KR20060106196A - Blue-emitting phosphors for long-middle ultraviolet ray and their production method - Google Patents

Abstract

The present invention relates to a blue phosphor, and a manufacturing method of the phase as a main phase or orthoclase (orthoclase) the α- cristobalite (α-cristobalite), Specifically, the _{Na 2 O · K 2 O ·} Al 2 O 3 · SiO 2 Europium (Eu) or cerium (Ce) is added as an activator to the parent-based composition, and cerium (Ce), dysprosium (Dy), samarium (Sm), ruthenium (Lu), thulium (Tm), Pr, Nb, Adding at least one element selected from the group consisting of Tb and Er as a deactivator, or at least one element selected from the group consisting of Ba, Ca, Sr, Mg, Li, Ge, B, Fe, Cu, Mn and Cr and intraday blue for wavelength ultraviolet phosphor was added to the matrix, wherein the _{Na 2 O · K 2 O ·} Al 2 O 3 compound to the SiO ₂ in the matrix is an alkaline or alkaline and natural alkali feldspar powder containing potassium, or nitrate, Acetates, chlorides, oxides and carbonates made from one or more selected mixtures from the group It is a method for producing a blue phosphor for long-wavelength ultraviolet light, characterized in that.

Blue Fluorescent, Ultraviolet, Light Emitting Device

Description

Blue-emitting phosphors for long-middle ultraviolet ray and their production method}

1 is a flowchart illustrating a process of manufacturing a blue phosphor according to the present invention.

2 is an XRD diffraction pattern of a blue phosphor of Chemical Formula 1 in which Eu ²⁺ is added as an activator to a natural alkali feldspar powder according to the present invention.

3 is a blue phosphor of formula 1 prepared using an oxide corresponding to a natural alkali feldspar composition according to the present invention (Na _0.66 K _0.34 ) _y Al ₂ Si ₆ O _{15 + y / 2} : Eu _0.02 ²⁺ XRD diffraction pattern for (0.1 ≦ y ≦ 2).

4 is a blue phosphor of formula 1 prepared using an oxide corresponding to a natural alkali feldspar composition according to the present invention (Na _0.66 K _0.34 ) _y Al ₂ Si ₆ O _{15 + y / 2} : Eu _0.02 ²⁺ Absorption and emission spectrum for (0.1 ≦ y ≦ 2).

5 is a blue phosphor of formula 1 prepared using an oxide corresponding to a natural alkali feldspar composition according to the present invention (Na _0.34 K _0.66 ) _y Al ₂ Si ₆ O _{15 + y / 2} : Eu _0.02 ²⁺ Absorption and emission spectrum for (0.1 ≦ y ≦ 2).

6 is (Na _0.66 K _0.34 ) Al _w Si ₆ O _{12.5 + 3w} according to the component ratio of aluminum in the blue phosphor component of Formula 1 prepared using an oxide corresponding to a natural alkali feldspar composition according to the present invention. _{/ 2} : absorption and emission spectrum of Eu _0.02 ²⁺ (0.1 ≦ y ≦ ² ).

7 is a blue phosphor of formula 2 prepared by using an oxide corresponding to a natural alkali feldspar composition as a raw material and adding a deactivator according to the present invention (Na _0.66 K _0.34 ) Al ₂ Si ₆ O _15.5 : Eu _0.02 ²⁺ Absorption and emission spectrum for + yRE ²⁺ .

FIG. 8 shows (Na _0.66 K _0.34 ) Al ₂ Si ₆ O _15.5 : Eu _0.02 prepared by adding iron to a blue phosphor of Formula 2 prepared using an oxide corresponding to a natural alkali feldspar composition according to the present invention as a raw material ²⁺ Absorption and emission spectrum of Fe _0.008 ²⁺ ,

9 is a natural alkali feldspar of the general formula (1) prepared by producing a blue phosphor according to the concentration of Eu ²⁺ in a natural alkali feldspar powder according to the present invention at a first calcining temperature of 800 ° C .: absorption for 0.5wt% Eu ²⁺ And emission spectrum.

10 is a natural alkali feldspar of the general formula (1) prepared by producing a blue phosphor according to the concentration of Eu ²⁺ in a natural alkali feldspar powder according to the present invention at a primary calcining temperature of 1000 ° C: 0.5 wt% Eu ²⁺ absorption And emission spectrum.

11 is a natural alkali feldspar of the formula (2) prepared by adding Eu ²⁺ as an activator and Dy ²⁺ , Sm ²⁺ , Tm ²⁺ , Lu ²⁺ as a surfactant to the natural alkali feldspar powder according to the present invention: 0.5 Absorption and luminescence spectrum for wt% Eu ²⁺ +0.5 wt% RE ₂ ⁺ .

12 is a natural alkali feldspar of the general formula (3) prepared by adding barium (Ba) to the natural alkali feldspar powder according to the present invention: 0.5wt% Eu ²⁺ Absorption and emission spectra for yBa ²⁺ .

13 is a blue phosphor ((Na _0.66 K _0.34 ) Al prepared using a blue phosphor (alkali feldspar: Eu _0.01 ²⁺ ) and an oxide corresponding to a natural alkaline feldspar composition using a natural alkali feldspar powder according to the present invention. ₂ Si ₆ O _15.5 : Eu _0.02 ²⁺ ] and the absorption and emission spectra of conventionally known blue phosphors.

The present invention relates to a blue phosphor for long-wavelength ultraviolet light and a manufacturing method thereof. Specifically, the present invention relates to a blue phosphor, and a method of manufacture prepared by the addition of europium (Eu) or cerium (Ce) to a composition of _{Na 2 O · K 2 O ·} Al 2 O 3 · SiO 2 as a matrix.

