TW200531320A - White light-emitting diode - Google Patents

Abstract

A white light-emitting diode (LED) at least includes a excitation light source and a fluorescent powder, wherein the excitation light source is capable of emitting a light source having a wavelength of 258 to 490nm, and the fluorescent powder is distributed around the excitation light source for receiving the light emitted from the excitation light source. Furthermore, the material of the fluorescent powder is selected from a group consisting of (Ca,Sr,Ba,)8Mg(SiO4)4Cl2: Eu<SP>2+</SP>, Dy<SP>3+</SP>, Mn<SP>3+</SP>. The invented white LED has a higher illumination efficiency and a better color rendering property.

Description

200531320 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a newly developed white light emitting diode, and in particular to a high color rendering property capable of generating three to four wavelengths by being excited by blue light. White light emitting diode. The present invention is a brand new phosphonium salt powder, which does not belong to the yag hidden material at all, and does not contain materials such as Y, Tb, A1, Ce 'and so on. As the luminous center, the phosphor of neolithium salt is based on Eu, which is completely different from patents such as N1Chm # 利 (YAG) and Qsraffl (TAG) phosphor, and can be changed to money = 来 _- Post packaging, poor color rendering, and even increase the brightness power = and improve the brightness of the 灿 -Can package, bringing the UV_ into the actual package. [Prior technology] = The conventional light-emitting diode (LED) belongs to a kind of semiconductor device, and the material of the second zf mainly uses chemical elements such as gallium (GaP), GaAs, and For compound semiconductors such as gallium (GaN), the principle of light conversion is changed to light, that is, the effect of applying electric current to the compound semiconductor through the combination of electrons and holes to emit excess energy as light. Because the light-emitting diode or discharge light, but belongs to cold hair Γ: =: is heated to light up to 100,000 small phases, and turned warm ^ with a long life of the diode 弁-托 贼 目 士 友 ^ Day time (idling time). In addition, it has low pollution (without mercury), high reliability, and is suitable for 4 industries :: The field of small energy applications is very wide, among which the most valuable; Note; its diode. Especially in recent years because of: It belongs to white light emitting, which makes white light emitting diodes used in some applications; It is used to continuously improve the efficiency. The back of the LCD screen can be adjusted to θ ^ or above, such as the light source of a scanner, "source," or 疋 lighting equipment, etc. , Has gradually replaced the traditional 200531320 light lamp and incandescent bulbs. And the general practice ^ self-luminous diode system with blue light-emitting diode chip with-yellow inorganic fluorescent # (or yellow organic fluorescent dye), The blue light emitted by the monitor light emitting diode wafer is between 44 ° F and 490nm, and the yellow inorganic fluorescent powder can emit yellow fluorescence after being irradiated with blue light. Fluorescent light is mixed with the original blue light to obtain the required white light. This white light emitting diode is easier to manufacture than the first white light emitting diode described above, and the production cost is lower, so At present, most white light emitting diodes on the market are in this form. However, due to the low light emitting efficiency of this white light emitting diode, and it is a two-wavelength type (only mixed with blue and yellow light) white light Glow The polar body is inferior to other three-wavelength white light emitting diodes in color rendering and display color temperature. In addition, in recent years, in view of the limitation of white light emitting diodes by Nichia, the patent uses k-light LEDs and YsAlsO ^ Ce31 fluorescent Powder (hereinafter commonly referred to as yag) packaged into LED white light diodes under the protection of powerful white light (w0 98 / 〇5〇78, w〇 98/12757), and there is 0sram fluorescent powder Tb3Al5012: Ce3 + ( The following is commonly referred to as TAG), etc., under the control of patents, the world has set off a battle for white LEDs! The white light patent defense battle 'all hastily rushes to find fluorescent powder that can replace yag &amp; TAG to break through this Nichia white light patent defense battle, In view of the fact that white light encapsulated by blue LEDs and YAG &amp; TAG phosphors is not as good as three-wavelength white light-emitting diodes in terms of color rendering and display color temperature, and the recent demand for high-power High-power LEDs, high color rendering is even more needed. The requirements of performance and high stability and high luminous efficiency; the invention is completely different from YAG &amp; TAG material, the development of a new silicate phosphor, with Eu as the center of light. [Inventive Content] Yes In view of this, the object of the present invention The invention is to provide a high color rendering white light emitting diode with two to four wavelengths which can be excited by ultraviolet and blue 200531320 light, so as to provide the luminous efficiency and better color rendering of the car driver. Based on the above purpose, the present invention is developed The new fluorescent powder is completely different from the patents such as Nichia patent (YAG) and 〇sram labor powder (TAG). The phosphor material does not contain γ, Tb, Al, Ce and other materials, and it is not based on Ce. Is the luminescence center; the newly developed silicate phosphor is changed from Ca, Si *, Ba, Mg, Cl, SiO4 and other materials, and Eu is the luminescence center. The advantage of this new phosphor is that the fluorescein powder has better water resistance than Ming salt, high light transmission, high luminous efficiency, and uses Eu as the luminous body, which is less prone to decay and more stable than Ce. . The new silicate phosphor uses Ca, Sr, Ba as the basic material of the phosphor, and the specific gravity is low (the specific gravity of the new silicate phosphor = 3.458), (the specific gravity of the YAG &amp; TAG phosphor = 4.33) This makes neolithic acid fluorescein that the LED package is less likely to settle, and the package will be better.

