KR100746338B1 - Phosphor for white light emitting apparatus, manufacturing method thereof and white light emitting apparatus using phosphor - Google Patents

Abstract

Provided are a phosphor, a method for preparing the phosphor, and a white light emitting device using the phosphor which is excellent in color reproducibility and color rendition and has a low color temperature. A phosphor is represented by X_(1-v-y) Al_11(2/3)+v+(2/3)s-z O_(19+s): yEu^2+, zMn^2+, wherein X is at least one element selected from La and Ce; 0<v<=0.5; 0<s<=0.5; 0<y<=0.5; and 0<z<=5. A method comprises the steps of a compound containing X, a compound containing Al, a compound containing Eu and a compound containing Mn; heat treating the mixture; cooling the heat treated phosphor; and pulverizing the cooled phosphor.

Description

Phosphor for white light emitting apparatus, manufacturing method, and white light emitting apparatus using phosphor}

1 is phosphor X _1-vy Al _{11 (2/3) + v + (2/3) sz} O 19+ _s : yEu ²⁺ , zMn ²⁺ (v = 0.173, s = 0.09, y = 0.21) , z = 0.6).

2 is phosphor X _1-vy Al _{11 (2/3) + v + (2/3) sz} O 19+ _s : yEu ²⁺ , zMn ²⁺ (v = 0.173, s = 0.09, y = 0.21) of the present invention. , z = 0 to 0.75).

3 is phosphor X _1-vy Al _{11 (2/3) + v + (2/3) sz} O 19+ _s : yEu ²⁺ , zMn ²⁺ (v = 0.173, s = 0.09, y = 0.21) of the present invention. , z = 0 to 0.75).

4 is phosphor X _1-vy Al _{11 (2/3) + v + (2/3) sz} O 19+ _s : yEu ²⁺ , zMn ²⁺ (v = 0.173, s = 0.09, y = 0.18) of the present invention. 0.3, z = 0.6).

5 is phosphor X _1-vy Al _{11 (2/3) + v + (2/3) sz} O 19+ _s : yEu ²⁺ , zMn ²⁺ (v = 0.173, s = 0.09, y = 0.18) of the present invention. 0.3, z = 0.6).

6 is phosphor X _1-vy Al _{11 (2/3) + v + (2/3) sz} O 19+ _s : yEu ²⁺ , zMn ²⁺ (v = 0.173, s = 0.09, y = 0.21) of the present invention. , z = 0.6).

7 is a schematic configuration diagram of a white light emitting device using a phosphor according to the present invention.

8 is a graph showing the emission spectrum of the white light emitting device to which the phosphor of the present invention is applied.

<Explanation of symbols for main parts of the drawings>

10: light emitting device chip 20: hole cup

30: molding layer 40, 50: lead

60: anode 70: cathode

80: exterior material

The present invention relates to a phosphor for a white light emitting device, a method for manufacturing the same, and a white light emitting device using the phosphor. More specifically, the light emitting device absorbs light in a region between near ultraviolet rays and ultraviolet rays, thereby realizing various emission colors of blue, green, and red on a single phase. The present invention relates to a white light emitting device having a white light having low color temperature and excellent color reproducibility, color control ability and color rendering property by applying a phosphor, a method of manufacturing the same, and a phosphor for wavelength conversion.

Among the white light emitting devices, if there is an ultraviolet light emitting diode (LED), the present invention is particularly directed to a white LED device among white light emitting devices.

The light emitting diode (LED) emits a wavelength corresponding to a band gap energy by recombination of carriers injected into the active layer. Recently, high-power white LEDs are rapidly emerging as next-generation lighting sources.

White LEDs have the advantages of low power consumption, long life and environmentally friendly. To realize a white LED, (1) a method of implementing white by combining three LEDs emitting red, green, and blue colors, and (2) a phosphor absorbs and emits light emitted from one LED and emits white light. There is a way to.