In general, phosphors are manufactured by mixing at a temperature of 600 ° C. to 1500 ° C. such that a solid phase reaction is performed in a furnace by mixing a high purity raw material and a flux. For various applications of phosphors, a phosphor that can display high brightness while having a low manufacturing price is required, and the raw material price and the fair price must be low in terms of the manufacturing price of the phosphor.

Currently, white LEDs, which are spotlighted as backlights for LCDs such as lighting, laptops, and mobile phones, are manufactured by combining blue or ultraviolet semiconductor light emitting devices and various phosphors. For example, YAG: Korean Patent Application Publication No. 2000-49728. Ce phosphors are disclosed. YAG: Ce phosphors are patented by Nichia, Japan, and are used by domestic and global companies as well as YAG: Ce phosphors. However, YAG: Ce phosphors have an excitation wavelength of 450 nm and suitable phosphors are limited. In order to improve these problems, the development of white LEDs combining R, G, B phosphors with long wavelength ultraviolet light emitting devices has been actively studied.

Patent related to the long wavelength (320 ~ 400nm) UV LED fluorescent material was produced in the US patent US6621211B1 by mixing the R, G, B phosphors, white light in the Republic of Korea Patent Publication No. 2003-0089947 (1-x) Al ₂ To develop white light by developing O _{3 ·} SiO ₂ : Eu ²⁺ _x phosphor and applying it to UV-LED, Korean Patent Publication No. 2003-0053919 discloses a blue phosphor developed for long-wavelength UV (Sr _{1- x} , Mg _x ) _10-y (PO ₄ ) ₆ Cl ₂ : Eu _y is shown. However, the components of such a blue phosphor composition are conventionally well known and have a problem in that luminescence intensity is decreased in long wavelength UV, and is merely applied by adding other elements to the existing composition. Therefore, it is urgent to manufacture a phosphor that emits blue light having high luminous efficiency while having a new composition by using a material easily obtained from the surroundings in addition to the blue phosphor based on conventional strontium (Sr) and barium (Ba). It is required to do so.

The present invention has been made to solve the above problems, to prepare a phosphor emitting blue light using a mixture having a composition completely different from the components of the conventional blue fluorescent substance composition, the mixture is a raw material It is intended to use materials that are easy to obtain and economically inexpensive.

The blue phosphor according to the present invention has an α-cristobalite phase or an orthoclase phase, which has not been reported to date, and can be excited by long-wavelength ultraviolet rays (220 nm to 400 nm), and 400 nm to 500 nm. It is an object of the present invention to provide a novel high efficiency blue light emitting phosphor having excellent light emission characteristics showing a wide wavelength blue light emission spectrum. Through this, the blue phosphor according to the present invention was intended to be applied as a high-efficiency phosphor to the long-term wavelength ultraviolet light emitting device, UV Lamp, PDP phosphor, fluorescent lamp.

In order to achieve the above object, in the present invention, sodium, potassium, aluminum, silicate-based blue phosphor for long-wavelength ultraviolet rays represented by the following formula 1,2,3 and a method for preparing the same, and long-wavelength ultraviolet light including the blue phosphor Provided is an element.

[Formula 1]

(Na _v K _1-v ) _w Al _{2 ± X} Si _{6 ± y} O _{15 ± (w + 3x + 4y) / 2} zRE

In the above formula, v, w, x, y, z are moles, respectively, v is 0 <v <1, w is 0.1 <w <2, x is 0≤x≤1, y is 0≤y≤2, and z is 0.0002 ≦ z ≦ 0.25 and RE means a rare earth element selected from at least one of Eu and Ce.

[Formula 2]

(Na _v K _1-v ) _w Al _{2 ± x} Si _{6 ± y} O _{15 ± (w + 3x + 4y) / 2} Eu _z ²⁺  M _u ²⁺

In the above formula, v, w, x, y, u, z are moles, respectively, v is 0 <v <1, w is 0.1 <w <2, x is 0≤x≤4, and y is 0≤y≤2 U is 0.0002 ≦ u ≦ 0.25, z is 0.0002 ≦ z ≦ 0.25, and is a composition in which one or more rare earth elements such as M = Ce, Dy, Sm, Tm, Lu, Pr, Nb, Tb, Er are combined .

[Formula 3]

(Na _v K _1-v ) _w Al _{2 ± x} Si _{6 ± y} O _{15 ± (w + 3x + 4y) / 2} Eu _z ²⁺ M _u

In the above formula, v, w, x, y, z are moles, respectively, v is 0 <v <1, w is 0.1 <w <2, x is 0≤x≤4, y is 0≤y≤2, u is 0.0002 ≦ u ≦ 0.5, z is 0.0002 ≦ z ≦ 0.25, and M = Fe, Ba, Mg, Li, Cu, Ca, Sr, Cr, Ge, B.

As shown above, the blue phosphor according to the present invention is characterized in that it is a blue phosphor for long-wavelength ultraviolet light having a matrix of Na ₂ O · K ₂ O · Al ₂ O ₃ · SiO ₂ . Formula (I) is the _{Na 2 O · K 2 O ·} Al 2 O 3 · in a SiO ₂ matrix to europium (Eu) or cerium (Ce) been made is added to the active agent, (2) is Na ₂ O · K ₂ O · Al ₂ O ₃ · the europium (Eu) of SiO ₂ as a matrix is added to the active agent cerium (Ce), dysprosium (Dy), samarium (Sm), ruthenium (Lu), thulium (Tm), Pr, Nb, been made, one or more from the group consisting of Tb and Er is the selected element is added to the unit active agent, formula (3) is in the europium (Eu) the active agent a _{Na 2 O · K 2 O ·} Al 2 O 3 · SiO 2 as a matrix A blue phosphor for long-wavelength ultraviolet light, which is added, and wherein one or more elements selected from the group consisting of Ba, Ca, Sr, Mg, Li, Ge, B, Fe, Cu, Mn and Cr are added.

