KR20070041838A - Luminescent material for emitting white light, preparation method thereof, and white light emitting diode using the material - Google Patents

Abstract

The present invention relates to a phosphor, a method for manufacturing the same, and a white light emitting device using the same. More specifically, in a phosphor capable of absorbing light in a region between near ultraviolet light and blue light, various emission colors of blue, green, and red can be implemented. ^{_{α B β C γ: wEu 2}} +, xMn 2+, yM, to a method of manufacturing the phosphor, which is represented by the formula of zN and white light emitting device using the same. The present invention is applied to the wavelength conversion of the light emitting device chip excellent in luminescence brightness and color rendering properties, the color temperature adjustable phosphor and its manufacturing method and a white light emitting device that can be applied to the white light source for LCD and home white lighting using the same To provide.

Phosphor for wavelength conversion, GaN series LED, white light emitting device

Description

Phosphor, Manufacturing Method thereof, and White Light Emitting Device Using the Same {LUMINESCENT MATERIAL FOR EMITTING WHITE LIGHT, PREPARATION METHOD THEREOF, AND WHITE LIGHT EMITTING DIODE USING THE MATERIAL}

1 is a phosphor Sr _0.965 Ba _0.965 SiO ₄ : 0.05Eu ²⁺ , according to the present invention; Graph showing relative emission spectrum for 0.01 Ce ³⁺ , 0.01Li ⁺

2 is a graph showing relative emission spectra for phosphors Ba _1.94 Si _0.99 O ₄ : 0.05Mn ²⁺ , 0.01Ce ³⁺ , 0.01Al ³⁺ according to the present invention;

3 is a graph showing relative emission spectra for phosphors Ca _0.88 MgSi ₂ O ₆ : 0.05Eu ²⁺ , 0.05Mn ²⁺ , 0.01Ce ³⁺ , 0.01Li ⁺ according to the present invention ^;

4 is a phosphor Ca _0.88 MgSi _1.95 Ge _0.05 O ₆ : 0.05Eu ²⁺ , 0.05Mn ²⁺ , according to the present invention. Graph showing relative emission spectrum for 0.01 Ce ³⁺ , 0.01Li ⁺

5 is a phosphor Ca _0.93 Si (O, S) ₃ : xMn ²⁺ according to the present invention; Graph showing relative emission spectra for yCe ³⁺ , zLi ⁺

6 is an ultraviolet LED and Ca _0.88 MgSi _1.95 Ge _0.05 O ₆ : 0.05Eu ²⁺ , 0.05Mn ²⁺ , according to the present invention. Structural Diagram of White Light Emitting Device with 0.01Ce ³⁺ , 0.01Li ⁺ Phosphor

<Explanation of symbols for main parts of drawing>

1: phosphor 2: epoxy

3: LED chip

The present invention relates to a phosphor, a method of manufacturing the same, and a white light emitting device using the same. More particularly, the present invention relates to a phosphor capable of absorbing light in a region between blue light and near-ultraviolet light to implement various emission colors of blue, green, and red. _{a α B β C γ: wEu} 2+, xMn 2 +, yM, zN ( satisfies the above formula, 2α + 4β-2γ = 0 , and a is composed of Ca, Sr, Ba, Mg, zn and Be At least one element selected from the group, B is mainly Si And at least one element selected from Ge, C is at least one element selected from the group consisting of O, S and Se, M is Ce ³⁺ , Pr ³⁺ , Sm ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Er ³⁺ , Tm ³⁺ and Yb ³⁺ are at least one cation selected from the group consisting of N ⁺ Li ⁺ , Na ⁺ , K ⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ and The present invention relates to a phosphor represented by the chemical formula of one or more cations selected from the group consisting of Y ³⁺ , a method of manufacturing the same, and a white light emitting device using the same.

A light emitting diode (LED), which is one of light emitting devices, occurs when carriers injected into the active layer recombine, and the light emission wavelength is determined in a band gap of the active layer. In order to realize a desired mixed color using the LED, 1) a method of controlling the light output of each light emitting device by combining a plurality of LEDs having different colors and then adjusting each current, and 2) using the light emitted from the LED There is a method in which the phosphor absorbs, converts the wavelength, and emits light. Whereas the method of 1) is not only complicated in configuration but also difficult to control the light output, the method of 2) uses only one LED and can realize a desired mixed color through selection and combination of appropriate phosphor materials. Advantageous in that respect, the present invention relates to the method of 2).

