KR100672972B1 - White diode - Google Patents

Abstract

A light source having at least an excitation light source and a fluorescent powder, the excitation light source can emit a light source having a wavelength between 258 nm and 490 nm, and the fluorescent powder is disposed around the excitation light source and receives the light source emitted by the excitation light source. In addition, the material of the fluorescent powder is selected from the group consisting of (Ca, Sr, Ba) ₃ Mg * SiO ₄ ) ₄ Cl ₂ : Eu ²⁺ , Dy ³⁺ , Mn ³⁺ . Such a white light emitting diode has high luminous efficiency and good color rendering.

Excitation light source, fluorescent material, white light emitting diode, color rendering

Description

White Light Emitting Diodes {WHITE DIODE}

Figure 1 shows an embodiment of a white light emitting diode according to the present invention,

Figure 2 shows another embodiment of a white light emitting diode according to the present invention,

Figure 3 shows another embodiment of a white light emitting diode according to the present invention,

Figure 4 shows another embodiment of a white light emitting diode according to the present invention,

5 is a side cross-sectional view of a white light emitting diode of a white light emitting diode according to the present invention;

Figure 6 shows a planar embodiment of a white light emitting diode of a white light emitting diode according to the present invention,

Figure 7 shows a planar embodiment of a white light emitting diode of a white light emitting diode according to the present invention,

8 shows a planar embodiment of a white light emitting diode of a white light emitting diode according to the present invention;

FIG. 9 shows that the emission spectrum becomes 508.2 nm in the excitation spectrum and radiation spectrum group of Ca _7.8 Mg (Sio ₄ ) ₄ Cl ₂ : Eu _0.12 Dy _0.08 of the present invention.

FIG. 10 shows an XRD spectrum group of green phosphor Ca _7.8 Mg (Sio ₄ ) ₄ Cl ₂ : Eu _0.12 Dy _0.08 added with europium and dysprosium at the same time of the present invention.

FIG. 11 shows that Eu is increased and the emission spectrum is 511.8 nm in the excitation spectrum and the emission spectrum group of Ca _7.6 Mg (Sio ₄ ) ₄ Cl ₂ : Eu _0.32 Dy _0.06 of the present invention.

FIG. 12 shows the emission spectrum of 563 nm in the (Sr _7.48 Ca _0.2 ) Mg (SiO ₄ ) ₄ Cl ₂ : Eu _0.12 Mm _0.2 excitation spectrum and radiation spectrum group of the present invention,

FIG. 13 shows a magenta phosphor (Sr _7.48 Ca _0.2 ) Mg (SiO ₄ ) ₄ Cl ₂ : Eu _0.12 Mm _0.2 XRD spectral group simultaneously added with europium and manganese of the present invention.

Fig. 14 shows that Eu is increased in the (Sr _7.28 Ca _0.2 ) Mg (SiO ₄ ) ₄ Cl ₂ : Eu _0.32 Mm _0.2 excitation spectrum and radiation spectrum group and the radiation spectrum is extended to 564.4 nm. Shown,

Fig. 15 shows that the radiation spectrum becomes 616.2 nm in the (Sr _0.78 Ca _0.17 ) S: Eu _0.1 Sm _0.015 excitation spectrum and radiation spectrum group of the present invention,

FIG. 16 shows an XRD spectrum group of red phosphor (Sr _0.78 Ca _0.17 ) S: Eu _0.1 Sm _0.015 added with europium and samarium at the same time of the present invention.

FIG. 17 shows that Ca is increased and the radiation spectrum is extended to 641.8 nm in the (Sr _0.35 Ca _0.6 ) S: Eu _0.1 Sm _0.015 excitation spectrum and radiation spectrum group of the present invention.

FIG. 18 shows that the radiation spectrum of the Sr _4.7 (PO ₄ ) ₂ Cl: Eu _0.15 Gdo _0.15 excitation spectrum and radiation spectrum group is increased by 2 times the intensity.

FIG. 19 shows an XRD spectrum group of blue phosphor Sr _4.7 (PO ₄ ) ₂ Cl: Euo _0.15 Gdo _0.15 at the same time of addition of europium and gadolinium of the present invention.

FIG. 20 shows the intensity of the radiation spectrum when Gd is not added in the Sr _4.85 (PO ₄ ) ₂ Cl: Eu _0.15 excitation spectrum and radiation spectrum group of the present invention.

FIG. 21 shows 20% of the green fluorescent substance Ca _7.8 Mg (SiO ₄ ) Cl ₂ : Eu _0.12 Dy _0.08 and 80% of the magenta phosphor (Sr _7.48 Ca _0.2 ) Mg (SiO ₄ ) ₄ Cl ₂ : Shows a spectral group of a three-wavelength white light emitting diode comprising a combination of Eu _0.12 Mm _0.2 and capable of emitting blue excitation light having a wavelength of 455 nm on a light emitting diode chip.

Fig. 22 is a chromaticity diagram of a light emitting diode using 100% green fluorescence Ca _7.8 Mg (SiO ₄ ) ₄ Cl ₂ : Eu _0.12 Dy _{0.08 according} to the present invention and capable of emitting blue excitation light having a wavelength of 455 nm to a light emitting diode chip. Shows the spectrum,

Figure 23 is formulated with a suitable fluorescence distribution ratio of the present invention and is characterized by magenta fluorescence, green fluorescence, red fluorescence (Sr _0.78 Ca _0.17 ) S: Eu _0.1 Sm _0.015 and blue fluorescence Sr _4.7 (PO ₄ ). ₂ Cl: Euo _0.15 Gdo _0.15 is used, and at the same time shows a spectrum with the excitation light having a wavelength of 385 nm.

[Description of Drawing Reference]

100 ... white light emitting diode 110 ... lead frame

110a ... recess 112a ... first contact

112b ... Second contact 120 ... Light emitting diode chip

122a ... anode electrode 122b ... cathode electrode

124 ... excitation light 130 ... bag resin

132 ... Fluorescent 134 ... Fluorescent

140 ... Adhesive 150 ... Bonding Wire

200 ... white light emitting diode 210 ... circuit board

210a ... concave hole 210b ... concave hole convex or flat convex

220 ... LED chip 230 ... Encapsulation resin

232 ... fluorescent powder 240 ... adhesive

310 ... base 320 ... anode

330 ... light emitting diode chip layer 340 ...

