KR101292320B1 - Phosphor and method for synthesizing of the same - Google Patents

Abstract

The present invention relates to a phosphor represented by Chemical Formula 1 and a method of manufacturing the same.
[Formula 1]
MSr _x Si ₂ N _y
In Formula 1, M is one or more selected from the group consisting of Ga, La, Mg, B, Zn and Ca; 0.1? X? 3 and 1? Y? 10 are satisfied.

Description

Phosphor and its manufacturing method {PHOSPHOR AND METHOD FOR SYNTHESIZING OF THE SAME}

The present invention relates to a phosphor having a novel composition and a method for producing the same.

The phosphor serves as a medium for converting the energy of the excitation source into the energy of the visible light, and is an essential element for realizing images of various display devices. In addition, the efficiency of phosphors is a key variable directly related to the efficiency of display products. As the display element including the phosphor, for example, there is an LED element emitting white light. The LED element contains a phosphor as a wavelength converting material, and a white LED is constituted by appropriately combining these phosphors.

As a method of configuring a white LED, there is a method of implementing white by combining a blue LED with a light source and a yellow phosphor. For example, YAG: Ce phosphors are combined with InGaN-based blue LEDs having a wavelength of 450 nm to realize white color. However, the white LED, which combines a blue LED with a YAG: Ce phosphor, has a low color rendering index of emitted light, a narrow emission range due to limited emission color, and absorbs a part of blue light emitted by the phosphor as white. have. In addition, white can be achieved by using both red, green, and blue LEDs. However, this has a problem in that three LEDs must be manufactured to form one white light source, so that the manufacturing cost is high, the volume of the product increases, and the driving circuit becomes complicated.

An object of the present invention is to provide a nitride-based phosphor having a novel structure and a method of manufacturing the same.

The present invention provides a phosphor having a structure of Formula 1 below.

[Formula 1]

MSr _x Si ₂ N _y

In Formula 1, M is one or more selected from the group consisting of Ga, La, Mg, B, Zn and Ca; 0.1? X? 3 and 1? Y? 10 are satisfied.

In the method for producing the phosphor,

Substance A having a structure of Formula 6; Active agent; And a mixing step of mixing at least one metal nitride of Ca, Zn, Mg, B, Ga, and La; And

It provides a phosphor manufacturing method comprising a firing step of heat-treating the mixture at 1200 to 1800 ℃.

[Formula 6]

Sr _a Si _b N _{(2a / 3 + 4b / 3)}

In formula (6), 0.1 ≦ a ≦ 3 and 1 ≦ b ≦ 5 are satisfied.

In addition, a device including the phosphor is provided, and the device may be an illumination or display device.

As described above, the present invention provides a phosphor having a novel structure and a method of manufacturing the same, and the light emitting device using the phosphor has excellent luminous efficiency.

1 is a flowchart schematically showing a process for producing an intermediate of a phosphor according to one embodiment of the present invention;
2 is a graph showing the emission wavelength of the excitation light source of 460 nm wavelength of the phosphor according to an embodiment of the present invention;
3 is a graph showing the emission wavelength of the excitation light source of 460 nm wavelength of the phosphor according to an embodiment of the present invention;
4 is a graph showing the emission wavelength of the excitation light source of 460 nm wavelength of the phosphor according to an embodiment of the present invention;
5 is a graph showing the results of measuring the excitation spectrum for 640 nm emission of the phosphor according to one embodiment of the present invention;
6 is a graph showing the emission wavelength of an excitation light source of 460 nm wavelength of the phosphor according to one embodiment of the present invention;
7 is a graph showing the emission wavelength of an excitation light source having a wavelength of 460 nm according to the type of flux added to the phosphor according to one embodiment of the present invention;
8 is a graph showing the emission wavelength for an excitation light source having a wavelength of 460 nm according to the amount of flux added to the phosphor according to one embodiment of the present invention;
9 is a graph showing the emission wavelength for an excitation light source having a wavelength of 460 nm according to the type of flux added to the phosphor according to one embodiment of the present invention;
10 is a graph showing the emission wavelength of an excitation light source having a wavelength of 460 nm according to the type of flux added to the phosphor according to one embodiment of the present invention;
FIG. 11 is a graph showing XRD measurement results of phosphors and conventional phosphors according to an embodiment of the present invention. FIG.

