CN104449722A - Yellow fluorescent material with oxyapatite structure, preparation method and white light diode device - Google Patents

Abstract

A yellow fluorescent material with an oxyapatite structure, a preparation method and a white light diode device thereof are provided. The foregoing yellow fluorescent material has _1-xEu_x)_8-yB_2+y(PO₄)_6-y(SiO₄)_y(O_1-zS_z)₂Wherein A and Eu are divalent metal ions, B is trivalent metal ion, and 0<x ≦ 0.6, 0 ≦ y ≦ 6, and 0 ≦ z ≦ 1. The A can be alkaline earth metal, Mn or Zn, and the B can be IIIA group metal, rare earth metal or Bi.

Description

Yellow fluorescent material with oxyapatite structure, preparation method and white light diode device

This application is a branch of the invention patent application filed by the applicant on December 20, 2010, with the application number 201010614571.6, and the invention title is "yellow light fluorescent material with oxyapatite structure, preparation method and white light diode device". case application.

technical field

The present invention relates to a yellow light fluorescent material, and in particular to a yellow light fluorescent material in the form of oxyapatite.

Background technique

Commercial white light-emitting diodes (WLEDs) have come a long way since the invention of InGaN-based photoluminescent chips in the early 20th century. By combining the blue light emitted by the InGaN chip and the yellow light emitted by the Y ₃ Al ₅ O ₁₂ :Ce ³⁺ (YAG:Ce ³⁺ )-based material, the white light obtained has surpassed incandescent light bulbs and even Can be compared with traditional fluorescent lamps. Compared with traditional light sources, white light diodes are energy-saving, long-lived and environmentally friendly light sources. However, the light color quality of white light diodes still needs to be improved in terms of white hue tunability, color temperature and color rendering properties, and these properties are all related to daily lighting.

Most of the fluorescent materials currently used in white light diodes cannot meet the optimum requirements for white light, and the color rendering properties in the red light region are quite insufficient. Therefore, new materials need to be found for white light diodes to meet the requirements for white light quality.

Contents of the invention

Therefore, one aspect of the present invention is to provide a yellow fluorescent material with an oxyapatite structure, which has (A _1-x Eu _x ) _8-y B _2+y (PO ₄ ) _6-y (SiO ₄ ) _y (O _1-z S _z ) ₂ chemical formula, where A and Eu are divalent metal ions, B is trivalent metal ion, and 0<x≦0.6, 0≦y≦6 and 0≦z≦ 1. The aforementioned A can be alkaline earth metal, Mn or Zn, and B can be Group IIIA metal, rare earth metal or Bi.

According to an embodiment of the present invention, when y=z=0, the yellow fluorescent material has a general chemical formula of (A _1-x Eu _x ) ₈ B ₂ (PO ₄ ) ₆ O ₂ .

According to another embodiment of the present invention, when y=6 and z=0, the yellow fluorescent material has a general chemical formula of (A _1-x Eu _x ) ₂ B ₈ (SiO ₄ ) ₆ O ₂ .

According to yet another embodiment of the present invention, when y=0 and z=1, the yellow fluorescent material has a general chemical formula of (A _1-x Eu _x ) ₈ B ₂ (PO ₄ ) ₆ S ₂ .

According to yet another embodiment of the present invention, when y=6 and z=1, the yellow fluorescent material has a general chemical formula of (A _1-x Eu _x ) ₂ B ₈ (SiO ₄ ) ₆ S ₂ .

Another aspect of the present invention is to provide a white light diode, which comprises a blue fluorescent material and any one of the aforementioned yellow fluorescent materials.