350 ... Contact layer 360 ... Cathode electrode

410 ... blue fluorescent light 420 ... green fluorescent light

430 ... magenta fluorescence 440 ... red fluorescence

The present invention relates to a kind of novel white light emitting diode, and more particularly to a white light emitting diode having high color rendering property capable of generating 3-4 kinds of wavelengths by blue excitation. The white light emitting diode of the present invention uses the fluorescent substance of sodium K acid of the present invention, which does not completely belong to the YAG & TAG material and additionally does not contain materials such as Y, Tb, Al, Ce, etc. Do not The fluorescent substance of sodium K acid of the present invention is Eu-emission-centered and completely different from patents such as Nicha patent (YAG) and Osram (TAG) fluorescent powders, and also poor color rendering of the blue-chip package. It improves the problem of light and improves the brightness while at the same time improving the brightness of the UV-chip package and UV-chip can be used in the actual package.

A well-known light emitting diode (LED) belongs to a semiconductor device, and the light emitting chip is made of a group III-V chemical element, for example, a compound semiconductor such as GaP, GaAs, GaN, and the like. That is to say, by applying a current to the compound semiconductor, by combining electrons and energy to emit excess energy in the form of light and achieve the effect of light emission. The light emitting phenomenon of the light emitting diode becomes overheated or discharged light and belongs to cold U light. For this purpose, the life time of the light emitting diode is achieved over 100,000 hours and no idling time is required. Other diodes have a fast response (approximately 10 ^-9 seconds), small volume, low power consumption, low contamination (contains no mercury), high reliability, and are suitable for mass production. It has the same place and the application area is wide enough for it. Most notable among them is white light emitting diodes. In particular, in recent years, in the light source of the light emitting diode, the backlight of the liquid crystal display, or the lighting equipment, there is a trend that is already changing to the traditional fluorescent lamp and incandescent lamp.

In general, known white light emitting diodes generate a white color by combining a yellow inorganic fluorescent substance (or yellow organic fluorescent dye) with a blue light emitting diode chip. The blue light wavelength of the blue light emitting diode generated therein is between 440 nm and 490 nm, after which yellow inorganic fluorescent light is irradiated with blue light, yellow fluorescence is generated and yellow fluorescent light and blue light are mixed to obtain necessary white light later. Such a white photodiode is easily manufactured by the above-mentioned one type of white light emitting diode, has a low production cost, and many of the white photodiodes on the market today are of this type. However, the luminous efficiency of such a white light emitting diode is low, and this becomes a white light emitting diode of two wavelengths (mixing blue light and yellow light), and thus, it does not become a white light emitting diode of three wavelengths different in color rendering and display color temperature.

In recent years, white light-emitting diodes are packaged using Nichia-owned blue LEDs and Y ₃ Al ₅ O ₁₂ : Ce ³⁺ fluorescent ^powders (hereinafter referred to as YAG) (see Patent Documents 1 and 2) and Osram Fluorescent Tb _3. A patented discharge of a white light emitting diode is carried out in the chage for Al ₅ O ₁₂ : Ce ³⁺ (hereinafter referred to as YAG), and the fluorescent substance to replace YAG & TAG is detected and the Nichia patent studio breaks through. In addition, the white light emitting diodes of the blue light emitting diodes and the white light emitting diodes of the YAG & TAG fluorescent powder package do not fall short of the three wavelength white light emitting diodes at the color rendering properties and the display color temperature, and also the demand for high power light emitting diodes and high color rendering properties. Reflecting the requirement of high stability and high luminous efficiency, the present invention uses the fluorescent substance of sodium K-acid of the present invention, which is completely different from the YAG & TAG material. It is to provide a white photodiode of the present invention, which serves as a light emitting center.

[Patent Document 1] European Patent WO 98/05078

[Patent Document 2] European Patent WO 98/12757

It is an object of the present invention to provide a high color rendering white light emitting diode capable of generating three kinds of light rays of three wavelengths excited by a kind of ultraviolet light and blue light, and to provide a relatively high luminous efficiency and good color rendering property.

Hereinafter, the most preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. . Other objects, features, and operational advantages, including the object, operation, and effect of the present invention will become more apparent from the description of the preferred embodiment.

For the above-mentioned object, the present invention develops the fluorescent powder of the present invention, which is completely different from Nichia patent (YAG) and OSRAM patent (TAG), among which the fluorescent material is Y, Tb, Al, Ce, etc. It does not contain and does not make Ce the light emitting center. The material of the fluorescent substance of sodium K acid of the present invention is selected from Ca, Sr, Ba, Mg, Cl, SiO ₄ and the like, and Eu is the light emission center. The location of the fluorescence component communicates with the following. That is, the fluorescent substance of sodium K acid has better water resistance than sodium aluminate, has high light transmittance, high luminous efficiency, is hard to decay with Eu as a light emitter, and is stable in comparison with Ce. Sodium K-phosphate phosphor employs Ca, Sr, Ba, and Mg as the base material for fluorescein and has a low specific gravity (the specific gravity of the new sodium phosphate K is 3.458 and the specific gravity of YAG & TAG phosphor is 4.33) As a result, the novel sodium K-acid fluorescent substance is less likely to settle in the light emitting diode package, and the package is satisfactory.

In addition, the wavelength of the excitation light is wide and the radiation wavelength is different from that applied to the UV-chip and the blue-chip with the excitation wavelength of 250 nm to 485 nm of the fluorescence of the present invention and the other fluorescence can absorb only the small local wavelength. It is stable and therefore has a high luminous efficiency and is applied to a 250 nm to 485 nm wavelength LED package, and the chromaticity after the package is stable and color rendering is also good.

The present invention provides a kind of white light emitting diode, which includes at least an excitation light source, a reload, an encapsulant and a fluorescent component. Among them, there is a concave hole on the surface of the retread, the excitation light source is disposed in the concave hole of the retread and electrically connected to the retread, the excitation light source emits a light beam and the wavelength of the light beam is between 250 nm and 490 nm. The encapsulation resin is disposed on top of the retread and also covers the excitation light source and adheres to the excitation light source. In addition, the fluorescent material receives a light source for emitting an excitation light source disposed around the excitation light source, and the fluorescent material of the present invention is (Ca, Sr, Ba) ₃ Mg (SiO ₄ ) ₄ Cl ₂ : Eu ²⁺ , Dy ³⁺ , Mn ³⁺ is selected from the group consisting of one or two or more.

