KR20190134057A - Phosphor, light emitting device package including the same - Google Patents

Abstract

According to an embodiment of the present invention, a phosphor represented by chemical formula 1, A_2M_(1-x)F_6:Mn^(4+)_x, comprises at least one layered structure on a surface. A fluorine-based coating layer is formed on the layered structure. The layered structure has a structure in which an n-polygon is stacked in two or more layers (herein, n is an integer of 3 or more). In the chemical formula 1, A is at least one alkali metal selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs), M is at least one element selected from the group consisting of Group 4 or Group 14 element, and x satisfies 0 < X <= 0.2.

Description

Phosphor and light emitting device package including the same {PHOSPHOR, LIGHT EMITTING DEVICE PACKAGE INCLUDING THE SAME}

The present invention relates to a phosphor and a light emitting device package including the same. More specifically, the present invention relates to a phosphor having improved reliability in a high temperature / high humidity environment and a light emitting device package including the same.

Light emitting devices, such as light emitting diodes or laser diodes, which use III-V or II-VI compound semiconductor materials of semiconductors, have a variety of characteristics such as red, green, blue and ultraviolet light due to the development of thin film growth technology and device materials. Color can be realized, and efficient white light can be realized by using fluorescent materials or combining colors, and low power consumption, semi-permanent life, fast response speed, safety and environmental friendliness compared to conventional light sources such as fluorescent and incandescent lamps. Has the advantage.

These advantages include light emitting diode backlights that replace the Cold Cathode Fluorescence Lamps (CCFLs) that make up the backlight of liquid crystal display (LCD) displays, white light emitting diode lighting devices that can replace fluorescent or incandescent bulbs, Applications are expanding to automotive headlights and traffic lights.

Meanwhile, in the method of implementing white light, a method of combining a fluorescent material on a blue or ultraviolet (UV) light emitting diode chip in a single chip form, and manufacturing a multi-chip form and combining them with each other to obtain white light Divided.

More specifically, a method of realizing white light using a single chip includes a method of obtaining white light by exciting light emitted from a blue LED and at least one phosphor by using the same. A method of realizing white light by using three types of chips (red, green, and blue) is used.

As a typical red phosphor used here is a CaAlSiN _3: a oxynitride-based fluorescent material such as Eu ^{2 +:} Eu ^{2 +} and Sr ₂ Si ₅ N _8. Such a nitride-based red phosphor has excellent emission luminance and thermal characteristics, but has a problem of exceeding a recognition limit due to a wide light emitting region, and reabsorption of the absorption region overlapping with a phosphor having a different color.

Accordingly, fluoride phosphors have emerged as phosphors that can replace nitride-based red phosphors. The fluoride phosphor does not interact with other expression colors and absorbs a wide range of wavelengths, but has an advantage of emitting light in a narrow region and expressing efficient and vivid red color. However, such fluoride phosphors are vulnerable to moisture, and thus have a problem in that luminescence brightness is reduced or color coordinates are changed under high temperature / high humidity environments. Therefore, there is a need for a phosphor that can solve these problems, the present invention relates to this.

The technical problem to be solved by the present invention is to provide a phosphor with improved reliability in a high temperature / high humidity environment and a light emitting device package including the same.

The technical problems of the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

Phosphor represented by the following formula 1 according to an embodiment of the present invention includes at least one layer structure on the surface, a fluorine-based coating layer is formed on the layer structure, the layer structure is n-square stacked in two or more layers Has a structure. In this case, n may be an integer of 3 or more.

[Formula 1]

A ₂ M _{1 - x} F ₆ : Mn ^{4 +} _x

Here, A is at least one alkali metal selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), and M is a group composed of Group 4 or 14 elements. Is at least one element selected from, and x satisfies 0 <x ≦ 0.2.

The fluorine-based coating layer may include F or KF.

The layered structure and the fluorine-based coating layer may be obtained through heat treatment.

In this case, the heat treatment may be performed under an F ₂ or HF atmosphere, the heat treatment temperature may be 150 ℃ or more to 250 ℃ or less.

The precursor of the fluorine-based coating layer may be HF, KHF ₂ or K ₂ SiF ₆ .

