KR20110093738A - Phosphor, light emitting device, surface light source apparatus, display apparatus and illumination apparatus - Google Patents

Abstract

PURPOSE: A β-sialon for emitting green light is provided to ensure high luminous efficiency and excellent reproducibility, to secure stable heat, and to enable the use for a high power LED chip. CONSTITUTION: A β-sialon for emitting green light has a β-type Si3N4 crystal structure and includes oxynitrides represented by chemical formula: Si_(6-z)Al_zO_zN_(8-z):Eu_a,M_b. In chemical formula, M is at least one kind selected from Sr and Ba; the amount added of Eu is in the range of 100~5000 ppm; the amount added of M in the range of 100~10000ppm; and an Al composition ratio(z) satisfies 0.1 < z < 1. The light having the peak wavelength in the range of 500~550 nm is emitted by irradiating an excitation source.

Description

Phosphor, Light Emitting Device, Surface Light Source Device, Display Device & Lighting Device {PHOSPHOR, LIGHT EMITTING DEVICE, SURFACE LIGHT SOURCE APPARATUS, DISPLAY APPARATUS AND ILLUMINATION APPARATUS}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to phosphors, and more particularly, to a β-sialon phosphor having high luminescence properties and excellent thermal and chemical stability, and a light emitting device, a surface light source device, a display device, and a lighting device using the same.

In general, the phosphor material for wavelength conversion is used as a material for converting specific wavelength light of various light sources into the desired wavelength light. In particular, since light emitting diodes among various light sources can be advantageously applied as LCD backlights, automobile lights, and home lighting devices due to low power driving and excellent light efficiency, phosphor materials have recently been spotlighted as a core technology for manufacturing white light LEDs.

The white light emitting device is usually manufactured by applying a yellow phosphor to a blue LED. More specifically, a yellow phosphor of YAG (Y ₃ Al ₅ O ₁₂ ): Ce is applied to the light emitting surface of the blue LED having the GaN / InGaN active layer to convert a part of the blue light to yellow, and to convert the part of the blue light to yellow. Blue light may be combined to provide white light.

The conventional white light emitting device composed of the above-described YAG: Ce phosphor (or TAG phosphor) -blue LED has a disadvantage of low color rendering. That is, since the wavelength of the white light obtained by using the yellow phosphor is distributed only in blue and yellow, the color rendering is low, and there is a limit in implementing desired natural white light.

On the other hand, the conventional wavelength conversion phosphor material has been provided limited to the light emitting color of the specific light source and the color of the specific output light, and the color distribution that can be implemented is also very limited, according to the user's needs, the light emitting color of the various light sources and / or the color of the various output light There is a limit to this.

In order to solve this problem, the present applicant has recently applied a color rendering index (CRI) through a mixture of three specific blue, green and red phosphors in Korean Patent Application No. 2004-0076300 (filed September 23, 2004). ), And further wide color distribution. In order to implement an excellent light emitting device through the combination of red, green and blue phosphors, each phosphor is required to have a high conversion efficiency.

In addition, conventional silicate phosphors are unstable to heat, and thus have disadvantages of being vulnerable to high power LED chips.

In order to improve this, since the first proposal of a new fluorescent material called β-sialon (Japanese Patent Laid-Open No. 60-206889 (published date: October 18, 1985)), the β-sialon phosphor has been steadily studied.

Japanese Patent No. 3921545 (Dec. 2007.03.02, Patent holder: NATIONAL INSTITUTE FOR MATERIALS SCIENCE) proposes β-sialon as a green light emitting phosphor. However, since the luminance is very low and the wavelength and color coordinates are not good for realizing the desired white light, there is a difficulty in practical use.

On the other hand, it has been reported to find new properties by modifying the basic crystal structure of β-sialon phosphor. The paper Fluorescence of Eu + in SiAlONs (2005 Journal of the Ceramic Society of Japan, RJ Xie et al.) Proposes an Sr sialon in which strontium (Sr) is substituted for Si or Al in the crystal structure. However, since Sr replaces the crystal structure, phase stabilization is somewhat lowered, so there is a problem that it is difficult to expect excellent thermal stability.

In addition, Korean Patent Publication No. 2009-0028724 also proposes β-sialon (SiAlON) as a green phosphor. However, since the particle size is considerably large, the precipitation rate is fast, and thus there is a problem in that the color coordinates of the product are large. In addition, there is a disadvantage in that a high firing temperature (more than 2000 ° C.) and a long firing time are required in comparison with the firing conditions (about 1600 ° C. level, about 3 hr) of the conventional silicate phosphor. These problems have made it difficult to add Group 1 and Group 2 elements as activators.

The present invention is to solve the above-described problems of the prior art, one of the objectives is to provide a phosphor and a manufacturing method for green light emission that can be used in high-power LED chip having a high luminous efficiency and excellent reproducibility, heat stable It is.

Another object of the present invention is to provide a white light emitting device, a surface light source device, an illumination device, and a display device using the phosphor.

In order to realize the above technical problem, one aspect of the present invention is

It has a β-type Si ₃ N ₄ crystal structure and comprises an oxynitride represented by the composition formula Si _{6 - z} Al _z O _z N _{8- z} : Eu _a , M _b , wherein M is selected from Sr and Ba It is at least one kind, Eu addition amount (a) is 0.1-5 mol% range, M addition amount (b) is 0.1-10 mol% range, Al composition ratio (z) satisfies 0.1 <z <1, Irradiation provides a phosphor that emits light having a peak wavelength in the range of 500 to 550 nm.

The excitation source may have a peak wavelength in the range of 300 nm to 480 nm. In addition, the peak wavelength of the light emitted from the phosphor by the excitation source irradiation may be 540nm or less.

When the light emitted from the phosphor by the excitation source irradiation is represented by the (x, y) value in the CIE 1931 chromaticity coordinate, x and y may satisfy x ≦ 0.336 and y ≧ 0.637, respectively.

The change in y in the CIE 1931 chromaticity coordinates of the light emitted from the phosphor may be less than -0.0065. Here, the y change amount is y1 in the CIE 1931 chromaticity coordinates measured by the light emitted therefrom under the condition of driving the blue light emitting diode to which the phosphor is applied at 3.3 V and 120 Hz, and the driving condition is 85. When y is y2 in the CIE 1931 chromaticity coordinates measured in the light emitted after continuous operation at 24 ° C., it is defined as y2-y1.

In one example, M may be strontium (Sr). In this case, the amount of Sr added (a) may be in the range of 0.5 to 3 mol%. Preferably, the amount of Sr added (a) may range from 1 to 1.5 mol%.

In addition, the Al composition ratio z may range from 0.1 to 0.3. The amount of Eu added (b) may range from 0.9 to 3 mol%.

In another example, M may include both barium (Ba) and strontium (Sr).

The particle size of the phosphor may have a D50 value ranging from 14.5 to 18.5 μm.

In a particular example, the phosphor may be further added with at least one element selected from the group consisting of Li, Na, K, Mg and Ca as the activator.

Here, the Eu addition amount (a) and M addition amount (b) may also be limited in ppm units. That is, the Eu addition amount (a) may be expressed in the range of 100 to 5000 ppm, and the M addition amount (b) may be expressed in the range of 100 to 10000 ppm.

In another aspect of the present invention, having a β-type Si ₃ N ₄ crystal structure, a composition formula _{Si 6 - zAl z O z N} 8-z: Eu a, M b ( wherein, at least one member M is selected from Sr and Ba and , Eu addition amount (a) is in the range of 0.1 to 5 mol%, M addition amount (b) is in the range of 0.1 to 10 mol%, Al composition ratio (z) satisfies 0.1 <z <1) In order to prepare, the step of weighing the raw materials including Si-containing oxides or nitrides, Al-containing oxides or nitrides, Eu-containing compounds and M-containing compounds; and mixing the raw materials except for the M-containing compounds to form a primary mixture And sintering the primary mixture and pulverizing the primary firing product; and mixing the M-containing compound with the pulverized primary firing product to prepare a secondary mixture. And secondary firing of the secondary mixture and grinding of the secondary firing product. Step; provides the phosphor production process comprising a.

The primary firing may be performed at a temperature range of 1850-2300 ° C., and the secondary firing may be performed at a temperature lower than the primary firing temperature. The primary and secondary firing may be performed in a nitrogen gas atmosphere.

The preparing of the secondary mixture may include adding, together with the M-containing compound, a compound containing at least one element selected from the group consisting of Li, Na, K, Mg, and Ca as an activator.

Still another aspect of the present invention provides an LED chip that emits excitation light, a green phosphor disposed around the LED chip and wavelength converting at least a portion of the excitation light, and including the β sialon phosphor described above, and the LED chip. And at least one light emitting element emitting light having a wavelength different from that of the green phosphor and provided by at least one of an additional LED chip and a phosphor of another kind.

The LED chip may be an LED chip emitting ultraviolet light or an LED chip emitting visible light having a peak wavelength greater than 470 nm.

Alternatively, the LED chip may be a blue LED chip having a peak wavelength in the range of 430 ~ 470nm.

In this case, the at least one light emitting element may comprise a red phosphor. The emission wavelength peak of the red phosphor may be 600 to 660 nm, and the emission wavelength peak of the green phosphor may be 500 to 550 nm. In addition, the blue LED chip may have a half width of 10 to 30 nm, the green phosphor may have a half width of 30 to 100 nm, and the red phosphor may have a half width of 50 to 150 nm.

In addition, the emission wavelength peak of the green phosphor may be 535 to 545 nm, and the half width of the emission wavelength may be 60 to 80 nm.

In the CIE 1941 color coordinate system, the color coordinates of light emitted from the red phosphor are in the range of 0.55 ≦ x ≦ 0.65, 0.25 ≦ y ≦ 0.35, and the color coordinates of light emitted from the blue LED chip are 0.1 ≦ x ≦ 0.2, 0.02 ≦ y ≦ 0.15. It can be located in a range.

