KR101256626B1 - Long phosphorescent phosphors and method of preparating powders of the same - Google Patents

Abstract

An ultra-long afterglow alkaline earth metal-aluminate-based phosphor comprising europium (Eu) as an activator and dysprosium (Dy) as a study agent, and a powder manufacturing method thereof are provided.

Description

LONG PHOSPHORESCENT PHOSPHORS AND METHOD OF PREPARATING POWDERS OF THE SAME}

The present application relates to an ultra-long afterglow alkaline earth metal-aluminate-based phosphor comprising europium (Eu) as an activator and dysprosium (Dy) as a study agent, and a powder manufacturing method thereof.

Currently, the solid state method used in the manufacture of general long afterglow phosphors is representative, but such a method has difficulties in the non-uniformity of phosphor particle size, device configuration, and multicomponent synthesis. In addition, as various attempts have been made in the development of long afterglow phosphors in recent years, application directions and developments have been made. However, the manufacture of phosphors that satisfy the requirements of uniform particle size, high luminance and long light lifetime, and multicomponent synthesis is still relevant. It remains an important challenge or technical obstacle in the field of research.

Accordingly, the present application is to solve the above-described problems of the prior art, and to provide an ultra long afterglow alkaline earth metal-aluminate-based phosphor and a powder manufacturing method thereof having excellent characteristics in terms of long afterglow, brightness and color taste.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

A first aspect of the present application relates to a method for preparing an ultra long afterglow alkaline earth metal-aluminate-based phosphor powder, comprising:

Preparing an aqueous mixed metal compound solution containing an alkaline earth metal compound, an aluminum (Al) compound, a compound of europium (Eu) as an activator, and a compound of dysprosium (Dy) as a activator;

Adding a flux to the aqueous mixed metal compound solution;

After impregnating the aqueous solution of the mixed metal compound to which the flux is added to the polymer material, the solution is rapidly calcined by being introduced into the furnace heated to a temperature of 400 to 1000 ° C. for a short time, and then cooled or continuously, 1000 ° C. Firing in a reducing atmosphere at a temperature of 1 to 1300 ℃.

The second aspect of the present application comprises europium (Eu) as an activator and dysprosium (Dy) as a activator, and is prepared by the method for producing an ultra long afterglow alkaline earth metal-aluminate-based phosphor powder according to the present application. It relates to an ultra-long afterglow alkaline earth metal-aluminate phosphor.

The third aspect of the present application relates to a light emitting device including a light emitting layer manufactured using the ultra-long afterglow alkaline earth metal-aluminate phosphor powder. The light emitting device may be used for an evacuation guidance display board, an automobile trunk lever, a night safety display board, a luminous paint, a luminous signboard, a luminous tape, a fishing feed, or an illumination lamp.

The ultra-long afterglow alkaline earth metal-aluminate-based phosphor exhibits excellent characteristics in terms of long afterglow, brightness, and color taste. By using these characteristics, the ultra-long afterglow phosphor is used as an evacuation induction panel of an aircraft, a car trunk lever, and a night light. Safety signs, luminous paints, luminous signs, luminous tapes, fishing supplies, lighting lamps, etc. can be used for light emitting devices used for safety, security, evacuation, play equipment, leisure, sports.

1 is a flowchart showing a method of preparing an ultra long afterglow alkaline earth metal-aluminate phosphor powder according to one embodiment of the present application,
Figure 2 is a flow chart showing a method for producing an ultra-long afterglow alkaline earth metal-aluminate phosphor powder according to an embodiment of the present application,
3, 5 and 6 are the results of analyzing the light emission wavelength of the ultra-long afterglow alkaline earth metal-aluminate phosphor powder according to an embodiment of the present application,
Figure 4 is an FE-SEM picture of the ultra-long afterglow alkaline earth metal-aluminate phosphor powder according to an embodiment of the present application.

Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

Throughout this specification, it is to be understood that when a layer or member is " on " another layer or member, it is not only the case where a layer or member is in contact with another layer or member, Or < / RTI > another member is present.

As used throughout this specification, the terms “about”, “substantially”, and the like, are used at, or in the vicinity of, numerical values when manufacturing and material tolerances inherent in the meanings indicated are given, and an understanding of the invention Accurate or absolute figures are used to help prevent unfair use by unscrupulous infringers. As used throughout this specification, the term “step of” or “step of” does not mean “step for”.

