KR20090036800A - Red phosphor and white light emitting device including the same - Google Patents

Abstract

A red phospher is provided to show high brightness and excellent chromatic purity by substituting Ca contained as a parent with alkaline earth metal and containing halogen ion or oxygen ion. A red phosphor has a structure represented by any one of the chemical formula 1: (Ca_(1-x)M_x)S:Eu^(2+), the chemical formula 2: CaS:Eu^(2+),Q, and the chemical formula 3: (Ca_(1-x)M_x)S:Eu^(2+),Q. In the chemical formulae, M is one or more alkaline earth metal selected from the group consisting of Be, Mg, Ca, Sr, Ba and Ra; Q is one or more ions selected from the group consisting of F^(-), Cl^(-), O^(2-) and Se^(2-); Q is included in an amount of 0.01-0.05 mole per Ca ion 1 mole; and 0 < x <= 0.4.

Description

Red phosphor and White Light Emitting Device Comprising It

The present invention relates to a red phosphor, a white light emitting device using the same, and a white light emitting device including the same. More specifically, the Ca and S elements are used as a mother and the Eu element is included as an activator. The present invention relates to a phosphor containing halogen ions or oxygen group ions and having excellent brightness and color purity, and a white light emitting device including the same.

Light Emitting Diode (LED) is a futuristic display device that is one of the most recently researched fields due to its application to flat panel displays as well as various instrument panels and TVs. Known. In the electroluminescence, when an electric field is applied to a light emitting material that emits light, electrons injected from the cathode and holes formed in the anode are combined in the light emitting layer to form a so-called "single excition". This single excitons form an excited state and emit a variety of light when it transitions to the ground state. The light emitting device of this principle is a semiconductor device having higher luminous efficiency, lower power consumption, and better thermal safety than the conventional ones, and has excellent characteristics with long life and good response.

Among these LEDs, white LEDs have various applicability and marketability, such as home lighting, liquid crystal display (LCD) panel backlighting, and interior lighting of automobiles.

As a method of implementing white in such a white LED, the blue, green, and red LEDs are turned on at the same time to adjust the brightness of the LED to display a mixed mixed color, and the brightness of the blue and yellow or orange LEDs There is a way to turn on at the same time. Recently, a method using three-color variable mixed color using a phosphor emitting blue, green and red light using an energy source of UV wavelength as a light source or a method of applying a yellow phosphor on a blue LED chip is also used. In this regard, a method of manufacturing a white light emitting device by combining a yttrium-aluminum-garnet ( Y ₃ Al ₅ O ₁₂ ) -based fluorescent material to which trivalent Y ions are added to a light emitting diode in a short wavelength region such as blue or ultraviolet light has been proposed (S Nakamura, The Blue Laser Diode, Springer-Verlag, pp 216-219 (1997). In general, white light-emitting phosphors for white light-emitting diodes that are currently practically used are (Re _{1-r S m r} ) ₃ (Al _1-s Ga _s ) ₅ O ₁₂ : Ce (where 0 ≦ r <1, 0 ≦ s < 1, a YAG-based phosphor represented by Re: Y or Gd), or Tb ₃ (Al, Ga) ₅ O ₁₂ : Ce, in which Tb was added to the phosphor to cause a long wavelength shift, thereby having a positive effect on the red component. There are TAG-based phosphors, but the phosphors have a limited emission color, and thus have a narrow reproduction range of white as a white light emitting diode, and have a strong yellow color in the phosphor itself, thereby absorbing part of blue light emission as white.

Therefore, the development of LEDs that are easy to implement a total natural color is being actively made, in particular, the development of a red phosphor of a white LED is required.

The present invention provides a red phosphor having excellent luminance and purity with Ca and S elements as a mother and an Eu element as an activator, wherein an alkaline earth metal element is substituted with a portion of Ca, and halogen ions or oxygen group ions are included.