In a specific example, the red phosphor is a nitride-based phosphor of M1AlSiN _x : Re (1≤x≤5), a sulfide-based phosphor of M1D: Re, and a silicate of (Sr, L) ₂ SiO _{4 - x} N _y : Eu At least one selected from phosphors (where 0 <x <4, y = 2x / 3), wherein M1 is at least one element selected from Ba, Sr, Ca, and Mg, and D is selected from S, Se, and Te At least one element selected and L is at least one group 2 element selected from the group consisting of Ba, Ca and Mg or at least one first group selected from the group consisting of Li, Na, K, Rb and Cs Element, and Re may be at least one selected from Y, La, Ce, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, F, Cl, Br, and I.

The at least one light emitting element may further include a yellow to yellow orange phosphor. In this case, the yellow to yellow orange phosphor may be a silicate-based phosphor, a garnet-based, sulfide-based, or α-SiAlON: Re phosphor of YAG and TAG.

Meanwhile, the at least one light emitting element may be a red LED chip.

In one example, the LED chip may have a structure in which the first and second electrodes face the same surface. In another example, the LED chip may have a structure in which the first and second electrodes face different surfaces opposite to each other.

In another example, the LED chip has a first and a second main surface facing each other, each having a first and a second conductivity type semiconductor layer providing the first and second main surface and an active layer formed therebetween. A semiconductor laminate, a contact hole connected to a region of the first conductive semiconductor layer from the second main surface through the active layer, and formed on a second main surface of the semiconductor laminate; The semiconductor device may include a first electrode connected to the contact hole in one region and a second electrode formed on a second main surface of the semiconductor stack and connected to the second conductive semiconductor layer.

In this case, any one of the first and second electrodes may have a structure that is laterally drawn out of the semiconductor laminate.

The package body may further include a package body having a groove portion on which the LED chip is mounted.

The LED chip may further include a resin encapsulation unit, wherein at least one of the plurality of phosphors may be dispersed in the resin encapsulation unit. Alternatively, the plurality of phosphors may form a plurality of phosphor-containing resin layers different from each other, and the plurality of phosphor-containing resin layers may have a stacked structure.

The color rendering index (CRI) of the white light emitted from the white light emitting device may be 70 or more.

In addition, the present invention provides a surface light source device, a display device and a lighting device using the above-described phosphor as a wavelength conversion material.

By adding a predetermined amount of Sr to the empty sphere of the host matrix, which is a β-sialon (SiAlON) crystal, it not only has a greatly improved luminance (eg, about 20%) than the conventional β-sialon (SiAlON) phosphor. In addition, a shorter wavelength green phosphor can be provided.

Such a green phosphor may contribute to providing vivid white by providing color characteristics that can satisfy the green region of standard RGB (sRGB) in the CIE 1931 color coordinate system. Furthermore, the doping of Sr contributes to the phase stabilization of β-sialon, thereby improving the reliability characteristics, and in particular, greatly reducing the change in the y color coordinate, which influences the efficiency change over time, and in terms of productivity and yield. There is a big improvement.

In addition, the β-sialon phosphor proposed in the present invention may be used together with other phosphors, for example, blue and red phosphors, to provide a wide color display and provide a light emitting device having excellent reproducibility. Furthermore, when implemented as a white light emitting device, it is possible to provide excellent white light with a greatly improved color rendering index.

The oxynitride phosphor according to the present invention can be advantageously applied to a white light emitting device, a surface light source device, a display device, and an illumination device according to various forms as a wavelength conversion material.

1 is a schematic diagram illustrating the crystal structure of a β-sialon phosphor according to the present invention.
2 is an XRD graph of β-sialon phosphors according to Example 1 and Comparative Example 1. FIG.
3 and 4 are charts and photographs of the β-sialon phosphors according to Example 1 and Comparative Example 1, respectively, using TOF-SIMS.
5 is a graph showing the brightness improving effect of the β-sialon phosphor according to Examples 1 to 4.
6 is a CIE 1931 color coordinate system for explaining color coordinates and time-lapse characteristics of light emitted from a phosphor.
7 is a graph showing the effect of shortening the wavelength of the β-sialon phosphor according to Examples 1 to 4.
8 is a graph showing the effect of improving the aging characteristics of the β-sialon phosphors according to Examples 1 to 4 (reduced amount of change in y color coordinates).
9 is a graph showing emission spectra of β-sialon phosphors according to Comparative Examples 1 to 4. FIG.
10 is a graph showing emission spectra of β-sialon phosphors according to Examples 1, 6 and 7. FIG.
11 is a graph showing emission spectra of β-sialon phosphors according to Examples 8 to 13 and Comparative Examples 5 and 6. FIG.
12 is a graph showing intensity integration values and peak intensities of β-sialon phosphors according to Examples 8 to 13 and Comparative Examples 5 and 6. FIG.
13 is a graph showing excitation spectra of β-sialon phosphors according to Examples 8 to 13 and Comparative Examples 5 and 6. FIG.
14 is a graph showing emission spectra of β-sialon phosphors according to Examples 14 to 23. FIG.
15 is a graph showing intensity integrals and peak intensities of the β-sialon phosphors according to Examples 14 to 23. FIG.
16 is a graph showing excitation spectra of β-sialon phosphors according to Examples 14 to 23. FIG.
17 is a graph showing peak intensities and half widths of β-sialon phosphors according to Examples 14 to 23. FIG.
18 is a graph showing the preferred particle size conditions of the β-sialon phosphor according to the present invention.
19 is a schematic diagram showing a white light emitting device according to an embodiment of the present invention.
20 is a schematic view showing a white light emitting device according to another embodiment of the present invention.
21 is a schematic diagram showing a white light emitting device according to another embodiment of the present invention.
Fig. 22 is the spectrum of the green phosphor employed in the present invention.
23A and 23B show spectra of red phosphors employed in the present invention.
24A and 24B are spectra for yellow or yellow orange phosphors employed in the present invention.
25 is a side sectional view schematically showing an LED light source module according to an embodiment of the present invention.
Fig. 26 is a side sectional view schematically showing an LED light source module according to another embodiment of the present invention.
27 is a side sectional view showing an example of a light emitting element employable in the white light emitting device according to the present invention.
Fig. 28 is a side sectional view showing another example of a light emitting element employable in the white light emitting device according to the present invention.
29 and 30 are plan and side cross-sectional views each showing an example of a light emitting device employable in the white light emitting device according to the present invention.
Fig. 31 is a side sectional view showing another example of a light emitting element employable in the white light emitting device according to the present invention.
32A and 32B are schematic diagrams illustrating a backlight unit according to various embodiments of the present disclosure.
33 is a cross-sectional view showing a direct type backlight unit according to an embodiment of the present invention.
34A and 34B are sectional views showing the edge type backlight unit according to another embodiment of the present invention.
35 is an exploded perspective view showing a display device according to an embodiment of the present invention.

Hereinafter, with reference to the accompanying drawings and embodiments will be described the present invention in more detail.

Phosphor according to an aspect of the present invention, has a β-type Si ₃ N ₄ crystal structure, and includes an oxynitride represented by the formula Si _{6 - z} Al _z O _z N _{8- z} : Eu _a , M _b , The composition formula satisfies the following conditions.

1) M is at least one selected from Sr and Ba;

2) Eu addition amount (a) is in the range of 0.1 to 5 mol%;

3) M addition amount (b) ranges from 0.1 to 5 mol%; And

4) Al composition ratio (z) is 0.1 <z <1.

The phosphor according to the present invention can be excited by a wavelength from the ultraviolet region to the blue region to provide green light emission. That is, a green phosphor is provided as a phosphor which irradiates an excitation source having a peak wavelength in a range of 300 nm to 480 nm to emit light having a peak wavelength in a range of 500 to 550 nm. In particular, in the case of excitation light in the ultraviolet band, higher conversion efficiency can be expected.

In this way, the phosphor is β-type Si ₃ N ₄ Si ₆ having a crystal structure according to the _invention the zAl _z O _z N _8-z of the host matrix, with Eu, Sr and Ba one or Sr and Ba of It is the β sialon type fluorescent substance added all.

As shown in FIG. 1, Sr (or Ba) added together with Eu is a form added as a dopant to an empty sphere without replacing elements (for example, Si or Al) constituting the host matrix. . That is, the addition of Sr or Ba in the present invention does not modify the host matrix (see Figure 2).

M, which is at least one selected from Sr and Ba, is added to contribute to the phase stabilization of the β-sialon phosphor to improve reliability, improve luminous efficiency, and serve to shorten the wavelength.

The amount of addition (b) of M may range from 0.1 to 5 mol%. If Sr is less than 0.1 mol%, the efficiency improvement effect and the shortening effect are not sufficient, and if it exceeds 5 mol%, there is a problem that the efficiency is lowered rather than the phosphor to which Sr is not added. Preferably, the amount of Sr added (a) may be in the range of 0.5 to 3 mol%. More preferably, the amount of Sr added (a) may be in the range of 1 to 1.5 mol%. In particular, since the luminance is improved to a level of 20% or more than when M is not added, high conversion efficiency can be improved.

The phosphor according to the above composition formula may exhibit a tendency that the peak wavelength of the light emitted from the phosphor by the excitation source irradiation is relatively short wavelength to 540nm or less. Therefore, the wavelength characteristic of green required by standard RGB can be satisfied at a relatively high level. That is, when the light emitted from the phosphor by the excitation source irradiation is represented by the (x, y) value in the CIE 1931 chromaticity coordinates, x and y can satisfy x≤0.336 and y≥0.637, respectively, so that bright white light Green phosphors that can provide can be advantageously used.