In the above method (1), there is a problem that the operating voltages of the three LED chips are uneven and the output of each chip is changed according to the ambient temperature, so that the color coordinates are different, whereas the method of (2) is only one LED. It is advantageous in that white can be achieved through the selection and combination of appropriate phosphor materials.

As one of the methods for the above (2), a white LED coated with a YAG (Y ₃ Al ₅ O ₁₂ : Ce ³⁺ ) -based phosphor that absorbs blue and emits yellow light has been developed. However, there is a problem in that the blue light emitted from the LED chip and the yellow light emitted from the phosphor are separated, and the blue light emitted from the LED chip has a problem of lowering color stability due to the change in emission luminance according to the ambient temperature. In addition, an appropriate amount of phosphor is applied to the LED chip to realize white color, but it is difficult to reproduce the same white color because it is very sensitive to the method of applying the phosphor and the operating conditions of the LED chip. In addition, due to the high color temperature in which the red light emission is insufficient and the blue light emission is predominant, there is a disadvantage in that the white light having a high color temperature is emitted.

Therefore, there is a demand for the development of a phosphor that emits white light having low color temperature and excellent luminous efficiency, color reproducibility, color stability, and color rendering index.

Meanwhile, as the related art of the present invention, Korean Patent Publication No. 1991-001218 discloses a white light emitting phosphor composition obtained by mixing a green light emitting phosphor, a red light emitting phosphor, and a blue light emitting phosphor at a predetermined ratio. As a content of the method of 1), a technical structure differs from this invention.

An object of the present invention is to provide a phosphor for a white light emitting device and a method of manufacturing the same, which do not need to adjust the amount of phosphors by implementing red, green, and blue in a single phase, and do not cause reabsorption problems between phosphors.

The phosphor for a white light emitting device of the present invention provides a white light emitting device that can provide a warm white light having excellent color reproducibility and color stability and low color temperature by using a light emitting device chip that emits light in near ultraviolet and blue region. For other purposes.

In order to achieve the above technical problem, the present invention represents a phosphor represented by the following formula (1).

X _1-vy Al _{11 (2/3) + v + (2/3) sz} O _{19 + s} : yEu ²⁺ , zMn ²⁺ .

In Formula (1), X is any one or more metals selected from La and Ce, and 0 <v ≦ 0.5, 0 <s ≦ 0.5, 0 <y ≦ 0.5, and 0 <z ≦ 5, and more preferably 0 < v≤0.3, 0 <s≤0.3, 0.005≤y≤0.4, and 0 <z≤1.

Phosphor represented by the formula (1) of the present invention can be implemented in full color by adjusting the amount of z. By adjusting the amount of z on a single phase, it is possible to realize blue, blue green, green, yellow, and red colors, which can be applied to various colors as well as low temperature white light for wavelength conversion of UV LED devices. .

The present invention includes a phosphor represented by the following formula (2).

X _1-y MgAl _11-z O ₁₉ : yEu ²⁺ , zMn ²⁺ ...... Formula (2)

In Formula (2), X is any one or more metals selected from La and Ce, and 0 <y ≦ 0.5 and 0 <z ≦ 5.

The present invention includes a method for producing a phosphor represented by the formula (1).

X _1-vy Al _{11 (2/3) + v + (2/3) sz} O _{19 + s} : yEu ²⁺ , zMn ²⁺ .

In Formula (1), X is any one or more metals selected from La and Ce, and 0 <v ≦ 0.5, 0 <s ≦ 0.5, 0 <y ≦ 0.5, and 0 <z ≦ 5, and more preferably 0 < v≤0.3, 0 <s≤0.3, 0.005≤y≤0.4, and 0 <z≤1.

The phosphor manufacturing method of the present invention represented by the formula (1) includes the following steps (1) to (4).

(1) mixing a compound containing X (X is any one or more metals selected from La and Ce), a compound containing Al, a compound containing Eu, and a compound containing Mn; (2) heat treating the milled mixture; (3) cooling the heat-treated phosphor; (4) pulverizing the cooled phosphor.

