DE112011102173T5 - Oxynitride phosphor, its production process and the light source made with such phosphor for lighting - Google Patents

Abstract

An oxynitride phosphor has chemical formula M1-yA4-xZ1 + xOxn7-x: Ry, where M is one or more alkali metals, alkaline earth metals, rare earth metals or transition metals; X is at least one of Si, Ge, B, Al and Si; Z is at least one of Al, Ga, In and Al; R is at least one of the elements of the luminous center of Eu, Ce, Tb, Yb, Sm, Pr, Dy; and 0 ≤ x <0.5; 0 <y <1.0. The phosphor can emit yellow or red light at wavelengths between 500 and 700 nm upon excitation of UV, near-UV, or blue light, and can emit UV, near-UV or blue-light LEDs and other phosphors such as green fluorescent powder Production of the novel white light LED light source can be combined. The phosphor of the present invention has characteristics such as broad excitation wavelength range, high efficiency and stability, and its production process is simple, easy for mass production and without environmental pollution.

Description

Technical area

The present invention relates to the field of the semiconductor, particularly to an oxynitride phosphor, its production method and the illumination light source made with such a phosphor.

background

GaN-based LED is a novel light-emitting device for 21st century solid state lighting. It has advantages such as small size, low power consumption, long life, free from polluting mercury, high efficiency, low maintenance, etc., and can be widely used in various lighting devices including interior lighting, traffic lights / indicators, car taillights / headlamps, ultra-large outdoor screens , Screens and advertising display, and may replace the currently used bulbs and fluorescent lamps. This novel environmentally friendly light source will certainly be a novel lighting system. It has great importance for saving energy, protecting the environment, improving the quality of life, etc. The manufacturing technology of white light LEDs mainly include: (1) the combination of three single-color LEDs (blue, green and red), (2) blue LED + yellow fluorescence Powder, (3) UV-LED + red, green and blue fluorescent powder. But there are very rarely the phosphors effectively excited by blue LED. Currently, white light is mainly produced by the combination of fluorescent substances of yttrium aluminum garnet YAG: Ce and blue LED according to the principle of complementary color. However, only white light with cool color and higher color temperature is produced because the light color produced by YAG is more yellow-green. It is expected to further improve the color rendering index. In order to produce white light with different color temperatures (from cool to warm color) and to obtain higher color rendering index, green, yellow or red fluorescent powders should be added therein.

At present, the green fluorescent powder that can be excited by blue light is mainly the divalent europium-doped sulfide, e.g. B. (Ca, Sr, Ba) GaS ₄ : Eu ²⁺ . But the chemical properties and the temperature resistance of the sulfide fluorescent powder are very poor. These fluorescent powders easily react with the moisture in air and are decomposed by heat, and in their manufacturing process, exhaust gases are emitted and the environment is polluted. Recently, the nitrides consisting of SiN ₄ basic units can largely be considered as the substrates of the fluorescent powders. Because of strong covalent bonding and large crystal field splitting, such compounds can emit long wavelength light, such as yellow, orange and red, e.g. When doped with rare earth elements such as europium. By changing the size of the luminous center atoms by selecting the substrate materials and the crystal field design, the adjustment of the emission characteristics and the development of the novel fluorescent powders are achieved. The present invention describes an oxynitride fluorescence powder which can emit yellow and red light by the excitation of UV and blue light. At the same time, the present invention also describes a white light LED electric light source made of oxynitride fluorescent powder and blue LED.

invention content

In contrast to the above-mentioned disadvantages, the present invention provides a yellow or red oxynitride phosphor having stable chemical properties and excellent emission characteristics, which can be excited by UV LED or blue LED and used in white light LED, the excitation wavelength being between 200 and 500 nm and the emission wavelength is between 500 and 750 nm.

Another object of the present invention is to provide a manufacturing method which is simple, easy to operate and mass-produce, without pollution, and low in cost. With this manufacturing method, fine fluorescent powders having high emission intensity, uniform particles and a diameter of particles smaller than 10 μm can be produced.

Another object of the invention is to provide a white light LED light source made with this phosphor.

An oxynitride phosphor having a chemical formula M _1-y A _4-x Z _1-x O _x N _7-x : R _y , wherein M is one or more alkali metals, alkaline earth metals, rare earth metals or transition metals; A is one or more of Si, Ge, B, Al is and Si includes; Z is one or more of Al, Ga, In and Al; R is one or more elements of the luminous center of Eu, Ce, Tb, Yb, Sm, Pr, Dy; and 0 ≤ x <0.5; 0 <y <1.0.