As described above, since the M dopant adopted in the present invention is added to the pores, the phase change of efficiency can be reduced by phase stabilizing the β-sialon phosphor. In general, the change in efficiency over time depends on the y color coordinate.

The y value of the CIE 1931 chromaticity coordinates measured from the light emitted when the phosphor is applied to the blue light emitting diode and starts to drive at 3.3 V and 120 Hz according to one measuring method is referred to as y1. When y is defined as y2 in the CIE 1931 chromaticity coordinates measured in the light emitted after being continued at 85 ° C. for 24 hours, y2-y1 may be defined. In this case, the change amount of y in the CIE 1931 chromaticity coordinate of the light emitted from the phosphor may be less than or equal to -0.0065.

In another aspect of the present invention, the above-described phosphor manufacturing method is provided.

First, raw materials including Si-containing oxides or nitrides, Al-containing oxides or nitrides, Eu-containing compounds and M-containing compounds are measured to satisfy the desired stoichiometry required by the above formula.

Subsequently, the raw material is mixed except for the M-containing compound to prepare a primary mixture. Next, the primary mixture is first fired, the primary firing result is ground / milled, and the M-containing compound is mixed with the ground primary firing result to prepare a secondary mixture. Subsequently, the above-described secondary mixture is calcined and the secondary calcined product may be ground to obtain the β-sialon phosphor described above. In addition, the obtained phosphor can be pickled to increase crystallization.

In the present invention, Sr can be added to the host matrix of β-sialon using a second baking process. In addition, by performing the secondary firing at a temperature lower than the primary firing it can be carried out smoothly.

In particular, since the secondary firing temperature is performed at a temperature lower than the primary firing temperature (1850 to 2300 ° C.), the secondary firing is carried out by mixing a compound containing desired Group 1 and Group elements with the primary firing result, As additional active agents, additional Group 1 and Group 2 elements can be added. The addition of these additional active agents can greatly contribute to shortening. Such Group 1 and Group 2 elements may be at least one element selected from the group consisting of Li, Na, K, Mg and Ca.

Hereinafter, each process example of the phosphor manufacturing method will be described in more detail.

The mixing of raw materials can be done in one of two ways: dry and wet.

First, according to the wet mixing method, the weighed mixture is mixed by inserting a ball and a solvent to help the mixing process and the grinding of the raw materials. In this case, a silicon oxide (Si ₃ N ₄ ) or zirconia (ZrO ₂ ) material or a ball generally used for mixing raw materials may be used. The solvent may be an alcohol such as DI Water, ethanol, or an organic solvent such as n-hexane. That is, the container is sealed after inserting the raw material, the solvent and the ball, and the raw material can be homogeneously mixed for about 1 to 24 hours using a device such as a miller. After the mixing process is completed, the mixed raw material and the ball can be separated, and most of the solvent can be dried by drying for about 1 to 48 hours in an oven. The dried powder may be uniformly classified to a desired micrometer size condition using a metal or polymer sieve.

On the other hand, according to the dry mixing method, the raw materials are inserted into the container without using a solvent and the raw materials are homogeneously mixed by using a milling machine. Mixing time is about 1 to 24 hours at this time by inserting the ball with the raw material, the mixing can be made easier to shorten the mixing time. Such a dry mixing method has an advantage of reducing the overall process time since it does not require a drying process of the solvent compared to wet. When the mixing of the raw materials is completed, as in the wet mixing, the powder, which has been completed in the mixing process, may be uniformly classified under a desired micrometer size condition using a sieve made of metal or polymer. The particle size condition of the phosphor will be described later with reference to FIG. 19.

In the firing process, the classified mixed powder may be filled in a boron nitride (BN) crucible and the firing process may be performed. At this time, the firing step is performed for about 1 to 24 hours at a temperature of a desired firing temperature (eg, 1850 to 2300 ° C, 1000 to 1800 ° C) using a heating furnace. The atmosphere during the firing process may use a mixed nitrogen gas containing 100% of nitrogen (N ₂ ) or 1 to 10% of hydrogen. After inducing or pulverizing the synthesized phosphor powder homogeneously using a pulverizer, the post-heat treatment process may be repeated once to three times to improve the luminance of the phosphor.

Hereinafter, the present invention will be described in more detail with reference to various embodiments.

( Example  One)

Raw material Si ₃ N ₄ , AlN, Al ₂ O ₃ , Eu ₂ O ₃ , SrCO ₃ is weighed by a stoichiometric ratio satisfying the composition ratio of Table 1 below to prepare a raw material group according to Example 1. Except for SrCO ₃ in the raw material group, the remaining raw materials are mixed with the ethanol solvent using a ball mill.

In the raw material mixture, the ethanol solvent is volatilized using a dryer, and the dried primary raw material mixture is filled in a boron nitride (BN) crucible. A boron nitride crucible filled with a primary raw material mixture is inserted into a heating furnace, and first calcined at 2050 ° C. for 10 hours in a gaseous state of N ₂ .

After pulverizing the primary calcined product, weighed SrCO ₃ is added and mixed together in a second manner using a miller. Subsequently, the secondary mixture was calcined again at 1750 ° C. to produce a phosphor according to the composition ratio of Example 1. After the grinding, and given the phosphors through the heat treatment and pickling process final _{Si 5 .8 Al 0 .2 O 0} .2 N 7 .8: Eu 0 .0152, a sialon phosphor of Sr between _{0 .01} β- Prepared.

( Comparative example  One)

Except for the matters related to the Sr raw material, the obtained phosphors were pulverized in the same manner as in Example 1 except the conditions of Example 1 were followed by the first firing conditions, and then Si _{5 was} subjected to post-heat treatment and pickling. _{.8 Al 0 .2 O 0 .2 N} 7 .8: prepared a sialon fluorescent substance between the Eu _{0 .0152} β-.

First, XRD analysis was performed on the β-sialon phosphors according to Example 1 and Comparative Example 1. The results are shown in the XRD graph of FIG.

As shown in FIG. 1, it can be seen that the β-sialon phosphor (Example 1) containing Sr and the β-sialon phosphor (Comparative Example 1) not containing Sr have the same crystal peaks. That is, the β-sialon phosphors according to Example 1 and Comparative Example 1 all have the same β-type Si ₃ N ₄ crystal structure.

As such, it can be confirmed that Sr added in Example 1 did not affect the crystal structure.

In addition, to confirm that Sr was added to Example 1, a TOF-SIMS measurement for detecting Sr concentration was performed.

Although Sr detection was not confirmed in the graph of FIG. 3B (Comparative Example 1), referring to FIG. 3A (Example 1), it was confirmed that Sr was doped (see fourth chart). This can be similarly confirmed in Figs. 4A and 4B, which are evaluated qualitatively. That is, while Sr does not exist in FIG. 4B (Comparative Example 1), Sr appears in FIG. 4A (Example 1).

According to the measurement and detection results, it can be seen that in Example 1, Sr is not substituted with a member element and is doped into the pores while maintaining the crystal structure.

division Al (z) Eu (a) Sr (b) Comparative Example 1 0.2 0.0152 none Example 1 0.2 0.0152 1mol% Example 2 0.2 0.0152 1.5mol% Example 3 0.2 0.0152 2mol% Example 4 0.2 0.0152 3mol% Example 5 0.2 0.0152 4mol%

( Example  2 to 5)

Examples 2 to 5 were carried out in the same manner as in Example 1, except that β-added 1.5 mol%, 2 mol%, 3 mol% and 4 mol% of Sr so as to satisfy the composition ratio of Table 1 above. An alon phosphor was prepared.

For the β-sialon phosphors according to Examples 1 to 5 and the β-sialon phosphors according to Comparative Example 1, luminance was measured along with color coordinates and emission spectra (peak wavelength and half width) at an excitation light source of 460 nm. .

division
Color coordinates Peak wavelength
(Nm) Half width
Luminance
(%) x y Comparative Example 1 0.3385 0.6352 540.6 51.0 100 Example 1 0.3344 0.6372 540.0 52.5 121.6 Example 2 0.3324 0.6398 539.5 52.0 123.5 Example 3 0.3273 0.6398 539.0 52.2 119.6

The luminance measurement results are shown in the graph of FIG. 5 together with Table 2 by displaying the luminance of Examples 1 to 5 with Comparative Example 1, in which Sr is not added, as a reference 100. As shown in FIG. 5, it can be seen that the β-sialon phosphors according to Examples 1 to 3 have improved relative luminance by 20% or more than the β-sialon phosphor of Comparative Example 1 to which Sr is not added. On the other hand, when the amount of Sr added is 3 mol%, 4 mol% (Examples 4 and 5), it was confirmed that the brightness increase was slightly reduced to 111.2% and 105%, respectively.

Therefore, in terms of improving luminance, that is, improving efficiency, the amount of Sr added may be set at 0.1 to 5 mol%. Preferably, the amount of Sr is 0.5 to 3 mol%, and more preferably, as shown in Examples 1 to 3, It may be 1 to 1.5 mol%.

On the other hand, the color coordinates of the β-sialon phosphors according to Examples 1 to 5 show distinct characteristics as compared with Comparative Example 1. That is, as shown in Table 2, the x value in the color coordinates of Examples 1 to 5 is lower than the x value of the β-sialon phosphor of Comparative Example 1 (short wavelength), and the y value tends to be high. In this regard, in the case of the peak wavelength, it was confirmed that in Example 1 to 5 all short wavelength to less than 540nm. In particular, this tendency can be increased as the amount of Sr added increases, as shown in FIG.

The color coordinates shown in Examples 1 to 5 provide an advantage of satisfying a high level of green luminous conditions of sRGB. That is, in the CIE 1931 color coordinate system of FIG. 6, green emission coordinates are generally advantageous as x is lower and y is higher. The emission color coordinates of the β-sialon phosphors according to Examples 1 to x were 0.336 or less, and y was 0.637 or more, indicating that they were more advantageous than Comparative Example 1.

