KR100958700B1 - Oxynitride phosphor, method for manufacturing the same and light-emitting device comprising the same - Google Patents

Abstract

PURPOSE: An oxynitride phosphor, a producing method thereof, and a light-emitting device including thereof are provided to easily perform a post treatment process, and to sinter and synthesize at the low temperature. CONSTITUTION: An oxynitride phosphor contains a crystal marked as chemical formula (A_(a-b)B_b)Si_cO_dN_e:xEu2+, zX-. In the chemical formula, A and B are different elements. A is a divalent metal except for Mg, and B at least comprises the Mg. X is a halogen group element. The range of a, b, c, d and e are 0.8<=a<=1.0, 0.02<=b<=0.1, 1.5<=c<=2.5, 0<d<=3.0 and 1.0<=e<=3.0.

Description

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

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 excellent luminescence efficiency and thermal stability, including an oxynitride crystal having a specific composition, and an inexpensive oxynitride phosphor. A manufacturing method which can be manufactured at a price, and a light emitting device including the oxynitride phosphor.

In general, a light emitting device includes an excitation light source (light emitting element) such as a light emitting diode (LED) and a phosphor as a wavelength converting material. The phosphor may be excited by an excitation light source (LED or the like) to emit light with white synthetic light. Phosphors generally contain a rare earth element as the parent and activator.

As the phosphor, for example, a YAG-based oxide represented by the chemical formula (formula) of (Y) ₃ (Al, Ga) ₅ O ₁₂ : Ce has been mainly used as the oxide phosphor. In the light emitting device using the same, white may be realized by a combination of blue light emitted from the LED and yellow light emitted from the YAG oxide phosphor. In addition, an oxide phosphor in which Gd is substituted for Y as a parent and Ge is substituted for Al in the YAG-based phosphor is also proposed. However, it is pointed out that oxide phosphors such as YAG system require high temperature during the manufacturing process and thus increase the cost, and lack of light emission in the green and red regions, making it difficult to control the color to white.

In addition, as a sulfide phosphor, Japanese Laid-Open Patent Publication No. 2002-531956 (prior patent document 1) discloses a green phosphor represented by the chemical formula of (Sr, Ca, Ba) (Al, Ga) ₂ S ₄ : Eu ²⁺ , and (Ca A white light emitting device using a red phosphor represented by the chemical formula of Sr) S: Eu ²⁺ is shown. However, although it emits light in a white color by the mixture of blue light in the vicinity of 460 nm and yellow green light in the vicinity of 565 nm, the light emission intensity in the vicinity of 500 nm is insufficient.

Moreover, as an oxynitride fluorescent substance, Unexamined-Japanese-Patent No. 2001-214162 (prior patent document 2) is represented by Si-O-N, Mg-Si-O-N, Ca-Al-Si-O-N, etc. Phosphor is shown, and Unexamined-Japanese-Patent No. 2002-76434 (prior patent document 3) has shown the oxynitride phosphor represented by Ca-Al-Si-O-N with which Eu was 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 which 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 above Patent Document 4 have a problem in that crystals are unstable and do not have good luminous efficiency (emission brightness, etc.). In addition, the conventional phosphor has a low thermal stability, there is a problem that the light emission luminance is lowered at high temperatures.

On the other hand, in the manufacture of conventional oxynitride phosphors, nitride is used as a starting material. However, nitride is expensive, and it is vulnerable to oxygen and moisture, and all the processes are inconvenient to proceed in a glove box purged with argon (Ar) or nitrogen (N ₂ ). Synthesis (firing) should be performed at firing temperatures and high pressures of several Mpa. Accordingly, the phosphor manufacturing according to the prior art has a problem that the manufacturing cost is very high due to the high cost of the raw material (nitride) and the expensive equipment according to the high temperature / high pressure, and explosion-proof equipment (high cost) due to the danger of high pressure. .

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

[Patent Document 2] Japanese Patent 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, it is excellent in luminous efficiency (luminescence brightness, etc.) and thermal stability, and can be spread at a low price An object of the present invention is to provide an oxynitride phosphor, a method of manufacturing the same, and a light emitting device including the oxynitride phosphor.

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

[Chemical Formula]

_{(A ab B b) Si c} O d N e: xEu 2 +, zX -

(In the above formula,

A and B are different elements, and A is a + divalent metal except Mg; B comprises at least Mg; X is a halogen group element;

a, b, c, d and e are 0.8 ≦ a ≦ 1.0, 0 <b ≦ 0.2, 1.5 ≦ c ≦ 2.5, 0 <d ≦ 3.0 and 1.0 ≦ e ≦ 3.0;

x and z are 0 <x <0.2 and 0 <z <0.25.)

In addition, the present invention,

As a method for producing the oxynitride phosphor,

(1) A precursor (A is a bivalent metal except Mg), a precursor of B comprising at least Mg precursor (B is an element different from A), a precursor of Si, a precursor of N, a precursor of Eu, and X A first step of mixing raw materials including precursors (X is a halogen group element), and adjusting the content of each precursor to satisfy the above formula; And

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

At this time, the second step,

Heat treatment at a temperature of 800 ° C. to 1300 ° C. in an inert gas atmosphere; And

It is preferred to include the step b) of firing at a temperature of 1000 ℃ to 1500 ℃ in the presence of the firing 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 (luminescence brightness, etc.), thermal stability and the like, including crystals represented by the chemical formula of the composition. In addition, the phosphor is soft and the post-treatment process is easy. In addition, according to the present invention, by using a precursor such as a metal salt or oxide as a starting material, it is calcined and synthesized at atmospheric pressure and low temperature, and thus can be supplied at a low price.

Hereinafter, the present invention will be described in detail.

The oxynitride phosphor according to the present invention includes a crystal represented by the following formula.