Preferably, M is one or more of the following: Li, Mg, Ca, Sr, Ba, Bi, Mn, Zn, La, Gd, Lu, Y;
more preferably, M is one or more of Li, Mg, Ca, Zn, Sr, Ba, Bi, Y, and includes at least Sr;
the Sr content is more than 0.8, A is Si; Z is Al; R is Eu, Ce or the composition thereof.

Preferably, it is 0 ≤ x ≤ 0.15, 0 <y ≤ 0.1.

More preferably, it is 0 ≦ x ≦ 0.1, 0.05 ≦ y ≦ 0.1.

• (1) M-haltiges Oxid, Nitrid, Nitrat oder Carbonat; A-haltiges Nitrid oder Oxid, Z-haltiges Nitrid oder Oxid und R-enthaltenes Nitrid, Oxid oder Nitrat werden als Ausgangstoffe gemahlen und gleichmäßig gemischt, ein Gemisch zu erzeugen;
• (2) das Gemisch im Schritt (1) wird mittels Gasdrucksintern-Verfahren oder Festphasenreaktionsverfahren unter dem Schutz des Inertgas bei Hochtemperatur kalziniert, ein Kalzinierungsprodukt zu erzeugen;
• (3) das Kalzinierungsprodukt im Schritt (2) wird weiter zerkleinert, aufbereitet, getrocknet und sortiert, den Oxynitrid-Leuchtstoff herzustellen.

The manufacturing method of the above oxynitride phosphor includes the following steps:

• (1) M-containing oxide, nitride, nitrate or carbonate; A-containing nitride or oxide, Z-containing nitride or oxide and R-containing nitride, oxide or nitrate are ground as starting materials and uniformly mixed to produce a mixture;
• (2) the mixture in step (1) is calcined by gas pressure sintering or solid phase reaction under the protection of the inert gas at high temperature to produce a calcination product;
• (3) The calcination product in the step (2) is further crushed, processed, dried and sorted to produce the oxynitride phosphor.

Optionally, the inert gas may be nitrogen in the gas pressure sintering process wherein the pressure of the nitrogen is 1 to 200 barometric pressure.

Alternatively, in the solid phase reaction process, the inert gas may be gas mixture of nitrogen and hydrogen, wherein the volume ratio of nitrogen and hydrogen is 95: 5 or 90:10 or 85:15 or 80:20 and the volume flow is 0.1 to 3 liters / min. is.

Optionally, the calcination temperature is between 1200 and 1800 ° C, the calcination time lasts 0.5 to 30 hours and the calcination can be carried out several times.

In carbothermal reduction and nitridation (a type of Hochtemperaturkalzinierungen), the temperature is between 1200 and 1600 ° C and the time takes 0.5 to 30 hours.

Optionally, flux is added in step (1), wherein the flux is one or more M-containing halides or boric acid.

Optionally, the amount of flux added is 0.01 to 10% of the total weight of the starting materials.

Alternatively, the treatment includes washing with acid or water.

A white light LED light source is characterized by comprising UV or near UV LED and the above oxynitride phosphor.

A white light LED light source for illumination or display is characterized by comprising blue LED and the above oxynitride phosphor.

The technical achievements of the present invention are as follows:
The oxynitride phosphor according to the invention can emit yellow or red light with a wavelength of 500 to 750 nm, especially over 560 nm, when exciting light with a wavelength between 200 and 500 nm.

In the synthesis method used in the present invention, besides oxides of metal M, oxides, carbonates, nitrates, etc. can also be used as starting materials for producing the above-mentioned phosphor, as far as such salts can be decomposed into metal oxide by high temperature calcination. Thus, the selection range of the starting materials will become wider and at the same time reduce the cost of synthesis. The salts are more stable and do not require special treatment in the synthesis process, so it is easy to control the reaction and realize mass production. Nitrides, oxides, carbonates, nitrates, etc. of metal M, oxides and nitrides of elements A and Y, and nitride or oxides of element R are synthesized by high temperature calcination for the synthesis of the phosphor of the present invention used. During high-temperature calcining process, inert gas is supplied for protection. The shielding gas serves: (1) for protection at high temperature against decomposition of some nitride raw materials and reaction products, and (2) as reduced gas. The commonly used inert gas is N ₂ or the gas mixture of N ₂ and H ₂ and at high pressure or atmospheric pressure. Prior to high temperature calcination, the solvents of ethanol or n-hexane may be added while milling the starting materials to obtain more uniform mixing of the starting materials. Flux of M-containing halides or boric acid may be added before calcination. During post-reaction processing, the impurities are removed from the reaction. After the high-temperature calcination of the starting materials, the impurities are normally oxides of M and / or A and / or Y and / or R, which can be removed by washing with acid and water. The other impurities flee as gas.