A first aspect of the present application relates to a method for preparing an ultra long afterglow alkaline earth metal-aluminate-based phosphor powder, comprising:

Preparing an aqueous mixed metal compound solution containing an alkaline earth metal compound, an aluminum (Al) compound, a compound of europium (Eu) as an activator, and a compound of dysprosium (Dy) as a activator;

Adding a flux to the aqueous mixed metal compound solution;

After impregnating the aqueous solution of the mixed metal compound to which the flux is added to the polymer material and then rapidly calcining it into a furnace heated to a temperature of 400 ° C. to 1000 ° C. for a short time, after cooling or continuously, 1000 Baking in a reducing atmosphere at a temperature of 1 ℃ to 1300 ℃ (see Figure 1).

In an exemplary embodiment, the rapid calcining may be performed by maintaining the temperature at a temperature of 400 ° C. to 1000 ° C. for 1 to 10 hours, but is not limited thereto.

In an exemplary embodiment, firing under the reducing atmosphere may include, but not limited to, firing under a reducing atmosphere at a temperature of 1000 ° C to 1300 ° C after cooling after the rapid calcining.

In an exemplary embodiment, firing under the reducing atmosphere may include, but is not limited to, firing under a reducing atmosphere at a temperature of 1000 ° C. to 1300 ° C. continuously after the rapid calcination.

In an exemplary embodiment, the ultra-long afterglow phosphor may be non-stoichiometrically containing Sr as the alkaline earth metal and represented by the general formula SrAlO: Eu, Dy, but is not limited thereto. In one embodiment, the ultra-long afterglow phosphor may be represented by the following Chemical Formula 1 by non-stoichiometrically containing Sr as the alkaline earth metal, but is not limited thereto.

[Formula 1]

Sr _v Al _W O _X : Eu _y Dy _z ;

Wherein 0.09400 ≦ v ≦ 2.00000, 1.5000 ≦ w ≦ 2.50000, 3.9500 ≦ x ≦ 5.30000, 0.0087 ≦ y ≦ 0.12000, and 0.02370 ≦ z ≦ 0.12075.

In an exemplary embodiment, the flux includes B ₂ O ₃ , but is not limited thereto.

In an exemplary embodiment, the flux may be 1 wt% to 5 wt% with respect to the alkaline earth metal-containing aluminate based ultra long afterglow phosphor powder, but is not limited thereto.

In an exemplary embodiment, the particle size of the ultra-long afterglow phosphor powder may range from 1 μm to 30 μm, but is not limited thereto.

In an exemplary embodiment, the metal compounds may be independently selected from the group consisting of chlorides, nitrates, acetates, sulfates, oxides, carbonates, and combinations thereof, but are not limited thereto.

In an exemplary embodiment, the polymer material may be selected from the group consisting of cellulose, pulp and rayon, and combinations thereof, but is not limited thereto.

In an exemplary embodiment, firing under the reducing atmosphere is N ₂ / H ₂ = (90 to 95) / (5 to 10), or Ar / H ₂ = (90 to 95) / (5 to 10) may be performed in a reducing atmosphere, but is not limited thereto.

According to a second aspect of the present application, an ultra long afterglow alkaline earth metal-aluminate system, which comprises europium (Eu) as an activator and dysprosium (Dy) as a activator, is prepared by the manufacturing method of the first aspect of the present application. It relates to a phosphor.

In an exemplary embodiment, the ultra-long afterglow phosphor may be represented by the following Chemical Formula 1 by non-stoichiometrically containing Sr as the alkaline earth metal, but is not limited thereto.

[Formula 1]

Sr _v Al _W O _X : Eu _y Dy _z ;

Wherein 0.09400 ≦ v ≦ 2.00000, 1.5000 ≦ w ≦ 2.50000, 3.9500 ≦ x ≦ 5.30000, 0.0087 ≦ y ≦ 0.12000, and 0.02370 ≦ z ≦ 0.12075.

In an exemplary embodiment, the phosphor may be in powder form having a particle size in the range of 1 μm to 30 μm, but is not limited thereto:

The third aspect of the present application relates to a light emitting device comprising a light emitting layer prepared using the ultra-long afterglow alkaline earth metal-aluminate phosphor powder.

In an exemplary embodiment, the light emitting device may be used in the evacuation guidance display panel, car trunk lever, night safety sign, luminous paint, luminous signage, luminous tape, fishing feed, or lighting lamp of the aircraft, but is not limited thereto. It doesn't happen.

Hereinafter, the present invention will be described in more detail through embodiments and examples, but the scope of the present invention is not limited to these embodiments and examples.

