KR100919315B1 - Oxynitride phosphor and method for manufacturing the same, and light-emitting device - Google Patents

Abstract

PURPOSE: An oxynitride phosphor, a method for manufacturing the same, and a light-emitting device are provided to ensure luminous efficiency by comprising oxynitride crystals with a specific composition. CONSTITUTION: An oxynitride phosphor includes crystals represented by formula 1: (Ba1-pMp)aSibOcNd : eR, wherein M is Sr, R is an activator including Eu as an essential component, 0 < p < 1.0, 1.0 <= a <= 2.0, 0 < b <= 1.0, 0 < c <= 1.0, 0 < d <= 2.0, and 0 < e <= 0.25. A method for manufacturing the oxynitride phosphor comprises the steps of: mixing raw materials including an activator precursor, wherein the activator precursor includes a precursor of Ba, a precursor of M, a precursor of Si and at least precursor of Eu; and injecting the raw materials into a furnace and calcining them.

Description

Oxynitride phosphors, method for manufacturing the same and light emitting device {OXYNITRIDE PHOSPHOR AND METHOD FOR MANUFACTURING THE SAME, AND LIGHT-EMITTING DEVICE}

The present invention relates to an oxynitride phosphor, a method for manufacturing the same, and a light emitting device, and more particularly to an oxynitride phosphor having high luminous efficiency including an oxynitride crystal having a specific composition, and the oxynitride phosphor at low price. The present invention relates to a light emitting device including the manufacturing method and the oxynitride phosphor.

The light emitting device generally includes a light emitting element such as a light emitting diode (LED) and a phosphor as a wavelength converting material. The phosphor may be excited with a blue LED to emit white synthetic light. The phosphor mainly uses a rare earth element as an activator in the emission center. For example, a YAG-based oxide represented by a composition formula of (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ : Ce is mainly used as a phosphor. In addition, Japanese Laid-Open Patent Publication No. 2002-531956 (Previous Patent Document 1) discloses (Sr, Ca, Ba) (Al, Ga) ₂ S ₄ : Eu ²⁺ as a green phosphor, and (Ca, Sr) S: Eu as a red phosphor. ^A white light emitting device using ²⁺ is shown. However, it emits light in a white color by mixing blue light in the vicinity of 460 nm and yellow green light in the vicinity of 565 nm, but the emission intensity in the vicinity of 500 nm is insufficient.

In addition, as an oxynitride phosphor, Japanese Laid-Open Patent Publication No. 2001-214162 (Previous Patent Document 2) shows an oxynitride represented by Si-O-N, Mg-Si-O-N, Ca-Al-Si-O-N or the like. Phosphors are shown, and Japanese Unexamined Patent Application Publication No. 2002-76434 (Previous Patent Document 3) discloses an oxynitride phosphor represented by Ca-Al-Si-O-N in which Eu is activated. However, it is pointed out that these phosphors have low light emission luminance and are insufficient for use in light emitting devices. To this end, Korean Patent Laid-Open Publication No. 2005-0062623 (Previous Patent Document 4) has a high luminous efficiency and is selected from the group consisting of Be, Mg, Ca, Sr, Ba, and Zn as phosphors that efficiently emit light in the short wavelength side region of visible light. At least one group II element; At least one group IV element selected from the group consisting of C, Si, Ge, Sn, Ti, Zr, and Hf; And an oxynitride phosphor comprising a crystal containing a rare earth element that is an activator (R).

However, the phosphors disclosed in the prior patent document 4 have a problem that crystals are unstable and do not have good luminous efficiency. In addition, since nitride is used as a starting material, a raw material price is high, and a high firing temperature according to the use of nitride is required.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2002-531956

[Previous Patent Document 2] Japanese Patent Application Laid-Open No. 2001-214162

[Patent Document 3] Japanese Unexamined Patent Publication No. 2002-76434

[Previous Patent Document 4] Korean Unexamined Patent Publication No. 2005-0062623

The present invention is to solve the problems of the prior art as described above, by including an oxynitride crystal having a specific composition, the oxynitride phosphor which can be disseminated at a high luminous efficiency and low price, and its manufacturing method, and the oxynitride It is an object of the present invention to provide a light emitting device including a phosphor.

In order to achieve the above object, the present invention provides an oxynitride phosphor comprising a crystal represented by the following general formula (1).

[Formula 1]

(Ba _1-p M _p ) _a Si _b O _c N _d : eR

(Wherein M is a + divalent metal except Ba; R is an activator with Eu as essential; 0 <p <1.0, 1.0 ≦ a ≦ 2.0, 0 <b ≦ 1.0, 0 <c ≦ 1.0, 0 <d <2.0, 0 <e <0.25.)

In addition, the present invention,

A first step of mixing a raw material comprising a precursor of Ba, a precursor of M (M is a bivalent metal except Ba), a precursor of Si, and an activator precursor including at least Eu precursor; And

It provides a method for producing an oxynitride phosphor comprising a second step of firing the raw material into a firing furnace.

At this time, the second step, the step of heating up to 800 ℃ ~ 1300 ℃ while injecting ammonia gas at 5 ~ 15mL / min in the kiln; And maintaining step b) at a temperature of 800 ° C. to 1300 ° C. for 2 to 5 hours in the presence of ammonia gas.