And the newly developed glory powder has an excitation wavelength of 250nm ~ 485nm, which is suitable for UV and Blue chip chips. Unlike other phosphors, it can only absorb small local wavelengths because of its acceptable excitation wavelength (excitation wavelength is wide) The emission wavelength is stable, so the energy of the wafer can be fully converted, so the luminous efficiency is high. It is suitable for the packaging of 250nm ~ 485nm, band LED. The package has stable chromaticity and good color rendering. The invention proposes a white light. The light-emitting diode includes at least an excitation light source, a carrier, a piece of glue and a brand-new fluorescent powder, wherein one surface of the carrier has a cavity, and the excitation light source is arranged in the cavity of the carrier, and It is electrically connected to the carrier, and the excitation light source emits a light, and the wavelength of the light is between 250nm and 490nm. The sealant is arranged on the carrier, and the sealant covers the excitation light source to fix the excitation light source on In addition, the phosphor powder is arranged around the excitation light source to receive the light emitted by the excitation light source, and the newly developed fluorescent powder material is temporarily selected from (Ca , Sr, Ba,) 8Mg (Si〇4) 4Cl2: Eu2 +, Dy3 +, Mn3 + One or more of the tribal groups. The white light-emitting diodes described in the present invention include, for example, a light-emitting diode. The bonding wire is electrically connected between the excitation light source and the carrier. In addition, the device # σ can be, for example, a package foot or a circuit substrate, and the excitation light source can be, for example, a photodiode wafer or a laser diode. Polar body wafers, etc. The material of the phosphor described in the present invention can be visualized by the light, line, and light emitted by the excitation light source, for example, when the wavelength of the light is between 250nm and 490nm in a simple degree. The material is one or more selected from the group consisting of (Ca, Sr, Ba,) 8Mg (Si04) 4Cl2: Eu2 +, Dy3 ^ 11. Among the above-mentioned materials of Rongxian powder (Me 卜 "ΕμCln :, 0 &lt; χ $ 0 · 8, and 0… 2.0, 0 1 1.〇, 〖Λ §ζ ㈣4) 1 &quot; '· 〇 ^ πι ^ 6.〇5〇1 = r ^ 3.0. In addition, Me series, One or two or more groups selected from the group consisting of Jo, Lu, and Barium, and Re is selected from one or more of the eight groups of 镝, 铕, 铕, and Li—or two or more. Salt phosphor can be adjusted by means of Ca, Sr Mg SiQ ratio of ingredient D :: depart other manufacturing green (Green) 'foreign ⑽ two red;

NaS ^ &quot;? A (Sr〇-78Ca〇--S: EU-Sm〇-〇15: S, 1 pass, and adding Sm can increase the luminous efficiency and heat resistance of red phosphor * Sr4 "POACH0 · With the addition of Gd, the production of 15% 15 blue-light camping light powder has a luminous efficiency of more than 2 times that of strong &amp; color phosphors. The white light-emitting diode system based on the above-mentioned Bensmin has a light emission wavelength of 2 μm to 4900 nm. The light emitting diode chip (or laser diode chip) is used to excite the light source, and it is used with fluorescent materials of different materials 8 200531320 to generate fluorescent light of different colors, such as yellow, red, green, and blue. The excitation light emitted by the original excitation light source is mixed to form a white light. The white light emitting diode system of the present invention is a three to four wavelength white light emitting diode and crystal grains, which can have a high light emission. Efficiency and better color rendering. [Embodiment] In order to make the above and other objects, features, and advantages of the present invention more comprehensible, the following describes specific embodiments with the accompanying drawings in detail, as follows: The phosphor synthesis of the present invention includes the following examples: Example 1 (green Color fluorescent powder solid state reaction method "1. According to the stoichiometric ratio, 5.0 g of calcium carbonate [CaC03], 1.83 g of SiO2 [Si02], 0.586 g of hafnium oxide [Eu2〇3], and 0. 4141 grams of dysprosium oxide (Dy203), 1.1185 grams of magnesium oxide [MgO], the raw materials weighed out are mixed uniformly in a grinding manner, and an appropriate amount of HC1 is added to form Ca7.8Mg (Si04) 4Cl2: EuQ. 12DyO8. 2. Put the mixture into a fire, and calcinate in nitrogen at a temperature of 5 ° (3 / πήη) to 120 ° C. After 6 hours, cool down at 5 ° C / min. The rate is cooled to room temperature. 