JP4430329B2 - Luminescent glass production method and light emitting device that emits light by ultraviolet excitation, and method of using the light emitting device - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an oxide glass that is excellent in chemical and mechanical stability and exhibits strong luminescence, and a method for using the same.
[0002]
[Prior art]
Phosphor materials using rare earths such as Eu (europium) and Tb (terbium) have already been put to practical use in lamps, cathode ray tubes and the like. The phosphor material is produced by a method in which a powdery phosphor containing a rare earth atom is coated on a carrier, or a method in which a phosphor is coated on a carrier by a sol-gel method (Patent Document 1, Non-Patent Document 1). Reference 1 and Non-Patent Document 2). That is, since the phosphor material is produced by a method of coating the surface with a phosphor, only surface fluorescence can be obtained.
[0003]
However, there is a need for a phosphor material that is transparent and can be bulk-molded for use in the adjustment of high-intensity lamps, displays, or short-wavelength lasers. As such a phosphor material, it is preferable to use a stable oxide glass. However, in the conventional oxide glass, since the bond between the rare earth atom as the emission center and the oxide glass matrix is strong, a luminescent glass that easily emits non-radiative transition and exhibits strong light emission cannot be obtained.
[0004]
In order to solve this problem, fluorescent glass using fluoride glass and oxyfluoride glass (see Patent Document 2 and Patent Document 3) has been developed. A method for producing oxide glass containing a large amount of rare earths is also disclosed (see Patent Document 4).
[0005]
As another method for producing luminescent glass, porous oxide glass (Vycor glass) is doped with ions (see Non-Patent Document 3 and Non-Patent Document 4) or semiconductor fine particles (Patent Document 5 and Non-Patent Document). 5-7) is disclosed.
[0006]
In addition, some lighting fixtures using the above-described luminescent glass and fluorescent fixtures using a fluorescent material are known. As a lighting technique using a fluorescent material and an ultraviolet lamp (for example, a black light), a technique for irradiating ultraviolet light onto a plate coated with a fluorescent paint and using it as a display device (Patent Document 6), light is emitted by the ultraviolet light. A sign device (Patent Document 7) using a phosphor and a black light is disclosed. Furthermore, a highly transparent planar light-emitting luminaire using fluoride glass and black light is known (Patent Document 8).
[0007]
Furthermore, underwater lighting fixtures that illuminate water tanks and the like from the inside are known, but as conventional underwater lighting fixtures, devices that feed power (power transmission) cords underwater, or waterproof lighting fixtures that use electromagnetic induction A lighting fixture that lights a waterproof lamp is also known (Patent Document 9).
[0008]
[Patent Document 1]
JP 2001-270733 A (publication date: October 2, 2001)
[0009]
[Patent Document 2]
JP-A-8-133780 (publication date May 28, 1996)
[0010]
[Patent Document 3]
JP 9-206422 A (publication date August 5, 1997)
[0011]
[Patent Document 4]
JP 10-167755 A (publication date June 23, 1998)
[0012]
[Patent Document 5]
US Pat. No. 6,211,526
[0013]
[Patent Document 6]
JP 2001-290447 A (publication date October 19, 2001)
[0014]
[Patent Document 7]
Japanese Patent Laid-Open No. 10-333619 (Publication date: December 18, 1998)
[0015]
[Patent Document 8]
Japanese Patent Laid-Open No. 11-283415 (publication date: October 15, 1999)
[0016]
[Patent Document 9]
JP 2002-251901 A (publication date September 6, 2002)
[0017]
[Non-Patent Document 1]
“Enhanced emission from Eu” by M. Nogami and Y. Abe ²⁺ ions in sol-gel derived Al ₂ O _Three -SiO ₂ glasses. ", Appl. Phys. Lett., 69 (25) 3776 (1996), published by the American Institute of Physics (issued December 16, 1996)
[0018]
[Non-Patent Document 2]
M. Nogami, "Fluorescence properties of Eu-doped GeO ₂ -SiO ₂ glass heated under an H ₂ atmosphere. ", J. Luminescence, 92, 329 (2001), published by Elsevier Science (published April 2001)
[0019]
[Non-Patent Document 3]
H. Mack, R. Reisfeld and D. Avnir, "Fluorescence of rate earth ions adsorbed on porous vycor glass.", Chem. Phys. Lett. Vol. 99, No. 3, 238 (1983), published by Elsevier Science. (Issued date: August 5, 1983)
[0020]
[Non-Patent Document 4]
R. Reisfeld, N. Manor and D. Avnir, “Transparent high surface area porous supports as new materials for luminescent solar concentrators.”, Solar Energy Materials, 8, 399 (1983), published by North-Holland Publishing Company 1983)
[0021]
[Non-Patent Document 5]
AL Huston, BL Justus and TL Johnson, "Fiber-optic-coupled, laser heated thermoluminescence dosimeter for remote radiation sensing.", Appl. Phys. Lett., 68 (24), 3377 (1996), published by American Institute of Physics. (Published June 10, 1996)
[0022]
[Non-Patent Document 6]
BL Justus and AL Huston, “Ultraviolet dosimetry using thermoluminescence of semiconductor-doped Vycor glass.”, Appl. Phys. Lett., 67 (9), 1179 (1995), published by American Institute of Physics (published in August 1995) 28th)
[0023]
[Non-Patent Document 7]
BL Justus, AL Huston and TL Johnson, “Laser-heated radiation dosimetry using transparent thermoluminescent glass.”, Appl. Phys. Lett., 68 (1), 1 (1996), published by American Institute of Physics. January 1,
[0024]
[Problems to be solved by the invention]
However, the above-described fluorescent glass using the conventional fluoride glass or oxyfluoride glass has a problem that it has not only poor heat resistance and chemical durability but also low mechanical strength. For this reason, in the said conventional fluorescent glass, preparation of a large sized glass plate etc. is difficult, and it was difficult to use it in air | atmosphere, especially outdoors over a long period of time. Further, fluoride and the like have many problems such as having an adverse effect on the environment.
[0025]
In addition, an oxide glass containing a large amount of rare earth has excellent heat resistance, chemical durability, and mechanical strength, but has a problem that its price is very high because it contains a large amount of rare earth.
[0026]
Furthermore, the luminescent glass obtained by the conventional method of doping porous oxide glass with ions or semiconductor fine particles has a problem that fluorescence with high emission intensity cannot be obtained. For example, when the above conventional luminescent glass is irradiated with ultraviolet rays using an ultraviolet lamp of about several watts, strong fluorescence that can be sufficiently confirmed by visual observation cannot be obtained.