In addition, since the β-sialon phosphor according to Examples 1 to 5 can increase the phase stability by adding Sr, it is possible to greatly reduce the change in conversion efficiency with time. In particular, such a change in efficiency can be compared and judged by a change in the y color coordinate. 8 is a graph showing the amount of y change in Examples 1 to 3 together with Comparative Example 1 as an effect of improving the characteristics over time.

There are various methods for measuring the amount of change in y, but in this experiment, the phosphor is applied to a blue light emitting diode of 460 nm and the CIE 1931 chromaticity coordinates measured from the light emitted when driving at 3.3 V and 120 Hz are started. The y value was defined as y1, and y2-y1 was defined as y2 in the CIE 1931 chromaticity coordinates measured in the light emitted after the driving condition was continued for 24 hours at 85 ° C.

As a result, in case of Comparative Example 1, it was found to be high as -0.0071. However, in Examples 1 to 3 corresponding to the present invention, the change amount of y in the CIE 1931 chromaticity coordinate of the light emitted from the phosphor may be -0.0065 or less. . It was confirmed that the time-lapse characteristics were also stabilized as the amount of Sr added.

The following Comparative Examples 2 to 5 and Examples 6 and 7 were carried out to confirm the presence or absence of effects when adding a composition other than Sr.

( Comparative example  2 to 4)

In Comparative Examples 2 to 4, except that CaCO ₃ is used as the Ca-containing compound instead of SrCO ₃ , the composition and the composition ratios of Comparative Examples 2 to 4 in Table 3 were satisfied under the same conditions and processes as in Example 1. Β-sialon phosphor to which 0.5 mol%, 1.0 mol% and 1.5 mol% Ca was added was prepared.

( Comparative example  5)

In Comparative Example 5, except that MgCO ₃ was used as the Ba-containing compound in place of SrCO ₃ , 1.0 mol of Mg was respectively satisfied so as to satisfy the composition ratio of Comparative Example 5 of Table 3 above under the same conditions and processes as in Example 1. Β-sialon phosphor to which% was added was prepared.

( Example  6)

The Sr, Ba respectively in this embodiment, so as to satisfy the composition ratio of the practice of the above Table 3 in the same conditions and process as in Example 1 except that it uses the additional Ba-containing compound is a BaCO ₃ with SrCO _3, and Example 6 Β-sialon phosphors, each added 0.5 mol%, were prepared.

( Example  7)

In the present Example, Ba is added to 1.0 in order to satisfy the composition ratio of Example 7 in Table 3 above under the same conditions and processes as in Example 1, except that BaCO ₃ , which is an additional Ba-containing compound, is used instead of SrCO ₃ . β-sialon phosphor added with mol% was prepared.

division Al (z) Eu (a) Additional dopant Kinds Amount added (mol%) Comparative Example 1 0.2 0.0152 none none Comparative Example 2 0.2 0.0152 Ca 0.5 Comparative Example 3 0.2 0.0152 Ca 1.0 Comparative Example 4 0.2 0.0152 Ca 1.5 Comparative Example 5 0.2 0.0152 Mg 1.0 Example 6 0.2 0.0152 Sr, Ba 0.5, 0.5 Example 7 0.2 0.0152 Ba 1.0

For the β-sialon phosphors according to Examples 6 and 7 and the β-sialon phosphors according to Comparative Examples 2 to 5, luminance was measured along with color coordinates and emission spectra (peak wavelength and half width) at an excitation light source of 460 nm. It measured and the result is shown in Table 4.

division
Color coordinates Peak wavelength
(Nm) Half width
Luminance
(%) x y Comparative Example 1 0.3385 0.6352 540.6 51.0 100 Comparative Example 2 0.3457 0.6272 541.5 55.4 75 Comparative Example 3 0.369 0.6052 541.5 61 54 Comparative Example 4 0.4132 0.5644 542.6 89 44 Comparative Example 5 0.3375 0.6356 540 52.7 90 Example 6 0.3328 0.6378 540 51.5 113.4 Example 7 0.3334 0.6375 540 51.5 116.3

First, looking at the results of the luminance measurement, it was found that in the case of Comparative Examples 2 to 5 to which Ca and Mg were added instead of Sr, all of them were lowered based on Comparative Example 1 (100) (see FIG. 9). Also, in the CIE 1913 color coordinates, the x value was rather large (long wavelength), and the y value was disadvantageous.

However, similarly to the case where only Sr, the β-sialon phosphor according to Examples 6 to 7, was added, the luminance was improved by 13.4% and 16.3% (see FIG. 10). In addition, in the CIE 1913 color coordinate, similarly to the previous embodiment, the x value was lowered (shorter wavelength), and the y value tended to be higher.

As described above, in the case of Ca and Mg in terms of color coordinates as well as luminance, Ca and Mg are not suitable to be used as an activator to replace Sr. However, similar effects can be expected when Ba is used together with Sr or Ba is added instead of Sr. It was confirmed.

Hereinafter, in order to confirm the conditions of Al composition ratio z, the following Examples 8-13 and Comparative Examples 5 and 6 were implemented.

( Example  8 to 13)

In the present examples, AlN and Al ₂ O ₃ are weighed so that the Al composition ratio (z) is 0.1, 0.2, 0.3, 0.4, 0.5, 1.0 (Examples 8 to 13, respectively) in the final phosphor, Except for mixing together, β-sialon phosphor was prepared under the same conditions and processes as in Example 1.

( Comparative example  5 and 6)

In this comparative example, AlN and Al ₂ O ₃ were weighed so that the Al composition ratio (z) was 1.5 and 2.0 (Examples 5 and 6, respectively) in the final phosphor, and mixed together in the primary raw material mixture. Β-sialon phosphor was prepared under the same conditions and processes as 1.

When the β-sialon phosphors according to Examples 8 to 13 and the β-sialon phosphors according to Comparative Examples 5 and 6 were excited with a light source of 460 nm, emission spectra were measured and shown in FIG. 11, respectively. Intensity integrals and peak intensities of Examples and Comparative Examples are shown.

11 and 12, in Examples 8 to 13 in which the Al composition ratio z is 1 or less, the normalized strength is high as about 0.8 or more, whereas the Al composition ratio z is 1.5 and 2.0, respectively. And 6, the luminance was slightly lowered.

As a result, Al composition ratio z is set to 0.01-1.0. Preferably, the Al composition ratio (z) is 0.1 to 0.3, showing the highest peak at 0.23.

Fig. 13 shows excitation spectra of the β-sialon phosphors according to Examples 8 to 13 and Comparative Examples 5 and 6 described above. As shown in FIG. 13, it was found that a high conversion efficiency can be expected in the ultraviolet band rather than the blue band (430 to 470 nm). Therefore, the present phosphor can be usefully used in an apparatus using ultraviolet light as an excitation light source.

Hereinafter, in order to confirm the conditions of addition amount (mol%) of Eu, the following Examples 14-23 were implemented.

( Example  14 to 23)

In this embodiment, the Eu ₂ O ₃ in the final phosphor Eu molar ratio (a) so that it is 0.65, 0.98, 1.30, 1.52, 1.73, 1.95, 2.17, 2.38, 2.60, 3.90 mol% ( Examples 14 to 23, respectively) Β-sialon phosphor was prepared under the same conditions and processes as in Example 1 except that it was weighed and mixed together in the primary raw material mixture.

When the β-sialon phosphors according to Examples 14 to 23 were excited with a light source of 460 nm, the emission spectrum was measured and shown in FIG. 14, and FIG. 15 shows the intensity integrals and peaks of the Examples and Comparative Examples. Indicates strength. Eu addition amount (a) is set to 0.1-5 mol%. In consideration of the half width (see Fig. 17) together with the luminance, the Eu addition amount (a) can preferably be seen in the range of 0.9 to 3 mol%.

Fig. 16 shows excitation spectra of the β-sialon phosphors according to Examples 8 to 13 and Comparative Examples 5 and 6 described above. As shown in Fig. 13, it was found that higher conversion efficiency can be expected in the ultraviolet band (particularly 355 nm) rather than the blue band and near ultraviolet (particularly 406 nm). Therefore, the present phosphor can also be usefully used for lighting or display devices employing ultraviolet rays as excitation light sources.

As such, the β-sialon phosphor proposed in the present invention may be advantageously applied to a light emitting device and various lighting and display devices. In this application, the phosphor can be used mixed with a transparent resin such as a silicone resin. When mixed with the transparent resin, the phosphor powder causes precipitation. For example, uneven distribution of the phosphors occurs due to precipitation in the state contained in the syringe before being applied to the package or before curing after application of the package, and there is a problem in that the color coordinate dispersion is increased depending on the package.

In order to reduce such scattering, the degree of precipitation must be kept constant, and the phosphor powder is preferably uniform. It can be appropriately controlled through particle size among many factors.

Β-sialon phosphor according to various embodiments of the present invention can also be appropriately controlled by the particle size distribution through the grinding and classification process. The particle size distribution of the preferred β-sialon phosphor shown in FIG. 17 is shown graphically. Preferred particle size conditions range from a D50 value of 14.5 to 18.5 μm, more preferably 14 to 18 μm. Additionally, D10 may range from 8-11 μm and D90 may range from 23-25 μm.

Hereinafter, various application forms including phosphors according to the present invention will be described with reference to the accompanying drawings.

19 is a schematic diagram showing a white light emitting device according to an embodiment of the present invention.

As shown in Fig. 19, the white light emitting device 10 according to the present embodiment includes a blue LED chip 15 and a resin packaging portion 19 having a lens shape convex upwardly.

