KR20110007482A - An oxynitride-based phosphor for white light emitting diode devices, a method of manufacturing the same, and a white LED device using the same - Google Patents

Abstract

The present invention provides an oxynitride-based phosphor for a white light emitting diode device based on a composition consisting of aMCO ₃ -bAlN-cSi ₃ N ₄ ternary system, a method for manufacturing the same, and a white light emitting conversion light emitting diode using the same (LUMINESCENCE CONVERSION LIGHT EMITTING DIODE) Abbreviated as "LED".

The oxynitride-based phosphor of the present invention is a composition consisting of aMCO ₃ -bAlN-cSi ₃ N ₄ ternary system, specifically, M is any one selected from alkaline earth metals, and 0.2 ≦ a / (a + b) ≦ 0.9 , 0.05 ≦ b / (b + c) ≦ 0.85, 0.4 ≦ c / (c + a) ≦ 0.9, and are phosphors having a parent composition. Particularly, phosphors of the same composition may be green-yellow- under the control of the manufacturing process. Among the three primary colors of red, an oxynitride-based phosphor having a desired emission center wavelength can be selectively produced. Furthermore, by using the oxynitride-based phosphor which selectively implements the green-yellow-red, a white LED having excellent color purity and excellent color rendering can be provided.

Crystal Structure, Ternometer, Phosphor, Firing Temperature, Flow Rate

Description

Oxynitride-based phosphor for white light emitting diode devices, a method of manufacturing the same, and a white LED device using the same, and a white LED device using the same.

The present invention relates to an oxynitride-based phosphor for a white light emitting diode device, a method of manufacturing the same, and a white LED device using the same. More specifically, the composition is composed of a matrix composed of aMCO ₃ -bAlN-cSi ₃ N ₄ ternary system. The present invention relates to a high purity oxynitride-based phosphor for white light emitting diode devices in which phosphors of the same composition are selectively emitted from three primary colors of green, yellow and red according to control of a manufacturing process, a method of manufacturing the same, and a white LED device using the same.

LED emitting white light is a method of using a secondary light source that emits light from the phosphor by applying a phosphor to the LED, a method of obtaining a white light by applying a YAG: Ce phosphor emitting a yellow to a blue LED [US Patent No. 6,069,440] It is common. However, the above method has disadvantages in that efficiency is reduced due to quantum deficits and re-radiation efficiency occurring while using secondary light, and color rendering is not easy. Therefore, the conventional white LED backlight is a combination of a blue LED chip and a yellow phosphor, and the green and red components are lacking to express an unnatural color, which is limited to the degree of use for a screen of a mobile phone or a notebook PC. Nevertheless, they are widely commercialized due to the advantages of easy driving and significantly lower prices.

In general, it is widely known that phosphors use silicates, phosphates, aluminates, or sulfides in the parent material, and transition metals or rare earth metals are used as emission centers.

On the other hand, with respect to white LEDs, development of phosphors which are excited by an excitation source having high energy such as ultraviolet light or blue light and emits visible light has been mainstream. However, the conventional phosphor has a problem that the luminance of the phosphor decreases when it is exposed to an excitation source, and recently, as a phosphor having a low decrease in luminance, studies on phosphors using silicon nitride-related ceramics as host crystals have shown that the crystal structure is poor. Nitride or oxynitride phosphors are attracting attention as a material that is stable and can shift excitation light and light emission to the long wavelength side.

In particular, in 2002, an alpha sialon (Eu) yellow phosphor was developed, which was superior to a YAG phosphor, and in August 2004, followed by a pure nitride CaAlSiN ₃ : Eu red phosphor. In March, beta sialon (Eu) green phosphors were developed. When such a phosphor is combined with a blue LED chip, color purity is good, and in particular, it is excellent in durability and has a small temperature change, which may contribute to long-term lifetime and reliability of the LED light source.

Recently developed new LEDs combine blue LED chips, β sialon green phosphors and red phosphors CaAlSiN ₃ (Kazen) to combine the light emitted from blue LEDs with a wavelength of 460 nm, green and yellow phosphors 540-570 nm, and red phosphors. It can convert to 650nm to generate three primary colors.

Therefore, a method of emitting the three primary colors of the light with a single color LED that generates white light by appropriately combining independent red, green, and blue LEDs has been proposed. However, the above method can achieve excellent color rendering because LEDs are individually optimized for performance and manufacturing method, while the three types of LED driving circuits are complicated and multiple LEDs must be combined. The downside is that manufacturing prices will rise.

An object of the present invention is to provide an oxynitride-based phosphor for a white light emitting diode device having a composition consisting of aMCO ₃ -bAlN-cSi ₃ N ₄ ternary system as a matrix.

Another object of the present invention is to provide a method for manufacturing the above-mentioned phosphor to control light emission from three primary colors of green, yellow, and red by controlling the conditions of the phosphor manufacturing step by step.