[0027]
In addition, the organic fluorescent paint used in the conventional lighting device has a problem that it is not suitable for long-term outdoor use because it lacks chemical durability, and the lighting device using the organic fluorescent paint is short-term. There is a problem that it is limited to signs for use and indoor use.
[0028]
Furthermore, as described above, a lighting device using fluoride glass has many problems with respect to the environment, and when used outdoors for a long period of time, there is a problem that it lacks stability.
[0029]
In addition, the conventional underwater lighting fixtures are not only poor in appearance, but also have a problem that there is a risk of electric leakage if the power transmission cord is damaged.
[0030]
The present invention has been made in view of the above-mentioned problems, and the purpose thereof is a light-emitting glass that exhibits excellent heat resistance, chemical durability, and mechanical strength, and exhibits strong light emission upon irradiation with ultraviolet rays or the like. And a method for producing the luminescent glass, and a method for using the luminescent glass.
[0031]
[Means for Solving the Problems]
As will be described later, the present inventors impregnate a porous glass (porous silica glass) produced using waste glass or the like with a rare earth compound or the like, and then perform firing in the air or in a reducing atmosphere. Thus, an oxide glass was obtained. As a result of detailed examination of the oxide glass, the oxide glass has excellent heat resistance, chemical durability, and mechanical strength, and does not contain a large amount of rare earth atoms. The inventors have found that they exhibit strong luminescence, and have completed the present invention based on these findings.
[0032]
That is, in order to solve the above problems, the method for producing a luminescent glass according to the present invention includes a first step of adsorbing rare earth atoms on the porous glass, and a rare earth atom-containing adsorbed porous glass obtained by the first step. And a second step of firing in air or in a reducing atmosphere.
[0033]
The luminescent glass produced by the above method is excited by irradiation with light in the ultraviolet region and emits strong fluorescence. That is, the luminescent glass can convert ultraviolet rays into visible light with high efficiency. Furthermore, since the light-emitting glass is an oxide glass, the light-emitting glass is excellent in heat resistance, chemical durability, and mechanical strength. Therefore, according to the above configuration, it is possible to easily produce an oxide glass that exhibits excellent heat resistance, chemical durability, and mechanical strength and exhibits strong light emission.
[0034]
In addition, since the glass matrix contains a large amount of silica, the light-emitting glass has the advantage that the mother glass has high ultraviolet transmittance and can be excited by light having a shorter wavelength, and defects due to ultraviolet irradiation are less likely to occur. In addition, since the above light-emitting glass emits light strongly without containing a large amount of rare earth, the cost can be reduced.
[0035]
The rare earth atom is preferably at least one kind of lanthanoid atom, and more preferably Eu, Ce, or Tb. With these atoms, it is possible to produce a luminescent glass that emits powerful light.
[0036]
In the luminescent glass production method according to the present invention, the first step is preferably a step of impregnating a porous glass with a solution containing the rare earth atom-containing compound.
[0037]
According to said structure, the compound which has the said rare earth atom (Hereafter, it may only be called a rare earth compound) can be easily infiltrated into porous glass. Therefore, it is possible to easily produce an oxide glass that has excellent heat resistance, chemical durability, and mechanical strength and exhibits strong light emission.
[0038]
Moreover, as for the luminescent glass production method which concerns on this invention, it is preferable that the calcination temperature in the said 2nd process is 900 degreeC or more.
[0039]
According to said structure, the porous glass which made the rare earth atom adsorb | suck can fully be sintered. For this reason, it is possible to produce an oxide glass that is excellent in heat resistance, chemical durability, and mechanical strength and exhibits strong light emission.
[0040]
In the luminescent glass production method according to the present invention, the first step preferably further includes a step of adsorbing a sensitizer to the porous glass.
[0041]
According to said structure, the valence control of rare earth ions can be performed with baking. For this reason, the luminescent glass which emits fluorescence more strongly can be produced.
[0042]
The luminescent glass production method according to the present invention preferably further includes a step of rapidly cooling after firing in the second step.
[0043]
According to said structure, it can prevent that a matrix (oxide glass base material) and a rare earth atom react. For this reason, the luminescent glass which emits stronger fluorescence can be produced.
[0044]
Moreover, in order to solve said subject, the luminescent glass which concerns on this invention is produced by one of said luminescent glass production methods.
[0045]
The luminescent glass according to the present invention is excited by irradiation with light in the ultraviolet region and emits strong fluorescence. That is, the luminescent glass can convert ultraviolet rays into visible light with high efficiency. Furthermore, since the light-emitting glass is an oxide glass, the light-emitting glass is excellent in heat resistance, chemical durability, and mechanical strength. In addition, since the glass matrix contains a large amount of silica, the light-emitting glass has the advantage that the mother glass has high ultraviolet transmittance and can be excited by light having a shorter wavelength, and defects due to ultraviolet irradiation are less likely to occur. Moreover, the light emitting glass can be produced at a low price.
[0046]
Moreover, in order to solve said subject, the illuminating device which concerns on this invention is equipped with said luminescent glass and an ultraviolet light source, It is characterized by the above-mentioned.
[0047]
As described above, the light-emitting glass according to the present invention is excellent in heat resistance, chemical durability, and mechanical strength, and further has high transparency, so that it can be excited not only by short-wavelength light but also by ultraviolet irradiation. There is an advantage that defects are hardly generated. Moreover, the said luminescent glass has the advantage that it can be manufactured at low cost.
[0048]
For this reason, the lighting device according to the present invention has little adverse effect on the environment, and can be used as a lighting fixture that is stable for a long time even outdoors. Furthermore, this lighting device can be used as a transparent glass that does not damage the environment during the daytime, and can be used as a lighting fixture that uses a light source such as a black light at night. It can be used for signboards that give a good impression. Moreover, since the said illuminating device does not use a lot of expensive rare earth atoms, it can be produced at low cost.
[0049]
In addition, an underwater lighting device according to the present invention is characterized by including the light emitting glass and the ultraviolet light source.
[0050]
The luminescent glass emits light when irradiated with ultraviolet rays even in water, as shown in Examples described later. For this reason, according to the illuminating device of this invention, it can be used as an underwater illuminating device with strong emitted light intensity | strength, for example by irradiating a light-emitting glass with an ultraviolet-ray from the outside of water or in water. Since such an underwater lighting device does not require a power transmission cord or the like, there is no risk of electric leakage even in water, and there is an advantage that the aesthetics are not impaired. In addition, the advantage as an illuminating device is as above-mentioned.
[0051]
In the illumination device according to the present invention, the illumination device further includes an optical fiber, one end of the optical fiber is connected to the ultraviolet light source, and the other end of the optical fiber is the light emitting device. It is preferably provided in the vicinity of the glass.