The fluorine-based coating layer may have a thickness of 2.5 nm or more and 40 nm or less.

Crystallinity of the phosphor represented by Formula 1 may be 47% or more.

On the other hand, the light emitting device package according to another embodiment of the present invention may include a phosphor represented by the above formula (1).

According to the present invention, since the surface of the phosphor has a layered structure and a fluorine-based coating layer is formed on the surface, moisture resistance is improved, and reliability in a high temperature / high humidity environment is improved.

Effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

1 is an optical picture of the phosphor represented by the formula (1), (A) is Comparative Example 1, (B) is an optical photograph of Comparative Example 2.
2 is an optical picture of the phosphor represented by the formula (1) having an Al ₂ O ₃ coating layer on the surface, (A) is Comparative Example 3, (B) is an optical photograph of Comparative Example 4.
3 is an optical picture of the phosphor represented by the formula (1) surface-treated in the HF atmosphere, (A) is Example 1, (B) is an optical picture of Example 2.
4 is an optical picture of the phosphor represented by the formula (1) surface-treated through the KHF ₂ precursor, (A) is an example 3, (B) is an optical image of Example 4.
5 is an optical picture of the phosphor represented by the formula (1) surface treated with a K ₂ SiF ₆ precursor, (A) is Example 5, (B) is Example 6, (C) is an optical photograph of Example 7 to be.
6 is an optical photograph before and after the surface treatment of the phosphor represented by the formula (1), (A) is a comparative example 1, (B) is an optical photograph of Example 6.
FIG. 7 is an optical photograph of a phosphor represented by Chemical Formula 1 by varying the type of precursor of a fluorine-based coating layer, wherein (A) is Example 2, (B) is Example 4, and (C) is Example 6 Optical photo.
FIG. 8 is an optical picture of a phosphor represented by Chemical Formula 1 surface treated with a KHF ₂ precursor, wherein (A) is Example 8, (B) is Example 9, and (C) is optical image of Example 10.
FIG. 9 is a diagram illustrating an X-ray diffraction (XRD) result according to a heat treatment temperature of a phosphor represented by Chemical Formula 1. FIG.
10 is a cross-sectional view of a light emitting device package according to an embodiment of the present invention.

Hereinafter, the details of the above-described objects and technical configurations of the present invention and the effects thereof will be more clearly understood by the following detailed description.

Singular expressions include plural expressions unless the context clearly indicates otherwise. Terms such as “include” or “having” are intended to indicate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, and that one or more other features, numbers, or steps are present. It can be interpreted that operations, components, parts or combinations thereof can be added.

As used herein, “comprises” and / or “comprising” refers to the presence of one or more other components, steps, operations and / or elements, or Does not exclude additional

In the description of the present invention, each layer (film), region, pattern or structure is "on" or "under" the substrate, each layer (film), region, pad or pattern. "Formed in" includes both those formed directly or through another layer. Criteria for the top / bottom or bottom / bottom of each layer will be described with reference to the drawings.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art and shall not be construed in ideal or excessively formal meanings unless expressly defined in this application. Do not.

Hereinafter, a phosphor according to an embodiment of the present invention, and a light emitting device package including the same will be described in detail.

The phosphor represented by Chemical Formula 1 may absorb excitation light having a broad wavelength and emit light of a red wavelength band having a peak at 630 nm or more and 635 nm. Here, the half width of the light in the red wavelength band is 10 nm or less, and has a high color reproducibility, which indicates the degree to which the image can be reproduced similar to the actual color due to the narrow half width.

[Formula 1]

A ₂ M _{1 - x} F ₆ : Mn ^{4 +} _x

Here, A is at least one alkali metal selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), and M is a group composed of Group 4 or 14 elements. Is at least one element selected from, and x satisfies 0 <X ≦ 0.2. However, since the phosphor has a crystal structure in which F is directly bonded to Mn, oxidation of Mn is easily performed by moisture in the air, and thus, when the phosphor is exposed to air for a long time, the luminescence brightness is decreased, and especially high humidity In the environment, lifespan characteristics may be degraded due to a sharp decrease in luminescence brightness.