In order to solve the above technical problem, in the present invention,

Provided is a red phosphor of any one of the following Formulas 1-3:

<Formula 1>

(Ca _1-x M _x ) S: Eu ²⁺

<Formula 2>

CaS: Eu ^{2 +,} Q

<Formula 3>

(Ca _1-x M _x ) S: Eu ²⁺ , Q

(Where, M is at least one alkaline earth metal selected from the group consisting of Be, Mg, Ca, Sr, Ba and Ra, wherein Q is ^{F -, Cl -, O 2} - and Se ^{2 -,} at least, selected from the group consisting of One ion, wherein Q is included in an amount of 0.01 to 0.05 moles per mole of Ca ions, and Eu ²⁺ is included in an amount of 0.002 to 0.02 moles per mole of Ca ions, and 0 <x ≦ 0.4.

According to an embodiment of the present invention, the red phosphor may be a red phosphor coated with a surface of SiO ₂ .

According to an embodiment of the present invention, the red phosphor may be an phosphor exhibiting an excitation band at 400 to 650 nm and an emission band at 580 to 750 nm.

In still another aspect, the present invention provides a red or white light emitting device including the red phosphor and a light emitting diode emitting light at 450 to 470 nm.

In another aspect, the present invention,

Mixing each one selected from the group consisting of MCl ₂ , MCO ₃ , MO and MF ₂ , CaCO ₃ , S and Eu ₂ O ₃ , where M consists of Be, Mg, Ca, Sr, Ba and Ra At least one alkaline earth metal selected from the group);

First calcining the mixture at 750-950 ° C. for 1-15 hours under H ₂ / N ₂ gas conditions; And

And calcining the first calcined calcined product at 750˜950 ° C. for 1 to 15 hours under H ₂ / N ₂ gas conditions.

It provides a method for producing a red phosphor having the formula (1) or (3).

In another aspect, the present invention,

Mixing any one of AlF ₃ , NH ₄ F and mixtures thereof, CaCO ₃ , S and Eu ₂ O ₃ , respectively;

First calcining the mixture at 750-950 ° C. for 1-15 hours under H ₂ / N ₂ gas conditions; And

And calcining the first calcined calcined product at 750˜950 ° C. for 1 to 15 hours under H ₂ / N ₂ gas conditions.

It provides a method for producing a red phosphor having the formula (2).

According to an embodiment of the present invention, the Eu ₂ O ₃ may include 0.1 to 1.0 mol% with respect to CaCO ₃ .

According to one embodiment of the present invention, any one selected from the group consisting of MCl ₂ , MCO ₃ , MO and MF ₂ may include 0.8 to 8 mol% based on CaCO ₃ .

According to one embodiment of the present invention, any one of the AlF ₃ , NH ₄ F and mixtures thereof may be included in 1 to 5 mol% based on CaCO ₃ .

According to one embodiment of the invention,

The second calcined calcined product may include a third calcined process for 1 to 15 hours at 750 to 950 ° C. under H ₂ / N ₂ gas conditions.

According to an embodiment of the present invention, the method of manufacturing the phosphor

Refluxing the mixed solvent of water and ethanol containing tetraethoxysilane at 80-90 ° C. for 30 minutes to 2 hours;

Hydrolyzing the mixed solution by mixing NH ₄ OH and acetic acid;

Adding the prepared phosphor to the mixed solution and refluxing for 10 minutes to 1 hour; And

After filtering and drying the mixed solution, the method may further include heat treatment at 300 to 500 ° C. for 30 minutes to 2 hours.

As described above, the red phosphor according to the present invention partially replaces Ca as a mother with an alkaline earth metal and contains halogen ions or oxygen group ions, and thus exhibits excellent high brightness and color purity, thereby making it possible to manufacture a white light emitting device using the same. .

Hereinafter, the red phosphor according to the present invention will be described in more detail.

In addition, prior to describing in detail the preferred embodiments of the present invention will be described the terms used in the present invention.

Here, the host refers to the constituent elements constituting the crystals of the phosphor. In the present invention, the host is composed of Ca and S elements. In one aspect of the present invention, an alkaline earth metal such as Be, Mg, Ca, Sr, Ba, and Ra may be used. It is made to include more.