In addition, the present invention,

Excitation light source; And a phosphor comprising:

The phosphor provides a light emitting device including the oxynitride phosphor according to the present invention.

According to the present invention, it has excellent luminous efficiency including the crystal represented by the general formula of the composition. And the decision is stable. Further, according to the present invention, starting materials may be synthesized and sintered at a low temperature and room temperature using precursors such as metal salts, and may be supplied at low prices.

Figure 1 is a graph showing the luminescence and excitation spectrum results of the phosphor prepared according to the embodiment of the present invention.

2 is an SEM image of a phosphor prepared according to an embodiment of the present invention.

Figure 3 (a) is an XRD graph of the phosphor prepared according to the embodiment of the present invention, (b) is a graph of the comparison with the XRD pattern of (Sr _1.9 Ba _0.1 ) SiO ₄ (ICSD # 36042).

Figure 4 is a graph showing the luminescence spectrum results according to the halogen type of the phosphor prepared according to the embodiment of the present invention.

5 is a graph showing the luminescence spectrum result according to the Si composition ratio of the phosphor prepared according to the embodiment of the present invention.

6 and 7 are graphs showing luminescence and excitation spectrum results according to the concentration of Eu ²⁺ of the phosphor prepared according to the embodiment of the present invention.

8 is a graph showing the luminescence spectrum result according to the composition ratio of Ba and Sr of the phosphor prepared according to the embodiment of the present invention.

9 is a graph showing the luminescence spectrum result according to the composition ratio of Eu and Pr of the phosphor prepared according to the embodiment of the present invention.

10 is a graph showing the luminescence spectrum result according to the composition ratio of Pr in the fixed Eu composition of the phosphor prepared according to the embodiment of the present invention.

11 is a graph showing light emission spectra of the white light emitting device to which the green phosphor is applied according to the present invention.

Hereinafter, the present invention will be described in detail.

The oxynitride phosphor according to the present invention includes at least the crystal represented by the following general formula (1).

[Formula 1]

(Ba _1-p M _p ) _a Si _b O _c N _d : eR

In Formula 1, M is a + divalent metal except Ba, and R is an activator having Eu as essential. In addition, in the general formula 1, 0 <p <1.0, 1.0 <a <2.0, 0 <b <1.0, 0 <c <1.0, 0 <d <2.0, 0 <e <0.25.

According to the present invention, the phosphor contains the crystal of the general formula 1, and has excellent luminous efficiency. The phosphor according to the present invention is excited and emitted by electromagnetic waves such as light and X-rays, electron beams, heat and the like in various wavelength ranges, and has a high luminescence intensity. The phosphor according to the present invention may include at least the crystals of the general formula (1), but may include other fluorescent substances.

M of Formula 1 may be at least one selected from the group consisting of alkaline earth metals except Ba, +2 valent transition metals, +2 valent non-transition metals, and the like. Specifically, M in Formula 1 is an alkaline earth metal (except Ba) consisting of Be, Mg, Ca, Sr and Ra; + Divalent transition metal consisting of Zn, Cd, Hg and the like; And it may be one or more selected from + bivalent non-transition metal, such as Pb, Sn, Ge and the like. At this time, according to a preferred embodiment, the composition of M to Ba is preferably Ba: M = 0.5 ~ 0.8: 0.2 ~ 0.5. That is, it is preferable that p of the general formula 1 satisfies 0.2 ≦ p ≦ 0.5. If this is satisfied (0.2 <p <0.5), it can have good luminescence. In addition, since the composition (p value) of M increases so much that red-shift may occur when the amount of substitution of M increases, p in Formula 1 satisfies 0.2 ≦ p ≦ 0.5.

In addition, in Formula 1, the composition of Si to (Ba _1-p M _p ) _a , that is, b in Formula 1 preferably satisfies 0.3 ≦ b ≦ 0.9. If the composition of Si increases too much, blue-shift may occur. When the composition of Si satisfies 0.3 ≦ b ≦ 0.9 in the general formula (1), it is possible to prevent blue-shift and to have a good luminescence intensity. More preferably, the composition of Si satisfies 0.45 ≦ b ≦ 0.56 in the general formula (1).

The activator R is Eu essential, but is composed of a molar ratio of 0.25 or less (0 <e ≦ 0.25) with respect to the parent (Ba _1-p M _p ) _a Si _b O _c N _d . In this case, preferably, the composition ratio of R, that is, in the general formula 1, e may satisfy 0.075 ≦ e ≦ 0.12.

According to a preferred embodiment of the present invention, the activator R is for improving the luminescence intensity, and may further include one or more (one or both) selected from Re and X. Specifically, the activator R is essential to Eu, but serves as an auxiliary (auxiliary), it is preferable to further include at least one selected from Re and X. Here, Re is at least one selected from + trivalent non-transition metal and + trivalent rare earth metal, and X is a halogen group element.

Specifically, according to the first preferred embodiment of the present invention, the crystal is represented by the following general formula (2).