In one embodiment of the present application, a water-soluble raw material including Sr, Al, Eu, Dy and flux is impregnated into the polymer material to obtain a precursor, and a furnace heated at 400 ° C. to 1000 ° C. The afterglow effect can be increased by calcination in air for 1 to 10 hours in a short time to completely oxidize the precursor and leave some residue. Subsequently, firing in a reducing atmosphere at 1000 ° C. to 1300 ° C. for 1 to 10 hours after continuous or cooling provides an ultra-long phosphor powder and a method of manufacturing the same. When the preferred firing temperature is 500 ° C to 800 ° C and 400 ° C or less, a large amount of impurities remain, thereby lowering the fluorescence characteristics in subsequent atmosphere firing, and coarsening of particles at a temperature of 1000 ° C or higher. Preferred calcination times are from 2 hours to 5 hours. Less than 1 hour may result in a large amount of impurities, resulting in a decrease in fluorescence in the atmosphere firing process, and more than 10 hours does not help to form a reducing atmosphere due to the extremely small amount of unremained material, which also reduces the afterglow time increase for the unremained material. . Moreover, the preferable baking time of atmospheric baking is 2 to 5 hours. When it is 1 hour or less, it exists in the tendency for the composition of a reducing atmosphere, and for 10 hours or more, there exists a tendency for particle coarsening.

In addition, the polymer material impregnated with the precursor aqueous solution into the preheated furnace is placed in the furnace for 5 seconds to 10 minutes under a room temperature condition for a short time, and the high-speed firing can shorten the manufacturing time of the overall phosphor and improve productivity. Here, the time for high speed firing is preferably 5 seconds to 30 seconds, and the polymer material is calcined by the short time firing.

In one embodiment, the ultra long and high luminescent phosphor powders of Formula 1 may be obtained through various compositional changes of Sr, Al, Eu, and Dy:

[Formula 1]

Sr _v Al _W O _X : Eu _y Dy _z (flux: 1-5 wt%);

Wherein 0.09400 ≦ v ≦ 2.00000, 1.5000 ≦ w ≦ 2.50000, 3.9500 ≦ x ≦ 5.30000, 0.0087 ≦ y ≦ 0.12000, and 0.02370 ≦ z ≦ 0.12075.

Increasing the composition of Eu, which is an additive (reactivator), increases the luminescence intensity and decreases afterglow, while increasing the composition of Dy, which is a study agent, increases the afterglow and decreases the luminescence intensity. In addition, as the composition of Sr increased nonstoichiometrically, the emission intensity and the afterglow increased. As for the addition amount of the flux of Sr-Al-O: Eu and Dy fluorescent substance, 1-5 wt% or 2-4 wt% is preferable, for example. If the flux is less than 1 wt%, the effect of the flux is small, and if the flux is 5 wt% or more, grain coarsening occurs rapidly. In addition, a fluorine (F) compound, a boron (B) compound, a sodium (Na) compound, a chlorine (Cl) compound, a vanadium (V) compound, which may serve as flux of the phosphor in the precursor aqueous solution containing the metal salts, and By adding an organic compound, particle size control, brightness improvement, particle dispersibility improvement and particle shape of the phosphor to be produced can be improved. For example, H ₃ BO ₃ which is a B (boron) compound may be used as the flux, but is not limited thereto.

The particle size of the super afterglow phosphor powder obtained through the above process is 1 to 30 μm, which can be adjusted by the concentration of temperature and time flux.

The alkaline earth metal salts and aluminum salts may be selected from the group consisting of chlorides, nitrates, sulfates, and combinations of the alkaline earth metals and aluminum, but are not limited thereto. For example, when used in the order of chloride, nitride, sulfide of the metal, it is preferable to synthesize the oxide of the final composition at a lower temperature, and it is preferable to use the chloride or nitride as an aqueous metal salt solution, but is not limited thereto. .

Further, in the type and selection of the polymer material in the method of producing the super-afterglow phosphor powder described above, the polymer material is crystalline cellulose (purity 99.99%), high purity pulp (99.8%) or rayon, preferably high purity pulp. The structure absorbs the metal saline solution into the fine crystal (40-250 mm) of the high-purity pulp as a fine form of the matrix, the high-purity pulp begins to oxidize in the calcination process of about 200 ° C or higher, and the polymer material is almost decomposed and It is suitable for the present invention of the luminescent super afterglow phosphor.