In the present invention, Na ₂ O, K ₂ O · Al ₂ O _3, is that the SiO ₂ as a matrix refers to sodium, potassium-aluminum-silicate-based blue phosphors in a blue phosphor for a UV wavelength intraday. This consists of sodium, potassium, aluminum and silicon as the main components constituting the phosphor, to which oxygen can be added as chloride or oxide of the main component. Conventional phosphors are mainly (Y _1-p Ce _p ) ₃ Al ₅ O ₁₂ , which implements white light, and phosphors that implement blue, such as Ba _x-2 Al _12-y O ₁₉ : Mn _y , Eu _z , (Sr _a Ba _b Ca _c ) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ or (Sr _1-x , Mg _x ) _10-y (PO ₄ ) ₆ Cl ₂ : Eu _y as a parent. However, the blue phosphors based on the conventional strontium (Sr), barium (Ba) and the like have a problem in that the luminescence intensity decreases in the long wavelength UV. According to the present invention, the blue phosphor composition has a conventional blue phosphor composition. A phosphor emitting blue light was prepared using a mixture having a composition completely different from that of the component.

As described above, the blue phosphor according to the present invention is characterized by using Na ₂ O · K ₂ O · Al ₂ O ₃ · SiO ₂ as a matrix, which is synthesized based on a general feldspar composition which is a kind of mineral. Therefore, the present invention can be produced using a natural alkali feldspar powder containing both alkali or alkali and kali produced in domestic and domestic feldspar mines, as a raw material having the same composition as the natural alkali feldspar as nitrate, acetate, carbonate It can also be prepared using salts, chlorides or oxides.

The present invention is _{Na 2 O · K 2 O ·} Al 2 O 3 · SiO 2 as the matrix, and sodium, potassium-aluminum-silicate-based blue phosphor to europium (Eu) as an activator, α- cristobalite (α-cristobalite) Orthoclase or feldspar (albite) as the main phase, characterized in that the amorphous glass phase and α-Al ₂ O ₃ is present in a small amount of the second phase. Such a matter can be confirmed by the following XRD diffraction pattern which shows the characteristic of the component which comprises a substance. Here, α-cristobalite refers to a silicate mineral whose chemical composition is SiO ₂ , the formal stone is a monoclinic mineral having sodium (Na) as a subsidiary component of the chemical composition KAlSiO ₃ , and the feldspar is a cosmetic stone composed of NaAlSiO as the chemical composition Refers to a single ingredient. That is, this invention is a blue fluorescent substance composition in which the mother component characterized by the above-mentioned mineral component in a columnar form is a sodium potassium aluminium silicate system. The present invention is a new phosphor composition which is excellent in luminescence intensity than the conventional blue phosphor CaMgSi ₂ O ₆ : Eu and has not been reported to date.

The excitation wavelength of the new blue phosphor composition according to the present invention exhibits a high absorption wavelength band from the medium wavelength ultraviolet region (220 nm to 320 nm) to the long wavelength ultraviolet region (320 nm to 400 nm), and the emission wavelength region is wide to 400 nm to 490 nm. The blue emission spectrum of the wavelength range shows the color purity. By varying the concentration of europium (Eu), a rare earth element added as an activator, and cerium (Ce), dysprosium (Dy), samarium (Sm), thulium (Tm), ruthenium (Lu), Color purity and brightness can be adjusted, and the color purity and brightness of the emission color can be changed with barium (Ba), iron (Fe), germanium (Ge), boron (B) or magnesium (Mg) added to the mother. Therefore, the developed blue phosphor can be applied to long-wavelength UV light emitting device and lighting UV lamp, PDP phosphor, fluorescent lamp and can be applied as a high efficiency phosphor.

Hereinafter, with reference to the accompanying drawings of the present invention will be described in detail the technical features of the present invention.

The blue phosphor for long-wavelength ultraviolet rays represented by Chemical Formulas 1,2.3 according to the present invention is prepared by a solid phase reaction method as shown in FIG. 1. That is, another aspect is _{Na 2 O · K 2 O ·} Al 2 O 3 · compound to SiO ₂ in the matrix and Europium (Eu) containing compounds, cerium (Ce) containing compounds, samarium-containing compound, a ruthenium-containing compound of the present invention Mixing at least one mixture selected from the group consisting of a transition element-containing compound such as dysprosium-containing compound, thulium-containing compound, barium-containing compound and iron with a solvent selected from ethanol, isopropylene alcohol, distilled water or water; Putting the mixed material in an oven and drying at 80 ° C. to 100 ° C. for 2 to 4 hours; The dried dried body was put into a high-purity alumina boat and first calcined for 1 to 8 hours in an air or oxygen atmosphere at a calcination temperature of 800 ° C. to 1000 ° C., followed by pulverization and 1 to 30% of the pulverized pulverized product. Method for producing a blue phosphor for long-wavelength ultraviolet light characterized in that the manufacturing process after the secondary firing for 1 hour to 8 hours at 1100 ℃ ~ 1250 ℃ in a reducing atmosphere using a mixed gas of hydrogen and 70 ~ 99% nitrogen to be.

Here, the blue phosphor according to the present invention is based on Na ₂ O · K ₂ O · Al ₂ O ₃ · SiO ₂ , and includes a natural alkali feldspar powder containing alkali or alkali and kali produced in domestic ore feldspar mines. It can be prepared by using, and as a raw material having the same composition as the natural alkali feldspar as described above can also be prepared using nitrate, acetate, carbonate, chloride or oxide. Thus, in the composition according to the present invention, which is based on a sodium potassium potassium aluminum silicate, europium (Eu) or cerium (Ce) is weighed as an activator if necessary (Formula 1), cerium (Ce), dysprosium ( Dy), samarium (Sm), ruthenium (Lu), thulium (Tm), at least one selected from the group consisting of Pr, Nb, Tb and Er as a deactivator (Formula 2) Ba, Ca, Sr, Mg One or more selected elements from the group consisting of Li, Ge, B, Fe, Cu, Mn, and Cr (Formula 3) are weighed on the mother body to match the composition ratio, and then uniformly by using ball milling or induction. To mix.