In addition, an activator is an element which is activated without forming a crystal | crystallization and is actually involved in light emission, and becomes Eu <^2+> in this invention. In addition, a co-dopant refers to an element that increases the luminous efficiency by activating the active agent, and in one aspect of the present invention, an anion such as alkaline earth metals such as Be, Mg, Ca, Sr, Ba, and Ra, halogens, and oxygen groups This deactivator becomes.

The phosphor of the present invention is a phosphor containing Ca and S elements as a parent and Eu ²⁺ as an activator, wherein alkaline earth metal elements such as Be, Mg, Ca, Sr, Ba, and Ra are substituted with some of Ca.

Specifically, in the present invention, a phosphor containing Ca and S elements as a parent and Eu ²⁺ as an activator, wherein some of the Ca elements are replaced with alkaline earth metal elements such as Be, Mg, Ca, Sr, Ba, and Ra. To provide, the specific formula is (Ca _1-x M _x ) S: Eu ²⁺ of the formula (1). Here, the europium (Eu ²⁺ ) is contained from 0.002 to 0.02 mol per mol of Ca ions. In addition, M is an alkaline earth metal, and 0 <x≤0.4. M substituted at the Ca element site contributes to increasing the luminescence intensity of the entire phosphor, and when less than 0.01 mol or more than 0.4 mol, it is not preferable because the luminous efficiency is not good.

In addition, in the present invention, a phosphor containing Ca and S elements as a parent and Eu ²⁺ as an activator and containing a halogen ion or an oxygen group ion is provided. The specific chemical formulas include CaS: Eu ²⁺ , Q. Here, the europium (Eu ²⁺ ) is contained from 0.002 to 0.02 mol per mol of Ca ions. Q is a halogen ion such as F ⁻ , Cl ⁻ , or an oxygen group ion such as O ^{2 −} , Se ^{2 −,} and it is preferable that Q is contained in an amount of 0.01 to 0.05 mole per mole of Ca ion to increase luminous efficiency.

Further, in the present invention, Ca and S elements as a parent and Eu ²⁺ as an activator, some of the Ca element is substituted with alkaline earth metal elements such as Be, Mg, Ca, Sr, Ba and Ra, halogen Phosphor containing ions or oxygen group ions, the specific formula is (Ca _1-x M _x ) S: Eu ²⁺ , Q of the formula (3). Here, the europium (Eu ²⁺ ) is contained from 0.002 to 0.02 mol per mol of Ca ions. In addition, M is an alkaline earth metal, and 0 < x &lt; 0.4, which contributes to increasing the luminescence intensity of the entire phosphor and changes the luminescence peak point. In addition, Q is halogen ions such as F ⁻ , Cl ⁻ , or oxygen group ions such as O ^{2 −} , Se ^{2 −,} and it is preferable to include 0.01 to 0.05 mol per mole of Ca ions to increase luminous efficiency.

The phosphor of the present invention absorbs a wavelength of 400 to 650 nm and emits light at 580 to 750 nm, and exhibits desirable luminescence properties as a phosphor used in a white light emitting device or a red light emitting device including a blue light emitting diode. In addition, the phosphor of the present invention has a high luminous efficiency, it is possible to manufacture a white or red light emitting device having high brightness and color purity.

Although not limited thereto, the red phosphor of the present invention can be prepared according to the following method.

Any one selected from the group consisting of MCl ₂ , MCO ₃ , MO and MF ₂ , CaCO ₃ , S and Eu ₂ O ₃ is mixed, preferably 0.001 to 0.4: 1: 1: 1 to 0.001 to 0.01, respectively. Mix in molar ratio (wherein M is at least one alkaline earth metal selected from the group consisting of Be, Mg, Ca, Sr, Ba, and Ra); and mix the mixture at 750-950 ° C. under H ₂ / N ₂ gas conditions. After the first firing for 15 hours, the first fired calcined product is secondary baked at 750 to 950 ° C. for 1 to 15 hours under H ₂ / N ₂ gas to prepare a phosphor.