Thus, in an embodiment of the present invention, the surface of the particle of the phosphor represented by Chemical Formula 1 includes at least one or more layered structures, and the layered structure provides a phosphor having a structure in which n-squares are stacked in two or more layers. N is an integer of 3 or more.

In addition, since the fluorine-based coating layer is formed on the surface of the phosphor through heat treatment, Mn is not easily oxidized, thereby reducing the emission luminance of the phosphor and improving reliability of the phosphor in a high temperature / high humidity environment.

The above-described layered structure has a high crystallinity of the phosphor and appears when a fluorine-based coating layer is formed on the surface of the phosphor. At this time, the higher the degree of crystallinity is advantageous to form a fluorine-based coating layer on the surface, the higher the crystallinity can be formed effectively the above-described layered structure.

That is, in the case of the phosphor having the above-described layered structure, the luminescence brightness is increased due to the high crystallinity and the moisture resistance is improved through the fluorine-based coating layer formed on the surface. Formation may be used.

In this case, the layered structure may be formed when the crystallinity of the phosphor is 47% or more.

Meanwhile, the thickness of the fluorine-based coating layer may be 2.5 nm or more and 40 nm or less. More preferably, it may be 5 nm or more and 30 nm or less. When the thickness of the fluorine-based coating layer is less than 2.5nm, it is difficult to secure sufficient moisture resistance, and when the thickness of the fluorine-based coating layer exceeds 40nm, the light emission characteristics of the phosphor particles may be reduced due to the excessively thick coating layer.

The fluorine-based coating layer may include F or KF, and may be coated on the surface of the phosphor particles by heat-treating the particles represented by Formula 1 together with the fluorine-based compound.

Meanwhile, the heat treatment temperature for forming the fluorine-based coating layer may be 150 ° C. or more and 250 ° C. or less, and preferably 170 ° C. or more and 210 ° C. or less. When the heat treatment temperature is less than 150 ° C., the heat energy for forming the fluorine-based coating layer is not sufficiently provided on the particle surface, so that the time required for forming the coating layer having a desired thickness may be long. In addition, since impurities contained in the phosphor are not sufficiently removed, it may be difficult to obtain a crystallinity improving effect, and thus, the formation of the layered structure described above is difficult, and as a result, an effect of improving water resistance may not be obtained.

On the other hand, even when the heat treatment temperature exceeds 250 ℃ crystallinity of the phosphor is lowered, it may be difficult to form a fluorine-based coating layer.

The heat treatment may be performed under an F ₂ or HF atmosphere, and the fluorine-based coating layer may be effectively formed on the surface of the phosphor particles by performing the heat treatment in this atmosphere.

The precursor of the fluorine-based coating layer formed on the surface of the phosphor particle may include one or more fluorine-based compounds of HF, KHF ₂ and K ₂ SiF ₆ . Here, the precursor may be a precursor having a weight ratio of 0.5 wt% or more to 6.5 wt% or less with respect to 10 wt% of the phosphor represented by Chemical Formula 1. More preferably, the precursor may be 0.6 wt% or more and 6 wt% or less. When the weight of the precursor is less than 0.5wt%, the amount of F or KF that can be supplied is not sufficient, so that the thickness of the fluorine-based coating layer may be thin, and when it exceeds 6.5wt%, the fluorine-based coating layer may be thickly formed. In both of these cases, since the thickness of the fluorine-based coating layer is formed within an undesired range, it is possible to lower the luminescence brightness of the phosphor as a result.

Hereinafter, the present invention will be described in more detail with reference to an embodiment and a comparative example. K ₂ SiF ₆ : Mn ^{4 +} phosphor (hereinafter referred to as KSF phosphor) was used as a phosphor represented by the following Chemical Formula 1 used below.

[Formula 1]

A ₂ M _{1 - x} F ₆ : Mn ^{4 +} _x

Here, A is at least one alkali metal selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), and M is a group composed of Group 4 or 14 elements. Is at least one element selected from, and x satisfies 0 <X ≦ 0.2.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples.

