TWI278505B - Phosphor and method for producing the same - Google Patents

Abstract

The invention relates to a phosphor, comprising a phosphor of formula [MSiO3:Eu3+]; wherein M is selected form the group consisting of M1 and M2; M1 is Mg; M2 is selected from the group consisting of Ca, Sr and Ba; and when M is M1, the phosphor is amorphous. The invention also relates to a method for producing the phosphor and a light emitting diode comprising the phosphor.

Description

1278505 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a phosphor powder, and more particularly to a red phosphor powder. [Prior Art]

Near-ultra-violet (NUV), especially shorter-wavelength ultraviolet light, combined with fluorescent powder is one of the main development directions of white-light LED (WLED). The light-emitting diode is combined with R (red), G (green) and B (blue) white primary light-emitting phosphor white light emitting diodes as a new illumination source. At present, the development trend of white light-emitting diodes is that the excitation light source is non-visible ultraviolet light and the white light is provided by the phosphor powder. The light color of the light-emitting diode is relatively stable, and does not shift with current change, color rendering. Higher. The white light-emitting diode using an ultraviolet wafer also has the advantage of a single-wafer light-emitting diode. However, in the conventional white light-emitting diodes, the mixing, dispersion and efficiency of the phosphor powder are still unsatisfactory. The traditional sulfide-based filaments are desulfurized by absorption of light, and the phosphors are easily hydrolyzed or oxidatively decomposed by moisture and oxygen. These disadvantages greatly reduce the work of the ultraviolet wafer type white light emitting diode. Life and increase the cost and difficulty of manufacturing. Therefore, the industry has developed a relatively stable oxygen: the series of fluorescent powder ^ ultraviolet light to stimulate the red, green, blue three primary color fluorescent powder, the red fluorescent powder, the most efficient and most difficult A lot of red glory powders are used to enhance the two glory powders, and the emission spectrum is sharp and sharp. The area covered by the compensation ratio + the gentle slope map is 106588.doc 1278505, and the wavelength range is also crossed. Narrow, so the luminous efficiency is difficult to improve. In order to improve the luminous efficiency of the red fluorescent powder for UV-LED, in addition to the modification of the original fluorescent powder, it is also directed to the development of novel host materials or activators. The red phosphor powders that have been reported so far are: Y2O2S: Eu, La202S: Eu, Gd202S: Eu, Y(PV)04: Eu+, Y203: Eu3+, La203: Eu3+, Gd203: Eu3+, SnO: Eu3+, ZnO: Eu3+ . However, the red phosphor powder has a relatively weak emission intensity when compared with the green and blue phosphor powder when the near-ultraviolet light is used as the excitation wavelength.

At present, red fluorescent powder containing magnesium citrate is disclosed in the literature (X·J· Wang, D. Jia and W. M. Yen, “Mn2+ Activated Green, Yellow, and

Red Long Persistent Phosphors, '' Journal of Luminescence, 102-103, 34-37 (2003); X. Fan, M. Wang, Y·Y and Q· Wu, ''Crystallization Process of MgSi〇3 Gel and Influence of Crystallization on Luminescence of Eu3+ Ions,'' Journal of Physics and Chemistry of Solids, 57, 1259-1262 (1996); X. Fan, M. Wang and Z. Wang, "Spectroscopic Studies of Rare Earth Ions in MgSi03

Gel-Derived Crystals, '' Materials Science and Engineering: B, 47, 252-256 (1997)), the magnesium silicate powders described in the above documents are all crystalline, that is, they are higher than magnesium citrate The crystallization temperature (900 ° C) is calcined, such as 1200 ° C. The high-temperature manufacturing method consumes a lot of energy and is not easy to operate, and the obtained phosphor powder has a high emission intensity at 613 nm when the excitation light source is 254 nm, but the current industry is excited by ultraviolet light. The development of the light-emitting diode of the light source does not reach the short-wavelength (254 nm) range, and the application is mainly in the near-ultraviolet range of 360 nm to 42 Onm. There are no reports of other phthalate phosphors other than citric acid 106588.doc 1278505 magnesium. For the above reasons, there is a need to develop a glory which is easy to synthesize, does not consume energy, is not easy to absorb water, has good color rendering properties, has high emission intensity, and has high luminous efficiency. β [Summary of the Invention] Summary of the Invention