Another aspect of the present invention is to provide a method for preparing the aforementioned yellow fluorescent material, which includes the following steps. First, weigh the raw materials of the required elements that meet the stoichiometric ratio, wherein the metal raw materials of the yellow fluorescent material are metal oxides or metal carbonates, the phosphate raw materials are diammonium hydrogen phosphate or ammonium dihydrogen phosphate, and the silicate raw materials Silica is included, and the sulfur feedstock includes sulfur powder. Then mix the weighed raw materials evenly, and then calcinate the mixed raw materials until the product with pure oxyapatite crystal phase is obtained. The calcining environment contains oxygen, and the calcining temperature is 1200-1400°C. Reducing Eu ³⁺ to Eu ²⁺ in ammonia gas at a temperature of 900-1200° C. to obtain the aforementioned yellow fluorescent material.

According to an embodiment of the present invention, before the reduction step, the calcined product can also be homogenized.

The wavelength of the main light-emitting region of the aforementioned yellow-light fluorescent material is relatively long, which is more inclined to the red-light region. Therefore, when the above-mentioned yellow fluorescent material is used to manufacture the white light diode, the color rendering property of the white light emitted by the white light diode in the red light region can be improved, so as to obtain better quality white light.

The above summary is intended to provide a simplified summary of the disclosure to provide readers with a basic understanding of the disclosure. This summary is not an extensive overview of the disclosure and it is not intended to identify key/critical elements of the embodiments of the invention or to delineate the scope of the invention. After referring to the following embodiments, those with ordinary knowledge in the technical field of the present invention can easily understand the basic spirit and other invention objectives of the present invention, as well as the technical means and implementation methods adopted by the present invention.

Description of drawings

In order to make the above and other objects, features, advantages and embodiments of the present invention more clearly understood, the accompanying drawings are described as follows:

Fig. 1 is a flowchart showing the preparation of a yellow fluorescent material with an oxyapatite structure; wherein 110, 120, 130, 140, 150 represent steps.

Figures 2, 3, 4 and 5 are respectively Ca ₈ La ₂ (PO ₄ ) ₆ O ₂ : xEu ²⁺ powder X-ray diffraction spectrum, photoexcitation spectrum, photoluminescence spectrum and UV-Vis Solid state reflectance spectra.

Fig. 6 is a comparison of the photoexcitation and photoluminescence spectra of Ca ₈ La ₂ (PO ₄ ) ₆ O ₂ : 0.03Eu ²⁺ and yellow light commercial product YAG: Ce ³⁺ .

7A-7E show the photoexcitation and photoluminescence spectra of Experimental Examples 1-5, respectively.

8A-8H show the photoexcitation and photoluminescence spectra of experimental examples 6-13, respectively.

FIG. 9 shows the photoexcitation and photoluminescence spectra of Experimental Example 14.

FIG. 10 shows the photoexcitation and photoluminescence spectra of Experimental Example 15.

FIG. 11 shows the light emission spectra of the white light diodes of Experimental Examples 16-24.

Detailed ways

Europium (Europium; Eu) is a lanthanide element and usually forms a trivalent compound because it has a relatively stable electronic configuration of 4f ⁷ , but its excitation and emission are linear, so its application in fluorescent materials is limited . The excitation and emission of divalent europium are broadband, so it has been widely used in light-emitting diodes. In light-emitting applications, divalent europium ions will emit light in different colors due to the different lattice structures, usually biased toward blue light.

In light-emitting applications, apatite is an efficient host material, and oxyapatite materials containing various rare earth metals have been synthesized, which have Ca ₈ M ₂ ( The general chemical formula of PO ₄ ) ₆ O ₂ , wherein M is a trivalent rare earth metal ion. In this series of Ca ₈ M ₂ (PO ₄ ) ₆ O ₂ compounds, different trivalent rare earth metal ions can be used as light sources of various wavelengths, for example, light sources of visible light or near-infrared light.

In addition, the phosphate group in the aforementioned oxyapatite structure may be partially substituted or fully substituted by silicate groups. The structure of oxyapatite fully substituted by silicate is called silicate oxyapatite structure, which has a general chemical formula of Ca ₂ M ₈ (SiO ₄ ) ₆ O ₂ , where M is a trivalent rare earth metal Ions, usually trivalent rare earth metal ions are also responsible for the light emission. In the structure of Ca ₂ M ₈ (SiO ₄ ) ₆ O ₂ , 6 Ca ²⁺ are replaced by 6 M ³⁺ to balance the 6 negative charges added by 6 silicates.