For the reducing atmosphere firing, a mixed gas selected from a single gas of argon (Ar), nitrogen (N ₂ ), hydrogen (H ₂ ) or a combination thereof may be used. For example, firing under the reducing atmosphere may be performed in a reducing atmosphere of N ₂ / H ₂ (90 to 95/5 to 10) or Ar / H ₂ (90 to 95/5 to 10), but is not limited thereto. It is not.

The pulverization process may be additionally performed on the phosphor powder produced by the continuous calcination process. For example, as a device used in the pulverization process, a ball mill, a roller mill, and a vibration ball mill may be used. Dry disperser or ultrasonic disperser, such as atorita mill, planetary ball mill, sand mill, cutter mill, hammer mill, jet mill, or One or more devices of a high pressure homogenizer can be used, and the pulverization process through this device can be used to further atomize the phosphor powder.

As the ultra-long light phosphor powder of the present application, for example, the powder of the above-described Sr-Al-O: Eu, Dy oxide phosphor can be used as a light emitting layer of a light emitting device, and thus it can be applied to the manufacture of displays, lamps and safety equipments. . For example, the light emitting device may be used in any one of a device such as an evacuation passage display plate, a car trunk levy, a night safety display plate, a luminous paint, a luminous signage, a luminous tape, a fishing feed, an illumination lamp, and the like, It is not limited.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present application is not limited thereto.

Sr - Al -O: Eu , Of Dy Protruding  effect

As shown in FIG. 2, an exemplary process flow diagram, a metal salt is dissolved in deionized water (DI water) to form Sr (NO ₃ ) ₂ nH ₂ O / deionized water 30 wt%, Al (NO ₃ ) ₃ nH ₂ O / A precursor aqueous solution comprising 50 wt% of deionized water, 30 wt% of Dy (NO ₃ ) ₃ nH ₂ O / deionized water, and 30 wt% of EuCl _{3 ·} nH ₂ O / deionized water was prepared, and the precursor aqueous solution was prepared using a polymer material. the impregnation after the short period of time through the calcination and firing, to thereby prepare a reducing atmosphere, and Eu ^{2 +} Dy ^{+ 3} doped with strontium aluminate (strontium aluminate doped Eu ^{+ 2,} Dy ^{+ 3).}

Specifically, an aqueous solution of the following weighed metal salts in deionized water was mixed with a stirrer (100 r / min) for 30 minutes to obtain a uniform precursor aqueous solution. Next, the high purity pulp and the precursor aqueous solution were impregnated with a weight ratio of 1: 1 for 1 hour or more. Next, the precursor aqueous solution impregnated with the polymer material was placed in a porous alumina crucible, and then put into an electric furnace substantially preheated to 800 ° C. within 10 seconds to be calcined in air for 2 hours to obtain a powder. _{Next, N 2 / H 2 (95/5} ) was reduced to the atmosphere used in the calcination for 3 hours at 1200 ℃ temperature with a heat rate 200 ℃ / h from room ^{Sr-Al-O: Eu 2+} , Dy ^{3 +} a Green and cyan ultra long afterglow phosphor powders were obtained.

This embodiment a composition of Sr-Al-O in accordance with the compositions shown in Table 1 below: Eu ^{2 +,} Dy ^{3 +} plus B ₂ O ₃ (boric acid), the B (boron) in the composition from 1 to 5 wt% change in The change in luminous intensity was shown in comparison with commercial luminous phosphors. The total sample of the one-time synthesis weighed each salt containing each metal element to be 5 g.

In comparison with the phosphor powders of Sr-Al-O: Eu ^{2 +} , Dy ^{3 +} green and cyan according to the respective composition, as the concentration of boron (B) of 1 to 3 wt% was increased, At wt%, the emission intensity decreased. Figure 3 shows the results of analyzing the light emission wavelength of this embodiment. In particular, it was confirmed that the coarsening of the particles occurs rapidly at 5 wt%. 4 is a FE-SEM photograph of the present embodiment.

Sr _{One -y- x} Al ₂ O ₄ : Eu _x , Dy _y  of Eu Wow Dy Influence of

The composition of this embodiment is used to change the emission intensity and emission position according to the change of Eu (x) and Dy (y) of Sr _{1- y- x} Al ₂ O ₄ : Eu _x , Dy _y shown in Table 2 below. Shown in comparison with luminous phosphors. Synthesis method other than the composition is the same as in Example 1.

