TW201231619A - Method of preparing nitride-based red phosphor powder and package structure of light emitting diode - Google Patents

Abstract

A method of preparing nitride-based red phosphor powder is provided. The method includes mixing MaAbDcEdXe crystals of 10 to 50 parts by weight to serve as seeds with raw materials for preparing MaAbDcEdXe crystals of 50 to 90 parts by weight to form a mixture. Thereafter, a step of sintering the mixture is conducted so as to form MaAbDcEdXe crystal product. M is an active center and includes Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb or combination thereof. A represents a group-IIA metal element having two valence electrons. D represents a group-IVA metal element having four valence electrons. E represents a group-IIIA metal element having three valence electrons. X represents nitrogen element. In addition, a+b=1, 0.00001 ≤ a ≤ 0.1, 0.5 ≤ c ≤ 4, 0.5 ≤ d ≤ 8 and 0.8x(2/3+4/3xc+d) ≤ e ≤ 1.2x(2/3+4/3xc+d).

Description

201231619 EL99092 36618twf.doc/n VI. Description of the Invention: [Technical Field] The present invention relates to a method for preparing a phosphor powder and a white light emitting diode package structure, and more particularly to an increase in light emission A method for preparing a red nitride phosphor of intensity and a white light emitting diode package structure.

[Prior Art] Based on the environmental awareness of energy saving and carbon reduction and sustainable development, the world's advanced countries are gradually eliminating traditional lighting and then selecting white light emitting diodes. The advantages of white light and the small size are small enough to fit the application equipment. Moreover, the white light diode consumes less power, which is only 1/8 to 1/10 of the conventional bulb, 1/2 of the fluorescent lamp, and has a long life of more than 100,000 hours. In addition, the white light diode has a low heat generation rate and a fast response speed, so it is very suitable for high frequency operation. The white light diode can solve the problem that incandescent light bulbs are difficult to overcome. It can be used as a lighting source and display light source in the 21st century, and has both power saving and environmental protection concepts. Therefore, it is called a "green lighting source." In the 19th year, U.S. Patent No. 5,998,925 proposes a first white light diode which is excited by a blue light emitting diode (LED) to promote the glory of the glory: stone weight = fluorescent color f light, this yellow fluorescent The yellow light emitted by the powder can be mixed with light to produce white light. However, in order to make the lighting and display of the lining: The color illuminating diode must have a complete full-spectrum band, of which L is currently developing 4 points. 1 color wave 1 is again 201231619 EL99092 36618twf.doc/n SUMMARY OF THE INVENTION The present invention provides a method of preparing a red nitride phosphor which can increase the light emission intensity of a red nitride phosphor. The invention provides a white light emitting diode package structure with red nitride phosphor powder, wherein the red nitride phosphor powder has sufficient light-emitting intensity. The invention provides a method for preparing a red nitride phosphor powder, which comprises Q1 parts by weight of MaAbDcEdXe crystals are seeded and mixed with Q2 parts by weight of the raw material for making MaAbDcEdXe crystals.

Ql+Q2=100. Sintering is then performed to form MaAbDcEdXe crystals.

