KR20180039572A - Nitride-based phosphor preparation and light emitting device including the same - Google Patents

Abstract

Provided is a nitiride fluorescent body which is represented by the chemical formula, A_mSi_3N_y:Tb_z, wherein A contains at least one element of La and Ce, may further include one or two elements of Lu and Y, and satisfies 0.6<=m<=1.2, 4.6<=y<=5.5, and 0.01<=z<=0.3. Moreover, provided are a production method thereof, and a light-emitting device including the same. By controlling the types of elements and content, it is possible to obtain a narrow-band green phosphor which is applied to near-ultraviolet excitation and has better thermal stability, thereby satisfying the demand for various white light-emitting devices (LEDs).

Description

TECHNICAL FIELD [0001] The present invention relates to a nitride phosphor, a method of manufacturing the same, and a light emitting device including the same. BACKGROUND ART [0002]

The present invention belongs to a rare earth functional material region, and particularly relates to a nitride phosphor of a kind, a method for producing the same, and a light emitting device including the same.

White light LED, the fourth green light source, has been widely used in the lighting and display fields due to its low energy consumption, high light efficiency, long lifetime and environmental friendliness. The phosphor powder is an important component of the light emitting device, and the excellent light emitting performance directly affects the determination of the main parameters such as the light emitting efficiency, the color temperature, the color rendering property, and the gamut of the white LED device.

Currently, there are systems such as (Ba, Sr) ₂ SiO ₄ : Eu ^{2 +,} LuAG: Ce ^{3 +} and β-sialon: Eu ^{2 +} as commercially available green powders. Silicates, for example, are relatively poor in thermal stability, and the raw material Lu ₂ O ₃ , which makes LuAG: Ce ^{3 +} , is very expensive, difficult to synthesize β-sialon, and patented exclusively by foreign countries. Therefore, a practical green phosphor having excellent temperature characteristics and meeting the needs of the market needs to be developed urgently. In particular, the key factor in determining high efficiency in high power LED applications is still the stability of the phosphor matrix material.

In the 80s of the last century, new nitride matrix materials were developed. Non-patent literature (J. Mater. Sci., 1980, 15, 2915-2920) shows that LaSi ₃ N ₅ has a structure similar to β-Si ₃ N ₄ and that silicon nitride, a common raw material of ceramics, And especially high temperature properties are superior to those of common materials. Based on the rule of structure crystallinity, LaSi ₃ N ₅ has high temperature properties and has a relatively low light attenuation downward tendency under high current driving, and is a potential phosphor substrate material in LED backlight or lighting area especially for high energy excitation Can be estimated.

In 2009, Japanese scholars reported a trivalent cerium-activated LaSi ₃ N ₅ blue phosphor, and the synthesis temperature was lower than 1500 ° C. in the non-patent document (Appl. Phys. Lett., 2009, 95, 051903) Is relatively poor, so that the temperature characteristics of the phosphor are not yet reached to the maximum. At the same time, silicon nitride has a very strong covalent bond as a starting material for general nitride phosphors, and when the rare earth activator Ce ^{3 +} / Eu ^{2 +} is strengthened by the influence of the crystal field, , And thus control adjustment of the emission spectrum can be achieved through parameter adjustment.

Although the phosphors related to the above document have comparatively excellent temperature characteristics, the spectrum is in the blue region, and the application region is limited to a certain extent. Therefore, it is necessary to develop a nitride green phosphor having a high optical efficiency and high stability by improving the existing technology.

Compared to the existing technical drawbacks, the present invention is a nitride phosphor of a kind which improves the problem of the narrow band green phosphor which lacks high stability and high light efficiency in the existing technology, and further improves the color rendering property of the device, A light emitting device is provided.

In order to attain the above object, on the other hand, in a kind of nitride phosphor provided by the present invention, the formula is A _m Si ₃ N _y : Tb _z , characterized in that the element A contains at least the elements lanthanum (La) and cerium And may further include one or two of the elements lutetium (Lu) and yttrium (Y), and 0.6? M? 1.2, 4.6? Y? 5.5 and 0.01? Z? 0.3.

