CN102925150B - A kind of tungstate fluorescent powder, preparation method and application thereof - Google Patents

Abstract

The invention discloses tungstate fluorescent powder as well as a preparation method and application thereof. The molecular formula of the tungstate fluorescent powder is Ba4RIII2-2xEu2xZrWO12, wherein the RIII is at least one of La3+, Ce3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Sc3+ and Y3+; the x is the doped mol percentage coefficient of the Eu3+, and is not less than 0.0001 and not more than 1.0. The tungstate fluorescent powder has strong excitation about 395 nm, and is matched perfectly with the emission wavelength of a near-ultraviolet LED chip. The invention provides a new matrix material of red fluorescent powder for white-light LED; the material has simple production method, good reproducibility, stable obtained product quality, operation facilitation and industrial production; the technique can be finished on the general equipment; the product is easily collected; the waste water and the waste gas are not discharged; and the environment is protected.

Description

A kind of tungstate fluorescent powder, preparation method and application thereof

technical field

The invention relates to an inorganic luminescent material, a preparation method and an application thereof, in particular to a tungstate fluorescent powder, a preparation method and an application of luminescence.

Background technique

White LED is a new solid-state lighting electric light source (SSL), and its principle and structure are different from previous vacuum electric light sources such as incandescent lamps and fluorescent lamps. SSL light source has many advantages, especially high luminous efficiency, energy saving, long service life, no pollution, and its application value and prospect are very promising. It has been paid attention by many governments, scientific and technological circles and industrial circles, and has formulated development plans and invested heavily in development. Rare earth phosphors used in white LEDs must meet two conditions. The first is that the excitation spectrum of the phosphor must match the emission spectrum of the selected light-emitting diode to ensure higher light conversion efficiency; the second is that the phosphor has a Under the excitation of ultraviolet light, its emission spectrum can emit white light, or the light emitted under the excitation of blue light is recombined with the blue light emitted by the light-emitting diode to form white light. The white light LED widely used in the market currently uses blue light InGaN tube core to excite YAG: Ce ³⁺ yellow phosphor powder, and yellow light and blue light are mixed to obtain white light. However, there are certain defects in the white light emitting system, and the color rendering of the white light emitted by the system is not high due to the lack of red light therein. Therefore, the preparation of stable red phosphors has become one of the current research hotspots.

Among the many red phosphors, tungstate-based phosphors have been extensively studied and discussed. Lin Haifeng et al. (Journal of Illuminating Engineering, 2010, 21(4)) prepared Li _(4-3x) W ₂ O ₈ series tungstate red phosphors by high-temperature solid-state method, and the results showed that the phosphors had a wide excitation Spectrum, suitable for use with near-ultraviolet and blue light chips, the color coordinates are located around (x=0.666, y=0.331), and have high color purity; V. Sivakumar et al. (J Solid State Chem. 181 (12): 8 (2008 )) reported Eu ³⁺ doped A ₂ CaWO ₆ (A=Sr, Ba) tungstate red phosphors, and the results showed that this series of phosphors had a wide charge transfer band and emitted orange-red light; Chinese patent CN 101812296B reports a tungstate red phosphor excited by near-ultraviolet or blue light, whose chemical structural formula is (M _1-x Eu _x ) ₁₀ W ₂ O ₂₁ , wherein M is Gd, La or Y, and the phosphor is compatible with The light-emitting diode has good matching performance, less W consumption, simple preparation method, and is used for white light LEDs. To sum up, tungstate red phosphors have been widely studied, however, there are still gaps in the type and variety of its matrix materials, such as Ba ₄ R ^III _2-2x Eu _2x ZrWO ₁₂ , (0.0001≤x≤ 1.0, R is a trivalent rare earth ion) as the matrix phosphor, etc., still need to further research and develop new substrates to make up for the existing vacancies, so as to expand the variety of tungstate red phosphors and provide them for the application of white light LEDs .

Contents of the invention

The purpose of the present invention is to make up for the vacancy of the matrix material in the current red phosphor powder for white LEDs, to provide a novel tungstate red phosphor powder with good luminous quality, suitable for continuous production, and pollution-free, a preparation method and its application.