3: Grind the powder after calcination, put it in a crucible and sinter in the air at 12,000 ° C for 5 hours, the temperature of the sintering step is still 5 ° C / min. 4. Grind the sintered powder, then place it in a reducing atmosphere of Η2 / N2 (15% / 85%) and reduce it at 1000 ° C for 6 hours. This is to reduce Eu3 + ions in the sample. It becomes Eu2 + to increase its luminous brightness, so this step depends on the situation and is not an absolutely necessary step. Example 1: CauMgCSiOACV.Eu ^ Dy. ^ Excitation spectrum and emission spectrum (Figure 4) An example is the 200531320 XRD spectrum of green phosphor cauMgCSiOJfl ^ EumDyoj with the addition of ytterbium and ytterbium. Figure 5: (emission) spectrum (Figure 6) Example 2 (magenta fine agenta) glory powder powder reaction method) ···; According to the stoichiometric ratio, 5.0 g of carbonic acid [SrC〇3] and 0.9 g of carbonic acid part [CaC03] ^ 3. 29 ^^^ b ^ [Si〇2]. I. 05i5 ^^^ b ^ [Eu203] # 1.145 grams of oxidized iron 11203), 2.007 grams of magnesium oxide [_, the raw materials weighed out are ground • Way to mix evenly. Then add an appropriate amount of HC1: The formula to form it is (Sr7 48Ca〇 2) Mg (Si04) 4Cl2: EU () 12MnQ 2. 2. Put the mixture into a towel, and heat it to · ° 0 for calcinations at a heating rate of 5 μ / min in Wei. After 6 hours a cooling rate of 5 ° C / min was cooled to room temperature. 3. Grind the calcined powder and put it in the air again and sinter it at 125 ° C for 5 hours. The temperature rise and fall rate of the sintering step is still 50c / min. 4. Grind the sintered powder, and then place it in a reducing atmosphere of Shouzhou 2 (15% / 85%) for reduction for 6 hours at 1000 ° 0. This is to reduce Eu3 + ions in the sample to Eu2 +, # to increase its luminous brightness, so this step depends on the situation and is not an absolutely necessary step. Example 4: (Sr * 7 ^ Cao aMgCSiC ^ Cl ^ EuQ uMno2 excitation spectrum and emission spectrum (Figure 7) Example 5: Add magenta and manganese magenta phosphors at the same time ( Xr spectrum of Sr ^ CamMgCSiOACV-Euo.uMn. "Figure 8: Example 6: (Sr7.28CaG.2) Mg (Si〇4) 4Cl2: Eu〇.32MnQ 2 excitation spectrum and emission ( emission) Spectral chart (Figure 9) Example 3 (Solid state reaction method of red phosphor) 200531320 I; Based on the stoichiometric ratio, 0.8859 g of carbonic acid is approximately [CaC〇3] and 5.0 g of Carbonic acid 0C03], 3.6945 g of sodium sulfide [Na2S], 1.6668 g of hafnium oxide [Eu2〇3] and 0.382 g of oxidation (Sm2 03), the raw materials weighed out are uniformly mixed by grinding. The resulting formula is (Sr. 78Ca〇17) S: Eu〇. —Ο. 〇15 〇 ·· The mixture is placed in a crucible, and then placed in H2 / N2 (15% / 85%) Calcinations and reductions were performed at 1100 C in a reducing atmosphere for 6 hours, and then cooled to room temperature at a temperature reduction rate of 5 ° C / min. 3. Grind the sintered powder and place it in h In a reducing atmosphere of 2 / N2 (15% / 85%), reduction is performed at 11000 ° C for 6 hours. This is to reduce the Eu3 + ions in the sample to Eu2 + to improve its luminous brightness, so this step depends on the situation It is not an absolutely necessary step. Four: NazS process is used for the production of red phosphor, and Sm is added to generate the luminous efficiency and financial properties of red phosphor. Example 7: (Sro ^ Cao mSzEuo.iSmo w5 excitation (Excitation) spectrum and emission spectrum (Fig. 10) Example 8: It is a lion spectrum with simultaneous addition of tritium and (red phosphor (Sr〇78Ca〇i7) s: Eu〇iSm_). Figure 11: Example 9: (SrQ ^ Cao ^ Euo iSmo oi5 excitation spectrum and emission spectrum chart (Figure 12) Example 4 (solid state reaction method of blue phosphor):-, according to Stoichiometric ratio: Take 5.0 g of carbonic acid [SrC〇3], 0 g of oxidized pin [EuA] and 0.3683 g of gadolinium oxide (Gd203), and mix the weighed raw materials uniformly by grinding. Add again The appropriate amount of HC1 and 2. 31 grams of phosphoric acid [H3P〇4] to make it into a formulation is 11 200531320