The substance 'where Μ is an activation center includes Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb or a combination thereof. a is a 2-valent IIA metal element. D is a tetravalent IVA metal element. E is a trivalent hIA metal element. X is one of elemental nitrogen, elemental oxygen, elemental fluorine or a mixture thereof. a+b=l,0.00001 with aSO.l,0.5 幺c 幺4,0.5 幺d幺8, 0.8 X (2/3+4/3 X c+d)SeS 1.2 X (2/3+4/3 X c+d). The invention further provides a method for preparing red nitride phosphor powder, comprising: seeding 10 to 50 parts by weight of MaAbDcEdXe crystal as a seed, and mixing 50 to 90 parts by weight of a raw material for preparing MaAbDcEdXe crystal, and then performing Sintering to form a MaAbDcEdXe crystalline product wherein Μ is a living center, including Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, or a combination thereof. A is a divalent IIA metal element. D is a tetravalent IVA metal element. E is a trivalent lanthanide metal element. X is the elemental nitrogen. a+b=l,〇.〇〇〇〇lSas〇.l,〇.5ScS4,〇.5<d<8, 201231619 EL99092 36618twf.doc/n 0·8χ(2/3+4/3xc+d) Sd · 2χ (2/3+4/3xc+d). According to an embodiment of the present invention, in the method for preparing a red nitride camping powder, the size of the MaAbDcEdXe crystallized as a seed crystal is less than 25 μm. According to an embodiment of the present invention, in the method for preparing the red nitride glazing powder, when X is elemental nitrogen, the raw material for preparing the MaAbDcEdXe crystal material comprises 28 mol% to 38 mol% of A nitrogen. , 28 mol% to 38 mol% of nitride of D, 28 mol% to 38 mol% of nitride of E, and 0.1 mol% to 5 mol% of niobium nitride, oxidation of μ Things. According to an embodiment of the present invention, in the method for preparing the red nitride phosphor, the sintering is performed under an atmosphere of nitrogen, ammonia or an inert gas, and the sintering temperature is 1600 to 1900 degrees Celsius, and the sintering time is 2. Hours to 10 hours, the pressure is 〇.3MPa to IMPa. According to an embodiment of the invention, the method for preparing the red nitride phosphor further comprises re-sintering the sintered MaAbDcEdXe crystal product and the material for forming the MaAbDcEdXe crystal. According to an embodiment of the invention, the method for preparing the red phosphor powder further comprises: screening the crystallized product of the MaAbDcEdXe obtained by the sintering to obtain a size of 3 micrometers to 25 micrometers before performing the re-sintering. According to an embodiment of the present invention, in the method for preparing the red phosphor, the re-sintering is the same as or different from the processing conditions of the sintering. According to an embodiment of the present invention, in the method of preparing the red nitride phosphor powder of 201231619 EL99092 36618twf.doc/n, the re-sintering is performed under an atmosphere of nitrogen, ammonia or an inert gas, and the sintering temperature is 1600 Celsius. To a degree of 19 degrees, the sintering time is 2 hours to 1 hour, and the pressure is 〇3 MPa to iMPa. The invention further provides a light emitting diode package structure comprising a light emitting element and a phosphor powder layer. The glory powder layer covers the surface and the periphery of the light-emitting element, and includes a first phosphor powder and a second phosphor powder. The first phosphor powder is a red nitride phosphor powder 'red nitride phosphor powder comprising 10 to 5 parts by weight of MaAbDcEdXe crystals having a size of less than 25 microns as seed crystals, and 50 to 90 parts by weight. The raw materials of the MaAbDcEdXe crystals were mixed and then sintered to form a MaAbDcEdXe crystalline product. M is an activation center and includes Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb or a combination thereof. A is a divalent group IIA metal element. D is a 4-valent IVA metal element. E is a trivalent lanthanide metal element. χ is an element of nitrogen, elemental oxygen, elemental fluorine or a mixture thereof. a+b=l, 0.00001<a<0.1 >0.5<c<4>0.5<d<8> 8x(2/3+4/3xc+d) put 1.2x(2/3+ 4/3xc+d). The above sintering is carried out under an atmosphere of nitrogen, ammonia or an inert gas at a sintering temperature of celsius to 1900 degrees, a sintering time of 2 hours to 10 hours, and a pressure of 〇 3 Μ ρ & The second phosphor is yellow phosphor or green phosphor. The red nitride phosphor of the present invention is simple in preparation and can increase the light-emitting intensity of the red nitride phosphor. The above described features and advantages of the present invention will become more apparent from the description of the appended claims. 201231619 EL99092 36618twf.doc/n [Embodiment] The present invention proposes a method for preparing red nitride phosphor powder. The red nitride phosphor has an emission wavelength of 57 Å to 7 Å and an excitation wavelength of 360 nm to 550 nm. The chemical formula of the red nitride phosphor can be expressed by MaAbDcEdXe, wherein Μ is the activation center 'including Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb or a combination thereof; A is 2 a metal element of Group IIA; D is a metal element of Group IA of 4 mussels; E is a metal element of a trivalent Group IIIA; X is an elemental nitrogen; and a+b=l » 0.00001<a<0.1 » 0.5<c<4 5 0.5<d<8 5 〇.8 x(2/3+4/3 xc+d)SeS 1.2X(2/3+4/3 xc+d). The red nitride phosphor is prepared by seeding Q1 parts by weight of MaAbDcEdXe crystals, and mixing it with Q2 parts by weight of a material for preparing MaAbDcEdXe crystals, followed by sintering to form MaAbDcEdXe crystal product. . Qi+Q2=i〇〇. In one embodiment, Q1 is from 10 to 50; Q2 is from 50 to 90. The MaAbDcEdXe crystals as seed crystals can be screened to a size of less than 25 microns. In one embodiment, the MaAbDcEdXe crystalline as a seed crystal is screened to a size of from 3 microns to 25 microns. The materials used to make the MaAbDcEdXe crystals include the X compounds of μ, a, d, and E. More specifically, when lanthanum is elemental nitrogen, the raw material used to make the MaAbDcEdXe crystal includes a nitride of d a 201231619 EL99092 36618 twf.doc/n nitride and a nitride of E and a nitride of M or M Oxide. In one embodiment, the material used to make the MaAbDcEdXe crystals comprises 28 mole% to 38 mole% of nitride of A, 28 mole% to 38 mole% of nitride of D, 28 mole% to 38 mol% of the nitride of E and 0.1 mol% to 5 mol% of the niobium nitride or niobium oxide. The material used to make the MaAbDcEdXe crystals can be post-milled and then mixed with the MaAbDcEdXe crystals as seed crystals. The seed crystal is sintered with the raw material in an atmosphere of nitrogen, ammonia, an inert gas or a combination thereof. The inert gas is, for example, helium, neon or argon. The sintering temperature is, for example, 1600 to 1900 degrees Celsius. The sintering time is, for example, 2 hours to 10 hours. The pressure is, for example, 0.3 MPa to 1 MPa. The method of preparing the red nitride phosphor powder of the above embodiment is described by mixing the raw material and the seed crystal once. However, the present invention is not limited thereto. In the actual application, the above steps may be repeated one to several times. More specifically, in one embodiment, the above-described sintered MaAbDcEdXe crystalline product can be re-fired with the material used to make the MaAbDcEdXe crystal. The crystallized product obtained by sintering was screened before re-sintering, and a size of 3 to 25 μm was selected. The process conditions for re-sintering may be the same as or different from the conditions for sintering. The re-sintering can be carried out in an atmosphere of nitrogen, ammonia, inert gas, or a combination thereof. The inert gas is, for example, helium, neon or argon. The re-sintering temperature is, for example, 16 degrees Celsius to 19 degrees Celsius, and the time is, for example, 2 hours to 1 hour. The pressure is, for example, 〇 to 1 Na & FIG. 8 is a cross-sectional view showing a light emitting diode package structure according to an embodiment of the present invention. 201231619 EL99092 36618twf.doc/n