The ratio of the total number of moles of the elements La and Ce to the total number of moles of the elements A is 60% or more based on the nitride phosphors, and the nitride phosphors have the same crystal structure as LaSi ₃ N ₅ .

Based on the above-mentioned nitride phosphors, the molar ratio range of the element Ce and La + Ce is 0.012? N? 0.2.

Based on the above-mentioned nitride phosphor, 0.01? Z? 0.2.

Based on the above-mentioned nitride phosphor, 0.96? M + z? 1.2.

Based on the above-mentioned nitride phosphor, 4.61? Y? 5.4 is satisfied.

On the basis of the above-mentioned nitride phosphor, 0.1? Tb: (La + Ce)? 0.3 is satisfied.

Based on the above-mentioned nitride phosphors, the peak value range of the laser wavelength of the nitride phosphor is 300 to 400 mm, and the peak value wavelength of the emission wavelength is 540 to 550 mm.

The emission brightness of Tb ^{3 +} doped phosphor powder is a common challenge faced by engineers in this area. Among the nitride phosphors of the present invention, high light intensity green light phosphors are obtained through blending of La: Ce: Tb ratio, A element type, and content. From the substrate of the present invention, Ce and 5d energy level nesting electrons are emitted photons of a specific energy in the process of transition to the 4f energy level, and that a series of the continuous spectrum photon is generated conspicuously and absorb light spam spectrum of Tb ^{3 +} Therefore, as the energy emitted by Ce ^{3 +} is absorbed by Tb ^{3 +} , the absorption intensity of Tb ³⁺ is effectively improved, and finally the output intensity of green light is improved. Therefore, the ratio of Ce ^{3 +} / Tb ^{3 +} content in the present invention directly determines the luminous efficiency. First, determination of a Ce ^{3 +} solid solution: If the Ce ^{3 +} solid solution is too low, the amount of Ce ^{3 +} as the luminescent center is very small, so the blue light is weaker and the Tb ^{3 +} The energy delivered is also less. If the Ce ^{3 +} solid solution is too high, the lattice distortion is enhanced first due to the difference in the La / Ce ion radius, which is disadvantageous to the stability of the phosphor. Next, if the solid solution is too high, the distance between the luminescent center ions Ce ^{3 +} is reduced, and as a result, the radiation energy is not transferred between Ce ^{3 +} - Ce ^{3 +} , thereby decreasing the light efficiency. Therefore, in the present invention, the ratio of the total number of moles of La and Ce to the total number of moles of A is 60% or more, and furthermore, the range of mole ratios of element Ce and La + Ce is 0.012? 0.2. Based on the above principle, the amount of Tb element doping is optimally 0.01? Z? 0.2, more effectively improving green light intensity to ensure a Ce ^{3 +} / Tb ^{3 +} content ratio, and further optimally 0.1? Tb: (La + Ce)? 0.3. For example, 1 mol of A _m Si ₃ N _y : Tb _z , M is 0.85, of which n is 0.12 and z is 0.15, and the molecular formula is La _{0 . 75} Ce _{0 . 1} Si ₃ N _5: Tb is _{0 .15.} On the basis of the experiment, the present invention remarkably improves the luminous brightness of the phosphor powder.

Through the doping Ce element in the substrate, the nitride phosphor powder of the present invention can effectively control the Tb excitation peak emission intensity, and is particularly prominent in the 542 mm green light region. The specific mechanism analysis is as follows. Tb doping In most phosphor matrix materials, the excitation peaks are located in the ultraviolet and near ultraviolet regions (280-400 mm), so absorption is relatively weak and under normal circumstances, their emission is relatively weak. According to many patents and non-patent documents, the emission intensity can be effectively increased through Ce / Tb synergistic doping, but the emission peak of the Ce single doped substrate material is relatively strong in the near ultraviolet region and excitation spectrum It is possible to improve the excitation strength of Tb and improve the problem of low light efficiency of the Tb phosphor powder at present and obtain a green light of high light efficiency.