The white light emitting diode of the present invention includes a plurality of bonding wires, which are electrically connected between the excitation light source and the rewind. In addition, the retread is a lead frame or a circuit board, and the excitation light source is a light emitting diode chip or a laser diode chip.

The material of the fluorescent powder described in the present invention can be adjusted according to the wavelength of the light source emitted by the excitation light source. For example, when the wavelength of the light source is between 250 nm and 490 nm, the material of the fluorescent powder is (Ca, Sr, Ba). One or two or more kinds are selected from the group consisting of ₃ Mg (SiO ₄ ) ₄ Cl ₂ : Eu ²⁺ , Dy ³⁺ , Mn ³⁺ .

Among the materials of the above-described fluorescent substance, (Me _1-xy Eu _x Re _y ) ₈ Mg _z (SiO ₄ ) _m , Cln; 0 <x ≦ 0.8, 0 ≦ y ≦ 2.0, 0 ≦ z ≦ 1.0, 0 ≦ m ≦ 6.0, and 0.1 ≦ n ≦ 3.0. In addition, Me is one or two or more selected from the group consisting of calcium and strontium, and Re is dysprosium, samarium, triumium, magnesium, manganese and zinc. One or two or more kinds are selected from the group consisting of.

The K-acid sodium fluorescence powder of the present invention can produce fluorescence of green light and magenta light by adjusting the component ratio of Ca, Sr, Mg, SiO ₄ , Eu, Dy, Mn, and the like (Sr _0.78 Ca _0.17 ) S: Eu _0.1 Sm _{0.015 The} red fluorescence production process employs the Na ₂ S process, and the luminous efficacy and heat resistance of the red fluorescence can be improved by adding Sm. In addition, the production of Sr _4.7 (PO ₄ ) ₂ Cl: Eu _0.15 Gd _0.15 blue light fluorescence can double the luminous efficiency of blue light fluorescence by adding Gd.

Based on the above description, the white pore-emitting diode of the present invention uses a light emitting diode chip (or laser diode chip) having a light emission wavelength of 250 nm to 490 nm as an excitation light source and simultaneously combines fluorescent materials of different materials, yellow, red, and green. Fluorescence of other colors, such as blue and the like, is mixed with the excitation light generated by the existing excitation light source at the time of dung to form white light. The white light emitting diode of the present invention is a four wavelength white light emitting diode and a chip at three wavelengths, which has a relatively high luminous efficiency and good color rendering property.

The invention of claim 1, wherein the white light emitting diode emits at least a light beam and has a wavelength of 250 nm to 490 nm and is disposed around an excitation light source and the excitation light source and simultaneously receives the light source for emitting the excitation light source. In minutes

The material of the fluorescent substance is (Me _1-xy Eu _x Re _y ) ₈ Mg _z (SiO ₄ ) _m , Cln, (Me _1-x Eu _x ) ReS and (Ca _1-xy Sr _x Ba _y ) ₅ (PO ₄ ) A white light emitting diode comprising the above-mentioned fluorescent substance selected from the group consisting of ₃ Cl: Eu ²⁺ and Gd ²⁺ is described.

In the white light emitting diode according to claim 1, the material of the fluorescence component is (Me _1-xy Eu _x Re _y ) ₈ Mg _z (SiO ₄ ) when the wavelength of the light beam is between 440 nm and 490 nm. A white light emitting diode is characterized in that at least one member is selected from the group consisting of _m ), Cln and (Me _1-x Eu _x ) ReS.

In the white light-emitting diode according to claim 1, the material of the fluorescence component is (Me _1-xy Eu _x Re _y ) ₈ Mg _z (SiO ₄ ) when the wavelength of the light beam is between 250 nm and 450 nm. ) _m , Cln and (Me _1-x Eu _x ) ReS and (Ca _1-xy Sr _x Ba _y ) ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ , at least one kind selected from the group consisting of Gd ²⁺ A white light emitting diode is described.

In the white light emitting diode according to claim 1, 0 <x ≤ 0.8, 0 ≤ y ≤ 2.0, 0 ≤ z ≤ 1.0, 0 ≤ m ≤ 6.0, 0.1 ≤ n ≤ 3.0, characterized in that A white light emitting diode is described.

According to the invention of claim 5, in the white light emitting diode according to claim 1, Me is a white light emitting diode in which at least one selected from the group consisting of calcium, strontium, trilium, magnesium, manganese and zinc is selected. It is described.

In the white light emitting diode according to claim 1, Re is at least one selected from the group consisting of dysprosium, samarium, trilium, magnesium, manganese and zinc. Is selected, and the fluorescent powder contains Ca, Sr, Mg, Cl, SiO ₄ , Dy elements, and among them, the raw material powder may be an oxide, acetate, organometallic compound or metal salt thereof. White light emitting diodes are described.

According to the invention of claim 7, in the red fluorescent substance, (Me _1-x Eu _x ) The luminous efficiency and heat resistance of the red fluorescence labeled ReS and produced by employing the Na ₂ S process and with Sm increases, and also contains the elements Ca, Sr, Ba, S, Cl, Eu and Sm in the red fluorescence. Among them, the raw powder describes a red fluorescence powder characterized in that oxides, acetates, organometallic compounds or metal salts of metal compounds can be used.

In the blue fluorescence, the invention of claim 8 is produced by adding Gd to (Ca _1-xy Sr _x Ba _y ) ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ to increase the luminous efficacy of the blue fluorescence ( Ca _1-xy Sr _x Ba _y ) ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ , Gd ²⁺ Blue fluorescence contains Ca, Sr, Ba, PO ₄ , Cl, Eu, Gd elements The red fluorescent substance is characterized in that an oxide, an acetate, an organometallic compound or a metal salt of the metal compound can be used.

According to a ninth aspect of the present invention, in the white light emitting diode according to claim 1, the white light emitting diode is characterized in that the excitation light source is received by either of the light emitting diode chip and the laser diode chip.

In the white light emitting diode, the present invention provides a light emitting diode comprising: a rewinding device having at least a concave hole convex portion or a planar convex portion on a surface thereof, and capable of increasing light emission efficiency to increase light emission efficiency;

An excitation light source disposed in the concave convex portion or planar convex portion of the retreader and simultaneously electrically connected to the retreader to emit light having a wavelength of 250 nm to 490 nm;

An encapsulation resin disposed on the zipping and covering the excitation light source and fixing the excitation light source to the zipping;

A fluorescent powder disposed in the encapsulating resin and receiving the emitted light of the excitation light source is provided, and the material of the fluorescent powder is (Me _1-xy Eu _x Re _y ) ₈ Mg _z (SiO ₄ ) _m , Cln and (Me _{1 -x} Eu _x) ReS and _{(Ca 1-xy Sr x Ba} y) 5 (PO 4) 3 Cl: Eu 2+, is one kinds or more selected from the group consisting of the minute fluorescent Gd ^2+; It describes a white light emitting diode comprising a.