 The present invention includes a white light emitting device in which the phosphor represented by Chemical Formula (1) is mixed with a light transmitting resin and molded to cover the light emitting device chip. The white light emitting device of the present invention is a light emitting device in which a phosphor is mixed with a light transmissive resin and molded on a light emitting device chip, wherein the light emitting device chip emits light in an area of 370 nm to 420 nm, and the chemical formula (1) A white light emitting device is manufactured by absorbing light emitted from a light emitting device chip by applying a phosphor denoted as and converting wavelengths to simultaneously emit blue, green, and red colors to make white.

 Hereinafter, the phosphor of the present invention, a manufacturing method thereof, and a white light emitting device using the same will be described in more detail.

Phosphor according to the present invention is represented by the following formula (1).

X _1-vy Al _{11 (2/3) + v + (2/3) sz} O _{19 + s} : yEu ²⁺ , zMn ²⁺ .

In Formula (1), X is any one or more metals selected from La and Ce, and 0 <v ≦ 0.5, 0 <s ≦ 0.5, 0 <y ≦ 0.5, and 0 <z ≦ 5, and more preferably 0 < v≤0.3, 0 <s≤0.3, 0.005≤y≤0.4, and 0 <z≤1.

It is preferable that the fluorescent substance of this invention represented by the said General formula (1) is a single phase. This is because when the single phase has a strong chemical bonding force between ions, the chemical properties are stable, and in particular, the luminescence brightness and the reproducibility of the spectrum are excellent.

Element X constituting X _1-vy Al _{112/3 + v + 2 / 3s-zO 19 + s} : yEu ²⁺ , zMn ²⁺ as a parent in the phosphor represented by Chemical Formula (1) is selected from La and Ce. It consists of a combination of any one or more elements selected.

In the phosphor of Formula (1), the v value is 0 <v ≦ 0.5, and the s value is 0 <s ≦ 0.5, more preferably 0 <v ≦ 0.3, 0 <s ≦ 0.3, and should have a distorted magnetoplumbite structure. Distorted magnetoplumbite structures have been known to be structurally stable as a classifying structure of hexagonal aluminate phosphors, which are widely known as phosphor materials. Distorted magnetoplumnite structure consists of the spinel block and the intermediate layer connecting the spinel block. In the phosphor of Formula (1), the y value is 0 <y≤0.5, more preferably 0.005≤y≤0.4, and the z value is 0 <z≤5, more preferably 0 <z≤1. . If the y value is less than 0 and the z value is less than 0 in the phosphor of Chemical Formula (1), it cannot act as an activator and an activator, and when the y value is more than 0.5 and the z value is more than 5, This is because the luminescence brightness drops rapidly.

The phosphor represented by Chemical Formula (1) of the present invention can realize full color by adjusting the z value. It is possible to realize blue, blue green, green, yellow, and red only by adjusting the value of z on a single phase, which can be applied to various colors as well as low temperature white light for wavelength conversion of UV LED devices. .

The present invention includes the method of preparing the phosphor of Chemical Formula 1 including the following steps (1) to (4).

(1) mixing a compound containing X (X is any one or more metals selected from La and Ce), a compound containing Al, a compound containing Eu, and a compound containing Mn

As one example of the compound containing X in step (1), any one or more selected from oxides containing X, carbides containing X, and nitrides containing X may be used.

As one example of the Al-containing compound in step (1), any one or more selected from an oxide containing Al, a carbide containing Al, and a nitride containing Al may be used.

As one example of the compound containing Eu in step (1), any one or more selected from an oxide containing Eu, a carbide containing Eu, and a nitride containing Eu may be used.

As one example of the compound containing Mn in step (1), any one or more selected from oxides containing Mn, carbides containing Mn, and nitrides containing X may be used.