[0052]
According to said structure, the ultraviolet-ray irradiated from the said ultraviolet light source is irradiated with respect to the said light emission glass from the said light emission glass vicinity via the said optical fiber. That is, ultraviolet rays can be introduced to the vicinity of the illumination part (light-emitting glass) by the optical fiber. For this reason, the illuminating device according to the present invention is more than the case of irradiating the illumination portion (light emitting glass) with ultraviolet rays from a position away from the illumination portion (light emitting glass), for example, outside the water tank. It can be used as a lighting device having a higher emission intensity. Furthermore, since ultraviolet rays are introduced through an optical fiber and no power transmission cord is required, there is no danger of leakage, and it can be used as an underwater lighting device with excellent aesthetics.
[0053]
Moreover, in order to solve said subject, the illumination method which concerns on this invention is characterized by utilizing said luminescent glass and an ultraviolet light source.
[0054]
The above method has little adverse effect on the environment and can be used as a stable lighting method for a long time even outdoors, not only as a method for displaying dangerous spots at night, or as a lighting method that gives a comfortable impression to people. It can also be used as an underwater lighting method.
[0055]
In addition, a display device according to the present invention includes the light emitting glass.
[0056]
With the above structure, light emission and transparency of the light-emitting glass can be used, so that a display device having a transmission arrangement and a three-dimensional (3D) display capability can be obtained.
[0057]
DETAILED DESCRIPTION OF THE INVENTION
One embodiment of the light emitting glass production method and the light emitting glass according to the present invention will be described below. The present invention is not limited to this.
[0058]
(1) Luminescent glass production method
The method for producing a luminescent glass according to the present invention includes a first step of adsorbing rare earth atoms on a porous glass and a rare earth atom-adsorbing porous glass obtained by the first step being fired in the atmosphere or in a reducing atmosphere. What is necessary is just to have a 2nd process. Below, each process, material, a product, etc. in the luminescent glass production method of this invention are demonstrated in detail.
[0059]
(1-1) First step
It is preferable that the porous glass used in the first step in the method for producing a luminescent glass of the present invention has a relatively small pore diameter. This is because it is considered that the pore size needs to be reduced by firing so that the pore diameter is confined in the matrix.
[0060]
Moreover, the said porous glass should just be a glass which has a silica as a main component, and the chemical composition etc. of each atom contained are not specifically limited. Moreover, a conventionally well-known method can be utilized for the preparation method of this porous glass. For example, as shown in the examples described later, a compound containing a predetermined proportion of Si, O, B, Na, and Al is added to a commercially available waste glass and melted at a high temperature, followed by cooling and molding. However, the present invention is not limited to this method.
[0061]
The step of adsorbing rare earth atoms on the porous glass may be a step of adsorbing rare earth atoms (including rare earth ions; the same applies to the present invention) or rare earth compounds on the surface and pores of the porous glass. Specific examples include a method of impregnating the porous glass with a solution containing a rare earth atom or a rare earth compound, or a method of applying a solution containing a rare earth atom or a rare earth compound to the porous glass. The solvent of the solution may be water or an organic solvent other than water, and is not particularly limited. The amount of rare earth atoms or rare earth compounds adsorbed on the porous glass can be set as appropriate.
[0062]
Further, conditions for adsorbing rare earth atoms or rare earth compounds on the porous glass, such as the time, temperature, number of times, the amount of solution, the pH of the solution, etc. for impregnating the porous glass into the solution, and the porosity The frequency | count etc. which apply | coat the said solution to a porous glass can be suitably set, and are not specifically limited.
[0063]
Alternatively, after the rare earth atom or rare earth compound is adsorbed on the porous glass, it is once dried and the rare earth atom or rare earth compound is adsorbed again. That is, a drying step may be inserted in the middle of the first step, and the step of adsorbing the rare earth atoms and the drying step may be repeated a plurality of times. Thereby, rare earth atoms or rare earth compounds can be reliably adsorbed to the porous glass, concentration quenching can be prevented, and luminescent glass with higher emission intensity can be produced.
[0064]
Examples of the rare earth atoms include Sc (scandium), Y (yttrium), and lanthanoids (La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium)) belonging to the group 3A of the long-period type periodic table. , Pm (promethium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium), Yb (ytterbium) , Lu (lutetium)). The rare earth atom referred to in the present invention includes a rare earth ion.
[0065]
Among these atoms, at least one atom of a lanthanoid is preferable, and Eu, Ce, and Tb are particularly preferable. This is because a light-emitting glass with high emission intensity can be easily produced with the above-mentioned atoms. Needless to say, the rare earth atoms may be used alone or in combination with a plurality of rare earth atoms.
[0066]
Examples of the rare earth compound include Sc compounds, Y compounds, and lanthanoid compounds. Specifically, for example, compounds such as nitrates, oxides, chlorides, carbonates, sulfates, organometallic salts containing rare earth atoms, and conventionally known compounds such as hydrates of these compounds can be mentioned, It is not particularly limited.
[0067]
Moreover, the 1st process in the luminescent glass production method of this invention may have further the process of making a porous glass adsorb | suck a sensitizer.
[0068]
The step of adsorbing the sensitizer on the porous glass is not particularly limited as long as it is a step of adsorbing the sensitizer on the surface and pores of the porous glass. Specifically, for example, as shown in the examples described later, a method of impregnating a porous glass with a solution containing a sensitizer, a method of applying a solution containing a sensitizer to the porous glass, etc. Can be mentioned. As the solvent of the solution, a conventionally known solvent such as water or an organic solvent can be used. Further, the step of adsorbing the sensitizer to the porous glass may be performed a plurality of times. Thereby, a sensitizer can be easily infiltrated into the porous glass, and a luminescent glass that emits light more strongly can be produced.
[0069]
Moreover, the said sensitizer should just be a compound (for example, oxide etc.) with a composition different from oxide glass (silica), and is not specifically limited. Specifically, for example, a compound containing at least one of atoms such as Al (aluminum), Zn (zinc), Sn (tin), and Mg (magnesium) can be given. Examples of these compounds include compounds such as nitrates, oxides, chlorides, sulfates or carbonates containing the above atoms, and conventionally known compounds such as hydrates of these compounds.
[0070]
The amount of the sensitizer adsorbed on the porous glass can be set as appropriate and is not particularly limited.
[0071]
The step of adsorbing the sensitizer to the porous glass may be performed at any stage before or after the step of adsorbing the rare earth atom to the porous glass. Further, the rare earth atom and the sensitizer are adsorbed to the porous glass. You may perform the process to make it simultaneously. In addition, a drying step may be provided between the step of adsorbing the rare earth atoms on the porous glass and the step of adsorbing the sensitizer on the porous glass, and a plurality of these two adsorption steps and drying steps may be provided. It can be repeated once.
