KR101227647B1 - 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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- KR101227647B1 KR101227647B1 KR1020100104937A KR20100104937A KR101227647B1 KR 101227647 B1 KR101227647 B1 KR 101227647B1 KR 1020100104937 A KR1020100104937 A KR 1020100104937A KR 20100104937 A KR20100104937 A KR 20100104937A KR 101227647 B1 KR101227647 B1 KR 101227647B1
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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. As a result of improving the point of inadequate use, it emits light only at 290nm wavelength at room temperature and does not emit light at 395nm wavelength, and the emission intensity of 290nm wavelength is about 1.3 to 1.6 times stronger than that of conventional. Effective as the phosphor used.
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.
Therefore, in order to solve the above problem, the present inventors manufactured SrB 4 O 7 : Ag + by solid-phase reaction using Gd 3 + as a charge compensator in the atmosphere, and thus, emits light having a wavelength of 290 nm in the ultraviolet region at room temperature. It confirmed that it became stronger, and completed this invention.
An object of the present invention relates to a non-visible region of 290nm with non-visible light emitting body and a method of manufacturing balgang strength is enhanced at a wavelength, and more particularly, SrB 4 O using Gd 3 + as the charge compensation system 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, and a method of manufacturing the same.
In order to achieve the above object, the present invention comprises the steps of mixing a strontium compound, boric acid (H 3 BO 3 ), monovalent silver compound and gadolinium compound;
Calcining the mixture under air; And
The invisible light-emitting body Sr 1 -x- y B 4 O 7 : Ag + x , Gd 3 + y (0 <x <1, 0 <y <1) comprising cooling the calcined mixture to room temperature and then grinding And 0 <x + y <1) and a light emitting body produced by the above method.
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 to 1.6 times stronger than the conventional one, 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 illustrates an excitation-emitting spectrum mapping image of an invisible light emitter according to an embodiment of the present invention.
Figure 2 shows the excitation and emission spectra of the luminous material prepared by 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 ), monovalent silver compound and gadolinium compound; Calcining the mixture under air; And cooling the calcined mixture to room temperature and then pulverizing the invisible light emitter Sr 1 -xy B 4 O 7 : Ag + x , Gd 3+ y (0 <x <1, 0 <y <1 and It relates to a method for producing 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 manufacture the invisible light emitter 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 a gadolinium compound as a charge compensator 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 present invention, to the non-visible light emitting body to be produced using Gd 3 + as the charge compensation system under an atmosphere of a non-nitrogen atmosphere such as in a conventional solid phase reaction method is confirmed to exhibit a strong emission intensity at the wavelength of 290nm.
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. That is, the matrix Sr + 2 are able to complement the lack of a positive charge by using the Gd 3+ in the charge compensation system because the positively charged one case lacking the active agent is replaced with Ag +. In the conventional light emitting manufacturing method, La 3 + was used as a charge compensator, but in the present invention, an invisible light emitting body was manufactured using Gd 3 + instead of La 3 + . As a result, it was confirmed that the luminescence intensity of the 290 nm wavelength is stronger than in the past. The gadolinium compound may preferably be a trivalent gadolinium compound, more preferably selected from the group consisting of gadolinium oxide (Gd 2 O 3 ), gadolinium nitrate (Gd (NO 3 ) 3 ) and gadolinium chloride (GdCl 3 ). There may be more than one.
That is, in one embodiment of the present invention, by using the charge compensator Gd 3 + instead of La 3 + , the emission intensity of the 290 nm wavelength was confirmed to be increased by 1.3 to 1.6 times.
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 a large amount of a monovalent silver compound, which is an active agent, is contained, concentration quenching may occur, which may rather inhibit luminescence intensity. In addition, in the present invention, the content of the gadolinium compound may be characterized in that 1 to 20 moles with respect to 100 moles of the strontium compound. When the gadolinium compound, which is a charge compensator, is contained in an excessive amount, it may be characterized by being 1 to 20 moles because the silver ions interfere with the process of being substituted with strontium ions. 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 , Gd 3 + y (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. 1 illustrates an excitation-emitting spectrum mapping image of an invisible light emitter according to an embodiment of the present invention. In the right graph of FIG. 1, it can be seen that the invisible light emitter according to the present invention is excited at a wavelength of 243 nm, and the bottom graph of FIG. 1 shows that the invisible light emitter according to the present invention exhibits an emission peak at 290 nm.
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)
0.3625 g (0.0010 mol) Gd 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 of 243 nm 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)
0.3625 g (0.0010 mol) Gd 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 of 243 nm using a fluorescence spectrophotometer.
SrCO 3 13.8772g (0.0940mol)
H 2 BO 3 24.7320g (0.4000mol)
AgNO 3 0.1700g (0.0010mol)
1.8125g (0.0050mol) Gd 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 of 243 nm 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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2 shows excitation-luminescence spectra according to Examples and Comparative Examples. In the graph of FIG. 2, the area in which each graph is integrated represents the emission intensity, and the calculated values are shown in Table 1. As a result, it was confirmed that the light-emitting body prepared according to Examples 1 to 3 of the present invention is about 1.3 to 1.6 times higher than the light-emitting body 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 body according to the embodiment of the present invention using the charge compensation system including a Ga 3 + It was prepared by, it can be seen that the above-mentioned effect is due to the difference in the charge compensation agent.
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
The invisible light - emitting body Sr 1-xy B 4 O 7 : Ag + x , Gd 3+ y (0 <x <1, 0 <y <1 and 0) comprising cooling the calcined mixture to room temperature and then grinding it. Method for producing <x + y <1).
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| KR20090093202A (en) * | 2008-02-28 | 2009-09-02 | 한국과학기술원 | White light emitting diode and its manufacture method |
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| KR20090093202A (en) * | 2008-02-28 | 2009-09-02 | 한국과학기술원 | White light emitting diode and its manufacture method |
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