Luminance luminance (%) D50 (μm) Comparative Example 1 100.0 28.80 Comparative Example 2 96.6 28.00 Comparative Example 3 100.5 26.40 Comparative Example 4 85.5 26.00

<Comparative Example 1>

KSF phosphors were prepared, SEM images of KSF phosphors were taken and shown in FIGS. 1 (A) and 6 (A), and the luminescence brightness and particle size (D50) of KSF phosphors were measured and described in Table 1.

<Comparative Example 2>

10 g of KSF phosphor was put into a closed oven, heat treated at 170 ° C. for 5 hours, and cooled at room temperature for 5 hours to prepare the phosphor of Comparative Example 2. Afterwards, the SEM photograph of the phosphor is shown in FIG. 1 (B), and the emission luminance and particle size (D50) were measured and described in Table 1.

<Comparative Example 3>

20 ml of PEG dispersion solution, 5.0 g of KSF phosphor, 1.25 g of Al (NO ₃ ) _3, and 2.5 g of reaction catalyst (Citric aicd) were mixed and reacted at a reaction temperature of 40 ° C. for 3 hours to prepare Al ₂ O ₃ coated phosphor. It was. Thereafter, the mixture was washed three times with 20 ml of IPA, and then dried at 90 캜 for 2 hours. A SEM photograph of the prepared phosphor is shown in FIG. 2 (A), and the luminescence brightness and particle size (D50) were measured and described in Table 1.

<Comparative Example 4>

10 g of the phosphor of Comparative Example 3 was placed in a sealed oven, heat treated at 170 ° C. for 5 hours, and cooled at room temperature for 5 hours to prepare the phosphor of Comparative Example 4. Then, the SEM photograph of the phosphor is shown in Figure 2 (B), and the emission luminance and particle size (D50) was measured and shown in Table 1.

Referring to Table 1, when the emission luminance of the surface-coated KSF phosphor (Comparative Example 1) is defined as 100%, it can be seen that the emission luminance of Comparative Example 2 obtained by heat-treating Comparative Example 1 is lowered.

In addition, referring to FIG. 1, the surface shape of Comparative Example 2 is similar to that of Comparative Example 1, and it was confirmed that when the KSF phosphor was simply heat treated, the layered structure as described above could not be obtained.

Referring back to Table 1, it can be seen that in Comparative Example 3 in which the surface of the KSF phosphor was coated with Al ₂ O ₃ , the luminance was slightly improved compared to Comparative Example 1. However, referring to FIG. 2, it can be seen that in Comparative Example 4 in which the Comparative Example 3 was heat-treated, the coating film was deteriorated and thus the surface was not smooth. From these results, it can be seen that it is difficult to further improve the brightness of the phosphor having the Al ₂ O ₃ coating layer.

Therefore, it was confirmed that it is difficult to obtain a high luminescence brightness improving effect by simply heat-treating only the KSF phosphor or coating a metal oxide such as Al ₂ O ₃ on the surface of the KSF phosphor.

Heat treatment temperature (℃) Luminance luminance (%) D50 (μm) Comparative Example 1 - 100.0 28.80 Example 1 170 101.3 26.04 Example 2 190 104.6 27.04 Example 3 170 101.4 29.70 Example 4 190 104.6 26.70 Example 5 170 102.8 25.70 Example 6 190 103.3 25.80 Example 7 210 104.0 25.30

<Example 1>

10 g of KSF phosphor and 5 ml of HF were added to a closed oven, and heat treated at 170 ° C. for 5 hours, and then cooled at room temperature for 5 hours to prepare the phosphor of Example 1. Afterwards, the SEM photograph of the phosphor is shown in FIG. 3 (A), and the luminescence brightness and particle size (D50) were measured and described in Table 2.

<Example 2>

A SEM photograph of the phosphor prepared in the same manner as in Example 1 but obtained at a heat treatment temperature of 190 ° C. is shown in FIG. 3 (B), and the luminescence brightness and particle size (D50) were measured and described in Table 2.