The oxynitride phosphor according to the invention can emit yellow or red light having a wavelength of 500 to 750 nm in the excitation of light having a wavelength of 200 to 500 nm, so that it with other phosphors such as red phosphor on blue LED chip or with others Phosphors such as blue or green phosphor can be applied to UV or near-UV LED chip to produce novel white light LED with high energy conversion yield. It can also be assembled with blue, UV or near-UV LEDs or mixed with other phosphors to produce colored LEDs.

Currently, the yellow fluorescent powder used in white light LED is mainly the Ce ³⁺ -doped YAG system, which has wide emission peak and high brightness and is mainly used for the production of white light LED with high color temperature (> 5000 K). However, the temperature characteristics of the YAG fluorescent powder is poor and component have significant light loss. The oxynitride phosphor according to the invention has a completely different chemical formula and crystal structure than the YAG system and is a novel phosphor. From this Ce ³⁺ -doped compound, a yellow phosphor emitting light having a longer wavelength than YAG can be obtained for producing whitish LED having a low color temperature (<5000 K). By altering the composition, it is also possible to produce a yellow phosphor of similar wavelength as YAG, which is used to make Whitish LED with high color temperature. The emission wavelength of the Eu ²⁺ -doped compound, which is a red phosphor, is in the red spectral range. The red phosphor can be compounded with other green fluorescent powders to produce the white light LED with high color rendering. In addition, because of the presence of the element N, the compound produced according to the present invention has strong covalent bonding and 3D matrix structure of tetrahedral SiN ₄ units, thus its temperature property is good. By changing the ratio of the elements O and N, a solid solution can be formed in the specific range, so that the emission wavelength can be adjusted and the application of the compound can be found in wider ranges.

The production method according to the invention is simple and easy for mass production. By partially replacing the elements, the emission wavelength can be adjusted and the emission intensity can be improved. The phosphor synthesis method of the present invention has the advantages of being simple, easy to operate and mass-produce, free from environmental pollution, low in cost, etc.

• (1) das erfindungsgemäße Leuchtstoffe ist ein Oxynitrid, das sehr stabile Eigenschaften und gute Temperaturverhalten aufweist.
• (2) das Anregungsspektralbereich des erfindungsgemäßen Leuchtstoffs ist sehr breit (200–500 nm) und die Anregungswirkung ist besonders gut.
• (3) die erfindungsgemäße Herstellungsverfahren des Leuchtstoffs ist einfach und praktisch, ohne Umweltverschmutzung, leicht für die Massenfertigung und Bedienung.
• (4) die erfindungsgemäß hergestellte Weißlich-LED weist hohes Farbwiedergabeindex, hohe Lichtausbeute und ein breites Farbtemperaturbereich auf.

The advantages of the present invention are:

• (1) The phosphor of the present invention is an oxynitride which has very stable properties and good temperature characteristics.
• (2) The excitation spectral region of the phosphor of the present invention is very broad (200-500 nm) and the excitation effect is particularly good.
• (3) the phosphor production process of the present invention is simple and practical, without environmental pollution, easy for mass production and operation.
• (4) The whitish LED produced according to the present invention has high color rendering index, high light output and wide color temperature range.

Brief description of the drawings:

1 : Emission spectrum and excitation spectrum of Example 1; Y represents the emission intensity and X represents the emission wavelength;

2 : Emission Spectrum and Excitation Spectrum of Example 9; Y represents the emission intensity and X represents the emission wavelength;

3 : Emission Spectrum of White Light LED from Example 9; Y represents the luminous flux and X represents the emission wavelength;

4 : Emission Spectrum of White Light LED Produced with Example 3; Y represents the luminous flux and X represents the emission wavelength;

5 : Emission Spectrum and Excitation Spectrum of Example 24; Y represents the emission intensity and X represents the emission wavelength;