In addition, the europium-containing compound used in the above may be one or more selected from europium oxide (Eu ₂ O ₃ ), europium nitrate, europium chloride salts if it contains the europium, silicon containing compound is amorphous One or more of silica (SiO ₂ ) and quartz silica (SiO ₂ ) may be selected and used. Further, the europium or cerium-containing compound is preferably added in a range of 0.0002 to 0.5 molar ratio with respect to the compound based on the sodium, potassium, aluminum, and silicate, and is a transition element-containing compound such as iron copper chromium manganese. Silver is preferably added in the range of 0.0002 to 0.1 molar ratio with respect to the compound based on the sodium potassium potassium aluminum silicate, and the barium, calcium, strontium, magnesium, and the compound containing sodium sodium potassium aluminum silicate. It is most preferable to add in the range of 0.001-0.3 molar ratio with respect to the compound based on a silicate system. The cerium, dysprosium, samarium, thulium, and ruthenium-containing compounds are preferably added in a range of 0.0002 to 0.5 molar ratio with respect to the amount of the compound based on the sodium, potassium, aluminum, and silicate systems.

When the phosphors are prepared according to the above-described manufacturing process of the blue phosphor compositions (Formulas 1, 2 and 3) according to the present invention, the emission wavelength is 220 nm to 400 nm and the emission wavelength is 380 nm to 480 nm. In addition, the luminescence brightness is similar or superior to that of a known ultraviolet-excited blue phosphor. Therefore, the blue phosphor of the present invention can be applied to the fields of ultraviolet LED, LCD backlight, fluorescent lamp, PDP phosphor and the like. The maximum excitation wavelength and the emission wavelength can be controlled by the chemical composition of the composition, the raw material, the additive element, and the like. The maximum absorption peak wavelength of the excitation spectrum when using natural alkaline feldspar powder as the parent material is 258 nm, and the maximum emission peak wavelength is 406 nm. When the blue phosphor matrix is prepared by combining a raw material containing alkali kali aluminum silicon, The peak wavelength is changed to 292 nm and the maximum emission peak wavelength is 432 nm.

On the other hand, the long-wavelength ultraviolet light-emitting device comprising a blue phosphor for the long-wavelength ultraviolet light according to the present invention as described above and the phosphors prepared according to the above-described manufacturing process in the light emitting layer The fact that it can be implemented is obvious to those of ordinary skill in the art.

The invention may be better understood by the following examples, which are intended for purposes of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example 1 Natural Alkali Feldspar Powder: ywt% Eu ²⁺ XRD diffraction pattern of (y = 0, 0.5)

Figure 2 shows the XRD diffraction pattern of the blue phosphor prepared by producing a natural alkaline feldspar blue phosphor according to the present invention at a primary gas temperature of 1000 ℃. Specifically, the natural alkali feldspar powder: ywt% Eu ²⁺ (y = 0, 0.5) was subjected to heat treatment in the air for 4 hours at 1000 ° C. in a primary calcining temperature, and then the powder obtained at 3 ° C. It is a graph showing the absorption and emission characteristics of the blue phosphor (Formula 1) according to the present invention obtained by treatment with a reducing atmosphere (95N ₂ -5H ₂ ) for a period of time. The upper graph is when y is 0.5 and the lower graph is when y is 0. In FIG. 2, an asterisk (★) represents orthoclase (KAlSi ₃ O ₈ ) and an inverted triangle (▼) represents an arsenite (Albite: NaAlSi ₃ O ₈ ) phase. In the sample without europium, the orthoclase (KAlSi ₃ O ₈ ) phase and the feldspar (albite: NaAlSi ₃ O ₈ ) phase were present, and when the europium was added 0.5 wt%, only the orthoclase phase was present.

Example 2: (Na _0.66 K _0.34 ) _y Al ₂ Si ₆ O _{15 + y / 2} Eu _0.02 ²⁺ XRD diffraction pattern of (0.1 ≦ y ≦ 2) (Formula 1)

3 is a blue phosphor (Na _0.66 K _0.34 ) _y Al ₂ Si ₆ O _{15 + y / 2} : Eu _0.022+ prepared using an oxide corresponding to a natural alkali feldspar composition represented by Chemical Formula 1 according to the present invention as a raw material The XRD diffraction pattern of (0.1 ≦ y ≦ 2) is shown. Specifically, a sample of formula (Na _0.66 K _0.34 ) _y Al ₂ Si ₆ O _{15 + y / 2} : Eu _0.02 ²⁺ (0.1 ≦ _y ≦ ² ) was heat-treated at 800 ° C. for 4 hours in the air. XRD diffraction pattern of the phosphor powder according to the present invention is obtained by further processing the powder obtained by the reduction atmosphere (95N ₂ -5H ₂ ) for 3 hours at the secondary firing temperature of 1150 ℃. The top graph is when y is 2, the middle graph is y is 1, and the bottom graph is y is 0.1. In FIG. 2, C represents α-cristobalite phase and A represents α-Al ₂ O ₃ phase. As a result of XRD diffraction pattern analysis, α-cristobalite phase and α-Al ₂ O ₃ phase were present. The glass phase, which is an amorphous phase, is also present, but the XRD pattern is not shown by being processed by a background removal program during data processing.

