶ ions / cm ² was implanted at keV.

The size of the molybdenum fine particles contained in the thus-obtained molybdenum fine particle-dispersed GaP crystal was measured with a transmission electron microscope (TEM), and the average radius was 22.4 nm. Further, when the light absorption characteristics of this molybdenum fine particle-dispersed GaP crystal were measured, the light absorption peak position was 1170 nm. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 2.4 × 10 ⁻¹² esu · cm (|
χ ⁽³⁾ | = 7.2 × 10 ^-8 esu, α = 30000 cm ^-1 )
Which is more than twice the value of | χ ⁽³⁾ | / α (Comparative Example 19) of the glass containing molybdenum fine particles using silica glass as the matrix.

Example 37 (Production of Optical Bistable Switch) Non-linear optical material (thickness 15) produced in the same manner as in Example 12.
An anti-reflection film was vapor-deposited on both sides of the mirror, and the film was inserted into a Fabry-Perot resonator having a mirror reflectance of 90% and a resonator length of 100 μm to fabricate an optical bistable switching element.

Next, light of 640 nm was made incident on this device, and the time waveforms of the incident light and the light emitted from the resonator for the same pulse were observed. As a result, an optical bistable switching operation was observed, and the time required for switching was 2 psec both on and off, and this element has extremely high-speed switching performance.

Example 38 (Fabrication of Waveguide-Type Element) First, 1 μm borosilicate glass was sputtered as a waveguide layer on a quartz substrate, and then copper fine particle dispersion K (Ta, Nb) was used as in Example 18. ) An O ₃ crystal film was formed to a thickness of 300 nm to produce a waveguide type device.

Next, light of 620 nm was made incident on the waveguide of this device. The prism-coupler method was used for guided mode excitation. Next, when 620 nm light is irradiated from the direction perpendicular to the substrate, the intensity of the light originally passing through the waveguide layer is increased ten times or more. The optical modulation by this light shows a high-speed response characteristic in the copper fine particle dispersed K (Ta, Nb) O ₃ crystal. The time it takes to switch is
Both off were less than 1 psec.

Comparative Example 1 (Using Conventional Phosphate Glass as the Matrix) As a raw material for the matrix glass, a composition of 50 mol% P ₂ O ₅ and 50 mol% BaO was used.
A mixture of 100 mol% of this composition with 6 mol% of SnO as a thermal reducing component and 6 mol% of Cu ₂ O (12 mol% as Cu) as a raw material of copper fine particles,
A glass was obtained in the same manner as in Example 1 except that a uniform glass melt was obtained by heating in a refractory crucible at 1,200 ° C. for 15 minutes. Next, when this glass was heat-treated at 440 ° C. for 16 hours, the glass was colored red.

When the glass thus obtained was measured by X-ray diffractometry, a copper metal crystal peak was observed in the same manner as in Example 1 and it was confirmed that a glass having copper fine particles dispersed therein was obtained. . Furthermore, when the size of the copper fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 29.0 nm.

When the light absorption characteristics of this copper fine particle dispersed glass were measured in the same manner as in Example 1, the light absorption peak position was 573 nm as shown by the broken line 2 in FIG. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 2.8 × 10 ⁻¹¹ esu ·
cm (| χ ⁽³⁾ | = 5.8 × 10 ^-8 esu, α = 2100 cm
^-1 ).

Comparative Example 2 (Using Conventional Phosphate Glass as the Matrix) In the same manner as in Comparative Example 1, a glass having the same composition was obtained. However, 6
Instead of mol% Cu ₂ O, 4 mol% Ag ₂ O was used.
Then, when this glass was heat-treated at 540 ° C. for 6 hours, the glass was colored.

When the glass thus obtained was measured by the X-ray diffraction method, a silver metal crystal peak was observed in the same manner as in Example 5, and it was confirmed that a silver fine particle dispersed glass was obtained. . Furthermore, when the size of the silver fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 15.3 nm.

When the light absorption characteristics of this silver fine particle dispersed glass were measured in the same manner as in Example 1, the light absorption peak position was 430 nm. Further, when the non-linear susceptibility was measured in the same manner as in Example 1, | χ ⁽³⁾ | / α
The value of is 2.7 × 10 ^-11 esu ・ cm (| χ ⁽³⁾ ｜ = 4.6 × 1
It was 0 ^-8 esu, α = 1700 cm ^-1 ).