Example 3

10 g of KSF phosphor in a closed oven, KHF ₂ 3 g and 5 ml of HF were added thereto, followed by heat treatment at 170 ° C. for 5 hours, and then cooled at room temperature for 5 hours to prepare the phosphor of Example 3. Then, the SEM photograph of the phosphor is shown in Figure 4 (A), and the emission luminance and particle size (D50) were measured and shown in Table 2.

<Example 4>

A SEM photograph of the phosphor prepared in the same manner as in Example 3 but obtained at a heat treatment temperature of 190 ° C. is shown in FIG. 4 (B), and the luminescence brightness and particle size (D50) were measured and described in Table 2.

Example 5

10 g KSF phosphor in a closed oven, K ₂ SiF ₆ 3 g and 5 ml of HF were added thereto, followed by heat treatment at 170 ° C. for 5 hours, and then cooled at room temperature for 5 hours to prepare the phosphor of Example 5. Afterwards, the SEM photograph of the phosphor is shown in FIG. 5 (A), and the luminescence brightness and particle size (D50) were measured and described in Table 2.

Example 6

SEM images of the phosphors prepared in the same manner as in Example 5 but obtained at a heat treatment temperature of 190 ° C. are shown in FIGS. 5 (B) and 6 (B), and the luminescence brightness and particle size (D50) were measured. 2 is described.

Example 7

A SEM photograph of the phosphor prepared in the same manner as in Example 5 but obtained at a heat treatment temperature of 210 ° C. is shown in FIG. 5 (C), and the luminescence brightness and particle size (D50) were measured and described in Table 2.

Referring to Table 2, when heat-treating the KSF phosphor under the same conditions, the luminescence brightness increases as the heat treatment temperature increases. The higher the heat treatment temperature, the higher the removal rate of impurities contained in the phosphor crystal, and the more crystalline. It is because it is formed densely.

3 to 6 compared with FIG. 1, unlike Comparative Example 2 in which a fluorine-free atmosphere was not set and heat-treated without a fluorine-containing precursor, only KSF phosphor, or KSF phosphor and KHF ₂ or K ₂ SiF ₆ in HF atmosphere When the heat treatment together, it can be seen that the above-described layered structure appears. In addition, referring to Table 2 and FIGS. 3 to 6, it can be seen that the light emission luminance is improved in the case of having the above-described layered structure as in the first to seventh embodiments.

That is, when heat treating only the KSF phosphor or the KSF phosphor and KHF ₂ or K ₂ SiF ₆ together in an atmosphere containing fluorine, the above-described layered structure appears, and the KSF phosphor having such a layered structure may have improved luminance. Can be.

Thereafter, the TEM photographs of Examples 2, 4, and 6 were taken and shown in FIGS. 7A, 7B, and 7C, respectively.

Referring to FIG. 7A, the thickness of the fluorine-based coating layer coated on the surface of the phosphor of Example 2 is 5 nm. Referring to FIG. 7B, in Example 4, 10 nm and FIG. For reference, in the case of Example 6, it is confirmed as 30 nm. Therefore, when using K ₂ SiF ₆ as a precursor of the fluorine-based coating layer, it can be expected that the coating layer is formed thick, so that the degree of improvement in resistance to moisture is the best.

Luminance luminance (%) D50 (μm) Comparative Example 1 100.0 28.80 Example 8 100.5 25.00 Example 9 101.3 29.60 Example 10 99.0 25.60

Example 8

10 g of KSF phosphor, 0.6 g of KHF ₂ , and 5 ml of HF were added to a closed oven, and heat treated at 170 ° C. for 5 hours, and then cooled at room temperature for 5 hours to prepare the phosphor of Example 8. After that, the SEM photograph of the phosphor is shown in Figure 8 (A), and the luminescence brightness and particle size (D50) was measured and shown in Table 3.

Example 9

Prepared in the same manner as in Example 8, except that the SEM image of the phosphor obtained by adding 3.0 g of KHF ₂ was shown in FIG. 8 (B), and the luminescence brightness and particle size (D50) were measured and described in Table 3. It was.

Example 10

Prepared in the same manner as in Example 8, the SEM image of the phosphor obtained by adding the amount of KHF ₂ in 6.0 g is shown in Figure 8 (C), and the luminescence brightness and particle size (D50) were measured and described in Table 3. It was.