6 : Emission spectrum of white light LED fabricated with Example 24 and another green fluorescent powder; Y represents the luminous flux and X represents the emission wavelength.

embodiment

The oxynitride phosphor of the present invention, which is capable of emitting yellow or red light having a wavelength of 500 to 750 nm upon excitation of light having a wavelength of 200 to 500 nm, has chemical formula M _{1 -y} X _{1 -x} Z _{4 + x} O _x N _7-x : R _y , where M is one or more alkali metals, alkaline earth metals, rare earth metals or transition metals; A is one or more of Si, Ge, B, Al and Si; Z is one or more of Al, Ga, In and Al; R is one or more of the elements of the luminous center of Eu, Ce, Tb, Yb, Sm, Pr, Dy; and 0 ≤ x <0.5; 0 <y <1.0.

Preferably, M is one or more of Li, Mg, Ca, Sr, Ba, Bi, Mn, Zn, La, Gd, Lu, Y;
more preferably, M is one or more of Li, Mg, Ca, Zn, Sr, Ba, Bi, Y, and includes at least Sr;
the Sr content is more than 0.8, A is Si; Z stands for Al; R is Eu, Ce or the composition thereof.

Preferably, it is 0 ≤ x ≤ 0.15, 0 <y ≤ 0.1.

More preferably, it is 0 ≦ x ≦ 0.1, 0.05 ≦ y ≦ 0.1.

Example 1: Preparation of Sr _0.90 Li _0.05 Si ₄ AlN ₇ : Ce _0.05 Luminescent Material

According to the composition described above, Sr ₃ N ₂ (27.0746 g), Li ₃ N (0.1803 g), Si ₃ N ₄ (57.6933 g), CeN (2.3798 g) and AlN (12.6719 g) were weighed and charged with argon Glove box ground and mixed evenly. Thereafter, the mixture was placed in a boron nitride crucible and calcined in a pneumatic oven under 0.3 MPa N ₂ at a temperature of 1700 ° C for 4 hours. The powders produced, after grinding, were again calcined under the same conditions to promote the growth of the crystal particles. The obtained phosphor was crushed, washed with hydrochloric acid and purified, thereby obtaining 100 g of the yellow phosphor of the present invention. In the 1 the emission spectrum and excitation spectrum is shown. After 1 it can be seen that the emission spectrum of the yellow phosphor is relatively broad, the FWHM of the spectrum is about 130 nm, and the emission main peak is in the 573 nm yellow region. However, it can be found that the excitation spectrum of the phosphor is very broad and extends from the UV region to the visible region, in particular the phosphor is simultaneously excited effectively by UV light (300-420 nm) and blue light (420-490 nm) can. Its emission intensity is shown in Table 1. The emission intensity is almost the same as the emission intensity of the YAG: Ce in the comparative example.

Example 9: Preparation of Sr _0.90 Li _0.05 Si _3.85 Al _1.15 O _0.15 N _6.85 : Ce _0.05 phosphor

According to the composition described above, Sr ₃ N ₂ (27,0204 g), Li ₃ N (0.1799 g), Si ₃ N ₄ (55,4185 g), Ce ₂ O ₃ (2.5293 g), Al ₂ O ₃ (1.5731 g), and AlN (13.2788 g) weighed and ground in an argon-filled glove box and mixed evenly. Thereafter, the mixture was placed in a boron nitride crucible and calcined in a pneumatic furnace with flux 0.1 g SrF ₂ under 0.3 MPa N ₂ at a temperature of 1700 ° C for 4 hours. The powders produced, after grinding, were again calcined under the same conditions to promote the growth of the crystal particles. The obtained phosphor was crushed, washed with hydrochloric acid, purified and dried, thereby obtaining 100 g of the yellow phosphor of the present invention. In the 2 the emission spectrum and excitation spectrum is shown. To 1 it can be seen that the emission spectrum of the yellow phosphor is relatively broad, the FWHM of the spectrum is about 132 nm, and the main emission peak is in the yellow spectral range of 573 nm. However, it can be found that the excitation spectrum of the phosphor is very broad and extends from the UV spectral range to the visible spectral range, in particular the phosphor can be effectively excited simultaneously by UV light (300-420 nm) and blue light (420-490 nm) , Its emission intensity is shown in Table 1. Compared to Example 1, the emission wavelength of the phosphor apparently shifts to blue, since oxygen is introduced into the crystal lattice, so that the covalent bond weakens, the lowest energy level of the 5d orbital of Ce ions increases, the energy of the emitting light increases , and the emission wavelength shortens. Although the phosphor's thickness is lower than YAG: Ce in the comparative example, whitish LED having higher color temperature can be produced because of its shorter emission wavelength.