Comparative Example 3 (Using Conventional Phosphate Glass as the Matrix) In the same manner as in Comparative Example 1, a glass having the same composition was obtained. However, 6
6 mol% of Sb ₂ O ₃ of ₂ mol% in place of SnO of mol%
1 mol% AuCl ₃ was used in place of Cu ₂ O. Then, when this glass was heat-treated at 520 ° C. for 16 hours, the glass was colored.

When the glass thus obtained was measured by the X-ray diffraction method, a gold metal crystal peak was observed in the same manner as in Example 6, and it was confirmed that a gold fine particle-dispersed glass was obtained. . Furthermore, when the size of the gold fine particles was measured by an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 14.9 nm.

When the light absorption characteristics of this gold fine particle-dispersed glass were measured in the same manner as in Example 6, the light absorption peak position was 545 nm. Further, when the non-linear susceptibility was measured in the same manner as in Example 1, | χ ⁽³⁾ | / α
The value of is 5.0 × 10 ^-12 esu ・ cm (| χ ⁽³⁾ | = 8.4 × 1
It was 0 ^-10 esu, α = 168 cm ^-1 ).

COMPARATIVE EXAMPLE 4 As a raw material for the glass to be the matrix, a composition comprising 60 mol% B ₂ O ₃ outside the range of the present invention and 40 mol% PbO outside the range of the present invention was used. 2 mol% SnO based on 100 mol% of the composition
A glass was obtained in the same manner as in Example 1, except that 1 mol% of Cu ₂ O ( ₂ mol% as Cu) was mixed as a raw material of copper fine particles. Then, when this glass was heat-treated at 400 ° C. for 1 hour, the glass was colored.

When the refractive index of this matrix glass was measured, it was found that n _d = 1.77. When the glass thus obtained was measured by the X-ray diffraction method,
A copper metal crystal peak was observed, and it was confirmed that a glass containing copper particles dispersed therein was obtained. Furthermore, when the size of the copper fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 30.5 nm.

When the light absorption characteristics of this copper fine particle dispersed glass were measured in the same manner as in Example 1, the light absorption peak position was 576 nm. Further, when the non-linear susceptibility was measured in the same manner as in Example 1, | χ ⁽³⁾ | / α
The value of is 3.2 × 10 ^-11 esu ・ cm (| χ ⁽³⁾ ｜ = 4.2 × 1
0 ^-8 esu, α = 1310 cm ^-1 ), and | χ of a copper fine particle dispersed glass using phosphate glass as a matrix
⁽³⁾ Similar to | / α (Comparative Example 1), and there was no difference in the optical nonlinear susceptibility.

Comparative Example 5 As a raw material of glass to be a matrix, 5 mol% of Ga ₂ O ₃ which is out of the limited range (10 to 70 mol%) of the present invention.
And a composition consisting of 35 mol% of Bi ₂ O ₃ and 60 mol% of PbO.
2 mol% Sb ₂ O ₃ as a thermal reducing component, and 1 mol%
Glass was obtained in the same manner as in Example 2 except that Cu ₂ O (2 mol% as Cu) was mixed as a raw material for the copper fine particles.
Then, this glass was heat-treated at 430 ° C. for 1 hour.

When the glass thus obtained was measured by the X-ray diffraction method, precipitation of copper metal crystal fine particles could not be confirmed, but crystallization of the glass was observed instead.

Comparative Example 6 60 mol% SiO ₂ and 20 mol% B ₂ O were used as a matrix.
A glass (n _d = 1.50) having a composition of ₃ and 10 mol% Na ₂ O and 10 mol% Al ₂ O ₃ was used. Copper ion (Cu ⁺ ) was added to this glass with an ion implanter at 160 keV
Then, a dose amount of 1 × 10 ¹⁷ ions / cm ² was implanted. Next, the obtained glass was heat-treated at 500 ° C. for 8 hours.

When the glass thus obtained was measured by the X-ray diffraction method, a copper metal crystal peak was observed, and it was confirmed that a copper fine particle-dispersed glass was obtained.
Furthermore, when the size of the copper fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 16.8 nm. Furthermore, when the light absorption characteristics of this copper fine particle-dispersed glass were measured, the light absorption peak position was 565 nm. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 5.1 × 10 ⁻¹² esu · cm (| χ ⁽³⁾ | = 2.1 × 10 ^-7 es
u, α = 41000 cm ⁻¹ ) and | χ ⁽³⁾ | of copper fine particle dispersed glass using phosphate glass as a matrix
/ Α (comparative example 1) was 0.2 times.