Sq. 7 (P04) 2C1: Eug 15Gd15. 2 '. The mixture was placed in a crucible and heated to 125 ° C. in a nitrogen gas at a temperature rising rate of 5 t: / min. It was calcinated. After 6 hours, cool to room temperature at a rate of 5 ° C / min. 3. Grind the calcined powder and place it in a crucible in the air for sintering for 5 hours. The temperature rise and fall rate of the sintering step is still yc / min. 4. Grind the sintered powder, and then place it in a reducing atmosphere of H2 / N2 (15% / 85%) at 1000 C for 6 hours. This is to reduce the Eu3 + ions in the sample to Eu2 + to increase its luminous brightness. Therefore, this step depends on the situation and is not an absolutely necessary step. Five: Gd is added in the production of blue fluorescent powder, which improves the luminous efficiency of blue fluorescent powder. Example 10: Sr47 (P〇4) 2Cl: EU () 15GdQ.15 excitation spectrum and emission spectrum (Figure 13). Example 11: The blue phosphor Sr4 7 (P〇4) 2C1: Eu is added at the same time. i5Gd. i52XRD spectrum (Figure 14). Example 12: Sr4 85 (P〇4) 2ci: EU (U5 excitation) spectrum and emission (emissi〇n) spectrum (Figure 15). Please refer to Figure 1 again, which illustrates the present invention A schematic diagram of a white light-emitting diode 100. For example, the white light-emitting diode 100 includes a package foot, a light-emitting diode wafer 120, and a piece of glue 130. The package foot 11 includes, for example, a first A contact 112a, a second contact 112b, and a cavity 110a, and the light emitting diode wafer 120 is disposed in the cavity 110a by an adhesive 140. In addition, the 'light emitting diode wafer 12' 〇 has an anode electrode 122a and a cathode electrode 122b, which are electrically connected to the first connection 12 200531320 point 112a and the second contact 112b of the package foot 11 through a bonding wire 15o, and the sealant 130 It is covered on the light-emitting diode wafer 120 to fix the light-emitting diode wafer 120 in the cavity 110a. Please refer to FIG. 1 again. The light-emitting diode wafer 120 can emit an excitation light 124, for example. For example, the sealing compound 130 is doped with a fluorescent powder 132, and a part of the light emission 124 is directly emitted through the sealing compound 130. The remaining part of the excitation light 124 will be irradiated onto the fluorescent powder 132. Among them, after being irradiated by the excitation light 124, the fluorescent substance in the fluorescent powder 132 will be excited, causing the transition of the electronic energy level, and then emitted.

A fluorescent light 134, and finally, by mixing the excitation light 124 and the fluorescent light 134, the white light emitting diode 100 can emit a white light. In addition, in addition to the above-mentioned package feet, the white light-emitting diode of the present invention can also use a circuit substrate instead of the package feet, please refer to FIG. 2 (a). It is a schematic diagram of another white light emitting diode of the present invention. The white light-emitting diode 200a includes, for example, a circuit substrate 21o, a light-emitting diode wafer ⑽, and a sealant 230 ′, wherein the light-emitting diode wafer 22o is disposed on the circuit substrate 21G through an adhesive 24o— The cavity 2 is formed on two of the cavity bumps or the planar bumps, and is electrically connected to the circuit substrate 210 by wire bonding. The sealing compound 23 is, for example, doped with phosphor powder 232, and the sealing compound covers the light-emitting diode wafer 220. However, the details of the related components mentioned above are the same as those described in the white paper. Another-a schematic diagram of a white light emitting diode. -The poles 200b and 200c can be used on the light-emitting diode chip-on-chip package. The light-emitting diode = In the above figure, both electrodes are located on the top of the chip 2 · concave at the same time, but in the actual cavity 2 发明Efficiency: Two or flat-cavity bumps can improve the light efficiency, thereby improving the light-emitting diode chip. Second: The light-emitting diodes with electrodes located on the top and bottom of the wafer have different positions of the electrodes. Package 13 200531320 pin substrate) connection methods are also different.蚺 Refer to Fig. 3, j: Gong Tai Gong's front view and front view. The white light crystals fluoresce 5 powders / the light-emitting diode white light crystal grains can cut out the light efficiency, and further improve the light emission efficiency. 'Zi 0.W3.0_, can improve the characteristics of luminescence: wave, ΐ ::' The wavelength of the excitation emitted by the above-mentioned light-emitting diode wafer can be, for example, between 250nms and 490nm, including green fluorescent powder, Magenta fluorescent powder, and ^ color fluorescent powder. In 1, the other 1m uncle fluorescein and i ,,, 彔, and Nisen red (Masenta) phosphors are, for example, from (Mei_x_yEUxRey) 8Mgz (SiOA, Cln: one of the groups of 2 = above, the material of the light-emitting phosphor may be selected from one of the eight groups of (Mei x yEUxRey) s: ..., and the material of the blue-fluorescent powder may be selected from (Ca ^ y, Srx) , Bay) 5 (P〇4) 3c1: Eu2 +, Gd2 + among the group _ 〇 · 8 and Saki S2.0, 〇 ^ ζ magic. 