The present invention provides a phosphor having a structure of Formula 1 below.

[Formula 1]

MSr _x Si ₂ N _y

In Formula 1, M is one or more selected from the group consisting of Ga, La, Mg, B, Zn and Ca; 0.1? X? 3 and 1? Y? 10 are satisfied.

In one embodiment, the phosphor according to the present invention can be represented by the following formula (2).

[Formula 2]

CaSrGa _z Si ₂ N _{(4 + z)}

In Chemical Formula 2, 0.1 ≦ z ≦ 2.5 is satisfied.

In another embodiment, the phosphor may be represented by the following formula (3).

(3)

CaSrSi ₂ GaN ₅

In addition, the phosphor may include various kinds of active agents. The kind of active agent added is not particularly limited, and may be, for example, europium ions. The phosphor including europium ions as an activator may be represented as in Chemical Formula 4 below.

[Formula 4]

MSr _x Si ₂ N _y : zEu ^{2 +}

In Formula 4, M, x and y are as defined in Formula 1, and may satisfy the condition of 0.1≤z≤5, more specifically 1≤z≤3. In the phosphor according to the present invention, the emission wavelength region may vary according to the molar ratio of europium ions added. For example, when the content of europium ions increases, the emission region may shift to red. In addition, when the content of the europium ions is reduced, activation may be insufficient for the phosphor, and when the content of the europium ions is excessively high, concentration quenching may occur to reduce luminance.

The phosphor may further include flux in addition to the activator. The phosphor prepared by adding the flux contains anion according to the kind of the flux in the structure. The kind of flux that can be used is not particularly limited, and for example, one or more of SrF ₂ , SrCl ₂ , NH ₄ Cl and NH ₄ F may be added to prepare a phosphor. Luminescence intensity can be improved by adding flux in the process of producing the phosphor. The prepared phosphor may be represented by the following Formula 5.

[Chemical Formula 5]

_{MSr x Si 2 N y: zEu} 2 +, D -

In Formula 5, M, x, y and z are as defined in Formula 4, D may be Cl or F.

In addition, the phosphor may be added to europium ions as a deactivator, and at least one ion selected from the group consisting of Er, Dy, Gd, and Ho may be added. Inclusion of the activator affects the emission region and the emission luminance of the phosphor.

The phosphor according to the present invention is characterized in that it exhibits maximum emission in the region of 500 to 700 nm under 460 nm excitation conditions. In addition, in the phosphor represented by Chemical Formula 1, when M contains Ca, it was confirmed that the maximum emission in the 630 to 650 nm region under 460 nm excitation conditions.

In addition, the present invention provides a method for producing the above-described phosphor.

In one embodiment, the phosphor manufacturing method,

Substance A having a structure of Formula 6; Active agent; And a mixing step of mixing at least one metal nitride of Ca, Zn, Mg, B, Ga, and La; And

It may include a firing step of heat-treating the mixture at 1200 to 1800 ℃.

[Formula 6]

Sr _a Si _b N _{(2a / 3 + 4b / 3)}

In formula (6), 0.1 ≦ a ≦ 3 and 1 ≦ b ≦ 5 are satisfied.

Material A corresponds to the intermediate for the production of phosphors. In one embodiment, the material A may be represented by the following formula (7).

[Formula 7]

SrSi ₂ N _10/3

The substance A can be prepared using the liquefied ammonia method. For example, the material A may comprise mixing and cooling Sr and Si ₃ N ₄ under an ammonia atmosphere; And heating the cooled mixture. In addition, ammonia can be subjected to a pretreatment process to remove moisture prior to mixing.