Referring to Fig. 8', the light emitting diode package structure 1 includes a substrate u, a light emitting element 120, and a phosphor layer 130. The substrate 11A is a base that carries the light-emitting element 120. The light emitting element 120 is attached to the substrate 11A. The light = device 120 is, for example, a blue light emitting diode chip. The light-emitting element 12〇 is composed of a conductor material, such as a VA group multi-component compound, including gallium nitride (InGaN) 'gallium nitride/carbonization; ε/ ic ( GaN/sic) or any of the above . The light-emitting element 120 is electrically connected to the holder pin 15 through the bonding wire 14A. The phosphor layer 130 is wrapped around the light-emitting element 12 and further covers a part of the two wires. The phosphor layer 130 has two or more types of phosphor powder, and this: the phosphor powder is uniformly dispersed in the phosphor layer 130. The above-mentioned glory powder 130 includes at least a first phosphor powder Hi and a second phosphor powder 132. In the embodiment, the first phosphor powder 131 is, for example, the red phosphor powder prepared in the above embodiment of the invention. The structure of the red phosphor is MaAbDcEdXe, wherein Μ, A, D, E, X, a, b, c, d and e are as defined above, and will not be described again. The second phosphor is, for example, yellow phosphor or green phosphor. The blue light emitted by the color-emitting diode chip can excite the red phosphor to emit red light, and can also excite the yellow phosphor to emit yellow light, so that the light-emitting diode package structure generates white light. X Example 1 After 0.1021 g through 500 mesh screening, take 25 μm