Still another object of the present invention is to provide a white LED device using an oxynitride-based phosphor that selectively implements the green-yellow-red of the present invention.

The present invention is a composition consisting of aMCO ₃ -bAlN-cSi ₃ N ₄ ternary system, specifically, M is any one selected from alkaline earth metals, 0.2≤a / (a + b) ≤0.9, 0.05≤b / ( An oxynitride-based phosphor for a white light emitting diode device having a composition of b + c) ≦ 0.85 and 0.4 ≦ c / (c + a) ≦ 0.9 as a mother is provided.

The oxynitride-based phosphor of the present invention has the characteristic of selectively emitting light among three primary colors of green-yellow-red.

That is, the oxynitride-based phosphors disclosed in the present invention include SrAlSi ₃ ON ₅ : Eu phosphors, SrAl ₂ Si ₃ ON ₆ : Eu phosphors, Sr ₂ Al ₃ Si ₂ O ₂ N _17/3 : Eu phosphors, and Sr ₂ Al ₂ Si ₂ O ₂ N _14/3 : Eu phosphors, wherein the same composition phosphors include green and yellow phosphors having an emission center wavelength of 500 nm to 570 nm; Alternatively, the red phosphor having a emission center wavelength of 610 nm to 650 nm may be selectively implemented.

Accordingly, the present invention provides a method for producing an oxynitride-based phosphor.

In the production method of the present invention, the first embodiment comprises 1) 0.2 ≦ a / (a + b) ≦ 0.9 and 0.05 ≦ b / (b + c) of a composition consisting of aMCO ₃ -bAlN-cSi ₃ N ₄ ternary systems. ) ≤ 0.85, 0.4 ≤ c / (c + a) ≤ 0.9, and then weighed to prepare a raw material salt by mixing; And 2) heat treating the mixed raw material salt in a reducing atmosphere controlled at 1300 to 1400 ° C. and reducing gas at 100 to 250 sccm. The same composition of phosphors has a green and yellow phosphor having a luminescence center wavelength of 500 nm to 570 nm. Can be prepared.

In the manufacturing method of the present invention, the second embodiment is to further heat-treat the oxynitride-based phosphor prepared in step 2) in the reducing atmosphere controlled at 1500 to 1700 ° C and reducing gas at 400 to 1000 sccm.

Further, in the production method of the present invention, the third embodiment is _{1) aMCO 3 -bAlN-cSi 3} N 4 0.2≤a a composition consisting of ternary / (a + b) ≤0.9, 0.05≤b / (b preparing a raw material salt by weighing within a range of + c) ≦ 0.85 and 0.4 ≦ c / (c + a) ≦ 0.9, and then mixing the mixture; And 2) heat treating the mixed raw material salt in a reducing atmosphere controlled at 1500 to 1700 ° C. and reducing gas at 400 to 1000 sccm. From the second and third embodiments, the emission center wavelength is 610 nm to 3 nm. A red phosphor of 650 nm can be produced.

In the production method of the present invention, the compound containing Eu ²⁺ is contained in a molar concentration of 0.001 to 0.95, the reducing gas is carried out at atmospheric pressure consisting of a mixing ratio of 95: 5 to 90:10 of nitrogen and hydrogen. It features.

Furthermore, the present invention provides a white LED device using an oxynitride-based phosphor selectively implementing the green-yellow-red of the present invention. More specifically, among the oxynitride-based phosphors of the present invention, a red phosphor and a green phosphor are uniformly dispersed in an epoxy resin to prepare a cured portion, and the cured portion is coated or thinly formed on a light emitting diode chip emitting blue light. To provide a white LED device prepared by curing for 1 hour at 100 to 160 ℃.

At this time, the addition amount of the red phosphor in the oxynitride-based phosphor contains 0.1 to 60 parts by weight based on 100 parts by weight of the epoxy resin. In addition, the amount of the green phosphor used as another phosphor required to realize white color is used in an amount of 3 to 50 parts by weight based on 100 parts by weight of the epoxy resin.

The present invention is a composition consisting of aMCO ₃ -bAlN-cSi ₃ N ₄ ternary system, specifically, M is any one selected from alkaline earth metals, 0.2≤a / (a + b) ≤0.9, 0.05≤b / An oxynitride-based phosphor having a stable crystal structure based on a composition having (b + c) ≦ 0.85 and 0.4 ≦ c / (c + a) ≦ 0.9 can be provided.

In particular, the oxynitride-based phosphor of the present invention is controlled to control the firing temperature and the flow rate of the reducing gas under specific conditions, so that the phosphor having the same emission intensity as the phosphor having the desired emission center wavelength among three primary colors of green-yellow-red is produced. To be manufactured.