[Formula 2]

_{(Ba 1-p M p)} a Si b O c N d: xEu 2+, zX -

Where M is a + divalent metal excluding Ba; X is a halogenated element; 0 <p <1.0, 1.0 ≤ a ≤ 2.0, 0 <b ≤ 1.0, 0 <c ≤ 1.0, 0 <d ≤ 2.0 , 0 <x ≤ 0.25, 0 <z ≤ 0.25.)

As shown in Formula 2, the oxynitride crystals according to the present invention preferably have a composition in which R as an activator requires Eu, but an anion X (a halogen element) is added as flux. At this time, the anion X added as flux acts as an auxiliary. According to the present invention, the addition of X as flux improves the luminescence intensity without affecting the crystal structure. At this time, the composition of X, that is, z in the general formula 2 is preferably satisfies 0.02 <z <0.15. If the concentration of X is too high and z exceeds 0.15, the recording phenomenon of the phosphor occurs, which is a hassle to lower the firing temperature. Therefore, when z satisfies 0.02 ≤ z ≤ 0.15 in Formula 2, even if the firing temperature is high, there is no recording phenomenon, and thus the temperature setting at the time of firing is free, and the luminescence intensity is more improved. Also, in the general formula 2, x satisfies 0.075 ≦ x ≦ 0.12.

X may be one or more selected from the group consisting of Cl, F, Br, I and At as a halogen group element, preferably one or more selected from the group consisting of Cl and F and the like.

According to a second preferred embodiment of the present invention, the crystal is represented by the following general formula (3).

[Formula 3]

_{(Ba 1-p M p)} a Si b O c N d: xEu 2+, yRe 3+, zX -

Wherein M is a + divalent metal excluding Ba; Re is at least one selected from + trivalent non-transition metals and + trivalent rare earth metals; X is a halogenated element; 0 <p <1.0, 1.0 ≤ a ≤ 2.0, 0 <b ≤ 1.0, 0 <c ≤ 1.0, 0 <d ≤ 2.0, 0 <x ≤ 0.25, 0 <y ≤ 0.15, 0 <z ≤ 0.25.)

As shown in Formula 3, the oxynitride crystal according to the present invention preferably has a composition in which R as an activator requires Eu, but an anion X (elemental halogen) is added as flux. At this time, the anion X added as flux acts as an auxiliary. In addition, as shown in the general formula (3), it has a composition to which Re is further added as an auxiliary (auxiliary) for improving the luminescence intensity of Eu. According to the present invention, further addition of Re and X as an auxiliary improves the luminescence intensity. In particular, in the general formula 3, y satisfies 0.01 ≦ y ≦ 0.1, and z has better characteristics than 0.02 ≦ z ≦ 0.15. In addition, in the general formula 3, x satisfies 0.075 ≦ x ≦ 0.12. Formula 3 is the most preferred form of the present invention, and has stability and excellent luminous efficiency when the crystal has a composition represented by Formula 3.

On the other hand, the method for producing a phosphor according to the present invention is a method for producing a phosphor of the composition at a low price, and includes at least the following two steps.

(1) mixing a raw material including a precursor of Ba, a precursor of M (M is a + 2-valent metal except Ba), a precursor of Si, and an activator precursor including a precursor of Eu (first step) )

(2) the step of firing the raw material to the firing furnace (second step)

At this time, the second step (firing step), the step of heating up to 800 ℃ ~ 1300 ℃ while injecting ammonia gas (NH ₃ gas) at 5 ~ 15mL / min in the kiln; And maintaining step b) at a temperature of 800 ° C. to 1300 ° C. for 2 to 5 hours in the presence of ammonia gas.

The precursor of Ba may be a compound containing Ba, for example, one or more selected from Ba salts (eg, BaCO ₃ and BaSO ₄ ), Ba oxide (BaO), Ba nitride (Ba ₃ N ₂ ), and the like may be used. have. Among them, at least one selected from BaCO ₃ and BaO and the like.

In addition, the precursor of M is a + divalent metal precursor excluding Ba precursor, for example, the precursor of M is one selected from Be, Mg, Ca, Sr, Ra, Zn, Cd, Hg, Pb, Sn and Ge, etc. Metal salts and metal oxides containing the above metals can be used. Precursor of M, it is possible to use at least one selected from consisting of a semi-like SrCO _3, ZnCO ₃ PbCO _3, and as a specific example. In addition, the precursor of Si may be selected from Si salts, Si oxides and Si nitrides. Preferably, the precursor of Si can usefully use Si ₃ N ₄ as Si nitride so that nitrogen can also be supplied into the raw material.

The activator precursor essentially includes a precursor of Eu, in addition, it is preferable to further include an auxiliary precursor. For example, the auxiliary precursor may further include a precursor of Re (Re is one or more selected from + trivalent non-transition metal and + trivalent rare earth metal) or a precursor of X (X is a halogen group element).