Yellow fluorescent material with oxyapatite structure

Provided here is a yellow fluorescent material with an oxyapatite structure, which has (A _1-x Eu _x ) _8-y B _2+y (PO ₄ ) _6-y (SiO ₄ ) _y (O _1-z The general chemical formula of S _z ) ₂ . Among them, Eu is a divalent ion, and A is also a divalent metal ion, both of which replace the calcium ion in the previous oxyapatite structure. Therefore, A may be an alkaline earth metal, Zn or Mn. B is a trivalent metal ion, replacing the rare earth metal ion in the previous oxyapatite structure. Therefore, B can be group IIIA metal, rare earth metal or Bi, wherein group IIIA metal can be Al, Ga, In, for example, rare earth metal can be Sc, Y and lanthanides, such as La, Ce, Pr, Nd, Pm , Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu. In the above chemical formula, the numerical ranges of x, y and z are 0<x≦0.6, 0≦y≦6 and 0≦z≦1, respectively. Phosphate and silicic acid occupy the same position in the crystal lattice, and O and S also occupy the same position in the crystal lattice.

In some special cases, the chemical formula of (A _1-x Eu _x ) _8-y B ₂ + _y (PO ₄ ) _6-y (SiO ₄ ) _y (O _1-z S _z ) ₂ can be simplified, see Table 1 below.

Table 1: Types of yellow fluorescent materials with oxyapatite structure

Because some literature will divide the number of each element in the general chemical formula Ca ₈ M ₂ (PO ₄ ) ₆ O ₂ of the above-mentioned oxyapatite structure by 2, and simplify it to Ca ₄ M(PO ₄ ) ₃ O Therefore, the general chemical formula of the above-mentioned yellow fluorescent material with an oxyapatite structure can also be simplified in the same way. The simplified general formula can be represented by (A _1-x Eu _x ) _4-d B _1+d (PO ₄ ) _3-d (SiO ₄ ) _d (O _1-z S _z ), the values of x and z The range is the same as above, also 0<x≦0.6 and 0≦z≦1, and the value range of d is 0≦d≦3.

Preparation method of yellow fluorescent material with oxyapatite structure

The preparation method of the above (A _1-x Eu _x ) _8-y B _2+y (PO ₄ ) _6-y (SiO ₄ ) _y (O _1-z S _z ) ₂ yellow fluorescent material is also provided here, please refer to Fig. 1 is a flowchart showing the preparation of a yellow fluorescent material with an oxyapatite structure.

In step 110 of FIG. 1 , according to the chemical formula of the above-mentioned yellow fluorescent material to be synthesized, the raw materials that meet the stoichiometric ratio are respectively weighed. For the metal ions of Eu, A and B, corresponding metal oxides can be selected as their sources. If the metal ions of Eu, A and B have carbonate, the corresponding metal carbonate can also be selected as its source. For example, calcium oxide or calcium carbonate can be selected as the source of calcium ions, and Eu ₂ O ₃ can be selected as the source of europium ions. In terms of phosphate, diammonium hydrogen phosphate or ammonium dihydrogen phosphate can be selected as its source. In terms of silicate, silicon oxide can be chosen as its source. Sulfur can directly choose sulfur powder as its source.

Then in step 120, the required raw materials are uniformly mixed, and the mixing method can be grinding, for example. In step 130 , the mixed raw material is calcine at a temperature of 1200-1400° C. in an oxygen-containing environment (for example, air) until a product having a pure oxyapatite crystal phase is obtained. Since the calcination in step 130 is carried out in an oxygen-containing environment, all europium ions in the product are Eu ³⁺ , so it is necessary to reduce the Eu ³⁺ occupying the calcium ion position in the oxyapatite structure to Eu ²⁺ .