In addition, the present invention provides a white LED device having excellent color purity and excellent color rendering property by using an oxynitride-based phosphor that selectively implements green-yellow-red of the present invention in a conventional method of implementing white. Can be.

Hereinafter, the present invention will be described in detail.

The present invention is a composition consisting of aMCO ₃ -bAlN-cSi ₃ N ₄ ternary system, specifically, M is any one selected from alkaline earth metals, 0.2≤a / (a + b) ≤0.9, 0.05≤b / ( An oxynitride-based fluorescent substance having a composition of b + c) ≦ 0.85 and 0.4 ≦ c / (c + a) ≦ 0.9 as a mother is provided.

The oxynitride-based phosphor of the present invention has the characteristic of selectively emitting light among three primary colors of green-yellow-red.

As a preferred oxynitride-based phosphor disclosed in the present invention, the SrAlSi ₃ ON ₅ : Eu phosphor has a light source of 350 to 480 nm wavelength as an excitation source [not shown], and a green and yellow emission center wavelength of 510 to 570 nm region. Phosphor; Or a red phosphor having a luminescence center wavelength of 610 nm to 650 nm [ FIGS. 1A to 1C and 2 ]; each of the yellow phosphors or the red phosphors formed of the SrAlSi ₃ ON ₅ : Eu composition exhibits a stable sialon crystal structure [ 3 ]. At this time, the sialon crystal structure is a structure in which a part of the Si-N bond of silicon nitride is substituted with an Al-N bond or an Al-O bond, and is stabilized by dissolving a metal element in an infiltration type between crystal lattice.

Further, as other phosphors disclosed in the present invention, SrAl ₂ Si ₃ ON ₆ : Eu phosphors [ FIGS. 4A , 4B , 5A , 5B and 6 ], and Sr ₂ Al ₃ Si ₂ O ₂ N _17/3 : Eu phosphors [ FIGS. 7A , 7B , 8A , 8B and 9 ] and Sr ₂ Al ₂ Si ₂ O ₂ N _14/3 : Eu phosphors [ FIGS. 10A , 10B , 11A , 11B, 12A And FIG. 12B ] may also selectively implement light emission of a yellow phosphor or a red phosphor in the same composition. In addition, each yellow phosphor or red phosphor has a stable crystal structure.

Thus, the oxynitride-based phosphor of the present invention is aMCO ₃ -bAlN-cSi ₃ N ₄ ternary system, 0.2≤a / (a + b) ≤0.9, 0.05≤b / (b + c) ≤0.85, 0.4≤c It is characterized by using a composition which consists of within the range of /(c+a)<=0.9 as a mother.

At this time, as a raw material salt for forming the phosphor matrix of the present invention, a compound including a compound capable of forming an oxide of metal element M, a silicon compound, an aluminum compound, and an element forming an emission center ion is reacted under a reducing gas atmosphere. To produce a phosphor.

At this time, the compound capable of producing an oxide of the metal element M is not particularly limited, but it is easy to obtain high-purity compounds, easy to handle in the air, and advantageous in terms of carbonates, oxates, nitrates, sulfates, acetates, and alkaline earth metals. At least one alkaline earth metal compound selected from oxides, peroxides, and hydroxides is preferable. More preferably, they are carbonate, hydroxide, oxide, and hydroxide of alkaline-earth metals. Especially preferably, the alkaline earth metal compound is in the form of a carbonate (MCO ₃ ) form.

Although it does not specifically limit about the property of the said alkaline earth metal compound, In order to manufacture a high performance fluorescent substance, a powder form is more preferable than a lump form.

In addition to the alkaline earth metal compounds, the properties of silicon nitride (Si ₃ N ₄ ) and aluminum nitride (AlN) raw salts used as the raw material salt of the present invention are also preferably powdery to produce high-performance phosphors. In addition, in order to increase the reactivity of the raw material salts, it may be reacted by adding a flux (flux), the flux may be an alkali metal compound (Na ₂ CO ₃ , NaCl, LiF) or a halogen compound (SrF ₂ , CaCl _2, etc. ) And ginseng salt, sulfide series can be selected appropriately.

The silicon compound of the present invention is not particularly limited as long as it is a silicon compound capable of forming the phosphor composition of the embodiment of the present invention, but is preferably a silicon nitride (Si ₃ N ₄ ) or silicon as a requirement for producing a high-performance phosphor. Diimide (Si (NH) ₂ ) is used, more preferably silicon nitride (Si ₃ N ₄ ).

The aluminum compound is also not particularly limited as long as it is an aluminum compound capable of forming the phosphor composition of the embodiment of the present invention. Preferably, aluminum nitride (AlN) is used to produce a high-performance phosphor.