In order to achieve the above purpose, the technical solution adopted by the present invention is to provide a tungstate phosphor, its active ion is trivalent europium ion Eu ³⁺ , and its chemical formula is Ba ₄ R ^III _2-2x Eu _2x ZrWO ₁₂ , wherein, R ^III is trivalent rare earth ion La ³⁺ , cerium Ce ³⁺ , praseodymium Pr ³⁺ , neodymium Nd ³⁺ , samarium Sm ³⁺ , europium Eu ³⁺ , gadolinium Gd ³⁺ , terbium Ions Tb ³⁺ , dysprosium ions Dy ³⁺ , holmium ions Ho ³⁺ , erbium ions Er 3+ , thulium ions Tm ³⁺ , ytterbium ions Yb ³⁺ , lutetium ions ^{Lu 3+ ,} scandium ions Sc ³⁺ , and yttrium ions Y At least one of ³⁺ , x is the molar percentage coefficient of Eu ³⁺ doping, 0.0001≤x≤1.0;

A kind of preparation method of tungstate fluorescent powder as above, comprises the steps:

1. Weigh the raw materials according to the molar ratio of each element in the chemical formula Ba ₄ R ^III _2-2x Eu _2x ZrWO _12. In the chemical formula, R ^III is the trivalent rare earth ion La ³⁺ , cerium ion Ce ³⁺ , praseodymium Ions Pr ³⁺ , neodymium ions Nd ³⁺ , samarium ions Sm ³⁺ , europium ions Eu ³⁺ , gadolinium ions Gd ³⁺ , terbium ions Tb ³⁺ , dysprosium ions Dy ³⁺ , holmium ions Ho ³⁺ , erbium ions Er ³⁺ , at least one of thulium ion Tm ³⁺ , ytterbium ion Yb ³⁺ , lutetium ion Lu ³⁺ , scandium ion Sc ³⁺ and yttrium ion Y ³⁺ , x is the molar percentage coefficient of Eu ³⁺ doping, 0.0001≤x≤1.0; the raw materials are compounds containing barium ions Ba ²⁺ , rare earth ions R ^III , europium ions Eu ³⁺ , zirconium ions Zr ⁴⁺ , and tungsten ions W ⁶⁺ ; the weighed raw materials are ground and mixed Homogeneously, a mixture is obtained;

2. Pre-sinter the mixture in an air atmosphere, the sintering temperature is 300-1000°C, and the time is 1-10 hours;

3. After natural cooling, grind and mix evenly, then calcined in the air atmosphere, the calcining temperature is 1000-1500℃, and the time is 1-10 hours;

4. Repeat step (3) 1-2 times to obtain a tungstate phosphor.

The compound containing barium ion Ba ²⁺ in the present invention is one of barium oxide, barium hydroxide, barium nitrate, barium carbonate, barium sulfate or a combination thereof.

The compound containing rare earth ion R ^III is one or a combination of rare earth ion R ^III oxides, nitrates, oxalates, sulfates, and rare earth organic complexes.

The compound containing europium ion Eu ³⁺ is one of europium oxide, europium nitrate, and organic complexes of Eu ³⁺ , or any combination thereof.

The compound containing zirconium ion Zr ⁴⁺ is zirconium oxide ZrO ₂ , zirconium hydroxide Zr(OH) ₄ , zirconium nitrate Zr(NO ₃ ) ₄ , zirconium oxychloride ZrOCl ₂ and hydrate ZrOCl ₂ ·8H ₂ O one of them, or any combination of them.

The compound containing tungsten ions W ⁶⁺ is one of tungsten oxide, ammonium tungstate, or any combination thereof.

An optimized solution provided by the present invention is: when the mixture is pre-sintered in an air atmosphere, the sintering temperature is 300-1000° C., and the sintering time is 1-10 hours. When calcining in air atmosphere, the calcining temperature is 1000-1500° C., and the calcining time is 1-10 hours.