Among the above-mentioned nitride phosphors of the present invention, the crystal structure thereof is an A-Si polyhedral structure, which is connected to the Si-N tetrahedron through an A-angle or side-by-side to obtain phosphors having different structures. The nitride phosphor of the present invention has the same crystal structure as that of LaSi ₃ N ₅ , but in order to prevent other impurities from entering, the nitride phosphor of the present invention is characterized in that the element A is composed of two of trivalent rare earth elements La, Ce, Among them, La and Ce must be included among them to ensure the stability of the crystal lattice of the phosphor, and the phosphor of high temperature properties can be obtained.

Among the A elements, since the radius of the Lu or Y ions is relatively small, it is possible to combine the theory of the crystal field to effectively emit (dissolve) if necessary, and then radiate the emission spectrum region from near ultraviolet to blue Therefore, the luminous efficiency of the phosphor powder can be remarkably improved.

In another aspect, the present invention provides a method of producing a nitride phosphor of the above type, and the manufacturing method thereof includes the following. The compound or alloy of La, Si, Ce and Tb is roughened with a selectable Lu and / or a compound or alloy of Y at a temperature of 1700 to 1900 占 폚 and a pressure of 2 to 3 MPa for 5 to 10 hours in an inert atmosphere, To obtain the above-mentioned nitride phosphor powder. In a specific embodiment _{, a} mixture of LaN, Si ₃ N _{4 ,} CeN, TbN and a selectable LuN and / or YN is roasted for 10 h at a temperature of 1700 to 1900 ° C and a pressure of 2 to 3 MPa in a nitrogen atmosphere, To obtain a nitride phosphor powder.

In another aspect, a kind of light emitting device provided by the present invention includes an excitation light source and a phosphor, wherein the phosphor includes a first phosphor, and the first phosphor is based on the nitride phosphor.

(Y, Gd, Lu, Tb) ₃ (Al, Ga) ₅ O ₁₂ : Ce ^{3 +} , and β-SiAlON ^{: Eu 2 +, (Ca,} Sr) AlSiN 3: Eu 2+, (Li, Na, K) 2 (Ti, Zr, Si, Ge) F 6: Mn 4 +, (Ca, Sr, Ba) MgAl 10 ^{_{O 17: Eu 2 +, Ca}} , Sr, Ba) MgAl 10 O 17: Eu 2+ , and Mg ₄ GeFO _{5. 5:} it is a branch or one or more of Mn ^{4 +} fluorescent material.

Based on the light emitting device, the excitation light source is a laser light source or a semiconductor light source, and its emission peak wavelength is 300 to 400 nm. The laser light source includes, but is not limited to, a vacuum ultraviolet ray emitting source, an ultraviolet ray emitting source, a purple light emitting source and the like. Semiconductor light sources include, but are not limited to, ultraviolet LEDs, blue-violet LEDs, blue LEDs, and the like.

Based on the light emitting device, the excitation light source is an ultraviolet light source and / or a blue light source.

On the surface of the ultraviolet light source, the above-mentioned nitride phosphor is coated. On the surface of the blue light source, (Li, Na, K) ₂ (Ti, Zr, Si, Ge) F ₆ : Mn ^{4 +} are coated.

Compared with existing technologies, the beneficial effects of the present invention are as follows.

(1) The nitride phosphor of the present invention improves the low light efficiency problem of the Tb phosphor powder by changing the La / Ce / Tb ratio of the green light excited and emitted from ultraviolet and near ultraviolet rays, have.

(2) Since the series of phosphors have a structure similar to that of silicon nitride, when the green phosphor is sintered at 1900 ° C, the obtained green phosphor has a comparatively large improvement in thermal stability in terms of having a similar? -Type silicon nitride structure, Emitting device of the present invention.

1 is an XRD diagram of the phosphor powder prepared in Example 1 of the present invention.
2 is an excitation spectrum diagram of the phosphor powder prepared in Example 1 of the present invention.
3 is an emission spectrum diagram of the phosphor powder prepared in Example 1 of the present invention.
4 is a SEM diagram of the phosphor powder prepared in Example 1 of the present invention.