The white light emitting diode according to claim 10, further comprising a plurality of bonding wires, wherein the bonding wires are electrically connected between the excitation light source and the rewinding. It is described.

A white light emitting diode according to a twelfth aspect of the present invention discloses a white light emitting diode according to claim 10, wherein retreading is accommodated in both the lead frame and the circuit board.

According to a thirteenth aspect of the present invention, in the white light emitting diode according to claim 10, the white light emitting diode is characterized in that the excitation light source is received by either the light emitting diode chip or the laser diode chip.

The invention of claim 14, wherein in the white light emitting diode according to claim 10, when the wavelength of the light beam is between 440 nm and 490 nm, the material of the fluorescent powder is (Me _1-xy Eu _x Re _y ) ₈ Mg _z (SiO ₄ A white light emitting diode is characterized in that at least one member is selected from the group consisting of _m ), Cln and (Me _1-x Eu _x ) ReS.

According to the invention of claim 15, in the white light emitting diode according to claim 10, when the wavelength of the light beam is between 250 nm and 440 nm, the material of the fluorescent powder is (Me _1-xy Eu _x Re _y ) ₈ Mg _z (SiO ₄ ) _m , Cln and (Me _1-x Eu _x ) ReS and (Ca _1-xy Sr _x Ba _y ) ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ , at least one kind selected from the group consisting of Gd ²⁺ A white light emitting diode is described.

According to a sixteenth aspect of the present invention, in the white light emitting diode according to claim 10, 0 <x ≦ 0.8, 0 ≦ y ≦ 2.0, 0 ≦ z ≦ 1.0, 0 ≦ m ≦ 6.0, and 0.1 ≦ n ≦ 3.0. White light emitting diodes are described.

According to a seventeenth aspect of the present invention, in the white light emitting diode according to claim 1, at least one Me is selected from the group consisting of calcium, strontium, triumium, and barium. White light emitting diodes are described.

According to the invention of claim 18, in the white light emitting diode according to claim 10, Re is praseodym, rubidium, samarium, dysprosium, holium ), At least one selected from the group consisting of yttrium, erbium, europium, triumium, thulium, ytterbium, gadolinium, magnesium and manganese A white light emitting diode is described.

19. The invention of claim 19, wherein the white light emitting diode comprises: a light emitting diode chip having a wavelength of 250 nm to 490 nm and a fluorescent sublayer;

At least a substrate;

A die layer sandwiching the conductive buffer layer in an upward direction of the substrate;

An anode electrode in contact with the conductive buffer layer and positioned over the contact layer;

A cathode electrode in contact with the conductive buffer layer and simultaneously isolated from the first and second clad layers, the light emitting layer, the contact layer, and the anode electrode;

The fluorescent layer is disposed around the fluorescent diode chip and at the same time receives the light emitted by the light emitting diode chip, the material of the fluorescent layer is (Me _1-xy Eu _x Re _y ) ₈ Mg _z (SiO ₄ ) _m , At least one member is selected from the group consisting of Cln, (Me _1-x Eu _x ) ReS and (Ca _1-xy Sr _x Ba _y ) ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ , Gd ²⁺ White light emitting diodes are described.

In the white light emitting diode of claim 19, when the wavelength of the light beam is between 440 nm and 490 nm, the material of the fluorescent powder is (Me _1-xy Eu _x Re _y ) ₈ Mg _z ( A white light emitting diode is described in which at least one member is selected from the group consisting of SiO ₄ ) _m , Cln and (Me _1-x Eu _x ) ReS.

According to the invention of claim 21, in the white light emitting diode according to claim 19, when the wavelength of the light beam is between 250 nm and 440 nm, the material of the fluorescent substance is (Me _1-xy Eu _x Re _y ) ₈ Mg _z ( SiO ₄ ) _m , Cln and (Me _1-x Eu _x ) ReS and (Ca _1-xy Sr _x Ba _y ) ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ , Gd ²⁺ A white light emitting diode is described which is selected.

In the white light emitting diode according to Claim 19, 0 <x≤0.8, 0≤y≤2.0, 0≤z≤1.0, 0≤m≤6.0, and 0.1≤n≤3.0 A white light emitting diode is described.

The invention according to claim 23 describes a white light emitting diode according to claim 19, wherein at least one Me is selected from the group consisting of calcium, strontium, and barium. have.

According to the invention of claim 24, in the white light emitting diode according to claim 19, Re is praseodym, rubidium, samarium, dysprosium, holium ), At least one selected from the group consisting of yttrium, erbium, europium, triumium, thulium, ytterbium, gadolinium, magnesium and manganese A white light emitting diode is described.

A white light emitting diode according to a twenty-ninth aspect of the invention provides a white light emitting diode according to claim 19, wherein a concave hole convex portion is provided in a concave hole at least on a surface thereof, and a light emitting diode chip is mounted.

A white light emitting diode according to a twenty-seventh aspect of the present invention discloses a white light emitting diode according to claim 19, wherein the thickness of the fluorescent layer is 0.5 mm to 3.0 mm.

In the white light emitting diode according to claim 19, the material of the substrate is any one of sapphire, silicon carbide, zinc oxide, silicon substrate, gallium phosphide, and gallium carbide. It describes a white light emitting diode characterized in that can be.

Fluorescence synthesis of the present invention includes the following examples:

Example (green fluorescence solid phase reaction method):

1. By chemical metering, 5.0 grams of calcium carbonate (CaC0 ₃ ), 1.83 grams of silicon dioxide (SiO ₂ ), 0.5860 grams of europium oxide (Eu ₂ O ₃ ), 0.4141 grams of dispersium oxide (Dy ₂ O ₃ ), The raw materials calculated with 1.1185 grams of magnesium oxide (MgO) are uniformly mixed by polishing method. Then add the appropriate HCL. The formulation thus formed is Ca _7.8 Mg (SiO ₄ ) ₄ Cl _2: Eu _0.12 Dy _0.08 .

2. Put the mixture into the crucible and heat it up to 1200 ° C and burn it with nitrogen gas at a rate of 5 ° C / min. After 6 hours, cool to room temperature at a rate of temperature of 5 degrees Celsius / minute.