In another method, any one of AlF ₃ , NH ₄ F and mixtures thereof, CaCO ₃ , S and Eu ₂ O ₃ is mixed, preferably 0.01 to 0.05: 1: 1 to 3: 0.001-0.01, respectively. And the mixture was first calcined at 750 to 950 ° C for 1 to 10 hours under H ₂ / N ₂ gas conditions, and then the first calcined calcined product was calcined at 750 under H ₂ / N ₂ gas conditions. Secondary firing at ˜950 ° C. for 1 to 10 hours to prepare a phosphor.

Also, but not limited to

In the method of manufacturing the red phosphor, the Eu ₂ O ₃ is contained by 0.1 to 1.0% by moles, based on CaCO _3, the MCl _2, MCO _3, any one selected from the group consisting of MO and MF ₂ is a CaCO ₃ It is contained in 0.8 to 8 mol%, and when the AlF ₃ or NH ₄ F is included in 1 to 5 mol% with respect to CaCO ₃ it is possible to manufacture a red phosphor excellent in luminous intensity.

Phosphors may reduce light intensity or damage light emitting devices or devices, such as LEDs, due to physical forces or chemical reactions occurring on the phosphor surface. In order to prevent this, it is preferable to coat the surface of the phosphor. In order to coat the phosphor with SiO ₂ , but is not limited thereto,

Water and ethanol mixed solvent was refluxed at 80 to 90 ° C. for 30 minutes to 2 hours, and the mixture was hydrolyzed by mixing TEOS (tetraethyl orthosilicate), NH ₄ OH and acetic acid, and then preparing the mixed solution. The phosphor was added and refluxed for 10 minutes to 1 hour, and then the mixed solution was filtered and dried, and then coated by heat treatment at 300 to 500 ° C. for 30 minutes to 2 hours. Through this step, a SiO ₂ coating may be formed on the surface of the phosphor to improve safety and durability.

The solvent is applicable to alcohol, such as ethanol, isopropanol.

In the present invention, the tetraethyl orthosilicate (TEOS) or sodium silicate is applicable.

In the above production method, the reflux, filtering or heat treatment method may be performed by methods conventionally performed in the art.

In the method of manufacturing the above-described phosphor, and the method of manufacturing the phosphor further comprising the step of coating the surface with SiO ₂ , it is possible to omit or add some of the manufacturing steps within a conventional range in the art.

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In the following description of the present invention, if it is determined that the detailed description of the related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.

Hereinafter, the present invention will be illustrated by the following examples, but the protection scope of the present invention is not limited only to the following examples.

Example 1 BaCl ₂ Preparation of Red Phosphor of the Present Invention

(1) Fluorescence intensity of red phosphor according to the concentration of Eu ²⁺

Of the ion density 0.60g CaCO _3, BaCl ₂ After mixing of the S and CaCO ₃ 2.4%, compared to moles of 0.34g, Eu ₂ O ₃ with a Ca ion 1 mole contrast Eu ²⁺ ion concentration of 0.2 to 2.0 moles of Mix with varying percent. Grind the mixture well with a mortar and pestle, place it in an alumina crucible, close the lid, and then H ₂ / N ₂ gas for 15 hours at 800 ° C (3 ° C / min) in a tube furnace. Primary firing was carried out at 35 mL / min. Thereafter, secondary phosphorous firing was performed at 800 ° C. (3 ° C./min) for 10 hours at 35 mL / min in H ₂ / N ₂ gas to prepare a phosphor according to the present invention.

Figure 1 is a graph showing the emission spectrum according to the concentration of Eu ²⁺ of the red phosphor prepared by the above method. As shown in FIG. 1, when 0.5 mol% of Eu ²⁺ ions were added to Ca ions, the strongest intensity was measured. In this case, the emission peak was 650 nm, and the spectral region was a red region of 580 to 750 nm.