Example 3: (Na _x K _1-x ) _y Al ₂ Si ₆ O _{15 + y / 2} Eu _0.02 ²⁺ (x = 0.66, 0.34 0.1≤y≤2) (Formula 1) Preparation of Blue Phosphor and Luminescent Properties

As shown in FIG. 1, Na ₂ CO ₃ , K ₂ CO ₃ , Al ₂ O ₃ , SiO ₂ , Eu ₂ O ₃ were weighed using a raw material, and used for 3 hours to obtain a uniform composition using a ball mill and a mortar in ethanol. The above was sufficiently mixed. The mixture was placed in an oven and dried at 80 ° C. for 2-3 hours, and then the dried mixture was placed in a high purity alumina boat, calcined at 800 ° C. for 4 hours using an electric furnace, and then the powder obtained by pulverization was 1150 ° C. using an electric furnace. After reheating for 3 hours, the reaction product was ground to obtain a blue phosphor. At this time, the firing atmosphere was maintained in a reducing atmosphere using 5% hydrogen and 95% nitrogen mixed gas. Absorption and emission spectra of the prepared blue phosphors are shown in FIGS. 4 and 5.

FIG. 4 is a blue phosphor prepared by using an oxide corresponding to a natural alkali feldspar composition represented by Chemical Formula 1 as a raw material (Na _0.66 K _0.34 ) _y Al ₂ Si ₆ O _{15 + y / 2} : Eu _0.02 ² Absorption emission characteristic of ⁺ (0.1 ≦ y ≦ 2) is shown. The wavelength showing the maximum emission intensity was blue at 432 nm [y = 0.1 (A), 0.3 (B), 0.7 (C), 1 (D), 1.5 (E), 2 (F)]. 5 is a blue phosphor (Na _0.34 K _0.66 ) _y Al ₂ Si ₆ O _{15 + y / 2} : Eu prepared using an oxide corresponding to a natural alkali feldspar composition represented by Chemical Formula 1 according to the present invention. Absorption emission characteristics of _0.02 ²⁺ (0.1 ≦ y ≦ ² ) are shown [y = 0.1 (A), 0.3 (B), 0.7 (C), 1 (D), 1.5 (E), 2 (F)]. . The wavelength showing the maximum emission intensity was 432 nm blue. As described above, the absorption spectra of FIGS. 4 and 5 show high absorption wavelengths in the long-wavelength UV range of 220-400 nm, and a broad blue wavelength range of 380-500 nm in the emission spectrum.

Example 4: (Na _0.66 K _0.34 ) Al _w Si ₆ O _{12.5 + 3w / 2} Eu _0.02 ²⁺ Formula 1) Preparation and Luminescent Properties of Blue Phosphors

As shown in Figure 1 Na ₂ CO ₃ , K ₂ CO ₃ , Al ₂ O ₃ , SiO ₂ , Eu ₂ O ₃ Weighing using the raw material and more than 3 hours to achieve a uniform composition using a ball mill and induction in ethanol Mix well. The mixture was placed in an oven and dried at 80 ° C. for 2-3 hours, and then the dried mixture was placed in a high purity alumina boat, calcined at 800 ° C. for 4 hours using an electric furnace, and then the powder obtained by pulverization was 1150 ° C. using an electric furnace. After reheating for 3 hours, the reaction product was ground to obtain a blue phosphor. At this time, the firing atmosphere was maintained in a reducing atmosphere using 5% hydrogen and 95% nitrogen mixed gas. The absorption and emission spectra of the prepared blue phosphors are shown in FIG. 6.

6 is a blue phosphor (Na _0.66 K _0.34 ) Al _w Si ₆ O _{12.5 + 3w / 2} : Eu _0.02 ²⁺ prepared using an oxide composition similar to the natural alkali feldspar composition represented by Chemical Formula 2 according to the present invention as a raw material Absorption emission characteristics of (0 ≦ w ≦ 2) are shown [W = 0 (A), 0.4 (B), 0.8 (C), 1.2 (D), 2 (E)]. The wavelengths showing the maximum emission intensity were blue at 432 nm (E) and 446 nm (D).

Example 5: (Na _0.66 K _0.34 ) Al ₂ Si ₆ O _15.5 Eu _0.02 ²⁺ + RE ²⁺ Formula 2 Preparation of Blue Phosphor

And luminescence properties

As shown in FIG. 1, Na ₂ CO ₃ , K ₂ CO ₃ , Al ₂ O ₃ , SiO ₂ , Eu ₂ O _3, Dy ₂ O ₃ , Sm ₂ O ₃ , TmCl ₃ xH ₂ O, Lu ₂ O ₃ , CeO ₂ raw materials were weighed and mixed well for at least 3 hours to achieve a uniform composition using ball mill and mortar in ethanol. The mixture was placed in an oven and dried at 80 ° C. for 2-3 hours, and then the dried mixture was placed in a high-purity alumina boat, calcined at 800 ° C. for 4 hours using an electric furnace, and then the powder obtained by pulverization was dried at 1100 ° C. using an electric furnace. After reheating for 3 hours, the reaction product was ground to obtain a blue phosphor. At this time, the firing atmosphere was maintained in a reducing atmosphere using 5% hydrogen and 95% nitrogen mixed gas. The absorption and emission spectra of the prepared blue phosphors are shown in FIG. 7.

FIG. 7 is a blue phosphor (Na _0.66 K _0.34 ) Al ₂ Si ₆ O _15.5 : Eu _0.022+ yRE ₂₊ (manufactured using an oxide composition corresponding to a natural alkali feldspar composition represented by Chemical Formula 2 according to the present invention as a raw material) Absorption emission characteristics of 0.005 ≦ y ≦ 0.01) are shown (y = 0.005Dy (A), 0.005Sm (B), 0.005Tm (C), 0.005Lu (D), 0.01Ce (E)). The wavelength showing the maximum emission intensity was 432 nm blue.