Specifically, cooling is performed at low temperature while Sr, Si ₃ N ₄ and ammonia gas are mixed in the reaction vessel. For example, the step of cooling the mixture of Sr, Si ₃ N ₄ and ammonia can be cooled to -100 to -33 ° C, specifically -100 to -60 ° C, more specifically -90 ° C. Before low temperature cooling, Sr and Si ₃ N ₄ are mixed according to the stoichiometric ratio, and ammonia gas is injected therein. In the low temperature cooled state, the reaction proceeds for 1 to 5 hours, or 1.5 to 2 hours, more specifically for 2 hours. In the low-temperature cooling state, the reaction is completed, the temperature is raised to room temperature, and ammonia is evaporated and removed. When ammonia is completely evaporated, the reaction is heated. The temperature to heat is 250-500 degreeC, specifically 350-450 degreeC, and a heating time is 1 to 5 hours, specifically about 1 to 3 hours.

1 schematically illustrates a process for preparing Material A according to one embodiment of the present invention. Referring to FIG. 1, first, ammonia gas from which moisture is completely removed from the moisture control unit 10 is supplied to the reaction unit 20. At this time, Sr metal and Si ₃ N ₄ according to the stoichiometric ratio are supplied to the reaction unit 20. After supplying ammonia gas to the reaction unit 20, the temperature of the reaction unit 20 is lowered to −90 ° C. to liquefy ammonia. After the reaction proceeds for about 2 hours in liquefied ammonia, the temperature is raised to room temperature and the ammonia, which was a liquid state, is evaporated. When the ammonia evaporation is completed, the temperature of the reaction unit 20 is raised to about 400 ° C and heated for about 2 hours. The gas flow rate confirming unit 40 fluidly connected to the reaction unit 20 serves to control the flow of ammonia gas, and has a structure filled with the ammonia trap. Gas ammonia discharged from the reaction unit 20 through the collection liquid is collected by the gas flow rate checking unit 40. In addition, the counter flow block 30 is formed between the reaction unit 20 and the gas flow rate checking unit 40. The reverse flow blocking unit 30 serves to prevent the collected ammonia from flowing backward. The collected ammonia can be burned and discharged into the atmosphere or stored after degassing.

The intermediate prepared by the above process is mixed with additional components for the production of phosphors, and then calcined under an ammonia atmosphere. The firing step may be heated at 1200 to 1800 ° C., specifically, at 1400 to 1500 ° C. The firing time may vary depending on the characteristics of the desired phosphor, and for example, may be heat treated for 6 to 10 hours, more specifically for 7 to 9 hours.

The kind of active agent added in the process of manufacturing the phosphor according to the present invention is not particularly limited, and for example, Eu ₂ O ₃ may be used.

In the mixing step, one or more fluxes of SrF ₂ , SrCl ₂ , NH ₄ Cl and NH ₄ F may be further mixed. By adding flux, the light emission intensity can be improved. The content of the flux may be 0.6 to 6% by weight, more specifically 1 to 3% by weight, based on the total weight of the raw material components.

In addition, in the mixing step, it is possible to further mix various kinds of inactive agent. For example, one or more surfactants selected from the group consisting of Er ₂ O ₃ , Dy ₂ O ₃ , Gd ₂ O _3, and Ho ₂ O ₃ can be further mixed. By adding the inactive agent, the emission area and the emission luminance of the phosphor are affected.

In addition, the present invention provides a light emitting device including the phosphor. The device may be an illumination or a display. In one embodiment, the light emitting device may be an LED. For example, the LED may be an LED that implements white light by further including a red phosphor in addition to the green yellow phosphor according to the present invention. The red phosphor may be variously selected from a range of materials that can be easily selected or modified by those skilled in the art. The structure of the light emitting device or the type and content of the added phosphor may be variously changed or added by those skilled in the art.

Hereinafter, the present invention will be described in detail by way of Examples and the like according to the present invention, but the scope of the present invention is not limited thereto.