The following is a further description of the invention which incorporates specific embodiments. It should be noted that this embodiment is only intended to illustrate the invention and does not limit the scope of the invention. In addition, it is to be understood that those skilled in the art, after reading the present disclosure, may make various changes and modifications to the present invention, and such equivalent forms are likewise included within the scope of the claims.

The following examples are intended to aid in the understanding of the present invention, but are not intended to limit the scope of the invention.

The test conditions of Examples and Comparative Examples of the present invention are as follows. The XRD pattern underwent X-ray diffraction using a Co target (lambda = 1.78892 nm). The excitation and emission spectra are obtained using a highly sensitive integrated fluorescence spectrometer from Horiba's FluoroMax-4 model. The luminous intensity and color coordinates are measured with a HAAS-2000 high-precision, high-speed spectrophotometer from Eberfine. The gamut range, color rendering index and color temperature are measured using ZVISION's ZWL-600 model photoelectric test system.

Comparative Example  One

The phosphor powder formula prepared in this Comparative Example was La _{0 . 45} Ce _{0 . 1} Si ₃ N _{4 . 7:} Tb _{0 .15,} and then the exact weight of 34.41g LaN, 7.71g CeN, 70.14g Si 3 N 4, 12.98g TbN a uniformly mixed in a glove box, placed in a tungsten crucible, and an N ₂ gas as a shielding gas The mixture was heated to 1900 占 폚 at a heating rate of 5 占 폚 / min and roasted for 10 hours at a pressure of 10 MPa. The roasted product was pulverized and washed with HCl to obtain a phosphor powder. The relative strength test results are shown in Table 1.

Comparative Example  2

The phosphor powder formula prepared in this comparative example was La _{1 . 2} Ce _{0 . 1} Si ₃ N _{5 . 45:} Tb _{0 .15,} and then the exact weight of 91.75g LaN, 7.712.31g CeN, 70.14g Si 3 N 4, 12.98g TbN a uniformly mixed in a glove box, placed in a tungsten crucible, N ₂ gas for protective gas , Heating to 1900 占 폚 at a heating rate of 5 占 폚 / min, roasting for 10 hours under a pressure of 10 MPa, crushing the roasted product, and HCI washing treatment to obtain a phosphor powder. The relative strength test results are shown in Table 1.

Example  One

The phosphor powder having a structure similar to that of Si ₃ N ₄ prepared in this Example has a La _0.84 Ce _0.01 Si ₃ N ₅ : Tb _0.15 and an accurate weight of 64.22 g LaN, 0.77 g CeN, 70.14 g Si ₃ N _{4 ,} 12.98 g TbN were uniformly mixed in a glove box, placed in a tungsten crucible, heated to 1900 캜 at a heating rate of 5 캜 / min using N ₂ gas as a protective gas, roasted for 10 hours under a pressure of 10 MPa, The XRD of the phosphor powder is the same as in FIG. 1, the emission spectrum thereof is as shown in FIG. 2 and FIG. 3, and the SEM is as shown in FIG. 4, The results of the light emission brightness and relative intensity test of the powder are shown in Table 1.

Example  2

The phosphor powder having a structure similar to that of Si ₃ N ₄ prepared in this example has La _0.77 Ce _0.077 Si ₃ N _4.997 : Tb _0.15 and an accurate weight of 62.37 g LaN, 2.31 g CeN, 70.14 g Si ₃ N _{4 ,} 12.98 g TbN were uniformly mixed in a glove box, placed in a tungsten crucible, heated to 1900 캜 at a heating rate of 5 캜 / min using N 2 gas as a protective gas, roasted for 10 hours under a pressure of 10 MPa, , HCI washing treatment was performed to obtain a phosphor powder. The results and the results of the luminous intensity and relative intensity test of the phosphor powder are shown in Table 1.