[0072]
That is, the step of adsorbing the sensitizer to the porous glass may be performed at any stage as long as it is before firing in the second step described below, and conditions such as the number of times can be appropriately set.
[0073]
(1-2) Second step
The second step in the luminescent glass production method of the present invention may be a step in which the rare earth atom-adsorbed porous glass obtained in the first step is baked in the atmosphere or in a reducing atmosphere. Etc. are not particularly limited. For example, as a method for firing in a reducing atmosphere, a method of firing in an alumina crucible containing carbon, as shown in Examples described later, and the like can be mentioned.
[0074]
The firing temperature is preferably 900 ° C. or higher. This is because, as shown in the examples described later, when firing at a temperature lower than 900 ° C., an oxide glass exhibiting sufficient light emission cannot be obtained. This is because the pore diameter and surface state of the porous glass on which rare earth atoms are adsorbed can be controlled by firing at 900 ° C. or higher.
[0075]
The upper limit of the firing temperature is preferably 1600 ° C. This is because the substrate glass softens when fired at a temperature higher than this.
[0076]
Moreover, the time for firing, the rate of increasing the temperature, and the like can be set as appropriate, and are not particularly limited.
[0077]
Moreover, it is preferable to include the process of rapidly cooling the oxide glass obtained after the said baking. This is because it is known that when the firing is performed for a long time or when the rapid cooling is not performed after the firing, the matrix (oxide glass base) reacts with the rare earth atoms, and the fluorescence becomes weak. . The method of rapid cooling is not particularly limited, and examples thereof include a method of cooling in a constant temperature bath and a method of leaving in the atmosphere. The cooling time, the cooling rate, etc. can be set as appropriate.
[0078]
(2) Luminescent glass
The luminescent glass according to the present invention may be a luminescent glass produced by the above method, and the chemical composition only needs to contain at least Si (silicon), O (oxygen), and rare earth atoms, and is particularly limited. Is not to be done.
[0079]
In addition, the luminescent glass according to the present invention is excited by irradiation with light in the ultraviolet region and emits strong fluorescence, as shown in Examples described later. That is, it can be said that the luminescent glass according to the present invention can convert ultraviolet rays or X-rays into visible light with high efficiency. Furthermore, since the light emitting glass according to the present invention is an oxide glass having a stable glass matrix, it has excellent heat resistance, chemical durability, and mechanical strength.
[0080]
In addition, since the glass base material contains a large amount of silica, the light-emitting glass according to the present invention has an advantage that the mother glass has high ultraviolet transmittance and can be excited by light having a shorter wavelength. In addition, there is an advantage that defects due to ultraviolet irradiation hardly occur. Further, since light is emitted strongly without containing a large amount of rare earth, it is possible to reduce the cost.
[0081]
Specifically, as shown in the examples described later, for example, a luminescent glass obtained by firing at 1100 ° C. in a reducing atmosphere using Eu as a rare earth atom has an emission intensity by ultraviolet light excitation. Exhibited large blue light emission. On the other hand, the luminescent glass obtained when fired in the atmosphere did not show sufficient luminescence (see FIGS. 2 and 3).
[0082]
Further, the luminescent glass obtained by firing at 1100 ° C. in a reducing atmosphere using Ce as a rare earth atom exhibited emission with high emission intensity by ultraviolet light excitation (see FIGS. 4 and 5). Further, Al (NO) as a sensitizer is further added to the porous glass on which Ce is adsorbed. _Three ) _Three The light-emitting glass obtained by baking after adsorbing luminescence showed stronger light emission (see FIGS. 4 and 5).
[0083]
When the rare earth atoms were baked at 1100 ° C. using Tb as the rare earth atoms, the resulting luminescent glass exhibited red luminescence with high emission intensity by ultraviolet light excitation (see FIGS. 6 and 7). .
[0084]
As described above, when a porous glass adsorbed with rare earth atoms such as Eu, Ce, and Tb is fired in the atmosphere, the rare earth atoms are usually stable trivalent or tetravalent ions (for example, Eu ³⁺ , Tb ³⁺ , Ce ⁴⁺ Etc.). For this reason, the light-emitting glass mainly exhibits red light emission or does not show so strong light emission due to ultraviolet light excitation. On the other hand, by firing the rare earth atom-adsorbed porous glass in a reducing atmosphere, for example, Eu ions are converted from trivalent to divalent ions (Eu ³⁺ → Eu ²⁺ ). For this reason, it is thought that luminescent glass will exhibit blue light emission with large luminescence intensity.
[0085]
When the sensitizer is present together with the rare earth atom, the sensitizer becomes an oxide by firing at a high temperature, and has an effect of enhancing fluorescence from the rare earth atom. For this reason, it is thought that the luminescent glass obtained by baking the porous glass which adsorb | sucked the rare earth atom and the sensitizer will exhibit stronger luminescence by ultraviolet light excitation.
[0086]
From these results, according to the method for producing a luminescent glass according to the present invention, the porous glass adsorbed with rare earth atoms is sufficiently baked in the presence or absence of a sensitizer, thereby producing rare earth ions and glass. It can be said that the control with the interface can be appropriately performed.
[0087]
Moreover, it is thought that the state of the interface between the rare earth ions and the glass is different from that of a normal oxide glass in the luminescent glass according to the present invention by firing in a reducing environment.
[0088]
Furthermore, as shown in the Example mentioned later, the light emission glass which concerns on this invention light-emits strongly, heating even with a burner. It also emits intense light even in warm water. From this, it can be said that the light-emitting glass emits strong light in both air and water under a high temperature environment, and has both excellent heat resistance and light emission. Of course, it goes without saying that the luminescent glass emits light strongly even in a high temperature environment.
[0089]
The luminescent glass according to the present invention has the excellent functions as described above. For this reason, for example, it can be used for optical axis adjustment of an excimer laser or the like. Further, it can be used for a fluorescent tube for a lamp, a fluorescent fiber, a display, an LCD backlight, a display device, or the like.
[0090]
Furthermore, the luminescent glass according to the present invention can be formed into various shapes such as tubes, plates, fibers, and the like by appropriately changing the manufacturing conditions. Specifically, for example, when producing a porous glass, there is a step of once melting at a high temperature as shown in Examples described later. After being melted at a high temperature, it is poured into a mold having various shapes and cooled to form a porous glass having a desired shape. Therefore, by using the porous glass having various shapes, it is possible to produce light-emitting glasses having various shapes such as tubes, plates, fibers and the like.