In step 140, in order to make the subsequent reduction reaction more complete and faster, the product obtained in step 130 needs to be homogenized again, for example, it can be ground again. Then in step 150, the homogenized product is reduced under ammonia gas at a temperature of 900-1200° C., which takes about 10 hours.

Example 1: Doping different proportions of Eu ²⁺ in Ca ₈ La ₂ (PO ₄ ) ₆ O ₂

First, Ca ₈ La ₂ (PO ₄ ) ₆ O ₂ is doped with different proportions of Eu ²⁺ to replace Ca ²⁺ to form a series of (Ca _1-x Eu _x ) ₈ La ₂ (PO ₄ ) ₆ O ₂ Fluorescent material (in this embodiment, denoted as Ca ₈ La ₂ (PO ₄ ) ₆ O ₂ : xEu ²⁺ ), observe its photoluminescent properties. In this experimental example, A 2+ in (A _1-x Eu _x ) _8-y B _2+y (PO ₄ ) _6-y (SiO ₄ ) _y (O _1-z S _z ) ₂ is ^{Ca 2 +} , B ³⁺ is La ³⁺ , and y=z=0, and x is 0, 0.001, 0.003, 0.005, 0.007, 0.010, 0.020, 0.030, 0.050, 0.070 and 0.100, respectively.

Figures 2, 3, 4 and 5 are respectively the powder X-ray diffraction spectrum, photoexcitation spectrum, photoluminescence spectrum and UV-Vis solid-state reflectance spectrum of this series of compounds. It can be seen from FIG. 2 that the lattice structure of Ca ₈ La ₂ (PO ₄ ) ₆ O ₂ will not be changed when the Eu ²⁺ doping amount is up to 10 mol%.

The photoexcitation spectrum in Fig. 3 is obtained by monitoring at 630nm. It can be seen from FIG. 3 that at the blue light of 450 nm, there is an absorption maximum when the x value is 0.030 (that is, when the Eu ²⁺ doping ratio is 3 mol%). The photoluminescence spectrum in Fig. 4 is obtained by excitation at 450 nm. It can be seen from Figure 4 that when x is 0.030, there is a maximum light intensity near 625nm. As can be seen from FIG. 5 , the Ca ₈ La ₂ (PO ₄ ) ₆ O ₂ doped with Eu ²⁺ has a rather strong absorption intensity in the region smaller than 500 nm. On the contrary, Ca ₈ La ₂ (PO ₄ ) ₆ O ₂ without Eu ²⁺ hardly absorbs light in the region below 500nm.

Fig. 6 shows the photoexcitation and photoluminescence of Ca ₈ La ₂ (PO ₄ ) ₆ O ₂ : 0.03Eu ²⁺ and yellow light commodity Y ₃ Al ₅ O ₁₂ : Ce ³⁺ (recorded here as YAG: Ce ³⁺ ). Comparison of luminescence spectra, where the solid line is the spectrum of Ca ₈ La ₂ (PO ₄ ) ₆ O ₂ : 0.03Eu ²⁺ , and the dotted line is the spectrum of YAG:Ce ³⁺ . It can be seen from Figure 6 that Ca ₈ La ₂ (PO ₄ ) ₆ O ₂ : 0.03Eu ²⁺ has a wider photoexcitation spectrum and photoluminescence spectrum, and the emission wavelength is more inclined to the red region, so it can solve this problem. The problem of insufficient color rendering of YAG: Ce ³⁺ in the red light region is well known in the field.

Example 2: Using different A ²⁺ to synthesize (A _1-x Eu _x ) ₈ B ₂ (PO ₄ ) ₆ O ₂

When y=z=0, the general chemical formula of (A _1-x Eu _x ) ₈ B ₂ (PO ₄ ) ₆ O ₂ can be obtained. The experimental examples synthesized here include A ²⁺ with 0.89mol% Ca ²⁺ , and 10mol% Mg ²⁺ , Sr ²⁺ , Ba ²⁺ , Mn ²⁺ , Zn ²⁺ , and the doped Eu ²⁺ The impurity ratio was 1 mol%. B ³⁺ are all La ²⁺ .