In addition, the activator precursor essentially includes a precursor of Eu, but may further include both a precursor of Re and a precursor of X as an auxiliary. In this case, the precursor of Eu is a compound containing Eu, for example, it may be selected from Eu salt (eg, EuCO _3, etc.), Eu oxide (Eu ₂ O ₃ ) and the like. In addition, the precursor of Re is a compound containing at least one metal selected from + trivalent non-transition metal and + trivalent rare earth metal, for example, Y, Sc, La, Ce, Pr, Nd, Pm, Sm, Gd One or more metal compounds (oxides or salts) selected from the group consisting of, Tb, Dy, Ho, Er, Tm, Yb and Lu can be used. More specifically, as a precursor of Re, one or more selected from Pr ₆ O ₁₁ , Y ₂ O _3, and La ₂ O ₃ may be used. In addition, the precursor of X is a halogen salt containing a halogen group element, for example, one or more selected from the group consisting of BaX ₂ and NH ₄ X can be used. Precursor (halogen salt) X is selected from, more specifically, BaCl _2, BaF _2, NH ₄ Cl and NH ₄ F, and the like may be used one or more selected from, preferably, BaCl ₂ and BaF ₂ and the like.

According to the manufacturing method of the present invention as described above, the starting material of the phosphor is selected from precursors (metal salts) having a lower purchase price than conventional nitrides, which requires less manufacturing costs. In particular, starting materials are selected from precursors such as metal salts. Synthesis (firing) at low temperature and room temperature is possible, so that the manufacturing cost can be lowered, and the phosphor can be supplied at low cost.

In addition, the light emitting device according to the present invention is an excitation light source; And a phosphor, wherein the phosphor includes at least an oxynitride phosphor according to the present invention as described above. In this case, the excitation light source may be selected from, for example, a light emitting diode (LED), an organic light emitting diode (OLED) laser diode (LD), and a light source for emitting (emitting) other blue light. In addition, the emission wavelength of the excitation light source may be 350nm to 480nm. Preferably, the excitation light source is a light emitting diode (LED), an organic light emitting diode (OLED) or a laser diode (LD) that emits light (blue light) in the wavelength range from 350nm to 480nm.

Hereinafter, the Example of this invention is illustrated. The following examples are merely provided to aid the understanding of the present invention, whereby the technical scope of the present invention is not limited.

Example 1

(Ba _0.5 M _0.5 Si _0.56 ON _0.75 xEu ²⁺ , zCl ^-  Phosphor Preparation of Composition

First, the raw materials were mixed and composed of ingredients and contents (molar ratio) as shown in the following [Table 1]. Next, the mixed raw material was put into an alumina kiln (crucible), and ammonia gas (NH ₃ gas) was injected at 10 mL / min, and the temperature in the kiln was raised to 900 ° C. at a temperature rising rate of 10 ° C./min. And while continuing to inject ammonia gas (NH ₃ gas) was maintained for 3 hours at 900 ℃ temperature in the kiln to obtain a crystal (phosphor) according to this embodiment. In Table 1 below, BaCl ₂ (Flux) was used as a halogen (Cl) precursor, and 2 wt% of BaCl ₂ solution (Flux) was used. The remaining raw materials used powder having a particle size of 2 to 4 μm. The number of moles of each raw material is shown in Table 1 below.

The luminescence and excitation spectra were evaluated for the phosphor crystals obtained as described above, and the results are shown in FIG. 1. The phosphor made according to the present embodiment has the formula _{(Ba 0.5 M 0.5) Si 0.56} ON 0.75: 0.075Eu 2+, 0.04Cl - λ exn = 460nm as was had a composition of (M = Sr), shown in Figure 1 Showed the luminescence peak of the largest century. And light emission at λ _ems = 525 nm. 2 is an SEM image of phosphor crystals prepared according to the present embodiment. As shown in FIG. 2, the phosphor crystal has a particle size in the range of 1 to 10 μm, and the particle size range corresponds to a suitable size as a phosphor.

                         <Composition of Raw Material> ingredient Content (based on solids) mol Molecular Weight BaCO ₃ 0.3947 g 2mmol 197.34 SrCO ₃ 0.2953 g 2mmol 147.21 Si ₃ N ₄ 0.1053 g 0.75 mmol 140.29 BaCl ₂ (flux) 0.0173 g 0.08mmol 208.24 Eu ₂ O ₃ 0.0528g 0.15 mmol 351.93

Example 2

(Ba _0.5 M _0.5 Si _0.56 ON _0.75 xEu ²⁺  Phosphor Preparation of Composition

In contrast to Example 1, except that the halogen precursor (BaCl ₂ ) was not used as Flux was carried out in the same manner. The composition of the raw material according to the present embodiment is shown in the following [Table 2].

                        <Composition of Raw Material> ingredient Content (based on solids) mol Molecular Weight BaCO ₃ 0.3947 g 2mmol 197.34 SrCO ₃ 0.2953 g 2mmol 147.21 Si ₃ N ₄ 0.1053 g 0.75 mmol 140.29 Eu ₂ O ₃ 0.0528g 0.15 mmol 351.93

The phosphor prepared according to the present example had a composition of the general formula (Ba _0.5 M _0.5 ) Si _0.56 ON _0.75 : 0.075Eu ²⁺ (M = Sr).

EXAMPLES 3-8

X ^- Phosphor Preparation According to Concentration

In order to determine the intensity of the luminescence according to the concentration (composition ratio) of X ⁻ , the same procedure as in Example 1 was carried out, but in the composition of each raw material, the content of BaCl ₂ (Flux) was varied.

