JPH09188543A - Eu2+ containing blue color emission glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a transparent glass capable of emitting blue color at high efficiency by excitation with radiation rays such as ultraviolet rays or X-rays. SOLUTION: This glass has a halide- or a halogen phosphate-based glass composition and contains Eu<2+> ion in <=50mol% based on the total of positive ions. In the case of a halide-based glass composition, the ratios of positive ions are as follows: Eu<2+> , 0.001=50mol%; Al<3+> , 10-60mol%; one or more selected from Mg<2+> , Ca<2+> , Sr<2+> and Ba<2+> , 8-70mol%; one or more selected from Y<3+> , La<3+> , Gd<3+> and Yb<3+> , 0-30mol%; Hf<4+> , 0-20mol%; one or more selected from Li<+> , Na<+> and K<+> , 0-20mol%; and the ratios of negative ions are as follows: Cl<-> , 0-20mol%; F<-> , 80-100mol%. In the case of halogen phosphate-based glass composition, the rations of positive ions are as follows: Eu<2+> , 0.001-50mol%; Al<3+> , 10-60mol%; P<5+> , 0.1-80mol%; one or more selected from Mg<2+> , Ca<2+> , Sr<2+> and Ba<2+> , 8-70mol%; one or more selected from Y<3+> , La<3+> , Gd<3+> and Yb<3+> , 0-30mol%, hf<4+> , 0-20mol%; one or more selected from Li<+> , Na<+> and K<+> , 0-20mol%, and the ratios of negative ions are as follows: O<2-> , 1-95mol%, Cl<-> , 0-20mol%; F<-> , 5-99mol%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet laser, confirmation of the position of a radiation beam such as an X-ray, pattern identification of mode shapes, an optical detector used for spatial distribution, an element for an optical power meter, an image display sensor, The present invention relates to a Eu ²⁺ -containing blue light-emitting glass used as a wavelength tunable laser from ultraviolet to blue.

[0002]

2. Description of the Related Art For the development of optical information technology, development of a wavelength tunable laser from ultraviolet to blue, visualization conversion display and detection of ultraviolet light and radiation beams such as X-rays have become important. There is. Regarding the solid-state wavelength conversion laser in the ultraviolet region, in recent years, C has been used as a wavelength region around 300 nm.
Crystal materials such as e ³⁺ -YLF and Ce ³⁺ -LSAF have been developed, and research toward the practical stage is under way. Ce ³⁺
In the case of -YLF, Ce ³⁺ -LSAF, etc., it is very difficult to produce a good quality crystalline material with a large size. In addition, there is still little research on blue wavelength conversion lasers.

Sr _0.96 Mg _0.81 Al _5.44 B _0.02 is used for visualization conversion display and detection of radiation beams such as ultraviolet light and X-rays.
O ₁₀ : Eu ²⁺ , Gd ₂ O ₂ S: Tb ³⁺ , BaFCl: E
Polycrystalline phosphors such as u ²⁺ have been used. However, the manufacturing process of these polycrystalline phosphors is very difficult.
For example, in manufacturing the Gd ₂ O ₂ S: Tb ³⁺ phosphor, 10 or more steps are required in total, the production time is long, and the cost is very high. Further, in order to improve the fluorescence intensity in the post-treatment stage, it is necessary to carry out pulverization and classification to make the particle size as appropriate as possible, so that the yield becomes very poor.

As a method of using the phosphor, a method of depositing or applying the phosphor in a powder state on a substrate to form a phosphor screen is adopted. In this case, since the phosphor powder has a polyhedral shape, unevenness is generated on the phosphor surface, and a highly accurate control step is required to form a uniform film. Moreover, it is almost impossible to form a uniform film. Also,
Due to the relatively coarse filling of the powder particles with each other and the uneven surface, scattering of the emitted light occurs and there is a limit to improving the resolution. The present invention has been devised to solve such problems and drawbacks, has practical durability and mechanical strength, enables blue light emission with high luminous efficiency, and is transparent in the visible region. ^An object is to provide a 2 ⁺ -containing blue light-emitting glass.