Example 6: (Na _0.66 K _0.34 ) Al ₂ Si ₆ O _15.5 Eu _0.02 ²⁺ + Fe _0.008 ²⁺ Formula 2) Preparation of Blue Phosphor and Luminescent Properties

As shown in FIG. 1, Na ₂ CO ₃ K ₂ CO ₃ Al ₂ O ₃ SiO ₂ Fe ₂ O ₃ Eu ₂ O ₃ was weighed using a raw material, and a ball mill and a mortar under an ethanol solvent were used to obtain a uniform composition. Mix well over time. The mixture was placed in an oven and dried at 80 ° C. for 2-3 hours, and then the dried mixture was placed in a high-purity alumina boat, calcined at 800 ° C. for 4 hours using an electric furnace, and then the powder obtained by pulverization was dried at 1100 ° C. using an electric furnace. After reheating for 3 hours, the reaction product was ground to obtain a blue phosphor. At this time, the firing atmosphere was maintained in a reducing atmosphere using 5% hydrogen and 95% nitrogen mixed gas. The absorption and luminescence properties of the blue phosphor according to the present invention obtained as described above are shown in FIG. 8.

8 is a blue phosphor (Na _0.66 K _0.34 ) Al ₂ Si ₆ O _15.5 : Eu _0.02 ²⁺ prepared using an oxide composition corresponding to a natural alkali feldspar composition represented by Chemical Formula 3 according to the present invention as a raw material Absorption emission characteristic of Fe _0.008 ²⁺ is shown. The wavelength showing the maximum emission intensity was 432 nm blue.

Example 7: Luminescence Characteristics of Primary Alkaline Feldspar Blue Phosphor (Formula 1) According to Primary Plasticization Temperature Change

In preparing blue phosphor using natural alkali feldspar and Eu ₂ O ₃ raw material, the first calcining temperature was calcined by dividing it into 800 ℃ and 1000 ℃, and the final temperature was obtained as in Example 1. The characteristics are shown in FIGS. 9 and 10. 9 and 10, it can be seen that the absorption and emission intensity were improved by 10% to 15% in the case of 1000 ° C than when the primary calcining temperature was set to 800 ° C.

9 is a graph showing absorption and luminescence properties of a blue phosphor prepared by producing a natural alkaline feldspar blue phosphor according to the present invention at a primary calcination temperature of 800 ° C. Specifically, the natural alkali feldspar powder: ywt% Eu ²⁺ (0.1≤y≤25) the sample obtained by heat treatment in the air for 6 hours at 800 ° C. at the primary calcining temperature is reduced again at the secondary firing temperature of 1150 ° C. A graph showing the absorption and luminescence properties of a blue phosphor according to the present invention obtained by treatment with an atmosphere (95N ₂ -5H ₂ ) [y = 0.1 (A), 0.5 (B), 1 (C), 5 (D), 10 (E), 15 (F), 20 (G), 25 (H)]. The maximum absorption peak wavelength showing the maximum absorption intensity was 258 nm, and the wavelength showing the maximum emission intensity was 406 nm.

10 is a graph showing absorption and luminescence properties of a blue phosphor prepared by varying the concentration of europium as an activator to natural alkali feldspar according to the present invention. Specifically, natural alkali feldspar powder: ywt% Eu ²⁺ (0.1 ≦ y ≦ 25) The powder obtained by heat-treating the sample at 1000 ° C. for 6 hours in the air is again reduced at a secondary firing temperature of 1150 ° C. (95N ₂ −). 5H ₂ ) shows the results obtained by measuring the absorption and luminescence properties of the phosphor powder according to the present invention [y = 0.1 (A), 0.5 (B), 1 (C), 5 (D), 10 (E ), 15 (F), 20 (G), 25 (H)]. The maximum absorption peak wavelength showing the maximum absorption intensity was 258 nm, and the wavelength showing the maximum emission intensity was 406 nm.

Example 8: Natural Alkali Feldspar Powder: 0.5 wt% Eu ²⁺ + 0.5 wt% RE ²⁺ (Formula 2) Blue type

Manufacture of Luminaries and Luminescent Properties

As shown in Fig. 1, natural alkali feldspar and Eu ₂ O ₃ , Dy ₂ O ₃ , Sm ₂ O ₃ , Tm ₂ O ₃ , Lu ₂ O ₃ were weighed using raw materials, The mixture was sufficiently mixed for at least 3 hours to obtain a uniform composition. Specifically, natural alkali feldspar powder: 0.5wt% Eu ²⁺ + 0.5wt% RE ²⁺ (RE = Dy, Sm, Tm, Lu) Put the sample in the oven and dry it for 2-3 hours at 80 ℃ The mixture was placed in a high purity alumina boat and calcined at 800 ° C. for 4 hours using an electric furnace, and then the powder obtained by pulverization was refired at 1150 ° C. for 3 hours using an electric furnace, and the reaction product was ground to obtain a blue phosphor. At this time, the firing atmosphere was maintained in a reducing atmosphere using 5% hydrogen and 95% nitrogen mixed gas. The photoluminescence characteristic of the blue fluorescent substance by this invention obtained as mentioned above is shown in FIG.

11 is a graph showing absorption and emission (absorption and emission) characteristics of a blue phosphor prepared by adding a rare earth element to a natural alkali feldspar according to the present invention [RE = Dy (A), Sm (B), and Tm (C ), Lu (D)]. The wavelength showing the maximum luminous intensity is 410 nm.

