KR101227648B1 - Invisible Luminescence Material and Method for Manufacturing The Same - Google Patents
Invisible Luminescence Material and Method for Manufacturing The Same Download PDFInfo
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- KR101227648B1 KR101227648B1 KR1020100104938A KR20100104938A KR101227648B1 KR 101227648 B1 KR101227648 B1 KR 101227648B1 KR 1020100104938 A KR1020100104938 A KR 1020100104938A KR 20100104938 A KR20100104938 A KR 20100104938A KR 101227648 B1 KR101227648 B1 KR 101227648B1
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Abstract
The present invention relates to an invisible light emitting body having silver (Ag) as an activator and a strontium tetraborate (SrB 4 O 7 ) as a matrix, and more particularly, by a light having a wavelength of 243 nm in which its color is white and an ultraviolet region. The present invention relates to a light-emitting body which is excited and emits light having a wavelength of 290 nm, which is an ultraviolet region, and a method of manufacturing the same.
The invisible light emitter manufactured by the manufacturing method according to the present invention is a phosphor for preventing forgery and modulation since the light emitter manufactured by the conventional method is weak at 290 nm wavelength of light emission at room temperature, and the light emission intensity of 395 nm wavelength is strong. By improving the unsuitable point of use, the luminescence intensity of the 290 nm wavelength is about 1.3-2.4 times stronger than the existing one at room temperature, and thus, it is effective as a phosphor used in a special printed material for preventing forgery and modulation.
In addition, in the present invention, it is possible to solve the risk of reducing the gas cost and the handling of the high-pressure gas by reacting in an atmospheric atmosphere without using a gas for artificially creating an oxidizing and reducing atmosphere.
Description
The present invention relates to an invisible light emitting body having silver (Ag) as an activator and a strontium tetraborate (SrB 4 O 7 ) as a matrix, and more particularly, by a light having a wavelength of 243 nm in which its color is white and an ultraviolet region. The present invention relates to a light-emitting body which is excited and emits light having a wavelength of 290 nm, which is an ultraviolet region, and a method of manufacturing the same.
Luminescence refers to a phenomenon of emitting light without accompanying heat, such as fluorescence or phosphorescence. Like incandescent bulbs, materials generally emit light when they are hot, meaning they emit light by stimuli other than heat, and are also called cold light. Generally, it refers to luminescence phenomena except heat radiation, Cherenkov radiation, Rayleigh scattering, Raman scattering, among the phenomenon that a substance absorbs energy and emits light by receiving light, X-ray, radiation and chemical stimulus. Bioluminescence, in which organisms such as fireflies and luminous insects shine on their own, is also a chemical luminescence that causes redox reactions.
In some cases, the luminescence is classified as fluorescence and phosphorescence, but this classification differs between inorganic and organic compounds. There are many definitions for inorganic light emitters, especially fluorescence. In an organic compound, it is distinguished by the spin multiplicity of two electron states that are involved in electron transition. Light emission due to transition between electron states having the same multiplicity is called fluorescence, and otherwise, phosphorescence is called.
The luminous material which emits light in the invisible region of infrared rays or ultraviolet rays is used to prevent forgery and modulation since it is applied in a specific wavelength region when it is used for special printed materials that need to be mixed with printing ink and emits in a specific invisible region. It is described in the Republic of Korea Patent Publication No. 10-0779237, which is suitable for use and can be applied to a special printed material for preventing forgery and tampering by using a near-infrared light emitter.
Conventional literature J. Phys. Chem. Solids Vol. 54, No. 8 (1993) 901 ~ 906 is prepared by mixing SrCO 3 , H 3 BO 3 (2% excess) and Ag 2 O in a platinum crucible and firing at 450 ℃ for 3 hours and 840 ℃ for 12 hours under dry nitrogen gas atmosphere. , the addition of La 3 + as the charge compensation system but within the sample that do not increase the amount of Ag + SrB 4 O 7: is the start of a polycrystalline sample of Ag + manufacturing method.
The SrB 4 O 7 : Ag + phosphor produced by the above method is excited by 235 nm light in the ultraviolet region and emits light in the wavelengths of 290 nm and 395 nm in the ultraviolet region. This becomes stronger, and at room temperature, the emission intensity of the 395 nm wavelength is about twice as strong as the emission intensity of the 290 nm wavelength. Therefore, when manufacturing a security ink or the like using light emission having a wavelength of 290 nm which is an invisible region at room temperature, since a large amount of light emitters must be used to obtain satisfactory emission intensity, the production cost of the security ink is expensive and the ink is expensive. There was also an uneven quality of its own.