Example 1 Preparation of Intermediates

After mixing the Sr metal, Si ₃ N ₄ and ammonia gas, the reaction was cooled to a temperature of −90 ° C. for about 2 hours. Then, the reaction temperature was raised to room temperature and ammonia was evaporated. After the ammonia evaporation was completed, the temperature was raised to about 400 ° C. and heated for about 2 hours to prepare an intermediate having a SrSi ₂ N _10/3 structure.

Example 2 MSrSi ₂ N _y : Eu ^{2 +} Phosphor Preparation and Spectroscopic Characteristic Experiment

Example 1 active agent to the intermediate, SrSi ₂ N _10/3 prepared in (Eu ₂ O ₃₎ and the divalent and trivalent addition of a nitride of the metal (Ca, Zn, Mg, B, Ga, La), and, in the mortar After mixing well, heat-treated at 1400 ~ 1500 ° C to synthesize a phosphor. Specific mixtures and ratios are shown in Table 1 below.

SrSi ₂ N _10/3 M Eu ₂ O ₃ 5.25mmol / 1g Non 0 0.295 mmol / 0.1026 g 5.25mmol / 1g Ca ₃ N ₂ 5.25mmol / 0.4396g 0.295 mmol / 0.1026 g 5.25mmol / 1g Zn ₃ N ₂ 5.25mmol / 0.3923g 0.295 mmol / 0.1026 g 5.25mmol / 1g Mg ₃ N ₂ 5.25mmol / 0.1767g 0.295 mmol / 0.1026 g 5.25mmol / 1g BN 5.25mmol / 0.1303g 0.295 mmol / 0.1026 g 5.25mmol / 1g GaN 5.25mmol / 0.4396g 0.295 mmol / 0.1026 g 5.25mmol / 1g LaN 5.25mmol / 0.8028g 0.295 mmol / 0.1026 g

For the phosphor prepared by mixing with the composition shown in Table 1, the emission wavelength was measured under 460 nm excitation conditions. The measurement results are shown in FIG. 2, and the results are summarized in Table 2 again.

M Wavelength (nm) No
Ga
La
Mg
B
Zn
Ca 530
534
-
534
532
535
645

Referring to FIG. 2 and Table 2, the luminescence was measured by excitation at 460 nm, and when Ga, La, Mg, B, or Zn was used as M, it was confirmed to exhibit maximum emission at 530 to 550 nm. In addition, when Ca was used as M, it was shown to exhibit maximum luminescence at 630 to 650 nm.

Example 3: Preparation of CaSrASi ₂ N ₅ : Eu ^{2 +} Phosphor and Measurement of Spectroscopic Characteristics

As shown in Table _{3 SrSi 2 N 10/3 A} (3 nitride) was added to react for well mixed, and then 1450 ℃ in an ammonia atmosphere, 6 hours CaSrASi ₂ to ₅ N: Eu ^{2 +} phosphor was synthesized.

SrSi ₂ N _10/3 Ca ₃ N ₂ A Eu ₂ O ₃ 5.25mmol / 1g 1.75 mmol / 0.2594 g Non - 0.295 mmol / 0.1026 g 5.25mmol / 1g 1.75 mmol / 0.2594 g GaN 5.25mmol / 0.4396g 0.295 mmol / 0.1026 g 5.25mmol / 1g 1.75 mmol / 0.2594 g BN 5.25mmol / 0.1303g 0.295 mmol / 0.1026 g 5.25mmol / 1g 1.75 mmol / 0.2594 g InN 5.25mmol / 0.7287g 0.295 mmol / 0.1026 g

Phosphors were prepared based on the ingredients and contents shown in Table 3, and the luminescence spectra were measured under 460 nm excitation conditions for the prepared phosphors. The measurement results are shown in FIG. 3. In addition, it is shown in Table 4 when the intensity of the luminescence based on the measured results as a relative intensity.