Example 9: Natural Alkali Feldspar: 0.5 wt% Eu ²⁺ + ywt% Ba ²⁺ Formula (3) of blue phosphor

Illumination and Luminescence Characteristics

As shown in FIG. 1, natural alkali feldspar and BaCO ₃ Eu ₂ O ₃ were weighed using a raw material and mixed well for more than 3 hours to obtain a uniform composition using a ball mill and a mortar in an ethanol solvent. Specifically, a natural alkali feldspar: 0.5wt% Eu ₂₊ + zwt% M ₂₊ (M = Ba 0.1 ≦ z ≦ 15) is placed in an oven, dried at 80 ° C. for 2-3 hours, and dried. It was put in a high purity alumina boat and calcined at 800 ° C. for 4 hours using an electric furnace, and the powder obtained by pulverization was refired at 1150 ° C. for 3 hours using an electric furnace, and the reaction product was ground to obtain a blue phosphor. At this time, the firing atmosphere was maintained in a reducing atmosphere using 5% hydrogen and 95% nitrogen mixed gas. 12 shows absorption and emission characteristics of the blue phosphor according to the present invention obtained as described above.

12 is a graph showing the absorption and emission (absorption emission) characteristics of the blue phosphor prepared by adding barium to the natural alkali feldspar according to the present invention [y = 0.1 (A), 0.5 (B), 1 (C), 5 (D), 10 (E), 15 (F)]. The wavelength representing the maximum emission intensity is 410 nm.

Example 8 Comparison between Blue Phosphor and Existing Blue Phosphor According to the Present Invention

Natural alkali feldspar according to the present invention prepared in Example 2: blue phosphor (Na _0.66 K _0.34 ) Al ₂ Si prepared using Eu _0.02 ²⁺ (A) and an oxide corresponding to the natural alkali feldspar composition as a raw material 13 is a graph comparing absorption and luminescence properties with ₆ O _15.5 : Eu _0.02 ²⁺ (C) and known CaMgSi ₂ O ₆ : Eu (CMS) blue phosphors (B).

13 is a blue phosphor prepared using a natural alkali feldspar blue phosphor alkali feldspar: 0.5 wt% Eu ²⁺ (A) and an oxide composition corresponding to a natural mineral alkali feldspar composition according to the present invention (Na _0.66 K _0.34 ). This is a graph comparing the absorption and emission (absorption and emission) characteristics of Al ₂ Si ₆ O _15.5 : Eu _0.02 ²⁺ (C) and known CaMgSi ₂ O ₆ : Eu (CMS) blue phosphors (B). Specifically, A is a natural alkali feldspar powder according to the present invention: ywt% Eu ²⁺ (0.1 ≦ y ≦ 25), the powder obtained by heat-treating in air for 4 hours at a primary calcining temperature of 1000 ° C. for the second time. This is a graph of a blue phosphor obtained by reducing atmosphere (95N ₂ -5H ₂ ) treatment for 3 hours at a calcination temperature of 1150 ℃. In addition, C is a secondary firing by pulverizing the powder obtained by heat-treating the sample of the formula (Na _0.66 K _0.34 ) Al ₂ Si ₆ O ₁₆ : Eu _0.01 ^{2+ according} to the present invention at a primary calcining temperature of 800 ° C. for 4 hours. It is a graph of blue phosphor obtained by reducing atmosphere (95N ₂ -5H ₂ ) treatment for 3 hours at a temperature of 1150 ℃. B is a graph comparing the absorption and emission characteristics of CaMgSi ₂ O ₆ : Eu (CMS), which is a conventional phosphor. As can be seen from the graph, the absorption and emission intensity of the A and B compositions are similar, and the C composition is relatively stronger than the A and B compositions. The maximum absorption wavelength is 258 nm, B is 350 nm, C is 292 nm, and the maximum emission wavelength is A at 405 nm, B at 450 nm, and c at 432 nm.

The blue phosphor according to the present invention is a natural mineral alkali feldspar powder or Na ₂ CO ₃ , K ₂ CO ₃ , Al ₂ O ₃ , SiO ₂ as a raw material prepared by adding europium (Eu) as an active material to the base matrix In addition, the blue phosphor for long-wavelength ultraviolet rays according to the present invention exhibits a blue emission spectrum with a wide wavelength ranging from 400 nm to 500 nm, and has a characteristic in which the maximum emission intensity varies depending on the concentration of europium added. In addition, active agents such as barium carbonate (BaCO ₃ ) and iron oxide (Fe ₂ O ₃ ) added to the base matrix and subsidiary agents such as cerium (Ce), dysprosium (Dy), samarium (Sm), ruthenium (Lu) and thulium (Tm) As a result, the color purity and luminance of the blue light emission color change. The blue phosphor according to the present invention having such color purity and luminance change characteristics can be applied as a high efficiency phosphor to long-term wavelength ultraviolet light emitting device, UV Lamp, PDP phosphor and fluorescent lamp.

Claims (11)