The present invention aims to develop a phosphor powder which is applicable to a UV-LED and which has high quality. An object of the present invention is to provide a phosphor powder comprising a red phosphor powder having the formula [MSi〇3:Eu3+], wherein... [selected from the group consisting of lanthanum and cerium: wherein 1 is For § § in Laos; Μ: is selected from the group consisting of Ca, SΓ and Ba, and when it is 馗! In the meantime, it is an uncrystallized red fluorescent powder. It is still another object of the present invention to provide a method for producing the above phosphor powder comprising the steps of: (a) providing a metal salt containing cerium, cerium oxide and cerium oxide or a precursor thereof; (b) colloidal step (a) a component formed in a colloid; (c) drying and grinding the colloid of step (b) + to form a powder, and (when the 乂 is made from a fluorescent powder, at 6 〇) 〇t: s9〇 (the powder of the rc calcination step (C); when the fluorene powder of the M2 is produced, the powder of the step (c) is calcined at 600 C to 1200 C to prepare the phosphor powder. A further object of the present invention is to provide a light-emitting diode comprising the above-mentioned phosphor powder. Detailed Description of the Invention 106588.doc 1278505 The present invention provides a novel tellurite-based phosphor powder, which is synthesized. The lower temperature 'host material replaces the rare earth element in the conventional phosphor powder with phthalate', thus contributing to cost reduction. The phosphor powder according to the present invention is excited by near- and external light (360 11111 to 395 nm). Both can emit red light and are in the red light area. There is a relatively wide emission spectrum, which can be applied to today's near The invention relates to a phosphor powder comprising a red phosphor powder having the formula [MSi〇3:Eu3+], wherein the ultraviolet light is used to improve the color rendering properties and efficiency of the light-emitting element. It is selected from the group consisting of % and ]\42, where Μι is Mg; the 2nd line is selected from the group consisting of Ca, Sr and Ba, and - when the country is %1, it is uncrystallized red a phosphor powder; when IV is M2, it is a crystalline or uncrystallized red phosphor powder. Preferably, the phosphor powder according to the present invention further comprises sodium ions; preferably, wherein the nanoparticle The ion system is provided by sodium oxide or sodium nitrate. In a preferred embodiment of the invention, the red phosphor powder according to the invention has [MgO-SiOHO.Oi~〇.2i)eU2〇3-(〇. 〇i~〇.06)Na〇] general formula, the red % phosphor powder has three emission peaks at 362 • nm, 380 rnn and 394 nm when the red light at 613 nm is the emission wavelength. The emission peaks are all located in the near-ultraviolet range and have the strongest emission intensity at the excitation wavelength of 394 nm, followed by the excitation wavelength of 380 nm; more preferably, The color fluorescent powder is [MgO-Si02_0.21Eu2〇3-〇.〇6Na〇] or [MgaSi02_0.12Eu2〇3_〇〇6Na〇]; the optimum system is [MgO_SiO2-0.21Eu2O3-0.06NaO]. The phosphor powder of the present invention has an excitation spectrum ranging from 35 〇 nm to 42 〇 nm; preferably from 350 nn ^ 4 〇〇 nm; more preferably from self-derivative to 400 nm. Compared with the light powder, the excitation light 106588.doc 1278505 according to the present invention is located in the near-ultraviolet region, in line with the industry's expectation for the uv light-emitting diode. The phosphor powder according to the present invention has an emission spectrum ranging from 58 〇 111 ^ to 640 nm; preferably from (10) (10) to (four) legs; more preferably from 6 〇〇 nm to 620 nm. The phosphor powder according to the present invention has an emission peak of an emission spectrum at 582 11111 to 6 〇〇 nm and 6 〇 6 nm to 630 nm, when 383 of a commercially available near-ultraviolet light-emitting diode is used as an excitation light source. The maximum value (;Lpeak) is 593 nm and 613 nm, respectively, with a wide emission band, and its light color is pink. At the same time, since the phosphor powder according to the present invention has a wider emission band, it has the advantage of better color rendering than the conventional white, red, green and blue powder mixed white light. The phosphor powder according to the present invention has excellent luminous intensity and luminous efficiency. As shown in the following example, the phosphor powder according to the present invention and the conventional phosphor powder (for example, Y2〇3:Eu3+17m〇1%) are excited by the excitation light source of 383 nm at the same time. The emission peak is located at 612 nm, and its emission intensity is higher than the emission intensity of the phosphor powder according to the present invention at 613 nm, but the phosphor powder according to the present invention is at 582 11111 to 600 nm and at 613 nm to 629 nm. The emission intensity is higher than the conventional phosphor powder. The integrated intensity value ratio of the emission spectrum (the conventional fluorescent powder·the fluorescent powder according to the present invention) is about 3 ·· 5 ', so that the luminous powder according to the present invention has higher luminous efficiency than the conventional fluorescent powder. The phosphor powder according to the present invention may contain other phosphor powders. In a preferred embodiment of the invention, it comprises a crystalline red fluorescent powder having the formula [MgSi03:Eu3+]. On the other hand, in order to be applied to a light-emitting diode, the phosphor powder further contains a green or blue phosphor powder. 106588.doc 1278505 The phosphor powder according to the present invention is not a sulfide, so it is not easy to absorb water, and has strong luminous intensity and longevity. The invention also provides a method for producing the above phosphor powder, comprising the steps of: (a) providing a metal salt containing cerium, cerium oxide and cerium oxide or a precursor thereof; (b) colloidalizing step (a) a component that forms a colloid,