[Chemical Formula]

_{(A ab B b) Si c} O d N e: xEu 2 +, zX -

In the formula, A and B are different elements. A is a + divalent metal excluding Mg, and B is an element (s) comprising at least Mg (magnesium). And X is a flux element as flux. At this time, each element constituting the chemical formula has a specific composition ratio (conditional formula). Specifically, in the formula, a, b, c, d and e satisfy 0.8 ≦ a ≦ 1.0, 0 <b ≦ 0.2, 1.5 ≦ c ≦ 2.5, 0 <d ≦ 3.0 and 1.0 ≦ e ≦ 3.0, respectively. X and z satisfy 0 <x ≦ 0.2 and 0 ≦ z ≦ 0.25, respectively.

In the above formula, A is not limited as long as it is a + divalent metal except for Mg. For example, in the above formula, A may be selected from the group consisting of Be, Ca, Sr, Ba, Ra, Zn, Cd, Hg, Pb, Sn, Ge, and the like. A may be one or a combination of two or more selected from these.

In addition, B in the above formula includes at least Mg. Specifically, in the above formula, B is composed of Mg or Mg, but may further include other elements in addition to Mg. For example, B requires Mg but is a + divalent metal (a metal other than A); Elements of group 3A (including lanthanide elements); A Group 3B element; And group 4A to 7B. More specifically, in the above formula, B includes at least Mg, but Be, Ca, Sr, Ba, Ra, Zn, Cd, Hg, Pb, Sn, Ge, B, Al, Ga, In, Ti, Sc , Y, S, La, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, etc. may further include one or more selected from the group consisting of, but It is not limited to these. Formula B in the present invention is included in the present invention as long as it contains at least Mg. In addition, in the above formula, if B requires Mg, but further includes other elements, it may be represented by B = B1 + B2, any one selected from B1 and B2 is Mg, and the other is one except Mg It selects from the above elements (elements different from A). At this time, the parent A _ab B _b of the formula is A _a-b B1 _b1 B2 _b2 (where, b1 + b2 = b, any one selected from B1 and B2 is Mg, the other one according to another embodiment of the present invention) It is an element other than Mg).

According to the present invention, luminescence characteristics, that is, luminescence brightness, are improved due to the substitution of Mg (B) in the mother. Mg has a small ion radius, so that the solid solution is well formed in the matrix, and the sintering property is increased to give high brightness. In addition, when the composition ratio of B in the chemical formula, that is, the value of b in the chemical formula increases so much, the substitution amount of B in the parent A is too large, a red-shift may occur. Accordingly, the composition ratio (b value) of B in the chemical formula may satisfy b ≦ 0.2. Preferably, the composition ratio (b value) of B may satisfy 0.02 ≦ b ≦ 0.1. If this is satisfied (0.02 ≦ b ≦ 0.1), it has better luminescence properties.

Eu in the above formula is included as an activator, which is composed of a molar ratio of 0 or less (0 <x ≤ 0.2) with respect to the parent A _ab B _b . Too much Eu can cause a red-shift. Preferably, the composition ratio of Eu, ie, x in the chemical formula, satisfies 0.02 ≦ x ≦ 0.2, and more preferably 0.04 ≦ x ≦ 0.15. If this is satisfied (preferably 0.02 ≦ x ≦ 0.2, more preferably 0.04 ≦ x ≦ 0.15), it has better luminescence properties.

In addition, X in the above formula is a flux for improving crystallinity, which is added as necessary, and it is selected from halogenated elements. Specifically, X in the formula is one selected from the group consisting of halogen group elements (anions) such as F, Cl, Br, I and At, preferably selected from F, Cl and Br. When the halogen group element (X) is added as the flux, the crystal of the phosphor is more stabilized, and the luminescence characteristic can be improved at the same time. At this time, if the composition ratio (z value) of the flux X is too high, the recording phenomenon of the phosphor may occur, which may cause the trouble of lowering the firing temperature. Specifically, when the composition ratio (molar ratio) of X to the parent A _ab B _b , that is, z in the chemical formula is greater than 0.25, recording phenomenon of the phosphor may occur. Therefore, when z satisfies 0 ≦ z ≦ 0.25 in the chemical formula, even if the firing temperature is high, there is no recording phenomenon, and thus the temperature setting at the firing is free, and the luminescence characteristics are well improved. Preferably, the composition ratio (z value) of X satisfies 0.02 ≦ z ≦ 0.12. When this is satisfied (0.02 ≦ z ≦ 0.12), excellent luminescence characteristics can be achieved together with stabilization of the crystal. In addition, according to a more preferred embodiment of the present invention, b, x and z of the formula preferably satisfy 0.02 ≦ b ≦ 0.1, 0.04 ≦ x ≦ 0.15 and 0.02 ≦ z ≦ 0.12, in which case the stability of the crystal And luminescence properties can be better improved.

According to the present invention, the phosphor comprises a crystal represented by the above formula, and has excellent luminous efficiency and thermal stability. Specifically, the phosphor according to the present invention is represented by the above formula, but as described above includes at least Mg as B, and includes a crystal that satisfies a specific composition ratio (molar ratio) and conditional formula, the light source (light And light emitted by electromagnetic waves such as X-rays, electron beams, heat, and the like, and have excellent luminescence intensity (luminescence brightness) and passion stability. That is, the light emission luminance is high and thermally stable even at high temperatures. In addition, the phosphor (powder) according to the present invention is soft, and the post-treatment process (mixing process with a binder, molding process, etc.) is easy. In addition, the phosphor according to the present invention can be effectively excited in the near ultraviolet region in the wavelength range of about 400 to 410 nm in addition to the blue chip region of 450 nm to 470 nm, and red-shifted compared to the conventional oxide phosphor under the influence of N ^3- . It is possible to shift the yellowsih-green wavelength band by changing the composition ratio.