The phosphor of the present invention may be X ₂ O ₃ , Al ₂ O ₃ when the raw material is an oxide, and Eu ₂ O ₃ and MnO may be used as raw materials of the activator and the activator. At this time, X ₂ O ₃ , Al ₂ O ₃ , Eu ₂ O ₃ , MnO are mixed in a molar ratio of 1-vy: 11 (2/3) + v + (2/3) sz: y: z, respectively. For more effective mixing, mix and grind to a uniform composition using agate motar or ball milling. In this case, the y value is 0.005 to 0.40, and the z value is preferably 0.005 to 1. The reason is as described above.

In addition to the raw material of Formula (1) in the step (1) may further comprise the step of adding a flux of 0.001 to 10% relative to the weight of the raw material. Since the flux has a low melting point, it melts faster than the raw material of the phosphor, thereby improving the fluidity of the entire mixture, thereby shortening the synthesis temperature and the synthesis time, and uniformly distributing the activator in the obtained phosphor, and simultaneously There is an effect of making the size distribution uniform. In addition, the flux melts faster than the other raw materials to cover the entire mixture to prevent volatilization of the phosphor raw materials and to control the chemical equivalence ratio of the final compound due to the effect that the anions of the flux materials compensate for the oxygen defects generated in the reducing atmosphere. Makes it easier.

In the flux it can be used for _{NH 4 F, NH 4 Cl,} AlF 3, LaF 3, BaF 2, Li 2 CO 3 at least one selected from the.

(2) heat-treating the mixture of step (1)

The mixture obtained from step (1) is heat treated at a temperature of 1000 to 1600 ° C. for 30 minutes to 10 hours. More preferably, it heat-processes for 2 to 5 hours at the temperature of 1300-1600 degreeC.

When the heat treatment temperature during the heat treatment of the mixture obtained from step (1) is less than 1000 ° C or more than 1600 ° C, single phase crystals are not completely formed on the phosphor and heterogeneous compounds are formed, so that light emission does not occur well, There is a problem that is difficult to control.

The heat treatment of the mixture obtained from step (1) is carried out in H ₂ / N ₂ mixed gas to reduce Eu ³⁺ to Eu ²⁺ and prevent Mn ²⁺ from being oxidized to Mn ³⁺ or Mn ⁴⁺ . It is preferable. In this case, the H ₂ / N ₂ mixed gas may be used in a weight ratio of 5 to 25% of the mixed gas mixed in a weight ratio of H ₂ : N ₂ = 1: 20 to 1:10 with respect to the weight of the mixture obtained in step (1). . Meanwhile, in addition to the H ₂ / N ₂ mixed gas, heat treatment may be performed under any one or more inert gas selected from nitrogen, helium, neon, argon, krypton, and xenon.

The heat treatment apparatus for the heat treatment of the mixture obtained from step (1) above can be used as long as it can perform heat treatment. As an example of heat treatment in the present invention, the mixture obtained in step (1) may be placed in a heat-resistant crucible and heat-treated in a furnace.

 (3) The heat treated phosphor is cooled

The phosphor heat-treated in the step (2) is preferably naturally cooled to room temperature, more preferably 20 to 25 ° C, and then the phosphor is removed from the heat treatment apparatus. This is because if the phosphor is not cooled to a sufficiently low temperature, the phosphors oxidize Eu ²⁺ and Mn ²⁺ due to the adsorption of oxygen around them, and the emission luminance is sharply reduced.

(4) phosphor crushing

After the heat treatment in step (2), the phosphor cooled to room temperature in step (3) is taken out of the heat treatment apparatus and pulverized to be pulverized into a powder having a diameter of several μm, preferably 2 to 10 μm in diameter. The size of the phosphor particles has a close correlation with the luminous efficiency. In other words, if the size of the particle is too small, the excitation light and the light emission will be scattered excessively, and the efficiency of the overall phosphor particle will be lowered. If the particle size is too large, the excitation light and the light emission will not be transmitted. When applied, it is difficult to disperse in the resin, thereby reducing the luminous efficiency. Therefore, the size of the preferable particle | grains which show luminous efficiency is good powder of 2-10 micrometers in diameter.