(c) drying and grinding the colloid in the step (b) to form a powder; and (d) preparing the powder of the calcining step (c) at 600 to 900 ° C when the luminescent powder is made of Μ! When the phosphor powder of the M2 is produced, the powder of the step (c) is prepared at 6 ° ° 0: to 1200 ° (satin), preferably, according to the present invention. The method, wherein the metal salt containing cerium in the step (a) is a nitrate or acetate salt. In one embodiment of the invention, the metal salt used is Magnesium nitme hexahydrate (Mg) N〇3)2 · 6h2〇) or magnesium oxide, calcium nitrate nhme tetrahydrate 'Ca(N〇3)2 · 4H2〇), strontium sulphate (st_ium nitrate, Sr(N〇3)2) or barium acetate (Bariumacetate) , Ba(cH3C〇〇) 2). Preferably, in the step (4) of the method according to the present invention, the t-box is W~ preferably 'in the step (4) of the method according to the present invention, the precursor of the oxidized stone is the tetrathoxysilan (TPnQ) Preferably, the cerium oxide is preferably dioxygen. Preferably, step (4) of the method according to the invention comprises providing a nanoparticle; more preferably, the sodium ion is provided by sodium nitrate or sodium oxide. 106588.doc I278505 According to the method of the present invention, step a (b) is a component of the colloidal gelation step (a), and the method of colloidalization and 4 colloidization is the invention. It is known in the art to have the general knowledge of the fly, and is exemplified in the following examples. In a relatively mild manner, the method step (C) of the root 摅 摅 象 象 I I 明 明 系 is dried at 100 ° c to 110 ° c. In a specific embodiment of the present invention, it was dried in an oven at 105 ° C for 24 hours.