[0091]
(3) Utilization of luminescent glass according to the present invention
The luminescent glass according to the present invention is excited by ultraviolet rays or X-rays and emits light in the visible range, and further has excellent heat resistance, chemical durability, and mechanical strength. In addition, the light-emitting glass according to the present invention has an advantage that it is excited by short-wavelength light and does not easily cause defects due to ultraviolet irradiation. In addition, production costs can be reduced.
[0092]
For this reason, the outstanding illuminating device can be produced using the said light emission glass. That is, the illuminating device according to the present invention only needs to include the light emitting glass and the ultraviolet light source, and other configurations may include various configurations of conventionally known illuminating devices, and are particularly limited. It is not something. Moreover, it can be said that the illuminating device which concerns on this invention should just utilize the said light emission glass.
[0093]
In addition, the “ultraviolet light source” in the present invention is not limited as long as it can irradiate the light emitting glass with an electromagnetic wave having a wavelength range called so-called X (X-ray) or ultraviolet light, and can emit light. In general, the intensity of ultraviolet rays, the number of watts (W), and the like can be appropriately set and are not particularly limited. Specifically, for example, a conventionally known commercially available black light or ultraviolet lamp can be used.
[0094]
The lighting device according to the present invention can also be used in water. This is because the luminescent glass emits light when it receives ultraviolet rays even in water, as shown in the examples described later.
[0095]
The lighting device according to the present invention further includes an optical fiber, one end of the optical fiber is connected to the ultraviolet light source, and the other end of the optical fiber is provided in the vicinity of the light emitting glass. It is preferable that According to the above configuration, for example, even when a luminescent glass is disposed in water and an ultraviolet light source is disposed outside water, ultraviolet light is emitted from the vicinity of the luminescent glass in water to the luminescent glass through the optical fiber. Can be irradiated. Unlike the power transmission cord, the optical fiber is not energized, so there is no risk of leakage, and the lighting device is composed of the minimum necessary components such as light-emitting glass, optical fiber, and ultraviolet light source. There is an advantage that there is nothing. In addition, it is preferable that the "near" here is in the range of the distance where the luminescent glass and the end of the optical fiber are in contact to the distance where the distance between the luminescent glass and the end of the optical fiber is 30 cm away, for example. This is because if the distance between the light emitting glass and the end of the optical fiber is more than the above range, the significance of introducing ultraviolet rays to the vicinity of the light emitting glass using the optical fiber is diminished.
[0096]
Below, although the specific structure of the illuminating device 1 which concerns on this Embodiment is demonstrated based on FIG. 10, the illuminating device which concerns on this invention is not restricted to this structure.
[0097]
As shown in FIG. 10, the lighting device 1 according to the present embodiment includes a base material 2, the luminescent glass 3, and a black light 4. The light emitting glass 3 and the black light 4 are provided on the base material 2. The luminescent glass 3 functions as an illumination member, and the black light 4 functions as an ultraviolet light source.
[0098]
The base material 2 may be any material as long as it does not hinder the light emission of the light emitting glass 3. For example, conventionally known base materials such as metal, glass, firewood, rock, wood, concrete, and plastic can be used and are not particularly limited. It is not something. The luminescent glass 3 may be the luminescent glass according to the present invention as it is, or may be used by connecting the luminescent glass according to the present invention and a base material (for example, glass, metal, rock, etc.). .
[0099]
Further, the means for providing the light emitting glass 3 and the black light 4 on the base material 2 are also conventionally known physical and chemical connections such as a method of physically fixing with a fastener or a method of adhering with an adhesive. A method, an adhesion method, or the like can be used, and is not particularly limited. Alternatively, the black light 4 may not be provided on the base material 2 but may be provided at a position appropriately separated from the base material 2 to irradiate the light emitting glass 3 with ultraviolet rays.
[0100]
According to said illuminating device 1, as a transparent glass which does not impair the surrounding environment at daytime, it can be stably used as a lighting fixture using the black light 4 at night even for a long time outdoors. Therefore, the illuminating device 1 can be used for, for example, display of a dangerous place at night and a signboard that gives a comfortable impression to people.
[0101]
Moreover, since the said light emission glass light-emits also in water, as shown in the Example mentioned later, it can be used also as an underwater illumination device.
[0102]
Specific configurations of the lighting device 10 and the lighting device 20 according to the present embodiment that can be used in water will be described with reference to FIGS. 11 and 12, but the lighting device according to the present invention is limited to this configuration. It is not a thing.
[0103]
As shown in FIG. 11, the lighting device 10 includes a light emitting glass 13 and an ultraviolet lamp 14. The luminescent glass 13 is disposed in water, and the ultraviolet lamp 14 is provided outside the water. As described above, the luminescent glass 13 according to the present invention may be used as it is, or the luminescent glass according to the present invention and a base material (for example, glass, metal, rock, etc.) connected to each other. May be. The distance between the ultraviolet lamp 14 and the light emitting glass 13 may be a distance that allows the light emitting glass 13 to emit light by the ultraviolet light irradiated from the ultraviolet lamp 14, and can be set as appropriate according to the irradiation intensity of the ultraviolet lamp 14. is there.
[0104]
According to the illuminating device 10, the luminescent glass 13 emits light in water by irradiating the luminescent glass 13 with the ultraviolet lamp 14 from the outside of water. For this reason, since the said illuminating device 10 does not have the necessity of power transmission unlike the conventional underwater illuminating device, there is no danger of electric leakage, and since it is comprised from fewer members, there is an advantage that the aesthetics are not impaired. is there.
[0105]
Moreover, as shown in the Example mentioned later, the light emission glass concerning this invention light-emits strongly with the ultraviolet-ray of wavelength 365nm vicinity. Here, ultraviolet rays in the vicinity of a wavelength of 365 nm have a property of being efficiently transmitted even in water. For this reason, according to the underwater illumination device using the light emitting glass that emits strong light when irradiated with ultraviolet light having such a wavelength, even when the ultraviolet light is irradiated to the underwater illumination device from the outside of the water, the ultraviolet light is made of the light emitting glass. Since the illumination portion can be sufficiently irradiated, there is an advantage that light can be emitted with sufficient intensity.
[0106]
Moreover, the illuminating device 20 is equipped with the light emission glass 23 and the ultraviolet fiber 26, as shown in FIG. The ultraviolet fiber 26 has a configuration in which one end of the optical fiber 25 and the ultraviolet lamp 24 are connected. The light emitting glass 23 is disposed in water, the ultraviolet lamp 24 is disposed outside water, the optical fiber 25 extends from the outside of the water to the water, and the other end of the optical fiber 25 emits light. It is provided in the vicinity of the glass 23.