The phosphor according to the present invention includes at least the crystal represented by the above formula, and may further include other fluorescent substances. In addition, the phosphor according to the present invention, that is, the crystal represented by the chemical formula is not particularly limited, but may have a size of several hundred nanometers (nm) to several tens of micrometers (μm), and preferably has a size of 1 to 30 μm. Can have

In addition, the phosphor according to the present invention, that is, the crystal represented by the above formula has excellent light emission characteristics in the blue region wavelength range, for example, in the blue region in the 450 nm to 470 nm wavelength range. That is, the preferred emission wavelength (luminescence wavelength range) of the phosphor according to the present invention is, for example, 450 nm to 470 nm. As described above, the phosphor according to the present invention is particularly excellent in light emission characteristics in a blue region (for example, a wavelength range of 450 nm to 470 nm), and can be usefully applied as a blue phosphor of a three wavelength white light device.

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 A, a precursor of B, a precursor of Si, a precursor of N, a precursor of Eu, and a precursor of X (first step)

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

At this time, in the first step (mixing step), by adjusting the content (molar ratio) of each raw material (precursor) so as to satisfy the formula (composition ratio and conditional formula). Specifically, a, b, c, d, and e of the formula satisfy 0.8 ≦ a ≦ 1.0, 0 <b ≦ 0.2, 1.5 ≦ c ≦ 2.5, 0 <d ≦ 3.0, and 1.0 ≦ e ≦ 3.0, respectively. x and z are mixed to adjust the content (molar ratio) of each raw material (precursor) to satisfy 0 <x <0.2 and 0 <z <0.25, respectively. For example, in the case of the Si precursor, the Si precursor is mixed at an appropriate weight such that 1.5 ≦ Si mole number ≦ 2.5 (1.5 ≦ c ≦ 2.5) with respect to 1.0 mole of the parent (A _ab B _b ). In another example, in the case of the Eu precursor, the Eu precursor is mixed at an appropriate weight such that 0 <Eu moles ≤ 0.2 (0 <x ≤ 0.2) with respect to 1.0 mole of the parent (A _ab B _b ).

In addition, wet and dry mixing are possible in the first step (mixing step). For example, the raw materials (precursors) are uniformly dispersed in a solvent such as acetone, and then 3 to 12 hours at 60 to 100 ° C. The wet mixing method used by drying is mentioned. In addition, in the first step (mixing step), the mixing and pulverization of each of the raw materials (precursors) through a ball mill and ultrasonic waves may be performed.

The precursors of the respective raw materials, that is, the precursors of A, B, Si, N, Eu, and X are compounds containing respective elements, and may be selected from salts, oxides, nitrides, and the like of each element. The precursor is preferably selected from carbonates and oxides which are inexpensive, easy to purchase and not vulnerable to the environment. For example, in the case of a metal precursor, a metal salt (carbonate, etc.), a metal oxide, etc. may be used.

More specifically, the precursor of A is a compound containing A (A is a bivalent metal except Mg), for example, Be, Ca, Sr, Ba, Ra, Zn, Cd, Hg, Pb, Sn and One or more selected from the group consisting of compounds of Ge (salts, oxides, nitrides, etc.) may be used. The precursor of A is preferably selected from carbonates and oxides as described above. Although not particularly limited, for example, when A = Sr, SrCO ₃ may be used as a precursor of Sr. When A = Ba, Ba salts (eg, BaCO ₃ and BaSO _4, etc.) may be used as precursors of Ba. ), One or more selected from the group consisting of Ba oxide (BaO) and Ba nitride (Ba ₃ N ₂ ). In another example, when A = Ca, at least one selected from CaO, CaCO ₃ , Ca ₃ N ₂ , and the like may be used as a precursor of Ca. Among them, it is preferable to select from SrCO ₃ , BaCO ₃ , CaO, CaCO ₃ and the like as carbonate and oxide.

In addition, the precursor of B comprises at least Mg precursor. As a precursor of Mg, Mg compounds, such as Mg salt and oxide, can be used, For example, MgO etc. are mentioned. In addition, the precursor of B includes at least the precursor of Mg, as a precursor of other elements, for example Be, Ca, Sr, Ba, Ra, Zn, Cd, Hg, Pb, Sn, Ge, B, Al, Ga, Consisting of compounds of In, Ti, Sc, Y, S, La, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu (salts, oxides, nitrides, etc.) It may further comprise one or more selected from the crowd, avoiding overlap with the precursor of A. More specifically, for example, precursors of B require Mg precursors (eg, MgO), optionally SrCO ₃ , BaCO ₃ , CaO, CaCO ₃ , BN, AlN, LaN, GaN, B ₂ O ₃ , It may further include one or more selected from the group consisting of Al ₂ O ₃ , La ₂ O ₃ , Ga ₂ O ₃ , Y ₂ O ₃ , S, ZnS, Ge ₂ O ₃ , TiO ₂ and ZnO.

In addition, the precursor of Si may be selected from Si salts, Si oxides and Si nitrides. Preferably, the precursor of Si may use Si nitride or Si oxide so that nitrogen (N) or oxygen (O) may be supplied into the raw material, and for example, Si ₃ N ₄ and SiO ₂ may be usefully used. Can be. In addition, the precursor of N may be a nitride, for example, BN, AlN, LaN, GaN, Si ₃ N ₄ and Ca ₃ N ₂ and the like, the precursor of N is an example of Si nitride (Si nitride (Si ₃ N _4, etc.) may not be added if used. In addition, oxygen (O) included in the crystal of the chemical formula may be included in the composition by using a metal oxide (eg, MgO) as one precursor (eg, a precursor of B). As the precursor of Eu, for example, one or more selected from Eu ₂ O ₃ and Eu ₂ (C ₂ O ₄ ) ₃ may be used.