A Relative strength Non One BN 1.25 GaN 1.3 InN 0.93

3 and Table 4 show that the luminescence intensity of the phosphor was improved when GaN or BN was added, and the strength enhancement effect was the best when GaN was added. However, it can be seen that the emission intensity is lowered when InN is added.

Example 4 CaSrGa _x Si ₂ N _{(4 + x)} : Eu ^{2 +} Phosphor Preparation and Spectroscopic Measurement

As shown in Table _{5 SrSi 2 N 10/3,} Ca 3 N 2, GaN, (+ x 4) Eu 2 O 3 to react for mixed and well mixed, and then ammonia atmosphere 1450 ℃, 6 hours in the CaSrGa _x Si ₂ N: ethylamine Eu ^{2 +} phosphor.

Sample number
(x value) SrSi ₂ N _10/3 Ca ₃ N ₂ GaN Eu ₂ O ₃ 0 5.25mmol / 1g 1.75 mmol / 0.2594 g 0 0.29 mmol / 0.1026 g One 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.29 mmol / 0.1026 g 2 5.25mmol / 1g 1.75 mmol / 0.2594 g 10.49 mmol / 0.0.8791 g 0.29 mmol / 0.1026 g 3 5.25mmol / 1g 1.75 mmol / 0.2594 g 15.75mmol / 1.3187g 0.29 mmol / 0.1026 g

Phosphors were prepared based on the components and contents shown in Table 5, and the luminescence spectra were measured under 460 nm excitation conditions for the prepared phosphors. The measurement results are shown in FIG. 4. In addition, the intensity of the luminescence based on the measured results is shown in Table 6 as a relative intensity.

x value Relative strength 0 1.00 One 1.08 2 1.21 3 0.91

From the results of FIG. 4 and Table 6, the strength-improving effect was found to be the best when the x value was 2 (GaN 10.49 mmol / 0.0.8791 g).

Moreover, among the phosphors, GaN CaSrSi _{2 5:} measured the excitation spectra for 640 nm emission for the Eu ^{+ 2.} The measurement result is shown in FIG. From the results of Figure _5, CaSrSi ₂ GaN 5: excitation spectrum of Eu ^{2 +} was showed a strong excitation spectrum in the blue range, this means that a blue LED is very suitable as a pumping light source.

Example 5: CaSrB _x Si ₂ N _{(4 + x)} : Eu ^{2 +} Phosphor Preparation and Spectroscopic Measurement

As shown in Table _{7 SrSi 2 N 10/3,} Ca 3 N 2, BN , and _{Eu 2 O 3 CaSrGa x Si 2} N (4 + x) were mixed and reacted for well mixed, and then ammonia atmosphere 1450 ℃, 6 hours in the: ethylamine Eu ^{2 +} phosphor.

Sample number
(x value) SrSi ₂ N _10/3 Ca ₃ N ₂ BN Eu ₂ O ₃ 0 5.25mmol / 1g 1.75 mmol / 0.2594 g 0 0.29 mmol / 0.1026 g 0.5 5.25mmol / 1g 1.75 mmol / 0.2594 g 2.63mmol / 0.0652g 0.29 mmol / 0.1026 g 1.0 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.1303g 0.29 mmol / 0.1026 g 1.5 5.25mmol / 1g 1.75 mmol / 0.2594 g 7.88 mmol / 0.1955 g 0.29 mmol / 0.1026 g 2.0 5.25mmol / 1g 1.75 mmol / 0.2594 g 10.5 mmol / 0.2606 g 0.29 mmol / 0.1026 g 2.5 5.25mmol / 1g 1.75 mmol / 0.2594 g 13.13 mmol / 0.3258 g 0.29 mmol / 0.1026 g 3.0 5.25mmol / 1g 1.75 mmol / 0.2594 g 15.75mmol / 0.3909g 0.29 mmol / 0.1026 g

Phosphors were prepared based on the ingredients and contents shown in Table 7, and the luminescence spectra were measured under 460 nm excitation conditions for the prepared phosphors. The measurement results are shown in FIG. 6. In addition, the intensity of the luminescence based on the measured results is shown in Table 8 as a relative intensity.

x value Relative strength 0 1.00 0.5 1.22 1.0 1.43 1.5 1.20 2.0 1.28 2.5 1.03 3.0 0.94

6 and Table 8 show that the luminous intensity is the best when x value is 1.