Referring to Table 3, in Example 9 in which the amount of KHF ₂ added during the heat treatment was 3.0 g, it was found that the luminescence brightness was most improved.

In Example 8, in which the amount of KHF ₂ was added, the emission luminance was slightly improved, which can be seen as an effect that the impurities existing in the phosphor were removed by heat treatment, and the surface of the phosphor had the layered crystal structure described above.

On the other hand, Example 10, in which the amount of KHF ₂ is added, is lowered in the luminescence brightness, which can be seen because the thickness of the coating layer is thickened due to the excessive content of the coating layer precursor, thereby lowering the luminescence properties of the phosphor.

Therefore, it was confirmed that the amount of KHF ₂ added during the heat treatment should be properly controlled to improve the emission luminance improvement rate of the phosphor.

On the other hand, referring to FIG. 8 (A), FIG. 8 (B), and FIG. 8 (C), it was confirmed that the change of the surface layer structure according to the amount of KHF ₂ did not appear.

Subsequently, X-ray diffraction (XRD: X-ray diffraction) of the phosphors of Comparative Examples 1 and 5 to 7 was performed to confirm the change in crystallinity of the phosphor according to the heat treatment temperature, and the results are shown in FIG. 9. Shown in

Referring to FIG. 9, the intensity of the peak shown in the X-ray diffraction analysis result was greater in the order of Example 7, Example 6, Example 5, and Comparative Example 1, compared to Comparative Example 1. It can be seen that the intensity of the peaks in the examples is significantly large. Since the intensity of the peak is inversely proportional to the half width, it can be predicted that the high color reproducibility is improved when the phosphor is heat treated, and that the high color reproducibility is improved as the heat treatment temperature is increased.

Thereafter, the crystallinity values calculated by the following Equation (1) using the X-ray diffraction analysis of FIG. 9 are shown in Table 4 below.

Comparative Example 1 Example 5 Example 6 Example 7 Crystallinity (%) 44.4 49.4 50.6 49.8

The higher the degree of crystallinity, the higher the hardness, the durability is increased, and since the fluorine-based coating layer can be easily coated on the surface, a phosphor having a high degree of crystallinity may be referred to as a better phosphor. Referring to Table 4, it was found that the crystallinity of the Examples is much higher than that of Comparative Example 1, and when the KSF phosphor is heat treated with K ₂ SiF ₆ , the crystallinity is increased. In addition, it can be seen that the crystallinity of Example 6 is higher than that of Examples 5 and 7, the crystallinity is maximized when the heat treatment temperature is about 190 ℃, the crystallinity gradually decreases as the temperature is lower or higher based on 190 ℃. .

Therefore, it can be seen that the crystallinity is effectively increased when the heat treatment temperature is 170 ° C or higher and 210 ° C or lower, so that the durability of the phosphor and the coating power of the fluorine-based coating layer can be improved.

On the other hand, in order to confirm the reliability of the phosphor according to an embodiment of the present invention in a high temperature / high humidity environment was manufactured a light emitting device package shown in Preparation Examples 1 to 4. The preparation examples included green phosphors having an emission peak of 543 nm, and each preparation example was prepared to include the phosphors of one of Comparative Examples 1 and 5 to 7.

After supplying 450 mA of current to the light emitting device package of the manufacturing example manufactured in a temperature of 85 ° C. and a humidity of 85%, measuring the luminous flux before lighting and after 250 hours, 500 hours, 700 hours, and 1000 hours of continuous lighting, The calculation is shown in Table 5.

Manufacture example Phosphor Luminous retention rate (%) 250h 500h 750h 1000h Manufacture example 1 Comparative Example 1 90.9 88.7 83.4 81.4 Manufacture example 2 Example 5 97.4 96.5 89.9 90.3 Manufacture example 3 Example 6 98.0 97.0 95.8 92.5 Manufacture example 4 Example 7 98.4 96.8 92.0 89.8

Referring to Table 5, the luminous flux retention of Preparation Examples 2 to 4 was increased by 6% or more compared to Preparation Example 1, and when the KSF phosphor was heat-treated with K ₂ SiF ₆ in HF atmosphere, the water resistance of the phosphor was increased. It was confirmed that the life characteristics were improved.