Comparative Example 7 A glass having the same composition was obtained as in Example 2. afterwards,
When this glass was heat-treated at 350 ° C. for 3 hours, the glass was colored.

When the glass thus obtained was measured by the X-ray diffraction method, a copper metal crystal peak was observed, and it was confirmed that a copper fine particle-dispersed glass was obtained.
Furthermore, when the size of the copper fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 0.7 nm. Furthermore, when the light absorption characteristics of this copper fine particle-dispersed glass were measured in the same manner as in Example 1, the light absorption peak position was 563 nm. further,
When the nonlinear susceptibility was measured in the same manner as in Example 1,
The value of │χ ⁽³⁾ ｜ / α is 8.4 × 10 ^-12 esu ・ cm (｜ χ ^{(3)
| = 2.7 × 10 - 9 esu} , are α = 320cm ^-1),
It was 0.3 times as large as | χ ⁽³⁾ | / α (Comparative Example 1) of the copper fine particle-dispersed glass using phosphate glass as a matrix.

Comparative Example 8 A glass having the same composition was obtained in the same manner as in Example 2. However, C
₂ mol% Ag ₂ O instead of u ₂ O (4 mol as Ag
%) Was used. After that, the glass is heated at 430 ° C.
When heat-treated under the condition of time, the glass was colored.

When the glass thus obtained was measured by the X-ray diffraction method, a silver metal crystal peak was observed, and it was confirmed that a silver fine particle dispersed glass was obtained.
Furthermore, when the size of the silver fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 125.3 nm. Further, the light absorption characteristics of this silver fine particle-dispersed glass were measured in the same manner as in Example 1, and the light absorption peak position was 596 nm. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 2.5 × 10 ⁻¹¹ esu · cm (| χ
⁽³⁾ | = 2.0 × 10 ⁻⁸ esu, α = 810 cm ⁻¹ ) and | χ ⁽³⁾ | / α of silver fine particle dispersed glass using phosphate glass as a matrix (Comparative Example 2) There was no difference in the optical non-linear susceptibility.

Comparative Example 9 A silica glass film containing a platinum component was prepared and obtained in the same manner as in Example 19 except that silica glass (n _d = 1.46) was used as the matrix and platinum was used as the metal. The film was heat-treated at 900 ° C. for 1 hour.

When the size of the platinum fine particles contained in the thus obtained platinum fine particle-dispersed silica glass film was measured by using a transmission electron microscope (TEM), the average radius was 14.5 nm. Further, when the light absorption characteristics of this platinum fine particle-dispersed silica glass film were measured, the light absorption peak position was in the ultraviolet region of a shorter wavelength than the absorption edge of the matrix and was not observed.

Comparative Example 10 A silica glass film containing a palladium component was prepared in the same manner as in Example 19 except that silica glass (n _d = 1.46) was used as the matrix and palladium was used as the metal. The film was heat-treated at 800 ° C. for 1 hour.

When the size of the palladium fine particles contained in the thus obtained palladium fine particle-dispersed silica glass film was measured by using a transmission electron microscope (TEM), the average radius was 9.7 nm. Furthermore, when the light absorption characteristics of this palladium fine particle-dispersed silica glass film were measured, the light absorption peak position was not observed because it was in the ultraviolet region of a wavelength shorter than the absorption edge of the matrix.

Comparative Example 11 The procedure of Example 19 was repeated except that silica glass (n _d = 1.46) was used as the matrix and nickel was used as the metal.
A silica glass film containing a nickel component was prepared, and the obtained film was heat-treated at 800 ° C. for 3 hours.

When the size of the nickel fine particles contained in the thus obtained nickel fine particle-dispersed silica glass film was measured by using a transmission electron microscope (TEM), the average radius was 15.8 nm. Further, when the light absorption characteristics of this nickel fine particle-dispersed silica glass film were measured, the light absorption peak position was not observed because it was in the ultraviolet region of a wavelength shorter than the absorption edge of the matrix.