Example _{6: CaSrSi 2 GaN 5: Eu} 2 + effect of the flux (Flux) on the phosphor and luminous

As shown in Table _{9 SrSi 2 N 10/3,} Ca 3 N 2, BN, Eu 2 O 3 and a mixture of a flux (Flux) and incubated for well mixed, and then 1450 ℃ in an ammonia atmosphere, 6 hours CaSrSi ₂ GaN _5: Eu ^{2 +} phosphor was synthesized.

SrSi ₂ N _10/3 Ca ₃ N ₂ GaN Eu ₂ O ₃ Flux 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.268 mmol / 0.0943 g X 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.268 mmol / 0.0943 g 1wt% / 0.0175g NH ₄ Cl 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.268 mmol / 0.0943 g 1wt% / 0.0175g NH ₄ F 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.268 mmol / 0.0943 g 1wt% / 0.0175g SrCl ₂ 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.268 mmol / 0.0943 g 1wt% / 0.0175g SrF ₂

Phosphors were prepared based on the components and contents shown in Table 9, and the luminescence spectra were measured under 460 nm excitation conditions for the prepared phosphors. The measurement results are shown in FIG. 7. In addition, the intensity of the luminescence based on the measured results is shown in Table 10 as a relative intensity.

Flux Relative strength NH ₄ Cl 1.86 NH ₄ F 1.65 SrCl ₂ 2.08 SrF ₂ 2.19 Non One

From the results of FIG. 7 and Table 10, irrespective of the flux, the emission wavelength of the phosphor appeared at 630 to 640 nm, and the intensity of luminescence was increased when SrF ₂ or SrCl ₂ was used.

Example 7 Preparation of CaSrSi ₂ GaN ₅ : Eu ^{2 +} , Cl ^- Phosphor According to Flux SrCl ₂ Content and Luminescence Measurement

As shown in Table _{11 SrSi 2 N 10/3,} Ca 3 N 2, BN, Eu 2 O 3 and SrCl ₂ mixed and reacted for a well mixed, and then 1450 ℃, 6 hours in an ammonia atmosphere ^{_{CaSrSi 2 GaN 5: Eu 2 +}} , Cl ^- phosphor was synthesized.

SrSi ₂ N _10/3 Ca ₃ N ₂ GaN Eu ₂ O ₃ Flux / SrCl ₂ 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.268 mmol / 0.0943 g 0 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.268 mmol / 0.0943 g 0.1wt% / 0.0019g 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.268 mmol / 0.0943 g 0.3wt% / 0.0054g 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.268 mmol / 0.0943 g 0.5wt% / 0.0090g 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.268 mmol / 0.0943 g 0.7wt% / 0.0126g 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.268 mmol / 0.0943 g 1.0wt% / 0.0179g 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.268 mmol / 0.0943 g 3.0wt% / 0.0538g 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.268 mmol / 0.0943 g 5.0wt% / 0.0897g

Phosphors were prepared based on the components and contents shown in Table 11, and the luminescence spectra were measured under 460 nm excitation conditions for the prepared phosphors. The measurement results are shown in FIG. 8. In addition, the intensity of the luminescence based on the measured results is shown in Table 12 as a relative intensity.

SrCl ₂ content (% by weight) Relative strength 0 1.0 0.1 0.91 0.3 0.86 0.5 1.02 0.7 1.05 1.0 1.22 3.0 1.21 5.0 1.08

8 and Table 12, the resulting phosphor has a maximum emission wavelength at 630 ~ 650 nm under 460 nm excitation conditions, when the content of SrCl ₂ is 0.6 to 6% by weight, specifically 0.7 to 5% by weight The emission intensity was found to increase. In particular, it is confirmed that in the range of 1 to 5% by weight, the light emission intensity is further increased.