In Table 2, the eight-coordinate ion radii of the above-mentioned Mg ²⁺ , Sr ²⁺ , Ba ²⁺ , Mn ²⁺ , and Zn ²⁺ and the related photoluminescence data of the above-mentioned experimental examples are listed. It can be seen from the data in Table 2 that although the ionic radii of the replaced A ²⁺ range from 89pm to 142pm, the range of light emission and the wavelength of light emission are roughly the same. The results show that substituting different A ²⁺ ions has little effect on the photoexcitation and photoluminescence properties of (Ca _0.89 A _0.1 Eu _0.01 ) ₈ La ₂ (PO ₄ ) ₆ O ₂ .

In FIGS. 7A-7E , the photoexcitation and photoluminescence spectra of Experimental Examples 1-5 are shown, respectively. It can be seen from Figures 7A–7E that, except for the (Ca _0.89 Mn _0.1 Eu _0.01 ) ₈ La ₂ (PO ₄ ) ₆ O ₂ photoexcitation and photoluminescence spectra of Experimental Example 3, which are special, Experimental Examples 1 and 2 , 4, 5 have similar shapes of photoexcitation and photoluminescence spectra. The results again show that substituting different A ²⁺ ions has little effect on the photoexcitation and photoluminescence properties of (Ca _0.89 A _0.1 Eu _0.01 ) ₈ La ₂ (PO ₄ ) ₆ O ₂ .

Table 2: Photoluminescence data related to (Ca _0.89 A _0.1 Eu _0.01 ) ₈ La ₂ (PO ₄ ) ₆ O ₂

Example 3: Using different B ³⁺ to synthesize (A _1-x Eu _x ) ₈ B ₂ (PO ₄ ) ₆ O ₂

When y=z=0, the general chemical formula of (A _1-x Eu _x ) ₈ B ₂ (PO ₄ ) ₆ O ₂ can be obtained. In the experimental example synthesized here, A ²⁺ is all Ca ²⁺ , and the doping ratio of Eu ²⁺ is 1 mol%. 90 mol% of B ³⁺ is La ³⁺ , and 10 mol% is Al ³⁺ , Ga ³⁺ , Sc ³⁺ , In ³⁺ , Lu ³⁺ , Y ³⁺ or Gd ³⁺ .

In Table 3, the six-coordinated ion radii of the above-mentioned Al ³⁺ , Ga ³⁺ , Sc ³⁺ , In ³⁺ , Lu ³⁺ , Y ³⁺ and Gd ³⁺ and the related photoinduced Light up the data. It can be seen from the data in Table 2 that although the ionic radius of the replaced B ³⁺ varies from 53.5pm to 103pm, the range of light emission and the wavelength of light emission are roughly the same. The results show that substituting different B ³⁺ ions has little effect on the photoexcitation and photoluminescence properties of (Ca _0.99 Eu _0.01 ) ₈ (La _0.9 B _0.1 ) ₂ (PO ₄ ) ₆ O ₂ .

Table 3: Photoluminescent data related to (Ca _0.99 Eu _0.01 ) ₈ (La _0.9 B _0.1 ) ₂ (PO ₄ ) ₆ O ₂

In FIGS. 8A-8H , the photoexcitation and photoluminescence spectra of Experimental Examples 6-13 are shown, respectively. It can be seen from Figures 8A–8H that, except for the special (Ca _0.99 Eu _0.01 ) ₈ (La _0.9 Bi _0.1 ) ₂ (PO ₄ ) ₆ O ₂ photoexcitation and photoluminescence spectra of Experimental Example 13, Experimental Example 6 The shape of the photoexcitation and photoluminescence spectra of -12 is almost the same as that of the previous experimental examples 2-5. The results again show that substituting different B ³⁺ ions has little effect on the photoexcitation and photoluminescence properties of (Ca _0.99 Eu _0.01 ) ₈ (La _0.9 B _0.1 ) ₂ (PO ₄ ) ₆ O ₂ .