〇, 1〇 ^ 6 〇, 〇. In addition, 龅Is selected from the group consisting of _, pin, and barium, and Re is selected from one or two of the group consisting of m steel, 纪, oblique, 铕, 录, mirror, mine, this, town, and It is worth noting that the emission spectrum output by the white light-emitting diode of the present invention is different with the wavelength (frequency) of the excitation light and the fluorescent powder that is matched with it. Embodiment 5 is described. Embodiment 5 (the wavelength of the excitation light is between 440nm and 490nm) As an example, Lu's LED is a blue wafer with a wavelength between 440nm and 490nm. When the light emitting diode chip is used, the fluorescent powder includes, for example, the above-mentioned green fluorescent powder and magenta fluorescent powder and other fluorescent materials with lower excitation energy levels. For details, refer to FIG. The emission spectrum of a white light-emitting diode according to the first embodiment of the present invention, wherein the ratio of the phosphors can be, for example, 20% of the green phosphor CawMgCSiOACV.EumDyo G8 with 80% of the magenta Fluorescence 14 200531320 powder (Sr? JCao 2) Mg (Si〇4) 4Cl2: EuQ 12Mn0.2, and the light emitting diode wafer emits blue excitation light with a wavelength of 455 nm, for example. After the excitation light is irradiated, the green The photo-fluorescent powder can emit green fluorescent light having a wavelength between 51 and 525 nm, and the magenta light-emitting phosphor can emit, for example, a Magenta color with a wavelength peak of 560 nm-590. Fluorescence. Under the mixed light of blue excitation light, green fluorescence and magenta fluorescence, a white light with high color rendering can be formed, and the white light emitting diode of the present invention is a three-wavelength white light emitting diode. Body (as shown in Figure 16). Embodiment 6 'Based on the fifth embodiment described above, Under the premise of changing the composition percentage of each material, the results output by the white light emitting diode will also be different. For example, the ratio of the phosphor powder to 100% green phosphor Ca78Mg ( Si〇4) 4Cl2: EuQ i2DyQ () 8, and the light emitting diode wafer can emit, for example, a blue excitation light having a wavelength of 455 nm. In this way, after the excitation light is irradiated, the green light emitted by the green fluorescent powder is emitted. The chromaticity can form a green light LED towards the Brahma. The blue light LED is directly packaged into a green light LED through a fluorescent powder, and it has a high degree of immunity, which is the world's priority product (see Figure 17). Example 7 (the wavelength of the excitation light is between 250 nm and 440 nm) Please refer to FIG. 18, which shows the emission spectrum of a white light emitting diode according to the fifth embodiment of the present invention, in which an appropriate fluorescent light is taken. Powder ratio, including magenta fluorescent powder, green fluorescent powder, red fluorescent powder ❿ 一 鸟 心 ^ and blue fluorescent powder SrJPC ^ CkEi ^ Mus, and provide -385-wavelength purple light as excitation Light. Among them, after being excited by the excitation light, the green fluorescent powder can emit green fluorescent light with a wavelength of 508_2nm, and the blue fluorescent powder can emit blue fluorescent light with a wavelength of 450. 2nm. The red fluorescent powder can be enhanced. The wavelength is 615.6 guanidine red Wei, and the magenta glorious powder can emit a running wave: the magenta fluorescent light 630, which in turn forms white light with four wavelengths and better color rendering (see figure w). 