FIG. 2 shows an excitation spectrum for 650 nm of a red phosphor having Eu ²⁺ added 0.5 mol%. The excitation spectrum is in the 400 to 650 nm range, with the sharp lines being the scattered light of the used Xe lamp.

(2) Fluorescence intensity of red phosphor according to the amount of BaCl ₂ added

The amount of Eu ₂ O ₃ added was fixed to 0.5 mol% as described above, to prepare a red phosphor in the composition ratio shown in Table 1 below. BaCl ₂ was calcined at 1, 2, 3, 5, 7, 10 wt% compared to CaCO ₃ (900 ℃ (3 ℃ / min) for 10 hours H ₂ / N ₂ gas 35cc / min), and then again Firing (800 ° C. (3 ° C./min) 15 hours H ₂ / N ₂ gas 35 cc / min) was performed.

TABLE 1

CaCO ₃ S Eu ₂ O ₃ BaCl ₂ wt% (mol%) A   0.8007 g   0.5130 g   0.5mol% 1 (0.8) B 2 (1.6) C 3 (2.4) D 5 (4.0) E 7 (5.6) F 10 (8)

Figure 3 shows the emission spectrum of the prepared red phosphor, emitted by 468 nm excitation light. The peak point was 649.7 nm, and the intensity varied greatly depending on the amount of BaCl ₂ added. As shown in FIG. 3, the highest luminescence intensity was shown when 4.0 mol% of Ba ²⁺ ions were added to Ca ²⁺ , which is increased by more than 50% compared to the case where BaCl ₂ was not added.

Example 2 Preparation of Red Phosphor of the Invention Containing F Ions

(1) F ion is to investigate the effect on the light emission of the phosphor, NH ₄ F was added to and / or AlF ₃ and CaS contained in the formula (2) is a halogen ion: Eu ^{2 +,} Q A phosphor was prepared. The composition ratio was mixed as shown in Table 2 below, and the first and second firings were similar to those of Example 1, but the first firing was performed at (900 ° C. (3 ° C./min) for 2 hours H ₂ / N ₂ gas 35 cc / min). ), And then calcined again (900 ° C. (3 ° C./min) for 2 hours H ₂ / N ₂ gas 35 cc / min).

TABLE 2

CaCO ₃ S Eu ₂ O ₃ NH ₄ F AlF3 G 1 mole Overdose 0.5 mol% 3 mol% - H - 3 mol% I 5 mol% - J - 5 mol% K 1.5 mol% 1.5 mol% L 2.5 mol% 2.5 mol%

Figure 4 shows the emission spectrum of the addition of F ^- ions of the red phosphor prepared according to the above method. The strongest luminescence intensity is shown when 3 mol% NH ₄ F is added to CaCO ₃ .

(2) A red phosphor was prepared such that O ^{2 −} ions were present by adjusting the firing frequency under the composition conditions of Sample G of Table 2. XRD spectra were measured to monitor the measured intensities at the strongest 2θ = 31.38 ° representing the CaS structure and at the strongest 2θ = 37.36 ° representing the CaO structure.

5 is a graph showing the effect of the amount of O ^{2 −} ions on the luminescence intensity, the x-axis shows I (2θ = 37.36 °) / I (2θ = 31.38 °). As shown in FIG. 5, the intensity of luminescence intensity increases as the amount of O ^2- ion decreases according to the firing conditions such as increasing the flow rate of the reducing gas or increasing the firing frequency. The maximum intensity luminescence was emitted at 30% relative to the XRD peak. However, O ² in the following ^- the concentrations started to decrease again, the luminescence. This shows that the intensity of luminescence is stronger when O ² ions are present in the degree of dopant.