[0107]
As the light emitting glass 23, the light emitting glass according to the present invention may be used as it is, or the light emitting glass according to the present invention and a base material (for example, glass, metal, rock, etc.) may be connected. Further, as the ultraviolet fiber 26, for example, when the light emitting glass 23 that is an illumination part and the ultraviolet lamp 24 exist at a distance, the ultraviolet lamp 24 and the optical fiber 25 are connected to each other through the optical fiber 25. As long as ultraviolet rays can be introduced into the vicinity of the light-emitting glass 23, it is not particularly limited. Specifically, as shown in FIG. 12, one end of a conventionally known optical fiber 25 that functions as a light guide and an ultraviolet lamp 24 that functions as an ultraviolet light source are connected to each other. An example is one in which the irradiated ultraviolet light passes through the optical fiber 25 and is irradiated from the vicinity of the light emitting glass 23 from the other end of the optical fiber 25. The ultraviolet fiber 26 can be installed in water since there is no need for power transmission (energization), and an ultraviolet light source can be provided in the vicinity of the luminescent glass 23 in practice.
[0108]
Therefore, according to the illuminating device 20, it is possible to irradiate the light emitting glass 23 with ultraviolet rays from the vicinity by the ultraviolet fiber 26. For this reason, the said illuminating device 20 becomes strong in emitted light intensity. In addition, if only the luminescent glass 23 and the optical fiber 25 are present in the water, they can function as an illuminating device and do not require many members, so that they can be used as an underwater lighting fixture with excellent aesthetics. Furthermore, since there is no need for power transmission, there is no danger of leakage.
[0109]
Note that the configurations, arrangements, designs, and the like of the various lighting devices described above are not limited to those described above, and it goes without saying that the configurations, arrangements, designs, etc. of conventionally known lighting devices can be used. . For example, the light emitting glass 23 may be attached to the distal end portion of the ultraviolet fiber 26, and the ultraviolet fiber 26 and the light emitting glass 23 may be integrated. Furthermore, although the said illuminating device can be used underwater as it is, it is needless to say that it can be used waterproofing.
[0110]
Moreover, the luminescent glass which concerns on this invention can be utilized also for the illumination method. That is, the illumination method according to the present invention is not particularly limited as long as the light emitting glass and the ultraviolet light source are used.
[0111]
Moreover, as shown in the Example mentioned later, the said light emission glass is an outstanding material which light-emits intensely even in the heated state, and has both heat resistance and luminescent property. For this reason, by using the light emitting glass, it is possible to manufacture a heat-resistant lighting device that emits light strongly even in a high temperature environment (in water or in air).
[0112]
In addition, a display device can be manufactured using the light-emitting glass. That is, the display device according to the present invention only needs to include the light emitting glass, and other specific configurations are not particularly limited. For example, it can be arranged and used as a backlight of a normal LCD, or can be provided in the front part of a display screen of a normal display device and used as a transmissive arrangement.
[0113]
As described above, by using the lighting device or the lighting method using the light emitting glass according to the present invention, for example, the light emitting glass is provided on a transparent plate material, and a black light is emitted at night to emit light. It is possible to create a space that gives a comfortable impression, and it can also be used as a marker for a road sign.
[0114]
Embodiments will be described below in more detail with reference to the accompanying drawings. Of course, the present invention is not limited to the following examples, and it goes without saying that various aspects are possible in detail.
[0115]
【Example】
[Example 1]
After melting commercially available waste glass, the composition of the additive after melting is 8.8 Na with respect to 100 parts by weight of waste glass after melting. ₂ O-95B ₂ O _Three -75SiO ₂ -6Al ₂ O _Three Na so that ₂ CO _Three , H _Three BO _Three , SiO ₂ , Al (OH) _Three Each was added and melted at 1400 ° C. Subsequently, after pouring out into the metal mold | die of a predetermined shape and cooling-molding, the process by 1N nitric acid was performed at 90 degreeC, and the porous silica glass was obtained.
[0116]
This porous silica glass was mixed with 0.5 g of Eu (NO _Three ) _Three XH ₂ An aqueous solution in which O was dissolved in 10 ml of distilled water was impregnated. After the porous silica glass was impregnated with the aqueous solution once, it was dried at 350 ° C. for 1 hour to decompose nitrates, and then further impregnated with the aqueous solution once more.
[0117]
Thereafter, the temperature was slowly increased at a rate of 2 ° C./min, and firing was performed at 1100 ° C. for 2 hours. When this firing was performed in the air, a luminescent glass exhibiting strong luminescence was not obtained. On the other hand, when firing was performed in a reducing atmosphere in an alumina crucible containing carbon, a luminescent glass exhibiting strong luminescence could be obtained. All of the obtained luminescent glasses were transparent in appearance.
[0118]
The result of measuring the transmission spectrum of the luminescent glass obtained by firing in the reducing atmosphere is shown in FIG. As shown in FIG. 1, it was found that the obtained luminescent glass has a high transmittance from around 300 nm and has a transmittance of 80% or more on the longer wavelength side than 400 nm.
[0119]
In addition, the fluorescence spectrum generated when the luminescent glass obtained by firing in the air and the luminescent glass obtained by firing in a reducing atmosphere are irradiated with ultraviolet light having a wavelength of 254 nm and excited. The measurement results are shown in FIG. The solid line shown in FIG. 2 shows the fluorescence spectrum generated from the luminescent glass obtained by firing in the atmosphere, and the broken line shows the fluorescence spectrum generated from the luminescent glass obtained by firing in the reducing atmosphere. As shown in FIG. 2, it was found that the luminescent glass obtained by firing in a reducing atmosphere strongly emitted blue fluorescence having a wavelength of about 430 nm. On the other hand, the luminescent glass obtained by firing in the atmosphere did not show so strong luminescence.
[0120]
Moreover, the result of having measured the excitation wavelength dependence of blue fluorescence with a wavelength of 430 nm in the light emission glass obtained by baking in FIG. 3 at reducing atmosphere is shown. The solid line shown in FIG. 3 shows the fluorescence spectrum generated from the luminescent glass obtained by firing in the atmosphere, and the broken line shows the fluorescence spectrum generated from the luminescent glass obtained by firing in the reducing atmosphere. As shown in FIG. 3, it was found that the light-emitting glass obtained by firing in a reducing atmosphere was excited by irradiation with ultraviolet rays having a wavelength of about 230 nm to 350 nm and emitted strong light.