In the phosphor of the present invention, various rare earth metals, transition metals, or these compounds are also used as raw materials for adding luminescent center ions. Such elements include lanthanoids or transition metals of atomic numbers 58 to 60 or 62 to 71, in particular Ce, Pr, Eu, Tb and Mn. Compounds containing such elements include oxides, nitrides, hydroxides, carbonates, oxalates, nitrates, sulfates, halides, and phosphates of the lanthanoids or transition metals. Specific examples include cerium carbonate, europium oxide, europium nitride, metal terbium, and manganese carbonate. A reducing atmosphere is preferable in order to generate a large number of ions, such as Ce ³⁺ , Eu ²⁺ , Tb ³⁺ , Mn ²⁺ , as the emission center ions.

The present invention is composed of a composition consisting of aMCO ₃ -bAlN-cSi ₃ N ₄ ternary system, the oxynitride-based fluorescent material of the same composition of the fluorescent material to selectively emit green-yellow-red three primary colors according to the manufacturing process It provides a method of manufacturing.

Thus, in the production method of the present invention, the first embodiment is 1) 0.2 ≤ a / (a + b) ≤ 0.9, 0.05 ≤ b / (b a composition consisting of aMCO ₃ -bAlN-cSi ₃ N ₄ ternary system preparing a raw material salt by weighing within a range of + c) ≦ 0.85 and 0.4 ≦ c / (c + a) ≦ 0.9, and then mixing the mixture; And

2) The mixed raw material salt is heat-treated in a reducing atmosphere controlled at 1300 to 1400 ° C. and 100 to 250 sccm of reducing gas, and provides a method for producing green and yellow phosphors having a wavelength of 500 nm to 570 nm.

In addition, in the manufacturing method of the present invention, the second embodiment is further heat-treated by the oxynitride-based phosphor prepared in step 2) of the manufacturing method in a reducing atmosphere controlled at 1500 to 1700 ℃ and reducing gas 400 to 1000 sccm The present invention provides a method for producing a red phosphor having a luminescence center wavelength of 610 nm to 650 nm.

Alternatively, the manufacturing method of the third embodiment of the present invention comprises: 1) 0.2 ≦ a / (a + b) ≦ 0.9 and 0.05 ≦ b / (b + c) of a composition consisting of aMCO ₃ -bAlN-cSi ₃ N ₄ ternary systems. Preparing a raw material salt by weighing within a range of ≦ 0.85 and 0.4 ≦ c / (c + a) ≦ 0.9, followed by mixing; And 2) heat treating the mixed raw material salt in a reducing atmosphere controlled at 1500 to 1700 ° C. and reducing gas at 400 to 1000 sccm. Thus, a red phosphor may be prepared.

In a general phosphor manufacturing process, the firing temperature is carried out at 1300 ℃ to 2000 ℃, for the purpose of high performance of the phosphor, preferably at least 1600 ℃ 2000 ℃, more preferably at 1700 ℃ 1900 ℃. On the other hand, for the purpose of mass production, it is carried out at 1400 ℃ 1800 ℃, more preferably 1600 ℃ 1700 ℃.

On the other hand, the present invention is to perform a general firing temperature step by step, by controlling the flow rate of the reducing gas, it is possible to produce a phosphor having a different crystal structure, in particular, it is possible to selectively control the emission of green, yellow and red It is possible to produce a phosphor of high purity.

That is, the present invention uses a composition consisting of aMCO ₃ -bAlN-cSi ₃ N ₄ ternary system as a matrix, but when the reducing gas is controlled to 100 to 250sccm at a firing temperature of 1300 to 1400 ℃, the optimum yellow color development efficiency Eggplants are yellow phosphors. At this time, if the baking temperature and the flow rate of the reducing gas are less than the above, the reaction or reduction is insufficient, the color purity is lowered, and a high quality phosphor cannot be obtained.

In addition, the present invention uses a composition consisting of aMCO ₃ -bAlN-cSi ₃ N ₄ ternary system as a parent, when the reducing gas is controlled to 400 to 1000sccm at a firing temperature of 1500 to 1700 ℃, a red phosphor is produced.

In the production method of the present invention, phosphors having a desired luminous efficiency and color can be easily produced by performing the firing temperature and the flow rate of the reducing gas step by step or individually. More specifically, the yellow phosphor prepared in a reducing gas atmosphere controlled at 100 to 250 sccm at a firing temperature of 1300 to 1400 ° C. is further maintained at a firing temperature and a flow rate of the reducing gas at a flow rate of 400 to 1000 sccm of reducing gas at 1500 to 1700 ° C. When performed, the red phosphor of high purity can be prepared. Alternatively, the same red phosphor may be produced even if the raw material salt is used as a starting material, even if the firing temperature is 1500 to 1700 ° C. and the reducing gas flow rate is 400 to 1000 sccm.