The phosphor prepared by the above-mentioned steps (1) to (4) was fabricated using an X-ray diffraction (XRD) and a scanning electron microscope (SEM). Analyzing the surface condition, single phase crystals of distorted magnetoplumbite structures of X _1-vy Al _{11 (2/3) + v + (2/3) sz} O _{19 + s} : yEu ²⁺ , zMn ²⁺ form well and It can be seen that the powder size is uniform.

As a result of investigating photoluminescence (PL) characteristics, the synthesized phosphor showed blue color from 400 nm to 450 nm, green color from 500 nm to 550 nm, red color from 600 nm to 680 nm, and the maximum light in the near ultraviolet region around 340 nm to 420 nm. It can be seen that absorption occurs.

Therefore, X _1-vy Al _{11 (2/3) + v + (2/3) sz} O _{19 + s} , which is a blue, green, and red light _- emitting phosphor prepared by the above steps (1) to (4): yEu ²⁺ and zMn ²⁺ can realize warm white by changing X, v, s, y, z values, and in particular, full color can be achieved by adjusting only the z value in the composition. By adjusting the value of z, it is possible to realize blue, blue green, green, yellow, and red, which can be applied to various colors for wavelength conversion of white light emitting devices such as UV LED devices.

The white light emitting device of the present invention is a phosphor of formula (1) or a formula (1) which absorbs and converts wavelengths of light emitted from a light emitting device chip that emits light in a region of 340 nm to 420 nm, such as a near ultraviolet GaN series light emitting device chip. 2) The phosphor of 2) is mixed with the light-transmitting resin to cover the light emitting device chip, and is molded. Indicates.

X _1-vy Al _{11 (2/3) + v + (2/3) sz} O _{19 + s} : yEu ²⁺ , zMn ²⁺ .

In Formula (1), X is any one or more metals selected from La and Ce, and 0 <v ≦ 0.5, 0 <s ≦ 0.5, 0 <y ≦ 0.5, and 0 <z ≦ 5.

X _1-y MgAl _11-z O ₁₉ : yEu ²⁺ , zMn ²⁺ ...... Formula (2)

In Formula (2), X is any one or more metals selected from La and Ce, and 0 <y ≦ 0.5 and 0 <z ≦ 5.

In the above, the light transmissive resin can be used as long as it is a resin that can transmit light. In the present invention, any one or more selected from an epoxy resin and a silicone resin may be used as one example of the light transmissive resin.

In the above, the phosphor of the formula (1) or the phosphor of the formula (2) may be used by adding 10 to 35% to the light transmitting resin and mixing the mixture with respect to the weight of the light transmitting resin.

Hereinafter, the content of the present invention will be described in detail through examples and test examples. However, these are intended to explain the present invention in more detail, and the scope of the present invention is not limited thereto.

Example 1 X _1-vy Al _{11 (2/3) + v + (2/3) sz} O _{19 + s} : yEu ²⁺ , zMn ²⁺ (v = 0.173, s = 0.09, y = 0.21, z = 0.6)

La ₂ O ₃ , Al ₂ O ₃ , Eu ₂ O ₃ , MnO uniformly mixed using agate mortar in a molar ratio of 1-vy: 11 (2/3) + v + (2/3) sz: y: z It was.

The obtained mixture was placed in a heat-resistant crucible, placed in a furnace, and calcined at 1400 ° C. for 3 hours while flowing a mixed gas (H ₂ / N ₂ ) mixed with hydrogen and nitrogen at a ratio of 5:95 at 20% by weight of the mixture.

The phosphor obtained after firing was naturally cooled in a furnace to 25 ° C., and then the phosphor was taken out of the furnace, and the phosphor was pulverized uniformly to be a powder having a diameter of 2 to 5 μm.

Example 2 X _1-vy Al _{11 (2/3) + v + (2/3) sz} O _{19 + s} : yEu ²⁺ , zMn ²⁺ (v = 0.173, s = 0.09, y = 0.21, z = 0 to 0.75)

La ₂ O ₃ , Al ₂ O ₃ , Eu ₂ O ₃ and MnO were agate mortar at a molar ratio of 1-vy: 11 (2/3) + v + (2/3) sz: y: z. Mixed evenly.