Example  3

The phosphorescent powder having a structure similar to that of Si ₃ N ₄ prepared in this Example is La _0.5 Ce _0.1 Y _0.1 Si ₃ N ₅ : Tb _0.3 and has an exact weight of 38.23 g LaN, 5.146 YN, 7.71 g CeN, 70.14 g Si ₃ N ₄ , and 25.95 g TbN were uniformly mixed in a glove box, placed in a tungsten crucible, heated to 1900 ° C. at a heating rate of 5 ° C./min using N ₂ gas as a protective gas, roasted for 10 hours at a pressure of 10 MPa , And the roasting product was pulverized and subjected to HCI washing treatment to obtain a phosphor powder. The above numerical values and the emission brightness and relative intensity test results of the phosphor powder are shown in Table 1.

Example  4

The phosphor powder having a structure similar to that of Si ₃ N ₄ prepared in this Example has a LaCe _0.2 Lu _0.2 Si ₃ N _5.5 : Tb _0.3 and an accurate weight of 78.46 g LaN, 18.89 g LuN, 15.42 g CeN, 70.14 g Si ₃ N ₄ , and 25.95 g TbN were uniformly mixed in a glove box, placed in a tungsten crucible, heated to 1900 ° C. at a heating rate of 5 ° C./min using N 2 gas as a protective gas, roasted for 10 hours under a pressure of 10 MPa, The resultant product was pulverized and subjected to HCI washing treatment to obtain a phosphor powder. The results and the results of the above luminous intensity and relative intensity ratio test of the phosphor powder are shown in Table 1.

Example  5 ~ Example  9

Except for Examples 5 to 9, except for the difference in La / Ce ratio, the other element types and production methods are the same as those in Example 1 and Example 2, and the raw material blend and the light emission of the series of phosphor powders Brightness and relative intensity ratio test results are shown in Table 1.

&Lt; Blending components and luminous performance of each raw material of Comparative Examples and Examples 1 to 9 > A
(element) n value m value z value y value Rare earth nitride weight
(g) Luminous brightness Relative intensity ratio Comparative Example 1 La + Ce 0.18 0.55 0.15 4.7 - - 22 0.22 Comparative Example 2 La + Ce 0.07 1.3 0.15 5.45 - - 13 0.13 Example 1 La + Ce 0.012 0.85 0.15 5 - - 17 0.17 Example 2 La + Ce 0.1 0.847 0.15 4.997 - - 52 0.52 Example 3 La + Ce 0.17 0.6 0.3 5 YN 5.146 87 0.87 Example 4 La + Ce 0.2 1.2 0.3 5.5 LuN 18.89 56 0.56 Example 5 La + Ce 0.2 One 0.01 5.01 - - 10 0.1 Example 6 La + Ce 0.2 0.849 0.15 4.99 - - 172 1.72 Example 7 La + Ce 0.2 0.6 0.01 4.61 - - 13 0.13 Example 8 La + Ce + Y 0.2 1.2 0.2 5.4 - - 96 0.96 Example 9 La + Ce + Lu 0.15 One 0.3 5.1 - - 101 1.01

 As can be seen from the numerical values in Table 1, Example 6 has a nitride green phosphor powder similar to a silicon nitride structure having a relatively high brightness due to a change in the composition thereof.

Comparative Example  3

The phosphor powder having a structure similar to that of Si ₃ N ₄ prepared in this comparative example was La _1.02 Ce _0.09 Si ₃ N _5.12 : _0.01 Tb and had an exact weight of 77.99 g LaN, 6.94 g CeN, 70.14 g Si ₃ N ₄ , 0.865 TbN was uniformly mixed in a glove box, placed in a tungsten crucible, heated to 1900 DEG C at a heating rate of 5 DEG C / min using N2 gas as a protective gas, roasted for 10 hours under a pressure of 10 MPa, HCl washing treatment to obtain a phosphor powder. The above numerical values and emission brightness and relative intensity test results of the phosphor powder are shown in Table 2.