In particular, the present invention is to fire the mixed raw material in a reducing atmosphere, but is carried out in a reducing gas atmosphere and atmospheric pressure conditions formed by a mixed gas of nitrogen and hydrogen. At this time, the mixed gas is preferably made of 95: 5 to 90:10 mixing ratio of nitrogen and hydrogen, in particular, it is possible to control the color development and efficiency of the phosphor, depending on the firing temperature and the supply rate of the mixed gas. In the production method of the present invention, the firing time is preferably performed within the range of 300 minutes to 12 hours in consideration of productivity.

In the production method of the present invention, the compound containing Eu ²⁺ is contained at a molar concentration of 0.001 to 0.95.

According to the manufacturing method of the present invention, a phosphor capable of selectively controlling a desired emission region can be manufactured by a relatively simple method, and in particular, an oxynitride-based phosphor which emits light selectively among three primary colors of high purity green-yellow-red can do.

Accordingly, the present invention provides a white LED device having excellent color purity and excellent color rendering properties by using an oxynitride-based phosphor which selectively implements the green-yellow-red.

In the white LED device of the present invention, among the oxynitride-based phosphors prepared above, a red phosphor and a green phosphor are uniformly dispersed in an epoxy resin to prepare a hardened portion, and the hardened portion is coated or deposited on a light emitting diode chip emitting blue light. After raising, it is prepared by curing for 1 hour at 100 to 160 ℃.

More specifically, FIG. 13 is a schematic configuration diagram of a white LED device of the present invention, in which a light emitting diode chip 11 emitting photons in a blue wavelength region on a substrate 17 selected from Al ₂ O ₃ or SiC is raised. In the oxidizing nitride-based fluorescent substance 10 of the present invention, the red phosphor and the green phosphor are mixed with the epoxy resin in the hardened portion 12 and interspersed. In addition to the phosphor, the yellow phosphor of the present invention may be further contained to increase the light efficiency of the device.

The light emitting diode chip 11 emitting photons in the blue wavelength region is preferably a GaN LED device emitting blue light in the wavelength region of 465 nm.

The light emitting diode chip 11 is mounted on the substrate 17, and then adhesively fixed to the anode electrode 15, the cathode electrode 16, and the lead frame 14 using silver paste or the like.

The hardened part 12 is manufactured by uniformly dispersing the oxynitride-based fluorescent material 10 synthesized in the present invention in an epoxy resin, and then applying the prepared hardened part 12 on the light emitting diode chip 11 or thin film type. After raising to, it is produced by curing by fixing for 1 hour at 100 to 160 ℃.

At this time, with respect to 100 parts by weight of the epoxy resin, the addition amount of the red phosphor in the oxynitride-based phosphor of the present invention can be adjusted according to the desired color coordinates, but preferably 0.1 to 60 parts by weight, more preferably 1 to 30 parts by weight Will be.

More specifically, the hardening part 12 is used to mix the green phosphor of the oxynitride-based fluorescent material 10 of the present invention for the white implementation. At this time, the green phosphor may be contained in 3 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin.

In addition, when manufacturing a white LED device, it can be easily understood by those skilled in the art that it may further contain a conventional yellow phosphor to increase the light efficiency of the device. In the present invention, the amount of the yellow phosphor added to the white material may be used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the epoxy resin.

In particular, the red phosphor of the present invention inside the hardened portion 12 is converted into visible light of 540 to 680 nm by using blue light emitted from the light emitting diode chip 11 as an excitation source. At this time, the light path difference between the phosphors contained in the hardened portion and the light emitting diode chip is reduced, thereby improving the light efficiency of the light conversion white LED device. Accordingly, the white LED device having excellent color purity and high light efficiency may be manufactured by minimizing the problem of deterioration of color rendering property than when white is realized using a single yellow phosphor using blue light as an excitation light source.

Hereinafter, the present invention will be described in more detail with reference to Examples.

This embodiment is intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

Example 1 SrAlSi ₃ ON ₅ Manufacturer

Step 1. Yellow Phosphor Preparation

As a raw material salt, SrCO ₃ , Si ₃ N ₄ , AlN, Eu ₂ O ₃ were quantitated and oxidized at a temperature of 800 to 1200 ° C. for 2 hours, and then placed in a ball mill to obtain acetone as a solvent for 2 to 24 hours. After milling it was dried. Thereafter, the hydrogen / nitrogen gas (95: 5v / v) was calcined under a reduced atmosphere at a flow rate of 100 to 300 sccm at a temperature of 1300 ° C. for 4 to 10 hours, and a yellow phosphor of SrAlSi ₃ ON ₅ : Eu Was prepared. At this time, the concentration of europium is 0 to 50% molar weight.

Step 2. Preparation of the red phosphor

After drying the yellow phosphor of SrAlSi ₃ ON ₅ : Eu prepared in step 1, the supply rate of hydrogen / nitrogen gas (95: 5v / v) is controlled at a flow rate of 400sccm or more for 4-10 hours at a temperature of 1500 ℃ It calcined in a reducing atmosphere.