The present invention provides a tungstate phosphor activated by trivalent europium ions Eu ³⁺ , its main emission peak is around 583nm, and it has a strong excitation efficiency in the near-ultraviolet region of 395nm, which is just a near-ultraviolet LED The emission wavelength of the chip, therefore, is a good orange-red phosphor for white LEDs.

Compared with the prior art, the advantages of the technical solution of the present invention are:

1. It can effectively absorb excitation light near 395nm, and its strongest emission peak is located near 583nm, which meets the application requirements of white light LEDs.

2. Compared with other sulfides Y ₂ O ₂ S:Eu ³⁺ and halides, the preparation process of the matrix material of the present invention is simple, the products are easy to collect, there is no waste water and gas discharge, the environment is friendly, and it is suitable for continuous production.

Description of drawings

Fig. 1 is the comparison of the XRD diffraction pattern of the material sample Ba ₄ La _1.8 Eu _0.2 ZrWO ₁₂ prepared by the technique of Example 1 of the present invention and the standard card PDF # 44-0254;

Fig. 2 is the emission and excitation spectra of the material sample Ba ₄ La _1.8 Eu _0.2 ZrWO ₁₂ prepared according to the technique of Example 1 of the present invention obtained by monitoring excitation light at 395nm and monitoring emission light at 583nm;

Fig. 3 is the material sample Ba ₄ La _1.8 Eu _0.2 ZrWO ₁₂ prepared according to the technique of Example 1 of the present invention, under the monitoring excitation light of 355 nm, the attenuation curve spectrum of 583 nm luminescence;

Fig. 4 is the comparison of the XRD diffraction pattern of the material sample Ba ₄ Gd _1.8 Eu _0.2 ZrWO ₁₂ prepared by the technique of Example 4 of the present invention and the standard card PDF # 44-0254;

Fig. 5 is the emission and excitation spectra of the material sample Ba ₄ Gd _1.8 Eu _0.2 ZrWO ₁₂ prepared according to the technique of Example 4 of the present invention obtained by monitoring the excitation light at 395nm and the emission light at 583nm;

Fig. 6 is a material sample Ba ₄ Gd _1.8 Eu _0.2 ZrWO ₁₂ prepared according to the technique of Example 4 of the present invention, under the monitoring excitation light of 355 nm, the attenuation curve spectrum of 583 nm luminescence;

Fig. 7 is the comparison between the XRD diffraction pattern of the material sample Ba ₄ Y _1.8 Eu _0.2 ZrWO ₁₂ prepared by the technique of Example 7 of the present invention and the standard card PDF # 44-0254;

Fig. 8 is the emission and excitation spectra of the material sample Ba ₄ Y _1.8 Eu _0.2 ZrWO ₁₂ prepared according to the technique of Example 7 of the present invention obtained by monitoring the excitation light at 395nm and the emission light at 583nm;

Fig. 9 is the attenuation curve of 583nm luminescence of the material sample Ba ₄ Y _1.8 Eu _0.2 ZrWO ₁₂ prepared according to the technique of Example 7 of the present invention under the monitoring excitation light of 355nm.

Figure 10 is a comparison of the XRD diffraction pattern of the material sample _Ba4Eu2ZrWO12 prepared by the technique of _{Example 10} of the present invention and the standard card PDF#44-0254;

Figure 11 is the emission and excitation spectra of the material sample Ba ₄ Eu ₂ ZrWO ₁₂ prepared according to the technique of Example 10 of the present invention obtained by monitoring the excitation light at 395nm and the emission light at 583nm;

Fig. 12 is the attenuation curve of 583nm luminescence of the material sample Ba ₄ Eu ₂ ZrWO ₁₂ prepared according to the technique of Example 10 of the present invention under the monitoring excitation light of 355nm.