Further, the ion concentration of CaCO _3, and S of CaCO ₃ 0.60g 0.34g of preparation after mixing BaCl ₂ 2.4% by mol, Eu ₂ O ₃ 0.5 to a concentration of Eu ²⁺ ions than Ca ion one mole of using molar Mix with varying percent. Grind the mixture well with a mortar and pestle, place it in an alumina crucible, close the lid, and then H ₂ / N ₂ gas for 15 hours at 800 ° C (3 ° C / min) in a tube furnace. Primary firing was carried out at 35 mL / min. Thereafter, secondary phosphorous firing was performed at 800 ° C. (3 ° C./min) for 10 hours at 35 mL / min in H ₂ / N ₂ gas to prepare a phosphor according to the present invention. In addition, a graph comparing the emission spectrum of the phosphors prepared in the same phosphor as above, or phosphors when oxygen ions do not exist according to the firing conditions as described above is shown in FIG. 6. Accordingly, it was found to have low luminescence when no oxygen ions were present.

Example 3 SiO of Red Phosphor ₂ Furnace coating

The surfaces of the red phosphors prepared in Examples 1 and 2 were coated with SiO ₂ . Experimental conditions are as shown in Table 3 below. The precursor was tetraethyl orthosilicate (TEOS), sample M was coated with 5% TEOS, and sample N was coated with 3%. When TEOS starts to undergo hydrolysis reaction, a sample is added and condensation reaction is performed. First, the solvent mixed with water and ethanol is refluxed for 1 hour in an 80 ° C. silicon oil bath, and then the mixed solution. TEOS, NH ₄ OH, and acetic acid were mixed and hydrolyzed, and the sample was put therein and refluxed again for 30 minutes. The sample was filtered and dried in an electric oven, and the dried sample was heat treated at 400 ° C. for 1 hour. The SEM photograph of the sample coated in this way was measured.

TABLE 3

Sample menstruum TEOS NH ₄ OH Acetic acid M 2.0060 g 6 mL 5% 240 μL pH 10 N 2.0770 g 6 mL 3% 240 μL

7 is a SEM photograph of the red phosphor before and after coating with SiO ₂ , wherein (a) and (b) are 3000x and 40000x magnification before coating, and (c) and (d) are 3000x and 40000x after coating, respectively. It is enlarged. As shown in (a) and (b), it can be seen that ice lands of SiO ₂ are formed on the surface and are not smooth after the coating, as compared with the surface of the phosphor before the coating.

Example 4 SiO ₂  Fabrication of Light Emitting Diode Using Coated Red Phosphor and Its Light Emission Spectrum

A white light emitting diode was manufactured using the red phosphor coated with SiO ₂ of Example 3.

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 μm was formed in order to prepare a blue light LED. Subsequently, a red phosphor prepared on the surface of the blue light LED was dispersed in an epoxy to prepare a white light emitting device.

The emission spectrum of the manufactured white light emitting diode is shown in FIG. 8. The light emitting diode coated with the red phosphor according to the present invention shows a blue luminescence band having a peak point at 452 nm corresponding to a light emitting band of a GaN blue LED and a main emission peak in the range of 600 to 740 nm emitted from a red phosphor. , The color coordinates were (0.30, 0.11).

Although the above has been described with reference to a preferred embodiment of the present invention, those skilled in the art to which the present invention pertains without departing from the spirit and scope of the present invention as set forth in the claims below It will be appreciated that modifications and variations can be made.

1 is a light emission spectrum (λ _ems = 470 nm) (1: 0.25 mol%; 2: 0.5 mol%; 3: 0.75 mol%; 4: according to the Eu ²⁺ concentration of the red phosphor prepared in Example 1 of the present invention) 1.0 mol% and 5: 2.0 mol%);

FIG. 2 is an excitation spectrum of 650 nm of a red phosphor added with 0.5 mol% of Eu ²⁺ in Example 1 of the present invention; FIG.