15 200531320 It can be known from various embodiments that the white light emitting diode system of the present invention is more suitable than the excitation light of Azimuth, for example, a 1-ray laser with a wavelength between 365nm and 395nm, or even a lower wavelength. (Less than 365 ·) ultraviolet light excitation light and phosphors in addition to the conventional red or magenta phosphors, including green phosphors or blue phosphors have higher excitation energy levels Of materials. In addition, the shorter the wavelength of the excitation light emitted by the invention's light-emitting diode wafer, the higher the energy, and the more types of phosphors that can react with this excitation light, and the more phosphors are excited. The degree is more complete. To sum up, the present invention is characterized in that an excitation light source with a wavelength between 25nm and 490nm is used to excite phosphors that can emit excitation light of different colors. Depending on the wavelength (frequency), the material of the phosphor from inscription to excitation is also different. Compared with the conventional two-wavelength white light-emitting diode, the three-to-four-wavelength white light-emitting diode of the present invention has higher luminous efficiency and better color rendering. In addition, compared with the conventional white light emitting diode which uses multiple light emitting diode wafers for light mixing, the "white light emitting diode" of the present invention also has a low production cost and a faster production speed. It is worth mentioning that the excitation light source of the white light emitting diode of the present invention, in addition to the light emitting diode wafer shown in the above embodiment, also includes other excitation light sources such as a laser diode. In addition, without departing from the spirit of the present invention, the proportion of the fluorescent powder of the present invention and the material f used in the present invention can be based on the required output light properties (such as color or brightness, etc.) and the excitation light source. The external conditions such as wavelength are changed, and the white light emitting triode of the present invention can further output light of a specific brightness or color by adjusting the material of the light powder, and then develop into a full color series of light emitting diodes. body. &quot; —Although the present invention has been disclosed in the preferred embodiment as above, it is not intended to limit the content of this technology. Anyone who does not depart from the spirit and scope of the present invention can make a few changes and Retouching, so the scope of protection of the present invention shall be determined by the scope of the attached patent application. [Brief description of the drawings] FIG. 1 is a schematic diagram of an embodiment of the white light emitting diode of the present invention. FIG. 2 is a schematic diagram of another embodiment of the white light emitting diode of the present invention. FIG. 3 shows a white light crystal structure of the white light emitting diode of the present invention. FIG. 4 is a CauMgCSiC ^ Cl ^ EuowDyo ^ i ^ (excitation) spectrum chart and an emission spectrum chart of the present invention. The emission spectrum is 508.2 nm. Figure 5 shows the XRD spectrum of the green phosphor Ca7.8Mg (SiO4) 4Cl2: EuQ.12Dy0.08 with the addition of europium and thoron. FIG. 6 is an excitation spectrum and a radiation spectrum of Ca7.6Mg (Si〇4) 4Cl2: Eu〇 32 ^ 0.08 in the present invention, Eu augmentation α, and the radiation spectrum increases to 511.8 nm. Figure 7 shows the present invention using (SiY ^ Cao.DMgCSiOACl ^ EumMnoj excitation spectrum and radiation spectrum chart, the radiation spectrum is 563nm. Figure 8 shows the present invention with simultaneous addition of thorium and manganese magenta phosphor (Sr7.48CaQ The XRD spectrum of OMgCSiOACVEuo 12Mn. 2. Figure 9 is the excitation spectrum and radiation spectrum of the present invention with (Sr7 28CaQ 2) Mg (Si04) 4Cl2: EuQ 32MnQ 2. Eu increases, and the emission spectrum increases to 564.4 nm. Figure 10 shows the present invention with (Sr〇78Ca〇i7) S: EU () iSin () () i5 excitation spectrum and radiation spectrum chart, the radiation spectrum is 616.2 nm. Figure 11 shows the invention with simultaneous addition XRD spectrum of red phosphor (Sr〇78Ca〇17) S: Eu〇θπίο 〇15. Figure 12 is the excitation spectrum and radiation spectrum of the present invention (SroiCao.OSJu ^ S% .⑽

8nm。 Ca increased, the emission spectrum increased to 641.8 nm. 17 200531320 Figure 13 shows the excitation spectrum and radiation spectrum of the invention with% 7 (p〇4) 2C1: eU () 15GdG15. As Gd increases, the radiation spectrum increases to twice the intensity. Figure U is a blue glazed body SrJPOACl '. "5 Lion Spectra. Figure I5 shows the excitation spectrum and emission spectrum of the rabbit with% 85 (p〇4) 2Cl • birdπ. The intensity of the emission spectrum when Gd element is not added.