GaN-based materials (GaN, InN, AlN, and combinations thereof) have the possibility of obtaining most wavelengths in the visible range from ultraviolet light because the bandgap energy is adjustable from 1.9 eV to 6.2 eV. . In addition, GaN (gallium nitride) -based LED is a semiconductor light emitting device having high luminous efficiency, low power consumption and good thermal stability compared to conventional light sources. A white light emitting device combining YAG (Y ₃ Al ₅ O ₁₂ ) -based phosphors with GaN-based LEDs has been developed.

However, since the combination of the blue light emitted from the LED chip and the yellow light emitted from the phosphor is very sensitive to the method of applying the phosphor and the operating conditions of the LED chip, the conventional YAG-based white light emitting device has many difficulties in reproducing the same white color. . In addition, the blue light emitted from the LED chip changes in luminance according to the ambient temperature, which has a problem of lowering the color stability of the device.

In addition, although the conventional YAG-based phosphor has the advantage of very high chemical stability, the high temperature of 1600 ℃ or more is required when manufacturing the solid state of the manufacturing process, which is a factor of the cost increase, the white made of the YAG-based phosphor The light emitting device has a drawback of low color rendering due to lack of light emission in the green and red regions. In addition, although a technique for replacing Y with Gd or Al with Ga for color control of the conventional YAG-based phosphor has been proposed, there is a difficulty in color control. In addition, the YAG phosphor has a drawback in that it emits cold white due to a lack of light emission in the green region and low color rendering and high color temperature in which light emission in the red region is insufficient and blue light is predominant. .

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

Accordingly, the technical problem to be achieved by the present invention is to provide a novel phosphor and a method of manufacturing the same, which can provide white light having excellent emission luminance and color rendering ability and color temperature control capable of overcoming the above problems.

In order to achieve the above technical problem, the present invention satisfies the formula of A _α B _β C _γ : wEu ²⁺ , xMn ²⁺ , yM, zN (wherein 2α + 4β-2γ = 0 in the above formula, A Is at least one element selected from the group consisting of Ca, Sr, Ba, Mg, Zn and Be, B is Si And at least one element selected from Ge; C is at least one element selected from the group consisting of O, S and Se; M is at least one cation selected from the group consisting of Ce ³⁺ , Pr ³⁺ , Sm ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Er ³⁺ , Tm ³⁺ and Yb ³⁺ ego,; N is Li ⁺ , Na ⁺ , K ⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ and At least one cation selected from the group consisting of Y ³⁺ ; The w, x, y and z are each independently 0≤w≤0.10, 0≤x≤0.10, 0≤y≤0.10 and 0≤z≤0.10, but expressed as 0.01≤w + x≤0.18) Provide a phosphor.

In addition, the present invention provides a phosphor characterized in that y and z are y = z, 0.01≤y + z≤0.18.

Another aspect of the invention _{A α B β C γ: wEu} 2 +, xMn 2 +, yM, in the manufacture of a phosphor represented by the formula of zN, ⅰ) A, B, C, Eu, Mn, M and For oxides or carbides containing N elements, w, x, y and z each independently satisfy 0≤w≤0.10, 0≤x≤0.10, 0≤y≤0.10 and 0≤z≤0.10, but 0.01≤ mixing at a predetermined molar ratio satisfying w + x ≦ 0.18, wherein A is at least one element selected from the group consisting of Ca, Sr, Ba, Mg, Zn, and Be; B is Si And at least one element selected from Ge; C is at least one element selected from the group consisting of O, S and Se; M is at least one cation selected from the group consisting of Ce ³⁺ , Pr ³⁺ , Sm ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Er ³⁺ , Tm ³⁺ and Yb ³⁺ ego,; N is Li ⁺ , Na ⁺ , K ⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ and At least one cation selected from the group consisting of Y ³⁺ ; Ii) subjecting the mixture to a first heat treatment for 1 to 5 hours in an inert gas atmosphere at a temperature in the range of 700 to 1350 ° C., followed by optionally cooling and pulverizing; Iii) subjecting the mixture to a second heat treatment for 1 to 5 hours at a temperature ranging from 1100 to 1450 ° C. under reducing atmosphere; Iii) providing a phosphor manufacturing method comprising the step of cooling, pulverizing, washing and sorting by the particle size of the heat-treated phosphor.

The present invention also provides a method for producing a phosphor, characterized in that the inert gas is at least one selected from the group consisting of He, Ne, Ar and nitrogen.