[0005]

In order to achieve the object, the Eu ²⁺ -containing blue light-emitting glass of the present invention comprises a halide-based or halogen-based compound containing Eu ²⁺ ions in an amount of 50 mol% or less based on all cations. Has a phosphate-based glass composition,
It is characterized in that it emits blue light when irradiated with ultraviolet rays or radiation. In the halide-based glass composition, the proportion of cations is Eu ²⁺ 0.001 to 50 mol%, Al ³⁺ 10 to 60 mol%, Mg ²⁺ , Ca ²⁺ , Sr ²⁺ and Ba ²⁺ . Species 8-70 mol%, Y ³⁺ , La ³⁺ , Gd ³⁺ and Yb ³⁺
0-30 mol% of Hf ^4+, 0-20 mol% of Hf ^4+, 0-20 of at least one of Li ⁺ , Na ⁺ and K ⁺
Mol%, and the proportions of anions are Cl ^- 0 to 20 mol% and F ^- 80 to 100 mol%.

In the halogen phosphate glass composition, the proportion of cations is Eu ²⁺ 0.001 to 50 mol%, Al ³⁺ 10
60 mol%, P ⁵⁺ 0.1 to 80 mol%, Ma ²⁺ , C
at least one of a ²⁺ , Sr ²⁺ and Ba ²⁺ 8 to 70 mol%, at least one of Y ³⁺ , La ³⁺ , Gd ³⁺ and Yb ³⁺ 0 to 30 mol%, Hf ⁴⁺ 0 ~ 20 mol%, Li ⁺ , Na
^At least one of ⁺ and K ⁺ is 0 to 20 mol%, and the proportion of anions is O ^{2 to 1 to} 95 mol%, Cl ^{− to} 0 to 20 mol%, and F ^{− to 5 to} 99 mol%. This blue light emitting glass is manufactured by melting in an inert atmosphere or a reducing atmosphere and, if necessary, shaping it into a plate shape, a rod shape, or a fiber shape.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The blue light-emitting glass according to the present invention is based on a halide system or a halogen phosphate system, and any system contains Eu ²⁺ as an essential active ion. The content of Eu ²⁺ is adjusted in the range of 0.001 to 50 mol% with respect to all the cations constituting the glass. When the Eu ²⁺ concentration is less than 0.001 mol%, the intensity of fluorescence emitted by irradiation with radiation is weak. On the contrary, when the concentration exceeds 50 mol%, concentration quenching occurs, and not only the fluorescence intensity is lowered, but also the glass is easily crystallized and the molding characteristics are deteriorated. When the luminous efficiency and the molding characteristics are comprehensively judged, the concentration of Eu ²⁺ is preferably in the range of 0.05 to 10 mol%.

The halide glass contains 10 to 60 mol% of Al ³⁺ as a glass forming cation. Al ³⁺
If the concentration is less than 10 mol% or more than 60 mol%, the glass tends to crystallize. The content of Al ³⁺ is 20 to 40
A range of mol% is preferred. Mg ²⁺ , C is used as a divalent modifying ion that acts to complement the network structure of glass.
It contains at least one of a ²⁺ , Sr ²⁺ and Ba ^{2+ in} an amount of 8 to 70 mol%, preferably 8 to 60 mol%. If the concentration of these divalent modifying ions is less than 8 mol% or more than 70 mol%, the glass tends to crystallize. Examples of trivalent modifying ions that have the effect of complementing the network structure of glass include Y ³⁺ ,
At least one of La ³⁺ , Gd ³⁺ and Yb ³⁺ is contained in an amount of 0 to 30.
Mol%, preferably 0 to 25 mol%. If the concentration of these trivalent modifying ions exceeds 30 mol%, the glass tends to crystallize.

As the glass network forming cations, 0-2
It contains 0 mol%, preferably 0 to 15 mol% Hf ⁴⁺ .
If the concentration of Hf ⁴⁺ exceeds 20 mol%, the glass tends to crystallize. At least one of Li ⁺ , Na ⁺ and K ⁺ is used as a monovalent modifying ion that complements the network structure of glass.
The seed is contained in an amount of 0 to 20 mol%, preferably 0 to 10 mol%.
If the concentration of the monovalent modifying ion exceeds 20 mol%, the glass tends to crystallize. On the other hand, the proportion of anions contained in the glass is Cl ⁻ 0 to 20 mol%, F ⁻ 80 to 100.
Set to mol%. The addition of a small amount of Cl ⁻ can increase the stability of the glass against crystallization.
^If the concentration of-exceeds 20 mol%, the chemical durability of the glass deteriorates and the glass tends to crystallize. The preferable concentration range of Cl ⁻ is 0 to 10 mol%, ^and the preferable concentration range of F ⁻ is 90 to 100 mol%.