Detailed ways

The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

Example 1:

According to the stoichiometric ratio of each element in the chemical formula Ba ₄ La _1.8 Eu _0.2 ZrWO ₁₂ , we weighed: barium carbonate BaCO ₃ : 3.947 grams, zirconia ZrO ₂ : 0.6161 grams, tungsten oxide WO ₃ : 1.1592 grams, lanthanum oxide La ₂ O ₃ : 1.4662 grams, Europium oxide Eu ₂ O ₃ : 0.176 grams After being ground in an agate mortar and mixed evenly, select the air atmosphere for the first calcination, the temperature is 300 ° C, the calcination time is 7 hours, then cool to room temperature, take out sample. After the first calcination of the raw materials, the mixture is fully mixed and ground again, and then sintered for the second time at 1000°C in an air atmosphere. The sintering time is 8 hours, and cooled to room temperature to obtain tungstate phosphor.

Referring to accompanying drawing 1, it is the XRD diffraction pattern of the material sample prepared according to the technical scheme of this embodiment, and they are consistent with standard card comparison.

Refer to Figure 2, which is the emission and excitation spectra of the material sample prepared according to the technical scheme of this embodiment obtained by monitoring the excitation light at 395nm and the emission light at 583nm, and the calculated chromaticity of the emission spectrum is (0.62, 0.38).

Referring to accompanying drawing 3, it is the attenuation curve diagram of 583nm luminescence of the material sample prepared according to the technical scheme of this embodiment under the monitoring excitation light of 355nm. The lifetime of light emission is 1.65ms.

Example 2:

According to the stoichiometric ratio of each element in the chemical formula Ba ₄ La _1.6 Eu _0.4 ZrWO ₁₂ , weighed separately, barium carbonate BaCO ₃ : 3.947 grams, zirconia ZrO ₂ : 0.6161 grams, tungsten oxide WO ₃ : 1.1592 grams, lanthanum oxide La ₂ O ₃ : 1.3033 grams, Europium oxide Eu ₂ O ₃ : 0.352 grams After being ground in an agate mortar and mixing evenly, select the air atmosphere for the first calcination, the temperature is 500 ° C, the calcination time is 8 hours, then cool to room temperature, take out sample. After the first calcination of the raw materials, the mixture is fully mixed and ground evenly, and the second sintering is performed at 1400°C in an air atmosphere. The sintering time is 10 hours, and cooled to room temperature to obtain tungstate phosphor. Its XRD diffraction pattern is similar to that of accompanying drawing 1, its excitation and emission spectrum is similar to that of accompanying drawing 2, and its attenuation curve of 583nm luminescence under excitation at 355nm is similar to that of accompanying drawing 3.

Example 3:

According to the stoichiometric ratio of each element in the chemical formula Ba ₄ La _1.4 Eu _0.6 ZrWO ₁₂ , weighed separately, barium carbonate BaCO ₃ : 3.947 grams, zirconia ZrO ₂ : 0.6161 grams, tungsten oxide WO ₃ : 1.1592 grams, lanthanum oxide La ₂ O ₃ : 1.1404 grams, Europium oxide Eu ₂ O ₃ : 0.528 grams After being ground in an agate mortar and mixing evenly, select the air atmosphere for the first calcination, the temperature is 800 ° C, the calcination time is 9 hours, then cool to room temperature, take out sample. After the first calcination of the raw materials, the mixture is fully mixed and ground again, and then sintered for the second time at 1500°C in an air atmosphere. The sintering time is 6 hours, and cooled to room temperature to obtain tungstate phosphor. Its XRD diffraction pattern is similar to that of accompanying drawing 1, its excitation and emission spectrum is similar to that of accompanying drawing 2, and its attenuation curve of 583nm luminescence under excitation at 355nm is similar to that of accompanying drawing 3.

Example 4:

According to the stoichiometric ratio of each element in the chemical formula Ba ₄ Gd _1.8 Eu _0.2 ZrWO ₁₂ , weighed separately, barium carbonate BaCO ₃ : 3.947 grams, zirconia ZrO ₂ : 0.6161 grams, tungsten oxide WO ₃ : 1.1592 grams, gadolinium oxide Gd ₂ O ₃ : 1.6313 grams, Europium oxide Eu ₂ O ₃ : 0.176 grams After being ground in an agate mortar and mixing evenly, select the air atmosphere for the first calcination, the temperature is 600 ° C, the calcination time is 3 hours, then cool to room temperature, take out sample. After the raw materials are calcined for the first time, the mixture is fully mixed and ground evenly, and then sintered for the second time at 1350°C in an air atmosphere. The sintering time is 9 hours and cooled to room temperature. Then the mixture was fully mixed and ground evenly, and then sintered for the third time in an air atmosphere at 1450°C for 8.5 hours, and cooled to room temperature to obtain tungstate phosphor.