Figure 1a is a green phosphor implemented with the prepared SrAlSi ₃ ON ₅ : Eu phosphor, Figure 1b is a yellow phosphor and Figure 1c shows the emission spectrum of the red phosphor, Figure 2 Examples of the powdery images of (a) green phosphors, (b) yellow phosphors, and (c) red phosphors, which are implemented by the SrAlSi ₃ ON ₅ : Eu phosphor of Example 1, are shown. Accordingly, it was confirmed that the present invention can selectively manufacture an oxynitride-based phosphor having a desired emission center wavelength among three primary colors of green, yellow, and red according to the control of the manufacturing process, even if the phosphor of the same composition.

FIG. 3 shows XRD spectra of yellow and red phosphors obtained according to the steps 1 and 2 for the SrAlSi ₃ ON ₅ : Eu phosphors of the same composition, and different crystal structures were identified.

Example 2 SrAl ₂ Si ₃ ON ₆ Manufacturer

Step 1. Yellow Phosphor Preparation

Each of SrCO ₃ , Si ₃ N ₄ , AlN, and Eu ₂ O ₃ was weighed, and the mixture of hydrogen / nitrogen gas (90: 10v / v) was heated at 100 ° C. for 4 to 10 hours. A phosphor of SrAl ₂ Si ₃ ON ₆ : Eu was prepared in the same manner as in Example 1, except that the product was calcined under a reducing atmosphere maintained at a flow rate of ˜300 sccm.

At this time, the emission spectrum [ FIG. 4a ] and the excitation spectrum [ FIG. 4b ] of the phosphor of the prepared SrAl ₂ Si ₃ ON ₆ : Eu were observed, and it was confirmed that a high-purity yellow phosphor was prepared.

Step 2. Preparation of the red phosphor

After drying the yellow phosphor of SrAl ₂ Si ₃ ON ₆ : Eu in step 1, a mixed gas of hydrogen / nitrogen gas (90: 10v / v) was maintained at a flow rate of 400sccm or more for 4-10 hours at a temperature of 1500 ° C. Except that calcined under a reducing atmosphere, the same process as in Example 1 was carried out.

It was confirmed through the emission spectrum and the excitation spectrum of the SrAl ₂ Si ₃ ON ₆ : Eu phosphor prepared in step 2 [ Fig. 5a and 5b ], a high-purity red phosphor was prepared.

FIG. 6 is an XRD spectrum of each of the SrAl ₂ Si ₃ ON ₆ : Eu phosphors prepared in Steps 1 and 2 in Example 2, and a yellow phosphor having a different crystal structure consisting of SrAl ₂ Si ₃ ON ₆ : Eu And it was confirmed that the red phosphor was prepared.

Example 3 Sr ₂ Al ₃ Si ₂ O ₂ N _17/3 Manufacturer

Step 1. Yellow Phosphor Preparation

Each of SrCO ₃ , Si ₃ N ₄ , AlN, Eu ₂ O ₃ was weighed, and the mixture of hydrogen / nitrogen gas (90: 10v / v) was used at a temperature of 1300 ° C. for 10 hours at 100-300 sccm. Except firing in a reducing atmosphere maintained at a flow rate of the same as in Example 1, to prepare a phosphor of Sr ₂ Al ₃ Si ₂ O ₂ N _17/3 : Eu.

Example 3 A Sr ₂ Al prepared in Step 1 of ₃ Si ₂ O ₂ N _17/3: Eu phosphor with respect to the emission spectrum [Fig. 7a] and excitation spectra [Figure 7b] check result, the high-purity Sr ₂ Al ₃ a It was confirmed that a Si ₂ O ₂ N _17/3 : Eu yellow phosphor was prepared.

2. Manufacture of red phosphor

Each of SrCO ₃ , Si ₃ N ₄ , AlN, Eu ₂ O ₃ was weighed, and the mixed composition of hydrogen / nitrogen gas (90: 10v / v) was not less than 500sccm for 12 hours at a temperature of 1500 ° C. Except firing in a reducing atmosphere maintained at a flow rate, it was carried out in the same manner as in Example 1, to prepare a phosphor of Sr ₂ Al ₃ Si ₂ O ₂ N _17/3 : Eu.

As a result of the emission spectrum [ FIG. 8a ] and the excitation spectrum [ FIG. 8b ] of the Sr ₂ Al ₃ Si ₂ O ₂ N _17/3 : Eu phosphor prepared in Step 2 of Example 3, it was confirmed that a high-purity red phosphor was produced. It was.