In the halogen phosphate system, the glass formability is improved by containing P ^{5+ in an amount} of 0.1 to 80 mol%, preferably 5 to 60 mol% in addition to the above-mentioned various cation concentrations. It When the P ⁵⁺ concentration is less than 0.1 mol%,
The effect of improving the formability of glass is insufficient. Conversely 8
At a P ⁵⁺ concentration exceeding 0 mol%, the chemical durability of the glass deteriorates. The proportion of anions in the halogen phosphate system is O ^{2 −} 1 to 95 mol% (preferably 1 to 50 mol%), Cl ⁻ 0 to 20 mol% (preferably 0 to 10 mol%), F ⁻ 5 to It is adjusted in the range of 99 mol% (preferably 40 to 99 mol%). O ²⁻ is effective in improving the moldability of glass and the stability against crystallization. But O
^{2-When the} concentration exceeds 95 mol%, the luminous efficiency is deteriorated and 1
If the O ^2- concentration is less than mol%, the effect of improving the moldability of glass is insufficient. Cl ⁻ is effective in improving the luminous efficiency, but if its concentration exceeds 20 mol%, the glass tends to crystallize. F ⁻ is effective in improving the luminous efficiency, but if its concentration is less than 5 mol%, the luminous efficiency becomes poor.

The Eu ₂ ⁺ -containing blue light-emitting glass according to the present invention is prepared by using a Eu ^{3 +} -containing raw material such as Eu ₂ O ₃ or EuF ₃ to prepare a glass and adding a reducing agent to a batch to melt the glass. Mold. In some cases, it is necessary to melt and mold in a reducing atmosphere. Even when the Eu ²⁺ -containing raw material is used, it is preferable to melt and mold in an inert atmosphere or a reducing atmosphere. If Eu ³⁺ remains in the glass,
For example, strong absorption occurs at 394 nm and Eu
Red emission due to ³⁺ is generated near 610 nm, and
No blue luminescence is observed upon excitation with 0 nm ultraviolet light.
This Eu ²⁺ -containing blue light-emitting glass has an excellent glass-forming ability and does not easily crystallize into a plate-like, rod-like,
It can be formed into a fiber shape. Further, since the matrix has a small non-linear optical effect and a large induction cross-sectional area, excellent blue light emission efficiency is exhibited.

[0012]

【Example】

Example 1: Proportion of cation is Eu ²⁺ 0.8 mol%, Al
³⁺ 18.8 mol%, Ca ²⁺ 19.3 mol%, Sr 2 ⁺ 1
7.8 mol%, Ba ²⁺ 7.7 mol%, P ⁵⁺ 27.9 mol% and anion ratio of O ^{2 −} 36 mol%, F ⁻ 64 mol% of the composition of the glass. And high-purity EuF
₃ , AlF ₃ , MgF ₂ , CaF ₂ , SrF ₂ , BaF
₂ and Al (PO ₃ ) ₃ raw materials were used and weighed and mixed in a glove box filled with N ₂ . The mixture was placed in a glassy carbon crucible and the mixture was placed in an atmosphere of N ₂ + 5% by volume H ₂ for 10 minutes.
After melting at 00 ° C. for 1 hour and maintaining the melt near the glass transition temperature T _g , the entire crucible was cooled.

The obtained glass was polished, and ultraviolet excitation fluorescence and X-ray excitation fluorescence were measured. When excited with 250 nm ultraviolet light dispersed from a xenon lamp, strong blue emission at 440 nm was observed as seen in the fluorescence spectrum of FIG. The peak at 500 nm is twice the excitation light at 250 nm, and is from the measurement system. FIG.
FIG. 2 shows the results of measuring the excitation emission spectrum by monitoring the emission peak of 440 nm of. Also, similar blue emission was observed by X-ray excitation. From the above results, the glass obtained in this example is 200 to 400 nm.
It was confirmed to emit blue light in a wide range of light.

Example 2: The proportion of cations is Eu ²⁺ 0.1.
Mol%, Al ³⁺ 35 mol%, Mg ²⁺ 10 mol%, Ca ²⁺
20 mol%, Sr ²⁺ 10 mol%, Ba ²⁺ 10 mol%, Y
EuF of high purity to obtain a glass having a composition of ^{3 +} 14.9 mol% and an anion ratio of F ^- 100 mol%.
₂ , AlF ₃ , CaF ₂ , SrF ₂ , BaF ₂ and YF
_{The three} raw materials were used and weighed and mixed in a glove box filled with N ₂ . Put the compound in a glassy carbon crucible,
After melting in an N ₂ atmosphere at 1000 ° C. for 1 hour and maintaining the melt near the glass transition temperature T _g , the whole crucible was cooled. The obtained glass was polished and the ultraviolet excitation fluorescence was measured. When excited with ultraviolet light of 250nm separated from a xenon lamp, outside light emission due to f-f transition of Eu ²⁺ to 360nm as seen in the fluorescence spectrum of FIG. 3, the 400nm of Eu ^2+: fd - a Strong blue emission due to the f transition was observed.