The precursor of the X (flux precursor) may be selected from halogen salts, for example, as the precursor of X halogen such as BaX ₂ , NH ₄ X, SrX ₂ and NaX (X is F, Cl, Br, etc.) One or more selected from salts can be used.

On the other hand, in the second step (firing step), inert gas is first injected into the kiln, heat treatment is carried out at a temperature of 800 ° C to 1300 ° C in an inert gas atmosphere (step a), and then a firing gas is injected into the kiln and then fired. In the presence of a gas it can proceed by firing, synthesis (step b) at a temperature of 1000 ℃ to 1500 ℃. In this case, an inert gas such as N ₂ gas and Ar gas may be used in the heat treatment (step a), and the heat treatment may be performed for about 2 to 10 hours. Through this heat treatment (step a), effective removal of carbonate or the like used as the precursor can be achieved. In addition, in the calcining and synthesis (step b), a calcining gas such as H ₂ / N ₂ mixed gas or NH ₃ gas may be used, and the calcining time may be performed for about 2 to 15 hours. At this time, the H ₂ / N ₂ mixed gas is not particularly limited, but the H ₂ content may be, for example, 2 to 20% by weight. In addition, the firing, synthesis (step b) is preferably carried out in the temperature range of atmospheric pressure, 1100 ℃ ~ 1300 ℃.

According to the manufacturing method of the present invention as described above, the starting material of the phosphor is selected from the precursor (metal salt or oxide) having a lower purchase price than the nitride used in the prior art, the manufacturing cost is low, in particular, the starting material is a metal salt or oxide as described above It is selected from precursors, such as synthesis | combination (baking) at normal pressure and low temperature is possible. Specifically, in the second step (firing step), it is possible to bake at a low temperature (preferably 1300 ° C. or less) of 1500 ° C. or less under normal pressure. Accordingly, according to the present invention, the manufacturing cost can be lowered due to the purchase of low cost of raw materials, low cost of energy and energy saving, and the phosphor can be supplied at a low price.

On the other hand, the light emitting device according to the present invention includes the oxynitride phosphor of the present invention as described above as the wavelength conversion material. Specifically, the light emitting device according to the present invention is an excitation light source; And phosphors, wherein the phosphors include at least the oxynitride phosphors of the invention as described above. The excitation light source may be selected from, for example, a light source emitting blue light or the like. More specifically, the excitation light source may be selected from light emitting diodes (LEDs), organic light emitting diodes (OLEDs), laser diodes (LDs), and other light sources that emit (emit) light. In this case, the emission wavelength of the excitation light source is not particularly limited, but may be 350 nm to 480 nm. Specifically, the excitation light source may be selected from light emitting diodes (LEDs), organic light emitting diodes (OLEDs), laser diodes (LDs), and the like that emit (emit) light (eg, blue light) in a wavelength range from 350 nm to 480 nm. have. In addition, the light emitting device according to the present invention may implement white light by the excitation light source and the phosphor.

In addition, the phosphor is mixed with a binder and then molded on an excitation light source, but the phosphor is not particularly limited, but may be used at 0.1 to 30% by weight. That is, the phosphor may be included in an amount of 0.1 to 30% by weight based on the total weight of the molding composition including the phosphor and the binder. In this case, the binder may be used as long as it has adhesiveness. For example, a polymer such as an epoxy resin, a silicone resin, a urethane resin, an acrylic resin may be used, but is not limited thereto.

Hereinafter, the Example and comparative example of this invention are 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

(Sr _0.82 Mg _0.08 Si ₂ O ₂ N ₂ : 0.1 Eu ^{2 +}  Phosphor Preparation of Composition

First, the raw materials were mixed with the ingredients and contents as shown in the following [Table 1]. At this time, each raw material (precursor) was used a powder of particle size 2 ~ 4㎛, uniformly mixed with acetone in agate induction, and then used to dry. Next, the mixed raw material was filled in an alumina crucible, and then mounted in a tubular electric furnace, followed by heat treatment at a temperature of 1200 ° C. for about 5 hours in an N ₂ atmosphere. Then, the mixture was maintained in an H ₂ / N ₂ mixed gas (H ₂ content of about 5% by weight) atmosphere, and then synthesized (fired) for about 6 hours at a temperature of 1400 ° C. to obtain a phosphor (crystal) according to this embodiment. .

The phosphor prepared according to the present example had a composition of formula (Sr _0.82 Mg _0.08 ) Si ₂ O ₂ N ₂ : 0.1Eu ²⁺ . The luminescence (luminance) and the excitation spectrum were evaluated for the prepared phosphors, and the results are shown in FIG. As shown in FIG. 1, the prepared phosphor showed the luminescence peak of the greatest intensity at about λ _exn = 460 nm and emitted light at about λ _ems = 545 nm. 2 is an SEM image of phosphor crystals prepared according to the present embodiment. As shown in Fig. 2, the phosphor crystal had a particle size in the range of 1 to 20 mu m, and the particle size range corresponds to a suitable size as the phosphor.

[Comparative Examples 1 to 10]

( Sr _{a - b} B _b ) Si ₂ O ₂ N ₂ : 0.1 Eu ^{2 +}  Phosphor preparation of composition (comparison with phosphor according to kind of B)

In order to determine the luminescence intensity according to the addition of B and the type of B, it was carried out in the same manner as in Example 1, but used in different precursors as shown in Table 1 in the composition of each raw material. Specifically, A = Sr was fixed, but a precursor of B was not used (Comparative Example 1), or a precursor of B was used in a different kind of precursor (Comparative Examples 2 to 10) than Example 1.