Thus, the present inventors to solve the above problems, without the use of La 3 + as the charge compensation system under an atmosphere of, by using the alkali metal salt compound as a flux to the solid-phase reaction method SrB 4 O 7: After manufacturing the Ag +, It was confirmed that light emission at the wavelength of 290 nm, which is an ultraviolet region at room temperature, was made stronger than before, and the present invention was completed.
An object of the present invention relates to a non-visible region of 290nm balgang non-visible light emitting intensity is enhanced and its manufacturing method in a wavelength, and more particularly, using an alkali metal salt compound as the flux, SrB 4 O 7: Ag + phosphor The present invention relates to a light emitting body suitable for use as a phosphor for preventing forgery and modulation by increasing the light emission intensity of a wavelength of 290 nm, which is an invisible region in, and a manufacturing method thereof.
In order to achieve the above object, a step of mixing a strontium compound, boric acid (H 3 BO 3 ), a monovalent silver compound and an alkali metal salt compound; Calcining the mixture under air; And cooling the calcined mixture to room temperature and then grinding the invisible light-emitting body Sr 1 -x- y B 4 O 7 : Ag + x , M + y (M = alkali metal, 0 <x <1, Provided are a method for producing 0 <y <1 and 0 <x + y <1) and an invisible light emitter produced by the method.
The invisible light emitter produced by the manufacturing method according to the present invention is a phosphor for preventing forgery and modulation since the light emitter manufactured by the conventional method is weak at 290 nm wavelength of light emission at room temperature, and the light intensity of 395 nm wavelength is strong. By improving the unsuitable point of use, the luminescence intensity of the 290 nm wavelength is about 1.3-2.4 times stronger than the existing one at room temperature, and thus, it is effective as a phosphor used in a special printed material for preventing forgery and modulation.
In addition, in the present invention, it is possible to solve the risk of reducing the gas cost and the handling of the high-pressure gas by reacting in an atmospheric atmosphere without using a gas for artificially creating an oxidizing and reducing atmosphere.
1 shows excitation and emission spectra of the luminous bodies prepared according to Examples 1 to 3 and Comparative Examples 1 and 2 of the present invention.
The present invention comprises the steps of mixing a strontium compound, boric acid (H 3 BO 3 ), a monovalent silver compound and an alkali metal salt compound; Calcining the mixture under air; And cooling the calcined mixture to room temperature and then grinding the invisible light-emitting body Sr 1 -x- y B 4 O 7 : Ag + x , M + y (M = alkali metal, 0 <x <1, 0 <y <1 and 0 <x + y <1).
The material constituting the light emitter is largely composed of a host, an activator, and a flux. The parent of the luminescent body holds the active agent forming the luminescent center, and since the luminescent property is represented by the activator which is substituted with the cation of the mother, the cation of the mother should be small in size so as to be able to be substituted with the activator. An activator refers to an ion that actually receives light by receiving energy from a mother, and is mainly substituted with a cation at a cation site of the mother to exhibit luminescent properties. In addition, in order to obtain the particle size of the desired light emitter, most of the high-temperature firing process at 1,000 ℃ or more, wherein the material added to help the particle growth by agglomeration between particles is a flux.
In order to prepare the invisible light emitting body according to the present invention, a strontium compound and boric acid (H 3 BO 3 ) as a parent, a monovalent silver compound as an activator, and an alkali metal salt compound as a flux may be composed of a raw material. In the present invention, the strontium compound may be at least one selected from the group consisting of strontium carbonate (SrCO 3 ), strontium chloride (SrCl 2 ) and strontium nitrate (Sr (NO 3 ) 2 ), wherein the monovalent silver compound is silver oxide (Ag 2 O), silver nitrate (AgNO 3 ) and other monovalent silver compounds.