Figure 3 is the first embodiment the light emission spectrum of the BaCl ₂ addition amount of the red phosphor manufactured by (λ _exn = 470nm) (A of the present invention: 0.8 mol%; B: 1.6 mol%; C: 2.4% by mol; D: 4.0 Mole%, E: 5.6 mole%, and F: 8 mole%);

4 is an emission spectrum of the red phosphor prepared in Example 2 of the present invention (λ _exn = 470 nm)

5 is a graph showing the luminescence intensity according to the influence of O ^2- ions with different firing times for the red phosphor of the present invention;

6 is a luminescence spectrum (a solid line shows the intensity of with and without the red phosphor containing the the O ^2- ions in the invention if the O ^2- ions contained; broken line: O ^2- ions are not contained If not);

7 is a SEM image of the SiO ₂ coated red phosphor according to the present invention ((a) and (b): 3000 times and 40000 times magnification before coating, (c) and (d): 3000 times and 40000 times magnification after coating One picture); And

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

Claims (11)

Red phosphor represented by any one of the following formula 1 to 3: <Formula 1> (Ca _1-x M _x ) S: Eu ²⁺ <Formula 2> CaS: Eu ²⁺ , Q <Formula 3> (Ca _1-x M _x ) S: Eu ²⁺ , Q (Wherein, M represents Be, Mg, Ca, Sr, and at least one alkaline earth metal selected from the group consisting of Ba and Ra, Q is ^{F -, Cl -, O 2} - and Se ^{2 -,} at least one selected from the group consisting of and the ions, and the Eu ^{2 +} Im is the Ca ion, 0.002 to 0.02 mol per mol of contained, and said Q comprises said Ca ion per mole of 0.01 to 0.05 mol, 0 <x ≤ 0.4). The method of claim 1, The red phosphor is the surface is coated with SiO ₂ red phosphor. The method of claim 1, The red phosphor exhibits an excitation band at 400 to 650 nm and a light emitting band at 580 to 750 nm.  A red or white light emitting device comprising the red phosphor of claim 1 and a light emitting diode emitting light at 450 to 470 nm. Mixing any one selected from the group consisting of MCl ₂ , MCO ₃ , MO and MF ₂ , CaCO ₃ , S and Eu ₂ O ₃ , where M is Be, Mg, Ca, Sr, Ba and Ra At least one alkaline earth metal selected from; First calcining the mixture at 750-950 ° C. for 1-15 hours under H ₂ / N ₂ gas conditions; And And calcining the first calcined calcined product at 750˜950 ° C. for 1 to 15 hours under H ₂ / N ₂ gas conditions. Method for producing a red phosphor having the formula (1) or (3). Mixing any one of AlF ₃ , NH ₄ F and mixtures thereof, CaCO ₃ , S and Eu ₂ O ₃ ; First calcining the mixture at 750-950 ° C. for 1-15 hours under H ₂ / N ₂ gas conditions; And And calcining the first calcined calcined product at 750˜950 ° C. for 1 to 15 hours under H ₂ / N ₂ gas conditions. Method for producing a red phosphor having the formula (2). The method according to claim 5 or 6, Eu ₂ O ₃ is a method of producing a red phosphor containing 0.1 to 1.0 mol% based on CaCO ₃ . The method of claim 5, MCl ₂ , MCO ₃ , MO and MF ₂ any one selected from the group consisting of 0.8 to 8 mol% of the CaCO ₃ method for producing a red phosphor. The method of claim 6, Any one of the AlF ₃ , NH ₄ F and mixtures thereof are produced in 1 to 5 mol% based on CaCO ₃ red phosphor. The method according to claim 5 or 6, And calcining the secondary calcined product for 3 hours at 750 to 950 ° C. for 1 to 15 hours under H ₂ / N ₂ gas conditions. The method according to claim 5 or 6, Refluxing the solvent mixed with water and ethanol at 80-90 ° C. for 30 minutes to 2 hours; Hydrolyzing TEOS, NH ₄ OH, and acetic acid in the mixed solution; Adding the prepared phosphor to the mixed solution and refluxing for 10 minutes to 1 hour; And After filtering and drying the mixed solution, the method of manufacturing a phosphor further comprising the step of heat treatment for 30 minutes to 2 hours at 300 ~ 500 ℃.

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