The phosphors prepared according to the Examples 3 to 8 of the general formula _{(Ba 0.5 M 0.5) Si 0.56} ON 0.75: 0.075Eu 2+, zCl - (M = Sr) having a composition, BaCl ₂ (flux according to each embodiment of the ), The z value of the general formula was changed as shown in the following [Table 3]. And the relative intensity of the luminescence for the phosphors according to each embodiment was measured, and the results are shown in the following [Table 3]. At this time, the relative intensity shown in the following [Table 3] was set as Example 2 (intensity = 1) of z = 0. Example 5 in the following [Table 3] is the same phosphor specimen as Example 1 above.

           <Relative intensity of luminescence according to the composition ratio (z value) of Cl> Remarks Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 BaCl ₂ content (mmol) 0 0.02 0.04 0.08 0.20 0.30 0.44 Composition (z) 0 0.01 0.02 0.04 0.10 0.15 0.22 Relative intensity One 0.971 1.093 1.132 0.911 0.907 0.824

The halogen group (X) element contributes to the stabilization of the crystal, but as shown in [Table 3], when z> 0.1 due to the excessive addition, a recording phenomenon occurs in the phosphor, thereby reducing the luminescence. In addition, it can be seen from the present experimental example that the relative intensity of luminescence is good as 0.9 or more when 0.02 ≤ z ≤ 0.15. It was found that the efficiency is very excellent. And when firing at 900 ℃ z = 0.04 it can be seen that the highest rating.

3 (a) shows the XRD patterns of (Ba _0.5 M _0.5 ) Si _0.56 ON _0.75 : 0.075Eu ²⁺ , zCl ⁻ (M = Sr) phosphors prepared in Examples 2, 5, 6, and 8 . As shown in (a) of FIG. 3, even if the content of BaCl ₂ is greatly increased, 2θ values and intensities of the measured peaks do not occur. This means that it acts as an adjuvant to improve luminescence intensity without causing a change in crystal structure and composition of the phosphor in the range of BaCl ₂ content (0.44 mmole) up to the level of Example 8. In addition, Figure 3 (b) shows a comparison graph with the XRD pattern of the conventional oxide-based (Sr _1.9 Ba _0.1 ) SiO ₄ (ICSD # 36042). As shown in (b) of FIG. 3, the XRD pattern tendency of the phosphor according to the present embodiment is similar to the XRD pattern of (Sr _1.9 Ba _0.1 ) SiO ₄ , and only 2θ values of about 0.4 to 1.6 result in blue-shift. You can see that it happened. This is attributable to the molar ratio of Ba and Sr and the reason that part of O is substituted with N. And oxynitride-based _{(Ba 0.5 M 0.5) Si 0.56} ON 0.75 according to this ^{embodiment: 0.075Eu 2+, zCl - (M} = Sr) crystal structure of the oxide-based phosphor is (Sr _1.9 Ba _0.1) determined similar to the SiO ₄ It can be seen that it has an orthorhombic crystal structure.

EXAMPLES 9-11

X ^- Phosphor Preparation According to Type

In order to determine the luminescence intensity according to the type of halogen precursor (halogen salt) (X ^- type), the same procedure as in Example 1 was carried out, but the composition of the halogen salt (X = Cl, F) The type was used differently as shown in the following [Table 4]. At this time, the content of the halogen salt was fixed to z = 0.04 as 0.08 mmol, which was best evaluated in the above experimental example.

The phosphors prepared according to Examples 9 to 11 have the composition of general formula (Ba _0.5 M _0.5 ) Si _0.56 ON _0.75 : 0.075Eu ²⁺ , 0.04X ⁻ (M = Sr). The luminescence relative intensity of the phosphor according to each of the prepared examples was measured, and the results are shown in the following [Table 4]. In this case, the relative intensity shown in the following [Table 4] was based on Example 1 (Intensity = 1) using BaCl ₂ as a halogen precursor. In addition, the relative intensities (based on Example 1) of Example 2 without adding a halogen precursor are also shown. In addition, FIG. 4 shows the luminescence spectra of the phosphors according to Example 1 (BaCl ₂ ), Example 9 (BaF ₂ ), and Example 2 (No flux).

<X ^- relative intensity of luminescence in accordance with the type of, z = 0.04> Remarks Example 1 Example 9 Example 10 Example 11 Example 2 Halogen precursor BaCl ₂ BaF ₂ NH ₄ Cl NH ₄ F No addition Relative intensity One 0.727 0.716 0.909 0.688

As shown in Table 4, the use of BaCl ₂ (Example 1) and NH ₄ F (Example 11) as the halogen precursors was excellently evaluated, and it was found that BaCl ₂ (Example 1) was best. Could. In addition, as shown in Figure 4, it can be seen that the change in the wavelength of 5 ~ 8nm depending on the presence of Cl and F.

Therefore, it can be seen from the present experimental example that the intensity of luminescence increased when X ⁻ was included in the phosphor composition. That is, Examples 1, 9 to 11 had a greater luminescence intensity than Example 2 without addition. In addition, it can be seen that the wavelength can be changed by the addition of X ⁻ as shown in FIG. 4. Specifically, it was found that the wavelength range can be adjusted by varying, adding or not adding the type of X ⁻ according to the desired wavelength.