[0121]
In addition, when a commercially available 6 W (watt) ultraviolet lamp for sterilization (wavelength: 250 nm) is used to irradiate UV light to a luminescent glass obtained by firing in a reducing atmosphere from a location 2 cm away, a remarkable blue color is obtained. Luminescence could be observed with the naked eye.
[0122]
For comparison, the luminescent glass obtained when a porous glass was prepared in the same manner as described above and baked at 850 ° C. did not exhibit fluorescence.
[0123]
[Example 2]
After melting the commercially available waste glass, the composition of the additive after melting is 7Na with respect to 100 parts by weight of the waste glass after melting. ₂ O-90B ₂ O _Three -75SiO ₂ -6Al ₂ O _Three Na so that ₂ CO _Three , H _Three BO _Three , SiO ₂ , Al (OH) _Three Each was added and melted at 1400 ° C. Subsequently, after pouring out into the metal mold | die of a predetermined shape and cooling-molding, the process by 1N nitric acid was performed at 90 degreeC, and the porous silica glass was obtained.
[0124]
This porous silica glass was mixed with 0.5 g of Ce (NO _Three ) _Three ・ 9H ₂ An aqueous solution in which O was dissolved in 10 ml of distilled water was impregnated. After the porous silica glass was impregnated with the aqueous solution once, it was dried at 350 ° C. for 1 hour to decompose nitrates, and then further impregnated with the aqueous solution once more.
[0125]
Thereafter, the temperature was slowly increased at a rate of 2 ° C./min, and firing was performed at 1100 ° C. for 2 hours. When this firing was performed in the air, a luminescent glass exhibiting strong luminescence was not obtained. On the other hand, when firing was performed in a reducing atmosphere in an alumina crucible containing carbon, a luminescent glass exhibiting strong luminescence could be obtained. Al (NO _Three ) _Three When the porous glass was impregnated with the aqueous solution in which the solution was dissolved and then baked in a reducing atmosphere, a luminescent glass exhibiting stronger luminescence could be obtained. The obtained luminescent glass was transparent in appearance. Also, impregnated Al (NO _Three ) _Three The nitrate is decomposed by firing, and Al ₂ O _Three It seems to have become.
[0126]
FIG. 4 shows the results of measuring the fluorescence spectra generated when the above-obtained three types of luminescent glass were excited by irradiating with ultraviolet rays having a wavelength of 310 nm to 345 nm. The broken line shown in FIG. 4 indicates the fluorescence spectrum generated from the luminescent glass obtained by firing in the atmosphere, the alternate long and short dash line indicates the fluorescence spectrum generated from the luminescent glass obtained by firing in the reducing atmosphere, and the solid line indicates Al ₂ O _Three The fluorescence spectrum which generate | occur | produced from the light emission glass obtained by making it adhere to the surface and baking by a reducing atmosphere is shown.
[0127]
As shown in FIG. 4, it was found that the luminescent glass obtained by firing in a reducing atmosphere strongly emitted fluorescence having a wavelength of about 400 nm. Al ₂ O _Three It was found that the light-emitting glass obtained by adhering to the surface and firing in a reducing atmosphere strongly emits fluorescence at a wavelength of about 390 nm. On the other hand, the luminescent glass obtained by firing in the atmosphere did not show so strong luminescence.
[0128]
Moreover, the result of having measured the excitation wavelength dependence of fluorescence with a wavelength of 380 nm in the three types of luminescent glass obtained above in FIG. 5 is shown. The broken line shown in FIG. 5 shows the fluorescence spectrum generated from the luminescent glass obtained by firing in the atmosphere, the alternate long and short dash line shows the fluorescence spectrum generated from the luminescent glass obtained by firing in the reducing atmosphere, and the solid line indicates Al ₂ O _Three The fluorescence spectrum which generate | occur | produced from the light emission glass obtained by making it adhere to the surface and baking by a reducing atmosphere is shown.
[0129]
As shown in FIG. 5, the luminescent glass obtained by firing in a reducing atmosphere, and Al ₂ O _Three It was found that both the luminescent glasses obtained by adhering to the surface and then baked in a reducing atmosphere were excited by irradiation with ultraviolet rays in the wavelength range of about 230 nm to 350 nm and emitted intensely.
[0130]
For comparison, when a porous glass was prepared in the same manner as described above and fired at 900 ° C., the fluorescence exhibited by the obtained luminescent glass was very weak.
[0131]
Example 3
After melting the colored waste glass mixture, the composition of the additive after melting is 7Na with respect to 100 parts by weight of the waste glass after melting. ₂ O-90B ₂ O _Three -75SiO ₂ -6Al ₂ O _Three Na so that ₂ CO _Three , H _Three BO _Three , SiO ₂ , Al (OH) _Three Each was added and melted at 1400 ° C. Subsequently, after pouring out into the metal mold | die of a predetermined shape and carrying out cooling molding, the process by 1N nitric acid was performed at 90 degreeC for 24 hours, and the porous silica glass was obtained.
[0132]
This porous silica glass was mixed with 0.14 g of Tb (NO _Three ) _Three XH ₂ An aqueous solution in which O was dissolved in 10 ml of distilled water was impregnated. After the porous silica glass was impregnated with the aqueous solution once, it was dried at 350 ° C. for 1 hour to decompose nitrates, and then further impregnated with the aqueous solution once more. Thereafter, the temperature was slowly increased at a rate of 2 ° C./min, and calcination was performed in the air at 1100 ° C. for 2 hours.
[0133]
FIG. 6 shows the result of measuring the fluorescence spectrum generated when the obtained luminescent glass was excited by irradiating it with ultraviolet rays having a wavelength of 233 nm. As shown in FIG. 6, it was found that the obtained luminescent glass emits strong fluorescence intermittently in a wavelength region of 375 nm to 550 nm.
[0134]
Moreover, the result of having measured the excitation wavelength dependence of the red fluorescence of wavelength 542nm in the light emission glass obtained in FIG. 7 is shown. As shown in FIG. 7, it was found that the obtained light emitting glass was excited by irradiation with ultraviolet rays in a wavelength range of about 220 nm to 250 nm and emitted strongly.
[0135]
Example 4
It was confirmed whether or not the luminescent glass emits light even in water, and the applicability as an underwater lighting fixture was examined. Specifically, it was performed as follows.
[0136]
First, as shown in FIG. 8A, after immersing a luminescent glass prepared by doping Eu by using the method of Example 1 in beaker hot water, 4 W (watts) of black light (wavelength) from outside the beaker : 365 nm) was irradiated to the luminescent glass. And when the periphery was darkened and observed, as shown in FIG.8 (b), the light emission glass inside a beaker emitted light brightly, and light emission was able to be confirmed clearly visually even from the outside of a beaker.