Example  10

The phosphor powder having a structure similar to that of Si ₃ N ₄ prepared in this Example is La _0.88 Ce _0.09 Si ₃ N ₅ : _0.03 Tb and has an accurate weight of 67.32 g LaN, 6.93 g CeN, 70.14 g Si ₃ N ₄ , 2.595 g TbN were uniformly mixed in a glove box, placed in a tungsten crucible, heated to 1900 캜 at a heating rate of 5 캜 / min using N 2 gas as a protective gas, roasted for 10 hours under a pressure of 10 MPa, , HCI washing treatment was performed to obtain a phosphor powder. The above numerical values and the emission brightness and relative intensity test results of the phosphor powder are shown in Table 2.

Example  11 ~ Example  13

Among Examples 11 to 13, the total La / Ce / Tb ratio of Ce was kept at 0.09, and the Tb content was changed in comparison with that of Example 10. The ratio of Tb / (La + Ce + Tb) 0.09, 0.02, 0.18, and 0.18, respectively. The other element types and manufacturing methods were the same as those of Example 10, and the results of the raw material blending and the La / Ce ratio and the emission brightness and relative intensity ratio test results of the phosphor powder of the series were as shown in Table 2 .

Example  14

The phosphor powder having a structure similar to that of Si ₃ N ₄ prepared in this example has La _0.82 Ce _0.03 Si ₃ N ₅ : Tb _0.15 and an accurate weight of 62.7 g LaN, 2.31 g CeN, 70.14 g Si ₃ N ₄ , 12.975 g TbN were uniformly mixed in a glove box, placed in a tungsten crucible, heated to 1900 캜 at a heating rate of 5 캜 / min using N 2 gas as a protective gas, roasted for 10 hours under a pressure of 10 MPa, , HCI washing treatment was performed to obtain a phosphor powder. The above numerical values and the emission brightness and relative intensity test results of the phosphor powder are shown in Table 2.

Example  15 ~ Example  17

Among Examples 15 to 17, the ratio of Ce / (La + Ce + Tb) in the Ce to Ce / Tb ratio was changed by maintaining the total La / Ce / Tb molar ratio of Tb at 0.15, 0.09, 0.15, 0.21, and the other element types and production methods are the same as those in Example 14, and the raw material blending and the La / Ce ratio and the emission brightness and relative intensity ratio test results of the series of phosphor powders are shown in Table 2 .

&Lt; Blending components and light emission performance of each raw material in Comparative Examples and Examples > A (element) n value m value z value y value Luminous brightness Relative intensity ratio Comparative Example 3 La + Ce 0.09 1.11 0.01 5.12 5 0.05 Example 10 La + Ce 0.093 0.97 0.03 5 46 0.46 Example 11 La + Ce 0.096 0.94 0.06 5 110 1.1 Example 12 La + Ce 0.102 0.88 0.12 5 196 1.96 Example 13 La + Ce 0.11 0.82 0.18 5 182 1.82 Example 14 La + Ce 0.035 0.85 0.15 5 86 0.86 Example 15 La + Ce 0.106 0.85 0.15 5 188 1.88 Example 16 La + Ce 0.176 0.85 0.15 5 149 1.49 Example 17 La + Ce 0.256 0.85 0.15 5 92 0.92

As can be seen from the numerical values in Table 2, the phosphor powders prepared in Examples 10 to 17 have a distinctly improved light emission intensity as compared with Examples 1 to 9 due to their specific components.

Example  18

The green phosphor powder obtained in Example 16, BaMgAl ₁₀ O ₁₇ : Eu ^{2 +} blue phosphor powder, and (Sr, Ca) AlSiN ₃ : Eu ²⁺ red phosphor powder were mixed in a mass ratio of 6: 3: Water was formed and the adhesive was coated on a 380 nm near-ultraviolet LED chip to obtain a white LED device. The LED product was measured using a remote SIS-3 1.0 m steel metering integrating sphere R98, and the driving current was 60 mA. 88, color coordinates (0.325, 0.3643), and light efficiency of 137 lm / W.