[Examples 12 to 18]

Phosphor Preparation According to Composition Ratio of Si and N

In order to determine the luminescence intensity according to the composition ratio (b value, d value) of Si and N, it was carried out in the same manner as in Example 1, but was carried out by varying the content of Si ₃ N _{4 in} the composition of each raw material.

The phosphor made according to the present Examples 12 to 18 are represented by the general formula _{(Ba 0.5 M 0.5) Si b} ON d: 0.075Eu 2+, 0.04Cl - (M = Sr) having a composition, Si ₃ N according to the embodiments of By changing the content (mol) of ₄ to change the b value and d value of the general formula as shown in Table 5 below. And relative intensity of the luminescence was measured for the phosphors according to each of the prepared examples, the results are shown in the following [Table 5]. At this time, the relative intensity shown in the following [Table 5] was b = 0.45, d = 0.6 was used as Example 16 (intensity = 1). And b = 0.56 and d = 0.75 relative strength of Example 1 is shown in Table 5 with Example 16 as the reference (intensity = 1). In addition, FIG. 5 shows the luminescence spectrum of the phosphor according to each of the above embodiments (composition ratio of Si and N).

          <Relative intensity of luminescence according to composition ratio (b, d) of Si, N> Remarks Example 12 Example 13 Example 14 Example 15 Example 16 Example 1 Example 17 Example 18 Si ₃ N ₄ content (mmol) 0.12 0.24 0.41 0.51 0.68 0.75 0.81 1.02 Furtherance b 0.09 0.15 0.21 0.3 0.45 0.56 0.6 0.9 d 0.12 0.2 0.28 0.4 0.6 0.75 0.8 1.2 Relative intensity 0.031 0.051 0.129 0.280 One 0.738 0.560 0.303

First, as shown in the accompanying FIG. 5, it can be seen that blue-shift occurs as the composition of Si increases. In addition, as shown in Table 5, the composition of Si to (Ba _0.5 M _0.5 ) has a relatively good luminescence intensity at 0.3 ≦ b ≦ 0.9, preferably when 0.45 ≦ b ≦ 0.56, and b = 0.45 was found to have the best characteristics.

[Examples 19 to 22]

Eu ²⁺ Phosphor Preparation According to the Concentration (e or x Value)

In order to determine the intensity of the luminescence according to the concentration (composition ratio) of Eu ²⁺ , it was carried out in the same manner as in Example 1, but was carried out by varying the content of Eu ₂ O _{3 in} the composition of the raw material.

The phosphors prepared according to the Examples 19 to 22 are represented by the general formula _{(Ba 0.5 M 0.5) Si 0.56} ON 0.75: xEu 2+, 0.04Cl - having a composition of (M = Sr), according to each embodiment Eu ₂ O ₃ By varying the content of, the x value of the general formula was changed as shown in the following [Table 6]. And relative intensity of the luminescence was measured for the phosphors according to each of the prepared examples, the results are shown in the following [Table 6]. At this time, the relative intensity shown in the following [Table 6] was set as Example 1 (intensity = 1) of x = 0.075. 6 and 7 show luminescence and excitation spectra of phosphors according to the respective examples (concentration of Eu ²⁺ ).

<Relative intensity of luminescence according to composition ratio (x value) of Eu ²⁺ > Remarks Example 19 Example 1 Example 20 Example 21 Example 22 Mo ₂ ratio of Eu ₂ O ₃ to (Ba _0.5 Sr _0.5 ) 0.025 0.0375 0.05 0.075 0.125 Composition (x) 0.05 0.075 0.1 0.15 0.25 Relative intensity 0.8 One One 0.7 0.8

As shown in Table 6, the composition of Eu ²⁺ relative to the parent [(Ba _0.5 M _0.5 ) Si _0.56 ON _0.75 ] had a relatively good luminescence intensity at x ≦ 0.25. In addition, it was found from the present experimental example that the preferred luminescence intensity was obtained when 0.075 ≤ x ≤ 0.12, and optimum characteristics when x = 0.07 and 0.1. In addition, as shown in Figure 6 and 7, it can be seen that there is little change in the wavelength of the luminescence and excitation spectrum according to the concentration of Eu ²⁺ .

[Examples 23 to 29]

Phosphor Preparation According to Composition Ratio of Ba and Sr

In order to determine the luminescence intensity according to the composition ratio (p value) of Ba and Sr, it was carried out in the same manner as in Example 1, except that the content of BaCO ₃ and SrCO _{3 in} the composition of each raw material.

Phosphors prepared according to Examples 23 to 29 have the composition of general formula (Ba _1-p Sr _p ) Si _0.56 ON _0.75 : 0.075Eu ²⁺ , 0.04Cl ⁻ , and BaCO ₃ and SrCO ₃ according to the examples. The p value of the general formula was changed as shown in [Table 7] by varying the content (mol). And relative intensity of the luminescence was measured for the phosphors according to each of the prepared examples, the results are shown in the following [Table 7]. In this case, the relative intensity shown in the following [Table 7] was set as Example (intensity = 1) of Example 26 having p = 0.4. In addition, FIG. 8 shows the luminescence spectrum of the phosphor according to each of the above examples (composition ratio of Ba and Sr).