3. Grind the powder after combustion and sinter it for 5 hours at 1200 degrees Celsius in air in the crucible, and the temperature increase rate of the sintering process is 5 degrees Celsius / minute.

4. Grind the powder after combustion and reduce it to 1000 degrees Celsius for 6 hours under reducing gas of H ₂ / N ₂ (15% / 85%). This reduces the Eu ³⁺ ions in the sample to make Eu ^2+, thereby increasing the emission luminance. The process is determined by the situation and is not an absolutely necessary process.

Legend 1: Ca7.8Mg (SiO ₄ ) ₄ Cl ₂ : Euo _0.12 Dy _0.08 Excitation Spectrum and Radiation Spectrum (Figure 9).

Legend 2: XRD spectrum of green phosphor Ca _7.8 Mg (SiO ₄ ) ₄ Cl ₂ : Euo _0.12 Dy _0.08 simultaneously with addition of europium and dysprosium (FIG. 10).

Legend 3: Ca _7.6 Mg (SiO ₄ ) ₄ Cl ₂ : Euo _0.32 Dy _0.06 Excitation spectrum and emission spectrum (FIG. 11).

Example 2 (magenta fluorescence solid phase reaction method):

1: 5.0 grams of strontium carbonate (SrCO ₃ ), 3.29 grams of silicon dioxide (SiO ₂ ), 1.0515 grams of europium oxide (Eu ₂ 0 ₃ ) and 1.145 grams of manganese oxide (Mn ₂ O ₃ ) The raw materials calculated with 2.007 grams of magnesium oxide (MgO) are uniformly mixed by polishing. Also add an appropriate amount of HCl. The formulation thus formed is (Sr7.48Ca0.2) Mg (SiO4) ₄ Cl ₂ : Eu _0.12 Mn _0.2 .

2. Put the mixture into the crucible and heat it up to 1250 degrees Celsius with nitrogen gas at a heating rate of 5 degrees / min. After 6 hours, cool to room temperature at a rate of temperature of 5 degrees Celsius / minute.

3. Grind the powder after combustion and sinter it at 1250 degrees Celsius for 5 hours in air in the crucible and the temperature increase rate of the sintering process will be 5 degrees Celsius / minute.

4. Grind the powder after sintering and reduce it to 1000 degrees Celsius for 6 hours under reducing gas of H ₂ / N ₂ (15% / 85%). As a result, Eu ³⁺ ions in the sample are reduced to Eu ²⁺ , thereby increasing the luminance. The process is determined by the situation and is not an absolutely necessary process.

Legend 4: (Sr _7.48 Ca _0.2 ) Mg (SiO ₄ ) ₄ Cl _2: Eu _0.12 Mn _0.2 Excitation spectrum and emission spectrum (FIG. 12)

Legend 5: Magenta phosphor added simultaneously with europium and manganese

(Sr _7.48 Ca _0.2 ) Mg (SiO ₄ ) ₄ Cl ₂ : XRD spectrum of Eu _0.12 Mn _0.2 (FIG. 13)

Legend 6: (Sr _7.48 Ca _0.2 ) Mg (SiO ₄ ) ₄ Cl ₂ : Eu _0.32 Mn _0.2 excitation spectrum and emission spectrum (FIG. 14)

Example 3 (red fluorescence solid phase reaction method);

1. 0.8059 grams of calcium carbonate (CaC0 ₃ ), 5.0 grams of strontium carbonate (SrCO ₃ ), 3.6945 grams of sodium emulsion (Na ₂ S), 1.6668 grams of europium oxide (Eu ₂ O ₃ ) and The raw materials calculated with 0.3812 grams of samarium oxide (Sm ₂ O ₃ ) are uniformly mixed by grinding. The mixture thus formed is (Sr _0.78 Ca _0.17 ) S: Eu _0.1 Sm _0.015 .

2. The mixture is placed in a crucible and burned at 1100 degrees Celsius under a reducing gas of H ₂ / N ₂ (15% / 85%) and the reduction is carried out for 6 hours. After cooling to room temperature at a temperature rate of 5 degrees Celsius / min.

3. The powder after sintering is reduced for 6 hours at 1100 degrees Celsius under a reducing gas of H ₂ / N ₂ (15% / 85%). As a result, Eu ³⁺ ions in the sample are reduced to Eu ²⁺ , thereby increasing the emission luminance. The process is determined by the situation and is not an absolutely necessary process.

4. The Na ₂ S process is adopted for the production of red fluorescence, or the temperature reduction rate and heat resistance of the red fluorescence are improved by adding Sm.

Legend 7: (Sr _0.78 Ca _0.17 ) S: Eu _0.1 Sm _0.015 excitation spectrum and radiation spectrum (FIG. 15).

Legend 8: Red phosphor added simultaneously with europium and samarium

XRD spectrum of (Sr _0.78 Ca _0.17 ) S: Eu _0.1 Sm _0.015 (FIG. 16).

Legend 9: (Sr _0.35 Ca _0.6 ) S: Eu _0.1 Sm _0.015 Excitation Spectrum and Radiation Spectrum (FIG. 17).

Example 4 (blue fluorescence solid phase reaction method)

1. A raw material calculated with 5.0 grams of strontium carbonate (SrCO ₃ ), 0.357 grams of europium oxide (Eu ₂ O ₃ ), and 0.3683 grams of gadolium oxide (Gd ₂ O ₃ ) by chemical meter ratio Mix evenly. Then add an appropriate amount of HCL. The so formed formulation is Sr _4.7 (PO ₄ ) ₂ Cl: Eu _0.15 Gd _0.15 .

2. The mixture is placed in a crucible and heated and burned in nitrogen gas to 1250 degrees Celsius at a heating rate of 5 degrees Celsius / minute. After six hours, cool to room temperature at a temperature drop rate of 5 degrees Celsius per minute.

3. Grind the powder after combustion and sinter it for 5 hours at 1250 degrees Celsius in air in the crucible and the temperature increase rate of the sintering process will be 5 degrees Celsius / minute.

4. Grind the powder after sintering and reduce it to 1000 degrees Celsius for 6 hours in a reducing gas atmosphere of H ₂ / N ₂ (15% / 85%). In this way, Eu ³⁺ ions in the sample are reduced to become Eu ²⁺ , whereby the luminescence brightness is increased and the process is determined by the situation and is not an absolutely necessary process.