CaAlSiN3:Eu2% (CaAlSiN3:Eu2% means that 2w.t.% of EU is doped in CaAlSiN3, wt% means weight percentage) as a seed crystal, and its synthesis method is 0.6940 g of Ca^, 0.6699 g of Si3N4, 0.5885 The 201231619 EL99092 36618twf.doc/n AIN and 0.0477 grams of EuN were mixed and ground, and then sintered at 1700 ° C and a nitrogen pressure of 〇.48 MPa for 4 hours to obtain a red product which was sieved to obtain the seed crystal. Comparative Example 1 0.1021 g of CaAlSiN3:Eu2°/〇 without mesh screening was used as Comparative Example 1, and the synthesis method was 0.6940 g of Ca3N2, 0.6699 g of Si3N4, 0.5885 g of A1N, and 0.0477 g of EuN, followed by mixing and grinding. After sintering at 4700 ° C and nitrogen pressure of 〇.48 MPa for 4 hours, a red product was obtained. Example 2 A CaAlSiN3:Eu2% sample having a size of less than 25 μm was used as a seed crystal. The seed crystal was mixed and ground with 0.3123 g of Ca3N2, 0.3015 g of Si3N4, 0.2649 g of A1N, and 0.0215 g of EuN, followed by sintering at 1,700 ° C and a nitrogen pressure of 0.48 MPa for 4 hours to obtain a red product. Example 3 A CaAlSiN3:Eu2% sample having a size of less than 25 μm was used as a seed crystal and 0.552 g of Ca3N2, 0.5359 g of Si3N4, 0.4708 g of A1N, and 0.0405 g of Eu203 were mixed and ground at 1,700 °C. Sintering was carried out for 4 hours under a nitrogen pressure of 0.48 MPa to obtain a red product. Comparative Example 2 0.3470 g of Ca3N2, 0.3350 g of Si3N4, 0.2943 g of A1N, and 0.0239 g of EuN were mixed and ground, and then sintered at 1,700 ° C and a nitrogen pressure of 0.48 MPa for 4 hours to obtain a red product. 201231619 EL99092 36618twf.doc/n The excitation spectrum of the red nitride phosphor powder compound formed in the above Example 1 and Comparative Example 1 is shown in Fig. 1, and the photographs of the scanning electron microscope (SEM) are shown in Fig. 2A and 2B is shown. The results of Fig. 1 and Figs. 2A and 2B show that the red nitride phosphor powder compound obtained by seeding CaAlSiN3:Eu2% as a seed crystal has a relatively uniform particle size and brightness compared with those which have not been sieved. high. The red nitride phosphor powder compound formed in the above Example 2 and Comparative Example 2 is shown in Fig. 3 through the X-ray powder diffraction pattern, and the results show that the red telluride phosphor powder compounds formed in Example 2 and Comparative Example 2 are both shown. It is pure phase. The excitation spectrum of the phosphor powder compound formed in the above Example 2 and Comparative Example 2 is shown in Fig. 4; the excitation spectrum of the red nitride phosphor powder compound formed in the above Example 3 and Comparative Example 2 is shown in Fig. 6. The results show that the red nitride phosphor powder formed in Example 2, Example 3, and Comparative Example 2 can be excited by a wavelength of 360 to 550 nm. Further, the luminescent powder compound formed in Examples 2 and 3 had a higher excitation intensity than the luminescent powder compound formed in Comparative Example 2. The emission spectrum of the phosphor powder compound formed in the above Example 2 and Comparative Example 2 is shown in Fig. 5; the emission spectrum of the red nitride phosphor powder compound formed in the above Example 3 and Comparative Example 2 is shown in Fig. 7 . The results are shown in Table 1. The results of Table 1 show that the red nitride phosphor powder formed in Example 2, Example 3, and Comparative Example 2 had a radiation wavelength of 570 to ' and the light emission intensity of Example 2 and Example 3 was larger than that of Comparative Example 2. 11 201231619 EL99092 36618twf.doc/n Excitation peak emission peak color -——~~____ Light intensity integral light intensity integral value Ex. Value Em. Intensity Int. Area RQO (nm) (nm) (%, relative) (%, Relative) Example 2 460 660 Red 107 110 Case 3 460 658 Red 119 118 mm2 460 664 Red 100 mn Half-height FWHM (nm) 92 92 93