Example 2-8 and 10-16:

The production processes of the above examples are the same as in Example 1 or 9, wherein Ce halides such as CeCl ₃ , or Ce nitrates such as Ce (NO ₃ ) ₃ can be used and the flux used for the reaction chloride or fluoride of Sr, Ca, Ba, Li, etc. is. The emission intensity of the phosphor produced is shown in Table 1. The phosphors, whose maximum emission wavelength is most in the yellow range, can be excited by blue light and UV light and used instead of the YAG fluorescent powder to produce the whitish LED. TABLE 1 Chemical formula of Examples 1-18 and their emission properties (excitation wavelength: 450 nm) example chemical formula Emission peak nm Relative intensity% 1 Sr _0.90 Li _0.05 Si ₄ AlN ₇ : Ce _0.05 573 100 2 Sr _0.80 Li _0.10 Si ₄ AlN ₇ : Ce _0.10 576 94 3 Sr _0.85 Ca _0.05 Li _0.05 Si ₄ AlN ₇ : Ce _0.05 580 85 4 Sr _0.85 Ba _0.05 Li _0.05 Si ₄ AlN ₇ : Ce _0.05 568 93 5 Sr _0.80 Ba _0.10 Li _0.05 Si ₄ AlN ₇ : Ce _0.05 565 90 6 Sr _0.80 Ca _0.05 Ba _0.05 Li _0.05 Si ₄ AlN ₇ : Ce _0.05 574 95 7 Sr _0.85 Zn _0.05 Li _0.05 Si ₄ AlN ₇ : Ce _0.05 573 97 8th Sr _0.90 Li _0.05 Si _3.90 Al _1.10 O _0.10 N _6.90 : Ce _0.05 567 101 9 Sr _0.90 Li _0.05 Si _3.85 Al _1.15 O _0.15 N _6.85 : Ce _0.05 562 84 10 Sr _0.90 Li _0.05 Si _3.95 Ge _0.05 AlN ₇ : Ce _0.05 568 90 11 Sr _0.90 Li _0.05 Si _3.95 B _0.05 AlN ₇ : Ce _0.05 568 103 12 Sr _0.85 Ba _0.05 Li _0.05 Si _3.95 B _0.05 AlN ₇ : Ce _0.05 566 100 13 Sr _0.90 Li _0.05 Si ₄ Al _0.95 Ga _0.05 N ₇ : Ce _0.05 569 83 14 Sr _0.85 Mg _0.05 Li _0.05 Si ₄ AlN ₇ : Ce _0.05 574 90 15 Sr _0.80 Bi _0.05 Li _0.10 Si ₄ AlN ₇ : Ce _0.05 576 98 16 Sr _0.80 Y _0.05 Li _0.10 Si ₄ AlN ₇ : Ce _0.05 565 91 Comparative example Y _2.95 Al ₅ O ₁₂ : Ce _0.05 557 110 Table 2 Optical parameters of the white light LED examples White LED example Color coordinates (x, y) Color rendering index x Color temperature / K Light output / lm / W Blue light LED + Example 9 Example 17 (0.3172, 0.3173) 75 6340 90 Blue light LED + example 3 Example 18 (0.4332, 0.391 2) 64 2950 95

Example 17 Production of white light LED electric light source

A certain amount of the fluorescent powder of Example 9 was weighed and uniformly distributed in the epoxy resin, after which the degassed mixture was coated on the commercially obtained blue light LED chip (emission wavelength of 450 nm) and at the temperature of 150 ° C for Dried for 0.5 hour. So the housing took place. The mixture of blue light emitted from blue light LED and yellow and red light emitted from fluorescent powder produces cool white light with color coordinates of x = 0.3172, y = 0.3173, color rendering index of Ra = 75 and a corresponding color temperature of T = 6340 K.