The resin packaging portion 19 employed in the present embodiment is exemplified in a form having a hemispherical lens shape so as to secure a wide orientation. The blue LED chip 15 may be directly mounted on a separate circuit board. The resin packaging unit 19 may be made of the silicone resin, the epoxy resin, or a combination thereof. The green phosphor 12 and the red phosphor 14 are dispersed in the resin packaging unit 19.

The green phosphor 12 employable in the present embodiment is, in addition to the β-sialon phosphor described above, an oxynitride phosphor or M _a A _b O _c represented by a composition formula of M _x A _y O _x N _{(4/3) y} . An oxynitride phosphor represented by N _{((2/3) a + (4/3) b- (2/3) c)} can be used. Here, M is at least one group II element selected from the group consisting of Be, Mg, Ca, Sr, Zn, A is at least selected from the group consisting of C, Si, Ge, Sn, Ti, Zr, Hf It is one kind of group IV element.

On the other hand, the red phosphor 14 employable in the present embodiment includes a nitride phosphor of M1AlSiN _x : Re (1≤x≤5), a chalcogenide phosphor of M1D: Re, and (Sr, L) _2. A silicate-based phosphor having SiO _4-x N _y : Eu (where 0 <x <4, y = 2x / 3), and

Wherein M 1 is at least one element selected from Ba, Sr, Ca, and Mg, D is at least one element selected from S, Se, and Te, and L is at least selected from the group consisting of Ba, Ca, and Mg One Group 2 element or at least one Group 1 element selected from the group consisting of Li, Na, K, Rb and Cs, D is at least one selected from S, Se and Te, and Re is Y, La , Ce, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, F, Cl, Br and I.

As such, in the present invention, white light having a high color rendering index of 70 or more can be provided by combining a specific green phosphor and a specific red phosphor in consideration of half width, peak wavelength, and / or conversion efficiency. In addition, since light of various wavelength bands is obtained through the plurality of phosphors, color reproducibility can be improved.

In the case of the silicate-based phosphor of (Sr, L) ₂ SiO _{4 - x} N _y : Eu among the red phosphors, preferably, the x range may be 0.15 ≦ x ≦ 3. Some of Si in the above formula may be substituted with other elements. For example, it may be substituted with at least one element selected from the group consisting of B, Al, Ga, and In. Alternatively, with at least one element selected from the group consisting of Ti, Zr, Gf, Sn, and Pb. Can be substituted.

The dominant wavelength of the blue LED chip may range from 430 nm to 470 nm. In this case, the emission wavelength peak of the green phosphor 12 is in the range of 500 to 550 nm, and the emission wavelength peak of the red phosphor 14 is in order to secure a broad spectrum in the visible light band and to improve a larger color rendering index. It may range from 600 to 660 nm.

Preferably, the blue LED chip may have a half width of 10 to 50 nm, the green phosphor may have a half width of 30 to 200 nm, and the red phosphor may have a half width of 50 to 250 nm.

In another embodiment of the present invention, in addition to the red phosphor 12 and the green phosphor 14 described above, it may further include a yellow to yellow orange phosphor. In this case, a more improved color rendering index can be obtained. This embodiment is shown in FIG.

Referring to FIG. 20, the white light emitting device 20 according to the present embodiment includes a package main body 21 having a reflection cup at the center, a blue LED chip 25 mounted at the bottom of the reflection cup, and a reflection cup. The transparent resin packaging part 29 which encloses the blue LED chip 25 is included.

The resin packaging part 29 may be formed using, for example, a silicone resin, an epoxy resin, or a combination thereof. In the present embodiment, the resin packaging portion 29 further includes yellow to yellowish orange phosphors 26 together with the green phosphors 22 and the red phosphors 24 described in FIG.

That is, in addition to the β-sialon phosphor described above, the green phosphor 22 may additionally contain M _x A _y O _x N _{(4/3) y} oxynitride phosphor or M _a A _b O _c N _{((2/3) a + ( 4/3) b- (2/3) c)} oxynitride phosphors. The red phosphor 24 may be at least one selected from a nitride phosphor of M 1 AlSiN _x : Re (1 ≦ _x ≦ 5) and a chalcogen compound phosphor of M 1D: Re.

In addition, the present embodiment further includes a third phosphor 26. The third phosphor may be a yellow to yellow orange phosphor capable of emitting light in a wavelength band positioned between the green and red wavelength bands. The yellow to yellow orange phosphor may be a silicate-based phosphor, and the yellow orange phosphor may be α-SiAlON: Re-based or a garnet-based phosphor of YAG or TAG.

In the above-described embodiment, a form in which two or more kinds of phosphor powders are mixed and dispersed in a single resin packaging portion region is illustrated, but other structures may be variously changed. More specifically, the two or three phosphors may be provided in different layer structures. In one example, the green phosphor, the red phosphor, and the yellow or yellow orange phosphor may be provided as a multilayered phosphor film by dispersing the phosphor powder at high pressure.

On the contrary, as shown in FIG. 21, it may be implemented with a plurality of phosphor-containing resin layer structures.

Referring to FIG. 21, the white light emitting device 30 according to the present embodiment, similar to the previous embodiment, has a package main body 31 having a reflection cup in the center and a blue LED 35 mounted on the bottom of the reflection cup. ) And a transparent resin package 39 encapsulating the blue LED 35 in the reflection cup.

On the resin packaging part 39, resin layers containing different phosphors are provided. That is, the wavelength conversion portion is formed into the first resin layer 32 containing the green phosphor, the second resin layer 34 containing the red phosphor, and the third resin layer 36 containing the yellow or yellow orange phosphor. Can be configured.

As the phosphor used in this embodiment, the same or similar phosphor as the phosphor shown and described in Fig. 19 may be adopted and used.

White light obtained through the combination of the phosphors proposed in the present invention can obtain a high color rendering index. That is, when the yellow phosphor is coupled to the blue LED chip, yellow light converted with the blue wavelength light can be obtained. Since there is little wavelength light in the green and red bands in the entire visible light spectrum, it is difficult to secure a color rendering index close to natural light. In particular, the converted yellow light has a narrow half-width in order to obtain high conversion efficiency, so that the color rendering index will be further lowered in this case. In addition, since the characteristics of the white light expressed by a single yellow conversion degree are easily changed, it is difficult to ensure excellent color reproducibility.

On the contrary, in the invention example combining the blue LED chip, the green phosphor (G) and the red phosphor (R), since the light is emitted in the green and red bands as compared with the conventional example, a broader spectrum can be obtained in the visible light band. This can greatly improve the color rendering index. In addition, the color rendering index may be further improved by further including a yellow or yellowish orange phosphor capable of providing an intermediate wavelength band between the green and red bands.

22 shows an example of an emission spectrum for the green phosphor employed in the present invention. As shown in FIG. 22, it can be seen that the peak wavelength of the green phosphor obtained from the oxynitride phosphor according to the present invention has an emission spectrum of about 540 nm and a half width of 76.7 nm.

23A and 23B show light emission spectra for the red phosphor employed in the present invention.

Referring to Fig. 23A, a nitride phosphor of MAlSiN _x : Re (1? _X? 5), wherein M is at least one element selected from Be, Ba, Sr, Ca, and Mg, and Re is Y, La, Spectra of Ce, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, F, Cl, Br and I). The converted red light has a peak wavelength of about 640 nm and a half width of about 85 nm.

Referring to FIG. 23B, a chalcogenide-based phosphor of MD: Eu, Re (wherein M is at least one element selected from Be, Ba, Sr, Ca, and Mg, and D is at least selected from S, Se, and Te). At least one member selected from Y, La, Ce, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, F, Cl, Br, and I; Soy spectrum) is shown. The converted red light has a peak wavelength of about 655 nm and a half width of about 55 nm.

24A and 24B show spectra for yellow or yellow orange phosphors that may be optionally employed in the present invention.

Referring to Fig. 24A, the spectrum of the silicate-based phosphor is shown. The converted yellow light has a peak wavelength of about 555 nm and a half width of about 90 nm.

Referring to Fig. 24B, the spectrum of phosphor of α-SiAlON: Re (where Re is Y, La, Ce, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, F, At least one selected from Cl, Br, and I, and Re ranges from 1 ppm to 50000 ppm. The converted yellow light has a peak wavelength of about 580 nm and a half width of about 88 nm.

As such, the present invention has a high color rendering index of 70 or more by adding a yellow to yellowish orange phosphor in the form of combining a specific green phosphor and a specific red phosphor in consideration of half width, peak wavelength, and / or conversion efficiency. White light can be provided. The color coordinates of the red light in the light are in an area where x and y coordinates are in the range of 0.55 ≦ x ≦ 0.65, 0.25 ≦ y ≦ 0.35 based on the CIE 1941 color coordinate system, and the color coordinates of the green light are 0.2 ≦ x The color coordinates of the blue light are in the range where x and y coordinates are 0.1 ≦ x ≦ 0.2 and 0.02 ≦ y ≦ 0.15.

When the dominant wavelength of the blue LED chip is in the range of 430 nm to 470 nm, the emission wavelength peak of the green phosphor may be in the range of 500 to 550 nm, and the emission wavelength peak of the red phosphor may be in the range of 600 to 660 nm. The emission wavelength peak of the yellow to yellow orange phosphor may be in the range of 550 to 600 nm.

In addition, when the blue LED chip has a half width of 10 to 50 nm, the green phosphor may have a half width of 30 to 200 nm, preferably 60 to 80 nm, and the red phosphor may have a half width of 50 to 250 nm. Yellow to yellow orange phosphor may have a half width of 20 ~ 100nm.

Through the selection and combination of each phosphor having such a condition, in the present invention, it is possible to secure a broad spectrum in the visible light band and to provide excellent white light having a larger color rendering index.