~~iu" Heart-to-heart method: After you add the seed crystal and then sinter to prepare the red nitride phosphor powder, the red vaporized glaze powder can be excited by the light of the light-emitting diode to the wavelength of 55Gnm. The emission wavelength is 57G to 7GGnm, and it can have the light-emitting intensity of the red nitride battalion powder. The (4) method material has great industrial application value. On the other hand, sintering with the seed crystals and the raw materials can make the particles of the formed red nitride phosphor powder very uniform and can increase the brightness thereof. ,child

The present invention has been disclosed in the above embodiments, and is not intended to limit the present invention. Any one of ordinary skill in the art can make a few changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing excitation spectra of a red nitride fluorescent powder compound formed in Example 1 and Comparative Example 1. Fig. 2A is a photograph of a scanning electron microscope of a compound of the red nitride phosphor powder 12 201231619 EL99092 36618 twf.doc/n formed in Example 1 of the present invention. Fig. 2B is a photograph of a scanning electron microscope of the red nitride fluorescent powder compound formed in Comparative Example 1. Fig. 3 is a view showing an X-ray powder diffraction pattern of the red nitride phosphor powder compound formed in Example 2 and Comparative Example 2 of the present invention. Fig. 4 is a view showing the excitation spectrum of the red nitride fluorescent powder compound formed in Example 2 and Comparative Example 2 of the present invention. Fig. 5 is a view showing the emission spectrum of the red nitride fluorescent powder compound formed in Example 2 and Comparative Example 2 of the present invention. Fig. 6 is a view showing the excitation spectrum of the red nitride fluorescent powder compound formed in Example 3 of the present invention and Comparative Example 2. Fig. 7 is a view showing the emission spectrum of the red nitride fluorescent powder compound formed in Example 3 of the present invention and Comparative Example 2. Figure 8 is a schematic illustration of a light emitting diode package structure in accordance with a preferred embodiment of the present invention. [Main component symbol description] 100: Light-emitting diode package structure 131: First phosphor powder 110: Substrate 132: Second phosphor powder 120: Light-emitting element 140: Wire bond 130: Fluorescent powder layer 150: Bracket lead Foot 13

Claims (1)