Example 3: The proportion of cations is Eu ²⁺ 1 mol%, Al ³⁺ 30 mol%, Mg ²⁺ 10 mol%, Ca ²⁺ 20
Mol%, Sr ²⁺ 10 mol%, Ba ²⁺ 10 mol%, Y ^{3 +} 1
0 mol%, Gd ³⁺ 2 mol%, La ³⁺ 2 mol%, Hf ⁴⁺ 5
Mol%, anion ratio of Cl ^- 10 mol%, F ^- 9
To obtain a glass having a composition of 0 mol%, high purity E
uF ₂ , AlF ₃ , MgF ₂ , CaF ₂ , SrF ₂ , B
aF ₂ , YF ₃ , GdF ₃ , LaF ₃ , HfF ₄ , Ba
A Cl ₂ raw material was used and weighed and mixed in a glove box filled with N ₂ . The compound was put into a glassy carbon crucible and melted at 1000 ° C. for 1 hour in an atmosphere of N ₂ + 5% by volume H ₂ , and the melt was kept near the glass transition temperature T _g .
The crucible was cooled. The obtained glass was polished and the ultraviolet excitation fluorescence was measured. 250 dispersed from a xenon lamp
A strong blue emission at 410 nm was observed upon excitation with UV light of nm.

Example 4: The proportion of cations is Eu ²⁺ 29.
3 mol%, Al ³⁺ 22.2 mol%, Mg ²⁺ 3.5 mol%, Ca ²⁺ 11 mol%, Sr ²⁺ 7.3 mol%, P ⁵⁺ 2
6.7 mol%, the proportion of anions is O ^2-36 mol%, F
^- so that the glass having a composition of 64 mol%, EuF ₂ of high _{purity, AlF 3, MgF 2, CaF} 2, SrF
₂ , Al (PO ₃ ) ₃ raw material was used, and weighed and mixed in a glove box filled with N ₂ . The blend was placed in a glassy carbon crucible, melted at 1100 ° C. for 1 hour in N ₂ atmosphere, and the melt was quenched to room temperature. The obtained glass was polished and the ultraviolet excitation fluorescence was measured. When excited with 250 nm ultraviolet light dispersed from a xenon lamp, strong blue emission was observed at 450 nm.

Example 5: The proportion of cations is Eu²⁺0.2
Mol%, Al³⁺22.9 mol%, Ca²⁺7.2 mol%,
Sr²⁺18.4 mol%, B²⁺15.7 mol%, Na⁺ 
2.6 mol%, P ⁵⁺33 mol%, the proportion of anions is O
^2-47.2 mol%, Cl^- 2.8 mol%, F^- 50 mol
% Of high purity EuF
_Two , AlF_Three, CaF_Two , SrF_Two , NaF, BaCl_Two
 , Al (PO_Three )_Three Using raw materials, N_Two Filling glow
Weighed and mixed in a box. Formulation with a glica
Put in a crucible, N_Two Melt at 1000 ° C for 1 hour in atmosphere
After melting, the melt was rapidly cooled to room temperature. Polish the resulting glass
Then, the ultraviolet excitation fluorescence was measured. Spectral from xenon lamp
When excited by 250 nm UV light,
Strong blue emission was observed.

Example 6: The proportion of cations is Eu ²⁺ 0.2.
Mol%, Al ³⁺ 38.8 mol%, Ca ²⁺ 19.4 mol%, Sr ²⁺ 9.6 mol%, B ²⁺ 9.7 mol%, Li ⁺
4.9 mol%, Na ⁺ 4.9 mol%, P 5 ⁺ 2.9 mol%
In order to obtain a glass having a composition in which the proportion of anions is O ² −4 mol% and F ⁻ 96 mol%, high-purity EuF ₂ , A
1F ₃ , CaF ₂ , SrF ₂ , BaF ₂ , LiF, Na
F, Al (PO ₃ ) ₃ raw materials were used and weighed and mixed in a glove box filled with N ₂ . The mixture was placed in a glassy carbon crucible and the mixture was placed in an atmosphere of N ₂ + 50% by volume H ₂ for 11
It was melted at 00 ° C. for 1 hour and the melt was quenched to room temperature. The obtained glass was polished and the ultraviolet excitation fluorescence was measured. When excited with 250 nm ultraviolet light dispersed from a xenon lamp, strong blue emission was observed at 420 nm.