The present invention can provide a white light source module that can be advantageously used as a light source of the LCD backlight unit. That is, the white light source module according to the present invention may be combined with various optical members (diffusion plate, light guide plate, reflector plate, prism sheet, etc.) as a light source of the LCD backlight unit to form a backlight assembly. 25 and 26 illustrate this white light source module.

First, referring to FIG. 25, the light source module 50 for an LCD backlight includes a circuit board 51 and an array of a plurality of white LED devices 10 mounted thereon. A conductive pattern (not shown) connected to the LED device 10 may be formed on the upper surface of the circuit board 51.

Each white LED device 10 can be understood as a white LED device shown and described in FIG. That is, the blue LED 15 is directly mounted on the circuit board 51 by a chip on board (COB) method. The configuration of each white LED device 10 includes a hemispherical resin packaging unit 19 having a lens function without having a separate reflective wall, so that each white LED device 20 can exhibit a wide orientation angle. have. The wide direct angle of each white light source can contribute to reducing the size (thickness or width) of the LCD display.

Referring to Fig. 26, a light source module 60 for an LCD backlight includes a circuit board 61 and an array of a plurality of white LED devices 20 mounted thereon. As illustrated in FIG. 20, the white LED device 20 includes a blue LED chip 25 mounted in a reflection cup of a package body 21 and a resin packing part 29 encapsulating the same. 29, yellow or yellowish orange phosphors 26 are dispersed and included together with the green and red phosphors 22 and 24.

The present invention can be implemented with various types of white light emitting devices using the above-described green phosphor as a wavelength changing material. Hereinafter, a light emitting device employable in a white light emitting device according to the present invention will be described with reference to the accompanying drawings.

First, the semiconductor stack structure of the light emitting device 100 illustrated in FIG. 27 may have a structure as follows. The protective layer 120 and the protective layer 120 formed on the upper and lower surfaces of the substrate 101 (hereinafter, referred to as a 'Si-Al alloy substrate') 101 and the Si-Al alloy substrate 101. The junction metal layer 102, the reflective metal layer 103, the p-type semiconductor layer 104, the active layer 105, and the n-type semiconductor layer 106 are sequentially stacked on the substrate. The p-type and n-type semiconductor layers 104 and 106 and the active layer 106 are GaN-based semiconductors, that is, Al _x Ga _y In _(1-xy) N (0≤x≤1, 0≤y≤1, 0≤x + y≤1) may be made of a semiconductor material or the like to form a light emitting structure.

An n-side electrode 107 is formed on the n-type semiconductor layer 106. The reflective metal layer 103 interposed between the junction metal layer 102 and the p-type semiconductor layer 104 further increases the luminance of the light emitting device by reflecting light incident from the semiconductor layer in an upward direction. The reflective metal layer 103 may be made of a metal having a high reflectance, for example, Au, Ag, Al, Rh, or a metal selected from the group consisting of two or more alloys thereof. However, the reflective metal layer 103 may not be formed as necessary.

The junction metal layer 102 serves to bond the Si-Al alloy substrate 101 to the light emitting structure, and Au may be used. Here, although the light emitting device 100 of the present invention includes the junction metal layer 102, the Si-Al alloy substrate 101 may be directly bonded on the p-type semiconductor layer 104 without the junction metal layer 102. have. Therefore, the light emitting device 100 of the present invention uses the Si-Al alloy substrate 101 as the conductive substrate.

Such Si-Al alloys are advantageous in terms of thermal expansion coefficient, thermal conductivity, mechanical workability and price. In other words, the coefficient of thermal expansion of the Si-Al alloy substrate 101 is similar to that of the sapphire substrate. Therefore, when manufacturing the light emitting device 100 using the Si-Al alloy substrate 101, the warpage of the substrate that occurred during the bonding process of the conventional conductive substrate made of Si and the separation process of the sapphire substrate by laser irradiation And it is possible to obtain a high quality light emitting device 100 with fewer defects by greatly reducing the occurrence of cracks in the light emitting structure.

In addition, the thermal conductivity of the Si-Al alloy substrate 101 is about 120 to 180 W / m · K, which is excellent in heat dissipation characteristics. In addition, since the Si-Al alloy substrate 101 can be easily manufactured by melting Si and AL at high pressure, the Si-Al alloy substrate 101 can be easily manufactured. Can be easily obtained at low cost.

In particular, in the light emitting device 100 of the present invention, a protective layer 120 is added to the upper and lower surfaces of the Si-Al alloy substrate 101 to prevent chemical penetration during the cleaning process to the Si-Al alloy substrate 101. It is formed. Here, the protective layer 120 may be made of a metal or a conductive dielectric. In this case, when the protective layer 120 is made of a metal, it may be made of any one of Ni, Au, Cu, W, Cr, Mo, Pt, Ru, Rh, Ti and Ta, or an alloy of at least two metal groups. .

In this case, the protective layer 120 may be formed by an electroless plating method, metal deposition, sputter or CVD, and at this time, between the Si-Al alloy substrate 101 and the metal protective layer 120. The seed metal layer 110 may be further formed in the plating process of the protective layer 120. The seed metal layer 110 may be made of Ti / Au or the like. In addition, when the protective layer 120 is made of a conductive dielectric, the conductive dielectric may be made of indium tin oxide (ITO), indium zinc oxide (IZO), or copper indium oxide (CIO). In this case, the protective layer 120 may be formed by deposition or sputtering. The protective layer 120 is preferably formed to a thickness of 0.01㎛ 20㎛ or less, it is preferably formed to a thickness of 1㎛ 10㎛ or less.

As described above, the light emitting device that can be employed in the white light emitting device of the present invention further forms a protective layer 120 such as Ni on the surface of the Si-Al alloy substrate 101, thereby performing cleaning after separation of the sapphire substrate. Al metal of the Si-Al alloy substrate 101 is etched by chemicals such as HCl, HF and KOH used in the process, and KOH used in the surface texturing process of the n-type semiconductor layer 106. There is an effect that can be prevented.

Therefore, the light emitting device employable in the present invention prevents the unevenness from being formed on the surface of the Si-Al alloy substrate 101, so that a defect occurs in that the light emitting structure bonded on the Si-Al alloy substrate 101 is peeled off. There is an effect that can prevent.

In addition, when a metal such as Ni is used as the protective layer 120, the surface roughness of the Si-Al alloy substrate 101 may be improved to firmly bond the Si-Al alloy substrate 101 to the light emitting structure. There is an advantage to this. That is, conventionally, the Si-Al alloy substrate 101 is subjected to a cleaning process using a chemical such as an acid for removing a natural oxide film before the bonding metal layer 102 is formed, and the surface of the Si-Al alloy substrate 101 is formed. As the Al metal was etched, surface irregularities of 200 to 500 nm were formed on the average, but as in the first embodiment of the present invention, a metal such as Ni was used as the protective layer 120 on the surface of the Si-Al alloy substrate 101. After the formation, the Ni CMP (Chemical Mechanical Polishing) treatment can reduce the surface irregularities to 5 nm or less, thereby improving the surface roughness like a mirror surface.

Thus, by improving the surface roughness of the Si-Al alloy substrate 101, there is an effect that can strengthen the bonding between the Si-Al alloy substrate and the light emitting structure, and improve the bonding yield.

As another example of the light emitting element employable in the white light emitting device according to the present invention, the light emitting element shown in Fig. 28 may be provided.

The light emitting device shown in Fig. 28 is similar to the light emitting device shown in Fig. 27, but the protective layer 120 is not formed on the entire upper and lower surfaces of the Si-Al alloy substrate 101, and the Si-Al alloy substrate 101 is formed. Is formed to expose a portion of the Si-Al alloy substrate 101 on the upper surface of the (), and a conductive layer 122 is further formed on the upper surface of the Si-Al alloy substrate 101 exposed by the protective layer 120 and the protective layer. It is formed and differs in that the contact metal layer 123 is formed in the lower surface of the Si-Al alloy substrate 101.

In particular, the protective layer 120 is preferably made of an insulating material rather than a metal or a conductive dielectric. That is, in the light emitting device according to the second embodiment of the present invention, instead of the protective layer 120 made of an insulating material other than a metal or a conductive dielectric, the Si-Al alloy substrate 101 having the protective layer 120 formed thereon is provided. In order to conduct electricity between the light emitting structure on the upper portion of the protective layer 120, the protective layer 120 is formed to expose a portion of the upper surface of the Si-Al alloy substrate 101, and includes the protective layer 120. The conductive layer 122 is further formed on the upper surface of the Si-Al alloy substrate 101. Here, the conductive layer 122 may be made of metal or the like.

On the other hand, the white light emitting device according to the present invention, unlike the light emitting device of the type illustrated above, may employ a light emitting device in which the arrangement of the electrode is changed to enable high current operation. 29 and 30 are plan views and cross-sectional views showing light emitting elements as another example of the light emitting elements employable in the present invention. 30 is a cross-sectional view taken along the line II ′ of FIG. 29.

29 and 30, the semiconductor light emitting device 200 may include a conductive substrate 210, a first electrode layer 220, an insulating layer 230, a second electrode layer 240, and a second conductive semiconductor layer ( 250, an active layer 260, and a first conductivity-type semiconductor layer 270, each of which is sequentially stacked.

The conductive substrate 210 may be formed of a material through which electricity can flow. For example, the conductive substrate 210 may be a metallic substrate including any one of Au, Ni, Cu, and W or a semiconductor substrate including any one of Si, Ge, and GaAs. The first electrode layer 220 is stacked on the conductive substrate 210, and the first electrode layer 220 is electrically connected to the conductive substrate 210 and the active layer 260, thereby providing the conductive substrate 210. ) And the active layer 260 are preferably made of a material which minimizes contact resistance.