201231619 EL99092 36618twf.doc/n VII. Patent Application Range: 1. A method for preparing red nitride phosphor powder, comprising 10 to 50 parts by weight of MaAbDcEdXe crystal as seed crystal, and 5 to 90 parts by weight The raw materials used to make the MaAbDcEdXe crystals are mixed, followed by sintering to form a MaAbDcEdXe crystalline product, wherein cerium is an activation center, including Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb Or a combination thereof; A is a divalent Group IIA metal element; _D is a tetravalent IVA metal element; E is a trivalent Group IIIA metal element; X is an elemental nitrogen; and a+b=l >0.00001<a< 0.1 , 0.5 < c < 4 » 〇.5 < d < 8 > 0.8x (2 / 3 + 4 / 3xc + d) SeSl. 2x (2 / 3 + 4 / 3xc + d). 2. The method of preparing a red nitride phosphor according to claim 1, wherein the MaAbDcEdXe crystallite as a seed crystal has a size of less than 25 μm. 3. The method for preparing a red nitride phosphor powder according to the invention of claim 2, wherein when X is elemental nitrogen, the raw material for preparing the MaAbDcEdXe crystal comprises 28 to 8 mol% to 3 8 Molar% of A nitride, 28 mole% to 38 mole% of D nitride, and 28 mole% to 38 mole% of E nitride and 〇丨mol% to $m% Niobium nitride or oxide of μ. 4. The method for preparing a red nitride phosphor according to claim 13 or claim 42, wherein the sintering is performed under a gas of I gas, ammonia gas or inert gas 14 201231619 EL99092 36618 twf.doc/n, sintering The temperature is from 1600 to 1900 degrees Celsius, and the sintering time is from 2 hours to 10 hours. The pressure is from 3 Mpa to 1 Mpa. 5. The method for preparing a red nitride phosphor according to the invention of claim 2, further comprising re-sintering the above-mentioned sintered MaAbDcEdXe crystalline product with a raw material for producing MaAb DeEdXe crystal. 6. The method for preparing a red phosphor according to claim 5, further comprising screening the sintered MaAbDeEdXe crystalline product to a size of 3 micrometers to 2 micrometers before performing the above re-sintering. 7. The method for preparing red nitride light-resistant powder according to claim 5, wherein the sintering of the towel is the same as the condition of the upper duty (four). 8. The method for preparing a red nitride light-polishing powder according to the fifth aspect of the patent application, wherein the above-mentioned re-sintering of the towel is in accordance with the process conditions of the sintering described above. The red nitride glory powder / '/ in the 51st (4th) is neutralized under nitrogen, ammonia or inert gas, gas nitrogen, and the sintering temperature is 1600 ° C to 10 ° C for 2 hours to 10 hours. The pressure is 0.3 MPu 1 MPa. 10. A light-emitting diode package structure comprising: a light-emitting element; a surface of the first light-emitting element and the periphery thereof, including - a first fluorescent film and a second fluorescent powder, wherein: the phosphor powder == =: Light powder 'The red coating with MaAbDcEdXe crystallized as a file with a size of less than 25 microns as a seed crystal, and 50 to 9 parts by weight for 15 201231619 EL99092 36618twf.doc/n MaAbDcEdXe crystal The raw materials of the materials are mixed, and then sintered, the formed MaAbDcEdXe crystalline product, wherein cerium is an activation center, including Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb or a combination thereof; A is a divalent Group IIA metal element; D is a tetravalent IVA group metal element; E is a trivalent Group IIIA metal element; X is an elemental nitrogen; and a+b=l >0.00001<a<0.1>0.5<;c<4 » 0.5<d<8 ? 0.8x(2/3+4/3 xc+d)<e<1.2x(2/3+4/3 xc+d) > where the above sintering It is carried out under an atmosphere of nitrogen, ammonia or an inert gas at a sintering temperature of 16 to 1900 degrees Celsius, a sintering time of 2 hours to 1 hour, and a pressure of 0.3 MPa to 1 MPa; The second phosphor is a yellow phosphor or green phosphor.