In joseongpyo _{above, Sr 1 -y- x Al 2 O} 4: the maximum light-emitting position was changed in accordance with the ratio of _x Eu, Dy _y of x and y. 1: 1, 1: 2 and 1: 3 and 2: 1 and 3: 1 as a result of adjusting the Eu ^{2 +} and Dy ^{3 +,} confirmed that the proportion of Eu more relatively increased to shorten the position of the maximum emission wavelength It was. 5 shows the results of analyzing the light emission wavelength of this embodiment. In particular, the emission intensity of 140% was obtained at x: 0.2 and y: 0.4.

Sr _w Al ₂ O ₄ : Eu _x , Dy _y  in  Influence of nonstoichiometric composition of w + x + y

The composition of the present embodiment was changed according to the non-stoichiometric composition of w + x + y in Sr _w Al ₂ O ₄ : Eu _x and Dy _y shown in Table 3 below. The comparison is shown. Synthesis method other than the composition is the same as in Example 1.

In the above composition table, maximum emission intensity and emission position were changed according to the nonstoichiometric composition change of w + x + y in Sr _w Al ₂ O ₄ : Eu _x and Dy _y . Luminous intensity increased dramatically as w + x + y = 0.8, 1.0, 1.2, 1.4. In particular, when w + x + y = 1.4, the emission intensity was 271.6%. However, there was no significant change in long afterglow. 6 shows the results of analyzing the light emission wavelength of this embodiment.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is shown by the following claims rather than the above description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present invention. do.

Claims (16)

Preparing an aqueous mixed metal compound solution containing an alkaline earth metal compound, an aluminum (Al) compound, a compound of europium (Eu) as an activator, and a compound of dysprosium (Dy) as a activator;
Adding a flux to the aqueous mixed metal compound solution;
After impregnating the aqueous solution of the mixed metal compound to which the flux is added to the polymer material, the mixture is introduced into the furnace heated at a temperature of 400 to 1000 ° C. for 5 seconds to 10 minutes and calcined for 1 hour to 10 hours in air. After cooling, or continuously, at a temperature of 1000 ° C. to 1300 ° C., the volume flow rate ratio of N ₂ / H ₂ is (90 to 95) / (5 to 10), or the volume flow rate ratio of Ar / H ₂ is (90 To 95) / (5 to 10) firing in a reducing atmosphere comprising:
Ultra long afterglow alkaline earth metal-aluminate phosphor powder manufacturing method.
The method of claim 1,
The calcination is carried out by maintaining for 1 to 10 hours at a temperature of 400 ℃ to 1000 ℃ from room temperature, ultra-long afterglow alkaline earth metal-aluminate-based phosphor powder manufacturing method.
The method of claim 1,
Firing under the reducing atmosphere is to cool after the calcination, and then firing under a reducing atmosphere at a temperature of 1000 ℃ to 1300 ℃, the method of producing an ultra-long afterglow alkaline earth metal-aluminate-based phosphor powder.
The method of claim 1,
Firing under the reducing atmosphere includes firing under a reducing atmosphere continuously at a temperature of 1000 ° C. to 1300 ° C. after the calcining, to prepare an ultra long afterglow alkaline earth metal-aluminate phosphor powder.
The method of claim 1,
The ultra-long afterglow alkaline earth metal-aluminate-based phosphor powder is non-stoichiometrically containing Sr as alkaline earth metal and is represented by the general formula SrAlO: Eu, Dy. Manufacturing method.
The method of claim 1,
A method for producing a super long afterglow alkaline earth metal-aluminate phosphor powder comprising B ₂ O ₃ as the flux.
The method of claim 1,
The flux is 1 wt% to 5 wt% with respect to the ultra-long afterglow alkaline earth metal-aluminate phosphor powder.
The method of claim 1,
Ultra long afterglow alkaline earth metal-aluminate phosphor powder The particle size of the ultra-long afterglow alkaline earth metal-aluminate phosphor powder.
The method of claim 1,
The alkaline earth metal compound, the aluminum compound, the compound of europium, and the compound of dysprosium are chlorides, nitrates, acetates, sulfates, oxides, carbonates of the alkaline earth metal, the aluminum, the europium, and the dysprosium, respectively. And it is independently selected from the group consisting of, a method for producing an ultra-long afterglow alkaline earth metal-aluminate-based phosphor powder.
The method of claim 1,
The polymer material is selected from the group consisting of cellulose, pulp, rayon, and combinations thereof, a method for producing ultra long afterglow alkaline earth metal-aluminate phosphor powder.
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