_{Na 2 O · K 2 O ·} Al 2 O 3 · SiO 2 Matrix with and europium blue phosphor for intraday wavelength ultraviolet rays, characterized in that represented by the following general formula (1) was added and (Eu) or cerium (Ce) as the activator : [Formula 1] (Na _v K _1-v ) _w Al _{2 ± X} Si _{6 ± y} O _{15 ± (w + 3x + 4y) / 2} zRE In the above formula, v, w, x, y, z are moles, respectively, v is 0 <v <1, w is 0.1 <w <2, x is 0≤x≤1, y is 0≤y≤2, and z is 0.0002 ≦ z ≦ 0.25 and RE means a rare earth element selected from at least one of Eu and Ce. A _{Na 2 O · K 2 O ·} Al 2 O 3 · SiO 2 as a matrix, and sikimyeo the addition of europium (Eu) as an activator, cerium (Ce), dysprosium (Dy), samarium (Sm), ruthenium (Lu), Blue phosphor for long-wavelength ultraviolet light, characterized in that represented by the following formula (2) in which at least one element selected from the group consisting of thulium (Tm), Pr, Nb, Tb and Er is added as a deactivator: [Formula 2] (Na _v K _1-v ) _w Al _{2 ± x} Si _{6 ± y} O _{15 ± (w + 3x + 4y) / 2} Eu _z ²⁺  M _u ²⁺ In the above formula, v, w, x, y, u, z are moles, respectively, v is 0 <v <1, w is 0.1 <w <2, x is 0≤x≤4, and y is 0≤y≤2 U is 0.0002 ≦ u ≦ 0.25, z is 0.0002 ≦ z ≦ 0.25, and is a composition in which at least one rare earth element such as M = Ce, Dy, Sm, Tm, Lu, Pr, Nb, Tb, Er is combined . _{Na 2 O · K 2 O ·} Al 2 O 3 · in a SiO ₂ matrix, europium (Eu) a sikimyeo added as an activator, Ba, Ca, Sr, Mg, Li, Ge, B, Fe, Cu, and Mn, and Blue phosphor for long-wavelength ultraviolet light, characterized in that represented by the formula (3) to which at least one element selected from the group consisting of Cr: [Formula 3] (Na _v K _1-v ) _w Al _{2 ± x} Si _{6 ± y} O _{15 ± (w + 3x + 4y) / 2} Eu _z ²⁺ M _u In the above formula, v, w, x, y, z are moles, respectively, v is 0 <v <1, w is 0.1 <w <2, x is 0≤x≤4, y is 0≤y≤2, u is 0.0002 ≦ u ≦ 0.5, z is 0.0002 ≦ z ≦ 0.25, and M = Fe, Ba, Mg, Li, Cu, Ca, Sr, Cr, Ge, B.  The blue phosphor for long-wavelength ultraviolet rays according to Claims 1 to 3, wherein the blue phosphor for ultraviolet rays is composed of α-cristobalite phase, orthoclase phase, or albite phase. A long wavelength ultraviolet light emitting device comprising the blue phosphor for long wavelength ultraviolet light according to claim 4 in a light emitting layer. _{Na 2 O · K 2 O ·} Al 2 O 3 · SiO 2 compound, and europium (Eu) containing compounds as a matrix, cerium (Ce) containing compounds, samarium-containing compound, a ruthenium-containing compound, dysprosium-containing compound, thulium-containing compound Mixing a mixture of at least one selected from the group consisting of a barium-containing compound and an iron-containing compound with a solvent selected from ethanol, isopropylene alcohol, distilled water or water; Putting the mixed material in an oven and drying at 80 ° C. to 100 ° C. for 2 to 4 hours; Putting the dried dried body into a high-purity alumina boat and sintering after first firing for 1 to 8 hours in an air or oxygen atmosphere at a calcination temperature of 800 ° C. to 1000 ° C., and The pulverized pulverized product comprising the step of secondary firing for 1 hour to 8 hours at 1100 ℃ ~ 1250 ℃ in a reducing atmosphere using a mixed gas of 1 ~ 30% hydrogen and 70 ~ 99% nitrogen The manufacturing method of the blue fluorescent substance for wavelength ultraviolet rays. The method of claim 6, wherein the blue phosphor for long-wavelength ultraviolet light is the following formula (1), (2) or (3). [Formula 1] (Na _v K _1-v ) _w Al _{2 ± X} Si _{6 ± y} O _{15 ± (w + 3x + 4y) / 2} zRE In the above formula, v, w, x, y, z are moles, respectively, v is 0 <v <1, w is 0.1 <w <2, x is 0≤x≤1, y is 0≤y≤2, and z is 0.0002 ≦ z ≦ 0.25 and RE means a rare earth element selected from at least one of Eu and Ce. [Formula 2] (Na _v K _1-v ) _w Al _{2 ± x} Si _{6 ± y} O _{15 ± (w + 3x + 4y) / 2} Eu _z ²⁺  M _u ²⁺ In the above formula, v, w, x, y, u, and z are moles, respectively, v is 0 <v <1, w is 0.1 <w <2, x is 0≤x≤4, and y is 0≤y≤2. U is 0.0002 ≦ u ≦ 0.25, z is 0.0002 ≦ z ≦ 0.25, and is a composition in which one or more rare earth elements such as M = Ce, Dy, Sm, Tm, Lu, Pr, Nb, Tb, Er are combined . [Formula 3] (Na _v K _1-v ) _w Al _{2 ± x} Si _{6 ± y} O _{15 ± (w + 3x + 4y) / 2} Eu _z ²⁺ M _u In the above formula, v, w, x, y, z are moles, respectively, v is 0 <v <1, w is 0.1 <w <2, x is 0≤x≤4, y is 0≤y≤2, u is 0.0002 ≦ u ≦ 0.5, z is 0.0002 ≦ z ≦ 0.25, and M = Fe, Ba, Mg, Li, Cu, Ca, Sr, Cr, Ge, B. The method of claim 6 wherein the compound of the _{Na 2 O · K 2 O ·} Al 2 O 3 · SiO 2 as a matrix is blue for intraday wavelength ultraviolet rays, characterized in that using natural alkali feldspar powder containing an alkali or alkali and potassium Method for producing a phosphor. 7. The method of claim _{6, Na 2 O · K 2 O} · Al 2 O 3 · compound to SiO ₂ as a matrix is made of one or more of the selected raw material from the group will be done as nitrates, acetates, chlorides, oxides, carbonates Method for producing a blue phosphor for long-wavelength ultraviolet light, characterized in that. The method for producing a blue phosphor for long-wavelength ultraviolet light according to claim 6, wherein the europium-containing compound is europium oxide (Eu ₂ O ₃ ), europium nitrate or europium chloride. The method for producing a blue phosphor for long-wavelength ultraviolet light according to claim 6, wherein the silicon-containing compound is amorphous silica (SiO ₂ ), quartz silica (SiO ₂ ) or silica gel.

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