The first electrode layer 220 is not only stacked on the conductive substrate 210, but as shown in FIG. 30, a portion of the first electrode layer 220 is formed in the insulating layer 230 and the second electrode layer 240. The first conductive semiconductor extends through the contact hole 280 penetrating through the second conductive semiconductor layer 250 and the active layer 260 and penetrating to a predetermined region of the first conductive semiconductor layer 270. In contact with the layer 270, the conductive substrate 210 and the first conductivity-type semiconductor layer 270 are provided to be electrically connected to each other. That is, the first electrode layer 220 electrically connects the conductive substrate 210 and the first conductive semiconductor layer 270, and electrically connects the contact hole 280 to the contact hole 280. ), More precisely, is electrically connected through the contact hole 280 through the contact area 290 where the first electrode layer 220 and the first conductive semiconductor layer 270 contact each other.

On the other hand, the insulating layer 220 to electrically insulate the first electrode layer 220 from the other layers except for the conductive substrate 210 and the first conductivity-type semiconductor layer 270 on the first electrode layer 220. Is provided. That is, the insulating layer 220 is not only between the first electrode layer 220 and the second electrode layer 240 but also the second electrode layer 240 and the second conductivity type semiconductor exposed by the contact hole 280. Also provided between side surfaces of the layer 250 and the active layer 260 and the first electrode layer 220. In addition, the insulating layer 220 may also be insulated from the side surface of the first conductive semiconductor layer 280 through which the contact hole 280 passes.

The second electrode layer 240 is provided on the insulating layer 220. Of course, as described above, the second electrode layer 240 does not exist in predetermined regions through which the contact hole 280 passes. In this case, as illustrated in FIG. 30, the second electrode layer 240 includes at least one exposed region, ie, an exposed region 245, in which a part of an interface contacting the second conductive semiconductor layer 250 is exposed. Doing. An electrode pad part 247 may be provided on the exposed area 245 to connect an external power source to the second electrode layer 240.

The second conductive semiconductor layer 250, the active layer 260, and the first conductive semiconductor layer 270, which will be described later, are not provided on the exposed region 245. In addition, the exposed region 245 is preferably formed at the corner of the semiconductor light emitting device 200, as shown in FIG. 30, in order to maximize the light emitting area of the semiconductor light emitting device 200. Meanwhile, the second electrode layer 240 preferably includes one of Ag, Al, and Pt metals, which is electrically connected to the second conductive semiconductor layer 250. As a layer having a property of minimizing contact resistance of the second conductivity-type semiconductor layer 250 and reflecting the light generated by the active layer 260 to the outside to increase the luminous efficiency It is because it is preferable to be provided.

The second conductivity type semiconductor layer 250 is provided on the second electrode layer 240, and the active layer 260 is provided on the second conductivity type semiconductor layer 250, and the first conductivity type semiconductor is provided. Layer 270 is provided on the active layer 260. In this case, the first conductive semiconductor layer 270 is an n-type nitride semiconductor, and the second conductive semiconductor layer 250 is preferably a p-type nitride semiconductor. Meanwhile, the active layer 260 may be formed by selecting different materials according to materials forming the first conductive semiconductor layer 270 and the second conductive semiconductor layer 250. That is, since the active layer 260 is a layer that emits energy by changing the recombination of electrons and electrons into light, the active layer 260 is larger than the energy band gap between the first conductive semiconductor layer 270 and the second conductive semiconductor layer 250. It is desirable to form a material with a small energy band gap.

Meanwhile, in another light emitting device employable in the present invention, unlike the light emitting device shown in FIG. 31, the first electrode layer connected to the contact hole may be exposed to the outside.

In the light emitting device 300 illustrated in FIG. 31, a second conductive semiconductor layer 350, an active layer 360, and a first conductive semiconductor layer 360 are formed on the conductive substrate 310. In this case, the second electrode layer 340 may be disposed between the second conductive semiconductor layer 350 and the conductive substrate 310, and unlike the previous embodiment, the second electrode layer 340 is not necessarily required.

In the present embodiment, the contact hole 380 having the contact region 390 in contact with the first conductivity-type semiconductor layer 370 is connected to the first electrode layer 320, and the first electrode layer 320 is moved to the outside. It is exposed and has an electrical connection 345. The electrode pad part 347 may be formed in the electrical connection part 345. The first electrode layer 320 may be electrically separated from the active layer 360, the second conductive semiconductor layer 350, the second electrode layer 340, and the conductive substrate 310 by the insulating layer 330.

In the above embodiment, unlike the contact hole was connected to the conductive substrate, in the present embodiment, the contact hole 380 is electrically separated from the conductive substrate 310 and the first electrode layer 320 connected to the contact hole 380. ) Is exposed to the outside. Accordingly, the conductive substrate 310 is electrically connected to the second conductivity-type semiconductor layer 340 and has a different polarity as in the previous embodiment.

Accordingly, such a light emitting device can partially secure the light emitting area by forming a part of the first electrode on the light emitting surface and placing the remaining part under the active layer, and high operation by uniformly disposing the electrode disposed on the light emitting surface. Even when the current is applied, the current can be uniformly distributed, thereby alleviating the current concentration phenomenon in the high current operation.

As described above, the light emitting device shown in FIGS. 30 and 31 has first and second main surfaces opposing each other, and the first and second conductivity type semiconductor layers providing the first and second main surfaces, respectively, and between them. A semiconductor laminate having an active layer formed thereon, a contact hole connected to a region of the first conductivity-type semiconductor layer from the second main surface through the active layer, and formed on a second main surface of the semiconductor laminate; It can be described as including a first electrode connected through the contact hole in one region of the conductive semiconductor layer, and a second electrode formed on the second main surface of the semiconductor laminate and connected to the second conductive semiconductor layer. have. Here, one of the first and second electrodes may have a structure that is drawn out in the lateral direction of the semiconductor laminate.

32A and 32B are schematic diagrams illustrating an example of a backlight unit according to various embodiments of the present disclosure.

Referring to FIG. 32A, an edge type backlight unit 1300 is illustrated as an example of a backlight unit to which a light emitting diode package according to the present invention may be applied as a light source.

The edge type backlight unit 1300 according to the present exemplary embodiment may include a light guide plate 1340 and an LED light source module 1310 provided on both side surfaces of the light guide plate 1340.

In this embodiment, the LED light source module 1310 is illustrated in the form provided on opposite sides of the light guide plate 1340, but may be provided only on one side, alternatively, the additional LED light source module 1310 is provided on the other side May be

As shown in FIG. 32A, a reflecting plate 1320 may be additionally provided under the light guide plate 1340. The LED light source module 1310 employed in the present embodiment includes a printed circuit board 1301 and a plurality of LED light sources 1305 mounted on an upper surface of the substrate 1301, wherein the LED light source 1305 is the above-described phosphor. The light emitting device package using is applied.

Referring to FIG. 32B, the direct type backlight unit 1400 is illustrated as an example of another type of backlight unit.

The direct type backlight unit 1400 according to the present exemplary embodiment may include a light diffusion plate 1440 and an LED light source module 1410 arranged on the bottom surface of the light diffusion plate 1440.

The backlight unit 1400 illustrated in FIG. 32B may include a bottom case 1420 that may accommodate the light source module 1410 under the light diffusion plate 1440.

The LED light source module 1410 employed in this embodiment includes a printed circuit board 1401 and a plurality of LED light sources 1405 mounted on an upper surface of the substrate 1401. The plurality of LED light sources 1405 may be light emitting device packages using the above-described phosphor as a wavelength conversion material.

In addition to the above-described embodiments, the phosphor may not be directly disposed in the package in which the LED is located, but may be disposed in other components of the backlight unit to convert light. This embodiment is shown in Figures 33-34.

First, as illustrated in FIG. 33, the direct type backlight unit 1500 according to the present exemplary embodiment may include a phosphor film 1550 and an LED light source module 1510 arranged on a lower surface of the phosphor film 1550. .

The backlight unit 1500 illustrated in FIG. 33 may include a bottom case 1520 that may accommodate the light source module 1510. In the present embodiment, the phosphor film 1550 is disposed on the upper surface of the bottom case 1520. At least a portion of the light emitted from the light source module 1510 may be wavelength-converted by the phosphor film 1550. The phosphor film 1550 may be manufactured and applied as a separate film, but may be provided in the form of being integrally coupled with the light diffusion plate.

Here, the LED light source module 1510 may include a printed circuit board 1501 and a plurality of LED light sources 1505 mounted on an upper surface of the board 1501.

34A and 34B show an edge type backlight unit according to another embodiment of the present invention.

The edge type backlight unit 1600 illustrated in FIG. 34A may include a light guide plate 1640 and an LED light source 1605 provided on one side of the light guide plate 1640. The LED light source 1605 may guide light into the light guide plate 1640 by the reflective structure 1620. In the present embodiment, the phosphor film 1650 may be located between the side of the light guide plate 1640 and the LED light source 1605.

The edge type backlight unit 1700 illustrated in FIG. 34B may include a light guide plate 1740 and an LED light source 1705 and a reflective structure 1720 provided on one side of the light guide plate 1740, similar to FIG. 34A. . In the present embodiment, the phosphor film 1750 is illustrated in the form applied to the light emitting surface of the light guide plate 1740.

As such, the phosphor according to the present invention may not be directly applied to the LED light source, but may be implemented in a form applied to other devices such as a backlight unit.

35 is an exploded perspective view showing a display device according to an embodiment of the present invention.

The display apparatus 2400 shown in FIG. 35 includes a backlight unit 2200 and an image display panel 2300 such as a liquid crystal panel. The backlight unit 2200 includes a light guide plate 224 and an LED light source module 2100 provided on at least one side of the light guide plate 2240.

In the present exemplary embodiment, the backlight unit 2200 may further include a bottom case 2210 and a reflector 2220 disposed under the light guide plate 2120 as shown.