Phosphors prepared according to Comparative Examples 1 to 10 are chemical formulas (Sr _{a - b} B _b ) Si ₂ O ₂ N ₂ : 0.1Eu ²⁺ (a = 0.9, b = 0 or 0.08, B = none, Y, Ga, La, Al, S, Ge, Ti, Zn). Luminescence (luminance) and excitation spectra were evaluated for the phosphors according to the comparative examples, and the results are shown together with the results of Example 1 in FIG. 1.

In addition, Table 1 shows the luminescence intensity (λ _exn = 460 _nm ) of the phosphors according to Example 1 and Comparative Examples 1 to 10. In this case, the luminescence intensity shown in the following [Table 1] was expressed as a relative intensity based on Comparative Example 1 (B = none) as a reference (intensity = 1).

<Composition of Raw Material> Remarks SrCO ₃ Precursor of B α-Si ₃ N ₄ SiO ₂ Eu ₂ O ₃ a value b value Intensity Example 1 (B = Mg) 2.42 g 0.06 g (MgO) 1.40 g 0.60 g 0.35 g 0.9 0.08 1.31 Comparative Example 1 (B = none) 2.65 g - 1.40 g 0.60 g 0.35 g 0.9 0 One Comparative Example 2 (B = Y) 2.42 g 0.36 (Y ₂ O ₃ ) 1.40 g 0.60 g 0.35 g 0.9 0.08 0.61 Comparative Example 3 (B = Ga) 2.42 g 0.29 (Ga ₂ O ₃ ) 1.40 g 0.60 g 0.35 g 0.9 0.08 0.55 Comparative Example 4 (B = La) 2.42 g 0.51 (La ₂ O ₃ ) 1.40 g 0.60 g 0.35 g 0.9 0.08 0.28 Comparative Example 5 (B = Al) 2.42 g 0.16 (A1 ₂ O ₃ ) 1.40 g 0.60 g 0.35 g 0.9 0.08 0.29 Comparative Example 6 (B = Al) 2.42 g 0.06 (AlN) 1.40 g 0.60 g 0.35 g 0.9 0.08 0.55 Comparative Example 7 (B = S) 2.42 g 0.05 (S) 1.40 g 0.60 g 0.35 g 0.9 0.08 0.69 Comparative Example 8 (B = Ge) 2.42 g 0.16 (Ge ₂ O ₃ ) 1.40 g 0.60 g 0.35 g 0.9 0.08 0.17 Comparative Example 9 (B = Ti) 2.42 g 0.12 (TiO ₂ ) 1.40 g 0.60 g 0.35 g 0.9 0.08 0.05 Comparative Example 10 (B = Zn) 2.42 g 0.13 (ZnO) 1.40 g 0.60 g 0.35 g 0.9 0.08 0.16

As shown in Table 1 and the accompanying FIG. 1, when a part of the parent (A = Sr) was substituted with Mg, it was found to have excellent luminescence intensity (intensity). Specifically, according to an embodiment of the present invention, when a part of the parent A is replaced with B, but Mg is used as B, B is not used (Comparative Example 1), or another element is used as B (Comparative Examples 2 to 2). It can be seen that it has an excellent luminescence intensity than 10).

[Examples 2 to 5]

( Sr _{a - b} Mg _b ) Si ₂ O ₂ N ₂ : 0.1 Eu ^{2 +}  Preparation of phosphor of composition Sr and Mg Phosphor depending on the content of

In order to determine the luminescence intensity according to the content (composition ratio a value, b value) of Sr (A = Sr) and Mg (B = Mg), the same procedure as in Example 1 was carried out, except that Sr The content of the precursor and the Mg precursor was varied. Specifically, as shown in the following [Table 2], by changing the content of SrCO ₃ and MgO according to each embodiment was changed the a value and b value of the formula.

Phosphors prepared according to Examples 2 to 5 are chemical formulas (Sr _{a - b} Mg _b ) Si ₂ O ₂ N ₂ : Had a composition of 0.1Eu ²⁺ . The luminescence intensity of the phosphors according to each of the prepared examples was measured, and the results are shown in FIG. 3. In addition, the luminescence intensity (λ _ems = 545 nm) according to Mg mol (mol)% is shown in FIG. 4. In FIG. 4, Mg mol% (x-axis) is a mole percentage (mol%) of Mg in the parent (mixture of Sr and Mg). In addition, Table 2 shows the luminescence intensity (λ _exn = 460 _nm ) of the phosphors according to the examples. In this case, the luminescence intensity shown in the following [Table 2] was expressed as a relative intensity based on Comparative Example 1 (b = 0) as a reference (intensity = 1).

<Composition of Raw Material According to Sr and Mg Content> Remarks SrCO ₃ MgO α-Si ₃ N ₄ SiO ₂ Eu ₂ O ₃ a value b value Intensity Comparative Example 1 2.65 g - 1.40 g 0.60 g 0.35 g 0.9 0 0.6 Example 2 2.56 g 0.02 g 1.40 g 0.60 g 0.35 g 0.9 0.03 0.9 Example 3 2.42 g 0.06 g 1.40 g 0.60 g 0.35 g 0.9 0.08 1.0 Example 4 2.36 g 0.08g 1.40 g 0.60 g 0.35 g 0.9 0.1 1.1 Example 5 2.21 g 0.12 g 1.40 g 0.60 g 0.35 g 0.9 0.15 1.08

First, as shown in [Table 2], and as shown in FIG. 3 and FIG. 4, the more substitution amount of Mg (B) instead of Sr (A) as a parent, that is, the content (b value) of Mg (B) is It can be seen that the increase in the luminescence intensity as the increase. In addition, as shown in Figure 4, according to the increase in the amount of Mg (B) the luminescence intensity is not continuously improved, if the excess is added rather the luminescence intensity is reduced (Example 4> Example 5) Could know. In the composition according to the present embodiments, it was found that b ≦ 1.5, more preferably b ≦ 1.0. In addition, as shown in Figure 3, even if the substitution amount of Mg (B) was found that there is no change in the wavelength band.