In the case of using an alkali metal salt compound as a flux, a uniform mixing of the parent and the activator occurs at the reaction temperature, so that the concentration quenching phenomenon due to the localization of the activator does not occur, thereby increasing the luminous efficiency. In addition to acting as a flux, it can also act as a charge compensator and contribute to the electrical stabilization of the final material. The charge compensator refers to a material that compensates for the overcharge of an overall charge when the charge amount of the active agent to be replaced with the cation charge of the parent is different. In the conventional light emitting manufacturing method, La 3 + was used as a charge compensator, but in the present invention, the invisible light emitter was more stably manufactured using a flux without using a charge compensator. As a result, it was confirmed that the luminescence intensity of the 290 nm wavelength is stronger than in the past. The alkali metal salt compound is preferably at least one selected from the group consisting of lithium compounds, potassium compounds and sodium compounds.
The raw materials are uniformly mixed and subjected to firing and heat treatment steps in an electric furnace under air. In the conventional solid phase reaction method, firing and heat treatment are performed in a nitrogen atmosphere, but in the present invention, the gas cost is reduced and the high pressure gas is handled by reacting in an atmospheric atmosphere without using a gas for artificially forming an oxidizing and reducing atmosphere. The risk was eliminated, and it was confirmed that the invisible light-emitting body of the present invention could be stably produced under an atmosphere other than a nitrogen atmosphere. The specific composition of the atmospheric atmosphere of the present invention is the same as the composition of general air, specifically, may be a configuration in which nitrogen and oxygen are mixed at a ratio of about 2: 8.
In the present invention, the mixture of the raw material is heated to 200 to 400 ℃ for 1 to 3 hours in the electric furnace under the atmosphere, and maintained for about 1 hour and then again to 700 to 800 ℃ for 2 to 4 hours and maintained for 2 to 5 hours It may be characterized by firing.
Preferably, in the method of manufacturing the light-emitting body of the present invention, the content of the monovalent silver compound may be characterized in that 1 to 10 moles with respect to 100 moles of strontium compound. When the monovalent silver compound, which is an activator, is contained in an excessive amount, concentration quenching may occur, rather it may inhibit luminescence intensity. In addition, in the present invention, the content of the alkali metal salts may be characterized in that 2 to 20 moles with respect to 100 moles of the strontium compound. When the content of alkali metal salts increases, there is a fear that the chemical resistance of the produced invisible light emitter deteriorates. In addition, in the present invention, the content of the boric acid may be characterized in that 350 to 450 moles with respect to 100 moles of the strontium compound. Within this molar range, boric acid has an appropriate composition ratio for forming SiB 4 O 7 .
That is, the invisible light emitter manufactured by the manufacturing method of the present invention may have a structure represented by the following chemical formula.
Sr 1 -x- y B 4 O 7 : Ag + x, M + y (M = alkali metal, 0 <x <1, 0 <y <1 and 0 <x + y <1)
It was confirmed that the invisible light emitter manufactured by the manufacturing method of the present invention was excited by 243 nm light, which is an ultraviolet region, to emit strong light at a wavelength of 290 nm, which is an ultraviolet region.
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for illustrating the present invention and that the scope of the present invention is not construed as being limited by these embodiments.
SrCO 3 14.4677 g (0.0980 mol)
H 2 BO 3 24.7320g (0.4000mol)
AgNO 3 0.1700g (0.0010mol)
Na 2 CO 3 · 10H 2 O 0.2861g (0.0010mol)
After weighing each of the above-mentioned raw materials and mixing them uniformly, the mixture was filled in an alumina crucible under the atmosphere, and then heated to 300 ° C. over 1 hour in an electric furnace, and then maintained at 750 ° C. over 2 hours, and then maintained at room temperature for 3 hours. Cool.
The resulting SrB 4 O 7 : Ag + phosphorescent phosphor was pulverized using a mortar and excited with 243 nm of ultraviolet light using a fluorescence spectrophotometer.
SrCO 3 13.8772g (0.0940mol)
H 2 BO 3 24.7320g (0.4000mol)
AgNO 3 0.8494 g (0.0050 mol)
K 2 CO 3 0.1382g (0.0010mol)
After weighing each of the above-mentioned raw materials and mixing them uniformly, the mixture was filled in an alumina crucible under the atmosphere, and then heated to 300 ° C. over 1 hour in an electric furnace, and then maintained at 750 ° C. over 2 hours, and then maintained at room temperature for 3 hours. Cool.
The resulting SrB 4 O 7 : Ag + phosphorescent phosphor was pulverized using a mortar and excited with 243 nm of ultraviolet light using a fluorescence spectrophotometer.