In addition, the present invention provides a method for producing a phosphor, characterized in that further adding at least one selected from the group consisting of LiF, NH ₄ Cl, B ₂ O ₃ and NaCl as a flux in the raw material mixing step of step (iii).

In addition, the present invention provides a white light emitting device manufactured using the phosphor.

Hereinafter, the present invention will be described in more detail.

The phosphor of the present invention is represented by the chemical formula of A _α B _β C _γ : wEu ²⁺ , xMn ²⁺ , yM, zN.

In the above formula, A is at least one element selected from the group consisting of Ca, Sr, Ba, Mg, Zn and Be.

B is Si and / or Ge. Ge is substituted at Si site as an activator, and has a larger atomic radius than Si and shows low electronegativity. Thus, the covalent bond of the fluorescent matrix is improved and the electrical conductivity is improved, so that the luminescence brightness due to the electron transition of the activators Eu and Mn is improved. Improve thermal properties.

C is at least one element selected from the group consisting of O, S and Se. As the activator, S or Se is substituted at the O site, and has an atomic radius greater than O and shows a low electronegativity, thereby improving the covalent bond of the fluorescent matrix and the electric conductivity, thereby emitting light due to the electron transition of the activators Eu and Mn. Improve brightness and thermal characteristics.

M is M is Ce ³⁺ , Pr ³⁺ , Sm ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Er ³⁺ , Tm ³⁺ and Yb ³⁺ The above is cation. Here, M ³⁺ absorbs near ultraviolet rays as an activator and emits light in blue, and light emission of the subsidiary agent M ³⁺ is absorbed by the active agents Eu and Mn, and consequently serves to improve the emission of Eu and Mn. In addition, M ³⁺ is substituted for A ²⁺ or B ²⁺ , resulting in charge imbalance and generation of impurities. In order to compensate for these charges, an additional element of N ⁺ or N ³⁺ is added to remove impurities due to charge imbalance, thereby improving light emission luminance.

N is Li ⁺ , Na ⁺ , K ⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ and At least one cation selected from the group consisting of Y ³⁺ . As mentioned above, N serves to eliminate charge imbalance due to the substitution of M. Preferably, the N is preferably added in the same molar ratio as M.

In the formulas representing the phosphor of the present invention, w, x, y and z each independently satisfy 0 ≦ w ≦ 0.10, 0 ≦ x ≦ 0.10, 0 ≦ y ≦ 0.10 and 0 ≦ z ≦ 0.10. The w, x, y, and z values represent the molar ratios of Eu ²⁺ , Mn ²⁺ , M, and N, respectively, and when the upper limit is exceeded, the luminance of emission due to the concentration quenching phenomenon rapidly decreases.

In addition, in the formula, w and x are preferably 0.01 ≦ w + x ≦ 0.18. The w + x value is a measure of the energy transfer degree in which part of Eu's emission excites Mn. When this value is less than 0.01, the energy transfer degree of Eu and Mn is too weak, and the luminance of Mn is lowered. If it exceeds, the degree of energy transfer of Eu and Mn is too strong and the emission luminance of Eu is lowered.

In the above formula, y and z are preferably 0.01 ≦ y + z ≦ 0.18, and more preferably, y and z have the same value.

The phosphor manufacturing method of the present invention includes the step of mixing oxides or carbides containing A, B, C, Eu, Mn, M and N elements in a predetermined molar ratio. Descriptions of the A, B, C, Eu, Mn, M and N are as described above. The phosphor manufacturing method of the present invention may further add flux in the mixing step. Flux is generally added for the purpose of interfering with contact with the atmosphere, because when metal or alloy is dissolved in metallurgy, the dissolved metal surface directly contacts with the atmosphere, it is oxidized or absorbs hydrogen by reacting with moisture in the atmosphere. Salt. The flux used in the phosphor manufacturing method of the present invention is not particularly limited, but may be washed with water after melting at a relatively low temperature and forming a final phosphor, and is characterized in that the material is not particularly reactive with the phosphor material. In particular, the pre-melted flux material plays a role of lowering the synthesis temperature and enhancing the particle size of the phosphor, and improves crystallinity because of the role of assisting chemical bonding between the raw materials by improving the flowability of the raw materials. The flux usable in the phosphor manufacturing method of the present invention is preferably at least one selected from the group consisting of LiF, NH ₄ Cl, B ₂ O ₃ and NaCl, but is not limited thereto.