FIG. 16 shows the present invention using 20% green fluorescent powder 0 &amp; 7. Na 104) 4 (: 12 for .12). .08 and 80% of magenta light yin and blood ) Rongguang powder (jiY ^ CaoKSiOACl ^ EumMn.2, and the light-emitting diode wafer uses 455nm blue excitation light to form a three-wavelength white light-emitting diode. Figure π is the present invention at 100% Green fluorescent powder ~ This machine is a win, and the light emitting diode chip uses a blue excitation light with a wavelength of 455 nm to make up a light emitting diode chromaticity spectrum chart. Figure 18 is the present invention to take the appropriate Light powder ratio, including magenta light camping light powder, green glory. 2 2 camping light powder (Sr ° 8Ca ° .mS: EU ° lSm_ ^ Second irony belongs to "5, and provides-wavelength of purple light as excitation Spectral chart of light 0 [Description of main component symbols] 100: white light emitting diode 110a: cavity 112b second contact 12 2a · anode electrode 124: excitation light 132: fluorescent powder 140: adhesive 200: white light emission Diode 11 〇: package stand 112a: _ contact 120: light-emitting diode wafer 122b cathode electrode 130 sealant 134 fluorescent 150 line 210: circuit board 18 200531320 2 10a: cavity 220: light-emitting diode wafer 232: phosphor 310: substrate 330: FI ip chip wafer layer 350: contact layer 410: blue fluorescence 430: magenta fluorescence 210b: cavity bump or flat Cavity bumps 230: sealant 240: adhesive 320: anode electrode 340: phosphor powder layer 360: cathode electrode 420: green fluorescent light 440: red fluorescent light

19

Claims (1)

200531320 10. Scope of patent application: 1. A white light-emitting diode, at least including: an excitation light source, which emits a light, and the wavelength of the light is between 25nm and 490nm; and a fluorescent powder, configuration Is located around the excitation light source and is suitable for receiving the light emitted by the excitation light source, and the material of the phosphor is selected from yEuxRey) 8Mgz (Si04) m, Cln, (Me and xEux) ReS and (ca • y , Srx, Bay) 1 2 3 (p〇4) 3C1: One or two or more of the group consisting of Eu2 +, Gd2 + 0 2. The white light-emitting diode described in item 丨 of the patent application scope, where When the wavelength of the light is between 440nm and 490nm, the material of the glorious powder is selected from the group consisting of (Mei_ ”EuxRey) 8Mgz (Si〇4) ffl, Cln :, and (Mei_xEux) ReS. One or more. 3. The white light emitting diode according to item 1 of the scope of the patent application, wherein when the wavelength of the light is between 25 Onm and 44 Onm, the material of the fluorescent light is selected from (MeH-yEUxRejMg / SiO ^ Cln : ,, and (Mei_xEux) ReS, and (one or two of (c) are composed of y, Srx, Bay) 5 (P04) 3Cl: Eu2 +, Gd2 +. 4 · As in the scope of Shenqing patent The white light-emitting diode described in item (2) &lt; χ $ 0 · 8, and 0 ^ 02.0, O ^ Z ^ lO, 1.0 ^ ιη ^ 6 · 〇, (ugn ^ 3.〇 ... 20 1 · The white light-emitting diode described in item 1 of the Shenqing Patent Scope, 2 of which 3 Me is selected from one or more of the group consisting of calcium, pin, and barium. 200531320 y 6 · Rushen The white light-emitting diode described in item 1 of the patent scope, wherein Re ^ L is composed of tritium, thorium, thallium, magnesium, zinc, among which-or two or more. The phosphor powder contains a Ca, &amp; For example, Si04, Dy το is the scope of the patent application. For example, the patented solid state reaction method, the raw materials of which can be used metal oxides, acid salts, organic It belongs to compounds or their gold salts. 7 · Red light fluorescent powder (Me ^ xEiOReS, produced by using Na2S process, and adding Sm, to improve the luminous efficiency of red glory powder and heat resistance, the red light glory powder contains ^, &amp; Here, s, ci, Eu, Sm ... element is the solid-state reaction method with patent application scope, such as patent application. The raw materials and powders can be oxides, acid salts, organometallic compounds or metal compounds. Metal salts. Srx, Bay) 5 (P〇4) 3Cl: Eu2 + ^ J. ^ n Gd, Luminous efficiency of fluorescent powder (CaH ^ Sr ^ BayhCPOJsCkEi ^ GcP Ca, Sr included in blue fluorescent powder , Ba, P04, Cl, Eu, Gd. · The elements are within the scope of patent application. For example, the patent-pending solid complaint reaction method can use metal oxides, petrolates, organometallic compounds or raw material powders. Metal salts. 9 · The white light emitting diode according to item 1 of the scope of the patent application, wherein the excitation light source includes one of a light emitting diode wafer and a laser diode wafer. 10 · —a kind of white light emitting diode The polar body includes at least: _ a carrier, one surface of the carrier has A recessed bump, or a planar bump, can improve the light efficiency and thus the luminous efficiency. An excitation light source is arranged in the recessed bump or the planar bump of the carrier, and is electrically connected to the carrier. , The excitation light source emits a light, and the wavelength of the light is between 250nm and 490nm; a glue is arranged on the carrier, and the sealing glue covers the excitation light source to fix the excitation light source on On the carrier; and a fluorescent powder, which is arranged in the sealant and is suitable for receiving the light emitted by the excitation light source 21 200531320, and the material of the fluorescent powder is selected from the group consisting of ⑽ and y * z (Si 〇4) „, cln :, and (Mei_xEUx) ReS and ⑹ ′ y 'Srx' Bay) 5 (p〇4) 3Cl: Eu2 +, Gd2 + is one of the groups. U. The white light-emitting diode described in item 10 of the scope of patent application, further comprising a plurality of materials, and the bonding wires are electrically connected between the excitation light source and the carrier. 