Example 4: Silicate-substituted (A _1-x Eu _x ) _8-y B _2+y (PO ₄ ) _6-y (SiO ₄ ) _y O ₂

When z=0, the general chemical formula of (A _1-x Eu _x ) _8-y B _2+y (PO ₄ ) _6-y (SiO ₄ ) _y O ₂ can be obtained. In this synthesized experimental example, A ²⁺ is Ca ²⁺ , the doping ratio of Eu ²⁺ is 1 mol%, B ³⁺ is La ³⁺ , and y=1. Therefore, the obtained chemical formula is (Ca _0.99 Eu _0.01 ) ₇ La ₃ (PO ₄ ) ₅ (SiO ₄ )O ₂ , and its related photoluminescent data are listed in Table 4. FIG. 9 shows the photoexcitation and photoluminescence spectra of Experimental Example 14.

It can be seen from Table 4 and Figure 9 that the photoluminescence data of (Ca _0.99 Eu _0.01 ) ₇ La ₃ (PO ₄ ) ₅ (SiO ₄ )O ₂ is not much different from the previous experimental examples 1-13, indicating that it is replaced by silicate After the phosphate radical, the photoexcitation and photoluminescence properties of this series of compounds have little effect.

Table 4: (Ca _0.99 Eu _0.01 ) ₇ La ₃ (PO ₄ ) ₅ (SiO ₄ )O ₂ related photoluminescence data.

Example 5: S ^2- substituted (A _1-x Eu _x ) ₈ B ₂ (PO ₄ ) ₆ (O _1-z S _z ) ₂

When y=0, the general chemical formula of (A _1-x Eu _x ) ₈ B ₂ (PO ₄ ) ₆ (O _1-z S _z ) ₂ can be obtained. In this synthesized experimental example, A ²⁺ is Ca ²⁺ , the doping ratio of Eu ²⁺ is 1 mol%, B ³⁺ is La ³⁺ , and z=0.1. Therefore, the obtained chemical formula is (Ca _0.99 Eu _0.01 ) ₈ La ₃ (PO ₄ ) ₆ (O _0.9 S _0.1 ) ₂ , and its related photoluminescent data are listed in Table 5. FIG. 10 shows the photoexcitation and photoluminescence spectra of Experimental Example 15.

Table 5: The relative photoluminescence data of (Ca _0.99 Eu _0.01 ) ₇ La ₃ (PO ₄ ) ₅ (SiO ₄ )O ₂ .

It can be seen from Table 5 and Figure 10 that (Ca _0.99 Eu _0.01 ) ₈ La ₃ (PO ₄ ) ₆ (O _0.9 S _0.1 ) ₂ is not much different from the photoluminescence data of the previous experimental examples 1-13, showing that the S ² After ^- replacing O ^2- , the photoexcitation and photoluminescence properties of this series of compounds have little effect.

Example 6: Different concentrations of (Ca _0.97 Eu _0.03 ) ₈ La ₂ (PO ₄ ) ₆ O ₂

Applications in White Light Diodes

In this embodiment, an InGaN blue chip capable of emitting 460nm blue light is used, and different concentrations of (Ca _0.97 Eu _0.03 ) ₈ La ₂ (PO ₄ ) ₆ O ₂ are doped into its encapsulant to form a white light diode. The (Ca _0.97 Eu _0.03 ) ₈ La ₂ (PO ₄ ) ₆ O ₂ doping concentration of the white light diode is listed in Table 6.

Table 6: (Ca _0.97 Eu _0.03 ) ₈ La ₂ (PO ₄ ) ₆ O ₂ doping concentration of white light diodes and the color coordinates of the white light emitted.