Comparative Example 12 A silica glass film containing an iridium component was prepared and obtained in the same manner as in Example 19 except that silica glass (n _d = 1.46) was used as the matrix and iridium was used as the metal. The film was heat-treated at 700 ° C. for 8 hours.

When the size of the iridium fine particles contained in the iridium fine particle-dispersed silica glass film thus obtained was measured by using a transmission electron microscope (TEM), the average radius was 41.6 nm. Furthermore, when the light absorption characteristics of this iridium fine particle-dispersed silica glass film were measured, the light absorption peak position was in the ultraviolet region of a shorter wavelength than the absorption edge of the matrix and was not observed.

Comparative Example 13 An iron fine particle-dispersed silica glass film was produced in the same manner as in Example 19 except that silica glass (n _d = 1.46) was used as the matrix and iron was used as the metal.

The size of the iron fine particles contained in the thus obtained iron fine particle-dispersed silica glass film was measured by using a transmission electron microscope (TEM), and the average radius was 8.6 nm. Furthermore, when the light absorption characteristics of this iron fine particle-dispersed silica glass film were measured, the light absorption peak position was 907 nm. Further, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 1.2 × 10 ⁻¹² esu · cm (| χ ⁽³⁾ | = 2.1 × 10
^-9 esu, α = 1740 cm ^-1 ).

Comparative Example 14 An osmium fine particle-dispersed silica glass film was prepared in the same manner as in Example 19 except that silica glass (n _d = 1.46) was used as the matrix and osmium was used as the metal.

The size of the osmium fine particles contained in the thus obtained osmium fine particle-dispersed silica glass film was measured with a transmission electron microscope (TEM), and the average radius was 7.2 nm. Furthermore, when the light absorption characteristics of this osmium fine particle-dispersed silica glass film were measured, the light absorption peak position was 981 nm.
Further, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 8.6 × 10 ⁻¹³ esu · cm.
(| Χ ⁽³⁾ | = 1.2 × 10 ^-9 esu, α = 1400c
m ⁻¹ ).

Comparative Example 15 Silica glass (n _d = 1.46) was used as the matrix, and tin ions (Sn ⁺ ) were added at 160 ke with an ion implanter.
A V dose of 2 × 10 ¹⁷ ions / cm ² was implanted.

When the glass thus obtained was measured by the X-ray diffraction method, a tin metal crystal peak was observed, and it was confirmed that a tin fine particle-dispersed glass was obtained.
Furthermore, when the size of the tin fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 17.3 nm. Furthermore, when the light absorption characteristics of this tin fine particle-dispersed silica glass film were measured, the light absorption peak position was 498 nm. Further, when the non-linear susceptibility was measured in the same manner as in Example 1, | χ ⁽³⁾ | /
The value of α is 1.1 × 10 ^-11 esu · cm (| χ ⁽³⁾ | = 5.3 ×
It was 10 ⁻⁷ esu, α = 48200 cm ⁻¹ ).

Comparative Example 16 50 mol% P ₂ O ₅ and 50 mol% BaO were used as a matrix.
With a composition of glass (n _d = 1.70), 160keV cobalt ions (Co ⁺⁾ by ion implantation apparatus
Then, a dose amount of 2 × 10 ¹⁷ ions / cm ² was implanted.

When the glass thus obtained was measured by an X-ray diffraction method, a cobalt metal crystal peak was observed, and it was confirmed that a glass containing cobalt fine particles was obtained. Furthermore, when the size of the cobalt fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 10.3 nm. further,
When the light absorption characteristics of this cobalt fine particle-dispersed glass were measured, the light absorption peak position was not observed because it was in the ultraviolet region of a wavelength shorter than the absorption edge of the matrix.

Comparative Example 17 60 mol% SiO ₂ and 20 mol% B ₂ O were used as a matrix.
_Using glass (n _d = 1.50) having a composition of ₃ and 10 mol% Na ₂ O and 10 mol% Al ₂ O ₃ , manganese ions (Mn ⁺ ) are 160 keV and a dose amount is 1 ×. 10 ¹⁷ ions / cm ² was injected.