12. The white light-emitting diode according to item 10 of the scope of patent application, wherein the 泫 carrier includes one of a package foot and a circuit substrate. 13. The white light emitting diode according to item 10 in the scope of the patent application, wherein the excitation light source includes one of the light emitting diode wafer and the laser diode wafer. 14 Said white light emitting diode, wherein when the wavelength of the light is between 440nm and 490nm, the material of the phosphor is selected from (Mei_x_yEUxRey) 8Mgz (Si〇4) m, Cln :, and (Mei_xEUx One of the thieves. '15. The white light-emitting diode according to item 10 of the scope of the patent application, wherein when the wavelength of the light is between 250nm and 440nm, the material of the phosphor is selected from (Mei-x- yEuxRey) 8Mgz (Si04) m, Cln :, and (MepxEuJReS, and (ca y, Srx, Bay) 5 (P〇4) 3Cl: Eu2 +, Gd2 + is one of the groups of groups. 16 · As for the scope of patent application The white light-emitting diode described in item 10, in which 0 &lt; χ $ 0 · 8 'and 〇 $ y $ 2.0, OSZ ^ 10, 1.0SmS6.0, 0.1 $ η $ 3 · 〇. Such as application 22 200531320 patented solid state In the reaction method, the raw material powder can use oxides, nitrates, organometallic compounds, or metal salts of metal compounds. 17. The white light-emitting diode described in item 10 of the scope of patent application, in which Me is selected One of the groups consisting of calcium, europium, and barium. 18. The white light emitting diode described in item 10 of the scope of patent application, wherein Re is selected from 镨, 录 1, 钐, 镝, 鈥, Ji, One of the groups consisting of steel 1, hafnium, steel, mirror, ore, hafnium, magnesium, 19. A white light-emitting diode grain, and The green diode chip includes at least a light-emitting white diode chip that emits a light with a wavelength between 250nm and 490nm. The light-emitting diode chip and the phosphor layer include at least: A substrate; a die layer on the substrate; a conductive buffer layer located between the substrate and the die layer; an anode electrode in contact with the conductive buffer layer on the contact layer; a cathode electrode Is in contact with the conductive buffer layer, and is isolated from the first and second binding layers, the light-emitting layer, the contact layer, and the anode electrode; and a phosphor powder layer, which is arranged around the excitation light source grains, and Suitable for receiving the light emitted by the excitation light source, and the material of the phosphor is selected from (Me! _ X_yEuxRey) 8Mgz (Si04) m, Cln :, and (MepxEuJReS, and (Cah-23 200531320 y ' kx'Bay) 5CP〇4) 3Cl: Eu2 +, one of the groups of Gd2 +. 2．The white light-emitting diode as described in item 19 of the patent claim, and green particles, where when the light When the wavelength is between 440nm and 490nm, the labor The light and light material is selected from the group consisting of mountain ci ^ and one of the groups. 21 · The white light-emitting diode and green light-emitting diode as described in item 19 of the scope of patent application Every day, Yazhongda. When the wavelength of the ray is between 250 ^ and 44nm, the material of the phosphor is selected from (MeityEUxRey) 8Mgz (Si〇4) A ^ y, Srx, Bay) 5 (P〇4) 3ci: eu2 +, Gd2. One of the groups formed by _. 22. The white light emitting diode as described in item 19 of the scope of the patent application, and the elementary monopolar crystal grains, 0 &lt; χ $ 0 · 8, and 〇 ^ y ^ 2 〇, 0 ^ z ^ 1〇 , 1〇 ^ m ^ 6 • ㈣ • ι == π $ 3 · 〇〇〇〇23 · The white light emitting diode described in item 19 of the scope of application for patent, and, in particular, a polar body, wherein Me is selected from One of the groups consisting of calcium, gills and barium. 24. The white light-emitting diodes and ytterbium-one, ytterbium, and ytterbium-one polar crystals as described in item 19 of the scope of application for patents, wherein Re is selected from the group consisting of scandium, scandium, scandium, scandium ', yttrium, and scandium , 族, qiaolu, Jing, 镏, 釓, Qian, Meng are one of the ethnic groups. 25. The white light-emitting diode described in item 19 of the scope of patent application, wherein the 210b recessed bumps in the cavity 210a of the present invention can improve the light emission efficiency and increase the light emission efficiency. 26. As described in the scope of the patent application, the light crystal phosphor powder layer, the white light emitting diode crystal described in item 19, wherein the thickness of the hair is 0.5 to 3.0, which can improve the light efficiency, 24 200531320 and further increase the light emission. effectiveness. 27. The white light emitting diode according to item 19 in the scope of the patent application, wherein the material of the substrate includes at least sapphire, SiC, ZnO, and Si substrates , Filled with gallium (GaP), deified gallium (GaAs). 25