[0137]
From this result, it was found that the luminescent glass can emit light even in warm water, and it has been found that it has both heat resistance and luminescence. Thus, it was found that an underwater lighting device having excellent heat resistance and strong emission intensity can be produced by using the above-described luminescent glass. In the above experiment, the luminescent glass is immersed in hot water and the light emission in the hot water is examined. Of course, light emission in unheated water is also possible.
[0138]
Example 5
Next, light emission in the air of the luminescent glass was examined. Specifically, it was performed as follows.
[0139]
First, as shown in FIG. 9A, a luminescent glass produced by doping Eu was held over a burner by the method of Example 1 and irradiated with 4 W of black light (wavelength: 365 nm). And when the surroundings were darkened and observed, as shown in FIG.9 (b), the said luminescent glass light-emitted brightly to such an extent that it could confirm visually.
[0140]
From this result, it was found that the luminescent glass can emit light even when heated, and has both excellent heat resistance and luminescence. Thus, it was found that by using the light emitting glass, a lighting device having excellent heat resistance and strong emission intensity can be produced. In the above experiment, light emission in the air is examined by holding a light emitting glass over a burner. Of course, light emission without heating is also possible.
[0141]
【The invention's effect】
As described above, according to the luminescent glass production method of the present invention, the effect of being able to produce a luminescent glass exhibiting excellent luminescence while having excellent heat resistance, chemical durability, and mechanical strength. Play.
[0142]
In addition, the luminescent glass according to the present invention can convert ultraviolet light into visible light with high efficiency, and since the glass base is a stable oxide glass, it has heat resistance, chemical durability, and mechanical properties. There is an effect that strength is excellent. Furthermore, since the glass substrate contains a large amount of silica, the light-emitting glass according to the present invention has a high ultraviolet transmittance of the mother glass and can be excited not only by light having a shorter wavelength, but also is less susceptible to defects caused by ultraviolet irradiation. Play. Moreover, since the light-emitting glass according to the present invention emits strong light without containing a large amount of rare earth, it has an effect of reducing the cost.
[0143]
In addition, since the lighting device or the lighting method according to the present invention uses the light emitting glass, not only has excellent heat resistance, chemical durability, and mechanical strength, but also has no adverse effect on the environment. The effect is that it can be used stably for a long time even outdoors. Further, since a large amount of expensive rare earth atoms are not used, there is an effect that production is possible at low cost. Further, since it emits intensely only by irradiating ultraviolet rays and there is no need for power transmission, it can be used as an illuminating device having excellent aesthetics without being at risk of leakage even when used in water.
[0144]
In addition, the display device according to the present invention has an effect of being able to perform transmissive arrangement and 3D utilization.
[Brief description of the drawings]
FIG. 1 is a graph showing a result of measuring a transmission spectrum of a luminescent glass (containing Eu) obtained by firing in a reducing atmosphere according to the present embodiment.
FIG. 2 shows ultraviolet light having a wavelength of 254 nm with respect to a luminescent glass (Eu-containing) obtained by firing in the atmosphere and a luminescent glass (Eu-containing) obtained by firing in a reducing atmosphere according to the present embodiment. It is a graph which shows the result of having measured the fluorescence spectrum generate | occur | produced when irradiating and exciting.
FIG. 3 is a graph showing the results of measuring the excitation wavelength dependence of blue fluorescence having a wavelength of 430 nm in a light-emitting glass (containing Eu) obtained by firing in a reducing atmosphere according to the present embodiment.
FIG. 4 is generated when an emission glass (containing Ce) obtained by firing under three kinds of conditions according to the present embodiment is irradiated with ultraviolet light having a wavelength of 310 nm to 345 nm and excited. It is a graph which shows the result of having measured the fluorescence spectrum.
FIG. 5 is a graph showing the results of measuring the excitation wavelength dependence of fluorescence at a wavelength of 380 nm in a light-emitting glass (containing Ce) obtained by firing under three types of conditions according to the present embodiment.
FIG. 6 is a graph showing a result of measuring a fluorescence spectrum generated when the luminescent glass (containing Tb) according to the present embodiment is irradiated with an ultraviolet ray having a wavelength of 233 nm and excited.
FIG. 7 is a graph showing the result of measuring the excitation wavelength dependence of red fluorescence having a wavelength of 542 nm in the luminescent glass (containing Tb) according to the present embodiment.
FIG. 8 is a diagram showing a result of an experiment for confirming whether the luminescent glass (containing Eu) according to the present embodiment can emit light even in water.
FIG. 9 is a diagram showing a result of an experiment for confirming whether the luminescent glass (containing Eu) according to the present embodiment can emit light even in the air.
FIG. 10 is a diagram schematically showing a configuration of an example of a lighting apparatus according to the present embodiment.
FIG. 11 is a diagram schematically showing the configuration of another example of the lighting apparatus according to the present embodiment.
FIG. 12 is a diagram schematically showing the configuration of another example of the lighting apparatus according to the present embodiment.
[Explanation of symbols]
1 Lighting device
2 Base material
3 Luminescent glass
4 Black light (ultraviolet light source)
10 Lighting equipment
13 Luminescent glass
14 UV lamp (UV light source)
20 Lighting device
23 Luminescent glass
24 UV lamp (UV light source)
25 Optical fiber
26 UV fiber

Claims (8)

Eu in the porous glass, a first step of adsorbing at least one rare earth atom selected from Ce and Tb, the in the original atmosphere changed to rare earth-containing adsorbent porous glass obtained in the first step, 1100 ° C. or higher A second step of firing at a temperature of
The first step further includes a step of adsorbing a sensitizer to the porous glass,
Emission glass production process which emits light by ultraviolet excitation, characterized in that the Al ₂ O ₃ the sensitizer by firing in the second step.   The method for producing a luminescent glass that emits light by ultraviolet excitation according to claim 1, wherein the first step is a step of impregnating a porous glass with a solution containing the compound having a rare earth atom. The light emitting device which light-emits by ultraviolet excitation using the light emission glass which can be produced by the production method of the light emission glass of Claim 1 or 2 . An illumination device comprising the light emitting device according to claim 3 and an ultraviolet light source. An underwater lighting device comprising the light emitting device according to claim 3 and an ultraviolet light source. The lighting device further includes an optical fiber, one end of the optical fiber is connected to the ultraviolet light source, and the other end of the optical fiber is provided in the vicinity of the light emitting device. The lighting device according to claim 4 or 5 , characterized in that: An illumination method using the light-emitting device according to claim 3 and an ultraviolet light source. A display apparatus comprising the light emitting device according to claim 3 .

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