SrCO 3 13.8772g (0.0940mol)
H 2 BO 3 24.7320g (0.4000mol)
AgNO 3 0.1700g (0.0010mol)
Li 2 CO 3 0.0739g (0.0010mol)
After weighing each of the above-mentioned raw materials and mixing them uniformly, the mixture was filled in an alumina crucible under the atmosphere, and then heated to 300 ° C. over 1 hour in an electric furnace, and then maintained at 750 ° C. over 2 hours, and then maintained at room temperature for 3 hours. Cool.
The resulting SrB 4 O 7 : Ag + phosphorescent phosphor was pulverized using a mortar and excited with 243 nm of ultraviolet light using a fluorescence spectrophotometer.
Comparative example One
SrCO 3 14.6154g (0.0990mol)
H 2 BO 3 24.7320g (0.4000mol)
AgNO 3 0.1700g (0.0010mol)
After weighing each of the above-mentioned raw materials and mixing them uniformly, the mixture was filled in an alumina crucible under the atmosphere, and then heated to 300 ° C. over 1 hour in an electric furnace, and then maintained at 750 ° C. over 2 hours, and then maintained at room temperature for 3 hours. Cool.
The resulting SrB 4 O 7 : Ag + phosphorescent phosphor was pulverized using a mortar and excited with ultraviolet light at a wavelength of 243 nm using a fluorescence spectrophotometer.
Comparative example 2
SrCO 3 14.4677 g (0.0980 mol)
H 2 BO 3 24.7320g (0.4000mol)
AgNO 3 0.1700g (0.0010mol)
0.3258 g (0.0010 mol) La 2 O 3
After weighing each of the above-mentioned raw materials and mixing them uniformly, the mixture was filled in an alumina crucible under the atmosphere, and then heated to 300 ° C. over 1 hour in an electric furnace, and then maintained at 750 ° C. over 2 hours, and then maintained at room temperature for 3 hours. Cool.
The resulting SrB 4 O 7 : Ag + phosphorescent phosphor was pulverized using a mortar and excited with ultraviolet light at a wavelength of 243 nm using a fluorescence spectrophotometer.
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1 shows excitation-luminescence spectra according to Examples and Comparative Examples. In the graph of FIG. 1, the area in which each graph is integrated represents light emission intensity, and the calculated values are shown in Table 1. As a result, it was confirmed that the luminous material prepared according to Examples 1 to 3 of the present invention is about 1.3 to 2.4 times higher than the luminous material of Comparative Examples 1 and 2. As shown in Table 1, in the case of the comparative example it did not use the charge compensation system, or, although use of the charge compensation system contains a La 3 +, luminous material according to an embodiment of the present invention is produced using the alkali metal salt compound as flux It can be confirmed that the above-mentioned effect was shown.
Having described the specific part of the present invention in detail, it is apparent to those skilled in the art that such a specific technology is only a preferred embodiment, thereby not limiting the scope of the present invention. something to do. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.
Claims (9)
Calcining the mixture under air; And
Cooling the calcined mixture to room temperature and then grinding the invisible light - emitting body Sr 1-xy B 4 O 7 : Ag + x , M + y (M = alkali metal, 0 <x <1, 0 <y <1 and 0 <x + y <1).
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100785492B1 (en) | 2006-04-17 | 2007-12-13 | 한국과학기술원 | Yellow emitting Ce??doped silicate phosphor and preparation method thereof, and white light emitting diodes comprising said Ce??doped silicate phosphor |
| KR20090093202A (en) * | 2008-02-28 | 2009-09-02 | 한국과학기술원 | White light emitting diode and its manufacture method |
| KR20100035773A (en) * | 2008-09-29 | 2010-04-07 | 홍익대학교 산학협력단 | Novel yellow emitting phosphor of strontium borate for application to white light-emitting diodes and method for preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100785492B1 (en) | 2006-04-17 | 2007-12-13 | 한국과학기술원 | Yellow emitting Ce??doped silicate phosphor and preparation method thereof, and white light emitting diodes comprising said Ce??doped silicate phosphor |
| KR20090093202A (en) * | 2008-02-28 | 2009-09-02 | 한국과학기술원 | White light emitting diode and its manufacture method |
| KR20100035773A (en) * | 2008-09-29 | 2010-04-07 | 홍익대학교 산학협력단 | Novel yellow emitting phosphor of strontium borate for application to white light-emitting diodes and method for preparing the same |
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| J. PHYS. CHEM. SOLIDS, 1993 * |
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