         <Relative intensity of luminescence according to composition ratio (p) of Ba and Sr> Remarks Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 BaCO ₃ content (mmol) 2 1.8 1.7 One 0.5 0.2 0 Content of SrCO ₃ (mmol) 0 0.2 0.5 One 1.7 1.8 2 Composition (p) 0 0.2 0.4 0.5 0.6 0.8 One Relative intensity 0.812 0.843 One 0.972 0.621 0.209 0.044

First, as shown in FIG. 7, when the Sr composition (p value) is increased and Ba ions are replaced with Sr ions, red-shift occurs. In addition, as shown in [Table 7], it has a good luminescence intensity at 0.2 ≤ p ≤ 0.5, and has an optimum characteristic when p = 0.4, that is, when Ba: Sr = 0.6: 0.4 there was.

[Examples 30 to 36]

(Ba _0.5 M _0.5 Si _0.56 ON _0.75 xEu ²⁺ , yRe ³⁺ , 0.04Cl ^-  Phosphor Preparation of Composition

As an activator (R) by substituting the portion of Eu ²⁺ to ³⁺ Re, evaluated the luminous intensity resulting from the concentration (x value, y values) of Eu ²⁺ and ³⁺ Re, the same as in Example 1 However, in forming each raw material, part of Eu ₂ O ₃ content was replaced with Pr ₆ O ₁₁ .

Having a composition of (M = Sr, Re = Pr ) - xEu 2+, yRe 3+, 0.04Cl: a phosphor according to the embodiment 30 to 36 is represented by the general formula _{(Ba 0.52 M 0.48) Si 0.56} O 0.96 N 0.75 According to each example, the contents of Eu ₂ O ₃ and Pr ₆ O ₁₁ were changed as shown in [Table 8] to change the x and y values of the general formula. And relative intensity of the luminescence for the phosphors according to each embodiment was measured, and the results are shown in the following [Table 8]. At this time, the relative intensity shown in the following [Table 8] was set as Example (intensity = 1) of Example 1 where x = 0.075 and y = 0.0. In addition, FIG. 9 shows the luminescence spectrum of the phosphor according to each of the above examples (the composition ratio of Eu and Pr).

       <Relative intensity of luminescence according to composition ratio (x, y) of Eu and auxiliary Pr> Remarks Example 1 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 Eu ₂ O ₃ content (mmol) 0.15 0.145 0.14 0.13 0.12 0.10 0.08 0.05 Pr ₆ O ₁₁ content (mmol) 0 0.005 0.01 0.02 0.03 0.05 0.07 0.10 Furtherance x 0.075 0.0725 0.07 0.065 0.06 0.05 0.04 0.025 y 0 0.0075 0.015 0.03 0.045 0.075 0.105 0.15 Relative intensity One 0.94 1.2 1.12 1.2 0.63 0.92 0.32

As shown in Table 8 and the accompanying FIG. 9, when a part of Eu is replaced with Pr, in certain regions, the luminescence intensity is superior to that of unsubstituted (y = 0). It can be seen that the decrease.

Therefore, it can be seen from the present experimental example that the luminescence intensity was improved when a part of Eu was replaced with Pr in the composition of the activator (R), and it was found to have good characteristics at 0.01 ≦ y ≦ 0.1. And, as shown in [Table 8], it can be seen that particularly having a very good characteristic at 0.015 ≤ y ≤ 0.045.

[Examples 37 to 42]

(Ba _0.5 M _0.5 Si _0.56 ON _0.75 0.075Eu ²⁺ , yRe ³⁺ , 0.04Cl ^-  Phosphor Preparation of Composition

To fix Eu ²⁺ of the activator and to determine the luminescence intensity according to the change of the concentration of Re ³⁺ (y value), it was carried out in the same manner as in Example 1, in the preparation of each raw material Pr ₆ It was carried out by further adding O ₁₁ .

The phosphor made according to the present embodiment, 37 to 42 of the general formula _{(Ba 0.5 M 0.5) Si 0.56} ON 0.75: - have a composition of (M = Sr, Re = Pr ), 0.075Eu 2+, yRe 3+, 0.04Cl According to each example, the content of Pr ₆ O ₁₁ was changed as shown in the following [Table 9] to change the y value of the general formula. And relative intensity of the luminescence for the phosphors according to each embodiment was measured, and the results are shown in the following [Table 9]. In this case, the relative intensity shown in the following [Table 9] was set as Example (intensity = 1) of Example 1 where x = 0.075 and y = 0. In addition, FIG. 10 shows excitation spectra of the phosphors according to the above embodiments (composition ratio of Pr).

        <Relative intensity of luminescence according to composition ratio (y) of adjuvant Pr> Remarks Example 1 Example 37 Example 38 Example 39 Example 40 Example 41 Example 42 Eu ₂ O ₃ content (mmol) 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Pr ₆ O ₁₁ content (mmol) 0 0.005 0.01 0.02 0.03 0.05 0.07 Furtherance x 0.075 0.075 0.075 0.075 0.075 0.075 0.075 y 0 0.0075 0.015 0.03 0.045 0.075 0.105 Relative intensity One 1.05 1.20 1.18 1.12 1.06 0.85

As shown in [Table 9] and the attached FIG. 10, when Pr is added as an adjuvant, in certain regions, it has a luminescence intensity superior to that of no addition (y = 0), and decreases as the amount of Pr added increases. Could know.

