TWI353379B - White light illumination device - Google Patents

Description

1353379 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a UV-excitable phosphate camping material, and more particularly to the use of such a material in a white light emitting device. [Prior Art]

The luminous efficiency of the light-emitting diode (LED) is south and has the characteristics of energy saving and environmental protection, which can be used to replace the traditional heat and fluorescent lamps. In the white LEDs, the composition of the most important fluorescent materials, which will affect the luminous efficiency, stability, color rendering, color temperature, and service life. The excitation source of the conventional fluorescent material is mostly a short-wavelength uv (such as 147, 172, 185 or 254 nm). This kind of fluorescent material has high absorption and light conversion efficiency of uv in this wavelength band. In contrast, fluorescent materials that are excited by long-wavelength uvs to visible light (350-470 nm) are less common. In the prior art, the host material of the phosphor is mostly an oxide of a sulfide, a nitride or a strontium oxide or an IS salt. The light conversion rate of sulfide phosphor is good, but the shortcoming is poor stability and easy to be inferior to water vapor or oxygen. 1. The stability of the phosphor is good, but its synthesis is not easy. It often requires high temperature and high pressure. Not only is it dangerous, but also the cost of the oxide phosphors such as the sulphuric acid sulphate is quite good, but its synthesis and use have been exposed in many patents. The $g under-salt fluorescent powder broadly includes two types: pure disc acid phosphor powder and tooth phosphate phosphor powder. In U.S. Patent Nos. 0,294,800 and 6,621,211, General Electric discloses a phosphate-based phosphor (Sr'Ba, Ca) 5 (P〇4) 3ci: Eu2+. In U.S. Patent No. 6,685,852, odd 1353379

The above-mentioned blue phosphoric acid phosphor material is formed by a sintering method, and firstly, a reagent of a suitable molar ratio is obtained by a stoichiometric scale. The reagent containing Eu may be Euci2 or Eu2〇3. The reagents containing ca, Sr, and Ba may be CaO, SrO, BaO, CaCl2, SrCl2, and BaCl2. The source of the phosphate may be (NH4)H2P〇4, and the source of F, Cl, Br, OH may be a halide or hydroxide of Eu, Ca, Sr, Br. The above reagents are uniformly mixed and ground, and then placed in a high temperature furnace and then sintered in a reducing atmosphere of 650-85 (TC for 6-8 hours to obtain the above-mentioned blue phosphate fluorescent material. The atmosphere may be hydrogen or carbon monoxide, or a mixture of the above gas and an inert gas such as helium or nitrogen. In one embodiment of the invention, 5% H2/95% N2 is the reducing atmosphere of the application. For the fluorescent material, if the host material is calcium chlorophosphate (Ca2P04Cl), the crystal system is orthorhombic, the space group is Pbcm, and there are four molecules in one unit crystal. The lattice constant is as follows: a= 6.1850(0.002) A,b=6.983(0.002) A,c=10.816(0.004)A. This structure consists of discontinuous and distorted P043·tetrahedron, in which calcium ions occupy two independent compartments. For example, the (Cao.spEuo)^PC^Cl fluorescent material has an excitation band between 250 nm and 450 nm, and the emission is mainly blue with a wavelength between 410 nm and 500 nm. The main emission wavelength of blue phosphoric acid phosphorescent material is blue light, which is non- A fluorescent material such as a yellow fluorescent material is combined with an excitation source such as a light-emitting diode or a laser diode to form a white light emitting device, wherein the yellow fluorescent material comprises Y3Al5012: Ce3+ (YAG), Tb3Al5〇i2: Ce3+ (TAG)' (Mg, Ca, Sr, Ba)2Si04:Eu2+> (Ca, Mg, 1353379