Example 7: The proportion of cations is Eu ²⁺ 0.4
Mol%, Al ³⁺ 16.9 mol%, Ba ²⁺ 8.1 mol%,
To obtain a glass having a composition of K ⁺ 8.5 mol%, P ⁵⁺ 66.1 mol% and anion ratios of O ^{2 −} 89.2 mol% and F ⁻ 10.8 mol%, Purity EuF ₂ , AlF
₃ , BaF ₂ , KF, KPO ₃ , Ba (PO ₃ ) ₃ , A
1 (PO ₃ ) ₃ raw material was used and weighed and mixed in a glove box filled with N ₂ . Put the compound in a glassy carbon crucible and 1200 ° C. in N ₂ + 50% by volume H ₂ atmosphere.
It was melted for 1 hour and the melt was quenched to room temperature. The obtained glass was polished and the ultraviolet excitation fluorescence was measured. 4 when excited by 250 nm UV light dispersed from a xenon lamp
Strong blue emission at 50 nm was observed.

[0020]

As described above, the Eu ^{2+ of} the present invention is
The contained blue light-emitting glass has a small nonlinear optical effect of the matrix and a large induction cross-sectional area, and thus exhibits excellent blue light-emission efficiency, and can be exposed to radiation such as ultraviolet rays and X-rays in 360 °.
Fluoresces at ~ 480 nm. In addition, it has excellent glass-forming ability, and it can easily be crystallized without being crystallized.
It can be molded into an appropriate shape such as fiber, and can be used to check the position of the radiation beam such as an ultraviolet laser and X-rays, pattern identification of mode shapes, optical disks used for spatial distribution, optical power meter elements, image display sensors. ，
It is used as a wavelength tunable laser from ultraviolet to blue.

[Brief description of the drawings]

FIG. 1 is a fluorescence spectrum of the glass of Example 1 excited by ultraviolet rays of 250 nm.

FIG. 2 Excitation spectrum measured by monitoring peak fluorescence emission of the glass of Example 1

FIG. 3 is a fluorescence spectrum of the glass of Example 2 excited by 250 nm ultraviolet light.

Claims (3)

[Claims] 1. An Eu characterized in that it has a halide-based or halogen-phosphate-based glass composition containing Eu ²⁺ ions in an amount of 50 mol% or less based on all cations, and emits blue light when irradiated with ultraviolet rays or radiation. ²⁺ containing blue light emitting glass. 2. The proportion of cations constituting the halide glass composition is Eu ²⁺ 0.001 to 50 mol%, Al ³⁺
10-60 mol%, Mg ²⁺ , Ca ²⁺ , Sr ²⁺ and Ba ²⁺
At least one of 8 to 70 mol%, Y ³⁺ , La ³⁺ , Gd
^At least one of ³⁺ and Yb ³⁺ , 0 to 30 mol%, Hf ⁴⁺
0 to 20 mol%, at least one of Li ⁺ , Na ⁺ and K ⁺ is 0 to 20 mol%, and the proportion of anions is Cl ⁻ 0.
20 mol% and F ^- 80 to 100 mol%.
The blue light-emitting glass containing Eu ²⁺ described above. 3. The proportion of cations constituting the halogen phosphate glass composition is Eu ²⁺ 0.001 to 50 mol%, Al ³⁺
10-60 mol%, P ⁵⁺ 0.1-80 mol%, Ma ²⁺ ,
At least one of Ca ²⁺ , Sr ²⁺ and Ba ²⁺ 8 to 70 mol%, at least 1 of Y ³⁺ , La ³⁺ , Gd ³⁺ and Yb ³⁺
Seed 0 to 30 mol%, Hf ⁴⁺ 0 to 20 mol%, Li ⁺ , N
at least one of a ⁺ and K ⁺ is 0 to 20 mol%,
The proportion of anions is O ² −1 to 95 mol%, Cl ⁻ 0 to 20
The Eu according to claim 1, wherein the Eu content is F ^{-5 to} 99 mol%.
²⁺ containing blue light emitting glass.