The method of polishing in step (4) according to the method of the present invention is well known to those of ordinary skill in the art to which the invention pertains. According to the method of the present invention, the step (4) is to burn the phosphor powder having a ruthenium or ruthenium at a crystallization temperature. 〇to 12〇〇, it calcines the phosphor powder having a ruthenium, preferably, step (d) is calcined at 6〇〇〇c to 1〇〇〇〇c; more preferably, step (d) Calcined at 7〇〇t to 9〇〇t. Preferably, step (d) is heated to a calcination temperature at a temperature increase rate of from 3 〇c /min to 8 C /min. On the other hand, the step (d) is preferably carried out at a calcining temperature for 1 hour to $ hours, more preferably at a satin temperature for 1 hour to 5 hours. In a preferred embodiment of the invention, step (d) is carried out at a temperature increase rate of /min to 800 ° C and held for 2 hours. In addition to the above methods, the method of producing the phosphor powder according to the present invention further comprises a solid phase method, a solution method, a chemical vapor method or a physical vapor deposition method. The manner in which the above methods operate is well known to those of ordinary skill in the art to which the invention pertains. For example, using the oxide as a starting material, the raw materials are mixed and calcined by a solid phase method; and the nitrate or the chlorinated salt is used as a starting material to be uniformly mixed by a solution method and then satin-fired; Or a thin film 106588.doc 12 1278505 film containing Mg-Si-Eb〇 or M-Si-Eu-Ο by chemical vapor deposition (CVD) or physical vapor deposition (PVD). The invention also provides a light-emitting diode comprising the above-mentioned phosphor powder. The invention is illustrated by the following examples, which are not intended to be construed as limiting the invention. [Examples] Example 1: Production of fluorescent powders Starting materials for synthesis:

1. Magnesium nitrate (Mg(N03)2 · 6H20) 2. Calcium nitrate (Ca(N03)2 · 4H20) 3. Strontium nitrate (Sr(N03)2) 4. Barium acetate (Ba(CH3COO)2) 5· Tetrathoxysilan (TEOS) 6. Oxidation pin (EU2O3) 7. Sodium nitrate 8. Nitric acid (HN〇3) 9. Alcohol starting material ratio: Synthetic stone silicate powder Body (Ειΐ2〇31~21 mole%, NaO 1~6 mole%) 'The details of the starting materials are shown in the table below. 106588.doc -13- 1278505

Eu3+ (M=Mg, Ca, Sr, Ba)] is an emission spectrum of a commercially available near-ultraviolet LED (383 nm) as an excitation source. Fig. 9 is an emission spectrum of a magnesium citrate phosphor powder synthesized at 600 ° C to 1200 ° C using a commercially available near-ultraviolet LED (383 nm) as an excitation light source. Fig. 10 is an emission spectrum of a calcium citrate phosphor powder synthesized at 600 ° C to 1200 ° C using a commercially available near-ultraviolet LED (383 nm) as an excitation light source.

Fig. 11 is an emission spectrum of a bismuth citrate phosphor powder synthesized at 600 ° C to 1200 ° C using a commercially available near-ultraviolet LED (383 nm) as an excitation light source. Fig. 12 is an emission spectrum of a bismuth ruthenate fluorite powder synthesized at 600 ° C to 1200 ° C using a commercially available near-ultraviolet LED (383 nm) as an excitation light source. Fig. 13 is an emission spectrum of a Y2O3·Eu3 17 mole% phosphor powder and a crushed acid phosphor powder, which are commercially available near-ultraviolet LEDs (383 nm) as an excitation light source. Figure 14 is a ciE chromaticity coordinate position of the emitted light when the commercially available near-ultraviolet LED (3 83 nm) is used as an excitation source for the phosphor powder synthesized at 800 °C. 106588.doc -19-

Claims (1)