[Examples 6 to 10]

(Sr _0.80 Mg _0.1 Si ₂ O ₂ N ₂ xEu ²⁺ , 0.04F ^-  Preparation of phosphor of composition (Eu ²⁺ Phosphor depending on the content of

To evaluate the luminous intensity in accordance with the content (composition ratio x value) of Eu ^{2 +,} but the same manner as in Example 1, in the following composition of the respective raw materials was carried out by varying the content of Eu precursor. In addition, a halogen precursor (BaF ₂ ) was further added as a flux. Specifically, by varying the content of Eu ₂ O ₃ as the Eu precursor according to each embodiment, as shown in the following [Table 3], the halogen precursor (BaF ₂ ) was further added while changing the x value of the formula.

The phosphors prepared according to the Examples 6 to 10 of the formula _{(Sr 0 .80 Mg 0 .1)} Si 2 O 2 N 2 : xEu ²⁺ , 0.04F ⁻ . For the phosphors according to each of the prepared examples, the luminescence intensity and the wavelength change according to Eu mol (mol)% were measured, and the results are shown in FIG. 5. 6 shows the luminescence intensity (λ _ems = 545 nm) according to Eu mol%. In addition, Table 3 shows the luminescence intensity (λ _exn = 460 _nm ) of the phosphors according to the examples. In this case, the luminescence intensity shown in the following [Table 3] is expressed as a relative intensity based on Example 8 (x = 0.1) as the reference (intensity = 1).

<Composition of Raw Material According to Eu Content> Remarks SrCO ₃ MgO α-Si ₃ N ₄ SiO ₂ BaF ₂ Eu ₂ O ₃ x value Intensity Example 6 2.53 g 0.08g 1.40 g 0.60 g 0.15 g 0.14 g 0.04 0.81 Example 7 2.42 g 0.08g 1.40 g 0.60 g 0.15 g 0.28 g 0.08 0.97 Example 8 2.36 g 0.08g 1.40 g 0.60 g 0.15 g 0.35 g 0.1 One Example 9 2.21 g 0.08g 1.40 g 0.60 g 0.15 g 0.52 g 0.15 0.9 Example 10 2.06g 0.08g 1.40 g 0.60 g 0.15 g 0.70 g 0.2 0.87

As shown in [Table 3] and the attached FIGS. 5 and 6, it was found that the luminescence intensity varies depending on the content (x value) of Eu. It can be seen from the present examples that Eu is added in an appropriate amount but has good luminescence intensity when x ≦ 0.2. In addition, it was found that the phosphor composition according to the present embodiments had excellent luminescence intensity when 0.08 ≤ x ≤ 0.15, and was most optimal when x = 0.1 (10 mol%). In addition, red-shift occurred as the content of Eu (x value) increased.

[Examples 11 to 16]

( Sr _{0 .8} Mg _{0 .One} ) Si ₂ O ₂ N ₂ : 0.1 Eu ^{2 +} , zF ^-  Preparation of phosphors (phosphor according to concentration of F)

In order to determine the luminescence intensity according to the content (composition ratio z value) of the halogen X as flux, the same process as in Example 8 was carried out, but the content of the halogen precursor was changed. Specifically, by varying the content of BaF ₂ (flux) as a halogen precursor according to each embodiment, the z value of the formula was changed as shown in Table 4 below.

Phosphor prepared according to Examples 11 to 16 of the formula (Sr_{0 .8}Mg_{0 .One}Si₂O₂N₂ 0.1Eu²⁺, zF^- Had the composition of. Luminescence intensity (λ) for the phosphors according to each of the prepared examples_exn = 460 nm), and the results are shown in the following [Table 4]. In this case, the luminescence intensity shown in the following [Table 4] is expressed as a relative intensity based on Example 8 (intensity = 1) of z = 0.04.

<Relative intensity of luminescence according to F content (z value)> Remarks Example 8 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 BaF ₂ content (g) 0.15 No flux 0.1 0.20 0.25 0.3 0.4 Composition (z value) 0.02 0 0.005 0.04 0.08 0.12 0.24 Relative intensity One 0.671 1.093 1.132 1.121 0.907 0.824

As shown in [Table 4], it was found that the luminescence intensity varies depending on the addition of the halogen group element as the flux. That is, it was found that the luminescence intensity was improved compared to the case where the halogenated element was added to contribute to the stabilization of the crystal (Example 8, Examples 12 to 16), but not added (Example 11). In addition, when too much was added (Example 16), it was found that the recording phenomenon of the phosphor occurred and the light emission decreased. In the phosphor composition according to the present embodiments, it was found that the relative intensity is good as 0.9 or more when 0.02 ≤ z ≤ 0.12, and the luminescence intensity is very high as the relative sega is 1 or more when 0.02 ≤ z ≤ 0.08. It was found to be excellent. In addition, the highest evaluation was at z = 0.04.

[Examples 17 to 23]

( Sr _{0 .8} Mg _{0 .One} ) Si ₂ O ₂ N ₂ : 0.1 Eu ^{2 +} , 0.04X ^-  Phosphor Preparation of Composition (Phosphor According to Type of X)

In order to determine the luminescence intensity according to the type (X type) of the halogen precursor as the flux, the same procedure as in Example 8 was carried out, but in the preparation of each raw material, as shown in the following [Table 5] halogen precursor (halogen salt) Different kinds of were carried out.