Y) SiwAlxOyNz: Eu2+ or other suitable yellow fluorescent material. However, it must be specially stated that if a yellow fluorescent material that can be excited by near ultraviolet light is used, the yellow fluorescent material is "directly excited" by an excitation source such as a near-ultraviolet light-emitting diode or a laser diode, if blue light is used. The excited yellow light fluorescent material is subjected to the "indirect excitation" of the blue light emitted by the blue fluorescent material through the ultraviolet light emitting diode or the laser diode, and the "direct excitation" and the "indirect excitation". In different applications, the combination of blue and yellow fluorescent materials has its own different optimum formulation or ratio. On the other hand, in order to improve the color rendering of the white light source, a red fluorescent material and a green fluorescent material may be used as the non-blue fluorescent material, and combined with the phosphate fluorescent material of the present invention, together with the light emitting diode An excitation source such as a body or a laser diode is used to form a white light emitting device. The red fluorescent material includes (Sr, Ca)S: Eu2+, (Y, La, Gd, Lu) 203: Eu3+, Bi3+, (Y, La, Gd, Lu) 202S: Eu3+, Bi3+, Ca2Si5N8: Eu2+, ZnCdS: AgCl or other suitable red fluorescent material; green fluorescent material may be BaMg2Al1G017: Eu2+, Mn2+, SrGa2S4: Eu2+, (Ca, Sr, Ba) Al204: Eu2+, Mn2+, (Ca, Sr, Ba) 4Al] 4025: Eu2+, Ca8Mg(Si04)4Cl2: Eu2+, Mn2+ or other suitable green light material. Similarly, if a red light and a green fluorescent material that can be excited by the near ultraviolet light are used, it is a "direct excitation" application method of an excitation source such as a near-ultraviolet light-emitting diode or a laser diode; if a blue light is used The stimulable red and green fluorescent materials are the "indirect excitation" application of blue light emitted by blue fluorescent materials. The application principle of "direct excitation" and "indirect excitation" is the same as that of the above-mentioned yellow light fluorescent material, and the combination of blue light, red light and green light fluorescent material also has the best formula or ratio of 1.353379. The white light device such as the above-mentioned light-emitting diode or white light-emitting diode can uniformly mix and disperse the above-mentioned various blue/yellow or blue/green/red phosphors in a transparent optical adhesive according to an optimal formula or ratio. It is fabricated by being packaged in a wafer such as a light emitting diode or a laser diode. However, it is worth noting that when ultraviolet light is used as the excitation source, ultraviolet light filters or other ultraviolet light isolation methods should be provided on the outermost side of the white light emitting device to avoid harm to the human body or eyes.

Since the composition of the phosphate fluorescent material of the present invention is simple and easy to synthesize, it is advantageous in comparison with commercially available fluorescent materials. On the other hand, the phosphate fluorescent material of the present invention has a narrow emission wavelength (small width at half maximum) and high color purity, and provides a better choice in the application of a white light emitting device. In order to more clearly illustrate the features of the present invention, the preferred embodiments are described below. Example 1 Take 0巳0, ugly 11203, (14114) 112?04, and €&(:12 (99.99% high purity chemicals, purchased from Aldrich Chemical Co.) and other raw materials, according to (Ca1.xEux) 2P〇4Cl(x=0.01 ' 0.03 ' 0.05 ' 0.09 ^ 0.11 ' A 0.13) The expected composition is adjusted to the required chemical dose, then uniformly mixed, ground, placed in a double crucible device, filled with graphite, placed in high temperature The furnace is sintered at 650-850 ° C for about 6-8 hours, then the pure phase (Ca〇99Eu〇.〇!) 2P〇4C1, (Ca〇.97Eu〇.〇3)2P〇4Cl is obtained. , (Ca〇.95Eu〇.〇5) 2P〇4Cl, (Ca〇.9]Eu〇.〇9)2P〇4Cl, (匚&.8疋11..)1)2?040, and (匚冱〇.8疋11〇.]3) 2?04(:1 such as blue phosphorescent phosphorescent material. The photoluminescence intensity of the above different Eu2+ doping ratio products is 10 1353379 (intensity) and relative brightness (brightness) As shown in Fig. 1. It is found from Fig. 1 "T found that 'Cao.ggEuo' has strong photoluminescence intensity and relative luminance. Example 2

