JP2004115294A - Fluorescent glass and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorescent glass of which the fluorescent properties are modified without degrading the chemical durability, and to provide a method for manufacturing the same. <P>SOLUTION: The method for manufacturing the fluorescent glass is characterized by injecting ions of copper element and ions of halogen elements into a substrate of glass containing 70mol% or more of SiO<SB>2</SB>by the ion injection method, and then heat-treating the same. The fluorescent glass having the copper element and the halogen element doped therein is provided by using the method. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a fluorescent glass and a method for manufacturing the same.
[0002]
[Prior art]
A fluorescent glass material doped with a copper element has high quantum efficiency (for example, see Non-Patent Document 1), and is transparent and easy to process, so that it can be used for an ultraviolet light detector, a display element, and a laser. Applications are being considered. In order to obtain a glass material having a desired fluorescence wavelength, it is necessary to change the type of atoms and the coordination structure coordinated to the copper element. For this purpose, conventionally, the composition of the glass base material in which the fluorescent ions are dispersed has been changed (for example, see Non-Patent Document 1). However, when the composition of the base material is changed, there is a problem of practically deteriorating the chemical durability.
[0003]
[Non-patent document 1]
C. Parent, "Optical Materials", 1994, Volume 4, p. 107
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a technique for changing the fluorescent characteristics of a fluorescent glass without deteriorating the chemical durability of the fluorescent glass.
[0005]
[Means for Solving the Problems]
The present inventors have conducted intensive studies, and as a result, the glass obtained by dispersing the copper element and the element to be coordinated with the copper element in a glass base material having high chemical durability and performing a heat treatment, The present inventors have found that not only the wavelength is changed, but also the same chemical durability as the base material is maintained, and the present invention has been completed.
[0006]
That is, the present invention provides a fluorescent glass and a method for producing the same as described below.
Item 1. A method for manufacturing a fluorescent glass, comprising: implanting ions of a copper element and ions of a halogen element into a glass substrate containing 70 mol% or more of SiO ₂ by an ion implantation method, followed by heat treatment.
Item 2. Item ^{3. The} method for producing a fluorescent glass according to Item 1, wherein the ion concentration of each of the copper element ion and the halogen element ion is 1 × 10 ¹⁹ to 1 × 10 ²¹ / cm ³ .
Item 3. Item 3. The method for producing a fluorescent glass according to Item 1 or 2, wherein the substrate subjected to the ion implantation is heat-treated at 200 to 900 ° C.
Item 4. Item 4. A fluorescent glass obtained by the method according to any one of Items 1 to 3, doped with a copper element and a halogen element.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
In the method of the present invention, ions of a copper element and ions of a halogen element are accelerated and injected into a glass material to be a substrate by an ion implantation method.
[0008]
The glass material used as the substrate is a silica-based glass containing 70 mol% or more of SiO ₂ and contains less than 30 mol% of other components such as Na ₂ O, CaO, Al ₂ O ₃ , B ₂ O ₃ , and GeO _2. You may go out.
[0009]
Examples of the halogen element include F, Cl, Br, and I, and at least one of these ions is implanted.
[0010]
Regarding the ion implantation method, there are no particular restrictions on the method of the apparatus for performing the ion implantation method, the implantation conditions (eg, acceleration voltage, ion current, degree of vacuum, substrate temperature), and the method can be performed according to a conventional method. However, the temperature of the substrate is preferably 900 ° C. or less in consideration of a temperature at which a heat treatment in a later step is performed.
[0011]
The concentration of each of the implanted ions of the copper element ion and the halogen element ion is preferably 1 × 10 ¹⁹ to 1 × 10 ²¹ / cm ³ . If the respective implanted ion concentrations of the copper element ion and the halogen element ion are less than 1 × 10 ¹⁹ / cm ³ or more than 1 × 10 ²¹ / cm ³ , sufficient fluorescence intensity is obtained. It tends to be difficult to obtain. The concentration ratio between the copper element ion and the halogen element ion is not particularly limited, but it is preferable that the halogen element ion concentration: copper element ion concentration = 0.5 to 2: 1.