When the glass thus obtained was measured by an X-ray diffraction method, a manganese metal crystal peak was observed, and it was confirmed that a manganese fine particle-dispersed glass was obtained. Furthermore, when the size of the manganese fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 14.5 nm. further,
When the light absorption characteristics of this silicate glass film with dispersed manganese particles were measured, the light absorption peak position was 471 nm. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 2.2 × 10 ^−12.
esu ・ cm (| χ ^{(3 )} | = 4.9 × 10 ^-8 esu, α = 220
It was 00 cm ^-1 ).

COMPARATIVE EXAMPLE 18 Silica glass (n _d = 1.46) was used as a matrix, and tungsten ion (W ⁺ ) was added to 1 by an ion implantation apparatus.
A dose of 1 × 10 ¹⁶ ions / cm ² was implanted at 60 keV.

When the glass thus obtained was measured by the X-ray diffraction method, a tungsten metal crystal peak was observed, and it was confirmed that a tungsten fine particle-dispersed glass was obtained. Furthermore, when the size of the tungsten fine particles was measured by an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 16.7 nm. Furthermore, when the light absorption characteristics of this tungsten fine particle-dispersed silica glass film were measured, the light absorption peak position was 1008 nm. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 1.0 × 10 ⁻¹² esu · cm (| χ ⁽³⁾ | = 9.4 ×. 10 ^-9 es
u, α = 9400 cm ⁻¹ ).

Comparative Example 19 Silica glass (n _d = 1.46) was used as a matrix, and molybdenum ions (Mo ⁺ ) were added to 1 by an ion implantation apparatus.
A dose of 1 × 10 ¹⁶ ions / cm ² was implanted at 60 keV.

When the glass thus obtained was measured by the X-ray diffraction method, a molybdenum metal crystal peak was observed, and it was confirmed that a glass containing fine molybdenum particles was obtained. Furthermore, when the size of the molybdenum fine particles was measured using an X-ray diffraction method and a transmission electron microscope (TEM), the average radius was 24.7 nm. Furthermore, the light absorption characteristics of this silica glass film in which molybdenum particles were dispersed were measured, and the light absorption peak position was 912n.
It was m. Furthermore, when the nonlinear susceptibility was measured in the same manner as in Example 1, the value of | χ ⁽³⁾ | / α was 1.1 × 1.
0 ^-12 esu · cm (| χ ⁽³⁾ ｜ = 2.9 × 10 ^-8 esu, α = 2
It was 6000 cm ^-1 ).

[0176]

As described above, according to the present invention,
By using the above matrix material, it is possible to manufacture a non-linear optical material in which fine metal particles are dispersed, which has a large | χ ⁽³⁾ | / α characteristic that is at least twice that of conventional materials. An optical element using the obtained nonlinear optical material has extremely fast response performance and excellent nonlinear characteristics as a nonlinear optical element.

[Brief description of drawings]

FIG. 1 is a graph showing a light absorption curve of copper fine particle-dispersed glass obtained in Example 1 of the present invention.

Claims (16)