5. Gd is added to the production of blue fluorescence to increase the luminous efficacy of blue fluorescence.

Legend 10: Sr _4.7 (PO ₄ ) ₂ Cl: Eu _0.15 Gd _0.015 excitation spectrum and radiation spectrum (FIG. 18).

Legend 11: XRD spectrum of blue phosphor Sr _4.7 (PO ₄ ) ₂ Cl: Eu _0.15 Gd _0.015 simultaneously with addition of europium and gadolium (FIG. 19).

Legend 12: Sr _4.85 (PO ₄ ) ₂ Cl: Eu _0.15 excitation spectrum and radiation spectrum (FIG. 20).

1 is a display diagram of a white light emitting diode of the present invention. The white light emitting diode 100 includes a lead frame 110, a light emitting diode chip 120, and an encapsulation resin 130. The lead frame 110 has a first contact point 112a, a second contact point 112b, and a concave hole 110a, and the light emitting diode chip 120 is disposed in the concave hole 110a with an adhesive 140. In addition, the light emitting diode chip 120 includes an anode electrode 122a and a cathode electrode 122b, and the first contact 112a and the second contact point (112a) of the lead frame 110 by respective bonding wires 150. And an encapsulation resin 130 covering the upper portion of the light emitting diode chip 120 and fixing the light emitting diode chip 120 into the concave hole 110a.

As shown in FIG. 1, the light emitting diode chip 120 emits an excitation light 124, and a phosphor 132 is doped in the encapsulation resin 130. Some of the excitation light 124 is emitted through the direct encapsulation resin 130 and the excitation light 124 in the other portion is irradiated to the fluorescent substance 132. Among these, after the projection of the excitation light 124, the fluorescent material 132 in the fluorescent substance 132 is excited to generate an acceleration of the electron energy level, thereby emitting the fluorescence 134, and finally the excitation light 124 and The fluorescence 134 is mixed so that the white light emitting diode 100 emits white light.

It is also possible for the white light emitting diode of the present invention to use a circuit board to replace the lead frame to be described above. 2 illustrates a white light emitting diode of another embodiment of the present invention. The white light emitting diode 200a includes a circuit board 210, a light emitting diode chip 220, and an encapsulation resin 230, and the light emitting diode chip 220 is formed by a recess 240 of the circuit board 210 using an adhesive 240. It is disposed above the concave hole convex portion or the planar convex portion 210b in 210a and is electrically connected to the circuit board 210 by wire bonding. In the encapsulation resin 230, the fluorescent powder 232 is doped and the encapsulation resin 230 covers the upper portion of the light emitting diode chip 220. Since the detailed operation and the connection relationship of the above-described related parts are similar to those of the embodiment shown in Fig. 1, it is preferable to omit duplicate description and refer to the description related to Fig. 1. 3, 4 and 5 show another type of white light emitting diode. The white light emitting diode 200b and the white light emitting diode 200c are used in a light emitting diode flip chip package.

In addition, although all the above-described drawings show a light emitting diode chip in which two electrodes are commonly located on a chip, in actual operation, the concave hole convex portion or the planar convex portion 210 in the concave hole 210a of the present invention emits light efficiency. In order to increase the luminous efficiency, the light emitting diode chip with two electrodes located at the top and bottom of the chip can be adopted, and the connection method between the light emitting diode chip and the lead frame (or the circuit board) can be adopted due to the difference in electrode position. different.

5 to 6 show a side view and a planar embodiment of a light emitting diode white light die employed in the present invention. This includes a circuit board base 310, a light emitting diode chip layer 330, and a fluorescent layer 340, and the diode chip layer 330 sandwiches the contact layer 350 to form the anode electrode 320 on the surface of the circuit board base 310. And the cathode electrode 360. In addition, the thickness of the light emitting diode fluorescent layer 340 can increase the light emission efficiency within 0.5mm ~ 3.0mm, thereby increasing the light emission efficiency.

According to the characteristics of the present invention, the wavelength of the excitation light emitted by the light emitting diode chip described above is, for example, between 250 nm and 490 nm, and the fluorescence component is, for example, green fluorescence, magenta fluorescence, red fluorescence, and blue fluorescence. It includes. The green light and magenta fluorescent material are selected from the group consisting of (Me _1-xy Eu _x Re _y ) ₈ Mg _z (SiO ₄ ) _m and Cln: one or two or more kinds thereof. At least one kind of material of the red light fluorescent substance is selected from the group consisting of (Me _1-x Eu _x ) ReS :. One kind of blue fluorescent material is selected from the group consisting of (Ca _1-xy Sr _x Ba _y ) ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ and Gd ²⁺ . 0 <x ≦ 0.8, 0 ≦ y ≦ 2.0, 0 ≦ z ≦ 1.0, 0 ≦ m ≦ 6.0, and 0.1 ≦ n ≦ 3.0. In addition, Me is selected from the group consisting of calcium, strontium and barium, and Re is selected from dysprosium, samarium, triumium, magnesium, manganese and zinc. One or two or more of the groups that are made up are chosen.

Note the following. The emission spectrum of the white light-emitting diode of the present invention also varies depending on the wavelength of the excitation light and the fluorescence component combined therewith. This will be described below with reference to some embodiments.

Example 5

For example, when the light emitting diode chip is a blue light emitting diode chip having a wavelength of 440 nm to 490 nm, it includes a fluorescent material having a relatively low excitation energy level such as the above-described green fluorescent powder and magenta fluorescent powder. Fig. 9 shows the emission spectrum of a kind of white light emitting diode as a first embodiment of the present invention. Examples of the combination of fluorescein are 20% of green fluorescein Ca _7.8 Mg (SiO ₄ ) ₄ Cl _2: Eu _0.12 Dy _0.08 to 80% magenta fluorescein (Sr _7.48 Ca _0.2 ) Mg (SiO ₄ ) ₄ Cl ₂ : Eu _0.12 Mn _0.2 is combined, and the light emitting diode chip can emit blue excitation light having a wavelength of 455 nm, for example. After excitation light, the green fluorescence emits green fluorescence with a wavelength of 510 nm to 525 nm, for example, and the magenta fluorescence emits magenta fluorescence with a wavelength peak value of 560 nm to 590 nm, for example. White light is formed with a higher color rendering property than a mixture of blue excitation light, green fluorescence and magenta fluorescence, and the white light emitting diode of the present invention becomes a three wavelength white light emitting diode (Fig. 21).