The obtained mixture was placed in a heat-resistant crucible, placed in a furnace, and calcined at 1400 ° C. for 3 hours while flowing a mixed gas (H ₂ / N ₂ ) mixed with hydrogen and nitrogen at a ratio of 5:95 at 20% by weight of the mixture.

The phosphor obtained after firing was naturally cooled in a furnace to 25 ° C., and then the phosphor was taken out of the furnace, and the phosphor was pulverized uniformly to be a powder having a diameter of 2 to 5 μm.

Example 3 X _1-vy Al _{11 (2/3) + v + (2/3) sz} O _{19 + s} : yEu ²⁺ , zMn ²⁺ (v = 0.173, s = 0.09, y = 0.18 to 0.3 , z = 0.6)

La ₂ O ₃ , Al ₂ O ₃ , Eu ₂ O ₃ , and MnO were the agate mortar at a molar ratio of 1-vy: 11 (2/3) + v + (2/3) sz: y: z. Mixed evenly.

The obtained mixture was placed in a heat-resistant crucible, placed in a furnace, and calcined at 1400 ° C. for 3 hours while flowing a mixed gas (H ₂ / N ₂ ) mixed with hydrogen and nitrogen at a ratio of 5:95 at 20% by weight of the mixture.

The phosphor obtained after firing was naturally cooled in a furnace to 25 ° C., and then the phosphor was taken out of the furnace, and the phosphor was pulverized uniformly to be a powder having a diameter of 2 to 5 μm.

<Test Example 1>

1 is phosphor X _1-vy Al _{11 (2/3) + v + (2/3) sz} O 19+ _s : yEu ²⁺ , zMn ²⁺ (v = 0.173, s = 0.09, y = 0.21, z = 0.6). From Figure 1 it can be confirmed that the phosphor of Example 1 has a single phase, and in the same manner it can be confirmed that Examples 2 and 3 are also single phase. As described above, when the phosphor has a single phase, the chemical bonding force between the ions is strong, so that the chemical properties are stable, and in particular, the luminance and the reproducibility of the emission spectrum are excellent.

<Test Example 2>

FIG. 2 shows phosphor X _1-vy Al _{11 (2/3) + v + (2/3) sz} O 19+ _s : yEu ²⁺ , zMn ²⁺ (v = 0.173, s = 0.09, y according to Example 2 _). The y value is fixed and the change in the relative emission spectrum and the emission intensity according to the z value under the near ultraviolet light wavelength excitation at 370 nm for z = 0.21, z = 0 to 0.75). As the z value increases, the blue color from 400nm to 450nm decreases, the green color from 500nm to 550nm increases and then decreases, and the red color from 600nm to 680nm does not appear, but the z value appears from 0.45. Could know. Therefore, the phosphor X _1-vy Al _{11 (2/3) + v + (2/3) sz} O 19+ _s according to Example 2 by adjusting the z value: yEu ²⁺ , zMn ²⁺ (v = 0.173, s = 0.09, y = 0.21, z = 0 ~ 0.75), blue, blue green, green, yellow, red can be realized.

<Test Example 3>

FIG. 3 shows the phosphor X _1-vy Al _{11 (2/3) + v + (2/3) sz} O _{19 + s} : yEu ²⁺ , zMn ²⁺ (v = 0.173, s = 0.09, y according to Example 2 _). The y value is fixed and the CIE color coordinate according to the z value under 370 nm ultraviolet light wavelength excitation for = 0.21, z = 0 to 0.75). According to this, it was found that full color could be realized according to the change of the z value. Thus phosphor 2 according to Example 2 X _1-vy Al _{11 (2/3) + v + (2/3) sz} O _{19 + s} : yEu ²⁺ , zMn ²⁺ (v = 0.173, s = 0.09, y = 0.21, z = 0 to 0.75) can be combined with a GaN LED chip that emits near ultraviolet rays to realize full color for wavelength conversion of the UV LED to be provided by the present invention.