[0012]
In order to generate fluorescence, it is necessary to heat (heat-treat) the substrate after ion implantation. If the heat treatment is not performed, fluorescence from defects caused by ion implantation is mainly used, and sufficient fluorescence intensity due to copper cannot be obtained. Further, since damage is caused by ion implantation, it is necessary to perform heat treatment after ion implantation in order to maintain the chemical durability and mechanical strength of the glass substrate before ion implantation. The heat treatment is preferably performed in a temperature range of 200 to 900C, more preferably in a temperature range of 500 to 700C. When the heat treatment is performed at a temperature exceeding 900 ° C., crystals made of the implanted element are precipitated, and fluorescence tends to be hardly observed. The heat treatment is preferably performed for 5 minutes to 1 hour.
[0013]
The fluorescent glass obtained as described above is doped with a copper element and a halogen element, and emits fluorescence.
[0014]
【The invention's effect】
According to the present invention, the fluorescent wavelength can be changed without impairing the chemical durability of the glass substrate, and the obtained fluorescent glass can be used as a fluorescent material in many products such as an ultraviolet ray detection device and a display device. Is possible.
[0015]
【Example】
Examples are shown below to further clarify features of the present invention.
[0016]
Example 1
1 × 10 ²⁰ ions / cm ^{3 of} Br element ions and Cu element ions were implanted into a silica glass substrate (100 mol% of SiO ₂ ). The ion implantation was performed using a tandem accelerator at an acceleration voltage of Br = 2.4 MeV, Cu = 2.0 MeV, a degree of vacuum of 10 ⁻⁷ Torr, and a substrate temperature of room temperature. After ion implantation, a fluorescent glass was obtained by performing a heat treatment at 600 ° C. for 30 minutes in the air. The fluorescence spectrum of this fluorescent glass was measured at an excitation wavelength of 235 nm using a fluorescence spectrometer (F-4500, manufactured by Hitachi, Ltd.). As shown in FIG. 1, the fluorescence spectrum was higher than that of silica glass doped only with Cu element. The fluorescence wavelength was shifted to the longer wavelength side by about 50 nm.
[0017]
The weight loss of a 1.0 gram sample immersed in 1000 ml of water at 30 ° C. was measured. The fluorescent glass of the present example was 0.0 gram, whereas the Cu-doped bromide glass was 1.0 gram. It was 0 grams. This also indicates that the chemical durability of the fluorescent glass of this example is significantly improved as compared with the bromide glass doped with Cu element.
[0018]
Example 2
1 × 10 ²⁰ ions / cm ^{3 of} I element ions and Cu element ions were implanted into a silica glass substrate (100 mol% of SiO ₂ ). The ion implantation was performed using a tandem accelerator at an acceleration voltage of I = 3.5 MeV, Cu = 2.0 MeV, a degree of vacuum of 10 ⁻⁷ Torr, and a substrate temperature of room temperature. After ion implantation, a fluorescent glass was obtained by performing a heat treatment at 600 ° C. for 30 minutes in the air. The fluorescence spectrum of this fluorescent glass was measured at an excitation wavelength of 235 nm using a fluorescence spectrometer (F-4500, manufactured by Hitachi, Ltd.). As shown in FIG. The fluorescence wavelength was shifted to the longer wavelength side by about 50 nm.
[0019]
The weight loss of a 1.0 gram sample immersed in 1000 ml of water at 30 ° C. was measured. The fluorescent glass of this example was 0.0 gram, whereas the Cu-doped iodide glass was 1 gram. Weighed 2.0 grams. From this, it can be seen that the chemical durability of the fluorescent glass of this example is significantly improved as compared with the iodide glass doped with Cu element.
[Brief description of the drawings]
FIG. 1 is a view showing a fluorescence spectrum of a fluorescent glass obtained in Example 1.
FIG. 2 is a view showing a fluorescence spectrum of the fluorescent glass obtained in Example 2.

Claims (4)

A method for manufacturing a fluorescent glass, comprising: implanting ions of a copper element and ions of a halogen element into a glass substrate containing 70 mol% or more of SiO ₂ by an ion implantation method, followed by heat treatment. Each implanted ion concentration of ions of the ion and the halogen element of the copper element, a manufacturing method of the fluorescent glass according to claim 1, characterized in that a ¹ × 10 19 ~1 × 10 ²¹ atoms / cm ^3. The method according to claim 1, wherein the ion-implanted substrate is heat-treated at 200 to 900 ° C. 4. A fluorescent glass doped with a copper element and a halogen element, obtained by the method according to claim 1.

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