9 is an XRD spectrum result of the Sr ₂ Al ₃ Si ₂ O ₂ N _17/3 : Eu phosphor prepared in Example 3, (a) is Sr ₂ Al ₃ Si ₂ O ₂ N _17/3 : The yellow phosphor of Eu, and (b) confirmed another crystal structure between red phosphors of Sr ₂ Al ₃ Si ₂ O ₂ N _17/3 : Eu.

Example 4 Sr ₂ Al ₂ Si ₂ O ₂ N _14/3 Manufacturer

Step 1. Yellow Phosphor Preparation

Each of SrCO ₃ , Si ₃ N ₄ , AlN, Eu ₂ O ₃ was weighed, and the mixture of hydrogen / nitrogen gas (90: 10v / v) was used at a temperature of 1300 ° C. for 10 hours at 100-300 sccm. Except firing in a reducing atmosphere maintained at a flow rate of the same as in Example 1, to prepare a phosphor of Sr ₂ Al ₂ Si ₂ O ₂ N _14/3 : Eu.

From the emission spectrum shown in FIG . 10A and the excitation spectrum shown in FIG . 10B , it was confirmed that the Sr ₂ Al ₂ Si ₂ O ₂ N _14/3 : Eu phosphor prepared in Step 1 was a yellow phosphor of high purity.

Step 2. Preparation of the red phosphor

Each of SrCO ₃ , Si ₃ N ₄ , AlN, and Eu ₂ O ₃ was weighed to use a raw material composition. Except firing in a reducing atmosphere maintained in the same manner as in Example 1, to prepare a red phosphor of Sr ₂ Al ₂ Si ₂ O ₂ N _14/3 : Eu.

11A is an emission spectrum of the Sr ₂ Al ₂ Si ₂ O ₂ N _14/3 : Eu phosphor prepared above, and FIG. 11B is an excitation spectrum (b), confirming that a high-purity red phosphor was produced.

In addition, it was confirmed from the XRD spectra of yellow and red that are implemented by the Sr ₂ Al ₂ Si ₂ O ₂ N _14/3 : Eu phosphor of Example 4, even though they have the same composition, they have different crystal structures [ FIGS. 12A and 12B ]. .

As described above, the present invention provides an oxynitride-based fluorescent substance having a composition consisting of a MCO ₃ -AlN-Si ₃ N ₄ ternary system, and the present invention is the same composition among the three primary colors of green-yellow-red An oxynitride-based phosphor capable of selectively expressing a desired emission center wavelength can be produced.

The present invention is a method for performing a conventional firing temperature conditions step by step in the manufacturing process, and to specify the flow rate of the reducing gas, the phosphor having the same composition of the phosphor having the desired emission center wavelength among the three primary colors of green-yellow-red Provided a method that can be selectively prepared.

Accordingly, the present invention can provide a white LED device having excellent color purity and excellent color rendering properties by using the oxynitride-based phosphor.

Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made within the technical scope of the present invention, and such modifications and modifications belong to the appended claims.

1A is an emission spectrum of a green phosphor embodied by the SrAlSi ₃ ON ₅ : Eu phosphor of Example 1 according to the present invention,

1B is a light emission spectrum of a yellow phosphor embodied by the SrAlSi ₃ ON ₅ : Eu phosphor of Example 1,

1C is a light emission spectrum of a red phosphor embodied by the SrAlSi ₃ ON ₅ : Eu phosphor of Example 1,

2 (A) green phosphor, (b) yellow phosphor, and (c) red phosphor embodying SrAlSi ₃ ON ₅ : Eu phosphor of Example 1,

3 is a result showing XRD spectra of yellow and red implemented with the SrAlSi ₃ ON ₅ : Eu phosphor of Example 1,

4A is a light emission spectrum of SrAl ₂ Si ₃ ON ₆ : Eu yellow phosphor of Example 2 according to the present invention;

4B is a du-based spectrum of SrAl ₂ Si ₃ ON ₆ : Eu Yellow Phosphor of Example 2,

5A is an emission spectrum of SrAl ₂ Si ₃ ON ₆ : Eu red phosphor of Example 2,

5B is an excitation spectrum for an SrAl ₂ Si ₃ ON ₆ : Eu red phosphor of Example 2,

FIG. 6 is a result showing XRD spectra of yellow and red implemented with the SrAl ₂ Si ₃ ON ₆ : Eu phosphor of Example 2,

7A is an emission spectrum of Sr ₂ Al ₃ Si ₂ O ₂ N _17/3 : Eu yellow phosphor of Example 3 according to the present invention,

7B is an excitation spectrum for an Sr ₂ Al ₃ Si ₂ O ₂ N _17/3 : Eu yellow phosphor of Example 3,

8A Example 3 is the emission spectrum of Sr ₂ Al ₃ Si ₂ O ₂ N _17/3 : Eu red phosphor,

8B is an excitation spectrum for an Sr ₂ Al ₃ Si ₂ O ₂ N _17/3 : Eu red phosphor of Example 3,