Referring to accompanying drawing 4, it is the XRD diffraction pattern of the material sample prepared according to the technical scheme of this embodiment. Contrast them with standard cards.

Refer to Figure 5, which is the emission and excitation spectra of the material sample prepared according to the technical scheme of this embodiment obtained by monitoring the excitation light at 395nm and the emission light at 583nm, and the calculated chromaticity of the emission spectrum is (0.65, 0.32).

Referring to accompanying drawing 6, it is the attenuation curve of 583nm luminescence of the material sample prepared according to the technical scheme of this embodiment under the monitoring excitation light of 355nm. The lifetime of light emission is 1.25ms.

Example 5:

According to the stoichiometric ratio of each element in the chemical formula Ba ₄ Gd _1.7 Eu _0.3 ZrWO ₁₂ , weighed separately, barium carbonate BaCO ₃ : 3.947 grams, zirconia ZrO ₂ : 0.6161 grams, tungsten oxide WO ₃ : 1.1592 grams, gadolinium oxide Gd ₂ O ₃ : 1.5407 grams, Europium oxide Eu ₂ O ₃ : 0.264 grams After being ground in an agate mortar and mixed evenly, select the air atmosphere for the first calcination, the temperature is 550 ° C, the calcination time is 4.5 hours, then cool to room temperature, take out sample. After the raw materials are calcined for the first time, the mixture is fully mixed and ground evenly, and then sintered for the second time at 1200°C in an air atmosphere. The sintering time is 5 hours, and cooled to room temperature to obtain tungstate phosphor. Its XRD diffraction pattern is similar to that of accompanying drawing 4, its excitation and emission spectrum is similar to that of accompanying drawing 5, and its attenuation curve of 583nm luminescence under excitation at 355nm is similar to that of accompanying drawing 6.

Embodiment 6:

According to the stoichiometric ratio of each element in the chemical formula Ba ₄ Gd _1.5 Eu _0.5 ZrWO ₁₂ , weighed separately, barium carbonate BaCO ₃ : 3.947 grams, zirconia ZrO ₂ : 0.6161 grams, tungsten oxide WO ₃ : 1.1592 grams, gadolinium oxide Gd ₂ O ₃ : 1.3594 grams, Europium oxide Eu ₂ O ₃ : 0.46 grams After being ground in an agate mortar and mixing evenly, select the air atmosphere for the first calcination, the temperature is 750 ° C, the calcination time is 9.5 hours, then cool to room temperature, take out sample. After the first calcination of the raw materials, the mixture is fully mixed and ground again, and then sintered for the second time at 1250°C in an air atmosphere. The sintering time is 7 hours, and cooled to room temperature to obtain tungstate phosphor. Its XRD diffraction pattern is similar to that of accompanying drawing 4, its excitation and emission spectrum is similar to that of accompanying drawing 5, and its attenuation curve of 583nm luminescence under excitation at 355nm is similar to that of accompanying drawing 6.

Embodiment 7:

According to the stoichiometric ratio of each element in the chemical formula Ba ₄ Y _1.8 Eu _0.2 ZrWO ₁₂ , weighed separately, barium carbonate BaCO ₃ : 3.947 grams, zirconia ZrO ₂ : 0.6161 grams, tungsten oxide WO ₃ : 1.1592 grams, yttrium oxide Y ₂ O ₃ : 1.0161 grams, europium oxide Eu ₂ O ₃ : 0.176 grams, ground in an agate mortar and mixed evenly, then select the air atmosphere for the first calcination, the temperature is 1000 ° C, the calcination time is 7.5 hours, then cool to room temperature, take out sample. After the first calcination of the raw materials, the mixture is fully mixed and ground again, and then sintered for the second time at 1450°C in an air atmosphere. The sintering time is 6 hours, and cooled to room temperature. Then the mixture is fully mixed and ground evenly, and then sintered for the third time in an air atmosphere at 1450°C for 3 hours, and then cooled to room temperature to obtain tungstate phosphor.