Example 18 Production of Electric White Light LED Light Source

A certain amount of the inventive fluorescent powder of Example 3 was weighed and uniformly distributed in the epoxy resin, then the degassed mixture was coated on the commercially obtained blue light LED chip (emission wavelength of 450 nm) and at the temperature of 150 ° C Dried for 0.5 hour. So the housing took place. After the mixture of the blue light emitted from blue light LED and yellow and red light emitted from fluorescent powder, cool white light with color coordinates of x = 0.4332, y = 0.3912, color rendering index of Ra = 64 and a corresponding color temperature of T = 2950 K is produced 3 Chemical formula of Examples 19-31 and their emission properties (excitation wavelength: 450 nm) example chemical formula Emission main peak nm Relative intensity% 19 Sr _0.95 Si ₄ AlN ₇ : Eu _0.05 630 100 20 Sr _0.9 Si ₄ AlN ₇ : Eu _0.10 638 96 21 Sr _0.90 Ca _0.05 Si ₄ AlN ₇ : Eu _0.05 623 110 22 Sr _0.90 Ba _0.05 Si ₄ AlN ₇ : Eu _0.05 632 103 23 Sr _0.90 Ba _0.05 Ca _0.05 Si ₄ AlN ₇ : Eu _0.05 627 105 24 Sr _0.90 Li _0.1 Si ₄ AlN ₇ : Eu _0.05 634 121 25 Sr _0.90 Y _0.033 Si ₄ AlN ₇ : Eu _0.05 631 91 26 Sr _0.90 Li _0.1 Si _3.95 Al _1.05 O _0.05 N _6.95 : Eu _0.05 630 107 27 Sr _0.95 Si _3.95 Al _1.05 O _0.05 N _6.95 : Eu _0.05 628 97 28 Sr _0.95 Si _3.90 Al _1.10 O _0.10 N _6.90 : Eu _0.05 625 93 29 Sr _0.85 Ba _0.10 Si _3.95 Al _1.05 O _0.05 N _6.95 : Eu _0.05 621 91 30 Sr _0.95 Si _3.95 Ge _0.05 AlN ₇ : Eu _0.05 626 93 31 Sr _0.90 Mg _0.05 Si ₄ AlN ₇ : Eu _0.05 627 97

Example 26: Preparation of Sr _0.90 Li _0.1 Si _3.95 Al _1.05 O _0.05 N _6.95 : Eu _0.05 phosphors

According to the composition described above, Sr ₃ N ₂ (26.9283 g), Li ₃ N (0.3586 g), Si ₃ N ₄ (56.6642 g), Eu ₂ O ₃ (2.7128 g), Al ₂ O ₃ (0.5226 g) and AlN (12.8135 g) and ground in an argon-filled glove box and mixed evenly. Thereafter, the mixture was placed in a boron nitride crucible and calcined in a pneumatic furnace with flux of 0.1 g of SrF ₂ under 0.3 MPa of N ₂ at a temperature of 1700 ° C for 4 hours. The produced powders were again calcined at the same conditions after milling to promote the growth of the crystal particles. The obtained phosphor was crushed, washed with hydrochloric acid and purified, thereby obtaining 100 g of the red phosphor of the present invention. In the 2 the emission spectrum and excitation spectrum is shown. To 2 it can be seen that the emission spectrum of the yellow phosphor is broad, the FWHM of the spectrum is about 133 nm, the emission peak is in the red region of 630 nm. However, it can be found that the excitation spectrum of the phosphor is very broad, extending from the UV spectral range to the visible spectral range, in particular the phosphor can be effectively excited simultaneously by UV light (300-420 nm) and blue light (420-490 nm) , Its emission intensity is shown in Table 3. The broad emission spectrum of the phosphor is due to the fact that Eu ²⁺ ions emit light instead of the Eu ^{3+ line} spectrum. This means that Eu ³⁺ ions of the phosphor in the high temperature reaction are reduced by the gas in the oven to Eu ²⁺ ions. Compared to Example 19, the emission wavelength of the phosphor apparently shifts to blue, since oxygen is introduced into the crystal lattice, so that the covalent bond weakens and the lowest energy level of the 5d orbital of Eu ions increases, thus the energy of the emitted light and the emission wavelength shortens.