[Claims] 1. A non-linear optical material characterized by comprising fine metal particles dispersed in an optically isotropic and transparent matrix having a refractive index of 1.9 or more and 4 or less. 2. Non-linear optical material according to claim 1, characterized in that the matrix is optically isotropic and transparent glass and / or crystals. 3. The glass is a glass containing B ₂ O ₃ and PbO as essential constituents, and the amount of B ₂ O ₃ is 15
The amount of PbO is 50 to 85 mol%, and the amount of PbO is 50 to 85 mol%. 4. The matrix is Ga ₂ O ₃ and Bi ₂ O.
₃ is a glass containing PbO and / or CdO as essential constituent components, and the amount of Ga ₂ O ₃ is 10 to 35 mol.
%, The amount of Bi ₂ O ₃ is 10 to 70 mol%, P
The non-linear optical material according to claim 1 or 2, wherein the total amount of bO and CdO is 20 to 80 mol%. 5. A glass whose matrix contains Bi ₂ O ₃ and / or PbO and at least one selected from ZnO, BaO, CdO and Al ₂ O ₃ as essential constituents, and Bi ₂ O ₃ The total amount of PbO is 30-85 mol
% And is, non-linear optical material according to claim 1 or 2 the total amount of ZnO and BaO and CdO and Al ₂ O ₃ is characterized in that it is a 15 to 70 mol%. 6. The matrix comprises GeO ₂ and Bi ₂ O ₃ ,
A glass containing at least one selected from T1 ₂ O and PbO as an essential constituent component, and having an amount of GeO _{2 of} 25 to 70 mol%, and containing Bi ₂ O ₃ , T1 ₂ O and PbO.
The non-linear optical material according to claim 1 or 2, wherein the total content is 30 to 75 mol%. 7. The glass is a matrix in which TiO ₂ and PbO are essential constituent components, the amount of TiO ₂ is 30 to 75 mol%, and the amount of PbO is 25 to 70 mol%.
%, The nonlinear optical material according to claim 1 or 2. 8. A glass in which the matrix contains TeO ₂ and / or Sb ₂ O ₃ and PbO as essential constituent components, and the total amount of TeO ₂ and Sb ₂ O ₃ is 20 to 95 mol%.
The amount of PbO is 5 to 80 mol%, and the nonlinear optical material according to claim 1 or 2. 9. The matrix comprises TeO ₂ and / or Sb ₂ O ₃ and BaO, BeO, MgO, SrO, ZnO.
And at least one selected from CdO, which is a glass containing as essential constituent components, the total amount of TeO ₂ and Sb ₂ O ₃ being 60 to 98 mol%, and BaO, BeO, and MgO.
The non-linear optical material according to claim 1 or 2, wherein the total amount of SrO, SrO, ZnO, and CdO is 2 to 40 mol%. 10. A matrix comprising Bi ₂ O ₃ , CdO and / or ZnO, B ₂ O ₃ , SiO ₂ and P ₂ O ₅
A glass containing at least one selected from the following as an essential constituent component, the amount of Bi ₂ O ₃ is 10 to 90 mol%, the total amount of CdO and ZnO is 5 to 85 mol%, and B ₂ O ₃
A nonlinear optical material according to claim 1 or 2 the total amount of SiO ₂ and P ₂ O ₅ is characterized in that it is a 1 to 30 mol%. 11. The matrix is As, Ge and Sb.
A glass containing at least one selected from the group consisting of S, Se and Te as an essential constituent component, and having a total amount of As, Ge and Sb of 10 to 60 at.
%, And the total amount of S, Se, and Te is 90 to 40 at%, The nonlinear optical material according to claim 1 or 2, wherein 12. The matrix is ZnS, ZnSe, Z.
nTe, CuCl, CuBr, CuI, TlI, CsP
bCl ₃ , AgGaSe ₂ , As ₂ S ₃ , Tl ₃ TaS 4, T
l ₃ TaSe ₄ , Tl ₃ VS ₄ , CdS, CdSe, Pb
S, GaSe, GaP, diamond, Y ₂ O ₃ , La ₂
O ₂ S, SrTiO ₃ , K (Ta, Nb) O ₃ , Tl ₃ T
aSe ₄ , Bi ₂ WO ₆ , Bi ₄ Ti ₃ O ₁₂ , Bi ₄ Ge ₃ O
₁₂ , Bi ₄ Si ₃ O ₁₂ , Y ₃ Ga ₅ O ₁₂ , Gd ₃ Ga ₅ O ₁₂ ,
(Ga, Al) As, Ga (As, P), Bi ₁₂ Ge
O ₂₀ , Bi ₁₂ SiO ₂₀ , CoFe ₂ O ₄ , PbGeO ₃ ,
Pb (Mg _1/3 , Nb _2/3 ) O ₃ , Pb (Mg _1/3 , Ta
_{2/3) O 3, Pb (Zn} 1/3, Nb 2/3) O 3, (Pb, L
a) At least one crystal selected from (Zr, Ti) O ₂ and ZnWO _4.
Alternatively, the nonlinear optical material according to item 2. 13. The dispersed metal fine particles are copper, silver, gold, platinum,
Palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, bismuth, antimony, lead, or an alloy of these or an alloy containing 80 mol% or more of these. The nonlinear optical material according to claim 1 or 2, wherein the nonlinear optical material is at least one selected from the group consisting of: 14. The dispersed metal fine particles have a radius of 1 to 100 n.
The nonlinear optical material according to claim 1 or 2, wherein m is m. 15. The method for producing a nonlinear optical material according to claim 1, wherein a melting / thermal deposition method, an ion implantation method, an ion exchange method or a sputtering method is used. 16. A non-linear optical element, characterized by using the non-linear material according to any one of claims 1 to 14.