After the mixing step, the phosphor manufacturing method according to the present invention undergoes a first heat treatment for 1 to 5 hours at a temperature range of 700 to 1350 ℃ in an inert gas atmosphere, and then optionally cooled and pulverized. The primary heat treatment is performed under an inert gas to improve the crystallinity of the phosphor and at the same time to produce a desired size and shape. After the first heat treatment, the mixture is subjected to a second heat treatment step, or optionally cooled and pulverized. The cooling and pulverization may be carried out using a general method, for example, using a pulverizer such as ultrasonic pulverization, ball milling or crusher after slow cooling to room temperature.

After the first heat treatment, the phosphor manufacturing method of the present invention includes a heat treatment step of the second heat treatment for 1 to 5 hours in a temperature range of 1100 to 1450 ℃ in a reducing atmosphere. The secondary heat treatment aims to reduce the Eu2 + or Mn2 +, which is an element emitting light such as Eu3 + or Mn3 +, which is a non-luminescent element under a reducing atmosphere.

After performing the second heat treatment, the phosphor manufacturing method of the present invention includes the step of cooling, pulverizing, washing and sorting by the particle size of the heat-treated phosphor. The pulverization may be carried out using a known pulverization method, for example, ultrasonic waves and the like, but is not particularly limited. After the pulverization may be further subjected to the process of separating by size of the particles. The separation process may also separate particles by 5 μm to 10 μm using a known method, for example, a centrifuge.

Hereinafter, the present invention will be described in more detail with reference to examples which are preferred embodiments of the present invention. However, the following examples are merely to help the understanding of the present invention, the scope of the present invention is not limited only to the following examples.

Example 1 Sr _0.965 Ba _0.965 SiO ₄ : 0.05Eu ²⁺ , 0.01Ce ³⁺ , 0.01Li ⁺

(A = Sr, Ba; B = Si; C = O; M = Ce 3 +, N = Li +; α = 2; β = 1; γ = 4; w = 0.05; y = 0.01; x = 0.01)

First, SrCO ₃ , BaCO ₃ , SiO ₂ , Eu ₂ O ₃ , CeO ₂ and LiF were uniformly mixed and ground in a molar ratio of 0.965: 0.965: 1: 0.025: 0.01: 0.01. The pulverized mixture was placed in a container sealed with nitrogen gas, and heated at a temperature of 1,100 ° C. for 4 hours, followed by primary heat treatment. After the first heat treatment, the resultant was cooled and pulverized, and then a second heat treatment was performed for 1 hour at a temperature of 1,200 ° C. in a reducing atmosphere of H ₂ / N ₂ (5:95). After the secondary heat treatment, the obtained phosphor powder was placed in an ultrasonic container and ground by exposure to ultrasonic waves for 2 hours. The pulverized phosphor separated particles by 5 μm to 10 μm using a centrifuge.

1 is a relative emission spectrum of the phosphors SrBaSiO ₄ : wEu ²⁺ , yCe ³⁺ , zLi ⁺ of Example 1. FIG. As shown in Figure 1, one embodiment of the phosphor of the present invention, SrSiO ⁴ : wEu ²⁺ , yCe ³⁺ , zLi ⁺ (Yellow) and BaSiO ₄ : wEu ²⁺ , yCe ³⁺ , zLi ⁺ (Green) Yellow-Green is used because of the coexistence of. Here, Ce absorbs near ultraviolet rays as an activator and emits light in blue, and blue emission of Ce is absorbed in Eu, and consequently, serves to improve yellow emission of Eu. Ce ³⁺ is also substituted with Sr ²⁺ or Ba ²⁺ or Si ⁴⁺ , leading to charge imbalance and generating impurities. In order to compensate for this charge, an additional element of Li ⁺ is added to remove impurities due to charge imbalance, thereby improving luminescence brightness.

Example 2: Ba _1.94 Si _0.99 O ₄ : 0.05Mn ²⁺ , 0.01Ce ³⁺ , 0.01Al ³⁺

(A = Ba; B = Si ; C = O; M = Ce 3 +, N = Al 3 +; α = 2; β = 1; γ = 4; y = 0.01;; x = 0.05 x = 0.01)

A phosphor was prepared in the same manner as in Example 1, except that a compound including BaCO ₃ , SiO ₂ , MnCO _3, CeO ₂ , and Al ₂ O ₃ was used in a molar ratio of 1.94: 0.99: 0.05: 0.01: 0.005. It was.