<Test Example 4>

4 is a phosphor X _1-vy Al _{11 (2/3) + v + (2/3) sz} O _{19 + s} according to Example 3: yEu ²⁺ , zMn ²⁺ (v = 0.173, s = 0.09, y The z value is fixed and the change in relative luminescence spectrum and luminescence intensity according to a value in which the z value is fixed and the y value is changed to 0.18, 0.21, 0.24, 0.3 under 370 nm ultraviolet light wavelength excitation for = 0.18 to 0.3 and z = 0.6). According to this, it was confirmed that blue light from 400 nm to 450 nm, green light from 500 nm to 550 nm, and red light emission from 600 nm to 680 nm appear.

<Test Example 5>

FIG. 5 shows Phosphor X _1-vy Al _{11 (2/3) + v + (2/3) sz} O _{19 + s} : yEu ²⁺ , zMn ²⁺ (v = 0.173, s = 0.09, y according to Example 3 _); Under the near-ultraviolet light wavelength excitation of 370 nm for = 0.18 to 0.3 and z = 0.6), the z-value is the CIE color coordinate according to the value of fixed and changing the y-value to 0.18, 0.21, 0.24, 0.3. According to this, it can be seen that the implementation of warm white light to be provided by the present invention by the blue, green, red light emission of the phosphor.

<Test Example 6>

6 shows phosphor X _1-vy Al _{11 (2/3) + v + (2/3) sz} O 19+ _s : yEu ²⁺ , zMn ²⁺ (v = 0.173, s = 0.09, y = in Example 1; 0.21, z = 0.6) as a result of observing with a scanning electron microscope (SEM), it can be seen that the phosphor particles are observed in the size of 2 ~ 5㎛.

Example 4 White Light Emitting Device

7 is an example of configuration diagram of a white light emitting device according to the present invention.

The phosphor X _1-vy Al _{11 (2/3) + v + (2/3) sz} O _{19 + s} : yEu ²⁺ of Example 1 on the surface of a commercially available near-ultraviolet GaN-based LED chip currently available commercially; zMn ²⁺ (v = 0.173, s = 0.09, y = 0.21, z = 0.6) was applied to the light-transmitting resin after mixing to prepare a white light emitting device according to the present invention. In this case, an optical resin was used as the epoxy resin, and the phosphor was used by mixing 20% with respect to the epoxy resin in the epoxy resin.

The structure of the white light emitting device manufactured as described above will be described in detail with reference to FIG. 8.

An anode (60) and a cathode (70) are connected to the light emitting device chip (10) stored in the hole cup (20) by the leads (40) and (50), and the phosphor is mixed with the light transmissive resin. The molding layer 30 is coated to cover the surface of the light emitting device chip 10 and then cured. The molding layer 30 includes the molding layer 30 and is formed in a package form made of the exterior material 80.

However, the present invention is not characterized by the internal structure of the white light emitting device, and the white light emitting device of FIG. 8 is just one example to which the phosphor of the present invention can be applied, and can be applied to the white light emitting device having various structures. Of course.

<Test Example 7>

The phosphor of Example 3 was applied to the white light emitting device of Example 4 to measure the emission spectrum of the white light emitting device, and the results are shown in FIG. 8. Referring to FIG. 8, it can be seen that a white light emitting device providing various colors can be provided because the green and red regions can be provided which cannot be provided by a conventional YAG-based white light emitting device.

The CIE color coordinates of the white light emitting device manufactured according to Example 3 are located at warm white light with x = 0.4 and y = 0.4, whereas the color temperature of a conventional white light emitting device of YAG series is more than 7000 Kelvin, which is cold white. It was found that the white light emitting device according to the present invention exhibits warm white color of about 4000 Kelvin.