Example  19

The green phosphor powder, BaMgAl ₁₀ O ₁₇ : Eu ^{2 +} blue phosphor powder, and (Sr, Ca) AlSiN ₃ : Eu ²⁺ red phosphor powder obtained in Example 12 were mixed in a mass ratio of 6: 3: 1, The water was formed and the adhesive was coated on a 380 nm near-ultraviolet LED chip to obtain a white LED device. The LED current was measured through a remote SIS-3 1.0 meter steel metering integrate R98, and the driving current was 60 mA. 90, a color coordinate of (0.33, 0.3564), and a light efficiency of 145 lm / W.

As can be seen from the above test results, the nitride phosphors of Examples 1 to 17 of the present invention were found to have a lower light efficiency of the Tb phosphor powder than green light emitted by being excited in ultraviolet light and near ultraviolet light, It is possible to obtain a green light of high light efficiency by remarkably improving the problem. At the same time, since the series of phosphors has a diatomic similar to silicon nitride, the green phosphor obtained has a comparatively great improvement in thermal stability in terms of having a similar? -Type silicon nitride structure even after being sintered at 1900 ° C, It is expected to be applied in devices.

The foregoing is merely an exemplary embodiment of the present invention, and the present invention is not limited thereto. Various changes and modifications may be made by those skilled in the art from this disclosure. Any modifications, equivalents, improvements, etc. made within the spirit and principle of the invention are included within the scope of protection of the present invention.

Claims (10)

A _m Si ₃ N _y : Tb _z ,
The A may include at least one element La (lanthanum) and Ce (cerium), and may further include one or both of the elements Lu (lutetium) and Y (yttrium), and 0.6? M? 1.2, &Lt; / RTI &gt;
&Lt; / RTI &gt; The method according to claim 1,
Wherein the ratio of the sum of the molar numbers of the elements La and Ce to the total molar number of the elements A is 60% or more, and the nitride phosphor has the same crystal structure as that of LaSi ₃ N ₅ . 3. The method according to claim 1 or 2,
Wherein the molar ratio of the element Ce to La + Ce is 0.012? N? 0.2. 3. The method according to claim 1 or 2,
0.96? M + z? 1.2. 3. The method according to claim 1 or 2,
0.1? Tb: (La + Ce)? 0.3. The method for producing a nitride phosphor according to any one of claims 1 to 5,
In the above manufacturing method,
The compound or alloy of La, Si, Ce and Tb is roughened with a selectable compound of Lu and / or Y and an alloy at a temperature of 1700 to 1900 ° C under a pressure of 2 to 3 MPa for 5 to 10 hours, The step of obtaining the nitride phosphor powder
The method of manufacturing the nitride phosphor according to claim 1, An excitation light and a phosphor,
Wherein the phosphor comprises a first phosphor, and the first phosphor is the nitride phosphor according to any one of claims 1 to 5
And a light emitting device. 8. The method of claim 7,
Wherein the excitation light source is a laser light source or a semiconductor light source, and the emission peak wavelength of the light source is 300 to 400 nm. 9. The method according to claim 7 or 8,
The phosphor may further include other phosphors, and the other phosphors may be one or more of the following fluorescent materials,
(Y, Gd, Lu, Tb ) 3 (Al, Ga) 5 O 12: Ce 3 +, β-SiAlON: Eu 2 +, (Ca, Sr) AlSiN 3: Eu 2 +, (Li, Na, K) _{2 (Ti, Zr, Si,} Ge) F 6: Mn 4+, (Ca, Sr, Ba) MgAl 10 O 17: Eu 2 +, (Ca, Sr, Ba) MgAl 10 O 17: Eu 2 + and Mg ₄ GeFO _{5 . 5} : Mn ^{4 +} . 10. The method of claim 9,
Wherein the excitation light source is an ultraviolet light source and a blue light source,
Wherein the surface of the ultraviolet light source is coated with the nitride phosphor according to any one of claims 1 to 5 and the surface of the blue light source is coated with (Li, Na, K) ₂ (Ti, Zr, Si, Ge) F ₆ : Mn ⁴⁺ is coated.

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