Referring to accompanying drawing 7, it is the XRD diffraction pattern of the material sample prepared according to the technical scheme of this embodiment. Contrast them with standard cards.

See Figure 8, which is the emission and excitation spectra of the material sample prepared according to the technical scheme of this embodiment obtained by monitoring the excitation light at 395nm and the emission light at 583nm, and the calculated chromaticity of the emission spectrum is (0.614, 0.34).

Referring to accompanying drawing 9, it is the attenuation curve of 583nm luminescence of the material sample prepared according to the technical scheme of this embodiment under the monitoring excitation light of 355nm. The lifetime of light emission is 1.5ms.

Embodiment 8:

According to the stoichiometric ratio of each element in the chemical formula Ba ₄ Y _1.2 Eu _0.8 ZrWO ₁₂ , weighed separately, barium carbonate BaCO ₃ : 3.947 grams, zirconia ZrO ₂ : 0.6161 grams, tungsten oxide WO ₃ : 1.1592 grams, yttrium oxide Y ₂ O ₃ : 0.6774 grams, Europium oxide Eu ₂ O ₃ : 0.704 grams After being ground in an agate mortar and mixing evenly, select the air atmosphere for the first calcination, the temperature is 750 ° C, the calcination time is 2 hours, then cool to room temperature, take out sample. After the first calcination of the raw materials, the mixture is fully mixed and ground again, and then sintered for the second time at 1250°C in an air atmosphere. The sintering time is 6.5 hours and cooled to room temperature. Then the mixture is fully mixed and ground evenly, and then sintered for the third time in an air atmosphere at 1450°C for 6.5 hours, and cooled to room temperature to obtain tungstate phosphor. Its XRD diffraction pattern is similar to that of accompanying drawing 7, its excitation and emission spectrum is similar to that of accompanying drawing 8, and its attenuation curve of 583nm luminescence under excitation at 355nm is similar to that of accompanying drawing 9.

Embodiment 9:

According to the stoichiometric ratio of each element in the chemical formula Ba ₄ Y _1.3 Eu _0.7 ZrWO ₁₂ , weighed separately, barium carbonate BaCO ₃ : 3.947 grams, zirconia ZrO ₂ : 0.6161 grams, tungsten oxide WO ₃ : 1.1592 grams, yttrium oxide Y ₂ O ₃ : 0.7339 grams, Europium oxide Eu ₂ O ₃ : 0.616 grams After being ground in an agate mortar and mixed evenly, select the air atmosphere for the first calcination, the temperature is 950 ° C, the calcination time is 7 hours, then cool to room temperature, take out sample. After the raw materials are calcined for the first time, the mixture is thoroughly mixed and ground evenly, and then sintered for the second time in an air atmosphere at 1150°C for 5.5 hours and cooled to room temperature. Then the mixture is fully mixed and ground evenly, and then sintered for the third time in an air atmosphere at 1150°C for 5.5 hours, and cooled to room temperature to obtain tungstate phosphor. Its XRD diffraction pattern is similar to that of accompanying drawing 7, its excitation and emission spectrum is similar to that of accompanying drawing 8, and its attenuation curve of 583nm luminescence under excitation at 355nm is similar to that of accompanying drawing 9.

Example 10:

According to the stoichiometric ratio of each element in the chemical formula Ba ₄ Eu ₂ ZrWO ₁₂ , weighed separately, barium carbonate BaCO ₃ : 2.6313 grams, zirconia ZrO ₂ : 0.411 grams, tungsten oxide WO ₃ : 0.7728 grams, europium oxide Eu ₂ O ₃ : 1.1733 g was ground and mixed uniformly in an agate mortar, and then calcined for the first time in an air atmosphere at a temperature of 1000° C. for 10 hours, then cooled to room temperature, and the sample was taken out. After the first calcination of the raw materials, the mixture is fully mixed and ground again, and the second sintering is carried out at 1500°C in an air atmosphere. The sintering time is 10 hours, and cooled to room temperature to obtain tungstate phosphor.