The phosphor made according to the present Examples 17 to 23 has the formula _{(Sr 0 .8 Mg 0 .1)} Si 2 O 2 N 2 : 0.1Eu ²⁺ , 0.04X ⁻ (X = F, Cl, Br). The luminescence relative intensity (λ _exn = 460 _nm ) of the phosphors according to each of the prepared examples was measured, and the results are shown in the following [Table 5]. Table 5 also shows the relative intensities of Example 11 without adding a halogen precursor. At this time, the relative intensity shown in the following [Table 5] was based on Example 8 using the BaF ₂ as a halogen precursor (intensity = 1).

          <Relative intensity of luminescence according to type X, z = 0.04> Remarks Example 8 Example 11 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Type of halogen precursor BaF ₂ No flux BaCl ₂ NH ₄ Cl NH ₄ F NaBr SrF ₂ SrCl ₂ SrCl ₂ + BaF ₂ Relative intensity One 0.67 0.89 0.95 0.67 0.81 0.9 0.98 0.88

As shown in Table 5, the halogen precursor as a flux was found to show a slight difference depending on the kind, the fluorescent material composition according to the present embodiments of BaF _2, NH ₄ Cl, and SrF ₂ as the halogen precursor It was found that the case was satisfactorily evaluated as a relative strength of 0.9 or more. And BaF ₂ (Example 8) was found to have the best characteristics.

[Examples 24 to 25]

(A _0.8 Mg _{0 .One} ) Si ₂ O ₂ N ₂ : 0.1 Eu ^{2 +} , 0.04F ^-  Phosphor Preparation of Composition (Phosphor According to Type of A)

In order to determine the luminescence intensity according to the type of A as a mother, it was carried out in the same manner as in Example 8, but in the composition of each raw material was carried out by varying the type of A precursor as shown in Table 6 below.

The phosphor made according to the present Examples 24 to 25 has the formula _{(A 0.8 Mg 0 .1) Si} 2 O 2 N 2 : 0.1Eu ²⁺ , 0.04F ⁻ (A = Ba or Ca). The luminescence relative intensity (λ _exn = 460 _nm ) was measured for the phosphors according to the examples, and the results are shown in the following [Table 6]. In this case, the relative intensity shown in the following [Table 6] was set as Example (intensity = 1) of Example 8 using SrCO ₃ (A = Sr) as the A precursor.

              <Relative intensity of luminescence according to A type> Remarks Example 8 Example 24 Example 25 Type of A precursor SrCO ₃ BaCO ₃ CaCO ₃ Relative intensity One 0.92 0.85

As shown in Table 6, it can be seen that the precursor of A as a parent showed a slight difference according to its type, and A = Sr and Ba were well evaluated as the relative strength of 0.9 or more.

[Examples 26 to 36]

( Sr _{0 .8} B _0.1 ) Si ₂ O ₂ N ₂ : 0.1 Eu ^{2 +} , 0.04F ^-  Phosphor Preparation of Composition (Phosphor According to Type of B)

In order to determine the luminescence intensity according to the type of B, it was carried out in the same manner as in Example 8, but in the composition of each raw material as shown in the following [Table 7] Mg precursor and a precursor of another metal mixed as a B precursor Used to change the element of B. That is, a part of Mg was replaced with another kind of element so that B = B1 + B2 (B1 is Mg and B2 is an element except Mg) in the above formula.

The phosphor made according to the present Examples 26 to 36 has the formula _{(Sr 0 .8 B 0.1) Si} 2 O 2 N 2 : 0.1Eu ²⁺ , 0.04F ^- composition (B = B1 + B2, B1 = Mg, B2 = Ba, Ca, Y, Ga, La, Al, S, Ge, Ti, Zn). The luminescence relative intensity (λ _exn = 460 _nm ) of the phosphors according to the prepared examples was measured, and the results are shown in the following [Table 7]. In this case, the relative intensity shown in the following [Table 7] was set as the reference (intensity = 1) of Example 8 using MgO (B = Mg) as the B precursor.

               <Relative intensity of luminescence according to B type> Remarks Precursor of B1 Precursor of B2 Molar ratio of B1 and B2 Relative strength Comparative Example 1 (B = none) - - - 0.148 Example 8 (B = Mg) MgO - 0.1: 0 One Example 26 (B = Mg + Ba) MgO BaCO ₃ 0.08: 0.02 1.019 Example 27 (B = Mg + Ca) MgO CaCO ₃ 0.08: 0.02 0.987 Example 28 (B = Mg + Y) MgO Y ₂ O ₃ 0.08: 0.02 1.274 Example 29 (B = Mg + Ga) MgO Ga ₂ O ₃ 0.08: 0.02 0.928 Example 30 (B = Mg + La) MgO La ₂ O ₃ 0.08: 0.02 1.071 Example 31 (B = Mg + Al) MgO A1 ₂ O ₃ 0.08: 0.02 0.917 Example 32 (B = Mg + Al) MgO AlN 0.02: 0.08 0.675 Example 33 (B = Mg + S) MgO S 0.08: 0.02 0.807 Example 34 (B = Mg + Ge) MgO Ge ₂ O ₃ 0.08: 0.02 0.603 Example 35 (B = Mg + Ti) MgO TiO ₂ 0.08: 0.02 0.574 Example 36 (B = Mg + Zn) MgO ZnO 0.08: 0.02 0.731

As shown in Table 7 above, when A = Sr is fixed and Mg is used as B, but a part of Mg is replaced with another element (B2), the substituted element (B2) The intensity of the luminescence varies depending on the type of. In the phosphor composition according to the present embodiments, when a part of Mg is replaced with Ba, Y or La, that is, when B = Mg + Ba, Mg + Y or Mg + La, Example 8 using only Mg as B (B = Mg) it can be seen that it has a luminescence intensity superior to.

<Thermal Stability Evaluation>

On the other hand, to determine the thermal stability of the phosphor according to an embodiment of the present invention was carried out as follows.