Phosphor X _1-vy Al _{11 (2/3) + v + (2/3) sz} O _{19 + s according} to the present invention by changing the value of z in yEu ²⁺ , zMn ²⁺ , blue, blue green, green, yellow It can be used for wavelength conversion of all colors of UV LED since red color can be realized.

As described above, the present invention has been described with reference to the preferred embodiments and test examples, but a person skilled in the art may vary the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. It will be understood that modifications and changes can be made.

The phosphor of the invention _{(X 1 -v- y Al 11 (} 2/3) + v + (2/3) s- z O 19 + s as described above: yEu ^{2 +,} zMn ²⁺ where X is La, At least one metal selected from Ce, and 0 <v≤0.5, 0 <s≤0.5, 0 <y≤0.5, and 0 <z≤5), because it has a single phase, it is chemically stable and has excellent reproducibility. It can be utilized for white light emitting devices such as an LCD backlight. Since the phosphor of the present invention has excellent color reproducibility and color stability and emits a warm white light having a low color temperature, it can provide natural color more naturally, so that it can be applied to white lighting required in department stores or clothing stores.

In addition, the phosphor of the present invention can realize full color by adjusting the z value. Blue, blue green, green, yellow, and red can be realized by adjusting the z value in a single phase, which can be applied to various colors as well as warm white for wavelength conversion of UV LED devices.

Claims (11)

Phosphor represented by following General formula (1). X _{1 -v- y} Al _{11 (2/3) + v + (2/3) s- z} O _{19 + s} : yEu ^{2 +} , zMn ^{2 +} ...... Formula (1) In Formula (1), X is any one or more metals selected from La and Ce, and 0 <v ≦ 0.5, 0 <s ≦ 0.5, 0 <y ≦ 0.5, and 0 <z ≦ 5. 2. The chemical formula (1) of claim 1, wherein the v value is 0 <v≤0.3, 0 <s≤0.3, y value is 0.005≤y≤0.40, and z value is 0 <z≤1. Phosphor. delete (1) mixing a compound containing X (X is any one or more metals selected from La and Ce), a compound containing Al, a compound containing Eu, and a compound containing Mn;  (2) heat-treating the mixture  (3) cooling the heat-treated phosphor  (4) pulverizing the cooled phosphor. The method of claim 4, wherein, (1) NH in step _{4 F, NH 4 Cl, AlF} 3, LaF 3, BaF 2, characterized in that it further comprises the step of adding any one or more fluxes selected from the group consisting of Li ₂ CO ₃ Method for producing a phosphor to be. The method of manufacturing a phosphor according to claim 5, wherein in step (1), the flux is added in an amount of 0.001 to 10% based on the weight of the mixed raw materials. The method of manufacturing a phosphor according to claim 4, wherein the heat treatment in step (2) is performed at a temperature of 1000 to 1600 ° C. for 30 minutes to 10 hours. The method of claim 7, wherein the heat treatment is performed under a H ₂ / N ₂ mixed gas, or a heat treatment is performed under one or more inert gases selected from nitrogen, helium, neon, argon, krypton, and xenon. Way. A white light emitting device in which a phosphor for absorbing light emitted from a light emitting device chip and converting wavelengths is mixed with a light transmitting resin and molded to cover the light emitting device chip. The light emitting device chip emits light in the region of 340nm to 420nm, and the phosphor is a phosphor represented by the following general formula (1). X _1-vy Al _{11 (2/3) + v + (2/3) sz} O _{19 + s} : yEu ²⁺ , zMn ²⁺ . In Formula (1), X is any one or more metals selected from La and Ce, and 0 <v ≦ 0.5, 0 <s ≦ 0.5, 0 <y ≦ 0.5, and 0 <z ≦ 5. The white light emitting device of claim 9, wherein the light transmitting resin is at least one selected from an epoxy resin and a silicone resin. 10. The white light emitting device according to claim 9, wherein the phosphor of formula (1) adds and mixes 10 to 35% to the light transmitting resin based on the weight of the light transmitting resin.

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