Taking X-ray diffraction of Example 1 (Cao.wEuo.nhPCUCl, the X-ray diffraction pattern is shown in Fig. 2. If the product is sold with Kasei Kasei KX501A (Ba, sold by Nippon Kasei Co., Ltd.) EU)MgAl]0〇17), its illuminating wave (450nm, see Figure 3) is longer, and the excitation band (optimal excitation wavelength is 370 nm 'see Figure 3) is also longer. In addition, the product Although the luminescent color of Kasei KX661 is blue light, the CIE coordinates have a slight difference'. See Fig. 4. The blue-pot acid fluorite material of the first embodiment of the present invention (Cao.MEuo.nhPC^Cl its color of light) The coordinates are (〇.15, 〇.〇4), and the commercially available Kasei KX501A has a chromaticity coordinate of (0.16, 〇.〇6). In addition to the above differences, the blue phosphosphate of the present invention has its light. The light emission intensity is also higher than that of the commercially available Kasei KX501A. Example 3 Take CaO, SrO, BaO, Eu203, (NH4)H2P04, CaCl2, SrCl2 BaCl2 (99.99% high purity chemicals, available from Aldrich Chemical Co.) And other raw materials, according to (〇 &, 89-) ^ 1) 311 〇. 11) 2? 04 (: 1 () ^ is 1 ^, 81 ', or ugly &, y is 0, 0.1, or 0 · 2) The estimated composition of the required proportion of the allocation After the dosage is applied, it is uniformly mixed and ground, placed in a double crucible device, filled with graphite, placed in a high temperature furnace, and sintered at 650-850 ° C for about 6-8 hours to obtain a pure phase (Ca〇). .89Eu〇,n)2P〇4Cl, (Ca〇.79Mg〇.iEu〇.i]) 2P〇4Cl, (Ca〇>69Mg〇.2Eu〇.ii) 2P〇4C1, (Ca〇.79Sr〇 .iEu〇.n )2^04^1 , 1353379 (Ca〇.69Sr〇.2Eu〇.ii) 2P〇4Cl, (Ca〇.79Ba〇.iEu〇.") 2P〇4Cl, and (Cao. epBao.sEuo.iihPC^Cl. After excitation with 365nni ultraviolet light, the emission spectrum of the above blue fluorescent material is shown in Fig. 5. (Xa light of Cao.wMwEuo.nhPCUCl (Μ is Mg, Sr, or Ba) The diffraction pattern is shown in Figure 6.

While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the scope of the present invention, and it is possible to make any changes without departing from the spirit and scope of the invention. The scope of the present invention is defined by the scope of the appended claims.

(s > 12 1353379 [Simplified Schematic] FIG. 1 is a comparison diagram of photoluminescence intensity and relative luminance of (X)(Ca) xEux)2p〇4Ci of the present invention - in the embodiment; In one embodiment of the invention, (Ca〇.89Eu〇.n) 2P〇4C1 χ light diffraction pattern;

Figure 3 is a comparison diagram of photoluminescence spectra of products sold in an embodiment of the present invention; Figure 4 is a comparison diagram of CIE chromaticity coordinates of products sold in an embodiment of the present invention; Mg, Sr, or Ba, spectral comparison map; and (Cao.wEuo uLPC^ci and city (Ca0.89Eu0 ]1) 2p〇4ci and the city of Baizhi, '(Ca0.89-yMyEu0 ")2p〇4ci y The photoluminescence of the 0, 〇·1, or 〇·2) is a X-ray diffraction pattern of the present invention (10) which is 峋 and 乂a).

[Main component symbol description] 13

Claims (1)