FIG. 2 is a relative emission spectrum of the phosphor Ba ₂ SiO ₄ : xMn ²⁺ , yCe ³⁺ , zAl ³⁺ of Example ² , and exhibits strong absorption at around 600 nm depending on the composition ratio of the element, and has a reddish orange color ( Orange-red).

Here, Ce absorbs near ultraviolet rays as an activator and emits light in blue, and blue emission of Ce is absorbed in Eu, and consequently, serves to improve yellow emission of Eu. Ce ³⁺ is also substituted by Ba ²⁺ , leading to charge imbalance and generation of impurities. In order to compensate for this charge, an additional element of Al ³⁺ is added to the Si ⁴⁺ site to remove impurities due to charge imbalance, thereby improving luminescence brightness.

Example 3 Ca _0.88 MgSi ₂ O ₆ : 0.05Eu ²⁺ , 0.05Mn ²⁺ , 0.01Ce ³⁺ , 0.01Li ⁺

(A = Ca, Mg; B = Si; C = O; M = Ce 3 +, N = Li +; α = 2; β = 2; γ = 6; w = 0.05; x = 0.05; y = 0.01; z = 0.01)

CaCO ₃ , MgO, SiO ₂ , Eu ₂ O _3, MnCO ₃ , A phosphor was prepared in the same manner as in Example 1, except that CeO ₂ and LiF were used in a composition having a molar ratio of 0.88: 1: 2: 0.025: 0.05: 0.01: 0.01.

3 is a relative emission spectrum of the phosphor CaMgSi ₂ O ₆ : wEu ²⁺ , xMn ²⁺ , yCe ³⁺ , zLi ⁺ of Example ³ , depending on the composition ratio of the element, blue from 430 nm to 480 nm, 560 nm To 600 nm green and 660 nm to 700 nm red, as a whole reddish-white (Reddish-White). While the color temperature of a conventional white light emitting device of YAG series is 7000 kelvin or more, which is cold white, the light emitting device of the present invention exhibits a warm white of about 4000 kelvin.

Example 4: Ca _0.88 MgSi _1.95 Ge _0.05 O ₆ : 0.05Eu ²⁺ , 0.05Mn ²⁺ , 0.01Ce ³⁺ , 0.01Li ⁺

(A = Ca, Mg; B = Si, Ge; C = O; M = Ce 3 +, N = Li +; α = 2; β = 2; γ = 6; w = 0.05; x = 0.05; y = 0.01; z = 0.01)

As a raw material, CaCO ₃ , MgCO 3, SiO 2, GeO ₂ , Eu ₂ O _3, MnCO _3, CeO ₂ , LiF were used, and the composition which consists of a molar ratio of 0.88: 1: 1.95: 10.050.0250.00.010.010.01 uses the flux A phosphor was prepared in the same manner as in Example 1 except that NH ₄ Cl was further mixed as a (Flux) material by 2 wt% based on the total weight of the entire composition, and the first heat treatment temperature was performed at 1,000 ° C. The flux is early melted to improve the fluidity of the raw material, thereby lowering the synthesis temperature due to the role of assisting chemical bonding between the raw materials.

4 is phosphor CaMg (Si, Ge) ₂ O ₆ of Example 4: wEu ²⁺ , xMn ²⁺ , Relative emission spectra for yCe ³⁺ , zLi ⁺ , depending on the composition of the element, blue for 430 nm to 480 nm, green for 560 nm to 600 nm, and red for 660 nm to 700 nm, and overall red It can be seen that the color represents reddish-white. Compared with Example 3, it can be found that the relative emission intensity decreases with the addition of Ge.

Example 5: Ca _0.93 Si (O, S) ₃ : xMn ²⁺ , yCe ³⁺ , zLi ⁺

(A = Ca; B = Si ; C = O, S; M = Ce 3 +, N = Li +; α = 1; β = 1; γ = 3; x = 0.05; y = 0.01; z = 0.01)

A phosphor was prepared in the same manner as in Example 1, except that CaCO ₃ , SiO 2, MnCO _3, CeO ₂ , and LiF were used in a molar ratio of 0.93: 1: 10.05: 10.01. 5 is phosphor CaSi (O, S) ₃ of Example 5: xMn ²⁺ , It was found that the relative emission spectrum of yCe ³⁺ and zLi ⁺ , and orange color appeared around 580 nm depending on the composition ratio of the element.