Example 8: ³ parts surfactant Re ⁺ is added to the _{^{CaSrGaSi 2 N 5: Eu 2 +}} , Cl -, Re Preparation and Luminescence Measurement of ^{3 +} Phosphor

As shown in Table _{13 SrSi 2 N 10/3,} Ca 3 N 2, BN, Eu 2 O 3, SrCl 2 , and mixing the Re and mixed well, and then 1450 ℃ in an ammonia atmosphere, reacted for 6 hours CaSrSi ₂ GaN _5: Eu ^{2 +} , Cl ⁻ , Re ^{3 +} phosphors were synthesized. Rare earth elements (Re) used Ce, Pr, Er, Nd, Sm, Gd, Dy and Ho.

SrSi ₂ N _10/3 Ca ₃ N ₂ GaN Eu ₂ O ₃
(0.268mmol) SrCl ₂
(1 wt%) Deactivator
(0.001wt%) 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.0943 g 0.0179 g 0.0002g CeO ₂ 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.0943 g 0.0179 g 0.0002g Pr ₆ O ₁₁ 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.0943 g 0.0179 g 0.0002g Er ₂ O ₃ 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.0943 g 0.0179 g 0.0002g Nd ₂ O ₃ 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.0943 g 0.0179 0.0002g Sm ₂ O ₃ 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.0943 g 0.0179 g 0.0002g Gd ₂ O ₃ 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.0943 g 0.0179 g 0.0002g Dy ₂ O ₃ 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.0943 g 0.0179 g 0.0002g Ho ₂ O ₃

Phosphors were prepared based on the ingredients and contents shown in Table 13, and the luminescence spectra were measured under 460 nm excitation conditions for the prepared phosphors. The measurement results are shown in FIG. 9. In addition, the intensity of the luminescence based on the measured results is shown in Table 14 as a relative intensity.

Re Relative strength Non (x) 1.00 Ce 0.88 Pr 0.84 Er 1.15 Nd 0.95 Sm 0.93 Gd 1.05 Dy 1.10 Ho 1.02

From the results in FIGS. 9 and 14, the prepared phosphor exhibits a maximum emission wavelength at 630 nm to 650 nm under 460 nm excitation conditions, and increases luminescence intensity when Er, Dy, Gd or Ho is added as a deactivator. I can see that. In particular, it was confirmed that the luminescence strength was the strongest when Er was used as the deactivator.

Example 9 Preparation of CaSrGaSi ₂ N ₅ : zEu ^{2 +} , Cl ^- Phosphor and Measurement of Luminescence

As shown in Table _{15 SrSi 2 N 10/3,} CaN, Eu 2 O 3 , and the reaction was performed for 1450 ℃, 6 hours of SrCl ₂ in the mixture and mix well, and then an ammonia atmosphere ^{_{CaSrSi 2 GaN 5: zEu 2 +}} , Cl - a phosphor Synthesized.

SrSi ₂ N _10/3 Ca ₃ N ₂ GaN Eu ₂ O ₃ Flux 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.268 mmol / 0.0943 g X 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.133mmol / 0.0467g O 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.200mmol / 0.0703g O 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.268 mmol / 0.0943 g O 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.336mmol / 0.1184g O 5.25mmol / 1g 1.75 mmol / 0.2594 g 5.25mmol / 0.4396g 0.406mmol / 0.1429g O

Phosphors were prepared based on the components and contents shown in Table 15, and the luminescence spectra were measured under 460 nm excitation conditions for the prepared phosphors. The measurement results are shown in FIG. 10. In addition, the intensity of the luminescence based on the measured results is shown in Table 16 as a relative intensity.

z value Eu ^{2 +} content (mmol) Relative strength No flux (2.0) 0.268 (no flux) One 1.0 0.133 1.55 1.5 0.200 1.41 2.0 0.268 1.27 2.5 0.336 1.27 3.0 0.406 1.15

From the results of Figure 10 and Table 16, the manufactured phosphor indicates a maximum emission wavelength at 460 nm where the conditions in _{630 ~ 640 nm, CaSrGaSi 2 N} 5 compared to Eu ^{2 +} represents the strongest luminescence in the case of 0.133 mmol , it can be seen that the shift (shift) phenomenon in which a red (red) with increasing quantities of Eu ^{2 +} appears.