1353379. 苐96141170 Patent Application Revision Amendment 3 Patent application scope: 1. A white light emitting device comprising: an excitation light source; and a blue phosphoric acid fluorescent material having the following structural formula: (Ca, .x.yMyEux) 2P〇4N; Μ including Mg, Sr, or Ba ; N includes F, Cl, Br, OH, or a combination thereof; 0.01Sx$0.2; 〇 &lt;y $ 0.8 ; and a phosphor material other than blue light; wherein the excitation light source is used to excite the blue phosphoric acid phosphor material to emit blue light having a wavelength between 410 nm and 500 nm. 2. The white light emitting device of claim 1, wherein the excitation light source is a semiconductor light source comprising a light emitting diode or a laser diode. 3. The white light emitting device of claim 1, wherein the excitation light source has a wavelength between 250 nm and 450 nm. 4. The white light emitting device according to claim 1, wherein the excitation light source has a wavelength range of 365 nm to 430 nm, and the main radiation peak of the blue phosphorate fluorescent material is close to a blue light of 450 nm, and The chromaticity coordinates of the blue light are (0.15-0.16, 0.04-0.06). 5. The white light emitting device of claim 1, wherein the fluorescent material other than the blue light comprises a yellow fluorescent material, and the yellow fluorescent material and the blue phosphate fluorescent material emit white light in combination. 6. The white light emitting device of claim 5, wherein 14 1353379. the yellow fluorescent material comprises Y3Al5012: Ce3+ (YAG), Tb3Al5〇12: Ce3+ (TAG), (Mg, Ca, Sr, Ba) 2Si〇4: Eu2+, or (ca, Mg, Y) SiwAlx〇yNz: Eu. 7. The white light emitting device of claim 1, wherein the fluorescent material other than the blue light comprises a red light camping material and a green fluorescent material and the red fluorescent material and the green The light-emitting material is combined with the blue-light-based strontium-barium light-emitting material to emit white light. g. The white light emitting device of claim 7, wherein: the light fluorescent material comprises (Sr, Ca)s: Eu2+, (γ, La, Gd, c 3 on u, Bi3+, ( </ RTI> <RTIgt; , Mn2+, BaUi4.tu, (Ca,Sr, Ba)Al204:Eu2+, Mn2+, (Ca, Sr, 4 kOwEuh, or Ca8Mg(si〇4)4Cl2:Eu2' 2+. The r·,. The white light emitting device according to item 1-4 of the patent application, the preparation method of the optical disk acid phosphor material comprises: and = stoichiometric weighing scale for Ca〇, Sr〇, Ba〇, Eu2〇3, (ΝΗ4)η2Ρ〇 4, &amp; 12 after 'uniform grinding; and ^ also the above-mentioned abrasives placed in a crucible and placed in a high temperature furnace, sintered 6_M under 650-850 material ^ '1 ^, then the blue light Linshiyingguang ^1·'' kinds of white light emitting device, including: a teaching light source; and 15-blue light salt salt fluorescent material, having the following structural formula: (Ca].xEux) 2P〇4N; &amp; 〇H, or And a phosphor material and a blue light other than;; wherein said combination of said excitation light source for exciting the blue line - salt fluorescent material to radiation to a wavelength of between · _ 410_ of blue light. 12. The white light emitting device of claim </RTI> wherein the excitation source is a semiconductor light source comprising a light emitting diode or a laser diode. 13. The white light emitting device of claim 11, wherein the excitation light source has a wavelength between 25 Å and 450 nm. 14. The white light emitting device of claim 5, wherein the wavelength of the sigma excitation source ranges from 365 nm to 430 nm, and the main radiation peak of the blue scale fluorite phosphor material is close to a blue light of 450 nm. The chromaticity coordinates of the blue light are (0.15-0.16, 0.04-0.06). The white light emitting device of the invention of claim 5, wherein the fluorescent material other than the blue light comprises a yellow fluorescent material, and the yellow fluorescent material and the blue light The combination of phytate phosphor materials emits white light. 16. The white light emitting device of claim 15, wherein the yellow fluorescent material comprises Y3Al50]2: Ce3+ (YAG), Tb3Al5〇]2: Ce3+ (TAG), (Mg, Ca, Sr, Ba) 2Si04: Eu2+, or (Ca, Mg, Y) SiwAlx〇yNz: Eu2+. The white light emitting device of claim 11, wherein the fluorescent material other than the blue light comprises a red fluorescent material and a green fluorescent 16 1353379 optical material, and the red fluorescent material and the The green phosphor material is combined with the blue phosphoric acid phosphor material to emit white light. 18. The white light emitting device of claim 17, wherein the red fluorescent material comprises (Sr, Ca)S: Eu2+, (Y, La, Gd, Lu) 203: Eu3+, Bi3+, (Y) , La, Gd, Lu) 202S: Eu3+, Bi3+, Ca2Si5N8: Eu2+, or ZnCdS: AgCl. 19. The white light emitting device of claim 17, wherein the green fluorescent material comprises BaMg2Al10O17: Eu2+, Mn2+, SrGa2S4: Eu2+, (Ca, Sr, Ba) Al204: Eu2+, Mn2+, (Ca, Sr, Ba) 4Al] 4 0 25: Eu2+, or Ca8Mg(Si04)4Cl2: Eu2+, Mn2+. 20. The white light emitting device according to claim 11, wherein the method for preparing the blue phosphoric acid phosphor material comprises: uniformly grinding the CaO, Eu203, (NH4)H2P04, and CaCl2 according to a stoichiometric scale. And the above-mentioned abrasive is placed in a crucible and placed in a high temperature furnace, and sintered under a reducing atmosphere of 650-850 ° C for 6-8 hours to obtain the blue phosphoric acid fluorescent material. 17