Therefore, it can be seen from the present experimental example that the luminescence intensity is improved by adding Pr, in particular, (Ba _0.5 M _0.5 ) Si _0.56 ON _0.75 : 0.075Eu ²⁺ , yRe ³⁺ , 0.04Cl ⁻ 0.015 ≦ y It was found to have excellent properties when ≤ 0.075.

<Light emitting diode manufacturing>

On the other hand, using a phosphor according to the embodiment was prepared a white light emitting diode as follows.

On the sapphire substrate, a GaN nucleation layer 25 nm, n-GaN layer (metal: Ti / Al) 1.2 μm, five InGaN / GaN multiquantum well layers, InGaN layer 4 nm, GaN layer 7 nm and p-GaN layer (metal : Ni / Au) 0.11 micrometer each was formed in order, and the blue light LED was manufactured. Subsequently, a white light emitting diode device was manufactured by dispersing the phosphor (green) prepared in Example 1 on an epoxy on a surface of the blue light LED. The emission spectrum of the manufactured white light emitting diode is shown in FIG. 11. As shown in Fig. 11, the light-emitting diode coated with the phosphor according to the present invention has a blue luminescence band having a peak point at 452 nm corresponding to a light emission band of a GaN blue LED and a main emission peak at 525 nm emitted from a green phosphor. I could see that.

Claims (22)

An oxynitride phosphor comprising a crystal represented by the following general formula (1). [Formula 1] (Ba _1-p M _p ) _a Si _b O _c N _d : eR Wherein M is Sr; R is an activator with Eu as essential; 0 <p <1.0, 1.0 ≤ a ≤ 2.0, 0 <b ≤ 1.0, 0 <c ≤ 1.0, 0 <d ≤ 2.0, 0 <e <0.25.) An oxynitride phosphor comprising a crystal represented by the following general formula (2). [Formula 2] _{(Ba 1-p M p)} a Si b O c N d: xEu 2+, zX - Where M is Sr; X is a halogen group; 0 <p <1.0, 1.0 ≤ a ≤ 2.0, 0 <b ≤ 1.0, 0 <c ≤ 1.0, 0 <d ≤ 2.0, 0 <x ≤ 0.25 , 0 <z ≤ 0.25) An oxynitride phosphor comprising a crystal represented by the following general formula (3). [Formula 3] _{(Ba 1-p M p)} a Si b O c N d: xEu 2+, yRe 3+, zX - Wherein M is Sr; Re is Pr; X is a halogen group; 0 <p <1.0, 1.0 ≤ a ≤ 2.0, 0 <b ≤ 1.0, 0 <c ≤ 1.0, 0 <d ≤ 2.0, 0 <x ≤ 0.25, 0 <y ≤ 0.15, 0 <z ≤ 0.25.) The method of claim 1, The oxynitride phosphors of the general formula (e) satisfy 0.075 ≦ e ≦ 0.12. The method of claim 2, Z in the general formula satisfies 0.02 ≦ z ≦ 0.15. The method of claim 3, Y in the general formula satisfies 0.01 ≦ y ≦ 0.1, and z satisfies 0.02 ≦ z ≦ 0.15. The method of claim 3, X in the general formula satisfies 0.075 ≦ x ≦ 0.12, y satisfies 0.01 ≦ y ≦ 0.1, and z satisfies 0.02 ≦ z ≦ 0.15. delete The method according to any one of claims 1 to 7, P in the general formula is 0.2 ≤ p ≤ 0.5, characterized in that the oxynitride phosphor. delete delete The method according to claim 2 or 3, The oxynitride phosphor according to claim X, wherein the halogen element is at least one selected from the group consisting of Cl and F. A first step of mixing a raw material comprising a precursor of Ba, a precursor of M (M is Sr), a precursor of Si, and an activator precursor comprising at least a precursor of Eu; And The method of manufacturing an oxynitride phosphor comprising the step of firing the raw material into a firing furnace. The method of claim 13, The second step, Heating a temperature of 800 ° C. to 1300 ° C. while injecting ammonia gas at 5 to 15 mL / min in the kiln; And A process for producing an oxynitride phosphor, characterized in that it comprises a step b) for 2 to 5 hours in the presence of ammonia gas at a temperature of 800 ℃ to 1300 ℃. The method of claim 13, Wherein the activator precursor comprises a precursor of Eu and a precursor of Re (Re is Pr). The method of claim 13, The activator precursor includes a precursor of Eu and a precursor of X (X is a halogen group element). The method of claim 13, The activator precursor includes a precursor of Eu, a precursor of Re (Re is Pr), and a precursor of X (X is a halogen group element). delete The method according to claim 16 or 17, The precursor of X is a method for producing an oxynitride phosphor, characterized in that at least one selected from the group consisting of BaX ₂ and NH ₄ X. Excitation light source; And a phosphor comprising: The phosphor includes a oxynitride phosphor according to any one of claims 1 to 7. The method of claim 20, The excitation light source may be a light emitting diode (LED), an organic light emitting diode (OLED) or a laser diode (LD). The method of claim 20, The light emission device of the excitation light source is characterized in that the emission wavelength is 350nm ~ 480nm.