Experimental example Doping concentration (wt%) Chromaticity coordinates (x,y) 16 50 (0.586,0.405) 17 45 (0.557,0.406) 18 40 (0.512,0.385) 19 35 (0.473,0.325) 20 30 (0.430,0.325) twenty one 25 (0.376,0.280) twenty two 20 (0.346,0.256) twenty three 15 (0.306,0.225) twenty four 10 (0.277,0.192)

In FIG. 11 , the emission spectra of the white light diodes of Experimental Examples 16-24 are shown, and the chromaticity coordinate values of the white light emitted by the white light diodes of Experimental Examples 16-24 are listed in Table 6. From the data in Figure 11 and Table 6, it can be known that when the doping concentration of (Ca _0.97 Eu _0.03 ) ₈ La ₂ (PO ₄ ) ₆ O ₂ phosphor in the encapsulant decreases, the relative emission of the blue chip near 460nm The intensity will increase, while the relative emission intensity of the yellow phosphor near 625nm will decrease. Therefore, the chromaticity coordinate value of the white light emitted by the white light diode can be adjusted from (0.586, 0.405) orange light to (0.277, 0.192) cool white light as the phosphor doping weight decreases.

Generally speaking, since the wavelength of the main light-emitting region of the yellow fluorescent materials with oxyapatite structure in the above experimental examples is longer, it is more inclined to the red light region. Therefore, when the above-mentioned yellow fluorescent material is used to manufacture the white light diode, the color rendering property of the white light emitted by the white light diode in the red light region can be improved, so as to obtain better quality white light.

Although the present invention has been disclosed above in terms of implementation, it is not intended to limit the present invention. Any person skilled in the art may make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the present invention The scope of protection shall prevail as defined by the appended claims.

Claims (10)

1. there is a yellow fluorescent material for oxidapatite structure, it has (A _1-xeu _x) ₂b ₈(SiO ₄) ₆(O _1-zs _z) ₂chemical general formula, wherein A and Eu is divalent-metal ion, and B is trivalent metal ion, and 0<x≤0.6 and 0≤z≤1.

2. yellow fluorescent material as claimed in claim 1, wherein as z=0, this yellow fluorescent material has (A _1-xeu _x) ₂b ₈(SiO ₄) ₆o ₂chemical general formula.

3. yellow fluorescent material as claimed in claim 1, wherein as z=1, this yellow fluorescent material has (A _1-xeu _x) ₂b ₈(SiO ₄) ₆s ₂chemical general formula.

4. the yellow fluorescent material as described in as arbitrary in claim 1-3, wherein A is alkaline-earth metal, Mn or Zn.

5. the yellow fluorescent material as described in as arbitrary in claim 1-3, wherein B is IIIA race metal, rare earth metal or Bi.

6. a white light-emitting diodes, comprises:

One blue-light fluorescent material; And

One gold-tinted fluorescent material, it has (A _1-xeu _x) ₂b ₈(SiO ₄) ₆(O _1-zs _z) ₂chemical general formula, wherein A and Eu is divalent-metal ion, and B is trivalent metal ion, and 0<x≤0.6 and 0≤z≤1.

7. white light-emitting diodes as claimed in claim 6, wherein A is alkaline-earth metal, Mn or Zn.

8. white light-emitting diodes as claimed in claim 6, wherein B can be IIIA race metal, rare earth metal or Bi.

9. a preparation method for gold-tinted fluorescent material as claimed in claim 1, comprises:

Take the raw material of the required element conforming with stoichiometric chemistry ratio, wherein the raw metal of this gold-tinted fluorescent material is metal oxide or metal carbonate, silicate raw material packet silicon oxide-containing, and sulphur raw material packet sulfur-bearing powder;

Mix these raw materials taken equably;

These raw materials that calcined mixed is good, until obtain the product with pure oxygen phosphatic rock crystalline phase, calcination environment is containing aerobic, and calcining temperature is 1200 – 1400 DEG C; And

At the temperature of ammonia and 900 – 1200 DEG C, by Eu ³⁺be reduced into Eu ²⁺, to obtain gold-tinted fluorescent material as claimed in claim 1.

10. preparation method as claimed in claim 9, wherein before reduction step, more comprises the product after the calcining that homogenizes.