Example 19-25, 27-31:

The preparation of the above examples are the same as Example 26, wherein Eu nitride such as EuN, Eu halide such as EuCl ₂ , or Eu nitrates such as Eu (NO ₃ ) ₃ , etc. can be used, and the flux used in the reaction Chloride or fluoride of Sr, Ca, Ba, Li, etc. The emission intensity of the produced phosphor is shown in Table 4. The maximum emission wavelength of the fluorescent powders is most in the red light range and they can be excited by blue light and UV light. Thus, they can be combined with blue or UV LED chip to produce white light LED with high color rendering index. Table 4 Optical parameters of embodiments of the white light LED White LED example Color coordinate (x, y) Color rendering index Color temperature / K Light output / lm / W Blue LED + example 24 + green Sr ₂ SiO ₄ : Eu ²⁺ fluorescent powder Example 32 (0.4632, 0.4184) 86 2800 46

Example 32 Production of Electric White Light LED Light Source with High Color Rendering

A certain amount of the red fluorescent powder of Example 26 and green fluorescent powder of silicate Sr ₂ SiO ₄ : Eu ²⁺ was weighed and evenly distributed in the epoxy resin, after which the degassed mixture was applied to the commercially obtained blue light LED. Chip (emission wavelength of 450 nm) applied, and dried at the temperature of 150 ° C for 0.5 hour. So the housing took place. After the mixture of blue light emitted from blue light LED and red and green light emitted from fluorescent powder, warm white light with color coordinates of x = 0.4632, y = 0.4184, color rendering index of Ra = 86 and a corresponding temperature of T = 2800 K is formed ,

The above-described embodiments serve to enable those skilled in the art to better understand the present invention. It should be noted that in addition to the limitations presented by the appended claims, the present invention is not limited to the described embodiments.

Claims (14)

Oxynitride phosphor having the chemical formula M _1-y A _4-x Z _{1 + x} O _x N _7-x : R _y , where M is one or more alkali metals, alkaline earth metals, rare earth metals or transition metals, A is one or more of Si, Ge, B, Al and Si, Z is one or more elements of Al, Ga, In and Al, and R is one or more elements of the luminous center selected from Eu, Ce, Tb, Yb, Sm, Pr, Dy is, and 0 ≤ x <0.5, 0 <y <1.0 holds. An oxynitride phosphor according to claim 1, wherein M is one or more of Li, Mg, Ca, Sr, Ba, Bi, Mn, Zn, La, Gd, Lu, Y. An oxynitride phosphor according to claim 2, wherein M is one or more of Li, Mg, Ca, Zn, Sr, Ba, Bi, Y and comprises at least Sr. An oxynitride phosphor according to claim 3, wherein the Sr content is more than 0.8, A is Si, Z is Al, and R is Eu, Ce or the composition thereof. Oxynitride phosphor according to one of claims 1 to 4, wherein 0 ≤ x ≤ 0.15, 0 <y ≤ 0.1 applies. Oxynitride phosphor according to claim 5, wherein 0 ≤ x ≤ 0.1, 0.05 ≤ y ≤ 0.1 applies. A production process of the oxynitride phosphor according to any one of claims 1 to 6, comprising the following steps: (1) M-containing oxide, nitride, nitrate or carbonate, X-containing nitride or oxide, Z-containing nitride or oxide and R-containing nitride, oxide or nitrate are ground as starting materials and uniformly mixed to form a mixture; (2) the mixture of step (1) is calcined by gas pressure sintering or solid phase reaction under the protection of the inert gas at high temperature to produce a calcination product; (3) The calcination product from step (2) is further comminuted, processed, dried and sorted to produce the oxynitride phosphor The manufacturing method according to claim 7, wherein in the gas pressure sintering method, the inert gas is nitrogen at a pressure of 1 to 200 bar pressure and in the solid phase reaction method the inert gas is a mixed gas of nitrogen and hydrogen, wherein the volume ratio of nitrogen and hydrogen is 95: 5 or 90:10 or 85:15 or 80:20 and the volume flow is 0.1 to 3 liters / min. is. A production method according to claim 7, wherein the high temperature in the calcination is between 1200 and 1800 ° C, the calcination time is 0.5 to 30 hours and the calcination can be carried out several times. The manufacturing method according to claim 9, wherein the high temperature calcination is a carbothermic reduction and nitriding and the temperature is between 1200 and 1600 ° C. A production process according to claim 7, wherein flux which is one or more M-containing halides or boric acid is added in step (1). The production method according to claim 11, wherein the addition amount of the flux is 0.01 to 10% of the total weight of the raw materials. The manufacturing method according to claim 7, wherein the processing comprises washing with acid or water. White light LED light source for illumination, characterized in that it comprises UV or near UV LED and the oxynitride phosphor according to any one of claims 1 to 6, or blue LED and the oxynitride phosphor according to any one of claims 1 to 6 includes.

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