Referring to accompanying drawing 10, it is the XRD diffraction pattern of the material sample prepared according to the technical scheme of this embodiment. Contrast them with standard cards.

See Figure 11, which is the emission and excitation spectra of the material sample prepared according to the technical scheme of this embodiment obtained by monitoring the excitation light at 395nm and the emission light at 583nm, and the calculated chromaticity of the emission spectrum is (0.618, 0.343).

Referring to accompanying drawing 12, it is the attenuation curve diagram of 583nm luminescence of the material sample prepared according to the technical scheme of this embodiment under the monitoring excitation light of 355nm. The lifetime of light emission is 400 μs.

Claims (8)

1. a tungstate fluorescent material, is characterized in that: its active ions are trivalent europium ion Eu ³⁺, chemical formula is Ba ₄r ^iII _2-2xeu _2xzrWO ₁₂, wherein, R ^iIIfor trivalent rare earth ions lanthanum ion La ³⁺, gadolinium ion Gd ³⁺with ruthenium ion Y ³⁺in a kind of, xfor Eu ³⁺the molar percentage coefficient of doping, 0.0001≤x≤1.0.

2. a preparation method for the tungstate fluorescent material as described in right 1 requirement, is characterized in that comprising the steps:

(1) press chemical formula Ba ₄r ^iII _2-2xeu _2xzrWO ₁₂in the mol ratio of each element take raw material, in described chemical formula, R ^iIIfor trivalent rare earth ions lanthanum ion La ³⁺, gadolinium ion Gd ³⁺with ruthenium ion Y ³⁺in a kind of, xfor Eu ³⁺the molar percentage coefficient of doping, 0.0001≤x≤1.0; Described raw material is for containing barium ion Ba ²⁺, rare earth ion R ^iII, europium ion Eu ³⁺, zirconium ion Zr ⁴⁺, tungsten ion W ⁶⁺compound; By the former abrasive lapping taking and mix, obtain mixture;

(2) by mixture presintering under air atmosphere, sintering temperature is 300～1000 ℃, and the time is 1～10 hour;

(3) after naturally cooling, grind and mix, in air atmosphere, to calcine, calcining temperature is 1000～1500 ℃, the time is 1～10 hour;

(4) repeating step is (3) 1～2 times, obtains a kind of tungstate fluorescent material.

3. the preparation method of a kind of tungstate fluorescent material according to claim 2, is characterized in that: the described barium ion Ba that contains ²⁺compound be a kind of in barium oxide, hydrated barta, nitrate of baryta, barium carbonate, barium sulfate or their combination.

4. the preparation method of a kind of tungstate fluorescent material according to claim 2, is characterized in that: the described rare earth ion R that contains ^iIIcompound be rare earth ion R ^iIIoxide compound, nitrate, oxalate, vitriol, and a kind of in rare earth organic complex or their combination.

5. the preparation method of a kind of tungstate fluorescent material according to claim 2, is characterized in that: the described europium ion Eu that contains ³⁺compound be europium sesquioxide, europium nitrate, and Eu ³⁺organic complex in a kind of, or their arbitrary combination.

6. the preparation method of a kind of tungstate fluorescent material according to claim 2, is characterized in that: the described zirconium ion Zr that contains ⁴⁺compound be zirconium white ZrO ₂, zirconium hydroxide Zr (OH) ₄, zirconium nitrate Zr (NO ₃) ₄, zirconyl chloride ZrOCl ₂and hydrate ZrOCl ₂8H ₂a kind of in O, or their arbitrary combination.

7. the preparation method of a kind of tungstate fluorescent material according to claim 2, is characterized in that: the described tungsten ion W that contains ⁶⁺compound is a kind of in Tungsten oxide 99.999, ammonium tungstate, or their arbitrary combination.

8. an application for tungstate fluorescent material as claimed in claim 1, is used for white light LEDs using it as orange-red fluorescence powder.

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