A phosphor according to Example _{1, (Sr 0 .82 Mg 0} .08) Si 2 O 2 N 2 : With respect to the phosphors having a composition of 0.1Eu ^{2 +,} evaluate luminous intensity variation (thermal stability) due to temperature, and are shown in the accompanying Figure 7 the results. Further, as a conventional _{phosphor, (Y) 3 (Al,} Ga) 5 O 12: Ce 3 + YAG -based oxide phosphor of the composition (Comparative Example 11) and (Ca, Sr) S: Eu ^{2 +} sulfide composition (Sulfide For the fluorescent substance (Comparative Example 12), the luminescence intensity change with temperature was evaluated in the same manner. The results are shown together in FIG. 7. In this case, the results shown in FIG. 7 are expressed as relative intensities (relative luminance) based on luminescence intensity measured at 20 ° C. of each phosphor as a reference (intensity = 100).

As shown in FIG. 7, the phosphor according to the embodiment of the present invention was compared with the conventional phosphors (Comparative Example 11 and Comparative Example 12), it was found that the thermal stability is very excellent at a high temperature of 140 ℃ or more. That is, the phosphor according to the embodiment of the present invention was found to have a low luminescence intensity reduction range at a high temperature of 140 ℃ or more.

1 is a graph showing the luminescence and excitation spectrum evaluation results of the phosphor [(Sr _0.82 Mg _0.08 ) Si ₂ O ₂ N ₂ : 0.1Eu ²⁺ ] prepared according to an embodiment of the present invention.

2 is an SEM image of a phosphor prepared according to an embodiment of the present invention ((Sr _0.82 Mg _0.08 ) Si ₂ O ₂ N ₂ : 0.1Eu ²⁺ ].

3 and 4 are graphs showing the results of luminescence evaluation according to the Mg content of the phosphor [(Sr _ab Mg _b ) Si ₂ O ₂ N ₂ : 0.1Eu ²⁺ ] prepared according to the embodiment of the present invention.

5 and 6 show the results of luminescence evaluation according to the Eu content of the phosphor [(Sr _0.8 Mg _0.1 ) Si ₂ O ₂ N ₂ : xEu ²⁺ , 0.04F ⁻ ] prepared according to an embodiment of the present invention. It is a graph.

FIG. 7 is a graph showing luminescence intensity change (thermal stability) according to a temperature of a phosphor [(Sr _0.82 Mg _0.08 ) Si ₂ O ₂ N ₂ : 0.1Eu ²⁺ ] prepared according to an embodiment of the present invention.

Claims (18)

delete delete delete delete An oxynitride phosphor comprising a crystal represented by the following formula. [Chemical Formula] _{(A ab B b) Si c} O d N e: xEu 2+, zX - (In the above formula, A and B are different elements, and A is a + divalent metal except Mg; B comprises at least Mg; X is a halogen group element; a, b, c, d and e are 0.8 ≦ a ≦ 1.0, 0.02 ≦ b ≦ 0.1, 1.5 ≦ c ≦ 2.5, 0 <d ≦ 3.0 and 1.0 ≦ e ≦ 3.0; x and z are 0.08 ≦ x ≦ 0.15 and z is 0.02 ≦ z ≦ 0.12.) The method of claim 5, A in the formula A is an oxynitride phosphor, characterized in that at least one selected from the group consisting of Be, Ca, Sr, Ba, Ra, Zn, Cd, Hg, Pb, Sn and Ge. The method of claim 5, B of the above formula includes at least Mg, Be, Ca, Sr, Ba, Ra, Zn, Cd, Hg, Pb, Sn, Ge, B, Al, Ga, In, Ti, Sc, Y, S, La , Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu oxynitride phosphor further comprises at least one selected from the group consisting of. The method of claim 5, X is a oxynitride phosphor, characterized in that at least one selected from the group consisting of F, Cl and Br. The method of claim 5, The size of the phosphor is an oxynitride phosphor, characterized in that 1 ~ 30㎛. A method of manufacturing the oxynitride phosphor according to claim 5, Precursors of A (A is a bivalent metal except Mg), precursors of B including at least Mg precursors (B is a different element from A), precursors of Si, precursors of N, precursors of Eu, and precursors of X (X A first step of mixing a raw material containing a halogen group element, and controlling the content of each precursor to satisfy the above formula; And The method of manufacturing an oxynitride phosphor comprising the step of firing the raw material into a firing furnace. The method of claim 10, The second step, Heat treatment at a temperature of 800 ° C. to 1300 ° C. in an inert gas atmosphere; And A process for producing an oxynitride phosphor comprising the step b) firing at a temperature of 1000 ℃ to 1500 ℃ in the presence of a firing gas. The method of claim 11, The firing gas of step b) is a method for producing an oxynitride phosphor, characterized in that the H ₂ / N ₂ mixed gas or NH ₃ gas. The method according to any one of claims 10 to 12, The precursor of A is a method for producing an oxynitride phosphor, characterized in that at least one selected from the group consisting of compounds of Be, Ca, Sr, Ba, Ra, Zn, Cd, Hg, Pb, Sn and Ge. The method according to any one of claims 10 to 12, The precursor of B comprises at least Mg compounds, Be, Ca, Sr, Ba, Ra, Zn, Cd, Hg, Pb, Sn, Ge, B, Al, Ga, In, Ti, Sc, Y, S , La, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu made of oxynitride phosphor further comprises at least one selected from the group consisting of compounds Way. The method according to any one of claims 10 to 12, The precursor of X is a method for producing an oxynitride phosphor, characterized in that at least one selected from the group consisting of salts of F, Cl and Br. Excitation light source; And a phosphor comprising: The phosphor comprises a oxynitride phosphor according to any one of claims 5 to 9. The method of claim 16, 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 16, The light emission device of the excitation light source is characterized in that the emission wavelength is 350nm ~ 480nm.

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