Example 6

Based on the above-described Example 5, the results of the white light emitting diode outputting also vary depending on the premise of changing the composition percentage of each material of the type of fluorescent powder. For example, 100% of the green fluorescent substance Ca _7.8 Mg (SiO ₄ ) ₄ Cl _2: Eu _0.12 Dy _0.08 is changed by changing the mixing ratio of the fluorescent _substance , and the light emitting diode chip can emit blue excitation light having a wavelength of 455 nm, for example. It becomes what there is. The green fluorescence intensity of the green fluorescence emitted after excitation light forms a high luminance green light emitting diode. The blue light emitting diode is packaged directly into a green light emitting diode by sandwiching the fluorescent powder, which has high brightness and is an advanced product of the world (Fig. 22).

Example 7 (Excitation light wavelength is between 250 nm and 440 nm):

Fig. 23 shows the emission spectrum of the white light emitting diode of Example 5 of the present invention. Magenta fluorescence, green fluorescence, and red fluorescence (Sr _0.78 Ca _0.17 ) S: Eu _0.1 Sm _0.015 : Eu _0.15 Dy _0.18 formulated at a suitable fluorescence content ratio and at the same time provide 385 nm of light as excitation light do. After being excited by the excitation light, the green fluorescence emits green fluorescence 420 having a wavelength of 508.2 nm, and the blue fluorescence emits blue fluorescent 410 having a wavelength of 450.2 nm, and the red light having a wavelength of 615.6 nm having red light enhancement (440) is enhanced. ) And magenta fluorescence emits a magenta fluorescence 430 of 564 nm, thereby forming white light having good color rendering properties at four wavelengths (Fig. 23).

As will be understood from the various examples above, the white light emitting diode of the present invention can apply relatively high energy excitation light, for example, ultraviolet light having a wavelength of 365 nm to 395 nm, and ultraviolet light having a low wavelength (lower than 365 nm). The excitation light is applied and the magnetic light includes a material having a relatively high excitation energy level such as green fluorescent light or blue light in addition to the known red fluorescent light or magenta fluorescent light. In addition, the excitation light emitted by the firing diode chip of the present invention has a short wavelength and high energy. There are also many kinds of fluorescent powder reacting with the excitation light and the degree to which the fluorescent powder is excited becomes even more complete.

A feature of the present invention is that a fluorescent material that is excited by a difference in the wavelength (frequency) of the excitation light is excited by the excitation operation for emitting a different color of light by an excitation light source having a wavelength of 250 nm to 490 nm. Different. Compared with the well-known two-wavelength white light emitting diode, the three-wavelength white light emitting diode from the three wavelengths of the present invention has a relatively high luminous efficiency and good color rendering property. In addition, the white light emitting diode of the present invention has a relatively low production cost and a relatively rapid production speed as compared with a white light emitting diode which is mixed by using a plurality of known light emitting diode chips.

Note that the excitation light source of the white light emitting diode of the present invention includes not only the light emitting diode chip of the embodiment described above, but also other excitation light sources such as a laser diode. As long as it does not depart from the scope of the spirit of the present invention, the formulation of the fluorescent substance of the present invention and the material to be selected may be changed by external conditions such as the sincerity of the required output light (for example, color or luminance) and the wavelength of the excitation light source. In addition, the white light emitting diode of the present invention can output a specific luminance or color output by adjusting the material of the fluorescent powder again, and thereby, it is possible to develop an alkaline light emitting diode.

For reference, the specific embodiments of the present invention are presented by selecting the most preferred embodiments to help those skilled in the art among various possible examples, and the technical spirit of the present invention is not necessarily limited or limited only by the embodiments. In addition, various changes, additions and changes are possible within the scope without departing from the spirit of the present invention, as well as other embodiments that are equally apparent.

Claims (27)