Example 10: CaSrSi ₂ GaN ₅ XRD Measurements on Phosphors

CaSrSi ₂ GaN ₅ according to an embodiment of the present invention X-ray diffraction (XRD) for the phosphor was measured. At the same time XRD was measured for some phosphors known in the art. The measurement results are shown in FIG. 11. In FIG. 11, (a) CaSrSi ₂ GaN ₅ , (b) SrSiN ₂ , (c) CaSiN ₂ , (d) Ca ₂ Si ₅ N _8, and (e) Sr ₂ Si ₅ N ₈ are meant.

From the results of FIG. 11, CaSrSi ₂ GaN ₅ according to an embodiment of the present invention. It can be seen that the phosphor is a novel structure with inconsistent XRD types compared to conventional commercially available nitride phosphors.

Table 17 compares the 2 theta values of the phosphors according to the present invention and conventional nitrides.

2 theta / century ICSD NO. (a) CaSrSi ₂ GaN ₅ 30.42 / 0.276 31.54 / 0.436 33.08 / 1.000 35.36 / 0.371 (b) SrSiN ₂ 30.26 / 0.450 31.00 / 0.676 32.72 / 1.000 34.96 / 0.214 170266 (c) CaSiN ₂ 31.02 / 0.197 34.64 / 1.000 35.14 / 0.597 39.28 / 0.097 170267 (d) Ca ₂ Si ₅ N ₈ 35.20 / 0.920 36.80 / 0.915 37.50 / 1.000 39.28 / 0.337 79070 (e) Sr ₂ Si ₅ N ₈ 30.50 / 0.689 31.56 / 0.735 35.36 / 1.000 36.18 / 0.728 401500

Table 18 summarizes the results of measuring the luminescence in the conventional nitrides compatible with the phosphor according to the present invention.

Luminesense Exn (nm) Ems (nm) _{(a) CaSrSi 2 GaN 5:} Eu 2 + 470.5 640-645 (b) SrSiN ₂ : Eu ^{2 +} 400 660-670 (c) CaSiN ₂ : Eu ^{2 +} 400-460 620 (d) Ca ₂ Si ₅ N ₈ : Eu ^{2 +} 400 610 (e) Sr ₂ Si ₅ N ₈ : Eu ^{2 +} 400 620

10: moisture control unit 20: reaction unit
30: countercurrent cutoff part 40: gas flow rate checking part

Claims (16)

delete delete delete delete delete delete delete delete Substance A having a structure of Formula 7; Active agent; And a mixing step of mixing at least one metal nitride of Ca, Zn, Mg, B, Ga, and La; And
A method for producing a phosphor comprising a firing step of heat-treating the mixture at 1200 to 1800 ° C.
(7)
SrSi ₂ N _10/3 delete The method of claim 9,
Activator is Eu ₂ O ₃ A phosphor manufacturing method. The method of claim 9,
Before the firing step, SrF ₂ , SrCl ₂ , NH ₄ Cl and NH ₄ F of at least one flux of the phosphor manufacturing method for further mixing. 13. The method of claim 12,
Flux content is 0.6 to 6% by weight based on the total weight of the raw material component manufacturing method. The method of claim 9,
Prior to the calcination step, a method for producing a phosphor further mixing one or more deactivators selected from the group consisting of Er ₂ O ₃ , Dy ₂ O ₃ , Gd ₂ O ₃ and Ho ₂ O ₃ . delete delete

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