Example 6: UV LEDs and Ca _0.88 MgSi _1.95 Ge _0.05 O ₆ : 0.05Eu ²⁺ , 0.05Mn ²⁺ , 0.01Ce ³⁺ , 0.01Li ⁺ White light emitting device

The phosphor Ca _0.88 MgSi _1.95 Ge _0.05 O ₆ : 0.05Eu ²⁺ , 0.05Mn ²⁺ , according to Example 4, was placed on the surface of a commercially available near-infrared InGaN-based LED chip. 0.01Ce ³⁺ and 0.01Li ⁺ were evenly mixed and applied in a silicone resin to prepare a white light emitting device according to the present invention. At this time, the phosphor was 25% by weight based on the silicone resin. 6 is a cross-sectional view showing an embodiment of a white light emitting device according to the present invention.

As described above, since the silicate phosphor according to the present invention has a single phase, it is chemically stable and excellent in reproducibility, and it is possible to provide a high brightness phosphor by primary and secondary heat treatment, and to change the composition ratio of the mother to the phosphor. Since the phosphor is used for wavelength conversion of the light emitting device chip, it is excellent in luminescence brightness and color rendering and emits white color which can be controlled in color temperature, thereby providing more natural natural color. There is an effect that can be applied to white lighting with the required high color rendering.

The embodiments of the present invention described above should not be construed as limiting the technical idea of the present invention. The protection scope of the present invention is limited only by the matters described in the claims, and those skilled in the art can change and change the technical idea of the present invention in various forms. Therefore, such improvements and modifications will fall within the protection scope of the present invention, as will be apparent to those skilled in the art.

Claims (6)

A _α B _β C _γ : phosphor represented by the chemical formula of wEu ²⁺ , xMn ²⁺ , yM, zN. In the above formula, the conditions of 2α + 4β-2γ = 0 are satisfied, A is at least one element selected from the group consisting of Ca, Sr, Ba, Mg, Zn and Be; B is Si And at least one element selected from Ge; C is at least one element selected from the group consisting of O, S and Se; M is at least one cation selected from the group consisting of Ce ³⁺ , Pr ³⁺ , Sm ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Er ³⁺ , Tm ³⁺ and Yb ³⁺ ego,; N is Li ⁺ , Na ⁺ , K ⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ and At least one cation selected from the group consisting of Y ³⁺ ; w, x, y and z each independently satisfy 0≤w≤0.10, 0≤x≤0.10, 0≤y≤0.10 and 0≤z≤0.10, but 0.01≤w + x≤0.18 The method of claim 1, Wherein y and z are y = z and 0.01 ≦ y + z ≦ 0.18.  A white light emitting device manufactured with the phosphor of claim 1. In the production of wEu ^{2 +,} a phosphor represented by xMn ^{2 +,} the formula of yM, zN,: _α A _β B _γ C Iii) oxides or carbides containing elements A, B, C, Eu, Mn, M and N, wherein w, x, y and z are each independently 0≤w≤0.10, 0≤x≤0.10, 0≤y Mixing ≤ 0.10 and 0 ≤ z ≤ 0.10 in a predetermined molar ratio satisfying 0.01≤w + x≤0.18 Wherein A is at least one element selected from the group consisting of Ca, Sr, Ba, Mg, Zn and Be; B is Si And at least one element selected from Ge; C is at least one element selected from the group consisting of O, S and Se; M is at least one cation selected from the group consisting of Ce ³⁺ , Pr ³⁺ , Sm ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Er ³⁺ , Tm ³⁺ and Yb ³⁺ ego,; N is Li ⁺ , Na ⁺ , K ⁺ , Al ³⁺ , Ga ³⁺ , In ³⁺ and At least one cation selected from the group consisting of Y ³⁺ ; Ii) subjecting the mixture to a first heat treatment for 1 to 5 hours in an inert gas atmosphere at a temperature in the range of 700 to 1350 ° C., followed by optionally cooling and pulverizing; Iii) subjecting the mixture to a second heat treatment for 1 to 5 hours at a temperature ranging from 1100 to 1450 ° C. under a reducing atmosphere; And iii) cooling, pulverizing, washing and sorting the heat treated phosphors by particle size. The method of claim 4, wherein The inert gas is at least one selected from the group consisting of He, Ne, Ar and nitrogen. The method according to claim 4 or 5, In the raw material mixing step of step iii), at least one selected from the group consisting of LiF, NH ₄ Cl, B ₂ O ₃ and NaCl as a flux further characterized in that the manufacturing method.

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