In white light emitting diodes, At least a wavelength of 250 nm to 490 nm that emits light and is disposed around the excitation light source and the excitation light source and at the same time includes a fluorescence component that receives the light source that emits the excitation light source; The material of the fluorescent substance is (Me _1-xy Eu _x Re _y ) ₈ Mg _z (SiO ₄ ) _m , Cln, (Me _1-x Eu _x ) ReS and (Ca _1-xy Sr _x Ba _y ) ₅ (PO ₄ ) A white light emitting diode comprising the above-mentioned fluorescing powder selected from the group consisting of ₃ Cl: Eu ²⁺ and Gd ²⁺ . The method of claim 1, When the wavelength of the light beam is between 440 nm and 490 nm, the material of the fluorescence component is (Me _1-xy Eu _x Re _y ) ₈ Mg _z (SiO ₄ ) _m , Cln and (Me _1-x Eu _x ) ReS White light emitting diodes, characterized in that at least one kind is selected from. The method of claim 1, When the wavelength of the light beam is between 250 nm and 450 nm, the material of the fluorescent powder is (Me _1-xy Eu _x Re _y ) ₈ Mg _z (SiO ₄ ) _m , Cln and (Me _1-x Eu _x ) ReS and (Ca _1-xy Sr _x Ba _y ) ₅ (PO ₄ ) ₃ White light-emitting diode, characterized in that at least one kind is selected from the group consisting of Cl: Eu ²⁺ , Gd ²⁺ . The method of claim 1, A white light emitting diode, wherein 0 <x ≦ 0.8, 0 ≦ y ≦ 2.0, 0 ≦ z ≦ 1.0, 0 ≦ m ≦ 6.0, and 0.1 ≦ n ≦ 3.0. The method of claim 1, Me is a white light emitting diode, characterized in that at least one selected from the group consisting of calcium, strontium (strontium), trilium (thulium), magnesium, manganese, zinc. The method of claim 1, Re is one or more selected from the group consisting of dysprosium, samarium, triumium, magnesium, manganese and zinc, and Ca, Sr, Mg, Cl, SiO ₄ And a Dy element, wherein the raw material powder is a white light emitting diode, characterized in that an oxide, acetate, organometallic compound or metal salts thereof can be used. In the red fluorescence, (Me _1-x Eu _x ) The luminous efficiency and heat resistance of the red fluorescence labeled ReS and produced by employing the Na ₂ S process and with Sm increases, and also contains the elements Ca, Sr, Ba, S, Cl, Eu and Sm in the red fluorescence. Among them, the raw powder is red fluorescence, characterized in that the oxide of the metal compound, acetate, organometallic compound or the metal salt can be used. In blue fluorescence, (Ca _1-xy Sr _x Ba _y ) ₅ (PO ₄ ) ₃ Produced by adding Gd to Cl: Eu ²⁺ , the luminous efficacy of blue fluorescence is increased and (Ca _1-xy Sr _x Ba _y ) ₅ (PO ₄ ) Ca, Sr, Ba, PO ₄ , Cl, Eu, Gd elements are contained in ₃ Cl: Eu ²⁺ , Gd ²⁺ blue fluorescein, among which raw powders are oxides of metal compounds, acetates, organometallic compounds or Red fluorescent substance, characterized in that the metal salts can be used. The method of claim 1, A white light emitting diode, wherein an excitation light source is received by any of a light emitting diode chip and a laser diode chip. In white light emitting diodes, A rewinding device having at least a concave hole convex portion or a planar convex portion on the surface thereof and capable of increasing light emission efficiency to increase light emission efficiency; An excitation light source disposed in the concave convex portion or planar convex portion of the retreader and simultaneously electrically connected to the retreader to emit light having a wavelength of 250 nm to 490 nm; An encapsulation resin disposed on the zipping and covering the excitation light source and fixing the excitation light source to the zipping; A fluorescent powder disposed in the encapsulating resin and receiving the emitted light of the excitation light source is provided, and the material of the fluorescent powder is (Me _1-xy Eu _x Re _y ) ₈ Mg _z (SiO ₄ ) _m , Cln and (Me ₁ in that it comprises; Eu ^2+, wherein the fluorescence is one where at least one kinds selected from the group consisting of Gd ^2+: _-x Eu _x) ReS and _{(Ca 1-xy Sr x Ba} y) 5 (PO 4) 3 Cl A white light emitting diode characterized in that. The method of claim 10, And a plurality of bonding wires, wherein the bonding wires are electrically connected between the excitation light source and the zipping. The method of claim 10, White light emitting diodes, characterized in that the retread is accommodated in any of the lead frame and the circuit board. The method of claim 10, A white light emitting diode, characterized in that the excitation light source is received by either the light emitting diode chip or the laser diode chip. The method of claim 10, When the wavelength of the light beam is between 440 nm and 490 nm, the material of the fluorescent powder is from the group consisting of (Me _1-xy Eu _x Re _y ) ₈ Mg _z (SiO ₄ ) _m , Cln and (Me _1-x Eu _x ) ReS. White light-emitting diode, characterized in that more than one type is selected. The method of claim 10, When the wavelength of the light beam is between 250 nm and 440 nm, the material of fluorescence is (Me _1-xy Eu _x Re _y ) ₈ Mg _z (SiO ₄ ) _m , Cln and (Me _1-x Eu _x ) ReS and (Ca _{1 -xy} Sr _x Ba _y ) ₅ (PO ₄ ) ₃ White light-emitting diode, characterized in that at least one kind is selected from the group consisting of Cl: Eu ²⁺ , Gd ²⁺ . The method of claim 1, A white light emitting diode, wherein 0 <x ≦ 0.8, 0 ≦ y ≦ 2.0, 0 ≦ z ≦ 1.0, 0 ≦ m ≦ 6.0, and 0.1 ≦ n ≦ 3.0. The method of claim 10, Me is a white light emitting diode, characterized in that at least one selected from the group consisting of calcium, strontium (strontium), triumium (thulium), barium (barium). The method of claim 10, Re is composed of praseodym, rubidium, samarium, dysprosium, holium, yttrium, erbium, europium, White light emitting diode, characterized in that at least one selected from the group consisting of trilium (yliumbium), ytterbium (gatterolin), magnesium, manganese. In white light emitting diodes, A light emitting diode chip emitting a light beam and having a wavelength of 250 nm to 490 nm, and a fluorescent sublayer, wherein the light emitting diode chip has at least A substrate; A die layer sandwiching the conductive buffer layer in an upward direction of the substrate; An anode electrode in contact with the conductive buffer layer and positioned over the contact layer; A cathode electrode in contact with the conductive buffer layer and simultaneously isolated from the first and second clad layers, the light emitting layer, the contact layer, and the anode electrode; The fluorescence layer is disposed around the fluorescence diode chip and receives light rays emitted by the light emitting diode chip in series, and the material of the fluorescence layer is (Me _1-xy Eu _x Re _y ) ₈ Mg _z (SiO ₄ ) _m At least one member selected from the group consisting of, Cln, (Me _1-x Eu _x ) ReS and (Ca _1-xy Sr _x Ba _y ) ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ , Gd ²⁺ White light emitting diodes. The method of claim 19, When the wavelength of the light beam is between 440 nm and 490 nm, the material of the fluorescence powder is from (Me _1-xy Eu _x Re _y ) ₈ Mg _z (SiO ₄ ) _m , Cln and (Me _1-x Eu _x ) ReS. White light-emitting diode, characterized in that at least one type is selected from the group consisting of. The method of claim 19, When the wavelength of the light beam is between 250 nm and 440 nm, the material of the fluorescent powder is (Me _1-xy Eu _x Re _y ) ₈ Mg _z (SiO ₄ ) _m , Cln and (Me _1-x Eu _x ) ReS and (Ca _1-xy Sr _x Ba _y ) ₅ (PO ₄ ) ₃ White light-emitting diode, wherein at least one kind is selected from the group consisting of Cl: Eu ²⁺ and Gd ²⁺ . The method of claim 19, A white light emitting diode, wherein 0 <x ≦ 0.8, 0 ≦ y ≦ 2.0, 0 ≦ z ≦ 1.0, 0 ≦ m ≦ 6.0, and 0.1 ≦ n ≦ 3.0. The method of claim 19, Me is a white light emitting diode, characterized in that at least one selected from the group consisting of calcium, strontium (barntium), barium (barium). The method of claim 19, Re is composed of praseodym, rubidium, samarium, dysprosium, holium, yttrium, erbium, europium, White light emitting diode, characterized in that at least one selected from the group consisting of trilium (yliumbium), ytterbium (gatterolin), magnesium, manganese. The method of claim 19, A white light emitting diode, wherein a concave hole convex portion is provided at least in a concave hole and a light emitting diode chip is mounted. The method of claim 19, The thickness of the fluorescent layer is a white light emitting diode, characterized in that formed in 0.5mm ~ 3.0mm. The method of claim 19, The material of the substrate may be any one of sapphire, silicon carbide, zinc oxide, silicon substrate, gallium phosphide (gallium), gallium carbide (gallium).

Images