In addition, although the initial maintenance (after 250 h lighting) of Luminous flux was high in Preparation Example 4, it was shown that the luminous flux retention in Preparation Example 3 was maintained higher than Preparation Example 4 as the lighting time was increased, which performed the crystallinity of the phosphor of Example 7. Example 6 It is judged to have appeared because it is lower than the phosphor.

Therefore, when the heat treatment temperature is 170 ° C or more and 210 ° C or less, the luminous flux retention is effectively improved, and when the temperature is about 190 ° C, the improvement of the high temperature / high humidity reliability can be confirmed.

10 is a cross-sectional view of a light emitting device package 100 according to an embodiment of the present invention.

Referring to FIG. 10, a light emitting device package 100 according to an exemplary embodiment may include a body 11, a first lead frame 21, a second lead frame 23, a light emitting device 25, and a phosphor composition 30. ) And the molding member 41.

The body 11 may include a resin-based insulating material, for example, a resin material such as polyphthalamide (PPA). In addition, the body 11 may fix a plurality of lead frames 21 and 23, and may include a cavity in which the light emitting device 25 is exposed.

The first lead frame 21 and the second lead frame 23 may be disposed on the body 11. Lower portions of the first lead frame 21 and the second lead frame 23 may be exposed to the lower portion of the body 11 and may be mounted on a circuit board to receive power.

The light emitting device 25 electrically connected to the first lead frame 21 and the second lead frame 23 through the connection member 27 may be disposed on the first lead frame 21, and the light emitting device 25 may be disposed on the first lead frame 21. The light emitting device having various structures emitting light of the blue peak wavelength or the ultraviolet wavelength band may be applied.

The molding member 41 may be disposed in the cavity. The molding member 41 may include the phosphor composition 30, and the phosphor composition 30 may be dispersed in the light transmitting resin.

The phosphor composition 30 may include a first phosphor 31 and a second phosphor 32 emitting different peak wavelengths. The first phosphor 31 and the second phosphor 32 may each include one or two or more kinds of phosphors. In this case, the first phosphor 31 may include a phosphor according to an embodiment of the present invention. .

Although the present invention has been described as described above, it will be appreciated by those skilled in the art that the present invention may be implemented in other forms while maintaining the technical spirit and essential features of the present invention. .

While the scope of the present invention will be defined by the claims, any changes or modifications derived from a configuration directly derived from the claims description as well as equivalent configurations are also included in the scope of the present invention. Should be interpreted as

100: light emitting device package
11: body
21: first lead frame
23: second lead frame
25: light emitting element
27: connecting member
30: phosphor composition
31: first phosphor
32: second phosphor
41: molding member

Claims (9)

At least one layered structure on the surface,
A fluorine-based coating layer is formed on the layered structure,
The layered structure is a phosphor represented by the following formula (1) having a structure in which the n-square is laminated in two or more layers.
Where n is an integer greater than or equal to 3.
[Formula 1]
A ₂ M _{1 - x} F ₆ : Mn ^{4 +} _x
Here, A is at least one alkali metal selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), and M is a group composed of Group 4 or 14 elements. Is at least one element selected from, and x satisfies 0 <X ≦ 0.2. The method of claim 1,
The fluorine-based coating layer is a phosphor containing F or KF. The method of claim 1,
The layered structure and the fluorine-based coating layer is a phosphor obtained through heat treatment. The method of claim 3,
The heat treatment is carried out under an F ₂ or HF atmosphere. The method of claim 3,
Heat treatment temperature is 150 degreeC or more and 250 degrees C or less. The method of claim 1,
The precursor of the fluorine-based coating layer is HF, KHF ₂ or K ₂ SiF ₆ phosphor. The method of claim 1,
The thickness of the fluorine-based coating layer is 2.5nm or more to 40nm or less. The method of claim 1,
Phosphor having a crystallinity of 47% or more. A light emitting device package comprising the phosphor according to any one of claims 1 to 8.

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