510 Patent Application Substitute Replacement (December 95) X. The scope of the patent application is 败 丨 月 月 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日 日The red fluorescent powder 'in which VI is selected from the group consisting of Mi and M2, wherein % is Mg; M2 is selected from the group consisting of ca, Sr and Ba, and when M is Μι, its system It is an uncrystallized red fluorescent powder. 2. According to the request item, the phosphor powder further contains sodium ions. 3. A phosphor powder according to the claim, wherein the sodium ion is supplied by sodium oxide or sodium nitrate. 4. The phosphor powder according to the claim, wherein the red phosphor powder has a formula of [MgO-SiCV (0.01 ～0·21) Ειΐ2〇3-(0·01~〇 )6)Na〇]. 5. The phosphor powder according to claim 4, wherein the red phosphor powder is [MgO-Si〇2.〇.21Eu2〇3-〇.〇6NaO] into [MgO_Si02-〇.i2Eu203-0.06NaO]. 6. The phosphor powder according to claim 5, wherein the uncrystallized red phosphor powder is [MgO-Si〇2-〇.21Eu203-0.06NaO]. According to the phosphor powder of claim 1, the excitation spectrum ranges from 35 〇 to 420 nm 〇8. According to the phosphor powder of claim 7, the excitation spectrum ranges from 35 〇 11 melon to 400 nm 〇 9· According to the phosphor powder of claim 8, the excitation spectrum ranges from 38 〇 to 400 nm. 萤ίο. The phosphor powder according to claim 1 has an emission spectrum ranging from 58〇 to 106588-951219.doc 1278505 640 Nm 〇11. The phosphor powder according to claim 10, which has an emission spectrum ranging from 58 〇 nm to 620 nm 0 _ 12. According to the fluorescent powder of claim 11, the emission spectrum ranges from 6 〇〇 to 620 nm 0 13 ·According to the glory powder of Ming 1 , with an excitation source of 3 8 3 nm, it has emission peaks at 582 nm to 600 nm and 606 nm to 630 nm. 14. According to the phosphor powder of claim 13, when the excitation light source is 383 nm, the emission peak maximum value (long-term peak) of the emission spectrum is 593 nm and 613 nm ° respectively. 15. The phosphor powder according to claim 1 It contains a crystalline red fluorescent powder having the formula [MgSi〇3:]Eu3+]. 16. The phosphor powder according to claim 1, which comprises a green or blue phosphor powder. Φ 17. A method of producing the phosphor powder according to any one of claims 1 to 16, comprising the steps of: (a) providing a metal salt containing cerium, cerium oxide and cerium oxide or a precursor thereof; a component of the colloidal step (a) to form a colloid; (c) drying and grinding the colloid in the step (b) to form a powder; and (d) when manufacturing the phosphor powder When calcining the powder of the step (c) at 600 ° C to 900 ° C; when preparing the phosphor powder of M 2 , calcination step at 600 ° C 106588-951219.doc • 127485 to 1200 ° C (C The powder is prepared to obtain the phosphor powder. 18. The method according to claim 17, wherein the metal salt containing cerium in the step (a) is a nitrate or acetate salt. The method according to claim 18, wherein the metal salt of the cerium in the step (a) is Magnesium nitrate hexahydrate (Mg(N03)2 · 6Η2〇) or Calcium nitrate tetrahydrate (Calcium nitrate tetrahydrate, Ca(N03)2 · 4H20), str〇ntiuin nitrate (Sr(N03)2) or barium acetate (Ba(CH3COO)2). 2. The method according to claim 17, wherein the lanthanum oxide in the step (a) is. 21. The method according to claim 17, wherein the precursor of the cerium oxide in the step (a) is tetrathoxysilan (TEOS). 22. The method according to claim 17, wherein in the step (4), the oxidized stone is a day of sulphur dioxide. According to the method of π, wherein the step (4) further comprises providing a nano-ion. The method of claim 23, wherein the sodium ion is provided by sodium nitrate or sodium oxide. 2 5 · According to the request, go, the eighth step (b) is the sol-gel method colloidal component of step (a). 2 6 · According to the request item, the law ', ', and v (0 is in 1〇〇. (: to ll〇 °C dry. 2 7 · According to the request item, ' '〆, 中v骤(4) 600 ° C to lOOOOt: satin 106588-951219.doc '1278505 2 8 · according to the requirements of item 27. The method (d) is at 700 ° C to 900 ° c 烺 2 9 · according to the spectrum, 7, The method wherein the step (d) is heated to a calcination temperature at a temperature increase rate of from 3 ° C/min to 8 ° C / min. 3 〇 According to the method of claim 17, wherein the step (d) is calcined The temperature is maintained for 1 hour to 8 hours at a temperature. 1) According to the method of claim 3, wherein step w) is maintained at a calcination temperature for 1 hour to 5 hours. According to the method of claim 17, step (d) It is heated to 800 at a temperature increase rate of 6 ° C / min and held for 2 hours. 33. A light-emitting diode comprising the phosphor powder according to any one of claims 1 to 16. 106588-951219.doc