9 is a result showing XRD spectra of yellow and red embodied by Sr ₂ Al ₃ Si ₂ O ₂ N _17/3 : Eu phosphor of Example 3,

10A is an emission spectrum of Sr ₂ Al ₂ Si ₂ O ₂ N _14/3 : Eu yellow phosphor of Example 4 according to the present invention,

10B is an excitation spectrum for Sr ₂ Al ₂ Si ₂ O ₂ N _14/3 : Eu yellow phosphor of Example 4,

11A is an emission spectrum of Sr ₂ Al ₂ Si ₂ O ₂ N _14/3 : Eu red phosphor of Example 4,

11B is an excitation spectrum for an Sr ₂ Al ₂ Si ₂ O ₂ N _14/3 : Eu red phosphor of Example 4,

12A and 12B show results of yellow and red XRD spectra implemented with Sr ₂ Al ₂ Si ₂ O ₂ N _14/3 : Eu phosphors of Example 4,

13 is a schematic configuration diagram of a white LED device of the present invention.

<Description of the symbols for the main parts of the drawings>

1: white LED element 10: oxynitride-based phosphor

11: light emitting diode chip 12: hardened part

13: reflector 14: leadframe

15: anode electrode 16: cathode electrode

17: substrate

Claims (15)

An oxynitride-based phosphor based on a composition consisting of aMCO ₃ -bAlN-cSi ₃ N ₄ ternary system: In the above, M is any one selected from alkaline earth metals, 0.2≤a / (a + b) ≤0.9, 0.05≤b / (b + c) ≤0.85, 0.4≤c / (c + a) ≤0.9 to be. The oxynitride-based phosphor according to claim 1, wherein the phosphor emits light selectively among three primary colors of green, yellow, and red. The oxynitride-based phosphor according to claim 1, wherein the oxynitride-based phosphor is SrAlSi ₃ ON ₅ : Eu. The oxynitride-based phosphor according to claim 1, wherein the oxynitride-based phosphor is SrAl ₂ Si ₃ ON ₆ : Eu. The oxynitride-based phosphor according to claim 1, wherein the oxynitride-based phosphor is Sr ₂ Al ₃ Si ₂ O ₂ N _17/3 : Eu. The oxynitride-based phosphor according to claim 1, wherein the oxynitride-based phosphor is Sr ₂ Al ₂ Si ₂ O ₂ N _14/3 : Eu. _{1) aMCO 3 -bAlN-cSi 3} N 4 0.2≤a a composition consisting of ternary / (a + b) ≤0.9, 0.05≤b / (b + c) ≤0.85, 0.4≤c / (c + a) Preparing a raw material salt by weighing in a range of? And 2) A method for producing the oxynitride-based fluorescent material of claim 1, wherein the mixed raw salt is heat-treated in a reducing atmosphere controlled at 1300 to 1400 ° C. and reducing gas at 100 to 250 sccm. The method of claim 7, wherein the oxynitride-based phosphor prepared in step 2) is further heat-treated in a reducing atmosphere controlled at 1500 to 1700 ° C. and a reducing gas of 400 to 1000 sccm. _{1) aMCO 3 -bAlN-cSi 3} N 4 0.2≤a a composition consisting of ternary / (a + b) ≤0.9, 0.05≤b / (b + c) ≤0.85, 0.4≤c / (c + a) Preparing a raw material salt by weighing in a range of? And 2) A method for producing the oxynitride-based fluorescent material of claim 1, wherein the mixed raw salt is heat-treated in a reducing atmosphere controlled at 1500 to 1700 ° C. and reducing gas at 400 to 1000 sccm. 8. The method of claim 7, wherein the oxynitride-based phosphor is a green or yellow phosphor having a light emission center wavelength of 500 nm to 570 nm. The method for producing the oxynitride-based phosphor according to claim 8 or 9, wherein the oxynitride-based phosphor is a red phosphor having a luminescence center wavelength of 610 nm to 650 nm. 10. The method for producing the oxynitride-based phosphor according to any one of claims 7 to 9, wherein the composition contains a compound containing Eu ²⁺ at a molar concentration of 0.001 to 0.95. Among the oxynitride-based phosphors of claim 1, a red phosphor and a green phosphor are uniformly dispersed in an epoxy resin to prepare a cured portion, and the cured portion is coated or thinly formed on a light emitting diode chip emitting blue light, and then 100 to 160 ° C. White LED device prepared by curing for 1 hour. The said white LED element of Claim 13 whose addition amount of a red phosphor among the said oxynitride fluorescent substance is 0.1-60 weight part with respect to an epoxy resin. The said white LED element of Claim 13 whose addition amount of a green fluorescent substance among the said oxynitride fluorescent substance is 3-50 weight part with respect to an epoxy resin.

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