In addition, according to the demand for various optical properties, the light guide plate 2240 and the liquid crystal panel 2300 may include various types of optical sheets 2260 such as a diffusion sheet, a prism sheet, or a protective sheet.

The LED light source module 2100 may be mounted on at least one side of the light guide plate 2240 and mounted on the printed circuit board 2110 to inject light into the light guide plate 2240. A plurality of LED light source 2150 is included. The plurality of LED light sources 2150 may be the above-described light emitting device package. The plurality of LED light sources employed in the present embodiment may be side view type light emitting device packages in which side surfaces adjacent to the light emitting surface are mounted.

As described above, the above-described phosphor may be applied to a package of various mounting structures to be applied to an LED light source module that provides various types of white light. The light emitting device package or the light source module including the same may be applied to various types of display devices or lighting devices.

It is intended that the invention not be limited by the foregoing embodiments and the accompanying drawings, but rather by the claims appended hereto. Accordingly, various forms of substitution, modification, and alteration may be made by those skilled in the art without departing from the technical spirit of the present invention described in the claims, which are also within the scope of the present invention. something to do.

Claims (40)

It has a β-type Si ₃ N ₄ crystal structure, comprising an oxynitride represented by the composition formula Si _{6 - z} Al _z O _z N _{8- z} : Eu _a , M _b ,
In the above formula, M is at least one selected from Sr and Ba, Eu addition amount (a) is in the range of 100 to 5000ppm, M addition amount (b) is in the range of 100 to 10000ppm, and Al composition ratio (z) is 0.1 <z < Satisfies 1
A phosphor that emits light having a peak wavelength in the range of 500 to 550 nm by irradiating an excitation source.
The method of claim 1,
The excitation source has a peak wavelength in the range of 300 nm to 480 nm.
The method of claim 2,
The peak wavelength of light emitted from the phosphor by the excitation source irradiation is 540 nm or less, characterized in that the phosphor.
The method of claim 1,
When the light emitted from the phosphor by the excitation source irradiation is represented by a (x, y) value in the CIE 1931 chromaticity coordinate, x and y satisfy x≤0.336 and y≥0.637, respectively.
The method of claim 1,
The change in y in the CIE 1931 chromaticity coordinates of the light emitted from the phosphor is less than -0.0065,
The y change amount is y1 in the CIE 1931 chromaticity coordinates measured from the light emitted initially under the condition that the phosphor is applied to the blue light emitting diode and driven at 3.3 V and 120 Hz, and the driving condition is 85. Phosphor characterized by being defined as y2-y1 when y is y2 in the CIE 1931 chromaticity coordinates measured in the light emitted after being carried out continuously for 24 hours at ℃.
The method of claim 1,
The phosphor is characterized in that M is strontium (Sr)
The method of claim 1,
The M is characterized in that it comprises both barium (Ba) and strontium (Sr).
The method of claim 1,
The particle size of the phosphor is characterized in that the D50 value is in the range of 14.5 ~ 18.5㎛.
The method of claim 1,
The phosphor is further characterized in that at least one element selected from the group consisting of Li, Na, K, Mg and Ca as an activator is further added.
It has a β-type Si ₃ N ₄ crystal structure and comprises an oxynitride represented by the composition formula Si _{6 - z} Al _z O _z N _{8- z} : Eu _a , M _b , wherein M is selected from Sr and Ba In order to produce an oxynitride phosphor having at least one kind, Eu addition amount (a) is in the range of 100 to 5000 ppm, M addition amount (b) is in the range of 100 to 10000 ppm, and Al composition ratio (z) satisfies 0.1 <z <1. Surveying raw materials comprising Si, oxide or nitride, Al-containing oxide or nitride, Eu-containing compound and M-containing compound
Preparing a primary mixture by mixing the raw materials except for the M-containing compound;
First firing the primary mixture and grinding the primary firing product;
Preparing a secondary mixture by mixing the M-containing compound with the pulverized primary firing product; And
Calcining the secondary mixture and pulverizing the secondary calcined product.
The method of claim 10,
The primary firing is performed at a temperature range of 1850-2300 ° C., and the secondary firing is performed at a temperature lower than the primary firing temperature. The method of claim 10,
The first and second firing is a method for producing a phosphor, characterized in that performed in a nitrogen gas atmosphere or a nitrogen and hydrogen mixed gas atmosphere.
The method of claim 10,
The M-containing compound is strontium (Sr) characterized in that the phosphor manufacturing method.
The method of claim 10,
The M-containing compound is a phosphor manufacturing method comprising a barium (Ba) containing compound and strontium (Sr) containing compound.
The method of claim 10,
Preparing the secondary mixture,
And adding a compound containing at least one element selected from the group consisting of Li, Na, K, Mg, and Ca as an activator together with the M-containing compound.
An LED chip emitting excitation light;
A green phosphor disposed around the LED chip to wavelength convert at least a portion of the excitation light, the green phosphor including the phosphor according to any one of claims 1 to 9; And
And at least one light emitting element emitting light of a different wavelength from the LED chip and the green phosphor and provided by at least one of an additional LED chip and phosphors of different species.
The method of claim 16,
The LED chip is a white light emitting device, characterized in that the LED chip for emitting ultraviolet light or visible light LED chip having a peak wavelength of 470nm or more.
The method of claim 16,
The LED chip is a blue LED chip having a peak wavelength in the range of 430 ~ 470nm,
The at least one light emitting element is a white light emitting device, characterized in that it comprises a red phosphor.
The method of claim 18,
The light emission wavelength peak of the red phosphor is 600 ~ 660nm, the light emission wavelength peak of the green phosphor is 500 ~ 550nm, characterized in that the white light emitting device.
The method of claim 18,
Wherein the blue LED chip has a half width of 10 to 50 nm, the green phosphor has a half width of 30 to 200 nm, and the red phosphor has a half width of 50 to 250 nm.
The method of claim 20,
The light emitting wavelength peak of the green phosphor is 535 to 545 nm, and the half width of the light emitting wavelength is 60 to 80 nm.
The method of claim 19,
In the CIE 1941 color coordinate system, the color coordinates of light emitted from the red phosphor are in the range of 0.55 ≦ x ≦ 0.65, 0.25 ≦ y ≦ 0.35, and the color coordinates of light emitted from the blue LED chip are 0.1 ≦ x ≦ 0.2, 0.02 ≦ y ≦ 0.15. White light emitting device, characterized in that within the range.
The method of claim 18,
The red phosphor may include a nitride phosphor of M1AlSiN _x : Re (1≤x≤5), a sulfide phosphor of M1D: Re, and a silicate phosphor of (Sr, L) ₂ SiO _{4 - x} N _y : Eu (here, 0 <x <4, y = 2x / 3)
Wherein M 1 is at least one element selected from Ba, Sr, Ca, and Mg, D is at least one element selected from S, Se, and Te, and L is at least selected from the group consisting of Ba, Ca, and Mg One Group 2 element or at least one Group 1 element selected from the group consisting of Li, Na, K, Rb and Cs, Re is Y, La, Ce, Nd, Pm, Sm, Gd, Tb, Dy At least one selected from among Ho, Er, Tm, Yb, Lu, F, Cl, Br and I.
The method of claim 18,
The at least one light emitting element further comprises a yellow or yellow orange phosphor.
25. The method of claim 24,
Wherein the yellow phosphor is a silicate-based phosphor, and the yellow orange phosphor is an α-SiAlON: Re phosphor.
The method of claim 16,
The at least one light emitting element is a white light emitting device, characterized in that the red LED chip.
The method of claim 16,
The LED chip has a structure in which the first and second electrodes are arranged to face the same surface.
The method of claim 16,
The LED chip has a structure in which the first and second electrodes are arranged to face different surfaces opposite to each other.
The method of claim 16,
The LED chip,
A semiconductor laminate having a first and a second main surface facing each other and having a first and a second conductivity type semiconductor layer providing the first and second main surfaces, respectively, and an active layer formed therebetween, from the second main surface A contact hole connected to a region of the first conductivity type semiconductor layer through the active layer, and formed on a second main surface of the semiconductor laminate and connected to the region of the first conductivity type semiconductor layer through the contact hole; And a second electrode formed on the second main surface of the semiconductor laminate and connected to the second conductive semiconductor layer.
The method of claim 29,
Any one of the first and second electrodes has a structure that is laterally drawn out of the semiconductor laminate.
The method of claim 16,
And a package main body having a groove portion in which the LED chip is mounted.
The method of claim 16,
Further comprising a resin packaging for encapsulating the LED chip,
At least one of the plurality of phosphors is dispersed in the resin packaging, characterized in that the white light emitting device.
The method of claim 16,
And the plurality of phosphors each form a plurality of phosphor-containing resin layers different from each other, and the plurality of phosphor-containing resin layers have a stacked structure.
The method of claim 18,
The color rendering index (CRI) of the white light emitted from the white light emitting device is characterized in that more than 70.
A surface light source device using the phosphor according to any one of claims 1 to 9 as a wavelength conversion material.
Light guide plate; And
And a LED light source module disposed on at least one side of the light guide plate to provide light inside the light guide plate.
The LED light source module includes a circuit board and a plurality of white light emitting devices mounted on the circuit board and using a phosphor according to any one of claims 1 to 9 as a wavelength converting material. Device.
Display device using the phosphor according to any one of claims 1 to 9 as a wavelength conversion material.
An image display panel for displaying an image; And
A display device comprising a backlight unit having the surface light source device according to claim 36 for providing light to the image display panel.
A lighting apparatus using the phosphor according to any one of claims 1 to 9 as a wavelength conversion material.
LED light source module; And
And a diffusion sheet disposed on the LED light source module and uniformly diffusing the light incident from the LED light source module.
The LED light source module includes a circuit board and a plurality of white light emitting devices mounted on the circuit board and using a phosphor according to any one of claims 1 to 9 as a wavelength converting material. .

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